CN105820034A - Method for preparing alcohol from ethyl acetate - Google Patents
Method for preparing alcohol from ethyl acetate Download PDFInfo
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- CN105820034A CN105820034A CN201610232107.8A CN201610232107A CN105820034A CN 105820034 A CN105820034 A CN 105820034A CN 201610232107 A CN201610232107 A CN 201610232107A CN 105820034 A CN105820034 A CN 105820034A
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- ethyl acetate
- catalyst
- ethanol
- hydrogenation
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 238000005070 sampling Methods 0.000 claims abstract description 4
- 230000008016 vaporization Effects 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000008246 gaseous mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 239000006200 vaporizer Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000005457 ice water Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000010949 copper Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002445 Co(NO3)3·6H2O Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- B01J35/50—
Abstract
The invention provides a method for preparing alcohol from ethyl acetate. The method comprises the following steps: step 1, preparation of a reduction catalyst; step 2, preparation of alcohol from ethyl acetate: vaporized ethyl acetate is sent into a fixed bed reactor laded with the reduction catalyst prepared in step 1, so as to be subjected to a gas phase catalysis hydrogenation reaction, H2 is mixed with ethyl acetate through a vaporizing chamber, the reaction pressure is 1.5-2.5 MPa, the reaction temperature is 220-280 DEG C, sampling is performed for 1 hour continuously at a preset temperature, and a product is collected through ice-water bath condensation. The Cu-Co-Zn-Zr-Al bimetallic catalyst adopted in the method has the obvious feature of adoption of a non-noble metal catalyst, the preparation technology is simple, and the production cost is low; in the reaction process, the catalytic activity and the stability are good; the method is environment-friendly and is suitable for industrial production.
Description
Technical field
The present invention relates to organic catalysis field, a kind of method refering in particular to ethyl acetate preparation of ethanol through hydrogenation.
Background technology
Ethanol is commonly called as under ethanol, normal temperature and pressure being a kind of colourless transparent liquid inflammable, volatile.Having many uses of ethanol, both
It is a kind of Elementary Chemical Industry raw material, is again a kind of new forms of energy.Based on following ethanol, the market direction of industry will be mainly reflected in three
Individual aspect: one is vehicle fuel, mainly ethanol petrol and ethanol diesel fuel；Two is the fuel as fuel cell；Three is to become
Support the basic material of the present petrochemical industry with ethylene as raw material.Therefore ethanol is currently the development weight of regenerative resource in the world
Point.
The industrial making method of ethanol has fermentation method, ethylene aquation method and coal chemical technology.Fermentation method is that grain route produces ethanol, this side
Method is difficult to large-scale production in China, because China is populous, per capita area of cultivated farmland is few, and Food Security does not allow us
Use substantial amounts of grain producing and ethanol in next life.Ethylene hydration method is that petroleum path produces ethanol, and production procedure is long, and economy is not
It is expected.Coal chemical technology best suits the national conditions of the oil-poor few gas of China's richness coal, it is possible to effectively reduces the production cost of ethanol, has
Important scientific meaning.
Acetic acid is a kind of important industrial chemicals, and current Processes for Producing Acetic Acid uses the oxo synthesis of Coal Chemical Industry Route substantially.I
State's Coal Chemical Industry methanol device high demand for investment has driven large-scale methanol acetic acid project investment, and supply exceed demand to make acetic acid, acetic acid
Price is hovered at relatively low level the most always.And current China chemical industry consumes technical grade ethanol every year more than 3,000,000 tons, city
Field demand annual rate of growth is about 8%-10% so that ethanol price Continued.Under the background that fermentation legal system ethanol stops development,
China, to the potential consumption demand that alcohol fuel the is huge deliverability limited with ethanol, brings well for acetic acid preparation of ethanol by hydrogenating
The market opportunity.Need to use expensive noble metal catalyst with acetic acid for raw material direct hydrogenation, such as platinum, palladium etc., and
Reaction unit is had higher requirement by the corrosivity having under acetic acid High Temperature High Pressure, increases the cost of investment.By acetic acid warp
Over-churning reaction repeated hydrogenation can also prepare ethanol, and acetate hydrogenation only needs cheap copper-based catalysts to be catalyzed, and keeps away
Having exempted from the corrosion of equipment, China's present acetic acid industry esterification techniques is the most ripe, so being hydrogenated with as raw material by ethyl acetate
Second processed also has good development prospect.Ethyl acetate catalytic hydrogenation ethanol technology realizes industrialized it is critical only that and prepares efficiently
And economical catalyst.Patent CN 104971725A discloses a kind of Cux-Aly-MzCatalyst is used for ethyl acetate
The reaction of preparation of ethanol by hydrogenating, wherein M is alkaline-earth metal (Mg, Ca, Sr or Ba).
