CN104211573B - The method of dehydrated alcohol is produced by acetic acid hydrogenation - Google Patents
The method of dehydrated alcohol is produced by acetic acid hydrogenation Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
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Abstract
The method that a kind of acetic acid hydrogenation disclosed by the invention produces ethanol belongs to the production technical field of alcohols material, in order to solve the defect of the ethanol production process that prior art exists, improve alcohol product quality and reduce energy consumption, it is crude ethanol product that contriver spy proposes a kind of acetic acid direct hydrogenation, then successively through isolating unreacted acetic acid, remove ketone component, isolate vinyl acetic monomer and remove the technological process of moisture, obtain dehydrated alcohol product.The present invention can isolate the ketone and the impurity such as acetaldehyde that acetic acid hydrogenation process produces effectively, and this not only contributes to the separating effect improving distillation tower, improves the quality of final alcohol product.
Description
Technical field
Invention relates to a kind of method of producing ethanol, more particularly, the present invention relates to and is a kind ofly ethanol by acetic acid direct hydrogenation and obtains the method for dehydrated alcohol product through treating process.
Background technology
Ethanol be find the earliest, a kind of fatty alcohol that purposes is the widest, be also the main component of wine.Under room temperature, ethanol is colourless, volatile, inflammable liquid.Ethanol of many uses, such as can be used to produce the industrial chemicals such as acetaldehyde, ether, vinyl acetic monomer, ethamine, ethyl propenoate, oxyethane, medicine, agricultural chemicals, can mix in gasoline and diesel oil, can be miscible with water, acetic acid, acetone, benzene, tetracol phenixin, chloroform, ether, ethylene glycol, glycerine, Nitromethane 99Min., pyridine and toluene equal solvent, also do several broad aspect such as sterilizing agent, beverage, thinner, environmental protection coating material, agricultural chemicals, medicine, rubber, plastics, regenerated fiber, washing composition.
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 the 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 if corn price was by 1100 yuan/ton of 2300 yuan/ton of going up extremely current of 2003, therefore alcohol fuel 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, is mainly used in PTA(19%), the industry such as vinyl acetate between to for plastic (19%), acetic ester (29%), monochloroacetic acid (9%), ketene dimer (5%), aceticanhydride (5%), agricultural chemicals, medicine intermediate (for proportion consumed by acetic acid in bracket).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.Because raw materials cost is with the obvious advantage, except the main production ways that grain fermentation method is food grade Glacial acetic acid, current global acetic acid is produced essentially by methyl alcohol carbonyl carbonylation method and ethane oxidation method.In recent years along with the fast development of carbonylation of methanol technology, although traditional oxidation of ethylene method steps down from the stage of history, but the expansion of the output of methanol carbonylation is more violent, from 1,020 ten thousand tons of 1,550 ten thousand tons of rising to 2010 of 2006, estimate that 2012 annual capacities are close to 1,900 ten thousand tons, and the growth of demand is relatively slow, it is estimated that superfluous production capacity in 2012 will more than 5,000,000 tons.Therefore, international acetic acid price is plummeted, and device working rate is lower.
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 why a lot of unit selects the first acetic acid through the reason of the method for esterification repeated hydrogenation.
In order to simplify ethanol production process process, the method for acetic acid direct hydrogenation is also studied.Such as U.S. Calenese company have submitted a large amount of patent application with regard to acetic acid direct 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, and the light constituents such as acetaldehyde are through first tower to the 3rd tower, even the 4th tower.Contriver analyzes from acetic acid hydrogenation mechanism, inevitably generates a small amount of or trace acetone in acetic acid hydrogenation process, is not gone out the impurity index of the final alcohol product of impact by ketone Component seperation.In addition, acetic acid direct hydrogenation ethanol process has a large amount of water and generates, and water can form binary azeotropic or ternary azeotropic with vinyl acetic monomer and ethanol, therefore, only can not obtain producing dehydrated alcohol by conventional distillation.Contriver is well thrashed out to propose and utilizes extraction agent that the water that acetic acid hydrogenation process generates is separated the processing method obtaining dehydrated alcohol.
Summary of the invention
In order to solve the defect of the ethyl alcohol purification process that prior art exists, and then improve alcohol product quality, it is crude ethanol product that contriver spy proposes a kind of acetic acid direct hydrogenation, then successively through being separated unreacted acetic acid, remove ketone component, isolate vinyl acetic monomer and remove the technique purification process of moisture, obtain dehydrated alcohol product.
Concrete technical scheme of the present invention is as follows:
The processing method that a kind of acetic acid hydrogenation that the present invention proposes produces dehydrated alcohol comprises the following steps:
(1) hydrogenation: pass into hydrogenator by after acetic acid raw material and hydrogen preheating, under the existence of hydrogenation catalyst, acetic acid is hydrogenated into crude ethanol product;
(2) depickling: at least part of crude ethanol product is delivered to extracting tower, is separated into the extracting tower overhead product containing vinyl acetic monomer and ethanol and the extracting tower resistates containing acetic acid;
(3) de-ketone: at least part of extracting tower overhead product is delivered to de-ketone tower, is separated into the de-ketone tower overhead product containing acetone and the de-ketone tower resistates containing second alcohol and water;
(4) de-ester: delivering to de-ester tower by taking off ketone tower resistates at least partly, being separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol, water and extraction agent;
(5) dewater: delivering to dehydration tower by taking off ester tower resistates at least partly, being separated into moisture and dehydration tower resistates that is extraction agent, overhead extraction dehydrated alcohol product;
(6) solvent recuperation: at least part of dehydration tower resistates is delivered to solvent recovery tower, is separated into moisture solvent recovery tower overhead product and the solvent recovery tower resistates containing extraction agent.
Preferably, described hydrogenation catalyst is the base metal type catalyzer containing cobalt.
Preferably, in described (1), the processing condition of acetic acid direct hydrogenation are: the liquid phase volume air speed 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 200 ~ 320 DEG C, and reaction pressure is that normal pressure is to 4.0MPa.
Preferably, in described step (3), the tower top temperature of described de-ketone tower is 55 ~ 70 DEG C, takes partial condensation mode, the liquid portion extraction of condensation, and partial reflux, uncooled gas phase portion cools recovery more further.
Preferably, in described step (2), before extracting tower resistates described is at least partly turned back to reactor, send into reactor or send into reactor after preheating.
Preferably, in described step (4), before de-ester tower overhead product described is at least partly turned back to reactor, send into reactor or send into reactor after preheating.
Preferably, in described step (4), described de-ester tower is extractive distillation column, and extraction agent is ethylene glycol or Diethylene Glycol.
Preferably, in described step (5), described dehydration tower is extractive distillation column, and extraction agent is ethylene glycol or Diethylene Glycol.
More preferably, in described step (4) and (5), ethylene glycol elected as by extraction agent.
Preferably, a part for the solvent recovery tower resistates in described step (6) is sent into described degreasing tower and described dehydration tower, described in described extracting tower and described dehydration tower, solvent recovery tower resistates is as the extraction agent of Separation of Water.
More specifically preferably, in described step (2), the number of theoretical plate of described extracting tower is 35 ~ 75 pieces, and opening for feed is positioned at middle and lower part, and tower top temperature is 60 ~ 85 DEG C, and tower top pressure is 0.01 ~ 0.20MPa; In described step (3), the number of theoretical plate of described de-ketone tower is 20 ~ 55 pieces, and opening for feed is positioned at middle and upper part, and tower top temperature is 50 ~ 70 DEG C, and tower top pressure is 0.05 ~ 0.20MPa; In described step (4), the number of theoretical plate of described de-ester tower is 35 ~ 75 pieces, and opening for feed is positioned at middle and upper part, and tower top temperature is 65 ~ 85 DEG C, and tower top pressure is 0.01 ~ 0.20MPa; In described step (5), the number of theoretical plate of described dehydration tower is 45 ~ 75 pieces, and opening for feed is positioned at middle and lower part, and tower top temperature is 70 ~ 90 DEG C, and tower top pressure is 0.01 ~ 0.20MPa; In described step (6), the number of theoretical plate of described solvent recovery tower is 20 ~ 60 pieces, and opening for feed is positioned at middle and upper part, and tower top temperature is 90 ~ 120 DEG C, and tower top pressure is 0.01 ~ 0.20MPa.
Of the present invention another more specifically in scheme, the method for being produced dehydrated alcohol by acetic acid hydrogenation comprises:
(1) hydrogenation: by acetic acid raw material, recycle stock and hydrogen preheating, then makes it pass through to be equipped with the reactor of hydrogenation catalyst, carries 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) depickling: at least part of crude ethanol product is delivered to extracting tower, is separated into the extracting tower overhead product containing vinyl acetic monomer and ethanol and the extracting tower resistates containing acetic acid;
(3) de-ketone: at least part of extracting tower overhead product is delivered to de-ketone tower, is separated into the de-ketone tower overhead product containing acetone and the de-ketone tower resistates containing second alcohol and water;
(4) de-ester: deliver to de-ester tower by taking off ketone tower resistates at least partly, extraction agent or the described solvent recovery tower resistates of part are delivered to degreasing tower middle and upper part, through extracting and separating, be separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol, water and extraction agent;
(5) dewater: deliver to dehydration tower by taking off ester tower resistates at least partly, extraction agent or the described solvent recovery tower resistates of part are delivered to degreasing tower middle and upper part, through extracting and separating, be separated into moisture and dehydration tower resistates that is extraction agent, overhead extraction dehydrated alcohol product;
(6) solvent recuperation: at least part of dehydration tower resistates is delivered to solvent recovery tower, is separated into moisture solvent recovery tower overhead product and the solvent recovery tower resistates containing extraction agent.
Described recycle stock be selected from least one in extracting tower resistates, de-ketone tower overhead product and de-ester tower overhead product at least partly or their any combination.
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 Catalysts and its preparation method 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 Catalysts and its preparation method 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 Catalysts and its preparation method 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.
Most preferred hydrogenation catalyst is the acetic acid hydrogenation catalyzer that Beijing Chemical Research Institute produces, and the trade mark is BC-E-20 and BC-ATE.
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 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 ~ 350 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 200 ~ 320 DEG C, and reaction pressure is 0.1 to 4.0MPa.Described liquid phase feeding volume space velocity refers to that the flow of acetic acid is according to percent by volume during acetic acid charging, the ratio of the feed volume in the unit time and the volume of catalyzer.The liquid phase feeding volume space velocity of acetic acid affects the treatment capacity of reactor, and affects composition and the content thereof of reaction product.In general, when acetic acid air speed is larger, the hydrogenation conversion of acetic acid can decrease, the ethanol generation esterification that under the temperature of reaction in reactor and pressure, unreacted acetic acid will generate with hydrogenation, generate vinyl acetic monomer, certain vinyl acetic monomer also can be hydrogenated to ethanol further.When acetic acid air speed is too little, under certain reaction conditions, the side reaction such as undesirable etherificate, dehydration repeated hydrogenation can be there is in the ethanol that hydrogenation generates, the not only increase of micro-by product, not only consume acetic acid, and increase later separation cost, therefore should select preferably reaction conditions in hydrogenation process.
After hydrogenator, 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.Reacting coarse product also has a certain amount of unreacted acetic acid to exist.Purification of products operation with unreacted acetic acid for cut point is separated.Being separated unreacted acetic acid uses common rectificating method namely can reach separation object, certainly the physico-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.In the present invention, unreacted acetic acid removes through the rectifying of depickling rectifying tower.
In hydrogenation process, acetic acid is the side reaction of meeting generating portion under catalyst action, generates the impurity such as ketone.For product purity need be removed.While being separated by letones, lighter component such as the component such as ether and acetaldehyde is also separated.Suitably the tower top temperature of the de-ketone tower of setting, makes the not condensation of part light constituent, but releases in gaseous form, thus can avoid those components that can not generate ethanol through further reaction in systems in which Cumulate Sum take in subsequent product.In the present invention, the tower top temperature of de-ketone tower is such as chosen to be 55 ~ 70 DEG C.
In reacting coarse product, inevitably there are some vinyl acetic monomers, unless material stops the sufficiently long time in the reactor, make the vinyl acetic monomer generated also be hydrogenated to ethanol, otherwise all can there are some vinyl acetic monomers more or less.From reacting coarse product, separating acetic acid ethyl ester is not easy, and vinyl acetic monomer easily forms azeotrope.In addition, produce in the process of ethanol, can generate a large amount of water at acetic acid direct hydrogenation, and water and ethanol and ethyl acetate easily form azeotrope, vinyl acetic monomer, second alcohol and water formation ternary azeotrope, azeotropic point is 70.23 DEG C; Vinyl acetic monomer and water form binary azeotrope, and azeotropic point is 70.38 DEG C; Vinyl acetic monomer and ethanol form binary azeotrope, and azeotropic point is 71.81 DEG C.Therefore to prepare dehydrated alcohol water just need be managed to separate.The present invention adopts extraction fractional distillation to be removed by water.Available extraction agent has the organic solvents such as glycerine glycerine, Diethylene Glycol, ether, isopropyl ether, methyl-formiate, methyl-sulphoxide.Contriver draws through analog calculation, makes spent glycol the most effective as the extraction agent of Separation of Water in native system.After removing vinyl acetic monomer, de-ester tower tower reactor resistates is the mixture containing ethanol, water and extraction agent.
The binary azeotrope that water and ethanol can be formed, azeotropic point is 78.15 DEG C, and azeotropic consists of alcohol 95 .6wt%, and water is 4.40wt%.Only it can't be obtained dehydrated alcohol by conventional distillation.In the present invention, introduce appropriate extraction agent at dehydration tower and just can obtain dehydrated alcohol.
Contriver studies discovery by experiment, the by-product acetaldehyde generated in acetic acid hydrogenation reaction and vinyl acetic monomer all reaction can generate ethanol under hydrogenation catalyst of the present invention exists, therefore, in the present invention by least one be selected from extracting tower resistates, de-ketone tower overhead product and de-ester tower overhead product at least partially or their any combination carry out recycle, the ethanol production produced is maximized.
In the present invention, those skilled in the art according to the charging of reacting coarse product and each rectifying tower and can be separated the ratio that object suitably selects reflux ratio and overhead extraction amount and inlet amount, and the various technology enlightenments that also can provide according to the present invention are modified to technical scheme of the present invention.
Compared with the conventional method, the inventive method can isolate the materials such as the ketone of acetic acid hydrogenation process generation effectively, and this not only contributes to the separating effect improving rectifying tower, and effectively can also reduce the impurity in product, thus improves the quality of final alcohol product.
Embodiment
Explain that acetic acid hydrogenation method of the present invention produces the method for dehydrated alcohol below by way of example further, but the present invention is not limited to this.
Embodiment 1
In the present embodiment, the catalyzer of acetic acid hydrogenation is the acetic acid hydrogenation catalyst 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, respectively accounts for the 2wt% of overall catalyst weight; Surplus is silicon oxide.Catalyzer is prepared by coprecipitation method.
The method of being produced ethanol by acetic acid hydrogenation comprises:
(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 16:1, and temperature of reaction is 290 DEG C, and reaction pressure is 2.0MPa.
(2) depickling: at least part of crude ethanol product is delivered to extracting tower, is separated into the extracting tower overhead product containing ethyl acetate and ethanol and the extracting tower resistates containing acetic acid; The number of theoretical plate of described extracting tower is 55 pieces, and crude ethanol product opening for feed is positioned at the 40th block of plate, and tower top temperature is 75 DEG C, and tower top pressure is 0.10MPa;
(3) de-ketone: at least part of extracting tower overhead product is delivered to de-ketone tower, is separated into the de-ketone tower overhead product containing acetone and the de-ketone tower resistates containing ethanol; The number of theoretical plate of described de-ketone tower is 40 pieces, and opening for feed is positioned at the 15th block of plate, and tower top temperature is 62 DEG C, and tower top pressure is 0.15MPa;
(4) de-ester: deliver to de-ester tower by taking off ketone tower resistates at least partly, and extraction agent ethylene glycol is delivered to de-ester tower the 6th block of plate, be separated into the de-ester tower overhead product containing ethyl acetate and the de-ester tower resistates containing ethanol, water and ethylene glycol.The number of theoretical plate of described de-ester tower is 50 pieces, and the opening for feed of de-ketone tower resistates is positioned at the 20th block of plate, and tower top temperature is 78 DEG C, and tower top pressure is 0.15MPa;
(5) dewater: deliver to dehydration tower by taking off ester tower resistates at least partly, and extraction agent ethylene glycol is delivered to dehydration tower the 6th block of plate, be separated into moisture and dehydration tower resistates that is ethylene glycol, overhead extraction dehydrated alcohol product; The number of theoretical plate of described dehydration tower is 65 pieces, and the opening for feed of de-ester tower resistates is positioned at the 35th block of plate, and tower top temperature is 82 DEG C, and tower top pressure is 0.10MPa;
(6) solvent recuperation: at least part of dehydration tower resistates is delivered to solvent recovery tower, is separated into the solvent recovery tower overhead product containing water and the solvent recovery tower resistates containing ethylene glycol.The number of theoretical plate of described solvent recovery tower is 50 pieces, and the opening for feed of dehydration tower resistates is positioned at the 20th block of plate, and tower top temperature is 105 DEG C, and tower top pressure is 0.15MPa.
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 catalyst 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, respectively accounts for the 2wt% of overall catalyst weight; Surplus is silicon oxide.Catalyzer is prepared by coprecipitation method.
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 16:1, and temperature of reaction is 290 DEG C, and reaction pressure is 2.0MPa.
(2) depickling: at least part of crude ethanol product is delivered to extracting tower, is separated into the extracting tower overhead product containing ethyl acetate and ethanol and the extracting tower resistates containing acetic acid; The number of theoretical plate of described extracting tower is 62 pieces, and crude ethanol product opening for feed is positioned at the 44th block of plate, and tower top temperature is 73 DEG C, and tower top pressure is 0.10MPa;
(3) de-ketone: at least part of extracting tower overhead product is delivered to de-ketone tower, is separated into the de-ketone tower overhead product containing acetone and the de-ketone tower resistates containing ethanol; The number of theoretical plate of described de-ketone tower is 45 pieces, and opening for feed is positioned at the 18th block of plate, and tower top temperature is 60 DEG C, and tower top pressure is 0.15MPa;
(4) de-ester: deliver to de-ester tower by taking off ketone tower resistates at least partly, and extraction agent ethylene glycol is delivered to de-ester tower the 8th block of plate, be separated into the de-ester tower overhead product containing ethyl acetate and the de-ester tower resistates containing ethanol, water and ethylene glycol.The number of theoretical plate of described de-ester tower is 60 pieces, and the opening for feed of de-ketone tower resistates is positioned at the 25th block of plate, and tower top temperature is 77 DEG C, and tower top pressure is 0.12MPa;
(5) dewater: deliver to dehydration tower by taking off ester tower resistates at least partly, and extraction agent ethylene glycol is delivered to dehydration tower the 8th block of plate, be separated into moisture and dehydration tower resistates that is ethylene glycol, overhead extraction dehydrated alcohol product; The number of theoretical plate of described dehydration tower is 68 pieces, and the opening for feed of de-ester tower resistates is positioned at the 40th block of plate, and tower top temperature is 81 DEG C, and tower top pressure is 0.10MPa;
(6) solvent recuperation: at least part of dehydration tower resistates is delivered to solvent recovery tower, is separated into the solvent recovery tower overhead product containing water and the solvent recovery tower resistates containing ethylene glycol.The number of theoretical plate of described solvent recovery tower is 55 pieces, and the opening for feed of dehydration tower resistates is positioned at the 25th block of plate, and tower top temperature is 103 DEG C, and tower top pressure is 0.10MPa.
The analytical results of each step is listed in the following table:
From the analysis result data in embodiment 1-2, the inventive method effectively can isolate the ketone and the material such as acetaldehyde that acetic acid hydrogenation process produces, and contributes to the quality improving final alcohol product.
Claims (12)
1. produced a method for dehydrated alcohol by acetic acid hydrogenation, it is characterized in that, said method comprising the steps of:
(1) hydrogenation: pass into hydrogenator by after acetic acid raw material and hydrogen preheating, under the existence of hydrogenation catalyst, acetic acid is hydrogenated into crude ethanol product;
(2) depickling: at least part of crude ethanol product is delivered to extracting tower, is separated into the extracting tower overhead product containing vinyl acetic monomer and ethanol and the extracting tower resistates containing acetic acid;
(3) de-ketone: at least part of extracting tower overhead product is delivered to de-ketone tower, is separated into the de-ketone tower overhead product containing acetone and the de-ketone tower resistates containing second alcohol and water;
(4) de-ester:
Delivering to de-ester tower by taking off ketone tower resistates at least partly, adding extraction agent on tower top, be separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol, water and extraction agent;
(5) dewater: delivering to dehydration tower by taking off ester tower resistates at least partly, adding extraction agent on tower top, being separated into moisture and dehydration tower resistates that is extraction agent, overhead extraction dehydrated alcohol product;
(6) solvent recuperation: at least part of dehydration tower resistates is delivered to solvent recovery tower, is separated into moisture solvent recovery tower overhead product and the solvent recovery tower resistates containing extraction agent.
2. produced the method for dehydrated alcohol as claimed in claim 1 by acetic acid hydrogenation, it is characterized in that, described hydrogenation catalyst is the base metal type catalyzer containing cobalt.
3. produced the method for dehydrated alcohol as claimed in claim 1 by acetic acid hydrogenation, it is characterized in that, in described step (1), the processing condition of acetic acid direct hydrogenation are: the liquid phase volume air speed 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 200 ~ 320 DEG C, and reaction pressure is that normal pressure is to 4.0MPa.
4. the method for dehydrated alcohol is produced as claimed in claim 1 by acetic acid hydrogenation, it is characterized in that, in described step (3), the tower top temperature of described de-ketone tower is 55 ~ 70 DEG C, take partial condensation mode, the liquid portion extraction of condensation, partial reflux, uncooled gas phase portion cools recovery more further.
5. produced the method for dehydrated alcohol as claimed in claim 1 by acetic acid hydrogenation, it is characterized in that, in described step (2), before extracting tower resistates described is at least partly turned back to reactor, send into reactor or send into reactor after preheating.
6. produced the method for dehydrated alcohol as claimed in claim 1 by acetic acid hydrogenation, it is characterized in that, in described step (4), before de-ester tower overhead product described is at least partly turned back to reactor, send into reactor or send into reactor after preheating.
7. produced the method for dehydrated alcohol as claimed in claim 1 by acetic acid hydrogenation, it is characterized in that, in described step (4), described de-ester tower is extractive distillation column, and extraction agent is ethylene glycol or Diethylene Glycol.
8. produced the method for dehydrated alcohol as claimed in claim 1 by acetic acid hydrogenation, it is characterized in that, in described step (5), described dehydration tower is extractive distillation column, and extraction agent is ethylene glycol or Diethylene Glycol.
9. produced as claimed in claim 7 or 8 the method for dehydrated alcohol by acetic acid hydrogenation, it is characterized in that, in described step (4) and (5), extraction agent is ethylene glycol.
10. the method for dehydrated alcohol is produced as claimed in claim 1 by acetic acid hydrogenation, it is characterized in that, a part for solvent recovery tower resistates in described step (6) is sent into described de-ester tower and described dehydration tower, and described in described de-ester tower and described dehydration tower, solvent recovery tower resistates is as the extraction agent of Separation of Water.
11., as claimed in claim 1 by the method for acetic acid hydrogenation production dehydrated alcohol, is characterized in that, in described step (2), the number of theoretical plate of described extracting tower is 35 ~ 75 pieces, opening for feed is positioned at middle and lower part, and tower top temperature is 60 ~ 85 DEG C, and tower top pressure is 0.01 ~ 0.20MPa; In described step (3), the number of theoretical plate of described de-ketone tower is 20 ~ 55 pieces, and opening for feed is positioned at middle and upper part, and tower top temperature is 50 ~ 70 DEG C, and tower top pressure is 0.05 ~ 0.20MPa; In described step (4), the number of theoretical plate of described de-ester tower is 35 ~ 75 pieces, and opening for feed is positioned at middle and upper part, and tower top temperature is 65 ~ 85 DEG C, and tower top pressure is 0.01 ~ 0.20MPa; In described step (5), the number of theoretical plate of described dehydration tower is 45 ~ 75 pieces, and opening for feed is positioned at middle and lower part, and tower top temperature is 70 ~ 90 DEG C, and tower top pressure is 0.01 ~ 0.20MPa; In described step (6), the number of theoretical plate of described solvent recovery tower is 20 ~ 60 pieces, and opening for feed is positioned at middle and upper part, and tower top temperature is 90 ~ 120 DEG C, and tower top pressure is 0.01 ~ 0.20MPa.
Produce the method for dehydrated alcohol by acetic acid hydrogenation for 12. 1 kinds, it is characterized in that, described method comprises:
(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) depickling: at least part of crude ethanol product is delivered to extracting tower, is separated into the extracting tower overhead product containing vinyl acetic monomer and ethanol and the extracting tower resistates containing acetic acid;
(3) de-ketone: at least part of extracting tower overhead product is delivered to de-ketone tower, is separated into the de-ketone tower overhead product containing acetone and the de-ketone tower resistates containing second alcohol and water;
(4) de-ester: deliver to de-ester tower by taking off ketone tower resistates at least partly, extraction agent or partial solvent recovery tower resistates are delivered to de-ester tower middle and upper part, through extracting and separating, be separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol, water and extraction agent;
(5) dewater: deliver to dehydration tower by taking off ester tower resistates at least partly, extraction agent or partial solvent recovery tower resistates are delivered to de-ester tower middle and upper part, through extracting and separating, be separated into moisture and dehydration tower resistates that is extraction agent, overhead extraction dehydrated alcohol product;
(6) solvent recuperation: at least part of dehydration tower resistates is delivered to solvent recovery tower, is separated into moisture solvent recovery tower overhead product and the solvent recovery tower resistates containing extraction agent;
Described recycle stock be selected from least one in extracting tower resistates, de-ketone tower overhead product and de-ester tower overhead product at least partly or their any combination.
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| CN102414153A (en) * | 2010-02-02 | 2012-04-11 | 国际人造丝公司 | Process for producing ethanol using an extractive distillation column |
| 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 |
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| CN102414153A (en) * | 2010-02-02 | 2012-04-11 | 国际人造丝公司 | Process for producing ethanol using an extractive distillation column |
| 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 |
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| 乙醇―水间歇萃取精馏生产过程研究;白鹏等;《海湖盐与化工》;20031117;第32卷(第06期);11-13页，前言、2.3实验条件的选择、表1分批萃取精馏实验结果、图1 * |
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