US20210229076A1 - Catalyst compositions having enhanced acidity for bi-reforming processes - Google Patents
Catalyst compositions having enhanced acidity for bi-reforming processes Download PDFInfo
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- US20210229076A1 US20210229076A1 US16/775,167 US202016775167A US2021229076A1 US 20210229076 A1 US20210229076 A1 US 20210229076A1 US 202016775167 A US202016775167 A US 202016775167A US 2021229076 A1 US2021229076 A1 US 2021229076A1
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- red mud
- catalyst composition
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- modified red
- mud catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000002407 reforming Methods 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 17
- -1 VIB metal oxide Chemical class 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003518 caustics Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 claims description 2
- 238000006057 reforming reaction Methods 0.000 claims 3
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 31
- 229910052759 nickel Inorganic materials 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
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- 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
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- 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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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/1047—Group VIII metal catalysts
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- C01B2203/1058—Nickel catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
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- C01B2203/1241—Natural gas or methane
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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
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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
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- 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
- Embodiments of the disclosure relate to catalyst compositions for use in reforming processes.
- certain embodiments of the disclosure relate to Periodic Table Group VIB metal oxide containing catalyst compositions for and methods of bi-reforming.
- Bi-reforming is a green method for the production of synthesis gas (syngas, H 2 and CO), since it utilizes the two greenhouse gases of CH 4 and CO 2 as reactants. In addition, it can offer certain advantages over dry reforming and steam reforming with respect to catalyst deactivation and final product ratio.
- synthesis gas syngas, H 2 and CO
- the general chemical equation representing bi-reforming is shown below.
- Bi-reforming technology combines dry reforming and steam reforming of methane to produce syngas. Unlike dry reforming, bi-reforming produces a syngas that is both flexible (with variability in the CO 2 /H 2 O ratio) and meets the 2/1 H 2 /CO ratio required by many higher-value products, for example, higher oxygenates. In addition, the presence of steam provides a higher oxidant level in bi-reforming that addresses the inevitable and typically intolerable carbon deposition in dry reforming.
- one of the main challenges of bi-reforming is to develop catalysts that are resistant to high temperatures and the presence of a more oxidative environment due to steam.
- Suitable catalysts for bi-reforming should be resistant to high temperatures and the presence of a more oxidative environment due to steam addition.
- Methane reforming can quickly deactivate catalysts due to coke formation on the surface of catalysts.
- high temperatures for methane conversion can lead to catalyst deactivation by coking or sintering.
- Nickel catalyst with aluminum oxide and magnesium oxide as supports is used for methane reforming.
- compositions of Periodic Table Group VIB Group VIB
- Enhanced-acidity Group VIB catalyst compositions are disclosed, in some embodiments further including nickel.
- the enhanced-acidity Group VIB catalysts also contain in some embodiments Fe, Al, Si, Na, Ca, and Ti oxides from red mud.
- red mud acts as a catalyst in addition to or alternative to a catalyst carrier.
- Disclosed compositions are useful as a catalyst in bi-reforming processes for the conversion of methane to syngas, according to Equation 1. Utilization of red mud in bi-reforming processes provides the concurrent advantages of utilizing a waste material (red mud) and producing useful H 2 , while also using two greenhouse gases (CO 2 and CH 4 ) as reactants.
- Red mud is a caustic waste material produced from bauxite ore processing for alumina extraction, and is utilized here as a catalyst for bi-reforming processes. Surprisingly and unexpectedly, without being specifically designed as a catalyst (for example using specific zeolitic structure), red mud waste material can be readily modified for use as a catalyst. Red mud generally includes a mixture of transition metals such as Ti, Fe, and Al, which make it an advantageous catalyst for bi-reforming processes, for example once modified with nickel and molybdenum.
- Embodiments disclosed here apply red mud as an active catalyst support, promotor, in addition to or alternative to catalyst to produce hydrogen through bi-reforming of methane, optionally followed by a water-gas shift reaction to produce additional H 2 .
