CN108940381A - A kind of tetragonal phase zirconium oxide carrier, the catalyst containing the carrier and its application in the reaction of methane dry reforming - Google Patents
A kind of tetragonal phase zirconium oxide carrier, the catalyst containing the carrier and its application in the reaction of methane dry reforming Download PDFInfo
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- CN108940381A CN108940381A CN201710389661.1A CN201710389661A CN108940381A CN 108940381 A CN108940381 A CN 108940381A CN 201710389661 A CN201710389661 A CN 201710389661A CN 108940381 A CN108940381 A CN 108940381A
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- carrier
- zro
- catalyst
- metal
- metal active
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002407 reforming Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 title claims description 97
- 238000006243 chemical reaction Methods 0.000 title claims description 38
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 title description 3
- 239000002184 metal Substances 0.000 claims abstract description 85
- 229910052751 metal Inorganic materials 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 53
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 40
- 239000000470 constituent Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 230000001376 precipitating effect Effects 0.000 claims description 18
- 229910002651 NO3 Inorganic materials 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 238000002803 maceration Methods 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000011240 wet gel Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000009938 salting Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 2
- 229910019020 PtO2 Inorganic materials 0.000 claims description 2
- 229910019603 Rh2O3 Inorganic materials 0.000 claims description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 2
- 229910003101 Y(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 229910006219 ZrO(NO3)2·2H2O Inorganic materials 0.000 claims description 2
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 2
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910000458 iridium tetroxide Inorganic materials 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 2
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 claims description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 238000004939 coking Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 238000006057 reforming reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940124274 edetate disodium Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/393—
-
- B01J35/394—
-
- B01J35/40—
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous 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
- C01B2203/10—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
-
- 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
- C01B2203/1058—Nickel 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
Abstract
The present invention provides a kind of tetragonal phase ZrO2Carrier, wherein including ZrO2With the modified additive selected from alkaline-earth metal and/or rare-earth oxide, in terms of total weight of carrier, the content of modified additive is 0.1~10 weight %, the ZrO of tetragonal phase structure occurs at 30.30 ° and 35.18 ° of peak positions in the XRD spectra of the carrier2Characteristic peak.ZrO provided by the invention2Carrier has pure tetragonal phase structure, while having biggish specific surface area, the tetragonal phase ZrO obtained in this way2Carrier loaded active metal can remarkably promote the evenly dispersed of active metal, so as to obtain lesser metal particle size.When prepared carrier loaded active metal is reacted for catalytic methane dry reforming in the process of the present invention, catalytic activity is significantly improved, and coking resistivity is significantly enhanced, being capable of long period continuous and steady operation 450 hours or more non-inactivations.
Description
Technical field
It is reacted the present invention relates to a kind of tetragonal phase zirconium oxide carrier, the catalyst containing the carrier and its in methane dry reforming
In application.
Background technique
Since methane dry reforming reacts synthesis gas H obtained2/ CO odds ratio methane steam reforming and methane portion oxidation
Synthesis gas H obtained2/ CO ratio is lower, is suitable for the raw material of F- T synthesis or methanol-fueled CLC, thus methane dry reforming is reacted
Synthesis gas is prepared as the important directions of methyl hydride catalyzed conversion by common concern.
From the point of view of thermodynamics, which is the endothermic reaction, and only reacting at high temperature can just go on smoothly, however institute
It is easy inactivation at high temperature with catalyst, which prevent the paces of methane dry reforming reaction industry application.Therefore, seek active height
Good catalyst is the important directions of methane dry reforming repercussion study with stability.
Domestic and foreign scholars carry out to by performance of the catalyst of active component in the reaction of methane dry reforming of different metal
Research.In the catalyst system reported, Ni base catalyst is concerned due to cheap, active high, however should
There is also coking deactivation phenomenons under the high temperature conditions for catalyst.Some researchers think that carrier is to methane dry reforming catalytic reaction
The activity and coking resistivity of agent have important influence, and the reaction of methane dry reforming can be divided into two steps on Ni base catalyst: firstly,
CH4Absorption is cracked to form CH on active metalxSpecies and H species, while CO2The Dissociative on carrier, the oxygen species of generation
By CHxOxidation, and the carbon deposit of catalyst depends on CHxThe oxidation supersession rate of species.
ZrO2It is metal oxide a kind of while that there is acid-base property and oxidation-reduction quality, due to the unique physics in its surface
Chemical property makes with ZrO2Research for carrier loaded active metal for the reaction of methane dry reforming is increasing.ZrO2Have three
The different crystal phase structure of kind: monoclinic phase, tetragonal phase and cubic phase.For the reaction of methane dry reforming, tetragonal phase ZrO2It is more suitable
In as catalyst carrier (J.M.Wei, Stud.Surf.Sci. Catal.2000,130,3687-3692).However, in low temperature
Lower monoclinic phase is ZrO2Stable crystalline phase.Therefore, the ZrO with tetragonal phase structure is prepared2Carrier, while making prepared
Tetragonal phase ZrO2Carrier has biggish specific surface area to improve the dispersibility of active component and stability and also just become people
The most important thing of research.
