CN110237852B - Sulfate ion-containing titanium compound modified sulfur-tolerant shift catalyst and preparation method thereof - Google Patents
Sulfate ion-containing titanium compound modified sulfur-tolerant shift catalyst and preparation method thereof Download PDFInfo
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- CN110237852B CN110237852B CN201810194070.3A CN201810194070A CN110237852B CN 110237852 B CN110237852 B CN 110237852B CN 201810194070 A CN201810194070 A CN 201810194070A CN 110237852 B CN110237852 B CN 110237852B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 150000003609 titanium compounds Chemical class 0.000 title claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 58
- 239000011593 sulfur Substances 0.000 claims abstract description 57
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 57
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002243 precursor Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000007598 dipping method Methods 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 24
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 23
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 17
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 17
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 17
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 17
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 15
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- -1 lanthanide metal oxide Chemical class 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 8
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 8
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012702 metal oxide precursor Substances 0.000 claims 2
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 150000002602 lanthanoids Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 229910001868 water Inorganic materials 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 12
- 238000006703 hydration reaction Methods 0.000 abstract description 10
- 230000036571 hydration Effects 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 238000005470 impregnation Methods 0.000 description 17
- 238000005303 weighing Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010335 hydrothermal treatment Methods 0.000 description 12
- 229910002706 AlOOH Inorganic materials 0.000 description 10
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical group [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B2203/1052—Nickel or cobalt catalysts
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention relates to the field of catalysts used in water gas shift reaction, and discloses a sulfur-tolerant shift catalyst and a preparation method thereof. The method comprises the following steps: dipping a carrier in a solution containing a precursor of an active assistant and a titanium compound containing sulfate ions, and then sequentially drying and roasting; (2) and (2) dipping the product obtained in the step (1) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst. The catalyst provided by the invention has the advantages of simple preparation method, high activity and good hydration resistance.
Description
Technical Field
The invention relates to the field of catalysts used in water gas shift reaction, in particular to a sulfur-tolerant shift catalyst modified by a sulfate ion-containing titanium compound and a preparation method thereof.
Background
The sulfur-tolerant shift reaction is a reaction process which is necessary to be undergone in the fields of ammonia synthesis, methanol synthesis, hydrogen production and the like, and the sulfur-tolerant shift catalyst is an essential important role in the fields. With the development of residual oil and heavy oil hydrogenation and coal-to-hydrogen technologies in China, especially the rapid progress of coal chemical technologies in China in recent years, the demand of sulfur-tolerant shift catalysts is over 2500 tons every year.
The sulfur tolerant shift catalyst has Co, Mo, K, Mg, Al, RE and other metals as main components. The catalyst is classified into a high-temperature sulfur-tolerant shift catalyst and a low-temperature sulfur-tolerant shift catalyst according to the use temperature. The high-temperature sulfur-tolerant shift catalyst adopts magnesium aluminate spinel as a carrier, and Co and Mo are active components. The low-temperature sulfur-tolerant shift catalyst adopts part of active alumina of magnesium aluminate spinel as a carrier, active components of Co and Mo and an auxiliary agent of K.
The shift reaction is carried out under the condition of high-temperature water vapor, the temperature can reach 470 ℃, and the ratio of the water vapor to the dry gas can reach 2:1 at most. Under the working condition of high-temperature high-water vapor-dry gas ratio, the carrier can be hydrated, and structural phase change can occur, so that the catalyst is inactivated. Thus, in addition to catalytic activity, stability is also an important factor that should be considered during the development of a shift catalyst.
CN103447049A discloses a Co-Mo CO sulfur-tolerant shift catalyst and a preparation method thereof, the catalyst comprises a carrier and active components, wherein the carrier is an aluminum-titanium based surface layer magnesia-alumina spinel, and the active components are Co and Mo. The catalyst was spherical in appearance. The preparation method of the catalyst comprises the following steps: introducing titanium on alumina to prepare an aluminum-titanium composite carrier; uniformly introducing magnesium on the aluminum-titanium composite carrier, and roasting to convert the magnesium into aluminum-titanium-based surface layer magnesium aluminate spinel; active components are introduced into the aluminum-titanium based surface layer magnesium aluminate spinel carrier to prepare the catalyst. The catalyst has good low-temperature activity and low-sulfur activity, strong stability and long service life.
