CN105367382A - Processes for maximizing ethanol formation in the hydrogenation of acetic acid - Google Patents
Processes for maximizing ethanol formation in the hydrogenation of acetic acid Download PDFInfo
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- CN105367382A CN105367382A CN201510850328.7A CN201510850328A CN105367382A CN 105367382 A CN105367382 A CN 105367382A CN 201510850328 A CN201510850328 A CN 201510850328A CN 105367382 A CN105367382 A CN 105367382A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
In one embodiment, the invention is to a process for purifying a crude ethanol product. The process comprises the step of hydrogenating acetic acid in a reactor in the presence of a catalyst to form the crude ethanol product. The process further comprises the step of separating at least a portion of the crude ethanol product in a purification zone. The purification zone preferably comprises a first column, which yields a first distillate comprising ethanol, water and ethyl acetate, and a first residue comprising acetic acid. The at least a portion of the crude ethanol product has a residence time from the reactor to the purification zone from 5 minutes to 5 days.
Description
The divisional application that the application is the applying date is on February 1st, 2011, application number is 201180001921.4, denomination of invention is the application for a patent for invention of " making the maximized method of the generation of ethanol in acetic acid hydrogenation ".
Priority request
This application claims the right of priority of following application: the U.S. Provisional Application No.61/300 that on February 2nd, 2010 submits to, 815, the U.S. Provisional Application No.61/332 that on May 7th, 2010 submits to, 702, with the U. S. application No.12/940 that on November 5th, 2010 submits to, 595, by reference their disclosures are incorporated to herein.
Invention field
Present invention relates in general to the method for producing ethanol, the generation particularly by reducing ethyl acetate in acetic acid hydrogenation makes the maximized method of the generation of ethanol.
Background of invention
Ethanol for industrial use is conveniently produced by petrochemical materials such as oil, Sweet natural gas or coal, is produced by raw material midbody such as synthetic gas, or by starchiness material or cellulose materials such as corn (corn) or sugarcane production.By petrochemical materials and the acid-catalyzed hydration, the methyl alcohol homologization, directly alcohol synthesis and Fiscber-Tropscb synthesis that are comprised ethene by the ordinary method of cellulose materials production ethanol.The unstable of petrochemical materials price impels the ethanol cost fluctuation conveniently produced, and makes the needs in the alternative source to alcohol production larger than ever when cost of material raises.Starchiness material and cellulose materials are ethanol by microbe conversion.But the consumer that fermentation is generally used for fuel use or consumption ethanol is produced.In addition, the fermentation of starchiness or cellulose materials and food sources form compete and to for industrial use the amount of producible ethanol be applied with restriction.
Extensively studied by the also original production ethanol of paraffinic acid and/or other carbonyl containing compound, be referred to the various combinations of catalyzer, carrier and operational condition in the literature.Between the reduction period of paraffinic acid such as acetic acid, other compound usually generates with ethanol or generates with side reaction.Such as, during hydrogenation and/or in follow-up side reaction, the ester of generation can form with ethanol and/or water the azeotrope being difficult to be separated together.These impurity can limit ethanol production and can costliness be needed and the serial purification of complexity (purificationtrains) so that impurity is isolated from ethanol.In addition, when transforming incomplete, unreacted acid is retained in crude ethanol product.This residual acetic acid can promote other harmful side reaction along with the time.Therefore, residual acetic acid must be shifted out to obtain purifying ethanol from crude ethanol product.
Therefore, still need to improve the rate of recovery from the crude product recovery ethanol making paraffinic acid such as acetic acid and/or other carbonyl containing compound reduces to obtain.In addition, the method reducing or suppress to be generated by harmful side reaction impurity is needed.
Summary of the invention
In the first embodiment, the present invention relates to the method for purification of crude ethanol product, the method comprises: under catalyzer exists, acetic acid hydrogenation is formed crude ethanol product in the reactor; In downstream purification district, one or more derivative stream is separated into by least part of crude ethanol product.Preferably, zone purification comprises the first tower, and this first tower produces the first overhead product comprising ethanol, water and ethyl acetate, and comprises the first resistates of acetic acid.In preferred embodiments, at least part of crude ethanol product have 5 minutes to 5 days from reactor to the residence time of the first tower.In some embodiments, between reactor and the first tower, configure storage tank and crude ethanol product have 1 little up to 5 days such as 1 day to 3 days from reactor to the residence time of the first tower.In other embodiments, when not using storage tank, crude ethanol product has the residence time from reactor to zone purification of hours such as 5 minutes to 30 minutes 1 second to 1 or 5 minutes to 15 minutes.
In this second embodiment, method of the present invention comprises the following steps: under catalyzer exists, acetic acid hydrogenation is formed crude ethanol product in the reactor; In flasher, crude ethanol product is separated into vapor stream and liquid stream; By at least part of liquid stream guiding downstream purification district; With in zone purification, at least part of liquid stream is separated at least one derivative stream.Preferably, zone purification comprises the first tower, and this first tower produces the first overhead product comprising ethanol, water and ethyl acetate, and comprises the first resistates of acetic acid.At least part of liquid material has the residence time from flasher to zone purification of 5 minutes to 5 days.
In the 3rd embodiment, method of the present invention comprises: under catalyzer exists, acetic acid hydrogenation is formed crude ethanol product in the reactor; And in flasher, crude ethanol product is separated into vapor stream and liquid stream, at least part of liquid stream is cooled to the temperature of 0-40 DEG C; By at least part of liquid stream guiding zone purification; And in zone purification, at least part of liquid stream is separated at least one derivative stream.
Accompanying drawing briefly describes
Below with reference to the accompanying drawings describe the present invention in detail, wherein identical numeral indicates similar part.
Fig. 1 is the schematic diagram with the hydrogenation system of storage tank according to an embodiment of the invention.
Fig. 2 is the coordinate diagram of the raising of display ethyl acetate content.
Fig. 3 is the coordinate diagram of the room temperature stability of crude ethanol product.
Fig. 4 is the coordinate diagram of crude ethanol product stability at 4 DEG C.
Fig. 5 is the coordinate diagram of crude ethanol product stability contrast at 4 DEG C and 21 DEG C.
Fig. 6 is the coordinate diagram of ethyl acetate concentration contrast at-78 DEG C, 4 DEG C and 21 DEG C.
Detailed Description Of The Invention
The present invention relates to the method reclaiming ethanol from crude ethanol product.Especially, the present invention relates to and reclaim and/or the method for purifying ethanol from crude ethanol product, described crude ethanol product is preferably generating in the technique of acetic acid hydrogenation in the presence of a catalyst.Once generate, zone purification of being led by crude ethanol product such as, in order to be separated wherein contained various components, ethanol, water and remaining acetic acid.
Especially, method of the present invention relate in zone purification, shift out remaining acetic acid before suppress and/or reduce the generation of ethyl acetate in crude ethanol product.As follows, there is uncatalyzed reaction in crude ethanol product, drive this crude ethanol product to reach balance between ethanol/acetic acid and ethyl acetate/water:
At the ethanol comprised and acetic acid than in ethyl acetate and the more product mixtures of water such as crude ethanol product, this balanced reaction can cause the generation of other ethyl acetate and water undesirably when damaging required ethanol product.This effect reduces alcohol yied and increases refuse.The speed of reaction of this balanced reaction improves with temperature.
In preferred embodiments, crude ethanol product, once generate, then zone purification of leading is in order to be separated component contained in this crude ethanol product.This zone purification produces at least one, such as at least two or at least three derivative streams.Remaining acetic acid is isolated from product ethanol in zone purification.Preferably, zone purification comprises the first tower, and this first tower produces the first overhead product comprising ethanol, water and ethyl acetate, and comprises the first resistates of acetic acid.In such circumstances, the first overhead product and the first resistates can think derivative stream.
