CN109126808A - A kind of additive modification copper-based catalysts and preparation method and applications - Google Patents
A kind of additive modification copper-based catalysts and preparation method and applications Download PDFInfo
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- CN109126808A CN109126808A CN201811240201.3A CN201811240201A CN109126808A CN 109126808 A CN109126808 A CN 109126808A CN 201811240201 A CN201811240201 A CN 201811240201A CN 109126808 A CN109126808 A CN 109126808A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000000654 additive Substances 0.000 title claims description 11
- 239000010949 copper Substances 0.000 title abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 34
- 229910052802 copper Inorganic materials 0.000 title abstract description 34
- 230000004048 modification Effects 0.000 title description 11
- 238000012986 modification Methods 0.000 title description 11
- 230000000996 additive effect Effects 0.000 title description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910001868 water Inorganic materials 0.000 claims abstract description 30
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 35
- 239000012018 catalyst precursor Substances 0.000 claims description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 35
- 239000006227 byproduct Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 28
- 239000012266 salt solution Substances 0.000 description 24
- 239000011787 zinc oxide Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- 239000003153 chemical reaction reagent Substances 0.000 description 16
- 230000001376 precipitating effect Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 230000032683 aging Effects 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 8
- 238000004886 process control Methods 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 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 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 241000611421 Elia Species 0.000 description 1
- 229910018107 Ni—Ca Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001666 catalytic steam reforming of ethanol Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 gallium metal oxide Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000005414 inactive ingredient Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical class CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种助剂改性铜基催化剂是由CuO，ZnO和Ce、Zr或Ga金属氧化物助剂组成，其中CuO:ZnO:Ce、Zr或Ga金属氧化物助剂质量比=4.5~6:3~4.5:1。本发明所制备的催化剂用于合成气加氢制甲醇反应，助剂改性铜基催化剂缓解了副产物水对催化剂性能的负面影响，提高了铜基催化剂的稳定性，稳定性提高了8~20%，并在催化剂活性方面也得到了进一步提高。A promoter-modified copper-based catalyst is composed of CuO, ZnO and Ce, Zr or Ga metal oxide promoters, wherein the mass ratio of CuO:ZnO:Ce, Zr or Ga metal oxide promoters=4.5~6:3 ~4.5:1. The catalyst prepared by the invention is used for the reaction of synthesis gas hydrogenation to methanol, and the modified copper-based catalyst by the auxiliary agent alleviates the negative impact of the by-product water on the performance of the catalyst, improves the stability of the copper-based catalyst, and the stability is increased by 8~8~ 20%, and the catalyst activity has also been further improved.
Description
Technical field
The invention belongs to field of catalyst preparation, in particular to a kind of high stability additive modification copper-based catalysts preparation side
Method is applied with it.
The prior art and background technique
Methanol (MeOH) toxicity is low, and easily stored transport is a kind of organic liquid phase hydrogen storage compound, may be used as automobile-used combustion
Material, in addition it, can be with importantization such as dehydrogenation preparing dimethy ether, dimethyl carbonate, iso-butanes as one of basic Organic Chemicals
Product, therefore the research in relation to synthesizing methanol receives the extensive concern of industry and academia.
In recent years, copper-based catalysts have played very important effect in synthesising gas systeming carbinol technical process, and become
The hot spot of research.Although Cu/ZnO/Al2O3Catalyst has been widely used in the reaction of the synthesising gas systeming carbinol in industry, however
For CO2Synthesizing methanol by hydrogenating reaction, the catalyst life significantly reduce, this is also a critical issue of urgent need to resolve.Cause
This, a significant challenge of related copper-based catalysts research is exactly that in reduction and reaction process copper particle can occur for copper particle
Recombination is reunited and is even sintered, when environment temperature reaches the Tamman's temperature (0.3T of catalystm) when, lattice can occur for metallic particles
The transfer of surface particle, when temperature reaches Huttig temperature (0.5Tm) when, it may occur that the migration in lattice body phase, and methanol closes
At the temperature of reaction generally in 493K-573K, the kinetic energy of metallic particles increases in the high temperature environment, it is easier to generate migration row
For metallic surface diffusion rate will increase, and the probability mutually collided between particle is caused to increase, and agglomeration occurs.In addition,
During synthesis gas preparing methanol by hydrogenation, steam conversion reaction can generate micro water, research hair as main side reaction
Existing water can be adsorbed on most of non-noble metal surfaces, cause the reversibly inactivated of catalyst, therefore, the presence of by-product water also can
The inactivation for accelerating copper-based catalysts, influences its catalytic performance.
