CN116393141A - Catalyst and method for preparing ethanol and methanol by methyl acetate hydrogenation - Google Patents
Catalyst and method for preparing ethanol and methanol by methyl acetate hydrogenation Download PDFInfo
- Publication number
- CN116393141A CN116393141A CN202310325287.4A CN202310325287A CN116393141A CN 116393141 A CN116393141 A CN 116393141A CN 202310325287 A CN202310325287 A CN 202310325287A CN 116393141 A CN116393141 A CN 116393141A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methyl acetate
- methanol
- ethanol
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 144
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 65
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 229920001983 poloxamer Polymers 0.000 claims description 3
- 229960000502 poloxamer Drugs 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 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 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- SQWOCMZNVYUDSE-UHFFFAOYSA-N [Zr+4].[Zr+4].[Zr+4].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] SQWOCMZNVYUDSE-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 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 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 1
- 229910052684 Cerium Inorganic materials 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- B01J23/84—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
-
- 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
- B01J23/007—Mixed salts
-
- 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
- B01J23/72—Copper
-
- 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
- B01J23/83—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C07C29/147—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst and a method for preparing ethanol and methanol by methyl acetate hydrogenation, wherein the catalyst is a composite oxide catalyst prepared by adopting a precipitation and hydrothermal two-step method, cu is taken as a main active component, any one or more of Zn, mn, zr, ce and Mg are taken as auxiliary agents, alumina is taken as a carrier, and the mass of the catalyst is 100%, wherein the mass of Cu is 20% -50%, the mass of Mg is 5% -15%, and the mass of the rest auxiliary agents is 3% -8%. Compared with the traditional coprecipitation and impregnation methods, the catalyst prepared by the two-step method has a hydrotalcite-like layered porous structure, so that Cu active components can be effectively dispersed, and interaction between an auxiliary agent and Cu in the catalyst is improved. The catalyst is used for continuously catalyzing methyl acetate hydrogenation to prepare ethanol and methanol, and improves the selectivity of ethanol and the stability of the catalyst.
Description
Technical Field
The invention belongs to the technical field of ester hydrogenation, and particularly relates to a hydrotalcite-like layered porous structure copper-based composite catalyst and a method for preparing ethanol and methanol by catalyzing methyl acetate hydrogenation by adopting the catalyst.
Background
Alcohol commonly known as alcohol (C) 2 H 5 OH) is colorless transparent liquid, is easy to burn and volatilize, has special fragrance, and is widely used in the aspects of society such as food, medicine, chemical industry, printing and dyeing, national defense and the like. The ethanol has strong permeability, solubility and bactericidal power, and can be used for preparing various organic solvents such as food preservative, disinfectant, extractant and the like. As an important organic chemical raw material, ethanol can also be used for preparing chemicals such as acetaldehyde, diethyl ether, butadiene, chloroethane and the like. In addition, the ethanol has lower heat value, higher vaporization latent heat, good antiknock performance and high oxygen content, can be used for producing ethanol gasoline as automobile fuel, and is considered as a green energy source in the 21 st century. Methanol is used as the simplest saturated monohydric alcohol, is ranked in the world trade chemicals and is widely applied to the industrial fields of transportation, agricultural national defense and the likeDomain, which is used for synthesizing bulk chemicals such as formaldehyde, acetic acid, chloromethane, methyl ammonia, pesticides, medicines and fine chemicals such as pesticides and medicines. Meanwhile, the methanol has high heat efficiency and good antiknock performance when being combusted, can be used as clean fuel after deep processing, can be added with gasoline for blending combustion, and has important significance in realizing energy diversification, improving energy structure and guaranteeing energy safety.
At present, ethanol is mainly obtained by a biomass fermentation method and a chemical synthesis method, and most of methanol is obtained by taking fossil energy as a raw material and indirectly synthesizing the raw material through synthesis gas catalysis, so that the processes are long in route, high in energy consumption and low in selectivity. Patent CN101665408A discloses a method for simultaneously preparing methanol and ethanol by using a chemical reaction of dead leaves, gasifying the dead leaves, and then adjusting the hydrocarbon ratio in the gasified products to achieve a hydrocarbon ratio suitable for synthesizing methanol and ethanol. However, the gasification of dead leaves generates a large amount of toxic gases such as carbon monoxide and the like, and the yield is low. The acetic acid is esterified and then hydrogenated on a copper-based catalyst to prepare equimolar ethanol and methanol, so that the yield is high, the cost and the requirements on equipment are low, and the method is one of the very attractive ethanol production routes in recent years. In addition, the vinylon industry in China can further accelerate the rapid development of the technology for preparing ethanol by hydrogenating the methyl acetate by producing more than million tons of methyl acetate per year. The copper-based catalyst used in the industry generally has the defects of lower dispersity of active components, easy sintering, weaker impurity interference resistance and the like, so that the activity of the catalyst is reduced and the stability is poor.