In another embodiment, the separation of remaining acetic acid from product ethanol is realized by other purification unit.In many chemical processes, such as distillation tower consumes the energy of significant quantity.Therefore, expect wherein to reduce in the embodiment of energy expenditure, use one or more film separation unit to carry out purification of crude ethanol product.Preferably, film separation unit comprises pervaporation (pervaporation) film.Crude ethanol product and/or one or more derivative stream can be made to pass through film separation unit.In one embodiment, film separation unit and distillation tower conbined usage.In some embodiments, film can substitute one or more, such as two or more distillation towers essential.The use of one or more film is low-yield alternative for distillation tower provides.In addition, the ability of " destruction (break) " azeotrope when use of film separation unit can be advantageously provided in and not use entrainment agent.Comprise the application of second alcohol and water for wherein crude ethanol product, one or more film can destroy ethanol-water azeotropic thing.Recyclable ethanol in distillation tower is limited to the ethanol product comprising about 92-96wt.% ethanol by ethanol-water azeotropic thing.Film is preferably suitable for providing ethanol product, such as, have higher amount ethanol, as the dehydrated alcohol product of at least 96wt.% or higher or at least 99wt.% or higher ethanol.
Typically, will substantially first be separated from crude ethanol product and/or shift out by all remaining acetic acid in zone purification.Once shift out remaining acetic acid, then generate ethyl acetate according to above-mentioned balanced reaction and effectively stoped.According to the preferred embodiments of the invention, the residence time between being separated and/or shifting out of the generation of crude ethanol product and remaining acetic acid in zone purification is made to keep enough low effectively to reduce the generation of ethyl acetate.In some embodiments, because the speed of reaction of described balanced reaction improves with temperature, the method additionally or alternatively relates to be made crude ethanol product maintain before remaining acetic acid can therefrom effectively shift out to be in the temperature being enough to slow down or suppress ethyl acetate to generate.
Therefore, in one embodiment, can by generating crude ethanol product and the amount that therefrom substantially shifts out the ethyl acetate providing the low residence time to make to generate in crude ethanol product between remaining acetic acid (such as in zone purification) minimizes.It should be noted that the concrete separation scheme used in zone purification can vary widely.Consequently, the step substantially shifting out remaining acetic acid can be first step in purification system or subsequent step.For embodiments more of the present invention, associated time section is the generation of crude ethanol product and this crude ethanol product is introduced the separating unit of zone purification with the time between the moment of therefrom shifting out remaining acetic acid.This time period can be crucial, this is because shifting out of remaining acetic acid may be the major cause stoping ethanol/ethyl acetate balanced reaction.Mainly bear shift out remaining acetic acid separating unit such as purification column in this article also referred to as depickling unit.
With reference to Fig. 1, in one embodiment, the residence time is the time period that crude ethanol product leaves between moment that moment of reactor 103 (position A) and crude ethanol product enter depickling unit 107 (position B).In this embodiment, crude ethanol product preferably has and is less than 5 days, such as, be less than 3 days, be less than 1 hour, be less than 30 minutes, be less than 15 minutes or be less than residence time of 5 minutes.With regard to scope, the residence time is optionally 5 minutes to 5 days, such as 5 minutes to 3 days or 5 minutes to 1 hour.
In some embodiments, as shown in fig. 1, in flasher 106, the crude ethanol product obtaining autoreactor 103 was carried out flash distillation therefrom to shift out hydrogen and lighter hydrocarbons before being incorporated into depickling unit 107.In this, the stream leaving flasher 106 may also be referred to as crude ethanol product stream.Therefore, in certain aspects, the invention is characterized in that crude ethanol product leaves the residence time between the moment of flasher (position C) and its moment of introducing depickling unit (position B) at it.In this embodiment, crude ethanol product can have and is less than 5 days, such as, be less than 3 days, be less than 1 hour, be less than 30 minutes, be less than 15 minutes or be less than residence time of 5 minutes.
By making the residence time of regulation the shortest, also can effectively make in introducing zone purification 102, and the amount of the other ethyl acetate generated before more specifically introducing depickling unit 107 is minimum.In some embodiments, reaction zone 101 and zone purification 102 compact siro spinning technology.
In other embodiments, such as storage tank 130 is provided between these Liang Ge districts and is used for purifying to make part crude ethanol product be transported to independent position.By all or part of crude ethanol product in introducing zone purification 102, such as, can be contained in storage tank before introducing depickling unit.The crude ethanol product residence time between A and C of position, when being contained in one or more storage tank, being preferably less than the residence time between C and B of position, can be 5 minutes to 5 days, such as 5 minutes to 3 days or 5 minutes to 1 hour.The exemplary residence time between C and B of position, when being contained in storage tank, is 5 minutes to 5 days, such as 5 minutes to 3 days or 5 minutes to 1 hour.In various optional embodiment, between A and C of position, between C and B of position, or one or more storage tank can be provided between A and C of position and between C and B of position simultaneously.
Do not use wherein in some embodiments of storage tank, compared with wherein using the situation of storage tank, crude ethanol product can have as from position A to position B or from the comparatively short residence time(SRT) measured by position C to position B.Such as, do not use wherein in some embodiments of storage tank, thick acetic acid product can have and is less than 1 hour, such as, be less than 30 minutes, be less than 15 minutes or be less than residence time of 5 minutes.With regard to scope, as can be 1 second to 1 hour from position A to position B or from the residence time measured by position C to position B, such as 5 minutes to 30 minutes or 5 minutes to 15 minutes.
Use in other embodiment of storage tank wherein, compared with wherein not using the situation of storage tank, crude ethanol product can have as from position A to position B or from the comparatively long residence time measured by position C to position B.Such as, use in some embodiments of storage tank wherein, thick acetic acid product can have and is less than 5 days, such as, be less than 3 days or be less than the residence time of 1 day.With regard to scope, as can be 1 little of 5 days from position A to position B or from the residence time measured by position C to position B, such as 1 day to 3 days.With regard to lower limit, the residence time in these situations can be at least 1 hour, such as at least 1 day.Compared with having storage tank and not having the residence time of storage tank, use residence time during storage tank can grow to few 10% than residence time when not using storage tank, such as at least 25%, at least 50%, at least 100% or at least 200%.
In another embodiment, as implied above, can be in and be less than 40 DEG C by making crude ethanol product maintain, such as, be less than 30 DEG C or the temperature that is less than 20 DEG C is come additionally or alternatively controls the other generation of ethyl acetate in crude ethanol product.With regard to scope, crude ethanol product can be made to maintain 0 DEG C-40 DEG C, the temperature of such as 0 DEG C-30 DEG C or 0 DEG C-20 DEG C.Between flasher and zone purification (such as depickling unit), such as, between position C and B in FIG, temperature preferably maintains these temperature.The temperature that one or more refrigerating unit or interchanger can be used to maintain or reduce (if necessary) crude ethanol product reaches these temperature.In one embodiment, crude ethanol product to be cooled within these temperature and to hold within the residence time provided above in one or more storage tank.
In some embodiments, the temperature of crude ethanol product relates to as from position A to position B or from the crude ethanol product residence time measured by position C to position B.Such as, crude ethanol product is maintained cooler temperature, the longer residence time can be allowed and do not generate ethyl acetate in addition.On the contrary, when crude ethanol product does not carry out cooling or maintaining comparatively high temps, other ethyl acetate can be generated more quickly.Therefore, in order to avoid other ethyl acetate generates, the residence time will can be preferably shorter.