Wang et al. (Wang D, Han Y, Tan Y, et al.Effect of H2O on Cu-based catalyst
in one-step slurry phase dimethyl ether synthesis[J].Fuel Processing
Technology, 2009,90 (3): 446-451.) using copper-based catalysts and γ-Al2O3Methanol dehydration catalyst is compound to urge
In the research of agent one-step synthesis method dimethyl ether, it is found that the deactivation rate of composite catalyst and copper-based catalysts is very close, and
Further investigation revealed that the addition of minor amount of water can aggravate the long main trend of copper-based catalysts metallic copper in unstripped gas, together
When also can with active ingredient copper occur chemical reaction generate inactive ingredients, convert marionite for carrier zinc oxide, reduce
Interaction force between metal, carrier, to accelerate the inactivation of catalyst.Therefore, the pair generated in hydrogenation process
Product water easily induces copper particle migration aggregation and oersted watt moral to cure effect, reunites so as to cause copper particle, activity
Site exposed amount is reduced, so that catalyst activity and stability glide.So either in laboratory or actual production,
How to avoid or slows down by-product water to the adverse effect of copper-based catalysts to improve catalyst activity and stability is our mesh
Front faces and an important problem to be solved.
Currently, domestic and foreign scholars are with regard to copper-based catalysts preparation method (coprecipitation, sol-gel method, microwave assisting method
Deng), preparation technology parameter (selection, catalyst metals ratio, pH value, roasting reduction condition of carrier, raw material etc. etc.) and auxiliary agent
Influence etc. has carried out a large amount of research work.Wherein additive modification is effective one of mode for inhibiting catalyst inactivation, Elias etc.
(Elias K F M,Lucrédio A F,Assaf E M.Effect of CaO addition on acid properties
of Ni–Ca/Al2O3,catalysts applied to ethanol steam reforming[J].International
Journal of Hydrogen Energy, 2013,38 (11): 4407-4417.) discovery, in Ni-Al2O3CaO is added in system
Afterwards, catalyst stability increases, and surface acidity reduces.The water generated in the adsorbable catalysis reaction of CaO, the heat for improving catalyst are steady
It is qualitative.Oliver et al. (Martin O, Mondelli C, Curullaferr é D, et al.Zinc-Rich Copper
Catalysts Promoted by Gold for Methanol Synthesis[J].Acs Catalysis,2015,5(9):
5607-5616.) the study found that Au is not deposited on catalyst surface after introducing noble metal Au in CuZnAl catalyst system, and not
Modified catalyst is compared, and catalyst easily restores, and improves Cu0Stability, promote the interaction force between Cu-Zn,
It improves the catalytic performance of catalyst and stablizes phasic property.Although preparation process has used more traditional coprecipitation, noble metal
Use be difficult to realize it is industrialized.Tan(Li T,Yang G,Yoneyama Y,et al.Iso-butanol direct
synthesis from syngas over the alkali metals modified Cr/ZnO catalysts[J]
.Applied Catalysis A General, 2015,505:141-149.) discovery such as, Cr/ZnO catalyze and synthesize gas prepare it is different
When butanol, alkali metal promoter influences the reproducibility of catalyst and the composition of key component strongly, to influence the catalysis of catalyst
Performance.
