CN102300638A

CN102300638A - Catalysts for making ethyl acetate from acetic acid

Info

Publication number: CN102300638A
Application number: CN2010800062262A
Authority: CN
Inventors: V·J·约翰斯顿; L·陈; B·F·金米奇; J·T·查普曼; J·H·津克; H·魏纳; J·L·波茨; R·耶夫蒂奇
Original assignee: Celanese International Corp
Current assignee: Celanese International Corp
Priority date: 2009-10-26
Filing date: 2010-02-02
Publication date: 2011-12-28
Also published as: AU2010313700A1; EP2493612A1; BR112012009856A2; MX2012004840A; CA2778771A1; WO2011053367A1

Abstract

Catalysts and processes for making catalysts suitable for use in processes for hydrogenating acetic acid to form of ethyl acetate and mixtures of ethyl acetate and ethanol. In a first embodiment, the catalyst includes a high loading of nickel, palladium or platinum. In a second embodiment, the catalyst comprises a first metal selected from nickel and palladium and a second metal selected from tin and zinc. In a third embodiment, the catalyst comprises one or more metals on a support that has been modified with an acidic support modifier or a redox support modifier.

Description

The catalyst for preparing ethyl acetate by acetate

Priority request

The application requires the exercise question submitted on October 26th, 2009 priority for No. 12/588,727, the U. S. application of " Tunable Catalyst Gas Phase Hydrogenation of Carboxylic Acids ", incorporates it into this paper in full by reference.

Invention field

Present invention relates in general to catalyst used in the method for the mixture that acetic acid hydrogenation is formed ethyl acetate or ethyl acetate and ethanol and the method for preparing catalyst, described catalyst has high selectivity to ethyl acetate.

Background of invention

Acetate need be converted into the economically feasible Catalyst And Method of ethyl acetate for a long time.Ethyl acetate is the important bulk raw material of various industrial products and is used as industrial solvent in the manufacturing of various chemicals.For example, can it easily be converted into ethene, can be translated into various other products then by ethyl acetate being carried out cracking handle.Ethyl acetate according to routine by the price fluctuation more tangible raw material production that becomes.In other words, it is the cost fluctuation of the ethyl acetate in source with oil or natural gas that the natural gas of fluctuation and crude oil price are impelled what produce according to routine, thereby causes the demand in the alternative source of ethyl acetate bigger than in the past when oil price rises.

Ethanol is another kind of important bulk chemical, and it can use by himself and for example act as a fuel, perhaps as the raw material that is used to form ethene, vinyl acetate, ethyl acetate or other chemical products.Carboxylic acid hydrogenation production alcohol on heterogeneous catalysis is fully reported.For example, U.S. Patent No. 2,607,807 disclose and can form ethanol reaching about 88% yield by acetate on the ruthenium catalyst under the extremely high pressure of 700-950 crust, and under the pressure of about 200 crust the low yield of acquisition only about 40%.Operation is inadvisable and uneconomic yet this extreme reaction condition is for commerce.

Recently, reported and under for example about 40-120 crust of superatmospheric pressure, to have used Co catalysts with acetic acid hydrogenation producing and ethanol in next life, although it is commercial still infeasible.For example, referring to the U.S. Patent No. 4,517,391 of Shuster etc.

On the other hand, the U.S. Patent No. 5,149,680 of Kitson etc. has been described and has been utilized the platinum group metal Au catalyst with carboxylic acid and their the acid anhydrides catalytic hydrogenation method for alcohol and/or ester.Described catalyst is by at least a periodic table group VIII noble metals and at least aly can constitute with the alloy of this group VIII noble metals alloyed metal (AM), is mixed with to comprise component at least a in rhenium metal, tungsten or the molybdenum.Though wherein declare with respect to the selectivity of prior art list of references acquisition, still reported and under they optimum catalyst states, during acetic acid hydrogenation is ethanol, formed alkane such as methane and the ethane of 3-9% as accessory substance to the improvement of the mixture of alcohol and ester and unreacted carboxylic acid.

Reported among the EP 0 372 847 by acetic acid hydrogenation being prepared the method for revising a little of ethyl acetate.In the method, in the presence of the carbon monoxide-olefin polymeric under the temperature that improves by make acid or acid anhydrides and hydrogen reaction by this carboxylic acid or its acid anhydrides with greater than 50% selectivity generation carboxylate, ethyl acetate for example, and produce corresponding alcohol with selectivity simultaneously less than 10%, described carbon monoxide-olefin polymeric comprises at least a group VIII noble metals as first component, comprise in molybdenum, tungsten and the rhenium at least a as second component and the oxide that comprises IVB family element as the 3rd component.Yet, even Bao Dao optimum condition wherein, but except that ethanol, also produce the obviously accessory substance of the methane that comprises, ethane, acetaldehyde and the acetone of amount.In addition, the conversion ratio of acetate usually low and wherein conversion ratio except that reaching high about 5-40% that to 80% rare cases, is.

Be apparent that by aforementioned existing method does not have needed selectivity to ethyl acetate and/or ethanol, use the height expensive catalysts, perhaps produce the accessory substance do not expected for example methane and ethane.Therefore, need to use more economic catalyst to form ethyl acetate (with optional ethanol), and the formation of the accessory substance of not expecting is minimized with high selectivity.

Summary of the invention

The present invention relates to catalyst and the method for preparing catalyst, described catalyst is suitable for high selectivity, conversion ratio and/or productive rate acetic acid hydrogenation being obtained the method for the mixture of ethyl acetate or optional ethyl acetate and ethanol.

