CN105418372A - Method for producing ethanol by acetic acid through hydrogenation - Google Patents

Method for producing ethanol by acetic acid through hydrogenation Download PDF

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CN105418372A
CN105418372A CN201410478057.2A CN201410478057A CN105418372A CN 105418372 A CN105418372 A CN 105418372A CN 201410478057 A CN201410478057 A CN 201410478057A CN 105418372 A CN105418372 A CN 105418372A
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ethanol
lightness
acetic acid
removing column
tower
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CN201410478057.2A
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CN105418372B (en
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唐国旗
田保亮
黄龙
戴伟
王国清
杨溢
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Abstract

The invention provides a method for producing ethanol by acetic acid through hydrogenation. The method comprises the steps of: (1) hydrogenation; (2) light component removal: feeding a coarse ethanol product to a light component removal tower, feeding an extractant to the light component removal tower, introducing a material flow containing an alkaline substance to the lower part of the light component removal tower or a tower kettle, wherein the light component removal tower adopts a two-step condensation modes and separates the light component into a distillate of the light component removal tower containing ethyl ether, acetaldehyde, acetone and acetic ether and a residue of the light component removal tower containing ethanol; before returning the part of distillate of the light component removal tower to a reactor, feeding the distillate to the reactor or feeding the distillate to the reactor after being pre-heated, and controlling the pH value of the residue of the light component removal tower containing ethanol at 7-10.5 by adjusting the material flow containing the alkaline substance; (3) dehydration; and (4) refining. The method can reduce the energy consumption and improve the quality of an ethanol product.

Description

A kind of acetic acid hydrogenation produces the method for ethanol

Technical field

The present invention relates to a kind of method of producing ethanol, more particularly, relate to a kind of by the method for acetic acid Hydrogenation for highly selective alcohol product.

Background technology

Ethanol be find the earliest, a kind of fatty alcohol that purposes is the widest, be also the main component of wine.The industrial process of current ethanol mainly contains fermentation method and ethylene hydration method.Ethylene hydration method develops along with the rise of petrochemical complex, comprises indirect hydration method and direct hydration method.In recent years by the raising of production cost of ethylene, in China, ethylene process is in end-of-life state substantially.The main raw material of fermentation method is farm crop (comprising corn, sugarcane, Chinese sorghum, cassava, paddy etc.), obtains ethanol by utilizing the amylofermentation in farm crop.

The raw material that main alcohol production enterprise of China uses is corn, wheat and cassava (mainly relying on import).In fact grain cost sharp rises in recent years, and therefore ethanol also exists the problem of striving grain with people.The non-grain ethanol raw material such as cassava, sweet sorghum price is also expected to rise always, and is that the two generations ethanol technology distance application of representative also has more difficulty to need to solve with cellulosic ethanol.

Acetic acid is a kind of important industrial chemicals, and the production technique of acetic acid has grain fermentation method, methanol carbonylation, oxidation of ethylene method, oxidation of ethanol method, acetaldehyde oxidation and ethane oxidation method etc.

Over nearly 10 years, acetic acid consumption still mainly concentrates on traditional field, and consumption structure considerable change does not occur, and does not form new demand growth point to support newly-increased production capacity.Estimate that China's acetic acid demand in 2012 is less than about 4,800,000 tons, problem of excess production capacity is given prominence to, and even occurs that namely new device stops production after driving.Therefore the downstream use exploitation of acetic acid is extremely urgent.

Use acetic acid to comprise two kinds as the approach of raw material production alcohol product, one is that acetic acid generates acetic ester through esterification, and then acetic ester hydrogenation generates ethanol, then carries out refined raw producing and ethanol product; Two is that acetic acid direct hydrogenation generates ethanol, then produces alcohol product through treating process.First method is compared second method and has been had more esterification process, and a large amount of ethanol needs circulation as esterification feed, corresponding add the size of hydrogenator and the interchanger of front and back thereof size and energy consumption, at least partly treating process also put and be twice, its advantage is that the corrosion strength of hydrogenation process may be lower, but also there is acetic acid more or less in its process, still there is corrodibility.But the key of second method develops the catalyzer of acetic acid direct hydrogenation, this difficult problem is also that many investigators select the first acetic acid through the reason of the method for esterification repeated hydrogenation.