Cai et al. (Cai W, Piscina P R D L, Toyir J, et al.CO2,hydrogenation to
methanol over CuZnGa catalysts prepared using microwave-assisted methods[J]
.Catalysis Today, 2015,242:193-199.) it is prepared for CuZnGa catalyst by a step microwave assistant precipitation method,
The dispersion degree for substantially increasing copper enhances the strong interaction between metal, carrier, so as to improve catalyst thermal stability,
The sintering for effectively improving metallic copper particle, improves the catalytic performance of catalyst.
Xu et al. (Xu X, Sun X, Han H, et al.Improving water tolerance of Co3O4by
SnO2addition for CO oxidation[J].Applied Surface Science,2015,355:1254-1260.)
When studying CO oxidation in relation to reaction, in Co3O4Middle incorporation SnO2Afterwards, effectively the anti-of cobaltosic oxide catalyst is improved
Aqueous, the water-resistance key factor for showing catalyst by infrared spectrum technology effectively alleviates water and is urging in the addition of tin
The suction-operated on agent surface, to obtain water resistance catalyst and considerable catalytic performance.In addition, Hou et al. (Hou X
D,Wang Y Z,Zhao Y X.Effect of CeO 2,Doping on Structure and Catalytic
Performance of Co3O4,Catalyst for Low-Temperature CO Oxidation[J].Catalysis
Letters, 2008,123 (3-4): 321-326.) discovery Ce addition can improve cobaltosic oxide catalyst water resistance and
The BET specific surface of catalyst, to improve catalyst catalytic performance.
In conclusion the prior art and research are primarily to improve the stability problem of catalyst, in relation to different auxiliary agents
The existing many reports of the catalytic performance of modified catalyst system, but related additive modification copper-based catalysts water repelling property and its surely
Qualitatively research report is very few.During synthesis gas synthesizing methanol by hydrogenating, CO2Add hydrogen or against the current vapour reaction generation water,
Al2O3There is strong hydrophily, water can reduce the stability of catalyst activity position.The present invention adds Ce, Zr, Ga metal oxide and helps
Agent is in copper-based catalysts, and and Cu/ZnO/Al2O3Catalyst catalytic performance compares, and probes into water and helps different metal oxides
The influence of the modified zinc-rich copper-based catalysts catalytic performance of agent and stability.
Summary of the invention
It is an object of the invention to reduce adverse effect of the water to copper-based catalysts catalytic performance, a kind of efficient stable is provided
Additive modification copper-based catalysts and preparation method thereof, and be applied to synthesis gas (H in fixed bed reactors2/CO/CO2) plus
Hydrogen methanol.
Additive modification copper-based catalysts prepared by the present invention alleviate influence of the water to catalyst catalytic performance significantly, from
And improve activity and its service life of synthesis gas preparing methanol by hydrogenation catalyst.
The purpose of the present invention is reached by following measure, and co-catalyst CeO is added in copper-zinc-based catalyst2, make to urge
Agent has higher activity and stability.
Additive modification copper-based catalysts of the present invention are by CuO, and ZnO and Ce, Zr or Ga metal oxide auxiliary agent form, wherein
CuO:ZnO:Ce, Zr or Ga metal oxide auxiliary agent mass ratio=4.5~6:3~4.5:1.
Additive modification copper-based catalysts preparation method of the present invention, the specific steps are as follows:
(1) copper nitrate (Cu (NO is weighed3)2·3H2O), zinc nitrate (Zn (NO3)2·6H2O) and promoter metal nitrate is molten
In deionized water, it is configured to the nitrate mixed solution that metal total ion concentration is 1.0~2.0mol/L；Separately take Na2CO3It is molten
In deionized water, it is equally made into the aqueous slkali that concentration is 1.0~2.0mol/L；
(2) sodium carbonate liquor is added dropwise in nitrate mixed solution, adjusts sodium carbonate drop speed to control pH of suspension=7
Between~7.5, after nitrate mixed solution is added dropwise to complete, continue stirring and 1~2h of aging, then heat is filtered, washed, dry overnight
It is dry, presoma is obtained, presoma obtains catalyst Precursors in 350~450 DEG C of temperature lower calcinations, and grinding, tabletting, granulation obtain
The catalyst of 20~40 mesh.