- a methane feed in the presence of carbon dioxide and steam to react over the modified red mud catalyst composition at increased temperature and increased pressure to produce synthesis gas comprising H 2 and CO, the composition comprising: red mud material produced from an alumina extraction process from bauxite ore; nickel oxide, the nickel oxide present at between about 5 wt. % to about 40 wt. % of the modified red mud catalyst composition; and a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the modified red mud catalyst composition.
- the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten. Still in other embodiments, the increased temperature is between about 500° C. to about 1000° C. In some embodiments, the increased temperature is between about 600° C. to about 800° C. In other embodiments, the increased temperature is about 750° C. In certain embodiments, the increased pressure is between about 5 bar and about 20 bar. In other embodiments, the increased pressure is between about 10 bar and about 15 bar. Still in other embodiments, the increased pressure is about 14 bar.
- gas hourly space velocity of the methane feed, carbon dioxide feed, and steam feed mixed is between about 1000 h ⁇ 1 to 10000 h ⁇ 1 .
- the composition includes at least one component selected from the group consisting of: Fe 2 O 3 , Al 2 O 3 , SiO 2 , Na 2 O, CaO, and TiO 2 .
- a majority of the particles of the composition have a particle size of less than about 70 ⁇ m.
- the nickel oxide is present at between about 10 wt. % to about 30 wt. % of the modified red mud catalyst composition.
- the nickel oxide is present at between about 15 wt. % to about 25 wt. % of the modified red mud catalyst composition. In certain embodiments, the nickel oxide is present at about 23 wt. % of the modified red mud catalyst composition. In some embodiments, the Group VIB metal oxide is present at between about 1 wt. % to about 20 wt. % of the modified red mud catalyst composition. Still in other embodiments, the Group VIB metal oxide is present at between about 1 wt. % to about 10 wt. % of the modified red mud catalyst composition. In certain embodiments, the Group VIB metal oxide is present at about 5 wt. % of the modified red mud catalyst composition.
- conversion percentage of methane reaches up to about 35%.
- a molar ratio of methane:carbon dioxide:steam is about 3:1:2.
- produced H 2 is at least about 4 mol. % of produced products from the reaction for at least about 5 hours.
- the Brunauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m 2 /g and about 90 m 2 /g.
- FIG. 1 is a graph showing conversion percentage for CH 4 in a bi-reforming process for unmodified red mud (RM) used as a catalyst and for acid nickel-molybdenum-modified red mud (ANMoMRM) used as a catalyst.
- RM unmodified red mud
- ANMoMRM acid nickel-molybdenum-modified red mud
- FIG. 2 is a graph showing mol. % of H 2 out of the total products produced from bi-reforming of CH 4 for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst.
- red mud is a caustic waste material generated during alumina extraction from bauxite ore.
- Red mud includes a mixture of transition metals, for example as listed in Table 1.
- Red mud was modified with nickel and molybdenum to be utilized and tested as a catalyst for bi-reforming as follows.
- nickel is not required.
- nickel in addition to or alternative to any one of or any combination of chromium, molybdenum, and tungsten can be used to modify red mud.
- Saudi Arabian red mud from Ma'aden Aluminium Company, based at Ras Al Khair, Saudi Arabia was used to prepare a modified catalyst composition. Table 2 shows the weight percent for certain components in the unmodified Saudi Arabian red mud composition.
- the untreated red mud exhibited a Brunauer-Emmett-Teller (BET) surface area of about 16 m 2 /g.
- BET Brunauer-Emmett-Teller
- Table 3 shows an example composition for one embodiment of produced nickel-molybdenum acid treated red mud for use as a modified catalyst.
- the unmodified red mud used as a catalyst precursor contained no detectable nickel or molybdenum.