Summary of the invention
A kind of method that it is an object of the invention to provide ethyl acetate preparation of ethanol through hydrogenation, the Cu-Co-Zn-Zr-Al bimetallic of employing
Catalyst is noteworthy characterized by employing non-precious metal catalyst, preparation technology simple production low cost；Course of reaction have good
Catalysis activity and stability.
The present invention is achieved through the following technical solutions:
A kind of method of ethyl acetate preparation of ethanol through hydrogenation, comprises the steps:
Step 1, preparation Cu-Co-Zn-Zr-Al catalyst；
Step 2, ethyl acetate preparation of ethanol through hydrogenation: the ethyl acetate after vaporization is sent into prepared by being mounted with in step 1
The fixed bed reactors of Cu-Co-Zn-Zr-Al catalyst carry out gas-phase catalytic hydrogenation reaction, H2By vaporizer and ethyl acetate
Mixing, reaction pressure is 1.5～2.5MPa, and reaction temperature is at 220～280 DEG C, continuous sampling lh at a given temperature, frozen water
Product is collected in bath condensation.
In step 1, in described Cu-Co-Zn-Zr-Al catalyst, the mass ratio of Cu, Co, Zn, Zr and Al element is
30～20:10～5:30～10:20:30～20, described Cu-Co-Zn-Zr-Al reducing catalyst granular size is 40～60 mesh.
The preparation method of described Cu-Co-Zn-Zr-Al catalyst is:
Step A, first the nitrate of a certain amount of Cu, Co, Zn, Zr, Al is dissolved in deionized water, be configured to sun from
Sub-total concentration is 1mol L-1Aqueous solution, secondly, configure 1mol L-1Sodium carbonate liquor, stirs at 65 DEG C of heating in water bath and magnetic force
Under the conditions of mixing, nitrate solution and sodium carbonate liquor stream are slowly dropped in the flask of the deionized water filling 200mL, control
The rate of addition of sodium carbonate liquor processed regulates pH in the range of 7.5～8.0, treats that nitrate solution all drips ageing 2h, so
After be filtrated to get solid sediment, solid sediment is washed, is then passed through being dried, roasting and tabletting, make catalyst
Parent；
Step B, catalyst Precursors is carried out reduction activation pretreatment in the gaseous mixture of nitrogen and hydrogen, under 0.1MPa pressure,
With 5 DEG C/min temperature programming to 340 DEG C, H in this section of process gaseous mixture2Volume fraction is 10%, and gaseous mixture flow velocity is
250ml/min；Again with 1.0 DEG C/min temperature programming to 400 DEG C, H during this2Volume fraction is adjusted to 40%, mixed airflow
Speed is 250ml/min, at 400 DEG C of constant temperature reduction 8h, obtains the catalyst after reduction.
In step A, described be dried, roasting, tabletting are: being dried 12h at 120 DEG C, 500 DEG C of roasting 4h, by sample pressure
Sheet, is sieved into the granule of 40～60 mesh.
Described fixed bed reactors are rustless steel tubular reactor, long 20cm, internal diameter 0.5cm.
In step 2, described loaded catalyst is 3g.
In step 2, the sample introduction flow velocity 6mL/h, H of described ethyl acetate2Flow velocity is 80mL/min.
Beneficial effect:
Cu-Co-Zn-Zr-Al bimetallic catalyst of the present invention is noteworthy characterized by employing non-precious metal catalyst, prepares work
Skill simple production low cost；There is in course of reaction good catalysis activity and stability；Environmental friendliness, is suitable for industry metaplasia
Produce.Such as, use the catalyst of the present invention, be 2h in liquid phase air speed-1Under left and right, 2.0MPa and 280 DEG C of reaction conditions, second
The conversion per pass of acetoacetic ester is up to 96%, and the selectivity of methyl formate reaches 97%.
