US2003303A - A process for the catalytic conversion of hydrocarbons - Google Patents
A process for the catalytic conversion of hydrocarbons Download PDFInfo
- Publication number
- US2003303A US2003303A US577561A US57756131A US2003303A US 2003303 A US2003303 A US 2003303A US 577561 A US577561 A US 577561A US 57756131 A US57756131 A US 57756131A US 2003303 A US2003303 A US 2003303A
- Authority
- US
- United States
- Prior art keywords
- hydrocarbons
- hydrocarbon
- catalytic material
- conversion
- copper
- 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.)
- Expired - Lifetime
Links
- 229930195733 hydrocarbon Natural products 0.000 title description 82
- 150000002430 hydrocarbons Chemical class 0.000 title description 82
- 230000003197 catalytic effect Effects 0.000 title description 43
- 238000000034 method Methods 0.000 title description 33
- 238000006243 chemical reaction Methods 0.000 title description 27
- 239000000463 material Substances 0.000 description 72
- 239000004215 Carbon black (E152) Substances 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 239000007789 gas Substances 0.000 description 25
- 239000004020 conductor Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 19
- 150000002736 metal compounds Chemical class 0.000 description 17
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 16
- 239000005750 Copper hydroxide Substances 0.000 description 15
- 229910001956 copper hydroxide Inorganic materials 0.000 description 15
- 239000007800 oxidant agent Substances 0.000 description 15
- 230000005855 radiation Effects 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 230000001590 oxidative effect Effects 0.000 description 11
- -1 butyl alcohols Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000008262 pumice Substances 0.000 description 8
- 229920001817 Agar Polymers 0.000 description 7
- 241000206672 Gelidium Species 0.000 description 7
- 235000010419 agar Nutrition 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- 244000215068 Acacia senegal Species 0.000 description 4
- 241000416162 Astragalus gummifer Species 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 229920000084 Gum arabic Polymers 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920001615 Tragacanth Polymers 0.000 description 4
- 235000010489 acacia gum Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229910052743 krypton Inorganic materials 0.000 description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229960001922 sodium perborate Drugs 0.000 description 4
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 4
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000006491 Acacia senegal Nutrition 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 3
- 229960004418 trolamine Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 239000012084 conversion product Substances 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- GVCGWXSZNUOTDW-UHFFFAOYSA-N sulfo cyanate Chemical compound OS(=O)(=O)OC#N GVCGWXSZNUOTDW-UHFFFAOYSA-N 0.000 description 2
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-N 0.000 description 1
- 239000005751 Copper oxide Substances 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
- 239000000205 acacia gum Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229940117013 triethanolamine oleate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G15/00—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S204/00—Chemistry: electrical and wave energy
- Y10S204/902—Production of desired compound by wave energy in presence of a chemically designated nonreactant chemical treating agent, excluding water, chloroform, carbon tetrachloride, methylene chloride or benzene
- Y10S204/903—Inorganic chemical treating agent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S204/00—Chemistry: electrical and wave energy
- Y10S204/902—Production of desired compound by wave energy in presence of a chemically designated nonreactant chemical treating agent, excluding water, chloroform, carbon tetrachloride, methylene chloride or benzene
- Y10S204/903—Inorganic chemical treating agent
- Y10S204/904—Metal treating agent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S204/00—Chemistry: electrical and wave energy
- Y10S204/902—Production of desired compound by wave energy in presence of a chemically designated nonreactant chemical treating agent, excluding water, chloroform, carbon tetrachloride, methylene chloride or benzene
- Y10S204/903—Inorganic chemical treating agent
- Y10S204/904—Metal treating agent
- Y10S204/905—Heavy metal agent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S204/00—Chemistry: electrical and wave energy
- Y10S204/902—Production of desired compound by wave energy in presence of a chemically designated nonreactant chemical treating agent, excluding water, chloroform, carbon tetrachloride, methylene chloride or benzene
- Y10S204/907—Silicon or boron treating agent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S204/00—Chemistry: electrical and wave energy
- Y10S204/902—Production of desired compound by wave energy in presence of a chemically designated nonreactant chemical treating agent, excluding water, chloroform, carbon tetrachloride, methylene chloride or benzene
- Y10S204/912—Oxygen treating agent
- Y10S204/913—Peroxide agent
Definitions
- NICKEL ME cnmLYsr CONTfll/VEB 4 meomeea/v mean/v6 cmmasz.
- the invention relates to a process for the conversion of hydrocarbons into oxygenated derivatives thereof. Moreparticularly it relates to the oxidation of hydrocarbons to form alcohols and ketones and includes corelated improvements and discoveries whereby oxygenated compounds may be produced directly from hydrocarbons.
- a raregas lamp as for example, a. positive column neon, argon or krypton lamp.
- Another object of the invention is to provide a, process in which hydrocarbons are subjected to the influence of a positive column rare gas lamp in the presence of a catalytic agent and of a conductive material.
- conductive material used throughout the specification and claims will be understood to mean a material, as a metal compound, i. e. a compound of a metallic element, which is introduced into the hydrocarbon undergoing treatment and which increases the electrical conductivity thereof or the effective area of the influence of the rare gas lamp.
