CN102307657B - Process for making ethanol from acetic acid using acidic catalysts - Google Patents

Process for making ethanol from acetic acid using acidic catalysts Download PDF

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Publication number
CN102307657B
CN102307657B CN201080003928.5A CN201080003928A CN102307657B CN 102307657 B CN102307657 B CN 102307657B CN 201080003928 A CN201080003928 A CN 201080003928A CN 102307657 B CN102307657 B CN 102307657B
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metal
catalyst
acetic acid
ethanol
weight
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CN102307657A (en
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R·耶夫蒂奇
V·J·约翰斯顿
R·J·沃纳
H·魏纳
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Celanese International Corp
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Celanese International Corp
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Priority claimed from US12/588,727 external-priority patent/US8309772B2/en
Priority claimed from US12/698,947 external-priority patent/US8471075B2/en
Priority claimed from US12/699,024 external-priority patent/US8680317B2/en
Priority claimed from US12/852,269 external-priority patent/US8304586B2/en
Priority claimed from US12/852,227 external-priority patent/US8309773B2/en
Application filed by Celanese International Corp filed Critical Celanese International Corp
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Abstract

A process for selective formation of ethanol from acetic acid by hydrogenating acetic acid in the presence of a catalyst comprises a first metal on an acidic support. The acidic support may comprise an acidic support material or may comprise an support having an acidic support modifier. The catalyst may be used alone to produced ethanol via hydrogenation or in combination with another catalyst. In addition, the crude ethanol product is separated to obtain ethanol.

Description

Use acidic catalyst by acetic acid, to be prepared the method for ethanol
Priority request
The application requires the priority of following application: the U. S. application No.12/588 that on October 26th, (1) 2009 submits to, 727; The U. S. application No.12/698 that on February 2nd, (2) 2010 submits to, 947; The U. S. application No.12/699 that on February 2nd, (3) 2010 submits to, 024; The U.S. Provisional Application No.61/300 that on February 2nd, (4) 2010 submits to, 815; The U.S. Provisional Application No.61/332 that on May 7th, (5) 2010 submits to, 696; The U.S. Provisional Application No.61/332 that on May 7th, (6) 2010 submits to, 699; The U. S. application No.12/852 that on August 6th, (7) 2010 submits to, 269; The U. S. application No.12/852 that on August 6th, (8) 2010 submits to, 227.The U. S. application No.12/588 that on October 26th, 2009 submits to, 727 is the U. S. application No.12/221 that submit on July 31st, 2008,141 continuation part.By reference these applications are incorporated to herein in full.
Invention field
Present invention relates in general to produce the method for ethanol, particularly use acidic catalyst by acetic acid hydrogenation, to be produced the method for ethanol.
Background of invention
For the ethanol of industrial use according to routine by petrochemical materials for example oil, natural gas or coal produce, by raw material midbody for example synthesis gas produce, or by starchiness material or cellulosic material for example corn (corn) or sugarcane production.By petrochemical materials and by the conventional method of cellulosic material production ethanol, comprise that acid catalysis hydration, methyl alcohol homologization, the direct alcohol of ethene synthesize and Fischer-Tropsch is synthetic.The unstability of petrochemical materials price is impelled the ethanol cost fluctuation of producing according to routine, when cost of material raises, make to the alternative source of alcohol production need to be than in the past larger.Starchiness material and cellulosic material are converted into ethanol by fermentation.Yet fermentation is generally used for fuel and uses or consume by the consumer of ethanol and produce.In addition, the fermentation of starchiness or cellulosic material and food sources form competition and to for industrial use the amount of producible ethanol applied restriction.
Also original production ethanol by alkanoic acid and/or other carbonyl containing compound obtains broad research, has mentioned in the literature the various combinations of catalyst, carrier and operating condition.At alkanoic acid, for example between the reduction period of acetic acid, other compound generates with ethanol or generates with side reaction.These impurity and by-products limit ethanol production and from the recovery of this class reactant mixture.For example, during hydrogenation, the ester of generation forms and is difficult to separated azeotropic mixture together with ethanol and/or water.In addition,, when conversion is incomplete, unreacted acid is retained in crude ethanol product, it must be removed to reclaim ethanol.
Therefore, still need improvedly by the alkanoic acid method of original production ethanol also, the method produces the crude ethanol product that contains less impurity and accessory substance.
Summary of the invention
In the first embodiment, the present invention relates to produce the method for ethanol, the method is included under catalyst existence acetic acid hydrogenation is formed to ethanol, it is selective that wherein said hydrogenation has at least 65% ethanol, wherein said catalyst is included in the first metal on acid carrier, described acid carrier is selected from: (i) the acid carrier material of chosen from Fe oxide (iron oxide), aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture, and the carrier material of (ii) using acid modification agent modification.
In the second embodiment, the present invention relates to produce the method for ethanol, the method comprises: under the first catalyst exists, acetic acid hydrogenation is formed to the intermediate product that comprises ethanol and unreacted acetic acid; Under the second catalyst exists, unreacted acetic acid hydrogenation is formed to ethanol.The catalyst that described the first catalyst comprises and contains one or more metals, contains silicon carrier and at least one basic supports modifier.Described the second catalyst is included in the first metal on acid carrier, described acid carrier is selected from: (i) the acid carrier material of chosen from Fe oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture, and the carrier material of (ii) using acid modification agent modification.
In the 3rd embodiment, the method that the present invention relates to produce ethanol, the method comprises: in reactor, under the first catalyst and the existence of the second catalyst, acetic acid hydrogenation is formed to ethanol.Described the first catalyst can be in the first reactor area and described the second catalyst can be in the second reactor area separating with described the first reactor area.The catalyst that described the first catalyst comprises and contains one or more metals, contains silicon carrier and at least one basic supports modifier.Described the second catalyst is included in the first metal on acid carrier, described acid carrier is selected from: (i) the acid carrier material of chosen from Fe oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture, and the carrier material of (ii) using acid modification agent modification.
In the 4th embodiment, the present invention relates to reclaim the method for ethanol, the method is included in the reactor that comprises catalyst acetic acid feed stream hydrogenation is formed to crude ethanol product.Described catalyst is included in the first metal on acid carrier, described acid carrier is selected from: (i) the acid carrier material of chosen from Fe oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture, and the carrier material of (ii) using acid modification agent modification.The method is also included in and in the first tower, at least part of crude ethanol product is separated into the first distillate that comprises ethanol, water and ethyl acetate and the first residue that comprises acetic acid; The second residue that in the second tower, at least part of the first distillate is separated into the second distillate that comprises ethyl acetate and comprises second alcohol and water; Make at least part of the second distillate turn back to described reactor; And at least part of the second residue is separated into the 3rd distillate that comprises ethanol and the 3rd residue that comprises water in the 3rd tower.
For the acid modification agent of embodiment of the present invention, be preferably selected from oxide, the oxide of VB family metal, the oxide of the oxide of group vib metal, VIIB family metal, oxide, aluminum oxide and their mixture of VIIIB family metal of IVB family metal.
Accompanying drawing is briefly described
Below with reference to accompanying drawing, describe the present invention in detail, wherein identical numeral is indicated similar parts.
Fig. 1 is the schematic diagram of hydrogenation system according to an embodiment of the invention.
Fig. 2 A is the schematic diagram of the reaction zone with double-reactor according to an embodiment of the invention.
Fig. 2 B is the schematic diagram of the reaction zone with reactor according to another embodiment of the invention, and described reactor is with two reactor area.
