CN103787830A - Method for producing ethanol by acetic acid hydrogenation - Google Patents
Method for producing ethanol by acetic acid hydrogenation Download PDFInfo
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- CN103787830A CN103787830A CN201210429219.4A CN201210429219A CN103787830A CN 103787830 A CN103787830 A CN 103787830A CN 201210429219 A CN201210429219 A CN 201210429219A CN 103787830 A CN103787830 A CN 103787830A
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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
- C07C29/132—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 invention discloses a method for producing ethanol by acetic acid hydrogenation, and belongs to the technical field of alcohol substance production. In order to solve the defects of ethanol purification process in the prior art and to improve ethanol product quality, through deep and intensive research, the inventor specially provides a method to obtain an ethanol product; according to the method, acetic acid is subjected to direct hydrogenation to obtain a crude ethanol product, and then processes of ketone component removal, unreacted acetic acid separation, acetic ester separation and water removal are carried out in order to obtain the ethanol product. The method can effectively separate substances of ketones and acetaldehydes generated in the acetic acid hydrogenation process, which not only facilitates the improvement of the separation effect of a distillation column, but also effectively reduces impurities in the product, and thus improves the quality of the final ethanol product.
Description
Technical field
Invention relates to a kind of method of producing ethanol, more particularly, the present invention relates to be a kind ofly hydrogenated to ethanol and be obtained the method for alcohol product through treating process by acetic acid.
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, for example 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 ethanol mainly contains fermentation method and ethylene hydration method at present.The rise that ethylene hydration method is accompanied by petrochemical complex develops, and comprises indirect hydration method and direct hydration method.Be subject in recent years the raising of production cost of ethylene, at China's ethylene process substantially in end-of-life state.The main raw material of fermentation method is farm crop (comprising corn, sugarcane, Chinese sorghum, cassava, paddy etc.), by utilizing the amylofermentation in farm crop to obtain ethanol.
The raw material that the main alcohol production enterprise of China is used is corn, wheat and cassava (mainly relying on import).In fact grain cost sharp rises in recent years, as corn price by 1100 yuan/ton of rises of 2003 to current 2300 yuan/ton, also there is the problem of striving grain with people in alcohol fuel therefore.The non-grain ethanol raw material such as cassava, sweet sorghum price is also expected to rise always, and two generations ethanol technology distance application take cellulosic ethanol as representative also has more difficulty to need to solve.
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 (in bracket for acetic acid is consumed proportion).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 grain fermentation method is the main production ways of food grade Glacial acetic acid, current global acetic acid substantially passes through methyl alcohol carbonyl carbonylation method and ethane oxidation method is produced.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, rise to 1,550 ten thousand tons of 2010 from 1,020 ten thousand tons in 2006, estimate that 2012 annual capacities approach 1,900 ten thousand tons, and the growth of demand is relatively slow, it is estimated that superfluous production capacity in 2012 will exceed 5,000,000 tons.Therefore, international acetic acid price is plummeted, and start up rate is lower.
Over nearly 10 years, acetic acid consumption still mainly concentrates on traditional field, and considerable change does not occur consumption structure, does not form new demand growth point and supports newly-increased production capacity.Estimate that China's acetic acid demand in 2012 is less than 4,800,000 tons of left and right, problem of excess production capacity is outstanding, even occurs stopping production after new device is driven.Therefore the exploitation of the downstream use of acetic acid is extremely urgent.
Use acetic acid to comprise two kinds as the approach of raw material production alcohol product, the one, acetic acid generates acetic ester through esterification, and then acetic ester hydrogenation generates ethanol, then carries out refined raw producing and ethanol product; The 2nd, 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 need to circulate as esterification feed, the corresponding size that has increased the size of hydrogenator and the interchanger of front and back thereof and energy consumption, treating process is also put and is twice at least partly, its advantage is that the corrosion strength of hydrogenation process may be lower, but in its process, also there is more or less acetic acid, still have corrodibility.But the key of second method is to develop the catalyzer of acetic acid direct hydrogenation, this difficult problem is also why a lot of units select the reason of the first acetic acid through the method for esterification repeated hydrogenation.