- Example composition for a produced ANMoMRM used as a catalyst Component Fe 2 O 3 Al 2 O 3 SiO 2 Na 2 O CaO TiO 2 NiO MoO Weight 16.76% 21.43% 19.56% 2.81% 2.76% 5.36% 23.7% 5.06% Percentage
- red mud is a highly variable waste material, elemental composition will vary between samples and test results.
- An acid nickel-molybdenum-modified red mud (ANMoMRM) catalyst with 23.7 wt. % nickel oxide and 5.06 wt. % molybdenum oxide was prepared using a homogeneous precipitation process.
- NAMoMRM acid nickel-molybdenum-modified red mud
- 20 wt. % of nickel oxide also referred to as NiO
- XRF X-ray fluorescence
- molybdenum oxide also referred to as MoO
- nickel oxide can be loaded to a red mud precursor from between about 1 wt. % to about 50 wt. %
- molybdenum oxide in addition to or alternative to other Group VIB metals, can be loaded to a red mud precursor from between about 1 wt. % to about 50 wt. %.
- nickel-containing compounds and molybdenum-containing compounds can be used in addition to or alternative to nickel nitrate and ammonium molybdate, including any nickel-containing compounds or molybdenum-containing compounds soluble in ethanol or other organic or inorganic alcohols, or in aqueous ammonia.
- XRF in embodiments of the present disclosure confirmed the presence of nickel and molybdenum oxide loading in the ANMoMRM.
- Nickel can be combined with red mud to result in nickel(II) oxide, NiO, in addition to or alternative to nickel(III) oxide, Ni 2 O 3 .
- Molybdenum can be combined with red mud to result in (molybdenum dioxide, MoO 2 ) or Molybdenum(VI) oxide (molybdenum trioxide, MoO 3 ).
- BET surface area analysis showed unmodified red mud surface area was about 16 m 2 /g.
- BET surface area for acid modified red mud was about 170 m 2 /g.
- BET surface area for acid modified red mud with nickel in addition to or alternative to molybdenum loading is, in some embodiments, between about 50 m 2 /g and about 90 m 2 /g, for example about 63 m 2 /g or about 89 m 2 /g.
- FIG. 1 is a graph showing conversion percentage for CH 4 in a bi-reforming process for unmodified red mud (RM) used as a catalyst and for ANMoMRM used as a catalyst. Effects of nickel addition to red mud were studied. Experimental conditions in the bi-reforming reactor included temperature at about 750° C., pressure at about 14 bar, and gas hourly space velocity (GHSV) at about 7362 h ⁇ 1 . The test was conducted for 6 hours. The feed was 50 mol. % methane, 17 mol. % CO 2 , and 33 mol. % steam for both catalysts tested. The GHSV was calculated for the mixed feed.
- GHSV gas hourly space velocity
- the feed composition can comprise, consist essentially of, or consist of CH 4 , CO 2 , and steam. Based in part on thermodynamics, a suitable molar ratio of methane:carbon dioxide:steam is about 3:1:2.
- Methane conversion illustrated in FIG. 1 shows ANMoMRM catalyst outperformed its counterpart, the untreated red mud. Methane conversion by ANMoMRM reached up to about 35%, then stabilized at about 5%. On the other hand unmodified red mud was not effective as a catalyst for conversion of methane.
- the greater conversion rate of ANMoMRM can be attributed to the addition of nickel and molybdenum, and synergies of the nickel and molybdenum with the existing transition metals in the red mud.
- FIG. 2 is a graph showing mol. % of H 2 out of the total products produced from bi-reforming of CH 4 for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst. Hydrogen production illustrated in FIG. 2 shows that untreated red mud produced low amounts of hydrogen, whereas ANMoMRM catalyst produced between about 4 mol. % and about 7 mol. % hydrogen. Nickel-molybdenum modification of red mud has enhanced the performance significantly.
