US20050274390A1 - Ultra-fine particle catalysts for carbonaceous fuel elements - Google Patents
Ultra-fine particle catalysts for carbonaceous fuel elements Download PDFInfo
- Publication number
- US20050274390A1 US20050274390A1 US10/868,126 US86812604A US2005274390A1 US 20050274390 A1 US20050274390 A1 US 20050274390A1 US 86812604 A US86812604 A US 86812604A US 2005274390 A1 US2005274390 A1 US 2005274390A1
- Authority
- US
- United States
- Prior art keywords
- fuel element
- carbon monoxide
- ultrafine particles
- carbon
- catalyst composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 138
- 239000011882 ultra-fine particle Substances 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 152
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 96
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 63
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 47
- 230000000391 smoking effect Effects 0.000 claims abstract description 44
- 239000000443 aerosol Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 70
- 239000000758 substrate Substances 0.000 claims description 44
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 25
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- 239000000779 smoke Substances 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000011002 quantification Methods 0.000 abstract description 15
- 241000208125 Nicotiana Species 0.000 description 85
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 73
- 229910052799 carbon Inorganic materials 0.000 description 60
- 238000002485 combustion reaction Methods 0.000 description 28
- 235000019504 cigarettes Nutrition 0.000 description 27
- 239000007789 gas Substances 0.000 description 19
- 239000000123 paper Substances 0.000 description 19
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 17
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 230000009467 reduction Effects 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000000796 flavoring agent Substances 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000003570 air Substances 0.000 description 11
- 230000009977 dual effect Effects 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- 235000019634 flavors Nutrition 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 9
- 229920002907 Guar gum Polymers 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000000665 guar gum Substances 0.000 description 8
- 235000010417 guar gum Nutrition 0.000 description 8
- 229960002154 guar gum Drugs 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013626 chemical specie Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000728 ammonium alginate Substances 0.000 description 3
- 235000010407 ammonium alginate Nutrition 0.000 description 3
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 229940044927 ceric oxide Drugs 0.000 description 3
- 238000004141 dimensional analysis Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 235000013980 iron oxide Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- -1 FeO Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011818 carbonaceous material particle Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011101 paper laminate Substances 0.000 description 2
- 230000001007 puffing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- QLRRUWXMMVXORS-UHFFFAOYSA-N Augustine Natural products C12=CC=3OCOC=3C=C2CN2C3CC(OC)C4OC4C31CC2 QLRRUWXMMVXORS-UHFFFAOYSA-N 0.000 description 1
- 241000282836 Camelus dromedarius Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 235000001453 Glycyrrhiza echinata Nutrition 0.000 description 1
- 244000303040 Glycyrrhiza glabra Species 0.000 description 1
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 description 1
- 235000017382 Glycyrrhiza lepidota Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000574138 Ozothamnus diosmifolius Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241001455273 Tetrapoda Species 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- HIJLKWFRGYZKKL-UHFFFAOYSA-N [O-2].[Ti+4].[Au+3] Chemical compound [O-2].[Ti+4].[Au+3] HIJLKWFRGYZKKL-UHFFFAOYSA-N 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229940010454 licorice Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
- A24B15/165—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes comprising as heat source a carbon fuel or an oxidized or thermally degraded carbonaceous fuel, e.g. carbohydrates, cellulosic material
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/285—Treatment of tobacco products or tobacco substitutes by chemical substances characterised by structural features, e.g. particle shape or size
- A24B15/286—Nanoparticles
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/287—Treatment of tobacco products or tobacco substitutes by chemical substances by inorganic substances only
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/287—Treatment of tobacco products or tobacco substitutes by chemical substances by inorganic substances only
- A24B15/288—Catalysts or catalytic material, e.g. included in the wrapping material
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D1/00—Cigars; Cigarettes
- A24D1/22—Cigarettes with integrated combustible heat sources, e.g. with carbonaceous heat sources
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/23—
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
- G01N30/466—Flow patterns using more than one column with separation columns in parallel
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
Definitions
- the present invention relates generally to fuel elements for smoking articles, and more particularly to fuel elements comprising a carbonaceous material and ultrafine particles.
- the fuel elements may be utilized in smoking articles to reduce the amount of carbon monoxide in the mainstream smoke and improve the thermal efficiency of the fuel.
- Cigarettes are popular smoking articles that use tobacco in various forms. Descriptions of cigarettes and the various components thereof are set forth in Tobacco Production, Chemistry and Technology , Davis et al. (Eds.) (1999).
- Cigarettes generally include a substantially cylindrical rod-shaped structure and include a charge, roll or column of smokeable material such as shredded tobacco (e.g., in cut filler form) surrounded by a paper wrapper thereby forming a so-called “tobacco rod.”
- a cigarette has a cylindrical filter element aligned in an end-to-end relationship with the tobacco rod.
- a filter element includes cellulose acetate tow circumscribed by plug wrap, and is attached to the tobacco rod using a circumscribing tipping material. It also has become desirable to perforate the tipping material and plug wrap, in order to provide dilution of drawn mainstream smoke with ambient air.
- Carbonaceous materials can be employed as components of combustible material components in a smoking article that are designed to burn and provide heat to aerosolize physically separate aerosol-forming materials.
- Cigarettes having carbonaceous combustible material components have been marketed by the R. J. Reynolds Tobacco Company under the tradenames Premier and Eclipse. See, for example, U.S. Pat. No. 4,708,151 to Shelar et al.; U.S. Pat. No. 5,016,654 to Bernasek et al.; U.S. Pat. No. 4,991,596 to Lawrence et al.; U.S. Pat. No. 5,038,802 to White et al.; U.S. Pat. No.
- the present invention provides fuel elements comprising ultrafine particles.
- the ultrafine particles catalyze the conversion of carbon monoxide to carbon dioxide, thereby reducing the amount of carbon monoxide present in the combustion gases produced by burning of the fuel element.
- a fuel element comprising ultrafine particles reduces the amount of carbon monoxide present in the aerosol and demonstrates a more efficient combustion by producing more energy per gram of fuel combusted.
- the present invention also provides methods for altering the performance characteristics of smoking articles to reduce the amount of carbon monoxide present in aerosol produced by the smoking article.
- the present invention provides a fuel element comprising a carbonaceous material and at least one catalyst composition, the catalyst composition comprising ultrafine particles.
- the present invention provides a method for reducing the amount of carbon monoxide produced by an article comprising a fuel element, the method comprising incorporating ultrafine particles in the fuel element.
- the present invention provides a smoking article having reduced amounts of carbon monoxide in the aerosol produced by the smoking article.
- the smoking article comprises: a fuel element comprising a carbonaceous material and ultrafine particles.
- the present invention provides methods and apparatus for the simultaneous relative quantification of carbon monoxide and carbon dioxide in a gaseous mixture.
- the method comprises injecting a gaseous mixture into a split single injector of a gas chromatograph for splitting the gaseous mixture onto two chromatographic columns; resolving the carbon monoxide content of the gaseous mixture on a first chromatographic column; simultaneously resolving the carbon dioxide content of the gaseous mixture on a second chromatographic column; and detecting and quantifying the resolved carbon monoxide and carbon dioxide contents with a mass spectrometer.
- Embodiments of the method may be utilized to simultaneously quantify the relative amounts of carbon monoxide and carbon dioxide in aerosol from a smoking article.
- An advantage of the present invention is that fuel elements of the present invention may be used in applications where it is desirable to reduce amounts of carbon monoxide.
- FIG. 1 illustrates a smoking article according to an embodiment of the present invention.
- FIG. 2 illustrates a method according to an embodiment of the present invention.
- FIG. 3 illustrates an apparatus according to an embodiment of the present invention.
- FIG. 4 illustrates an ion chromatogram of a standard gaseous mixture resolved on dual columns according to an embodiment of the present invention.
- FIG. 5 illustrates an ion chromatogram of a standard gaseous mixture resolved on a Molsieve column according to an embodiment of the present invention.
- FIG. 6 illustrates an ion chromatogram of a standard gaseous mixture resolved on a Carbon Plot column according to an embodiment of the present invention.
- FIG. 7 illustrates an ion chromatogram of heated tobaccos resolved on dual columns according to an embodiment of the present invention.
- FIG. 8 illustrates an ion chromatogram of cigarette smoke resolved on dual columns according to an embodiment of the present invention.
- FIG. 9 illustrates the reduced production of carbon monoxide by carbon upon combustion in the presence of various ultrafine particles according to embodiments of the present invention.
- FIG. 10 illustrates the reduced production of carbon monoxide by combustion of carbon and mixtures comprising carbon, Guar gum, graphite, and tobacco in the presence of iron oxide ultrafine particles of various sizes according to embodiments of the present invention.
- FIG. 11 illustrates the reduced production of carbon monoxide by combustion of carbon in the presence of various metal oxide ultrafine particles according to embodiments of the present invention.
- FIG. 12 illustrates the effect of catalyst compositions on a CO/CO 2 ratio when tobacco is pyrolized in the presence of various ultrafine particles according to embodiments of the present invention.
- the present invention provides fuel elements comprising a carbonaceous material and at least one catalyst composition.
- the present invention additionally provides articles of manufacture including, but not limited to, smoking articles.
- the present invention further provides methods for altering the performance characteristics of smoking articles.
- the present invention provides methods and apparatus for the simultaneous quantification of the carbon monoxide content and carbon dioxide content of a gaseous mixture comprising these and various other chemical species.
- a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more, e.g., 1 to 6.1, and ending with a maximum value of 10 or less, e.g., 5.5 to 10, as well as all ranges beginning and ending within the end points, e.g., 2 to 9, 3 to 8, 3.2 to 9.3, 4 to 7, and finally to each number 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 contained within the range.
- any reference referred to as being “incorporated herein” is to be understood as being incorporated in its entirety.
- a fuel element comprises a carbonaceous material and at least one catalyst composition.
- the catalyst composition comprises ultrafine particles of a metal oxide, metal, or mixtures thereof.
- the term ultrafine particle is generally used to indicate particles with dimensions less than 100 nanometers (one nanometer is one-billionth of a meter).
- the metal oxide and metal ultrafine particles can demonstrate activity for catalyzing chemical reactions, such as the oxidation of carbon monoxide to carbon dioxide.
- Ultrafine particles suitable for use in catalytic compositions of the present invention comprise, but are not limited to, iron oxides (e.g. FeO, Fe 2 O 3 and Fe 3 O 4 ), gold, copper, silver, platinum, palladium, rhodium, nickel, zinc, zirconium, other transition metals, metal oxides, and mixtures thereof.
- iron oxides e.g. FeO, Fe 2 O 3 and Fe 3 O 4
- gold gold
- copper silver
- platinum palladium
- rhodium nickel
- zinc, zirconium other transition metals, metal oxides, and mixtures thereof.
- the catalyst compositions comprising ultrafine particles facilitate a more complete production of carbon dioxide by catalyzing the oxidation reaction of carbon to carbon dioxide.
- the catalyst composition acts upon carbon monoxide in the gaseous stream.
- Ultrafine particles of the catalyst compositions may also improve the performance characteristics of a fuel element for particular applications. For example, the ultrafine particles of the catalyst compositions can increase the caloric output of a particular fuel.
- ultrafine particles of the catalyst compositions may have an average particle size of 10 nanometers, generally between 1 nanometer and 1 micron. In an embodiment of a smoking article of the present invention, the ultrafine particles may have an individual particle size of up to about five nanometers. In another embodiment of a smoking article of the present invention, the ultrafine particles may have an individual particle size between about two and four nanometers.
- Ultrafine particles according to the present invention may be produced by a variety of methods including sol-gel synthesis, chemical deposition, deposition precipitation, inert gas condensation, mechanical alloying or high-energy ball milling, plasma synthesis, and electrodeposition. Using such methods, ultrafine particles can be produced in various symmetric shapes, such as spheres, cylinders, prisms, cubes, tetrapods and amorphous clusters.
- the physical properties of the ultrafine particles including for example, their electrical, optical, chemical, mechanical, and magnetic properties, may be selectively controlled for example by engineering the size, morphology, and/or composition of the ultrafine particles.
- the resulting materials may have enhanced or entirely different properties from their parent materials.
- ultrafine particles and materials for use in the present invention are of the type, and may be produced by methods, described in U.S. Pat. No. 6,503,475 to McCormick U.S. Pat. No. 6,472,459 to Morales et al., U.S. Pat. No. 6,467,897 to Wu et al., U.S. Pat. No. 6,479,146 to Caruso et al., and U.S. Pat. No. 6,479,156 to Schmidt et al. and U.S. Published Pat.
- Ultrafine particles for use in the catalyst composition can be obtained commercially.
- Superfine Iron oxide (Fe 2 O 3 ) can be obtained from MACH-1 Inc. of King of Prussia, Pa.
- Nanopowder Enterprise Inc. of Piscataway, N.J. is an additional commercial source of ultrafine particles for use in catalyst compositions of the present invention.
- the fuel element additionally comprises a carbonaceous material.
- the fuel element may additionally comprise binders like Guar gum, other metallic particles such as aluminum or the like, inert filler material like graphite, and/or burn modifiers such as sodium or potassium carbonate.
- the carbonaceous materials for use in the fuel element include at least 50%, by weight carbon.
- the carbonaceous materials for use in the fuel element can include about 60-95% by weight carbon.
- the carbonaceous materials for use in the fuel element can include about 70-80% by weight carbon.
- the carbonaceous materials may be in powder form and may be partially activated.
- the carbonaceous materials may also be heat treated.
- the carbonaceous materials may comprise organic carbon containing materials, for example tobacco.
- the carbonaceous materials of the present invention may be prepared from several starting materials. Suitable starting materials include, but are not limited to, cellulosic materials with a high (i.e., greater than about 80%) alpha-cellulose content, such as cotton, rayon, paper, and the like.
- the carbonaceous materials of fuel elements of the present invention may be generally prepared by pyrolysis of the starting material at a temperature between about 400° C. and 1300° C., preferably between about 500° C. and 950° C., in a non-oxidizing atmosphere, for a period of time sufficient to ensure that a large portion or substantially all of the starting material has reached the desired carbonization temperature.
- a slow pyrolysis employing a gradually increasing heating rate, e.g., from about 1° C. to 20° C. per hour, preferably from about 5° C. to 25° C. per hour, over many hours, produces a uniform and higher carbon yield.
- the carbonaceous material may be pulverized.
- the carbonaceous material is pulverized to a fine powder.
- This powder may be subjected to a second pyrolysis or polishing step, wherein the carbonized particulate material, is again pyrolyzed in a non-oxidizing atmosphere, at a temperature between about 650° C. to about 1250° C., preferably from about 700° C. to 900° C.
- the carbonaceous material is ready for combination with the ultrafine particle catalyst composition along with the other components of the fuel to produce a fuel element composition.
- the ultrafine particles of the catalyst compositions can be combined with a carbonaceous material in a number of ways to produce the fuel element composition.
- One method of combination comprises intimately mixing the carbonaceous material with the ultrafine particles.
- Ultrafine particles in dry powder form e.g. nanopowder
- the ultrafine particles may be mixed directly in a carbon mix along with other dry ingredients for extrusion.
- the ultrafine particles may be suspended in a liquid and the suspension mixed with extrudate.
- Another method of combining the ultrafine catalyst compositions with a carbonaceous material comprises forming the carbonaceous material so as to concentrate the catalytic compositions in one or more longitudinal passageways extending partially through the fuel element.
- the fuel element may comprise an inner core/outer shell arrangement where the outer shell comprises a carbonaceous material surrounding the inner core, and the inner core comprises ultrafine particle catalyst compositions.
- the fuel element may include at least one longitudinal passageway extending at least partially therethrough.
- ultrafine particle catalyst compositions can be combined with a carbonaceous material.
- the ultrafine particle catalyst compositions can be placed on inert support located directly behind the fuel element in an end to end relationship.
- the support for the ultrafine particles can be an inert carbon material such as graphite or a porous material such as alumina or porous graphite.
- the catalyst composition may comprise up to 10% by weight of the resulting mixture. In some embodiments, the catalyst compositions may comprise 1% by weight of the resulting mixture. In another embodiment, catalyst composition may comprise 0.5% to 2% by weight of the resulting mixture.
- the density of a fuel element according to some embodiments of the present invention can be generally greater than about 0.5 g/cc, greater than about 0.7 g/cc and greater than about 1 g/cc.
- the overall length of the fuel element, prior to burning, can be generally less than about 20 mm, often less than about 15 mm, and can be typically about 12 mm. However, shorter fuel elements may be used if desired, depending upon the configuration of the cigarette in which they are employed. In an embodiment, the overall outside diameter of the fuel element can be less than about 8 mm, less than about 6 mm, and can be about 4.2 mm.
- the carbonaceous and binder portions of the fuel compositions useful herein may be any of those carbonaceous and binder materials described in the patents recited in the Background of the Invention, supra.
- Several carbonaceous and binder materials are described in U.S. application Ser. No. 07/722,993, filed 28 Jun. 1991, now U.S. Pat. No. 5,178,167 the disclosure of which is hereby incorporated herein by reference.
- a smoking article comprises a fuel element comprising a carbonaceous material and at least one catalyst composition, the catalyst composition comprising ultrafine particles.
- the cigarette further includes an aerosol generating means, which includes a substrate and at least one aerosol-forming material.
- An aerosol-generating means includes an aerosol forming material (e.g. glycerin), tobacco in some form (e.g. tobacco powders, tobacco extract or tobacco dust) and other aerosol forming materials and/or tobacco flavoring agents such as cocoa, licorice, and sugar.
- the aerosol forming material generally is carried on a substrate material such as a reconstituted tobacco cut filler or on a substrate such as tobacco cut filler, gathered paper, gathered tobacco paper, or the like.
- the substrate is reconstituted tobacco, which is formed into a continuous rod or substrate tube assembly on a conventional cigarette making machine.
- the overwrap material for the rod is a barrier material such as a paper foil laminate.
- the foil serves as a barrier, and is located on the inside of the overwrap.
- the substrate may be a gathered paper formed into a rod or plug. When the substrate is a paper-type material, it can be positioned in a spaced-apart relationship from the fuel element comprising a carbonaceous material and a catalyst composition.
- a spaced-apart relationship is desired to minimize contact between the fuel element and the substrate, thereby preventing migration of the aerosol forming materials to the fuel element, as well as limiting the scorching or burning of the paper substrate.
- the spacing is normally provided during manufacture of the cigarette in accordance with one method of making the present invention.
- Appropriately spaced substrate plugs are overwrapped with a barrier material to form a substrate tube assembly having spaced substrate plugs therein.
- the substrate tube assembly is cut between the substrate plugs to form substrate sections.
- the substrate sections include a tube with a substrate plug and void(s), which can be at each end.
- the barrier material for making the tube aids in preventing migration of the aerosol former to other components of the cigarette.
- the barrier material forming the tube is a relatively stiff material so that when formed into a tube, it will maintain its shape and will not collapse during manufacture and use of the cigarette.
- fuel elements of a smoking article can be advantageously circumscribed by an insulating and/or retaining jacket material.
- the insulating and retaining material is adapted such that drawn air can pass therethrough, and is positioned and configured so as to hold the fuel element in place.
- the jacket is flush with the ends of the fuel element, however, it may extend from about 0.5 mm to about 3 mm beyond each end of the fuel element.
- the components of the insulating and/or retaining material which surrounds the fuel element can vary.
- suitable materials include glass fibers and other materials as described in U.S. Pat. No. 5,105,838; European Patent Publication No. 339,690; and pages 48-52 of the RJR Monograph, supra.