In order to omit esterification process, the method for acetic acid direct hydrogenation is also studied.For example U.S. Calenese company has submitted a large amount of patent applications to regard to acetic acid hydrogenation.For example PCT application enters the CN102414153A in China national stage, disclose first acetic acid has been hydrogenated into crude ethanol product, then in first tower, isolate unreacted acetic acid, the overhead product of first tower is isolated in second tower to the second overhead product containing vinyl acetic monomer, obtain the second resistates containing second alcohol and water, the second resistates is separated into containing the overhead product of ethanol and moisture resistates in the 3rd tower.In addition, selectively the second overhead product is delivered to the 4th tower, is separated into the 4th overhead product and the four-infirm excess containing acetaldehyde, then by the 4th overhead product Returning reacting system to improve ethanol yield, four-infirm excess is as solvent or be used in during ester produces.In disclosed other patent applications of the said firm, the method ethanol production of this hydrogenation and separation sequence is all disclosed substantially.
In the flow process of the Patent Application Publication of Calenese company, all do not mention that the ketone component of by-product is as the separation of acetone, and the light constituent such as acetaldehyde is through three towers of first tower to the, even the 4th tower.Ketone component is not separated 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 the easy polymerization of acetaldehyde, generates heavy constituent, thereby affects alcohol product quality.
Summary of the invention
The defect of ethyl alcohol purification process existing in order to solve prior art, improve alcohol product quality, contriver is through intensive research, it is crude ethanol product through direct hydrogenation that spy has proposed a kind of acetic acid, then successively through removing ketone component, separate unreacted acetic acid, isolating vinyl acetic monomer and remove moisture process, obtain alcohol product.
Concrete technical scheme of the present invention is as follows:
The method by acetic acid production ethanol that the present invention proposes comprises the following steps:
(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then make it by the reactor of hydrogenation catalyst is housed, acetic acid is hydrogenated into crude ethanol product;
(2) de-ketone: at least part of crude ethanol product is delivered to de-ketone tower, be separated into the de-ketone tower overhead product that contains acetone and contain the de-ketone tower resistates of ethanol;
(3) depickling: will take off at least partly ketone tower overhead product and deliver to extracting tower, and be separated into the extracting tower overhead product that contains second alcohol and water and the extracting tower resistates that contains 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 that contains vinyl acetic monomer and contain the de-ester tower resistates of ethanol;
(5) dehydration: will take off at least partly ester tower resistates and deliver to dehydration tower, and be separated into the dehydration tower overhead product that contains ethanol and the dehydration tower resistates that contains water.
Preferably, described hydrogenation catalyst is the base metal type catalyzer that contains 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 ℃, 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 ℃, takes the part type of cooling, the liquid portion extraction of condensation, and partial reflux, uncooled gas phase part is further cooling to reclaim organic substance again.
Preferably, described at least partly extracting tower resistates is turned back to before reactor, send into reactor or after preheating, send into reactor.
Preferably, described at least partly de-ester tower overhead product is turned back to before reactor, send into reactor or after preheating, send into reactor.
Preferably, in described step (4), described de-ester tower is extractive distillation column, and extraction agent is Diethylene Glycol or water.
Preferably, a part for the dehydration tower resistates in described step (5) is sent into described de-ester tower, the extraction agent at dehydration tower resistates described in described de-ester tower as separating acetic acid ethyl ester.
Preferably, a part for described dehydration tower resistates is sent into described de-ester tower, the extraction agent at dehydration tower resistates described in described de-ester tower as separating acetic acid ethyl ester.
More specifically preferably, in described step (2), the number of theoretical plate of described de-ketone tower is 20～60, and opening for feed is positioned at middle and upper part, and tower top temperature is 55～75 ℃, 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, and opening for feed is positioned at middle and lower part, and tower top temperature is 60～95 ℃, 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, and the opening for feed of extracting tower resistates is positioned at middle part, and tower top temperature is 60～95 ℃, 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, and the opening for feed of de-ester tower resistates is positioned at middle and lower part, and tower top temperature is 60～95 ℃, and tower top pressure is 0.01～0.30MPa.
If de-ester tower is extractive distillation column, the opening for feed of extraction agent is positioned at the top of de-ester tower, for example position of 3～10 theoretical stages.