Detailed description of the invention
Below in conjunction with being embodied as example, the present invention will be further described:
Embodiment 1
The preparation of catalyst:
Cu-Co-Zn-Zr-Al catalyst is prepared by coprecipitation: first weigh the raw material copper nitrate of respective quality
(Cu(NO3)2·3H2O), cobalt nitrate (Co (NO3)3·6H2O), zinc nitrate (Zn (NO3)2·6H2O), zirconium nitrate (Zr (NO3)4·5H2O)
With aluminum nitrate (Al (NO3)3·9H2O), be dissolved in deionized water being configured to cation concn is 1mol L-1Aqueous solution so that Cu,
The mass ratio of Co, Zn, Zr, Al element is 20:10:20:20:30.By nitrate mixed solution and 1mol L-1Sodium carbonate is molten
Liquid stream are slowly dropped in the flask of the deionized water filling 200mL, and the rate of addition controlling sodium carbonate liquor regulates pH
In the range of 7.5～8.0, treat that nitrate solution all drips ageing 2h, be then filtrated to get solid sediment, solid is sunk
Shallow lake thing washs, and is dried 12h, roasting 4h under the conditions of 500 DEG C, obtains described catalyst under the conditions of 120 DEG C.It is sieved into
The granule of 40-60 mesh, makes catalyst Precursors.
Catalyst Precursors is carried out reduction activation pretreatment, under 0.1MPa pressure, with 5 DEG C in the nitrogen gaseous mixture with hydrogen
/ min temperature programming to 340 DEG C, H in this section of process gaseous mixture2Volume fraction is 10%, and gaseous mixture flow velocity is 250ml/min；
Again with 2 DEG C/min temperature programming to 400 DEG C, H during this2Volume fraction is adjusted to 40%, and gaseous mixture flow velocity is 250ml/min,
At 400 DEG C of constant temperature reduction 8h, obtain the catalyst after reduction.
By ethyl acetate, after overflash, (vapourizing temperature 220 DEG C) enters the fixed bed reactors (institute loading reduction rear catalyst
Stating fixed bed reactors is rustless steel tubular reactor, long 20cm, internal diameter 0.5cm) in carry out gas-phase catalytic hydrogenation reaction, its
Middle loaded catalyst is 3g sample introduction flow velocity 6mL/h, H2Flow velocity is to carry out, instead under 80mL/min, reaction pressure 2.0MPa
Answering temperature 220～280 DEG C, continuous sampling lh at a given temperature, product is collected in ice-water bath condensation.The result of test is listed in table 1.
Table 1.Cu-Co-Zn-Zr-Al catalysis methanol dehydrogenation feed conversion ratio and product select
Embodiment 2
With embodiment 1, only changing reaction pressure is 1.5Mpa, and acquired results is shown in Table 2.
Table 2.Cu-Co-Zn-Zr-Al catalysis methanol dehydrogenation feed conversion ratio and product select
Embodiment 3
With embodiment 1, only changing reaction pressure is 2.5Mpa, and acquired results is shown in Table 3.
Table 3.Cu-Co-Zn-Zr-Al catalysis methanol dehydrogenation feed conversion ratio and product select
Embodiment 4
With embodiment 1, but change the mass ratio of each element in catalyst so that Cu, Co, Zn, Zr, Al element in catalyst
Mass ratio be 30:10:10:20:30, acquired results is shown in Table 4.
Table 4.Cu-Co-Zn-Zr-Al catalysis methanol dehydrogenation feed conversion ratio and product select
Embodiment 5
With embodiment 1, but change the mass ratio of each element in catalyst so that Cu, Co, Zn, Zr, Al element in catalyst
Mass ratio be 20:10:30:20:20, acquired results is shown in Table 5.
Table 5.Cu-Co-Zn-Zr-Al catalysis methanol dehydrogenation feed conversion ratio and product select
Embodiment 6
With embodiment 1, but change the mass ratio of each element in catalyst so that Cu, Co, Zn, Zr, Al element in catalyst
Mass ratio be 20:5:25:20:30, acquired results is shown in Table 6.
Table 6.Cu-Co-Zn-Zr-Al catalysis methanol dehydrogenation feed conversion ratio and product select
Claims (7)
1. the method for an ethyl acetate preparation of ethanol through hydrogenation, it is characterised in that comprise the steps:
Step 1, preparation Cu-Co-Zn-Zr-Al catalyst；
Step 2, ethyl acetate preparation of ethanol through hydrogenation: the ethyl acetate after vaporization is sent into prepared by being mounted with in step 1
The fixed bed reactors of Cu-Co-Zn-Zr-Al catalyst carry out gas-phase catalytic hydrogenation reaction, H2By vaporizer and ethyl acetate
Mixing, reaction pressure is 1.5～2.5MPa, and reaction temperature is at 220～280 DEG C, continuous sampling lh at a given temperature, frozen water
Product is collected in bath condensation.
The method of a kind of ethyl acetate preparation of ethanol through hydrogenation the most according to claim 1, it is characterised in that in step 1,
In described Cu-Co-Zn-Zr-Al catalyst, the mass ratio of Cu, Co, Zn, Zr and Al element is
30～20:10～5:30～10:20:30～20, described Cu-Co-Zn-Zr-Al reducing catalyst granular size is 40～60 mesh.
