CN102307657A

CN102307657A - Process for making ethanol from acetic acid using acidic catalysts

Info

Publication number: CN102307657A
Application number: CN2010800039285A
Authority: CN
Inventors: R·耶夫蒂奇; V·J·约翰斯顿; R·J·沃纳; H·魏纳
Original assignee: Celanese International Corp
Current assignee: Celanese International Corp
Priority date: 2009-10-26
Filing date: 2010-10-26
Publication date: 2012-01-04
Anticipated expiration: 2030-10-26
Also published as: RU2012121872A; WO2011056597A2; EP2493610A2; KR20120086717A; WO2011056597A3; CN102307657B; BR112012009824A2; JP2013508424A; NZ599463A; CA2778959A1; AU2010315554A1; MX2012004842A; ZA201202850B

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 to prepare the method for ethanol by acetate

Priority request

The application requires the priority of following application: the U. S. application No.12/588 that on October 26th, (1) 2009 submitted to, 727; The U. S. application No.12/698 that on February 2nd, (2) 2010 submitted to, 947; The U. S. application No.12/699 that on February 2nd, (3) 2010 submitted to, 024; The U.S. Provisional Application No.61/300 that on February 2nd, (4) 2010 submitted to, 815; The U.S. Provisional Application No.61/332 that on May 7th, (5) 2010 submitted to, 696; The U.S. Provisional Application No.61/332 that on May 7th, (6) 2010 submitted to, 699; The U. S. application No.12/852 that on August 6th, (7) 2010 submitted to, 269; The U. S. application No.12/852 that on August 6th, (8) 2010 submitted to, 227.The U. S. application No.12/588 that on October 26th, 2009 submitted to, 727 is the U. S. application No.12/221 that submitted on July 31st, 2008,141 continuation part.Incorporate these applications into this paper in full by reference.

Invention field

Present invention relates in general to produce the method for ethanol, particularly use acidic catalyst to produce the method for ethanol by acetic acid hydrogenation.

Background of invention

The ethanol that is used for industrial use according to routine by for example oil, natural gas or coal production of petrochemical materials, by for example synthesis gas production of raw material midbody, perhaps by starchiness material or cellulosic material for example corn (corn) or sugarcane production.Comprise that by petrochemical materials and by the conventional method of cellulosic material production ethanol 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 be than bigger in the past.Starchiness material and cellulosic material are converted into ethanol through fermentation.Yet fermentation is generally used for fuel and uses or consume the consumer production with ethanol.In addition, the fermentation of starchiness or cellulosic material and food source constitute competition and to be used for industrial use the amount of producible ethanol applied restriction.

Also original production ethanol through alkanoic acid and/or other carbonyl containing compound obtains broad research, in document, has mentioned the various combinations of catalyst, carrier and operating condition.For example between the reduction period of acetate, other compound generates with ethanol or generates with side reaction at alkanoic acid.These impurity and by-products limit ethanol production and from the recovery of this type reactant mixture.For example, during hydrogenation, the ester of generation forms the azeotropic mixture that is difficult to separate with ethanol and/or water.In addition, when conversion was incomplete, unreacted acid was retained in the coarse ethanol product, it must be removed to reclaim ethanol.

Therefore, still need the improved also method of original production ethanol of alkanoic acid of passing through, this method produces the coarse 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; This method is included in the catalyst existence and down acetic acid hydrogenation is formed ethanol; Wherein said hydrogenation has at least 65% ethanol selectivity; Wherein said catalyst is included in first metal on the acid carrier; Said 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 second embodiment, the present invention relates to produce the method for ethanol, this method comprises: in the presence of first catalyst, acetic acid hydrogenation is formed the intermediate product that comprises ethanol and unreacted acetate; In the presence of second catalyst, unreacted acetic acid hydrogenation is formed ethanol.Said first catalyst comprises and contains one or more metals, contains the catalyst of silicon carrier and at least a basic supports modifier.Said second catalyst is included in first metal on the acid carrier; Said 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 present invention relates to produce the method for ethanol, this method comprises: in reactor, in the presence of first catalyst and second catalyst, acetic acid hydrogenation is formed ethanol.Said first catalyst can be in first reactor area and said second catalyst can be in second reactor area that separates with said first reactor area.Said first catalyst comprises and contains one or more metals, contains the catalyst of silicon carrier and at least a basic supports modifier.Said second catalyst is included in first metal on the acid carrier; Said 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, this method is included in the reactor that comprises catalyst the acetic acid feed stream hydrogenation is formed the coarse ethanol product.Said catalyst is included in first metal on the acid carrier; Said 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.This method is included in also in first tower at least that part coarse ethanol product separates into first distillate that comprises ethanol, water and ethyl acetate, and first residue that comprises acetate; At least part first distillate separates into second distillate that comprises ethyl acetate and second residue that comprises the second alcohol and water in second tower; Making at least, part second distillate turns back to said reactor; And part second residue separates into the 3rd distillate that comprises ethanol and the 3rd residue that comprises water at least in the 3rd tower.

The acid modification agent that is used for embodiment of the present invention is preferably selected from the oxide of the oxide of IVB family metal, VB family metal, the oxide of group vib metal, the oxide of VIIB family metal, oxide, aluminum oxide and their mixture of VIIIB family metal.

Accompanying drawing is briefly described

Describe the present invention below with reference to the accompanying drawings in detail, wherein identical numeral is indicated similar parts.

Fig. 1 is the sketch map of hydrogenation system according to an embodiment of the invention.

Fig. 2 A is the sketch map of the reaction zone with double-reactor according to an embodiment of the invention.

Fig. 2 B is the sketch map of the reaction zone with reactor according to another embodiment of the invention, and said reactor has two reactor area.

Fig. 3 is the coordinate diagram according to the acetate conversion ratio of the embodiment of the invention.

Fig. 4 is the coordinate diagram according to the acetate conversion ratio of the different catalysts of the embodiment of the invention.

Detailed Description Of The Invention

The present invention relates to produce the method for ethanol and reclaim the method for ethanol from the coarse ethanol product.In one embodiment, thick acetic acid product is produced the method for hydrotreating of acetic acid hydrogenation down through being included in the acidic catalyst existence.In one embodiment, said acidic catalyst is included in first metal of acid carrier.In one embodiment, said acidic catalyst is included in first metal and the acid carrier modifier on the carrier.