Of the present invention another more specifically in scheme, comprised the following steps by the method for acetic acid production ethanol:
(1) hydrogenation: by acetic acid raw material, recycle stock and hydrogen preheating, then make it by the reactor of hydrogenation catalyst is housed, carry out hydrogenation reaction, the mixture of autoreactor is cooling in the future, through gas-liquid separation, the gas that is separated into crude ethanol product and contains hydrogen, uses gas circulation;
(2) de-ketone: at least part of crude ethanol product is delivered to de-ketone tower, be separated into the de-ketone tower overhead product that contains acetone and contain the de-ketone tower resistates of ethanol;
(3) depickling: will take off at least partly ketone tower overhead product and deliver to extracting tower, and be separated into the extracting tower overhead product that contains second alcohol and water and the extracting tower resistates that contains acetic acid;
(4) de-ester: at least part of extracting tower overhead product is delivered to the middle and lower part of de-ester tower, extraction agent is delivered to the middle and upper part of de-ester tower, through extracting rectifying, be separated into the de-ester tower overhead product that contains vinyl acetic monomer and contain the de-ester tower resistates of ethanol;
(5) dehydration: will take off at least partly ester tower resistates and deliver to dehydration tower, and be separated into the dehydration tower overhead product that contains ethanol and the dehydration tower resistates that contains water, at least part of dehydration tower resistates is delivered to de-ester tower as described extraction agent;
Described recycle stock be selected from de-ketone tower overhead product, extracting tower resistates and de-ester tower overhead product at least one at least a portion or their any combination.
In technical scheme of the present invention, suitable hydrogenation catalyst is selected from and loads on catalyzer or the catalyzer of at least one metal active constituent that catalyzed agent carrier disperses.Described metal active constituent is selected from IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIIIB group 4 transition metal, lanthanide series metal and IIIA, IVA, VA, the VIA family metal of the periodic table of elements one or more combination.As illustrative metal active ingredient, for example, be 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 that includes cobalt metal component, in catalyzer, except containing cobalt, 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 is modulation arbitrarily.
Be suitable as the material of support of the catalyst including, but not limited to conventional catalyst support material, for example 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, titanium dioxide-aluminum oxide 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, being applicable to catalyzer and the support of the catalyst of acetic acid preparation of ethanol by hydrogenating can be through any-mode modification.For example, 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 acid-basicity that certain metallic compound regulates carrier to improve catalyst activity preparing carrier process; And for example, by carrier, add certain metal as lanthanum etc. to improve the stability of catalyzer, this can effectively improve catalyst life; Further, can by catalyzer is carried out alkylation process regulate its surface properties reduce some compound in the deposition of catalyst surface with the extending catalyst life-span.
Catalyzer of the present invention can be prepared by ordinary method, preparation method is not had to special requirement, for example, take a certain amount of carrier, by the presoma of pickling process loaded metal active ingredient on carrier, then dry, roasting, reduction, finally obtains described catalyst prod.Can also use spraying method to be sprayed on carrier through the presoma of active ingredient, then dry, roasting, reduction, finally obtains described catalyst prod.For another example, can active ingredient presoma be loaded on carrier by co-precipitation mode, then dry, decompose, then obtain needed catalyst prod through steps such as granulation, compressing tablet, reduction.
Catalyzer of the present invention can use multiple preparation method that active ingredient and support of the catalyst are combined.For instance, the first catalyzer is: catalyzer at least contains: (1) cobalt, wherein cobalt metal content accounts for the 15wt% ~ 50wt% of catalyzer gross weight, (2) second metals, the second described metal is a kind of in group vib element (molybdenum, tungsten and chromium) and more than one, accounts for the 0.5wt% ~ 15.0wt% of catalyzer gross weight; Described catalyzer also contains oxide compound, and described oxide compound is selected from one or more of silicon oxide, diatomite, Calucium Silicate powder, zirconium white, titanium oxide, and its content accounts for the 20wt% ~ 80wt% of catalyzer gross weight; Described catalyzer is by co-precipitation, deposition-precipitation or sol-gel process preparation.The second catalyzer is: catalyzer at least contains: (1) cobalt, wherein cobalt metal content accounts for the 15wt% ~ 50wt% of catalyzer gross 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 catalyzer gross weight, (3) one or more in IB family element, account for the 0.1wt% ~ 15.0wt% of catalyzer gross weight; Described catalyzer also contains oxide compound, and described oxide compound is selected from one or more of silicon oxide, diatomite, zirconium white, titanium oxide, and its content accounts for the 10wt% ~ 80wt% of catalyzer gross weight; One or more in co-precipitation in described catalyzer, deposition-precipitation, ammonia still process precipitation or sol-gel process are in conjunction with preparation.The third catalyzer is: catalyzer at least contains cobalt and silver, and wherein cobalt metal content accounts for the 15wt% ~ 50wt% of catalyzer gross weight, and silver metal accounts for the 0.1wt% ~ 10.0wt% of catalyzer gross weight; One or more in employing co-precipitation, deposition-precipitation, ammonia still process precipitation or sol-gel process are in conjunction with preparation.These are only exemplary illustrations, and the present invention is not limited to these examples.