Summary of the invention
The object of the present invention is to provide a kind of tetragonal phase ZrO2Carrier and preparation method thereof.
The present invention also provides one kind to contain above-mentioned tetragonal phase ZrO2Loaded catalyst of carrier and preparation method thereof.
The present invention also provides above-mentioned catalyst to prepare the application in synthesis gas in methane dry reforming.
A kind of ZrO of tetragonal phase structure provided by the invention2Carrier, wherein including ZrO2With selected from alkaline-earth metal and/or dilute
The modified additive of soil metal oxide, in terms of total weight of carrier, the content of modified additive is 0.1~10 weight %, the carrier
XRD spectra in there is the ZrO of tetragonal phase structure at 30.30 ° and 35.18 ° of peak positions2Characteristic peak.
Tetragonal phase ZrO provided by the invention2The preparation method of carrier the following steps are included:
(1) solution containing zirconates and modified additive precursor salt is prepared, and prepares ammonia spirit as precipitating reagent；
(2) salting liquid and precipitating reagent are added dropwise in precipitation tank simultaneously and carry out precipitation reaction；
(3) gained wet gel is washed, dry, roasting obtains the ZrO of tetragonal phase structure2。
Loaded catalyst provided by the invention, including carrier and metal active constituent, wherein carrier is above-mentioned tetragonal phase
The ZrO of structure2Carrier, metal active constituent is selected from I B and VIII family metal oxide, on the basis of overall catalyst weight, with metal member
Element meter, the content of the metal active constituent are 2~20 weight %.
The present invention also provides a kind of preparation methods of loaded catalyst, this method comprises: by above method preparation
Tetragonal phase ZrO2Carrier is impregnated with maceration extract, finally dry, roasting, wherein the maceration extract contains metal active constituent
Water soluble compound and complexing agent.
ZrO provided by the invention2The preparation method of carrier when prepared by carrier due to having alkaline-earth metal or rare earth metal to help
The addition of agent, thus the available ZrO with pure tetragonal phase structure2；Simultaneously as to precipitating gained wet gel using organic
Solvent wash and the modes such as dry are dried using freeze-drying, vacuum drying or in slumpability atmosphere, thus
Prepared ZrO2Carrier has biggish specific surface area, the tetragonal phase ZrO obtained in this way2Carrier loaded active metal can
To remarkably promote the evenly dispersed of active metal, so as to obtain lesser metal particle size.It is made in the process of the present invention
When standby carrier loaded active metal is reacted for catalytic methane dry reforming, compared with previous similar catalyst, catalytic activity
It significantly improves, coking resistivity is significantly enhanced, being capable of long period continuous and steady operation 450 hours or more non-inactivations.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is ZrO made from the embodiment of the present invention 12ZrO made from carrier and comparative example 12The XRD spectrogram of carrier.
Fig. 2 is the reactivity worth of the resulting catalyst methane dry reforming of embodiment 1 reaction.
Fig. 3 is the reactivity worth of the resulting catalyst methane dry reforming of comparative example 1 reaction.
Specific embodiment
A kind of ZrO of tetragonal phase structure provided by the invention2Carrier, wherein including ZrO2With selected from alkaline-earth metal and/or dilute
The modified additive of soil metal oxide, in terms of total weight of carrier, the content of modified additive is 0.1~10 weight %, preferably
0.5~5 weight %.
There is the ZrO of tetragonal phase structure in 30.30 ° and 35.18 ° of peak positions in the XRD spectra of the carrier2Feature
Peak.
0.3~0.7cm of Kong Rongwei of the carrier3/ g, preferably 0.5~0.7cm3/ g, specific surface area are 100~150 m2/
G, preferably 125~150m2/ g, average pore size are 6~11nm, preferably 7~9nm.
The modified additive is selected from alkaline-earth metal or rare-earth oxide, such as MgO, CaO, SrO, BaO, CeO2、
La2O3、Sm2O3And Y2O3One of or a variety of, preferably MgO, CaO, CeO2、La2O3And Y2O3One of or it is a variety of, into one
Step is preferably MgO, La2O3Or Y2O3。
Tetragonal phase ZrO provided by the invention2The preparation method of carrier the following steps are included:
(1) solution containing zirconates and modified additive precursor salt is prepared, and prepares ammonia spirit as precipitating reagent；
(2) salting liquid and precipitating reagent are added dropwise in precipitation tank simultaneously and carry out precipitation reaction；
(3) gained wet gel is washed, dry, roasting obtains the ZrO of pure tetragonal phase structure2。
According to the method for the present invention, it is counted by oxide and on the basis of resulting vehicle, the dosage of the modified additive is 0.1
~10 weight %, preferably 0.5~5 weight %.
