WO2002053492A1 - Method for steam reforming hydrocarbons using a sulfur-tolerant catalyst - Google Patents
Method for steam reforming hydrocarbons using a sulfur-tolerant catalyst Download PDFInfo
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- WO2002053492A1 WO2002053492A1 PCT/US2001/000081 US0100081W WO02053492A1 WO 2002053492 A1 WO2002053492 A1 WO 2002053492A1 US 0100081 W US0100081 W US 0100081W WO 02053492 A1 WO02053492 A1 WO 02053492A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 55
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000000629 steam reforming Methods 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 87
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 37
- 239000011593 sulfur Substances 0.000 claims abstract description 37
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000446 fuel Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 229910052788 barium Inorganic materials 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229910052712 strontium Inorganic materials 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 229910052727 yttrium Inorganic materials 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 229910052684 Cerium Inorganic materials 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 13
- 150000002602 lanthanoids Chemical class 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052772 Samarium Inorganic materials 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- -1 oxygen ion Chemical class 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 229910052776 Thorium Inorganic materials 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 238000004939 coking Methods 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052770 Uranium Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910052953 millerite Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 238000009877 rendering Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000011148 porous material Substances 0.000 description 11
- 238000002407 reforming Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 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
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001193 catalytic steam reforming Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011532 electronic conductor Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229920001247 Reticulated foam Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 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
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/681—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
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- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2208/00008—Controlling the process
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- B01J2208/00008—Controlling the process
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- B01J2208/00477—Controlling the temperature by thermal insulation means
- B01J2208/00495—Controlling the temperature by thermal insulation means using insulating materials or refractories
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/1052—Nickel or cobalt catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/1094—Promotors or activators
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- This invention relates to steam reforming of gaseous or liquid hydrocarbons, and more particularly to steam reforming of sulfur bearing hydrocarbons using a sulfur tolerant steam reforming catalyst.
- the present invention is directed to catalytic steam reforming of hydrocarbons. More particularly, the present invention is directed to a method for steam reforming of hydrocarbons, especially sulfur-containing hydrocarbons, using a sulfur-tolerant catalyst, and an apparatus therefor.
- Steam reforming is a process whereby a hydrocarbon is reacted with high temperature steam to form hydrogen, carbon monoxide, and carbon dioxide.
- the product gas can be reacted as a fuel or used in chemical processing.
- Hydrocarbons which can be reacted according to the present invention include methane, natural gas (including landfill gas) and heavier hydrocarbons (including diesel and jet fuel).
- Gas oil for example, may contain as much as 1500 ppm sulfur.
- reforming of sulfur-containing hydrocarbons can lead to increased expense.
- catalytic steam reforming of natural gas or heavier hydrocarbon feeds is achieved by using a nickel catalyst.
- nickel metal to sulfur-containing compounds which are a severe poison to the nickel catalyst
- the hydrocarbon feed must generally be purified of sulfur, to less than 1 ppm, prior to steam reforming. This requirement results in additional expense for the hydrocarbon steam reforming process.
- light fractions may be amenable to hydrodesulfurization, desulfurization of heavy fractions is extremely difficult.
- An alternative is to use the nickel catalyst for hydrocarbon steam reforming and allow it to be poisoned by the sulfur, but to operate at higher temperatures and with higher volumes of catalyst to counteract the loss of catalyst activity due to poisoning. This alternative also results in additional cost and weight to the process.
- a second alternative is to use noble metal catalysts, such as platinum, palladium, or rhodium in place of nickel. While the noble metal catalysts are very active for steam reforming and are somewhat tolerant of sulfur-containing feeds, they are very impractical because of their high cost.
- An object of the present invention is to provide an improved process for steam reforming of sulfur-containing hydrocarbons.
- a further object of this invention is to provide a process for steam reforming of hydrocarbons in which sulfur-containing hydrocarbons are available as raw materials without being desulfurized in advance.
- Another object of this invention is to provide a process for steam reforming of sulfur-containing hydrocarbons using a catalyst that gives stable performance, substantially without coking, and with substantially complete conversion of heavy hydrocarbon feeds.
- a still further object of this invention is to provide an apparatus for the practice of the above steam reforming processes.
- a sulfur-tolerant catalyst useful in the steam reforming of hydrocarbons, comprising an active phase and a support phase, and optionally a promoter, which provides substantially complete conversion of the hydrocarbon to a mixture of hydrogen, carbon monoxide, and carbon dioxide.
