CN102093162B - 一种用醋酸酯加氢制备乙醇的方法 - Google Patents
一种用醋酸酯加氢制备乙醇的方法 Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 235000019439 ethyl acetate Nutrition 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000004480 active ingredient Substances 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 14
- 230000001476 alcoholic effect Effects 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- -1 silicon ester Chemical class 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 claims description 4
- 229940099204 ritalin Drugs 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229940045511 barium chloride Drugs 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002075 main ingredient 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
- 239000008188 pellet Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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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
- C07C29/147—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J23/84—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
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
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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
- B01J23/84—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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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B01J35/615—
Abstract
本发明公开了一种用醋酸酯加氢制备乙醇的方法,该方法是在有还原活化的铜基催化剂存在下,在180~300℃的反应温度和1.0~5.0MPa的反应压力下使醋酸酯加氢生成乙醇。所述的铜基催化剂以Cu为活性组分,以SiO2为载体,以过渡金属或/和碱金属中的至少一种为助剂。本方法具有高的时空收率和高的乙醇选择性,制作简单,成本低廉,对环境友好,利于工业化生产。
Description
技术领域
本发明涉及一种制备乙醇的方法,特别涉及一种用醋酸酯加氢制备乙醇的方法。
背景技术
乙醇,俗称酒精,其结构简式为CH3CH2OH。乙醇的用途很广,可用乙醇来制造醋酸、饮料、香精、染料、燃料等。医疗上也常用体积分数为70%——75%的乙醇作消毒剂。乙醇是一种很好的溶剂,既能溶解许多无机物,又能溶解许多有机物,所以常用乙醇来溶解植物色素或其中的药用成分,也常用乙醇作为反应的溶剂,使参加反应的有机物和无机物均能溶解,增大接触面积,提高反应速率。
关于乙醇的制备技术,目前主要采用的方法有食物发酵法,乙烯水化法以及羧酸酯加氢制备醇的方法。通过羧酸酯加氢制备醇以前曾有过描述,例如,在CN1230458A,CN86105765A,DE-A-3401896,DE-A-3443277,EP-A-95408,DE-A-3217492,USP4346240,BE892958,EP-A-36939及USP4405819中都有叙述。
CN1230458A公开了一种用合成气合成乙醇的方法,即用一氧化碳制备乙醇的方法,它涉及一种从乙醛、乙酸乙酯、乙酸或其混合物气相加氢制备乙醇的方法,其氢气来源于合成气,所用催化剂主要成分是CuO,担体是Al2O3,助剂是一种碱金属氧化物如CaO、MgO、BaO或者过渡金属氧化物如FeO、CoO、WO、MoO、ZnO,或者上述氧化物的组合。催化剂化学组成,主要组分CuO:10-70W%,担体Al2O3:1-50W%,助剂:1-55W%。这就要求活性组分Cu含量要在40%以上才能具有较好的活性。催化剂采用浸渍法或共沉淀法制备,催化剂干燥温度10-200℃,焙烧温度300-600℃,焙烧时间1-10小时。