According to the present invention, the zirconates is water soluble salt, can be selected from ZrO (NO3)2·2H2O、 Zr(NO3)4·5H2O or
ZrOCl2·8H2O。
The modified additive precursor salt can be selected from Mg (NO3)2·6H2O、Ca(NO3)2·6H2O、 Sr(NO3)2·6H2O、
Ce(NO3)3·6H2O、La(NO3)3·9H2O、Y(NO3)3·6H2O and Sm (NO3)3·6H2One of O or a variety of, preferably
Mg(NO3)2·6H2O、Ca(NO3)2·6H2O、Ce(NO3)3·6H2O、La(NO3)3·9H2O and Y (NO3)3·6H2One of O
Or a variety of, further preferably Mg (NO3)2·6H2O、La(NO3)3·9H2O or Y (NO3)3·6H2O, the precursor salt is 400
Oxide can be changed under~1000 DEG C of roasting condition.
According to the present invention, for above-mentioned preparation method in the process for preparation of step (1), the preparation mixing salt solution is by one
Quantitative zirconates and alkaline-earth metal or rare earth metal soluble salt is dissolved in a certain amount of deionized water, with the concentration of zirconates for 0.05
On the basis of the range of~0.5mol/L, required water is calculated；The preparation precipitating reagent is to prepare ammonia concn as 0.5~15 weight
Measure the ammonia spirit of %, preferably 0.5~5 weight %.
According to the present invention, above-mentioned preparation method is in the precipitation process of step (2), with vigorous stirring, by the mixing
Salting liquid and precipitating reagent are instilled in precipitation tank simultaneously in a manner of co-precipitation, while the pH value for controlling precipitation solution is 7~13,
Preferably 8~12.
According to the present invention, above-mentioned preparation method in the washing process of step (3), use by the sediment that step (2) are obtained
Deionized water is washed, and when filtrate pH value is neutral, then can also optionally be washed with organic solvent；Institute
Stating organic solvent is one of methanol, ethyl alcohol, propyl alcohol, butanol, ether and acetone or a variety of, preferably methanol, ethyl alcohol or third
Ketone.The volume ratio of the organic solvent and wet gel is 1~10:1, preferably 3~6:1 when washing every time, is washed 1~6 time.Again
The wet gel that washing obtains is dried, drying mode can be for freeze-drying, vacuum drying or in slumpability atmosphere
It is dry.Sample after drying is placed into Muffle furnace and is roasted 1~10 hour for 600~1000 DEG C, pure four directions can be directly obtained
The ZrO of phase structure2。
Loaded catalyst provided by the invention, including carrier and metal active constituent, wherein carrier is above-mentioned tetragonal phase
The ZrO of structure2Carrier, metal active constituent are selected from least one of I B and VIII family metal oxide, are with overall catalyst weight
Benchmark, with elemental metal, the content of the metal active constituent is 2~20 weight %.
The metal active constituent is selected from I B and VIII family metal oxide, preferably CuO, Co3O4、NiO、 Fe2O3、PtO2、
Rh2O3And IrO4One of or a variety of, more preferably Co3O4And/or NiO.
The content of the metal active constituent is preferably 3~15 weight %, further preferably 4~12 weight %.
The metal active component dispersion of the catalyst is 3~12%, preferably 6~11%.
The metal active constituent mean particle size d of the catalyst is 2~20nm, preferably 4~15nm.
The present invention also provides a kind of loaded catalyst preparation method, this method comprises: by the above method preparation
Tetragonal phase ZrO2Carrier is impregnated with maceration extract, finally dry, roasting, wherein the maceration extract contains metal active constituent
Water soluble compound and complexing agent.
According to the present invention, in the maceration extract, with elemental metal, the concentration of the soluble compound of metal active constituent
For 14.6~191.6 grams per liters, the dosage of carrier makes in gained catalyst on the basis of the total weight of catalyst, with metal member
The content of the metal active constituent of element meter is 2~20 weight %, preferably 3~15 weight %, further preferably 4~12
Weight %.
According to the present invention, the soluble compound of the metal active constituent can be the various solvable of metal active constituent
Property compound, such as nitrate and/or chloride and its hydrate.Under preferable case, the solubilityization of the metal active constituent
Conjunction object is Cu (NO3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、 Fe(NO3)3·9H2O、(NH4)2PtCl6、
RhCl3·3H2O and H2IrCl6·6H2One of O or a variety of, more preferably Co (NO3)2·6H2O and/or Ni (NO3)2·
6H2O。
According to the present invention, alkali of the complexing agent selected from hydroxycarboxylic acid or hydroxycarboxylate or hydramine type, such as lactic acid,
One of tartaric acid, malic acid, EDETATE SODIUM or tetrasodium salt and citric acid, diethanol amine, triethanolamine are a variety of, preferably
Citric acid, tartaric acid or triethanolamine；The molar ratio of the complexing agent and metallic atom is 0.01~2, preferably 0.05~1.