- a further object of the invention is to provide a process whereby alcohols may be obtained from hydrocarbons by subjecting the, hydrocarbons to the influence of a positive column rare gas lamp in the presence of a conductive material and of a catalytic material containing an oxidizing.
- An additional object of the invention is to provide a process for converting hydrocarbons into oxygenated compounds in which the electrical conductivity of the hydrocarbon is increased by the addition thereto of a metal compound and which may be efliciently, readily and economically carried out on a commercial scale.
- a still further object of the invention is to provide a conductive material for addition to a hydrocarbon which is to be subjected to-the influence of radiations from a positive column rare gas lamp whereby the hydrocarbon is converted into an oxygenated derivative.
- the invention accordingly comprises the several stepsand the relation of oneor more of such stepswith respect to each of the others thereof, which will be exemplified in the process hereinafter disclosed, and the scope of the invention will be indicated in the claims.
- a hydrocarbon material which may be composed either of aliphatic or aromatic hydrocarbons or their derivatives, but more particularly of aliphatic hydrocarbons and specifically those which are found in a gasolene, may be subjected to the influence of a positive column rare gas lamp, such as a neon, argon or krypton tube, preferably an argon tube, in the presence of a conductive material and of a catalytic material which may be impregnated with a suitable compound.
- the conversion may also be, and preferably is, carried out with the addition of water.
- the reaction may be accomplishedby placing a hydrocarbon material, such as ordinary gasolene, into a suitable receptacle, introducing into the hydrocarbon a rare gas lamp, at least a portion of which is surrounded by a container carrying a catalytic material, and adding a conductive material, as a metal compound, such as a composition consisting of copper hydroxide and agar agar dispersed in gasolene.
- a hydrocarbon material such as ordinary gasolene
- a rare gas lamp as a metal compound, such as a composition consisting of copper hydroxide and agar agar dispersed in gasolene.
- the container may be closed and connected with a reflux condenser.
- the rare gas lamp is connected to a suitable source of electrical energy and may have impressed thereupon a voltage of from 12,000 to 15,000 volts with a current flow of from 15 to 20 milliamperes.
- the hydrocarbon may be sub jected to the influence of the radiations from the rare gas lamp for varying periods of time, depending upon the type of oxygenated compound desired, but under the electrical impress above mentioned a period of from 1 to 2 hours is sumcient to effect conversion. If desired, the nattu'e of the current cycle may be changed by inserting an oxidized aluminum chain in the circuit.
- a suitable apparatus for converting hydrocarbon material is that shown in the drawing. It is to be understood that while this apparatus is for conversion by a batch operation, nevertheless the invention is not so limited but contemplates also the conversion of hydrocarbonsin a continuous manner.
- the apparatus shown comprises a container l, which may be of non-conductive material, such as glass orthe like, in which there may be positioned a foraminous member 2.
- This member is preferably formed of a metallic material such as, for example, a nickel wire gauze and is adapted to hold a catalytic material 3.
- a rare gas lamp 4 which may be U shaped as shown, or in the form of a coil or other shape as desired.
- the rare gas lamp may be filled with any of the rare gases, more particularly neon, argon or krypton and is provided with electrodes 5 by means of which electrical energy may be led into and out of the lamp from a suitable source of alternating current having a potential of from 12,000 to 15,000 volts and of about 60 cycles.
- a.lid"or closing member 6 having openings 1 and II therein which are fitted respectively with a closure 8 and a reflux condenser 9.
- the container I may be wholly or partially surrounded by a metallic material as a gauze of nickel wire, which is grounded.
- the conversion of a hydrocarbon material into an alcohol is brought about by introducing into the container I a hydrocarbon material, as an ordinary gasolene, and placing therein a positive column argon lamp surrounded by and embedded in a catalytic material containing an oxidizing agent, as a perborate, a perchlorate, a percarbonate etc. and contained in a foraminous member 2.
- a hydrocarbon material there may also be added a small amount of water and of a conductive material such as a dispersion of copper hydroxide and agar agar in gasolene.
- An alternating 60 cycle current having the cycle modifled by the presence of an oxidized aluminum chain in the circuit with a potential of about 12,000 volts and a current flow of about 18 milliamperes is then passed through the rare gas lamp,
- hydrocarbon material will be subjected to the influence of its radiations in the presence of the catalytic material and of the conductive material.
- the electrical energy is permitted to be impressed for a period of from 1 to 2 hours, when the apparatus is electrically disconnected, the rare gas tube and the catalytic material removed and the conversion product separated into components.
- the separation may be made by distilling the conversion product and collecting the distillates over desired ranges.
- the hydrocarbon material is according to the foregoing procedure converted into oxygenated compounds, more particularly alcohols and ketones, specifically normal propyl and isopropyl alcohol, the butyl alcohols, the aznyl alcohols, acetone etc.
- the catalytic material may be prepared in a number of ways, the requirement generally being that it shall be granular in form, catalytically active and substantially non-conductive per se. It
- a preferred form of catalytic material may be prepared by treating an active carbon, for example a granular decolorizing carbon such as "Darco, by washing, then treating with an organic acid such as acetic acid, thereafter washing thoroughly and steaming to remove the residue of the organic acid.