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Abstract
Methods for bi-reforming over a modified red mud catalyst composition, one method including providing a methane feed in the presence of carbon dioxide and steam to react over the modified red mud catalyst composition at increased temperature and increased pressure to produce synthesis gas comprising H2 and CO, the composition comprising red mud material produced from an alumina extraction process from bauxite ore; nickel oxide, the nickel oxide present at between about 5 wt. % to about 40 wt. % of the modified red mud catalyst composition; and a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the modified red mud catalyst composition.
Description
- Embodiments of the disclosure relate to catalyst compositions for use in reforming processes. In particular, certain embodiments of the disclosure relate to Periodic Table Group VIB metal oxide containing catalyst compositions for and methods of bi-reforming.
- Bi-reforming is a green method for the production of synthesis gas (syngas, H2 and CO), since it utilizes the two greenhouse gases of CH4 and CO2 as reactants. In addition, it can offer certain advantages over dry reforming and steam reforming with respect to catalyst deactivation and final product ratio. The general chemical equation representing bi-reforming is shown below.
- Bi-reforming technology combines dry reforming and steam reforming of methane to produce syngas. Unlike dry reforming, bi-reforming produces a syngas that is both flexible (with variability in the CO2/H2O ratio) and meets the 2/1 H2/CO ratio required by many higher-value products, for example, higher oxygenates. In addition, the presence of steam provides a higher oxidant level in bi-reforming that addresses the inevitable and typically intolerable carbon deposition in dry reforming.
- However, one of the main challenges of bi-reforming is to develop catalysts that are resistant to high temperatures and the presence of a more oxidative environment due to steam. Suitable catalysts for bi-reforming should be resistant to high temperatures and the presence of a more oxidative environment due to steam addition. Methane reforming can quickly deactivate catalysts due to coke formation on the surface of catalysts. In addition, high temperatures for methane conversion can lead to catalyst deactivation by coking or sintering. Nickel catalyst with aluminum oxide and magnesium oxide as supports is used for methane reforming.
- However, present catalyst technology is insufficient in some processes to provide cost-effective and durable means for bi-reforming.
- Applicant has recognized a need for compositions of Periodic Table Group VIB (Group VIB) metal oxide containing red mud to be applied in systems and processes for bi-reforming. Enhanced-acidity Group VIB catalyst compositions are disclosed, in some embodiments further including nickel. The enhanced-acidity Group VIB catalysts also contain in some embodiments Fe, Al, Si, Na, Ca, and Ti oxides from red mud. In embodiments of the present disclosure, red mud acts as a catalyst in addition to or alternative to a catalyst carrier. Disclosed compositions are useful as a catalyst in bi-reforming processes for the conversion of methane to syngas, according to
Equation 1. Utilization of red mud in bi-reforming processes provides the concurrent advantages of utilizing a waste material (red mud) and producing useful H2, while also using two greenhouse gases (CO2 and CH4) as reactants. - Red mud is a caustic waste material produced from bauxite ore processing for alumina extraction, and is utilized here as a catalyst for bi-reforming processes. Surprisingly and unexpectedly, without being specifically designed as a catalyst (for example using specific zeolitic structure), red mud waste material can be readily modified for use as a catalyst. Red mud generally includes a mixture of transition metals such as Ti, Fe, and Al, which make it an advantageous catalyst for bi-reforming processes, for example once modified with nickel and molybdenum.
- Embodiments disclosed here apply red mud as an active catalyst support, promotor, in addition to or alternative to catalyst to produce hydrogen through bi-reforming of methane, optionally followed by a water-gas shift reaction to produce additional H2.
- Therefore, disclosed here are methods for bi-reforming over a modified red mud catalyst composition, one method including providing a methane feed in the presence of carbon dioxide and steam to react over the modified red mud catalyst composition at increased temperature and increased pressure to produce synthesis gas comprising H2 and CO, the composition comprising: red mud material produced from an alumina extraction process from bauxite ore; nickel oxide, the nickel oxide present at between about 5 wt. % to about 40 wt. % of the modified red mud catalyst composition; and a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the modified red mud catalyst composition.