- suitable insulating and/or retaining materials are glass fiber and tobacco mixtures such as those described in U.S. Pat. Nos. 5,105,838, 5,065,776 and 4,756,318; and U.S. patent application Ser. No. 07/354,605, filed 22 May 1989 now U.S. Pat. No. 5,119,837.
- Suitable insulating and/or retaining materials are gathered paper-type materials which are spirally wrapped or otherwise wound around the fuel element, such as those described in U.S. patent application Ser. No. 07/567,520, filed 15 Aug. 1990, now U.S. Pat. No. 5,105,836.
- the paper-type materials can be gathered or crimped and gathered around the fuel element; gathered into a rod using a rod making unit available as CU-10 or CU2OS from DeCoufle s.a.r.b., together with a KDF-2 rod making apparatus from Hauni-Werke Korber & Co., KG, or the apparatus described in U.S. Pat. No.
- the fuel element may be extruded into the insulating jacket material as set forth in U.S. patent application Ser. No. 07/856,239, filed 25 Mar. 1992, the disclosure of which is incorporated herein by reference.
- paper-type sheet materials are available as P-2540-136-E carbon paper and P-2674-157 tobacco paper from Kimberly-Clark Corp.; and the longitudinally extending strands of such materials (e.g., strands of about 1/32 inch width) extend along the longitude of the fuel element.
- the fuel element also can be circumscribed by tobacco cut filler (e.g., flue-cured tobacco cut filler treated with about 2 weight percent potassium carbonate). The number and positioning of the strands or the pattern of the gathered paper is sufficiently tight to maintain, retain or otherwise hold the composite fuel element structure within the cigarette.
- the fuel element-jacket assembly is combined with a substrate section or substrate tube assembly by a wrapper material, which has a propensity not to burn, to form a fuel element/substrate section.
- the wrapper typically extends from the mouthend of the substrate section, over a portion of the jacketed fuel element, whereby it is spaced from the lighting end of the fuel element.
- the wrapper material assists in limiting the amount of oxygen which will reach the burning portion of the fuel element during use, thereby causing the fuel element to extinguish after an appropriate number of puffs.
- the wrapper is a paper/foil/paper laminate.
- the foil provides a path to assist in dissipating or transferring the heat generated by the fuel element during use.
- the jacketed fuel element and the substrate section are joined by the overwrap.
- a tobacco section can be formed by a reconstituted tobacco cut filler rod, made on a typical cigarette making machine, and cut into appropriate lengths.
- a filter rod is formed and cut into appropriate lengths for joining to the tobacco section to form a mouthend section.
- the fuel element/substrate section and the mouthend section are joined by aligning the reconstituted ends of each section, and overwrapped to form a cigarette.
- a tobacco paper rod and a reconstituted cut filler rod are formed and cut into appropriate lengths and joined to form a tobacco section.
- the tobacco section and the fuel element assembly/substrate section are joined by aligning the tobacco paper plug end of the tobacco section with the substrate end of the fuel element assembly/substrate section and joining the sections with a wrapper which extends from the rear end of the tobacco roll to an appropriate length past the junction of the two sections for forming the tobacco roll/fuel element assembly.
- the tobacco roll/fuel element assembly is then joined to a filter by a tipping material.
- the substrate carries aerosol forming materials and other ingredients, e.g., flavorants and the like, which, upon exposure to heated gases passing through the aerosol generating means during puffing, are vaporized and delivered to the user as a smoke-like aerosol.
- Aerosol forming materials used herein include glycerin, propylene glycol, water, and the like, flavorants, and other optional ingredients.
- the patents referred to in the Background of the Invention (supra) teach additional useful aerosol forming materials that need not be repeated here.
- Cast sheets of tobacco dust or powder, a binder, such as an alginate binder, and glycerin can also be used to form useful substrates herein.
- Suitable cast sheet materials for use as substrates are described in U.S. Pat. No. 5,101,839 and U.S. patent application Ser. No. 07/800,679, filed Nov. 27, 1991.
- Suitable cast sheet materials typically contain between about 30 to 75 weight percent of an aerosol former such as glycerin; about 2 to 15 weight percent of a binder, such as ammonium alginate; 0 to about 2 weight percent of a sequestering agent such as potassium carbonate; about 15 to about 70 to 75 weight percent of organic, inorganic filler materials, or mixtures thereof, such as tobacco dust, aqueous extracted tobacco powder, starch powder, rice flower, ground puffed tobaccos, carbon powder, calcium carbonate powder, and the like, and from about 0 to about 20 weight percent of flavors such as tobacco extracts, and the like.
- an aerosol former such as glycerin
- a binder such as ammonium alginate
- a sequestering agent such as potassium carbonate
- organic, inorganic filler materials or mixtures thereof, such as tobacco dust, aqueous extracted tobacco powder, starch powder, rice flower, ground puffed tobaccos, carbon powder, calcium carbonate powder, and the like, and from about 0
- a cast sheet material includes 60 weight percent glycerin, 5 weight percent ammonium alginate binder, 1 weight percent potassium carbonate, 2 weight percent flavors such as tobacco extracts and 32 weight percent aqueous extracted tobacco powder.
- the cast sheets are formed by mixing aqueous extracted tobacco powder, water and the potassium carbonate in a high sheer mixer to produce a smooth, flowable paste. Glycerin and ammonium alginate are then added and the high shear mixing is continued until a homogenized mixture is produced.
- the homogenized mixture is cast on a heated belt (about 200.degree. F.) with a 0.0025 to 0.0035 inch casting clearance and is dried to yield a 0.0004 to 0.0008 inch thick sheet under high temperature air (about 200.degree. to 250.degree. F.).
- the sheet is doctored from the belt and either wound onto spools for slitting into webs or chopped into rectangular pieces about 2 inches by 1 inch which are formed into cut filler.
- the substrate will be from about 10 mm to 40 mm in length and extend from the rear end of the fuel element to the tobacco segment or the front end of an extra long filter segment (e.g., about 30 mm to 50 mm in length). In such instances the tobacco paper plug can be omitted.
- the combination of the fuel element and the substrate (also known as the front end assembly) is attached to a mouthend piece; although a disposable fuel element/substrate combination can be employed with a separate mouthend piece, such as a reusable cigarette holder.
- the mouthend piece provides a passageway which channels vaporized aerosol forming materials into the mouth of the smoker; and can also provide further flavor to the vaporized aerosol forming materials.
- Flavor segments i.e., segments of gathered tobacco paper, tobacco cut filler, or the like
- Gathered carbon paper can be incorporated, particularly in order to introduce menthol flavor to the aerosol.
- Such papers are described in European Patent Publication No. 342,538.
- Other flavor segments useful herein are described in U.S. patent application Ser. No. 07/414,835, filed 29 Sep. 1989, now U.S. Pat. No. 5,076,295 Ser. No. 07/606,287, filed 6 Nov. 1990; now U.S. Pat. No. 5,105,834 and Ser. No. 07/621,499, filed 7 Dec. 1990, now abandoned.
- FIG. 1 illustrates a smoking article according to an embodiment of the present invention.
- the smoking article depicted in FIG. 1 comprises a fuel element 10 of the present invention comprising a carbon source and at least one catalytic composition comprising ultrafine particles of a metal oxide and/or metal.
- the fuel element displays a plurality of passageways 11 therethrough, about thirteen passageways altogether.
- the fuel element 10 is surrounded by insulating sheet material 16 having a plurality of grooves which facilitate the formation of the sheet material into a jacket surrounding the fuel element.
- the jacket can be made of calcium sulfate (CaSO 4 ).
- a metallic capsule 12 overlaps a portion of the mouthend of the fuel element 10 and encloses the physically separate aerosol generating means which contains a substrate material 14 .
- the substrate material carries one or more aerosol forming materials.
- the substrate may be in particulate form, in the form of a rod, and other geometric shapes advantageous for generating an aerosol.
- Capsule 12 is circumscribed by a roll of tobacco 18 .
- the capsule may be circumscribed with an additional or continuous jacket of an insulating sheet material.
- Insulating sheet materials suitable for use in smoking articles of the present invention are further described in U.S. Pat. No. 5,303,720 to Banerjee which is hereby incorporated by reference.
- Two slit-like passageways 20 are provided at the mouth of the capsule in the center of the crimped tube.
- a mouthend piece 22 comprising a cylindrical segment of a flavored carbon filled sheet material 24 and a segment of non-woven thermoplastic fibers 26 through which the aerosol passes to the user.
- the smoking article, or portions thereof, is overwrapped with one or more layers of cigarette papers 30 - 36
- catalyst compositions comprising metal oxide and/or metal ultrafine particles are incorporated into the filter element of the smoking article as described in U.S. patent application Ser. No. 10/730,962 which is hereby incorporated by reference.
- convective heating is the predominant mode of energy transfer from the burning fuel element comprising a carbonaceous material and at least one catalyst composition to the aerosol-generating means disposed longitudinally behind the fuel element.
- a foil/paper laminate is used as an overwrap to join the fuel/substrate section some heat may be transferred to the substrate by the foil layer.
- the heat transferred to the substrate volatilizes the aerosol-forming material(s) and any flavorant materials carried by the substrate, and, upon cooling, these volatilized materials are condensed to form a smoke-like aerosol which is drawn through the cigarette during puffing, and which exits the filter piece.
- This smoke-like aerosol can contain reduced amounts of carbon monoxide resulting from the reduced carbon monoxide production of a fuel element of the present invention upon combustion.
- the catalyst compositions can be deposited on a porous support such as graphite or alumina wherein the porous support is placed behind the fuel in an end to end relationship.
- the present invention provides a method for facilitating the reduction in the amount of carbon monoxide produced by a smoking article, comprising incorporating at least one catalyst composition comprising ultrafine particles of a metal oxide and/or metal into the fuel element of a smoking article.
- the present invention provides methods and apparatus for the simultaneous quantification of the carbon monoxide content and carbon dioxide content of a gaseous mixture.
- a method for quantifying the carbon monoxide content and carbon dioxide content of a gaseous mixture comprises injecting the gaseous mixture into a split injection tube of a gas chromatograph through a single injector, resolving a relative carbon monoxide content of the gaseous mixture on a first chromatographic column, simultaneously resolving a relative carbon dioxide content on a second chromatographic column, and detecting and quantifying the eluate carbon monoxide and carbon dioxide with a mass spectrometer.
- the gaseous mixture containing carbon monoxide and carbon dioxide comprises mainstream smoke or a smoke-like aerosol produced from a smoking article.
- GC/MS gas chromatography/mass spectrometry
- FIG. 2 illustrates a flowchart for the quantification of carbon monoxide and carbon dioxide contents of a gaseous mixture according to an embodiment of the present invention.
- the gaseous mixture comprises mainstream smoke or smoke-like aerosol from a smoking article.
- the gaseous mixture is injected into the split injector of the gas chromatogram 201 .
- the split injector 201 splits the gaseous mixture for simultaneous resolution on dual chromatographic columns.
- the carbon monoxide content of the mainstream smoke is resolved on a first chromatographic column 202
- the carbon dioxide content is simultaneously resolved on a second chromatographic column 203 .
- the first chromatographic column can be selected for optimal resolution of carbon monoxide while the second chromatographic column can be selected for the optimal resolution of carbon dioxide.
- a Molsieve column can be used to resolve carbon monoxide and a wide-bore GS-CarbonPLOT column can be used to resolve carbon dioxide.
- the carbon monoxide content and carbon dioxide content of the mainstream smoke are quantified by a mass spectrometer 204 .
- the use of a mass spectrometer adds a second dimension of analysis that is not present with traditional gas chromatographic detection devices.
- a mass spectrometer can further resolve the carbon monoxide content and carbon dioxide content of a gaseous mixture allowing for greater accuracy and precision when quantifying these chemical species.
- an apparatus for quantifying the carbon monoxide content and carbon dioxide content of a gaseous mixture comprises: a gas chromatograph comprising a single split injector, dual chromatographic columns; and a mass spectrometer.
- FIG. 3 illustrates an apparatus for the simultaneous quantification of the carbon monoxide content and carbon dioxide content of a gaseous mixture comprising the two-dimensional analysis of gas chromatography and mass spectrometry in an embodiment according to the present invention.
- the gas chromatograph 301 comprises a single injector 302 which splits the sample onto two chromatographic columns 303 , 304 .
- the temperature of the split single injector 302 can be varied in accordance with desired analytical conditions.
- the temperature variance of the single split injector 302 can be controlled manually by a user or can be controlled electronically with any processor-equipped device such as a computer and/or dedicated controller.
- one of the two columns 303 is suitable for resolving the carbon monoxide content of a gaseous mixture while the other column 304 is suitable for resolving the gaseous mixture's carbon dioxide content.
- Chromatographic columns for use in the gas chromatograph of the present apparatus are available commercially.
- Mass spectrometers suitable for use in further resolving and quantifying the carbon monoxide content and carbon dioxide content eluting from the two columns of the gas chromatograph can comprise mass analyzers comprising magnetic sector analyzers, double-focusing spectrometers, quadrupole mass filters, ion trap analyzers, and time-of-flight (TOF) analyzers.
- TOF time-of-flight
- Graphite in the fuel elements comprising graphite, BKO carbon, Guar gum, and tobacco, is inactive up to the temperatures attained by combustion of the fuel element and remains substantially unchanged throughout the combustion of the fuel element.
- the remaining three carbonaceous components undergo oxidation during the combustion to provide energy and oxides of carbon.
- BKO carbon is the major component and hence chosen for the study of the fuel elements in the examples below.
- the materials prepared for analysis by the method and apparatus were a standard gaseous mixture (CO:CO 2 :N 2 ), tobaccos from 1R4F cigarettes, and 1R4F cigarette smoke.
- a small quantity of each sample was heated to 700° C. for 20 seconds in the presence of air.
- the standard gaseous mixture was analyzed in the absence of air to preserve the composition of the sample.
- a pyroprobe was used for sample heating. The temperatures of the pyroprobe interface and the gas chromatograph injector were set at ambient temperature.
- the gas chromatograph utilized was a Hewlett-Packard 5890 Series II. A single injection onto dual chromatographic columns was used for the carbon monoxide and carbon dioxide analysis. A Molsieve column (Chrompack, 25 M ⁇ 0.32 mm I.D., 30 ⁇ m film) was used for carbon monoxide resolution, and a GS-CarbonPLOT column (J&W Scientific, 60 M ⁇ 0.32 mm I.D., 1.5 ⁇ m film) was used for carbon dioxide resolution. The temperatures of the columns were held at 35° C. for 10 minutes, programmed to 150° C. at 25° C./min and held for 10 min.
- a single mass spectrometer was used to identify and quantify the resolved carbon monoxide and carbon dioxide peaks eluting from the chromatographic columns.
- the mass spectrometer utilized was a Hewlett-Packard 5972 mass selective detector.
- the mass spectrometer was operated at 70 eV in the EI mode with the temperature of the ion source being maintained at 180° C.
- the mass range scanned was 20-200 atomic mass units.
- the carbon monoxide and carbon dioxide quantified were only a fraction of the total carbon monoxide and carbon dioxide generated from the heated materials. Only the resolved carbon monoxide and carbon dioxide peak areas were used for quantification.
- FIG. 4 The results of the standard gaseous mixture resolved on the dual chromatographic columns are illustrated in FIG. 4 .
- the ion chromatogram of FIG. 4 demonstrates a completely resolved carbon monoxide peak and a completely resolved carbon dioxide peak.
- the standard gaseous mixture CO:CO 2 :N 2
- the standard gaseous mixture was resolved on a single column gas chromatograph comprising a Molsieve column.
- FIG. 5 As demonstrated in the ion chromatogram of FIG. 5 , the Molsieve column completely resolved the carbon monoxide content but failed to completely resolve the carbon dioxide content of the standard gaseous mixture.
- FIG. 6 The results of this resolution are illustrated in FIG. 6 .
- the ion chromatogram of FIG. 6 displays a complete resolution of carbon dioxide and an incomplete resolution of carbon monoxide. The carbon monoxide co-eluted with nitrogen and oxygen.
- FIGS. 7 and 8 The results of the remaining sample materials comprising tobaccos from 1R4F cigarettes and 1R4F cigarette smoke resolved on dual chromatographic columns in accordance with the present invention are illustrated in FIGS. 7 and 8 respectively.
- the ion chromatograms of FIGS. 7 and 8 demonstrate completely and sharply resolved carbon monoxide and carbon dioxide peaks.
- a pyroprobe was used to heat a small quantity of each sample to 700° C. for 20 seconds in the presence of air.
- 700° C. is the average temperature of a fuel element during combustion.
- the gaseous mixture resulting from the combustion of each sample was analyzed in accordance with the method delineated in FIG. 2 .
- the pyroprobe and gas chromatogram injector were set at ambient temperature.
- a Molsieve chromatographic column was used for carbon monoxide resolution and a GS-CarbonPLOT chromatographic column was used for carbon dioxide resolution.
- a mass spectrometer was used as a second dimension of analysis in the quantification of the carbon monoxide and carbon dioxide contents generated by the samples.
- a pyroprobe was used to heat a small quantity of each sample to 700° C. in the presence of air for 20 seconds.
- 700° C. is the average temperature of a fuel element during combustion.
- the gaseous mixture resulting from the combustion of each sample was analyzed in accordance with the method delineated in FIG. 2 .
- the pyroprobe and gas chromatogram injector were set at ambient temperature.
- a Molsieve chromatographic column was used for carbon monoxide resolution and a GS-CarbonPLOT chromatographic column was used for carbon dioxide resolution.
- a mass spectrometer was used as a second dimension of analysis in the quantification of the carbon monoxide and carbon dioxide contents generated by the samples.
- sample testing further demonstrate the catalytic activity of ferric oxide ultrafine particles in fuel elements that comprise the additional components of Guar gum and graphite.
- Sample (7) is an example of a fuel element containing these additional components.
- Sample (8) comprises the components of sample (7) with the addition of 5% by weight of ferric oxide (Fe 2 O 3 ) ultrafine particles.
- the ferric oxide (Fe 2 O 3 ) ultrafine particles reduced the carbon monoxide production of the fuel element of sample (8) by 68% in comparison with sample (7) which did not contain ferric oxide (Fe 2 O 3 ) ultrafine particles.
- Sample (5) is a fuel element containing a 5.05% tobacco content in addition to BKO Carbon 950, Guar gum, and graphite.
- Sample (6) comprises the components of sample (5) with the addition of 5% by weight of ferric oxide (Fe 2 O 3 ) nanoparticle.
- the ferric oxide (Fe 2 O 3 ) ultrafine particles reduced the carbon monoxide production of the fuel element of sample (6) by 15.4% in comparison with sample (5) which did not contain ferric oxide (Fe 2 O 3 ) ultrafine particles.
- the catalytic activity of the ferric oxide (Fe 2 O 3 ) ultrafine particles in sample (6) was diminished due to the tobacco content in the fuel element composition.
- the combustion of tobacco produces several chemical species that inhibit the catalytic behavior of the ultrafine particles. This catalytic inhibition is displayed in the 15.4% reduction of carbon monoxide production.
- the sample were: (1) Control Carbon (BKO 950), (2) Carbon with 5% Fe 2 O 3 ultrafine particles obtained from MACH-1, Inc., (3) Carbon with 5% Al 2 O 3 ultrafine particles obtained from NEI, Inc., (4) Carbon with 5% CeO 2 ultrafine particles obtained from NEI, Inc., (5) Carbon with 5% TiO 2 ultrafine particles obtained from NEI, Inc., (6) Carbon with 5% tobacco and 5% Fe 2 O 3 ultrafine particles obtained from MACH-1, Inc., and (7) Carbon with 5% tobacco (heat treated) and 5% Fe 2 O 3 ultrafine particles obtained from MACH-1, Inc.