- the carbon may also be prepared by first treating with a dilute solution of zinc sulphate, washing and then treating with a dilute solution of sodium bisulphate.
- the carbon so prepared is impregnated with a solution of a substance having an oxidizing character, such as sodium perborate, which has previously been put into colloidal form by boiling with a trace of a dispersing agent, as a gum, such as agar agar, gum acacia, gum tragacanth, or with other suitable materials as glue, gelatine, glucose or the like.
- a substance having an oxidizing character such as sodium perborate
- sodium perborate there may be used other perborates, perchlorates, persulphates, percarbonates, bichromates, hydrogen peroxide or other oxidizing agent.
- The; amount of such added material may be about 5 pericentof theweight of the carbon.
- a catalytic material containing an oxidizing agent, as above prepared, may, while still moist, be placed in the nickel gauze container 2 and utilized for' the" conversion of hydrocarbon into, for example, an alcohol or alcohols.
- catalytic material may be prepared by using pumice as the carrying material.
- the pumice which has been cracked is soaked in a solution of, copper sulphate to which may be added sodium hydroxide until the resolution of the copper hydroxide formed has not quite commenced, that is until a blue precipitate is formed as distinct from an initially green precipitate.
- the precipitate should have approximately a neutral reaction and the liquid should be slightly acid.
- the treatment In order that the catalytic material may be in the most active form, the treatment must be carried out at a temperature suflrlciently low to prevent the formation of a black precipitate and I have found a temperature of 14 C. or below to be suitable.
- This material may beutilized in the place of the active carbon material above described and in a like manner.
- the carbon .or other carrying material may be impregnated with materials other than those hereinbefore mentioned, for example compounds such as sodium acid sulphite, ferrous sulphate, nitre-cake, chlor-acetic acid and a sulphocyanate.
- materials other than those hereinbefore mentioned for example compounds such as sodium acid sulphite, ferrous sulphate, nitre-cake, chlor-acetic acid and a sulphocyanate.
- the impregnation of the carbon with these compounds may be attained in the above described manner.
- a metallized carrying material may be prepared by impregnating cracked pumice stone with the copper mixture above mentioned and then placing the pumice so impregnated in a suitable vessel, as a Gooch crucible or the like, removing the soluble compounds and heating to about C. Black copper oxide is thus formed which may be reduced to a spongy formof metallic copper by causing the hot copper oxide to contact with methyl alcohol.
- the metallized pumice stone is susceptible to oxidation and accordingly should be preserved in an'inert medium, for example by covering it withbenzol or the like.
- a similarly impregnated pumice carrying material may be prepared by soaking pumice in a. 60
- the catalytic material prepared by any of the foregoing procedures may be rendered more effective by treating-with a hydrocarbon material, as a gasolene, and refluxing for a period of several hours prior to utilization in the conversion ofhydrocarbons.
- the conductive material to be added to the hydrocarbon undergoing conversion may comprise a metal compound which may be dispersed in a hydrocarbon material with the aid of a dispersing agent such as a gum. More particularly agar agar, gum acacia, gum tragacanth or glue, gelatine, glucose and the like. More particularly, the metal compound may be a suitable hydroxide, oxide, stearate, resinate, oleate etc. which in conjunction, or forming an emulsion with a hydrocarbon material is adapted to increase the electrical conductivity thereof and to render larger the active area of radiations from a rare gas lampv This material may be prepared, for example, to contain a copper compound, as copper hydroxide.
- Copper hydroxide which may be prepared by adding sodium hydroxide to copper sulphate, may be dispersed in water to which agar agar has been added (this may require a number of hours). Then there is addedgradually a hydrocarbon, such as gasolene, and the admixture subjected to repeated shaking.
- the copper hydroxide forms an emulsion with the hydrocarbon and constitutes the conductive material utilized in the conversion treatment.
- the conductive material may comprise a metallic element, as copper, nickel, etc., in colloidal form, or it may be made up of a plurality of components, as copper and nickel in colloidal condition, or compounds of such elements, as a mixture of the" hydroxides of copper and of nickel.
- the conductive material may also be prepared from a metal compound as copper hydroxide through the use of triethanolamine or a combination thereof with oleic acid.
- copper hydroxide may be emulsified with triethanolamine and introduced. into the hydrocarbon or it may be emulsified by means of a triethanolamine oleate.
- Such emulsions are soluble in a hydrocarbon material.
- 5 parts of oleic acid and one part of triethanolamine may be I united to form a compound or emulsion to which there is added 0.5 part copper hydroxide.
- the admixture thus obtained may then be taken-up in a hydrocarbon material and utilized in the conversion procedure.
- the hydrocarbon material may be converted in accordance with my procedure utilizing an argon tube and a period of about two hours with the formation of alcohols, more particularly butyl amounts of from .1 to .001 of 1 percent.
- the resinates here referred to are compounds of the resin acids, ior example C11 (CzoHzaOz) 2, F8(C20H2902) 3, Ni (C20H29O2) 2,
- the oleates as barium, strontium, iron, copper etc. may also be employed.
- the oleates while effective as a conductive material, decompose under the influence of the electric energy. This renders the process less eflicient and makes impossible their recovery.