In addition, the carrying out speed and can improve due to the raising of crude product temperature of uncatalyzed reaction.Such as, when in pipeline 115, the temperature of crude product brings up to 21 DEG C from 4 DEG C, the generating rate of ethyl acetate can from about 0.01wt.%/hour to bring up to about 0.005wt.%/hour.Therefore, in one embodiment, the temperature of the liquid ingredient in pipeline 115 or in optional storage tank is maintained the temperature being less than 21 DEG C.
Because crude ethanol product is typically rich in ethanol and containing remaining acetic acid, the ethyl acetate concentration before shifting out remaining acetic acid in crude ethanol product may trend towards increasing.In a preferred embodiment of the invention, the raising compared with the ethyl acetate content in the crude ethanol product taken out from reactor of the ethyl acetate before acid is shifted out in crude ethanol product is not more than 5wt.%, such as, be not more than 3wt.% or be not more than 2wt.%.Such as, when the crude ethanol product leaving reactor 103 comprises 5wt.% ethyl acetate, preferably comprise to the amount of the crude ethanol product entering depickling unit (the first tower 107) and be not more than 10wt.% ethyl acetate.Preferably, between reactor and depickling unit, substantially other ethyl acetate is not generated.
Embodiment of the present invention can be advantageously used in industrial application to reclaim ethanol by economically feasible scale.
Suitable hydrogenation catalyst comprises and optionally comprises the first metal on a catalyst support and one or more the catalyzer optionally comprised in the second metal, the 3rd metal or other metal.First with optional second and the 3rd metal can be selected from: IB, Π Β, IIIB, IVB, VB, VIB, VIIB, VIII transition metal, lanthanide series metal, actinide metals or be selected from the metal of any race in IIIA, IVA, VA and VIA race.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, silver/palladium, copper/palladium, nickel/palladium, gold/palladium, ruthenium/rhenium and ruthenium/iron.Exemplary catalyzer is also described in U.S. Patent No. 7,608,744 and 7,863,489 and the U.S. announce in No.2010/0197485, by reference their disclosure is incorporated to herein.
In an exemplary embodiment, this catalyzer comprises the first metal being 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.When the first metal comprises platinum, due to the high demand to platinum, catalyzer preferably comprises the platinum of amount being less than 5wt.% and being such as less than 3wt.% or being less than 1wt.%.
As indicated above, this catalyzer optionally also comprises the second metal, and this second metal can play promotor usually.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.
If this catalyzer comprises two or more metals, such as the first metal and the second metal, then the first metal optionally exists with the amount of 0.1-10wt.% such as 0.1-5wt.% or 0.1-3wt.% in the catalyst.Second metal preferably exists with the amount of 0.1-20wt.% such as 0.1-10wt.% or 0.1-5wt.%.For the catalyzer comprising two or more metals, two or more metals described can alloying or can comprise metal solid solution or the mixture of no-alloyed each other.
Preferred metal ratio can depend on metal used in catalyzer and change.In some example embodiments, the first metal and bimetallic mol ratio are preferably 10:1-1:10, such as 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 any metal listed by the first or second metal, as long as the 3rd metal is different from the first and second metals.In 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.When it is present, the gross weight of the 3rd metal is preferably 0.05-4wt.%, such as 0.1-3wt.% or 0.1-2wt.%.
Except one or more metals, exemplary catalyst also comprises carrier or modified support, and modified support refers to the carrier comprising 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 overall catalyst weight gauge, such as 78-97wt.% or 80-95wt.%.In the preferred embodiment using modified support, support modification agent is with based on overall catalyst weight gauge 0.1-50wt.%, and the amount of such as 0.2-25wt.%, 0.5-15wt.% or 1-8wt.% exists.
Suitable solid support material can comprise such as stable metal oxide base carrier or ceramic base carrier.Preferred carrier comprises containing silicon carrier, and such as silicon-dioxide, silica/alumina, IIA race silicate are as calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.Other carrier can include but not limited to ferriferous oxide (ironoxide), aluminum oxide, titanium dioxide, zirconium white, magnesium oxide, carbon, graphite, high surface area graphite carbon, gac and their mixture.
In the production of ethanol, support of the catalyst can carry out modification with support modification agent.Preferably, support modification agent is the basic modifier with low volatility or non-volatility.This kind of basic modifier such as 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 race metal metasilicates, (vii) IIIB family metal oxide, (viii) IIIB race metal metasilicates and their mixture.Except oxide compound and metasilicate, the properties-correcting agent of other type comprising nitrate, nitrite, acetate and lactic acid salt can be used.Preferably, support modification agent is selected from oxide compound and the metasilicate of arbitrary element in sodium, potassium, magnesium, calcium, scandium, yttrium, zinc, and their mixture.Preferably, support modification agent is Calucium Silicate powder, more preferably calcium metasilicate (CaSiO
3).If support modification agent comprises calcium metasilicate, then calcium metasilicate be at least partially preferably crystallized form.
Preferred silica support materials is SS61138 high surface area (HSA) silica catalyst supports from Saint-GobainNorPro.Saint-GobainNorProSS61138 silicon-dioxide is 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 about 1.0cm that pressure mercury hole method of masurement is measured
3the average pore sizes of/g and about 0.352g/cm
3(22lb/ft
3) tap density.
Preferred silica/alumina solid support material is KA-160 (SudChemie) silica spheres, and it has the specific diameter of about 5mm, the density of about 0.562g/ml, about 0.583gH
2the specific absorption of O/g carrier, about 160-175m
2the surface-area of/g and the pore volume of about 0.68ml/g.
Under those of skill in the art would recognize that the processing condition that select to make catalyst body to tie up to for generating ethanol to solid support material, there is suitable activity, selectivity and robustness (robust).
The metal of catalyzer can disperse throughout whole carrier, applies (eggshell) or modification (decorate) on the outer surface of the support on carrier surface.
Be applicable to catalyst composition of the present invention formed, although the such as chemical vapour deposition of other method can also be used preferably by the metal impregnation of modified support.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, their disclosure is incorporated to by reference herein.
As the skilled person will be readily appreciated, embodiment of the present invention can comprise the various structures using fixed-bed reactor or fluidized-bed reactor.In many embodiments of the present invention, " thermal insulation " reactor can be used; That is, have and seldom or not need the internal pipe arrangements (plumbing) through reaction zone add or remove heat.In other embodiments, radial flow reactor or multiple reactor can be used, or the serial reaction device that there is or do not have heat exchange, cooling or introduce other charging can be used.Or, the shell-tube type reactor being equipped with heat transmission medium can be used.In many cases, 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 such as pipeline or catheter shape, the reactant typically wherein being vaporous form through or by described catalyzer.Other reactor can be used, such as fluidized-bed or ebullated bed reactor.In some cases, hydrogenation catalyst can be combined with inert material to regulate reaction mass to flow through the pressure drop of catalyst bed and the duration of contact of reactant compound and granules of catalyst.
Hydrogenation reaction can be carried out in liquid phase or gas phase.Preferably, under following condition, this reaction is carried out in the gas phase.Temperature of reaction can be 125 DEG C-350 DEG C, such as 200 DEG C-325 DEG C, 225 DEG C-300 DEG C or 250 DEG C-300 DEG C.Pressure can be 10KPa-3000KPa (about 1.5-435psi), such as 50KPa-2300KPa or 100KPa-1500KPa.Can by reactant to be greater than 500hr
-1, such as, be greater than 1000hr
-1, be greater than 2500hr
-1or be even greater than 5000hr
-1gas hourly space velocity (GHSV) to entering reactor.With regard to scope, GHSV can be 50hr
-1-50,000hr
-1, such as 500hr
-1-30,000hr
-1, 1000hr
-1-10,000hr
-1or 1000hr
-1-6500hr
-1.
