CN103781749A - Reducing acetals during ethanol separation process - Google Patents

Reducing acetals during ethanol separation process Download PDF

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Publication number
CN103781749A
CN103781749A CN201180073465.4A CN201180073465A CN103781749A CN 103781749 A CN103781749 A CN 103781749A CN 201180073465 A CN201180073465 A CN 201180073465A CN 103781749 A CN103781749 A CN 103781749A
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ethanol
resistates
tower
overhead product
acetal
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Chinese (zh)
Inventor
D·李
A·奥罗斯科
L·萨拉戈
R·J·瓦尼尔
R·瓦尔拉伯
V·J·约翰斯顿
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Celanese International Corp
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Celanese International Corp
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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
    • 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

Abstract

To reduce acetal concentrations when separating ethanol from a crude product in one or more distillation column, at least one of the columns is operated at a higher pressure to increase the equilibrium constant that favors hydrolysis of the acetal. The crude product may comprise ethanol, acetaldehyde, water and one or more acetals, such as diethyl acetal. The acetal concentration may be reduced thus reducing the need to separate acetal from the crude product.

Description

In separation of ethanol process, reduce acetal
Invention field
Present invention relates in general to the method for the production of ethanol, particularly for the distillation towers that operate under one or more pressure in improving from crude product separating alcohol to reduce the method for acetal concentration.
Background of invention
Ethanol for industrial use is produced by petrochemical materials for example oil, Sweet natural gas or coal according to routine, produced by for example synthetic gas of raw material midbody, or by starchiness material or for example corn of cellulose materials (corn) or sugarcane production.For comprising that by petrochemical materials and by the ordinary method of cellulose materials production ethanol acid catalysis hydration, methyl alcohol homologization, the direct alcohol of ethene synthesize and fischer-tropsch is synthetic.The unstable of petrochemical materials price is impelled the ethanol cost fluctuation of producing according to routine, and what in the time that cost of material raises, make alternative source to alcohol production need to be than in the past larger.Starchiness material and cellulose materials are converted into ethanol by fermentation.But fermentation is generally used for the consumer of the ethanol that is suitable for fuel or human consumption and produces.In addition, the fermentation of starchiness or cellulose materials and food sources form competition and to for industrial use the amount of producible ethanol applied restriction.
Also original production ethanol by paraffinic acid and/or other carbonyl containing compound obtains broad research, has mentioned in the literature the various combinations of catalyzer, carrier and operational condition.Between the reduction period of for example acetic acid of paraffinic acid, other compound forms with ethanol or forms in side reaction.These impurity have limited the production of ethanol and the recovery from this class reaction mixture.For example, during hydrogenation, the ester of generation forms the azeotrope that is difficult to separation together with ethanol and/or water.In addition,, in the time that conversion is incomplete, unreacted acid is retained in coarse ethanol mixture, it must be removed to reclaim ethanol.
EP02060553 has described the method for hydrocarbon being converted into ethanol, and the method comprises hydrocarbon is converted into acetic acid (ethanoic acid) and acetic acid hydrogenation is obtained to alcohol.Material stream from hydrogenator is separated to obtain ethanol product and acetic acid and ethyl acetate material stream, described acetic acid and ethyl acetate material stream are recycled to hydrogenator.
U.S. Patent No. 3,102,150 disclose the formation that makes spent hydroprocessing catalyst and Zeo-karb aldehyde is hydrogenated into alcohol and reduce acetal.
Still need to improve the method that reclaims ethanol for the crude product from being obtained by the reduction of for example acetic acid of paraffinic acid and/or other carbonyl containing compound.
Summary of the invention
In the first embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form the coarse ethanol mixture that comprises acetaldehyde, ethanol, water and acetal; Comprise with described coarse ethanol mixture being separated to reclaim in one or more towers the ethanol product that is less than 1wt.% acetal, wherein at least one tower operates more than normal atmosphere.In one embodiment, ethanol product can comprise 0.0001-0.01wt.% acetal.
In the second embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture, and described part coarse ethanol mixture is separated to produce the first resistates that comprises paraffinic acid and the first overhead product that comprises ethanol and acetaldehyde in the first distillation tower.In the second column operating, part the first overhead product is further separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde more than normal atmosphere.The second resistates comprises and is less than 1wt.% acetal.
In the 3rd embodiment, the present invention relates to the method for the production of ethanol, the method comprises: the coarse ethanol that comprises acetic acid, acetaldehyde, ethanol, water and acetal mixture is provided; Described part coarse ethanol mixture is separated to produce the first resistates that comprises acetic acid and the first overhead product that comprises ethanol and acetaldehyde in the first distillation tower; With in the second column operating, part the first overhead product is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde more than normal atmosphere, wherein the second resistates comprises and is less than 1wt.% acetal.
In the 4th embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Described part coarse ethanol mixture is separated to produce the first resistates that comprises paraffinic acid and the first overhead product that comprises ethanol, water, ethyl acetate and acetaldehyde in the first distillation tower; In the second column operating, part the first overhead product is separated to produce the second resistates that comprises second alcohol and water and the second overhead product that comprises ethyl acetate and acetaldehyde more than normal atmosphere; With in the 3rd distillation tower of operation, part the second resistates is separated to produce the 3rd resistates that comprises water and the 3rd overhead product that comprises ethanol, wherein the 3rd overhead product comprises and is less than 1wt.% acetal.
In the 5th embodiment, the present invention relates to the method for the production of ethanol, the method comprises: the coarse ethanol that comprises acetic acid, acetaldehyde, ethanol, water and acetal mixture is provided; Described part coarse ethanol mixture is separated to produce the first resistates that comprises acetic acid and the first overhead product that comprises ethanol, water, ethyl acetate and acetaldehyde in the first distillation tower; In the second column operating, part the first overhead product is separated to produce the second resistates that comprises second alcohol and water and the second overhead product that comprises ethyl acetate and acetaldehyde more than normal atmosphere; With in the 3rd distillation tower of operation, part the second resistates is separated to produce the 3rd resistates that comprises water and the 3rd overhead product that comprises ethanol, wherein the 3rd overhead product comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Described part coarse ethanol mixture is separated to produce first resistates and the first overhead product of comprising ethanol, acetaldehyde and water of most of water comprising to entering distillation tower in the first distillation tower; Shift out water to produce alcohol mixture material stream from the first overhead product; And in the second column operating more than normal atmosphere, part alcohol mixture material stream is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde, wherein the second resistates comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Described part coarse ethanol mixture is separated to produce first resistates and the first overhead product of comprising ethanol, ethyl acetate, acetaldehyde and water of most of water comprising to entering distillation tower in the first distillation tower; Shift out water to produce alcohol mixture material stream from the first overhead product; In the second column operating more than normal atmosphere, the alcohol mixture material stream of first part is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises ethyl acetate and acetaldehyde, wherein the second resistates comprises and is less than 1wt.% acetal; In the 3rd distillation tower operating under 0.1-100kPa pressure, the alcohol mixture material stream of second section is separated to produce the 3rd resistates that comprises ethanol and the 3rd overhead product that comprises ethyl acetate and acetaldehyde, wherein the 3rd resistates comprises and is less than 1wt.% ethyl acetate; With reclaim ethanol from the second resistates and/or the 3rd resistates.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form the coarse ethanol mixture that comprises ethanol, water, ethyl acetate, acetaldehyde and acetal; Described part coarse ethanol mixture is separated to produce first resistates and the first overhead product of comprising ethanol, ethyl acetate, acetaldehyde and water of most of water comprising to entering distillation tower in the first distillation tower; Shift out water to produce alcohol mixture material stream from the first overhead product; In the second column operating more than normal atmosphere, the alcohol mixture material stream of part is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises ethanol, ethyl acetate and acetaldehyde, wherein the second resistates comprises and is less than 1wt.% acetal; In the 3rd distillation tower operating under 0.1-100kPa pressure, part the second overhead product is separated to produce the 3rd resistates that comprises ethanol and the 3rd overhead product that comprises ethyl acetate and acetaldehyde, wherein the 3rd resistates comprises and is less than 1wt.% ethyl acetate; With reclaim ethanol from the second resistates and/or the 3rd resistates.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form the coarse ethanol mixture that comprises ethanol, water, ethyl acetate, acetaldehyde and acetal; Described part coarse ethanol mixture is separated to produce first resistates and the first overhead product of comprising ethanol, ethyl acetate, acetaldehyde and water of most of water comprising to entering the first distillation tower in the first distillation tower; Shift out water to produce alcohol mixture material stream from the first overhead product; In the second column operating under 0.1-100kPa pressure, part alcohol mixture material stream is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises ethyl acetate and acetaldehyde, wherein the second resistates comprises and is less than 1wt.% ethyl acetate; In the 3rd distillation tower operating more than normal atmosphere, part the second overhead product is separated to produce the 3rd overhead product that comprises acetaldehyde and the 3rd resistates that comprises ethanol, wherein the 3rd resistates comprises and is less than 1wt.% acetal; With reclaim ethanol from the second resistates and/or the 3rd resistates.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: the coarse ethanol that comprises acetic acid, water, acetaldehyde, ethanol and acetal mixture is provided; Described part coarse ethanol mixture is separated to produce first resistates and the first overhead product of comprising ethanol, acetaldehyde and water of most of water comprising to entering distillation tower in the first distillation tower; Shift out water to produce alcohol mixture material stream from the first overhead product; And in the second column operating more than normal atmosphere, part alcohol mixture material stream is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde, wherein the second resistates comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; In the first distillation tower operating, described part coarse ethanol mixture is separated to produce the first resistates that comprises paraffinic acid and the first overhead product that comprises ethanol and acetaldehyde more than normal atmosphere; With part the first overhead product is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde in second column, wherein the second resistates comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: the coarse ethanol that comprises acetic acid, acetaldehyde, ethanol and acetal mixture is provided; In the first distillation tower operating, described part coarse ethanol mixture is separated to produce the first resistates that comprises acetic acid and the first overhead product that comprises ethanol and acetaldehyde more than normal atmosphere; With part the first overhead product is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde in second column, wherein the second resistates comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; In the first distillation tower operating, described part coarse ethanol mixture is separated to produce the first resistates that comprises second alcohol and water and the first overhead product that comprises ethyl acetate and acetaldehyde more than normal atmosphere; With part the first resistates is separated to produce the second resistates that comprises water and the second overhead product that comprises ethanol in second column, wherein the second overhead product comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: the coarse ethanol that comprises acetic acid, acetaldehyde, ethyl acetate, ethanol and acetal mixture is provided; In the first distillation tower operating, described part coarse ethanol mixture is separated to produce the first resistates that comprises acetic acid, second alcohol and water and the first overhead product that comprises ethyl acetate and acetaldehyde more than normal atmosphere; With part the first resistates is separated to produce the second resistates that comprises water and acetic acid and the second overhead product that comprises ethanol in second column, wherein the second overhead product comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form the coarse ethanol mixture that comprises paraffinic acid, water, acetaldehyde, ethanol and acetal; Comprise with described coarse ethanol mixture being separated to reclaim in one or more towers the ethanol product that is less than 1wt.% acetal, wherein at least one tower has the stripping stage that comprises at least 40 levels (stage).