Fig. 3 is according to the coordinate diagram of the acetic acid conversion ratio of the embodiment of the present invention.
Fig. 4 is according to the coordinate diagram of the acetic acid conversion ratio of the different catalysts of the embodiment of the present invention.
Detailed Description Of The Invention
The method that the present invention relates to produce the method for ethanol and reclaim ethanol from crude ethanol product.In one embodiment, thick acetic acid product is produced the method for hydrotreating of acetic acid hydrogenation by being included under acidic catalyst existence.In one embodiment, described acidic catalyst is included in the first metal of acid carrier.In one embodiment, described acidic catalyst is included in the first metal and the acid carrier modifier on carrier.
During acetic acid hydrogenation, there is other side reaction that produces impurity and accessory substance.A main side reaction is the balanced reaction also occurring between acetic acid/ethanol and ethyl acetate/water.These two main reactions are:
reaction 1
reaction 2
Reaction 2 is reversible and equilibrium constant K balanceby following equation 1, provide:
equation 1
Conventionally, for producing ethanol, than reaction condition, be conducive to first with the second reacting phase that consumes the ethyl acetate accessory substance in ethanol and raising crude ethanol product and react.In the open No.2010/0197985 of the U.S. (by reference it being incorporated in full herein), the catalyst that comprises alkaline modifier by use is conducive to and promotes first to react.
In some embodiments, the present invention uses acidic catalyst, and this acidic catalyst preferably is contained in the first metal on acid carrier.Although not bound by theory, think and promote the second reaction under acid exists.Equally in gas phase, think K under higher temperature balancereduce.In embodiments of the invention, K balancecan be less than 20, for example, be less than 15 or be less than 12.Preferably, K balancecan be less than 6, for example, be less than 4 or be less than 3.Like this, acidic catalyst has improved forward and the backward reaction speed of this balanced reaction.K therein balancein the embodiment of > 1, and be conducive under the reaction condition of high acetic acid conversion ratio, ethanol selectively unexpectedly and unexpectedly high.Under high conversion, the productive rate of ethanol also improves.Improve conversion ratio and ethanol and selectively advantageously reduce the amount of accessory substance in crude ethanol product, consequently, can improve the efficiency that reclaims ethanol.
For the present invention, term " conversion ratio " refers to the amount that is converted into the acetic acid of the compound except acetic acid in charging.Conversion ratio represents by the mole percent based on acetic acid in charging.Selectively by the mole percent of the acetic acid based on transforming, represent.Should understand the every kind of compound being transformed by acetic acid have independently selective and this selectively do not rely on conversion ratio.For example, if 50 % by mole of the acetic acid transforming are converted into ethanol, ethanol is selectively 50%.
Under lower acetic acid conversion ratio, be for example less than approximately 50%, acidic catalyst tends to demonstrate for ethyl acetate and is compared to the selective of raising that ethanol is high.Therefore, in some embodiments of the present invention, the producing and ethanol of making a living, the conversion ratio of acetic acid is preferably greater than 70%, for example, be greater than 80%, be greater than 90% or be greater than 95%.
In the method for the invention, ethanol is selectively preferably at least 65%, for example at least 70%, at least 80%, at least 85%, or at least 90%.Approximately 70% compared with low acetate conversion ratio under, ethanol can be selectively about 30%-40%.Preferably, along with acetic acid conversion ratio improves, the selectively also raising of ethanol.In addition, ethyl acetate can be selectively low, be for example less than 35%, be less than 30%, be less than 10% or be less than 5%.Preferably, this hydrogenation process also has less desirable product methane, ethane and carbon dioxide low selective for example.To these less desirable products be selectively preferably less than 4%, be for example less than 2% or be less than 1%.More preferably, these less desirable products are not easy to detect at crude ethanol product.The formation of alkane can be low.Ideally, through the acetic acid of catalyst, be less than 2% and be for example less than 1% or be less than 0.5% and be converted into alkane.
Embodiment of the present invention provide the alcohol yied improving under high acetic acid conversion ratio.When acetic acid conversion ratio is preferably greater than 90%, ethanol be selectively preferably at least 70%.Selectively can continue along with the raising of acetic acid conversion ratio to improve.
Term " productive rate " refers to during hydrogenation for example grams of ethanol of every kilogram of used catalyst formed regulation product per hour as used herein.Preferred every kg catalyst alcohol yied hourly is at least 200 grams, for example 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, 400-2 for example, 500 or 600-2,000.
Embodiment of the present invention provide the productivity ratio improving under high acetic acid conversion ratio.Under more than 70% acetic acid conversion ratio, the productive rate of ethanol is every kg catalyst at least 350 grams of ethanol per hour.Productive rate can continue along with the raising of acetic acid conversion ratio to improve.
Under acidic catalyst exists, carry out acetic acid hydrogenation and form second alcohol and water.In one embodiment, hydrogenation catalyst is included in the first metal and optional one or more second metals, the 3rd metal or other metal on acid carrier.First can be selected from the optional second and the 3rd metal: IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII group 4 transition metal, lanthanide series metal, actinide metals or be selected from IIIA, IVA, VAHe 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, silver/palladium, copper/palladium, nickel/palladium, gold/palladium, ruthenium/rhenium and ruthenium/iron.Exemplary catalyst is also described in U.S. Patent No. 7,608,744 and the U.S. announce in No.2010/0029995 and 2010/0197985, by reference they are incorporated in full herein.
In an exemplary, this catalyst 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.When the first metal comprises platinum, due to the high demand to platinum, catalyst preferably comprises and is less than the platinum that 5 % by weight are for example less than 3 % by weight or are less than the amount of 1 % by weight.
As indicated above, this catalyst optionally also comprises the second metal, and this second metal can play promoter conventionally.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 catalyst comprises two or more metals, for example the first metal and the second metal, the first metal optionally in catalyst with 0.1-10 % by weight for example the amount of 0.1-5 % by weight or 0.1-3 % by weight exist.The second metal preferably with 0.1-20 % by weight for example the amount of 0.1-10 % by weight or 0.1-5 % by weight exist.In one embodiment, can reduce the metal carrying capacity of acidic catalyst.This can advantageously reduce the relevant expense of the catalyst higher with metal carrying capacity.Therefore,, in the embodiment of metal carrying capacity with reduction, the first metal can by the amount existence of 0.1-1.7 % by weight, the second metal can exist by the amount of 0.1-1.3 % by weight.For the catalyst that comprises two or more metals, described two or more metals are alloying or can comprise no-alloyed metal solid solution or mixture each other.
Preferred metal ratio can depend on metal used in catalyst and change.In some exemplary, the first metal and bimetallic mol ratio are 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.In one embodiment, comprise platinum and Xi Shi be conducive to selective to ethanol at catalyst, Pt/Sn mol ratio is preferably 0.4: 0.6-0.6: 0.4, for example 0.45: 0.55-0.55: 0.45 or approximately 1: 1.In another embodiment, in the embodiment that catalyst comprises rhenium and palladium therein for being conducive to selective to ethanol, Re/Pd mol ratio is preferably 0.6: 0.4-0.85: 0.15, for example 0.7: 0.3-0.85: 0.15, or the about mol ratio of 0.75: 0.25.
This catalyst 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.When existing, the gross weight of the 3rd metal is preferably 0.05-4 % by weight, for example 0.1-3 % by weight or 0.1-2 % by weight.