- the resinates have been found to be more stable and are to be preferred.
- the result obtained that is the alcohol or the mixture of alcohols, will vary depending upon the variations of the electrical impress.
- the process may be operated with a 2,000 volt impress and a current of 6 milliamperes or with a 15,000 volt impress and a current of 30 milliamperes, the current being 60 cycle alternating type which may be, modified by the placement of an oxidized aluminum chain in the circuit.
- conversion has been obtained through the use of from 12,000 to.
- a process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of a. catalytic material containing an oxidizing agent and of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment to the action of radiations from a rare gas lamp.
- a process for the conversion of liquid hydrocarbons into oxygenated-compounds which comprises subjecting said hydrocarbons in the presence of a catalytic material containing an oxidizing agent and of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment to the action of radiations from a positive column rare gas lamp.
- a process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of water, of a catalytic material containing an oxidizing agent and of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment to the action of radiations from a positive column argon lamp.
- a process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of a catalytic material consisting of a carrier and a compound having an oxidizing character and of a copper compound as a conductive material to the action of radiations from a positive column rare gas lamp.
- a process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of a catalytic material consisting of a carrier and a compound having an oxidizing character and of an aluminum compound as a conductive material to the action of radiations from a positive column rare gas lamp.
- a process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of a catalytic material consisting of a carrier and a compound having an oxidizing character and of a barium compound as a conductive material to the action of radiations from a positive column rare gas lamp.
- a process for the conversion of a liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of water, of a catalytic material consisting of a carrier and a compound having an oxidizing character and of copper hydroxide as a conductive material to the action of radiations from a positive column argon lamp.
- a process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of water, ofa catalytic material consisting of a carrier and a compound having an oxidizing character and of aluminum stearate as a conductive material to the action of radiations from a positive column argon lamp.
- a process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of water, of a catalytic material consisting of a carrier and a compound having an oxidizing character and of barium resinate as a conductive material to the action of radiations from a positive column argon lamp.
- the step which comprises assembling the desired hydrocarbons in the presence of a catalyst containing an oxidizing agent and of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and under the influence of radiations from a-positive column rare gas lamp.
- a process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material being composed ,of an insoluble granular porous substance impregnated with an oxidizing material.
- a process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material being composed of active carbon impregnated with an oxidizingmaterial'.
- a process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing. treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material being composed of granular active carbon impregnated with oxidizing material in a colloidal state.
- a process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column argon lamp, said catalytic material being composed of granular active carbon impregnated with a colloidal mixture of a material belonging to the group consisting of agar agar, gum arabic, gum tragacanth, glue, gelatin and glucose and an oxidizing agent belonging to the group consisting of a perborate, a perchlorate, a persulphate, a percarbonate, a bichromate and hydrogen peroxide.
- a process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material being composed of an insoluble porous substance impregnated with a mixture of copper hydroxide, copper carbonate and a small amount of copper sulphate.
- a process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the'presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material. being composed of metallized broken pumice prepared by impregnating with a colloidal mixture of copper hydroxide, copper carbonate and a small amount of copper sulphate, and subsequently reducing to metallic copper, impregnated with an oxidizing material belonging to the group consisting of a perborate, a perchlorate, a persulphate, a percarbonate, a bichromate and hydrogen peroxide.
- a process for converting liquid hydrocarbons which comprises subjecting said hydrocarbons in the presence of water and a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment com prising copper hydroxide and of a catalytic material to the action of a positive column argon lamp, said catalytic material being composed of granular active carbon impregnated with a colloidal material belonging to the group consisting of agar agar, gum acacia, gum tragacanth, glue, gelatin, glucose and withya substance belonging to the group consisting of a perborate,-a perchlorate, a persulphate, a percarbonate, a bichromate, hydrogen peroxide, an acid sulphite, ferrous sulphate, ,nitre-cake, chlor-acetic acid and a sulphocyanate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
June 4, 1935-. w. o. MITSC HERLING. 2,003,303
PROCESS FOR THE CATALYTIC CONVERSION OF HYDRQCARBONS Filed NOV. 27, 1931.
NICKEL ME: cnmLYsr CONTfll/VEB 4 meomeea/v mean/v6 cmmasz.
BY WW Patented June 4, 1935 UNITED STATES PATENT OFFICE I A PROCESS FOR THE CATALYTIC CON- VERSION OF HYDROCABBONS cut Application November 27, 1931, Serial No. 577,561
18 Claims.
The invention relates to a process for the conversion of hydrocarbons into oxygenated derivatives thereof. Moreparticularly it relates to the oxidation of hydrocarbons to form alcohols and ketones and includes corelated improvements and discoveries whereby oxygenated compounds may be produced directly from hydrocarbons.
It is an object of the invention to provide a process for the preparation of oxygenated compounds from hydrocarbons by subjecting a hydrocarbon to the influence of radiations from a raregas lamp, as for example, a. positive column neon, argon or krypton lamp.
Another object of the invention is to provide a, process in which hydrocarbons are subjected to the influence of a positive column rare gas lamp in the presence of a catalytic agent and of a conductive material. The term conductive material used throughout the specification and claims will be understood to mean a material, as a metal compound, i. e. a compound of a metallic element, which is introduced into the hydrocarbon undergoing treatment and which increases the electrical conductivity thereof or the effective area of the influence of the rare gas lamp.