CN102327774a discloses a catalyst for preparing ethanol by hydrogenation of acetate, wherein the active metal copper accounts for 30-60%, the auxiliary metal accounts for 5-40%, and the carrier accounts for 20-50%; wherein the auxiliary metal is one or more than two of Mg, zn, mn, ni, sn, ag, pd and lanthanide, and the carrier is silicon dioxide or aluminum oxide. In the embodiment, the conversion rate is 85% and the selectivity is 79% at the reaction pressure of 3MPa, the temperature of 210 ℃ and the liquid space velocity of 1.2 g/gcat.h.
CN111151261a discloses a methyl acetate hydrogenation catalyst and its use, the catalyst comprises one or two of Cu, zn, mn and La oxides, and silicon dioxide, and adopts a coprecipitation-ammonia distillation preparation method, so that the active components are uniformly dispersed, and all the performances are good, but the preparation process is long-term and continuous with release of a large amount of irritant gas ammonia.
The invention discloses a method for preparing ethanol by acetate, wherein in a Cu-M/SiO2 catalyst, cu is an active component, and CuO accounts for 10-85 wt% of the total catalyst; m is one or more than two of Mn, zn, fe, co, ni, and accounts for 0.1-20wt%; siO (SiO) 2 The proportion of (C) is 10-89.9 wt%. The catalyst disclosed by the invention can obviously increase the activity of methyl acetate hydrogenation reaction in hydrogen (synthesis gas) containing CO, and obviously improve the yield of reaction products.
Disclosure of Invention
Aiming at the problems of the prior art, one of the purposes of the invention is to provide a layered high-dispersion copper-based composite catalyst and a method for preparing ethanol and methanol by catalyzing methyl acetate hydrogenation under milder conditions by adopting the catalyst.
In order to achieve the aim, the copper-based composite catalyst adopted by the invention is of a hydrotalcite-like porous layered structure, wherein Cu is taken as an active component, one or more of Zn, mn, zr, ce and Mg are taken as an auxiliary agent, and alumina is taken as a carrier; the mass of the catalyst is calculated as 100%, the mass of the active component is 20% -50%, the mass of Mg is 5% -15%, the mass of the rest auxiliary agents is 3% -10%, the mass fraction of the preferred active component is 40% -45%, the mass of the Mg is 8% -10%, and the mass of the rest auxiliary agents is 5% -7%.
The copper-based composite catalyst disclosed by the invention is prepared by adopting the following method:
(1) Dissolving copper nitrate, soluble salt of an auxiliary agent and an alumina source into deionized water to prepare a salt solution with the total concentration of metal ions of 0.04-2 mol/L; dropwise adding the salt solution into 1-3 mol/L of precipitant aqueous solution at 50-80 ℃, and vigorously stirring to obtain a uniform solution, wherein the final pH value of the obtained solution is 6-10; the precipitant is mixed alkali of any one of ammonium carbonate, sodium carbonate and urea and sodium hydroxide in the molar ratio of 1:2-4.
(2) Adding a template agent into the uniform solution in the step (1), and stirring for 1-5 hours at 50-80 ℃; the template agent is any one of cetyl trimethyl ammonium bromide, polyethylene glycol and poloxamer P123.
(3) Transferring the mixture obtained after stirring in the step (2) to a closed high-pressure reaction kettle, and carrying out hydrothermal treatment for 20-30 hours at the temperature of 80-120 ℃; centrifugal filtration, washing the obtained solid with deionized water or ethanol, drying at 80-150 ℃ for 10-18 hours, and roasting in a muffle furnace at 300-600 ℃ for 4-8 hours to obtain the catalyst.
In the step (1), the alumina source is any one or more of aluminum nitrate, aluminum sol and aluminum isopropoxide, and the soluble salt of the auxiliary agent is a mixture of any one of manganese nitrate, zirconium borate, zinc nitrate and cerium nitrate and magnesium nitrate.
In the step (2), the ratio of the template agent to the total molar amount of the metal ions in the step (1) is 0.01-0.08:1.
The method for preparing ethanol and methanol by methyl acetate hydrogenation provided by the invention comprises the following steps: tabletting the copper-based composite catalyst into 10-60 mesh particles, filling the particles into a continuous fixed bed reactor, reducing the catalyst by hydrogen, preheating methyl acetate to 150-280 ℃ and controlling the mass space velocity to be 1-6.0 h -1 Introducing the catalyst into a continuous fixed bed reactor, continuously introducing hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 5-25:1, and carrying out catalytic hydrogenation reaction at the temperature of 170-350 ℃ and the pressure of 0.5-8.0 MPa to obtain ethanol and methanol.