Optionally under being just enough to overcome the pressure 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 high air speed such as 5000hr
-1or 6,500hr
-1the lower sizable pressure drop may experienced by reactor beds.
Although the every mole of acetic acid of this reaction consumes 2 mol of hydrogen thus produce 1 moles ethanol, in incoming flow, the actual mol ratio of hydrogen and acetic acid can be about 100:1-1:100, such as 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, such as, be greater than 4:1 or be greater than 8:1.
Contact or the residence time also can vary widely, and these depend on the variable as the amount of acetic acid, catalyzer, reactor, temperature and pressure.When using catalyst system except fixed bed, typical duration of contact, at least for gas-phase reaction, preferred duration of contact was 0.1-100 second for part second is to being greater than some hours, such as 0.3-80 second or 0.4-30 second.
The raw material, acetic acid and the hydrogen that use about the inventive method derived from any suitable source, can comprise Sweet natural gas, oil, coal, biomass etc.As an example, carbonylation of methanol, oxidation of acetaldehyde, oxidation of ethylene, oxidative fermentation and production of acetic acid by anaerobic fermentation can be passed through.Due to oil and natural gas price volalility, more or less become expensive, so cause concern gradually by alternative carbon source production acetic acid and the method for intermediate e as methyl alcohol and carbon monoxide.Especially, when oil and gas is compared relatively costly, produce acetic acid by the synthesis gas (" synthetic gas ") derived from any available carbon source and may become favourable.Such as, U.S. Patent No. 6,232,352 (its disclosure being incorporated to by reference herein) teach transformation methanol device in order to manufacture the method for acetic acid.By transformation methanol device, for new acetic acid device, produce relevant substantial contribution expense with CO and be significantly reduced or eliminate to a great extent.Make all or part of synthetic gas turn to from methanol-fueled CLC loop and be supplied to separator unit to reclaim CO and hydrogen, then by them for the production of acetic acid.In addition to acetic acid, this method can also for the preparation of the available hydrogen of relevant the present invention.
The methanol carbonylation process being suitable for acetic acid production is described in U.S. Patent No. 7,208, and 624,7,115,772,7,005,541,6,657,078,6,627,770,6,143,930,5,599,976,5,144,068,5,026,908,5,001,259 and 4,994, in 608, their disclosure is incorporated to herein by reference.Optionally, alcohol production and this methanol carbonylation process can be integrated.
U.S. Patent No. RE35,377 (being incorporated to by reference herein) provide a kind of by making the method for carbonaceous material such as oil, coal, Sweet natural gas and conversion of biomass material methanol.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 to form synthetic gas.Be can turn to the methyl alcohol of acetic acid by carbonyl by this Synthetic holography.The method produces equally as the above-mentioned relevant spendable hydrogen of the present invention.U.S. Patent No. 5,821,111 (it discloses a kind of method useless biomass being converted into synthetic gas by gasification) and the disclosure of U.S. Patent No. 6,685,754 are incorporated to herein by reference.
In an optional embodiment, other carboxylic acid and acid anhydrides can also be comprised to the acetic acid entering hydrogenation reaction, and acetaldehyde and acetone.Preferably, suitable acetic acid feed stream comprises the compound that one or more are selected from acetic acid, diacetyl oxide, acetaldehyde, ethyl acetate and their mixture.In the method for the invention can also by these other compound hydrogenation.In some embodiments, in propyl alcohol is produced, the existence of carboxylic acid such as propionic acid or its acid anhydrides can be useful.
Or, can directly from U.S. Patent No. 6, the flasher of the class methanol carbonylation unit described in 657,078 (its disclosure being incorporated to by reference herein) takes out the acetic acid of vaporous form as crude product.Such as, thick vapor product can not needed condense acetic acid and lighting end directly to entering ethanol building-up reactions district of the present invention or except anhydrating, thus save overall craft expense.
Acetic acid can be made to gasify at the reaction temperatures, then the acetic acid of gasification can be fed together in company with undiluted state or with the hydrogen that carrier gas such as nitrogen, argon gas, helium, the carbonic acid gas etc. of relative inertness dilute.For making reaction run in the gas phase, the temperature in Controlling System is answered to make it not drop to dew point lower than acetic acid.In one embodiment, acetic acid can be made at a particular pressure in the gasification of acetic acid boiling point, then the acetic acid of gasification can be heated to reactor inlet temperature further.In another embodiment, be passed in lower than the acetic acid at the temperature of acetic acid boiling point by making hydrogen, circulation gas, another kind of suitable gas or their mixture and make acetic acid change vapor state into, thus soak carrier gas by acetic acid vapor, then the steam of mixing is heated to reactor inlet temperature always.Preferably, by making hydrogen and/or circulation gas through being in or making acetic acid change steam into lower than the acetic acid at the temperature of 125 DEG C, then the gaseous stream of merging is heated to reactor inlet temperature.
Especially, the hydrogenation of acetic acid can obtain acetic acid advantageous conversion rate and to the favourable selectivity of ethanol and productive rate.For the present invention, term " transformation efficiency " refers in charging the amount of the acetic acid of the compound be converted in addition to acetic acid.Transformation efficiency represents by based on the molecular fraction of acetic acid in charging.Described transformation efficiency can be at least 10%, such as at least 20%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%.Although expect the catalyzer with high conversion such as at least 80% or at least 90%, when the selectivity height of ethanol, low transformation efficiency also can accept in some embodiments.Certainly, should fully understand, in many cases, make up transformation efficiency by suitable recycle stream or the larger reactor of use, but be comparatively difficult to make up poor selectivity.
Selectivity represents by the molecular fraction based on the acetic acid transformed.The often kind of compound transformed by acetic acid should be understood there is independently selectivity and this selectivity does not rely on transformation efficiency.Such as, if 50 of the acetic acid transformed % by mole are converted into ethanol, then ethanol selectivity is 50%.Preferably, catalyzer is at least 60% to the selectivity of ethoxylate, such as at least 70% or at least 80%.As used herein, term " ethoxylate " specifically refers to compound ethanol, acetaldehyde and ethyl acetate.Preferably, the selectivity of ethanol is at least 80%, such as at least 85% or at least 88%.The preferred embodiment of this hydrogenation process also has the low selectivity to less desirable product such as methane, ethane and carbonic acid gas.Preferably 4% is less than to the selectivity of these less desirable products, such as, is less than 2% or be less than 1%.More preferably, these less desirable products can't detect.The formation of alkane can be low, and ideally, the acetic acid through catalyzer is less than 2%, be less than 1% or be less than 0.5% and be converted into alkane, and this alkane has very little value in addition to being a fuel.
Based on the grams of kilogram regulation product such as ethanol that meter is per hour formed of used catalyst during " productive rate " refers to hydrogenation as used herein, the term.Preferably every kg catalyst alcohol yied hourly is at least 200 grams, such as at least 400 grams or at least 600 grams.With regard to scope, described productive rate is preferably every kg catalyst 200-3 per hour, 000 gram of ethanol, such as 400-2, and 500 or 600-2,000.