In one embodiment, catalyst comprises first metal, second metal and carrier, wherein first metal is selected from nickel, palladium and platinum and to exist based on the amount of total catalyst weight greater than 1wt.%, wherein second metal is selected from molybdenum, rhenium, zirconium, copper, cobalt, tin and zinc, and wherein said catalyst has the ethyl acetate selectivity greater than 40%.Preferably, first metal is to exist greater than 1wt.% and less than the amount of 25wt% based on total catalyst weight.

In another embodiment, catalyst comprises first metal, second metal and silica/alumina carrier, wherein first metal is selected from nickel, palladium and platinum, second metal is selected from molybdenum, rhenium, zirconium, copper, cobalt, tin and zinc, and wherein the silica/alumina carrier comprises based on the gross weight meter of high surface area silica/alumina support greater than the aluminium of the amount of 1wt.% and have 150m at least ²The surface area of/g, wherein catalyst has the ethyl acetate selectivity greater than 40%.

In another embodiment, catalyst comprises first metal, carrier and at least a support modification agent, and described support modification agent is selected from: the IVB family metal oxide, the VB family metal oxide, group vib metal oxide, ferriferous oxide (iron oxides), aluminum oxide and their mixture.First metal can be selected from IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII group 4 transition metal, lanthanide series metal, actinide metals, the perhaps metal of any family in IIIA, IVA, VA or the VIA family.In another embodiment, first metal is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten.In addition, this catalyst can comprise second metal that is different from first metal and is selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel.Preferably, first metal exists in the amount based on total catalyst weight 0.1-25wt.%.More preferably, first metal is a platinum, and second metal is a tin, and randomly the mol ratio of platinum and tin is 0.65: 0.35-0.95: 0.05, and perhaps first metal is a palladium, and second metal is a rhenium, and randomly the mol ratio of rhenium and palladium is 0.65: 0.35-0.95: 0.05.Select as another kind, this catalyst also comprises the 3rd metal that is different from first and second metals and is selected from cobalt, palladium, ruthenium, copper, zinc, platinum, tin and rhenium.The 3rd metal can exist in the amount based on total catalyst weight 0.05 and 4wt.%.

As noted above, this catalyst can be suitable for transforming at the acetate that acetate is converted into be used as hydrogenation catalyst in the ethyl acetate and can makes at least 10% during hydrogenation usually.In addition, described hydrogenation can be in gas phase carries out in the pressure of 125 ℃-350 ℃ temperature, 10KPa-3000KPa with under greater than 4: 1 hydrogen and acetate mol ratio.In addition, this catalyst can have greater than 40% for example greater than 50% selectivity for ethyl acetate, and can have selectivity less than 4% for methane, ethane and carbon dioxide.In one embodiment, this catalyst has per 100 hours catalyst and uses the productive rate that reduces less than 6%.

In one embodiment, carrier exists in the amount based on total catalyst weight 25wt.%-99wt.%, and chosen from Fe oxide, silica, aluminium oxide, silica/alumina, titanium dioxide, zirconia, magnesia, calcium silicates, carbon, graphite, high surface graphitized carbon, active carbon and their mixture.As a kind of selection, this catalyst can comprise at least a support modification agent, described support modification agent be selected from (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate (metasilicate), (iv) alkali metal silicate, (v) the IIB family metal oxide, (vi) IIB family metal metaphosphate silicate, (vii) the IIIB family metal oxide, (viii) IIIB family metal metaphosphate silicate and their mixture are preferably CaSiO ₃In another kind was selected, described support modification agent was selected from IVB family metal oxide, VB family metal oxide, group vib metal oxide, ferriferous oxide, aluminum oxide and their mixture.As another selection, described support modification agent can be selected from WO ₃, MoO ₃, Fe ₂O ₃, Cr ₂O ₃, TiO ₂, ZrO ₂, Nb ₂O ₅, Ta ₂O ₅And Al ₂O ₃Described support modification agent can exist in the amount based on total catalyst weight 0.1wt.%-50wt.%.

Except that catalyst, the invention still further relates to the method for preparing catalyst, this method comprises that (a) makes first metal precursor of first metal contact with carrier, wherein said first metal is selected from nickel, palladium and platinum; (b) second metal precursor of second metal is contacted with carrier, wherein said second metal is selected from molybdenum, rhenium, zirconium, copper, cobalt, tin and zinc; And (c) at effective reduction described first metal and second metal and form the described carrier of heating under the condition of catalyst, wherein said catalyst comprises based on first metal of total catalyst weight meter greater than the amount of 1wt%.

In another embodiment, the present invention relates to prepare the method for catalyst, this method comprises that (a) makes first metal precursor of first metal contact with carrier, and wherein said first metal is selected from nickel and palladium; (b) second metal precursor of second metal is contacted with carrier, wherein said second metal is selected from tin and zinc; And (c) at effective reduction described first metal and second metal and form the described carrier of heating under the condition of catalyst.

In another embodiment, the present invention relates to prepare the method for catalyst, this method comprises the steps: that (a) makes first metal precursor of first metal contact with the modified support that comprises at least a support modification agent, described support modification agent is selected from the IVB family metal oxide, the VB family metal oxide, group vib metal oxide, ferriferous oxide, aluminum oxide and their mixture; (b) at effective described first metal of reduction and form the described modified support of heating under the condition of catalyst, wherein said catalyst has the ethyl acetate selectivity greater than 40%.Preferably, this method comprises the steps: that also (c) contacts to form the precursor carrier of modification at least a support modification agent or its precursor with carrier material; (d) precursor carrier of the described modification of heating under the condition that effectively forms modified support.

Preferably, described heating is carried out in step (a) with (b) to reduce first metal and/or carry out afterwards to reduce second metal in step (a) with (b).Randomly, step (b) is carried out before in step (a).