' A further object of the invention is to provide a process whereby alcohols may be obtained from hydrocarbons by subjecting the, hydrocarbons to the influence of a positive column rare gas lamp in the presence of a conductive material and of a catalytic material containing an oxidizing.
agent.
. An additional object of the invention is to provide a process for converting hydrocarbons into oxygenated compounds in which the electrical conductivity of the hydrocarbon is increased by the addition thereto of a metal compound and which may be efliciently, readily and economically carried out on a commercial scale.
A still further object of the invention is to provide a conductive material for addition to a hydrocarbon which is to be subjected to-the influence of radiations from a positive column rare gas lamp whereby the hydrocarbon is converted into an oxygenated derivative.
Other objects of the invention will in part be obvious and will in part appear hereinafter.
The invention accordingly comprises the several stepsand the relation of oneor more of such stepswith respect to each of the others thereof, which will be exemplified in the process hereinafter disclosed, and the scope of the invention will be indicated in the claims.
For afuller understanding of the nature and objects of the invention reference should be had to the following detailed description taken in connection with the accompanying drawing, in which there is shown an apparatus adapted for efiecting the conversion of hydrocarbons in accordance with the invention.
In the practice of the invention a hydrocarbon material which may be composed either of aliphatic or aromatic hydrocarbons or their derivatives, but more particularly of aliphatic hydrocarbons and specifically those which are found in a gasolene, may be subjected to the influence of a positive column rare gas lamp, such as a neon, argon or krypton tube, preferably an argon tube, in the presence of a conductive material and of a catalytic material which may be impregnated with a suitable compound. The conversion may also be, and preferably is, carried out with the addition of water.
The reaction may be accomplishedby placing a hydrocarbon material, such as ordinary gasolene, into a suitable receptacle, introducing into the hydrocarbon a rare gas lamp, at least a portion of which is surrounded by a container carrying a catalytic material, and adding a conductive material, as a metal compound, such as a composition consisting of copper hydroxide and agar agar dispersed in gasolene. The container may be closed and connected with a reflux condenser. The rare gas lamp is connected to a suitable source of electrical energy and may have impressed thereupon a voltage of from 12,000 to 15,000 volts with a current flow of from 15 to 20 milliamperes. The hydrocarbon may be sub jected to the influence of the radiations from the rare gas lamp for varying periods of time, depending upon the type of oxygenated compound desired, but under the electrical impress above mentioned a period of from 1 to 2 hours is sumcient to effect conversion. If desired, the nattu'e of the current cycle may be changed by inserting an oxidized aluminum chain in the circuit.
A suitable apparatus for converting hydrocarbon material is that shown in the drawing. It is to be understood that while this apparatus is for conversion by a batch operation, nevertheless the invention is not so limited but contemplates also the conversion of hydrocarbonsin a continuous manner.
The apparatus shown comprises a container l, which may be of non-conductive material, such as glass orthe like, in which there may be positioned a foraminous member 2. This member is preferably formed of a metallic material such as, for example, a nickel wire gauze and is adapted to hold a catalytic material 3. Within the body of the catalytic material there is positioned a rare gas lamp 4, which may be U shaped as shown, or in the form of a coil or other shape as desired. The rare gas lamp may be filled with any of the rare gases, more particularly neon, argon or krypton and is provided with electrodes 5 by means of which electrical energy may be led into and out of the lamp from a suitable source of alternating current having a potential of from 12,000 to 15,000 volts and of about 60 cycles. Upon the container I is positioned a.lid"or closing member 6, having openings 1 and II therein which are fitted respectively with a closure 8 and a reflux condenser 9. If desired the container I may be wholly or partially surrounded by a metallic material as a gauze of nickel wire, which is grounded.
The conversion of a hydrocarbon material into an alcohol is brought about by introducing into the container I a hydrocarbon material, as an ordinary gasolene, and placing therein a positive column argon lamp surrounded by and embedded in a catalytic material containing an oxidizing agent, as a perborate, a perchlorate, a percarbonate etc. and contained in a foraminous member 2. To the hydrocarbon material there may also be added a small amount of water and of a conductive material such as a dispersion of copper hydroxide and agar agar in gasolene. An alternating 60 cycle current having the cycle modifled by the presence of an oxidized aluminum chain in the circuit with a potential of about 12,000 volts and a current flow of about 18 milliamperes is then passed through the rare gas lamp,
whereupon the hydrocarbon material will be subjected to the influence of its radiations in the presence of the catalytic material and of the conductive material. The electrical energy is permitted to be impressed for a period of from 1 to 2 hours, when the apparatus is electrically disconnected, the rare gas tube and the catalytic material removed and the conversion product separated into components. The separation may be made by distilling the conversion product and collecting the distillates over desired ranges. The hydrocarbon material is according to the foregoing procedure converted into oxygenated compounds, more particularly alcohols and ketones, specifically normal propyl and isopropyl alcohol, the butyl alcohols, the aznyl alcohols, acetone etc.
The catalytic material may be prepared in a number of ways, the requirement generally being that it shall be granular in form, catalytically active and substantially non-conductive per se. It
is desirable also that water be present and that the material be impregnated as, for example, with an oxidizing agent.
A preferred form of catalytic material may be prepared by treating an active carbon, for example a granular decolorizing carbon such as "Darco, by washing, then treating with an organic acid such as acetic acid, thereafter washing thoroughly and steaming to remove the residue of the organic acid. The carbon may also be prepared by first treating with a dilute solution of zinc sulphate, washing and then treating with a dilute solution of sodium bisulphate. The carbon so prepared is impregnated with a solution of a substance having an oxidizing character, such as sodium perborate, which has previously been put into colloidal form by boiling with a trace of a dispersing agent, as a gum, such as agar agar, gum acacia, gum tragacanth, or with other suitable materials as glue, gelatine, glucose or the like.
Instead of sodium perborate there may be used other perborates, perchlorates, persulphates, percarbonates, bichromates, hydrogen peroxide or other oxidizing agent. The; amount of such added material;may be about 5 pericentof theweight of the carbon.
A catalytic material containing an oxidizing agent, as above prepared, may, while still moist, be placed in the nickel gauze container 2 and utilized for' the" conversion of hydrocarbon into, for example, an alcohol or alcohols.
Another suitable. catalytic material may be prepared by using pumice as the carrying material. The pumice which has been cracked is soaked in a solution of, copper sulphate to which may be added sodium hydroxide until the resolution of the copper hydroxide formed has not quite commenced, that is until a blue precipitate is formed as distinct from an initially green precipitate. There may then be added a small amount of sodium bicarbonate in order to throw back the precipitation slightly and to give a gelatinous mixture containing about 1 to 2 per cent of copper sulphate admixed with some copper carbonate and copper hydroxide. The precipitate should have approximately a neutral reaction and the liquid should be slightly acid. In order that the catalytic material may be in the most active form, the treatment must be carried out at a temperature suflrlciently low to prevent the formation of a black precipitate and I have found a temperature of 14 C. or below to be suitable. This material may beutilized in the place of the active carbon material above described and in a like manner. l
The carbon .or other carrying material may be impregnated with materials other than those hereinbefore mentioned, for example compounds such as sodium acid sulphite, ferrous sulphate, nitre-cake, chlor-acetic acid and a sulphocyanate. The impregnation of the carbon with these compounds may be attained in the above described manner.
A metallized carrying material may be prepared by impregnating cracked pumice stone with the copper mixture above mentioned and then placing the pumice so impregnated in a suitable vessel, as a Gooch crucible or the like, removing the soluble compounds and heating to about C. Black copper oxide is thus formed which may be reduced to a spongy formof metallic copper by causing the hot copper oxide to contact with methyl alcohol. The metallized pumice stone is susceptible to oxidation and accordingly should be preserved in an'inert medium, for example by covering it withbenzol or the like.
A similarly impregnated pumice carrying material may be prepared by soaking pumice in a. 60
The catalytic material prepared by any of the foregoing procedures may be rendered more effective by treating-with a hydrocarbon material, as a gasolene, and refluxing for a period of several hours prior to utilization in the conversion ofhydrocarbons.
The conductive material to be added to the hydrocarbon undergoing conversion may comprise a metal compound which may be dispersed in a hydrocarbon material with the aid of a dispersing agent such as a gum. more particularly agar agar, gum acacia, gum tragacanth or glue, gelatine, glucose and the like. More particularly, the metal compound may be a suitable hydroxide, oxide, stearate, resinate, oleate etc. which in conjunction, or forming an emulsion with a hydrocarbon material is adapted to increase the electrical conductivity thereof and to render larger the active area of radiations from a rare gas lampv This material may be prepared, for example, to contain a copper compound, as copper hydroxide. Copper hydroxide, which may be prepared by adding sodium hydroxide to copper sulphate, may be dispersed in water to which agar agar has been added (this may require a number of hours). Then there is addedgradually a hydrocarbon, such as gasolene, and the admixture subjected to repeated shaking. The copper hydroxide forms an emulsion with the hydrocarbon and constitutes the conductive material utilized in the conversion treatment. Furthermore the conductive material may comprise a metallic element, as copper, nickel, etc., in colloidal form, or it may be made up of a plurality of components, as copper and nickel in colloidal condition, or compounds of such elements, as a mixture of the" hydroxides of copper and of nickel.
The conductive material may also be prepared from a metal compound as copper hydroxide through the use of triethanolamine or a combination thereof with oleic acid. Thus, for example, copper hydroxide may be emulsified with triethanolamine and introduced. into the hydrocarbon or it may be emulsified by means of a triethanolamine oleate. Such emulsions are soluble in a hydrocarbon material. For example 5 parts of oleic acid and one part of triethanolamine may be I united to form a compound or emulsion to which there is added 0.5 part copper hydroxide. The admixture thus obtained may then be taken-up in a hydrocarbon material and utilized in the conversion procedure.
When using an active carbon impregnated with sodium perborate as a catalytic material, and a copper hydroxide emulsion as a. conductive ma terial, the hydrocarbon material may be converted in accordance with my procedure utilizing an argon tube and a period of about two hours with the formation of alcohols, more particularly butyl amounts of from .1 to .001 of 1 percent.