In various embodiments, the crude ethanol product produced by method of hydrotreating, before any processing example is subsequently as purification and separation, typically will comprise unreacted acetic acid, second alcohol and water.As used herein, term " crude ethanol product " refers to any composition comprising 5-70wt.% ethanol and 5-35wt.% water.In some example embodiments, crude ethanol product comprises based on this crude ethanol product total weight 5-70wt.%, the ethanol of the amount of such as 10-60wt.% or 15-50wt.%.Preferably, crude ethanol product contains at least 10wt.% ethanol, at least 15wt.% ethanol or at least 20wt.% ethanol.Depend on transformation efficiency, crude ethanol product typically also will comprise unreacted acetic acid, such as, be less than 90wt.%, such as, be less than 80wt.% or be less than the amount of 70wt.%.With regard to scope, unreacted acetic acid is preferably 0-90wt.%, such as 5-80wt.%, 15-70wt.%, 20-70wt.% or 25-65wt.%.Because form water in reaction process, water will usually such as with 5-35wt.%, and the amount as 10-30wt.% or 10-26wt.% is present in crude ethanol product.During acetic acid hydrogenation or by side reaction, also can produce ethyl acetate, and it can such as with 0-20wt.%, the amount as 0-15wt.%, 1-12wt.% or 3-10wt.% exists.Also can produce acetaldehyde by side reaction and it can such as with 0-10wt.%, the amount as 0-3wt.%, 0.1-3wt.% or 0.2-2wt.% exists.Other component is ester, ether, aldehyde, acetal, ketone, alkane and carbonic acid gas such as, if can detect, can altogether to be less than 10wt.%, and the amount being such as less than 6wt.% or being less than 4wt.% exists.With regard to scope, other component can by 0.1-10wt.%, and the amount of such as 0.1-6wt.% or 0.1-4wt.% exists.The exemplary of coarse ethanol compositing range is provided in table 1.
Fig. 1 shows and is suitable for acetic acid hydrogenation and the hydrogenation system 100 from crude ethanol product separating alcohol according to one embodiment of the invention.The storage tank 130 that system 100 comprises reaction zone 101, zone purification 102 and is placed between reaction zone 101 and zone purification 102.Reaction zone 101 comprises reactor 103, hydrogen feed line 104 and acetic acid feed pipeline 105.Zone purification 102 comprises flasher 106, first tower 107, second tower 108 and the 3rd tower 109.Respectively by pipeline 104 and 105 by hydrogen and acetic acid to entering vaporizer 110 to produce vapor feed stream in the pipeline 111 being directed to reactor 103.In one embodiment, pipeline 104 and 105 can merge and such as with a kind of stream containing hydrogen and acetic acid jointly to entering vaporizer 110.In pipeline 111, the temperature of vapor feed stream is preferably 100 DEG C-350 DEG C, such as 120 DEG C-310 DEG C or 150 DEG C-300 DEG C.As shown in fig. 1, any charging of not gasification is shifted out from vaporizer 110, and can be recycled to wherein.In addition, although Fig. 1 shows the top of pipeline 111 directed response device 103, pipeline 111 can the sidepiece of directed response device 103, top or bottom.Described below other amendment and other integral part of reaction zone 101.
Reactor 103 contains for making carboxylic acid, the catalyzer of preferred acetic acid hydrogenation.In one embodiment, one or more protection bed (not shown) guard catalyst can be used to avoid suffering charging or return/recycle stream in contained toxic substance or less desirable impurity.This kind of protection bed can use in vapor stream or liquid stream.Suitable protection bed material is known in the art and comprises such as carbon, silicon-dioxide, aluminum oxide, pottery or resin.On the one hand, make protection bed medium functionalized to trap particular matter such as sulphur or halogen.During hydrogenation process, by pipeline 112, crude ethanol product stream is preferably taken out from reactor 103 continuously.The condensation of crude ethanol product stream, to entering flasher 106, can be this in turn provides steam stream and liquid stream.Flasher 106, preferably at 50 DEG C-500 DEG C, such as, operates at the temperature of 70 DEG C-400 DEG C or 100 DEG C-350 DEG C.The pressure of flasher 106 is preferably 50KPa-2000KPa, such as 75KPa-1500KPa or 100KPa-1000KPa.In a preferred embodiment, the temperature and pressure of flasher is similar to the temperature and pressure of reactor 103.
The vapor stream leaving flasher 106 can comprise hydrogen and hydrocarbon, can be carried out cleaning and/or turning back to reaction zone 101 by pipeline 113.As shown in fig. 1, the returning part of vapor stream passes compressor 114 and merges with hydrogen feed, jointly to entering vaporizer 110.
In one embodiment, taken out and be pumped into zone purification as feed composition by pipeline 115 by the liquid from flasher 106, this zone purification comprises the first tower 107 also referred to as depickling unit.Pipeline 115 can such as to the sidepiece entering the first tower 107.The content of pipeline 115 typically will be substantially similar to the product directly obtained from reactor, and in fact can also be called crude ethanol product.
As implied above, storage tank 130 is arranged between reaction zone 101 and zone purification 102.Can by the part or all of liquid feeding in pipeline 115 by pipeline 131 to enter in storage tank 130 and to turn back to pipeline 115 by pipeline 132.The partially liq charging be stored in storage tank 130 cooperatively can be fed directly to entering in depickling unit 107 or with the remainder of liquid feeding in pipeline 115 by pipeline 132.
Optionally, can also by the part crude ethanol product in pipeline 112 to entering in independent storage tank (not shown).
Although show a storage tank in Fig. 1, imagination can use other independent tank.Such as, when both the liquid feedings in the crude ethanol product in pipeline 112 and pipeline 115 want separate storage, independent storage tank can be used.
Except storage tank 130, its temperature before introducing depickling unit of the liquid feeding in pipeline 112 in crude ethanol product and/or pipeline 115 can be maintained or be cooled.Such as, crude ethanol product in pipeline 112 or 115 can be carried out maintaining or directly cooling or storage tank 130 can be carried out maintaining or cooling, reach and be such as less than 40 DEG C, such as be less than 30 DEG C or be less than 20 DEG C, or with regard to scope 0 DEG C-40 DEG C, the temperature of such as 0 DEG C-30 DEG C or 0 DEG C-20 DEG C.If the temperature of pipeline 112 and/or 115 exceedes these temperature, then can cool the content of pipeline 112 and/or 115 if desired.One or more sensor or monitoring instrument can be combined with the refrigerating unit for holding temperature.
In one embodiment, the content of pipeline 115 is substantially similar to the crude ethanol product obtained from reactor, condition is that the content of ethyl acetate in the charging of going to depickling unit 107 does not have raising to be greater than 5wt.% compared with the content of ethyl acetate in the crude ethanol product taken out from reactor, such as, be greater than 3wt.% or be greater than 2wt.%.In addition, liquid feeding can be different from crude ethanol product, this is because said composition does not preferably have hydrogen, carbonic acid gas, methane or ethane substantially, they are removed ideally by flasher 106.Provide the exemplary composition of pipeline 115 in table 2.It should be understood that pipeline 115 can containing the component in other component (unlisted) such as charging.
In the table of whole the application, be less than (<) and if shown in amount be preferably do not exist then to exist by trace or with the amount being 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 Anaesthetie 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.Feed composition such as pipeline 115 can comprise with the propyl alcohol of the amount of 0.001-0.1wt.%, 0.001-0.05wt.% or 0.001-0.03wt.% 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 to be further described herein.
When the content of acetic acid is less than 5wt.% in pipeline 115, acid separation column 107 can be skipped over and pipeline 115 can be introduced directly into the second tower 108 (being also called light fraction tower herein).
In embodiment in FIG, pipeline 115 is introduced the bottom of depickling unit (the first tower) 107, such as Lower Half or lower 1/3rd.In depickling unit 107, unreacted acetic acid, part water and other heavy component (if existence) are shifted out from the composition pipeline 115 and preferably take out as resistates continuously.Some or all resistatess can be made to be returned by pipeline 116 and/or reaction zone 101 is got back in recirculation.Depickling unit (the first tower) 107 yet forms both overhead product, it is taken out in pipeline 117, and can by it such as with 10:1-1:10, as ratio condensation and the backflow of 3:1-1:3 or 1:2-2:1.
