CN107698425A - A kind of synthetic method of absolute ethyl alcohol and anhydrous liquid alcohol - Google Patents
A kind of synthetic method of absolute ethyl alcohol and anhydrous liquid alcohol Download PDFInfo
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- CN107698425A CN107698425A CN201710817844.9A CN201710817844A CN107698425A CN 107698425 A CN107698425 A CN 107698425A CN 201710817844 A CN201710817844 A CN 201710817844A CN 107698425 A CN107698425 A CN 107698425A
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The synthetic method of a kind of absolute ethyl alcohol and anhydrous liquid alcohol, it is related to a kind of ethanol synthetic method, this method opens the synthesis path of brand-new absolute ethyl alcohol and other anhydrous liquid alcohol, while is also low-quality（Aqueous and other organic matters）The method that acetic acid and other liquid alcohols prepare absolute ethyl alcohol and anhydrous liquid alcohol.Esters are obtained by esterification with liquid alcohol under solid acid system by acetic acid（Such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate）, acetic acid and liquid alcohol can not be required material purity with aqueous and other organic matters.React obtained esters and be mostly slightly soluble in water or not soluble in water, both easily separate product, can pass through static separation, basic noenergy consumption；Obtained esters directly obtain absolute ethyl alcohol and anhydrous raw alcohol, without any accessory substance, whole process is realized by the conversion of acetic acid to absolute ethyl alcohol by hydrogenation reaction.The response path product is single, and raw material is simple and easy to get, and selectivity of product is high and without harsh reaction condition.
Description
Technical field
The present invention relates to a kind of ethanol synthetic method, more particularly to the synthesis side of a kind of absolute ethyl alcohol and anhydrous liquid alcohol
Method.
Background technology
Liquid alcohol is the positive carbon alcohol of unitary that carbon number is less than 13（Such as methanol, ethanol, propyl alcohol, n-butanol）, polyalcohol
（Ethylene glycol, 1,2 one propane diols, neopentyl glycol, Diethylene Glycol etc.）Or cyclic alcohol（Such as phenol, catechol, to benzene two
Phenol, resorcinol etc.）, formula R-OH, colourless liquid.It is widely used in the fields such as organic synthesis, derived energy chemical.Ethanol
（Ethanol, it is abbreviated as EtOH）, it is commonly called as alcohol.Ethanol is a kind of inflammable, volatile water white transparency liquid under normal temperature, normal pressure
Body, hypotoxicity, not directly drink, there is peat-reek, and slightly stimulate.Ethanol is large industrial chemicals, by ethanol
The chemical products such as ethyl acetate, monoethanolamine and ethene etc. of many high added values can be produced, ethanol can be used as fuel additive,
The raw material of the products such as dyestuff, coating, detergent can also be produced.Other ethanol is in works such as chemical industry, food, national defence, medicine, printing and dyeing
Industry field also has a wide range of applications.
At present, the synthetic method of ethanol mainly has, grain fermentation method, ethylene hydration method, synthesis gas Ethanol Method, other
It is bonded into gas ethanol procedure, acetic acid hydrogenation Ethanol Method etc..
1）Biological fermentation process：Fermentation method is traditional production method, and consuming grain is more, and cost is high, and waste residue, waste water treatment are stranded
It is difficult.With the Continued of international grain price and increasingly sharpening for food shortage, national governments have also halted grain fermentation in succession
Project.
2）Ethylene hydration method：Under catalyst existence condition, ethene directly reacts with water, generates ethanol.Reaction equation
It is as follows：
CH2=CH2+H2O→C2H5O……………………………………………………(1)
Ethylene hydration method is industrially the main production process of ethanol, hydration method are divided into indirect hydration method and direct hydration again at present
Two kinds of method.Indirect hydration method is also referred to as sulfuric acid ester process, and reaction is carried out in two steps.Sulfuric ester is first generated, second step is sulfate ester hydrolysis
Ethanol is obtained, while generates accessory substance ether.By ethene and water, high temperature, high pressure in the presence of phosphoric acid catalyst are hydrated direct hydration method
It is made.This law flow is simple, corrosivity is small, is not required to special rolling-mill section, and by-product ether amount is few, but requires Ethylene purity height, power consumption
Greatly.