For acetic acid direct hydrogenation, investigator and research data have many, as Sinopec, Celanese company of the U.S. etc. have submitted a large amount of patent application with regard to acetic acid hydrogenation.Such as PCT application enters the CN102414153A of National Phase in China, disclose and first acetic acid is hydrogenated into crude ethanol product, then in first tower, unreacted acetic acid is isolated, the overhead product of first tower is isolated in second tower the second overhead product containing vinyl acetic monomer, obtain the second resistates containing second alcohol and water, the second resistates is separated into overhead product containing ethanol and moisture resistates in the 3rd tower.In addition, selectively the second overhead product is delivered to the 4th tower, be separated into the 4th overhead product containing acetaldehyde and the 4th resistates, then by the 4th overhead product Returning reacting system to improve ethanol yield, the 4th resistates is used as solvent or is used in ester production.In other patent applications disclosed in the said firm, substantially all disclose the method ethanol production of this hydrogenation and separation sequence.

In flow process disclosed in the patent application of Calenese company, all do not mention that the ketone component of by-product is as the separation of acetone, but the acetaldehyde of by-product is separated.Acetone is contained in alcohol product will affect the quality product of ethanol, in China's alcohol product national standard, have defined to carbonyl.Contriver through detailed research, and analyzes from mechanism, inevitably generates a small amount of acetone in acetic acid hydrogenation process.Contriver, through research careful in a large number, thinks and can isolate acetone from ethanol, then acetone recycle is returned reactor, become Virahol, and Virahol is contained in alcohol product as impurity through hydrogenation process acetone.China's ethanol national standard allows wherein containing a certain amount of Virahol, if ethanol uses as alcohol fuel in addition, and applying containing not affecting it of Virahol.Further, unreacted acetic acid all adopts the mode of rectifying to be separated, and a large amount of second alcohol and waters goes out from rectifying tower top part by this separate mode undoubtedly, needs to consume a large amount of steam, and in general this process need consumes the steam consumption of 1/2 ~ 1/3 of whole flow process.

Summary of the invention

In order to solve the defect of the ethyl alcohol purification process that prior art exists, inventors herein proposing a kind of acetic acid through direct hydrogenation is crude ethanol product, then through removing ketone component and ethyl acetate and remove a small amount of acetic acid, remove moisture process simultaneously, alcohol product is obtained.

A kind of acetic acid hydrogenation of the present invention produces the method for ethanol, comprises the following steps:

(1) hydrogenation: by raw material acetic acid and hydrogen preheating, makes it pass through to be equipped with the reactor of hydrogenation catalyst, acetic acid is hydrogenated into crude ethanol product;

(2) de-light: described crude ethanol product is delivered to lightness-removing column, extraction agent is delivered to lightness-removing column, the logistics containing alkaline matter is introduced to described lightness-removing column bottom or tower reactor, described lightness-removing column takes two step condensing modes, be separated into containing ether, acetaldehyde, the lightness-removing column overhead product of acetone and vinyl acetic monomer and the lightness-removing column resistates containing ethanol, before lightness-removing column overhead product described is at least partly turned back to reactor, send into reactor or send into reactor after preheating, the pH value containing the lightness-removing column resistates of ethanol by the operating mode pattern regulated containing alkaline matter is 7 ~ 10.5,

(3) dewater: at least part of lightness-removing column resistates is delivered to dehydration tower, be separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water;

(4) refining: separating step (3) obtain containing the water in the dehydration tower overhead product of ethanol, obtain alcohol product.

Preferably, described hydrogenation catalyst is the base metal type catalyzer containing cobalt.

Preferably, in described step (1), the processing condition of acetic acid hydrogenation are: the liquid phase volume air speed of acetic acid is 0.05 ~ 1.50h -1, the mol ratio of hydrogen and acetic acid is 5 ~ 50:1, and temperature of reaction is 220 ~ 290 DEG C, and reaction pressure is that normal pressure is to 5.0MPa.

Preferably, before lightness-removing column resistates described is at least partly turned back to reactor, send into reactor or send into reactor after preheating.

Preferably, in described step (2), described lightness-removing column is extractive distillation column, and extraction agent is Diethylene Glycol or water, passes into extraction agent on lightness-removing column top.