According to the present invention, the method and condition of dipping is referred to prior art progress, such as can be incipient impregnation,
It is also possible to supersaturated dipping.Dipping can carry out at 10~80 DEG C.
The temperature of the drying can be 60~140 DEG C, preferably 100~120 DEG C after dipping；Time can be 1~24
Hour, preferably 5~10 hours.The temperature of the roasting can be 400~1000 DEG C, preferably 500~800 DEG C；Time can
Think 1~10 hour, preferably 2~5 hours.
The present invention also provides a kind of method of methane dry reforming preparing synthetic gas, this method includes negative after above-mentioned reduction
In the presence of supported catalyst, under the conditions of methane dry reforming preparing synthetic gas, make methane and CO2Contact.
The condition of contact includes CH by volume4/CO2=0.7~1.1, preferably 0.8~1.0, reaction temperature is
550-850 DEG C, preferably 600~800 DEG C, more preferably 700~800 DEG C, pressure (gauge pressure) be 0~3MPa, preferably 0~
1MPa, unstripped gas air speed are 2000~120000mlg-1·h-1, preferably 60000~120000mlg-1·h-1。
According to the method for the present invention, above-mentioned loaded catalyst needs to deposit in hydrogen before for the reaction of methane dry reforming
Active metal is subjected to reduction activation, reducing condition lower are as follows: reduction temperature be 300~800 DEG C, preferably 400~750 DEG C,
Further preferably 550~700 DEG C；Recovery time is 0.5~10 hour, preferably 1~5 hour, further preferably 2~4
Hour, the reduction can be carried out in pure hydrogen, can also be carried out in the gaseous mixture of hydrogen and inert gas, such as in hydrogen and nitrogen
It is carried out in the gaseous mixture of gas and/or argon gas, Hydrogen Vapor Pressure is 0~2MPa, preferably 0~1MPa, more preferably 0~0.5MPa.
In the present invention, catalyst carrier is with isothermal nitrogen adsorption methods characterization specific surface area, Kong Rong and aperture.
In the present invention, catalyst metals active component dispersion degree is by H2Chemiadsorption uses Micromeritics
(ASAP-2010C) chemical adsorption instrument measures.Specifically, by 0.2g sample first through 300 DEG C degassing process 1 hour, then rise
Temperature is to 700 DEG C of reductase 12 hours, then is cooled to 40 DEG C of progress H2Chemisorption operation.Later according to chemisorption H2Amount pass through under
It states formula and calculates metal active component dispersion and metal active constituent mean particle size.
Metal active component dispersion D:
Metal active constituent mean particle size d:
Wherein VadRefer to H under standard state2Monolayer adsorption amount, unit mL；WsIt is sample quality, unit g；FWMe
It is the molal weight of metal Me, unit g/mol；FMeIt is the load capacity of metal in catalyst, unit %；VmRefer under standard state
Moles of gas volume, unit mL/mol；SAMeIt is the specific surface area of metal Me, unit m2/gcat；ρMeBe Me metal it is close
Degree, unit g/cm3。
The present invention is described further for the following examples, but does not answer therefore understands that for limitation of the invention.
Embodiment 1
(1)ZrO2The preparation of carrier
Weigh 12g ZrO (NO3)2·2H2Y (the NO of O and 0.383g3)3·6H2O be dissolved in 450mL deionized water stir it is molten
Solution, is configured to mixing salt solution.The concentrated ammonia liquor (25 weight %) for measuring 20mL uses deionized water to dilute 10 times as precipitating reagent.
Salting liquid and precipitating reagent are instilled in precipitation tank simultaneously using co-precipitation mode, the rate of addition of the two is controlled, so that heavy
The pH stable of shallow lake solution is in 10.Precipitating terminates, and stands aging 2 hours.Then it is filtered, washed to obtain wet gel, then is used instead
Dehydrated alcohol washs wet gel, and the volume ratio of solvent and solid is 4:1 when washing every time, washs 3 times.Washing terminates,
Put it into -25 DEG C drying 24 hours in freeze drying box；Sample after drying is put into Muffle furnace and roasts 3 hours for 700 DEG C, institute
It obtains carrier and is denoted as ZrO2- 1, property is listed in Table 1 below, and XRD spectra is shown in Figure 1.