During acetic acid hydrogenation, there is other side reaction that produces impurity and accessory substance.A main side reaction is the balanced reaction that also takes place between acetate/ethanol and the ethyl acetate/water.These two main reactions are:

reaction 1

Reaction 2

Reaction 2 is reversible and equilibrium constant K _BalanceProvide through following equation 1:

Equation 1

Usually, for producing ethanol, help first reaction than reaction condition with second reacting phase that consumes the ethyl acetate accessory substance in ethanol and the raising coarse ethanol product.In the open No.2010/0197985 (incorporating it into this paper in full by reference) of the U.S., the catalyst that comprises alkaline modifier through use helps and promotes first reaction.

In some embodiments, the present invention uses acidic catalyst, and this acidic catalyst preferably is contained in first metal on the acid carrier.Though do not accept the opinion constraint, think in the presence of acid, to promote second reaction.Equally in gas phase, think K under higher temperature _BalanceReduce.In embodiments of the invention, K _BalanceCan be less than 20, for example, less than 15 or less than 12.Preferably, K _BalanceCan be less than 6, for example less than 4 or less than 3.Like this, acidic catalyst has improved the forward and the backward reaction speed of this balanced reaction.K therein _BalanceIn＞1 the embodiment and under the reaction condition that helps high acetate conversion ratio, the selectivity of ethanol unexpectedly and unexpectedly high.Ethanol yield also improves under high conversion.Improve the amount that conversion ratio and ethanol selectivity advantageously reduce accessory substance in the coarse ethanol product, consequently, can improve the efficient that reclaims ethanol.

With regard to the present invention, term " conversion ratio " is meant the amount of the acetate that is converted into the compound except that acetate in the charging.Conversion ratio is by representing based on the mole percent of acetate in the charging.Selectivity is by representing based on the mole percent of the acetate that transforms.Should understand that the every kind of compound that is transformed by acetate has independently selectivity and this selectivity does not rely on conversion ratio.For example, if 50 moles of % of the acetate that is transformed are converted into ethanol, then the ethanol selectivity is 50%.

Under lower acetate conversion ratio, for example less than about 50%, acidic catalyst tends to demonstrate the selectivity that is compared to the high raising of ethanol for ethyl acetate.Therefore, in some embodiments of the present invention, the producing and ethanol of making a living, the conversion ratio of acetate is preferably greater than 70%, for example greater than 80%, greater than 90% or greater than 95%.

In the method for the invention, the selectivity of ethanol is preferably at least 65%, and for example at least 70%, at least 80%, at least 85%, or at least 90%.About 70% than the low acetate conversion ratio under, the selectivity of ethanol can be about 30%-40%.Preferably, along with the acetate conversion ratio improves, the selectivity of ethanol also improves.In addition, the selectivity of ethyl acetate can be low, for example less than 35%, less than 30%, less than 10% or less than 5%.Preferably, this hydrogenation process also has the product the do not expected low selectivity of methane, ethane and carbon dioxide for example.To these product selectivity of not expecting preferably less than 4%, for example less than 2% or less than 1%.More preferably, these products of not expecting are not easy to detect at the coarse ethanol product.The formation of alkane can be low.Ideally, the acetate that passes catalyst less than 2% for example less than 1% or be converted into alkane less than 0.5%.

Embodiment of the present invention provide the alcohol yied that improves under high acetate conversion ratio.When the acetate conversion ratio was preferably greater than 90%, the selectivity of ethanol was preferably at least 70%.Selectivity can continue along with the raising of acetate conversion ratio to improve.

Be meant during the hydrogenation the for example gram number of ethanol of every kilogram of per hour formed regulation product of catalyst system therefor like term used herein " productive rate ".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, said productive rate is preferably per hour 200-3 of every kg catalyst, 000 gram ethanol, 400-2 for example, 500 or 600-2,000.

Embodiment of the present invention provide the productivity ratio that improves under high acetate conversion ratio.Under the acetate conversion ratio more than 70%, ethanol yield is per hour at least 350 gram ethanol of every kg catalyst.Productive rate can continue along with the raising of acetate conversion ratio to improve.

In the presence of acidic catalyst, carry out acetic acid hydrogenation and form the second alcohol and water.In one embodiment, hydrogenation catalyst is included in first metal and optional one or more second metals, the 3rd metal or other metal on the acid carrier.First can be selected from the second and the 3rd optional metal: IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII group 4 transition metal, lanthanide series metal, actinide metals or be selected from the metal of any family in IIIA, IVA, VA and the VIA family.Preferable alloy combination with regard to the certain exemplary carbon monoxide-olefin polymeric 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 also is described in U.S. Patent No. 7,608,744 and u. s. published No.2010/0029995 and 2010/0197985 in, incorporate them into this paper in full by reference.

In an exemplary, this catalyst comprises first metal that is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten.Preferably, first metal is selected from platinum, palladium, cobalt, nickel and ruthenium.More preferably, first metal is selected from platinum and palladium.When first metal comprised platinum, because to the high demand of platinum, catalyst preferably comprised less than 5 weight % for example less than 3 weight % or less than the platinum of the amount of 1 weight %.

Shown in above, this catalyst is optional also to comprise second metal, and this second metal can play promoter usually.If exist, 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, second metal is selected from copper, tin, cobalt, rhenium and nickel.More preferably, second metal is selected from tin and rhenium.

If this catalyst comprises two kinds or more kinds of metal, for example first metal and second metal, then first metal choose wantonly in catalyst with 0.1-10 weight % for example the amount of 0.1-5 weight % or 0.1-3 weight % exist.Second metal preferably with 0.1-20 weight % for example the amount of 0.1-10 weight % or 0.1-5 weight % exist.In one embodiment, can reduce the metal carrying capacity of acidic catalyst.This can advantageously reduce the catalyst relevant expense higher with the metal carrying capacity.Therefore, in the embodiment of the metal carrying capacity with reduction, first metal can second metal can exist by the amount of 0.1-1.3 weight % by the amount existence of 0.1-1.7 weight %.For the catalyst that comprises two kinds or more kinds of metals, said two kinds or more kinds of metal be alloying or can comprise non-metal of alloying solid solution or mixture each other.

Preferred metal ratio can depend on metal used in the catalyst and change.In the certain exemplary embodiment, the mol ratio of first metal and second metal is 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 is the selectivity that helps ethanol at catalyst, the 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 about 1: 1.In another embodiment; Catalyst comprises in the embodiment of rhenium and palladium for helping the selectivity to ethanol therein; The Re/Pd mol ratio is preferably 0.6: 0.4-0.85: 0.15, for example 0.7: 0.3-0.85: 0.15, and perhaps about 0.75: 0.25 mol ratio.