3）Synthesis gas Ethanol Method：Refer to synthesis gas（CO + H2）C1-C6 low-carbon alcohols are converted under catalyst existence condition
Mixture, based on ethanol product.IFP-Idemistsu techniques using Cu-Co as Catalyst Production C1-C7 mixed alcohols, wherein
Low-carbon alcohols mass fraction accounts for 20-70%.LURGI's Octamix techniques use modified catalyst for methanol, add different oxidations
Thing auxiliary agent such as Cr, Ce, La, Mn etc., product is mainly methanol, is secondly ethanol product.Italian Snam companies and Denmark
The MAS techniques of Topsoe companies exploitation, the kt/a of pilot scale 15 demonstration plant is built up using Zn-Cr catalyst.Synthesis gas ethanol
Catalyst is generally divided into rhodium base, modified copper-based, modified Fischer-Tropsch synthesis base catalyst.
4）Other indirect synthesis gas ethanol procedures：Iglesiaetal. one is reported by dimethyl ether（DME）Without water bar
Efficient preparing methyl acetate by carbonylating under part（MAc）Route.On this basis, Japanese scholars Tsubaki uses two-stage catalytic
Agent, first paragraph are DME carbonylation MAc catalyst, and second segment is MAc hydrogenation catalysts, and wherein ethanol yield can reach
46.3%.In theory, methyl acetate preparation of ethanol by hydrogenating method, ethanol highest are selectively only 66.7%.
5）Acetic acid hydrogenation Ethanol Method：The advantages of acetic acid direct hydrogenation technique is can to save esterif iotacation step, and technological process is short.
But the shortcomings that following several respects be present：1. hydrogenation catalyst is expensive；2. acetic acid conversion is low, equipment material requires high；3. product
Separating energy consumption is high.
The content of the invention
It is an object of the invention to provide the synthetic method of a kind of absolute ethyl alcohol and anhydrous liquid alcohol, the present invention uses low product
Matter（Aqueous or other organic matters）Liquid alcohol and acetic acid are raw material, and esters are first generated in the presence of solid acid catalyst, then
Absolute ethyl alcohol is obtained by Cu bases or noble metal catalyst Hydrogenation.Hydrogenation reaction raw material is not aqueous, and reaction efficiency is high, and the energy is basic
Do not waste.The path technique is simple, and raw material sources are convenient, and accessory substance only has water, and simultaneous reactions post processing simplicity is for environment
Less pollution.A kind of new idea and method is provided for large-scale industrial production.
The purpose of the present invention is achieved through the following technical solutions：
A kind of synthetic method of absolute ethyl alcohol and anhydrous liquid alcohol, i.e., it is low-quality, such as aqueous and other organic matter acetic acid and other
The method that liquid alcohol prepares absolute ethyl alcohol and anhydrous liquid alcohol, methods described include procedure below：Closed by acetic acid by indirect method
Absolute ethyl alcohol is prepared into absolute ethyl alcohol and by aqueous or other organic matters low-quality purification of acetic acid purification；Simultaneously be adapted to it is aqueous and
The refined purification of the liquid alcohol compounds of other organic matters prepares anhydrous high-quality other alcohols；The response path first step, such as
Equation（1）It is shown, it is low-quality with certain proportion（Aqueous or other organic matters）Acetic acid and other liquid alcohols are raw material, one
Determine under temperature and pressure, esters are first generated in the presence of solid acid catalyst；Second step such as equation（2）It is shown, then pass through
Cu bases or noble metal catalyst Hydrogenation obtain absolute ethyl alcohol and other anhydrous alcohols；
R-OH+CH3CH2COOH→ CH3CH2COO-R+H2O………………...………(1)；
CH3CH2COO-R+H2→C2H5OH+R-OH……………………….……...……..…(2)；
Solid acid catalyst is zirconium sulfate, ferric sulfate, titanium sulfate, SO4 2-/ZrO2、SO4 2-/Fe2O3、SO4 2-/Al2O3、SO4 2-/
TiO2, Resin Acid catalyst, such as the catalyst such as D009-B, NKC-9, A-15, DA330, heteropoly acid；Heteropolyacid catalyst is adopted
Prepared with equi-volume impregnating, activated carbon, TiO2、Al2O3、SiO2, at least one of SBA-15 and MCM-41 be used as carrier.