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Described part coarse ethanol mixture is separated to produce the first resistates that comprises paraffinic acid and the first overhead product that comprises ethanol and acetaldehyde in the first distillation tower; With part the first overhead product is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde in the second column with the stripping stage that comprises at least 40 levels, wherein the second resistates comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Described part coarse ethanol mixture is separated to produce the first resistates that comprises paraffinic acid and the first overhead product that comprises ethanol, water, ethyl acetate and acetaldehyde in the first distillation tower; Part the first overhead product is separated to produce the second resistates that comprises second alcohol and water and the second overhead product that comprises ethyl acetate and acetaldehyde in the second column with the stripping stage that comprises at least 40 grades; With in the 3rd distillation tower of operation, part the second resistates is separated to produce the 3rd resistates that comprises water and the 3rd overhead product that comprises ethanol, wherein the 3rd overhead product comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Described part coarse ethanol mixture is separated to produce first resistates and the first overhead product of comprising ethanol, acetaldehyde and water of most of water comprising to entering distillation tower in the first distillation tower; Shift out water to produce alcohol mixture material stream from the first overhead product; And part alcohol mixture material stream is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde in the second column with the stripping stage that comprises at least 40 grades, wherein the second resistates comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Part coarse ethanol mixture is separated to produce the first resistates that comprises second alcohol and water and the first overhead product that comprises ethyl acetate and acetaldehyde in first distillation tower with the stripping stage that comprises at least 40 grades; With part the first resistates is separated to produce the second resistates that comprises water and the second overhead product that comprises ethanol in second column, wherein the second overhead product comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Described part coarse ethanol mixture is separated to produce the first resistates that comprises paraffinic acid and the first overhead product that comprises ethanol, water, ethyl acetate and acetaldehyde in the first distillation tower; Part the first overhead product is separated to produce the second resistates that comprises second alcohol and water and the second overhead product that comprises ethyl acetate and acetaldehyde in the second column with the stripping stage that comprises at least 40 grades; With in the 3rd distillation tower of operation, part the second resistates is separated to produce the 3rd resistates that comprises water and the 3rd overhead product that comprises ethanol, wherein the 3rd overhead product comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Described part coarse ethanol mixture is separated to produce first resistates and the first overhead product of comprising ethanol, acetaldehyde and water of most of water comprising to entering distillation tower in the first distillation tower; Shift out water to produce alcohol mixture material stream from the first overhead product; And part alcohol mixture material stream is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde in the second column with the stripping stage that comprises at least 40 grades, wherein the second resistates comprises and is less than 1wt.% acetal.
In another embodiment, the present invention relates to the method for the production of ethanol, the method comprises: in reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture; Part coarse ethanol mixture is separated to produce the first resistates that comprises second alcohol and water and the first overhead product that comprises ethyl acetate and acetaldehyde in first distillation tower with the stripping stage that comprises at least 40 grades; With part the first resistates is separated to produce the second resistates that comprises water and the second overhead product that comprises ethanol in second column, wherein the second overhead product comprises and is less than 1wt.% acetal.
Accompanying drawing explanation
Describe the present invention in detail below with reference to accompanying drawing, wherein identical numeral is indicated similar part.
Fig. 1 is the schematic diagram of the hydrogenation technique with 4 towers according to an embodiment of the invention.
Fig. 2 is the schematic diagram of hydrogenation technique according to an embodiment of the invention, and this hydrogenation technique has two towers, and described two towers have the water of insertion and separate.
Fig. 3 is the schematic diagram that the insertion water with the Fig. 2 that uses high-pressure tower in parallel and lower pressure column according to an embodiment of the invention separates.
Figure 4 and 5 are schematic diagram that the insertion water of the high-pressure tower with the series connection of using according to an embodiment of the invention and Fig. 2 of lower pressure column separates.
Fig. 6 is the schematic diagram of another hydrogenation technique with two towers according to an embodiment of the invention.
Detailed Description Of The Invention
Foreword
The present invention relates to for from by making crude mixture that paraffinic acid and/or its ester through hydrogenation obtain reclaim the method for ethanol.During hydrogenation, in crude mixture, can form some other organism with ethanol.Described organism can also generate between ethanol payback period, and therefore further reduces ethanol yield.Especially, aldehyde may reside in crude mixture and the acetalation of aldehyde can produce acetal.In the time that acetic acid hydrogenation is ethanol, acetaldehyde can be used as intermediate and generates.Acetaldehyde (AcH) acetal turns to acetal (DEA) for balanced reaction as follows:
Figure BDA0000476917920000091
Owing to comparing relative large alcohol concn with acetaldehyde and/or acetal concentration in crude mixture, this balance can be conducive to acetalation.In addition, reaction mixture can contain acetic acid, and this acetalation can obtain further catalysis under mineral acid or carboxylic acid existence.Therefore, during reclaiming ethanol from crude mixture, acetal concentration can improve.May be difficult to shift out acetal from ethanol, this is because other organism that acetal forms during with respect to hydrogenation is high boiling point organic compound.Other application that ethanol just calls the turn as ethanol industry and fuel-grade ethanol may need the acetal concentration reducing, for example, be less than 1wt.% acetal, is less than 0.1wt.% acetal or is less than 0.01wt.% acetal.With regard to scope, acetal can be 0.0001-1wt.%, for example 0.0001-0.1wt.% or 0.0001-0.01wt.%.
The invention provides for the method reducing acetal concentration between ethanol payback period.Not bound by theory, the present invention can strengthen balance to promote acetal hydrolysis or to reduce the acetalation towards acetal formation direction.In one embodiment, can in the tower improving under pressure, make 10-75%, the acetal decomposition of for example 15-60% or more preferably 20-40%.
In one embodiment, can be by crude mixture or derivatives thereof material stream be separated to reduce acetal concentration in the distillation tower operating under raising pressure.From crude mixture separating alcohol, can have several distillation towers and acetal concentration can be by operating at least one in several distillation towers to be reduced under the pressure improving.The pressure improving in tower can reduce acetal concentration.Described pressure can depend on to enter the acetal in tower enriched material concentration and improve.In one embodiment, the pressure of raising is greater than normal atmosphere, for example, be 101kPa-5,000kPa, for example 120kPa-4,000kPa, or 150kPa-3,000kPa.
In some embodiments, in the tower in separation can operate further strengthen the acetal hydrolysis in this tower under pressure higher compared with other tower.
In the time reclaiming ethanol from crude mixture, can in any of described tower, form acetal, therefore the tower of most end in separating technology can be operated under the pressure improving.All the other towers can operate with further separating alcohol under pressure arbitrarily as required.For example, low pressure conditioned disjunction vacuum condition can strengthen separating of ethyl acetate and ethanol.
In another embodiment, at least 40 levels can be there are, for example, in the distillation tower of the stripping stage of at least 50 levels or at least 60 levels, by reducing acetal concentration from crude mixture or derivatives thereof material stream separating alcohol.Preferably, in the resistates of such tower, reclaim ethanol.The distillation tower with this stripping stage also can be at the pressure operation improving further to reduce acetal concentration.
Except acetal, embodiment of the present invention can also make other acetal, for example, be selected from those hydrolysis of ethyl propyl acetal, ethyl-butyl acetal, dimethylacetal, methylethyl acetal and hemiacetal and their mixture.
The inventive method can be used with together with any method of hydrotreating for the production of ethanol.Further describe material, catalyzer, reaction conditions and the separation method that can in acetic acid hydrogenation, use below.
Can, derived from any suitable source, comprise Sweet natural gas, oil, coal, biomass etc. to the raw material, acetic acid and the hydrogen that enter the reactor using about the inventive method.As an example, can produce acetic acid by carbonylation of methanol, oxidation of acetaldehyde, oxidation of ethylene, oxidative fermentation and anaerobically fermenting.The methanol carbonylation process that is suitable for acetic acid production is described in U.S. Patent No. 7,208, and 624,7,115,772,7,005,541,6,657,078,6,627,770,6,143,930,5,599,976,5,144,068,5,026,908,5,001, in 259 and 4,994,608, their whole disclosures are incorporated to herein by reference.Optionally, alcohol production and this methanol carbonylation process can be integrated.
Due to oil and natural gas price volalility, become more expensive or more cheap, for causing gradually concern by the method that substitutes carbon source and produce acetic acid and for example methyl alcohol of intermediate and carbon monoxide.Especially, in the time that oil is relatively costly, produces acetic acid by the synthesis gas (" synthetic gas ") of the carbon source derived from comparatively using and may become favourable.For example, U.S. Patent No. 6,232,352(is incorporated to its disclosure herein by reference) instruct transformation methanol device in order to manufacture the method for acetic acid.By transformation methanol device, for new acetic acid device, produce with CO that relevant substantial contribution expense is significantly reduced or eliminate to a great extent.Make all or part synthetic gas shunt and be supplied to separator unit to reclaim CO from the synthetic loop of methyl alcohol, then use it for production acetic acid.In a similar manner, can be supplied with by synthetic gas for the hydrogen of hydrogenation step.
In some embodiments, can be partly or entirely derived from synthetic gas for the some or all of raw materials of above-mentioned acetic acid hydrogenation method.For example, acetic acid can be formed by methyl alcohol and carbon monoxide, and methyl alcohol and carbon monoxide all can be derived from synthetic gas.Synthetic gas can be reformed or steam reformation formation by partial oxidation, and carbon monoxide can be isolated from synthetic gas.Similarly, can will isolate from synthetic gas with the hydrogen that forms coarse ethanol mixture step for acetic acid hydrogenation.And then synthetic gas can be derived from several kinds of carbon source.Carbon source for example can be selected from Sweet natural gas, oil, oil, coal, biomass and their combination.Synthetic gas or hydrogen can also derive from biologically-derived methane gas, the biologically-derived methane gas for example being produced by refuse landfill refuse (landfill waste) or agricultural waste.
In another embodiment, can be formed by biomass ferment for the acetic acid of hydrogenation step.Fermentation process preferably utilizes product acetic acid (acetogenic) method or homoacetogenesis microorganism also to produce little (if any) carbonic acid gas as by product so that carbohydrate fermentation obtains acetic acid.Compared with conventionally having the conventional yeast method of approximately 67% carbon efficiencies, the carbon efficiencies of described fermentation process is preferably greater than 70%, be greater than 80% or be greater than 90%.Optionally, the microorganism using in fermenting process is to be selected from following genus: fusobacterium (Clostridium), lactobacillus (Lactobacillus), Moore Bordetella (Moorella), hot anaerobic bacillus(cillus anaerobicus) belongs to (Thermoanaerobacter), propiono-bacterium (Propionibacterium), propionic acid spirillum (Propionispera), Anaerobiospirillum (Anaerobiospirillum) and Bacteroides (Bacteriodes), be particularly selected from following species: formic acid clostridium aceticum (Clostridium formicoaceticum), clostridium butylicum (Clostridium butyricum), hot vinegar Moore Salmonella (Moorella thermoacetica), Kai Wure anerobe (Thermoanaerobacter kivui), lactobacillus delbruckii (Lactobacillus delbrukii), produce propionibacterium acide-propionici (Propionibacterium acidipropionici), tree propionic acid spirillum (Propionispera arboris) dwells, Anaerobiospirillum succinoproducens (Anaerobiospirillum succinicproducens), bacteroides amylophilus (Bacteriodes amylophilus) and bacteroides ruminicola (Bacteriodes ruminicola).Optionally, in this process, all or part of for example lignan of resistates that do not ferment that carrys out authigenic material can be gasified to form the hydrogen that can be used for hydrogenation step of the present invention.The exemplary fermentation process that is used to form acetic acid is disclosed in U.S. Patent No. 6,509,180; 6,927,048; 7,074,603; 7,507,562; 7,351,559; 7,601,865; 7,682,812; With 7,888, in 082, by reference their are incorporated to herein in full.Also announce No.2008/0193989 and 2009/0281354 referring to the U.S., by reference they are incorporated to herein in full.
The example of biomass includes but not limited to agricultural wastes, forestry products, grass and other cellulose materials, harvesting of wood residuum, soft wood fragment, hardwood fragment, branch, tree root, leaf, bark, sawdust, defective paper pulp, corn (corn), maize straw, Wheat Straw, rice straw, bagasse, switch grass, Chinese silvergrass, animal excrement, municipal garbage, municipal sludge (municipal sewage), commercial waste, grape skin, almond shell, pecan shell, coconut husk, coffee grounds, grass grain, hay grain, wood substance grain, cardboard, paper, plastics and cloth.Referring to for example U.S. Patent No. 7,884,253, by reference it is incorporated to herein in full.Another kind of biomass sources is black liquor, i.e. thick dark-coloured liquid, its for for timber being transformed into paper pulp, then pulp dryer is manufactured to the by product of the Kraft method of paper.Black liquor is the aqueous solution of xylogen resistates, hemicellulose and Inorganic chemical substance.
U.S. Patent No. RE35,377(is also incorporated to herein by reference) provide a kind of due to by making for example method of oil, coal, Sweet natural gas and conversion of biomass material methanol of carbonaceous material.The method comprises makes solid and/or the hydrogasification of liquid carbon-containing material to obtain process gas, with other Sweet natural gas by this process gas steam pyrolysis with formation synthetic gas.This synthetic gas is converted into the methyl alcohol that can carbonyl turns to acetic acid.The method is same to be produced as the above-mentioned relevant spendable hydrogen of the present invention.U.S. Patent No. 5,821,111 disclose a kind of for useless biomass are converted into the method for synthesis gas by gasification, and U.S. Patent No. 6,685,754 disclose the method that for example comprises the synthesis gas of hydrogen and carbon monoxide for the production of hydrogen-containing gas composition, by reference they are incorporated to herein in full.
Can also comprise other carboxylic acid and acid anhydrides to the acetic acid that enters hydrogenator, and aldehyde and/or ketone, for example acetaldehyde and acetone.Preferably, suitable acetic acid feed stream comprises one or more and is selected from the compound of acetic acid, diacetyl oxide, acetaldehyde, ethyl acetate and their mixture.In the method for the invention can also be by these other compound hydrogenation.In some embodiments, in propyl alcohol is produced, the existence of for example propionic acid of carboxylic acid or its acid anhydrides can be useful.In acetic acid feed, can also there is water.
Alternatively, can be directly from U.S. Patent No. 6,657,078(be in full incorporated to it herein by reference) described in the flasher of a class carbonylation of methanol unit take out steam form acetic acid as crude product.For example, thick vapor product directly can not needed to condensation acetic acid and lighting end to entering hydrogenator or except anhydrating, saved overall craft expense.
Can make acetic acid gasify under temperature of reaction, then the acetic acid of gasification can be fed together in company with undiluted state or with the hydrogen of the dilutions such as carrier gas such as nitrogen, argon gas, helium, the carbonic acid gas of relative inertness.For reaction is moved in gas phase, answer the temperature in Controlling System to make it below dew point that does not drop to acetic acid.In one embodiment, can under specified pressure, make acetic acid gasify under acetic acid boiling point, then the acetic acid of gasification further can be heated to reactor inlet temperature.In another embodiment, acetic acid is mixed with other gas before gasification, then mixed vapour is heated to reactor inlet temperature always.Preferably, by making hydrogen and/or circulation gas make acetic acid change vapor state into through the acetic acid at the temperature below 125 ℃ or 125 ℃, then the gaseous stream of combination is heated to reactor inlet temperature.
Reactor can comprise the various structures that use fixed-bed reactor or fluidized-bed reactor in some embodiments.In many embodiments of the present invention, can use " thermal insulation " reactor; , seldom or not need internal pipe arrangements (plumbing) through reaction zone to add or remove heat.In other embodiments, can use a reactor of radial flow or multiple reactor as reactor, or can use the serial reaction device that there is or do not have heat exchange, chilling or introduce other feed material.Alternatively, can use the shell-tube type reactor that is equipped with heat transmission medium.In many situations, reaction zone can be contained in single container or between have in the series containers of interchanger.
In preferred embodiments, catalyzer uses in the fixed-bed reactor of for example pipeline or catheter shape, the reactant that typically wherein is steam form on described catalyzer by or through described catalyzer.Can use other reactor, for example fluidized-bed or ebullated bed reactor.In some cases, the pressure drop that hydrogenation catalyst can be combined with inert material to regulate educt flow to pass through catalyst bed and the duration of contact of reactant compound and granules of catalyst.
Hydrogenation in reactor can carry out in liquid phase or gas phase.Preferably, in gas phase, under following condition, carry out this reaction.Temperature of reaction can be 125 ℃-350 ℃, for example 200 ℃-325 ℃, 225 ℃-300 ℃ or 250 ℃-300 ℃.Pressure can be 10kPa-3000kPa, for example 50kPa-2300kPa or 100kPa-1500kPa.Can be by reactant to be greater than 500hr -1, for example, be greater than 1000hr -1, be greater than 2500hr -1or be even greater than 5000hr -1gas hourly space velocity (GHSV) entered reactor.With regard to scope, GHSV can be 50hr -1-50,000hr -1, for example 500hr -1-30,000hr -1, 1000hr -1-10,000hr -1or 1000hr -1-6500hr -1.
Optionally under the pressure that is just enough to overcome through the pressure drop of catalytic bed, carry out hydrogenation with selected GHSV, although do not limit the higher pressure of use, should be understood that at such as 5000hr of high air speed -1or 6,500hr -1the lower sizable pressure drop that may experience by reactor beds.
Thereby produce 1 mole of ethanol although the every mole of acetic acid of this reaction consumes 2 mol of hydrogen, in incoming flow, the actual mol ratio of hydrogen and acetic acid can be about 100:1-1:100, for example 50:1-1:50,20:1-1:2 or 12:1-1:1.Most preferably, the mol ratio of hydrogen and acetic acid is greater than 2:1, for example, be greater than 4:1 or be greater than 8:1.
Contact or the residence time also can vary widely, and these depend on as the variable of the amount of acetic acid, catalyzer, reactor, temperature and pressure.In the time using catalyst system except fixed bed, typical duration of contact, at least for gas-phase reaction, be preferably 0.1-100 second duration of contact for part is second to being greater than some hours, for example 0.3-80 second or 0.4-30 second.
Hydrogenation catalyst in reactor carries out acetic acid hydrogenation to form ethanol under existing.Suitable hydrogenation catalyst comprises the catalyzer that optionally comprises the first metal in support of the catalyst and optionally comprise the other metal of one or more second metals, the 3rd metal or arbitrary number.First with optional second and the 3rd metal can be selected from: IB, Π Β, IIIB, IVB, VB, VIB, VIIB, VIII group 4 transition metal, lanthanide series metal, actinide metals or be selected from IIIA, IVA, VA and VIA family the metal of family arbitrarily.Preferable alloy combination with regard to some exemplary catalyst compositions comprises platinum/tin, platinum/ruthenium, platinum/rhenium, palladium/ruthenium, palladium/rhenium, cobalt/palladium, cobalt/platinum, cobalt/chromium, cobalt/ruthenium, cobalt/tin, silver/palladium, copper/palladium, copper/zinc, nickel/palladium, gold/palladium, ruthenium/rhenium and ruthenium/iron.Exemplary catalyzer is also described in U.S. Patent No. 7,608,744 and the U.S. announce in No.2010/0029995, by reference their are incorporated to herein in full.In another embodiment, catalyzer comprises that the U.S. announces the Co/Mo/S catalyzer of type described in No.2009/0069609, by reference it is incorporated to herein in full.
In one embodiment, this catalyzer comprises the first metal that is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten.Preferably, the first metal is selected from platinum, palladium, cobalt, nickel and ruthenium.More preferably, the first metal is selected from platinum and palladium.In the embodiment of the present invention that comprises platinum at the first metal, due to the high business demand to platinum, catalyzer preferably comprises and is less than the platinum that 5wt.% is for example less than 3wt.% or is less than the amount of 1wt.%.
As implied above, in some embodiments, catalyzer also comprises the second metal, and this second metal typical ground can play promotor.If existed, the second metal is preferably selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel.More preferably, the second metal is selected from copper, tin, cobalt, rhenium and nickel.More preferably, the second metal is selected from tin and rhenium.
Comprise two or more metals at catalyzer, for example, in the first metal and bimetallic some embodiment, the first metal is with 0.1-10wt.%, and the amount of for example 0.1-5wt.% or 0.1-3wt.% is present in catalyzer.The second metal preferably exists with the amount of for example 0.1-10wt.% of 0.1-20wt.% or 0.1-5wt.%.For the catalyzer that comprises two or more metals, described two or more metals alloying or can comprise no-alloyed metal solid solution or mixture each other.
Preferred metal ratio can depend on metal used in catalyzer and change.In some exemplary, the first metal and bimetallic mol ratio are preferably 10:1-1:10, for example 4:1-1:4,2:1-1:2,1.5:1-1:1.5 or 1.1:1-1:1.1.
This catalyzer can also comprise the 3rd metal, and the 3rd metal is selected from above about the listed any metal of the first or second metal, as long as the 3rd metal is different from the first and second metals.Aspect preferred, the 3rd metal is selected from cobalt, palladium, ruthenium, copper, zinc, platinum, tin and rhenium.More preferably, the 3rd metal is selected from cobalt, palladium and ruthenium.In the time existing, the gross weight of the 3rd metal is preferably 0.05-4wt.%, for example 0.1-3wt.% or 0.1-2wt.%.
In some embodiments of the present invention, except one or more metals, catalyzer also comprises carrier or modified support.As used herein, term " modified support " refers to the carrier that comprises solid support material and support modification agent, and described support modification agent regulates the acidity of solid support material.
The gross weight of carrier or modified support is preferably 75-99.9wt.% based on this total catalyst weight meter, for example 78-97wt.% or 80-95wt.%.In the preferred embodiment of utilizing modified support, support modification agent is in based on total catalyst weight 0.1-50wt.%, and for example the amount of 0.2-25wt.%, 0.5-15wt.% or 1-8wt.% exists.The metal of catalyzer can disperse to spread all over whole carrier, and layering in whole carrier is coated on the outside surface of carrier (being eggshell) or modifies (decorate) on carrier surface.
One of skill in the art will appreciate that selecting to make catalyst body to tie up to solid support material has suitable activity, selectivity and robustness (robust) under the processing condition for generating ethanol.
Suitable solid support material for example can comprise stable metal oxide base carrier or ceramic base carrier.Preferred carrier comprises that for example silicon-dioxide, silica/alumina, IIA family silicate are as calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture containing silicon carrier.Other carrier can include but not limited to ferriferous oxide (iron oxide), aluminum oxide, titanium dioxide, zirconium white, magnesium oxide, carbon, graphite, high surface area graphitized carbon, gac and their mixture.
As shown, support of the catalyst can be carried out modification with support modification agent.In some embodiments, support modification agent can be the acid modification agent that improves catalyst acidity.Suitable acid modification agent can be selected from the oxide compound of IVB family metal, the oxide compound of VB family metal, the oxide compound of group vib metal, the oxide compound of VIIB family metal, oxide compound, aluminum oxide and their mixture of VIIIB family metal.Acid carrier properties-correcting agent comprises and is selected from TiO 2, ZrO 2, Nb 2o 5, Ta 2o 5, Al 2o 3, B 2o 3, P 2o 5and Sb 2o 3those.Preferred acid carrier properties-correcting agent comprises and is selected from TiO 2, ZrO 2, Nb 2o 5, Ta 2o 5and Al 2o 3those.Acid modification agent can also comprise WO 3, MoO 3, Fe 2o 3, Cr 2o 3, V 2o 5, MnO 2, CuO, Co 2o 3and Bi 2o 3those.
In another embodiment, support modification agent can be the alkaline properties-correcting agent with low volatility or non-volatility.This class alkalescence properties-correcting agent for example can be selected from: (i) alkaline earth metal oxide, (ii) alkalimetal oxide, (iii) alkali earth metasilicate, (iv) alkali metal silicate, (v) IIB family metal oxide, (vi) IIB family metal metaphosphate silicate, (vii) IIIB family metal oxide, (viii) IIIB family metal metaphosphate silicate and their mixture.Except oxide compound and metasilicate, can use the properties-correcting agent of other type including nitrate, nitrite, acetate and lactic acid salt.Preferably, support modification agent is selected from oxide compound and the metasilicate of arbitrary element in sodium, potassium, magnesium, calcium, scandium, yttrium and zinc, and aforesaid any mixture.More preferably, basic supports properties-correcting agent is the silicate of calcium, more preferably calcium metasilicate (CaSiO 3).If basic supports properties-correcting agent comprises calcium metasilicate, at least a portion of calcium metasilicate is preferably crystallized form.
Preferred silica support materials is SS61138 high surface area (HSA) the SiO 2 catalyst carrier from Saint-Gobain NorPro.Saint-Gobain NorPro SS61138 silicon-dioxide shows following character: containing the high surface area silica of the 95wt.% that has an appointment; About 250m 2the surface-area of/g; The mean pore sizes of about 12nm; By the approximately 1.0cm that presses mercury hole method of masurement to measure 3the average pore volume of/g and about 0.352g/cm 3(22lb/ft 3) tap density.
Preferred silica/alumina solid support material is the KA-160 silica spheres from Sud Chemie, and it has the specific diameter of about 5mm, the density of about 0.562g/ml, about 0.583g H 2the specific absorption of O/g carrier, about 160-175m 2the surface-area of/g and the pore volume of about 0.68ml/g.
Be applicable to catalyst composition of the present invention and preferably form by the metal impregnation of modified support, although can also use the such as chemical vapour deposition of other method.Such dipping technique is described in U.S. Patent No. 7,608,744 and 7,863,489 mentioned above and the U.S. announces in No.2010/0197485, by reference they is incorporated to herein in full.
Especially, the hydrogenation of acetic acid can produce the favourable transformation efficiency of acetic acid and favourable selectivity and productive rate to ethanol in reactor.For the present invention, term " transformation efficiency " refers to the amount that is converted into the acetic acid of the compound except acetic acid in charging.Transformation efficiency represents by the molecular fraction based on acetic acid in charging.As indicated above, the transformation efficiency with regard to the first embodiment is 40%-70%, and the transformation efficiency with regard to the second embodiment is greater than 85%.
Selectivity represents by the molecular fraction of the acetic acid based on transforming.Should understand that the every kind of compound being transformed by acetic acid has independently selectivity and this selectivity does not rely on transformation efficiency.For example, if 60 % by mole of the acetic acid transforming are converted into ethanol, ethanol selectivity is 60%.Preferably, catalyzer is at least 60% to the selectivity of ethoxylate, for example at least 70% or at least 80%.As used herein, term " ethoxylate " specifically refers to compound ethanol, acetaldehyde and ethyl acetate.Preferably, in reactor, be at least 80% to the selectivity of ethanol, for example at least 85% or at least 88%.The preferred embodiment of this hydrogenation process also has the low selectivity to for example methane, ethane and carbonic acid gas of less desirable product.The selectivity of these less desirable products is preferably less than to 4%, for example, is less than 2% or be less than 1%.More preferably, these less desirable products exist with the amount can't detect.The formation of alkane can be low, and ideally, the acetic acid passing through on catalyzer is less than 2%, be less than 1% or be less than 0.5% and be converted into alkane, and this alkane is except as having very little value fuel.
Term " productive rate " refers to the grams of kilogram for example ethanol of regulation product that meter is per hour formed based on used catalyst during hydrogenation as used herein.Preferred productive rate is every kg catalyst at least 100 grams of ethanol per hour, for example every kg catalyst at least 400 grams of ethanol per hour or every kg catalyst at least 600 grams of ethanol per hour.With regard to scope, described productive rate is preferably every kg catalyst 100-3 per hour, 000 gram of ethanol, and for example 400-2, the per hour or 600-2 of 500 grams of every kg catalyst of ethanol, 000 gram of every kg catalyst of ethanol is per hour.
Under condition of the present invention operation can approximately produce at least 0.1 ton of ethanol/hour, for example at least 1 ton of ethanol/hour, at least 5 tons of ethanol/hour or at least 10 tons of ethanol/hour alcohol yied.Fairly large ethanol industry produce (depending on scale) conventionally should be at least 1 ton of ethanol/hour, for example at least 15 tons of ethanol/hour or at least 30 tons of ethanol/hour.With regard to scope, produce for large-scale ethanol industry, method of the present invention can produce 0.1-160 ton ethanol/hour, for example 15-160 ton ethanol/hour or 30-80 ton ethanol/hour.By fermentative production of ethanol, due to scale economics, conventionally do not allow the single equipment alcohol production can the application of the invention embodiment realizing.
In various embodiments of the present invention, the crude ethanol product being produced by reactor, before any processing example is subsequently as purification and separation, will typically comprise unreacted acetic acid, second alcohol and water.As used herein, term " crude ethanol product " refers to any composition that comprises 5-70wt.% ethanol and 5-40wt.% water.The exemplary composition scope of crude ethanol product is provided in table 1.In table 1, " other " of indication can comprise for example ester, ether, aldehyde, ketone, alkane and carbonic acid gas.
Figure BDA0000476917920000181
In one embodiment, coarse ethanol mixture can comprise and be less than 20wt.%, for example, be less than 15wt.%, be less than 10wt.% or be less than the acetic acid of the amount of 5wt.%.In having compared with the embodiment of low acetate amount, the transformation efficiency of acetic acid is preferably greater than 75%, for example, be greater than 85% or be greater than 90%.In addition, also preferably high to ethanol selectivity, and be greater than 75%, be for example greater than 85% or be greater than 90%.
Separation of ethanol
Can use some different technology to reclaim the ethanol of producing.In Fig. 1, the separation of coarse ethanol mixture is used 4 towers.In one embodiment, the first tower 120, the second tower 123 and/or the 3rd tower 128 can operate under the pressure improving.In one embodiment, the second tower 123 can have stripping stage, and this stripping stage comprises at least 40 levels, for example at least 50 levels or at least 60 levels.
In Fig. 2, in two towers with the separation of insertion water, coarse ethanol mixture is separated.Any tower in Fig. 2 can operate under the pressure improving.Fig. 3 separates with Fig. 2 is similar, and difference is to use the tower that operates under vacuum condition to separate the material stream containing ethanol with the tower operating under pressure improving with parallel way.Fig. 4 uses lower pressure column, is then that the tower operating under the pressure improving separates the material stream containing ethanol with series system.Fig. 5 uses the tower operating under the pressure improving, and is then in lower pressure column, to separate overhead product to separate the material stream containing ethanol with series system.In Figure 4 and 5, the resistates of the tower that can operate by the resistates of lower pressure column and under the pressure improving combines to form ethanol product.
In Fig. 6, the separation of coarse ethanol mixture is used two towers.In Fig. 6, any tower can operate under the pressure improving, but can preferably under higher pressure, operate the first tower 170.
Can also use other separation system for embodiment of the present invention.For convenience, the tower in each exemplary separation method can be called to the first tower, the second tower, the 3rd tower etc.
In each figure, hydrogenation system 100 comprises reaction zone 101 and disengaging zone 102.By pipeline 104 and 105, hydrogen and acetic acid are flowed to produce vapor feed in the pipeline 107 that is directed to reactor 103 to entering gasifier 106 respectively.In one embodiment, pipeline 104 and 105 can combine and jointly to entering gasifier 106.In pipeline 107, the temperature of vapor feed stream is preferably 100 ℃-350 ℃, for example 120 ℃-310 ℃ or 150 ℃-300 ℃.Any charging of not gasification is shifted out and can is recycled to or abandon to this gasifier from gasifier 106.In addition, although shown the top of pipeline 107 directed response devices 103, sidepiece, top or bottom that pipeline 107 can directed response device 103.
Reactor 103 makes carboxylic acid containing being useful on, preferably the catalyzer of acetic acid hydrogenation.In one embodiment; can be in the upstream of reactor, optionally use one or more protections (not shown) in the upstream of gasifier 106, with guard catalyst avoid suffering charging or return/recycle stream in contained toxic substance or less desirable impurity.This class protection bed can use in vapor stream or liquid stream.Suitable protection bed material can comprise for example carbon, silicon-dioxide, aluminum oxide, pottery or resin.On the one hand, protection bed medium is functionalization, and for example silver-colored functionalization, to trap for example sulphur of predetermined substance or halogen.During hydrogenation process, by pipeline 109, coarse ethanol mixture stream is preferably taken out from reactor 103 continuously.
Can and be entered separator 110 by the coarse ethanol mixture stream condensation in pipeline 109, this so that provide vapor stream 111 and liquid stream 112.In some embodiments, separator 110 can comprise flasher or knockout drum.Separator 110 can at 20 ℃-250 ℃, for example, operate at the temperature of 30 ℃-225 ℃ or 60 ℃-200 ℃.The pressure of separator 110 can be 50kPa-2000kPa, for example 75kPa-1500kPa or 100kPa-1000kPa.Optionally, can make the coarse ethanol mixture in pipeline 109 pass one or more films with separating hydrogen gas and/or other non-condensable gases.
The vapor stream 111 of leaving separator 110 can comprise hydrogen and hydrocarbon, and can clean and/or turn back to reaction zone 101.By vapor stream 110 in the time turning back to reaction zone 101 and hydrogen feed 104 combines and jointly entered gasifier 106.In some embodiments, the vapor stream 111 of returning can be compressed before combining with hydrogen feed 104.
In Fig. 1, in the future the liquid stream 112 of self-separation device 110 takes out and is pumped into the first tower 120(also referred to as acid " knockout tower ") sidepiece.In one embodiment, the content of liquid stream 112 is substantially similar to the coarse ethanol mixture obtaining from reactor, and difference is the poor hydrogen of said composition, carbonic acid gas, methane and/or ethane, and they are removed by separator 110.Therefore, liquid stream 112 can also be called coarse ethanol mixture.The exemplary compositions of liquid stream 112 is provided in table 2.It should be understood that liquid stream 112 can contain other component unlisted in table 2.
Figure BDA0000476917920000211
In the table of whole specification sheets, be less than (<) and if shown in amount preferably not exist can exist by trace or with the amount that is greater than 0.0001wt.%.
" other ester " in table 2 can include but not limited to ethyl propionate, methyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate or their mixture." other ether " in table 2 can include but not limited to diethyl ether, methyl ethyl ether, isobutyl-ethyl ether or their mixture." other alcohol " in table 2 can include but not limited to methyl alcohol, Virahol, n-propyl alcohol, propyl carbinol or their mixture.In one embodiment, the propyl alcohol of amount that liquid stream 112 can comprise 0.001-0.1wt.%, 0.001-0.05wt.% or 0.001-0.03wt.% is as Virahol and/or n-propyl alcohol.Should be understood that these other components can carrier band in any distillate flow described herein or residual stream, and unless otherwise indicated, will not be further described herein.
Optionally, the coarse ethanol mixture in pipeline 109 or in liquid stream 112 can also be given and entered esterifier, hydrogenolysis device or their combination.Esterifier can be for consuming residual acetic acid in the coarse ethanol mixture amount with the acetic acid that further reduces original needs and remove that is present in.Hydrogenolysis can be for being converted into ethanol by the ethyl acetate in coarse ethanol mixture.
In the embodiment shown in Fig. 1, pipeline 112 is introduced in the bottom of the first tower 120 to for example Lower Half or lower 1/3rd.In the first tower 120, acetic acid, part water and other heavy component (if existence) composition from pipeline 121 is shifted out and preferably taken out as resistates continuously.Can make some or all resistatess return by pipeline 121 and/or reaction zone 101 is got back in recirculation.Acetic acid in pipeline 121 is recycled to gasifier 106 and can reduces the amount that need to clean the heavy substance (heavies) that removes (purge) from gasifier 106.The amount that reduces heavy substance to be cleaned can improve the efficiency of described method and reduce byproduct simultaneously.
The first tower 120 has also formed overhead product, it taken out in pipeline 122, and can be by it for example with 10:1-1:10, as ratio condensation and the backflow of 3:1-1:3 or 1:2-2:1.Overhead product in pipeline 122 mainly comprises ethanol, and water, ethyl acetate, acetaldehyde and/or acetal.For example, overhead product can comprise 20-75wt.% ethanol and 10-40wt.% ethanol.Preferably, in overhead product, the concentration of acetic acid is less than 2wt.%, for example, be less than 1wt.% or be less than 0.5wt.%.
Under the pressure of the raising that in one embodiment, tower 120 can be more than normal atmosphere, operation is to strengthen to the hydrolysis of acetal that enters tower 120.In the time of operational tower 120 under the pressure of raising, in pipeline 121, in the first overhead product, the concentration of acetal can be less than 1wt.%, for example, be less than 0.1wt.% or be less than 0.01wt.%.
In the time operating under the pressure that another tower of the purification section 102 of Fig. 1 is improving, the first tower 120 can operate under environmental stress.In other embodiments, the pressure of the first tower 120 can be 0.1kPa-510kPa, for example 1kPa-475kPa or 1kPa-375kPa.In the time that the first tower 120 operates under standard atmospheric pressure, the temperature of the resistates leaving in pipeline 121 is preferably 95 ℃-120 ℃, for example 110 ℃-117 ℃ or 111 ℃-115 ℃.The temperature of the overhead product leaving in pipeline 122 is preferably 70 ℃-110 ℃, for example 75 ℃-95 ℃ or 80 ℃-90 ℃.
In one embodiment, even under the pressure improving, do not operating under the situation of the first tower 120, not bound by theory, unexpected and unexpectedly find, when detect the acetal of any amount in charging time, acetal seems in this tower to decompose and makes to exist in overhead product and/or resistates less or even there is no a detectable amount.The pressure that improves the first tower 120 can further reduce the concentration of acetal.In one embodiment, in the first tower 120, can make 10-75%, the acetal of for example 15-60% or more preferably 20-40% decomposes.
For further separating overhead product, pipeline 122 is incorporated into the second tower 123(also referred to as " light fraction tower "), preferably in the middle portion of tower 123, introduce.Preferably, the second tower 123 can be extractive distillation tower, and can extraction agent be joined wherein by pipeline 124 and/or 125.Extractive distillation is the method that separates for example azeotrope of the approaching component of boiling point by distilling charging under existing at extraction agent.Extraction agent preferably has higher boiling point than the component separating in charging.In preferred embodiments, extraction agent is mainly made up of water.As indicated above, comprise ethanol, water and ethyl acetate to the first overhead product in the pipeline 122 that enters the second tower 123.These compounds tend to form binary and ternary azeotrope, and this reduces separation efficiency.As shown, in one embodiment, extraction agent comprises the 3rd resistates in pipeline 124.Preferably, by the 3rd resistates of recirculation in pipeline 124 at the point that distillates object height than first in pipeline 122 to entering the second tower 123.In one embodiment, the 3rd resistates of recirculation in pipeline 124 is fed at the top that approaches the second tower 123, or for example in pipeline 122 charging above and from feeding below the reflux pipeline of condensation overhead materials.In column plate tower, the 3rd resistates in pipeline 124 is fed continuously at the top that approaches the second tower 123, make below there is obviously the 3rd resistates of amount in liquid phase on all column plates.In another embodiment, by pipeline 125, extraction agent is given and entered the second tower 123 by the source of technique 100 outsides.Preferably, this extraction agent comprises water.
Water in extraction agent is preferably at least 0.5:1, for example at least 1:1 or at least 3:1 with the mol ratio of going to ethanol in the charging of the second tower.With regard to scope, preferred mol ratio can be 0.5:1-8:1, for example 1:1-7:1 or 2:1-6.5:1.Can use higher mol ratio, but the alcohol concn in the second tower overhead product that returns and reduce of use minimizing with regard to ethyl acetate other in the second overhead product.
In one embodiment, for example following other extraction agent can be joined to the second tower 123: from water, methyl-sulphoxide, glycerine, Diethylene Glycol, 1-naphthols, Resorcinol, the N of external source, N'-dimethyl formamide, BDO; Ethylene glycol-1,5-PD; Propylene glycol-Tetraglycol 99-polyoxyethylene glycol; Glycerine-propylene glycol-Tetraglycol 99-1,4-butyleneglycol, ether, methyl-formiate, hexanaphthene, N, N'-dimethyl-1,3-propylene diamine, N, N'-dimethyl-ethylenediamine, diethylenetriamine, hexamethylene-diamine and 1,3-1,5-DAP, alkylating thiophene (thiopene), dodecane, tridecane, the tetradecane, chloroalkane hydrocarbon.Some suitable extraction agents comprise U.S. Patent No. 4,379,028,4,569,726,5,993,610 and 6,375, and those described in 807, are incorporated to their full content and disclosure herein by reference.Recirculation in other extraction agent and pipeline 124 the 3rd resistates combination and common giving can be entered to the second tower 123.Other extraction agent can also be joined separately to the second tower 123.On the one hand, extraction agent comprises the such as water of extraction agent that derives from external source by pipeline 125, and extraction agent does not all derive from the 3rd resistates.
The second tower 123 can be column plate tower or packing tower.In one embodiment, the second tower 123 is to have 5-120 column plate, for example column plate tower of 15-80 column plate or 20-70 column plate.In one embodiment, the stripping stage of the second tower 123 can have at least 40 levels, for example at least 50 levels or at least 60 levels.As indicated above, the stripping stage of the increase of the second tower 123 can strengthen the hydrolysis of acetal.
In Fig. 1, the second tower 123 can for example be greater than under normal atmosphere and operate at the pressure improving.In other embodiments, in the time operating under the pressure that the first tower 123 or the 3rd tower 128 are improving, the pressure of the second tower 123 can be 0.1kPa-510kPa, for example 1kPa-475kPa or 1kPa-375kPa.
Under atmospheric pressure the temperature of the second tower 123 can change.In one embodiment, the temperature of the second resistates leaving in pipeline 126 is preferably 60 ℃-90 ℃, for example 70 ℃-90 ℃ or 80 ℃-90 ℃.The temperature of the second overhead product leaving from the second tower 123 in pipeline 127 is preferably 50 ℃-90 ℃, for example 60 ℃-80 ℃ or 60 ℃-70 ℃.
The second resistates in pipeline 126 comprises second alcohol and water.The second resistates can comprise the ethyl acetate that is less than 3wt.%, for example, be less than the ethyl acetate of 1wt.% or be less than the ethyl acetate of 0.5wt.%.The second overhead product in pipeline 127 comprises ethyl acetate, acetaldehyde and/or acetal.In addition in the second overhead product, can comprise, the ethanol of small amount.In the second resistates with the second overhead product in the weight ratio of ethanol be preferably at least 3:1, for example at least 6:1, at least 8:1, at least 10:1 or 15:1 at least.
All or part of the 3rd resistates is recycled to the second tower.In one embodiment, all the 3rd resistatess can be carried out to recirculation until technique 100 reaches stable state, then by part the 3rd resistates recirculation, be accompanied by and the remainder cleaning out from system 100.The composition of the second resistates will tend to have the ethanol of lower amount compared with when not by the 3rd resistates recirculation.Because by the 3rd resistates recirculation, the composition of the second resistates comprises and is less than 30wt.%, for example, be less than the ethanol of 20wt.% or 15wt.%.The major portion of the second resistates preferably comprises water.Although have that effect, extractive distillation step also advantageously reduces the amount of the ethyl acetate that is sent to the 3rd tower, and this is highly useful in the high-purity ethanol product of final formation.
As shown, the second resistates from the second tower 123 (it comprises second alcohol and water) is entered to the 3rd tower 128(also referred to as " product tower " by pipeline 126).More preferably, the second resistates in pipeline 126 is introduced to the bottom of the 3rd tower 128, for example Lower Half or lower 1/3rd.The 3rd tower 128 reclaims the ethanol (being preferably pure substantially about organic impurity and except azeotropic water-content) as the overhead product in pipeline 129.The overhead product of the 3rd tower 128 is preferably pressed shown in Fig. 1, for example, reflux as the reflux ratio of 1:3-3:1 or 1:2-2:1 with 1:10-10:1.Preferably the 3rd resistates (it mainly comprises water) in pipeline 124 is turned back to the second tower 123 as said extracted agent.In one embodiment, the first part of the 3rd resistates in pipeline 124 is recycled to the second tower and second section is cleaned and shifted out from system by pipeline 130.In one embodiment, once this technique reaches stable state, second section water to be cleaned is similar to the amount of the water forming in acetic acid hydrogenation substantially.In one embodiment, can use part the 3rd resistates to make any other material stream, for example one or more material flowing water solutions that comprise ethyl acetate.In one embodiment, at the temperature of the service temperature higher than the second tower 123, the 3rd resistates in pipeline 124 is taken out from the 3rd tower 128.Preferably, the 3rd resistates in pipeline 124 integrated to heat one or more other material stream or boiled again before turning back to the second tower 123.
Although Fig. 1 shows, the 3rd resistates is directly recycled to the second tower 123, but the 3rd resistates can also be returned indirectly, for example, in tank (not shown) or in one or more other tower (not shown), the 3rd resistates be processed further to separate any less component for example aldehyde, higher molecular weight alcohols or ester by part or all of the 3rd resistates is stored in.
Preferably column plate tower of the 3rd tower 128.In one embodiment, the 3rd tower 128 can operate to reduce acetal concentration under the pressure improving.In the time operating under the pressure that the first tower 120 or the second tower 123 are improving, the 3rd tower can, at 0.1kPa-510kPa, for example, operate under the pressure of 1kPa-475kPa or 1kPa-375kPa.
Under atmospheric pressure, the temperature of the 3rd overhead product leaving in pipeline 129 is preferably 60 ℃-110 ℃, for example 70 ℃-100 ℃ or 75 ℃-95 ℃.The temperature of the 3rd resistates in pipeline 124 is preferably 70 ℃-115 ℃, for example 80 ℃-110 ℃ or 85 ℃-105 ℃.
In still-process, be conventionally less than 0.1wt.% in the gross weight based on the 3rd overhead product composition from any compound of charging or crude reaction product carrier band, the amount that is for example less than 0.05wt.% or is less than 0.02wt.% is retained in the 3rd overhead product.In one embodiment, one or more side line material stream can be removed impurity by any tower from system 100.Preferably use at least one side line material to flow to remove impurity from the 3rd tower 128.Impurity can be cleaned and/or is retained in system 100.In following table 3, show the ethanol product that derives from the 3rd overhead product in Fig. 1.Preferably, ethanol composition can comprise and be less than 1wt.%, for example, be less than 0.5wt.% or be less than 0.01wt.% acetal.
Can use one or more additional separation systems, for example distillation tower, absorbing unit, film or molecular sieve are further purified the 3rd overhead product in pipeline 129 to form dehydrated alcohol product flow, i.e. " finished product dehydrated alcohol ".Suitable absorbing unit comprises psa unit and Temp .-changing adsorption unit.
In Fig. 1, any in the first tower 120, the second tower 123 or the 3rd tower 128 can be at the pressure improving, for example 101kPa-5, and 000kPa, for example 120kPa-4,000kPa, or 150kPa-3, operate under 000kPa.Preferably, operation at least the second tower 123 under the pressure improving.In some embodiments, can under the pressure improving, operate two in described tower, for example the second tower 123 and the 3rd tower 128.
Turn back to the second tower 123, the second overhead products and preferably press shown in Fig. 1, with 1:10-10:1, as the reflux ratio of 1:5-5:1 or 1:3-3:1 refluxes.The second overhead product in pipeline 127 can be cleaned or reaction zone is got back in recirculation.Can in the 4th optional tower 131 also referred to as " acetaldehyde shifts out tower ", the second overhead product in pipeline 127 further be processed.In the 4th optional tower 131, the second overhead product is separated into and in pipeline 132, comprises the 4th overhead product of acetaldehyde and the four-infirm excess that comprises ethyl acetate in pipeline 133.The 4th overhead product is preferably with 1:20-20:1, and the reflux ratio of for example 1:15-15:1 or 1:10-10:1 refluxes, and part the 4th overhead product turns back to reaction zone 101.For example, the 4th overhead product and acetic acid feed can be combined, join in gasifier 106 or directly join in reactor 103.Preferably the acetic acid in the 4th overhead product and feeding line 105 is jointly given and entered gasifier 106.Not bound by theory, because can, by acetaldehyde hydrogenation to form ethanol, the material stream that contains acetaldehyde be recycled to reaction zone to improve the yield of ethanol and to reduce by product and the generation of refuse.In another embodiment, can in the situation that carrying out or be not further purified, acetaldehyde be collected and be used, to prepare the useful products that includes but not limited to propyl carbinol, 1,3 butylene glycol and/or crotonic aldehyde and derivative.
Can the four-infirm excess of the 4th optional tower 131 be cleaned by pipeline 133.Four-infirm excess mainly comprises ethyl acetate and ethanol, and they can be suitable as solvent mixture or be used in ester production.In a preferred embodiment, the second overhead product by acetaldehyde from the 4th tower 131 shifts out, make not exist in the resistates of tower 131 can detection limit acetaldehyde.
Optional the 4th tower 131 is preferably column plate tower as above and preferably more than normal atmosphere, operates.In one embodiment, pressure is 120kPa-5000kPa, for example 200kPa-4,500kPa or 400kPa-3000kPa.In preferred embodiments, the 4th tower 131 can operate under than the high pressure of the pressure of other tower.Although can strengthen acetal hydrolysis in the 4th optional tower 131 under the pressure improving, owing to not reclaiming ethanol from the 4th optional tower 131, the pressure of described raising can have very little impact to acetal concentration in ethanol product.
The temperature of the 4th overhead product leaving at pipeline 132 is preferably 60 ℃-110 ℃, for example 70 ℃-100 ℃ or 75 ℃-95 ℃.The temperature of the resistates in pipeline 133 is preferably 70 ℃-115 ℃, for example 80 ℃-110 ℃ or 85 ℃-110 ℃.
In one embodiment, the 3rd resistates of part in pipeline 124 is recycled to the second tower 123.In one embodiment, in the second overhead product that the 3rd resistates recirculation is further reduced to the aldehyde component in the second resistates and these aldehyde components is concentrated in pipeline 127, also deliver to thus the 4th tower 131, wherein said aldehyde can separate more easily.The 3rd overhead product in pipeline 129 is that intermediate stream can have lower aldehyde and ester concentration due to the recirculation of the 3rd resistates in pipeline 124.
Fig. 2 has described another exemplary separation system, and this system has with the similar reaction zone 101 of Fig. 1 and produces the liquid stream 112 separating for further, for example coarse ethanol mixture.In a preferred embodiment, the reaction zone 101 of Fig. 2 is with more than 70% acetic acid transformation efficiency, and for example transformation efficiency more than more than 85% transformation efficiency or 90% operates.Therefore, the acetic acid concentration in liquid stream 112 can be low.
Liquid stream 112 is entered to the first tower 134 to produce the first overhead product 135 and the first resistates 136.Liquid stream 112 can be introduced to the first tower 134(also referred to as acid-water tower) middle part or bottom in.In one embodiment, do not add entrainer to the first tower 134.By water and acetic acid, shift out and preferably take out continuously as the first resistates pipeline 136 from liquid stream 112 with any other heavy component (if existence).Preferably, in the first resistates, shift out to the most of water entering in the coarse ethanol mixture of the first tower 134, be for example moved to from coarse ethanol mixture how about 75%, or approximately 90% water at the most.In one embodiment, in resistates, remove the water of 30-90% in coarse ethanol mixture, the water of for example 40-88% or the water of 50-84%.
Can under the pressure improving, operate the first tower 134 separates to strengthen acetal.In the time that tower 134 operates under about 170kPa, the temperature of the resistates leaving in pipeline 136 is preferably 90 ℃-130 ℃, for example 95 ℃-120 ℃ or 100 ℃-115 ℃.The temperature of the overhead product leaving in pipeline 135 is preferably 60 ℃-90 ℃, for example 65 ℃-85 ℃ or 70 ℃-80 ℃.In some embodiments, the pressure of the first tower 134 can also be 0.1kPa-510kPa, for example 1kPa-475kPa or 1kPa-375kPa.
The first overhead product in pipeline 135 also comprises water except comprising ethanol and other organism.With regard to scope, the water concentration in pipeline 135 in the first overhead product is preferably 4wt.%-38wt.%, for example 7wt.%-32wt.% or 7-25wt.%.Can be by a part for the first overhead product in pipeline 137 for example with 10:1-1:10, as ratio condensation and the backflow of 3:1-1:3 or 1:2-2:1.Should be understood that reflux ratio can change along with progression, feed entrance point, column efficiency and/or feed composition.May be not too preferably to be greater than the reflux ratio operation of 3:1, this is because may need more multipotency to operate the first tower 134.The condensation portion of the first overhead product can also be given and entered the second tower 138.
The first overhead product of the remainder in pipeline 139 is given and entered water separation unit 140.Water separating unit 140 can be absorbing unit, film, molecular sieve, extraction column distillation or their combination.Can also use film or membrane array so that water is isolated from overhead product.Film or membrane array can be selected from can be from also comprising the material of ethanol and ethyl acetate drift any suitable film of infiltration current.
In preferred embodiments, water separator 140 is pressure-variable adsorption (PSA) unit.Optionally, at 30 ℃-160 ℃, for example temperature and the 0.01kPa-550kPa of 80 ℃-140 ℃, for example, operate PSA unit under the pressure of 1kPa-150kPa.PSA unit can comprise 2-5 bed.Water separator 140 can shift out at least 95% water by part the first overhead product from pipeline 139, and more preferably in water material stream 141, shifts out the water of 99%-99.99% from the first overhead product.Can in pipeline 142, all or part of current 141 be turned back to the first tower 134, wherein preferably in the first resistates in pipeline 136 from the final recycle-water of tower 134.Additionally or alternatively, can all or part of current 141 be cleaned by pipeline 143.The remainder of the first overhead product flows 144 leaving water separators 140 as alcohol mixture material.Alcohol mixture material stream 144 can have the 10wt.% of being less than, for example, be less than 6wt.% or be less than the low water concentration of 2wt.%.
Preferably, alcohol mixture material stream 144 is not returned to or is back to the first tower 135.The condensation portion of the first overhead product in pipeline 137 and alcohol mixture material stream 144 can be combined to control to the concentration of water that enters the second tower 138.For example, the first overhead product can be divided in some embodiments to aliquot (equal portions), and in other embodiments, can or all the first overhead products can be processed in water separating unit all the first distillate condensings.In Fig. 2, the condensation portion in pipeline 137 and common the giving of alcohol mixture material stream 144 are entered to the second tower 138.In other embodiments, the condensation portion in pipeline 137 and alcohol mixture material stream 144 can be given and entered the second tower 138 respectively.Overhead product and the alcohol mixture of combination have the 0.5wt.% of being greater than, for example, be greater than 2wt.% or be greater than total water concentration of 5wt.%.With regard to scope, the concentration of the overhead product of combination and total water of alcohol mixture can be 0.5-15wt.%, for example 2-12wt.% or 5-10wt.%.
The second tower 138(in Fig. 2 is also referred to as " light fraction tower ") the first overhead product from pipeline 137 and/or alcohol mixture material stream 144 shifts out ethyl acetate and acetaldehyde.Ethyl acetate and acetaldehyde are shifted out in pipeline 145 as the second overhead product and ethanol is shifted out in pipeline 146 as the second resistates.The ethyl acetate, acetaldehyde and/or the acetal that are for example less than 1wt.% or are more preferably less than 0.5wt.% with low amount reclaim ethanol.In following table 3, show the ethanol product that derives from the second resistates in Fig. 2.Preferably, ethanol composition comprises and is less than 1wt.%, for example, be less than 0.5wt.% or be less than 0.01wt.% acetal.
The second tower 138 can be column plate tower or packing tower.In one embodiment, the second tower 138 is to have 5-120 column plate, for example column plate tower of 15-100 column plate or 20-90 column plate.In one embodiment, in the stripping stage of the second tower 138, can there are at least 40 levels, for example at least 50 levels or at least 60 levels.In stripping stage, extra level can strengthen acetal hydrolysis.
In one embodiment, the second tower 138 can be at 101kPa-5,000kPa, and for example 120kPa-4,000kPa or 150kPa-3, operate under the pressure of the raising of 000kPa.The pressure improving in the second tower 138 can further strengthen the hydrolysis of acetal, particularly acetal in the second tower 138.In the time operating under the pressure that the first tower 134 is improving, the second tower 138 can, at 0.1kPa-510kPa, for example, operate under the pressure of 10kPa-450kPa or 50kPa-350kPa.Although the temperature of the second tower 138 can change, under about 20kPa-70kPa, the temperature of the second resistates leaving in pipeline 146 is preferably 30 ℃-75 ℃, for example 35 ℃-70 ℃ or 40 ℃-65 ℃.The temperature of the second overhead product leaving in pipeline 145 is preferably 20 ℃-55 ℃, for example 25 ℃-50 ℃ or 30 ℃-45 ℃.
As discussed above, be preferably less than 10wt.% to the total concn of the water that enters the second tower 138.When the first overhead product in pipeline 137 and/or alcohol mixture material stream 144 comprises small amount, for example, when being less than 1wt.% or being less than the water of 0.5wt.%, other water can be entered to the second tower 138 as extraction agent in the top of tower.Preferably add the water of q.s for example to make to the total concn of water that enters the second tower 138, based on counting 1-10wt.%, 2-6wt.% water to all components gross weight that enters the second tower 138 by extraction agent.If extraction agent comprises water, water can obtain or obtain from the return/recirculation line of inside from one or more other towers or water separator from external source.
Suitable extraction agent can also comprise for example methyl-sulphoxide, glycerine, Diethylene Glycol, 1-naphthols, Resorcinol, N, N'-dimethyl formamide, BDO; Ethylene glycol-1,5-PD; Propylene glycol-Tetraglycol 99-polyoxyethylene glycol; Glycerine-propylene glycol-Tetraglycol 99-1,4-butyleneglycol, ether, methyl-formiate, hexanaphthene, N, N'-dimethyl-1,3-propylene diamine, N, N'-dimethyl-ethylenediamine, diethylenetriamine, hexamethylene-diamine and 1,3-1,5-DAP, alkylating thiophene, dodecane, tridecane, the tetradecane, chloroalkane hydrocarbon or their combination.In the time using extraction agent, can use for example other distillation tower of suitable recovery system to make extraction agent recirculation.
The second overhead product in pipeline 145, it comprises ethyl acetate and/or acetaldehyde, preferably presses shown in Fig. 2, for example, with 1:30-30:1, as the reflux ratio of 1:10-10:1 or 1:3-3:1 refluxes.On the one hand, not shown, the second overhead product 145 or its part can be turned back to reactor 103.
In one embodiment, can be by the second overhead product in pipeline 145 and/or the second refining overhead product, or a part in these two kinds material streams one or both of further separates to produce containing the material stream of acetaldehyde with containing the material stream of ethyl acetate.For example, can separate the second overhead product in pipeline 145 with optional the 4th tower 131 of Fig. 1.The part that this material that can allow gained to contain acetaldehyde flows or flows containing the material of ethyl acetate is recycled to reactor 103 and cleans out other material stream simultaneously.Purge flow can have value as the source of ethyl acetate and/or acetaldehyde.
In one embodiment, can be preferably with the second tower 138 in subatmospheric pressure operation Fig. 2 to reduce separating ethyl acetate and the required energy of ethanol.But the pressure of reduction may not have advantages of the hydrolysis of the acetal of enhancing.Fig. 3 has shown the similar technique with Fig. 2, difference be by the first overhead product in pipeline 137 and/or alcohol mixture material stream 144 separately (split) and by first part by pipeline 147 to entering high pressure the second tower 148, second section is given and is entered low pressure the second tower 150 by pipeline 149.Can give the relative quantity that enters high pressure the second tower 148 and low pressure the second tower 150 based on the concentration control containing acetal in the resistates of ethanol and/or ethyl acetate.In the time that the acetal concentration containing in the resistates of ethanol improves, the major part of the first overhead product in pipeline 137 and/or alcohol mixture material stream 144 can be entered in pipeline 147.Equally, in the time that ethyl acetate concentration improves, can major part be entered in low pressure the second tower 150 by pipeline 149.Can use control valve to regulate the flow (flow) between the first and second parts.