This catalyst can also comprise the 3rd metal, and the 3rd metal is selected from above about the listed any metal of first or second metal, as long as the 3rd metal is different from 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 weight %, for example 0.1-3 weight % or 0.1-2 weight %.

In some embodiments, except that 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 is regulated the acidity of carrier material.The gross weight of the carrier material of carrier material or modification is preferably 75 weight %-99.9 weight % based on this total catalyst weight meter, for example 78 weight %-97 weight % or 80 weight %-95 weight %.In the embodiment of using the modified support material; Catalyst can comprise based on this total catalyst weight meter 0.1 weight %-50 weight %, for example the support modification agent of the amount of 0.2 weight %-25 weight %, 0.5 weight %-15 weight % or 1 weight %-8 weight %.

The suitable carriers material can comprise for example 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, can use the acid carrier material for this catalyst.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 the support modification agent.Preferably, with acid carrier modifier will be alkalescence or neutral catalyst carrier material for example silica, metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide, carbon or their mixture carry out modification.The acid carrier material can also carry out modification with acid carrier modifier.In some embodiments, acid carrier modifier is regulated carrier material through the quantity or the accessibility that improve the acid position.Acidic site promotes the kinetic rate of esterification balance.Preferably, the 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 the oxide of IVB family metal, 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.The 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) comprise first metal of VIII family metal,

Second metal that (ii) comprises copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel, and

(iii) acid carrier, it comprises the acid carrier material of 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) comprise first metal of VIII family metal,

The acid carrier that (iii) 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 contains the high surface area silica of the 95 weight % that have an appointment; About 250m ²The surface area of/g; The mean pore sizes of about 12nm; Through the about 1.0cm that presses mercury hole mensuration (mercury intrusion porosimetry) to measure ³The average pore volume of/g and about 0.352g/cm ³(22lb/ft ³) bulk density.

Preferred silica 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 carrier material selected to make caltalyst tie up to and be used to generate under the process conditions of ethanol and have suitable activity, selectivity 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 that carbon monoxide-olefin polymeric of the present invention preferably forms through the metal impregnation of modified support, although can also use the for example chemical vapour deposition (CVD) of other method.This dipping technique is described in U.S. Patent No. 7,608, and 744, among the u. s. published No.2010/0029995 and 2010/0197985, incorporate them into this paper in full by reference.

To recognize easily that like those skilled in the art 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 the internal pipe arrangements (plumbing) that need not pass reaction zone adds or removes and reduce phlegm and internal heat.In other embodiments, can use a reactor or a plurality of reactor of Radial Flow, perhaps can use the serial reaction device that has or do not have heat exchange, cooling or introduce other charging.Perhaps, can use the shell-tube type reactor that is equipped with heat transmission medium.In many situations, reaction zone can be contained in the single container or between have in the series containers of heat exchanger.

In preferred embodiments, catalyst uses in the fixed bed reactors of for example pipeline or catheter shape, and the reactant that wherein typically is the steam form passes or through said catalyst.Can use other reactor, for example fluid bed or fluidized bed reactor.In some situations, hydrogenation catalyst can be used in combination with inert material with the conditioned reaction streams through the pressure drop of 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 with reactant with greater than 500hr ^-1, for example greater than 1000hr ^-1, greater than 2500hr ^-1Or 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

Choose wantonly just being enough to overcome under the pressure of the pressure drop of passing catalytic bed and carry out hydrogenation, use higher pressure, should be understood that at high air speed 5000hr for example although do not limit with selected GHSV ^-1Or 6,500hr ^-1Possibly experience sizable pressure drop down through reactor beds.

Thereby produce 1 mole of ethanol though the every mole of acetic acid of this reaction consumes 2 mol of hydrogen, the actual mol ratio of hydrogen and acetate can be about 100 in the incoming flow: 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 acetate is greater than 2: 1, for example greater than 4: 1 or greater than 8: 1.

The contact or the time of staying also can vary widely, and these depend on the variable of amount like acetate, catalyst, reactor, temperature and pressure.When the antigravity system that uses except that fixed bed, be that part second is arrived greater than some hrs typical time of contact, and at least for gas-phase reaction, preferably be 0.1-100 second time of contact, for example 0.3-80 second or 0.4-30 second.

About the employed raw material of the inventive method, acetate and hydrogen can comprise natural gas, oil, coal, living beings etc. derived from any suitable source.As an example, can produce acetate through carbonylation of methanol, oxidation of acetaldehyde, ethene oxidation, oxidative fermentation and anaerobic fermentation.Because the oil and natural gas price fluctuation, more or less become expensive, so by substitute carbon source produce acetate and intermediate for example the method for methyl alcohol and carbon monoxide cause concern gradually.Especially, when oil is compared with natural gas when relatively costly, possibly become favourable by producing acetate derived from the forming gas (" synthesis gas ") of any available carbon source.For example, U.S. Patent No. 6,232 was instructed and has been transformed methanol plant in order to make the method for acetate 352 (incorporating its disclosure into this paper by reference).Through transforming methanol plant,, be significantly reduced or elimination to a great extent with the relevant substantial contribution expense of CO generation for new acetate factory.Make all or part synthesis gas turn to and supply to separator unit to reclaim CO and hydrogen, then they are used to produce acetate from the synthetic loop of methyl alcohol.Except that acetate, this method can also be used to prepare 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, incorporate their disclosure into this paper by reference.Randomly, alcohol production and this methanol carbonylation process can be integrated.

It is a kind of through making the for example method of oil, coal, natural gas and conversion of biomass material production methyl alcohol of carbonaceous material that U.S. Patent No. RE 35,377 (also incorporating it into this paper by reference) provides.This method comprises makes solid and/or the hydrogasification of liquid carbon-containing material to obtain process gas, with other natural gas with this process gas steam pyrolysis with the formation synthesis gas.This synthesis gas is converted into the methyl alcohol that can carbonyl turns to acetate.This 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 a kind of living beings of will giving up and be converted into the method for synthesis gas through gasification, incorporate their disclosure into this paper by reference.

In an optional embodiments, can also comprise other carboxylic acid and acid anhydrides for the acetate that enters hydrogenation reaction, and acetaldehyde and acetone.Preferably, suitable acetic acid feed stream comprises the compound that one or more are selected from acetate, acetic anhydride, acetaldehyde, ethyl acetate and their mixture.In the method for the invention can also be with these other compound hydrogenation.In some embodiments, in propyl alcohol production carboxylic acid for example the existence of propionic acid or its acid anhydrides can be useful.