CN86105765A公开了通过羧酸酯加氢制醇的方法,在含有铜和至少一种镁、镧系金属或锕系金属的催化剂存在下于高温、常压或高压下使羧酸酯加氢以制备醇,该种方法的时空收率为1.54g/(g催化剂·h-1)。但是镧系或锕系金属价格昂贵,成本较高,不利于工业化生产。
DE-A-3443277公开了在以二氧化碳来提高还原态氧化铜和氧化锌催化剂活性的情况下脂族酯的氢解。
DE892958公开了通过羧酸酯的氢解制醇,其方法是在75~300℃的温度及0.1~100千克/平方厘米的绝压下使气态的酯/氢混合物与包括还原态的氧化铜/氧化锌混合物的催化剂相接触。
USP4405819公开了羧酸酯加氢催化剂。他们是过渡元素的金属和氧化物,并根据需要负载在膨润土、佛拉土、活性炭、氧化铝等之上。
其它的文献公开了非铜催化剂,如铑(DE3401896A),一种载体,铑与锡,锗和/或铅(EP-A-95408),铑和一种贵金属(DE3217429),置于载体上的含碱金属组分的VIII族金属(US4346240)以及VIII族金属,置于炭载体上的碱金属和自由基阴离子(EP-A-36939)。
发明内容
本发明的目的就在于提供一种用醋酸酯加氢制备乙醇的方法,即在有还原活化的铜基催化剂存在下,在一定的反应温度和反应压力下使醋酸酯加氢生成乙醇。
醋酸乙酯加氢反应方程式为:CH3COOC2H5+2H2→2CH3CH2OH
醋酸甲酯加氢反应方程式为:CH3COOCH3+2H2→CH3CH2OH+CH3OH
为了实现上述目的,本发明采用的技术方案是这样的:一种用醋酸酯加氢制备乙醇的方法,该方法是在有还原活化的铜基催化剂存在下,在180~300℃的反应温度和1.0~5.0MPa的反应压力下使醋酸酯加氢生成乙醇。
所述的醋酸酯为醋酸乙酯或/和醋酸甲酯,所述的过渡金属为Zn、Mn、Mo、Co中的至少一种,所述的碱金属为Mg、Ba中的至少一种,所述的载体来源于硅酸盐、硅溶胶、硅酸酯中的至少一种。
所述的铜基催化剂以Cu为活性组分,以SiO2为载体,以过渡金属或/和碱金属中的至少一种为助剂;所述催化剂中各化学组成的用量比例为:活性组分含量为载体重量的5~50%,助剂含量为载体重量的1%~10%。
所述的铜基催化剂的制备方法包括以下步骤:
(1)将金属铜盐和助剂金属盐配制成水溶液,加入质量分数28%的氨水溶液,调节溶液pH值为7~14;
(2)将硅酸盐或硅溶胶或硅酸酯加入步骤(1)所述水溶液中,搅拌混合2~8小时;
(3)将溶液加热至40~80℃,控制溶液终点pH值为5~7;
(4)将加热后的溶液过滤,收集滤饼,用去离子水洗涤;
(5)将洗涤后的滤饼在80~120℃温度下干燥10~48小时;
(6)干燥后滤饼在空气或氮气气氛中于300~500℃温度下焙烧2~6小时;(7)焙烧后滤饼在氢气或氢气与氮气的混合气氛中还原3~6小时,还原温度250~350℃,气体流速80~150ml/min。
与现有技术相比,本发明的优点在于:本发明一种用醋酸酯加氢制备乙醇的方法具有高的时空收率和高的乙醇选择性,在最佳工艺条件下,该方法乙醇选择性可达97%,时空收率为1.55g/(g催化剂·h-1)。本发明所述的铜基催化剂稳定性好,活性高,对活性组分的含量要求低,只需活性组分Cu含量在15%以上即可。同时本发明方法制作简单,成本低廉,对环境友好,利于工业化生产。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,本发明进一步用以下具体实施例进行说明,但本发明绝非限于这些例子。
实施例1
称取24.1g Cu(NO3)2和1.0g Mn(NO3)2加入去离子水配制成浓度为0.2M的混合盐溶液,滴加28%的氨水,搅拌混合均匀,控制pH值为11,将70.5g JA-25型硅溶胶滴入到盐溶液中,搅拌2h;加热上述溶液至70℃,恒温反应5h,直至溶液pH值为7.0;将料液趁热过滤,再用去离子水洗涤三次,抽滤;催化剂经80℃干燥10小时后,在500℃下焙烧2小时;压片成型置于反应管中,用100ml/min的纯氢气,在250℃下还原5小时,得催化剂A。
将上述催化剂用于醋酸乙酯加氢制乙醇的反应中,装置采用固定床反应器,反应管为内径20mm,长50cm的的不锈钢管,在反应管中部装填5ml催化剂,上下端则采用直径3mm的不锈钢环或玻璃小球。反应管采用管式炉加热,反应管内置热电偶。
原料气醋酸酯经预热汽化后,自上而下通过催化剂床层,在温度180℃,压力1.5Mpa条件下与催化剂接触,产物乙醇由反应器底部引出,经冷凝后收集,离线分析。乙醇选择性90%,时空收率1.32g/(g催化剂·h-1)。
实施例2
称取12.0g Cu(NO3)2和2.0g Zn(NO3)2加入去离子水配制成浓度为0.2M的混合盐溶液,滴加28%的氨水,搅拌混合均匀,控制pH值为14,将81.0g JA-25型硅溶胶滴入到盐溶液中,搅拌8h;加热上述溶液至80℃,恒温反应5h,直至溶液pH值为6.0;将料液趁热过滤,再用去离子水洗涤三次,抽滤;催化剂经80℃干燥24小时后,在300℃下焙烧6小时;压片成型置于反应管中,用150ml/min的纯氢气,在350下还原3小时,催化剂得催化剂B。
将本实例催化剂B用于醋酸乙酯加氢制乙醇反应中,反应装置及工艺处理与分析方法同实例1。不同的是反应温度250℃,反应压力为2.5Mpa。乙醇选择性96%,时空收率1.52g/(g催化剂·h-1)。
实施例3
催化剂选用上述催化剂B,将B应用于醋酸甲酯加氢制乙醇的反应中,加氢反应装置与工艺处理同醋酸乙酯。反应温度250℃,反应压力为2.5Mpa。乙醇选择性57%,时空收率0.70g/(g催化剂·h-1)。
实施例4
称取24.1g Cu(NO3)2和2.0g Co(NO3)2加入去离子水配制成浓度为2.0M的混合盐溶液,搅拌混合均匀,加热至40℃,滴加硅酸钠的水溶液到盐溶液中,直至溶液pH值为7.0;将料液趁热过滤,再用去离子水洗涤三次,抽滤;催化剂经120℃干燥10小时后,在400℃下焙烧4小时;压片成型置于反应管中,用80ml/min的纯氢气,在300℃下还原3小时,得催化剂C。
将本实例催化剂C用于醋酸乙酯加氢制乙醇反应中,反应装置及工艺处理与分析方法同实例1。不同的是反应温度300℃,反应压力为5.0Mpa。乙醇选择性97%,时空收率1.55g/(g催化剂·h-1)。
实施例5
称取3.85g Cu(NO3)2和0.72g二钼酸铵[(NH4)2Mo2O7.4H2O]加入去离子水配制成浓度为5.0M的混合盐溶液,滴加28%的氨水,搅拌混合均匀,控制pH值为13,将60g硅酸乙酯加入到盐溶液中,搅拌5h;加热上述溶液至90℃,恒温反应5h直至溶液pH值为5.0;将料液趁热过滤,再用去离子水洗涤三次,抽滤;催化剂经100℃干燥48小时后,在400℃下焙烧3小时;压片成型置于反应管中,用120ml/min的纯氢气,在300℃下还原3小时,得催化剂D。
将本实例催化剂D用于醋酸乙酯加氢制乙醇反应中,反应装置及工艺处理与分析方法同实例1。不同的是反应温度280℃,反应压力为4.0Mpa。乙醇选择性94%,时空收率1.44g/(g催化剂·h-1)。
实施例6
称取12g Cu(NO3)2和1.6g氯化钡BaCl2加入去离子水配制成浓度为2.0M的混合盐溶液,滴加28%的氨水,搅拌混合均匀,控制pH值为12,将50g正硅酸钠加入到盐溶液中,搅拌5h;加热上述溶液至70℃,恒温反应5h直至溶液pH值为6.5;将料液趁热过滤,再用去离子水洗涤三次,抽滤;催化剂经100℃干燥12小时后,在400℃下焙烧3小时;压片成型置于反应管中,用120ml/min的纯氢气,在300℃下还原3小时,得催化剂E。
将本实例催化剂E用于醋酸乙酯加氢制乙醇反应中,反应装置及工艺处理与分析方法同实例1。不同的是反应温度240℃,反应压力为3.0Mpa。乙醇选择性95%,时空收率1.48g/(g催化剂·h-1)。
实施例7
称取24.1g Cu(NO3)2和9.5g硝酸镁Mg(NO3)2加入去离子水配制成浓度为2.0M的混合盐溶液,滴加28%的氨水,搅拌混合均匀,控制pH值为13,将36.6g硅酸乙酯加入到盐溶液中,搅拌5h;加热上述溶液至70℃,恒温反应5h直至溶液pH值为6.0;将料液趁热过滤,再用去离子水洗涤三次,抽滤;催化剂经100℃干燥12小时后,在400℃下焙烧3小时;压片成型置于反应管中,用120ml/min的纯氢气,在300℃下还原3小时,得催化剂F。
将本实例催化剂F用于醋酸乙酯加氢制乙醇反应中,反应装置及工艺处理与分析方法同实例1。反应温度260℃,反应压力为2.5Mpa。乙醇选择性96%,时空收率1.51g/(g催化剂·h-1)。
Claims (4)
1.一种用醋酸酯加氢制备乙醇的方法,该方法是在有还原活化的铜基催化剂存在下,在一定的反应温度和反应压力下使醋酸酯加氢生成乙醇,其特征在于:所述的铜基催化剂以Cu为活性组分,以SiO2为载体,以过渡金属或/和碱金属中的至少一种为助剂;
所述的过渡金属为Zn、Mn、Mo、Co中的至少一种,所述的碱金属为Mg、Ba中的至少一种,所述的载体来源于硅酸盐、硅溶胶、硅酸酯中的至少一种;
所述的铜基催化剂的制备方法包括以下步骤:
(1)将金属铜盐和助剂金属盐配制成水溶液,加入质量分数28%的氨水溶液,调节溶液pH值为7~14;
(2)将硅酸盐或硅溶胶或硅酸酯加入步骤(1)所述水溶液中,搅拌混合2~8小时;
(3)将溶液加热至40~80℃,控制溶液终点pH值为5~7;
(4)将加热后的溶液过滤,收集滤饼,用去离子水洗涤;
(5)将洗涤后的滤饼在80~120℃温度下干燥10~48小时;
(6)干燥后滤饼在空气或氮气气氛中于300~500℃温度下焙烧2~6小时;
(7)焙烧后滤饼在氢气或氢气与氮气的混合气氛中还原3~6小时,还原温度250~350℃,气体流速80~150ml/min。
2.根据权利要求1所述的一种用醋酸酯加氢制备乙醇的方法,其特征在于:所述的醋酸酯为醋酸乙酯或/和醋酸甲酯。
3.根据权利要求1所述的一种用醋酸酯加氢制备乙醇的方法,其特征在于:所述的反应温度为180~300℃,反应压力为1.0~5.0MPa。
4.根据权利要求1所述的一种用醋酸酯加氢制备乙醇的方法,其特征在于:活性组分含量为载体重量的5~50%,助剂含量为载体重量的1%~10%。
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