Preferably, a part for the dehydration tower resistates in described step (3) is sent into described lightness-removing column, described dehydration tower resistates is as the extraction agent of separating acetic acid ethyl ester.

Preferably, in described step (2), described alkaline matter is selected from least one in volatile salt, bicarbonate of ammonia, ammoniacal liquor, caustic soda, sodium carbonate, sodium bicarbonate and potassium hydroxide.The described logistics containing alkaline matter is preferably the aqueous solution of above-mentioned alkaline matter.Alkaline matter concentration in aqueous has no particular limits, such as, can be 10% ~ 50%.Because lower in reactor outlet acetic acid residual content, the amount of the alkaline matter that neutralization reaction needs neither be a lot, thus do not need to provide a scope, when certain concentration is higher to concentration, the volume of this logistics will be less, consumes less steam when follow-up dehydration tower is separated.

More specifically preferably, in described step (2), the number of theoretical plate of described lightness-removing column is 25 ~ 80 pieces, the opening for feed of crude ethanol product is positioned at middle part, the opening for feed of the logistics containing alkaline matter is positioned at bottom or tower reactor, tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa; By in described step (3), the number of theoretical plate of described dehydration tower is 10 ~ 40 pieces, and the opening for feed of lightness-removing column resistates is positioned at middle and lower part, and tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa.

If lightness-removing column is extractive distillation column, the opening for feed of extraction agent is positioned at the top of lightness-removing column, such as the position of 3 ~ 10 pieces of theoretical stages.

In scheme more specifically of the present invention, comprised the following steps by the method for acetic acid production ethanol:

(1) hydrogenation: by acetic acid raw material, recycle stock and hydrogen preheating, then it is made to pass through to be equipped with the reactor of hydrogenation catalyst, carry out hydrogenation reaction, the mixture cooling of autoreactor in the future, through gas-liquid separation, be separated into crude ethanol product and the gas containing hydrogen, gas circulation is used;

(2) de-light: the middle and lower part at least part of crude ethanol product being delivered to lightness-removing column, extraction agent is delivered to the middle and upper part of lightness-removing column, the logistics containing alkaline matter is introduced to described lightness-removing column bottom or tower reactor, described lightness-removing column takes fractional condensation mode, through extracting rectifying, at lightness-removing column tower top, the liquid portion extraction of the first step condensation is sent into reactor or send into reactor after preheating, the liquid residual partial reflux of the first step condensation, uncooled gas phase portion is again through second step condensation, by the liquid extraction of condensation, the lightness-removing column resistates of ethanol is contained from tower reactor extraction, the pH value containing the lightness-removing column resistates of ethanol by the operating mode pattern regulated containing alkaline matter is 7 ~ 10.5,

(3) dewater: at least part of lightness-removing column resistates is delivered to dehydration tower, be separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water, at least part of dehydration tower resistates is delivered to lightness-removing column as described extraction agent;

(4) refining: the water contained in the dehydration tower overhead product of ethanol adopting azeotropic technology or membrane separation technique separating step (4) to obtain, obtains alcohol product;

Described recycle stock to be selected from lightness-removing column overhead product at least partially.

In the inventive solutions, suitable hydrogenation catalyst is selected from load on a catalyst or the catalyzer of at least one metal active constituent of catalyzed agent carrier dispersion.Described metal active constituent to be selected from IB, the IIB of the periodic table of elements, IIIB, IVB, VB, VIB, VIIB, Group VIIIB, lanthanide series metal and IIIA, IVA, VA, VIA race metal one or more combination.Exemplarily property metal active constituent is such as platinum, palladium, nickel, cobalt, copper, manganese, ruthenium, tin, iron, tungsten, rhenium and/or rhodium.Preferably, the active ingredient of hydrogenation catalyst is one or more the arbitrary combination in cobalt, nickel, copper, ruthenium, tin and rhenium.

As described in technical scheme, hydrogenation catalyst is the non-precious metal catalyst including cobalt metal component, except containing except cobalt in catalyzer, also can comprise other above-mentioned metal active constituents.Wherein, in the degree of integer catalyzer, cobalt contents is 10wt% ~ 45wt%.If catalyzer comprises two or more metal active constituent, the mol ratio of cobalt and other metal active constituents can modulation arbitrarily.