Accompanying drawing is briefly described

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

Figure 1A is to use SiO ₂-Pt _mSn _1-mDuring catalyst for the optionally coordinate diagram of ethanol and ethyl acetate;

Figure 1B is the coordinate diagram of the catalyst of Figure 1A for the productive rate of ethanol and ethyl acetate;

Fig. 1 C is the coordinate diagram of acetate conversion ratio of the catalyst of Figure 1A;

Fig. 2 A is to use SiO ₂-Re _nPd _1-nDuring catalyst for the optionally coordinate diagram of ethanol and ethyl acetate;

Fig. 2 B is the coordinate diagram of the catalyst of Fig. 2 A for the productive rate of ethanol and ethyl acetate;

Fig. 2 C is the coordinate diagram of acetate conversion ratio of the catalyst of Fig. 2 A;

Fig. 3 is that activity of such catalysts is than the coordinate diagram of the productive rate of catalyst according to one embodiment of the invention mixture for ethyl acetate and ethanol under various temperature; With

Fig. 4 is that activity of such catalysts is than the coordinate diagram of selection of catalysts according to one embodiment of the invention mixture for ethyl acetate and ethanol under various temperature.

Detailed Description Of The Invention

Foreword

The present invention relates to used catalyst in the method for the mixture by acetic acid hydrogenation being produced ethyl acetate or ethyl acetate and ethanol.The invention still further relates to the method for these catalyst of preparation.

Acetic acid hydrogenation forms ethyl acetate and can represent by following reaction:

Depend on employed catalyst and process conditions, described hydrogenation reaction can be produced ethanol outside ethyl acetate.Embodiment of the present invention can be advantageously used in commercial Application with by economically feasible large-scale production ethyl acetate and/or ethanol.

Typically, described catalyst can comprise first metal, and optional comprises in second metal, the 3rd metal and the optional other metal one or more.One or more metals are preferably placed on the carrier, for example on silica or the titanium dioxide.In the first embodiment, described catalyst comprises nickel, palladium or the platinum of high carrying capacity.In second embodiment, described catalyst comprises first metal that is selected from nickel and palladium and is selected from tin and second metal of zinc.In the 3rd embodiment, described catalyst is included in one or more metals on the carrier of acid carrier modifier or oxidation-reduction type support modification agent modification.Have now found that these carbon monoxide-olefin polymerics can formation unexpected and that preparation unexpectedly becomes for ethyl acetate (optional and ethanol combination) be selectivity.

The nickel of high carrying capacity, palladium and platinum catalyst

In the first embodiment, the present invention relates to comprise one or more catalyst in nickel, palladium or the platinum of high metal carrying capacity.For example, described catalyst can be included on the carrier in total catalyst weight greater than 1wt.%, for example greater than 1.1wt.% or greater than first metal that is selected from nickel, palladium and platinum of the amount of 1.2wt.%.With regard to scope, the amount of first metal is preferably 1-25wt.% on the carrier, for example 1.2-15wt.% or 1.5wt.%-10wt.%.With regard to this specification, except as otherwise noted, percetage by weight is based on the gross weight meter of the catalyst that comprises metal and carrier.

Metal in the catalyst can exist by the form of one or more elemental metals and/or one or more metal oxides.With regard to the percetage by weight of metal in determining catalyst, ignore the weight of any oxygen that combines with metal.In aspect preferred, first metal is selected from platinum and palladium.When first metal comprised platinum, because the availability of platinum, preferred catalyst comprised greater than 1wt.%, but less than 10wt.%, for example less than 5wt.% or less than the platinum of the amount of 3wt.%.

Except that first metal, catalyst of the present invention is optional also to comprise in second metal, the 3rd metal or the additional metals one or more.In this context, digital term " first ", " second ", " the 3rd " etc., when being used to modify word " metal ", expression is meant that metal separately differs from one another.If exist, second metal is preferably selected from molybdenum, rhenium, zirconium, copper, cobalt, tin and zinc.More preferably, second metal is selected from molybdenum, rhenium, tin and cobalt.Even more preferably, second metal is selected from tin and rhenium.

When catalyst comprised two or more metals, a kind of metal can serve as promoter metals and other metal is main metal.For example, for platinum/tin catalyst, platinum can be considered to main metal, and tin can be considered to promoter metals.For convenience, this specification specify first metal as major catalyst and second metal (with optional metal) as promoter.But this should be as the indication of the basic mechanism of catalytic activity.

In the first embodiment, when catalyst comprises two or more metals, for example when first metal and second metal, first metal is optional with 1-10wt.%, and for example the amount of 1.2-5wt.% or 1.5-3wt.% is present in the catalyst.Second metal is optional with 0.1-20wt.%, and for example the amount of 0.1-10wt.% or 0.1-5wt.% exists.For the catalyst that comprises two or more metals, described two or more metals are alloying or can comprise non-alloyed metal (AM) solid solution or mixture each other.

Preferred metal is change a little than depending on metal used in the catalyst.In some embodiments, 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.

The preferred mol ratio except that 1: 1, this depends on the composition of employed catalyst.Reveal people's expectation and discovery unexpectedly, as shown in Figure 1A, 1B and 1C, for example for platinum/tin catalyst, especially preferably less than 0.4: 0.6 or greater than 0.6: 0.4 platinum and tin mol ratio to form ethyl acetate with high selectivity, conversion ratio and productive rate by acetate.More preferably, Pt/Sn for example is 0.65: 0.35-1: 0 or 0.7: 0.3-1: 0 than greater than 0.65: 0.35 or greater than 0.7: 0.3.The selectivity of ethyl acetate can also be further improved by being incorporated herein described modified support.

About rhenium/palladium catalyst, as shown in Fig. 2 A, 2B and 2C, for forming ethyl acetate, with regard to selectivity, conversion ratio and productive rate, preferred rhenium and palladium mol ratio are less than 0.7: 0.3 or greater than 0.85: 0.15.For produce ethyl acetate in the presence of the Re/Pd catalyst, preferred Re/Pd ratio is 0.2: 0.8-0.4: 0.6.Again, the selectivity of ethyl acetate can also be further improved by being incorporated herein described modified support.