Perhaps, can be directly from U.S. Patent No. 6,657, the flash vessel of one type of carbonylation of methanol unit described in 078 (incorporating it into this paper in full by reference) takes out the acetate of steam form as crude product.For example, can directly not need condensation acetate and light fraction perhaps to remove thick vapor product and anhydrate, thereby save the overall craft expense to entering ethanol synthetic reaction district of the present invention.

Can make acetate in the reaction temperature gasified, then can with the acetate of gasification in company with undiluted state or with the carrier gas of relative inertness for example the hydrogen of dilutions such as nitrogen, argon gas, helium, carbon dioxide feed together.Move for making to be reflected in the gas phase, the temperature in should the control system makes it not drop to the dew point that is lower than acetate.In one embodiment, can under specified pressure, make acetate, the acetate of gasification further can be heated to reactor inlet temperature then in the gasification of acetate boiling point.In another embodiment; Acetate through hydrogen, circulating air, another kind of suitable gas or their mixture are passed under the temperature that is lower than the acetate boiling point makes acetate change vapor state into; Thereby, then the steam that mixes is heated to reactor inlet temperature always with the wetting carrier gas of acetic acid vapor.Preferably, make acetate change steam into through the acetate that hydrogen and/or circulating air is passed be in or be lower than under 125 ℃ the temperature, then the gaseous stream that will merge is heated to reactor inlet temperature.

In various embodiments, the coarse ethanol product that produces by method of hydrotreating, any for example handle purifying subsequently and separate before, will typically comprise unreacted acetate, second alcohol and water.As used herein, term " coarse ethanol product " is meant any composition that comprises 5-70 weight % ethanol and 5-35 weight % water.In the certain exemplary embodiment, the coarse ethanol product comprises based on this coarse ethanol product gross weight meter 5 weight %-70 weight %, the for example ethanol of the amount of 10 weight %-60 weight % or 15 weight %-50 weight %.Preferably, the coarse ethanol product contains at least 10 weight % ethanol, at least 15 weight % ethanol or at least 20 weight % ethanol.Depend on conversion ratio, the coarse ethanol product typically also will comprise unreacted acetate, for example less than 90 weight %, for example less than 80 weight % or less than the amount of 70 weight %.With regard to scope, unreacted acetate is preferably 0-90 weight %, for example 5-80 weight %, 15-70 weight %, 20-70 weight % or 25-65 weight %.Because in course of reaction, form water, water will be usually for example with 5-35 weight %, is present in the coarse ethanol product like the amount of 10-30 weight % or 10-26 weight %.During acetic acid hydrogenation or through side reaction, also can produce ethyl acetate, and it can be for example with 0-20 weight %, like the amount existence of 0-15 weight %, 1-12 weight % or 3-10 weight %.Also can produce acetaldehyde and its through side reaction can be for example with 0-10 weight %, exists like the amount of 0-3 weight %, 0.1-3 weight % or 0.2-2 weight %.Other component is ester, ether, aldehyde, ketone, alkane and carbon dioxide for example, if can detect, can be altogether with less than 10 weight %, for example exist less than 6 weight % or less than the amount of 4 weight %.With regard to scope, other component can be by 0.1-10 weight %, and for example the amount of 0.1-6 weight % or 0.1-4 weight % exists.The exemplary of coarse ethanol compositing range is provided in the 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, first tower 107, second tower 108 and the 3rd tower 109.Through

pipeline

104 and 105 hydrogen and acetate are flowed in the pipeline 111 that is directed to reactor 103, to produce vapor feed to entering evaporimeter 110 respectively.In one embodiment,

pipeline

104 and 105 can merge and for example enter evaporimeter 110 with a kind of common giving of materials flow of containing hydrogen and acetate.The temperature of vapor feed stream is preferably 100 ℃-350 ℃, for example 120 ℃-310 ℃ or 150 ℃-300 ℃ in the pipeline 111.As shown in fig. 1, will shift out from evaporimeter 110 less than any charging of gasification, and it can be recycled to wherein.In addition, though 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 other part of reaction zone 101 have been described among Fig. 2 A and the 2B below.

Reactor 103 contains to be useful on makes carboxylic acid, the catalyst of preferred acetic acid hydrogenation.In one embodiment, can use one or more protection bed (not shown) guard catalysts to avoid suffering charging or return/contained noxious material or the impurity of not expecting in the recycle stream.This type protection bed can use 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 the protection bed medium functionalized to capture particular matter for example sulphur or halogen.During hydrogenation process, coarse ethanol product stream is preferably taken out from reactor 103 continuously through pipeline 112.Can and give the condensation of coarse ethanol product stream and enter flash vessel 106, this so that steam flow is provided and liquid stream.In one embodiment, flash vessel 106 is for example operated under 70 ℃-400 ℃ or 100 ℃-350 ℃ the temperature preferably at 50 ℃-500 ℃.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, it can be cleaned and/or turns back to reaction zone 101 through pipeline 113.As shown in fig. 1, the returning part of vapor stream passes compressor 114 and merges with hydrogen feed, and common giving enters evaporimeter 110.

To be pumped into the sidepiece of first tower 107 (being also referred to as acid separation column) from the liquid taking-up of flash vessel 106 and as feed composition through pipeline 115.The content of pipeline 115 typically will be substantially similar to the product that directly obtains from reactor, and in fact can also be called the coarse ethanol product.Yet the feed composition in the pipeline 115 preferably is substantially free of hydrogen, carbon dioxide, methane or ethane, and they are moved out of through flash vessel 106.The exemplary compositions of liquid in the pipeline 115 is provided in the table 2.It should be understood that liquid line 115 can contain the for example component in the charging of other component (unlisted).

In whole the application's table less than (＜) if shown in amount be preferably not exist and exist then can exist by trace or with amount greater than 0.0001 weight %.

" other ester " in the 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 the table 2 can include but not limited to Anaesthetie Ether, methyl ethyl ether, isobutyl group ethylether or their mixture." other alcohol " in the 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 such as isopropyl alcohol and/or normal propyl alcohol with the amount of 0.001-0.1 weight %, 0.001-0.05 weight % or 0.001-0.03 weight %.Should be understood that these other components can carrier band any distillating in logistics or the residual stream described herein, and unless otherwise indicated, this paper will not be further described.

In one embodiment, the conversion ratio of acetate can be greater than 95%, and the coarse ethanol product in the pipeline 115 can contain less than 5 weight % acetate.In this embodiment, can skip over acid separation column 107 and pipeline 115 can be introduced directly into second tower 108 (this paper also is called light fraction tower).