For those skilled in the art, thereby can gain enlightenment support of the catalyst of the present invention and preparation method are made to various changes according to above detailed description.For example, can adopt the support of the catalyst after any known hydrogenation catalyst, support of the catalyst or modification.
In technical scheme of the present invention, described reactor can be fixed bed form or the useful form of 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 gas phase 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 instance, hydrogenation reaction is carried out under normal pressure, and temperature of reaction is 200～300 ℃, and the liquid phase feeding volume space velocity of acetic acid is 0.05～0.5h
-1.Acetic acid hydrogenation also can carry out adding to depress, and for example, 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 ℃, and reaction pressure is that normal pressure is to 3.0MPa.The liquid phase volume meter of the flow that described liquid phase feeding volume space velocity refers to acetic acid during according to 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, and under the temperature of reaction in reactor and pressure, unreacted acetic acid is by the ethanol generation esterification generating with hydrogenation, generate vinyl acetic monomer, vinyl acetic monomer also can further be hydrogenated to ethanol certainly.Acetic acid air speed too hour, under certain reaction conditions, can there is the side reaction such as undesirable etherificate, dehydration repeated hydrogenation 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 in hydrogenation process, should select preferably reaction conditions.
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 separate take letones as cut point, letones is take acetone as main.Along with letones is separated when, lighter component is also separated as the component such as ether and acetaldehyde.The tower top temperature of suitably setting de-ketone tower, makes the not condensation of part light constituent, but emits with gas form, thereby can avoid those components that can not generate through further reacting ethanol in system, accumulate and take in subsequent product.In the present invention, the tower top temperature of de-ketone tower is for example chosen to be 55～75 ℃.
Reacting coarse product, through removing after light constituent, for fear of unreacted acetic acid and the ethanol generation esterification of reacting generation, generates vinyl acetic monomer, should as soon as possible unreacted acetic acid separated be gone out in separation process scheme.Separating unreacted acetic acid uses common rectificating method can reach separation object, certainly do not get rid of the chemical process that uses other yet, for example use alkaline matter as calcium hydroxide, calcium carbonate or Calcium hydrogen carbonate etc. and acetic acid reaction, generation is insoluble in the salts substances of ethanol, thereby reach, acetic acid is removed.Use in the present invention the resistates of extracting tower using acetic acid as extracting tower to separate.
In reacting coarse product, inevitably there are some vinyl acetic monomers, unless material stops the sufficiently long time in reactor, make the vinyl acetic monomer generating also be hydrogenated to ethanol, otherwise all can have more or less some vinyl acetic monomers.From reacting coarse product, separating acetic acid ethyl ester is not easy, vinyl acetic monomer easily forms azeotrope, generally uses extraction rectifying method, and spendable extraction agent is a lot, such as glycerine, Diethylene Glycol, ether, methyl-formiate, methyl-sulphoxide etc., even can make water.Through comparing and calculating, find to make water as extraction agent more economically.Water exists in reacting coarse product, introduce water and make extraction agent and do not introduce novel substance, and water also need to isolate from ethanol, and isolated water can return and be used as extraction agent, and therefore selecting water is a good selection as extraction agent.The present invention makes to use water as extraction agent vinyl acetic monomer is separated in de-ester tower.
Reacting coarse product, through isolating after above-mentioned various impurity, also contains second alcohol and water in reacting coarse product.In ethanol, separate water outlet, can use any thinkable method, for example the combination of conventional distillation method, extraction rectifying method, membrane separating method or these methods.For instance, utilize rectificating method that ethanol concentrate is above and below 95wt%, the azeotropic of ethanol and water forms about 95wt% to 90wt%, for more saving energy, alcohol concn is carried to 90wt% to 93wt% and being advisable, then use membrane separating method by ethanol concentrate to needed 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 like this discharge of waste water.