- a pyroprobe was used to heat a small quantity of each sample to 700° C. in the presence of air for 20 seconds.
- 700° C. is the average temperature of a fuel element during combustion.
- the gaseous mixture resulting from the combustion of each sample was analyzed in accordance with the method delineated in FIG. 2 .
- the pyroprobe and gas chromatogram injector were set at ambient temperature.
- a Molsieve chromatographic column was used for carbon monoxide resolution and a GC-CarbonPLOT chromatographic column was used for carbon dioxide resolution.
- a mass spectrometer was used as a second dimension of analysis in the quantification of the carbon monoxide and carbon dioxide contents generated by the samples.
- ferric oxide (Fe 2 O 3 ) ultrafine particles demonstrate a greater reduction in the carbon monoxide production of heated fuel elements.
- samples (3) and (5) containing aluminum oxide (Al 2 O 3 ) and titanium oxide (TiO 2 ) ultrafine particles respectively exhibited a slight increase in carbon monoxide content.
- sample (4) comprising ceric oxide (CeO 2 ) ultrafine particles displayed a carbon monoxide reduction of 13%.
- Sample (2) comprising ferric oxide (Fe 2 O 3 ) ultrafine particles exhibited a carbon monoxide reduction of 80%.
- ferric oxide (Fe 2 O 3 ) ultrafine particles were additionally incorporated into fuel elements that contained tobacco as well. The reduction of carbon monoxide produced from these fuel elements when heated was diminished due to the catalyst poisoning chemical species generated upon tobacco combustion.
- a Chemical Data System (CDS) Model 2000 pyroprobe was used for sample heating. A small quantity of each sample (approximately 7 mg) was heated at 700° C. in the presence of air for 20 seconds. The gaseous mixture resulting from the heating of each sample was analyzed in accordance with the method delineated in FIG. 2 . The temperatures of the pyroprobe interface and the injector on the gas chromatogram were set at ambient temperature. The GC used was a Hewlett-Packard 5890 Series II gas chromatograph. A single injection onto dual columns was used for CO and CO 2 analysis. A Molsieve column (Chrompack, 25 M ⁇ 0.32 mm I.D., 30 ⁇ m film) was used for CO analysis.
- CDS Chemical Data System
- a GS-CarbonPLOT column (J&W Scientific, 60 M ⁇ 0.32 mm I.D., 1.5 ⁇ m film) was used for CO 2 analysis.
- the temperature of the CG columns was held at 35° C. for 10 minutes, programmed to 150° C. at 25° C./min and held for 10 min.
- a mass spectrometer (MS) was used to identify and quantify the resolved CO and CO 2 peaks eluting from the gas chromatograph.
- the MS used was a Hewlett-Packard 5972 mass selective detector.
- the mass spectrometer was operated at 70 eV in the El mode.
- the temperature of the ion source was maintained at 180° C. and the mass range scanned was 20-200 atomic mass units.
- a small component of tobacco within the fuel element does not destroy the catalytic activity of the metal oxide and metal ultrafine particles an appreciable amount and is, therefore, tolerable.
- the inclusion of a tobacco component in the fuel element of a smoking article can provide more flavor to the aerosol comprising the mainstream smoke of a smoking article.
Abstract
Description
- The present invention relates generally to fuel elements for smoking articles, and more particularly to fuel elements comprising a carbonaceous material and ultrafine particles. In an embodiment, the fuel elements may be utilized in smoking articles to reduce the amount of carbon monoxide in the mainstream smoke and improve the thermal efficiency of the fuel.
- Cigarettes are popular smoking articles that use tobacco in various forms. Descriptions of cigarettes and the various components thereof are set forth in Tobacco Production, Chemistry and Technology, Davis et al. (Eds.) (1999).
- Cigarettes generally include a substantially cylindrical rod-shaped structure and include a charge, roll or column of smokeable material such as shredded tobacco (e.g., in cut filler form) surrounded by a paper wrapper thereby forming a so-called “tobacco rod.” Normally, a cigarette has a cylindrical filter element aligned in an end-to-end relationship with the tobacco rod. Typically, a filter element includes cellulose acetate tow circumscribed by plug wrap, and is attached to the tobacco rod using a circumscribing tipping material. It also has become desirable to perforate the tipping material and plug wrap, in order to provide dilution of drawn mainstream smoke with ambient air.
- Carbonaceous materials can be employed as components of combustible material components in a smoking article that are designed to burn and provide heat to aerosolize physically separate aerosol-forming materials. Cigarettes having carbonaceous combustible material components have been marketed by the R. J. Reynolds Tobacco Company under the tradenames Premier and Eclipse. See, for example, U.S. Pat. No. 4,708,151 to Shelar et al.; U.S. Pat. No. 5,016,654 to Bernasek et al.; U.S. Pat. No. 4,991,596 to Lawrence et al.; U.S. Pat. No. 5,038,802 to White et al.; U.S. Pat. No. 4,793,365 to Sensabaugh et al.; U.S. Pat. No. 4,961,438 to Korte; U.S. Pat. No. 4,991,606 to Serrano et al.; U.S. Pat. No. 5,020,548 to Farrier et al.; U.S. Pat. No. 5,076,297 to Farrier et al.; U.S. Pat. No. 5,148,821 to Best et al.; U.S. Pat. No. 5,178,167 to Riggs et al.; U.S. Pat. No. 5,183,062 to Clearman et al.; U.S. Pat. No. 5,345,955 to Clearman et al.; U.S. Pat. No. 5,551,451 to Riggs et al.; and U.S. Pat. No. 5,595,577 to Bensalem et al. The disclosure of each of these patents is incorporated herein by reference. See, also, Chemical and Biological Studies on New Cigarette Prototypes that Heat Instead of Burn Tobacco, R. J. Reynolds Tobacco Company Monograph (1988).
- It also has been suggested to incorporate non-combustible materials into the carbonaceous combustible material components of certain types of smoking articles. See, for example, U.S. Pat. No. 5,040,551 to Schlatter et al.; U.S. Pat. No. 5,211,684 to Shannon et al.; U.S. Pat. No. 5,240,014 to Deevi et al.; and U.S. Pat. No. 5,258,340 to Augustine et al. The disclosure of each of these patents is incorporated herein by reference.
- It would be desirable to provide a fuel element for a smoking article that reduces the amount of carbon monoxide present in the aerosol of the smoking article. It would additionally be desirable to provide a fuel element that displays a more efficient combustion.
- The present invention provides fuel elements comprising ultrafine particles. In an embodiment of the present invention, the ultrafine particles catalyze the conversion of carbon monoxide to carbon dioxide, thereby reducing the amount of carbon monoxide present in the combustion gases produced by burning of the fuel element. In a smoking article embodiment, a fuel element comprising ultrafine particles reduces the amount of carbon monoxide present in the aerosol and demonstrates a more efficient combustion by producing more energy per gram of fuel combusted.
- The present invention also provides methods for altering the performance characteristics of smoking articles to reduce the amount of carbon monoxide present in aerosol produced by the smoking article.
- In one aspect, the present invention provides a fuel element comprising a carbonaceous material and at least one catalyst composition, the catalyst composition comprising ultrafine particles.
- In another aspect, the present invention provides a method for reducing the amount of carbon monoxide produced by an article comprising a fuel element, the method comprising incorporating ultrafine particles in the fuel element.
- In a further aspect, the present invention provides a smoking article having reduced amounts of carbon monoxide in the aerosol produced by the smoking article. In an embodiment, the smoking article comprises: a fuel element comprising a carbonaceous material and ultrafine particles.
- In a still further aspect, the present invention provides methods and apparatus for the simultaneous relative quantification of carbon monoxide and carbon dioxide in a gaseous mixture. In an embodiment, the method comprises injecting a gaseous mixture into a split single injector of a gas chromatograph for splitting the gaseous mixture onto two chromatographic columns; resolving the carbon monoxide content of the gaseous mixture on a first chromatographic column; simultaneously resolving the carbon dioxide content of the gaseous mixture on a second chromatographic column; and detecting and quantifying the resolved carbon monoxide and carbon dioxide contents with a mass spectrometer. Embodiments of the method may be utilized to simultaneously quantify the relative amounts of carbon monoxide and carbon dioxide in aerosol from a smoking article.
- An advantage of the present invention is that that fuel elements of the present invention may be used in applications where it is desirable to reduce amounts of carbon monoxide.
- Further features and advantages of the present invention are set forth in the following more detailed description.
-
FIG. 1 illustrates a smoking article according to an embodiment of the present invention. -
FIG. 2 illustrates a method according to an embodiment of the present invention. -
FIG. 3 illustrates an apparatus according to an embodiment of the present invention. -
FIG. 4 illustrates an ion chromatogram of a standard gaseous mixture resolved on dual columns according to an embodiment of the present invention. -
FIG. 5 illustrates an ion chromatogram of a standard gaseous mixture resolved on a Molsieve column according to an embodiment of the present invention. -
FIG. 6 illustrates an ion chromatogram of a standard gaseous mixture resolved on a Carbon Plot column according to an embodiment of the present invention. -
FIG. 7 illustrates an ion chromatogram of heated tobaccos resolved on dual columns according to an embodiment of the present invention. -
FIG. 8 illustrates an ion chromatogram of cigarette smoke resolved on dual columns according to an embodiment of the present invention. -
FIG. 9 illustrates the reduced production of carbon monoxide by carbon upon combustion in the presence of various ultrafine particles according to embodiments of the present invention. -
FIG. 10 illustrates the reduced production of carbon monoxide by combustion of carbon and mixtures comprising carbon, Guar gum, graphite, and tobacco in the presence of iron oxide ultrafine particles of various sizes according to embodiments of the present invention. -
FIG. 11 illustrates the reduced production of carbon monoxide by combustion of carbon in the presence of various metal oxide ultrafine particles according to embodiments of the present invention. -
FIG. 12 illustrates the effect of catalyst compositions on a CO/CO2 ratio when tobacco is pyrolized in the presence of various ultrafine particles according to embodiments of the present invention. - The present invention provides fuel elements comprising a carbonaceous material and at least one catalyst composition. The present invention additionally provides articles of manufacture including, but not limited to, smoking articles. The present invention further provides methods for altering the performance characteristics of smoking articles. Moreover, the present invention provides methods and apparatus for the simultaneous quantification of the carbon monoxide content and carbon dioxide content of a gaseous mixture comprising these and various other chemical species.
- Reference is made below to specific embodiments of the present invention. Each embodiment is provided by way of explanation of the invention, not as a limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment may be incorporated into another embodiment to yield a further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the appended claims and their equivalents.
- For the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification are approximations that can vary, depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
- Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein, and every number between the end points. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more, e.g., 1 to 6.1, and ending with a maximum value of 10 or less, e.g., 5.5 to 10, as well as all ranges beginning and ending within the end points, e.g., 2 to 9, 3 to 8, 3.2 to 9.3, 4 to 7, and finally to each
number - It is further noted that, as used in this specification, the singular forms “a,” “an,” and “the” include plural referents unless expressly and unequivocally limited to one referent.
- In one embodiment of the present invention, a fuel element comprises a carbonaceous material and at least one catalyst composition. The catalyst composition comprises ultrafine particles of a metal oxide, metal, or mixtures thereof. As used herein, the term ultrafine particle is generally used to indicate particles with dimensions less than 100 nanometers (one nanometer is one-billionth of a meter). The metal oxide and metal ultrafine particles can demonstrate activity for catalyzing chemical reactions, such as the oxidation of carbon monoxide to carbon dioxide.
- Ultrafine particles suitable for use in catalytic compositions of the present invention comprise, but are not limited to, iron oxides (e.g. FeO, Fe2O3 and Fe3O4), gold, copper, silver, platinum, palladium, rhodium, nickel, zinc, zirconium, other transition metals, metal oxides, and mixtures thereof.
- The catalyst compositions comprising ultrafine particles facilitate a more complete production of carbon dioxide by catalyzing the oxidation reaction of carbon to carbon dioxide. In an embodiment wherein combustion of a fuel element generates a gaseous stream comprising carbon monoxide, the catalyst composition acts upon carbon monoxide in the gaseous stream. Ultrafine particles of the catalyst compositions may also improve the performance characteristics of a fuel element for particular applications. For example, the ultrafine particles of the catalyst compositions can increase the caloric output of a particular fuel.
- In an embodiment of the present invention, ultrafine particles of the catalyst compositions may have an average particle size of 10 nanometers, generally between 1 nanometer and 1 micron. In an embodiment of a smoking article of the present invention, the ultrafine particles may have an individual particle size of up to about five nanometers. In another embodiment of a smoking article of the present invention, the ultrafine particles may have an individual particle size between about two and four nanometers.
- Ultrafine particles according to the present invention may be produced by a variety of methods including sol-gel synthesis, chemical deposition, deposition precipitation, inert gas condensation, mechanical alloying or high-energy ball milling, plasma synthesis, and electrodeposition. Using such methods, ultrafine particles can be produced in various symmetric shapes, such as spheres, cylinders, prisms, cubes, tetrapods and amorphous clusters. In embodiments of the present invention, the physical properties of the ultrafine particles, including for example, their electrical, optical, chemical, mechanical, and magnetic properties, may be selectively controlled for example by engineering the size, morphology, and/or composition of the ultrafine particles. The resulting materials may have enhanced or entirely different properties from their parent materials.
- Representative types of ultrafine particles and materials for use in the present invention are of the type, and may be produced by methods, described in U.S. Pat. No. 6,503,475 to McCormick U.S. Pat. No. 6,472,459 to Morales et al., U.S. Pat. No. 6,467,897 to Wu et al., U.S. Pat. No. 6,479,146 to Caruso et al., and U.S. Pat. No. 6,479,156 to Schmidt et al. and U.S. Published Pat. Applications 2002/0194958 to Lee et al., 2002/014453 to Lilly Jr., et al., 2003/0000538 to Bereman et al., 2002/0167118, 2002/0172826 and 2002/0127351, the disclosure of each patent and published application being incorporated herein by reference.
- Ultrafine particles for use in the catalyst composition can be obtained commercially. For example, Superfine Iron oxide (Fe2O3) can be obtained from MACH-1 Inc. of King of Prussia, Pa. Nanopowder Enterprise Inc. of Piscataway, N.J. is an additional commercial source of ultrafine particles for use in catalyst compositions of the present invention.
- In embodiments of the present invention, the fuel element additionally comprises a carbonaceous material. The fuel element may additionally comprise binders like Guar gum, other metallic particles such as aluminum or the like, inert filler material like graphite, and/or burn modifiers such as sodium or potassium carbonate. In some embodiments, the carbonaceous materials for use in the fuel element include at least 50%, by weight carbon. In other embodiments the carbonaceous materials for use in the fuel element can include about 60-95% by weight carbon. In still further embodiments, the carbonaceous materials for use in the fuel element can include about 70-80% by weight carbon. The carbonaceous materials may be in powder form and may be partially activated. The carbonaceous materials may also be heat treated. The carbonaceous materials may comprise organic carbon containing materials, for example tobacco.
- The carbonaceous materials of the present invention may be prepared from several starting materials. Suitable starting materials include, but are not limited to, cellulosic materials with a high (i.e., greater than about 80%) alpha-cellulose content, such as cotton, rayon, paper, and the like. The carbonaceous materials of fuel elements of the present invention may be generally prepared by pyrolysis of the starting material at a temperature between about 400° C. and 1300° C., preferably between about 500° C. and 950° C., in a non-oxidizing atmosphere, for a period of time sufficient to ensure that a large portion or substantially all of the starting material has reached the desired carbonization temperature. Although the pyrolysis may be conducted at a constant temperature, it has been found that a slow pyrolysis, employing a gradually increasing heating rate, e.g., from about 1° C. to 20° C. per hour, preferably from about 5° C. to 25° C. per hour, over many hours, produces a uniform and higher carbon yield.
- After cooling, the carbonaceous material may be pulverized. In some embodiments, the carbonaceous material is pulverized to a fine powder. This powder may be subjected to a second pyrolysis or polishing step, wherein the carbonized particulate material, is again pyrolyzed in a non-oxidizing atmosphere, at a temperature between about 650° C. to about 1250° C., preferably from about 700° C. to 900° C. At this point, the carbonaceous material is ready for combination with the ultrafine particle catalyst composition along with the other components of the fuel to produce a fuel element composition.
- In embodiments of the present invention, the ultrafine particles of the catalyst compositions can be combined with a carbonaceous material in a number of ways to produce the fuel element composition. One method of combination comprises intimately mixing the carbonaceous material with the ultrafine particles. Ultrafine particles in dry powder form (e.g. nanopowder) may be mixed directly in a carbon mix along with other dry ingredients for extrusion. Alternatively, the ultrafine particles may be suspended in a liquid and the suspension mixed with extrudate.
- Another method of combining the ultrafine catalyst compositions with a carbonaceous material comprises forming the carbonaceous material so as to concentrate the catalytic compositions in one or more longitudinal passageways extending partially through the fuel element. For example, the fuel element may comprise an inner core/outer shell arrangement where the outer shell comprises a carbonaceous material surrounding the inner core, and the inner core comprises ultrafine particle catalyst compositions. In some embodiments, the fuel element may include at least one longitudinal passageway extending at least partially therethrough.
- Other methods of combining ultrafine particle catalyst compositions with a carbonaceous material can include wash coating, dipping, painting, spraying, or other methods known to those ordinary skill in the art. In another embodiment, the ultrafine particle catalyst compositions can be placed on inert support located directly behind the fuel element in an end to end relationship. The support for the ultrafine particles can be an inert carbon material such as graphite or a porous material such as alumina or porous graphite.
- Once combined with the carbonaceous material, the catalyst composition may comprise up to 10% by weight of the resulting mixture. In some embodiments, the catalyst compositions may comprise 1% by weight of the resulting mixture. In another embodiment, catalyst composition may comprise 0.5% to 2% by weight of the resulting mixture.
- The density of a fuel element according to some embodiments of the present invention can be generally greater than about 0.5 g/cc, greater than about 0.7 g/cc and greater than about 1 g/cc.
- The overall length of the fuel element, prior to burning, can be generally less than about 20 mm, often less than about 15 mm, and can be typically about 12 mm. However, shorter fuel elements may be used if desired, depending upon the configuration of the cigarette in which they are employed. In an embodiment, the overall outside diameter of the fuel element can be less than about 8 mm, less than about 6 mm, and can be about 4.2 mm.
- The carbonaceous and binder portions of the fuel compositions useful herein may be any of those carbonaceous and binder materials described in the patents recited in the Background of the Invention, supra. Several carbonaceous and binder materials are described in U.S. application Ser. No. 07/722,993, filed 28 Jun. 1991, now U.S. Pat. No. 5,178,167 the disclosure of which is hereby incorporated herein by reference.
- In a further aspect, the present invention provides smoking articles. In an embodiment, a smoking article comprises a fuel element comprising a carbonaceous material and at least one catalyst composition, the catalyst composition comprising ultrafine particles. With reference to a cigarette as a smoking article, the cigarette further includes an aerosol generating means, which includes a substrate and at least one aerosol-forming material. An aerosol-generating means includes an aerosol forming material (e.g. glycerin), tobacco in some form (e.g. tobacco powders, tobacco extract or tobacco dust) and other aerosol forming materials and/or tobacco flavoring agents such as cocoa, licorice, and sugar. The aerosol forming material generally is carried on a substrate material such as a reconstituted tobacco cut filler or on a substrate such as tobacco cut filler, gathered paper, gathered tobacco paper, or the like.