The prior method improves the catalytic activity and stability of the sulfur-tolerant shift catalyst to a certain extent, but still needs to be further improved.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art, and to provide a sulfur tolerant shift catalyst and a method for preparing the same, which can effectively improve the stability of the sulfur tolerant shift catalyst without reducing the activity.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a sulfur-tolerant shift catalyst comprising a carrier modified with a sulfate ion-containing titanium compound and a co-agent, and a metal active component supported on the carrier.
Preferably, the metal active component contains cobalt oxide and molybdenum oxide; more preferably, the content of the carrier is 64 to 90 wt% based on the total weight of the sulfur-tolerant shift catalyst; the content of the cobalt oxide is 2-6 wt%; the content of the molybdenum oxide is 5-10 wt%; the content of the active auxiliary agent is 2-15 wt%; the content of the sulfate ion-containing titanium compound is 2 to 6% by weight.
In a second aspect of the present invention, there is provided a process for producing a sulfur tolerant shift catalyst, the process comprising the steps of:
(1) dipping a carrier in a solution containing a precursor of an active assistant and a titanium compound component containing sulfate ions, and then sequentially drying and roasting;
(2) and (2) dipping the product obtained in the step (1) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst.
In a third aspect of the present invention, there is provided a process for producing a sulfur tolerant shift catalyst, comprising the steps of:
(1) impregnating a carrier in a solution containing a sulfate ion-containing titanium compound component, and then sequentially drying and roasting;
(2) dipping the product obtained in the step (1) in a solution containing an active auxiliary agent precursor, and then sequentially drying and roasting;
(3) and (3) dipping the product obtained in the step (2) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst.
In a fourth aspect of the present invention, there is provided a process for producing a sulfur tolerant shift catalyst, comprising the steps of:
(1) dipping a carrier in a solution containing an active auxiliary agent precursor, and then sequentially drying and roasting;
(2) dipping the product obtained in the step (1) in a solution containing a sulfate ion-containing titanium compound component, and then sequentially drying and roasting;
(3) and (3) dipping the product obtained in the step (2) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst.
In a fifth aspect of the invention, there is provided a sulfur tolerant shift catalyst prepared by the method described above.
The carrier of the catalyst provided by the invention is modified by the titanium compound containing sulfate ions and the active assistant, so that the hydration resistance stability of the catalyst is effectively improved, and the activity of the catalyst is not influenced. Preferably, the carrier is gradually modified by the titanium compound containing sulfate ions and the active component, so that the hydration resistance stability of the catalyst is further improved. In addition, compared with organic titanium and titanium tetrachloride, the titanium compound containing sulfate ions is soluble in water, the preparation process is simple, and the cost is low.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is an XRD chart of the sulfur tolerant shift catalyst obtained in example 1, comparative example 1 and comparative example 2 after hydrothermal treatment.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The inventor of the present invention found in the research process that one of the reasons for the low activity and stability of the prior art sulfur-tolerant shift catalyst is that the carrier is modified by using a water-insoluble titanium compound (e.g., organic titanium or titanium tetrachloride), and the carrier is modified by adding a co-agent after the water-insoluble titanium compound (e.g., organic titanium or titanium tetrachloride) is replaced by a titanium compound containing sulfate ions, on the one hand, the hydration resistance of the catalyst is effectively improved without reducing the activity; on the other hand, the preparation process is simplified, and the cost is reduced.
Based on the above findings, the first aspect of the present invention provides a sulfur tolerant shift catalyst comprising a carrier modified with a sulfate ion-containing titanium compound and a co-agent, and a metal active component supported on the carrier.
Preferably, the titanium compound containing sulfate ions is titanyl sulfate and/or titanium sulfate.
Preferably, the metal active components are cobalt oxide and molybdenum oxide.
In the sulfur tolerant shift catalyst provided by the present invention, preferably, the carrier is contained in an amount of 60 to 96 wt%, preferably 64 to 90 wt%, based on the total weight of the sulfur tolerant shift catalyst; the content of the cobalt oxide is 0.5-10 wt%, preferably 2-6 wt%; the content of the molybdenum oxide is 3 to 15 wt%, preferably 5 to 10 wt%; the content of the active auxiliary agent is 0.5-20 wt%, preferably 2-15 wt%; the content of the sulfate ion-containing titanium compound is 0.5 to 8% by weight, preferably 2 to 6% by weight.
The selection range of the carrier is wide, various carriers which are conventionally used in the field can be used in the invention, and in order to further improve the strength and the activity of the catalyst, the carrier is preferably Al2O3And (3) a carrier.