In Fig. 3, under the raising pressure more than normal atmosphere, operate high pressure the second tower 148 is to be created in the overhead product that comprises ethyl acetate, acetaldehyde and acetal in pipeline 151 and the resistates that comprises ethanol in pipeline 152.In one embodiment, the resistates in pipeline 152 contains lower concentration, for example, be less than 1wt.%, or is less than the acetal of 0.5wt.%.High pressure the second tower 148 can also have at least 40 levels, for example stripping stage of the increase of at least 50 levels or at least 60 levels.
Low pressure the second tower 150 in a vacuum or be less than normal atmosphere, for example, is less than 70kPa or is less than under the pressure of 50kPa and operate.With regard to the second tower, low pressure the second tower 150 can be at 0.1-100kPa, for example 0.1-70kPa, or operate under 0.1-35kPa.The pressure reducing can also strengthen separating of ethyl acetate and ethanol.Low pressure the second tower 150 is also created in the overhead product that comprises ethyl acetate, acetaldehyde and acetal in pipeline 153 and the resistates that comprises ethanol in pipeline 154.In one embodiment, the resistates in pipeline 154 contains lower concentration, for example, be less than 1wt.%, or is less than the ethyl acetate of 0.5wt.%.
Can by with Fig. 2 above in the similar fashion discussed by the overhead product combination of each tower and turn back to reactor 103.In addition, the resistates of each tower in Fig. 3 can be combined to produce ethanol product.In some embodiments, each that may expect from Fig. 3 the second tower 148 and 150 produces independent ethanol product.
Fig. 3 has described high-pressure tower in parallel and lower pressure column.In some embodiments, may be necessary high-pressure tower and lower pressure column serial operation.Fig. 4 has described wherein by the first overhead product in pipeline 137 and/or the initial technique to entering in low pressure the second tower 150 of alcohol mixture material stream 144.As indicated above, the resistates in pipeline 154 can have the ethyl acetate of lower concentration, but can also have the acetal of higher concentration.Resistates in pipeline 154 is given and entered high pressure the second tower 148 to strengthen the hydrolysis of acetal.In high pressure the second tower 148, the overhead product that makes acetal be hydrolyzed to be created in to comprise acetaldehyde in pipeline 151 and the resistates that comprises ethanol at pipeline 152.Use high pressure the second tower 148, can make in the interior resistates of pipeline 154 at least 20%, for example at least 30% or at least 50% acetal hydrolysis.Therefore, the acetal concentration in pipeline 152 in resistates can be less than 1wt.%, for example, be less than 0.5wt.%.
Fig. 5 has put upside down from low pressure the second tower 150 of Fig. 4 and the order of high pressure the second tower 148.Fig. 5 has described wherein by the first overhead product in pipeline 137 and/or the initial technique to entering in high pressure the second tower 148 of alcohol mixture material stream 144.As indicated above, the resistates in pipeline 152 can have the acetal of lower concentration, but can also have the ethyl acetate of higher concentration.In high pressure the second tower 148, make acetal be hydrolyzed to be created in the overhead product and the resistates that comprises ethanol in pipeline 152 in pipeline 151.Overhead product in pipeline 151 is entered in low pressure the second tower 150.Overhead product in pipeline 151 can comprise ethyl acetate and ethanol and may need to reclaim ethanol rather than ethanol is recycled to reactor 103.Use low pressure the second tower 150, the resistates using any ethanol in interior pipeline 151 overhead product in pipeline 154 separates and the overhead product in pipeline 153 shifts out using ethyl acetate.Overhead product in pipeline 153 is recycled to reactor 103.Resistates in resistates in pipeline 154 and pipeline 152 can be combined to form ethanol product.In some embodiments, can use every kind of salvage stores stream as the ethanol product separating.
Turn back to Fig. 2, the pressure of the second tower 138 can change according to the concentration of acetal in the second resistates in pipeline 146.In the time the acetal concentration in the second resistates in above pipeline 146 being improved for example to 1wt.%, can also improve the pressure of the second tower 138.In addition,, in the time the ethyl acetate concentration in the second resistates in above pipeline 146 being improved for example to 1wt.%, can reduce the pressure of the second tower 138.This allows to regulate (if needs) second tower 138 and there is no the extra investment with regard to other distillation tower.
In another embodiment, can use the method shown in Fig. 6 that liquid stream 112 is isolated from reaction zone 103.In a preferred embodiment, the reaction zone 101 of Fig. 6 is with more than 80% acetic acid transformation efficiency, and for example transformation efficiency more than more than 90% transformation efficiency or 99% operates.Therefore, the acetic acid concentration in liquid stream 112 can be low.
In the exemplary shown in Fig. 6, liquid stream 112 is introduced in the top of the first tower 160 to for example first half or upper 1/3rd.In one embodiment, do not add entrainer to the first tower 160.In the first tower 160, the ethanol of most of weight, water, acetic acid and other heavy component (if existence) are shifted out and preferably taken out continuously pipeline 162 as resistates from liquid stream 112.The first tower 160 also forms overhead product, it taken out in pipeline 161, and can be by it for example with 30:1-1:30, as ratio condensation and the backflow of 10:1-1:10 or 1:5-5:1.The first overhead product in pipeline 161 preferably comprises the ethyl acetate from liquid line 112 of most of weight.In addition, the overhead product in pipeline 161 also can comprise acetaldehyde.
In one embodiment, can under the pressure improving, operate the first tower 160 to strengthen acetal hydrolysis.In addition, the first tower 160 can have stripping stage, and this stripping stage comprises at least 40 levels, for example at least 50 levels or at least 60 levels.
In the time that tower 160 operates under about 170kPa, the temperature of the resistates leaving in pipeline 162 is preferably 70 ℃-155 ℃, for example 90 ℃-130 ℃ or 100 ℃-110 ℃.The salvage stores stream that comprises ethanol, water and acetic acid by taking-up can make the substrate of tower 160 maintain at relative low temperature, thereby Energy Efficient sexual clorminance is provided.The temperature of the overhead product leaving in pipeline 161 under 170kPa is preferably 75 ℃-100 ℃, for example 75 ℃-83 ℃ or 81 ℃-84 ℃.
In some embodiments, in the time operating under the pressure that the second tower 163 of Fig. 6 is improving, the pressure of the first tower 170 can be 0.1kPa-510kPa, for example 1kPa-475kPa or 1kPa-375kPa.
In embodiments of the invention, due to the formation of binary and ternary azeotrope, the tower 160 of Fig. 6 can drift most water, ethanol and acetic acid go out and only a small amount of second alcohol and water is collected at the temperature distillating streams and be operated from salvage stores therein.The weight ratio of the water in the water in pipeline 162 in resistates and pipeline 161 in overhead product can be greater than 1:1, for example, be greater than 2:1.The weight ratio of the ethanol in ethanol and overhead product in resistates can be greater than 1:1, for example, be greater than 2:1.
In the first resistates, the amount of acetic acid can change, and this depends primarily on the transformation efficiency in reactor 103.In one embodiment, in the time that transformation efficiency is high, the amount that is for example greater than acetic acid in 90%, the first resistates can be less than 10wt.%, for example, be less than 5wt.% or be less than 2wt.%.In other embodiments, in the time that transformation efficiency is lower, the amount that is for example less than acetic acid in 90%, the first resistates can be greater than 10wt.%.
Described overhead product does not preferably basically contain acetic acid, for example, comprise and be less than 1000ppm, be less than 500ppm or be less than the acetic acid of 100ppm.Described overhead product can be cleaned out or by its all or part of reactor 103 that is recycled to from system.In some embodiments, can for example described overhead product be further separated into acetaldehyde material stream and ethyl acetate material stream in the 4th optional tower of Fig. 1.Any in these material stream can be turned back to reactor 103 or isolate from system 100 as independent product.
In order to reclaim ethanol, can in the second tower 163 also referred to as " acid separation column ", the resistates in pipeline 162 further be separated.In the time that the acetic acid concentration in the first resistates is greater than 1wt.% and is for example greater than 5wt.%, can use acid separation column.The first resistates in pipeline 162 is incorporated into the second tower 163, and preferably in the top of tower 163, introduce at for example top 1/2nd or top 1/3rd.The second tower 163 is created in the second resistates that comprises acetic acid and water in pipeline 165, with the second overhead product that comprises ethanol in pipeline 164.
The second tower 163 can be column plate tower or packing tower.In one embodiment, the second tower 163 is to have 5-150 column plate, for example column plate tower of 15-50 column plate or 20-45 column plate.Similar with the first tower 160, the second tower can have at least 40 levels, for example the stripping stage of at least 50 levels or at least 60 levels.
In one embodiment, can under the pressure improving, operate the second tower 163 to strengthen acetal hydrolysis.In Fig. 6, more preferably under the pressure improving, operate the first tower 160, this is because acetaldehyde and/or the acetal that the second tower 163 comprises low-down amount.Conventionally, the pressure of the second tower 163 can be 0.1kPa-510kPa, for example 1kPa-475kPa or 1kPa-375kPa.Under atmospheric pressure, the temperature of the second resistates leaving in pipeline 165 is preferably 95 ℃-130 ℃, for example 100 ℃-125 ℃ or 110 ℃-120 ℃.The temperature of the second overhead product leaving in pipeline 164 is preferably 60 ℃-105 ℃, for example 75 ℃-100 ℃ or 80 ℃-100 ℃.
The weight ratio of the ethanol in the ethanol in pipeline 164 in the second overhead product and pipeline 165 in the second resistates is preferably at least 35:1.In one embodiment, the weight ratio of the water in the water in the second resistates 165 and the second overhead product 164 is greater than 2:1, for example, be greater than 4:1 or be greater than 6:1.In addition, the weight ratio of the acetic acid in the acetic acid in the second resistates 165 and the second overhead product 164 is preferably greater than 10:1, for example, be greater than 15:1 or be greater than 20:1.Preferably, the second overhead product in pipeline 164 does not basically contain acetic acid and can contain (if any) only acetic acid of trace.Preferably, the second overhead product in pipeline 164 does not basically contain ethyl acetate.
Can be shifted out in other embodiments of the present invention the remaining water of the second overhead product in pipeline 164.Depend on the concentration of water, ethanol product can derive from the second overhead product in pipeline 164.Some application examples can be allowed water as industrial alcohol is applied in product, and other application examples can need dehydrated alcohol as fuel applications.In the overhead product of pipeline 164 amount of water can be close to the azeotropic amount of water, for example 4wt.% at least, is preferably less than 20wt.%, for example, be less than 12wt.% or be less than 7.5wt.%.Can use some different separation techniques as herein described that water is shifted out in the second overhead product from pipeline 164.Particularly preferred technology comprises use distillation tower, film, absorbing unit and their combination.
Some resistatess that take out from disengaging zone 102 comprise acetic acid and water.Depend on for example, in the resistates of the first tower (resistates 120 in Fig. 1) contained water and the amount of acetic acid, can in one or more following technique, described resistates be processed.That the illustrative processes with regard to further processing resistates and should understanding can be used with lower any one and irrelevant with acetic acid concentration below.When described resistates comprises most acetic acid, for example, while being greater than 70wt.%, can in the situation that water not being carried out to any separation, described resistates be recycled to reactor.In one embodiment, when described resistates comprises most acetic acid, for example, while being greater than 50wt.%, described resistates can be separated into acetic acid material stream and water material stream.Can also reclaim acetic acid from having compared with the resistates of low acetate concentration in some embodiments.Can described resistates be separated into acetic acid material stream and water material stream by distillation tower or one or more film.If use film or membrane array that acetic acid is separated with water, film or membrane array can be selected from any suitable acidproof film that can shift out infiltration water material stream.Optionally gained acetic acid material stream is turned back to reactor 103.Gained current can or make containing ester material flowing water solution as extraction agent in hydrolysis unit.