- In an embodiment of the present invention, the substrate is reconstituted tobacco, which is formed into a continuous rod or substrate tube assembly on a conventional cigarette making machine. Typically, the overwrap material for the rod is a barrier material such as a paper foil laminate. The foil serves as a barrier, and is located on the inside of the overwrap. Alternatively, the substrate may be a gathered paper formed into a rod or plug. When the substrate is a paper-type material, it can be positioned in a spaced-apart relationship from the fuel element comprising a carbonaceous material and a catalyst composition. A spaced-apart relationship is desired to minimize contact between the fuel element and the substrate, thereby preventing migration of the aerosol forming materials to the fuel element, as well as limiting the scorching or burning of the paper substrate. The spacing is normally provided during manufacture of the cigarette in accordance with one method of making the present invention. Appropriately spaced substrate plugs are overwrapped with a barrier material to form a substrate tube assembly having spaced substrate plugs therein. The substrate tube assembly is cut between the substrate plugs to form substrate sections. The substrate sections include a tube with a substrate plug and void(s), which can be at each end.
- The barrier material for making the tube aids in preventing migration of the aerosol former to other components of the cigarette. The barrier material forming the tube is a relatively stiff material so that when formed into a tube, it will maintain its shape and will not collapse during manufacture and use of the cigarette.
- In embodiments of the present invention, fuel elements of a smoking article can be advantageously circumscribed by an insulating and/or retaining jacket material. The insulating and retaining material is adapted such that drawn air can pass therethrough, and is positioned and configured so as to hold the fuel element in place. The jacket is flush with the ends of the fuel element, however, it may extend from about 0.5 mm to about 3 mm beyond each end of the fuel element.
- The components of the insulating and/or retaining material which surrounds the fuel element can vary. Examples of suitable materials include glass fibers and other materials as described in U.S. Pat. No. 5,105,838; European Patent Publication No. 339,690; and pages 48-52 of the RJR Monograph, supra. Examples of other suitable insulating and/or retaining materials are glass fiber and tobacco mixtures such as those described in U.S. Pat. Nos. 5,105,838, 5,065,776 and 4,756,318; and U.S. patent application Ser. No. 07/354,605, filed 22 May 1989 now U.S. Pat. No. 5,119,837.
- Other suitable insulating and/or retaining materials are gathered paper-type materials which are spirally wrapped or otherwise wound around the fuel element, such as those described in U.S. patent application Ser. No. 07/567,520, filed 15 Aug. 1990, now U.S. Pat. No. 5,105,836. The paper-type materials can be gathered or crimped and gathered around the fuel element; gathered into a rod using a rod making unit available as CU-10 or CU2OS from DeCoufle s.a.r.b., together with a KDF-2 rod making apparatus from Hauni-Werke Korber & Co., KG, or the apparatus described in U.S. Pat. No. 4,807,809 to Pryor et al.; wound around the fuel element about its longitudinal axis; or provided as longitudinally extending strands of paper-type sheet using the types of apparatus described in U.S. Pat. No. 4,889,143 to Pryor et al. and U.S. Pat. No. 5,025,814 to Raker, the disclosures of which are incorporated herein by reference.
- If desired, the fuel element may be extruded into the insulating jacket material as set forth in U.S. patent application Ser. No. 07/856,239, filed 25 Mar. 1992, the disclosure of which is incorporated herein by reference.
- Examples of paper-type sheet materials are available as P-2540-136-E carbon paper and P-2674-157 tobacco paper from Kimberly-Clark Corp.; and the longitudinally extending strands of such materials (e.g., strands of about 1/32 inch width) extend along the longitude of the fuel element. The fuel element also can be circumscribed by tobacco cut filler (e.g., flue-cured tobacco cut filler treated with about 2 weight percent potassium carbonate). The number and positioning of the strands or the pattern of the gathered paper is sufficiently tight to maintain, retain or otherwise hold the composite fuel element structure within the cigarette.
- In embodiments of the present invention, the fuel element-jacket assembly is combined with a substrate section or substrate tube assembly by a wrapper material, which has a propensity not to burn, to form a fuel element/substrate section. In some embodiments of the cigarettes, the wrapper typically extends from the mouthend of the substrate section, over a portion of the jacketed fuel element, whereby it is spaced from the lighting end of the fuel element. The wrapper material assists in limiting the amount of oxygen which will reach the burning portion of the fuel element during use, thereby causing the fuel element to extinguish after an appropriate number of puffs. In an embodiment of the cigarette, the wrapper is a paper/foil/paper laminate. The foil provides a path to assist in dissipating or transferring the heat generated by the fuel element during use. The jacketed fuel element and the substrate section are joined by the overwrap.
- A tobacco section can be formed by a reconstituted tobacco cut filler rod, made on a typical cigarette making machine, and cut into appropriate lengths. A filter rod is formed and cut into appropriate lengths for joining to the tobacco section to form a mouthend section. The fuel element/substrate section and the mouthend section are joined by aligning the reconstituted ends of each section, and overwrapped to form a cigarette.
- When a paper substrate is used, a tobacco paper rod and a reconstituted cut filler rod are formed and cut into appropriate lengths and joined to form a tobacco section. The tobacco section and the fuel element assembly/substrate section are joined by aligning the tobacco paper plug end of the tobacco section with the substrate end of the fuel element assembly/substrate section and joining the sections with a wrapper which extends from the rear end of the tobacco roll to an appropriate length past the junction of the two sections for forming the tobacco roll/fuel element assembly. The tobacco roll/fuel element assembly is then joined to a filter by a tipping material.
- As described above, the substrate carries aerosol forming materials and other ingredients, e.g., flavorants and the like, which, upon exposure to heated gases passing through the aerosol generating means during puffing, are vaporized and delivered to the user as a smoke-like aerosol. Aerosol forming materials used herein include glycerin, propylene glycol, water, and the like, flavorants, and other optional ingredients. The patents referred to in the Background of the Invention (supra) teach additional useful aerosol forming materials that need not be repeated here.
- Cast sheets of tobacco dust or powder, a binder, such as an alginate binder, and glycerin can also be used to form useful substrates herein. Suitable cast sheet materials for use as substrates are described in U.S. Pat. No. 5,101,839 and U.S. patent application Ser. No. 07/800,679, filed Nov. 27, 1991.
- Suitable cast sheet materials typically contain between about 30 to 75 weight percent of an aerosol former such as glycerin; about 2 to 15 weight percent of a binder, such as ammonium alginate; 0 to about 2 weight percent of a sequestering agent such as potassium carbonate; about 15 to about 70 to 75 weight percent of organic, inorganic filler materials, or mixtures thereof, such as tobacco dust, aqueous extracted tobacco powder, starch powder, rice flower, ground puffed tobaccos, carbon powder, calcium carbonate powder, and the like, and from about 0 to about 20 weight percent of flavors such as tobacco extracts, and the like.
- In one embodiment, a cast sheet material includes 60 weight percent glycerin, 5 weight percent ammonium alginate binder, 1 weight percent potassium carbonate, 2 weight percent flavors such as tobacco extracts and 32 weight percent aqueous extracted tobacco powder.
- The cast sheets are formed by mixing aqueous extracted tobacco powder, water and the potassium carbonate in a high sheer mixer to produce a smooth, flowable paste. Glycerin and ammonium alginate are then added and the high shear mixing is continued until a homogenized mixture is produced. The homogenized mixture is cast on a heated belt (about 200.degree. F.) with a 0.0025 to 0.0035 inch casting clearance and is dried to yield a 0.0004 to 0.0008 inch thick sheet under high temperature air (about 200.degree. to 250.degree. F.). The sheet is doctored from the belt and either wound onto spools for slitting into webs or chopped into rectangular pieces about 2 inches by 1 inch which are formed into cut filler. If the cast sheet material is used in a web or cut filler form, normally the substrate will be from about 10 mm to 40 mm in length and extend from the rear end of the fuel element to the tobacco segment or the front end of an extra long filter segment (e.g., about 30 mm to 50 mm in length). In such instances the tobacco paper plug can be omitted.
- In embodiments of the present invention, the combination of the fuel element and the substrate (also known as the front end assembly) is attached to a mouthend piece; although a disposable fuel element/substrate combination can be employed with a separate mouthend piece, such as a reusable cigarette holder. The mouthend piece provides a passageway which channels vaporized aerosol forming materials into the mouth of the smoker; and can also provide further flavor to the vaporized aerosol forming materials.
- Flavor segments (i.e., segments of gathered tobacco paper, tobacco cut filler, or the like) can be incorporated in the mouthend piece or the substrate segment, e.g., either directly behind the substrate or spaced apart therefrom, to contribute flavors to the aerosol. Gathered carbon paper can be incorporated, particularly in order to introduce menthol flavor to the aerosol. Such papers are described in European Patent Publication No. 342,538. Other flavor segments useful herein are described in U.S. patent application Ser. No. 07/414,835, filed 29 Sep. 1989, now U.S. Pat. No. 5,076,295 Ser. No. 07/606,287, filed 6 Nov. 1990; now U.S. Pat. No. 5,105,834 and Ser. No. 07/621,499, filed 7 Dec. 1990, now abandoned.
-
FIG. 1 illustrates a smoking article according to an embodiment of the present invention. The smoking article depicted inFIG. 1 comprises afuel element 10 of the present invention comprising a carbon source and at least one catalytic composition comprising ultrafine particles of a metal oxide and/or metal. The fuel element displays a plurality of passageways 11 therethrough, about thirteen passageways altogether. Thefuel element 10 is surrounded by insulatingsheet material 16 having a plurality of grooves which facilitate the formation of the sheet material into a jacket surrounding the fuel element. In embodiments of the smoking article, the jacket can be made of calcium sulfate (CaSO4). - A
metallic capsule 12 overlaps a portion of the mouthend of thefuel element 10 and encloses the physically separate aerosol generating means which contains asubstrate material 14. The substrate material carries one or more aerosol forming materials. The substrate may be in particulate form, in the form of a rod, and other geometric shapes advantageous for generating an aerosol. -
Capsule 12 is circumscribed by a roll oftobacco 18. Alternatively, in other smoking articles, the capsule may be circumscribed with an additional or continuous jacket of an insulating sheet material. Insulating sheet materials suitable for use in smoking articles of the present invention are further described in U.S. Pat. No. 5,303,720 to Banerjee which is hereby incorporated by reference. Two slit-like passageways 20 are provided at the mouth of the capsule in the center of the crimped tube. - At the mouth end of the
tobacco roll 18, is amouthend piece 22, comprising a cylindrical segment of a flavored carbon filledsheet material 24 and a segment of non-woventhermoplastic fibers 26 through which the aerosol passes to the user. The smoking article, or portions thereof, is overwrapped with one or more layers of cigarette papers 30-36 - In some embodiments, catalyst compositions comprising metal oxide and/or metal ultrafine particles are incorporated into the filter element of the smoking article as described in U.S. patent application Ser. No. 10/730,962 which is hereby incorporated by reference.
- In certain embodiments of the cigarettes of the present invention, convective heating is the predominant mode of energy transfer from the burning fuel element comprising a carbonaceous material and at least one catalyst composition to the aerosol-generating means disposed longitudinally behind the fuel element. When a foil/paper laminate is used as an overwrap to join the fuel/substrate section some heat may be transferred to the substrate by the foil layer. As described above, the heat transferred to the substrate volatilizes the aerosol-forming material(s) and any flavorant materials carried by the substrate, and, upon cooling, these volatilized materials are condensed to form a smoke-like aerosol which is drawn through the cigarette during puffing, and which exits the filter piece. This smoke-like aerosol can contain reduced amounts of carbon monoxide resulting from the reduced carbon monoxide production of a fuel element of the present invention upon combustion.
- In some embodiments, the catalyst compositions can be deposited on a porous support such as graphite or alumina wherein the porous support is placed behind the fuel in an end to end relationship.
- In a further aspect, the present invention provides a method for facilitating the reduction in the amount of carbon monoxide produced by a smoking article, comprising incorporating at least one catalyst composition comprising ultrafine particles of a metal oxide and/or metal into the fuel element of a smoking article.
- In another aspect, the present invention provides methods and apparatus for the simultaneous quantification of the carbon monoxide content and carbon dioxide content of a gaseous mixture. In an embodiment, a method for quantifying the carbon monoxide content and carbon dioxide content of a gaseous mixture comprises injecting the gaseous mixture into a split injection tube of a gas chromatograph through a single injector, resolving a relative carbon monoxide content of the gaseous mixture on a first chromatographic column, simultaneously resolving a relative carbon dioxide content on a second chromatographic column, and detecting and quantifying the eluate carbon monoxide and carbon dioxide with a mass spectrometer. In further embodiments, the gaseous mixture containing carbon monoxide and carbon dioxide comprises mainstream smoke or a smoke-like aerosol produced from a smoking article.
- Under some circumstances, carbon monoxide and carbon dioxide can be resolved on a single chromatographic column. Single columns that are capable of resolving both carbon monoxide and carbon dioxide, however, use carrier gas at flow rates that are too high for use with a mass spectrometer. As a result, their use precludes the numerous advantages gained by the two-dimensional analysis of GC/MS. Moreover, other single chromatographic columns that use a carrier gas at acceptable flow rates for use with a mass spectrometer cannot effectively resolve both carbon monoxide and carbon dioxide.
- The utilization of dual chromatographic columns allows for the complete resolution of the carbon monoxide and carbon dioxide contents of the gaseous mixture at flow rates that are acceptable for use with a mass spectrometer. The two-dimensional analysis provided by gas chromatography/mass spectrometry (GC/MS) can provide precise relative quantifications of carbon monoxide and carbon dioxide amounts present in gaseous mixtures.
-
FIG. 2 illustrates a flowchart for the quantification of carbon monoxide and carbon dioxide contents of a gaseous mixture according to an embodiment of the present invention. In particular embodiments, the gaseous mixture comprises mainstream smoke or smoke-like aerosol from a smoking article. The gaseous mixture is injected into the split injector of thegas chromatogram 201. Thesplit injector 201 splits the gaseous mixture for simultaneous resolution on dual chromatographic columns. The carbon monoxide content of the mainstream smoke is resolved on afirst chromatographic column 202, and the carbon dioxide content is simultaneously resolved on asecond chromatographic column 203. The first chromatographic column can be selected for optimal resolution of carbon monoxide while the second chromatographic column can be selected for the optimal resolution of carbon dioxide. For example, a Molsieve column can be used to resolve carbon monoxide and a wide-bore GS-CarbonPLOT column can be used to resolve carbon dioxide. - Once resolved, the carbon monoxide content and carbon dioxide content of the mainstream smoke are quantified by a
mass spectrometer 204. The use of a mass spectrometer adds a second dimension of analysis that is not present with traditional gas chromatographic detection devices. A mass spectrometer can further resolve the carbon monoxide content and carbon dioxide content of a gaseous mixture allowing for greater accuracy and precision when quantifying these chemical species. - In an embodiment, an apparatus for quantifying the carbon monoxide content and carbon dioxide content of a gaseous mixture comprises: a gas chromatograph comprising a single split injector, dual chromatographic columns; and a mass spectrometer.
-
FIG. 3 illustrates an apparatus for the simultaneous quantification of the carbon monoxide content and carbon dioxide content of a gaseous mixture comprising the two-dimensional analysis of gas chromatography and mass spectrometry in an embodiment according to the present invention. Thegas chromatograph 301 comprises asingle injector 302 which splits the sample onto twochromatographic columns single injector 302 can be varied in accordance with desired analytical conditions. The temperature variance of thesingle split injector 302 can be controlled manually by a user or can be controlled electronically with any processor-equipped device such as a computer and/or dedicated controller. As previously discussed, one of the twocolumns 303 is suitable for resolving the carbon monoxide content of a gaseous mixture while theother column 304 is suitable for resolving the gaseous mixture's carbon dioxide content. Chromatographic columns for use in the gas chromatograph of the present apparatus are available commercially. - The two chromatographic columns feed into a
mass spectrometer 305. Mass spectrometers suitable for use in further resolving and quantifying the carbon monoxide content and carbon dioxide content eluting from the two columns of the gas chromatograph can comprise mass analyzers comprising magnetic sector analyzers, double-focusing spectrometers, quadrupole mass filters, ion trap analyzers, and time-of-flight (TOF) analyzers. - The embodiments described above in addition to other embodiments can be further understood with reference to the following examples. Several of the fuel elements provided in the examples below comprise percentages of BKO carbon, Guar gum, graphite, and tobacco. Combustion of all the fuel elements in the examples below provides energy used to generate aerosol from tobacco and other aerosol formers like glycerin. Combustion of the fuel elements, however, also produces carbon monoxide and carbon dioxide. Moreover, complete combustion of the fuel elements produces a maximum amount of energy and a carbon dioxide by-product. Complete combustion is demonstrated by the chemical reaction:
C (s)+O2 (g)→CO2 (g)
Incomplete combustion, nevertheless, produces much less energy and a substantial carbon monoxide by-product. Incomplete combustion is demonstrated by the reaction sequence:
C (s)+O (g)→CO (g)
C (s)+O2 (g)→CO2 (g)
As a result, complete combustion of the fuel element in desirable. - Graphite in the fuel elements comprising graphite, BKO carbon, Guar gum, and tobacco, is inactive up to the temperatures attained by combustion of the fuel element and remains substantially unchanged throughout the combustion of the fuel element. The remaining three carbonaceous components undergo oxidation during the combustion to provide energy and oxides of carbon. Among the carbonaceous components, BKO carbon is the major component and hence chosen for the study of the fuel elements in the examples below.
- Several materials were prepared to evaluate the efficacy of a method and apparatus for simultaneously resolving the carbon monoxide content and carbon dioxide content of a gaseous mixture according to an embodiment of the present invention. The materials prepared for analysis by the method and apparatus were a standard gaseous mixture (CO:CO2:N2), tobaccos from 1R4F cigarettes, and 1R4F cigarette smoke. A small quantity of each sample was heated to 700° C. for 20 seconds in the presence of air. The standard gaseous mixture was analyzed in the absence of air to preserve the composition of the sample. A pyroprobe was used for sample heating. The temperatures of the pyroprobe interface and the gas chromatograph injector were set at ambient temperature. The gas chromatograph utilized was a Hewlett-Packard 5890 Series II. A single injection onto dual chromatographic columns was used for the carbon monoxide and carbon dioxide analysis. A Molsieve column (Chrompack, 25 M×0.32 mm I.D., 30 μm film) was used for carbon monoxide resolution, and a GS-CarbonPLOT column (J&W Scientific, 60 M×0.32 mm I.D., 1.5 μm film) was used for carbon dioxide resolution. The temperatures of the columns were held at 35° C. for 10 minutes, programmed to 150° C. at 25° C./min and held for 10 min. A single mass spectrometer was used to identify and quantify the resolved carbon monoxide and carbon dioxide peaks eluting from the chromatographic columns. The mass spectrometer utilized was a Hewlett-Packard 5972 mass selective detector. The mass spectrometer was operated at 70 eV in the EI mode with the temperature of the ion source being maintained at 180° C. The mass range scanned was 20-200 atomic mass units. The carbon monoxide and carbon dioxide quantified were only a fraction of the total carbon monoxide and carbon dioxide generated from the heated materials. Only the resolved carbon monoxide and carbon dioxide peak areas were used for quantification.