According to the present invention, the co-agent may be a co-agent conventionally used in the art for modifying a support, but in order to further improve the activity and stability of the sulfur tolerant shift catalyst, the co-agent is an alkaline earth metal oxide and/or a lanthanide metal oxide; the alkaline earth metal oxide is preferably magnesium oxide and/or calcium oxide, and the lanthanide metal oxide is preferably lanthanum oxide and/or cerium oxide
The method for producing the sulfur-tolerant shift catalyst of the present invention is not particularly limited, and any method can be used as long as the catalyst can be obtained.
In a second aspect of the present invention, there is provided a process for preparing a sulfur tolerant shift catalyst, the process comprising the steps of:
(1) dipping a carrier in a solution containing a precursor of an active assistant and a titanium compound component containing sulfate ions, and then sequentially drying and roasting;
(2) and (2) dipping the product obtained in the step (1) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst.
In a third aspect of the present invention, there is provided a process for preparing a preferred sulfur tolerant shift catalyst, the process comprising the steps of:
(1) dipping a carrier in a solution containing an active auxiliary agent precursor, and then sequentially drying and roasting;
(2) dipping the product obtained in the step (1) in a solution containing a sulfate ion-containing titanium compound component, and then sequentially drying and roasting;
(3) and (3) dipping the product obtained in the step (2) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst.
Under such preferable conditions, the stability of the obtained sulfur-tolerant shift catalyst can be further improved.
In a fourth aspect of the present invention, there is provided a more preferred method for preparing a sulfur tolerant shift catalyst, comprising the steps of:
(1) dipping a carrier in a solution of a titanium compound component containing sulfate ions, and then sequentially drying and roasting;
(2) dipping the product obtained in the step (1) in a solution containing an active auxiliary agent precursor, and then sequentially drying and roasting;
(3) and (3) dipping the product obtained in the step (2) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst.
Under such more preferable conditions, the stability of the obtained sulfur-tolerant shift catalyst can be further improved.
In each of the above-mentioned methods of the present invention, the solution used in each step is preferably an aqueous solution, for example, an aqueous solution containing a coagent precursor and a sulfate ion-containing titanium compound, an aqueous solution of a sulfate ion-containing titanium compound, an aqueous solution containing a coagent precursor, an aqueous solution containing a metal active component precursor. The amount of water used in each solution depends, inter alia, on the water absorption of the carrier, which is generally greater than 0.4, preferably greater than 0.5.
In each of the above processes of the present invention, the sulfate ion-containing titanium compound component used is preferably titanyl sulfate or titanium sulfate, which may further contain sulfuric acid, wherein the sulfuric acid content may be 0.1 to 30% by weight.
In the above methods of the present invention, the morphology of the carrier is not particularly limited, and may be those of various alumina carriers having oxide modification known in the art, such as spherical, strip, clover type and dentate sphere, and the present invention is preferably spherical.
In each of the above methods of the present invention, the metal active component is preferably cobalt oxide or molybdenum oxide, and the selection of the precursor thereof is not particularly limited as long as a precursor impregnation solution can be prepared, and for example, the cobalt oxide precursor may be at least one selected from cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt hydroxide; the molybdenum oxide precursor is selected from at least one of ammonium tetramolybdate, ammonium heptamolybdate and potassium molybdate.
In each of the above-described methods of the present invention, preferably, the carrier, the sulfate ion-containing titanium compound, the co-agent precursor, the cobalt oxide precursor, and the molybdenum oxide precursor are used in amounts such that the sulfur-tolerant shift catalyst obtained contains the carrier in an amount of 60 to 96 wt%, preferably 64 to 90 wt%, based on the total weight of the sulfur-tolerant shift catalyst; the content of the cobalt oxide is 0.5-10 wt%, preferably 2-6 wt%; the content of the molybdenum oxide is 3 to 15 wt%, preferably 5 to 10 wt%; the content of the active auxiliary agent is 0.5-20 wt%, preferably 2-15 wt%; the content of the sulfate ion-containing titanium compound is 0.5 to 8% by weight, preferably 2 to 6% by weight.
In each of the above methods of the present invention, the coagent may be a coagent conventionally used in the art for modifying a support, but in order to further improve the activity and stability of the sulfur-tolerant shift catalyst, the coagent is preferably an alkaline earth metal oxide and/or a lanthanide metal oxide, wherein the alkaline earth metal oxide is preferably magnesium oxide and/or calcium oxide, and the lanthanide metal oxide is preferably lanthanum oxide and/or cerium oxide; thus, the magnesium oxide precursor is selected from at least one of magnesium nitrate, magnesium acetate and magnesium chloride; the calcium oxide precursor is selected from at least one of calcium nitrate, calcium acetate and calcium chloride; the lanthanum oxide precursor is selected from at least one of lanthanum nitrate, lanthanum acetate and lanthanum chloride; the cerium oxide is at least one selected from cerium nitrate, cerium acetate and cerium chloride.