Catalyst of the invention is suitable for the synthesis gas preparing methanol by hydrogenation on fixed bed reactors and reacts, and catalyst first exists
H2/N2Normal pressure restores under gaseous mixture atmosphere, and reduction temperature is 240~260 DEG C, and the recovery time is 4~6h and gaseous mixture air speed is
4500~9000mL/g/h is later 3.0~5.0MPa in reaction pressure, and reaction temperature is 230~250 DEG C, air speed 3000
The reaction of synthesis gas preparing methanol by hydrogenation is carried out under the reaction condition of~6000mL/g/h, percentage by volume shared by component is in each raw material
H254~64%, CO 24~32%, CO24~8%, Ar4-10%.
The invention discloses a kind of preparation methods for adulterating different additive modification copper-based catalysts, and the catalyst is used for
Contain a small amount of CO2Synthesis gas preparing methanol by hydrogenation reaction, this method and tradition pass through the precipitation method prepare Cu/ZnO/Al2O3Load
Type copper-based catalysts are compared, and substantive features of the present invention and progress are:
(1) metal oxide auxiliary agent is doped into Cu/ZnO catalyst by the present invention using traditional co-precipitation mode.With
Traditional Cu/ZnO/Al2O3Compare, be added cerium, zirconium and gallium metal oxide in Cu/ZnO catalyst, CuO crystallite dimension it is small and
It is uniform, the dispersion degree of catalyst can be improved, catalyst granules is evenly dispersed, and the small grains of active component are spaced apart,
Thermal stability is good, and large specific surface area is not easy to reunite.In addition to this, the incorporation of metal oxide strengthens between metal, carrier
Interaction force, meanwhile, the absorption of water on a catalyst is effectively inhibited, toxic action of the water to catalyst is reduced.
(2) present invention is adulterated using in copper-zinc-based catalyst except Al2O3Except metal oxide, and in the same way
The Cu/ZnO/Al of preparation2O3Catalyst is compared, and catalyst is in the reaction of synthesis gas preparing methanol by hydrogenation, catalyst activity and stabilization
Property is greatly improved, wherein stability highest has been increased to 20%, and methanol yield improves 17% or so.
(3) doping auxiliary agent copper-based catalysts prepared by the co-precipitation mode that the present invention uses, show higher urge
Change performance and stability, therefore there is broader market application prospect.
Specific embodiment
Preparation method disclosed in this patent and application are further described below by specific embodiment, but the present invention is not
It is limited by following embodiments.
Embodiment 1
9.108g copper nitrate, 5.474g zinc nitrate, 1.260g cerous nitrate is weighed respectively to be dissolved in deionized water and be made into 1mol/
The metal mixed salt solution of L, meanwhile, it weighs 10.599g natrium carbonicum calcinatum and is dissolved in deionized water and be made into 1mol/L solution conduct
Precipitating reagent is spare.Then under 65 DEG C of stirrings, two kinds of solution cocurrents is added dropwise in the beaker for filling 300mL distilled water, were added dropwise
The drop speed of process control metal mixed salt solution is constant, and the rate of addition for adjusting precipitating reagent sodium carbonate liquor was entirely titrated with controlling
The pH of solution is 7 in journey, pH value of solution pH electrode detection, after metal salt solution has titrated, stops the drop of sodium carbonate liquor immediately
It is fixed, old 1h is stirred at 65 DEG C, the above whole process is completed in water-bath, and aging mother liquor filters while hot, and washing, 80 DEG C are being dried
Dry 12h, obtains presoma, presoma calcines 4h at 350 DEG C in Muffle furnace, obtains catalyst Precursors in case.Later, it urges
Agent parent is stand-by by the catalyst precursor particles that grinding, tabletting, granulation obtain 20~40 mesh.Gained catalyst elements composition
Mass fraction percentage are as follows: CuO:ZnO:CeO2=6:3:1.