Further preferred conditions for the hydrogen reduction catalyst are: the pressure is 0.1-5.0 MPa, the hydrogen volume airspeed is 3000-8000 h -1 Raising the temperature to 180-250 ℃ at the speed of 0.5-5 ℃/min, and reducing for 1-24 hours.
In the method for preparing ethanol and methanol by hydrogenating methyl acetate, preferably, the methyl acetate is preheated to 190-220 ℃ and the mass space velocity is 0.5-3.0 h -1 Introducing the catalyst into a continuous fixed bed reactor, continuously introducing hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 8-15:1, and carrying out catalytic hydrogenation reaction at the temperature of 180-230 ℃ and the pressure of 1.0-5.0 MPa.
The beneficial effects of the invention are as follows:
1. compared with the traditional coprecipitation and impregnation method, the catalyst prepared by the two-step method has high active component content, has a hydrotalcite-like layered porous structure, is favorable for the internal and external diffusion of reactants and products, can promote the dispersion of active component Cu, improves the interaction between auxiliary agents and Cu in the catalyst, exposes more catalytic active centers, and ensures that the catalyst has high reaction activity and stability.
2. The catalyst is used for catalyzing the reaction of preparing ethanol and methanol by taking methyl acetate as a raw material, has excellent catalytic performance, the highest conversion rate of the methyl acetate can reach more than 97%, the selectivity of the ethanol and the methanol is more than 98%, the catalyst is stable for 2000 hours, the activity of the catalyst is basically unchanged, and the catalyst has the advantages of high selectivity, stable catalyst and the like, and has wide application prospect.
Drawings
FIG. 1 is a graph of 43% Cu-9% Mg-6% Ce/Al in example 4 2 O 3 And XRD patterns of commercial 50% cuznal catalyst in the oxidized state.
Detailed Description
The present invention is described in further detail below with reference to the drawings and examples, which are not to be construed as limiting the scope of the invention as claimed.
Example 1
(1) According to the atomic mole ratio of Cu to Mg to Al to Mn of 8:4:6:1, cu (NO) was treated with deionized water 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3)3 ·9H 2 O and manganese nitrate are dissolved into a salt solution with the total metal ion concentration of 1.5 mol/L; naOH and (NH) were added in a molar ratio of 3:1 with deionized water 4 ) 2 CO 3 Dissolving into 1.5mol/L alkali solution of precipitant, weighing 500mL of the two solutions in a beaker, gradually dripping salt solution into the alkali solution under intense stirring at 50deg.C, and maintaining for 1 hr to form uniform solutionThe pH at the point is controlled between 6 and 8.
(2) 13.65g of cetyltrimethylammonium bromide is weighed according to the ratio of the template agent to the total molar amount of metal ions of 0.05:1, added into the uniform solution in the step (1) under the stirring condition, and stirred and aged for 3 hours in a water bath at 50 ℃.
(3) Transferring the mixture obtained after stirring in the step (2) to a closed high-pressure reaction kettle, and carrying out hydrothermal treatment at 100 ℃ for 24 hours. Centrifugal filtration, washing the obtained solid with deionized water to pH 7, drying at 120deg.C for 12 hours, and roasting at 550deg.C in a muffle furnace for 6 hours to obtain catalyst 43% Cu-9% Mg-5% Mn/Al 2 O 3 . Low temperature N of the resulting catalyst 2 Physical adsorption test results are shown in Table 1.
43% Cu-9% Mg-5% Mn/Al of the catalyst 2 O 3 Tabletting into 10-60 mesh particles, filling the particles into a continuous fixed bed reactor, introducing high-purity hydrogen, and controlling the pressure to be 0.5MPa and the hydrogen volume space velocity to be 5000h -1 Next, the temperature was raised to 195℃at a rate of 1℃per minute, and the mixture was reduced for 5 hours. Then a high-pressure constant flow pump is adopted to pump methyl acetate liquid preheated to 160 ℃ into a continuous fixed bed reactor, and the mass airspeed of the methyl acetate is 2h -1 And continuing to introduce hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 15:1, and carrying out catalytic hydrogenation reaction at the temperature of 180 ℃ and the pressure of 3.0MPa to prepare ethanol and methanol. The reaction product obtained was analyzed by gas chromatography, and the conversion of methyl acetate and the selectivity of ethanol and methanol are shown in Table 2.
Example 2
In step (1) of this example, an equimolar amount of Zr (NO 3 ) 4 ·5H 2 O replaces the manganese nitrate of example 1, and the other steps are the same as in example 1, resulting in a catalyst of 42% Cu-9% Mg-7% Zr/Al 2 O 3 . Low temperature N of the resulting catalyst 2 Physical adsorption test results are shown in Table 1.