- The results of the standard gaseous mixture resolved on the dual chromatographic columns are illustrated in
FIG. 4 . The ion chromatogram ofFIG. 4 demonstrates a completely resolved carbon monoxide peak and a completely resolved carbon dioxide peak. For comparative purposes, the standard gaseous mixture (CO:CO2:N2) was injected and resolved on single column gas chromatographs under experimental conditions consistent with resolution on dual chromatographic columns. The standard gaseous mixture was resolved on a single column gas chromatograph comprising a Molsieve column. The results are illustrated inFIG. 5 . As demonstrated in the ion chromatogram ofFIG. 5 , the Molsieve column completely resolved the carbon monoxide content but failed to completely resolve the carbon dioxide content of the standard gaseous mixture. Similarly, the standard gaseous mixture was additionally resolved on a single GS-CarbonPLOT chromatographic column. The results of this resolution are illustrated inFIG. 6 . The ion chromatogram ofFIG. 6 displays a complete resolution of carbon dioxide and an incomplete resolution of carbon monoxide. The carbon monoxide co-eluted with nitrogen and oxygen. - The results of the remaining sample materials comprising tobaccos from 1R4F cigarettes and 1R4F cigarette smoke resolved on dual chromatographic columns in accordance with the present invention are illustrated in
FIGS. 7 and 8 respectively. The ion chromatograms ofFIGS. 7 and 8 demonstrate completely and sharply resolved carbon monoxide and carbon dioxide peaks. - Seven samples were generated for analysis of carbon monoxide/carbon dioxide (CO/CO2) ratios. These samples were: (1) Control Carbon Black 950, (2) Carbon Black 950 with 5% Fe2O3 ultrafine particles, (3) Carbon Black 950 with 2% Fe2O3 ultrafine particles, (4) Carbon Black 950 with 5% TiO2—Au ultrafine particles and (5) Carbon Black 950 with 2% TiO2—Au ultrafine particles, (6) Carbon Black 950 with 5% CeO2 ultrafine particles, and (7) Carbon Black 950 with 2% CeO2 ultrafine particles.
- To simulate combustion of the fuel element, a pyroprobe was used to heat a small quantity of each sample to 700° C. for 20 seconds in the presence of air. 700° C. is the average temperature of a fuel element during combustion. The gaseous mixture resulting from the combustion of each sample was analyzed in accordance with the method delineated in
FIG. 2 . The pyroprobe and gas chromatogram injector were set at ambient temperature. A Molsieve chromatographic column was used for carbon monoxide resolution and a GS-CarbonPLOT chromatographic column was used for carbon dioxide resolution. A mass spectrometer was used as a second dimension of analysis in the quantification of the carbon monoxide and carbon dioxide contents generated by the samples. It should be noted that the carbon monoxide and the carbon dioxide contents quantified were only a fraction of the carbon monoxide and carbon dioxide contents produced by the samples and that the resolved peak areas were used for quantification. Table 1 summarizes the results produced by the samples in this example.TABLE 1 MASS ABUNDANCE (COUNTS)A CO/CO2 SAMPLES CO CO2 Ratio (1) Control Carbon 383,013,104 1,284,639,516 0.298 (2) Carbon and 5% Fe2O3 53,357,015 1,202,285,067 0.0444 (3) Carbon and 2% Fe2O3 65,069,392 1,093,984,395 0.0595 (4) Carbon and 5% TiO2-Au 131,461,228 926,581,662 0.142 (5) Carbon and 2% TiO2-Au 264,095,113 956,314,408 0.276 (6) Carbon and 5% CeO2 268,205,948 965,498,063 0.278 (7) Carbon and 2% CeO2 279,547,847 977,688,888 0.286 Air Blank 655,583 7,602,213
AMass abundance is the total abundance of ions in a mass spectrum for compound with unit of counts.
- The results displayed in Table 1, which are additionally illustrated in
FIG. 9 , demonstrate that ferric oxide (Fe2O3) ultrafine particles effectuate a significant reduction in the amount of carbon monoxide produced by the fuel element. Fuel element sample (2) comprising 5% ferric oxide (Fe2O3) ultrafine particles by weight exhibited an 85% reduction in the amount of carbon monoxide produced when heated. Similarly, fuel element sample (3) comprising 2% ferric oxide (Fe2O3) ultrafine particles by weight displayed an 80% reduction in the amount of carbon monoxide produced upon sample heating. The titanium oxide-gold (TiO2—Au) ultrafine particles of sample (4) demonstrated a carbon monoxide reduction of 52% while the ceric oxide (CeO2) ultrafine particles of sample (6) resulted in approximately a 7% reduction. - Eight fuel element samples were generated for analysis of (CO/CO2) ratios. These samples were: (1) BKO Carbon 950, (2) BKO Carbon 950 with 5% gamma-Fe2O3-large particle, (3) BKO 950 Carbon with 5% Fe2O3-nanoparticle, (4) BKO 950 Carbon with 2% Fe2O3-nanoparticle, (5) Carbon Mix 1 (78.3% BKO 950 Carbon, 10.1% Guar gum, 6.55% graphite, and 5.05% tobacco), (6)
Carbon Mix 1 with 5% Fe2O3-nanoparticle, (7) Carbon Mix 2 (82.4% BKO Carbon 950, 10.6% Guar gum, and 7.0% graphite) and (8)Carbon Mix 2 with 5% Fe2O3-nanopaticle. - To simulate combustion of the fuel element, a pyroprobe was used to heat a small quantity of each sample to 700° C. in the presence of air for 20 seconds. 700° C. is the average temperature of a fuel element during combustion. The gaseous mixture resulting from the combustion of each sample was analyzed in accordance with the method delineated in
FIG. 2 . The pyroprobe and gas chromatogram injector were set at ambient temperature. A Molsieve chromatographic column was used for carbon monoxide resolution and a GS-CarbonPLOT chromatographic column was used for carbon dioxide resolution. A mass spectrometer was used as a second dimension of analysis in the quantification of the carbon monoxide and carbon dioxide contents generated by the samples. It should be noted that the carbon monoxide and the carbon dioxide contents quantified were only a fraction of the carbon monoxide and carbon dioxide contents produced by the samples and that the resolved peak areas were used for quantification. Table 2 summarizes the results produced by the samples in this example.TABLE 2 MASS ABUNDANCE (COUNTS)A SAMPLES CO CO2 CO/CO2 Ratio (1) BKO Carbon 950 136,632,880 439,836,557 0.311 (2) BKO Carbon 950 and 34,403,969 511,214,899 0.0673 5% γ-Fe2O3-large particle (3) BKO 950 and 5%16,068,614 489,909,229 0.0328 Fe2O3-nanoparticle (4) BKO 950 and 2%26,802,880 508,261,449 0.0527 Fe2O3-nanoparticle (5) Carbon Mix 198,093,373 458,829,259 0.214 (6) Carbon Mix 89,003,804 491,290,439 0.181 Fe2O3-nanoparticle (7) Carbon Mix 2105,287,470 463,439,227 0.227 (8) Carbon Mix 34,534,408 478,608,718 0.0722 Fe2O3-nanoparticle
AMass abundance is the total abundance of ions in a mass spectrum for compound with unit of counts.
- The results summarized in Table 2, which are further illustrated in
FIG. 10 , demonstrate that ferric oxide (Fe2O3) ultrafine particles can effectuate a reduction in the amount of carbon monoxide produced by a fuel element. Comparison of the CO/CO2 ratios of sample (2) comprising 5% gamma-Fe2O3-large particle and sample (3) comprising 5% Fe2O3 nanoparticle reveals the dependency of catalytic activity on particle size. The smaller Fe2O3 ultrafine particles exhibit a greater surface area than the γ—Fe2O3-large particles which leads to higher catalyst turnover rates and a greater reduction in the amount of carbon monoxide produced by the fuel element upon heating. The Fe2O3 ultrafine particles of sample (3) reduced the carbon monoxide content of the gaseous mixture analyzed by 89.5%, which is an 11% increase over the γ—Fe2O3-large particles. - The results of the sample testing further demonstrate the catalytic activity of ferric oxide ultrafine particles in fuel elements that comprise the additional components of Guar gum and graphite. Sample (7) is an example of a fuel element containing these additional components. Sample (8) comprises the components of sample (7) with the addition of 5% by weight of ferric oxide (Fe2O3) ultrafine particles. The ferric oxide (Fe2O3) ultrafine particles reduced the carbon monoxide production of the fuel element of sample (8) by 68% in comparison with sample (7) which did not contain ferric oxide (Fe2O3) ultrafine particles.
- Fuel elements containing tobacco components were additionally analyzed in this example. Sample (5) is a fuel element containing a 5.05% tobacco content in addition to BKO Carbon 950, Guar gum, and graphite. Sample (6) comprises the components of sample (5) with the addition of 5% by weight of ferric oxide (Fe2O3) nanoparticle. The ferric oxide (Fe2O3) ultrafine particles reduced the carbon monoxide production of the fuel element of sample (6) by 15.4% in comparison with sample (5) which did not contain ferric oxide (Fe2O3) ultrafine particles. The catalytic activity of the ferric oxide (Fe2O3) ultrafine particles in sample (6) was diminished due to the tobacco content in the fuel element composition. The combustion of tobacco produces several chemical species that inhibit the catalytic behavior of the ultrafine particles. This catalytic inhibition is displayed in the 15.4% reduction of carbon monoxide production.
- Seven carbon samples were generated for analysis of CO/CO2 ratios. The sample were: (1) Control Carbon (BKO 950), (2) Carbon with 5% Fe2O3 ultrafine particles obtained from MACH-1, Inc., (3) Carbon with 5% Al2O3 ultrafine particles obtained from NEI, Inc., (4) Carbon with 5% CeO2 ultrafine particles obtained from NEI, Inc., (5) Carbon with 5% TiO2 ultrafine particles obtained from NEI, Inc., (6) Carbon with 5% tobacco and 5% Fe2O3 ultrafine particles obtained from MACH-1, Inc., and (7) Carbon with 5% tobacco (heat treated) and 5% Fe2O3 ultrafine particles obtained from MACH-1, Inc.
- To simulate combustion of the fuel element, a pyroprobe was used to heat a small quantity of each sample to 700° C. in the presence of air for 20 seconds. 700° C. is the average temperature of a fuel element during combustion. The gaseous mixture resulting from the combustion of each sample was analyzed in accordance with the method delineated in
FIG. 2 . The pyroprobe and gas chromatogram injector were set at ambient temperature. A Molsieve chromatographic column was used for carbon monoxide resolution and a GC-CarbonPLOT chromatographic column was used for carbon dioxide resolution. A mass spectrometer was used as a second dimension of analysis in the quantification of the carbon monoxide and carbon dioxide contents generated by the samples. It should be noted that the carbon monoxide and the carbon dioxide contents quantified were only a fraction of the carbon monoxide and carbon dioxide contents produced by the samples and that the resolved peak areas were used for quantification. Table 3 summarizes the results produced by the samples in this example.TABLE 3 CO/ MASS ABUNDANCE CO2 (COUNTS)B Ra- SAMPLESA CO CO2 tio (1) Control Carbon (BKO 349,722,771 1,097,283,105 0.319 950) (2) Carbon and 5% Fe2O3 73,461,112 1,171,782,023 0.0627 ultrafine particles (3) Carbon and 5% Al2O3 323,332,586 988,477,673 0.327 ultrafine particles (4) Carbon and 5% CeO2 285,376,477 1,032,058,820 0.277 ultrafine particles (5) Carbon and 5% TiO2 379,654,967 1,164,775,102 0.326 ultrafine particles (6) Carbon, 5% Tobacco, 184,501,337 1,042,248.352 0.177 and 5% Fe2O3 ultrafine particles (7) Carbon, 5% Tobaccoc, 199,972,837 1,165,685,787 0.172 and 5% Fe2O3 ultrafine particles Air Blank 2,501,751 12,070,258
AAll carbon samples were baked at 950 C. prior to the analysis.
BMass abundance is the total abundance of ions in a mass spectrum for compound with unit of counts.
cTobacco was heat-treated at 100° C. for 4 hours.
- The results summarized in Table 3 and further illustrated in
FIG. 11 reiterate the efficacy of ferric oxide (Fe2O3) ultrafine particles in reducing the carbon monoxide production of fuel elements according to the present invention. When compared to titanium oxide (TiO2), aluminum oxide (Al2O3), and ceric oxide (CeO2) ultrafine particles, ferric oxide (Fe2O3) ultrafine particles demonstrate a greater reduction in the carbon monoxide production of heated fuel elements. In this example, samples (3) and (5) containing aluminum oxide (Al2O3) and titanium oxide (TiO2) ultrafine particles respectively exhibited a slight increase in carbon monoxide content. Moreover, sample (4) comprising ceric oxide (CeO2) ultrafine particles displayed a carbon monoxide reduction of 13%. Sample (2) comprising ferric oxide (Fe2O3) ultrafine particles, however, exhibited a carbon monoxide reduction of 80%. - In samples (6) and (7), ferric oxide (Fe2O3) ultrafine particles were additionally incorporated into fuel elements that contained tobacco as well. The reduction of carbon monoxide produced from these fuel elements when heated was diminished due to the catalyst poisoning chemical species generated upon tobacco combustion.
- Seven tobacco samples were generates for analysis of CO/CO2 ratios. The samples were: (1) Control Camel LT® Tobacco, (2) Camel LT® Tobacco with 5% Fe2O3 ultrafine particles, (3) Camel LT® Tobacco with 2% Fe2O3 ultrafine particles (4) Camel LT® Tobacco with 5% TiO2—Au ultrafine particles, (5) Camel LT® Tobacco with 2% TiO2—Au ultrafine particles, (6) Camel LT® Tobacco with 5% CeO2 ultrafine particles, and (7) Camel LT® Tobacco with 2% CeO2 ultrafine particles.
- A Chemical Data System (CDS) Model 2000 pyroprobe was used for sample heating. A small quantity of each sample (approximately 7 mg) was heated at 700° C. in the presence of air for 20 seconds. The gaseous mixture resulting from the heating of each sample was analyzed in accordance with the method delineated in
FIG. 2 . The temperatures of the pyroprobe interface and the injector on the gas chromatogram were set at ambient temperature. The GC used was a Hewlett-Packard 5890 Series II gas chromatograph. A single injection onto dual columns was used for CO and CO2 analysis. A Molsieve column (Chrompack, 25 M×0.32 mm I.D., 30 μm film) was used for CO analysis. A GS-CarbonPLOT column (J&W Scientific, 60 M×0.32 mm I.D., 1.5 μm film) was used for CO2 analysis. The temperature of the CG columns was held at 35° C. for 10 minutes, programmed to 150° C. at 25° C./min and held for 10 min. A mass spectrometer (MS) was used to identify and quantify the resolved CO and CO2 peaks eluting from the gas chromatograph. The MS used was a Hewlett-Packard 5972 mass selective detector. The mass spectrometer was operated at 70 eV in the El mode. The temperature of the ion source was maintained at 180° C. and the mass range scanned was 20-200 atomic mass units. It should be noted that the CO and CO2 quantities determined were only a fraction of the total CO and CO2 content generates from the samples. Only the resolved CO and CO2 peak areas were used for quantification. Table 4 summarizes the results produced by the samples in this example.TABLE 4 MASS ABUNDANCE (COUNTS)A CO/CO2 SAMPLES CO CO2 Ratio (1) Camel LT Tobacco 544,728,554 1,383,849,048 0.394 (2) Camel LT ® Tobacco 526,196,075 1,343,828,130 0.392 with 5% Fe2O3 (3) Camel LT ® Tobacco 532,589,297 1,354,841,196 0.393 with 2% Fe2O3 (4) Camel LT ® Tobacco 540,678,974 1,370,604,676 0.395 with 5% TiO2-Au (5) Camel LT ® Tobacco 536,124,377 1,392,004,504 0.385 with 2% TiO2-Au (6) Camel LT ® Tobacco 529,191,513 1,361,128,568 0.389 with 5% CeO2 (7) Camel LT ® Tobacco 523,482,876 1,365,668,545 0.383 with 2% CeO2 Air Blank 655,583 7,602,213
AMass abundance is the total abundance of ions in a mass spectrum for each compound with unit of counts.
- The results summarized in Table 4 and further illustrated in
FIG. 12 display that the catalytic activities of the metal and metal-oxide ultrafine particles comprising the catalyst compositions of the present invention are inhibited when combined with only tobacco to compose a fuel element. These results are consistent with fuel element samples of previous examples that contained specific amounts of tobacco. When heated or combusted, the tobacco content of the fuel element produces several chemical species that poison the catalytic ultrafine particles and thereby significantly reduce, if not eliminate, the catalytic oxidation of carbon monoxide to carbon dioxide. Consequently, tobacco components of fuel elements according to the present invention are disfavored. As displayed in the previous examples, however, a small component of tobacco within the fuel element does not destroy the catalytic activity of the metal oxide and metal ultrafine particles an appreciable amount and is, therefore, tolerable. The inclusion of a tobacco component in the fuel element of a smoking article can provide more flavor to the aerosol comprising the mainstream smoke of a smoking article.