In the embodiment when catalyst comprises the 3rd metal, the 3rd metal can be selected from above about the listed any metal of first or second metal, as long as described the 3rd metal is different from described first and second metals.In 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 the 3rd metal existed, carbon monoxide-olefin polymeric preferably comprised 0.05-4wt.%, for example the 3rd metal of the amount of 0.1-3wt.% or 0.1-2wt.%.

Except that metal, the catalyst of first embodiment also comprises carrier, optional modified support.As those of skill in the art would recognize that carrier material is selected to make caltalyst tie up to and be used to form to have suitable activity, selectivity and robustness (robust) under the process conditions of mixture of ethyl acetate or ethyl acetate and ethanol.The suitable carriers material can comprise for example stable metal oxide base carrier or ceramic base carrier and molecular sieve, for example zeolite.The example of suitable carriers material includes but not limited to graphitized carbon, active carbon and their mixture of ferriferous oxide, silica, aluminium oxide, silica/alumina, titanium dioxide, zirconia, magnesia, calcium silicates, carbon, graphite, high surface.Exemplary preferred carrier is selected from silica/alumina, titanium dioxide and zirconia.Total weight of carrier in the described catalyst is preferably 25wt.%-99wt.% based on the total catalyst weight meter, for example 30wt.%-98.5wt.% or 35wt.%-98wt.%.

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.

In one embodiment, carrier material comprises siliceous carrier material, and this siliceous carrier material is selected from silica, silica/alumina, IIA family silicate for example calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.Silica can be as containing in the embodiment of silicon carrier therein, the amount of advantageously guaranteeing aluminium (it is the common pollutant of silica) can be low, be preferably based on described total weight of carrier meter below 1wt.%, for example below the 0.5wt.% or below the 0.3wt.%.Thus, preferred pyrolytic silicon dioxide is because it generally obtains with the purity that surpasses 99.7wt.%.As employed in the whole text among the application, high-purity silicon dioxide be meant wherein acid contaminant for example aluminium (if any) with less than 0.3wt.%, for example less than 0.2wt.% or the silica that exists less than the level of 0.1wt.%.

The surface area of carrier can vary widely, and this depends on the type of carrier.In certain aspects, carrier material for example the surface area of material can be at least about 50m ²/ g is for example at least about 100m ²/ g, at least about 150m ²/ g, at least about 200m ²/ g or most preferably at least about 250m ²/ g.With regard to scope, carrier material preferably has 50-600m ²/ g, for example 100-500m ²/ g or 100-300m ²The surface area of/g.Employed in the whole text as the application, high surface area silica is meant to have at least about 250m ²The silica of the surface area of/g.Employed in the whole text as the application, high surface area silica/aluminium oxide is meant to have at least about 150m ²The silica/alumina of the surface area of/g.With regard to this specification, surface area is meant BET nitrogen surface area, refers to the surface area of measuring by ASTM D6556-04 (incorporating it into this paper in full by reference).

Carrier material for example material also preferably has as the 5-100nm by pressing mercury hole mensuration (mercury intrusion porosimetry) to measure, the for example average pore size of 5-30nm, 5-25nm or about 5-10nm, and as 0.5-2.0cm by pressing mercury hole mensuration to measure ³/ g, for example 0.7-1.5cm ³/ g or about 0.8-1.3cm ³The average pore volume of/g.

Carrier material and thus the form of the carbon monoxide-olefin polymeric of gained can vary widely.In some exemplary, the form of carrier material and/or carbon monoxide-olefin polymeric can be pill, extrudate, ball, spray-dried microspheres, ring, five spoke wheels (pentaring), trilobal thing, quatrefoil thing, leafy shape thing or thin slice, although the pref. cylindrical pill.Preferably, carrier material for example material have that to allow bulk density be 0.1-1.0g/cm ³, 0.2-0.9g/cm for example ³Or 0.5-0.8g/cm ³Form.With regard to size, carrier material for example material preferably has 0.01-1.0cm, the average grain diameter of 0.1-0.5cm or 0.2-0.4cm for example, and average grain diameter is meant the equivalent spherical diameter of the diameter or the aspherical particle of spheric granules.Because be positioned on the modified support or within the size of one or more metals very little usually, they should not influence the size of overall catalyst granules basically.Therefore, above-mentioned particle diameter is applicable to the size of modified support and final catalyst granules usually.

Preferred silica support materials is SS61138 high surface (HSA) the SiO 2 catalyst carrier from Saint Gobain NorPro.Saint-Gobain NorPro SS61138 silica contains the high surface area silica of the 95wt.% that has an appointment; About 250m ²The surface area of/g; The mean pore sizes of about 12nm; By the about 1.0cm that presses mercury hole mensuration to measure ³The total pore volume of/g and about 0.352g/cm ³(22lb/ft ³) bulk density.

The carrier that is used for first embodiment can also comprise the support modification agent.The support modification agent is to join in the carrier rather than natural being present in the carrier.The acidity effect of carrier material is regulated in the support modification agent.For example, the acid position on the carrier material as

The acid position can be regulated to help the selectivity to the mixture of ethyl acetate and ethyl acetate during acetic acid hydrogenation by the support modification agent.Unless context indicates in addition, surface acidity or the sour bit quantity on it can be edited by F.Delannay, " Characterization of Heterogeneous Catalysts "; Chapter III:Measurement of Acidity of Surfaces, the 370-404 page or leaf; Technology described in the Marcel Dekker, Inc., N.Y.1984 is measured, and incorporates it into this paper in full by reference.

In certain aspects, for forming ethyl acetate, may not expect that carrier material acidity is excessive with high selectivity.In this case, carrier material can carry out modification with basic supports modifier.For example, suitable basic supports modifier 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 in embodiment of the present invention, use the modifier that comprises nitrate, nitrite, acetate and Lactated other type.Preferably, alkaline modifier has low volatility or non-volatility.Low volatility modifier has enough low forfeiture rate during catalyst life makes the acidity of support modification agent not be reversed (reverse).For example, the support modification agent can be selected from sodium, potassium, magnesium, calcium, scandium, yttrium and the zinc any oxide and metasilicate, and aforementioned mixture arbitrarily.Particularly preferred basic supports modifier is calcium metasilicate (CaSiO ₃).

In certain aspects, the excessive or acid deficiency of carrier material alkalescence and do not form ethyl acetate with high selectivity.In this case, described carrier can carry out modification with the support modification agent, and described support modification agent is regulated carrier material by quantity or the availability of using oxidation-reduction type support modification agent or acid carrier modifier to improve the acid position.Suitable oxidation-reduction type and acid carrier modifier can be selected from: IVB family metal oxide, VB family metal oxide, group vib metal oxide, ferriferous oxide, aluminum oxide and their mixture.These support modification agent are oxidation-reduction type or acid nonvolatile vehicle modifier.Preferred oxidation-reduction type support modification agent comprises and is selected from WO ₃, MoO ₃, Fe ₂O ₃And Cr ₂O ₃Those.Preferred acid carrier modifier comprises and is selected from TiO ₂, ZrO ₂, Nb ₂O ₅, Ta ₂O ₅And Al ₂O ₃Those.Though not bound by theory, think that the acidity that improves carrier can help ethyl acetate and form.Yet raising carrier acidity can also form ether and can add alkaline modifier comes offset carrier acidity.

The catalyst that comprises nickel or palladium and tin or zinc

In second embodiment of the present invention, the present invention relates to prepare the catalyst of the mixture of ethyl acetate or optional ethyl acetate and ethanol, this catalyst comprises first metal that is selected from nickel and palladium, second metal and the carrier that is selected from tin and zinc, and optional is modified support.With above-mentioned first embodiment forms contrast is in second embodiment, can use first metal of low carrying capacity.For example, this catalyst can comprise 0.1-10wt.%, for example first metal of the amount of 0.1-5wt.% or 0.1-3wt.%.Second metal is preferably with 0.1-20wt.%, and for example the amount of 0.1-10wt.% or 0.1-5wt.% exists.The mol ratio of first metal and second metal is preferably 10: 1-1: 10, for example 4: 1-1: 4,2: 1-1: 2,1.5: 1-1: 1.5 or 1.1: 1-1: 1.1.Randomly, the catalyst of second embodiment can also comprise above about described the 3rd metal of first embodiment.

In second embodiment, catalyst comprises the carrier of above discussing about first embodiment, optional modified support.For second embodiment, the gross weight of described carrier is preferably 25wt.%-99.9wt.% based on the total catalyst weight meter, for example 30wt.%-97wt.% or 35wt.%-95wt.%.

Supported catalyst in acidity or oxidation-reduction type modification

In the 3rd embodiment of the present invention, catalyst is included in first metal on the carrier of oxidation-reduction type support modification agent or acid carrier modifier modification and optional second metal, the 3rd metal or one or more in the metal in addition.The gross weight of all metals that exist in this catalyst is preferably 0.1-25wt.%, for example 0.1-15wt.% or 0.11-10wt.%.

First metal can be IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII group 4 transition metal, lanthanide series metal, actinide metals, the perhaps metal of any family in IIIA, IVA, VA or the VIA family.In preferred embodiments, first metal 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 the limited availability of platinum, preferred catalyst comprised less than 5wt.%, for example less than 3wt.% or less than the platinum of the amount of 1wt.%.

Catalyst is optional also to comprise second metal, and this second metal is 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 catalyst comprises two or more metals, for example first metal and second metal, then first metal is optional with 0.1-10wt.%, and for example the amount of 0.1-5wt.% or 0.1-3wt.% is present in the catalyst.Second metal is preferably with 0.1-20wt.%, and for example the amount of 0.1-10wt.% or 0.1-5wt.% exists.For the catalyst that comprises two or more metals, described two or more metals are alloying or can comprise non-alloyed metal (AM) solid solution or mixture each other.

Described in first embodiment, preferred metal changes a little than depending on metal used in the catalyst in the 3rd embodiment as mentioned.In some embodiments, the mol ratio of first metal and second metal is preferably 10: 1-1: 10, for example 4: 1-1: 4,2: 1-1: 2,1.5: 1-1: 1.5 or 1.1: 1-1: 1.1.

For other catalyst, the preferred mol ratio except that 1: 1.Reveal people's expectation and discovery unexpectedly, as shown in Figure 1A, 1B and 1C, for example for platinum/tin catalyst, especially preferably less than 0.4: 0.6 or greater than 0.6: 0.4 platinum and tin mol ratio to form ethyl acetate with high selectivity, conversion ratio and productive rate by acetate.For producing ethyl acetate in the presence of the Pt/Sn catalyst, preferred Pt/Sn mol ratio is 0.65: 0.35-0.95: 0.05, for example 0.7: 0.3-0.95: 0.05.The selectivity of ethyl acetate can also be further improved by introducing the described modified support of this specification in the whole text.

About rhenium/palladium catalyst, as shown in Fig. 2 A, 2B and 2C, for forming ethyl acetate, with regard to selectivity, conversion ratio and productive rate, preferred rhenium and palladium mol ratio are less than 0.7: 0.3 or greater than 0.85: 0.15.For produce ethyl acetate in the presence of the Re/Pd catalyst, preferred Re/Pd ratio is 0.2: 0.8-0.4: 0.6.Again, the selectivity of ethyl acetate can also be further improved by introducing the described modified support of this specification in the whole text.

In the embodiment when catalyst comprises the 3rd metal, the 3rd metal can be selected from above about the listed any metal of first or second metal, as long as described the 3rd metal is different from described first and second metals.In 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 0.05-4wt.%, for example 0.1-3wt.% or 0.1-2wt.%.

In one embodiment, catalyst comprises first metal and does not have other metal (not having second metal etc.).In this embodiment, first metal preferably exists with the amount of 0.1-10wt.%.In another embodiment, catalyst comprises the combination of two or more metals on the carrier.Provide the concrete preferable alloy of the various catalyst of the embodiment of the present invention to form in the following table 1.When catalyst comprised first metal and second metal, first metal preferably exists with the amount of 0.1-5wt.% and second metal preferably exists with the amount of 0.1-5wt.%.When catalyst comprised first metal, second metal and the 3rd metal, first metal preferably existed with the amount of 0.1-5wt.%, and second metal preferably exists with the amount of 0.1-5wt.%, and the 3rd metal preferably exists with the amount of 0.1-2wt.%.When first metal was platinum, first metal preferably existed with the amount of 0.1-3wt.%, and second metal exists with the amount of 0.1-5wt.%, and the 3rd metal, if exist, preferably the amount with 0.1-2wt.% exists.

Depend primarily on and how to make catalyst, the metal of catalyst of the present invention can disperse to spread all over whole carrier, is coated on the outer surface of carrier (eggshell) or modifies (decorate) on carrier surface.

Except that one or more metals, the catalyst of third embodiment of the invention also comprises modified support, and modified support is meant the carrier that comprises carrier material and support modification agent.Especially, use acidity or oxidation-reduction type modified support now unexpectedly to compare the formation that more helps ethyl acetate with other hydrogenation products with unexpectedly proving.

The example of suitable carriers material comprise above about first embodiment described those, and be not limited to comprise ferriferous oxide, silica, aluminium oxide, silica/alumina, titanium dioxide, zirconia, magnesia, calcium silicates, carbon, graphite, high surface graphitized carbon, active carbon and their mixture.Described carrier also comprises the support modification agent, and described support modification agent for example can be selected from: IVB family metal oxide, VB family metal oxide, group vib metal oxide, ferriferous oxide, aluminum oxide and their mixture.These support modification agent are oxidation-reduction type or acid carrier modifier.Preferred oxidation-reduction type support modification agent comprises and is selected from WO ₃, MoO ₃, Fe ₂O ₃And Cr ₂O ₃Those.Preferred acid carrier modifier comprises and is selected from TiO ₂, ZrO ₂, Nb ₂O ₅, Ta ₂O ₅And Al ₂O ₃Those.Preferably, to comprise be to have low volatility or be nonvolatile acidity or the support modification agent of oxidation-reduction type modifier to carrier.Low volatility modifier has enough low forfeiture rate during catalyst life makes the acidity of support modification agent not be reversed (reverse).As implied above, the support modification agent is to join in the carrier rather than natural being present in the carrier.

The modified support gross weight that comprises carrier material and support modification agent is preferably 25wt.%-99.9wt.% based on the total catalyst weight meter, for example 30wt.%-97wt.% or 35wt.%-95wt.%.The support modification agent that q.s preferably is provided is to improve activity

The availability of the quantity of acid position or these acid positions.In preferred embodiments, the support modification agent is in based on total catalyst weight 0.1wt.%-50wt.%, and for example the amount of 0.2wt.%-25wt.%, 0.5wt.%-15wt.% or 1wt.%-8wt.% exists.In preferred embodiments, carrier material is with 25wt.%-99wt.%, and for example the amount of 30wt.%-97wt.% or 35wt.%-95wt.% exists.

If required, this paper also can be used for support modification with above-mentioned first embodiment or second embodiment about the described acidity of third embodiment of the invention or the agent of oxidation-reduction type support modification.

Catalyst of the present invention is being not that to be similar to that automobile catalyst and diesel oil cigarette ash capturing device be impregnated in the washcoated layer on only stone carrier like that be pellet type catalyst on this meaning, catalyst of the present invention is preferably shaped to particle, sometimes be also referred to as pearl or pill, have any different shape, place reactor and catalytic metal is provided to reaction zone by catalyst with a lot of these moulding.Common shape comprises the extrudate with any cross section, the bus that limits the extrudate surface (generator) be parallel lines meaning the above be shaped as the broad sense cylinder.As implied above, can use any grain shape easily that comprises pill, extrudate, ball, spray-dried microspheres, ring, five spoke wheels, trilobal thing, quatrefoil thing and leafy shape thing, although the pref. cylindrical pill.Typically, according to cognition to the gas phase that makes shape is selected according to experience with the ability that catalyst effectively contacts.

In all above-mentioned embodiments, an advantage of catalyst of the present invention is the stability of this catalyst mixture of being used to produce ethyl acetate and ethyl acetate and ethanol or active.Therefore, what can recognize is that catalyst of the present invention can be used in the commercial size commercial Application, particularly production of ethyl of acetic acid hydrogenation fully.Especially, can obtain such extent of stability, this extent of stability makes catalyst activity can have per 100 hours catalyst and uses less than 6%, for example per 100 hours less than 3% or per 100 hours less than 1.5% productive rate fall off rate.Preferably, in case catalyst is realized lower state, just measure the productive rate fall off rate.

The Preparation of catalysts method

Preferably the metal impregnation by carrier and/or modified support forms the carbon monoxide-olefin polymeric of the present invention first, second and the 3rd embodiment, although can also use for example chemical vapour deposition (CVD) of other method.Before impregnating metal, be desirably in usually in case of necessity and form modified support by step with support modification agent impregnated carrier material.On the one hand, in waterborne suspension with support modification agent (WO for example ₃Or TiO ₂) or support modification agent precursor join in the carrier material.For example, can be by solid carrier modifier being joined in the deionized water, then adding the waterborne suspension that the colloidal carrier material forms the support modification agent to it.Can stir the gained mixture and use the profit dipping technique that for example begins that it is joined in the other carrier material, in described beginning profit dipping technique, the support modification agent be joined in the pore volume carrier material identical with the volume of support modification agent solution.Capillarity is with in the hole in the support modification agent suction carrier material then.Can remove water and any volatile component in the support modification agent solution and the support modification agent is deposited on by dry and calcining then and form modified support on the carrier material.Drying can be for example at 50 ℃-300 ℃, for example choose 1-24 hour wantonly under 100 ℃-200 ℃ or the about 120 ℃ temperature, for example the period of 3-15 hour or 6-12 hour.In case form, modified support can be shaped to has the particle that required size distributes, and for example forms the particle that average grain diameter is 0.2-0.4cm.Carrier can be extruded, granulation, compressing tablet, compacting, crushing or screening be the required size distribution.Can use carrier material is shaped to any known method that required size distributes.The calcining of the modified support of moulding can be for example at 250 ℃-800 ℃, for example choose 1-12 hour wantonly under 300-700 ℃ or the about 500 ℃ temperature, for example 2-10 hour, 4-8 hour or about 6 hours period.

In the method for optimizing of preparation catalyst, make metal impregnation on carrier or modified support.The precursor of first metal (first metal precursor) is preferred for the metal impregnation step, and described precursor for example comprises the water soluble compound or the water dispersible compound/complex compound of relevant first metal.Depend on employed metal precursor, can preferably use for example solvent of water, glacial acetic acid or organic solvent.Second metal also preferably is impregnated in carrier or the modified support by second metal precursor.If desired, the 3rd metal or the 3rd metal precursor are impregnated in carrier or the modified support.

By any one or two kinds of addings (the optional dropping) in first metal precursor and/or second metal precursor and/or the other metal precursor (preferably in suspension or solution) are flooded in carrier of doing or modified support.Can for example choose under vacuum heating gained mixture then wantonly desolvates to remove.Can choose wantonly then along with oblique line ascending manner heating is carried out other drying and thereby calcining forms final carbon monoxide-olefin polymeric.When heating and/or applying vacuum, the metal of metal precursor preferably is decomposed into their simple substance (or oxide) form.In some cases, before catalyst comes into operation and calcines the high temperature that for example stands to meet with during operation, can not finish for example removal of water of liquid-carrier.During calcining step, perhaps at least during using the starting stage of catalyst, make these compounds be converted into catalytic activity form or its catalytic activity oxide of metal.

To can (be total to dipping) simultaneously in first and second metals (and optionally other metal) immersion carrier or the modified support or carry out in succession.When flooding at the same time, first and second metal precursors (and optionally other metal precursor) are mixed and it is joined in carrier or the modified support together, then carry out drying and calcining to form final carbon monoxide-olefin polymeric.For dipping simultaneously, if for example water is incompatible for described arbitrary or two kinds of precursors and desired solvent, then can expect to use dispersant, surfactant or solubilizer for example ammonium oxalate to promote dispersing or dissolving of described first and second metal precursors.

When flooding in succession, at first first metal precursor is joined in carrier or the modified support, then carry out drying and calcining, with second metal precursor dipping gained material, then carry out other drying and calcining step then to form final carbon monoxide-olefin polymeric.Additional metals precursor (for example the 3rd metal precursor) can add or the 3rd independent impregnation steps with first and/or second metal precursor, then carries out drying and calcining.Certainly, can use if desired the time in succession and the combination of dipping simultaneously.

Suitable metal precursor comprises for example metal halide of required metal, metal hydroxides, metal nitrate or the metal oxalate of amine solubilising.For example, the suitable combination thing of platinum precursor and palladium precursor comprises platinic hydroxide, platinum nitrate, four ammino platinum nitrates, platinum chloride, JM-216, palladium nitrate, four ammino palladium nitrates, palladium bichloride, oxalic acid palladium, sodium chloride palladium and the sodium chloride platinum of chloroplatinic acid, ammonium chloroplatinate, amine solubilising.Usually, from the viewpoint of economics and environment aspect simultaneously, the aqueous solution of the soluble compound of preferred platinum.In one embodiment, first metal precursor is not metal halide and is substantially free of metal halide.

On the one hand, at first " promoter " metal or metal precursor being joined in the modified support, then is " main (main) " or " primary (primary) " metal or metal precursor.It can certainly be opposite addition sequence.The exemplary precursors of promoter metals comprises metal hydroxides, metal nitrate or the metal oxalate of metal halide, amine solubilising.As implied above, in the sequent embodiment, preferably after each impregnation steps, then carry out drying and calcining.In the situation of the aforesaid bimetallic catalyst that is promoted, can use in succession dipping, add promoter metals during beginning, then comprise for example second impregnation steps of the common dipping of Pt and Sn of two kinds of major metals.

The hydrogenation of acetate

When using the catalyst of first, second and the 3rd embodiment, to recognize easily that as those skilled in the art the method that acetic acid hydrogenation is formed the mixture of ethyl acetate or ethyl acetate and ethanol according to one embodiment of the invention can be carried out in the various structures that use fixed bed reactors or fluidized-bed reactor.In many embodiments of the present invention, can use " thermal insulation " reactor; That is, the internal pipe arrangements (plumbing) that has seldom or do not need to pass a reaction zone adds or removes and reduce phlegm and internal heat.Perhaps, can use the shell-and-tube 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.Obviously recognize in order that the acetate method of reducing of use catalyst of the present invention can carry out in adiabatic reactor, and is little usually a lot of because this reactor structure is compared capital intensity with the shell-and-tube structure.