The synthetic method of a kind of described absolute ethyl alcohol and anhydrous liquid alcohol, the carried heteropoly acid catalyst include miscellaneous
Polyacid and the carrier for carried heteropoly acid, the one kind or more of heteropoly acid in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid and silicomolybdic acid
Kind.
The synthetic method of a kind of described absolute ethyl alcohol and anhydrous liquid alcohol is miscellaneous more in the carried heteropoly acid catalyst
It is still more preferably 5~40% that acid, which accounts for carried heteropoly acid catalyst gross weight,.
The synthetic method of a kind of described absolute ethyl alcohol and anhydrous liquid alcohol, the Cu bases catalyst include Cu/ZnO, Cu/
Cr2O3、Cu/Al2O3、Cu/CeO2, noble metal catalyst is including Pt, Pd, Rh or is supported on carrier, such as：TiO2、
Al2O3、Fe2O3、CeO2。
The synthetic method of a kind of described absolute ethyl alcohol and anhydrous liquid alcohol, the Cu bases catalyst is with coprecipitated and impregnate
Prepared by method, noble metal catalyst Pt, Pd, Rh.
Advantages of the present invention is with effect：
The present invention opens the synthesis path of brand-new absolute ethyl alcohol and other anhydrous liquid alcohol, while is also low-quality（It is aqueous
And other organic matters）The method that acetic acid and other liquid alcohols prepare absolute ethyl alcohol and anhydrous liquid alcohol.Purpose is to protect by second
Acid synthesizes absolute ethyl alcohol by indirect method and prepares absolute ethyl alcohol by aqueous or other organic matters low-quality purification of acetic acid purification；
It is adapted to the refined purification of aqueous and other organic matters liquid alcohol compound to prepare anhydrous high-quality other alcohols simultaneously.
The first step is to obtain esters by esterification with liquid alcohol under solid acid system by acetic acid（As methyl acetate,
Ethyl acetate, propyl acetate, n-butyl acetate etc.）, acetic acid and liquid alcohol can not have with aqueous and other organic matters to material purity
Require.React obtained esters and be mostly slightly soluble in water or not soluble in water, both easily separate product, can pass through static point
From basic noenergy consumption；Obtained esters are directly obtained absolute ethyl alcohol and anhydrous raw alcohol, not appointed by hydrogenation reaction
What accessory substance, whole process are realized by the conversion of acetic acid to absolute ethyl alcohol.The present invention is prepared for being adapted to two steps of esterification and hydrogenation
The high-performance solid catalyst of reaction.The response path product is single, and raw material is simple and easy to get, and selectivity of product is high and anti-without high pressure
Condition is answered just to carry out.Most acetic acid is changed into absolute ethyl alcohol to the present invention at last, meets the present situation that domestic acetic acid is superfluous at present, and
And absolute ethyl alcohol has broader demand compared with acetic acid, gasoline additive can be used as, therefore have a good application prospect.And
Raw acetic acid needed for this method and liquid alcohol are cheap and easy to get, and whole flow process is simple to operate, while this method does not produce any dirt
The chemical substance of environment is contaminated, belongs to environmentally friendly processing route.
Brief description of the drawings
Fig. 1 is present invention process process schematic.
Embodiment
With reference to embodiment, the present invention is described in detail.
Product is detected and determined by gas-chromatography and GC-MS analysis in the present invention.Pass through gas-matter
Compose combination analysis detection, it is determined that reacted mixture composition is simple, only acetic acid, liquid alcohol and esters.
Embodiment 1
1000 g liquid alcohol, 1200 g acetic acid and 50 g catalyst are added in 2.5 L reactors, catalyst is solid acid sulphur
Sour titanium.Catalyst is directly added at ambient temperature, carries out heat temperature raising reaction, 500 revs/min of reactor mixing speed, reaction
98 DEG C of temperature, the h of reaction time 4, liquid alcohol are respectively methanol, ethanol, propyl alcohol, n-butanol, n-amyl alcohol, n-hexyl alcohol, positive heptan
Alcohol, n-octyl alcohol, n-nonyl alcohol, Decanol, undecyl alcohol, lauryl alcohol, ethylene glycol, 1,2 one propane diols, neopentyl glycol, two contracting diethyls two
Alcohol, phenol, catechol, hydroquinones, resorcinol.Reaction result is as shown in table 1.