Claims (20)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/868,126 US20050274390A1 (en) | 2004-06-15 | 2004-06-15 | Ultra-fine particle catalysts for carbonaceous fuel elements |
PCT/US2005/020406 WO2006002001A2 (en) | 2004-06-15 | 2005-06-09 | Ultra-fine particle catalysts for carbonaceous fuel elements |
EP05759387A EP1781125A2 (en) | 2004-06-15 | 2005-06-09 | Ultra-fine particle catalysts for carbonaceous fuel elements |
JP2007516566A JP2008505990A (en) | 2004-06-15 | 2005-06-09 | Ultrafine particle catalysts for carbonaceous fuel elements |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/868,126 US20050274390A1 (en) | 2004-06-15 | 2004-06-15 | Ultra-fine particle catalysts for carbonaceous fuel elements |
Publications (1)
Publication Number | Publication Date |
---|---|
US20050274390A1 true US20050274390A1 (en) | 2005-12-15 |
Family
ID=35355344
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/868,126 Abandoned US20050274390A1 (en) | 2004-06-15 | 2004-06-15 | Ultra-fine particle catalysts for carbonaceous fuel elements |
Country Status (4)
Country | Link |
---|---|
US (1) | US20050274390A1 (en) |
EP (1) | EP1781125A2 (en) |
JP (1) | JP2008505990A (en) |
WO (1) | WO2006002001A2 (en) |
Cited By (75)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070207079A1 (en) * | 2005-01-04 | 2007-09-06 | Brady John T | Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold |
WO2007108877A2 (en) | 2006-03-16 | 2007-09-27 | R.J. Reynolds Tobacco Company | Smoking article |
US20100065075A1 (en) * | 2008-09-18 | 2010-03-18 | R.J. Reynoldds Tobacco Company | Method for Preparing Fuel Element For Smoking Article |
US20100125039A1 (en) * | 2008-11-20 | 2010-05-20 | R. J. Reynolds Tobacco Company | Carbonaceous Material Having Modified Pore Structure |
US20100122708A1 (en) * | 2008-11-20 | 2010-05-20 | R. J. Reynolds Tobacco Company | Adsorbent Material Impregnated with Metal Oxide Component |
EP2241203A2 (en) | 2006-03-16 | 2010-10-20 | R. J. Reynolds Tobacco Company | Smoking Article |
WO2011028372A1 (en) | 2009-08-24 | 2011-03-10 | R.J. Reynolds Tobacco Company | Segmented smoking article with insulation mat |
US20110108044A1 (en) * | 2009-11-11 | 2011-05-12 | R.J. Reynolds Tobacco Company | Filter element comprising smoke-altering material |
US20110180082A1 (en) * | 2008-09-18 | 2011-07-28 | R.J. Reynolds Tobacco Company | Method for preparing fuel element for smoking article |
WO2011139730A1 (en) | 2010-05-06 | 2011-11-10 | R.J. Reynolds Tobacco Company | Segmented smoking article |
WO2011140430A1 (en) | 2010-05-07 | 2011-11-10 | R. J. Reynolds Tobacco Company | Filtered cigarette with modifiable sensory characteristics |
WO2012016051A2 (en) | 2010-07-30 | 2012-02-02 | R. J. Reynolds Tobacco Company | Filter element comprising multifunctional fibrous smoke-altering material |
WO2012138630A1 (en) | 2011-04-08 | 2012-10-11 | R. J. Reynolds Tobacco Company | Filtered cigarette comprising a tubular element in filter |
WO2013043806A2 (en) | 2011-09-23 | 2013-03-28 | R. J. Reynolds Tobacco Company | Mixed fiber product for use in the manufacture of cigarette filter elements and related methods, systems, and apparatuses |
WO2013043299A2 (en) | 2011-09-20 | 2013-03-28 | R.J. Reynolds Tobacco Company | Segmented smoking article with substrate cavity |
US8424538B2 (en) | 2010-05-06 | 2013-04-23 | R.J. Reynolds Tobacco Company | Segmented smoking article with shaped insulator |
WO2013098380A1 (en) * | 2011-12-29 | 2013-07-04 | Philip Morris Products S.A. | Composite heat source for a smoking article |
WO2013148810A1 (en) | 2012-03-28 | 2013-10-03 | R. J. Reynolds Tobacco Company | Smoking article incorporating a conductive substrate |
WO2013158323A1 (en) | 2012-04-17 | 2013-10-24 | R.J. Reynolds Tobacco Company | Method for preparing smoking articles |
WO2014004648A1 (en) | 2012-06-28 | 2014-01-03 | R. J. Reynolds Tobacco Company | Reservoir and heater system for controllable delivery of multiple aerosolizable materials in an electronic smoking article |
WO2014018645A1 (en) | 2012-07-25 | 2014-01-30 | R. J. Reynolds Tobacco Company | Mixed fiber sliver for use in the manufacture of cigarette filter elements |
WO2014037794A2 (en) | 2012-09-04 | 2014-03-13 | R. J. Reynolds Tobacco Company | Electronic smoking article comprising one or more microheaters |
WO2014058678A1 (en) | 2012-10-08 | 2014-04-17 | R. J. Reynolds Tobacco Company | An electronic smoking article and associated method |
WO2014120479A1 (en) | 2013-01-30 | 2014-08-07 | R. J. Reynolds Tobacco Company | Wick suitable for use in an electronic smoking article |
US8839799B2 (en) | 2010-05-06 | 2014-09-23 | R.J. Reynolds Tobacco Company | Segmented smoking article with stitch-bonded substrate |
US8910639B2 (en) | 2012-09-05 | 2014-12-16 | R. J. Reynolds Tobacco Company | Single-use connector and cartridge for a smoking article and related method |
US9078473B2 (en) | 2011-08-09 | 2015-07-14 | R.J. Reynolds Tobacco Company | Smoking articles and use thereof for yielding inhalation materials |
US20150237913A1 (en) * | 2012-10-18 | 2015-08-27 | Japan Tobacco Inc. | Non-burning type flavor inhaler |
US9149072B2 (en) | 2010-05-06 | 2015-10-06 | R.J. Reynolds Tobacco Company | Segmented smoking article with substrate cavity |
WO2015180167A1 (en) * | 2014-05-30 | 2015-12-03 | 深圳麦克韦尔股份有限公司 | Electronic cigarette and atomizer thereof |
US9220302B2 (en) | 2013-03-15 | 2015-12-29 | R.J. Reynolds Tobacco Company | Cartridge for an aerosol delivery device and method for assembling a cartridge for a smoking article |
US9277770B2 (en) | 2013-03-14 | 2016-03-08 | R. J. Reynolds Tobacco Company | Atomizer for an aerosol delivery device formed from a continuously extending wire and related input, cartridge, and method |
US9301546B2 (en) | 2010-08-19 | 2016-04-05 | R.J. Reynolds Tobacco Company | Segmented smoking article with shaped insulator |
WO2016119273A1 (en) * | 2015-01-26 | 2016-08-04 | 梅小建 | Packaging structure of electronic cigarette oil |
US9423152B2 (en) | 2013-03-15 | 2016-08-23 | R. J. Reynolds Tobacco Company | Heating control arrangement for an electronic smoking article and associated system and method |
US9451791B2 (en) | 2014-02-05 | 2016-09-27 | Rai Strategic Holdings, Inc. | Aerosol delivery device with an illuminated outer surface and related method |
US9491974B2 (en) | 2013-03-15 | 2016-11-15 | Rai Strategic Holdings, Inc. | Heating elements formed from a sheet of a material and inputs and methods for the production of atomizers |
US20170000188A1 (en) * | 2015-06-30 | 2017-01-05 | R.J. Reynolds Tobacco Company | Heat generation segment for an aerosol-generation system of a smoking article |
WO2017040608A2 (en) | 2015-08-31 | 2017-03-09 | R. J. Reynolds Tobacco Company | Smoking article |
US9597466B2 (en) | 2014-03-12 | 2017-03-21 | R. J. Reynolds Tobacco Company | Aerosol delivery system and related method, apparatus, and computer program product for providing control information to an aerosol delivery device via a cartridge |
US9609893B2 (en) | 2013-03-15 | 2017-04-04 | Rai Strategic Holdings, Inc. | Cartridge and control body of an aerosol delivery device including anti-rotation mechanism and related method |
WO2017098464A1 (en) | 2015-12-10 | 2017-06-15 | R. J. Reynolds Tobacco Company | Smoking article |
WO2017145095A1 (en) | 2016-02-24 | 2017-08-31 | R. J. Reynolds Tobacco Company | Smoking article comprising aerogel |
US9788571B2 (en) | 2013-09-25 | 2017-10-17 | R.J. Reynolds Tobacco Company | Heat generation apparatus for an aerosol-generation system of a smoking article, and associated smoking article |
US9833019B2 (en) | 2014-02-13 | 2017-12-05 | Rai Strategic Holdings, Inc. | Method for assembling a cartridge for a smoking article |
US9839238B2 (en) | 2014-02-28 | 2017-12-12 | Rai Strategic Holdings, Inc. | Control body for an electronic smoking article |
US9839237B2 (en) | 2013-11-22 | 2017-12-12 | Rai Strategic Holdings, Inc. | Reservoir housing for an electronic smoking article |
US9877510B2 (en) | 2014-04-04 | 2018-01-30 | Rai Strategic Holdings, Inc. | Sensor for an aerosol delivery device |
US9918495B2 (en) | 2014-02-28 | 2018-03-20 | Rai Strategic Holdings, Inc. | Atomizer for an aerosol delivery device and related input, aerosol production assembly, cartridge, and method |
US9924741B2 (en) | 2014-05-05 | 2018-03-27 | Rai Strategic Holdings, Inc. | Method of preparing an aerosol delivery device |
US9974334B2 (en) | 2014-01-17 | 2018-05-22 | Rai Strategic Holdings, Inc. | Electronic smoking article with improved storage of aerosol precursor compositions |
US10031183B2 (en) | 2013-03-07 | 2018-07-24 | Rai Strategic Holdings, Inc. | Spent cartridge detection method and system for an electronic smoking article |
US10117460B2 (en) | 2012-10-08 | 2018-11-06 | Rai Strategic Holdings, Inc. | Electronic smoking article and associated method |
US10172387B2 (en) | 2013-08-28 | 2019-01-08 | Rai Strategic Holdings, Inc. | Carbon conductive substrate for electronic smoking article |
US10188140B2 (en) | 2005-08-01 | 2019-01-29 | R.J. Reynolds Tobacco Company | Smoking article |
US10238145B2 (en) | 2015-05-19 | 2019-03-26 | Rai Strategic Holdings, Inc. | Assembly substation for assembling a cartridge for a smoking article |
US10405579B2 (en) | 2016-04-29 | 2019-09-10 | Rai Strategic Holdings, Inc. | Methods for assembling a cartridge for an aerosol delivery device, and associated systems and apparatuses |
US10575558B2 (en) | 2014-02-03 | 2020-03-03 | Rai Strategic Holdings, Inc. | Aerosol delivery device comprising multiple outer bodies and related assembly method |
WO2020089799A1 (en) | 2018-10-30 | 2020-05-07 | R. J. Reynolds Tobacco Company | Smoking article cartridge |
US10888119B2 (en) | 2014-07-10 | 2021-01-12 | Rai Strategic Holdings, Inc. | System and related methods, apparatuses, and computer program products for controlling operation of a device based on a read request |
US11219244B2 (en) | 2014-12-22 | 2022-01-11 | R.J. Reynolds Tobacco Company | Tobacco-derived carbon material |
US11229239B2 (en) | 2013-07-19 | 2022-01-25 | Rai Strategic Holdings, Inc. | Electronic smoking article with haptic feedback |
US11636870B2 (en) | 2020-08-20 | 2023-04-25 | Denso International America, Inc. | Smoking cessation systems and methods |
US11641871B2 (en) | 2006-10-18 | 2023-05-09 | Rai Strategic Holdings, Inc. | Tobacco-containing smoking article |
US11666098B2 (en) | 2014-02-07 | 2023-06-06 | Rai Strategic Holdings, Inc. | Charging accessory device for an aerosol delivery device and related system, method, apparatus, and computer program product for providing interactive services for aerosol delivery devices |
US11696604B2 (en) | 2014-03-13 | 2023-07-11 | Rai Strategic Holdings, Inc. | Aerosol delivery device and related method and computer program product for controlling an aerosol delivery device based on input characteristics |
US11744296B2 (en) | 2015-12-10 | 2023-09-05 | R. J. Reynolds Tobacco Company | Smoking article |
EP4241584A2 (en) | 2012-10-10 | 2023-09-13 | R. J. Reynolds Tobacco Company | Filter material for a filter element of a smoking article and associated method |
US11760169B2 (en) | 2020-08-20 | 2023-09-19 | Denso International America, Inc. | Particulate control systems and methods for olfaction sensors |
US11760170B2 (en) | 2020-08-20 | 2023-09-19 | Denso International America, Inc. | Olfaction sensor preservation systems and methods |
US11813926B2 (en) | 2020-08-20 | 2023-11-14 | Denso International America, Inc. | Binding agent and olfaction sensor |
US11828210B2 (en) | 2020-08-20 | 2023-11-28 | Denso International America, Inc. | Diagnostic systems and methods of vehicles using olfaction |
US11881093B2 (en) | 2020-08-20 | 2024-01-23 | Denso International America, Inc. | Systems and methods for identifying smoking in vehicles |
US11932080B2 (en) | 2020-08-20 | 2024-03-19 | Denso International America, Inc. | Diagnostic and recirculation control systems and methods |
US11957163B2 (en) | 2020-01-15 | 2024-04-16 | R.J. Reynolds Tobacco Company | Multi-segment filter element including smoke-altering flavorant |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011118043A1 (en) * | 2010-03-26 | 2011-09-29 | 日本たばこ産業株式会社 | Fuel element of non-combustion smoking article and method for producing same |
UA112440C2 (en) | 2011-06-02 | 2016-09-12 | Філіп Морріс Продактс С.А. | SMOKING SOURCE OF HEAT FOR SMOKING PRODUCTS |
KR102501825B1 (en) * | 2014-09-26 | 2023-02-22 | 필립모리스 프로덕츠 에스.에이. | Aerosol-generating system comprising a novel delivery enhancing compound source |
CN107348561B (en) | 2016-05-10 | 2021-11-02 | 韩力 | Micro-explosion microcapsule for smoking article and smoking article comprising same |
Citations (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4708151A (en) * | 1986-03-14 | 1987-11-24 | R. J. Reynolds Tobacco Company | Pipe with replaceable cartridge |
US4756318A (en) * | 1985-10-28 | 1988-07-12 | R. J. Reynolds Tobacco Company | Smoking article with tobacco jacket |
US4793365A (en) * | 1984-09-14 | 1988-12-27 | R. J. Reynolds Tobacco Company | Smoking article |
US4807809A (en) * | 1988-02-12 | 1989-02-28 | R. J. Reynolds Tobacco Company | Rod making apparatus for smoking article manufacture |
US4889143A (en) * | 1986-05-14 | 1989-12-26 | R. J. Reynolds Tobacco Company | Cigarette rods and filters containing strands provided from sheet-like materials |
US4961438A (en) * | 1989-04-03 | 1990-10-09 | Brown & Williamson Tobacco Corporation | Smoking device |
US4991606A (en) * | 1988-07-22 | 1991-02-12 | Philip Morris Incorporated | Smoking article |
US4991596A (en) * | 1989-07-11 | 1991-02-12 | R. J. Reynolds Tobacco Company | Smoking article |
US5016654A (en) * | 1988-12-21 | 1991-05-21 | R. J. Reynolds Tobacco Company | Flavor substances for smoking articles |
US5020548A (en) * | 1985-08-26 | 1991-06-04 | R. J. Reynolds Tobacco Company | Smoking article with improved fuel element |
US5025814A (en) * | 1987-05-12 | 1991-06-25 | R. J. Reynolds Tobacco Company | Cigarette filters containing strands of tobacco-containing materials |
US5038802A (en) * | 1988-12-21 | 1991-08-13 | R. J. Reynolds Tobacco Company | Flavor substances for smoking articles |
US5040551A (en) * | 1988-11-01 | 1991-08-20 | Catalytica, Inc. | Optimizing the oxidation of carbon monoxide |
US5065776A (en) * | 1990-08-29 | 1991-11-19 | R. J. Reynolds Tobacco Company | Cigarette with tobacco/glass fuel wrapper |
US5076295A (en) * | 1989-09-29 | 1991-12-31 | R. J. Reynolds Tobacco Company | Cigarette filter |
US5076297A (en) * | 1986-03-14 | 1991-12-31 | R. J. Reynolds Tobacco Company | Method for preparing carbon fuel for smoking articles and product produced thereby |
US5101839A (en) * | 1990-08-15 | 1992-04-07 | R. J. Reynolds Tobacco Company | Cigarette and smokable filler material therefor |
US5105834A (en) * | 1989-12-18 | 1992-04-21 | R.J. Reynolds Tobacco Company | Cigarette and cigarette filter element therefor |
US5105836A (en) * | 1989-09-29 | 1992-04-21 | R. J. Reynolds Tobacco Company | Cigarette and smokable filler material therefor |
US5105838A (en) * | 1990-10-23 | 1992-04-21 | R.J. Reynolds Tobacco Company | Cigarette |
US5148821A (en) * | 1990-08-17 | 1992-09-22 | R. J. Reynolds Tobacco Company | Processes for producing a smokable and/or combustible tobacco material |
US5178167A (en) * | 1991-06-28 | 1993-01-12 | R. J. Reynolds Tobacco Company | Carbonaceous composition for fuel elements of smoking articles and method of modifying the burning characteristics thereof |
US5183062A (en) * | 1990-02-27 | 1993-02-02 | R. J. Reynolds Tobacco Company | Cigarette |
US5211684A (en) * | 1989-01-10 | 1993-05-18 | R. J. Reynolds Tobacco Company | Catalyst containing smoking articles for reducing carbon monoxide |
US5240014A (en) * | 1990-07-20 | 1993-08-31 | Philip Morris Incorporated | Catalytic conversion of carbon monoxide from carbonaceous heat sources |
US5246018A (en) * | 1991-07-19 | 1993-09-21 | Philip Morris Incorporated | Manufacturing of composite heat sources containing carbon and metal species |
US5258340A (en) * | 1991-02-15 | 1993-11-02 | Philip Morris Incorporated | Mixed transition metal oxide catalysts for conversion of carbon monoxide and method for producing the catalysts |
US5303720A (en) * | 1989-05-22 | 1994-04-19 | R. J. Reynolds Tobacco Company | Smoking article with improved insulating material |
US5345955A (en) * | 1992-09-17 | 1994-09-13 | R. J. Reynolds Tobacco Company | Composite fuel element for smoking articles |
US5396911A (en) * | 1990-08-15 | 1995-03-14 | R. J. Reynolds Tobacco Company | Substrate material for smoking articles |
US5551451A (en) * | 1993-04-07 | 1996-09-03 | R. J. Reynolds Tobacco Company | Fuel element composition |
US5595577A (en) * | 1993-06-02 | 1997-01-21 | Bensalem; Azzedine | Method for making a carbonaceous heat source containing metal oxide |
US20020014453A1 (en) * | 2000-02-07 | 2002-02-07 | Lilly A. Clifton | Filtering unsaturated hydrocarbons using intermetallic nano-clusters |
US20020127351A1 (en) * | 2001-03-12 | 2002-09-12 | Futaba Corporation | Method for preparing nano-carbon and nano-carbon prepared by such method and composite material or mixed material containing nano-carbon and metal fine particle, apparatus for preparing nano-carbon, method for patterning nano-carbon and nano carbon base material patterned by the use of such method, as well as electron emission source using such patterned nano-carbon base material |
US6467897B1 (en) * | 2001-01-08 | 2002-10-22 | 3M Innovative Properties Company | Energy curable inks and other compositions incorporating surface modified, nanometer-sized particles |
US6472459B2 (en) * | 1999-06-02 | 2002-10-29 | Sandia Corporation | Fabrication of metallic microstructures by micromolding nanoparticles |
US6479146B1 (en) * | 1998-03-19 | 2002-11-12 | Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften, E.V. | Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates |
US6479156B1 (en) * | 1997-05-14 | 2002-11-12 | Institut für Neue Materialien Gemeinnützige GmbH | Nanocomposite for thermal insulation |
US20020167118A1 (en) * | 2001-03-23 | 2002-11-14 | Romain Billiet | Porous nanostructures and method of fabrication thereof |
US20020172826A1 (en) * | 1998-11-06 | 2002-11-21 | Tapesh Yadav | Nanoscale catalyst compositions from complex and non-stoichiometric compositions |
