CN111250098B - 一种用于费托合成反应水加氢催化剂及其制备方法和应用 - Google Patents
一种用于费托合成反应水加氢催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- 238000004537 pulping Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 159000000021 acetate salts Chemical class 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 150000001299 aldehydes Chemical class 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 11
- 150000002576 ketones Chemical class 0.000 abstract description 8
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 230000003472 neutralizing effect Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- -1 aldehyde compounds Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/002—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
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
本发明涉及一种用于费托合成反应水加氢催化剂及其制备方法和应用，催化剂主要由Cu、Zn、Al、Cr或Zr或V或K或Mn金属元素的氧化物组成，其中各金属元素在催化剂中的重量份含量为：Cu：20～60，Zn：10～55，Al：2～10，Cr或Zr或V或K或Mn：0.1～1，将Cu、Zn盐溶液与碳酸盐中和制备出的活性母体，与铝盐溶液和碳酸盐沉淀出的载体混合打浆、添加助剂、干燥、焙烧，打片成型得到催化剂。与现有技术相比，本发明对C2～C7醛、酮、酸、酯类含氧有机物加氢活性高，耐水性好，适用于费托合成水中醛酮酸酯混合液加氢。
Description
技术领域
本发明涉及催化剂技术领域，尤其是涉及一种用于费托合成反应水加氢催化剂及其制备方法和应用。
背景技术
费托合成技术是将合成气(CO+H2)通过化学方法转化为液体燃料和化学品的技术。合成的燃料油是不含硫、氮和芳香族化合物的清洁燃料。随着国际油气资源的日益减少和市场情况的变化，以及环保的要求，以费托合成为核心的煤液化和天然气液化技术的开发与工业化，对保障国家能源供应安全、节能减排具有越来越重要的意义。
在费托合成反应过程中，CO中的氧原子大部分生成了水，少量生成了含氧化合物，这些含氧化合物易溶于水，因此，从费托合成反应器出来经过分离得到的水产物中含有一定量的含氧有机物。反应水中含氧化合物浓度和组成与费托合成工艺条件、催化剂种类等有关。低温费托合成反应水中含氧化合物浓度为3％左右，高温费托合成反应水中含氧化合物浓度约为10％。费托合成工业装置的规模都很大，分离提纯反应水中的含氧有机物可提高企业的经济效益。
费托合成反应水组成复杂，包括C1～C8的醇、醛、酮、酸、酯，有约30种组分。含氧有机物与水，不同物系含氧化合物之间形成多种共沸物。醛类化合物性质不稳定，容易发生自聚和氧化反应，这些特点决定了直接用精馏法分离出的含氧化学品的纯度不高，难以达到产品的标准。
反应水中的醛、铜、酸、酯在一定的条件下都可以加氢还原为醇，开发一种适合费托反应水加氢的催化剂，将反应水中的醛酮酸酯都转化为醇，以醇的形式回收水中不同物系的含氧有机物，可大大简化反应水组成，降低反应水中含氧有机物的分离难度，提高产品纯度。
专利CN104148079A公开了一种醋酸酯加氢制乙醇的催化剂及方法，该催化剂主要包括5～80份金属铜或其氧化物，0.05～60份助催化剂，助催化剂选自过渡金属中的至少一种元素或其氧化物，5～90份二氧化硅载体。催化剂的比表面积为150～500平米/克，总孔容为0.1～3.0毫升/克，孔直径＜20纳米的孔容占总孔容的40～90％，孔直径20～50纳米的孔容占总孔容的5～75％，孔直径＞50纳米的孔容占总孔容的5～75％，可用于醋酸酯加氢制乙醇的工业生产中。