42% Cu-9% Mg-7% Zr/Al of the catalyst 2 O 3 Tabletting into 10-60 mesh particles, filling the particles into a continuous fixed bed reactor, introducing high-purity hydrogen, and controlling the pressure to be 0.5MPa and the hydrogen volume space velocity5000h -1 Next, the temperature was raised to 195℃at a rate of 1℃per minute, and the mixture was reduced for 5 hours. Then a high-pressure constant flow pump is adopted to pump methyl acetate liquid preheated to 170 ℃ into a continuous fixed bed reactor, and the mass airspeed of the methyl acetate is 2h -1 And continuing to introduce hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 15:1, and carrying out catalytic hydrogenation reaction at the temperature of 170 ℃ and the pressure of 3.0MPa to prepare ethanol and methanol. The reaction product obtained was analyzed by gas chromatography, and the conversion of methyl acetate and the selectivity of ethanol and methanol are shown in Table 2.
Example 3
In step (1) of this example, zn (NO 3 ) 4 ·6H 2 O replaces the manganese nitrate of example 1, and the other steps are the same as in example 1, resulting in a catalyst of 43% Cu-9% Mg-5% Zn/Al 2 O 3 . The resulting fresh catalyst was characterized by XRD, as shown in figure 1, mirror size.
43% Cu-9% Mg-5% Zn/Al of the catalyst 2 O 3 Tabletting into 10-60 mesh particles, filling the particles into a continuous fixed bed reactor, introducing high-purity hydrogen, and controlling the pressure to be 0.5MPa and the hydrogen volume space velocity to be 5000h -1 Next, the temperature was raised to 195℃at a rate of 1℃per minute, and the mixture was reduced for 5 hours. Then a high-pressure constant flow pump is adopted to pump methyl acetate liquid preheated to 180 ℃ into a continuous fixed bed reactor, and the mass airspeed of the methyl acetate is 2.0h -1 And continuously introducing hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 15:1, and carrying out catalytic hydrogenation reaction at the temperature of 180 ℃ and the pressure of 3.5MPa to prepare ethanol and methanol. The reaction product obtained was analyzed by gas chromatography, and the conversion of methyl acetate and the selectivity of ethanol and methanol are shown in Table 2.
Example 4
In step (1) of this example, cu (NO) was treated with deionized water according to a Cu: mg: al: ce atomic molar ratio of 8:4:6:0.5 3 ) 2 ·3H 2 O、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3)3 ·9H 2 O and Ce (NO) 3 ) 4 ·6H 2 O is dissolved into a salt solution with the total metal ion concentration of 1.5mol/LThe procedure is the same as in example 1, giving a catalyst of 43% Cu-9% Mg-6% Ce/Al 2 O 3 . The X-ray diffraction pattern of the oxidized catalyst is shown in figure 1, and the crystal size (9.8 nm) of the catalyst prepared by the method on a (002) crystal face is obviously smaller than that of a commercial 50% CuZnAl catalyst (40.1 nm) through the calculation of a Scherrer formula.
43% Cu-9% Mg-6% Ce/Al of the catalyst 2 O 3 Tabletting into 10-60 mesh particles, filling the particles into a continuous fixed bed reactor, introducing high-purity hydrogen, and controlling the pressure to be 0.5MPa and the hydrogen volume space velocity to be 5000h -1 Next, the temperature was raised to 195℃at a rate of 1℃per minute, and the mixture was reduced for 5 hours. Then a high-pressure constant flow pump is adopted to pump methyl acetate liquid preheated to 170 ℃ into a continuous fixed bed reactor, and the mass airspeed of the methyl acetate is 2.5h -1 And continuously introducing hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 10:1, and carrying out catalytic hydrogenation reaction at the temperature of 170 ℃ and the pressure of 4.0MPa to prepare ethanol and methanol. The reaction product obtained was analyzed by gas chromatography, and the conversion of methyl acetate and the selectivity of ethanol and methanol are shown in Table 2.
Example 5
In step 2 of this example, cetyltrimethylammonium bromide in example 4 was replaced with 30g of polyethylene glycol having a number average molecular weight of 4000 in a ratio of 0.01:1 of the total molar amount of the template agent to the metal ions, and the other steps were the same as in example 4, to obtain 43% Cu-9% Mg-6% Ce/Al catalyst 2 O 3 。
43% Cu-9% Mg-6% Ce/Al of the catalyst 2 O 3 Tabletting into 10-60 mesh granules, filling into a continuous fixed bed reactor, and catalyzing methyl acetate hydrogenation to prepare ethanol and methanol according to the method of the example 4. The reaction product obtained was analyzed by gas chromatography, and the conversion of methyl acetate and the selectivity of ethanol and methanol are shown in Table 2.