- In some embodiments, the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten. Still in other embodiments, the increased temperature is between about 500° C. to about 1000° C. In some embodiments, the increased temperature is between about 600° C. to about 800° C. In other embodiments, the increased temperature is about 750° C. In certain embodiments, the increased pressure is between about 5 bar and about 20 bar. In other embodiments, the increased pressure is between about 10 bar and about 15 bar. Still in other embodiments, the increased pressure is about 14 bar.
- In some embodiments, gas hourly space velocity of the methane feed, carbon dioxide feed, and steam feed mixed is between about 1000 h−1 to 10000 h−1. Still in other embodiments, the composition includes at least one component selected from the group consisting of: Fe2O3, Al2O3, SiO2, Na2O, CaO, and TiO2. In certain embodiments, a majority of the particles of the composition have a particle size of less than about 70 μm. And in other embodiments, the nickel oxide is present at between about 10 wt. % to about 30 wt. % of the modified red mud catalyst composition.
- Still in other embodiments, the nickel oxide is present at between about 15 wt. % to about 25 wt. % of the modified red mud catalyst composition. In certain embodiments, the nickel oxide is present at about 23 wt. % of the modified red mud catalyst composition. In some embodiments, the Group VIB metal oxide is present at between about 1 wt. % to about 20 wt. % of the modified red mud catalyst composition. Still in other embodiments, the Group VIB metal oxide is present at between about 1 wt. % to about 10 wt. % of the modified red mud catalyst composition. In certain embodiments, the Group VIB metal oxide is present at about 5 wt. % of the modified red mud catalyst composition.
- In some embodiments, conversion percentage of methane reaches up to about 35%. In other embodiments, a molar ratio of methane:carbon dioxide:steam is about 3:1:2. Still in other embodiments, produced H2 is at least about 4 mol. % of produced products from the reaction for at least about 5 hours. In certain embodiments, the Brunauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m2/g and about 90 m2/g.
- These and other features, aspects, and advantages of the present disclosure will become better understood with regard to the following descriptions, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the disclosure and are therefore not to be considered limiting of the disclosure's scope as it can admit to other equally effective embodiments.
-
FIG. 1 is a graph showing conversion percentage for CH4 in a bi-reforming process for unmodified red mud (RM) used as a catalyst and for acid nickel-molybdenum-modified red mud (ANMoMRM) used as a catalyst. -
FIG. 2 is a graph showing mol. % of H2 out of the total products produced from bi-reforming of CH4 for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst. - So that the manner in which the features and advantages of the embodiments of compositions of Group VIB metal modified red mud, in some embodiments including nickel, along with systems and methods for bi-reforming with such compositions and for producing such compositions, may be understood in more detail, a more particular description of the embodiments of the present disclosure briefly summarized previously may be had by reference to the embodiments thereof, which are illustrated in the appended drawings, which form a part of this specification. It is to be noted, however, that the drawings illustrate only various embodiments of the disclosure and are therefore not to be considered limiting of the present disclosure's scope, as it may include other effective embodiments as well.
- As noted, red mud is a caustic waste material generated during alumina extraction from bauxite ore. Red mud includes a mixture of transition metals, for example as listed in Table 1.
-
TABLE 1 Example composition ranges for global red mud. Component Fe2O3 Al2O3 SiO2 Na2O CaO TiO2 Approx. 30-60% 10-20% 3-50% 2-10% 2-8% 10% Weight Percentage - Red mud was modified with nickel and molybdenum to be utilized and tested as a catalyst for bi-reforming as follows. In some embodiments, nickel is not required. In some embodiments, nickel in addition to or alternative to any one of or any combination of chromium, molybdenum, and tungsten can be used to modify red mud. Saudi Arabian red mud from Ma'aden Aluminium Company, based at Ras Al Khair, Saudi Arabia was used to prepare a modified catalyst composition. Table 2 shows the weight percent for certain components in the unmodified Saudi Arabian red mud composition.