Any one in tower 107,108 or 109 can comprise can carry out being separated and/or any purification column of purifying.Described tower preferably comprises and has 1-150 column plate, the such as tray column 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 other suitable design any known in the art.In other embodiments, packing tower can be used.For packing tower, structured packing or random packing can be used.Described tower or filler can be carried out arranging or they can being carried out arranging by two or more towers making the steam from first paragraph enter second segment and make the liquid from second segment enter first paragraph simultaneously by a kind of continuous tower, etc.
The associated condenser that can use together with each purification column and liquid separation container can have any conventional design and be simplified in FIG.As shown in fig. 1, heat supply can be supplied to recycle column bottoms stream to the bottom of each tower or by interchanger or reboiler.In some embodiments, the reboiler of other type can also be used, such as internal reboiler.Any heat produced during the heat being supplied to reboiler can be obtained from the process integrated with described reboiler or be obtained from that external source is such as another kind of produces hot chemical process or boiler.Although show a reactor and a flasher in FIG, additional reactor, flasher, condenser, heating unit and other parts can be used in embodiments of the invention.As those skilled in the art can recognize, the various condensers, pump, compressor, reboiler, rotary drum, valve, junctor, separation vessel etc. that are generally used for carrying out chemical process can also be carried out combining and are used in method of the present invention.
Temperature and pressure used in any tower can change.As practical situation, usually can use the pressure of 10KPa-3000KPa in that region, although subatmospheric pressure and superatmospheric pressure can be used in some embodiments.Temperature in regional is using in the scope between the boiling point of the usual composition being removed as overhead product and the boiling point of composition be removed as resistates.Those skilled in the art will recognize that, in the purification column of operation, the temperature of given position depends on material composition in this position and the pressure of tower.In addition, feeding rate can depend on production technique scale and change, if be described, then can generally refer to according to feed weight ratio.
When tower 107 operates at normal atmospheric pressure, the temperature of the resistates left from tower 107 in pipeline 116 is preferably 95 DEG C-120 DEG C, such as 105 DEG C-117 DEG C or 110 DEG C-115 DEG C.The temperature of the overhead product left from tower 107 in pipeline 117 is preferably 70 DEG C-110 DEG C, such as 75 DEG C-95 DEG C or 80 DEG C-90 DEG C.In other embodiments, the pressure of the first tower 107 can be 0.1KPa-510KPa, such as 1KPa-475KPa or 1KPa-375KPa.Exemplary overhead product and the resistates composition of the first tower 107 is provided in following table 3.Should also be understood that described overhead product and resistates can also containing other unlisted components, such as, component in charging.Conveniently, the overhead product of the first tower and resistates may also be referred to as " the first overhead product " or " the first resistates ".The overhead product of other tower or resistates also can be mentioned they to be distinguished from each other out with similar digital modifier (second, third etc.), but this kind of modifier should not be interpreted as requiring any special separation sequence.
As shown in table 3, although not bound by theory, unexpected and unexpectedly find, when detecting the acetal of any amount in the charging being incorporated into acid separation column (the first tower 107), acetal seems to decompose in this tower to make to exist less in overhead product and/or resistates or even do not have detectable amount.
In addition, have now found that, above-mentioned balanced reaction can also promote to form ethanol in the top area of the first tower 107.
As shown in fig. 1, optionally the overhead product of tower 107 such as top stream is carried out condensation and the preferred reflux ratio with 1:5-10:1 refluxes.Overhead product in pipeline 117 preferably comprises ethanol, ethyl acetate and water and other impurity, its formation due to binary and ternary azeotrope and may be difficult to be separated.
The first overhead product in pipeline 117 is incorporated into the second tower 108 (also referred to as " light fraction tower "), preferably introduces at the middle portion such as middle 1/2nd or middle 1/3rd of tower 108.In one embodiment, the second tower 108 can be extraction purification tower.Extraction agent such as water can be joined the second tower 108.Water as extraction agent can obtain from external source or return from the inside from other tower one or more/and recirculation line obtains.
Second tower 108 can be tray column or packing tower.In one embodiment, the second tower 108 has 5-70 column plate, such as the tray column of 15-50 column plate or 20-45 column plate.
Although the temperature and pressure of the second tower 108 can change, the temperature of second resistates that ought under atmospheric pressure leave from the second tower 108 in pipeline 118 is preferably 60 DEG C-90 DEG C, such as 70 DEG C-90 DEG C or 80 DEG C-90 DEG C.The temperature of the second overhead product left from the second tower 108 in pipeline 120 is preferably 50 DEG C-90 DEG C, such as 60 DEG C-80 DEG C or 60 DEG C-70 DEG C.Tower 108 can under atmospheric pressure operate.In other embodiments, the pressure of the second tower 108 can be 0.1KPa-510KPa, such as 1KPa-475KPa or 1KPa-375KPa.Exemplary overhead product and the resistates composition of the second tower 108 is provided in following table 4.Should also be understood that described overhead product and resistates can also containing other unlisted components, such as, component in charging.
The weight ratio of the ethanol in the ethanol in the second resistates and the second overhead product is preferably at least 3:1, such as at least 6:1, at least 8:1, at least 10:1 or at least 15:1.The weight ratio of the ethyl acetate in the ethyl acetate in the second resistates and the second overhead product is preferably less than 0.4:1, such as, be less than 0.2:1 or be less than 0.1:1.Using water as in the embodiment of the extraction column into extraction agent as the second tower 108, the weight ratio of the ethyl acetate in the ethyl acetate in the second resistates and the second overhead product is close to zero.
Not bound by theory, maintained the ethyl acetate in crude ethanol product or prevented its increase from can improve the efficiency of the second tower 108 due to lower ethyl acetate content before introducing depickling unit 107.
As shown, by from the second resistates (it comprises second alcohol and water) bottom the second tower 108 by pipeline 118 to entering the 3rd tower 109 (also referred to as " product tower ").More preferably, the second resistates in pipeline 118 is introduced the bottom of the 3rd tower 109, such as Lower Half or lower 1/3rd.3rd tower 109 reclaims ethanol (being preferably pure substantially except azeotropic water-content) with the overhead product in pipeline 119.The overhead product of the 3rd tower 109 is preferably pressed shown in Fig. 1, such as, reflux with the reflux ratio of 1:10-10:1 as 1:3-3:1 or 1:2-2:1.The 3rd resistates (preferably mainly comprising water) in pipeline 121 preferably shifts out from system 100 or partly can turn back to any part of system 100.3rd tower 109 is preferably tray column as above and preferably under atmospheric pressure operates.The temperature of the 3rd overhead product left from the 3rd tower 109 in pipeline 119 is preferably 60 DEG C-110 DEG C, such as 70 DEG C-100 DEG C or 75 DEG C-95 DEG C.When this tower under atmospheric pressure operates, the temperature leaving the 3rd resistates of the 3rd tower 109 is preferably 70 DEG C-115 DEG C, such as 80 DEG C-110 DEG C or 85 DEG C-105 DEG C.Exemplary overhead product and the resistates composition of the 3rd tower 109 is provided in following table 5.Should also be understood that described overhead product and resistates can also containing other unlisted components, such as, component in charging.
In purge process from any compound of charging or crude reaction product carrier band usually to be less than 0.1wt.% based on the total weight of the 3rd overhead product composition, the amount being such as less than 0.05wt.% or being less than 0.02wt.% is retained in the 3rd overhead product.In one embodiment, one or more side line stream can remove impurity from any one tower 107,108 and/or 109 of system 100.At least one side line stream of preferred use removes impurity from the 3rd tower 109.Impurity can be carried out cleaning and/or being retained in system 100.
Can use one or more additional separation system, such as purification column (as finishing column) or molecular sieve are further purified the 3rd overhead product in pipeline 119 to form dehydrated alcohol product flow, i.e. " finished product dehydrated alcohol ".
Now turn back to the second tower 108, the overhead product in pipeline 120 is preferably pressed shown in Fig. 1, and such as, with 1:10-10:1, the reflux ratio as 1:5-5:1 or 1:3-3:1 refluxes.Overhead product from the second tower 108 can be cleaned.Or, because it contains ethyl acetate, can by pipeline 120 by all or part of reaction zone 101 that is recycled to of overhead product from the second tower 108 so that ethyl acetate is converted into other ethanol.All or part of overhead product can be recycled to reactor 103 as shown in pipeline 120, and cooperatively can feed with acetic acid feed pipeline 105.In another embodiment, one or more other tower (not shown) can be used to be further purified to remove impurity by the second overhead product in pipeline 120, such as acetaldehyde.
Finished product ethanol
The finished product ethanol composition obtained by the inventive method preferably comprises based on this finished product ethanol composition total weight 75-96wt.% ethanol, the ethanol of such as 80-96wt.% or 85-96wt.%.Exemplary finished product ethanol compositing range is provided in following table 7.
The finished product ethanol composition of being produced by embodiment of the present invention may be used for various application, comprises fuel, solvent, chemical feedstocks, medicament production, sanitising agent, disinfectant, hydrocracking or consumption.In fuel applications, this finished product ethanol composition and gasoline concoction can be made for Motor vehicles such as automobile, ship and small-sized piston engine aircraft.In non-fuel application, this finished product ethanol composition can be used as the solvent of makeup and cosmetic formulations, purification agent, sterilizing agent, coating, ink and medicine.This finished product ethanol composition can also with dealing with solvent in the manufacturing processed of medicinal product, food preparation, dyestuff, photochemistry and latex process.
This finished product ethanol composition can also be used as chemical feedstocks to prepare other chemical such as vinegar, ethyl propenoate, ethyl acetate, ethene, glycol ethers, ethamine, aldehyde and higher alcohols, particularly butanols.In the preparation of ethyl acetate, or itself and polyvinyl acetate can be reacted by this finished product ethanol composition acid esterification.This finished product ethanol composition can be made to dewater to produce ethene.Any known dehydration catalyst can be used to make ethanol dehydration, and described dehydration catalyst such as discloses those described in No.2010/0030002 and 2010/0030001 in the U.S., their disclosures is incorporated to by reference herein at this.Such as, 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 being selected from mordenite, ZSM-5, X zeolite and zeolite Y.Such as X zeolite is described in U.S. Patent No. 2, and 882, in 244, zeolite Y is described in U.S. Patent No. 3, and 130, in 007, by reference their disclosure is incorporated to herein at this.
In order to more effectively understand invention disclosed herein, provide embodiment below.
Embodiment
Embodiment 1
By acetic acid hydrogenation being obtained crude ethanol product with platinum/tin catalyst.Reaction conditions is: acetic acid is 3.66g/min and the recirculation flow comprising acetic acid is 10.53L/min, and the hydrogen feed going to the reactor with 220-300 DEG C of temperature distribution is 1.05L/min.From reactor to the residence time of the first purification column be 2 days, do not have temperature to control.From the crude ethanol product taking from reactor adopt fixed point sample and with GC measure composition.Also adopt to obtain the second sample, namely to the large bottle of thin mouth (carboy) sample of liquid feeding entering purification column, and measure composition with GC.Compared for fixed point sample and the second sample show result in fig. 2.Report ethyl acetate content between described sample and improve 1.2wt.%.
Embodiment 2
By acetic acid hydrogenation being obtained crude ethanol product with platinum/tin catalyst.Through measuring the stability of crude ethanol product over 57 days.As shown in Figure 3, in this period, the amount of ethyl acetate increases and the reduction of the amount of ethanol and acetic acid.
Embodiment 3
By acetic acid hydrogenation being obtained crude ethanol product with platinum/tin catalyst.Through measuring the stability of crude ethanol product over 27 days at 4 DEG C.In this period, measure the amount of ethanol, water and acetic acid and be shown in Fig. 4.
Embodiment 4
By acetic acid hydrogenation being obtained crude ethanol product with platinum/tin catalyst.To be stored in refrigerator (F) at 4 DEG C through measuring the stability of crude ethanol product over 61 days and its stability with the crude ethanol product be stored at room temperature (RT) such as 21 DEG C being contrasted.In this period, measure the amount of ethanol, ethyl acetate and acetic acid and be shown in Fig. 5.In top (top) figure line (RT), the increase of ethyl acetate growing amount is greater than the increase of ethyl acetate growing amount in bottom (bottom) figure line (F).
Embodiment 5
By acetic acid hydrogenation being obtained crude ethanol product with platinum/tin catalyst.Analyze the stability of the crude ethanol product stored at three different temperatures.Analyze at room temperature (RT) such as 21 DEG C, in refrigerator (F) at 4 DEG C, and the crude ethanol product at-78 DEG C, dry ice (DI).In this period, measure the amount of ethyl acetate and represented in Fig. 6.The increase being stored in the ethyl acetate growing amount of the coarse ethanol composition under room temperature (RT) is greater than the increase of the ethyl acetate growing amount of the coarse ethanol composition be stored in refrigerator (F), and the latter is greater than the ethyl acetate growing amount of the coarse ethanol composition be stored on dry ice (DI).
Although describe the present invention in detail, various amendments within the spirit and scope of the present invention will be apparent to those skilled in the art.In view of the above discussion, above about background technology with describe this area relevant knowledge of discussing and reference in detail, by reference their disclosure is all incorporated to herein.In addition, should understand and can partly or entirely carry out combining or exchanging in the various piece of all respects of the present invention hereafter and/or in the dependent claims quoted from and multiple embodiment and multiple feature.In the description of each embodiment aforementioned, as those skilled in the art can recognize, the embodiment quoting another embodiment suitably can 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 (28)
1. a method for purification of crude ethanol product, the method comprises:
Under catalyzer exists, acetic acid hydrogenation is formed crude ethanol product in the reactor; And
In zone purification, at least part of crude ethanol product is separated into one or more derivative stream, wherein at least partly crude ethanol product has the residence time from reactor to zone purification of 5 minutes to 5 days, and described method also comprises the temperature at least part of crude ethanol product being cooled to 0 DEG C-40 DEG C.
2. the process of claim 1 wherein that described zone purification comprises the first tower.
3. the method any one of claim 1 and 2, wherein said separation is included in the first tower and at least part of crude ethanol product is separated into the first overhead product comprising ethanol, water and ethyl acetate and the first resistates comprising acetic acid.
4. the method for claim 3, the method also comprises and being turned back in reactor by least part of first resistates.
5. the method for claim 3, wherein said first resistates comprises based on the first resistates total weight 60-100wt.% acetic acid.
6. the method for claim 3, the method also comprises:
In flasher, crude ethanol product is separated into vapor stream and liquid stream,
At least part of vapor stream is turned back to reactor; And
Lead at least part of liquid stream the first tower.
7. the method for claim 3, the method also comprises:
At least part of liquid stream is cooled to the temperature of 0 DEG C-40 DEG C.
8. the method any one of claim 1 and 2, wherein said separation comprises the zone purification containing film separation unit, and makes crude ethanol product and/or at least one derivative stream by described film separation unit.
9. the method for claim 8, wherein said film separation unit comprises osmotic evaporation film.
10. the method any one of claim 1 and 2, wherein the ethyl acetate content raising of crude ethanol product before introducing zone purification is not more than 5wt.%.
Method any one of 11. claims 1 and 2, wherein crude ethanol product has the residence time from reactor to zone purification of 5 minutes to 3 days at least partly.
Method any one of 12. claims 1 and 2, wherein by least part of crude ethanol product guiding storage tank.
The method of 13. claims 12, at least part of crude ethanol product of the storage tank that wherein leads had for the 1 little residence time from reactor to zone purification up to 5 days.
Method any one of 14. claims 1 and 2, wherein said crude ethanol product comprises ethanol, water, ethyl acetate and acetic acid.
The method of 15. 1 kinds of purification of crude ethanol product, the method comprises:
Under catalyzer exists, acetic acid hydrogenation is formed crude ethanol product in the reactor;
In flasher, crude ethanol product is separated into vapor stream and liquid stream;
By at least part of liquid stream guiding zone purification; And
In zone purification, at least part of liquid stream is separated at least one derivative stream, wherein at least part of described liquid material has the residence time from flasher to zone purification of 5 minutes to 5 days, and described method also comprises the temperature at least part of liquid stream being cooled to 0-40 DEG C.
The method of 16. claims 15, wherein said zone purification comprises the first tower.
Method any one of 17. claims 15 and 16, wherein said separation is included in the first tower and at least part of liquid stream is separated into the first overhead product comprising ethanol, water and ethyl acetate and the first resistates comprising acetic acid.
The method of 18. claims 16, wherein at least partly liquid stream have 5 minutes to 30 minutes from flasher to the residence time of the first tower.
Method any one of 19. claims 15 and 16, the method also comprises the step at least part of vapor stream turned back in reactor.
Method any one of 20. claims 15 and 16, wherein the ethyl acetate content raising of crude ethanol product before introducing zone purification is not more than 5wt.%.
The method of 21. 1 kinds of purification of crude ethanol product, the method comprises:
Under catalyzer exists, acetic acid hydrogenation is formed crude ethanol product in the reactor; And
In flasher, crude ethanol product is separated into vapor stream and liquid stream,
At least part of liquid stream is cooled to the temperature of 0 DEG C-40 DEG C;
By at least part of liquid stream guiding zone purification; And
In zone purification, at least part of liquid stream is separated at least one derivative stream,
Wherein the ethyl acetate content raising of crude ethanol product before introducing zone purification is not more than 5wt.%.
The method of 22. claims 21, wherein said zone purification comprises the first tower.
Method any one of 23. claims 21 and 22, wherein said separation is included in the first tower and at least part of liquid stream is separated into the first overhead product comprising ethanol, water and ethyl acetate and the first resistates comprising acetic acid.
The method of 24. claims 23, the method also comprises and being turned back in reactor by least part of first resistates.
The method of 25. claims 23, wherein said first resistates comprises based on the first resistates total weight 60-100wt.% acetic acid.
Method any one of 26. claims 21 and 22, the method also comprises the step at least part of vapor stream turned back in reactor.
Method any one of 27. claims 21 and 22, wherein by least part of crude ethanol product conductance to storage tank.
Method any one of 28. claims 21 and 22, wherein said crude ethanol product comprises ethanol, water, ethyl acetate and acetic acid.
Applications Claiming Priority (7)
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|---|---|---|---|
| US30081510P | 2010-02-02 | 2010-02-02 | |
| US61/300,815 | 2010-02-02 | ||
| US33270210P | 2010-05-07 | 2010-05-07 | |
| US61/332,702 | 2010-05-07 | ||
| US12/940,595 US8552224B2 (en) | 2010-05-07 | 2010-11-05 | Processes for maximizing ethanol formation in the hydrogenation of acetic acid |
| US12/940,595 | 2010-11-05 | ||
| CN2011800019214A CN102421729A (en) | 2010-02-02 | 2011-02-01 | Processes for maximizing ethanol formation in the hydrogenation of acetic acid |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800019214A Division CN102421729A (en) | 2010-02-02 | 2011-02-01 | Processes for maximizing ethanol formation in the hydrogenation of acetic acid |
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| CN105367382A true CN105367382A (en) | 2016-03-02 |
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| CN2011800019214A Pending CN102421729A (en) | 2010-02-02 | 2011-02-01 | Processes for maximizing ethanol formation in the hydrogenation of acetic acid |
| CN201510850328.7A Pending CN105367382A (en) | 2010-02-02 | 2011-02-01 | Processes for maximizing ethanol formation in the hydrogenation of acetic acid |
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|---|---|---|---|
| CN2011800019214A Pending CN102421729A (en) | 2010-02-02 | 2011-02-01 | Processes for maximizing ethanol formation in the hydrogenation of acetic acid |
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| EP (1) | EP2531469A2 (en) |
| CN (2) | CN102421729A (en) |
| AU (1) | AU2011213126B2 (en) |
| BR (1) | BR112012019371A2 (en) |
| CA (1) | CA2787404A1 (en) |
| MX (1) | MX2012008929A (en) |
| SG (1) | SG182666A1 (en) |
| TW (1) | TWI588121B (en) |
| WO (1) | WO2011097190A2 (en) |
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|---|---|---|---|---|
| US9126125B2 (en) | 2010-07-09 | 2015-09-08 | Celanese International Corporation | Reduced energy alcohol separation process having water removal |
| US8884080B2 (en) | 2010-07-09 | 2014-11-11 | Celanese International Corporation | Reduced energy alcohol separation process |
| TW201245128A (en) * | 2011-04-26 | 2012-11-16 | Celanese Int Corp | Reduced energy alcohol separation process having water removal |
| CA3239832A1 (en) | 2021-12-08 | 2023-06-15 | Gunther Kracker | Method and system for producing one or more hydrocarbons |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US2607807A (en) * | 1950-02-24 | 1952-08-19 | Du Pont | Preparation of alcohols from carboxylic acids |
| DE3221077A1 (en) * | 1982-06-04 | 1983-12-08 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE CONTINUOUS PRODUCTION OF ETHANOL |
| EP0990638A1 (en) * | 1998-10-01 | 2000-04-05 | Kvaerner Process Technology Limited | Process |
| KR100654271B1 (en) * | 2003-02-21 | 2006-12-08 | 가부시키가이샤 붓산 나노테크 겐큐쇼 | Method for concentrating water-soluble organic material |
| WO2009009322A1 (en) * | 2007-07-06 | 2009-01-15 | Best Energies, Inc. | Integrated facility for producing alcohol using homoacidogenic fermentation |
| EP2060553A1 (en) * | 2007-11-14 | 2009-05-20 | BP p.l.c. | Process for the conversion of hydrocarbons into alcohol |
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2011
- 2011-02-01 CN CN2011800019214A patent/CN102421729A/en active Pending
- 2011-02-01 CN CN201510850328.7A patent/CN105367382A/en active Pending
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- 2011-02-01 CA CA2787404A patent/CA2787404A1/en not_active Abandoned
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- 2011-02-01 EP EP11702770A patent/EP2531469A2/en not_active Withdrawn
- 2011-02-01 BR BR112012019371A patent/BR112012019371A2/en not_active IP Right Cessation
Also Published As
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| MX2012008929A (en) | 2012-08-15 |
| CN102421729A (en) | 2012-04-18 |
| TW201134795A (en) | 2011-10-16 |
| AU2011213126A1 (en) | 2012-08-02 |
| AU2011213126B2 (en) | 2015-07-23 |
| BR112012019371A2 (en) | 2018-05-22 |
| EP2531469A2 (en) | 2012-12-12 |
| WO2011097190A2 (en) | 2011-08-11 |
| TWI588121B (en) | 2017-06-21 |
| WO2011097190A3 (en) | 2011-11-24 |
| SG182666A1 (en) | 2012-08-30 |
| CA2787404A1 (en) | 2011-08-11 |
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