I have also obtained conversion, producing a mixture of propyl, butyl and amyl alcohols when utilizing an argon or a krypton tube with a conductive material comprising barium hydroxide, barium oxide, aluminum stearate, barium resinate, iron resinate, nickel resinate, aluminum resinate or copper resinate, these materials being added to the hydrocarbon undergoing.
treatment in an amount, for example, of about 0.1 percent. It will be understood that the resinates here referred to are compounds of the resin acids, ior example C11 (CzoHzaOz) 2, F8(C20H2902) 3, Ni (C20H29O2) 2,
etc. The oleates, as barium, strontium, iron, copper etc. may also be employed. The oleates, while effective as a conductive material, decompose under the influence of the electric energy. This renders the process less eflicient and makes impossible their recovery. The resinates have been found to be more stable and are to be preferred.
The result obtained, that is the alcohol or the mixture of alcohols, will vary depending upon the variations of the electrical impress. Thus the process may be operated with a 2,000 volt impress and a current of 6 milliamperes or with a 15,000 volt impress and a current of 30 milliamperes, the current being 60 cycle alternating type which may be, modified by the placement of an oxidized aluminum chain in the circuit. For the production of isopropyl and butyl alcohols from an ordinary gasolene using an active carbonsodium perborate catalytic material and a copper hydroxide conductive material, conversion has been obtained through the use of from 12,000 to.
ing out the above process without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the-scope of the invention which, as a matter of language, might be said to fall therebetween.
Having described my invention, what I claim as new and desire to secure by Letters Patent, is:
1. A process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of a. catalytic material containing an oxidizing agent and of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment to the action of radiations from a rare gas lamp.
2. A process for the conversion of liquid hydrocarbons into oxygenated-compounds which comprises subjecting said hydrocarbons in the presence of a catalytic material containing an oxidizing agent and of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment to the action of radiations from a positive column rare gas lamp.
3. A process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of water, of a catalytic material containing an oxidizing agent and of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment to the action of radiations from a positive column argon lamp.
4. A process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of a catalytic material consisting of a carrier and a compound having an oxidizing character and of a copper compound as a conductive material to the action of radiations from a positive column rare gas lamp.
5. A process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of a catalytic material consisting of a carrier and a compound having an oxidizing character and of an aluminum compound as a conductive material to the action of radiations from a positive column rare gas lamp.
6. A process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of a catalytic material consisting of a carrier and a compound having an oxidizing character and of a barium compound as a conductive material to the action of radiations from a positive column rare gas lamp.
7. A process for the conversion of a liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of water, of a catalytic material consisting of a carrier and a compound having an oxidizing character and of copper hydroxide as a conductive material to the action of radiations from a positive column argon lamp.
8. A process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of water, ofa catalytic material consisting of a carrier and a compound having an oxidizing character and of aluminum stearate as a conductive material to the action of radiations from a positive column argon lamp.
9. A process for the conversion of liquid hydrocarbons into oxygenated compounds which comprises subjecting said hydrocarbons in the presence of water, of a catalytic material consisting of a carrier and a compound having an oxidizing character and of barium resinate as a conductive material to the action of radiations from a positive column argon lamp.
10. In a process for effecting oxygenation of liquid hydrocarbons, the step which comprises assembling the desired hydrocarbons in the presence of a catalyst containing an oxidizing agent and of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and under the influence of radiations from a-positive column rare gas lamp.
11. A process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material being composed ,of an insoluble granular porous substance impregnated with an oxidizing material.
12. A process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material being composed of active carbon impregnated with an oxidizingmaterial'.
13. A process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing. treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material being composed of granular active carbon impregnated with oxidizing material in a colloidal state.
14. A process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column argon lamp, said catalytic material being composed of granular active carbon impregnated with a colloidal mixture of a material belonging to the group consisting of agar agar, gum arabic, gum tragacanth, glue, gelatin and glucose and an oxidizing agent belonging to the group consisting of a perborate, a perchlorate, a persulphate, a percarbonate, a bichromate and hydrogen peroxide.
15. A process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material being composed of an insoluble porous substance impregnated with a mixture of copper hydroxide, copper carbonate and a small amount of copper sulphate.
16. A process of converting liquid hydrocarbons into oxygenated compounds which comprises subjecting such hydrocarbons in the'presence of a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment and a catalytic material containing an oxidizing agent to the action of a positive column rare gas lamp, said catalytic material. being composed of metallized broken pumice prepared by impregnating with a colloidal mixture of copper hydroxide, copper carbonate and a small amount of copper sulphate, and subsequently reducing to metallic copper, impregnated with an oxidizing material belonging to the group consisting of a perborate, a perchlorate, a persulphate, a percarbonate, a bichromate and hydrogen peroxide.