- the present invention provides a process for steam reforming a sulfur- containing hydrocarbon feed comprising: providing a sulfur-tolerant catalyst and contacting the catalyst with a gas stream comprising steam and a sulfur-containing hydrocarbon feed, wherein sulfur species are present in the hydrocarbon feed in an amount of at least 2 ppm; the sulfur-tolerant catalyst comprising a mixed oxygen ion conducting and electron conducting material having both an active catalytic phase and a catalyst support phase, and optionally a promoter, a) wherein the active catalytic phase is at least one of:
- a metal selected from the group consisting of Ag, Co, Cr, Cu, Fe, Ru, Rh, N, and alloys and mixtures thereof;
- a perovskite of the general formula (A ⁇ -aA'a)(BbB' ⁇ -b) ⁇ 3-c wherein A is selected from lanthanides, La, Y, Pb and mixtures thereof, A' is selected from alkaline earth metals such as Ba, Ca, Sr and mixtures thereof, B is selected from transition elements such as Fe, Co, Cr, ⁇ i and mixtures thereof, and B' is selected from Al, Co, Cr, Mg, ⁇ b, Ti, Zr and mixtures thereof, wherein 0.9 ⁇ (A+A')/(B+B') ⁇ 1.1, preferably 0.99 ⁇ (A+A')/(B+B') ⁇ 1.01; and wherein 0 ⁇ a ⁇ 1; 0 ⁇ b ⁇ 1; and c is a number that renders the composition charge neutral in the absence of an applied potential; and erein the catalyst support phase and the optional promoter is at least one of:
- (VIII) A Brown-Millerite material of the general formula Mc2Mc'2 ⁇ 5 wherein Mc is an alkaline earth element such as Ba or Sr, and Mc' is Gd, Dy or Ga.
- the present invention further provides an apparatus comprising a reaction zone, a catalyst bed contained within the reaction zone, and wherein the above sulfur- tolerant catalyst is included in the catalyst bed.
- the catalyst bed is preferably a fixed bed.
- the present invention therefore also provides a process for steam reforming a sulfur bearing hydrocarbon feed, such as in a steam reforming apparatus containing a bed of the sulfur-tolerant catalyst, including introducing steam and a hydrocarbon feed containing at least about 2 ppm sulfur species into the apparatus, and reacting said steam and hydrocarbon feed in the catalyst bed.
- sulfur-tolerant catalysts useful in the steam reforming of hydrocarbons which provide stable performance, substantially without coking, and with substantially complete conversion of hydrocarbon feeds, including heavy hydrocarbons and distillate fuels.
- sulfur tolerant catalyst is intended to mean one which maintains a substantially stable operating performance after equilibration, during and after exposure to sulfur-bearing hydrocarbons.
- the sulfur-tolerant catalyst useful for the steam reforming of hydrocarbons comprises an active catalytic phase set forth in formulas I, II, and III of Table A, and a catalyst support, and optionally a promoter, phase set forth in formulas IV, V, VI, VII and VIII of Table A.
- Table A Active Catalyst Phase (I) Metals such as Ag, Co, Cr, Cu, Fe, Ru, Rh, V, and the like, and alloys and mixtures thereof; (II) Oxides of the general formula MyMAOx, wherein at least one M element is different than at least one M' element, wherein M is selected from Ba, Ce, Nb, Sm, Sr, and mixtures thereof, M' is selected from Ti, Y, Sm, Nb and mixtures thereof, and wherein 0 ⁇ y ⁇ 1 and x is a number sufficient to satisfy the valence requirements of the other elements;
- Perovskites of the general formula (A ⁇ -aA'a)(BbB' ⁇ -b) ⁇ 3-c wherein A is selected from lanthanides, La, Y, Pb and mixtures thereof, A' is selected from alkaline earth metals such as Ba, Ca, Sr and mixtures thereof, B is selected from transition elements such as Fe, Co, Cr, Ni and mixtures thereof, and B' is selected from Al, Co, Cr, Mg,
- Ma'gMa"n ⁇ 2 wherein Ma is Th, Zr, Ce, or a rare earth element
- Ma' is Sc, TI, Ta or an alkaline earth such as Ca, Sr, Ba, Mg, Y or a rare earth element different from Ma, wherein 0 ⁇ g ⁇ 0.5, Ma" is
- Mb is Ga, or Gd, a rare earth element such as La,
- Mb' is Zr, a transition metal element such as Mo, Ti, Fe, an alkaline earth element such as Ca, Sr, Ba or Mg, wherein
- Mb" is a transition metal element different from Mb', such as Mo, Ti, or Fe;
- VIII A Brown-Millerite material of the general formula Mc2Mc'2 ⁇ 5 wherein Mc is an alkaline earth element such as Ba or Sr, and Mc' is Gd, Dy or Ga.
- the rare earth of formulas (VI) and (VJT) is preferably Gd, and the transition metal element of formula (VII) is preferably Ti.
- the sulfur-tolerant catalyst used in the inventive process comprises a mixed oxygen ion conducting and electron conducting material, in addition to its having both an active catalytic phase and a catalyst support phase.
- the materials set forth in formulas (I), (II), and (III), of Table A are electronic conductors
- the materials set forth in formulas (IV), (V), (VI), (VII), and (VIII) of Table A are ionic or mixed ionic/electronic conductors. These characteristics are postulated to be related to both the catalytic activity of the materials for hydrocarbon steam reforming as well as their sulfur tolerance.
- the catalyst is prepared by optionally first preparing a promoter, in an embodiment utilizing a promoter compound, preferably in powder form.
- a catalyst support also in powder form, is mixed with the promoter, if any, and calcined.
- the resultant powder is then mixed with the active phase of the catalyst.
- the mixture containing the respective electron conducting and oxygen ion conducting materials, is extruded and cut to an appropriate size.
- porosity is provided in the support as interconnected porosity so as to permit the flow of gas through the material.
- the interconnected porosity can be made by the preparation of a green body of precursors to the catalyst support into which green body has been incorporated a thermoset or thermoplastic binder and a pore former such as wax or a salt, for example calcium chloride. After the formation of the green body, the pore former is dissolved out of the green body by heating or by immersion in a solvent for the pore former, leaving an interconnected pathway of voids in the material which can then be fired by conventional procedures.
- Alternate methods of forming the interconnected porosity within the catalyst support include the use of woven sintered ceramic fibers, or pressed ceramic particles. In the latter method, it is necessary to use particle sizes which are large, in the range of about 40 mesh to 80 mesh (0.177-0.42mm), and in which there are not a significant amount of smaller sized particles present, which could block the pores between the larger particles. Where a particulate support is used, interconnected porosity can still be considered to be fixed if the particle size range is such that small particles do not block pores, and the shifting of large particles into a pore or a passageway between pores creates a shifted void that reestablishes an interconnection to the same or another pore. In a method related to the pore forming method, a reticulated foam is used as a substrate for the deposition of a catalyst support to form a precursor, and then the foam is dissolved to form the interconnected pores.
- the process of the present invention is highly flexible with respect to the hydrocarbon feed source, as the subject catalyst is suitable for the utilization of gaseous hydrocarbon sources such as natural gas, sometimes having sulfur species present in amounts of up to 10 ppm (volume) or more, landfill methane gas having sulfur species present in amounts of 25 to 75 ppm or more, hydrocarbon fuels, such as coal derived fuel gas having sulfur present in amounts up to 1000 ppm or more, and fuel gas from liquid fuels such as diesel and jet fuels having sulfur species present in amounts of up to 0.5 percent by weight. Stable performance of the catalyst has been realized, even with feeds having 2000 ppm (volume in gas feed) sulfur species.
- the process and apparatus, according to the invention may therefore utilize any of the above feeds, as well as clean fuels, interchangeably.
- Fig. 1 is a cross section elevational view showing that the heating jacket 11 consists of a reaction zone 12, immediately surrounded by a heating zone 13 containing heating coils 14. The heating zone is substantially surrounded by an outer insulating wall 15.
- Fig. 2 shows the reaction vessel which is positioned inside the reaction zone 12.
- a steam feed line 22 and a hydrocarbon feed line 23 empty into a premix zone 24.
- the catalyst bed may contain an inert material, such as alumina, in addition to the catalyst, to contain the fine particles in the catalyst bed.
- the gaseous products of the steam reforming reaction are collected from the reaction vessel by a product outlet line 28.
- the process for steam reforming sulfur bearing hydrocarbons includes providing the sulfur-tolerant catalyst.
- the catalyst is positioned in the reaction vessel, optionally together with an inert material such as alumina.
- the reaction vessel is positioned inside the heating jacket.
- the premix zone is fed by liquid water or steam and by a liquid or gaseous hydrocarbon feed.
- the premix zone is heated to a temperature sufficient to completely vaporize all liquids fed.
- the resulting vapors and/or gases mix thoroughly as they pass through the orifice into the catalyst chamber.
- the catalyst bed is heated to a relatively high temperature where both the catalyst activity is high and the chemical reaction equilibria for the reforming reactions are favorable.
- a temperature gradient will naturally exist within the bed, with the feed end being cooler.
- the height-to-diameter ratio of the bed should be sufficiently large so that flow "channeling" does not occur.