(2) preparation of catalyst
Weigh the Ni (NO of 1.765g3)2·6H2The citric acid of O and 0.576g is dissolved in stirring and dissolving in 4.8mL deionized water,
This maceration extract is impregnated in the above-mentioned carrier of 4g, is placed on Rotary Evaporators within stewing process 2 hours and is dried in vacuo, be subsequently placed in
110 DEG C drying 8 hours in baking oven.Sample after drying is placed into Muffle furnace and is roasted 3 hours for 600 DEG C, and gained catalyst is denoted as
Ni/ZrO2-1.Metal active component dispersion is 9.7% in the catalyst measured by hydrogen chemisorption method, metal active
The average grain diameter of component particles is 6.1nm.
(3) activity rating
Weigh Ni/ZrO2- 1 catalyst 0.1g is diluted to 2ml with 40~60 mesh quartz sands, is packed into internal diameterQuartz ampoule
In reactor, 700 DEG C of reduction are activated for 3 hours in pure hydrogen atmosphere under normal pressure.After reduction, heat up in a hydrogen atmosphere
To 750 DEG C, switch unstripped gas (CH4/CO2=1/1) it is reacted, reaction velocity 120000mlg-1·h-1, reaction pressure
For normal pressure.After stable reaction carries out 200 hours, it is made of gas-chromatography on-line period analysis tail gas.It is calculated: XCH4=
71.8%, XCO2=72.1%, H2/ CO=1.02.
The reactivity worth of catalyst obtained in embodiment 1 is listed in Fig. 2, and the specially reaction time is 0-450 hour
The methane dry reforming reactivity worth that is catalyzed of the catalyst.Figure it is seen that the reactivity worth of catalyst is very steady
It is fixed.
Embodiment 2
(1)ZrO2The preparation of carrier
Weigh 19.28g Zr (NO3)4·5H2La (the NO of O and 0.613g3)3·9H2O, which is dissolved in 160mL deionized water, to be stirred
Dissolution is mixed, mixing salt solution is configured to.The concentrated ammonia liquor (25 weight %) for measuring 20mL uses deionized water to dilute 5 times as precipitating
Agent.Salting liquid and precipitating reagent are instilled in precipitation tank simultaneously using co-precipitation mode, control the rate of addition of the two, so that
The pH stable of precipitation solution is in 12.Precipitating terminates, and stands aging 2 hours.Then it is filtered, washed to obtain wet gel, then is changed
Wet gel is washed with acetone, the volume ratio of solvent and solid is 6:1 when washing every time, is washed 1 time.Washing terminates, will
It is put into 60 DEG C drying 24 hours in vacuum oven；Sample after drying is put into Muffle furnace and roasts 3 hours for 700 DEG C, gained
Carrier is denoted as ZrO2- 2, property is listed in Table 1 below.
(2) preparation of catalyst
Weigh the Co (NO of 2.834g3)2·6H2The tartaric acid of O and 0.073g is dissolved in stirring and dissolving in 4.8mL deionized water,
This maceration extract is impregnated in the above-mentioned modified support of 4g, is placed on Rotary Evaporators within stewing process 2 hours and is dried in vacuo, then
It is placed in 120 DEG C drying 5 hours in baking oven.Sample after drying is placed into Muffle furnace and is roasted 2 hours for 750 DEG C, gained catalyst
It is denoted as Co/ZrO2-2.Metal active component dispersion is 7.9% in the catalyst measured by hydrogen chemisorption method, metal
The average grain diameter of active component particles is 8.2 nm.
(3) activity rating
Activated catalyst and carry out methane dry reforming reaction under the same conditions as example 1.Stable reaction carries out 200
After hour, it is made of gas-chromatography on-line period analysis tail gas.It is calculated: XCH4=73.2%, XCO2=74.0%, H2/CO
=1.03.
Embodiment 3
(1)ZrO2The preparation of carrier
Weigh 8.0g ZrOCl2·8H2Mg (the NO of O and 0.356g3)2·6H2O be dissolved in 900mL deionized water stir it is molten
Solution, is configured to mixing salt solution.The concentrated ammonia liquor (25 weight %) for measuring 20mL uses deionized water to dilute 50 times as precipitating reagent.
Salting liquid and precipitating reagent are instilled in precipitation tank simultaneously using co-precipitation mode, the rate of addition of the two is controlled, so that heavy
The pH stable of shallow lake solution is in 8.Precipitating terminates, and stands aging 2 hours.Then it is filtered, washed to obtain wet gel, then uses second instead
Ether washs wet gel, and the volume ratio of solvent and solid is 3:1 when washing every time, washs 5 times.Washing terminates, and is put
Enter to be warming up to 120 DEG C of dryings 24 hours in nitrogen atmosphere in tube furnace；Sample after drying is put into 700 DEG C of roastings in Muffle furnace
3 hours, resulting vehicle was denoted as ZrO2- 3, property is listed in Table 1 below.