Be suitable as the catalyst support material of material including, but not limited to routine of support of the catalyst, such as be selected from silicon-dioxide, aluminum oxide, titanium dioxide, zirconium white, magnesium oxide, gac, graphite or the arbitrary combination in them, such as silica-alumina, titania-alumina etc.Preferably, catalyst carrier for hydrgenating is silicon-dioxide, aluminum oxide, gac, zirconium white or the arbitrary combination in them.More preferably, support of the catalyst is silicon-dioxide, aluminum oxide or its composition.

In addition, the catalyzer and the support of the catalyst that are applicable to acetic acid preparation of ethanol by hydrogenating can through any-mode modifications.Such as, utilize expanding agent or hydrothermal treatment consists mode to regulate the pore structure of carrier to improve selectivity of catalyst and stability; And for example, by adding certain metallic compound and regulate the acid-basicity of carrier to improve catalyst activity preparing carrier process; And for example, by adding certain metal in the carrier as the stability to improve catalyzer such as lanthanum, this effectively can improve catalyst life; Further, regulate its surface properties to reduce the deposition of some compound at catalyst surface with the extending catalyst life-span by carrying out alkylation process to catalyzer.

Catalyzer of the present invention can be prepared by ordinary method, to the not special requirement of preparation method, such as, take a certain amount of carrier, by the presoma of pickling process at supported on carriers metal active constituent, then dry, roasting, reduction, finally obtains described catalyst prod.Spraying method can also be used to be sprayed on carrier through the presoma of active ingredient, and then dry, roasting, reduction, finally obtains described catalyst prod.For another example, co-precipitation mode can be passed through by the load of active ingredient presoma on carrier, then dry, decompose, then the catalyst prod required for obtaining through steps such as granulation, compressing tablet, reduction.

Catalyzer of the present invention can use multiple preparation method by active ingredient together with catalyst carrier combination.For example, the first catalyzer is: catalyzer at least contains: (1) cobalt, wherein cobalt metal content accounts for the 15wt% ~ 50wt% of overall catalyst weight, (2) second metals, the second described metal be one in group vib element (molybdenum, tungsten and chromium) and more than one, account for the 0.5wt% ~ 15.0wt% of overall catalyst weight; Described catalyzer also containing oxide compound, described oxide compound be selected from silicon oxide, diatomite, Calucium Silicate powder, zirconium white, titanium oxide one or more, its content accounts for the 20wt% ~ 80wt% of overall catalyst weight; Described catalyzer is by co-precipitation, deposition-precipitation or sol-gel process preparation.The second catalyzer is: catalyzer at least contains: (1) cobalt, wherein cobalt metal content accounts for the 15wt% ~ 50wt% of overall catalyst weight, (2) alkaline-earth metal, described alkaline-earth metal is one or more in calcium, magnesium and barium, its content accounts for the 1wt% ~ 30wt% of overall catalyst weight, (3) one or more in IB race element, account for the 0.1wt% ~ 15.0wt% of overall catalyst weight; Described catalyzer also containing oxide compound, described oxide compound be selected from silicon oxide, diatomite, zirconium white, titanium oxide one or more, its content accounts for the 10wt% ~ 80wt% of overall catalyst weight; One or more in co-precipitation in described catalyzer, deposition-precipitation, ammonia still process precipitation or sol-gel process combine preparation.The third catalyzer is: catalyzer is at least containing cobalt and silver, and wherein cobalt metal content accounts for the 15wt% ~ 50wt% of overall catalyst weight, and silver metal accounts for the 0.1wt% ~ 10.0wt% of overall catalyst weight; Adopt one or more combination preparations in co-precipitation, deposition-precipitation, ammonia still process precipitation or sol-gel process.These are only exemplary illustrations, and the present invention is not limited to these examples.

For those skilled in the art, can gain enlightenment according to above detailed description in detail thus various change is made to support of the catalyst of the present invention and preparation method.Such as, any known hydrogenation catalyst, support of the catalyst or modified support of the catalyst can be adopted.