- the gaseous products leaving the catalyst bed will consist primarily of hydrogen, steam, carbon monoxide, and carbon dioxide.
- the sulfur will be present chiefly as hydrogen sulfide. Small percentages of other species (including methane) will also be present, depending upon the bed exit pressure, temperature, and residence time.
- the apparatus may be operated at various pressures (ranging from subatmospheric to many atmospheres), exit temperatures, and residence times, depending primarily upon the requirements for the product gas.
- the selection of pressure and temperature will affect the chemical equilibria in well-known manners.
- the selection of temperature and space velocity will affect the reaction kinetics and hence the approach to equilibrium. We have used a 1000°C exit temperature for most experimental trials but the catalysts of the present invention will perform well down to
- the ratio of oxidizing species (steam and carbon dioxide) to the carbon contained in the hydrocarbon feed must be high enough to prevent solid carbon "coke” deposition in the catalyst bed.
- Good reforming catalysts such as those of the present invention, can operate at lower ratios of oxidizing species than poor catalysts, especially in the presence of sulfur.
- One preferred embodiment of the sulfur-tolerant catalyst used in the process of the present invention includes a catalyst supported on a support compound, promoted with a promoter compound.
- a catalyst supported on a support compound promoted with a promoter compound.
- suitable catalysts, promoters and supports are listed in Table B.
- Table B were fabricated by first preparing the promoted support in powdered form. A support compound powder was thoroughly mixed with the promoter compound powder by ball milling, followed by calcination of the powder at 1450 °C for two hours. The resultant ceramic powder was then mixed with a powder of the catalyst by milling. The powder of the catalyst/promoter/support were mixed with pore formers and, binders and extruded to form long strands. The extruded strands were then cut to produce small cylinders approximately 1/16" outer diameter (O.D.) by 4 cm long. The cylinders were then calcined at 1200- 1400 °C to form the final catalyst extrudates.
- Catalysts of Example A were tested for steam reforming on distillate fuels, namely JP-8 jet fuel and DF-2 diesel fuel.
- the catalysts exhibited stable performance (demonstrating no increase in catalyst bed pressure) for up to 500 hours.
- the test conditions are shown in Table 1 for experimental runs with DF-2 diesel and JP-8 jet fuels. No coking was observed.
- Example 3 In the reforming of DF-2 diesel fuel with the above prepared sulfur- tolerant catalysts, the chemical composition of the product gas was measured and is shown in Table 2. The product gas was passed through a cold trap to remove water prior to injection into the gas chromatograph. For this example, the reaction condition included a steam to hydrocarbon volume ratio of 3.6, residence time of 1646 ms, and fuel flow of 6.3 ml/hr.
- Additional representative sulfur-tolerant catalysts of the present invention include, but are not limited to, the following:
- the sulfur tolerant reforming catalyst used in the process of the present invention demonstrates high activity, combined with low weight, as compared to conventional reforming catalysts. These characteristics provide the capability of utilizing the catalyst in the process in a relatively small, lightweight reforming apparatus, useful for mobile operations.
- the inventive apparatus may be disposed within a vehicle, to provide the reforming process product gases for use as fuel, such as for combustion in a fuel cell capable of providing electrical power.
- the reforming apparatus according to this embodiment may advantageously have its outlet communicating with an inlet of the fuel cell.