The catalyst is used for synthesis gas CO/CO2Hydrogen is added to prepare methanol reaction, reducing condition, the activity rating item of catalyst
Part and evaluation result see attached list 1, the specific steps are as follows:
Catalyst activity evaluation is carried out with fixed bed reactors, 0.4g catalyst granules is fitted into stainless steel reaction pipe
Equigranular quartz sand is filled at (stainless steel reactor length is 450mm, internal diameter 8mm), reaction tube both ends, and reaction procatalyst is used
Hydrogen and nitrogen restore 4h at 250 DEG C, after being cooled to 80 DEG C or less, switch to raw material reaction gas.Unstripped gas gas volume group
At CO:CO2:H2: Ar=24:8:64:4 first uses feed gas washing pipeline, then in 230 DEG C, 3MPa, air speed 4500mL/g/h
Under the conditions of react 60h.
Embodiment 2
9.108g copper nitrate, 5.474g zinc nitrate, 1.717g zirconium nitrate is weighed respectively to be dissolved in deionized water and being made into
The metal mixed salt solution of 1.5mol/L, meanwhile, it weighs 10.599g natrium carbonicum calcinatum and is dissolved in deionized water and be made into 1.5mol/L
Solution is spare as precipitating reagent.Then under 70 DEG C of stirrings, two kinds of solution cocurrents are added dropwise to the beaker for filling 300mL distilled water
In, the drop speed that process control metal mixed salt solution is added dropwise is constant, adjusts the rate of addition of precipitating reagent sodium carbonate liquor to control
The pH of solution is 7.5 in entire titration process, and pH value of solution pH electrode detection after metal salt solution has titrated, stops carbon immediately
The titration of acid sodium solution stirs old 1.5h at 70 DEG C, and the above whole process is completed in water-bath, and aging mother liquor is taken out while hot
Filter, washing, 120 DEG C are dried 8h in an oven, obtain presoma, presoma is calcined 4h at 450 DEG C in Muffle furnace, urged
Agent parent.Later, the catalyst precursor particles that catalyst Precursors obtain 20~40 mesh by grinding, tabletting, granulation are stand-by.Institute
It obtains catalyst elements and forms mass fraction percentage are as follows: CuO:ZnO:ZrO2=6:3:1.
The catalyst is used for synthesis gas CO/CO2Hydrogen is added to prepare methanol reaction, reducing condition, the activity rating item of catalyst
Part and evaluation result see attached list 1, and specific steps are referring to embodiment 1.
Embodiment 3
6.834g copper nitrate, 8.225g zinc nitrate, 1.355g gallium nitrate is weighed respectively to be dissolved in deionized water and be made into 2mol/
The metal mixed salt solution of L, meanwhile, it weighs 10.599g natrium carbonicum calcinatum and is dissolved in deionized water and be made into 2mol/L solution conduct
Precipitating reagent is spare.Then under 75 DEG C of stirrings, two kinds of solution cocurrents is added dropwise in the beaker for filling 300mL distilled water, were added dropwise
The drop speed of process control metal mixed salt solution is constant, and the rate of addition for adjusting precipitating reagent sodium carbonate liquor was entirely titrated with controlling
The pH of solution is 7 in journey, pH value of solution pH electrode detection, after metal salt solution has titrated, stops the drop of sodium carbonate liquor immediately
It is fixed, aging 1h is stirred at 75 DEG C, the above whole process is completed in water-bath, and aging mother liquor filters while hot, washing, 80 DEG C
Dry 12h, obtains presoma, presoma calcines 4h at 350 DEG C in Muffle furnace, obtains catalyst Precursors in baking oven.Later,
Catalyst Precursors are stand-by by the catalyst precursor particles that grinding, tabletting, granulation obtain 20~40 mesh.Gained catalyst elements group
At mass fraction percentage are as follows: CuO:ZnO:Ga2O3=4.5:4.5:1.