In the inventive solutions, described reactor can be the useful form of fixed bed form or other Dichlorodiphenyl Acetate hydrogenation techniques.Described hydrogenation reaction can be carried out under gas phase or liquid-phase condition.Preferably, reaction raw materials acetic acid carries out hydrogenation reaction with vapor mode and hydrogen at beds.The processing condition of hydrogenation reaction, without particular requirement, can regulate according to acetic acid transformation efficiency and ethanol yield.For example, hydrogenation reaction is carried out at ambient pressure, and temperature of reaction is 200 ~ 300 DEG C, and the liquid phase feeding volume space velocity of acetic acid is 0.05 ~ 0.5h -1.Acetic acid hydrogenation also can carry out under elevated pressure, and such as, the processing condition of acetic acid hydrogenation are: the liquid phase feeding volume space velocity of acetic acid is 0.05 ~ 1.5h -1, the mol ratio of hydrogen and acetic acid is 5 ~ 30:1, and temperature of reaction is 220 ~ 290 DEG C, and reaction pressure is 0.01MPa to 3.0MPa.

After hydrogenator, reacting coarse product reclaims heat and cooling through heat exchange, then carries out gas-liquid separation, and gas recycles through compressor, then fills into some fresh hydrogen, and liquid enters follow-up separation phase.In order to avoid the ethanol generation esterification that unreacted acetic acid generates with reaction, generate vinyl acetic monomer, should as soon as possible unreacted acetic acid separated be gone out in separation process scheme.Being separated unreacted acetic acid uses common rectificating method namely can reach separation object, certainly the chemical process using other is not got rid of yet, such as use alkaline matter as calcium hydroxide, calcium carbonate or Calcium hydrogen carbonate etc. and acetic acid reaction, generate and be insoluble in the salts substances of ethanol, thus reach acetic acid is removed.Lightness-removing column is used to be separated by the resistates of acetic acid as lightness-removing column in the present invention.

Through comparing and calculating, find to use water as extraction agent more economically.Water exists in reacting coarse product, and introduce water and make extraction agent and do not introduce novel substance, and water also needs to isolate from ethanol, isolated water can return and be used as extraction agent, and therefore selection water is a good selection as extraction agent.The present invention makes to use water as extraction agent and is separated by vinyl acetic monomer in lightness-removing column.

Reacting coarse product, after isolating above-mentioned various impurity, also contains Virahol, second alcohol and water in reacting coarse product.Be separated water outlet in ethanol, any thinkable method can be used, such as the combination of conventional distillation method, azeotropic distillation method, extraction rectifying method, membrane separating method or these methods.For example, utilize rectificating method by ethanol concentrate to more than 90wt% and below 95wt%, the azeotropic of ethanol and water forms about 95wt%, for more saving energy consumption of unit product, alcohol concn is carried and being advisable to 90wt% to 93wt%, then uses membrane separating method by ethanol concentrate to required concentration.Isolated a part of water turns back to lightness-removing column and from crude product, isolates vinyl acetic monomer as extraction agent, can reduce the discharge of waste water like this, realizes environmental friendliness cleaner production.Isolated vinyl acetic monomer Returning reactor carries out repeated hydrogenation, also isolate the acetone that side reaction generates simultaneously, acetone does not separate will affect the carbonyl index of alcohol product, and acetone separate and Returning reactor be hydrogenated into Virahol, Virahol, as alcohol, can not affect the use of ethanol as alcohol fuel.

Compared with the conventional method, the inventive method adopts tower top fractional condensation mode in the process of acetone, acetaldehyde and ethyl acetate, ethyl acetate condensation gets off to reflux by the first step condensation, and recycle before extraction and Returning reactor, second step condensation can isolate ketone and the material such as acetaldehyde and ether of the generation of acetic acid hydrogenation process effectively, this not only simplifies separation process and reduces energy consumption, and effectively can also reduce the impurity in product, thus improves the quality of final alcohol product.Method of the present invention eliminates depickling rectifying tower, significantly reduces making the steam energy consumption of whole flow process.With unreacted acetic acid in the logistics that the bottom of lightness-removing column or tower reactor are introduced containing alkaline matter, first, the tower body of acetic acid and ethanol lightness-removing column can be made to react further; Secondly, in lightness-removing column bottom and tower reactor, the content of acetic acid is relatively high, and the content of ethyl acetate is lower, if allow acetic acid and ethanol to react further in lightness-removing column tower reactor, the ethyl acetate that reaction generates will be brought in follow-up alcohol product, affects the quality of ethanol, lightness-removing column bottom or tower reactor introduce alkaline matter by unreacted acetic acid completely in and remove, the esterification generating ethyl acetate can be stopped; 3rd, introduce alkaline matter in lightness-removing column bottom or tower reactor, not only can omit neutralization reactor, and there is violent flowing in tower body and tower reactor, the object of fully neutralization can be reached.The inventive method not only can isolate ethanol effectively from acetic acid hydrogenation crude ethanol product, and reduces separating energy consumption.