(2) preparation of catalyst
Weigh the Ni (NO of 1.06g3)2·6H2The triethanolamine of O and 0.544g be dissolved in 4.8mL deionized water stir it is molten
Solution, this maceration extract is impregnated in the above-mentioned modified support of 4g, is placed on Rotary Evaporators within stewing process 2 hours and is dried in vacuo,
It is subsequently placed in 100 DEG C drying 10 hours in baking oven.Sample after drying is placed into Muffle furnace and is roasted 5 hours for 500 DEG C, and gained is urged
Agent is denoted as Ni/ZrO2-3.Metal active component dispersion is 10.3% in the catalyst measured by hydrogen chemisorption method,
The average grain diameter of metal active constituent particle is 5.5 nm.
(3) activity rating
Activated catalyst and carry out methane dry reforming reaction under the same conditions as example 1.Stable reaction carries out 200
After hour, it is made of gas-chromatography on-line period analysis tail gas.It is calculated: XCH4=65.4%, XCO2=67.1%, H2/CO
=1.02.
Embodiment 4
(1)ZrO2The preparation of carrier
Catalyst carrier is prepared in the same manner as shown in Example 1, except that Y (NO3)3·6H2The dosage of O is
0.681g.Resulting vehicle is denoted as ZrO2- 4, property is listed in Table 1 below.
(2) preparation of catalyst
Catalyst is made according to mode supported active metals Ni in the same manner as in Example 1, and through drying, roasting, is denoted as
Ni/ZrO2-4.Metal active component dispersion is 10.6% in the catalyst measured by hydrogen chemisorption method, metal active
The average grain diameter of component particles is 5.4nm.
(3) activity rating
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction operation 200
Reaction result after hour is as follows:
XCH4=72.5%, XCO2=73.3%, H2/ CO=1.01.
Embodiment 5
(1)ZrO2The preparation of carrier
Catalyst carrier is prepared according to method in the same manner as in Example 1.
(2) preparation of catalyst
Weigh the Ni (NO of 2.27g3)2·6H2The EDETATE DISODIUM of O and 0.581g be dissolved in 4.8mL deionized water stir it is molten
Solution, this maceration extract is impregnated in the above-mentioned modified support of 4g, is placed on Rotary Evaporators within stewing process 1 hour and is dried in vacuo,
It is subsequently placed in 110 DEG C drying 15 hours in baking oven.Sample after drying is placed into Muffle furnace and is roasted 3 hours for 600 DEG C, and gained is urged
Agent is denoted as Ni-1/ZrO2-1.Metal active component dispersion is in the catalyst measured by hydrogen chemisorption method
9.2%, the average grain diameter of metal active constituent particle is 6.3nm.
(3) activity rating
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction operation 200
Reaction result after hour is as follows:
XCH4=71.3%, XCO2=72.8%, H2/ CO=1.01.
Embodiment 6
(1)ZrO2The preparation of carrier
Catalyst carrier is prepared according to method in the same manner as in Example 1.
(2) preparation of catalyst
According to mode supported active metals Ni in the same manner as in Example 1, except that the dosage of citric acid is
1.166g, gained catalyst are denoted as Ni-2/ZrO2-1.Metal active constituent in the catalyst measured by hydrogen chemisorption method
Dispersion degree is 10.1%, and the average grain diameter of metal active constituent particle is 5.7nm.
(3) activity rating
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction operation 200
Reaction result after hour is as follows:
XCH4=73.6%, XCO2=74.5%, H2/ CO=1.03.
Embodiment 7
(1) preparation of catalyst carrier
Catalyst carrier is prepared according to method in the same manner as in Example 1.
(2) preparation of catalyst
Weigh the Ni (NO of 0.872g3)2·6H2O, the Co (NO of 0.873g3)2·6H2The citric acid of O and 0.576g is dissolved in
This maceration extract is impregnated in the above-mentioned modified support of 4g by stirring and dissolving in 4.8mL deionized water, is placed within stewing process 2 hours
It is dried in vacuo on Rotary Evaporators, is subsequently placed in 110 DEG C drying 8 hours in baking oven.Sample after drying places into Muffle furnace
600 DEG C roast 3 hours, and gained catalyst is denoted as Ni-Co/ZrO2-1.It is golden in the catalyst measured by hydrogen chemisorption method
Belonging to active component dispersion degree is 9.9%, and the average grain diameter of metal active constituent particle is 6.3nm.
(3) activity rating
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, stable reaction operation 200
Reaction result after hour is as follows:
XCH4=77.2%, XCO2=78.3%, H2/ CO=1.01.
Comparative example 1
(1)ZrO2The preparation of carrier
Catalyst carrier is prepared according to method in the same manner as in Example 1, except that not to ZrO2Middle addition auxiliary agent
It is modified, resulting vehicle is denoted as ZrO2- D1, property are listed in Table 1 below, and XRD spectra is shown in Figure 1.