The method of a kind of ethyl acetate preparation of ethanol through hydrogenation the most according to claim 2, it is characterised in that described
The preparation process of Cu-Co-Zn-Zr-Al catalyst is:
Step A, first the nitrate of a certain amount of Cu, Co, Zn, Zr, Al is dissolved in deionized water, be configured to sun from
Sub-total concentration is 1mol L-1Aqueous solution, secondly, configure 1mol L-1Sodium carbonate liquor, stirs at 65 DEG C of heating in water bath and magnetic force
Under the conditions of mixing, nitrate solution and sodium carbonate liquor stream are slowly dropped in the flask of the deionized water filling 200mL, control
The rate of addition of sodium carbonate liquor processed regulates pH in the range of 7.5～8.0, treats that nitrate solution all drips ageing 2h, so
After be filtrated to get solid sediment, solid sediment is washed, is then passed through being dried, roasting and tabletting, make catalyst
Parent；
Step B, catalyst Precursors is carried out reduction activation pretreatment in the gaseous mixture of nitrogen and hydrogen, under 0.1MPa pressure,
With 5 DEG C/min temperature programming to 340 DEG C, H in this section of process gaseous mixture2Volume fraction is 10%, and gaseous mixture flow velocity is
250ml/min；Again with 1.0 DEG C/min temperature programming to 400 DEG C, H during this2Volume fraction is adjusted to 40%, mixed airflow
Speed is 250ml/min, at 400 DEG C of constant temperature reduction 8h, obtains the catalyst after reduction.
The method of a kind of ethyl acetate preparation of ethanol through hydrogenation the most according to claim 3, it is characterised in that in step A,
Described be dried, roasting, tabletting are: be dried 12h, 500 DEG C of roasting 4h at 120 DEG C, by sample tabletting, be sieved into 40～60
Purpose granule.
The method of a kind of ethyl acetate preparation of ethanol through hydrogenation the most according to claim 1, it is characterised in that described fixed bed
Reactor is rustless steel tubular reactor, long 20cm, internal diameter 0.5cm.
The method of a kind of ethyl acetate preparation of ethanol through hydrogenation the most according to claim 1, it is characterised in that in step 2,
Described loaded catalyst is 3g.
The method of a kind of ethyl acetate preparation of ethanol through hydrogenation the most according to claim 1, it is characterised in that in step 2,
The sample introduction flow velocity 6mL/h, H of described ethyl acetate2Flow velocity is 80mL/min.
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|---|---|---|---|
| CN201610232107.8A CN105820034A (en) | 2016-04-14 | 2016-04-14 | Method for preparing alcohol from ethyl acetate |
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| CN201610232107.8A CN105820034A (en) | 2016-04-14 | 2016-04-14 | Method for preparing alcohol from ethyl acetate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107793294A (en) * | 2017-09-12 | 2018-03-13 | 沈阳化工大学 | A kind of absolute ethyl alcohol, low-grade ethanol process for refining and purifying |
| CN108014803A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | The catalyst and method of alcohol processed |
| CN108997085A (en) * | 2018-07-11 | 2018-12-14 | 高化学（江苏）化工新材料有限责任公司 | The recovery method and recovery system of by-product in a kind of dimethyl oxalate synthesis technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103896732A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method for preparing ethanol through low carbon ester hydrogenation |
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| CN1105907A (en) * | 1989-12-21 | 1995-08-02 | 联合碳化化学品及塑料有限公司 | Hydrogenation with Cu-Al-X catalysts |
| CN102093162A (en) * | 2010-12-13 | 2011-06-15 | 西南化工研究设计院 | Method for preparing ethanol by hydrogenation of acetic ester |
| CN103896732A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method for preparing ethanol through low carbon ester hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108014803A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | The catalyst and method of alcohol processed |
| CN107793294A (en) * | 2017-09-12 | 2018-03-13 | 沈阳化工大学 | A kind of absolute ethyl alcohol, low-grade ethanol process for refining and purifying |
| CN108997085A (en) * | 2018-07-11 | 2018-12-14 | 高化学（江苏）化工新材料有限责任公司 | The recovery method and recovery system of by-product in a kind of dimethyl oxalate synthesis technology |
| CN108997085B (en) * | 2018-07-11 | 2021-08-17 | 高化学（江苏）化工新材料有限责任公司 | Method and system for recovering by-products in dimethyl oxalate synthesis process |
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