In each of the above processes of the present invention, in order to facilitate uniform dispersion of the sulfate ion-containing titanium compound, the coagent, and the active ingredient on the support, the impregnation conditions in each of the above processes may be the same or different, and each independently comprises: the dipping temperature is 25-50 ℃, and the dipping time is 2-12 h.
In each of the above methods of the present invention, the drying conditions in each step may be the same or different, and preferably, the drying conditions in each step independently include: the temperature is 100 ℃ and 200 ℃, and the time is 4-30 hours.
In each of the above methods of the present invention, the calcination conditions in each step may be those conventional in the art, and the calcination conditions in each step may be the same or different, preferably, the calcination conditions in each step independently include: the temperature is 400 ℃ and 800 ℃, and the time is 2-8 hours.
The sulfur tolerant shift catalyst of the present invention as described above and the sulfur tolerant shift catalyst obtained by the above preparation method can be used in water gas shift reaction, and specifically, the method for use in water gas shift reaction comprises: at H2S/H2The sulfur-tolerant shift catalyst is subjected to sulfurization treatment in a mixed atmosphere, then the water gas is contacted with the sulfur-tolerant shift catalyst subjected to sulfurization treatment, and the water gas shift reaction is carried out under the water gas shift reaction condition, wherein the sulfur-tolerant shift catalyst is the sulfur-tolerant shift catalyst prepared by the method provided by the invention.
According to the present invention, the conditions of the vulcanization treatment may include: the vulcanization temperature is 200 ℃ and 500 ℃, H2S/H2The sulfur content in the mixed atmosphere of (A) is 0.3-5 vol%, H2S/H2The volume space velocity of the mixed gas is 100-3000h-1The vulcanizing time is 5-10 h.
In a preferred embodiment, the conditions of the vulcanization process include: the vulcanization temperature is 450 ℃, H2S/H2In a mixed atmosphere of (A) has a sulfur content of 3 vol.%, H2S/H2The volume space velocity of the mixed gas is 3000h-1The vulcanization time is 5 h.
The water gas shift reaction conditions are not particularly limited in the present invention and may be conventionally selected in the art, for example, the water gas shift reaction conditions may include: the reaction is carried out in a fixed bed reactor, the reaction temperature is 150-: 0.4-1.5, raw material dry gas composition: 30-90% by volume of CO, 2-6% by volume of N25-20% by volume of CO20.05 to 2% by volume of H2S and the balance of H2The volume space velocity of the raw material dry gas is 1000-20000h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples,
the composition of the sulfur-tolerant shift catalyst was determined by a ZSX Primus type II X-ray fluorescence spectrometer from Rigaku corporation;
water gas shift ratio (%) - (C1-C2)/[ C1(1+ C2) ] × 100%
In the formula: c1 is the CO content in the raw material gas,% (dry basis);
c2 is the CO content,% (dry basis) in the product gas.
The method for measuring the hydration resistance of the catalyst comprises the following steps: and (3) putting the prepared sulfur-resistant conversion catalyst into a hydrothermal kettle, adding deionized water to the hydrothermal kettle to submerge the catalyst, carrying out hydrothermal treatment for 24 hours under a severe condition, namely 200 ℃, and testing the hydration condition of the catalyst alumina through XRD (X-ray diffraction) to characterize the hydration-resistant stability of the catalyst. Wherein, partial alumina after the catalyst is hydrothermally treated is subjected to hydration reaction to generate AlOOH, the smaller the peak of the AlOOH with a characteristic peak of 14.3 degrees is, the stronger the hydration resistance is shown,
the titanyl sulfate is industrial grade titanyl sulfate, and the sulfuric acid content is less than or equal to 7 weight percent.
The particle size of the alumina ball carrier is 3-5 mm.
Example 1
This example illustrates a sulfur tolerant shift catalyst and a method for preparing the same
Weighing 1.2g of industrial-grade titanyl sulfate, 6.5g of magnesium nitrate and 0.6g of lanthanum nitrate, dissolving in deionized water, carrying out isochoric impregnation on 15.5g of alumina balls, drying at room temperature, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 3h to obtain the modified carrier.