In the embodiment shown in Figure 1A, with the bottom of pipeline 115 introducings first tower 107, for example Lower Half or following 1/3rd.In first tower 107, unreacted acetate, part water and other heavy component (if existence) composition from pipeline 115 is shifted out and preferably takes out as residue continuously.Can make some or all residue return and/or recycle through pipeline 116 and get back to reaction zone 101.First tower 107 has also formed overhead, it taken out in pipeline 117, and can be with it for example with 10: 1-1: 10, as 3: 1-1: 3 or 1: 2-2: 1 ratio condensation and backflow.

In the tower 107,108 or 109 any one can comprise can separate and/or any destilling tower of purifying.Said 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.Said tower or filler can be arranged by a kind of continuous tower or they can be arranged by two or more towers and make and get into second section and make liquid get into first section simultaneously from second section from first section steam, or the like.

Relevant condenser that can use together with each destilling tower and fluid separation applications container can have any conventional design and in Fig. 1, simplify.As shown in fig. 1, can be with heat supply to the bottom of each tower or supply to the recycle column bottoms stream through 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 that is produced during the process of integrating with said reboiler or be obtained from for example another kind of chemical method or the boiler that produces heat of external source.Though in Fig. 1, shown a reactor and a flash vessel, can use additional reactor, flash vessel, condenser, heating element heater and other parts in embodiments of the invention.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 made up and are used for method of the present invention.

Temperature and pressure used in any tower can change.As actual conditions, in these zones, can use the pressure of 10KPa-3000KPa usually, although can use pressure below atmospheric pressure and superatmospheric pressure in some embodiments.Temperature in each zone will be usually in the scope between the boiling point of the boiling point of the composition that is removed as distillate and the composition that is removed as residue.Those skilled in the art will recognize that the temperature of given position depends at the material composition of this position and the pressure of tower in the destilling tower of operation.In addition, feed rate can depend on the production technology scale and change, if describe, then can generally be meant according to the feed weight ratio.

When tower 107 was operated under standard atmospheric pressure, the temperature of the residue that in pipeline 116, leaves from tower 107 was preferably 95 ℃-120 ℃, for example 105 ℃-117 ℃ or 110 ℃-115 ℃.The temperature of the distillate that in pipeline 117, leaves from tower 107 is preferably 70 ℃-110 ℃, for example 75 ℃-95 ℃ or 80 ℃-90 ℃.In other embodiments, the pressure of first tower 107 can be 0.1KPa-510KPa, for example 1KPa-475KPa or 1KPa-375KPa.

The exemplary compositions of the distillate and the residue composition of first tower 107 is provided in the following table 3.Should also be understood that said distillate and residue can also contain other unlisted component, the for example component in the charging.For ease, the distillate of first tower and residue may also be referred to as " first distillate " or " first residue ".The distillate of other tower or residue also can use similar digital modifier (second, third etc.) to be mentioned so that they are distinguished from each other out, but this type modifier should not be interpreted as and requires any special separation sequence.

As shown in table 3; Though do not accept the opinion constraint; Unexpected and unexpectedly find; When detecting the acetal of any amount in the charging that is being incorporated into acid separation column (first tower 107), as if acetal decomposes in this tower to make and in distillate and/or residue, exists less or even do not have a detectable amount.

Depend on reaction condition, the coarse ethanol product that in pipeline 112, leaves reactor 103 can comprise ethanol, acetate (unconverted), ethyl acetate and water.After leaving reactor 103, non-catalytic balanced reaction can take place joining between the component that is wherein comprised before the flash vessel 106 and/or first tower 107 in the coarse ethanol product.As (reaction 2) shown in following, this balanced reaction trends towards driving the coarse ethanol product and reaches the balance between ethanol/acetate and the ethyl acetate/water.

Reaction 2

In this situation, the coarse ethanol product for example temporarily was stored in before guiding distillation zone 102 in the storage tank, so can meet with the time of staying of prolongation.Usually, the time of staying between reaction zone 101 and the distillation zone 102 is long more, and ethyl acetate forms manyly more.For example, when time of staying between reaction zone 101 and the distillation zone 102 during, can form significantly more ethyl acetate with the loss of ethanol greater than 5 days.Therefore, usually between preferred reaction district 101 and the distillation zone 102 short time of staying so that the amount maximization of the ethanol that forms.In one embodiment, the storage tank (not shown) is included in and is used for interim storage between reaction zone 101 and the distillation zone 102 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 jar and the liquid of condensation is direct to entering first destilling tower 107.In addition, the uncatalyzed reaction speed of carrying out can improve along with the temperature of the for example coarse ethanol product in pipeline 115 and improve.Surpass 30 ℃, for example surpassing 40 ℃ or surpass that these reaction rates can have problems especially under 50 ℃ the temperature.Therefore, in one embodiment, make in the pipeline 115 or the temperature maintenance of the liquid component in the optional storage tank is in less than 40 ℃, for example less than 30 ℃ or less than 20 ℃ temperature.Can use one or more cooling devices to reduce the temperature of liquid in the pipeline 115.

As discussed above; The storage tank (not shown) can be included in and be used to choose wantonly under about 21 ℃ temperature interim storage between reaction zone 101 and the distillation zone 102 from the liquid component of pipeline 115 for example 1-24 hour, and the ethyl acetate that corresponds respectively to 0.01 weight %-1.0 weight % forms.In addition, the uncatalyzed reaction speed of carrying out can improve along with the temperature of coarse ethanol product and improve.For example, along with the coarse ethanol product temperature in the pipeline 115 is brought up to 21 ℃ from 4 ℃, form ethyl acetate speed can from the about 0.005 weight % of about 0.01 weight %/hour bring up to/hour.Therefore, in one embodiment, make the liquid component temperature maintenance in the pipeline 115 or in the optional storage tank be in temperature, for example less than 4 ℃ or less than-10 ℃ less than 21 ℃.

In addition, have now found that above-mentioned balanced reaction can also promote in the top area of first tower 107, to form ethanol.

As shown in fig. 1, optional distillate with tower 107 for example top stream carry out condensation and preferably with 1: 5-10: 1 reflux ratio refluxes.Distillate in the pipeline 117 preferably comprises ethanol, ethyl acetate and water and other impurity, and it possibly be difficult to separate owing to the formation of binary and ternary azeotrope.

First distillate in the pipeline 117 is incorporated into second tower 108 (being also referred to as " light fraction tower "), preferably for example middle 1/2nd or middle 1/3rd introduces at the mid portion of tower 108.As an instance, when using the tower of 25 column plates in the tower that does not have the water extracting, pipeline 117 is introduced at column plate 17 places.In one embodiment, second tower 108 can be the extractive distillation tower.In this embodiment, can with extractant for example water join second tower 108.If extractant comprises water, then its can obtain or return from external source from inside from one or more other towers/recirculation line for example obtains through optional pipeline 121 '.