17. A process for converting liquid hydrocarbons which comprises subjecting said hydrocarbons in the presence of water and a metal compound which increases the electrical conductivity of the hydrocarbon undergoing treatment com prising copper hydroxide and of a catalytic material to the action of a positive column argon lamp, said catalytic material being composed of granular active carbon impregnated with a colloidal material belonging to the group consisting of agar agar, gum acacia, gum tragacanth, glue, gelatin, glucose and withya substance belonging to the group consisting of a perborate,-a perchlorate, a persulphate, a percarbonate, a bichromate, hydrogen peroxide, an acid sulphite, ferrous sulphate, ,nitre-cake, chlor-acetic acid and a sulphocyanate.
18. A process for converting liquid hydrocarcatalytic material to the action of a positive column argon lamp under an impress of from 12,000 to 15,000 volts and witha current flow of from 15 t0 20 milliamperes for a period of from 1 to 2 hours, said catalytic material being com- 4 posed of granular active carbon impregnated with sodium perborate.
WALDEMAR O. MITSCHERLING.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US577561A US2003303A (en) | 1931-11-27 | 1931-11-27 | A process for the catalytic conversion of hydrocarbons |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US577561A US2003303A (en) | 1931-11-27 | 1931-11-27 | A process for the catalytic conversion of hydrocarbons |
Publications (1)
Publication Number | Publication Date |
---|---|
US2003303A true US2003303A (en) | 1935-06-04 |
Family
ID=24309249
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US577561A Expired - Lifetime US2003303A (en) | 1931-11-27 | 1931-11-27 | A process for the catalytic conversion of hydrocarbons |
Country Status (1)
Country | Link |
---|---|
US (1) | US2003303A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2423949A (en) * | 1943-01-30 | 1947-07-15 | Shell Dev | Controlled catalytic photochemical oxidation of organic compounds |
US4344918A (en) * | 1980-03-05 | 1982-08-17 | Xertex Corporation | Determination of total carbon in liquid samples |
US20060002483A1 (en) * | 2004-07-02 | 2006-01-05 | Dae-Gyu Kim | LVDS receiver for controlling current based on frequency and method of operating the LDVS receiver |
US20190258207A1 (en) * | 2016-12-23 | 2019-08-22 | Comadur Sa | Reduced-friction shaft support bearing |
-
1931
- 1931-11-27 US US577561A patent/US2003303A/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2423949A (en) * | 1943-01-30 | 1947-07-15 | Shell Dev | Controlled catalytic photochemical oxidation of organic compounds |
US4344918A (en) * | 1980-03-05 | 1982-08-17 | Xertex Corporation | Determination of total carbon in liquid samples |
US20060002483A1 (en) * | 2004-07-02 | 2006-01-05 | Dae-Gyu Kim | LVDS receiver for controlling current based on frequency and method of operating the LDVS receiver |
US7667546B2 (en) * | 2004-07-02 | 2010-02-23 | Samsung Electronics Co., Ltd. | LVDS receiver for controlling current based on frequency and method of operating the LVDS receiver |
US20190258207A1 (en) * | 2016-12-23 | 2019-08-22 | Comadur Sa | Reduced-friction shaft support bearing |
US11036186B2 (en) * | 2016-12-23 | 2021-06-15 | Comadur Sa | Reduced-friction shaft support bearing |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4028274A (en) | Support material for a noble metal catalyst and method for making the same | |
EP0234875A2 (en) | Photocatalytic treatment of water for the preparation of extrapure water | |
ATE162158T1 (en) | METHOD FOR SEPARATING CATALYST-FREE WORKING SOLUTION FROM THE HYDROGENATION CIRCUIT OF THE ANTHRACHINONE PROCESS FOR PRODUCING HYDROGEN PEROXIDE | |
US2003303A (en) | A process for the catalytic conversion of hydrocarbons | |
DE69525626T2 (en) | REMOVE BINDS FROM Ta PRODUCTS | |
JPH03111586A (en) | Electrolytic bath for reduction of carbon dioxide | |
US4409129A (en) | Method of manufacturing catalyst | |
US4054687A (en) | Method for making a fuel cell electrode | |
US1377021A (en) | Process of clarifying and decolorizing oils | |
DE69221958T2 (en) | Fuel cell with phosphoric acid electrolytes | |
CN107914009B (en) | A kind of production method of tin plating copper powder | |
US2003898A (en) | Treatment of hydrocarbons | |
US1448036A (en) | Reduction of oxides of metals of the chromium group | |
JPS51128939A (en) | Process for preparing cycloolefins | |
US942207A (en) | Process of treating the spent liquor of paper-mills. | |
US3037938A (en) | Resistance to depreciation of electroluminescent phosphors | |
DE140804T1 (en) | HYPOCHLORITE TREATMENT OF CHEMICAL PAPER PULPS. | |
US2208616A (en) | Reactivation of spent hydrogenation catalysts | |
SE8204364D0 (en) | POWER OVERLOAD RECOVERY PROCESS | |
JPH0251865A (en) | Manufacture of fuel electrode catalyser for liquid fuel cell | |
US2707673A (en) | Method of treating furnace carbon black | |
FI82724B (en) | REDUKTIONSBLEKNING AV LIGNOCELLULOSAMASSA. | |
DE564111C (en) | Manufacture of diaphragms for devices for the production of oxygen and hydrogen | |
JPS5844748B2 (en) | How to split water | |
US2319453A (en) | Process for activating catalytic surfaces |