Weighing 2.0g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate by using ammonia water, adding 1.9g of citric acid and 2.5g of cobalt acetate, stirring and dissolving to prepare a co-impregnation solution, carrying out isochoric impregnation, drying at room temperature, drying at 12 ℃ for 12h, and roasting at 500 ℃ for 3h to obtain the sulfur-resistant shift catalyst.
The catalyst comprises the following components: 77.5 wt.% support, 3.2 wt.% Co2O38.0% by weight of MoO3MgO in an amount of 5.1 wt%, La in an amount of 0.7 wt%2O3And 5.5 wt% titanyl sulfate.
XRD of the obtained sulfur tolerant shift catalyst after hydrothermal treatment is shown in fig. 1, and peak heights are shown in table 1.
Comparative example 1
Comparative example to illustrate a reference Sulfur tolerant shift catalyst and method of making
A sulfur tolerant shift catalyst was prepared by the method of example 1 except that technical grade titanyl sulfate was not added and the weight thereof was supplemented to the support.
The catalyst comprises the following components: 83 wt.% carrier, 3.2 wt.% Co2O38.0% by weight of MoO35.1 wt.% MgO and 0.7 wt.% La2O3。
XRD of the obtained sulfur tolerant shift catalyst after hydrothermal treatment is shown in fig. 1, and peak heights are shown in table 1.
Comparative example 2
Comparative example to illustrate a reference Sulfur tolerant shift catalyst and method of making
Weighing 2.1g of tetrabutyl titanate, dissolving in ethanol, carrying out isometric impregnation on 15.5g of alumina balls, drying at room temperature, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 3 h.
Weighing 6.5g of magnesium nitrate and 0.6g of lanthanum nitrate, dissolving in deionized water, carrying out second equal-volume impregnation, drying at room temperature, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 3 h.
Weighing 2.0g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate by using ammonia water, adding 1.9g of citric acid and 2.5g of cobalt acetate, stirring and dissolving to prepare a co-impregnation solution, carrying out isochoric impregnation, drying at room temperature, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 3h to obtain the sulfur-resistant shift catalyst.
The catalyst comprises the following components: 80.5 wt.% carrier, 3.2 wt.% Co2O38.0% by weight of MoO35.1 wt% MgO, 0.7 wt% La2O3And 2.5 wt% TiO2。
XRD of the obtained sulfur tolerant shift catalyst after hydrothermal treatment is shown in fig. 1, and peak heights are shown in table 1.
Comparative example 3
Comparative example to illustrate a reference Sulfur tolerant shift catalyst and method of making
The procedure of comparative example 2 was followed except that titanium tetrachloride in an amount equimolar to titanyl sulfate was weighed, dissolved in acetone, isovolumetrically impregnated on 15.5g of alumina spheres, air-dried at room temperature, dried at 120 ℃ for 12 hours, and calcined at 500 ℃ for 3 hours.
The catalyst comprises the following components: 80.5 wt.% carrier, 3.2 wt.% Co2O38.0% by weight of MoO35.1 wt% MgO, 0.7 wt% La2O3And 2.5 wt% TiO2。
The AlOOH height of the catalyst after hydrothermal treatment at 200 ℃ for 24h is shown in Table 1.
Example 2
This example illustrates a sulfur tolerant shift catalyst and a method for preparing the same
Weighing 0.45g of industrial-grade titanyl sulfate, 7.6g of magnesium nitrate and 1.3g of lanthanum nitrate, dissolving in deionized water, carrying out isochoric impregnation on 16.7g of alumina balls, drying at room temperature, drying at 100 ℃ for 8h, and roasting at 400 ℃ for 5h to obtain the modified carrier.
Weighing 1.25g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate by using ammonia water, adding 1.8g of citric acid and 0.63g of basic cobalt carbonate, stirring and dissolving to prepare a co-soaking solution, carrying out isochoric soaking, drying at room temperature for 10h at 150 ℃, and roasting at 600 ℃ for 3h to obtain the sulfur-resistant shift catalyst.
The catalyst comprises the following components: 83.5 wt.% support, 2 wt.% Co2O35% by weight of MoO36% by weight of MgO and 1.5% by weight of La2O3And 2 wt% titanyl sulfate.
The AlOOH height of the catalyst after hydrothermal treatment at 200 ℃ for 24h is shown in Table 1.
Example 3
This example illustrates a sulfur tolerant shift catalyst and a method for preparing the same
Weighing 1.36g of industrial-grade titanyl sulfate, 7.0g of magnesium nitrate and 0.5g of cerium nitrate, dissolving in deionized water, carrying out isochoric impregnation on 14.3g of alumina balls, drying at room temperature, drying at 180 ℃ for 6h, and roasting at 800 ℃ for 2h to obtain the modified carrier.
Weighing 2.5g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate by using ammonia water, adding 3.6g of citric acid and 4.7g of cobalt acetate, stirring and dissolving to prepare a co-impregnation solution, carrying out isochoric impregnation, drying at room temperature, drying at 200 ℃ for 12h, and roasting at 500 ℃ for 3h to obtain the sulfur-resistant shift catalyst.
The catalyst comprises the following components: 71.5 wt.% support, 6 wt.% Co2O310% by weight of MoO35.5% by weight of MgO and 1% by weight of CeO2And 6 wt% titanyl sulfate.
The AlOOH height of the catalyst after hydrothermal treatment at 200 ℃ for 24h is shown in Table 1.
Example 4
This example illustrates a sulfur tolerant shift catalyst and a method for preparing the same
A sulfur tolerant shift catalyst was prepared by the method of example 1 except that technical grade titanyl sulfate was used in an amount of 1.75 g.
The catalyst comprises the following components: 75.0 wt.% carrier, 3.2 wt.% Co2O38.0% by weight of MoO35.1 wt% MgO, 0.7 wt% La2O3And 8 wt% titanyl sulfate.
The AlOOH height of the catalyst after hydrothermal treatment at 200 ℃ for 24h is shown in Table 1.
Example 5
This example illustrates a sulfur tolerant shift catalyst and a method for preparing the same
Weighing 1.2g of industrial-grade titanyl sulfate, dissolving in deionized water, carrying out equal-volume impregnation on 15.5g of alumina balls, drying at room temperature, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 3 h.
Weighing 6.5g of magnesium nitrate and 0.6g of lanthanum nitrate, dissolving in deionized water, carrying out second equal-volume impregnation, drying at room temperature, drying at 120 ℃ for 4h, and roasting at 500 ℃ for 3 h.
Weighing 2.0g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate by using ammonia water, adding 1.9g of citric acid and 2.5g of cobalt acetate, stirring and dissolving to prepare a co-soaking solution, carrying out third equal-volume soaking, drying at room temperature for 24 hours after drying, and roasting at 500 ℃ for 3 hours.
The catalyst comprises the following components: 77.5 wt.% support, 3.2 wt.% Co2O38.0 weight％MoO35.1 wt% MgO, 0.7 wt% La2O3And 5.5 wt% titanyl sulfate.
The AlOOH height of the catalyst after hydrothermal treatment at 200 ℃ for 24h is shown in Table 1.
Example 6
This example illustrates a sulfur tolerant shift catalyst and a method for preparing the same
Weighing 6.5g of magnesium nitrate and 0.6g of lanthanum nitrate, dissolving in deionized water, carrying out equal-volume impregnation on 15.5g of alumina balls, drying at room temperature, drying for 12h at 120 ℃, and roasting for 3h at 500 ℃.
Weighing 1.2g of industrial-grade titanyl sulfate, dissolving in deionized water, carrying out second equal-volume impregnation, drying at room temperature, drying at 120 ℃ for 4h, and roasting at 500 ℃ for 3 h.
Weighing 2.0g of ammonium heptamolybdate, dissolving the ammonium heptamolybdate by using ammonia water, adding 1.9g of citric acid and 2.5g of cobalt acetate, stirring and dissolving to prepare a co-soaking solution, carrying out third equal-volume soaking, drying at room temperature for 24 hours after drying, and roasting at 500 ℃ for 3 hours.
The catalyst comprises the following components: 77.5 wt.% support, 3.2 wt.% Co2O38.0% by weight of MoO35.1 wt% MgO, 0.7 wt% La2O3And 5.5 wt% titanyl sulfate.
The AlOOH height of the catalyst after hydrothermal treatment at 200 ℃ for 24h is shown in Table 1.
Example 7
This example illustrates a sulfur tolerant shift catalyst and a method for preparing the same
The procedure is as in example 1, except that 0.04g of 98% H are added to the aqueous solution2SO4Replacing titanyl sulfate with titanium sulfate with equal mass to obtain the sulfur-resistant shift catalyst.
The catalyst comprises the following components: 77.5 wt.% support, 3.2 wt.% Co2O38.0% by weight of MoO35.1 wt% MgO, 0.7 wt% La2O3And 5.5 wt% titanium sulfate.
The AlOOH height of the catalyst after hydrothermal treatment at 200 ℃ for 24h is shown in Table 1.