US20020194958A1 (en) * | 2001-06-08 | 2002-12-26 | Chien-Liang Lee | Process for preparing noble metal nanoparticles |
US20030000538A1 (en) * | 2000-11-10 | 2003-01-02 | Bereman Robert D. | Method and product for removing carcinogens from tobacco smoke |
US6503475B1 (en) * | 1998-05-15 | 2003-01-07 | Advanced Nano Technologies Pty Ltd. | Process for the production of ultrafine powders of metal oxides |
US20030131859A1 (en) * | 2001-08-31 | 2003-07-17 | Ping Li | Oxidant/catalyst nanoparticles to reduce tobacco smoke constituents such as carbon monoxide |
US20040173229A1 (en) * | 2003-03-05 | 2004-09-09 | Crooks Evon Llewellyn | Smoking article comprising ultrafine particles |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1990010394A1 (en) * | 1989-03-16 | 1990-09-20 | R.J. Reynolds Tobacco Company | Catalyst containing smoking articles for reducing carbon monoxide |
JPH03296659A (en) * | 1990-04-17 | 1991-12-27 | Osaka Oxygen Ind Ltd | Analysis of carbon monoxide in gas |
CA2079495A1 (en) * | 1991-10-03 | 1993-04-04 | John H. Kolts | Smoking article with co oxidation catalyst |
US6769437B2 (en) * | 2002-04-08 | 2004-08-03 | Philip Morris Incorporated | Use of oxyhydroxide compounds for reducing carbon monoxide in the mainstream smoke of a cigarette |
JP4388379B2 (en) * | 2002-04-12 | 2009-12-24 | フィリップ・モーリス・プロダクツ・ソシエテ・アノニム | Partially reduced nanoparticle additives for reducing the amount of carbon monoxide and / or nitric oxide in cigarette mainstream smoke |
-
2004
- 2004-06-15 US US10/868,126 patent/US20050274390A1/en not_active Abandoned
-
2005
- 2005-06-09 WO PCT/US2005/020406 patent/WO2006002001A2/en active Application Filing
- 2005-06-09 JP JP2007516566A patent/JP2008505990A/en active Pending
- 2005-06-09 EP EP05759387A patent/EP1781125A2/en not_active Withdrawn
Patent Citations (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4793365A (en) * | 1984-09-14 | 1988-12-27 | R. J. Reynolds Tobacco Company | Smoking article |
US5020548A (en) * | 1985-08-26 | 1991-06-04 | R. J. Reynolds Tobacco Company | Smoking article with improved fuel element |
US4756318A (en) * | 1985-10-28 | 1988-07-12 | R. J. Reynolds Tobacco Company | Smoking article with tobacco jacket |
US5076297A (en) * | 1986-03-14 | 1991-12-31 | R. J. Reynolds Tobacco Company | Method for preparing carbon fuel for smoking articles and product produced thereby |
US4708151A (en) * | 1986-03-14 | 1987-11-24 | R. J. Reynolds Tobacco Company | Pipe with replaceable cartridge |
US4889143A (en) * | 1986-05-14 | 1989-12-26 | R. J. Reynolds Tobacco Company | Cigarette rods and filters containing strands provided from sheet-like materials |
US5025814A (en) * | 1987-05-12 | 1991-06-25 | R. J. Reynolds Tobacco Company | Cigarette filters containing strands of tobacco-containing materials |
US4807809A (en) * | 1988-02-12 | 1989-02-28 | R. J. Reynolds Tobacco Company | Rod making apparatus for smoking article manufacture |
US4991606A (en) * | 1988-07-22 | 1991-02-12 | Philip Morris Incorporated | Smoking article |
US5040551A (en) * | 1988-11-01 | 1991-08-20 | Catalytica, Inc. | Optimizing the oxidation of carbon monoxide |
US5016654A (en) * | 1988-12-21 | 1991-05-21 | R. J. Reynolds Tobacco Company | Flavor substances for smoking articles |
US5038802A (en) * | 1988-12-21 | 1991-08-13 | R. J. Reynolds Tobacco Company | Flavor substances for smoking articles |
US5211684A (en) * | 1989-01-10 | 1993-05-18 | R. J. Reynolds Tobacco Company | Catalyst containing smoking articles for reducing carbon monoxide |
US4961438A (en) * | 1989-04-03 | 1990-10-09 | Brown & Williamson Tobacco Corporation | Smoking device |
US5303720A (en) * | 1989-05-22 | 1994-04-19 | R. J. Reynolds Tobacco Company | Smoking article with improved insulating material |
US4991596A (en) * | 1989-07-11 | 1991-02-12 | R. J. Reynolds Tobacco Company | Smoking article |
US5076295A (en) * | 1989-09-29 | 1991-12-31 | R. J. Reynolds Tobacco Company | Cigarette filter |
US5105836A (en) * | 1989-09-29 | 1992-04-21 | R. J. Reynolds Tobacco Company | Cigarette and smokable filler material therefor |
US5105834A (en) * | 1989-12-18 | 1992-04-21 | R.J. Reynolds Tobacco Company | Cigarette and cigarette filter element therefor |
US5183062A (en) * | 1990-02-27 | 1993-02-02 | R. J. Reynolds Tobacco Company | Cigarette |
US5240014A (en) * | 1990-07-20 | 1993-08-31 | Philip Morris Incorporated | Catalytic conversion of carbon monoxide from carbonaceous heat sources |
US5101839A (en) * | 1990-08-15 | 1992-04-07 | R. J. Reynolds Tobacco Company | Cigarette and smokable filler material therefor |
US5396911A (en) * | 1990-08-15 | 1995-03-14 | R. J. Reynolds Tobacco Company | Substrate material for smoking articles |
US5148821A (en) * | 1990-08-17 | 1992-09-22 | R. J. Reynolds Tobacco Company | Processes for producing a smokable and/or combustible tobacco material |
US5065776A (en) * | 1990-08-29 | 1991-11-19 | R. J. Reynolds Tobacco Company | Cigarette with tobacco/glass fuel wrapper |
US5105838A (en) * | 1990-10-23 | 1992-04-21 | R.J. Reynolds Tobacco Company | Cigarette |
US5258340A (en) * | 1991-02-15 | 1993-11-02 | Philip Morris Incorporated | Mixed transition metal oxide catalysts for conversion of carbon monoxide and method for producing the catalysts |
US5178167A (en) * | 1991-06-28 | 1993-01-12 | R. J. Reynolds Tobacco Company | Carbonaceous composition for fuel elements of smoking articles and method of modifying the burning characteristics thereof |
US5246018A (en) * | 1991-07-19 | 1993-09-21 | Philip Morris Incorporated | Manufacturing of composite heat sources containing carbon and metal species |
US5345955A (en) * | 1992-09-17 | 1994-09-13 | R. J. Reynolds Tobacco Company | Composite fuel element for smoking articles |
US5551451A (en) * | 1993-04-07 | 1996-09-03 | R. J. Reynolds Tobacco Company | Fuel element composition |
US5595577A (en) * | 1993-06-02 | 1997-01-21 | Bensalem; Azzedine | Method for making a carbonaceous heat source containing metal oxide |
US6479156B1 (en) * | 1997-05-14 | 2002-11-12 | Institut für Neue Materialien Gemeinnützige GmbH | Nanocomposite for thermal insulation |
US6479146B1 (en) * | 1998-03-19 | 2002-11-12 | Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften, E.V. | Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates |
US6503475B1 (en) * | 1998-05-15 | 2003-01-07 | Advanced Nano Technologies Pty Ltd. | Process for the production of ultrafine powders of metal oxides |
US20020172826A1 (en) * | 1998-11-06 | 2002-11-21 | Tapesh Yadav | Nanoscale catalyst compositions from complex and non-stoichiometric compositions |
US6472459B2 (en) * | 1999-06-02 | 2002-10-29 | Sandia Corporation | Fabrication of metallic microstructures by micromolding nanoparticles |
US20020014453A1 (en) * | 2000-02-07 | 2002-02-07 | Lilly A. Clifton | Filtering unsaturated hydrocarbons using intermetallic nano-clusters |
US20030000538A1 (en) * | 2000-11-10 | 2003-01-02 | Bereman Robert D. | Method and product for removing carcinogens from tobacco smoke |
US6467897B1 (en) * | 2001-01-08 | 2002-10-22 | 3M Innovative Properties Company | Energy curable inks and other compositions incorporating surface modified, nanometer-sized particles |
US20020127351A1 (en) * | 2001-03-12 | 2002-09-12 | Futaba Corporation | Method for preparing nano-carbon and nano-carbon prepared by such method and composite material or mixed material containing nano-carbon and metal fine particle, apparatus for preparing nano-carbon, method for patterning nano-carbon and nano carbon base material patterned by the use of such method, as well as electron emission source using such patterned nano-carbon base material |
US20020167118A1 (en) * | 2001-03-23 | 2002-11-14 | Romain Billiet | Porous nanostructures and method of fabrication thereof |
US20020194958A1 (en) * | 2001-06-08 | 2002-12-26 | Chien-Liang Lee | Process for preparing noble metal nanoparticles |
US20030131859A1 (en) * | 2001-08-31 | 2003-07-17 | Ping Li | Oxidant/catalyst nanoparticles to reduce tobacco smoke constituents such as carbon monoxide |
US20040173229A1 (en) * | 2003-03-05 | 2004-09-09 | Crooks Evon Llewellyn | Smoking article comprising ultrafine particles |
Cited By (187)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8058202B2 (en) | 2005-01-04 | 2011-11-15 | 3M Innovative Properties Company | Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold |
US8664149B2 (en) | 2005-01-04 | 2014-03-04 | 3M Innovative Properties Company | Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold |
WO2006074126A3 (en) * | 2005-01-04 | 2007-12-27 | 3M Innovative Properties Co | Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold |
US8314046B2 (en) | 2005-01-04 | 2012-11-20 | 3M Innovative Properties Company | Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold |
US8518854B2 (en) | 2005-01-04 | 2013-08-27 | 3M Innovative Properties Company | Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold |
US20070207079A1 (en) * | 2005-01-04 | 2007-09-06 | Brady John T | Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold |
AU2006204145B2 (en) * | 2005-01-04 | 2011-03-17 | 3M Innovative Properties Company | Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold |
US8678013B2 (en) | 2005-08-01 | 2014-03-25 | R.J. Reynolds Tobacco Company | Smoking article |
US10188140B2 (en) | 2005-08-01 | 2019-01-29 | R.J. Reynolds Tobacco Company | Smoking article |
US9220301B2 (en) | 2006-03-16 | 2015-12-29 | R.J. Reynolds Tobacco Company | Smoking article |
EP2241203A2 (en) | 2006-03-16 | 2010-10-20 | R. J. Reynolds Tobacco Company | Smoking Article |
EP2486812A1 (en) | 2006-03-16 | 2012-08-15 | R.J. Reynolds Tobacco Company | Smoking article |
EP2762020A2 (en) | 2006-03-16 | 2014-08-06 | R. J. Reynolds Tobacco Company | Smoking article |
US10258079B2 (en) | 2006-03-16 | 2019-04-16 | R.J. Reynolds Tobacco Company | Smoking article |
EP3569079A1 (en) | 2006-03-16 | 2019-11-20 | R. J. Reynolds Tobacco Company | Smoking article |
WO2007108877A2 (en) | 2006-03-16 | 2007-09-27 | R.J. Reynolds Tobacco Company | Smoking article |
US11647781B2 (en) | 2006-10-18 | 2023-05-16 | Rai Strategic Holdings, Inc. | Tobacco-containing smoking article |
US11758936B2 (en) | 2006-10-18 | 2023-09-19 | Rai Strategic Holdings, Inc. | Tobacco-containing smoking article |
US11785978B2 (en) | 2006-10-18 | 2023-10-17 | Rai Strategic Holdings, Inc. | Tobacco-containing smoking article |
US11805806B2 (en) | 2006-10-18 | 2023-11-07 | Rai Strategic Holdings, Inc. | Tobacco-containing smoking article |
US11641871B2 (en) | 2006-10-18 | 2023-05-09 | Rai Strategic Holdings, Inc. | Tobacco-containing smoking article |
US11925202B2 (en) | 2006-10-18 | 2024-03-12 | Rai Strategic Holdings, Inc. | Tobacco-containing smoking article |
US20130255703A1 (en) * | 2008-09-18 | 2013-10-03 | R. J. Reynolds Tobacco Company | Method for preparing fuel element for smoking article |
US9332784B2 (en) | 2008-09-18 | 2016-05-10 | R.J. Reynolds Tobacco Company | Method for preparing fuel element for smoking article |
US8469035B2 (en) * | 2008-09-18 | 2013-06-25 | R. J. Reynolds Tobacco Company | Method for preparing fuel element for smoking article |
US10624390B2 (en) * | 2008-09-18 | 2020-04-21 | R.J. Reynolds Tobacco Company | Method for preparing fuel element for smoking article |
US20100065075A1 (en) * | 2008-09-18 | 2010-03-18 | R.J. Reynoldds Tobacco Company | Method for Preparing Fuel Element For Smoking Article |
US8617263B2 (en) | 2008-09-18 | 2013-12-31 | R. J. Reynolds Tobacco Company | Method for preparing fuel element for smoking article |
US20110180082A1 (en) * | 2008-09-18 | 2011-07-28 | R.J. Reynolds Tobacco Company | Method for preparing fuel element for smoking article |
US8511319B2 (en) | 2008-11-20 | 2013-08-20 | R. J. Reynolds Tobacco Company | Adsorbent material impregnated with metal oxide component |
US8119555B2 (en) | 2008-11-20 | 2012-02-21 | R. J. Reynolds Tobacco Company | Carbonaceous material having modified pore structure |
US20100125039A1 (en) * | 2008-11-20 | 2010-05-20 | R. J. Reynolds Tobacco Company | Carbonaceous Material Having Modified Pore Structure |
US20100122708A1 (en) * | 2008-11-20 | 2010-05-20 | R. J. Reynolds Tobacco Company | Adsorbent Material Impregnated with Metal Oxide Component |
US8464726B2 (en) | 2009-08-24 | 2013-06-18 | R.J. Reynolds Tobacco Company | Segmented smoking article with insulation mat |
WO2011028372A1 (en) | 2009-08-24 | 2011-03-10 | R.J. Reynolds Tobacco Company | Segmented smoking article with insulation mat |
US9486013B2 (en) | 2009-08-24 | 2016-11-08 | R.J. Reynolds Tobacco Company | Segmented smoking article with foamed insulation material |
WO2011060008A1 (en) | 2009-11-11 | 2011-05-19 | R. J. Reynolds Tobacco Company | Filter element comprising smoke-altering material |
US8997755B2 (en) | 2009-11-11 | 2015-04-07 | R.J. Reynolds Tobacco Company | Filter element comprising smoke-altering material |
US20110108044A1 (en) * | 2009-11-11 | 2011-05-12 | R.J. Reynolds Tobacco Company | Filter element comprising smoke-altering material |
US9439453B2 (en) | 2010-05-06 | 2016-09-13 | R.J. Reynolds Tobacco Company | Segmented smoking article with substrate cavity |
WO2011139730A1 (en) | 2010-05-06 | 2011-11-10 | R.J. Reynolds Tobacco Company | Segmented smoking article |
EP2647300A2 (en) | 2010-05-06 | 2013-10-09 | R.J. Reynolds Tobacco Company | Segmented smoking article |
EP2647301A2 (en) | 2010-05-06 | 2013-10-09 | R.J. Reynolds Tobacco Company | Segmented smoking article |
US9149072B2 (en) | 2010-05-06 | 2015-10-06 | R.J. Reynolds Tobacco Company | Segmented smoking article with substrate cavity |
EP3520636A1 (en) | 2010-05-06 | 2019-08-07 | R. J. Reynolds Tobacco Company | Segmented smoking article |
US8839799B2 (en) | 2010-05-06 | 2014-09-23 | R.J. Reynolds Tobacco Company | Segmented smoking article with stitch-bonded substrate |
US8424538B2 (en) | 2010-05-06 | 2013-04-23 | R.J. Reynolds Tobacco Company | Segmented smoking article with shaped insulator |
WO2011140430A1 (en) | 2010-05-07 | 2011-11-10 | R. J. Reynolds Tobacco Company | Filtered cigarette with modifiable sensory characteristics |
US9119420B2 (en) | 2010-07-30 | 2015-09-01 | R.J. Reynolds Tobacco Company | Filter element comprising multifunctional fibrous smoke-altering material |
WO2012016051A2 (en) | 2010-07-30 | 2012-02-02 | R. J. Reynolds Tobacco Company | Filter element comprising multifunctional fibrous smoke-altering material |
US8720450B2 (en) | 2010-07-30 | 2014-05-13 | R.J. Reynolds Tobacco Company | Filter element comprising multifunctional fibrous smoke-altering material |
US9301546B2 (en) | 2010-08-19 | 2016-04-05 | R.J. Reynolds Tobacco Company | Segmented smoking article with shaped insulator |
WO2012138630A1 (en) | 2011-04-08 | 2012-10-11 | R. J. Reynolds Tobacco Company | Filtered cigarette comprising a tubular element in filter |
US10609955B2 (en) | 2011-04-08 | 2020-04-07 | R.J. Reynolds Tobacco Company | Filtered cigarette comprising a tubular element in filter |
US10492542B1 (en) | 2011-08-09 | 2019-12-03 | Rai Strategic Holdings, Inc. | Smoking articles and use thereof for yielding inhalation materials |
US9078473B2 (en) | 2011-08-09 | 2015-07-14 | R.J. Reynolds Tobacco Company | Smoking articles and use thereof for yielding inhalation materials |
US9930915B2 (en) | 2011-08-09 | 2018-04-03 | Rai Strategic Holdings, Inc. | Smoking articles and use thereof for yielding inhalation materials |
US10362809B2 (en) | 2011-08-09 | 2019-07-30 | Rai Strategic Holdings, Inc. | Smoking articles and use thereof for yielding inhalation materials |
US10588355B2 (en) | 2011-08-09 | 2020-03-17 | Rai Strategic Holdings, Inc. | Smoking articles and use thereof for yielding inhalation materials |
US11779051B2 (en) | 2011-08-09 | 2023-10-10 | Rai Strategic Holdings, Inc. | Smoking articles and use thereof for yielding inhalation materials |
WO2013043299A2 (en) | 2011-09-20 | 2013-03-28 | R.J. Reynolds Tobacco Company | Segmented smoking article with substrate cavity |
EP4115756A1 (en) | 2011-09-20 | 2023-01-11 | R. J. Reynolds Tobacco Company | Segmented smoking article with substrate cavity |
EP3456212A1 (en) | 2011-09-23 | 2019-03-20 | R. J. Reynolds Tobacco Company | Mixed fiber product for use in the manufacture of cigarette filter elements and related methods, systems, and apparatuses |
WO2013043806A2 (en) | 2011-09-23 | 2013-03-28 | R. J. Reynolds Tobacco Company | Mixed fiber product for use in the manufacture of cigarette filter elements and related methods, systems, and apparatuses |
RU2608274C2 (en) * | 2011-12-29 | 2017-01-17 | Филип Моррис Продактс С.А. | Composite heat source for smoking article |
US10440990B2 (en) | 2011-12-29 | 2019-10-15 | Philip Morris Products S.A. | Composite heat source for a smoking article |
WO2013098380A1 (en) * | 2011-12-29 | 2013-07-04 | Philip Morris Products S.A. | Composite heat source for a smoking article |
JP2015503334A (en) * | 2011-12-29 | 2015-02-02 | フィリップ・モーリス・プロダクツ・ソシエテ・アノニム | Composite heat source for smoking articles |
CN103929984A (en) * | 2011-12-29 | 2014-07-16 | 菲利普莫里斯生产公司 | Composite heat source for a smoking article |
WO2013148810A1 (en) | 2012-03-28 | 2013-10-03 | R. J. Reynolds Tobacco Company | Smoking article incorporating a conductive substrate |
US11602175B2 (en) | 2012-03-28 | 2023-03-14 | Rai Strategic Holdings, Inc. | Smoking article incorporating a conductive substrate |
US11246344B2 (en) | 2012-03-28 | 2022-02-15 | Rai Strategic Holdings, Inc. | Smoking article incorporating a conductive substrate |
US9345268B2 (en) | 2012-04-17 | 2016-05-24 | R.J. Reynolds Tobacco Company | Method for preparing smoking articles |
WO2013158323A1 (en) | 2012-04-17 | 2013-10-24 | R.J. Reynolds Tobacco Company | Method for preparing smoking articles |
WO2014004648A1 (en) | 2012-06-28 | 2014-01-03 | R. J. Reynolds Tobacco Company | Reservoir and heater system for controllable delivery of multiple aerosolizable materials in an electronic smoking article |
US10004259B2 (en) | 2012-06-28 | 2018-06-26 | Rai Strategic Holdings, Inc. | Reservoir and heater system for controllable delivery of multiple aerosolizable materials in an electronic smoking article |
US11140921B2 (en) | 2012-06-28 | 2021-10-12 | Rai Strategic Holdings, Inc. | Reservoir and heater system for controllable delivery of multiple aerosolizable materials in an electronic smoking article |