Influence of the titanium sulfate of table 1. at 98 DEG C to acetic acid and liquid alcohol reactivity and product yield
It was found from the response data of table 1, different liquids alcohol is at 98 DEG C, when catalyst is solid acid titanyl sulfate, goal response production
The yield of thing esters is on a declining curve with the increase of carbon chain lengths, wherein methyl acetate yield highest, is 90.61 %.
Embodiment 2
1000 g n-octyl alcohols, 1200 g acetic acid and 50 g catalyst are added in 2.5 L reactors, catalyst is zirconium sulfate, sulphur
Sour iron, titanium sulfate, SO4 2-/ZrO2、SO4 2-/Fe2O3、SO4 2-/Al2O3、SO4 2-/TiO2, Resin Acid catalyst（Such as D009-
B, NKC-9, A-15, DA330 etc.）, heteropolyacid catalyst.Catalyst is directly added at ambient temperature, and it is anti-to carry out heat temperature raising
Should, 500 revs/min of reactor mixing speed, reaction temperature is 98 DEG C, the h of reaction time 4, and reaction result is as shown in table 2.
Influence of the different catalysts of table 2. at 98 DEG C to acetic acid n-octyl alcohol reactivity and product yield
It was found from the response data of table 2, the g of n-octyl alcohol 1000, the g of acetic acid 1200, catalyst quality is 50 g, the difference at 98 DEG C
Catalyst has a great influence to the yield of acetic acid n-octyl, acetic acid n-octyl when wherein catalyst is solid acid catalyst titanium sulfate
Yield is maximum, is 75.47%.
Embodiment 3
1000 g n-octyl alcohols are added in 2.5 L reactors, 1200 g acetic acid and 50 g catalyst, catalyst are titanium sulfate.
Catalyst is directly added under room temperature condition, carries out heat temperature raising reaction, 500 revs/min of reactor mixing speed, reaction temperature point
Not Wei 78 DEG C, 88 DEG C, 98 DEG C, 108 DEG C, 118 DEG C, 128 DEG C of h of reaction time 4, reaction result is as shown in table 3.
Influence of the Catalyzed by Titanic Sulfate agent of table 3. to reactivity and product yield under differential responses temperature conditionss
It was found from the response data of table 3, using titanium sulfate as catalyst, the g of n-octyl alcohol 1000, the g of acetic acid 1200, catalyst quality 50
G, 4 h are reacted, with increasing for temperature, the yield of acetic acid product n-octyl is first raised and reduced afterwards, at 98 DEG C selectively most
Height, it is 75.47%.After temperature raises again, the yield that the conversion ratio of acetic acid and n-octyl alcohol also has acetic acid n-octyl reduces.It is therefore anti-
Answer temperature convenient in 98 DEG C of ratios.
Embodiment 4
In fixed bed reaction pipe, load homemade copper-based catalysts Cu/ZnO, Cu/Cr2O3、Cu/Al2O3、Cu/CeO2It is or expensive
Metallic catalyst Pt, Pd, Rh.Acetic acid n-octyl is pumped into reactor using constant flow pump, is passed through hydrogen.Ensure it is air tight
Under conditions of, carry out heat temperature raising reaction, the MPa of reaction pressure 2.0,220 DEG C, reaction time 200h of reaction temperature, liquid matter
Amount air speed is 0.5 h-1Reaction result is as shown in table 4.
Influence of the 4. different copper-based catalysts of table to acetic acid n-octyl hydrogenation reaction activity and product yield
It was found from the response data of table 4, when using different copper-based catalysts and noble metal catalyst, 220 DEG C of reaction temperature,
The h of reaction time 200, liquid quality air speed are 0.5 h-1, during 2.0 MPa of pressure, variety classes catalyst is to target product ethanol
The influence of yield, wherein when making catalyst with Cu/ZnO, the yield of ethanol is maximum, is 89.36 %.
Embodiment 5
In fixed bed reaction pipe, it is Cu/ZnO to load homemade copper-based catalysts.Acetic acid n-octyl is pumped into using constant flow pump
Into reactor, hydrogen is passed through.Ensure it is gastight under the conditions of, carry out heat temperature raising reaction, carry out heat temperature raising reaction, instead
The MPa of pressure 2.0 is answered, the reaction time is 200 h, and liquid quality air speed is 0.5 h-1, reaction temperature is respectively 220 DEG C, 230
DEG C, 240 DEG C, 250 DEG C, 260 DEG C of reaction results it is as shown in table 5.