Test example 1
Evaluation of the sulfur tolerant shift catalysts of examples 1 to 7 and comparative examples 1 to 3 provided by the present invention
The reaction was carried out on a microreaction evaluating apparatus. The packing amount of the 20-40 mesh catalyst is 1 g.
1. Catalyst sulfidation
The catalyst is mixed with a sulfiding gas (H)2S and H2In which H is2The volume content of S is 3 percent) is contacted for 5 hours at the vulcanization temperature of 450 ℃ for vulcanization. Obtaining the sulfuration catalyst.
2. Catalyst evaluation
And contacting the sulfurized catalyst serving as a fresh agent with feed gas to evaluate the catalyst.
The conditions are as follows: 450 ℃, 0.1MPa, the raw material gas composition (v/v) is H2O/CO/N2/H2/H2S＝49.89％/40.76％/4.33％/4.86％/0.15％。
The results are shown in Table 1.
TABLE 1
| Catalyst and process for preparing same | Activity (CO conversion,%) | Peak height of AlOOH |
| Example 1 | 41 | 535 |
| Comparative example 1 | 39 | 1517 |
| Comparative example 2 | 40 | 815 |
| Comparative example 3 | 39 | 850 |
| Example 2 | 31 | 585 |
| Example 3 | 52 | 531 |
| Example 4 | 40 | 519 |
| Example 5 | 41 | 432 |
| Example 6 | 41 | 480 |
| Example 7 | 40 | 541 |
As can be seen from the examples and the results in table 1, the catalyst provided by the present invention has significantly improved hydration resistance without reducing its activity. In addition, the method for preparing the sulfur-tolerant shift catalyst provided by the invention uses the sulfate ion-containing titanium compound which is water-soluble, has high safety, can be used for jointly impregnating a carrier with an active assistant, has a simple preparation process, and is very suitable for industrial production.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. A sulfur tolerant shift catalyst comprises a carrier and a metal active component loaded on the carrier, and is characterized in that the carrier is modified with a titanium compound containing sulfate ions and a coagent;
wherein the carrier is Al2O3A carrier;
wherein, the sulfate ion-containing titanium compound is titanyl sulfate and/or titanium sulfate;
wherein the active assistant is alkaline earth metal oxide and/or lanthanide metal oxide.
2. The sulfur-tolerant shift catalyst of claim 1, wherein the metal active component comprises cobalt oxide and molybdenum oxide.
3. The sulfur-tolerant shift catalyst of claim 2, wherein the support is present in an amount of 60 to 96 wt.%, based on the total weight of the sulfur-tolerant shift catalyst; the content of the cobalt oxide is 0.5-10 wt%; the content of the molybdenum oxide is 3-15 wt%; the content of the active auxiliary agent is 0.5-20 wt%; the content of the sulfate ion-containing titanium compound is 0.5 to 8% by weight.
4. The sulfur-tolerant shift catalyst of claim 3, wherein the support is present in an amount of 64-90 wt.%; the content of the cobalt oxide is 2-6 wt%; the content of the molybdenum oxide is 5-10 wt%; the content of the active auxiliary agent is 2-15 wt%; the content of the sulfate ion-containing titanium compound is 2 to 6% by weight.
5. The sulfur-tolerant shift catalyst according to claim 1, wherein the alkaline earth metal oxide is magnesium oxide and/or calcium oxide, and the lanthanoid metal oxide is lanthanum oxide and/or cerium oxide.
6. A method of making a sulfur tolerant shift catalyst, comprising the steps of:
(1) dipping a carrier in a solution containing a precursor of an active assistant and a titanium compound component containing sulfate ions, and then sequentially drying and roasting;
(2) dipping the product obtained in the step (1) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst;
wherein the carrier is Al2O3A carrier;
wherein, the sulfate ion-containing titanium compound is titanyl sulfate and/or titanium sulfate;
wherein the active assistant is alkaline earth metal oxide and/or lanthanide metal oxide.
7. A method of making a sulfur tolerant shift catalyst, comprising the steps of:
(1) impregnating a carrier in a solution containing a sulfate ion-containing titanium compound component, and then sequentially drying and roasting;
(2) dipping the product obtained in the step (1) in a solution containing an active auxiliary agent precursor, and then sequentially drying and roasting;
(3) dipping the product obtained in the step (2) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst;
wherein the carrier is Al2O3A carrier;
wherein, the sulfate ion-containing titanium compound is titanyl sulfate and/or titanium sulfate;
wherein the active assistant is alkaline earth metal oxide and/or lanthanide metal oxide.