In the present invention, those skilled in the art can be according to the chargings of reacting coarse product and each rectifying tower and are separated object and suitably select the ratio of 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 be isolated the material such as ketone and acetaldehyde that acetic acid hydrogenation process produces effectively, this not only contributes to improve the separating effect of distillation tower, and can also effectively reduce the impurity in product, thereby improves the quality of final alcohol product.
Embodiment
Further explain the method for acetic acid hydrogenation method production ethanol of the present invention below in the mode of embodiment, 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 catalyzer gross weight; (2) molybdenum and chromium, accounts for respectively the 2wt% of catalyzer gross weight; Surplus is silicon oxide.Described catalyzer is prepared by co-precipitation.
Method by acetic acid production ethanol comprises the following steps:
(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then make it by the reactor of hydrogenation catalyst is housed, 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 ℃, and reaction pressure is 2.0MPa.
(2) de-ketone: at least part of crude ethanol product is delivered to de-ketone tower, be separated into the de-ketone tower overhead product that contains acetone and contain the de-ketone tower resistates of ethanol; The number of theoretical plate of described de-ketone tower is 50, and opening for feed is positioned at the 20th block of plate, and tower top temperature is 60 ℃, and tower top pressure is 0.15MPa;
(3) depickling: will take off at least partly ketone tower overhead product and deliver to extracting tower, and be separated into the extracting tower overhead product that contains second alcohol and water and the extracting tower resistates that contains acetic acid; The number of theoretical plate of described extracting tower is 75, and opening for feed is positioned at the 60th block of plate, and tower top temperature is 65 ℃, and tower top pressure is 0.13MPa;
(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 that contains vinyl acetic monomer and contain the de-ester tower resistates of ethanol; The number of theoretical plate of described de-ester tower is 75, and the opening for feed of extracting tower resistates is positioned at the 40th block of plate, makes water as extraction agent, and the weight ratio of the inlet amount of water and extracting tower resistates is 0.3:1, and tower top temperature is 79 ℃, and tower top pressure is 0.20MPa;
(5) dehydration: will take off at least partly ester tower resistates and deliver to dehydration tower, and be separated into the dehydration tower overhead product that contains ethanol and the dehydration tower resistates that contains water.The number of theoretical plate of described dehydration tower is 38, and the opening for feed of de-ester tower resistates is positioned at the 33rd block of plate, and tower top temperature is 85 ℃, 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 catalyzer gross weight; (2) molybdenum and chromium, accounts for respectively the 2wt% of catalyzer gross weight; Surplus is silicon oxide.Described catalyzer is prepared by co-precipitation.
Method by acetic acid production ethanol comprises the following steps:
(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then make it by the reactor of hydrogenation catalyst is housed, 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 ℃, and reaction pressure is 1.75MPa.
(2) de-ketone: at least part of crude ethanol product is delivered to de-ketone tower, be separated into the de-ketone tower overhead product that contains acetone and contain the de-ketone tower resistates of ethanol; The number of theoretical plate of described de-ketone tower is 55, and opening for feed is positioned at the 23rd block of plate, and tower top temperature is 57 ℃, and tower top pressure is 0.15MPa;
(3) depickling: will take off at least partly ketone tower overhead product and deliver to extracting tower, and be separated into the extracting tower overhead product that contains second alcohol and water and the extracting tower resistates that contains acetic acid; The number of theoretical plate of described extracting tower is 60, and opening for feed is positioned at the 45th block of plate, and tower top temperature is 79 ℃, and tower top pressure is 0.12MPa;
(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 that contains vinyl acetic monomer and contain the de-ester tower resistates of ethanol; The number of theoretical plate of described de-ester tower is 60, and the opening for feed of extracting tower resistates is positioned at the 30th block of plate, makes water as extraction agent, and the weight ratio of the inlet amount of water and extracting tower resistates is 0.45:1, and tower top temperature is 80 ℃, and tower top pressure is 0.15MPa;
(5) dehydration: will take off at least partly ester tower resistates and deliver to dehydration tower, and be separated into the dehydration tower overhead product that contains ethanol and the dehydration tower resistates that contains water.The number of theoretical plate of described dehydration tower is 45, and the opening for feed of de-ester tower resistates is positioned at the 39th block of plate, and tower top temperature is 83 ℃, 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 catalyzer gross weight; (2) molybdenum and chromium, accounts for respectively the 2wt% of catalyzer gross weight; Surplus is silicon oxide.Described catalyzer is prepared by co-precipitation.