(2) preparation of catalyst
It is then passed through according to mode supported active metals Ni in the same manner as in Example 1 except that not adding complexing agent
Catalyst is made in dry, roasting, is denoted as Ni/ZrO2-D1.Metal active group in the catalyst measured by hydrogen chemisorption method
Dividing dispersion degree is 3.2%, and the average grain diameter of metal active constituent particle is 32.2nm.
(3) activity rating
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, reaction operation 20 hours
Reaction result afterwards is as follows:
XCH4=24.0%, XCO2=33.7%, H2/ CO=0.98.
The reactivity worth of catalyst obtained in comparative example 1 is shown in Fig. 3, and the specially reaction time is 0-30 hours described
The methane and carbon dioxide conversion ratio in the reaction of methane dry reforming that catalyst is catalyzed.
Comparative example 2
(1)ZrO2The preparation of carrier
Catalyst carrier is prepared in the same manner as shown in Example 1, except that sediment is washed without organic solvent
It washs, but is directly placed into Muffle furnace and is roasted, resulting vehicle is denoted as ZrO2- D2, property are listed in Table 1 below.
(2) preparation of catalyst
Catalyst is made according to mode supported active metals Ni in the same manner as in Example 1, and through drying, roasting, is denoted as
Ni/ZrO2-D2.Metal active component dispersion is 3.6% in the catalyst measured by hydrogen chemisorption method, metal active
The average grain diameter of component particles is 30.2nm.
(3) activity rating
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, reaction operation 20 hours
Reaction result afterwards is as follows:
XCH4=32.5%, XCO2=36.3%, H2/ CO=0.99.
Comparative example 3
(1)ZrO2The preparation of carrier
Catalyst carrier is prepared according to method in the same manner as in Example 1.
(2) preparation of catalyst
It is then passed through according to mode supported active metals Ni in the same manner as in Example 1 except that not adding complexing agent
Catalyst is made in dry, roasting, is denoted as Ni-1/ZrO2-1.Metal active in the catalyst measured by hydrogen chemisorption method
Component dispersion degree is 3.9%, and the average grain diameter of metal active constituent is 28.9nm.
(3) activity rating
Activated catalyst and methane dry reforming reaction is carried out under the same conditions as example 1, reaction operation 20 hours
Reaction result afterwards is as follows:
XCH4=39.4%, XCO2=40.6%, H2/ CO=1.01.
In order to investigate auxiliary agent to ZrO2The influence of carrier crystal phase structure carries out embodiment 1 and 1 resulting vehicle of comparative example
XRD characterization, it is as a result shown in Figure 1.As seen from the figure, the 1 gained ZrO of comparative example without additive modification2Carrier is in experience high temperature roasting
After burning, crystal phase structure is pure monoclinic phase, and uses the 1 gained ZrO of embodiment of the method for the present invention2For pure tetragonal phase.
From embodiment 1-4 gained ZrO2The isothermal nitrogen adsorption methods characterization result of carrier can be seen that using present invention side
The ZrO of method preparation2Carrier has the specific surface area significantly increased.
It can be seen that from the reaction result of embodiment 1-6 and be suitable for since the carrier prepared using the method for the present invention is had
Crystal phase structure and biggish specific surface area can obtain higher active metal dispersion degree with these carrier loaded active metals,
The also smaller thus prepared catalyst of the average grain diameter of metallic particles has better reactivity and stability and resists
Coking Behavior, can long period continuous and steady operation non-inactivation.
It can be seen that from the result of embodiment 1 and comparative example 1 and use support preparation method provided by the invention and preparation
Obtained catalyst has better reactivity and stability and coking resistivity, and energy continuous high-efficient stable operation is more than
450 hours.And the catalyst reaction activity not using the comparative example 1 of the method for the present invention is low, stability is poor.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
The texture property of 1 carrier of table
Claims (23)
1. a kind of ZrO of tetragonal phase structure2Carrier, wherein including ZrO2With selected from alkaline-earth metal and/or rare-earth oxide
Modified additive, in terms of total weight of carrier, the content of modified additive is 0.1~10 weight %, in the XRD spectra of the carrier
There is the ZrO of tetragonal phase structure in 30.30 ° and 35.18 ° of peak positions2Characteristic peak.
2. ZrO described in accordance with the claim 12Carrier, wherein 0.3~0.7cm of Kong Rongwei of the carrier3/ g, specific surface area are
100~150m2/ g, average pore size are 6~11nm.
3. ZrO described in accordance with the claim 12Carrier, wherein the modified additive is selected from MgO, CaO, SrO, BaO, CeO2、
La2O3、Sm2O3And Y2O3One of or it is a variety of.
4. a kind of tetragonal phase ZrO2The preparation method of carrier, comprising the following steps:
(1) solution containing zirconates and modified additive precursor salt is prepared, and prepares ammonia spirit as precipitating reagent；
(2) salting liquid and precipitating reagent are added dropwise in precipitation tank simultaneously and carry out precipitation reaction；
(3) gained wet gel is washed, dry, roasting obtains the ZrO of tetragonal phase structure2Carrier.