The catalyst is used for synthesis gas CO/CO2Hydrogen is added to prepare methanol reaction, reducing condition, the activity rating item of catalyst
Part and evaluation result see attached list 1, and specific steps are referring to embodiment 1.
Embodiment 4
6.834g copper nitrate, 8.255g zinc nitrate, 1.260g cerous nitrate is weighed respectively to be dissolved in deionized water and be made into 1mol/
The metal mixed salt solution of L, meanwhile, it weighs 10.599g natrium carbonicum calcinatum and is dissolved in deionized water and be made into 1mol/L solution conduct
Precipitating reagent is spare.Then under 65 DEG C of stirrings, two kinds of solution cocurrents is added dropwise in the beaker for filling 300mL distilled water, were added dropwise
The drop speed of process control metal mixed salt solution is constant, and the rate of addition for adjusting precipitating reagent sodium carbonate liquor was entirely titrated with controlling
The pH of solution is 7 in journey, and pH value of solution is monitored with pH electrode, after metal salt solution has titrated, stops the drop of sodium carbonate liquor immediately
It is fixed, aging 1h is stirred at 65 DEG C, the above whole process is completed in water-bath, and aging mother liquor filters while hot, washing, and 120 DEG C
8h is dried in an oven, obtains presoma, presoma calcines 4h at 450 DEG C in Muffle furnace, obtains catalyst Precursors.It
Afterwards, the catalyst precursor particles that catalyst Precursors obtain 20~40 mesh by grinding, tabletting, granulation are stand-by.Gained catalyst member
Element composition mass fraction percentage are as follows: CuO:ZnO:CeO2=4.5:4.5:1.
The catalyst is used for synthesis gas CO/CO2Hydrogen is added to prepare methanol reaction, reducing condition, the activity rating item of catalyst
Part and evaluation result see attached list 1, and specific steps are referring to embodiment 1, it is pointed out that during the reaction in order to investigate water pair
The vapor that volume fraction is 1.5% is added by cylinder in unstripped gas for the influence of catalyst activity.
Embodiment 5
7.593g copper nitrate, 7.311g zinc nitrate, 1.717g zirconium nitrate is weighed respectively to be dissolved in deionized water and be made into 2mol/
The metal mixed salt solution of L, meanwhile, it weighs 10.599g natrium carbonicum calcinatum and is dissolved in deionized water and be made into 2mol/L solution conduct
Precipitating reagent is spare.Then under 65 DEG C of stirrings, two kinds of solution cocurrents is added dropwise in the beaker for filling 300mL distilled water, were added dropwise
The drop speed of process control metal mixed salt solution is constant, and the rate of addition for adjusting precipitating reagent sodium carbonate liquor was entirely titrated with controlling
The pH of solution is 7.5 in journey, pH value of solution pH electrode detection, after metal salt solution has titrated, stops sodium carbonate liquor immediately
It titrating, stirs old 1.5h at 65 DEG C, the above whole process is completed in water-bath, and aging mother liquor filters while hot, washing, and 120
8h is dried DEG C in an oven, obtains presoma, presoma calcines 4h at 400 DEG C in Muffle furnace, obtains catalyst Precursors.It
Afterwards, the catalyst precursor particles that catalyst Precursors obtain 20~40 mesh by grinding, tabletting, granulation are stand-by.Gained catalyst member
Element composition mass fraction percentage are as follows: CuO:ZnO:ZrO2=5:4:1.