Example 6
In step 2 of this example, the cetyltrimethylammonium bromide of example 4 was replaced with 87mL of 0.5g/mL poloxamer P123 methanol solution at a ratio of template agent to total metal ion molar mass of 0.01:1, the othersThe procedure is as in example 4 to give a catalyst of 43% Cu-9% Mg-6% Ce/Al 2 O 3 。
43% Cu-9% Mg-6% Ce/Al of the catalyst 2 O 3 Tabletting into 10-60 mesh particles, filling the particles into a continuous fixed bed reactor, introducing high-purity hydrogen, and controlling the pressure to be 0.5MPa and the hydrogen volume space velocity to be 5000h -1 Next, the temperature was raised to 200℃at a rate of 1℃per minute, and the mixture was reduced for 5 hours. Then a high-pressure constant flow pump is adopted to pump methyl acetate liquid preheated to 190 ℃ into a continuous fixed bed reactor, and the mass airspeed of the methyl acetate is 2.5h -1 And continuously introducing hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 10:1, and carrying out catalytic hydrogenation reaction at the temperature of 190 ℃ and the pressure of 4.0MPa to prepare ethanol and methanol. The reaction product obtained was analyzed by gas chromatography, and the conversion of methyl acetate and the selectivity of ethanol and methanol are shown in Table 2.
Example 7
In step (1) of this example, naOH and Na in a molar ratio of 4:1 were treated with deionized water 2 CO 3 Dissolving into alkali solution with total concentration of precipitant of 1.5mol/L, otherwise obtaining catalyst 43% Cu-9% Mg-6% Ce/Al by the same procedure as in example 4 2 O 3 . Low temperature N of the resulting catalyst 2 Physical adsorption test results are shown in Table 1.
43% Cu-9% Mg-6% Ce/Al of the catalyst 2 O 3 Tabletting into 10-60 mesh particles, filling the particles into a continuous fixed bed reactor, introducing high-purity hydrogen, and controlling the pressure to be 0.5MPa and the hydrogen volume space velocity to be 5000h -1 Next, the temperature was raised to 190℃at a rate of 1℃per minute, and the mixture was reduced for 5 hours. Then a high-pressure constant flow pump is adopted to pump methyl acetate liquid preheated to 200 ℃ into a continuous fixed bed reactor, and the mass airspeed of the methyl acetate is 2.5h -1 And continuously introducing hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 10:1, and carrying out catalytic hydrogenation reaction at the temperature of 190 ℃ and the pressure of 3.0MPa to prepare ethanol and methanol. The conversion of methyl acetate and the selectivity of ethanol and methanol are shown in Table 2 by quantitative analysis.
Example 8
This practice isIn step (1) of the example, naOH and urea in a molar ratio of 2:1 were dissolved with deionized water to give an alkali solution having a total concentration of precipitants of 1.5mol/L, and the other steps were the same as in example 4 to give a catalyst of 43% Cu-9% Mg-6% Ce/Al 2 O 3 。
43% Cu-9% Mg-6% Ce/Al of the catalyst 2 O 3 Tabletting into 10-60 mesh granules, filling into a continuous fixed bed reactor, and catalyzing methyl acetate hydrogenation to prepare ethanol and methanol according to the method of the example 7. The reaction product obtained was analyzed by gas chromatography, and the conversion of methyl acetate and the selectivity of ethanol and methanol are shown in Table 2.
Example 9
In step (1) of the present embodiment, al (NO) is replaced with an alumina sol 3)3 ·9H 2 O, other procedures were carried out in the same manner as in example 8 to obtain a catalyst of 43% Cu-9% Mg-6% Ce/Al 2 O 3 。
43% Cu-9% Mg-6% Ce/Al of the catalyst 2 O 3 Tabletting into 10-60 mesh particles, filling the particles into a continuous fixed bed reactor, introducing high-purity hydrogen, and controlling the pressure to be 0.5MPa and the hydrogen volume space velocity to be 5000h -1 Next, the temperature was raised to 200℃at a rate of 1℃per minute, and the mixture was reduced for 5 hours. Then a high-pressure constant flow pump is adopted to pump methyl acetate liquid preheated to 200 ℃ into a continuous fixed bed reactor, and the mass airspeed of the methyl acetate is 2.5h -1 And continuously introducing hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 10:1, and carrying out catalytic hydrogenation reaction at the temperature of 200 ℃ and the pressure of 4.0MPa to prepare ethanol and methanol. The reaction products obtained were analyzed by gas chromatography, and the conversion of methyl acetate and the selectivity of ethanol and methanol are shown in Table 2.