When table 5. makees catalyst with Cu/ZnO under differential responses temperature conditionss reactivity and product yield influence
It was found from the response data of table 5, using Cu/ZnO as catalyst, 200 h are reacted under the MPa of pressure 2.0, liquid air speed is 0.5
h-1, with increasing for temperature, the yield of product ethanol is first raised and reduced afterwards, the yield highest at 230 DEG C, is 90.27 %.Temperature
After degree raises again, the conversion ratio of acetic acid n-octyl and the yield of ethanol decline.Therefore reaction temperature is convenient in 230 DEG C of ratios.
Embodiment 6
In fixed bed reaction pipe, it is Cu/ZnO to load homemade copper-based catalysts.Acetic acid n-octyl is pumped into using constant flow pump
Into reactor, hydrogen is passed through.Ensure it is gastight under the conditions of, carry out heat temperature raising reaction, carry out heat temperature raising reaction, instead
The MPa of pressure 2.0 is answered, reaction temperature is respectively 230 DEG C, and liquid air speed is 0.5 h-1, the reaction time is respectively 2 h, 5 h, 200
H, 500 h, 1000 h, 2000 h, 5000 h reaction results are as shown in table 6.
Influence of the table 6.Cu/ZnO catalyst under differential responses time conditions to reactivity and selectivity of product
It was found from the response data of table 6, when using Cu/ZnO catalyst, 230 DEG C of 2.0 MPa pressure, temperature, liquid air speed is
0.5 h-1When, the reaction time conversion ratio of acetic acid n-octyl and yield of ethanol in 5 h reach balance, from response data
The catalyst is substantially non-deactivated in prolonged course of reaction, and catalyst stability is high.
Embodiment 7
In fixed bed reaction pipe, it is Cu/ZnO to load homemade copper-based catalysts.Acetic acid n-octyl is pumped into using constant flow pump
Into reactor, hydrogen is passed through.Ensure it is gastight under the conditions of, carry out heat temperature raising reaction, carry out heat temperature raising reaction, instead
It is respectively 230 DEG C to answer temperature, and the reaction time is 200 h, and liquid air speed is 0.5 h-1, reaction pressure is respectively 1.0 MPa, 2.0
MPa, 3.0 MPa, 4.0 MPa, reaction result are as shown in table 7.
Influence of the table 7.Cu/ZnO catalyst under differential responses pressure condition to reactivity and selectivity of product
It was found from the response data of table 7, when using Cu/ZnO catalyst, the h of reaction time 200,230 DEG C of temperature, liquid air speed
For 0.5 h-1When, the reaction pressure conversion ratio of acetic acid n-octyl and yield of ethanol in 3.0 MPa reach maximum, pressure after
Height of continuing rising, the conversion ratio of acetic acid n-octyl and the yield of ethanol are on a declining curve, therefore reaction pressure is 3.0 MPa relatively more suitable
Preferably.Now the yield of ethanol is 91.36%.
Embodiment 8
In fixed bed reaction pipe, it is Cu/ZnO to load homemade copper-based catalysts.Acetic acid n-octyl is pumped into using constant flow pump
Into reactor, hydrogen is passed through.Ensure it is gastight under the conditions of, carry out heat temperature raising reaction, carry out heat temperature raising reaction, instead
It is respectively 230 DEG C to answer temperature, and the reaction time is 200 h, and reaction pressure is 3.0 MPa, and reaction liquid air speed is respectively 0.5 h-1、0.6 h-1、0.7 h-1、0.8 h-1、0.9 h-1、1.0 h-1Reaction result is as shown in table 8.
Influence of the table 8.Cu/ZnO catalyst under the conditions of differential responses liquid air speed to reactivity and selectivity of product
It was found from the response data of table 8, when using Cu/ZnO catalyst, 230 DEG C of 3.0 MPa pressure, temperature, the reaction time is
200 h, reaction liquid air speed are 0.7 h-1When the conversion ratio of acetic acid n-octyl and the yield of ethanol reach maximum, therefore reaction solution
Body air speed is 0.7 h-1Than convenient.Now the yield of ethanol is 93.16%.