In some embodiments, except one or more metals, acidic catalyst of the present invention also comprises the carrier material of acid carrier material or modification.The carrier material of modification comprises carrier material and acid carrier modifier.Acid carrier modifier regulates the acidity of carrier material.The gross weight of the carrier material of carrier material or modification is preferably 75 % by weight-99.9 % by weight based on this total catalyst weight meter, for example 78 % by weight-97 % by weight or 80 % by weight-95 % by weight.In using the embodiment of modified support material, catalyst can comprise based on this total catalyst weight meter 0.1 % by weight-50 % by weight, for example the support modification agent of the amount of 0.2 % by weight-25 % by weight, 0.5 % by weight-15 % by weight or 1 % by weight-8 % by weight.
Suitable carrier material for example can comprise stable metal oxide base carrier or ceramic base carrier.Preferred carrier material comprises and is selected from silica, silica/alumina, calcium metasilicate (calcium metasilicate), pyrolytic silicon dioxide, high-purity silicon dioxide, carbon, ferriferous oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture.In a preferred embodiment, for this catalyst, can use acid carrier material.Acid carrier material chosen from Fe oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture.
In the production of ethanol, catalyst carrier material can carry out modification with support modification agent.Preferably, with acid carrier modifier, by being alkalescence or neutral catalyst carrier material, for example silica, metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide, carbon or their mixture carry out modification.Acid carrier material can also carry out modification with acid carrier modifier.In some embodiments, acid carrier modifier regulates carrier material by improving quantity or the accessibility of acid position.Acidic site promotes the kinetic rate of esterification balance.Preferably, support modification agent is the acid modification agent with low volatility or non-volatility.Suitable acid carrier modifier can be selected from: the oxide of the oxide of IVB family metal, the oxide of VB family metal, the oxide of group vib metal, VIIB family metal, the oxide of VIIIB family metal, aluminum oxide and their mixture.Acid carrier modifier 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 modifier 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 3, Bi 2o 3.
Of the present invention one preferred aspect in, acidic catalyst comprises:
(i) the first metal that comprises VIII family metal,
(ii) the second metal that comprises copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel, and
(iii) acid carrier, the acid carrier material that it comprises chosen from Fe oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture.
Acid carrier can also comprise acid carrier modifier.
Of the present invention another preferred aspect in, acidic catalyst comprises:
(i) the first metal that comprises VIII family metal,
(ii) the second metal that comprises copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel, and
(iii) acid carrier that comprises carrier material and acid carrier modifier.
Preferred silica support materials is SS61138 high surface (HSA) the SiO 2 catalyst carrier from Saint-Gobain NorPro.Saint-Gobain NorProSS61138 silica is containing the high surface area silica of 95 % by weight of having 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 mensuration (mercuryintrusion porosimetry) to measure 3the average pore volume of/g, and about 0.352g/cm 3(22lb/ft 3) bulk density.
Preferred silica/alumina carrier material is KA-160 (Sud Chemie) silica spheres, and it has the nominal diameter of about 5mm, the density of about 0.562g/ml, about 0.583gH 2the absorptivity of O/g carrier, about 160-175m 2the surface area of/g and the pore volume of about 0.68ml/g.
Those of skill in the art would recognize that to carrier material, selecting to make caltalyst to tie up to for generating under the process conditions of ethanol has suitable activity, selective and robustness (robust).
The metal of catalyst can disperse to spread all over whole carrier, is coated on the outer surface of carrier (eggshell) or modifies (decorate) on carrier surface.
Be applicable to carbon monoxide-olefin polymeric of the present invention and preferably by the metal impregnation of modified support, form, although can also use for example chemical vapour deposition (CVD) of other method.This dipping technique is described in U.S. Patent No. 7,608, and 744, the U.S. announces in No.2010/0029995 and 2010/0197985, by reference they are incorporated in full herein.
As the skilled person will be readily appreciated, embodiment of the present invention can comprise the various reactor structures that use fixed bed reactors or fluidized-bed reactor.In many embodiments of the present invention, can use " thermal insulation " reactor; That is, have seldom or do not need the internal pipe arrangements (plumbing) through reaction zone add or remove and reduce phlegm and internal heat.In other embodiments, can use a reactor or a plurality of reactor of Radial Flow, or can use there is or do not have heat exchange, cooling or introduce the serial reaction device of other charging.Or, 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 heat exchanger.
In preferred embodiments, catalyst is used in the fixed bed reactors of for example pipeline or catheter shape, the reactant that typically wherein is steam form through or by described catalyst.Can use other reactor, for example fluid bed or fluidized bed reactor.In some cases, the pressure drop that hydrogenation catalyst can be combined with inert material to regulate reactant streams to pass through catalyst bed and the time of contact of reactant compound and catalyst granules.
Can in liquid phase or gas phase, carry out hydrogenation reaction.Preferably, in gas phase, under following condition, carry out this reaction.Reaction temperature can be 125 ℃-350 ℃, for example 200 ℃-325 ℃, 225 ℃-300 ℃ or 250 ℃-300 ℃.Pressure can be 10KPa-3000KPa (about 1.5-435psi), 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) give and to enter reactor.With regard to scope, GHSV can be 50hr -1-50,000hr -1, 500hr for example -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, with selected GHSV, carry out hydrogenation, although do not limit the higher pressure of use, should be understood that at high air speed 5000hr for example -1or 6,500hr -1the lower sizable pressure drop that may experience by reactor beds.
Thereby although this reacts every mole of acetic acid, consume 2 mol of hydrogen and produce 1 mole of ethanol, in incoming flow, the actual mol ratio of hydrogen and acetic acid can be approximately 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 time of staying also can vary widely, and these depend on the variable of amount as acetic acid, catalyst, reactor, temperature and pressure.When use except fixed bed antigravity system time, typical time of contact, at least for gas-phase reaction, be preferably 0.1-100 second time of contact for part is second to being greater than some hours, for example 0.3-80 second or 0.4-30 second.
The raw material, acetic acid and the hydrogen that about the inventive method, use can, derived from any suitable source, comprise natural gas, oil, coal, living beings etc.As an example, can produce acetic acid by carbonylation of methanol, oxidation of acetaldehyde, ethylene, oxidative fermentation and anaerobic fermentation.Due to oil and natural gas price fluctuation, more or less become expensive, so by substitute carbon source produce acetic acid and intermediate for example the method for methyl alcohol and carbon monoxide cause gradually concern.Especially, when oil and gas is compared when relatively costly, by the forming gas derived from any available carbon source (" synthesis gas "), produce acetic acid and may become favourable.For example, U.S. Patent No. 6,232,352 (by reference its disclosure being incorporated to herein) have instructed transformation methanol plant in order to manufacture the method for acetic acid.By transformation methanol plant, for new acetic acid factory, produce with CO that relevant substantial contribution expense is significantly reduced or eliminate to a great extent.Make all or part synthesis gas turn to and be supplied to separator unit with recovery CO and hydrogen from the synthetic loop of methyl alcohol, then by them for the production of acetic acid.Except acetic acid, this method can also be for the preparation of the available hydrogen of relevant the present invention.
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, by reference their disclosure is incorporated to herein.Optionally, alcohol production and this methanol carbonylation process can be integrated.
U.S. Patent No. RE 35,377 (being also incorporated to by reference herein) provides a kind of by making for example method of oil, coal, 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 natural gas by this process gas steam pyrolysis with formation synthesis gas.This synthesis 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 and U.S. Patent No. 6,685,754 disclose and a kind of useless living beings be converted into the method for synthesis gas by gasification, by reference their disclosure is incorporated to herein.
In an optional embodiment, can also comprise other carboxylic acid and acid anhydrides to the acetic acid that enters hydrogenation reaction, and acetaldehyde and acetone.Preferably, suitable acetic acid feed stream comprises one or more compounds that is selected from acetic acid, acetic anhydride, 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 carboxylic acid for example the existence of propionic acid or its acid anhydrides can be useful.
Or, can be directly from U.S. Patent No. 6,657, the acetic acid that the flash vessel of the class carbonylation of methanol unit described in 078 (by reference it being incorporated in full herein) takes out steam form is as crude product.For example, thick vapor product directly can not needed to condensation acetic acid and light fraction or removes and anhydrate to entering ethanol synthetic reaction district of the present invention, thereby saving overall craft expense.
Can make acetic acid gasify under reaction temperature, 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 the nitrogen of relative inertness, argon gas, helium, carbon dioxide.For reaction is moved in gas phase, answer the temperature in control system to make it not drop to the dew point lower than acetic acid.In one embodiment, can under specified pressure, make acetic acid in the gasification of acetic acid boiling point, then the acetic acid of gasification further can be heated to reactor inlet temperature.In another embodiment, by being passed in lower than the acetic acid at the temperature of acetic acid boiling point, hydrogen, circulating air, another kind of suitable gas or their mixture make acetic acid change vapor state into, thereby with the wetting carrier gas of acetic acid vapor, then the steam of mixing is heated to reactor inlet temperature always.Preferably, by making hydrogen and/or circulating air pass in or make acetic acid change steam into lower than the acetic acid at the temperature of 125 ℃, then the gaseous stream of merging is heated to reactor inlet temperature.
In various embodiments, the crude ethanol product being produced by method of hydrotreating, 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 5-70 % by weight ethanol and 5-35 % by weight water.In some exemplary, crude ethanol product for example comprises, based on this crude ethanol product gross weight meter 5 % by weight-70 % by weight, the ethanol of the amount of 10 % by weight-60 % by weight or 15 % by weight-50 % by weight.Preferably, crude ethanol product contains at least 10 % by weight ethanol, at least 15 % by weight ethanol or at least 20 % by weight ethanol.Depend on conversion ratio, crude ethanol product typically also will comprise unreacted acetic acid, for example, be less than 90 % by weight, for example, be less than 80 % by weight or be less than the amount of 70 % by weight.With regard to scope, unreacted acetic acid is preferably 0-90 % by weight, for example 5-80 % by weight, 15-70 % by weight, 20-70 % by weight or 25-65 % by weight.Because form water in course of reaction, water will be conventionally for example with 5-35 % by weight, as the amount of 10-30 % by weight or 10-26 % by weight is present in crude ethanol product.During acetic acid hydrogenation or by side reaction, also can produce ethyl acetate, and it can be for example with 0-20 % by weight, as the amount of 0-15 % by weight, 1-12 % by weight or 3-10 % by weight exists.By side reaction, also can produce acetaldehyde and its can be for example with 0-10 % by weight, as the amount of 0-3 % by weight, 0.1-3 % by weight or 0.2-2 % by weight exists.Other component is ester, ether, aldehyde, ketone, alkane and carbon dioxide for example, if can detect, can be altogether to be less than 10 % by weight, and the amount that is for example less than 6 % by weight or is less than 4 % by weight exists.With regard to scope, other component can be by 0.1-10 % by weight, and for example the amount of 0.1-6 % by weight or 0.1-4 % by weight exists.The exemplary of coarse ethanol compositing range is provided in table 1.
Fig. 1 has shown according to one embodiment of the invention and has been suitable for acetic acid hydrogenation and from the hydrogenation system 100 of crude product mixture separating alcohol.System 100 comprises reaction zone 101 and distillation zone 102.Reaction zone 101 comprises reactor 103, hydrogen feed line 104 and acetic acid feed pipeline 105.Distillation zone 102 comprises flash vessel 106, the first tower 107, the second tower 108 and the 3rd tower 109.By pipeline 104 and 105, hydrogen and acetic acid are flowed to produce vapor feed in being directed to the pipeline 111 of reactor 103 to entering evaporimeter 110 respectively.In one embodiment, pipeline 104 and 105 can merge and be for example common to entering evaporimeter 110 with a kind of material stream that contains hydrogen and acetic acid.In pipeline 111, the temperature of vapor feed stream is preferably 100 ℃-350 ℃, for example 120 ℃-310 ℃ or 150 ℃-300 ℃.As shown in fig. 1, any charging of not gasification is shifted out from evaporimeter 110, and can be recycled to wherein.In addition, although Fig. 1 has shown the top of pipeline 111 directed response devices 103, sidepiece, top or bottom that pipeline 111 can directed response device 103.Other modification and the other part of reaction zone 101 have been described in Fig. 2 A and 2B below.
Reactor 103 makes carboxylic acid containing being useful on, preferably the catalyst of acetic acid hydrogenation.In one embodiment, can use one or more protections bed (not shown) guard catalysts to avoid suffering charging or return/recycle stream in contained noxious material or less desirable impurity.This class protection bed can be used in vapor stream or liquid stream.Suitable protection bed material is known in this area and comprises for example carbon, silica, aluminium oxide, pottery or resin.On the one hand, make to protect bed medium functionalized to trap particular matter for example sulphur or halogen.During hydrogenation process, by pipeline 112, coarse ethanol product stream is preferably taken out from reactor 103 continuously.Can and give the condensation of coarse ethanol product stream and enter flash vessel 106, this so that provide steam flow and liquid stream.In one embodiment, flash vessel 106 preferably at 50 ℃-500 ℃, for example, operates at the temperature of 70 ℃-400 ℃ or 100 ℃-350 ℃.In one embodiment, the pressure of flash vessel 106 is preferably 50KPa-2000KPa, for example 75KPa-1500KPa or 100-1000KPa.In a preferred embodiment, the temperature and pressure of flash vessel is similar to the temperature and pressure of reactor 103.
The vapor stream of leaving flash vessel 106 can comprise hydrogen and hydrocarbon, can clean and/or turn back to reaction zone 101 by pipeline 113.As shown in fig. 1, the returning part of vapor stream merges through compressor 114 and with hydrogen feed, and common giving enters evaporimeter 110.
Liquid from flash vessel 106 is taken out and is pumped into by pipeline 115 as feed composition the sidepiece of the first tower 107 (also referred to as acid separation column).The content of pipeline 115 typically will be substantially similar to the product directly obtaining from reactor, and in fact can also be called crude ethanol product.Yet the feed composition in pipeline 115 does not preferably basically contain hydrogen, carbon dioxide, methane or ethane, they are moved out of by flash vessel 106.The exemplary compositions of liquid in pipeline 115 is provided in table 2.It should be understood that liquid line 115 can contain for example component in charging of other component (unlisted).
In whole the application's table, be less than (<) and if shown in amount be preferably not exist and can exist by trace or to be greater than the amount of 0.0001 % by weight.
" 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 group ethylether or their mixture." other alcohol " in table 2 can include but not limited to methyl alcohol, isopropyl alcohol, normal propyl alcohol, n-butanol or their mixture.In one embodiment, feed composition for example pipeline 115 can comprise propyl alcohol with the amount of 0.001-0.1 % by weight, 0.001-0.05 % by weight or 0.001-0.03 % by weight as isopropyl alcohol and/or normal 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.
In one embodiment, the conversion ratio of acetic acid can be greater than 95%, and the crude ethanol product in pipeline 115 can contain and is less than 5 % by weight acetic acid.In this embodiment, can skip over acid separation column 107 and pipeline 115 can be introduced directly into the second tower 108 (being also called light fraction tower herein).
In the embodiment shown in Figure 1A, the bottom that pipeline 115 is introduced to the first tower 107, for example Lower Half or lower 1/3rd.In the first tower 107, unreacted acetic acid, part water and other heavy component (if existence) composition from pipeline 115 is shifted out and preferably as residue, taken out continuously.Can make some or all residues return and/or recycle by pipeline 116 and get back to reaction zone 101.The first tower 107 has also formed overhead, it taken out in pipeline 117, and can be by it for example with 10: 1-1: 10, as 3: 1-1: 3 or 1: 2-2: 1 ratio condensation and backflow.
Any one in tower 107,108 or 109 can comprise any destilling tower that can carry out separation and/or purifying.Described tower preferably comprises and has 1-150 column plate, for example the plate 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 plate or any other suitable design known in the art.In other embodiments, can use packed tower.For packed tower, can use structured packing or random packing.Can by described tower or filler is arranged by a kind of continuous tower or they can be arranged to the steam making from first paragraph by two or more towers enter second segment and make to enter first paragraph from the liquid of second segment simultaneously, etc.
The relevant condenser that can use together with each destilling tower and fluid separation applications container can have any conventional design and be simplified in Fig. 1.As shown in fig. 1, heat supply can be supplied to recycle column bottoms stream to the bottom of each tower or by heat exchanger or reboiler.In some embodiments, 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 for example hot chemical method or the boiler of another kind of generation of external source.Although shown a reactor and a flash vessel in Fig. 1, can use in embodiments of the invention additional reactor, flash vessel, condenser, heating element heater and other parts.As those skilled in the art can recognize, various condensers, pump, compressor, reboiler, rotary drum, valve, connector, separation container of being generally used for carrying out chemical method etc. can also be combined and for method of the present invention.
Temperature and pressure used in any tower can change.As actual conditions, in these regions, can conventionally use the pressure of 10KPa-3000KPa, although can use in some embodiments subatmospheric pressure and superatmospheric pressure.Temperature in regional is in the common scope between the boiling point of the composition being removed as distillate and the boiling point of the composition that is removed as residue.Those skilled in the art will recognize that, in the destilling tower of operation, the temperature of given position depends at the material composition of this position and the pressure of tower.In addition, feed rate can depend on production technology scale and change, if be described, can generally refer to according to feed weight ratio.
When tower 107 operates under standard atmospheric pressure, the temperature of the residue leaving from tower 107 in pipeline 116 is preferably 95 ℃-120 ℃, for example 105 ℃-117 ℃ or 110 ℃-115 ℃.The temperature of the distillate leaving from tower 107 in pipeline 117 is preferably 70 ℃-110 ℃, for example 75 ℃-95 ℃ or 80 ℃-90 ℃.In other embodiments, the pressure of the first tower 107 can be 0.1KPa-510KPa, for example 1KPa-475KPa or 1KPa-375KPa.
The exemplary compositions of distillate and the residue composition of the first tower 107 is provided in following table 3.Should also be understood that described distillate and residue can also contain other unlisted component, for example component in charging.For convenient, distillate and the residue of the first tower may also be referred to as " the first distillate " or " the first residue ".The distillate of other tower or residue also can be mentioned to they are distinguished from each other out with similar digital modifier (second, third etc.), but this class modifier should not be interpreted as requiring any special separation sequence.
As shown in table 3, although it is not bound by theory, unexpected and unexpectedly find, while detecting the acetal of any amount in the charging that is being incorporated into acid separation column (the first tower 107), acetal seems in this tower to decompose and makes to exist in distillate and/or residue less or even there is no a detectable amount.
Depend on reaction condition, the crude ethanol product that leaves reactor 103 in pipeline 112 can comprise ethanol, acetic acid (unconverted), ethyl acetate and water.After leaving reactor 103, can there is non-catalytic balanced reaction joining between the component that wherein comprised before flash vessel 106 and/or the first tower 107 in crude ethanol product.As (reaction 2) shown below, this balanced reaction trends towards driving crude ethanol product to reach the balance between ethanol/acetic acid and ethyl acetate/water.
reaction 2
In this case, crude ethanol product is in guiding is for example temporarily stored in storage tank before distillation zone 102, so can meet with the time of staying of prolongation.Conventionally, the time of staying between reaction zone 101 and distillation zone 102 is longer, and ethyl acetate forms manyly.For example, when the time of staying between reaction zone 101 and distillation zone 102 is greater than 5 days, can form with the loss of ethanol significantly more ethyl acetate.Therefore, conventionally between 101He distillation zone 102, preferred reaction district the shorter time of staying so that the amount of the ethanol forming maximize.In one embodiment, storage tank (not shown) is included between reaction zone 101 and distillation zone 102 for interim storage and continues to many 5 days from the liquid component of pipeline 115, for example at the most 1 day or 1 hour at the most.In preferred embodiments, do not comprise tank and the liquid of condensation is direct to entering the first destilling tower 107.In addition the speed that, uncatalyzed reaction is carried out can improve along with the temperature of for example crude ethanol product in pipeline 115 and improve.Surpass 30 ℃, for example, surpassing 40 ℃ or surpass these reaction rates at the temperature of 50 ℃ and can have problems especially.Therefore, in one embodiment, the temperature of the liquid component in pipeline 115 or in optional storage tank is maintained in being less than 40 ℃, for example, be less than 30 ℃ or be less than the temperature of 20 ℃.Can reduce with one or more cooling devices the temperature of liquid in pipeline 115.
As discussed above, storage tank (not shown) can be included between reaction zone 101 and distillation zone 102 for optional that interim storage is from the liquid component of pipeline 115 1-24 hour for example at the temperature of approximately 21 ℃, and the ethyl acetate that corresponds respectively to 0.01 % by weight-1.0 % by weight forms.In addition the speed that, uncatalyzed reaction is carried out can improve along with the temperature of crude ethanol product and improve.For example, along with the crude ethanol product temperature in pipeline 115 is brought up to 21 ℃ from 4 ℃, form ethyl acetate speed can from approximately 0.01 % by weight/hour bring up to approximately 0.005 % by weight/hour.Therefore, in one embodiment, liquid component temperature in pipeline 115 or in optional storage tank is maintained in temperature and be less than 21 ℃, for example, be less than 4 ℃ or be less than-10 ℃.
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 by the distillate of tower 107 for example top stream carry out condensation and preferably with 1: 5-10: 1 reflux ratio refluxes.Distillate 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 separated.
The first distillate in pipeline 117 is incorporated into the second tower 108 (also referred to as " light fraction tower "), preferably at the mid portion of tower 108, for example middle 1/2nd or middle 1/3rd introduces.As an example, when when there is no to use the tower of 25 column plates in the tower of water extracting, pipeline 117 is introduced at column plate 17 places.In one embodiment, the second tower 108 can be extractive distillation tower.In this embodiment, can by extractant for example water join the second tower 108.If extractant comprises water, it can obtain or for example by optional pipeline 121 ', obtain from return/recirculation line of the inside from one or more other towers from external source.
The second tower 108 can be plate column or packed tower.In one embodiment, the second tower 108 is to have 5-70 column plate, for example the plate 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 residue that ought under atmospheric pressure leave from the second tower 108 in pipeline 118 is preferably 60 ℃-90 ℃, for example 70 ℃-90 ℃ or 80 ℃-90 ℃.The temperature of the second distillate leaving from the second tower 108 in pipeline 120 is preferably 50 ℃-90 ℃, for example 60 ℃-80 ℃ or 60 ℃-70 ℃.Tower 108 can under atmospheric pressure operate.In other embodiments, the pressure of the second tower 108 can be 0.1KPa-510KPa, for example 1KPa-475KPa or 1KPa-375KPa.The exemplary compositions of distillate and the residue composition of the second tower 108 is provided in following table 4.It should be understood that described distillate and residue can also contain other unlisted component, for example component in charging.
The weight ratio of the ethanol in the ethanol in the second residue and the second distillate is preferably at least 3: 1, and for example 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 residue and the second distillate is preferably and is less than 0.4: 1, for example, be less than 0.2: 1 or be less than 0.1: 1.Using water as the extraction column of extractant in the embodiment as the second tower 108, the weight ratio of the ethyl acetate in the ethyl acetate in the second residue and the second distillate approaches zero.
As shown, the second residue from the second tower 108 bottoms (it comprises second alcohol and water) is given and entered the 3rd tower 109 (also referred to as " product tower ") by pipeline 118.More preferably, the second residue in pipeline 118 is introduced to the bottom of the 3rd tower 109, for example Lower Half or lower 1/3rd.The 3rd tower 109 reclaims ethanol (being preferably pure substantially except azeotropic water content) with the distillate in pipeline 119.The distillate of the 3rd tower 109 is preferably pressed shown in Figure 1A, for example, with 1: 10-10: 1 as 1: 3-3: 1 or 1: 2-2: 1 reflux ratio refluxes.The 3rd residue in pipeline 121 (preferably mainly comprising water) preferably shifts out or can partly turn back to any part of system 100 from system 100.The 3rd tower 109 is preferably plate column as above and preferably under atmospheric pressure operation.The temperature of the 3rd distillate leaving from the 3rd tower 109 in pipeline 119 is preferably 60 ℃-110 ℃, for example 70 ℃-100 ℃ or 75 ℃-95 ℃.When this tower under atmospheric pressure operates, the temperature of leaving the 3rd residue of the 3rd tower 109 is preferably 70 ℃-115 ℃, for example 80 ℃-110 ℃ or 85 ℃-105 ℃.The exemplary compositions of distillate and the residue composition of the 3rd tower 109 is provided in following table 5.It should be understood that distillate and residue can also contain other unlisted component, for example component in charging.
In still-process, from any compound of charging or crude reaction product carrier band, conventionally in the gross weight based on the 3rd distillate composition, be less than 0.1 % by weight, the amount that is for example less than 0.05 % by weight or is less than 0.02 % by weight is retained in the 3rd distillate.In one embodiment, in any that one or more side line material streams can be from the tower 107,108 and/or 109 of system 100, remove impurity.Preferably use at least one side line material stream to remove impurity from the 3rd tower 109.Impurity can be cleaned and/or is retained in system 100.
Can use one or more additional piece-rate systems, for example destilling tower (as fine finishining tower) or molecular sieve are further purified the 3rd distillate in pipeline 119 to form absolute ethyl alcohol product stream, i.e. " finished product absolute ethyl alcohol ".
Turn back to the second tower 108, the distillate in pipeline 120 is preferably pressed shown in Fig. 1, for example, with 1: 10-10: 1, as 1: 5-5: 1 or 1: 3-3: 1 reflux ratio refluxes.In one embodiment, can all or part of distillate from the second tower 108 be recycled to reaction zone 101 by pipeline 120.As shown in fig. 1, all or part of distillate can be recycled to reactor 103 as shown in pipeline 120, and can jointly feed together with acetic acid feed pipeline 105.In one embodiment, the ethyl acetate in pipeline 120 is not accumulated in reaction zone 101 and/or distillation zone 102 due to the existence of the catalyst that comprises acid carrier.Due to the dynamic (dynamical) raising of balanced reaction, embodiment of the present invention can also be processed the ethyl acetate in charging and/or recycle stream.Therefore, due to the dynamics improving, can make the recirculation ethyl acetate in pipeline 120 be converted into ethanol, or the ethyl acetate producing can equal the ethyl acetate transforming, therefore will exist the concentration of the ethyl acetate of certain stable state of obtaining relatively fast and recirculation will keep constant; And be not accumulated in closed circuit.Can the part distillate from the second tower 108 be cleaned by pipeline 122.Optionally, as common unsettled U. S. application No.12/852, described in 269, (by reference it is incorporated in full herein), the second distillate in pipeline 120 can be used one or more other tower (not shown) to be further purified to remove for example acetaldehyde of impurity before turning back to reaction zone.
Fig. 2 A and 2B have shown respectively improved reaction zone 130 and 140.As discussed above, embodiments more of the present invention can be used a plurality of reactors.In the reaction zone 130 of Fig. 2 A, vapor feed stream 111 is given and entered the first reactor 131.Reactor effluent 133 is given and entered the second reactor 132.Preferably, reactor effluent 133 comprises ethanol and unreacted acetic acid and can have the composition described in as above table 1.Optionally, fresh reactant thing (not shown) can be given and entered the second reactor 132.The crude ethanol product of the second reactor 134 is given and entered flash vessel 106.For purpose of explanation, Fig. 2 A has shown 2 reactors.Yet, in other embodiments, can have more than 2 reactors, for example, more than 3 or more than 4.Each in the reactor 131 and 132 of Fig. 2 A operates in reaction condition mentioned above.
In the reaction zone 140 of Fig. 2 B, vapor feed stream 111 is given and entered the reactor 141 that comprises a plurality of conversion zones.Reactor 141 at least comprises the first conversion zone 142 and territory, second reaction zone 143.Each region can have different catalyst.As shown in Figure 2 B, the first conversion zone 142 and territory, second reaction zone 143 can separate in reactor 141.In other embodiments, the overlapping and catalyst separately in the first conversion zone 142 and territory, second reaction zone 143 can be dispersed between described region.Can by reactor 141 for example the crude ethanol product 144 of the second reactor area 143 give and enter flash vessel 106.142He region, region 143 operates in reaction condition as described above.
In preferred embodiments, different catalyst can be for each reactor of reaction zone 130 in Fig. 2 B or for each conversion zone of reaction zone 140 shown in Fig. 2 B.Different catalyst can have different metals and/or different carriers.In preferred embodiments, catalyst in the first reactor 131 or the first reactor area 142 can be U.S. Patent No. 7,608, Co catalysts described in 744, platinum/tin catalyst described in the open No.2010/0029995 of the U.S., or the metallic catalyst that comprises alkaline modifier described in the open No.2010/0197959 of the U.S., at this, by reference they are incorporated in full herein.
In some embodiments, the catalyst in the first reactor 131 or the first reactor area 142 is base catalyst.The suitable metallic catalyst that comprises alkaline modifier comprise have the first metal and optional bimetallic those.These metals can be with above about acid loaded catalyst of the present invention, described those be identical.Preferably, the first metal is VIII family metal, chosen from Fe, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.Optional the second metal preferably can be selected from copper, tin, cobalt, rhenium and nickel.Described catalyst can comprise 0.1-10 % by weight the first metal and 0.1-10 % by weight the second metal.
Suitable carrier material for example can comprise stable metal oxide base carrier or ceramic base carrier.Preferred carrier comprises that for example silica, 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, aluminium oxide, titanium dioxide, zirconia, magnesia, carbon, graphite, high surface graphitized carbon, active carbon and their mixture.
Catalyst carrier can be carried out modification with support modification agent.Preferably, support modification agent is the alkaline modifier with low volatility or non-volatility.This class alkalescence modifier for example can be selected from: (i) alkaline earth oxide, (ii) alkali metal 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 and metasilicate, can use the modifier of other type that comprises nitrate, nitrite, acetate and lactate.Preferably, support modification agent is selected from oxide and the metasilicate of arbitrary element in sodium, potassium, magnesium, calcium, scandium, yttrium and zinc, and aforesaid any mixture.Preferably, support modification agent is calcium silicates, more preferably calcium metasilicate (CaSiO 3).If support modification agent comprises calcium metasilicate, at least a portion of calcium metasilicate is preferably crystal form.In using the preferred embodiment of basic supports modifier, basic supports modifier is in based on total catalyst weight 0.1 % by weight-50 % by weight, and for example the amount of 0.2 % by weight-25 % by weight, 0.5 % by weight-15 % by weight or 1 % by weight-8 % by weight exists.
Acidic catalyst of the present invention is preferred in the second reactor 132 or the second reactor area 143.In an exemplary, the first reactor 131 or the first reactor area 142 can comprise SiO 2-CaSiO 3-Pt-Sn catalyst, and the second reactor 133 or the second reactor 143 can comprise SiO 2-TiO 2-Pt-Sn catalyst.In alternate embodiment, acidic catalyst can be in the first reactor 131 or the first reactor area 142.
Acetic acid conversion ratio in the first reactor 131 or the first reactor area 142 can be distinguished relatively lower than the acetic acid conversion ratio in the second reactor 132 or the second reactor area 143.The acetic acid conversion ratio of the first reactor 131 or the first conversion zone 142 can be at least 10%, for example at least 20%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%.In one embodiment, the acetic acid conversion ratio in the first reactor 131 or the first reactor area 142 is 10%-80% and lower than the conversion ratio of unreacted acetic acid in the second reactor 132 or the second reactor area 143.In the second reactor 132 or the second reactor area 143, can make the conversion ratio of unreacted acetic acid bring up at least 70%, for example at least 80% or at least 90%.Advantageously, in the first reactor 131 or the first reactor area 142, compared with low acetic acid conversion ratio, make the unreacted acid of the first reactor 131 or the first reactor area 142 in the second reactor 132 or the second reactor area 143, carry out hydrogenation and not add fresh acetic acid.
Total ethanol in the double-reactor region shown in the double-reactor shown in Fig. 2 A and/or Fig. 2 B can be selectively at least 65%, for example at least 70%, at least 80%, at least 85% or at least 90%.The ethyl acetate that can produce by the first reactor 131 or the first reactor area 142 can be consumed in the second reactor 132 or the second reactor area 143.
Finished product ethanol
The finished product ethanol composition obtaining by the inventive method for example preferably comprises, based on this finished product ethanol composition gross weight meter 75-96 % by weight ethanol, the ethanol of 80-96 % by weight or 85-96 % by weight.Exemplary finished product ethanol compositing range is provided in following table 6.
Finished product ethanol composition of the present invention preferably contains very low amount, for example, be less than other alcohol of 0.5 % by weight, for example methyl alcohol, butanols, isobutanol, isoamyl alcohol and other C 4-C 20alcohol.In one embodiment, in finished product ethanol, the amount of isopropyl alcohol is 80-1,000wppm, 95-1 for example, 000wppm, 100-700wppm or 150-500wppm.In one embodiment, finished product ethanol composition does not preferably basically contain acetaldehyde, can comprise the acetaldehyde that is less than 8wppm, for example, be less than 5wppm or be less than 1wppm.
The finished product ethanol composition of being produced by embodiment of the present invention can, for various application, comprise fuel, solvent, chemical raw material, drug products, cleaning agent, disinfectant, hydro-conversion or consumption.In fuel applications, can make this finished product ethanol composition and gasoline concoction for motor vehicles for example automobile, ship and small-sized piston engine aircraft.In on-fuel application, this finished product ethanol composition can be as the solvent of cosmetics and cosmetic formulations, detersive, disinfectant, coating, ink and medicine.This finished product ethanol composition can also be with dealing with solvent in the manufacture process of medicinal product, food preparation, dyestuff, photochemistry and latex processing.
This finished product ethanol composition can also be as chemical raw material to prepare other chemicals for example vinegar, ethyl acrylate, ethyl acetate, ethene, glycol ethers, ethamine, aldehyde and higher alcohol, particularly butanols.In the preparation of ethyl acetate, can be by this finished product ethanol composition with acid esterification or it is reacted with polyvinyl acetate.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 for example at common unsettled U. S. application No.12/221,137 and U. S. application No.12/221, those described in 138, are incorporated to their full content and disclosure herein by reference 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 modenite, 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, at this, by reference they is incorporated in full herein.
In order more effectively to understand invention disclosed herein, provide following examples below.
Embodiment
Embodiment 1
Comprising SiO 2-TiO 2under the acidic catalyst of (10 % by weight)-Pt (1.6 % by weight)-Sn (1.0 % by weight) exists by acetic acid hydrogenation.In reactor, at 200psig, 250 ℃, with this catalyst, carry out 2 rounds.First round is with 4500hr -1gHSV, second round is with 2200hr -1gHSV.In Fig. 3, the calculated results K balancebe 4, and K flat weighing apparatusbe 12.As shown in Figure 3, under lower acetic acid conversion ratio, the amount of ethyl acetate is greater than the amount of ethanol.Yet under higher acetic acid conversion ratio, balanced reaction dynamics unexpectedly makes ethyl acetate content reduce and improves ethanol content.Table 7 has gathered result.
Embodiment 2
Comprising SiO 2-TiO 2the acidic catalyst of (10 % by weight)-Pt (1.6 % by weight)-Sn (1.0 % by weight) and comprise SiO 2-Al 2o 3under the acidic catalyst of (7 % by weight)-Pt (1.6 % by weight)-Sn (1.0 % by weight) exists by acetic acid hydrogenation.Under different acetic acid transform levels, carry out every kind of hydrogenation several times.In Fig. 4, compared result.Under lower conversion ratio, SiO 2-Al 2o 3it is selective that (7 % by weight)-Pt (1.6 % by weight)-Sn (1.0 % by weight) catalyst demonstrates the ethanol of raising.Yet, under higher conversion ratio, SiO 2-TiO 2it is selective that (10 % by weight)-Pt (1.6 % by weight)-Sn (1.0 % by weight) catalyst demonstrates similar ethanol.In addition, unexpected and unexpectedly, under higher acetic acid conversion ratio, the productive rate of acidic catalyst demonstrates obvious improvement.
Embodiment 3
Under the following different reaction condition providing, also with some rounds, use the SiO that comprises from embodiment 2 in table 8 2-Al 2o 3the acidic catalyst of (7 % by weight)-Pt (1.6 % by weight)-Sn (1.0 % by weight) is by acetic acid hydrogenation.
Although describe the present invention in detail, various modifications 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 list of references above about background technology and detailed description, discussed, be all incorporated to their disclosure herein by reference.In addition, should understand below and/or the various piece of the various aspects of the present invention of quoting from appended claims and a plurality of embodiment and a plurality of features can partly or entirely combine or exchange.In the description of aforementioned each embodiment, as those skilled in the art can recognize, the embodiment 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 (31)

1. produce a method for ethanol, the method be included in catalyst exist under, under the pressure of the temperature of 250 ℃-300 ℃ and 100KPa-1500KPa, acetic acid hydrogenation is formed to ethanol, wherein by reactant with 1000hr -1-6500hr -1gas hourly space velocity feed, wherein acetic acid conversion ratio for be greater than 80% and ethanol be selectively at least 65%, wherein said catalyst is included in the first metal and the second metal on the carrier material of acid modification agent modification, described the first metal is selected from copper, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten, the second metal is selected from tin and rhenium, and condition is that the second metal is different from the first metal.
2. the process of claim 1 wherein that described carrier material is selected from silica, silica/alumina, calcium metasilicate, carbon, ferriferous oxide, aluminium oxide, titanium dioxide, zirconia and their mixture.
3. the method for claim 2, wherein said silica is selected from pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.
4. the process of claim 1 wherein that described acid modification agent is selected from the oxide of the oxide of IVB family metal, the oxide of VB family metal, the oxide of group vib metal, VIIB family metal, oxide, aluminum oxide and their mixture of VIIIB family metal.
5. the process of claim 1 wherein that described acid modification agent is selected from TiO 2, ZrO 2, Nb 2o 5, Ta 2o 5, Al 2o 3, B 2o 3, P 2o 5and Sb 2o 3.
6. the process of claim 1 wherein that described acid modification agent is selected from WO 3, MoO 3, Fe 2o 3, Cr 2o 3, V 2o 5, MnO 2, CuO, Co 2o 3, Bi 2o 3.
7. the process of claim 1 wherein that described catalyst comprises 0.1 % by weight-50 % by weight acid modification agent.
8. the process of claim 1 wherein that described catalyst comprises 25 % by weight-99 % by weight carrier materials.
9. the process of claim 1 wherein that described catalyst comprises 25 % by weight-99 % by weight acid carrier materials.
10. the process of claim 1 wherein that catalyst comprises 0.1-25 % by weight the first metal.
11. the process of claim 1 wherein that described the first metal is platinum, and the second metal is tin.
The method of 12. claims 11, wherein the mol ratio of platinum and tin is 0.4:0.6-0.6:0.4.
13. the process of claim 1 wherein that described the first metal is palladium, and the second metal is rhenium.
The method of 14. claims 13, wherein the mol ratio of rhenium and palladium is 0.7:0.3-0.85:0.15.
15. the process of claim 1 wherein that described catalyst comprises 0.1-10 % by weight the second metal.
16. the process of claim 1 wherein that described hydrogenation has that to be less than 35% ethyl acetate selective.
17. the process of claim 1 wherein that described hydrogenation carries out being greater than under the hydrogen of 4:1 and acetic acid mol ratio.
18. 1 kinds of methods of producing ethanol, the method comprises:
Under the first catalyst exists, acetic acid hydrogenation is formed to the intermediate product that comprises ethanol and unreacted acetic acid; And
Under the second catalyst exists, unreacted acetic acid hydrogenation is formed to ethanol, wherein the second catalyst is different from the first catalyst, wherein said the second catalyst is included in the first metal and the second metal on acid carrier, described the first metal chosen from Fe, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten, the second metal is selected from molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel, condition is that the second metal is different from the first metal, and described acid carrier is selected from:
The acid carrier material of chosen from Fe oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture, and
Carrier material with acid modification agent modification.
The method of 19. claims 18 is wherein carried out the hydrogenation of acetic acid in the first reactor, carries out the hydrogenation of unreacted acetic acid in the second reactor.
The method of 20. claims 19 wherein makes at least 10% acetic acid conversion in the first reactor, makes at least 70% unreacted acetic acid conversion in the second reactor.
21. 1 kinds of methods of producing ethanol, the method comprises:
In reactor, under the first catalyst and the existence of the second catalyst, acetic acid hydrogenation is formed to ethanol, wherein the second catalyst is different from the first catalyst, wherein said the second catalyst is included in the first metal and the second metal on acid carrier, described the first metal chosen from Fe, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten, the second metal is selected from molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel, condition is that the second metal is different from the first metal, and described acid carrier is selected from:
The acid carrier material of chosen from Fe oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture, and
Carrier material with acid modification agent modification.
The method of 22. claims 21, wherein said the first catalyst is in the first reactor area, and the second catalyst is in the second reactor area, and wherein the firstth district and Second Region separate.
23. claims 18 or 21 method, wherein said the first catalyst comprises and contains one or more metals, containing the catalyst of silicon carrier and at least one basic supports modifier.
The method of 24. claims 23, wherein said at least one basic supports modifier is selected from (i) alkaline earth oxide, (ii) alkali metal 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.
The method of 25. claims 23, the wherein said silicon carrier that contains is selected from silica, silica/alumina, calcium metasilicate and their mixture.
The method of 26. claims 25, wherein said silica is selected from pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.
27. 1 kinds of methods that reclaim ethanol, the method comprises
In comprising the reactor of catalyst, acetic acid feed stream hydrogenation is formed to crude ethanol product, wherein said catalyst is included in the first metal on acid carrier, and described acid carrier is selected from:
The acid carrier material of chosen from Fe oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture, and
Carrier material with acid modification agent modification;
At least part of crude ethanol product is separated into the first distillate that comprises ethanol, water and ethyl acetate in the first tower, and the first residue that comprises acetic acid;
The second residue that in the second tower, at least part of the first distillate is separated into the second distillate that comprises ethyl acetate and comprises second alcohol and water;
Make at least part of the second distillate turn back to described reactor; And
At least part of the second residue is separated into the 3rd distillate that comprises ethanol and the 3rd residue that comprises water in the 3rd tower.
The method of 28. claims 27, wherein said acetic acid feed stream comprises one or more compounds that are selected from acetic acid, acetic anhydride, acetaldehyde, ethyl acetate and their mixture.
The method of 29. claims 27, at least a portion of wherein said crude ethanol product comprises acetic acid.
The method of 30. claims 27, the method also comprises makes at least part of the first residue turn back to described reactor directly or indirectly, and wherein said the first residue comprises the acetic acid based on this first residue gross weight meter 60-100 % by weight.
The method of 31. claims 27, wherein said the second distillate comprises 10-90 % by weight ethyl acetate.
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US12/588,727 US8309772B2 (en) 2008-07-31 2009-10-26 Tunable catalyst gas phase hydrogenation of carboxylic acids
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US30081510P 2010-02-02 2010-02-02
US12/699,024 2010-02-02
US12/698,947 US8471075B2 (en) 2008-07-31 2010-02-02 Processes for making ethanol from acetic acid
US12/698,947 2010-02-02
US61/300,815 2010-02-02
US12/699,024 US8680317B2 (en) 2008-07-31 2010-02-02 Processes for making ethyl acetate from acetic acid
US33269910P 2010-05-07 2010-05-07
US33269610P 2010-05-07 2010-05-07
US61/332,699 2010-05-07
US61/332,696 2010-05-07
US12/852,269 US8304586B2 (en) 2010-02-02 2010-08-06 Process for purifying ethanol
US12/852,269 2010-08-06
US12/852,227 2010-08-06
US12/852,227 US8309773B2 (en) 2010-02-02 2010-08-06 Process for recovering ethanol
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