TABLE 1
TABLE 2
| Catalyst | Methyl acetate conversion% | Ethanol selectivity% |
| Example 1 | 92.3 | 98.6 |
| Example 2 | 95.5 | 91.1 |
| Example 3 | 93.5 | 95.6 |
| Example 4 | 97.5 | 91.1 |
| Example 5 | 92.5 | 96.7 |
| Example 6 | 85.4 | 96.7 |
| Example 7 | 92.5 | 96.7 |
| Example 8 | 91.5 | 98.6 |
| Example 9 | 87.5 | 96.6 |
Note that: one molecule of methyl acetate is hydrogenated to simultaneously produce one molecule of ethanol and one molecule of methanol, and thus, the selectivity of methanol and the selectivity of ethanol in the table are almost equal.
Claims (9)
1. A catalyst for preparing ethanol and methanol by methyl acetate hydrogenation is characterized in that: the catalyst is of a hydrotalcite-like layered porous structure, any one or more of Cu and Zn, mn, zr, ce are used as an active component, mg is used as an auxiliary agent, and alumina is used as a carrier; the mass of the active component is 20-50%, the mass of Mg is 5-15% and the mass of the rest auxiliary agent is 3-10% based on 100% of the mass of the catalyst;
the catalyst is prepared by the following method:
(1) Dissolving copper nitrate, soluble salt of an auxiliary agent and an alumina source into deionized water to prepare a salt solution with the total concentration of metal ions of 0.04-2 mol/L; dropwise adding the salt solution into 1-3 mol/L of precipitant aqueous solution at 50-80 ℃, and vigorously stirring to obtain a uniform solution, wherein the final pH value of the obtained solution is 6-10; the precipitant is mixed alkali of any one of ammonium carbonate, sodium carbonate and urea and sodium hydroxide in a molar ratio of 1:2-4;
(2) Adding a template agent into the uniform solution in the step (1), and stirring for 1-5 hours at 50-80 ℃; the template agent is any one of cetyl trimethyl ammonium bromide, polyethylene glycol and poloxamer P123;
(3) Transferring the mixture obtained after stirring in the step (2) to a closed high-pressure reaction kettle, and carrying out hydrothermal treatment for 20-30 hours at the temperature of 80-120 ℃; centrifugal filtration, washing the obtained solid with deionized water or ethanol, drying at 80-150 ℃ for 10-18 hours, and roasting in a muffle furnace at 300-600 ℃ for 4-8 hours to obtain the catalyst.
2. The catalyst for preparing methanol and ethanol by hydrogenating methyl acetate according to claim 1, wherein the catalyst is characterized by: the mass fraction of the active components is 40-45%, the mass fraction of Mg is 8-10% and the mass fraction of the rest auxiliary agents is 5-7% based on 100% of the mass of the catalyst.
3. The catalyst for preparing ethanol and methanol by hydrogenating methyl acetate according to claim 1, wherein the catalyst is characterized by: the alumina source is any one or more of aluminum nitrate, aluminum sol and aluminum isopropoxide.
4. The catalyst for preparing ethanol and methanol by hydrogenating methyl acetate according to claim 1, wherein the catalyst is characterized by: the soluble salt of the auxiliary agent is a mixture of any one of manganese nitrate, zirconium borate, zinc nitrate and cerium nitrate and magnesium nitrate.
5. The catalyst for preparing ethanol and methanol by hydrogenating methyl acetate according to claim 1, wherein the catalyst is characterized by: in the step (2), the ratio of the template agent to the total molar amount of the metal ions in the step (1) is 0.01-0.08:1.
6. A method for preparing methanol and ethanol by methyl acetate hydrogenation is characterized by comprising the following steps: tabletting the catalyst according to claim 1 into 10-60 mesh particles, filling the particles into a continuous fixed bed reactor, reducing the catalyst by hydrogen, preheating methyl acetate to 150-280 ℃ and controlling the mass space velocity to be 0.5-10.0 h -1 Introducing the catalyst into a continuous fixed bed reactor, continuously introducing hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 5-40:1, and carrying out catalytic hydrogenation reaction at the temperature of 170-350 ℃ and the pressure of 0.5-8.0 MPa to obtain ethanol and methanol.
7. The method for preparing ethanol and methanol by hydrogenating methyl acetate according to claim 6, wherein the hydrogen reduction catalyst is prepared by the following conditions: the pressure is 0.1-5.0 MPa, the hydrogen volume airspeed is 3000-12000 h -1 Raising the temperature to 180-250 ℃ at the speed of 0.5-5 ℃/min, and reducing for 1-24 hours.
8. The method for preparing ethanol and methanol by hydrogenating methyl acetate according to claim 6, wherein the hydrogen reduction catalyst is prepared by the following conditions: the pressure is 0.5-1.5 MPa, the hydrogen volume airspeed is 5000-8000 h -1 Heating to 190-220 deg.c at the speed of 1-3 deg.c/min and reducing for 10-12 hr.