8. A method of making a sulfur tolerant shift catalyst, comprising the steps of:
(1) dipping a carrier in a solution containing an active auxiliary agent precursor, and then sequentially drying and roasting;
(2) dipping the product obtained in the step (1) in a solution containing a sulfate ion-containing titanium compound component, and then sequentially drying and roasting;
(3) dipping the product obtained in the step (2) in a solution containing a metal active component precursor, and then sequentially drying and roasting to obtain the sulfur-resistant shift catalyst;
wherein the carrier is Al2O3A carrier;
wherein, the sulfate ion-containing titanium compound is titanyl sulfate and/or titanium sulfate;
wherein the active assistant is alkaline earth metal oxide and/or lanthanide metal oxide.
9. The method of any of claims 6-8, wherein the metal active component comprises cobalt oxide and molybdenum oxide.
10. The process of claim 9, wherein the support, the sulfate ion-containing titanium compound, the co-agent precursor, the cobalt oxide precursor, and the molybdenum oxide precursor are used in amounts to produce a sulfur-tolerant shift catalyst having a support content of from 60 to 96 wt%, based on the total weight of the sulfur-tolerant shift catalyst; the content of the cobalt oxide is 0.5-10 wt%; the content of the molybdenum oxide is 3-15 wt%; the content of the active auxiliary agent is 0.5-20 wt%; the content of the sulfate ion-containing titanium compound is 0.5 to 8% by weight.
11. The process of claim 10, wherein the support, the sulfate ion-containing titanium compound, the co-agent precursor, the cobalt oxide precursor, and the molybdenum oxide precursor are used in amounts to produce a sulfur-tolerant shift catalyst having a support content of from 64 to 90 wt.%, based on the total weight of the sulfur-tolerant shift catalyst; the content of the cobalt oxide is 2-6 wt%; the content of the molybdenum oxide is 5-10 wt%; the content of the active auxiliary agent is 2-15 wt%; the content of the sulfate ion-containing titanium compound is 2 to 6% by weight.
12. The method of claim 9, wherein the cobalt oxide precursor is selected from at least one of cobalt nitrate, cobalt acetate, cobalt hydroxycarbonate, and cobalt hydroxide; the molybdenum oxide precursor is selected from at least one of ammonium tetramolybdate, ammonium heptamolybdate and potassium molybdate.
13. The method of claim 9, wherein the alkaline earth metal oxide precursor is an oxide precursor and/or a calcium oxide precursor, and the lanthanide metal oxide precursor is a lanthanum oxide precursor and/or a cerium oxide precursor; the magnesium oxide precursor is selected from at least one of magnesium nitrate, magnesium acetate and magnesium chloride; the calcium oxide precursor is selected from at least one of calcium nitrate, calcium acetate and calcium chloride; the lanthanum oxide precursor is selected from at least one of lanthanum nitrate, lanthanum acetate and lanthanum chloride; the cerium oxide is at least one selected from cerium nitrate, cerium acetate and cerium chloride.
14. The method of any of claims 6-8, wherein the drying conditions comprise: the temperature is 100-200 ℃ and the time is 4-30 hours; the roasting conditions include: the temperature is 400 ℃ and 800 ℃, and the time is 2-8 hours.
15. The process as claimed in any one of claims 6 to 8, wherein the sulfate ion-containing titanium compound component further contains sulfuric acid in an amount of 0.1 to 30% by weight, based on the weight of the sulfate ion-containing titanium compound.
16. A sulfur tolerant shift catalyst prepared by the process of any one of claims 6 to 15.
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| CN107398262A (en) * | 2016-05-19 | 2017-11-28 | 神华集团有限责任公司 | Catalyst for methanation in presence of sulfur and preparation method thereof and magnesium aluminate spinel complex carrier and preparation method thereof |
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| US5336651A (en) * | 1990-05-03 | 1994-08-09 | Sakai Chemical Industry Co., Ltd. | Catalysts and methods for denitrization |
| CN1241452A (en) * | 1998-07-15 | 2000-01-19 | 中国石化齐鲁石油化工公司 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
| JP2000135440A (en) * | 1998-10-30 | 2000-05-16 | Catalysts & Chem Ind Co Ltd | Hydrogenation catalyst and its production |
| CN102049257A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst for simultaneously reducing SO2 and NO with CO as well as preparation and application of catalyst |
| CN107398262A (en) * | 2016-05-19 | 2017-11-28 | 神华集团有限责任公司 | Catalyst for methanation in presence of sulfur and preparation method thereof and magnesium aluminate spinel complex carrier and preparation method thereof |
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