The catalyst is used for synthesis gas CO/CO2Hydrogen is added to prepare methanol reaction, reducing condition, the activity rating item of catalyst
Part and evaluation result see attached list 1, and specific steps are referring to embodiment 1, it is pointed out that during the reaction in order to investigate water pair
The vapor that volume fraction is 5% is added by cylinder in unstripped gas for the influence of catalyst activity.
Embodiment 6
7.593g copper nitrate, 7.311g zinc nitrate, 1.355g gallium nitrate is weighed respectively to be dissolved in deionized water and being made into
The metal mixed salt solution of 1.5mol/L, meanwhile, it weighs 10.599g natrium carbonicum calcinatum and is dissolved in deionized water and be made into 1.5mol/L
Solution is spare as precipitating reagent.Then under 75 DEG C of stirrings, two kinds of solution cocurrents are added dropwise to the beaker for filling 300mL distilled water
In, the drop speed that process control metal mixed salt solution is added dropwise is constant, adjusts the rate of addition of precipitating reagent sodium carbonate liquor to control
The pH of solution is 7.5 in entire titration process, and pH value of solution pH electrode detection after metal salt solution has titrated, stops carbon immediately
Aging 1h is stirred in the titration of acid sodium solution at 75 DEG C, and the above whole process is completed in water-bath, and aging mother liquor is taken out while hot
Filter, washing, 80 DEG C are dried 12h in an oven, obtain presoma, presoma is calcined 4h at 350 DEG C in Muffle furnace, urged
Agent parent.Later, the catalyst precursor particles that catalyst Precursors obtain 20~40 mesh by grinding, tabletting, granulation are stand-by.Institute
It obtains catalyst elements and forms mass fraction percentage are as follows: CuO:ZnO:Ga2O3=5:4:1.
The catalyst is used for synthesis gas CO/CO2Hydrogen is added to prepare methanol reaction, reducing condition, the activity rating item of catalyst
Part and evaluation result see attached list 1, and specific steps are referring to embodiment 1, it is pointed out that during the reaction in order to investigate water pair
The vapor that volume fraction is 10% is added by cylinder in unstripped gas for the influence of catalyst activity.
Comparative example 1
9.108g copper nitrate, 5.474g zinc nitrate, 3.676g aluminum nitrate is weighed respectively to be dissolved in deionized water and be made into 1mol/
The metal mixed salt solution of L, meanwhile, it weighs 10.599g natrium carbonicum calcinatum and is dissolved in deionized water and be made into 1mol/L solution conduct
Precipitating reagent is spare.Then under 65 DEG C of stirrings, two kinds of solution cocurrents is added dropwise in the beaker for filling 300mL distilled water, were added dropwise
The drop speed of process control metal mixed salt solution is constant, and the rate of addition for adjusting precipitating reagent sodium carbonate liquor was entirely titrated with controlling
The pH of solution is 7 in journey, and pH value of solution is monitored with pH electrode, after metal salt solution has titrated, stops the drop of sodium carbonate liquor immediately
It is fixed, aging 1h is stirred at 70 DEG C, the above whole process is completed in water-bath, and aging mother liquor filters while hot, washing, 80 DEG C
Dry 12h, obtains presoma, presoma calcines 4h at 350 DEG C in Muffle furnace, obtains catalyst Precursors in baking oven.Later,
Catalyst Precursors are stand-by by the catalyst precursor particles that grinding, tabletting, granulation obtain 20~40 mesh.Gained catalyst elements group
At mass fraction percentage are as follows: CuO:ZnO:Al2O3=6:3:1.
The catalyst is used for synthesis gas CO/CO2Hydrogen is added to prepare methanol reaction, reducing condition, the activity rating item of catalyst
Part and evaluation result see attached list 1, specific steps reference implementation example 1.