Method by acetic acid production ethanol comprises the following steps:
(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then make it by the reactor of hydrogenation catalyst is housed, 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 ℃, and reaction pressure is 1.5MPa.
(2) de-ketone: at least part of crude ethanol product is delivered to de-ketone tower, be separated into the de-ketone tower overhead product that contains acetone and contain the de-ketone tower resistates of ethanol; The number of theoretical plate of described de-ketone tower is 55, and opening for feed is positioned at the 15th block of plate, and tower top temperature is 61 ℃, and tower top pressure is 0.14MPa;
(3) depickling: will take off at least partly ketone tower overhead product and deliver to extracting tower, and be separated into the extracting tower overhead product that contains second alcohol and water and the extracting tower resistates that contains acetic acid; The number of theoretical plate of described extracting tower is 60, and opening for feed is positioned at the 50th block of plate, and tower top temperature is 80 ℃, and tower top pressure is 0.15MPa;
(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 that contains vinyl acetic monomer and contain the de-ester tower resistates of ethanol; The number of theoretical plate of described de-ester tower is 70, and the opening for feed of extracting tower resistates is positioned at the 35th block of plate, makes water as extraction agent, and the weight ratio of the inlet amount of water and extracting tower resistates is 0.6:1, and tower top temperature is 81 ℃, and tower top pressure is 0.15MPa;
(5) dehydration: will take off at least partly ester tower resistates and deliver to dehydration tower, and be separated into the dehydration tower overhead product that contains ethanol and the dehydration tower resistates that contains water.The number of theoretical plate of described dehydration tower is 45, and the opening for feed of de-ester tower resistates is positioned at the 41st block of plate, and tower top temperature is 81 ℃, 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 can effectively be isolated the material such as ketone and acetaldehyde that acetic acid hydrogenation process produces, and contributes to improve the quality of final alcohol product.
Claims (10)
1. by a method for acetic acid production ethanol, it is characterized in that, said method comprising the steps of:
(1) hydrogenation: by acetic acid raw material and hydrogen preheating, then make it by the reactor of hydrogenation catalyst is housed, acetic acid is hydrogenated into crude ethanol product;
(2) de-ketone: at least part of crude ethanol product is delivered to de-ketone tower, be separated into the de-ketone tower overhead product that contains acetone and contain the de-ketone tower resistates of ethanol;
(3) depickling: will take off at least partly ketone tower overhead product and deliver to extracting tower, and be separated into the extracting tower overhead product that contains second alcohol and water and the extracting tower resistates that contains 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 that contains vinyl acetic monomer and contain the de-ester tower resistates of ethanol;
(5) dehydration: will take off at least partly ester tower resistates and deliver to dehydration tower, and be separated into the dehydration tower overhead product that contains ethanol and the dehydration tower resistates that contains water.
2. the method by acetic acid production ethanol as claimed in claim 1, is characterized in that, described hydrogenation catalyst is the base metal type catalyzer that contains cobalt.
3. the method by acetic acid production ethanol as claimed in claim 1, 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 ℃, and reaction pressure is that normal pressure is to 3.0MPa.
4. the method by acetic acid production ethanol as claimed in claim 1, it is characterized in that, in described step (2), the tower top temperature of described de-ketone tower is 55～75 ℃, take the part type of cooling, the liquid portion extraction of condensation, partial reflux, uncooled gas phase part is further cooling to reclaim organic substance again.
5. the method by acetic acid production ethanol as claimed in claim 1, is characterized in that, described at least partly extracting tower resistates is turned back to before reactor, sends into reactor or after preheating, sends into reactor.
6. the method by acetic acid production ethanol as claimed in claim 1, is characterized in that, described at least partly de-ester tower overhead product is turned back to before reactor, sends into reactor or after preheating, sends into reactor.
7. the method by acetic acid production ethanol as claimed in claim 1, is characterized in that, in described step (4), described de-ester tower is extractive distillation column, and extraction agent is Diethylene Glycol or water.