9. The method for preparing ethanol and methanol by hydrogenating methyl acetate according to claim 6, wherein: preheating methyl acetate to 190-220 ℃ and controlling the mass airspeed to be 0.5-4.0 h -1 Introducing the catalyst into a continuous fixed bed reactor, continuously introducing hydrogen, controlling the molar ratio of the hydrogen to the methyl acetate to be 5-30:1, and carrying out catalytic hydrogenation reaction at the temperature of 180-240 ℃ and the pressure of 1.0-5.0 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310325287.4A CN116393141A (en) | 2023-03-30 | 2023-03-30 | Catalyst and method for preparing ethanol and methanol by methyl acetate hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310325287.4A CN116393141A (en) | 2023-03-30 | 2023-03-30 | Catalyst and method for preparing ethanol and methanol by methyl acetate hydrogenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116393141A true CN116393141A (en) | 2023-07-07 |
Family
ID=87011683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310325287.4A Pending CN116393141A (en) | 2023-03-30 | 2023-03-30 | Catalyst and method for preparing ethanol and methanol by methyl acetate hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116393141A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5019547A (en) * | 1989-04-24 | 1991-05-28 | Institut Francais Du Petrole | Process for preparing precursors of catalysts containing copper, aluminum and zinc, usable for the synthesis and the decomposition of methanol and catalysts obtained from the precursors |
| EP0721799A1 (en) * | 1995-01-11 | 1996-07-17 | United Catalysts, Inc. | Promoted and stabilized copper oxide and zinc oxide catalyst and preparation method |
| JP2012001441A (en) * | 2010-06-14 | 2012-01-05 | Sekisui Chem Co Ltd | Method for producing ethanol and system for producing ethanol |
| CN102327774A (en) * | 2011-07-06 | 2012-01-25 | 山东华鲁恒升化工股份有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic ester and preparation method and application of catalyst |
| WO2012079496A1 (en) * | 2010-12-13 | 2012-06-21 | 西南化工研究设计院 | Method for preparing ethanol by hydrogenation of acetic ester, catalyst and preparation method thereof |
| CN103028403A (en) * | 2011-09-30 | 2013-04-10 | 北京化工大学 | Body type copper-based ester hydrogenation catalyst and preparation method and application thereof |
| CN103240095A (en) * | 2012-02-14 | 2013-08-14 | 南京汇文新材料科技开发有限公司 | Methyl acetate hydrogenation catalyst and preparation method thereof |
| CN103331160A (en) * | 2013-07-16 | 2013-10-02 | 扬州大学 | Preparation method of high-dispersion copper-based catalyst based on non-precious metal |
| CN105413695A (en) * | 2015-12-22 | 2016-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing 1,3-butadiene through ethanol condensation, preparation method of catalyst and application of catalyst |
| CN111151261A (en) * | 2020-01-03 | 2020-05-15 | 新地能源工程技术有限公司 | Catalyst for preparing ethanol by acetate hydrogenation and application thereof |
| CN113244928A (en) * | 2021-05-28 | 2021-08-13 | 平顶山市拓青科技有限公司 | Novel catalyst for preparing ethanol by methyl acetate hydrogenation and preparation method thereof |
| CN115445601A (en) * | 2022-08-15 | 2022-12-09 | 南京工业大学 | Load type SiO 2 @M x O y -TiO 2 Catalyst, preparation method and application thereof |
| CN115845869A (en) * | 2022-11-24 | 2023-03-28 | 西安凯立新材料股份有限公司 | Catalyst for preparing ethanol by methyl acetate hydrogenation, preparation method and application thereof |
-
2023
- 2023-03-30 CN CN202310325287.4A patent/CN116393141A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5019547A (en) * | 1989-04-24 | 1991-05-28 | Institut Francais Du Petrole | Process for preparing precursors of catalysts containing copper, aluminum and zinc, usable for the synthesis and the decomposition of methanol and catalysts obtained from the precursors |
| EP0721799A1 (en) * | 1995-01-11 | 1996-07-17 | United Catalysts, Inc. | Promoted and stabilized copper oxide and zinc oxide catalyst and preparation method |
| JP2012001441A (en) * | 2010-06-14 | 2012-01-05 | Sekisui Chem Co Ltd | Method for producing ethanol and system for producing ethanol |
| WO2012079496A1 (en) * | 2010-12-13 | 2012-06-21 | 西南化工研究设计院 | Method for preparing ethanol by hydrogenation of acetic ester, catalyst and preparation method thereof |
| CN102327774A (en) * | 2011-07-06 | 2012-01-25 | 山东华鲁恒升化工股份有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic ester and preparation method and application of catalyst |
| CN103028403A (en) * | 2011-09-30 | 2013-04-10 | 北京化工大学 | Body type copper-based ester hydrogenation catalyst and preparation method and application thereof |