Second tower 108 can be plate column or packed tower.In one embodiment, second tower 108 is to have 5-70 column plate, the for example plate column of 15-50 column plate or 20-45 column plate.

Though the temperature and pressure of second tower 108 can change, the temperature of second residue that ought be under atmospheric pressure in pipeline 118, leaves from second tower 108 is preferably 60 ℃-90 ℃, for example 70 ℃-90 ℃ or 80 ℃-90 ℃.The temperature of second distillate that in pipeline 120, leaves from second tower 108 is preferably 50 ℃-90 ℃, for example 60 ℃-80 ℃ or 60 ℃-70 ℃.Tower 108 can under atmospheric pressure be operated.In other embodiments, the pressure of second tower 108 can be 0.1KPa-510KPa, for example 1KPa-475KPa or 1KPa-375KPa.The exemplary compositions of the distillate and the residue composition of second tower 108 is provided in the following table 4.It should be understood that said distillate and residue can also contain other unlisted component, the for example component in the charging.

The weight ratio of the ethanol in the ethanol in second residue and 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 second residue and second distillate is preferably less than 0.4: 1, for example less than 0.2: 1 or less than 0.1: 1.In using extraction column the embodiment as second tower 108 of water as extractant, the weight ratio of the ethyl acetate in the ethyl acetate in second residue and second distillate is near zero.

As shown, will give through pipeline 118 from second residue (it comprises the second alcohol and water) of second tower, 108 bottoms and enter the 3rd tower 109 (being also referred to as " product tower ").More preferably, the bottom that second residue in the pipeline 118 is introduced the 3rd tower 109, for example Lower Half or down 1/3rd.The 3rd tower 109 reclaims ethanol (preferably being pure basically) with the distillate in the pipeline 119 except that the azeotropic water content.The distillate of the 3rd tower 109 is preferably pressed shown in Figure 1A, and for example with 1: 10-10: 1 as 1: 3-3: 1 or 1: 2-2: 1 reflux ratio refluxes.The 3rd residue in the 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 aforesaid plate column and preferably operation under atmospheric pressure.The temperature of the 3rd distillate that in pipeline 119, leaves from the 3rd tower 109 is preferably 60 ℃-110 ℃, for example 70 ℃-100 ℃ or 75 ℃-95 ℃.When this tower was under atmospheric pressure operated, the temperature of leaving the 3rd residue of the 3rd tower 109 was preferably 70 ℃-115 ℃, for example 80 ℃-110 ℃ or 85 ℃-105 ℃.The exemplary compositions of the distillate and the residue composition of the 3rd tower 109 is provided in the following table 5.It should be understood that distillate and residue can also contain other unlisted component, the for example component in the charging.

In the still-process from any compound of charging or crude reaction product carrier band usually in based on the gross weight of the 3rd distillate composition less than 0.1 weight %, for example be retained in the 3rd distillate less than 0.05 weight % or less than the amount of 0.02 weight %.In one embodiment, remove impurity in any that one or more side line materials flows can be from the tower 107,108 and/or 109 of system 100.Preferred at least one side line materials flow of use is removed impurity from the 3rd tower 109.Impurity can be cleaned and/or is retained in the system 100.

Can use one or more additional piece-rate systems, for example destilling tower (like the fine finishining tower) or molecular sieve are further purified the 3rd distillate in the pipeline 119 to form absolute ethyl alcohol product stream, i.e. " finished product absolute ethyl alcohol ".

Turn back to second tower 108, the distillate in the 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 will be recycled to reaction zone 101 from all or part of distillate of second tower 108 through pipeline 120.As shown in fig. 1, all or part of distillate can be recycled to reactor 103 shown in pipeline 120, and can feed jointly with acetic acid feed pipeline 105.In one embodiment, the ethyl acetate in the pipeline 120 is not accumulated in reaction zone 101 and/or the distillation zone 102 owing to the existence of the catalyst that comprises acid carrier.Because the dynamic (dynamical) raising of balanced reaction, embodiment of the present invention can also be handled the ethyl acetate in charging and/or the recycle stream.Therefore; Because the dynamics that improves; Can make the recirculation ethyl acetate in the pipeline 120 be converted into ethanol, therefore the perhaps ethyl acetate of the Chan Shenging ethyl acetate that can equal to transform will exist the concentration of ethyl acetate of certain stable state and the recirculation of acquisition relatively fast will keep constant; And be not accumulated in the closed circuit.Can will clean from the part distillate of second tower 108 through pipeline 122.Randomly; Like common unsettled U. S. application No.12/852; (incorporate it into this paper in full by reference) described in 269, second distillate in the pipeline 120 can use 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 improved

reaction zone

130 and 140 respectively.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 is flowed 111 to entering first reactor 131.Reactor effluent 133 given enter second reactor 132.Preferably, reactor effluent 133 comprises ethanol and unreacted acetate and can have the as above described composition of table 1.Randomly, can be with fresh reactant thing (not shown) to entering second reactor 132.The coarse ethanol product of second reactor 134 given enter flash vessel 106.For purpose of explanation, Fig. 2 A has shown 2 reactors.Yet, in other embodiments, can have, for example more than 3 or more than 4 more than 2 reactors.In the

reactor

131 and 132 of Fig. 2 A each is operated in reaction condition mentioned above.

In the reaction zone 140 of Fig. 2 B, vapor feed is flowed 111 to entering the reactor 141 that comprises a plurality of conversion zones.Reactor 141 comprises first conversion zone 142 and second conversion zone 143 at least.Each zone can have different catalyst.Shown in Fig. 2 B, first conversion zone 142 and second conversion zone 143 can separate in reactor 141.In other embodiments, first conversion zone 142 and second conversion zone, 143 overlappings and catalyst separately can be dispersed between the said zone.Can with reactor 141 for example the coarse ethanol product 144 of second reactor area 143 give and enter flash vessel 106.Operate in reaction condition as indicated above with zone 143 in zone 142.

In preferred embodiments, different catalyst can be used for each reactor of Fig. 2 B reaction zone 130 or be used for each conversion zone of reaction zone 140 shown in Fig. 2 B.Different catalyst can have different metallic and/or different carriers.In preferred embodiments; Catalyst in first reactor 131 or first reactor area 142 can be a 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., incorporate them into this paper in full by reference at this.