In other embodiments, for example, in the time that resistates comprises the acetic acid that is less than 50wt.%, possible selection comprises with lower one or more: (i) described part resistates is turned back to reactor 103, (ii) in and acetic acid, (iii) acetic acid is reacted with alcohol, or (iv) in sewage treatment equipment, process described resistates.Can also use and can add wherein the weak acid recovery distillation tower of solvent (optionally serving as entrainer) to separate to comprise the resistates that is less than 50wt.% acetic acid.The exemplary solvent that can be applicable to this object comprises ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, vinyl-acetic ester, Di Iso Propyl Ether, dithiocarbonic anhydride, tetrahydrofuran (THF), Virahol, ethanol and C 3-C 12alkane.When in and when acetic acid, resistates preferably comprises and is less than 10wt.% acetic acid.Acetic acid can be with any suitable alkali or alkaline earth metal alkali, for example sodium hydroxide or potassium hydroxide neutralization.In the time that acetic acid is reacted with alcohol, described resistates preferably comprises and is less than 50wt.% acetic acid.Described alcohol can be any suitable alcohol, for example methyl alcohol, ethanol, propyl alcohol, butanols or their mixture.Reaction forms ester, can be by itself and other system, and for example carbonylation production technique or ester production technique are integrated.Preferably, described alcohol comprises ethanol, and gained ester comprises ethyl acetate.Optionally, gained ester can be given and entered hydrogenator.
In some embodiments, when resistates comprises extremely less amount, for example, while being less than the acetic acid of 5wt.%, can in the situation that further not processing, described resistates be disposed into sewage treatment equipment.The microorganism that the organic content of resistates is used as acetic acid content can advantageously be suitable for supporting in sewage treatment equipment.
Tower shown in figure can comprise any distillation tower that can carry out required separation and/or purifying.For example, except above-mentioned acid tower, other tower preferably has 1-150 column plate, for example the column plate tower of 10-100 column plate, a 20-95 column plate or 30-75 column plate.Column plate can be sieve plate, fixed float valve plate, mobile valve tray or any other suitable design known in the art.In other embodiments, can use packing tower.For packing tower, can use structured packing or random packing.Can by described column plate or filler be arranged in a continuous tower or they can be arranged in two or more towers and make to enter second segment simultaneously make to enter first paragraph from the liquid of second segment from the steam of first paragraph, etc.
The relevant condenser that can use together with each distillation tower and liquid separation container can have any conventional design and be simplified in the drawings.Heat supply can be supplied to recycle column bottoms stream to the bottom of each tower or by interchanger or reboiler.Can also use the reboiler of other type, for example internal reboiler.The heat that offers reboiler can be obtained from any heat producing during the process of integrating with described reboiler or be obtained from external source that for example another produces hot chemical process or boiler.Although shown in the drawings a reactor and a flasher, can use extra reactor, flasher, condenser, heating unit and other parts in various embodiments of the present invention.As those skilled in the art can recognize, can also will be generally used for carrying out the combination such as various condensers, pump, compressor, reboiler, rotary drum, valve, junctor, separation vessel of chemical process and for method of the present invention.
Temperature and pressure used in tower can change.Temperature in regional is in the common scope between the boiling point of the composition being removed as overhead product and the boiling point of the composition that is removed as resistates.Those skilled in the art will recognize that, in the distillation tower of operation, the temperature of given position depends at the material composition of this position and the pressure of tower.In addition, feeding rate can depend on production technique scale and change, if be described, can generally refer to the form with feed weight ratio.
The final alcohol product making by the inventive method can be obtained from the material stream that mainly comprises ethanol from example system shown in figure.Alcohol product can be technical grade ethanol, comprises the ethanol based on this alcohol product gross weight meter 75-96wt.%, for example 80-96wt.% or 85-96wt.% ethanol.Exemplary finished product ethanol compositing range is provided in following table 3.
Figure BDA0000476917920000381
Finished product ethanol composition of the present invention preferably contains very low amount, for example, be less than other alcohol of 0.5wt.%, for example methyl alcohol, butanols, isopropylcarbinol, primary isoamyl alcohol and other C 4-C 20alcohol.In one embodiment, in finished product ethanol composition, the amount of Virahol is 80-1,000wppm, for example 95-1,000wppm, 100-700wppm or 150-500wppm.In one embodiment, finished product ethanol composition does not basically contain acetaldehyde, optionally comprises and is less than 8wppm, for example, be less than 5wppm or be less than the acetaldehyde of 1wppm.
In some embodiments, in the time adopting further water to separate, can as discussed above ethanol product be taken out from water separating unit as material stream.In such embodiments, the alcohol concn of alcohol product can, higher than shown in table 3, be preferably greater than the ethanol of 97wt.%, for example, be greater than 98wt.% or be greater than 99.5wt.%.Preferably comprise and be less than 3wt.% at alcohol product aspect this, for example, be less than 2wt.% or be less than the water of 0.5wt.%.
The finished product ethanol composition of being produced by embodiment of the present invention can be for various application, comprise fuel, solvent, chemical feedstocks, medicament production, sanitising agent, disinfectant, hydrogenation transportation or consumption.In fuel applications, can make this finished product ethanol composition and blended into gasoline for Motor vehicles for example automobile, ship and small-sized piston engine aircraft.In non-fuel application, this finished product ethanol composition can be with the solvent that acts on makeup and cosmetic formulations, purification agent, sterilizing agent, coating, ink and medicine.This finished product ethanol composition can also be in the manufacturing processed for medicinal product, food formulation, dyestuff, Photochemicals and latex processing with dealing with solvent.
This finished product ethanol composition can also be as chemical feedstocks to prepare other chemical for example vinegar, ethyl propenoate, ethyl acetate, ethene, glycol ethers, ethamine, ethylbenzene, aldehyde, divinyl and higher alcohols, particularly butanols.In the preparation of ethyl acetate, can be by this finished product ethanol composition acid esterification.In Another application, can make this finished product ethanol composition dewater to produce ethene.Can use any known dehydration catalyst to make ethanol dehydration, described dehydration catalyst is those described in the open No.2010/0030002 and 2010/0030001 of the common unsettled U.S. for example, by reference their full content and disclosure are incorporated to herein at this.For example, zeolite catalyst can be used as dehydration catalyst.Preferably, described zeolite has the aperture at least about 0.6nm, and preferred zeolite comprises the dehydration catalyst that is selected from mordenite, ZSM-5, X zeolite and zeolite Y.For example X zeolite is described in U.S. Patent No. 2,882, and in 244, zeolite Y is described in U.S. Patent No. 3,130, in 007, by reference their is incorporated to herein in full at this.
Although describe the present invention in detail, modification within the spirit and scope of the present invention will be apparent to those skilled in the art.In view of the above discussion, this area relevant knowledge and the reference above discussed about background technology and detailed description, be all incorporated to their disclosure herein by reference.In addition, should understand below and/or in appended claims, quote from of the present invention aspect and the part of multiple embodiment and multiple features can combine whole or in part or exchange.In the description of aforementioned each embodiment, as those skilled in the art can recognize, those embodiments of quoting another embodiment can suitably combine with other embodiment.In addition, those skilled in the art will recognize that aforementioned description is only way of example, and be not intended to limit the present invention.

Claims (21)

1. for the production of a method for ethanol, the method comprises:
In reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form the coarse ethanol mixture that comprises acetaldehyde, ethanol, water and acetal;
In one or more towers, described coarse ethanol mixture is separated to reclaim and comprise the ethanol product that is less than 1wt.% acetal, wherein at least one tower operates more than normal atmosphere.
2. the process of claim 1 wherein that at least one tower operates under the pressure of 100kPa-5000kPa.
3. the process of claim 1 wherein in the resistates of at least one tower of operating more than normal atmosphere and reclaim ethanol.
4. the process of claim 1 wherein that described ethanol product comprises 0.0001wt.%-0.01wt.% acetal.
5. the method for claim 1, is also included at least one tower operating more than normal atmosphere at least acetal of 10-75% is decomposed.
6. for the production of a method for ethanol, the method comprises:
In reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture;
Described part coarse ethanol mixture is separated to produce the first resistates that comprises paraffinic acid and the first overhead product that comprises ethanol and acetaldehyde in the first distillation tower; With
In the second column operating, part the first overhead product is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde more than normal atmosphere,
Wherein the second resistates comprises and is less than 1wt.% acetal.
7. the method for claim 6, wherein second column operates under the pressure of 100kPa-5000kPa.
8. the method for claim 6, wherein second column operates under the pressure higher than the first tower.
9. the method for claim 6, wherein the second resistates comprises 0.0001wt.%-0.01wt.% acetal.
10. the method for claim 6, it also comprises part the first resistates is turned back in reactor.
The method of 11. claims 6, it also comprises part the second overhead product is turned back in reactor.
The method of 12. claims 6, wherein said paraffinic acid is formed by methyl alcohol and carbon monoxide, wherein methyl alcohol, carbon monoxide and for the hydrogen of hydrogenation step separately derived from synthetic gas, and the wherein said syngas-derived carbon source from being selected from Sweet natural gas, oil, oil, coal, biomass and their combination.
13. 1 kinds of methods for the production of ethanol, the method comprises:
The coarse ethanol that comprises acetic acid, acetaldehyde, ethanol, water and acetal mixture is provided;
Described part coarse ethanol mixture is separated to produce the first resistates that comprises acetic acid and the first overhead product that comprises ethanol and acetaldehyde in the first distillation tower; With
In the second column operating, part the first overhead product is separated to produce the second resistates that comprises ethanol and the second overhead product that comprises acetaldehyde more than normal atmosphere,
Wherein the second resistates comprises and is less than 1wt.% acetal.
14. 1 kinds of methods for the production of ethanol, the method comprises:
In reactor under catalyzer exists by paraffinic acid and/or its ester through hydrogenation to form coarse ethanol mixture;
Described part coarse ethanol mixture is separated to produce the first resistates that comprises paraffinic acid and the first overhead product that comprises ethanol, water, ethyl acetate and acetaldehyde in the first distillation tower;
In the second column operating, part the first overhead product is separated to produce the second resistates that comprises second alcohol and water and the second overhead product that comprises ethyl acetate and acetaldehyde more than normal atmosphere; With
In the 3rd distillation tower of operation, part the second resistates is separated to produce the 3rd resistates that comprises water and the 3rd overhead product that comprises ethanol,
Wherein the 3rd overhead product comprises and is less than 1wt.% acetal.
The method of 15. claims 14, wherein second column operates under the pressure of 100kPa-5000kPa.
The method of 16. claims 14, wherein second column operates under the pressure higher than the first tower.
The method of 17. claims 14, wherein the 3rd overhead product comprises 0.0001wt.%-0.01wt.% acetal.
The method of 18. claims 14, it also comprises part the first resistates is turned back in reactor.
The method of 19. claims 14, it also comprises part the second overhead product is turned back in reactor.
The method of 20. claims 14, it also comprises part the 3rd resistates is turned back to second column.
21. 1 kinds of methods for the production of ethanol, the method comprises:
The coarse ethanol that comprises acetic acid, acetaldehyde, ethanol, water and acetal mixture is provided;
Described part coarse ethanol mixture is separated to produce the first resistates that comprises acetic acid and the first overhead product that comprises ethanol, water, ethyl acetate and acetaldehyde in the first distillation tower;
In the second column operating, part the first overhead product is separated to produce the second resistates that comprises second alcohol and water and the second overhead product that comprises ethyl acetate and acetaldehyde more than normal atmosphere; With
In the 3rd distillation tower of operation, part the second resistates is separated to produce the 3rd resistates that comprises water and the 3rd overhead product that comprises ethanol,
Wherein the 3rd overhead product comprises and is less than 1wt.% acetal.
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