5. according to the method for claim 4, wherein on the basis of resulting vehicle, and the modified additive in terms of oxide
Dosage be 0.1~10 weight %.
6. according to the method for claim 4, wherein the zirconates is selected from ZrO (NO3)2·2H2O、Zr(NO3)4·5H2O or
ZrOCl2·8H2One of O or a variety of.
7. according to the method for claim 4, wherein the modified additive precursor salt is selected from Mg (NO3)2·6H2O、Ca
(NO3)2·6H2O、Sr(NO3)2·6H2O、Ce(NO3)3·6H2O、La(NO3)3·9H2O、Y(NO3)3·6H2O and Sm (NO3)3·
6H2One of O or a variety of.
8. according to the method for claim 4, wherein in the washing process of step (3), by the sediment of step (2) acquisition
It is washed with deionized water, is washed till filtrate pH value as neutrality, is then also optionally washed with organic solvent.
9. according to the method for claim 8, wherein the organic solvent be selected from methanol, ethyl alcohol, propyl alcohol, butanol, ether and
One of acetone is a variety of, and the volume ratio of the organic solvent and wet gel is 1~10:1 when washing every time.
10. according to the method for claim 4, wherein drying mode is freeze-drying, is dried in vacuo or in slumpability gas
It is dry in atmosphere.
11. a kind of loaded catalyst, including carrier and metal active constituent, wherein carrier is described in one of claims 1 to 3
The ZrO of tetragonal phase structure2Carrier, metal active constituent is selected from least one of I B and VIII family metal oxide, with catalyst
On the basis of gross weight, with elemental metal, the content of the metal active constituent is 2~20 weight %.
12. catalyst according to claim 11, wherein the metal active constituent is selected from CuO, Co3O4、NiO、Fe2O3、
PtO2、Rh2O3And IrO4One of or it is a variety of.
13. catalyst according to claim 11, wherein the content of the metal active constituent is 3~15 weight %, institute
Stating metal active component dispersion is 3~12%, and the metal active constituent mean particle size d is 2~20nm.
14. catalyst according to claim 11, wherein the metal active component dispersion is 6~11%, described
Metal active constituent mean particle size d is 4~15nm.
15. a kind of preparation method of loaded catalyst, comprising: by tetragonal phase ZrO described in one of claims 1 to 32Carrier
It is impregnated with maceration extract, then dry, roasting, wherein the maceration extract contains the water soluble compound of metal active constituent
And complexing agent.
16. according to the method for claim 15, wherein in the maceration extract, with elemental metal, metal active constituent
The concentration of water soluble compound is 14.6~191.6 grams per liters, and the dosage of carrier makes in gained catalyst with the gross weight of catalyst
On the basis of amount, the metal active constituent is with the content of elemental metal for 2~20 weight %.
17. according to the method for claim 15, wherein the dosage of carrier makes in gained catalyst with the gross weight of catalyst
On the basis of amount, the metal active constituent is with the content of elemental metal for 3~15 weight %.
18. according to the method for claim 15, wherein the water soluble compound of the metal active constituent is selected from nitrate
And/or chloride and its hydrate.
19. according to the method for claim 15, wherein the soluble compound of the metal active constituent is selected from Cu
(NO3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Fe(NO3)3·9H2O、(NH4)2PtCl6、RhCl3·3H2O and
H2IrCl6·6H2One of O or a variety of.
20. according to the method for claim 15, wherein the complexing agent is selected from the alkali of hydroxycarboxylic acid or hydramine type.
21. according to the method for claim 15, wherein the complexing agent is selected from lactic acid, tartaric acid, malic acid, EDTA bis-
Sodium or one of tetrasodium salt and citric acid, diethanol amine, triethanolamine or a variety of, mole of the complexing agent and metallic atom
Than being 0.01~2.
22. a kind of method of methane dry reforming preparing synthetic gas, including the support type after being restored described in one of claims 1 to 3
In the presence of catalyst, under the conditions of methane dry reforming preparing synthetic gas, make methane and CO2Contact.
23. according to the method for claim 22, the condition of contact includes CH by volume4/CO2=0.7~1.1, reaction
Temperature is 550-850 DEG C, and pressure is 0~3MPa, and unstripped gas air speed is 2000~120000mlg-1·h-1。
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| CN115646500A (en) * | 2022-10-31 | 2023-01-31 | 上海簇睿低碳能源技术有限公司 | Catalyst for preparing hydrogen by decomposing ammonia and preparation method and application thereof |
| CN115646500B (en) * | 2022-10-31 | 2024-01-30 | 上海簇睿低碳能源技术有限公司 | Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof |
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Application publication date: 20181207 |