-
TABLE 2 Certain component weight percentages in Saudi Arabian red mud (RM) catalyst/catalyst support composition. Component Fe2O3 Al2O3 SiO2 Na2O CaO TiO2 Weight 18.75% 25.22% 18.88% 11.77% 7.97% 6.89% Percentage - The untreated red mud exhibited a Brunauer-Emmett-Teller (BET) surface area of about 16 m2/g.
- Table 3 shows an example composition for one embodiment of produced nickel-molybdenum acid treated red mud for use as a modified catalyst. The unmodified red mud used as a catalyst precursor contained no detectable nickel or molybdenum.
-
TABLE 3 Example composition for a produced ANMoMRM used as a catalyst. Component Fe2O3 Al2O3 SiO2 Na2O CaO TiO2 NiO MoO Weight 16.76% 21.43% 19.56% 2.81% 2.76% 5.36% 23.7% 5.06% Percentage - Because red mud is a highly variable waste material, elemental composition will vary between samples and test results.
- Catalyst Preparation. An acid nickel-molybdenum-modified red mud (ANMoMRM) catalyst with 23.7 wt. % nickel oxide and 5.06 wt. % molybdenum oxide was prepared using a homogeneous precipitation process. Using an unmodified red mud catalyst precursor, 20 wt. % of nickel oxide (also referred to as NiO) was targeted to be loaded in the red mud to enhance bi-reforming activity, and 23.7 wt. % of nickel oxide was confirmed by X-ray fluorescence (XRF) analysis. Using the unmodified red mud catalyst precursor, 5 wt. % of molybdenum oxide (also referred to as MoO) was targeted to be loaded in the red mud to enhance bi-reforming activity, and 5.06 wt. % of molybdenum oxide was confirmed by XRF analysis. Depending on the catalyst application, nickel oxide can be loaded to a red mud precursor from between about 1 wt. % to about 50 wt. %, and molybdenum oxide, in addition to or alternative to other Group VIB metals, can be loaded to a red mud precursor from between about 1 wt. % to about 50 wt. %.
- First, 10 g of Saudi Arabian red mud from Ma'aden Aluminium Company, based at Ras Al Khair, Saudi Arabia was modified by dissolving dried, unmodified red mud in 100 mL of deionized water, and then the pH was neutralized using 40.5 mL of 37 wt. % hydrochloric acid. Afterward, 10 g of nickel(II) nitrate hexahydrate was dissolved in 50 mL of ethanol. Then, 0.92 grams of ammonium molybdate tetrahydrate was dissolved in 50 mL of ethanol. The three separate solutions were mixed to form a mixed solution. Next the mixed solution was filtered solids were dried in an oven at 105° C., and then calcined at 600° C. for 4 hours. The final ANMoMRM solid product was ground to have a particle size of less than about 70 μm. The step of drying in an oven can last from about 2 to about 24 hours.
- Other nickel-containing compounds and molybdenum-containing compounds can be used in addition to or alternative to nickel nitrate and ammonium molybdate, including any nickel-containing compounds or molybdenum-containing compounds soluble in ethanol or other organic or inorganic alcohols, or in aqueous ammonia. XRF in embodiments of the present disclosure confirmed the presence of nickel and molybdenum oxide loading in the ANMoMRM. Nickel can be combined with red mud to result in nickel(II) oxide, NiO, in addition to or alternative to nickel(III) oxide, Ni2O3. Molybdenum can be combined with red mud to result in (molybdenum dioxide, MoO2) or Molybdenum(VI) oxide (molybdenum trioxide, MoO3).
- BET surface area analysis showed unmodified red mud surface area was about 16 m2/g. BET surface area for acid modified red mud was about 170 m2/g. BET surface area for acid modified red mud with nickel in addition to or alternative to molybdenum loading is, in some embodiments, between about 50 m2/g and about 90 m2/g, for example about 63 m2/g or about 89 m2/g.