In some embodiments, the catalyst in first reactor 131 or first reactor area 142 is a base catalyst.The suitable metallic catalyst that comprises alkaline modifier comprises those with first metal and optional second metal.These metals can be with above described those be identical about acid loaded catalyst of the present invention.Preferably, first metal is a VIII family metal, chosen from Fe, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.Optional second metal preferably can be selected from copper, tin, cobalt, rhenium and nickel.Said catalyst can comprise 0.1-10 weight % first metal and 0.1-10 weight % second metal.

The suitable carriers material can comprise for example stable metal oxide base carrier or ceramic base carrier.Preferred carrier comprises and contains silicon carrier, for example silica, silica/alumina, IIA family silicate such as calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.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 the support modification agent.Preferably, the support modification agent is the alkaline modifier with low volatility or non-volatility.The alkaline modifier of this type for example can be selected from: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal 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 that oxide and metasilicate, can use the modifier of other type that comprises nitrate, nitrite, acetate and lactate.Preferably, the support modification agent is selected from the oxide and the metasilicate of arbitrary element in sodium, potassium, magnesium, calcium, scandium, yttrium and the zinc, and aforesaid any mixture.Preferably, the support modification agent is a calcium silicates, more preferably calcium metasilicate (CaSiO ₃).If the support modification agent comprises calcium metasilicate, then at least a portion of calcium metasilicate is preferably crystal form.In the preferred embodiment of using basic supports modifier, basic supports modifier is in based on total catalyst weight 0.1 weight %-50 weight %, and for example the amount of 0.2 weight %-25 weight %, 0.5 weight %-15 weight % or 1 weight %-8 weight % exists.

Acidic catalyst of the present invention is preferred in second reactor 132 or second reactor area 143.In an exemplary, first reactor 131 or first reactor area 142 can comprise SiO ₂-CaSiO ₃-Pt-Sn catalyst, and second reactor 133 or second reactor 143 can comprise SiO ₂-TiO ₂-Pt-Sn catalyst.In alternate embodiment, acidic catalyst can be used for first reactor 131 or first reactor area 142.

Acetate conversion ratio in first reactor 131 or first reactor area 142 can be lower than the acetate conversion ratio in second reactor 132 or second reactor area 143 respectively relatively.The acetate conversion ratio of first reactor 131 or 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 acetate conversion ratio in first reactor 131 or first reactor area 142 be 10%-80% and be lower than second reactor 132 or second reactor area 143 in the conversion ratio of unreacted acetate.In second reactor 132 or second reactor area 143, can make the conversion ratio of unreacted acetate bring up at least 70%, for example at least 80% or at least 90%.Advantageously, lower acetate conversion ratio makes the unreacted acid of first reactor 131 or first reactor area 142 in second reactor 132 or second reactor area 143, carry out hydrogenation and not add fresh acetate in first reactor 131 or first reactor area 142.

Total ethanol selectivity in double-reactor shown in the double-reactor shown in Fig. 2 A and/or Fig. 2 B zone can be at least 65%, for example at least 70%, at least 80%, at least 85% or at least 90%.Can in second reactor 132 or second reactor area 143, be consumed through the ethyl acetate that first reactor 131 or first reactor area 142 produce.

Finished product ethanol

The finished product ethanol composition that obtains through the inventive method preferably comprises ethanol, the for example ethanol of 80-96 weight % or 85-96 weight % based on this finished product ethanol composition gross weight meter 75-96 weight %.Exemplary finished product ethanol compositing range is provided in the following table 6.

Finished product ethanol composition of the present invention preferably contains very low amount, for example less than other alcohol of 0.5 weight %, and for example methyl alcohol, butanols, isobutanol, isoamyl alcohol and other C ₄-C ₂₀Alcohol.In one embodiment, the amount of isopropyl alcohol is 80-1 in the finished product ethanol, 000wppm, 95-1 for example, 000wppm, 100-700wppm or 150-500wppm.In one embodiment, the finished product ethanol composition preferably is substantially free of acetaldehyde, can comprise the acetaldehyde less than 8wppm, for example less than 5wppm or less than 1wppm.

The finished product ethanol composition of being produced by embodiment of the present invention can be used for various application, comprises 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 be used for motor vehicles for example automobile, ship and small-sized piston engine aircraft.In on-fuel was used, this finished product ethanol composition can be as the solvent of cosmetics and cosmetic formulations, detersive, disinfectant, coating, printing ink and medicine.This finished product ethanol composition can also be with dealing with solvent in the manufacture process that medicinal product, food preparation, dyestuff, photochemistry and latex are handled.

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 with acid esterification itself and polyvinyl acetate be reacted this finished product ethanol composition.Can make this finished product ethanol composition dehydration to produce ethene.Can use any known dehydration catalyst to make ethanol dehydration; Said dehydration catalyst is for example at common unsettled U. S. application No.12/221; 137 with U. S. application No.12/221, those described in 138 are incorporated their full content and disclosure into this paper by reference at this.For example, zeolite catalyst can be used as dehydration catalyst.Preferably, said 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, incorporates them into this paper in full by reference at this.

In order more effectively to understand this paper invention disclosed, following examples are provided below.

Embodiment

Embodiment 1

Comprising SiO ₂-TiO ₂The acidic catalyst of (10 weight %)-Pt (1.6 weight %)-Sn (1.0 weight %) exists down acetic acid hydrogenation.In reactor, carry out 2 rounds with this catalyst down in 200psig, 250 ℃.First round is with 4500hr ^-1GHSV, second round is with 2200hr ^-1GHSV.In Fig. 3, Theoretical Calculation is K as a result _BalanceBe 4, and K _Flat _{Weighing apparatus}Be 12.As shown in Figure 3, under lower acetate conversion ratio the amount of ethyl acetate greater than the amount of ethanol.Yet under higher acetate conversion ratio, balanced reaction dynamics unexpectedly makes ethyl acetate content reduce and improves ethanol content.Table 7 has gathered the result.

Embodiment 2

Comprising SiO ₂-TiO ₂The acidic catalyst of (10 weight %)-Pt (1.6 weight %)-Sn (1.0 weight %) with comprise SiO ₂-Al ₂O ₃The acidic catalyst of (7 weight %)-Pt (1.6 weight %)-Sn (1.0 weight %) exists down acetic acid hydrogenation.Under different acetate transform levels, carry out every kind of hydrogenation several times.In Fig. 4, compared the result.Under lower conversion ratio, SiO ₂-Al ₂O ₃(7 weight %)-Pt (1.6 weight %)-Sn (1.0 weight %) catalyst demonstrates the ethanol selectivity of raising.Yet, under higher conversion ratio, SiO ₂-TiO ₂(10 weight %)-Pt (1.6 weight %)-Sn (1.0 weight %) catalyst demonstrates similar ethanol selectivity.In addition, unexpected and unexpectedly, the productive rate of acidic catalyst demonstrates obvious improvement under higher acetate conversion ratio.

Embodiment 3

Also use the SiO that comprises under the following different reaction conditions that in table 8, provides from embodiment 2 with some rounds ₂-Al ₂O ₃The acidic catalyst of (7 weight %)-Pt (1.6 weight %)-Sn (1.0 weight %) is with acetic acid hydrogenation.

Though describe the present invention in detail, various modifications within the spirit and scope of the present invention will be conspicuous to those skilled in the art.In view of the above discussion, above this area relevant knowledge and the list of references of being discussed about background technology and detailed description all incorporated their disclosure into this paper by reference.In addition, should understand hereinafter and/or the various aspects of the present invention in appended claims, quoted from and the various piece of a plurality of embodiment and a plurality of characteristics can partly or entirely make up or exchange.In the description of aforementioned each embodiment, as those skilled in the art can recognize that the embodiment of quoting another embodiment can suitably make up with other embodiment.In addition, those skilled in the art will recognize that aforementioned description only is a way of example, and be not intended to limit the present invention.

Claims

1. method of producing ethanol; This method is included in the catalyst existence and down acetic acid hydrogenation is formed ethanol; Wherein said hydrogenation has at least 65% ethanol selectivity, and wherein said catalyst is included in first metal on the acid carrier, and said 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.

2. the process of claim 1 wherein that said carrier material is selected from silica, silica/alumina, calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide, carbon, ferriferous oxide, aluminium oxide, silica/alumina, titanium dioxide, zirconia and their mixture.

3. the process of claim 1 wherein that said acid modification agent is selected from the oxide of the oxide of the oxide of the oxide of IVB family metal, VB family metal, group vib metal, VIIB family metal, oxide, aluminum oxide and their mixture of VIIIB family metal.

4. the process of claim 1 wherein that said 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

5. the process of claim 1 wherein that said 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

6. the process of claim 1 wherein that said catalyst comprises 0.1 weight %-50 weight % acid modification agent.

7. the process of claim 1 wherein that said catalyst comprises 25 weight %-99 weight % carrier materials.

8. the process of claim 1 wherein that said catalyst comprises 25 weight %-99 weight % acid carrier materials.

9. the process of claim 1 wherein that said first metal is selected from: IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIIIB group 4 transition metal, lanthanide series metal, actinide metals perhaps are selected from the metal of any family in IIIA, IVA, VA or the VIA family.

10. the process of claim 1 wherein that said first metal is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten.

11. the process of claim 1 wherein that catalyst comprises 0.1-25 weight % first metal.

12. the method for claim 11, wherein said catalyst also comprise second metal that is different from first metal.

13. the method for claim 12, wherein said first metal is a platinum, and second metal is a tin.

14. the method for claim 13, wherein the mol ratio of platinum and tin is 0.4: 0.6-0.6: 0.4.

15. the method for claim 12, wherein said first metal is a palladium, and second metal is a rhenium.

16. the method for claim 15, wherein the mol ratio of rhenium and palladium is 0.7: 0.3-0.85: 0.15.

17. the method for claim 12, wherein said second metal is selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel.

18. the method for claim 12, wherein said catalyst comprise 0.1-10 weight % second metal.

19. the process of claim 1 wherein and make at least 70% acetate conversion.

20. the process of claim 1 wherein that said hydrogenation has the ethyl acetate selectivity less than 35%.

21. the process of claim 1 wherein that said hydrogenation carries out in the pressure of 125 ℃-350 ℃ temperature, 10KPa-3000KPa with under greater than 4: 1 hydrogen and acetate mol ratio in gas phase.

22. a method of producing ethanol, this method comprises:

In the presence of first catalyst, acetic acid hydrogenation is formed the intermediate product that comprises ethanol and unreacted acetate; And

In the presence of second catalyst, unreacted acetic acid hydrogenation is formed ethanol, wherein said second catalyst is included in first metal on the acid carrier, and said acid carrier is selected from:

Carrier material with acid modification agent modification.

23. the method for claim 22 is wherein carried out the hydrogenation of acetate in first reactor, in second reactor, carry out the hydrogenation of unreacted acetate.

24. the method for claim 23 wherein makes at least 10% acetate conversion in first reactor, in second reactor, make at least 70% unreacted acetate conversion.

25. a method of producing ethanol, this method comprises:

In reactor, in the presence of first catalyst and second catalyst, acetic acid hydrogenation is formed ethanol, wherein said second catalyst is included in first metal on the acid carrier, and said acid carrier is selected from:

Carrier material with acid modification agent modification.

26. the method for claim 25, wherein said first catalyst are in first reactor area, second catalyst is in second reactor area, and wherein first district and second district separate.

27. the method for claim 22 or 25, wherein said first catalyst comprise and contain one or more metals, contain the catalyst of silicon carrier and at least a basic supports modifier.

28. the method for claim 26, wherein said at least a basic supports modifier are selected from (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal 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.

29. the method for claim 26, the wherein said silicon carrier that contains is selected from silica, silica/alumina, calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.

30. a method that reclaims ethanol, this method comprises

In comprising the reactor of catalyst, the acetic acid feed stream hydrogenation is formed the coarse ethanol product, wherein said catalyst is included in first metal on the acid carrier, and said acid carrier is selected from:

Carrier material with acid modification agent modification;

At least part coarse ethanol product separates into first distillate that comprises ethanol, water and ethyl acetate in first tower, and first residue that comprises acetate;

At least part first distillate separates into second distillate that comprises ethyl acetate and second residue that comprises the second alcohol and water in second tower;

Making at least, part second distillate turns back to said reactor; And

At least part second residue separates into the 3rd distillate that comprises ethanol and the 3rd residue that comprises water in the 3rd tower.

31. the method for claim 33, wherein said acetic acid feed stream comprise one or more compounds that are selected from acetate, acetic anhydride, acetaldehyde, ethyl acetate and their mixture.

32. the method for claim 33, at least a portion of wherein said coarse ethanol product comprises acetate.

Make directly or indirectly at least that part first residue turns back to said reactor 33. the method for claim 33, this method also comprise, wherein said first residue comprises the acetate based on this first residue gross weight meter 60-100 weight %.

34. the method for claim 33, wherein said second distillate comprise 10-90 weight % ethyl acetate.