| CN103240095A (en) * | 2012-02-14 | 2013-08-14 | 南京汇文新材料科技开发有限公司 | Methyl acetate hydrogenation catalyst and preparation method thereof |
| CN103331160A (en) * | 2013-07-16 | 2013-10-02 | 扬州大学 | Preparation method of high-dispersion copper-based catalyst based on non-precious metal |
| CN105413695A (en) * | 2015-12-22 | 2016-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing 1,3-butadiene through ethanol condensation, preparation method of catalyst and application of catalyst |
| CN111151261A (en) * | 2020-01-03 | 2020-05-15 | 新地能源工程技术有限公司 | Catalyst for preparing ethanol by acetate hydrogenation and application thereof |
| CN113244928A (en) * | 2021-05-28 | 2021-08-13 | 平顶山市拓青科技有限公司 | Novel catalyst for preparing ethanol by methyl acetate hydrogenation and preparation method thereof |
| CN115445601A (en) * | 2022-08-15 | 2022-12-09 | 南京工业大学 | Load type SiO 2 @M x O y -TiO 2 Catalyst, preparation method and application thereof |
| CN115845869A (en) * | 2022-11-24 | 2023-03-28 | 西安凯立新材料股份有限公司 | Catalyst for preparing ethanol by methyl acetate hydrogenation, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| RUN-PING YE ET AL.: "Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon-oxygen bonds", 《CATAL. SCI. TECHNOL.》, vol. 8, no. 14, 11 June 2018 (2018-06-11), pages 3428 - 3449 * |
| 谢鲜梅 等: "含铜三元类水滑石化合物的合成及其性质", 《催化学报》, vol. 24, no. 8, 30 August 2003 (2003-08-30), pages 569 - 573 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108236955A (en) | A kind of preparation method of Hydrogenation of Dimethyl Oxalate synthesizing alcohol catalyst and thus obtained catalyst and its application | |
| CN107899575B (en) | Nano-gold catalyst for generating ester by one-step oxidation esterification of aldehyde and alcohol and preparation method and application thereof | |
| CN105498756B (en) | The catalyst of hydrogenation of carbon dioxide methanol | |
| CN107774263B (en) | A kind of preparation method of catalst for synthesis of methanol | |
| CN105854888A (en) | Copper-based low-temperature conversion catalyst and preparation method thereof | |
| CN101670301A (en) | Method for preparing loaded catalyst for hydrogenation | |
| CN111992213B (en) | Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol | |
| CN105562009A (en) | Layer-structured copper-based catalyst and preparation method and application thereof | |
| CN107983356B (en) | Catalyst for synthesizing higher branched chain alcohol, preparation method and application | |
| CN111185195B (en) | Preparation method and application of platinum-supported catalyst taking hydrotalcite as precursor gadolinium terbium nickel magnesium aluminum compound | |
| CN112246273B (en) | Catalyst for preparing low-carbon alcohol through carbon dioxide conversion, preparation method and application | |
| CN103769092B (en) | Hydrogenation catalyst of a kind of hydrogen dioxide solution production by anthraquinone process and preparation method thereof | |
| CN116393141A (en) | Catalyst and method for preparing ethanol and methanol by methyl acetate hydrogenation | |
| CN111686740B (en) | Preparation method of methanol synthesis catalyst | |
| CN106861706A (en) | Synthesize nickel-base catalyst and preparation method and the application of gamma butyrolactone | |
| CN105363457B (en) | For carboxylic ester hydrogenation catalyst | |
| CN113522296B (en) | CuZn catalyst for preparing ethanol by CO hydrogenation and preparation method and application thereof | |
| CN114618501B (en) | Copper-based catalyst for preparing neopentyl glycol by hydrogenation method and preparation method thereof | |
| CN111250098B (en) | Water hydrogenation catalyst for Fischer-Tropsch synthesis reaction and preparation method and application thereof | |
| CN114984991A (en) | g-C 3 N 4 Preparation method of modified hydrotalcite catalyst and application of modified hydrotalcite catalyst in condensation reaction of furfural and cyclic ketone | |
| CN113117686B (en) | Preparation method and application of supported catalyst for catalyzing dimethyl oxalate hydrogenation | |
| CN105363459B (en) | Ester through hydrogenation copper catalyst | |
| CN105435798B (en) | Carboxylate hydrogenation copper base catalyst | |
| CN115160324A (en) | Method for synthesizing TADB by HBIW hydrogenolysis debenzylation under catalysis of monoatomic palladium | |
| CN108607562A (en) | Catalyst and preparation method and application for hexanedioic acid dialkyl ester hexylene glycol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |