CN104211569A - Method for production of ethanol by direct hydrogenation of acetic acid - Google Patents
Method for production of ethanol by direct hydrogenation of acetic acid 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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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- 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
Belonging to the field of production technologies for alcohol substances, the invention discloses a method for production of ethanol by direct hydrogenation of acetic acid. In order to solve the defects of an ethanol purification process in the prior art, improve the ethanol product quality and reduce energy consumption, the inventor specifically puts forward a technological process through in-depth and meticulous research. The process includes: subjecting acetic acid to direct hydrogenation to obtain a crude ethanol product, then removing ketone components, separating unreacted acetic acid and ethyl acetate, and removing water in order, thus obtaining the ethanol product. The method provided by the invention can effectively separate ketone, acetaldehyde and other substances generated in the hydrogenation process, thus facilitating improving the separation effect of a distillation tower and effectively reducing impurities in the product. Therefore, the quality of the final ethanol product can be improved.
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 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 omit esterification 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 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.Ketone Component seperation is not gone out the impurity index of the final alcohol product of impact.The existence of the light constituents such as acetaldehyde will affect the pressure of each distillation tower, and pressure surge will affect the separating effect of distillation tower, and acetaldehyde is easily polymerized, and generate heavy constituent, thus affect alcohol product quality.Further, in existing related application, de-ester tower generally adopts extraction rectifying method, and energy consumption is relatively high, and process is complicated.
Summary of the invention
In order to solve the defect of the ethyl alcohol purification process that prior art exists, improve alcohol product quality and reduce energy consumption, contriver is through intensive research, it is crude ethanol product that spy proposes a kind of acetic acid through direct hydrogenation, then successively through removing ketone component, being separated unreacted acetic acid, isolating vinyl acetic monomer and remove moisture process, alcohol product is obtained.
Concrete technical scheme of the present invention is as follows:
What the present invention proposed is 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 is hydrogenated into crude ethanol product;
(2) de-ketone: at least part of crude ethanol 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;
(3) depickling: delivering to extracting tower by taking off ketone tower overhead product at least partly, being separated into the extracting tower overhead product containing second alcohol and water and the extracting tower resistates containing acetic acid;
(4) de-ester: at least part of extracting tower overhead product is delivered to de-ester tower, be separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol, the return tank of de-ester tower is oil-water decanter, do not add in return tank or add water and be beneficial to layering, it is front to send into reactor or send into reactor after preheating that oil reservoir turns back to reactor, and water layer is all back to de-ester tower;
(5) dewater: delivering to dehydration tower by taking off ester tower resistates at least partly, being separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water.
Preferably, described hydrogenation catalyst is the base metal type catalyzer containing cobalt.
Preferably, in described step (1), the processing condition of acetic acid hydrogenation are: the liquid phase volume air speed of acetic acid is 0.05 ~ 1.5h
-1, the mol ratio of hydrogen and acetic acid is 5 ~ 30:1, and temperature of reaction is 220 ~ 290 DEG C, and reaction pressure is that normal pressure is to 3.0MPa.
Preferably, in described step (2), the tower top temperature of described de-ketone tower is 55 ~ 75 DEG C, takes the part type of cooling, the liquid portion extraction of condensation, partial reflux, and uncooled gas phase portion cools to reclaim organic substance more further.
Preferably, before extracting tower resistates described is at least partly turned back to reactor, send into reactor or send into reactor after preheating.
Preferably, a part for the dehydration tower resistates in described step (5) is sent into the return tank of described de-ester tower.
More specifically preferably, in described step (2), the number of theoretical plate of described de-ketone tower is 20 ~ 60 pieces, and opening for feed is positioned at middle and upper part, and tower top temperature is 55 ~ 75 DEG C, and tower top pressure is 0.05 ~ 0.30MPa; In described step (3), the number of theoretical plate of described extracting tower is 25 ~ 80 pieces, and opening for feed is positioned at middle and lower part, and tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa; In described step (4), the number of theoretical plate of described de-ester tower is 25 ~ 80 pieces, and the opening for feed of extracting tower resistates is positioned at middle part, and tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa; By in described step (5), the number of theoretical plate of described dehydration tower is 10 ~ 40 pieces, and the opening for feed of de-ester tower resistates is positioned at middle and lower part, and tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa.
Of the present invention another more specifically in scheme, the method for being produced ethanol by acetic acid direct hydrogenation comprises the following steps:
(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) de-ketone: at least part of crude ethanol 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;
(3) depickling: delivering to extracting tower by taking off ketone tower overhead product at least partly, being separated into the extracting tower overhead product containing second alcohol and water and the extracting tower resistates containing acetic acid;
(4) de-ester: at least part of extracting tower overhead product is delivered to de-ester tower, be separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol, the return tank of de-ester tower is oil-water decanter, do not add in return tank or add water and be beneficial to layering, it is front to send into reactor or send into reactor after preheating that oil reservoir turns back to reactor, and water layer is all back to de-ester tower;
(5) dewater: delivering to dehydration tower by taking off ester tower resistates at least partly, being separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water, at least part of dehydration tower resistates being delivered to the return tank of de-ester tower;
Described recycle stock be selected from least one in the oil reservoir of the return tank of de-ketone tower overhead product, extracting tower resistates and de-ester tower at least partially 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 ~ 300 DEG C, and the liquid phase feeding volume space velocity of acetic acid is 0.05 ~ 0.5h
-1.Acetic acid hydrogenation also can carry out under elevated pressure, and such as, the processing condition of acetic acid hydrogenation are: the liquid phase feeding volume space velocity of acetic acid is 0.05 ~ 1.5h
-1, the mol ratio of hydrogen and acetic acid is 5 ~ 30:1, and temperature of reaction is 220 ~ 290 DEG C, and reaction pressure is that normal pressure is to 3.0MPa.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, then fills into some fresh hydrogen, and liquid enters follow-up separation phase.First be that cut point is separated with letones, letones is based on acetone.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 ~ 75 DEG C.
Reacting coarse product, after removing light constituent, in order to avoid the ethanol generation esterification that unreacted acetic acid generates with reaction, generates vinyl acetic monomer, should unreacted acetic acid separated be gone out as soon as possible in separation process scheme.Being separated unreacted acetic acid uses common rectificating method namely can reach separation object, certainly the chemical process using other is not got rid of yet, such as use alkaline matter as calcium hydroxide, calcium carbonate or Calcium hydrogen carbonate etc. and acetic acid reaction, generate and be insoluble in the salts substances of ethanol, thus reach acetic acid is removed.Extracting tower is used to be separated by the resistates of acetic acid as extracting tower in the present invention.
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.Vinyl acetic monomer, second alcohol and water form ternary azeotrope, and 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.In de-ester tower, through rectifying, the material distillated from tower top contains vinyl acetic monomer, second alcohol and water, flows to return tank again, in return tank, layering occurs through cooling, forms the oil reservoir containing vinyl acetic monomer and the water layer containing second alcohol and water.Can add water in return tank, adding appropriate water can promote layering.Before oil reservoir turns back to reactor, circulation hydrogenation utilizes.Water layer all passes back into de-ester tower.
Reacting coarse product, after isolating above-mentioned various impurity, also contains second alcohol and water in reacting coarse product.Be separated water outlet in ethanol, any thinkable method can be used, such as the combination of conventional distillation method, azeotropic distillation method, extraction rectifying method, membrane separating method or these methods.For example, utilize rectificating method by ethanol concentrate to more than 90wt% and below 95wt%, the azeotropic of ethanol and water forms about 95wt%, for more saving energy, alcohol concn is carried and being advisable to 90wt% to 93wt%, then uses membrane separating method by ethanol concentrate to required concentration.Isolated a part of water turns back to de-ester tower and from crude product, isolates vinyl acetic monomer as extraction agent, can reduce the discharge of waste water like this.
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 ketone and the material such as acetaldehyde that acetic acid hydrogenation process produces effectively, this not only contributes to the separating effect improving distillation tower, and effectively can also reduce the impurity in product, thus improves the quality of final alcohol product.In de-ester tower, adopt the quantizer of organic phase and aqueous phase as return tank, compared with extractive distillation column, energy consumption reduces, and process is simple.
Embodiment
Explain that acetic acid hydrogenation method of the present invention produces the method for ethanol 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, accounts for the 2wt% of overall catalyst weight respectively; Surplus is silicon oxide.Described catalyzer is prepared by co-precipitation.
Comprised the following steps by the method for acetic acid production ethanol:
(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then makes it pass through to be equipped with the reactor of hydrogenation catalyst, acetic acid is hydrogenated into crude ethanol product; The processing condition of acetic acid hydrogenation are: the liquid phase volume air speed of acetic acid is 0.5h
-1, the mol ratio of hydrogen and acetic acid is 20:1, and temperature of reaction is 280 DEG C, and reaction pressure is 2.0MPa.
(2) de-ketone: at least part of crude ethanol 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 50 pieces, and opening for feed is positioned at the 20th block of plate, and tower top temperature is 60 DEG C, and tower top pressure is 0.15MPa;
(3) depickling: delivering to extracting tower by taking off ketone tower overhead product at least partly, being separated into the extracting tower overhead product containing second alcohol and water and the extracting tower resistates containing acetic acid; The number of theoretical plate of described extracting tower is 75 pieces, and opening for feed is positioned at the 60th block of plate, and tower top temperature is 65 DEG C, and tower top pressure is 0.13MPa;
(4) de-ester: at least part of extracting tower overhead product is delivered to de-ester tower, is separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol; The number of theoretical plate of described de-ester tower is 75 pieces, the opening for feed of extracting tower resistates is positioned at the 40th block of plate, tower top temperature is 79 DEG C, tower top pressure is 0.20MPa, in return tank, form layering, and upper strata is the organic phase containing vinyl acetic monomer, lower floor is the aqueous phase containing second alcohol and water, organic phase extraction, before turning back to reactor, aqueous phase all refluxes; A small amount of water can be added and promote layering;
(5) dewater: delivering to dehydration tower by taking off ester tower resistates at least partly, being separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water.The number of theoretical plate of described dehydration tower is 38 pieces, and the opening for feed of de-ester tower resistates is positioned at the 33rd block of plate, and tower top temperature is 85 DEG C, and tower top pressure is 0.16MPa.
The analytical results of each step is listed in the following table.
Embodiment 2
In the present embodiment, the catalyzer of acetic acid hydrogenation is the acetic acid hydrogenation 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, accounts for the 2wt% of overall catalyst weight respectively; Surplus is silicon oxide.Described catalyzer is prepared by co-precipitation.
Comprised the following steps by the method for acetic acid production ethanol:
(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then makes it pass through to be equipped with the reactor of hydrogenation catalyst, acetic acid is hydrogenated into crude ethanol product; The processing condition of acetic acid hydrogenation are: the liquid phase volume air speed of acetic acid is 0.75h
-1, the mol ratio of hydrogen and acetic acid is 15:1, and temperature of reaction is 270 DEG C, and reaction pressure is 1.75MPa.
(2) de-ketone: at least part of crude ethanol 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 55 pieces, and opening for feed is positioned at the 23rd block of plate, and tower top temperature is 57 DEG C, and tower top pressure is 0.15MPa;
(3) depickling: delivering to extracting tower by taking off ketone tower overhead product at least partly, being separated into the extracting tower overhead product containing second alcohol and water and the extracting tower resistates containing acetic acid; The number of theoretical plate of described extracting tower is 60 pieces, and opening for feed is positioned at the 45th block of plate, and tower top temperature is 79 DEG C, and tower top pressure is 0.12MPa;
(4) de-ester: at least part of extracting tower overhead product is delivered to de-ester tower, is separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol; The number of theoretical plate of described de-ester tower is 60 pieces, the opening for feed of extracting tower resistates is positioned at the 30th block of plate, tower top temperature is 80 DEG C, tower top pressure is 0.15MPa, in return tank, form layering, and upper strata is the organic phase containing vinyl acetic monomer, lower floor is the aqueous phase containing second alcohol and water, organic phase extraction, before turning back to reactor, aqueous phase all refluxes; A small amount of water can be added and promote layering;
(5) dewater: delivering to dehydration tower by taking off ester tower resistates at least partly, being separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water.The number of theoretical plate of described dehydration tower is 45 pieces, and the opening for feed of de-ester tower resistates is positioned at the 39th block of plate, and tower top temperature is 83 DEG C, and tower top pressure is 0.15MPa.
The analytical results of each step is listed in the following table.
Embodiment 3
In the present embodiment, the catalyzer of acetic acid hydrogenation is the acetic acid hydrogenation 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, accounts for the 2wt% of overall catalyst weight respectively; Surplus is silicon oxide.Described catalyzer is prepared by co-precipitation.
Comprised the following steps by the method for acetic acid production ethanol:
(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then makes it pass through to be equipped with the reactor of hydrogenation catalyst, acetic acid is hydrogenated into crude ethanol product; The processing condition of acetic acid hydrogenation are: the liquid phase volume air speed of acetic acid is 1.25h
-1, the mol ratio of hydrogen and acetic acid is 12:1, and temperature of reaction is 280 DEG C, and reaction pressure is 1.5MPa.
(2) de-ketone: at least part of crude ethanol 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 55 pieces, and opening for feed is positioned at the 15th block of plate, and tower top temperature is 61 DEG C, and tower top pressure is 0.14MPa;
(3) depickling: delivering to extracting tower by taking off ketone tower overhead product at least partly, being separated into the extracting tower overhead product containing second alcohol and water and the extracting tower resistates containing acetic acid; The number of theoretical plate of described extracting tower is 60 pieces, and opening for feed is positioned at the 50th block of plate, and tower top temperature is 80 DEG C, and tower top pressure is 0.15MPa;
(4) de-ester: at least part of extracting tower overhead product is delivered to de-ester tower, is separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol; The number of theoretical plate of described de-ester tower is 70 pieces, the opening for feed of extracting tower resistates is positioned at the 35th block of plate, tower top temperature is 81 DEG C, tower top pressure is 0.15MPa, in return tank, form layering, and upper strata is the organic phase containing vinyl acetic monomer, lower floor is the aqueous phase containing second alcohol and water, organic phase extraction, before turning back to reactor, aqueous phase all refluxes; A small amount of water can be added and promote layering;
(5) dewater: delivering to dehydration tower by taking off ester tower resistates at least partly, being separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water.The number of theoretical plate of described dehydration tower is 45 pieces, and the opening for feed of de-ester tower resistates is positioned at the 41st block of plate, and tower top temperature is 81 DEG C, and tower top pressure is 0.12MPa.
The analytical results of each step is listed in the following table.
From the analysis result data in embodiment 1-3, the inventive method effectively can isolate the ketone and the material such as acetaldehyde that acetic acid hydrogenation process produces, and contributes to the quality improving final alcohol product.The return tank of top of the tower of de-ester tower adopts oil-water decanter, can reduce energy consumption.
Claims (8)
1. produced a method for ethanol by acetic acid direct hydrogenation, it is characterized in that, said method comprising the steps of:
(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 is hydrogenated into crude ethanol product;
(2) de-ketone: at least part of crude ethanol 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;
(3) depickling: delivering to extracting tower by taking off ketone tower overhead product at least partly, being separated into the extracting tower overhead product containing second alcohol and water and the extracting tower resistates containing acetic acid;
(4) de-ester: at least part of extracting tower overhead product is delivered to de-ester tower, be separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol, the return tank of de-ester tower is oil-water decanter, do not add in return tank or add water and be beneficial to layering, it is front to send into reactor or send into reactor after preheating that oil reservoir turns back to reactor, and water layer is all back to de-ester tower;
(5) dewater: delivering to dehydration tower by taking off ester tower resistates at least partly, being separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water.
2. produced the method for ethanol as claimed in claim 1 by acetic acid direct hydrogenation, it is characterized in that, described hydrogenation catalyst is the base metal type catalyzer containing cobalt.
3. produced the method for ethanol as claimed in claim 1 by acetic acid direct hydrogenation, it is characterized in that, in described step (1), the processing condition of acetic acid hydrogenation are: the liquid phase volume air speed of acetic acid is 0.05 ~ 1h
-1, the mol ratio of hydrogen and acetic acid is 5 ~ 30:1, and temperature of reaction is 220 ~ 290 DEG C, and reaction pressure is that normal pressure is to 3.0MPa.
4. the method for ethanol is produced as claimed in claim 1 by acetic acid direct hydrogenation, it is characterized in that, in described step (2), the tower top temperature of described de-ketone tower is 55 ~ 75 DEG C, take the part type of cooling, the liquid portion extraction of condensation, partial reflux, uncooled gas phase portion cools to reclaim organic substance more further.
5. produced the method for ethanol as claimed in claim 1 by acetic acid direct hydrogenation, it is characterized in that, 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 ethanol as claimed in claim 1 by acetic acid direct hydrogenation, it is characterized in that, a part for the dehydration tower resistates in described step (5) is sent into the return tank of described de-ester tower.
7., as claimed in claim 1 by the method for acetic acid production ethanol, it is characterized in that, in described step (2), the number of theoretical plate of described de-ketone tower is 20 ~ 60 pieces, opening for feed is positioned at middle and upper part, and tower top temperature is 55 ~ 75 DEG C, and tower top pressure is 0.05 ~ 0.30MPa; In described step (3), the number of theoretical plate of described extracting tower is 25 ~ 80 pieces, and opening for feed is positioned at middle and lower part, and tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa; In described step (4), the number of theoretical plate of described de-ester tower is 25 ~ 80 pieces, and the opening for feed of extracting tower resistates is positioned at middle part, and tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa; By in described step (5), the number of theoretical plate of described dehydration tower is 10 ~ 40 pieces, and the opening for feed of de-ester tower resistates is positioned at middle and lower part, and tower top temperature is 60 ~ 95 DEG C, and tower top pressure is 0.01 ~ 0.30MPa.
8. produced a method for ethanol by acetic acid direct hydrogenation, it is characterized in that, said method comprising the steps of:
(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) de-ketone: at least part of crude ethanol 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;
(3) depickling: delivering to extracting tower by taking off ketone tower overhead product at least partly, being separated into the extracting tower overhead product containing second alcohol and water and the extracting tower resistates containing acetic acid;
(4) de-ester: at least part of extracting tower overhead product is delivered to de-ester tower, be separated into the de-ester tower overhead product containing vinyl acetic monomer and the de-ester tower resistates containing ethanol, the return tank of de-ester tower is oil-water decanter, do not add in return tank or add water and be beneficial to layering, it is front to send into reactor or send into reactor after preheating that oil reservoir turns back to reactor, and water layer is all back to de-ester tower;
(5) dewater: delivering to dehydration tower by taking off ester tower resistates at least partly, being separated into the dehydration tower overhead product containing ethanol and the dehydration tower resistates containing water, at least part of dehydration tower resistates being delivered to the return tank of de-ester tower;
Described recycle stock be selected from least one in the oil reservoir of de-ketone tower overhead product, extracting tower resistates and de-ester tower return tank at least partially or their any combination.
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