CN105418372B - A kind of method of acetic acid hydrogenation production ethanol - Google Patents
A kind of method of acetic acid hydrogenation production ethanol Download PDFInfo
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Abstract
The invention provides a kind of method of acetic acid hydrogenation production ethanol, comprise the following steps：(1) it is hydrogenated with；(2) take off light：The crude ethanol product is delivered into lightness-removing column, extractant is delivered into lightness-removing column, the logistics containing alkaline matter is introduced to the lightness-removing column bottom or tower reactor, described lightness-removing column takes two step condensing modes, it is separated into containing ether, acetaldehyde, the lightness-removing column distillate of acetone and ethyl acetate and the lightness-removing column residue containing ethanol, lightness-removing column distillate described at least part is returned to before reactor, feeding reactor after sending into reactor or being preheated, pH value by the lightness-removing column residue containing ethanol described in the regulation operating mode pattern containing alkaline matter is 7~10.5；(3) it is dehydrated；(4) refine.This method can reduce energy consumption, improve the quality of alcohol product.
Description
Technical field
The present invention relates to a kind of method for producing ethanol, more specifically to one kind by acetic acid Hydrogenation for Gao Xuan
The method of selecting property alcohol product.
Background technology
Ethanol be find earliest, a kind of purposes most wide fatty alcohol, be also the main component of wine.The industry of current ethanol is raw
Production method mainly has fermentation method and ethylene hydration method.Ethylene hydration method is accompanied by the rise of petrochemical industry and developed, including
Indirect hydration method and direct hydration method.Improved in recent years by production cost of ethylene, stopping production shape is substantially in China's ethylene process
State.The primary raw material of fermentation method is crops (including corn, sugarcane, sorghum, cassava, paddy etc.), by using in crops
Amylofermentation obtain ethanol.
The raw material that main alcohol production enterprise of China uses is corn, wheat and cassava (relying primarily on import).It is true
On in recent years grain cost sharp rise, therefore ethanol there is also grain is striven with people the problem of.The non-grain ethanol raw material such as cassava, sugar grass
Price is also expected to rise always, and the two generation ethanol technology distances by representative of cellulosic ethanol need solution using also more difficulty
Certainly.
Acetic acid is a kind of important industrial chemicals, and the production technology of acetic acid has grain fermentation method, methanol carbonylation, ethene
Oxidizing process, oxidation of ethanol method, acetaldehyde oxidation and ethane oxidation method etc..
Acetic acid consumption is still concentrated mainly on traditional field over nearly 10 years, and significant change does not occur for consumption structure, without shape
Cheng Xin demand growth point supports newly-increased production capacity.It is expected that China's acetic acid demand in 2012 is less than 4,800,000 tons or so, production capacity mistake
Surplus outstanding problem, or even there is i.e. stopping production after new equipment driving.Therefore the downstream use exploitation of acetic acid is extremely urgent.
The approach of alcohol product is produced using acetic acid as raw material includes two kinds, and one is that acetic acid generates acetate through esterification,
Then acetate is hydrogenated to ethanol, then carries out refined raw producing and ethanol product；Two be acetic acid direct hydrogenation generation ethanol, then through essence
Process processed produces alcohol product.First method has had more esterification process compared to second method, and a large amount of ethanol need to follow
Ring accordingly adds the size of hydrogenation reactor and its size of front and rear heat exchanger and energy consumption, at least portion as esterification feed
Point subtractive process, which is also put, to be twice, and its advantage is that the corrosion strength of hydrogenation process may be lower, but during it also or it is many or
There is acetic acid less, still suffer from corrosivity.But, the key of second method is to develop the catalyst of acetic acid direct hydrogenation,
The reason for this problem is also the method that many researchers select the first acetic acid through being esterified repeated hydrogenation.
For acetic acid direct hydrogenation, researcher and the existing many of research data, such as Sinopec, Celanese companies of the U.S.
A large amount of patent applications are have submitted Deng with regard to acetic acid hydrogenation.Such as PCT application enters the CN102414153A of National Phase in China, open
First acetic acid is hydrogenated into crude ethanol product, unreacted acetic acid is then isolated in first tower, by first tower
Distillate isolates the second distillate containing ethyl acetate in second tower, obtains the second residue of the alcohol and water containing second, the
Two residues are separated into distillate and aqueous residue containing ethanol in the 3rd tower.Additionally or alternatively, second is evaporated
Go out thing and deliver to the 4th tower, be separated into the 4th distillate and the 4th residue containing acetaldehyde, then the 4th distillate is returned into reaction
System is to improve ethanol yield, and the 4th residue is used as solvent or in ester production.Other patent Shens disclosed in the said firm
Please in, be substantially all the method ethanol production for disclosing the hydrogenation and separation sequence.
In the flow of the patent application publication of Calenese companies, do not refer to the ketone component of by-product such as acetone
Separation, but the acetaldehyde of by-product is separated.Acetone, which is contained in alcohol product, to influence the product quality of ethanol, in China's second
There is defined to carbonyl in alcohol product national standard.Inventor passes through detailed research, and is analyzed from mechanism, acetic acid
A small amount of acetone is inevitably generated in hydrogenation process.Inventor is by a large amount of careful researchs, it is believed that can divide from ethanol
Acetone is separated out, then acetone recycle is returned into reactor, hydrogenated process acetone becomes isopropanol, and isopropanol is contained in second as impurity
Alcohol product.China's ethanol national standard allows wherein to contain a certain amount of isopropanol, if ethanol makes as alcohol fuel in addition
With containing for isopropanol does not influence it to apply.Also, unreacted acetic acid is separated by the way of rectifying, this separation side
Formula undoubtedly goes out substantial amounts of second alcohol and water from rectifying tower top part, it is necessary to consume substantial amounts of steam, and in general the process needs
Consume 1/2~1/3 steam consumption of whole flow process.
The content of the invention
In order to solve the defect for the ethyl alcohol purification process that prior art is present, a kind of acetic acid is inventors herein proposed through directly adding
Hydrogen is crude ethanol product, then simultaneously removes a small amount of acetic acid, removing moisture mistake simultaneously by removing ketone component and ethyl acetate
Journey, obtains alcohol product.
A kind of method of acetic acid hydrogenation production ethanol of the present invention, comprises the following steps：
(1) it is hydrogenated with：Raw material acetic acid and hydrogen are preheated, the reactor equipped with hydrogenation catalyst is passed to, by acetic acid plus
Hydrogen is into crude ethanol product；
(2) take off light：The crude ethanol product is delivered into lightness-removing column, extractant is delivered into lightness-removing column, under the lightness-removing column
Portion or tower reactor introduce the logistics containing alkaline matter, and described lightness-removing column is taken two step condensing modes, is separated into containing ether, second
The lightness-removing column distillate of aldehyde, acetone and ethyl acetate and the lightness-removing column residue containing ethanol, will be de- described at least part
Light tower distillate is returned to before reactor, feeding reactor or preheated rear feeding reactor, contains alkaline matter by regulation
Operating mode pattern contain ethanol lightness-removing column residue pH value be 7~10.5；
(3) it is dehydrated：At least part lightness-removing column residue is delivered into dehydrating tower, the dehydrating tower distillate containing ethanol is separated into
With the dehydrating tower residue containing water；
(4) refine：Water in the dehydrating tower distillate containing ethanol that separating step (3) is obtained, obtains alcohol product.
Preferably, described hydrogenation catalyst is the base metal type catalyst containing cobalt.
Preferably, the process conditions of acetic acid hydrogenation are in the step (1)：The liquid phase volume air speed of acetic acid be 0.05~
1.50h-1, the mol ratio of hydrogen and acetic acid is 5~50:1, reaction temperature be 220~290 DEG C, reaction pressure be normal pressure extremely
5.0MPa。
Preferably, the lightness-removing column residue described at least part is returned to before reactor, sends into reactor or preheated
After send into reactor.
Preferably, in the step (2), the lightness-removing column is extractive distillation column, and extractant is diethylene glycol or water, de-
Light tower top is passed through extractant.
Preferably, a part for the dehydrating tower residue in the step (3) is sent into the lightness-removing column, the dehydrating tower
Residue is used as the extractant for separating ethyl acetate.
Preferably, in the step (2), the alkaline matter is selected from ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor, caustic soda, carbonic acid
At least one of sodium, sodium acid carbonate and potassium hydroxide.The logistics containing alkaline matter is preferably above-mentioned alkaline matter
The aqueous solution.The concentration of alkaline matter in aqueous has no particular limits, for example, can be 10%~50%.Because in reaction
Device outlet acetic acid surplus is than relatively low, and the amount of the alkaline matter that neutralization reaction needs is nor a lot, thus to concentration not
Need to provide a scope, when certain concentration is higher, the volume of the logistics will be smaller, is consumed in follow-up dehydrating tower separation
Less steam.
It is more specific preferably, in the step (2), the number of theoretical plate of the lightness-removing column is 25~80 pieces, coarse ethanol
The charging aperture of product is located at middle part, and the charging aperture of the logistics containing alkaline matter is located at bottom or tower reactor, and tower top temperature is 60~
95 DEG C, tower top pressure is 0.01~0.30MPa；By in the step (3), the number of theoretical plate of the dehydrating tower is 10~40 pieces,
The charging aperture of lightness-removing column residue is located 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 charging aperture of extractant is located at the top of lightness-removing column, such as 3~10 pieces theories
The position of plate.
In the more specifically scheme of the present invention, comprised the following steps by the method for acetic acid production ethanol：
(1) it is hydrogenated with：By the preheating of acetic acid raw material, recycle stock and hydrogen, then it is passed to anti-equipped with hydrogenation catalyst
Device is answered, hydrogenation reaction is carried out, future, the mixed material of autoreactor was cooled down, and through gas-liquid separation, is separated into crude ethanol product and is contained
There is the gas of hydrogen, gas circulation is used；
(2) take off light：At least part crude ethanol product is delivered to the middle and lower part of lightness-removing column, extractant is delivered in lightness-removing column
Top, introduces the logistics containing alkaline matter, described lightness-removing column takes fractional condensation side to the lightness-removing column bottom or tower reactor
Formula, through extracting rectifying, the liquid portion that lightness-removing column tower top condenses the first step produce and send into reactor or it is preheated after give
Enter reactor, the liquid residual partial reflux of first step condensation, uncooled gas phase portion is condensed by second step, will condensed again
Liquid extraction, from tower reactor produce the lightness-removing column residue containing ethanol, contained by adjusting the operating mode pattern containing alkaline matter
The pH value for having the lightness-removing column residue of ethanol is 7~10.5；
(3) it is dehydrated：At least part lightness-removing column residue is delivered into dehydrating tower, the dehydrating tower distillate containing ethanol is separated into
With the dehydrating tower residue containing water, at least part dehydrating tower residue is delivered into lightness-removing column as the extractant；
(4) refine：The dehydrating tower containing ethanol obtained using azeotropic technology or membrane separation technique separating step (4) is distillated
Water in thing, obtains alcohol product；
At least a portion of the recycle stock in lightness-removing column distillate.
In the inventive solutions, suitable hydrogenation catalyst is selected from load on a catalyst or by catalyst carrier
The catalyst of scattered at least one metal active constituent.The metal active constituent be selected from the IB of the periodic table of elements, IIB,
In IIIB, IVB, VB, VIB, VIIB, Group VIIIB, lanthanide series metal and IIIA, IVA, VA, Group VIA metal it is a kind of or
Two or more combinations.It is used as illustrative metal active component, for example, platinum, palladium, nickel, cobalt, copper, manganese, ruthenium, tin, iron, tungsten, rhenium
And/or rhodium.Preferably, the active component of hydrogenation catalyst is more than one or both of cobalt, nickel, copper, ruthenium, tin and rhenium appointing
Meaning combination.
As described in technical scheme, during hydrogenation catalyst is the non-precious metal catalyst for including cobalt metal component, catalyst
In addition to containing cobalt, other above-mentioned metal active constituents are may also include.Wherein, in terms of the degree of integer catalyzer, cobalt
Content is 10wt%~45wt%.If catalyst includes two or more metal active constituent, cobalt is lived with other metals
The mol ratio of property component can any modulation.
The material for being suitable as catalyst carrier includes but is not limited to conventional catalyst carrier material, is selected from two
Silica, aluminum oxide, titanium dioxide, zirconium oxide, magnesia, activated carbon, graphite or any combination in them, such as titanium dioxide
Silicon-aluminum oxide, titania-alumina etc..Preferably, catalyst carrier for hydrgenating is silica, aluminum oxide, activated carbon, oxygen
Change zirconium or any combination in them.It is highly preferred that catalyst carrier is silica, aluminum oxide or its composition.
In addition, can be modified suitable for the catalyst and catalyst carrier of acetic acid preparation of ethanol by hydrogenating through any-mode.For example, sharp
The pore structure of carrier is adjusted with expanding agent or hydro-thermal process mode to improve the selectivity and stability of catalyst；And for example, lead to
Cross and add certain metallic compound to adjust the acid-base property of carrier to improve catalyst activity preparing carrier process；And for example, pass through
Certain metal is added in the carrier as lanthanum etc. to improve the stability of catalyst, and this can effectively improve catalyst life；Further, it can lead to
Cross that catalyst is alkylated to handle and adjust its surface nature to reduce some compounds in the deposition of catalyst surface to prolong
Long catalyst life.
The catalyst of the present invention can be prepared with conventional method, preparation method not required particularly, for example, weighing one
Quantitative carrier, by infusion process in the presoma of supported on carriers metal active constituent, is then dried, and is calcined, reduction, finally
Obtain the catalyst prod.Presoma of the spraying process through active component can also be used to be sprayed on carrier, then dried, roasted
Burn, reduction finally obtains the catalyst prod.For another example, active component presoma can be supported on by co-precipitation mode
On carrier, then dry, decompose, then by the catalyst prod required for the acquisition of the steps such as granulation, tabletting, reduction.
The catalyst of the present invention can use a variety of preparation methods by active component together with catalyst carrier combination.Lift
For example, the first catalyst is：Catalyst at least contains：(1) cobalt, wherein cobalt tenor account for the 15wt% of overall catalyst weight
~50wt%, (2) second metals, described the second metal be one kind in group vib element (molybdenum, tungsten and chromium) and more than one,
Account for 0.5wt%~15.0wt% of overall catalyst weight；Described catalyst also contains oxide, and described oxide is selected from oxidation
Silicon, diatomite, calcium silicates, zirconium oxide, the one or more of titanium oxide, its content account for the 20wt% of overall catalyst weight~
80wt%；Described catalyst is prepared by co-precipitation, deposition-precipitation or sol-gel process.Second of catalyst be：
Catalyst at least contains：(1) cobalt, wherein cobalt tenor account for 15wt%~50wt% of overall catalyst weight, (2) alkaline-earth metal,
Described alkaline-earth metal is the one or more in calcium, magnesium and barium, and its content accounts for 1wt%~30wt% of overall catalyst weight, (3)
One or more in IB races element, account for 0.1wt%~15.0wt% of overall catalyst weight；Described catalyst is also containing oxidation
Thing, described oxide is selected from silica, diatomite, zirconium oxide, the one or more of titanium oxide, and it is total that its content accounts for catalyst
10wt%~80wt% of weight；In described catalyst in co-precipitation, deposition-precipitation, ammonia still process precipitation or sol-gel process
One or more kinds of combine prepare.The third catalyst is：Catalyst at least contains cobalt and silver, and wherein cobalt tenor, which is accounted for, urges
15wt%~50wt% of agent gross weight, silver metal accounts for 0.1wt%~10.0wt% of overall catalyst weight；Using co-precipitation, sink
It is prepared by one or more kinds of combine in product-precipitation, ammonia still process precipitation or sol-gel process.These are merely exemplary
Bright, the present invention is not limited to these examples.
For those skilled in the art, it can be gained enlightenment according to discussed in detail above so as to the catalysis to the present invention
Agent carrier and preparation method do various changes.For example, any of hydrogenation catalyst, catalyst carrier or modified can be used
Catalyst carrier.
In the inventive solutions, the reactor can be that fixed bed form or other Dichlorodiphenyl Acetate hydrogenation techniques have
Form.The hydrogenation reaction can be carried out under gas phase or liquid-phase condition.Preferably, reaction raw materials acetic acid with vapor mode with
Hydrogen carries out hydrogenation reaction in beds.The process conditions of hydrogenation reaction without particular/special requirement, can according to acetic acid conversion ratio and
Ethanol yield is adjusted.For example, hydrogenation reaction is carried out at ambient pressure, and reaction temperature is 200~300 DEG C, the liquid of acetic acid
Phase feed volume air speed is 0.05~0.5h-1.Acetic acid hydrogenation can also be carried out under elevated pressure, for example, the technique bar of acetic acid hydrogenation
Part is：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, reaction temperature
For 220~290 DEG C, reaction pressure is 0.01MPa to 3.0MPa.
After hydrogenation reactor, reacting coarse product reclaims heat and cooling by heat exchange, then carries out gas-liquid separation, gas warp
Compressor cycle is used, then fills into some fresh hydrogen, and liquid enters follow-up separation phase.In order to avoid unreacted vinegar
Esterification occurs for acid and the ethanol of reaction generation, generates ethyl acetate, should as soon as possible will be unreacted in separating technology flow
Acetic acid separated is gone out.Separation purpose can be reached using common rectificating method by separating unreacted acetic acid, also not arranged certainly
Except using other chemical methodes, as calcium hydroxide, calcium carbonate or calcium bicarbonate and acetic acid reaction, given birth to such as with alkaline matter
Into the salts substances for being insoluble in ethanol, acetic acid is removed so as to reach.Use lightness-removing column that acetic acid is light as taking off in the present invention
The residue separation of tower.
By comparing and calculating, discovery uses water more economical as extractant.Water has existed in reacting coarse product,
Introducing water makees extractant and does not introduce novel substance, and water is also required to isolate from ethanol, and the water isolated, which can be returned, to be come
As extractant, therefore selection water is a good selection as extractant.The present invention makees extractant in lightness-removing column using water
Ethyl acetate is separated.
Reacting coarse product also contains isopropanol, second alcohol and water after isolating above-mentioned various impurity in reacting coarse product.
Water outlet is separated in ethanol, any thinkable method, such as conventional distillation method, azeotropic distillation method, extraction essence can be used
Evaporate the combination of method, membrane separating method or these methods.For example, using rectificating method by ethanol concentrate to more than 90wt%
And below 95wt%, the azeotropic composition about 95wt% of ethanol and water, is more to save energy consumption of unit product, concentration of alcohol carry to
90wt% to 93wt% is advisable, then using membrane separating method by ethanol concentrate to required concentration.The part isolated
Water returns to lightness-removing column as extractant and ethyl acetate is isolated from crude product, can so reduce the discharge of waste water, realizes
Environment-friendly clean manufacturing.The ethyl acetate Returning reactor isolated carries out repeated hydrogenation, while also isolating side reaction generation
Acetone, acetone, which is not separated, will influence the carbonyl index of alcohol product, and acetone is separated and Returning reactor is hydrogenated into isopropanol,
Isopropanol does not interfere with ethanol as the use of alcohol fuel as alcohol.
Compared with the conventional method, the inventive method uses tower top substep in the process of acetone, acetaldehyde and ethyl acetate
Condensing mode, first step condensation, which condenses out ethyl acetate, to be flowed back, and is recycled before extraction and Returning reactor, the
The ketone and the material such as acetaldehyde and ether of the generation of acetic acid hydrogenation process can be effectively separated in the condensation of two steps, and this is not only simplified point
From flow and reduction energy consumption, and the impurity in product can also be effectively reduced, so as to improve the quality of final alcohol product.This hair
Bright method eliminates depickling rectifying column, and the steam energy consumption for making whole flow process is greatly lowered.In the bottom of lightness-removing column or tower
Kettle is introduced into the logistics containing alkaline matter and unreacted acetic acid, it is possible, firstly, to enter acetic acid and the tower body of ethanol lightness-removing column
Single step reaction；Secondly, in lightness-removing column bottom and tower reactor, the content of acetic acid is of a relatively high, and the content of ethyl acetate is relatively low, if
Acetic acid and ethanol is allowed further to be reacted in lightness-removing column tower reactor, the ethyl acetate of reaction generation will bring follow-up alcohol product into
In, the quality of ethanol is influenceed, introduce alkaline matter in lightness-removing column bottom or tower reactor neutralizes removing completely by unreacted acetic acid, can
To terminate the esterification of generation ethyl acetate；3rd, alkaline matter is introduced in lightness-removing column bottom or tower reactor, in can not only omitting
And reactor, and there is violent flowing in tower body and tower reactor, the purpose fully neutralized can be reached.The inventive method is not
Only ethanol effectively can be isolated from acetic acid hydrogenation crude ethanol product, and reduce separating energy consumption.
Embodiment
Following examples are citing descriptions more detailed to the present invention, but the invention is not limited in these embodiments.
Embodiment 1
In the present embodiment, the catalyst of acetic acid hydrogenation is the acetic acid hydrogenation catalyst that Beijing Chemical Research Institute is produced, board
Number it is BC-E-20, catalyst contains：(1) cobalt, wherein cobalt tenor account for the 30wt% of overall catalyst weight；(2) molybdenum and chromium, point
The 2wt% of overall catalyst weight is not accounted for；Surplus is silica.Described catalyst is prepared by being co-precipitated.
Comprised the following steps by the method for acetic acid production ethanol：
(1) it is hydrogenated with：Acetic acid raw material and hydrogen are preheated, the reactor equipped with hydrogenation catalyst is then passed to, by second
Acid is hydrogenated into crude ethanol product；The process conditions of acetic acid hydrogenation are：The liquid phase volume air speed of acetic acid is 0.5h-1, hydrogen and acetic acid
Mol ratio be 20:1, reaction temperature is 280 DEG C, and reaction pressure is 2.0MPa.
(2) take off light：At least part crude ethanol product is delivered into lightness-removing column, tower top takes two step fractional condensation modes, separated
Recycled into the lightness-removing column distillate Returning reactor containing ethyl acetate, the liquid of second step condensation is to contain acetaldehyde, second
The lightness-removing column distillate of ether and acetone, the lightness-removing column residue containing ethanol is produced from lightness-removing column tower reactor；The reason of the lightness-removing column
It it is 75 pieces by plate number, the charging aperture of coarse ethanol product is located at the 40th block of plate, using water as extractant, draws at the 15th block of plate
Enter, the weight ratio of water and the inlet amount of coarse ethanol product is 0.3:1, it is 30% to be introduced in tower reactor containing mass percent concentration
Sodium hydrate aqueous solution, controls the flow of sodium hydrate aqueous solution make it that the pH value of tower reactor residue is 8, tower top temperature is 79
DEG C, tower top pressure is 0.20MPa；
(3) it is dehydrated：At least part lightness-removing column residue is delivered into dehydrating tower, the dehydrating tower distillate containing ethanol is separated into
With the dehydrating tower residue containing water.The number of theoretical plate of the dehydrating tower is 38 pieces, and the charging aperture of lightness-removing column residue is located at the
33 blocks of plates, tower top temperature is 85 DEG C, and tower top pressure is 0.16MPa.
The analysis result of each step is listed in the following table.
Embodiment 2
In the present embodiment, the catalyst of acetic acid hydrogenation is the acetic acid hydrogenation catalyst that Beijing Chemical Research Institute is produced, board
Number it is BC-E-20, catalyst contains：(1) cobalt, wherein cobalt tenor account for the 30wt% of overall catalyst weight；(2) molybdenum and chromium, point
The 2wt% of overall catalyst weight is not accounted for；Surplus is silica.Described catalyst is prepared by being co-precipitated.
Comprised the following steps by the method for acetic acid production ethanol：
(1) it is hydrogenated with：Acetic acid raw material and hydrogen are preheated, the reactor equipped with hydrogenation catalyst is then passed to, by second
Acid is hydrogenated into crude ethanol product；The process conditions of acetic acid hydrogenation are：The liquid phase volume air speed of acetic acid is 0.75h-1, hydrogen and acetic acid
Mol ratio be 15:1, reaction temperature is 270 DEG C, and reaction pressure is 1.75MPa.
(2) take off light：At least part crude ethanol product is delivered into lightness-removing column, tower top takes two step fractional condensation modes, separated
Recycled into the lightness-removing column distillate Returning reactor containing ethyl acetate, the liquid of second step condensation is to contain acetaldehyde, second
The lightness-removing column distillate of ether and acetone, the lightness-removing column residue containing ethanol is produced from lightness-removing column tower reactor；The reason of the lightness-removing column
It it is 60 pieces by plate number, the charging aperture of coarse ethanol product is located at the 30th block of plate, using water as extractant, draws at the 15th block of plate
Enter, the weight ratio of water and the inlet amount of coarse ethanol product is 0.45:1, it is 25% to be introduced in tower reactor containing mass percent concentration
Aqueous sodium carbonate, control aqueous sodium carbonate flow cause tower reactor residue pH value be 7.5, tower top temperature is 80
DEG C, tower top pressure is 0.15MPa；
(3) it is dehydrated：At least part lightness-removing column residue is delivered into dehydrating tower, the dehydrating tower distillate containing ethanol is separated into
With the dehydrating tower residue containing water.The number of theoretical plate of the dehydrating tower is 45 pieces, and the charging aperture of lightness-removing column residue is located at the
39 blocks of plates, tower top temperature is 83 DEG C, and tower top pressure is 0.15MPa.
The analysis result of each step is listed in the following table.
Embodiment 3
In the present embodiment, the catalyst of acetic acid hydrogenation is the acetic acid hydrogenation catalyst that Beijing Chemical Research Institute is produced, board
Number it is BC-E-20, catalyst contains：(1) cobalt, wherein cobalt tenor account for the 30wt% of overall catalyst weight；(2) molybdenum and chromium, point
The 2wt% of overall catalyst weight is not accounted for；Surplus is silica.Described catalyst is prepared by being co-precipitated.
Comprised the following steps by the method for acetic acid production ethanol：
(1) it is hydrogenated with：Acetic acid raw material and hydrogen are preheated, the reactor equipped with hydrogenation catalyst is then passed to, by second
Acid is hydrogenated into crude ethanol product；The process conditions of acetic acid hydrogenation are：The liquid phase volume air speed of acetic acid is 1.25h-1, hydrogen and acetic acid
Mol ratio be 12:1, reaction temperature is 280 DEG C, and reaction pressure is 1.5MPa.
(2) take off light：At least part crude ethanol product is delivered into lightness-removing column, tower top takes two step fractional condensation modes, separated
Recycled into the lightness-removing column distillate Returning reactor containing ethyl acetate, the liquid of second step condensation is to contain acetaldehyde, second
The lightness-removing column distillate of ether and acetone, the lightness-removing column residue containing ethanol is produced from lightness-removing column tower reactor；The reason of the lightness-removing column
It it is 70 pieces by plate number, the charging aperture of coarse ethanol product is located at the 35th block of plate, using water as extractant, draws at the 15th block of plate
Enter, the weight ratio of water and the inlet amount of coarse ethanol product is 0.6:1, it is 35% to be introduced in tower reactor containing mass percent concentration
Sodium hydrate aqueous solution, controls the flow of sodium hydrate aqueous solution make it that the pH value of tower reactor residue is 7.5, tower top temperature is 81
DEG C, tower top pressure is 0.15MPa；
(3) it is dehydrated：At least part lightness-removing column residue is delivered into dehydrating tower, the dehydrating tower distillate containing ethanol is separated into
With the dehydrating tower residue containing water.The number of theoretical plate of the dehydrating tower is 45 pieces, and the charging aperture of lightness-removing column residue is located at the
41 blocks of plates, tower top temperature is 81 DEG C, and tower top pressure is 0.12MPa.
The analysis result of each step is listed in the following table.
Analysis result data in embodiment 1-3, the inventive method can efficiently separate out the production of acetic acid hydrogenation process
The materials such as raw ketone, acetaldehyde and ethyl acetate, are favorably improved the quality of final alcohol product.
Claims (10)
1. a kind of method of acetic acid hydrogenation production ethanol, comprises the following steps：
(1) it is hydrogenated with：Raw material acetic acid and hydrogen are preheated, the reactor equipped with hydrogenation catalyst is passed to, acetic acid is hydrogenated into
Crude ethanol product；
(2) take off light：The crude ethanol product is delivered into lightness-removing column, extractant is delivered into lightness-removing column, to the lightness-removing column bottom or
Tower reactor introduces the logistics containing alkaline matter, and described lightness-removing column takes two step condensing modes, be separated into containing ether, acetaldehyde,
The lightness-removing column distillate of acetone and ethyl acetate and the lightness-removing column residue containing ethanol, by the lightness-removing column described at least part
Distillate is returned to before reactor, feeding reactor or preheated rear feeding reactor, by adjusting the thing containing alkaline matter
The pH value that flow control contains the lightness-removing column residue of ethanol is 7~10.5；
(3) it is dehydrated：At least part lightness-removing column residue is delivered into dehydrating tower, the dehydrating tower distillate containing ethanol is separated into and contains
There is the dehydrating tower residue of water；
(4) refine：Water in the dehydrating tower distillate containing ethanol that separating step (3) is obtained, obtains alcohol product.
2. a kind of method of acetic acid hydrogenation production ethanol according to claim 1, it is characterised in that described step (2) is
At least part crude ethanol product is delivered to the middle and lower part of lightness-removing column, extractant is delivered to the middle and upper part of lightness-removing column, takes off light to described
Tower bottom or tower reactor introduce the logistics containing alkaline matter, and described lightness-removing column takes two step condensing modes, through extracting rectifying,
The liquid portion that the first step is condensed is produced and sends into reactor or preheated rear feeding reactor by lightness-removing column tower top, and the first step is cold
Solidifying liquid residual partial reflux, uncooled gas phase portion is condensed by second step again, is produced from tower reactor de- containing ethanol
Light tower residue, by adjust the pH value for the lightness-removing column residue that the operating mode pattern containing alkaline matter contains ethanol for 7~
10.5。
3. the method for a kind of acetic acid hydrogenation production ethanol according to claim 1, it is characterised in that in described step (2)
Described lightness-removing column is extractive distillation column, and extractant is diethylene glycol or water, and extractant is passed through on lightness-removing column top.
4. the method for a kind of acetic acid hydrogenation production ethanol according to claim 1, it is characterised in that in described step (2)
The plate number of lightness-removing column is 25~80 pieces, and the charging aperture of crude ethanol product is located at middle part, the charging aperture of the material containing alkaline matter
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 method of acetic acid hydrogenation production ethanol according to claim 1, it is characterised in that the dehydration in step (3)
The plate number of tower is 10~40 pieces, and the charging aperture of lightness-removing column residue is located at the middle and lower part of dehydrating tower, and tower top temperature is 60~95 DEG C,
Tower top pressure is 0.01~0.30MPa.
6. a kind of method of acetic acid hydrogenation production ethanol according to claim 1, it is characterised in that the dehydration in step (3)
Tower residual fraction returns to lightness-removing column.
7. the method for a kind of acetic acid hydrogenation production ethanol according to claim 1, it is characterised in that described in step (2)
Alkaline matter is at least one of ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor, caustic soda, sodium carbonate, sodium acid carbonate and potassium hydroxide.
8. a kind of method of acetic acid hydrogenation production ethanol according to claim 1, it is characterised in that the liquid of step (1) acetic acid
Phase volume air speed is 0.05~1.50h-1, the mol ratio of hydrogen and acetic acid is 5~50:1, reaction temperature is 220~290 DEG C, instead
It is normal pressure to 5.0MPa to answer pressure.
9. the method for a kind of acetic acid hydrogenation production ethanol according to claim 1, it is characterised in that step (4) uses azeotropic
Water in the dehydrating tower distillate containing ethanol that technology or membrane separation technique separating step (3) are obtained, obtains alcohol product.
10. the method for a kind of acetic acid hydrogenation production ethanol according to claim 1, it is characterised in that described in step (1)
Catalyst is the base metal type catalyst containing cobalt.
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| 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 |
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| 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 |
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