Embodiment

Following examples describe the present invention's citing specifically, but the present invention is not limited to these embodiments.

Embodiment 1

In the present embodiment, the catalyzer of acetic acid hydrogenation is the acetic acid hydrogenation catalyzer that Beijing Chemical Research Institute produces, and the trade mark is BC-E-20, and catalyzer contains: (1) cobalt, and wherein cobalt metal content accounts for the 30wt% of overall catalyst weight; (2) molybdenum and chromium, accounts for the 2wt% of overall catalyst weight respectively; Surplus is silicon oxide.Described catalyzer is prepared by co-precipitation.

Comprised the following steps by the method for acetic acid production ethanol:

(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then makes it pass through to be equipped with the reactor of hydrogenation catalyst, acetic acid hydrogenation is become crude ethanol product; The processing condition of acetic acid hydrogenation are: the liquid phase volume air speed of acetic acid is 0.5h -1, the mol ratio of hydrogen and acetic acid is 20:1, and temperature of reaction is 280 DEG C, and reaction pressure is 2.0MPa.

(2) de-light: at least part of crude ethanol product is delivered to lightness-removing column, tower top takes two step fractional condensation modes, the lightness-removing column overhead product Returning reactor be separated into containing ethyl acetate recycles, the liquid of second step condensation is the lightness-removing column overhead product containing acetaldehyde, ether and acetone, contains the lightness-removing column resistates of ethanol from the extraction of lightness-removing column tower reactor; The number of theoretical plate of described lightness-removing column is 75 pieces, the opening for feed of coarse ethanol product is positioned at the 40th block of plate, use water as extraction agent, introduce at the 15th piece of plate place, the weight ratio of the inlet amount of water and coarse ethanol product is 0.3:1, and introducing containing mass percent concentration in tower reactor is the aqueous sodium hydroxide solution of 30%, and the flow controlling aqueous sodium hydroxide solution makes the pH value of tower reactor resistates be 8, tower top temperature is 79 DEG C, and tower top pressure is 0.20MPa;

(3) dewater: at least part of lightness-removing column resistates is delivered to dehydration tower, be separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water.The number of theoretical plate of described dehydration tower is 38 pieces, and the opening for feed of lightness-removing column resistates is positioned at the 33rd block of plate, and tower top temperature is 85 DEG C, and tower top pressure is 0.16MPa.

The analytical results of each step is listed in the following table.

Embodiment 2

In the present embodiment, the catalyzer of acetic acid hydrogenation is the acetic acid hydrogenation catalyzer that Beijing Chemical Research Institute produces, and the trade mark is BC-E-20, and catalyzer contains: (1) cobalt, and wherein cobalt metal content accounts for the 30wt% of overall catalyst weight; (2) molybdenum and chromium, accounts for the 2wt% of overall catalyst weight respectively; Surplus is silicon oxide.Described catalyzer is prepared by co-precipitation.

Comprised the following steps by the method for acetic acid production ethanol:

(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then makes it pass through to be equipped with the reactor of hydrogenation catalyst, acetic acid hydrogenation is become crude ethanol product; The processing condition of acetic acid hydrogenation are: the liquid phase volume air speed of acetic acid is 0.75h -1, the mol ratio of hydrogen and acetic acid is 15:1, and temperature of reaction is 270 DEG C, and reaction pressure is 1.75MPa.

(2) de-light: at least part of crude ethanol product is delivered to lightness-removing column, tower top takes two step fractional condensation modes, the lightness-removing column overhead product Returning reactor be separated into containing ethyl acetate recycles, the liquid of second step condensation is the lightness-removing column overhead product containing acetaldehyde, ether and acetone, contains the lightness-removing column resistates of ethanol from the extraction of lightness-removing column tower reactor; The number of theoretical plate of described lightness-removing column is 60 pieces, the opening for feed of coarse ethanol product is positioned at the 30th block of plate, use water as extraction agent, introduce at the 15th piece of plate place, the weight ratio of the inlet amount of water and coarse ethanol product is 0.45:1, and introducing containing mass percent concentration in tower reactor is the aqueous sodium carbonate of 25%, and the flow controlling aqueous sodium carbonate makes the pH value of tower reactor resistates be 7.5, tower top temperature is 80 DEG C, and tower top pressure is 0.15MPa;

(3) dewater: at least part of lightness-removing column resistates is delivered to dehydration tower, be separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water.The number of theoretical plate of described dehydration tower is 45 pieces, and the opening for feed of lightness-removing column resistates is positioned at the 39th block of plate, and tower top temperature is 83 DEG C, and tower top pressure is 0.15MPa.

The analytical results of each step is listed in the following table.

Embodiment 3

In the present embodiment, the catalyzer of acetic acid hydrogenation is the acetic acid hydrogenation catalyzer that Beijing Chemical Research Institute produces, and the trade mark is BC-E-20, and catalyzer contains: (1) cobalt, and wherein cobalt metal content accounts for the 30wt% of overall catalyst weight; (2) molybdenum and chromium, accounts for the 2wt% of overall catalyst weight respectively; Surplus is silicon oxide.Described catalyzer is prepared by co-precipitation.

Comprised the following steps by the method for acetic acid production ethanol:

(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then makes it pass through to be equipped with the reactor of hydrogenation catalyst, acetic acid hydrogenation is become crude ethanol product; The processing condition of acetic acid hydrogenation are: the liquid phase volume air speed of acetic acid is 1.25h -1, the mol ratio of hydrogen and acetic acid is 12:1, and temperature of reaction is 280 DEG C, and reaction pressure is 1.5MPa.

(2) de-light: at least part of crude ethanol product is delivered to lightness-removing column, tower top takes two step fractional condensation modes, the lightness-removing column overhead product Returning reactor be separated into containing ethyl acetate recycles, the liquid of second step condensation is the lightness-removing column overhead product containing acetaldehyde, ether and acetone, contains the lightness-removing column resistates of ethanol from the extraction of lightness-removing column tower reactor; The number of theoretical plate of described lightness-removing column is 70 pieces, the opening for feed of coarse ethanol product is positioned at the 35th block of plate, use water as extraction agent, introduce at the 15th piece of plate place, the weight ratio of the inlet amount of water and coarse ethanol product is 0.6:1, and introducing containing mass percent concentration in tower reactor is the aqueous sodium hydroxide solution of 35%, and the flow controlling aqueous sodium hydroxide solution makes the pH value of tower reactor resistates be 7.5, tower top temperature is 81 DEG C, and tower top pressure is 0.15MPa;

(3) dewater: at least part of lightness-removing column resistates is delivered to dehydration tower, be separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water.The number of theoretical plate of described dehydration tower is 45 pieces, and the opening for feed of lightness-removing column resistates is positioned at the 41st block of plate, and tower top temperature is 81 DEG C, and tower top pressure is 0.12MPa.

The analytical results of each step is listed in the following table.

From the analysis result data in embodiment 1-3, the inventive method effectively can isolate the material such as ketone, acetaldehyde and ethyl acetate that acetic acid hydrogenation process produces, and contributes to the quality improving final alcohol product.

Claims (10)

1. acetic acid hydrogenation produces a method for ethanol, comprises the following steps:
(1) hydrogenation: by raw material acetic acid and hydrogen preheating, makes it pass through to be equipped with the reactor of hydrogenation catalyst, acetic acid is hydrogenated into crude ethanol product;
(2) de-light: described crude ethanol product is delivered to lightness-removing column, extraction agent is delivered to lightness-removing column, the logistics containing alkaline matter is introduced to described lightness-removing column bottom or tower reactor, described lightness-removing column takes two step condensing modes, be separated into containing ether, acetaldehyde, the lightness-removing column overhead product of acetone and vinyl acetic monomer and the lightness-removing column resistates containing ethanol, before lightness-removing column overhead product described is at least partly turned back to reactor, send into reactor or send into reactor after preheating, the pH value containing the lightness-removing column resistates of ethanol by the operating mode pattern regulated containing alkaline matter is 7 ~ 10.5,
(3) dewater: at least part of lightness-removing column resistates is delivered to dehydration tower, be separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water;
(4) refining: separating step (3) obtain containing the water in the dehydration tower overhead product of ethanol, obtain alcohol product.
2. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that described step (2) is at least part of crude ethanol product is delivered to the middle and lower part of lightness-removing column, extraction agent is delivered to the middle and upper part of lightness-removing column, the logistics containing alkaline matter is introduced to described lightness-removing column bottom or tower reactor, described lightness-removing column takes two step condensing modes, through extracting rectifying, at lightness-removing column tower top, the liquid portion extraction of the first step condensation is sent into reactor or send into reactor after preheating, the liquid residual partial reflux of the first step condensation, uncooled gas phase portion is again through second step condensation, the lightness-removing column resistates of ethanol is contained from tower reactor extraction, the pH value containing the lightness-removing column resistates of ethanol by the operating mode pattern regulated containing alkaline matter is 7 ~ 10.5.
3. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, and it is characterized in that the described lightness-removing column described in step (2) is extractive distillation column, extraction agent is Diethylene Glycol or water, passes into extraction agent on lightness-removing column top.
4. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that the plate number of lightness-removing column is 25 ~ 80 pieces in described step (2), the opening for feed of crude ethanol product is positioned at middle part, the opening for feed of the material containing alkaline matter is positioned at bottom or tower reactor, tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa.
5. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that the plate number of the dehydration tower in step (3) is 10 ~ 40 pieces, the opening for feed of lightness-removing column resistates is positioned at the middle and lower part of dehydration tower, tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa.
6. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that the dehydration tower residual fraction in step (3) returns lightness-removing column.
7. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that the alkaline matter described in step (2) is at least one in volatile salt, bicarbonate of ammonia, ammoniacal liquor, caustic soda, sodium carbonate, sodium bicarbonate and potassium hydroxide.
8. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that the liquid phase volume air speed of step (1) acetic acid is 0.05 ~ 1.50h -1, the mol ratio of hydrogen and acetic acid is 5 ~ 50:1, and temperature of reaction is 220 ~ 290 DEG C, and reaction pressure is that normal pressure is to 5.0MPa.
9. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that obtaining alcohol product by the water contained in the dehydration tower overhead product of ethanol that step (4) adopts azeotropic technology or membrane separation technique separating step (3) to obtain.
10. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, and the catalyzer that it is characterized in that described in step (1) is the base metal type catalyzer containing cobalt.
CN201410478057.2A 2014-09-18 2014-09-18 A kind of method of acetic acid hydrogenation production ethanol CN105418372B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107349947A (en) * 2017-05-24 2017-11-17 沈阳三聚凯特催化剂有限公司 A kind of acetic acid hydrogenation catalyst and its application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012148434A1 (en) * 2011-04-26 2012-11-01 Celanese International Corporation Process for removing aldehydes from ethanol reaction mixture
CN103108853A (en) * 2011-04-26 2013-05-15 国际人造丝公司 Process to recover alcohol from an ethyl acetate residue stream
CN103787830A (en) * 2012-10-31 2014-05-14 中国石油化工股份有限公司 Method for producing ethanol by acetic acid hydrogenation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012148434A1 (en) * 2011-04-26 2012-11-01 Celanese International Corporation Process for removing aldehydes from ethanol reaction mixture
CN103108853A (en) * 2011-04-26 2013-05-15 国际人造丝公司 Process to recover alcohol from an ethyl acetate residue stream
CN103787830A (en) * 2012-10-31 2014-05-14 中国石油化工股份有限公司 Method for producing ethanol by acetic acid hydrogenation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107349947A (en) * 2017-05-24 2017-11-17 沈阳三聚凯特催化剂有限公司 A kind of acetic acid hydrogenation catalyst and its application

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