US10524512B2 (en) | 2012-06-28 | 2020-01-07 | Rai Strategic Holdings, Inc. | Reservoir and heater system for controllable delivery of multiple aerosolizable materials in an electronic smoking article |
WO2014018645A1 (en) | 2012-07-25 | 2014-01-30 | R. J. Reynolds Tobacco Company | Mixed fiber sliver for use in the manufacture of cigarette filter elements |
US8881737B2 (en) | 2012-09-04 | 2014-11-11 | R.J. Reynolds Tobacco Company | Electronic smoking article comprising one or more microheaters |
US11825567B2 (en) | 2012-09-04 | 2023-11-21 | Rai Strategic Holdings, Inc. | Electronic smoking article comprising one or more microheaters |
US11044950B2 (en) | 2012-09-04 | 2021-06-29 | Rai Strategic Holdings, Inc. | Electronic smoking article comprising one or more microheaters |
WO2014037794A2 (en) | 2012-09-04 | 2014-03-13 | R. J. Reynolds Tobacco Company | Electronic smoking article comprising one or more microheaters |
EP4014764A1 (en) | 2012-09-04 | 2022-06-22 | RAI Strategic Holdings, Inc. | Electronic smoking article comprising one or more microheaters |
EP3858168A1 (en) | 2012-09-04 | 2021-08-04 | RAI Strategic Holdings, Inc. | Electronic smoking article comprising one or more microheaters |
US9980512B2 (en) | 2012-09-04 | 2018-05-29 | Rai Strategic Holdings, Inc. | Electronic smoking article comprising one or more microheaters |
US8910639B2 (en) | 2012-09-05 | 2014-12-16 | R. J. Reynolds Tobacco Company | Single-use connector and cartridge for a smoking article and related method |
US9949508B2 (en) | 2012-09-05 | 2018-04-24 | Rai Strategic Holdings, Inc. | Single-use connector and cartridge for a smoking article and related method |
US10531691B2 (en) | 2012-10-08 | 2020-01-14 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
US11856997B2 (en) | 2012-10-08 | 2024-01-02 | Rai Strategic Holdings, Inc. | Electronic smoking article and associated method |
US10117460B2 (en) | 2012-10-08 | 2018-11-06 | Rai Strategic Holdings, Inc. | Electronic smoking article and associated method |
US11019852B2 (en) | 2012-10-08 | 2021-06-01 | Rai Strategic Holdings, Inc. | Electronic smoking article and associated method |
WO2014058678A1 (en) | 2012-10-08 | 2014-04-17 | R. J. Reynolds Tobacco Company | An electronic smoking article and associated method |
US9854841B2 (en) | 2012-10-08 | 2018-01-02 | Rai Strategic Holdings, Inc. | Electronic smoking article and associated method |
US10881150B2 (en) | 2012-10-08 | 2021-01-05 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
EP4241584A2 (en) | 2012-10-10 | 2023-09-13 | R. J. Reynolds Tobacco Company | Filter material for a filter element of a smoking article and associated method |
US20150237913A1 (en) * | 2012-10-18 | 2015-08-27 | Japan Tobacco Inc. | Non-burning type flavor inhaler |
US10420372B2 (en) * | 2012-10-18 | 2019-09-24 | Japan Tobacco Inc. | Non-burning type flavor inhaler |
US10258089B2 (en) | 2013-01-30 | 2019-04-16 | Rai Strategic Holdings, Inc. | Wick suitable for use in an electronic smoking article |
US9854847B2 (en) | 2013-01-30 | 2018-01-02 | Rai Strategic Holdings, Inc. | Wick suitable for use in an electronic smoking article |
US8910640B2 (en) | 2013-01-30 | 2014-12-16 | R.J. Reynolds Tobacco Company | Wick suitable for use in an electronic smoking article |
WO2014120479A1 (en) | 2013-01-30 | 2014-08-07 | R. J. Reynolds Tobacco Company | Wick suitable for use in an electronic smoking article |
US10274539B2 (en) | 2013-03-07 | 2019-04-30 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
US10031183B2 (en) | 2013-03-07 | 2018-07-24 | Rai Strategic Holdings, Inc. | Spent cartridge detection method and system for an electronic smoking article |
US11428738B2 (en) | 2013-03-07 | 2022-08-30 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
US10753974B2 (en) | 2013-03-07 | 2020-08-25 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
US9277770B2 (en) | 2013-03-14 | 2016-03-08 | R. J. Reynolds Tobacco Company | Atomizer for an aerosol delivery device formed from a continuously extending wire and related input, cartridge, and method |
US10306924B2 (en) | 2013-03-14 | 2019-06-04 | Rai Strategic Holdings, Inc. | Atomizer for an aerosol delivery device formed from a continuously extending wire and related input, cartridge, and method |
US11000075B2 (en) | 2013-03-15 | 2021-05-11 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
US9609893B2 (en) | 2013-03-15 | 2017-04-04 | Rai Strategic Holdings, Inc. | Cartridge and control body of an aerosol delivery device including anti-rotation mechanism and related method |
US10426200B2 (en) | 2013-03-15 | 2019-10-01 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
US10492532B2 (en) | 2013-03-15 | 2019-12-03 | Rai Strategic Holdings, Inc. | Cartridge and control body of an aerosol delivery device including anti-rotation mechanism and related method |
US11871484B2 (en) | 2013-03-15 | 2024-01-09 | Rai Strategic Holdings, Inc. | Aerosol delivery device |
US9220302B2 (en) | 2013-03-15 | 2015-12-29 | R.J. Reynolds Tobacco Company | Cartridge for an aerosol delivery device and method for assembling a cartridge for a smoking article |
US9423152B2 (en) | 2013-03-15 | 2016-08-23 | R. J. Reynolds Tobacco Company | Heating control arrangement for an electronic smoking article and associated system and method |
US11247006B2 (en) | 2013-03-15 | 2022-02-15 | Rai Strategic Holdings, Inc. | Cartridge and control body of an aerosol delivery device including anti-rotation mechanism and related method |
US10143236B2 (en) | 2013-03-15 | 2018-12-04 | Rai Strategic Holdings, Inc. | Cartridge for an aerosol delivery device and method for assembling a cartridge for a smoking article |
US11785990B2 (en) | 2013-03-15 | 2023-10-17 | Rai Strategic Holdings, Inc. | Heating elements formed from a sheet of a material and inputs and methods for the production of atomizers |
US9491974B2 (en) | 2013-03-15 | 2016-11-15 | Rai Strategic Holdings, Inc. | Heating elements formed from a sheet of a material and inputs and methods for the production of atomizers |
US10595561B2 (en) | 2013-03-15 | 2020-03-24 | Rai Strategic Holdings, Inc. | Heating elements formed from a sheet of a material and inputs and methods for the production of atomizers |
US11229239B2 (en) | 2013-07-19 | 2022-01-25 | Rai Strategic Holdings, Inc. | Electronic smoking article with haptic feedback |
US10667562B2 (en) | 2013-08-28 | 2020-06-02 | Rai Strategic Holdings, Inc. | Carbon conductive substrate for electronic smoking article |
US10172387B2 (en) | 2013-08-28 | 2019-01-08 | Rai Strategic Holdings, Inc. | Carbon conductive substrate for electronic smoking article |
US10701979B2 (en) | 2013-08-28 | 2020-07-07 | Rai Strategic Holdings, Inc. | Carbon conductive substrate for electronic smoking article |
US11375745B2 (en) | 2013-09-25 | 2022-07-05 | R.J. Reynolds Tobacco Company | Heat generation apparatus for an aerosol-generation system of a smoking article, and associated smoking article |
US11707083B2 (en) | 2013-09-25 | 2023-07-25 | R.J. Reynolds Tobacco Company | Heat generation apparatus for an aerosol-generation system of a smoking article, and associated smoking article |
US10314330B2 (en) | 2013-09-25 | 2019-06-11 | R.J. Reynolds Tobacco Company | Heat generation apparatus for an aerosol-generation system of a smoking article, and associated smoking article |
US9788571B2 (en) | 2013-09-25 | 2017-10-17 | R.J. Reynolds Tobacco Company | Heat generation apparatus for an aerosol-generation system of a smoking article, and associated smoking article |
US10653184B2 (en) | 2013-11-22 | 2020-05-19 | Rai Strategic Holdings, Inc. | Reservoir housing for an electronic smoking article |
US9839237B2 (en) | 2013-11-22 | 2017-12-12 | Rai Strategic Holdings, Inc. | Reservoir housing for an electronic smoking article |
US11357260B2 (en) | 2014-01-17 | 2022-06-14 | RAI Srategic Holdings, Inc. | Electronic smoking article with improved storage of aerosol precursor compositions |
US10721968B2 (en) | 2014-01-17 | 2020-07-28 | Rai Strategic Holdings, Inc. | Electronic smoking article with improved storage of aerosol precursor compositions |
US9974334B2 (en) | 2014-01-17 | 2018-05-22 | Rai Strategic Holdings, Inc. | Electronic smoking article with improved storage of aerosol precursor compositions |
US10531690B2 (en) | 2014-01-17 | 2020-01-14 | Rai Strategic Holdings, Inc. | Electronic smoking article with improved storage of aerosol precursor compositions |
US10575558B2 (en) | 2014-02-03 | 2020-03-03 | Rai Strategic Holdings, Inc. | Aerosol delivery device comprising multiple outer bodies and related assembly method |
US9451791B2 (en) | 2014-02-05 | 2016-09-27 | Rai Strategic Holdings, Inc. | Aerosol delivery device with an illuminated outer surface and related method |
US11666098B2 (en) | 2014-02-07 | 2023-06-06 | Rai Strategic Holdings, Inc. | Charging accessory device for an aerosol delivery device and related system, method, apparatus, and computer program product for providing interactive services for aerosol delivery devices |
US10609961B2 (en) | 2014-02-13 | 2020-04-07 | Rai Strategic Holdings, Inc. | Method for assembling a cartridge for a smoking article |
US10588352B2 (en) | 2014-02-13 | 2020-03-17 | Rai Strategic Holdings, Inc. | Method for assembling a cartridge for a smoking article |
US9833019B2 (en) | 2014-02-13 | 2017-12-05 | Rai Strategic Holdings, Inc. | Method for assembling a cartridge for a smoking article |
US10470497B2 (en) | 2014-02-13 | 2019-11-12 | Rai Strategic Holdings, Inc. | Method for assembling a cartridge for a smoking article |
US11083857B2 (en) | 2014-02-13 | 2021-08-10 | Rai Strategic Holdings, Inc. | Method for assembling a cartridge for a smoking article |
US10856570B2 (en) | 2014-02-13 | 2020-12-08 | Rai Strategic Holdings, Inc. | Method for assembling a cartridge for a smoking article |
US11234463B2 (en) | 2014-02-28 | 2022-02-01 | Rai Strategic Holdings, Inc. | Atomizer for an aerosol delivery device and related input, aerosol production assembly, cartridge, and method |
US9839238B2 (en) | 2014-02-28 | 2017-12-12 | Rai Strategic Holdings, Inc. | Control body for an electronic smoking article |
US11864584B2 (en) | 2014-02-28 | 2024-01-09 | Rai Strategic Holdings, Inc. | Control body for an electronic smoking article |
US10524511B2 (en) | 2014-02-28 | 2020-01-07 | Rai Strategic Holdings, Inc. | Control body for an electronic smoking article |
US9918495B2 (en) | 2014-02-28 | 2018-03-20 | Rai Strategic Holdings, Inc. | Atomizer for an aerosol delivery device and related input, aerosol production assembly, cartridge, and method |
US11659868B2 (en) | 2014-02-28 | 2023-05-30 | Rai Strategic Holdings, Inc. | Control body for an electronic smoking article |
US9597466B2 (en) | 2014-03-12 | 2017-03-21 | R. J. Reynolds Tobacco Company | Aerosol delivery system and related method, apparatus, and computer program product for providing control information to an aerosol delivery device via a cartridge |
US11696604B2 (en) | 2014-03-13 | 2023-07-11 | Rai Strategic Holdings, Inc. | Aerosol delivery device and related method and computer program product for controlling an aerosol delivery device based on input characteristics |
US10568359B2 (en) | 2014-04-04 | 2020-02-25 | Rai Strategic Holdings, Inc. | Sensor for an aerosol delivery device |
US9877510B2 (en) | 2014-04-04 | 2018-01-30 | Rai Strategic Holdings, Inc. | Sensor for an aerosol delivery device |
US9924741B2 (en) | 2014-05-05 | 2018-03-27 | Rai Strategic Holdings, Inc. | Method of preparing an aerosol delivery device |
US10645974B2 (en) | 2014-05-05 | 2020-05-12 | Rai Strategic Holdings, Inc. | Method of preparing an aerosol delivery device |
WO2015180167A1 (en) * | 2014-05-30 | 2015-12-03 | 深圳麦克韦尔股份有限公司 | Electronic cigarette and atomizer thereof |
US10888119B2 (en) | 2014-07-10 | 2021-01-12 | Rai Strategic Holdings, Inc. | System and related methods, apparatuses, and computer program products for controlling operation of a device based on a read request |
US11219244B2 (en) | 2014-12-22 | 2022-01-11 | R.J. Reynolds Tobacco Company | Tobacco-derived carbon material |
WO2016119273A1 (en) * | 2015-01-26 | 2016-08-04 | 梅小建 | Packaging structure of electronic cigarette oil |
US11607759B2 (en) | 2015-05-19 | 2023-03-21 | Rai Strategic Holdings, Inc. | Assembly substation for assembling a cartridge for a smoking article and related method |
US11065727B2 (en) | 2015-05-19 | 2021-07-20 | Rai Strategic Holdings, Inc. | System for assembling a cartridge for a smoking article and associated method |
US11135690B2 (en) | 2015-05-19 | 2021-10-05 | Rai Strategic Holdings, Inc. | Method for assembling a cartridge for a smoking article |
US11006674B2 (en) | 2015-05-19 | 2021-05-18 | Rai Strategic Holdings, Inc. | Assembly substation for assembling a cartridge for a smoking article and related method |
US10238145B2 (en) | 2015-05-19 | 2019-03-26 | Rai Strategic Holdings, Inc. | Assembly substation for assembling a cartridge for a smoking article |
US10154689B2 (en) * | 2015-06-30 | 2018-12-18 | R.J. Reynolds Tobacco Company | Heat generation segment for an aerosol-generation system of a smoking article |
WO2017004185A2 (en) | 2015-06-30 | 2017-01-05 | R. J. Reynolds Tobacco Company | Heat generation segment for an aerosol-generation system of a smoking article |
EP3815551A2 (en) | 2015-06-30 | 2021-05-05 | R. J. Reynolds Tobacco Company | Heat generation segment for an aerosol-generation system of a smoking article |
US20170000188A1 (en) * | 2015-06-30 | 2017-01-05 | R.J. Reynolds Tobacco Company | Heat generation segment for an aerosol-generation system of a smoking article |
EP4338630A2 (en) | 2015-08-31 | 2024-03-20 | R. J. Reynolds Tobacco Company | Smoking article |
WO2017040608A2 (en) | 2015-08-31 | 2017-03-09 | R. J. Reynolds Tobacco Company | Smoking article |
US11744296B2 (en) | 2015-12-10 | 2023-09-05 | R. J. Reynolds Tobacco Company | Smoking article |
WO2017098464A1 (en) | 2015-12-10 | 2017-06-15 | R. J. Reynolds Tobacco Company | Smoking article |
US10874140B2 (en) | 2015-12-10 | 2020-12-29 | R.J. Reynolds Tobacco Company | Smoking article |
US10314334B2 (en) | 2015-12-10 | 2019-06-11 | R.J. Reynolds Tobacco Company | Smoking article |
WO2017145095A1 (en) | 2016-02-24 | 2017-08-31 | R. J. Reynolds Tobacco Company | Smoking article comprising aerogel |
US11717018B2 (en) | 2016-02-24 | 2023-08-08 | R.J. Reynolds Tobacco Company | Smoking article comprising aerogel |
US11278686B2 (en) | 2016-04-29 | 2022-03-22 | Rai Strategic Holdings, Inc. | Methods for assembling a cartridge for an aerosol delivery device, and associated systems and apparatuses |
US10405579B2 (en) | 2016-04-29 | 2019-09-10 | Rai Strategic Holdings, Inc. | Methods for assembling a cartridge for an aerosol delivery device, and associated systems and apparatuses |
WO2020089799A1 (en) | 2018-10-30 | 2020-05-07 | R. J. Reynolds Tobacco Company | Smoking article cartridge |
US11957163B2 (en) | 2020-01-15 | 2024-04-16 | R.J. Reynolds Tobacco Company | Multi-segment filter element including smoke-altering flavorant |
US11813926B2 (en) | 2020-08-20 | 2023-11-14 | Denso International America, Inc. | Binding agent and olfaction sensor |
US11828210B2 (en) | 2020-08-20 | 2023-11-28 | Denso International America, Inc. | Diagnostic systems and methods of vehicles using olfaction |
US11760170B2 (en) | 2020-08-20 | 2023-09-19 | Denso International America, Inc. | Olfaction sensor preservation systems and methods |
US11760169B2 (en) | 2020-08-20 | 2023-09-19 | Denso International America, Inc. | Particulate control systems and methods for olfaction sensors |
US11881093B2 (en) | 2020-08-20 | 2024-01-23 | Denso International America, Inc. | Systems and methods for identifying smoking in vehicles |
US11932080B2 (en) | 2020-08-20 | 2024-03-19 | Denso International America, Inc. | Diagnostic and recirculation control systems and methods |
US11636870B2 (en) | 2020-08-20 | 2023-04-25 | Denso International America, Inc. | Smoking cessation systems and methods |
Also Published As
Publication number | Publication date |
---|---|
EP1781125A2 (en) | 2007-05-09 |
WO2006002001A3 (en) | 2006-08-10 |
WO2006002001A2 (en) | 2006-01-05 |
JP2008505990A (en) | 2008-02-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20050274390A1 (en) | Ultra-fine particle catalysts for carbonaceous fuel elements | |
RU2744289C2 (en) | Heat-generating segment for a smoking product aerosol formation system | |
JP7383077B2 (en) | smoking articles | |
US20220046976A1 (en) | Smoking article and associated manufacturing method | |
JP5244782B2 (en) | Smoking article | |
US8469035B2 (en) | Method for preparing fuel element for smoking article | |
RU2600296C2 (en) | Segmented smoking article with substrate cavity | |
US8617263B2 (en) | Method for preparing fuel element for smoking article | |
RU2611262C2 (en) | Smoking article | |
JP2023166554A (en) | Smoking article with heat transfer component | |
EP1996037B1 (en) | Smoking article | |
JP5007305B2 (en) | Smoking article | |
EP1670326B1 (en) | Smokable rod for a cigarette | |
US20040173229A1 (en) | Smoking article comprising ultrafine particles | |
US20230354921A1 (en) | Smoking article |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: R.J. REYNOLDS TOBACCO COMPANY, NORTH CAROLINA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BANERJEE, CHANDRA KUMAR;SEARS, STEPHEN BENSON;CASH, SHELIA LYNNETTE;AND OTHERS;REEL/FRAME:015875/0126;SIGNING DATES FROM 20040920 TO 20040928 |
|
AS | Assignment |
Owner name: R. J. REYNOLDS TOBACCO COMPANY, NORTH CAROLINA Free format text: MERGER;ASSIGNORS:BROWN & WILLIAMSON U.S.A., INC.;R. J. REYNOLDS TOBACCO COMPANY;REEL/FRAME:015701/0552 Effective date: 20040730 Owner name: R. J. REYNOLDS TOBACCO COMPANY, NORTH CAROLINA Free format text: CHANGE OF NAME;ASSIGNOR:BROWN & WILLIAMSON U.S.A., INC.;REEL/FRAME:015701/0587 Effective date: 20040730 |
|
AS | Assignment |
Owner name: JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT,NEW Free format text: SECURITY INTEREST;ASSIGNOR:R.J. REYNOLDS TOBACCO COMPANY;REEL/FRAME:017906/0671 Effective date: 20060526 Owner name: JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT, NE Free format text: SECURITY INTEREST;ASSIGNOR:R.J. REYNOLDS TOBACCO COMPANY;REEL/FRAME:017906/0671 Effective date: 20060526 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |