CN106187692A - A kind of containing ethanol with the mixed solvent of ethyl acetate - Google Patents
A kind of containing ethanol with the mixed solvent of ethyl acetate Download PDFInfo
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Abstract
The invention provides a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised, in described solvent product, ethanol content is 30～75wt%, ethyl acetate content is 20～60wt%, is 0～5mg/L with the acid number of Acetometer, and water content is 0～20wt%.
Description
Technical field
The present invention relates to a kind of mixed solvent product, obtain this solvent product it is more particularly related to a kind of by acetic acid hydrogenation, and its production and use.
Background technology
Ethyl acetate has another name called ethyl acetate, is one of the important downstream product of acetic acid, has the dissolubility of excellence, quick-drying.The production method of ethyl acetate mainly has acid esterification method, acetaldehyde condensation method, alcohol dehydrogenase method and acetic acid with ethylene addition process 4 kinds, and current global ethyl acetate mainly uses acid esterification method to produce.
Ethanol be find the earliest, a kind of fatty alcohol that purposes is the widest.The raw material that the main alcohol production enterprise of China uses is Semen Maydis, Semen Tritici aestivi and Maninot esculenta crantz. (relying primarily on import).The most in recent years grain cost sharp rises, and therefore ethanol there is also the problem striving grain with people.The non-grain ethanol raw material price such as Maninot esculenta crantz., sugar grass is expected to rise the most always, and the secondary ethanol technology distance application with cellulosic ethanol as representative also has more difficulty to need to solve.
Acetic acid is a kind of important industrial chemicals, and the production technology 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 is still concentrated mainly on traditional field, and consumption structure does not occur significant change, is formed without new demand growth point and supports newly-increased production capacity.Anticipated China acetic acid demand in 2012 is less than about 4,800,000 tons, and problem of excess production capacity highlights, and even occurs that new equipment i.e. stops production after driving.Therefore the downstream use exploitation of acetic acid is extremely urgent.
Using acetic acid to include two kinds as the approach of raw material production alcohol product, one is that acetic acid generates acetate through esterification, and then acetate is hydrogenated to ethanol, then carries out refined raw producing and ethanol product；Two is that acetic acid direct hydrogenation generates ethanol, then produces alcohol product through subtractive process.First method is compared second method and has been had more esterification process, and a large amount of ethanol need circulation as esterification feed, add the size of hydrogenation reactor and the size of heat exchanger front and back thereof and energy consumption accordingly, at least part of subtractive process is also put and is twice, its advantage is that the corrosion strength of hydrogenation process may be lower, but there is acetic acid during it the most more or less, still suffer from corrosivity.But, second method it is crucial that develop the catalyst of acetic acid direct hydrogenation, this difficult problem is also that many researcheres select the first acetic acid through the reason of the method for esterification repeated hydrogenation.
Many existing for acetic acid direct hydrogenation, researcher and research data, 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, isolate unreacted acetic acid, the distillation of first tower is isolated the second distillation containing ethyl acetate in second tower, obtaining the second residue containing second alcohol and water, the second residue is separated into the distillation containing ethanol and aqueous residue in the 3rd tower.Additionally or alternatively, the second distillation is delivered to the 4th tower, is separated into the 4th distillation containing acetaldehyde and the 4th residue, then by the 4th distillation Returning reacting system to improve ethanol yield, the 4th residue is used as solvent or is used in ester production.In these patents, first acetic acid typically remove by the way of rectification, thus can reduce material requirement in later separation, thus realize the reduction of cost of investment, but so there is also some problems: accounting for product quality most of second alcohol and water needs by vaporization, therefore the energy consumption of rectification deacidification is high, and the size of extracting tower is relatively big and material requires higher, and cost of investment is high；And in the rectification of reality separates, it is understood that there may be tower top exists the situation of denier acetic acid, and is all to have strict demand to acidity as alcohol fuel and industrial alcohol product, therefore cause product defective when operation fluctuation.
On the other hand a certain amount of ethyl acetate can be generated during acetic acid direct hydrogenation, ethyl acetate and ethanol are binary azeotropes, ethyl acetate, second alcohol and water are ternary azeotrope, in prior art such as CN102414153, ethyl acetate predominantly returns hydrogenation reactor, this will result in reactor load and energy consumption increases, and therefore as product extraction, ethyl acetate is had economy and practicality.
In order to solve the defect of the ethyl alcohol purification process that prior art exists, overcome the reuse problem of by-product ethyl acetate, inventor is through intensive research, spy proposes the scheme of a kind of low energy consumption: acetic acid is crude ethanol product through direct hydrogenation, then in turn through gas-liquid separator, refined (comprising neutralization reactor), it is thus achieved that obtain mixed solvent while alcohol product.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of containing ethanol with the mixed solvent of ethyl acetate.
Of the present invention a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised, in described solvent product, ethanol content is 30～75wt%, ethyl acetate content is 20～60wt%, is 0～5mg/L with the acid number of Acetometer, and water content is 0～20wt%.
Concrete technical scheme is:
A kind of mixed solvent containing ethanol and ethyl acetate of the present invention is obtained by following preparation method, and this preparation method comprises the following steps:
(1) gas phase hydrogenation: form steam feed stream after acetic acid raw material and hydrogen being preheated, wherein reaction pressure 0.5～5MPa, hydrogen and the mol ratio 10～40 of acetic acid, described steam feed stream is incorporated into equipped with in the reactor of hydrogenation catalyst, acetic acid is hydrogenated into the crude ethanol product containing water, ethyl acetate, acetaldehyde, acetone, butanol and acetic acid.
(2) gas-liquid separation: in the future after the mixed material condensation of autoreactor, through gas-liquid separation, it is separated into crude ethanol product and the gas containing hydrogen, described hydrogen gas at least partly loops back gas phase hydrogenation reaction device use, in the coarse ethanol product of gained, acetic acid content is less than 0～2wt%, ethyl acetate content 0～10wt%.
(3) product purification: crude ethanol product is delivered to first rectifying column, be separated into containing ethyl acetate, ethanol, water coarse ethanol product the first tower bottom distillate and containing acetaldehyde, ether, acetone, the first overhead fraction of ethyl acetate, in the first described tower bottom distillate, content of acetone is 0～0.1wt%；First tower bottom distillate is delivered to second rectifying column, is separated into containing ethyl acetate, the second overhead fraction of ethanol and contains water, ethanol, butanol and the second tower bottom distillate of acetate, solvent of the present invention that is second overhead fraction；Injecting alkali liquor in the middle part of the second tower reactor or tower, control tower reactor pH value is 8.0～11.0, and described alkaline matter is selected from the one in ammonium carbonate, ammonium hydrogen carbonate, ammonia, caustic soda, sodium carbonate, sodium bicarbonate, potassium hydroxide.Second tower bottom distillate is sent into the 3rd rectifying column, overhead extraction alcohol product, content 85～95wt%, acidity value 0～5mg/L.
Preferably, in described (1), acetic acid gas phase hydrogenation catalyst is on a catalyst or by the catalyst of catalyst carrier at least one metal active constituent scattered selected from load.Described metal active constituent is one or more combination in the IB of the periodic table of elements, IIB, IIIB, IVB, VB, VIB, VIIB, Group VIIIB, lanthanide series metal and IIIA, IVA, VA, Group VIA metal.It is furthermore preferred that acetic acid gas phase hydrogenation catalyst is one or more in Supported Co series catalysts, molybdenum series catalyst or noble metal catalyst in described (1).More specifically, described hydrogenation catalyst is selected from following:
In described (1), hydrogenation catalyst I is selected from loading on a catalyst or by the scattered Co catalysts of catalyst carrier, wherein cobalt tenor accounts for 15wt%～45wt% of overall catalyst weight, described catalyst is possibly together with the noble metal of trace, one or more in palladium, platinum and rhenium of wherein said trace noble metal, its weight is 1:100～1:300 with the ratio of cobalt weight metal.
In described (1), hydrogenation catalyst is selected from loading on a catalyst or by the scattered Co catalysts of catalyst carrier, in described (1), hydrogenation catalyst is selected from loading on a catalyst or by the scattered Co catalysts of catalyst carrier, described catalyst is possibly together with boron, wherein cobalt tenor accounts for 10wt%～50wt% of overall catalyst weight, and boron accounts for 1.0wt%～10wt% of overall catalyst weight；
In described (1), hydrogenation catalyst is selected from loading on a catalyst or by the scattered Co catalysts of catalyst carrier, in described (1), hydrogenation catalyst I is selected from loading on a catalyst or by the scattered Co catalysts of catalyst carrier, described catalyst is possibly together with bismuth, wherein cobalt tenor accounts for 10wt%～50wt% of overall catalyst weight, wherein cobalt tenor accounts for 10wt%～50wt% of overall catalyst weight, and bismuth metal accounts for 0.1wt%～50wt% of overall catalyst weight；
In described (1), hydrogenation catalyst is selected from loading on a catalyst or by the scattered Co catalysts of catalyst carrier, in described (1), hydrogenation catalyst is selected from loading on a catalyst or by the scattered Co catalysts of catalyst carrier, described catalyst is possibly together with stannum, wherein cobalt tenor accounts for 10wt%～50wt% of overall catalyst weight, wherein cobalt tenor accounts for 10wt%～50wt% of overall catalyst weight, and tin metal accounts for 10wt%～40wt% of overall catalyst weight.
In described (1), hydrogenation catalyst is selected from loading on a catalyst or by the scattered Co catalysts of catalyst carrier, in described (1), hydrogenation catalyst is selected from loading on a catalyst or by the scattered Co catalysts of catalyst carrier, described catalyst is possibly together with silver, wherein cobalt tenor accounts for 10wt%～50wt% of overall catalyst weight, and silver metal accounts for 0.1wt%～10wt% of overall catalyst weight.
In described (1), hydrogenation catalyst contains carrier, cobalt element, group vib element, wherein the content of cobalt element accounts for 15wt%～50wt% of overall catalyst weight, at least one in molybdenum, tungsten, chromium of group vib element, its content accounts for 0.5wt%～15wt% of overall catalyst weight, described carrier selected from silicon oxide, kieselguhr, calcium silicates, zirconium oxide, titanium oxide at least one, its content accounts for 20wt%～80wt% of overall catalyst weight.
Described (1) hydrogenation catalyst contains carrier, cobalt element, silver element, wherein the content of cobalt element accounts for 15wt%～50wt% of overall catalyst weight, the content of silver element accounts for 0.1wt%～10wt% of overall catalyst weight, described carrier selected from silicon oxide, kieselguhr, calcium silicates, zirconium oxide, titanium oxide at least one, its content accounts for 20wt%～80wt% of overall catalyst weight.
In described (1), hydrogenation catalyst contains carrier, cobalt element, alkali earth metal, IB race element, wherein the content of cobalt element accounts for 15wt%～50wt% of overall catalyst weight, the content of alkali earth metal accounts for 1wt%～30wt% of overall catalyst weight, the content of IB race element accounts for 0.1wt%～15.0wt% of overall catalyst weight, described carrier is oxide, and its content accounts for 10wt%～80wt% of overall catalyst weight.
In described (1), hydrogenation catalyst I is a kind of in silicon dioxide carried platinum-tin catalyst, activated carbon supported palladium-rhenium catalyst.
Described patent one in the patent that Sinopec Beijing Chemical Research Institute applies for or combination, concrete patent is: CN 201210429219.4, CN201210429218.X, CN201210429995.4, CN201210429959.8, CN201210429785.5, CN201210430033.0, CN201210429960.0, CN201210429958.3, CN201210428055.3, CN201210429720.0, CN201210428802.3.
It addition, the catalyst being applicable to acetic acid preparation of ethanol by hydrogenating before use can be modified through any-mode.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 Acidity of Aikalinity of carrier to improve catalyst activity preparing carrier process；And for example, by adding certain metal in the carrier as lanthanum etc. is to improve the stability of catalyst, this can be effectively improved catalyst life；Further, can process and regulate its surface special nature by catalyst being carried out surface silicon alkylation or aluminum alkylation and reduce some compound in the deposition of catalyst surface or the loss of active component to extend catalyst life.
For those skilled in the art, can gain enlightenment thus catalyst carrier and preparation method to the present invention makes various change according to discussed in detail above.Such as, any of hydrogenation catalyst, catalyst carrier or modified catalyst carrier can be used.
In the inventive solutions, described gas phase hydrogenation reaction device can be to be fixed bed form or the useful form of other Dichlorodiphenyl Acetate hydrogenation techniques.The process conditions of gas phase hydrogenation reaction, without particular/special requirement, can be adjusted according to acetic acid conversion ratio and ethanol yield.For example, hydrogenation reaction is carried out at ambient pressure, and reaction temperature is 200 DEG C～350 DEG C, and the liquid phase feeding volume space velocity of acetic acid is 0.05～0.5h-1.Acetic acid hydrogenation can also be carried out under elevated pressure, and such as, the process conditions of acetic acid hydrogenation are: the liquid phase feeding volume space velocity of acetic acid is 0.05～1.5h-1, hydrogen is 5～30:1 with the mol ratio of acetic acid, and reaction temperature is 80 DEG C～150 DEG C, and reaction pressure is 3.0 to 9.0MPa.Described liquid phase feeding volume space velocity refers to the percent by volume when flow of acetic acid feeds according to acetic acid, the ratio of the feed volume in the unit interval and the volume of catalyst.The liquid phase feeding volume space velocity of acetic acid affects the treating capacity of reactor, and affects composition and the content thereof of product.
After gas phase hydrogenation reaction device, reacting coarse product reclaims heat and cooling through heat exchange, then carries out gas-liquid separation, and gas recycles through compressor, more suitably fills into some fresh hydrogen, and liquid enters follow-up separation phase.
Although present invention uses the most highly active catalyst, reacting coarse product also has a certain amount of unreacted acetic acid to exist, this is probably during industrial implementation, the solid phase of the present invention needs to exist with certain particle diameter (1～8mm), owing to reactor exists many non-ideal mobility status, short circuit, channel, dead angles etc. as everyone knows, Another reason is exactly that catalyst can exist activity decrease at last stage reaction.
After the present invention is by described high activated catalyst, after hydrogenation reaction, the acetic acid content of outlet controls, within 2wt%, to be optimized for 1.5wt%, and situation about more optimizing is 1wt%.
Acetic acid content has important effect for the product quality of ethanol, and as in industrial alcohol CNS, acid number not can exceed that 10mg/L, in alcohol fuel Chinese national standard, acid number is less than 56mg/L, and it is necessary for therefore removing acetic acid in thick product.Acetic acid is mainly removed by the way of rectification by prior art, and accounting for product quality most of second alcohol and water needs by vaporization, and therefore the energy consumption of rectification deacidification is high, and the size of extracting tower is relatively big and material requires higher, and cost of investment is high；And in the rectification of reality separates, it is understood that there may be tower top exists the situation of denier acetic acid, and all has strict demand to acidity as alcohol fuel and industrial alcohol product, therefore cause product defective when operation fluctuation.Acidity value is the measurement index that alcohol product is main, particularly when being applied in alcohol fuel, the acetic acid of denier will make the corrosion rate of electromotor and oil circuit double, and also a certain degree of stability affecting oil product of meeting, therefore causes oil quality to decline.
The inventors discovered that the control of neutralization reactor is extremely important for the separation of subsequent product, be one of successful important control parameter of the present invention, neutralization reactor PH is 8.0～11.0 in control, and the value more optimized is 8.5～10.
For the alkaline matter neutralized, can be selected from the one in ammonium carbonate, ammonium hydrogen carbonate, ammonia, caustic soda, sodium carbonate, sodium bicarbonate, potassium hydroxide, calcium hydroxide, preferred alkali is the aqueous solution of caustic soda.
The position of neutralization reactor selects the effect to the present invention to be important, the position of application claims is that inventor is through test of meticulously deriving, through material test, the inventors discovered that the material corrosion speed after neutralizing is greatly reduced, 0.01mm/a can be less than at common carbon steel material medium-rate, product color is limpid, if and not by material acetic acid neutralize, find the material needing to use higher level, even so, still there is certain color in tower reactor product, therefore equipment investment can be reduced before neutralization reactor is placed on rectifying column, and tower bottoms body colour degree is reduced.
It is known that, the present inventor is found by the test on small-sized rectification process device, (as ASPEN software is simulated) can realize in Theoretical Calculation acetic acid be kept completely separate when, result of the test shows that the acid content in alcohol product is higher, in many times test, acidity value overwhelming majority situation exceedes product Chinese national standard requirement, and acidity value is the most all 10～about 100mg/L.
The acetic acid control of export of trace is not only by the selection of high activated catalyst, combination for reactor and reactor also requires, preferably mode is one or more than two calandria type fixed bed reactors, self-heating reactor and tower reactor, the preferred combination with self-heating reactor and shell and tube reactor, and it is poor to have inlet temperature.
Due in acetic acid and alkali and after, the loss of acetic acid material can be caused, obviously this is that inventor is unwilling to see, therefore the present invention adds an esterifier after hydrogenation reactor, acetic acid is converted into ethyl acetate, is can to loop back reactor to be hydrogenated to ethanol in the method for the invention due to ethyl acetate.The present inventor is by finding after careful investigation, and the coupling of gas-liquid separation and esterifier can greatly reduce.After gas-liquid separation, the crude product of condensation is some or all of by an esterifier, and it is 80～130 DEG C that the temperature of esterifier controls, the design optimization adiabatic reactor reactor of esterifier.Described middle esterifier is filled with esterification catalyst, described esterification catalyst one in ion exchange resin, molecular sieve, aluminium oxide, super acids.Preferred esterification catalyst is strong acidic ion resin and super acids, the A-15 etc. produced such as Rhom and Hass of the U.S..The mode optimized is, after gas phase hydrogenation reaction device, to obtain coarse ethanol product and be first cooled to 60～130 DEG C, then through one-level gas-liquid separation, the liquid phase after separating sends into middle esterifier, gas phase is cooled down further and sends into product purification after gas-liquid separation.Material consumption can be farthest reduced by the way of two grades of described gas-liquid separators combine ester reactor.
In the present invention implements, those skilled in the art can come suitable selection gas-liquid separator and the use of esterifier according to the ratio of each component in the gas phase hydrogenation reaction crude product of factory's reality, it is also possible to modifies technical scheme according to the various technology enlightenment that the present invention is given.
Ethyl acetate is conventional low poison solvent, and ethanol is also conventional low poison solvent, has bigger prospect in the field such as ink, coating.Inventor is through careful contrast, find ethyl acetate and the ethanol of specific composition, and in the case of containing a small amount of water, the alternative existing required organic solvent in fields such as ink, coating, paint, adhesive, leather production process, such as acetone, butanone, methyl acetate, methyl acetate and methanol mixed solvent etc., and there is hypotoxicity.This composition is as described below:
In described solvent product, ethanol content is 30～85wt%, and ethyl acetate content is 20～60wt%, and acid number (with Acetometer) is 0～5mg/L, and water content is 0～20wt%.
Under optimum condition, in described solvent product, ethanol content is 40～70wt%, and ethyl acetate content is 30～50wt%, and acid number (with Acetometer) is 0～3mg/L, and water content is 0～12wt%.
The present inventor is through carefully experimental study, it is thus achieved that this composition solvent and not affect major product ethanol yield situation be restricted, and having effective control is the operating condition by the first and second rectifying columns, specific as follows:
First tower bottom temperature 60 of product purification section～70 DEG C, tower top temperature 50～60 DEG C, tower top pressure controls in 0.02～0.2MPa (gauge pressure).Second tower bottom temperature 75 of product purification section～85 DEG C, tower top temperature 58～70 DEG C, tower top pressure controls in 0.01～0.15MPa (gauge pressure).
Compared with the conventional method, the inventive method can be effectively reduced the acetic acid content in product, and this not only helps the quality improving final alcohol product, and can also effectively reduce the energy consumption of subsequent separation process.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention, wherein
R101: gas phase hydrogenation reaction device
E101: condenser
V101: gas-liquid separator
E102: condenser
R102: esterifier
R201: neutralization reactor
T201: the first rectifying column
T202: Second distillation column
V202: gas-liquid separator
Detailed description of the invention
Following example are that citing more detailed to the present invention describes, but the invention is not limited in these embodiments.
In the present embodiment, concrete flow chart is as shown in Figure 1.
First by acetic acid raw material, material and hydrogen pre-thermosetting steam feed stream are returned, described steam feed stream is incorporated into equipped with in the reactor R101 of gas phase hydrogenation catalyst, the catalyst of acetic acid gas phase hydrogenation is acetic acid hydrogenation catalyst (1) cobalt that Beijing Chemical Research Institute produces, and wherein cobalt tenor accounts for the 24wt% of overall catalyst weight；(2) molybdenum and stannum, accounts for 3wt% and 30wt% of overall catalyst weight respectively；(3) boron and bismuth, accounts for 2wt% and 5wt% of overall catalyst weight respectively, and surplus is silicon dioxide.Acetic acid is hydrogenated into crude ethanol product.The process conditions of acetic acid gas phase hydrogenation are: the liquid phase volume air speed of acetic acid is 0.75h-1, hydrogen is 25:1 with the mol ratio of acetic acid, and reaction temperature is 220 DEG C, and reaction pressure is 2.5MPa.Removing on-condensible gas (hydrogen, CO, CO2, CH4, C2H6) outer ethanol content in thick product after hydrogenation is 62.4wt%, and ethyl acetate 7wt%, acetic acid 0.05wt%, water 30wt%, surplus is acetaldehyde, ether and butanol.
Acetic acid content in R102 exit liquid phase is 0.25wt%, this liquid phase is cooled to 20 DEG C of laggard row gas-liquid separations through subcooler E103, gas phase portion returns hydrogenation reactor, liquid phase enters in neutralization reactor, neutralization reactor is tubular reactor, mean residence time is 18min, and the alkali of employing is the caustic soda aqueous solution of 30wt%, and exporting liquid phase P H-number after neutralization is 8.8～about 9.0.
Liquid-phase product after neutralizing delivers to the first rectifying column T201, this rectifying column is pressurization plate column, and composition of tower shell material is ordinary carbon steel material, and the first overhead fraction and tower bottom distillate mass ratio are 6:100, wherein overhead fraction ethanol mass fraction is 22.8wt%, and in tower reactor fraction, content of acetone is 15wtppm.70wt% in first overhead fraction is returned hydrogenation reactor, and the first rectification tower reactor product colour is limpid.Bottom temperature is 68 DEG C, column bottom temperature 56 DEG C, reflux ratio 2.5, tower top pressure 0.12MPa.
First tower reactor fraction is sent in Second distillation column T202, this rectifying column is packed tower, composition of tower shell material is ordinary carbon steel, it is separated into the second tower bottom distillate and the second overhead fraction by Second distillation column, described the second overhead fraction i.e. mixed solvent, specifically comprise ethanol 62wt%, ethyl acetate 35wt%, water content 3wt%.Bottom temperature is 87 DEG C, column bottom temperature 72 DEG C, reflux ratio 2.0, tower top pressure 0.08MPa.
Second tower reactor fraction is sent in the 3rd rectifying column T203, this rectifying column is packed tower, composition of tower shell material is ordinary carbon steel, it is separated into the 3rd tower bottom distillate and the 3rd overhead fraction by the 3rd rectifying column, wherein tower reactor fraction delivers to waste water process, in 3rd overhead fraction, water content is 9.0wt%, and after titration, acidity value is 2.0mg/L, and remaining indices all meets industrial alcohol Chinese Industrial Standards (CIS) requirement.
After 3rd overhead fraction is delivered to the dehydration of molecular sieve tower, water content is 0.15wt%, and remaining indices all meets alcohol fuel Chinese Industrial Standards (CIS) requirement.
Claims (10)
1. it is the mixed solvent product mainly comprised with ethyl acetate and ethanol, ethanol in described solvent product
Content is 30～75wt%, and ethyl acetate content is 20～60wt%, is 0～5mg/L with the acid number of Acetometer,
Water content is 0～20wt%.
The most according to claim 1 a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised,
It is characterized in that, with acetic acid as raw material, produce ethanol by hydrogenation and obtain described mixed solvent product,
Described production method comprises the following steps:
(1) gas phase hydrogenation: form steam feed stream after acetic acid raw material and hydrogen being preheated, described steam is entered
Stream is incorporated into equipped with carrying out hydrogenation reaction in the hydrogenation reactor of hydrogenation catalyst；
(2) gas-liquid separation: hydrogenation reaction thing condensation step 1 obtained, through gas-liquid in gas-liquid separator
After separation, obtain coarse ethanol product and the gas containing hydrogen, by least part of for described hydrogen gas
Looping back gas phase hydrogenation reaction device to use, in the coarse ethanol product of gained, acetic acid content is less than 0～2wt%,
Ethyl acetate content 0～10wt%；
(3) product purification: crude ethanol product is delivered to first rectifying column, be separated into containing ethyl acetate,
Ethanol, water coarse ethanol product the first tower bottom distillate and containing acetaldehyde, ether, acetone, ethyl acetate
The first overhead fraction, in the first described tower bottom distillate, content of acetone is 0～0.1wt%；By first
Tower bottom distillate delivers to second rectifying column, and being separated into ethyl acetate and ethanol is that the mixing mainly comprised is molten
Agent product and containing water, ethanol, butanol and the second tower bottom distillate of acetate；In the second tower reactor or tower
Alkaline matter is injected in portion；Second tower bottom distillate is sent into the 3rd rectifying column, overhead extraction alcohol product, contains
Amount 85～95wt%, acidity value 0～5mg/L.
The most according to claim 2 a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised,
It is characterized in that first tower bottom of rectifying tower temperature 60～70 DEG C, tower top temperature 50～60 DEG C, tower top gauge
It is 0.02～0.2MPa；Second tower bottom of rectifying tower temperature 75～85 DEG C, tower top temperature 58～70 DEG C, tower top table
Pressure pressure is 0.01～0.15MPa.
The most according to claim 2 a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised,
It is characterized in that the PH controlling second rectifying column is 8.0～11.0.
The most according to claim 2 a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised,
It is characterized in that the PH of described neutralization reactor is 8.5～10.
The most according to claim 2 a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised,
It is characterized in that the alkaline matter in step (3) is selected from ammonium carbonate, ammonium hydrogen carbonate, ammonia, caustic soda, carbon
One in acid sodium, sodium bicarbonate, potassium hydroxide, calcium hydroxide.
The most according to claim 2 a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised,
It is characterized in that the aqueous solution selected from caustic soda of the alkaline matter in step (3).
The most according to claim 2 a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised,
It is characterized in that the mol ratio 10～40 of the reaction pressure 0.5～5MPa in step (1), hydrogen and acetic acid.
The most according to claim 2 a kind of take ethyl acetate and ethanol as the mixed solvent product mainly comprised,
It is characterized in that hydrogenation reactor is that one or more than two calandria type fixed bed reactors, self-heating are anti-
Answer device and tower reactor.
The most according to claim 1 and 2 a kind of be that the mixed solvent that mainly comprises produces with ethyl acetate and ethanol
Product, it is characterised in that in described solvent product, ethanol content is 40～70wt%, ethyl acetate content is
30～50wt%, it is 0～3mg/L with the acid number of Acetometer, water content is 0～12wt%.
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| CN103025690A (en) * | 2010-07-09 | 2013-04-03 | 国际人造丝公司 | Esterification of vapor crude product in the production of alcohols |
| CN104211571A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Method for production of anhydrous ethanol by acetic acid hydrogenation |
| CN104211573A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Method for production of anhydrous ethanol by acetic acid hydrogenation |
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| CN114478193A (en) * | 2022-01-06 | 2022-05-13 | 北京泽华化学工程有限公司 | Separation method and separation device for preparing ethanol from dimethyl ether |
| CN114478193B (en) * | 2022-01-06 | 2024-04-30 | 北京泽华化学工程有限公司 | Separation method and separation device for preparing ethanol from dimethyl ether |
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Application publication date: 20161207 |