Comparative example 2
9.108g copper nitrate, 5.474g zinc nitrate, 3.676g aluminum nitrate is weighed respectively to be dissolved in deionized water and be made into 1mol/
The metal mixed salt solution of L, meanwhile, it weighs 10.599g natrium carbonicum calcinatum and is dissolved in deionized water and be made into 1mol/L solution conduct
Precipitating reagent is spare.Then under 65 DEG C of stirrings, two kinds of solution cocurrents is added dropwise in the beaker for filling 300mL distilled water, were added dropwise
The drop speed of process control metal mixed salt solution is constant, and the rate of addition for adjusting precipitating reagent sodium carbonate liquor was entirely titrated with controlling
The pH of solution is 7 in journey, and pH value of solution is monitored with pH electrode, after metal salt solution drips off, stops the titration of sodium carbonate liquor immediately,
Aging 1h is stirred at 65 DEG C, the above whole process is completed in water-bath, and aging mother liquor filters while hot, and washing, 80 DEG C are being dried
Dry 12h, obtains presoma, presoma calcines 4h at 350 DEG C in Muffle furnace, obtains catalyst Precursors in case.Later, it urges
Agent parent is stand-by by the catalyst precursor particles that grinding, tabletting, granulation obtain 20~40 mesh.Gained catalyst elements composition
Mass fraction percentage are as follows: CuO:ZnO:Al2O3=6:3:1.
The catalyst is used for synthesis gas CO/CO2Hydrogen is added to prepare methanol reaction, reducing condition, the activity rating item of catalyst
Part and evaluation result see attached list 1, and specific steps are referring to embodiment 1, it is pointed out that during the reaction in order to investigate water pair
The vapor that volume fraction is 1.5% is added by cylinder in unstripped gas for the influence of catalyst activity.
After being compared by 1 embodiment of table it is found that adding vapor in unstripped gas, catalyst catalytic performance is reduced, under stability
Drop.To show by-product water really can accelerator activator deactivation rate, aggravate catalyst metal particles migration reunite, make
Decline at the utilization rate of catalyst activity component.In addition to this, water can also be adsorbed on catalyst surface, cover active site, sternly
It can also be chemically reacted with active component if weight, convert non-active species for active specy, meanwhile, it can also change copper object
The valence state of kind, directly affects Cu0/Cu+Proportion, to influence catalyst activity.In addition, water is to addition different metal auxiliary agent
Copper-based catalysts influence it is different, wherein the catalyst that cerium promoter is added is influenced minimum by water, and zirconium takes second place, and is followed by gallium.
By the Activity evaluation of embodiment and comparative example in table 1 it can be concluded that, under vapor existence condition, zinc-rich copper
The addition of the metal oxide auxiliary agents such as base Cerium in Catalysts, zirconium, gallium, with traditional Cu/ZnO/Al2O3Catalyst is compared, catalyst
Stability is greatly improved, and catalyst activity is slightly promoted, and the addition of auxiliary agent promotes the reduction of catalyst, adds
Adding assistant and the crystal phase structure for having not been changed catalyst.But be conducive to catalyst dispersion degree and heat-staple raising, it is effective to inhibit
The migration of catalyst granules is grown up, and copper oxide crystallite dimension is smaller, expose more active sites, substantially increase and urge
The utilization rate of agent active site, to enhance the catalytic activity of catalyst, the addition of especially rare-earth oxide can
Significantly improve COxConversion ratio and methanol space-time receipts amount.
The foregoing is merely the preferred embodiment of the embodiment of the present invention, the present invention is not limited to above-described embodiment, for
For those skilled in the art, the present invention can have transformation and replacement, such as using other metals or metal oxide to statistics
Catalyst is modified.Therefore, any modification for being made under the principle of all embodiments described in the method for the present invention and spirit, equivalent
Replacement, improvement etc., belong to protection scope of the present invention.
Table 1
Note: (1) catalyst activity evaluates duration 60h.(2) activity decline percentage is relative value (relative to catalyst
For initial activity), activity decline percentage is smaller, and it is better to represent catalyst stability.(3)COxIt represents and originates total C conversion
Rate.
Claims (3)
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