It is described above, be only several embodiments of the application, any type of limitation not done to the application, although the application with
Preferred embodiment discloses as above, but and be not used to limit the application, any person skilled in the art, do not departing from this
In the range of applying for technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to equivalent reality
Case is applied, is belonged in the range of technical scheme.
Claims (5)
1. the synthetic method of a kind of absolute ethyl alcohol and anhydrous liquid alcohol, i.e., low-quality, such as aqueous and other organic matter acetic acid and its
The method that his liquid alcohol prepares absolute ethyl alcohol and anhydrous liquid alcohol, it is characterised in that methods described includes procedure below：By acetic acid
Absolute ethyl alcohol is synthesized by indirect method and absolute ethyl alcohol is prepared by aqueous or other organic matters low-quality purification of acetic acid purification；Together
Shi Shihe is aqueous and the refined purification of the liquid alcohol compound of other organic matters prepares anhydrous high-quality other alcohols；The reaction road
The footpath first step, such as equation（1）It is shown, it is low-quality with certain proportion（Aqueous or other organic matters）Acetic acid and other liquid alcohols
For raw material, under certain temperature and pressure, esters are first generated in the presence of solid acid catalyst；Second step such as equation（2）
It is shown, then absolute ethyl alcohol and other anhydrous alcohols are obtained by Cu bases or noble metal catalyst Hydrogenation；
R-OH+CH3CH2COOH → CH3CH2COO-R+H2O……………………………(1)；
CH3CH2COO-R+H2→C2H5OH+R-OH…………………………………(2)；
Solid acid catalyst is zirconium sulfate, ferric sulfate, titanium sulfate, SO4 2-/ZrO2、SO4 2-/Fe2O3、SO4 2-/Al2O3、SO4 2-/
TiO2, Resin Acid catalyst, such as the catalyst such as D009-B, NKC-9, A-15, DA330, heteropoly acid；Heteropolyacid catalyst is adopted
Prepared with equi-volume impregnating, with activated carbon, TiO2、Al2O3、SiO2, at least one of SBA-15 and MCM-41 be as carrying
Body.
2. the synthetic method of a kind of absolute ethyl alcohol according to claim 1 and anhydrous liquid alcohol, it is characterised in that described negative
Load type heteropolyacid catalyst includes heteropoly acid and the carrier for carried heteropoly acid, and heteropoly acid is selected from phosphotungstic acid, silico-tungstic acid, phosphorus molybdenum
One or more in acid and silicomolybdic acid.
3. the synthetic method of a kind of absolute ethyl alcohol according to claim 1 and anhydrous liquid alcohol, it is characterised in that described negative
It is still more preferably 5~40% that heteropoly acid, which accounts for carried heteropoly acid catalyst gross weight, in load type heteropolyacid catalyst.
4. the synthetic method of a kind of absolute ethyl alcohol according to claim 1 and anhydrous liquid alcohol, it is characterised in that the Cu
Base catalyst includes Cu/ZnO, Cu/Cr2O3、Cu/Al2O3、Cu/CeO2, noble metal catalyst is including Pt, Pd, Rh or is loaded
On carrier, such as：TiO2、Al2O3、Fe2O3、CeO2。
5. the synthetic method of a kind of absolute ethyl alcohol according to claim 1 and anhydrous liquid alcohol, it is characterised in that the Cu
Base catalyst is prepared with coprecipitated and dipping method, noble metal catalyst Pt, Pd, Rh.
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| CN103946200A (en) * | 2011-11-22 | 2014-07-23 | 国际人造丝公司 | Esterifying an ethanol and acetic acid mixture to produce an ester feed for hydrogenolysis |
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| CN101965324A (en) * | 2008-02-28 | 2011-02-02 | 埃讷肯公司 | Production of ethanol from methanol |
| CN102421736A (en) * | 2010-02-02 | 2012-04-18 | 国际人造丝公司 | Processes for producing anhydrous ethanol compositions |
| CN103946200A (en) * | 2011-11-22 | 2014-07-23 | 国际人造丝公司 | Esterifying an ethanol and acetic acid mixture to produce an ester feed for hydrogenolysis |
| CN103664529A (en) * | 2012-09-18 | 2014-03-26 | 中国石油化工股份有限公司 | Method for coproducing cyclohexanol and ethanol |
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Application publication date: 20180216 |