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Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2001/000081 WO2002053492A1 (en) | 2001-01-02 | 2001-01-02 | Method for steam reforming hydrocarbons using a sulfur-tolerant catalyst |
CA002432065A CA2432065C (en) | 2001-01-02 | 2001-01-02 | Method for steam reforming hydrocarbons using a sulfur-tolerant catalyst |
EP01901674A EP1353874A4 (en) | 2001-01-02 | 2001-01-02 | Method for steam reforming hydrocarbons using a sulfur-tolerant catalyst |
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PCT/US2001/000081 WO2002053492A1 (en) | 2001-01-02 | 2001-01-02 | Method for steam reforming hydrocarbons using a sulfur-tolerant catalyst |
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CA (1) | CA2432065C (en) |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2427574A (en) * | 2005-06-24 | 2007-01-03 | Ngimat Co | Catalytic method of reducing sulphur content of a petroleum fluid and reforming a hydrocarbon to produce hydrogen |
EP1908859A1 (en) * | 2006-10-02 | 2008-04-09 | Siemens Aktiengesellschaft | Pyrochlore materials and a thermal barrier coating with these pyrochlore materials |
US7481856B2 (en) | 2001-12-05 | 2009-01-27 | Daimler Ag | Reactor for autothermal reforming of hydrocarbons |
US7625482B1 (en) | 2006-06-23 | 2009-12-01 | Ngimat Co. | Nanoparticulate-catalyzed oxygen transfer processes |
WO2011039761A3 (en) * | 2009-07-20 | 2011-05-26 | Council Of Scientific & Industrial Research | Ceaio3 perovskites containing transition metal |
EP2756540A4 (en) * | 2011-09-15 | 2015-12-02 | Lg Fuel Cell Systems Inc | Systems and methods for steam reforming |
CN114425395A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Porous perovskite type sulfur-tolerant shift catalyst and preparation method and application thereof |
RU2781559C1 (en) * | 2022-06-10 | 2022-10-13 | Общество с ограниченной ответственностью "Чистая энергия" | Method for hydrogen production by landfill gas conversion method |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108786784A (en) * | 2018-06-15 | 2018-11-13 | 南京中科水治理股份有限公司 | A kind of preparation method of photocatalytic degradation composite material |
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US5130114A (en) * | 1983-08-04 | 1992-07-14 | Akira Igarashi | Catalyst for steam reforming of hydrocarbon |
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BE794625A (en) * | 1972-01-27 | 1973-05-16 | British Gas Corp | DEVELOPMENTS RELATING TO CATALYSTS |
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US4755498A (en) * | 1986-04-30 | 1988-07-05 | International Fuel Cells Corporation | Steam reforming catalyst |
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2001
- 2001-01-02 CA CA002432065A patent/CA2432065C/en not_active Expired - Fee Related
- 2001-01-02 EP EP01901674A patent/EP1353874A4/en not_active Withdrawn
- 2001-01-02 WO PCT/US2001/000081 patent/WO2002053492A1/en active Application Filing
Patent Citations (2)
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US5130114A (en) * | 1983-08-04 | 1992-07-14 | Akira Igarashi | Catalyst for steam reforming of hydrocarbon |
US5028036A (en) | 1986-06-27 | 1991-07-02 | The Carborundum Company | Filter for molten ferrous metal |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7481856B2 (en) | 2001-12-05 | 2009-01-27 | Daimler Ag | Reactor for autothermal reforming of hydrocarbons |
GB2427574B (en) * | 2005-06-24 | 2009-04-08 | Ngimat Co | Nanoparticulate-catalyzed oxygen transfer processes |
GB2427574A (en) * | 2005-06-24 | 2007-01-03 | Ngimat Co | Catalytic method of reducing sulphur content of a petroleum fluid and reforming a hydrocarbon to produce hydrogen |
US7625482B1 (en) | 2006-06-23 | 2009-12-01 | Ngimat Co. | Nanoparticulate-catalyzed oxygen transfer processes |
EP2302101A1 (en) * | 2006-10-02 | 2011-03-30 | Siemens Aktiengesellschaft | Pyrochlore materials and a thermal barrier coating with these pyrochlore materials |
WO2008040574A1 (en) | 2006-10-02 | 2008-04-10 | Siemens Aktiengesellschaft | Pyrochlore materials and a thermal barrier coating with these pyrochlore materials |
EP1908859A1 (en) * | 2006-10-02 | 2008-04-09 | Siemens Aktiengesellschaft | Pyrochlore materials and a thermal barrier coating with these pyrochlore materials |
US8278232B2 (en) | 2006-10-02 | 2012-10-02 | Siemens Aktiengesellschaft | Pyrochlore materials and a thermal barrier coating with these pyrochlore materials |
WO2011039761A3 (en) * | 2009-07-20 | 2011-05-26 | Council Of Scientific & Industrial Research | Ceaio3 perovskites containing transition metal |
EP2756540A4 (en) * | 2011-09-15 | 2015-12-02 | Lg Fuel Cell Systems Inc | Systems and methods for steam reforming |
CN114425395A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Porous perovskite type sulfur-tolerant shift catalyst and preparation method and application thereof |
CN114425395B (en) * | 2020-10-10 | 2024-02-20 | 中国石油化工股份有限公司 | Porous perovskite sulfur-resistant shift catalyst and preparation method and application thereof |
RU2781559C1 (en) * | 2022-06-10 | 2022-10-13 | Общество с ограниченной ответственностью "Чистая энергия" | Method for hydrogen production by landfill gas conversion method |
Also Published As
Publication number | Publication date |
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EP1353874A4 (en) | 2009-07-29 |
CA2432065C (en) | 2009-10-27 |
EP1353874A1 (en) | 2003-10-22 |
CA2432065A1 (en) | 2002-07-11 |
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