- Catalyst testing. Several tests on red mud catalytic activity and ANMoMRM catalytic activity for bi-reforming were experimentally conducted. Red mud was tested as received without any modifications, and it was placed in a Micromeritics® PID Eng & Tech brand microactivity reactor designed for catalyst activity and selectivity analysis, and the same was done for the prepared ANMoMRM catalyst. The results are compared, for example, in
FIGS. 1 and 2 . Results show that ANMoMRM catalytic activity for bi-reforming is advantageously improved over non-modified red mud catalytic activity for bi-reforming. -
FIG. 1 is a graph showing conversion percentage for CH4 in a bi-reforming process for unmodified red mud (RM) used as a catalyst and for ANMoMRM used as a catalyst. Effects of nickel addition to red mud were studied. Experimental conditions in the bi-reforming reactor included temperature at about 750° C., pressure at about 14 bar, and gas hourly space velocity (GHSV) at about 7362 h−1. The test was conducted for 6 hours. The feed was 50 mol. % methane, 17 mol. % CO2, and 33 mol. % steam for both catalysts tested. The GHSV was calculated for the mixed feed. GHSV generally measures the flow rate of the feed gases divided by the catalyst volume, which indicates the residence time of the reactants on the catalyst. For bi-reforming, the feed composition can comprise, consist essentially of, or consist of CH4, CO2, and steam. Based in part on thermodynamics, a suitable molar ratio of methane:carbon dioxide:steam is about 3:1:2. - Methane conversion illustrated in
FIG. 1 shows ANMoMRM catalyst outperformed its counterpart, the untreated red mud. Methane conversion by ANMoMRM reached up to about 35%, then stabilized at about 5%. On the other hand unmodified red mud was not effective as a catalyst for conversion of methane. The greater conversion rate of ANMoMRM can be attributed to the addition of nickel and molybdenum, and synergies of the nickel and molybdenum with the existing transition metals in the red mud. -
FIG. 2 is a graph showing mol. % of H2 out of the total products produced from bi-reforming of CH4 for unmodified red mud used as a catalyst and for ANMoMRM used as a catalyst. Hydrogen production illustrated inFIG. 2 shows that untreated red mud produced low amounts of hydrogen, whereas ANMoMRM catalyst produced between about 4 mol. % and about 7 mol. % hydrogen. Nickel-molybdenum modification of red mud has enhanced the performance significantly. - The singular forms “a,” “an,” and “the” include plural referents, unless the context clearly dictates otherwise. The term “about” when used with respect to a value or range refers to values including plus and minus 5% of the given value or range.
- In the drawings and specification, there have been disclosed example embodiments of the present disclosure, and although specific terms are employed, the terms are used in a descriptive sense only and not for purposes of limitation. The embodiments of the present disclosure have been described in considerable detail with specific reference to these illustrated embodiments. It will be apparent, however, that various modifications and changes can be made within the spirit and scope of the disclosure as described in the foregoing specification, and such modifications and changes are to be considered equivalents and part of this disclosure.
Claims (21)
1. A method for bi-reforming over an enhanced-acidity modified red mud catalyst composition, the method comprising the steps of:
providing a methane feed in the presence of carbon dioxide and steam to react in a bi-reforming reaction over the enhanced-acidity modified red mud catalyst composition at a temperature between about 500° C. to about 1000° C. and a pressure between about 5 bar and 20 bar to produce synthesis gas comprising H2 and CO, the enhanced-acidity modified red mud catalyst composition prepared by a homogeneous precipitation process comprising the steps of:
providing an unmodified caustic red mud waste material produced from an alumina extraction process from bauxite ore;
dissolving in water the unmodified caustic red mud waste material and neutralizing pH of the unmodified red mud waste material with an acid comprising hydrochloric acid;
combining nickel oxide, the nickel oxide present at between about 5 wt. % to about 40 wt. % of the enhanced-acidity modified red mud catalyst composition; and
combining a Periodic Table Group VIB metal oxide, the Group VIB metal oxide present at between about 1 wt. % and about 30 wt. % of the enhanced-acidity modified red mud catalyst composition.