8. the method by acetic acid production ethanol as claimed in claim 1, it is characterized in that, a part for dehydration tower resistates in described step (5) is sent into described de-ester tower, the extraction agent at dehydration tower resistates described in described de-ester tower as separating acetic acid ethyl ester.
9. the method by acetic acid production ethanol as claimed in claim 1, is characterized in that, in described step (2), the number of theoretical plate of described de-ketone tower is 20～60, opening for feed is positioned at middle and upper part, and tower top temperature is 55～75 ℃, 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, and opening for feed is positioned at middle and lower part, and tower top temperature is 60～95 ℃, 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, and the opening for feed of extracting tower resistates is positioned at middle part, and tower top temperature is 60～95 ℃, 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, and the opening for feed of de-ester tower resistates is positioned at middle and lower part, and tower top temperature is 60～95 ℃, and tower top pressure is 0.01～0.30MPa.
10. by a method for acetic acid production ethanol, it is characterized in that, said method comprising the steps of:
(1) hydrogenation: by acetic acid raw material, recycle stock and hydrogen preheating, then make it by the reactor of hydrogenation catalyst is housed, carry out hydrogenation reaction, the mixture of autoreactor is cooling in the future, through gas-liquid separation, the gas that is separated into crude ethanol product and contains hydrogen, uses gas circulation;
(2) de-ketone: at least part of crude ethanol product is delivered to de-ketone tower, be separated into the de-ketone tower overhead product that contains acetone and contain the de-ketone tower resistates of ethanol;
(3) depickling: will take off at least partly ketone tower overhead product and deliver to extracting tower, and be separated into the extracting tower overhead product that contains second alcohol and water and the extracting tower resistates that contains acetic acid;
(4) de-ester: at least part of extracting tower overhead product is delivered to the middle and lower part of de-ester tower, extraction agent is delivered to the middle and upper part of de-ester tower, through extracting rectifying, be separated into the de-ester tower overhead product that contains vinyl acetic monomer and contain the de-ester tower resistates of ethanol;
(5) dehydration: will take off at least partly ester tower resistates and deliver to dehydration tower, and be separated into the dehydration tower overhead product that contains ethanol and the dehydration tower resistates that contains water, at least part of dehydration tower resistates is delivered to de-ester tower as described extraction agent;
Described recycle stock be selected from de-ketone tower overhead product, extracting tower resistates and de-ester tower overhead product at least one at least a portion or their any combination.
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| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| CN105198704A (en) * | 2014-05-29 | 2015-12-30 | 中国石油化工股份有限公司 | Method for low-energy consumption acetic acid hydrogenation production of ethanol |
| CN105198703A (en) * | 2014-05-29 | 2015-12-30 | 中国石油化工股份有限公司 | Method for producing ethanol by acetic acid hydrogenation |
| CN105418372A (en) * | 2014-09-18 | 2016-03-23 | 中国石油化工股份有限公司 | Method for producing ethanol by acetic acid through hydrogenation |
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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 |
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| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9458072B2 (en) | 2014-04-28 | 2016-10-04 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
| CN105198703A (en) * | 2014-05-29 | 2015-12-30 | 中国石油化工股份有限公司 | Method for producing ethanol by acetic acid hydrogenation |
| CN105198704A (en) * | 2014-05-29 | 2015-12-30 | 中国石油化工股份有限公司 | Method for low-energy consumption acetic acid hydrogenation production of ethanol |
| CN105481649A (en) * | 2014-09-18 | 2016-04-13 | 中国石油化工股份有限公司 | Method for preparing ethanol through hydrogenating acetic acid |
| CN105418372A (en) * | 2014-09-18 | 2016-03-23 | 中国石油化工股份有限公司 | Method for producing ethanol by acetic acid through hydrogenation |
| CN105481649B (en) * | 2014-09-18 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of method that acetic acid hydrogenation prepares ethanol |
| CN105418372B (en) * | 2014-09-18 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of method of acetic acid hydrogenation production ethanol |
| CN105566058A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Method for production of ethanol by acetic acid hydrogenation |
| CN107349947A (en) * | 2017-05-24 | 2017-11-17 | 沈阳三聚凯特催化剂有限公司 | A kind of acetic acid hydrogenation catalyst and its application |
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