专利CN102847544A公开了一种醋酸加氢制乙醇催化剂以及制备方法，该催化剂由活性金属、助剂、保护剂和载体组成，通过浸渍法制备，活性金属为铂、钌、钯，助剂为铁、钴、镍，保护剂为硼酸或四乙氧基硅烷、载体为碳纳米管或二氧化硅。保护剂的引入可极大提高催化剂的热稳定性。
专利CN107952473A公开了一种丙酮加氢制备异丙醇的催化剂，该催化剂由Beta沸石为载体，镍元素或氧化物为活性金属，0～5％锌、铑元素或其氧化物组成，催化剂通过浸渍法制备。在反应温度为80～180℃、压力1～4MPa条件下，可将丙酮转化为异丙醇。
专利CN104857962A公开了一种醛或酮加氢生产醇的催化剂及其使用方法，该催化剂是以硅、铝的氧化物和钙的碳酸盐及其氧化物复合物为载体，活性组份镍或钴或镍加钴的质量含量为：15～40％、15～30％、30～40％(镍：钴＝1:0.3～3)，其余为载体，其中Si:Al:Ca＝5～7:0～3:2～5。载体及催化剂均用共沉淀法制得。该催化剂具有强度高，反应温度低，活性好，选择性好等优点。
上述专利都是针对、醛、酮、酸、酯某一组分或某一物系而开发的催化剂，而费托合成反应水中含有不同碳数的醇醛酮酸酯和水，体系非常复杂，如何开发出一种对费托合成反应水中C2～C7的醛酮酸酯混合液都有很高的加氢活性和醇选择性的催化剂成了现在亟待解决的技术问题。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种用于费托合成反应水加氢催化剂及其制备方法和应用，解决了现有技术中无法对费托合成反应水中C1～C7的醛酮酸酯混合液都有很高的加氢活性和醇选择性的技术问题。
本发明的目的可以通过以下技术方案来实现：
一种用于费托合成反应水加氢催化剂，主要由Cu、Zn、Al、Cr或Zr或V或K或Mn金属元素的氧化物组成，
其中各金属元素在催化剂中的重量份含量为：Cu：20～60，Zn：10～55，Al：2～10，Cr或Zr或V或K或Mn：0.1～1。
作为的技术方案，Cr或Zr或V或K或Mn为助剂元素，优选Cr或Mn，重量份含量为0.3～0.7。
一种用于费托合成反应水加氢催化剂的制备方法，包括：
将浓度为50～200g/L的可溶性铜盐和浓度为30～200g/L的可溶性锌盐的混合溶液加热后加入20～150g/L的碳酸盐溶液，形成沉淀，经老化、洗涤、过滤、得到活性母体；
将浓度为5～200g/L的可溶性铝盐溶液加入20～150g/L碳酸盐溶液中进行沉淀反应，经老化、洗涤、过滤，得到载体；
将活性母体和载体混合打浆，在打浆过程中加入助剂，50～100℃下搅拌浸渍30～60分钟，得到催化剂浸渍液；
将催化剂浸渍液过滤、烘干、焙烧、加入少量石墨和去离子水压片成型，得到用于费托合成反应水加氢催化剂。
上述可溶性金属盐为硝酸盐或醋酸盐。
所述碳酸盐为碳酸氢钠或碳酸钠。
可溶性铜盐、可溶性锌盐与碳酸盐溶液沉淀、老化的温度为50～100℃，优选的技术方案可以采用65～85℃，利于将大小不同的晶体得到颗粒大小较为均匀的粗晶体，改善孔隙结构和表面积。
可溶性铜盐、可溶性锌盐与碳酸盐溶液沉淀反应的终点pH值为6.5～7.5，优选的技术方案可以采用6.8～7.2，使沉淀更加均匀，增强催化剂各组分的相互作用。
所述助剂为Cr、Zr、V或K中的一种或几种的碳酸盐、醋酸盐或硝酸盐中的一种或几种，优选Cr(NO3)3或Mn(NO3)2，助剂的加入有利于阻止CuO晶粒长大，促进CuO分散、增加催化剂表面积，提高催化剂活性。
制备得到的催化剂适用于提浓后的费托合成水物流的加氢，物流中水含量为0～50wt％，将物流中C2～C7醛酮酸酯都加氢转化为醇。
催化剂对费托合成水加氢反应条件为：温度200～240℃、压力1～4MPa、液体空速0.2～3h-1，氢羰摩尔比10～30。
与现有技术相比，本发明通过添加助剂，提高了活性组分CuO的分散度和催化剂表面积，促进了Cu(II)向反应活性物种Cu(I)转化，增强了催化剂活性和稳定性。使得本发明所公开的技术方案对C2～C7的醛酮酸酯混合液都有很高的加氢活性和醇选择性，且能适用于含一定量水的物料加氢。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