2. The method according to claim 1 , where the Group VIB metal oxide comprises at least one metal selected from the group consisting of: chromium, molybdenum, and tungsten.
3. (canceled)
4. The method according to claim 1 , where the increased temperature is between about 600° C. to about 800° C.
5. The method according to claim 1 , where the increased temperature is about 750° C.
6. (canceled)
7. The method according to claim 1 , where the increased pressure is between about 10 bar and about 15 bar.
8. The method according to claim 1 , where the increased pressure is about 14 bar.
9. The method according to claim 1 , where gas hourly space velocity of the methane feed in the presence of carbon dioxide and steam is between about 1000 h−1 to 10000 h−1.
10. The method according to claim 1 , where the enhanced-acidity modified red mud catalyst composition includes at least one component selected from the group consisting of Fe2O3, Al2O3, SiO2, Na2O, CaO, and TiO2.
11. The method according to claim 1 , where a majority of particles of the enhanced-acidity modified red mud catalyst composition have a particle size of less than about 70 μm.
12. The method according to claim 1 , where the nickel oxide is present at between about 10 wt. % to about 30 wt. % of the enhanced-acidity modified red mud catalyst composition.
13. The method according to claim 1 , where the nickel oxide is present at between about 15 wt. % to about 25 wt. % of the enhanced-acidity modified red mud catalyst composition.
14. The method according to claim 1 , where the nickel oxide is present at about 23 wt. % of the enhanced-acidity modified red mud catalyst composition.
15. The method according to claim 1 , where the Group VIB metal oxide is present at between about 1 wt. % to about 20 wt. % of the enhanced-acidity modified red mud catalyst composition.
16. The method according to claim 1 , where the Group VIB metal oxide is present at between about 1 wt. % to about 10 wt. % of the enhanced-acidity modified red mud catalyst composition.
17. The method according to claim 1 , where the Group VIB metal oxide is present at about 5 wt. % of the enhanced-acidity modified red mud catalyst composition.
18. The method according to claim 1 , where conversion percentage of methane reaches up to about 35%.
19. The method according to claim 1 , where a molar ratio of methane:carbon dioxide:steam is about 3:1:2.
20. The method according to claim 1 , where produced H2 from the bi-reforming reaction is at least about 4 mol. % of produced products from the bi-reforming reaction for at least about 5 hours.
21. The method according to claim 1 , where the Brunauer-Emmett-Teller (BET) surface area of the modified red mud catalyst composition is between about 50 m2/g and about 90 m2/g.
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CN104627960B (en) | 2015-01-20 | 2016-06-29 | 河南理工大学 | A kind of method of changed red mud catalytic methane cracking hydrogen production |
CN105478120B (en) | 2015-11-18 | 2017-12-15 | 河南理工大学 | A kind of preparation method of red mud base Fe-series catalyst and its application in methane cracking hydrogen production |
CN107433200A (en) | 2017-06-28 | 2017-12-05 | 广西启明氢能源有限公司 | A kind of hydrous ethanol reformation hydrogen production solid catalyst |
CA3087818A1 (en) | 2018-01-10 | 2019-07-18 | Steen B. Iversen | Process for upgrading oxygen containing renewable oil |
US11534746B2 (en) | 2018-04-06 | 2022-12-27 | Utah State University | Red mud compositions and methods related thereto |
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2020
- 2020-01-28 US US16/775,167 patent/US11059030B1/en active Active
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2021
- 2021-01-28 WO PCT/US2021/015371 patent/WO2021154911A1/en active Application Filing
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Publication number | Priority date | Publication date | Assignee | Title |
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US11981615B1 (en) | 2023-03-14 | 2024-05-14 | King Fahd University Of Petroleum And Minerals | Method for chemically reducing carbon dioxide with red mud catalyst composition |
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