一种用于费托合成反应水加氢催化剂，主要由Cu、Zn、Al、Cr或Zr或V或K或Mn金属元素的氧化物组成，各金属元素在催化剂中的重量份含量为：Cu：20～60，Zn：10～55，Al：2～10，Cr或Zr或V或K或Mn：0.1～1。
该种催化剂采用以下方法制备得到：
(1)将浓度为50～200g/L的硝酸铜或醋酸铜和浓度为30～200g/L的硝酸锌或醋酸锌的混合溶液加热后加入20～150g/L的碳酸氢钠或碳酸钠溶液，形成沉淀，经50～100℃老化、洗涤、过滤、得到活性母体；
(2)将浓度为5～200g/L的硝酸铝或醋酸铝溶液加入20～150g/L碳酸氢钠或碳酸钠溶液中进行沉淀反应，沉淀反应的终点pH值为6.5～7.5，再经50～100℃老化、洗涤、过滤，得到载体；
(3)将活性母体和载体混合打浆，在打浆过程中加入助剂，例如可以采用Cr、Zr、V或K或Mn中的一种或几种的碳酸盐、醋酸盐或硝酸盐中的一种或几种，50～100℃下搅拌浸渍30～60分钟，得到催化剂浸渍液；
(4)将催化剂浸渍液过滤、烘干、焙烧、加入少量石墨和去离子水压片成型，得到用于费托合成反应水加氢催化剂。
制备得到的催化剂适用于提浓后的费托合成水物流的加氢，物流中水含量为0～50wt％，将物流中C2～C7醛酮酸酯都加氢转化为醇。催化剂对费托合成水加氢反应条件为：温度200～240℃、压力1～4MPa、液体空速0.2～3h-1，氢羰摩尔比10～30。
以下是更加详细的实施案例，通过以下实施案例进一步说明本发明的技术方案以及所能够获得的技术效果。
实施例1
配制1L含有140gCu(NO3)2和120gZn(NO3)2的混合溶液，加热至65～85℃，待用。用去离子水配制3L含250g碳酸氢钠的溶液，作为沉淀剂，加热至65～85℃待用。搅拌下将酮、锌混合溶液加入碳酸氢钠溶液，中和过程中控制温度为65～85℃，控制终点PH至为6.8～7.2，经老化、洗涤、过虑得到活性母体。将20g Al(NO3)3溶于500ml去离子水中，用1～30％碳酸氢钠中和Al(NO3)3溶液至PH至为7～7.5制成氧化铝凝胶，经老化、洗涤、过虑得到载体。将活性母体、载体和催化剂重量0.5wt％的硝酸铬助剂混合打浆，然后经过虑、烘干、焙烧、成型得到催化剂1。
实施例2
配制1L含有150gCu(NO3)2和90gZn(NO3)2的混合溶液，加热至65～85℃，待用。用去离子水配制3L含250g碳酸氢钠的溶液，作为沉淀剂，加热至65～85℃待用。搅拌下将酮、锌混合溶液加入碳酸氢钠溶液，中和过程中控制温度为65～85℃，控制终点PH至为6.8～7.2，经老化、洗涤、过虑得到活性母体。将10gAl(NO3)3溶于500ml去离子水中，用1～30％碳酸氢钠中和Al(NO3)3溶液至PH至为7～7.5制成氧化铝凝胶，经老化、洗涤、过虑得到载体。将活性母体、载体和催化剂重量0.8wt％的醋酸钾助剂混合打浆，然后经过虑、烘干、焙烧、成型得到催化剂2。
实施例3
配制1L含有130gCu(NO3)2和100g Zn(NO3)2的混合溶液，加热至65～85℃，待用。用去离子水配制3L含250g碳酸钠的溶液，作为沉淀剂，加热至65～85℃待用。搅拌下将酮、锌混合溶液加入碳酸钠溶液，中和过程中控制温度为65～85℃，控制终点PH至为6.8～7.2，经老化、洗涤、过虑得到活性母体。将15g Al(NO3)3溶于500ml去离子水中，用1～35％碳酸钠中和Al(NO3)3溶液至PH至为7～7.5制成氧化铝凝胶，经老化、洗涤、过虑得到载体。将活性母体、载体和催化剂重量0.6wt％的硝酸锰助剂混合打浆，然后经过虑、烘干、焙烧、成型得到催化剂3。
实施例4
配制1L含有120gCu(NO3)2和120g Zn(NO3)2的混合溶液，加热至65～85℃，待用。用去离子水配制3L含250g碳酸钠的溶液，作为沉淀剂，加热至65～85℃待用。搅拌下将酮、锌混合溶液加入碳酸钠溶液，中和过程中控制温度为65～85℃，控制终点PH至为6.8～7.2，经老化、洗涤、过虑得到活性母体。将8g Al(NO3)3溶于500ml去离子水中，用1～35％碳酸钠中和Al(NO3)3溶液至PH至为7～7.5制成氧化铝凝胶，经老化、洗涤、过虑得到载体。将活性母体、载体和催化剂重量0.6wt％硝酸锆溶液助剂混合打浆，然后经过虑、烘干、焙烧、成型得到催化剂4。
实施例5
活性测试
将成型的催化剂破碎筛分成20～40目，装入微型固定床反应器，催化剂装填量为8ml，催化剂在的还原在低氢(H2：N2＝5：95)气氛，程序升温(20℃/h)升到180℃还原10h，然后将温度升到230℃还原4h。还原结束后将温度降到220℃，将原料气切换成氢气，用初分精馏塔提浓的水含量约为30wt％费托合成水为原料，对催化剂进行加氢活性评价。费托合成水加氢活性评价的反应条件为：温度220℃、压力、2.5MPa、液体进料空速1h-1、氢羰摩尔比为20。评价结果见表1所示。
表1催化剂对费托合成加氢实验结果
在本说明书的描述中，参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
上述对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (8)
1.一种费托合成反应水加氢催化剂的应用，其特征在于，该催化剂适用于提浓后的费托合成水物流的加氢，物流中水含量为0～50wt％，将物流中C2～C7醛酮酸酯都加氢转化为醇；
所述催化剂由Cu、Zn、Al、Cr或Zr或V或K或Mn金属元素的氧化物组成，
其中各金属元素在催化剂中的重量份含量为：Cu：20～60，Zn：10～55，Al：2～10，Cr或Zr或V或K或Mn：0.1～1；
所述催化剂的制备方法包括：
将浓度为50～200g/L的可溶性铜盐和浓度为30～200g/L的可溶性锌盐的混合溶液加热后加入20～150g/L的碳酸盐溶液，形成沉淀，经老化、洗涤、过滤、得到活性母体；
将浓度为5～200g/L的可溶性铝盐溶液加入20～150g/L碳酸盐溶液中进行沉淀反应，经老化、洗涤、过滤，得到载体；
将活性母体和载体混合打浆，在打浆过程中加入助剂，50～100℃下搅拌浸渍30～60分钟，得到催化剂浸渍液；
将催化剂浸渍液过滤、烘干、焙烧、加入少量石墨和去离子水压片成型，得到用于费托合成反应水加氢催化剂。
2.根据权利要求1所述的一种费托合成反应水加氢催化剂的应用，其特征在于，Cr或Zr或V或K或Mn为助剂元素，助剂元素的重量份含量为0.3～0.7。
3.根据权利要求1所述的一种费托合成反应水加氢催化剂的应用，其特征在于，上述可溶性金属盐为硝酸盐或醋酸盐。
4.根据权利要求1所述的一种费托合成反应水加氢催化剂的应用，其特征在于，所述碳酸盐为碳酸氢钠或碳酸钠。
5.根据权利要求1所述的一种费托合成反应水加氢催化剂的应用，其特征在于，可溶性铜盐、可溶性锌盐与碳酸盐溶液沉淀、老化的温度为50～100℃。
6.根据权利要求1所述的一种费托合成反应水加氢催化剂的应用，其特征在于，可溶性铜盐、可溶性锌盐与碳酸盐溶液沉淀反应的终点pH值为6.5～7.5。
7.根据权利要求1所述的一种费托合成反应水加氢催化剂的应用，其特征在于，所述助剂为Cr、Zr、V、K、Mn中的一种或几种的盐，所述盐为碳酸盐、醋酸盐、硝酸盐中的一种或几种。
8.根据权利要求7所述的一种费托合成反应水加氢催化剂的应用，其特征在于，催化剂对费托合成水加氢反应条件为：温度200～240℃、压力1～4MPa、液体空速0.2～3h-1，氢羰摩尔比10～30。
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| CN101185894A (zh) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | 一种铜基催化剂的制备方法 |
| CN105268442A (zh) * | 2014-06-30 | 2016-01-27 | 大唐国际化工技术研究院有限公司 | 一种铜基甲醇合成催化剂及其制备方法 |
| CN107790138A (zh) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | 一种铜锌催化剂及其制备方法 |
| CN110818531A (zh) * | 2019-11-12 | 2020-02-21 | 上海兖矿能源科技研发有限公司 | 一种费托合成反应水中含氧有机物的处理方法 |
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| CN1306884A (zh) * | 2000-01-28 | 2001-08-08 | 中国科学院大连化学物理研究所 | 一种铜基双助四组分甲醇蒸汽重整制氢催化剂 |
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