Typically, catalyst uses in the fixed bed reactors of pipeline that for example is shaped as elongation or conduit, and the reactant that wherein typically is the steam form passes or by described catalyst.If, can use other reactor, for example fluid bed or fluidized bed reactor as wanting.In some cases, hydrogenation catalyst can be used in combination with inert material with the conditioned reaction material flow by 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 ℃-Yue 300 ℃ or 250 ℃-Yue 300 ℃.Pressure can be 10KPa-3000KPa (about 0.1-30 atmospheric pressure), 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 ^-1With in addition 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

In the inventive method on the other hand, carry out hydrogenation with suitable GHSV just being enough to overcome under the pressure of the pressure drop of passing catalytic bed, use higher pressure, should be understood that at for example about 5000hr of high air speed although do not limit ^-1Or 6,500hr ^-1May experience sizable pressure drop down by reactor beds.

Thereby produce 1 mole of acetic acid ethyl ester though per 2 mole of acetic acid of this reaction consume 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 4: 1, for example greater than 5: 1 or greater than 10: 1.

The contact or the time of staying also can vary widely, and depend on amount, catalyst, the reactor of acetate for example, the variable of 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.

Acetate is gasified under reaction temperature, 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, answer the temperature in the control system to make it not drop to the dew point that is lower than acetate.

Especially, use Catalyst And Method of the present invention can obtain the favourable conversion ratio of acetate and to the favourable selectivity and the productive rate of the mixture of ethyl acetate or ethyl acetate and ethanol.For 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.Use the conversion ratio of following equation by gas-chromatography (GC) data computation acetate (AcOH):

For the present invention, described conversion ratio can be at least 10%, for example at least 20%, at least 40%, at least 50%, at least 60% or at least 70% or at least 80%.Though expectation has a for example catalyst of at least 80% or at least 90% of high conversion, low conversion ratio also can be accepted when the selectivity of the mixture of ethyl acetate or ethyl acetate and ethanol is high.Certainly, should fully understand, in many situations, can or use bigger reactor to remedy conversion ratio by suitable recycle stream, but be difficult to remedy poor selectivity.

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 ethyl acetate, claim that then the ethyl acetate selectivity is 50%.The selectivity of the mixture of ethyl acetate (EtOAc) and EtOAc and ethanol (EtOH) uses following equation to calculate by gas-chromatography (GC) data:

Wherein " total mmol C (GC) " is meant the total mole number of the carbon of all products that go out by gc analysis.

For the present invention, catalyst is at least 60% for the selectivity of ethoxylate, for example at least 70% or at least 80%.As used herein, term " ethoxylate " specifically is meant the compound that is transformed for example ethanol, acetaldehyde and the ethyl acetate etc. with at least 2 carbon atoms, but gets rid of ethane.Preferably, the selectivity of ethyl acetate is at least 40%, for example at least 50% or at least 60%.

Preferably, be at least 50%, for example at least 60% or at least 70% for the selectivity of the mixture of ethyl acetate and ethanol.In one embodiment of the invention, ethyl acetate preferably accounts for the major part of product mixtures, for example 50wt.%, for example 55wt.% or 60wt.% at least at least at least.Except that ethyl acetate, also form ethanol, selectivity is for example at least 20%, for example at least 30% or at least 40%.In another embodiment of the invention, this method forms the ethanol as major part, and it is measured for example greater than 50wt.%, as 55wt.% or 60wt.% at least at least.Aspect this, can also form ethyl acetate, selectivity for example is at least 20%, for example at least 30% or at least 40%.Should be understood that in such mixture, if desired, perhaps can make ethyl acetate further react the more ethanol of formation, ethanol is further reacted form more polyacetic acid ethyl ester.

In embodiments of the invention, expect that also for example methane, ethane and carbon dioxide have low selectivity to the product do not expected.These do not expect that product selectivity preferably should be less than 4%, for example less than 2% or less than 1%.Preferably, during hydrogenation, do not generate can detected amount these products of not expecting.In some embodiments of the present invention, the generation of alkane is low, is usually less than 2%, often is lower than 1%, and in many situations, pass catalyst acetate be converted into alkane below 0.5%, described alkane has very little value except that acting as a fuel.

Productive rate is meant based on the regulation product that per hour forms during hydrogenation of the kilogram number meter of the catalyst system therefor gram number of ethyl acetate for example.In one embodiment, preferred every kg catalyst is at least 200 gram ethyl acetate per hour, for example the productive rate of at least 400 gram ethyl acetate or at least 600 gram ethyl acetate.In another embodiment, the per hour ethyl acetate of at least 200 grams and the mixture of ethanol, for example productive rate of the mixture of the ethyl acetate of the ethyl acetate of at least 400 grams and the mixture of ethanol or at least 600 grams and ethanol of preferred every kg catalyst.With regard to scope, the productive rate of ethyl acetate is preferably per hour 200-3 of every kg catalyst, and 000 restrains for example 400-2,500 or 600-2,000 gram ethyl acetate.

Catalyst more of the present invention can be realized at least 10% acetate conversion ratio, and at least 60% ethyl acetate selectivity and every kg catalyst be the productive rate of 200g ethyl acetate at least per hour.Some catalyst in the scope of the invention can be realized at least 50% acetate conversion ratio, at least 70% ethyl acetate selectivity, and the selectivity of not expecting compound less than 4% and every kg catalyst be the productive rate of 600g ethyl acetate at least per hour.

Thick ethyl acetate product

In another embodiment, the present invention relates to the thick ethyl acetate product that forms by any means of the present invention.The thick ethyl acetate product of producing by method of hydrotreating of the present invention, any for example handle purifying subsequently and separate before, typically will mainly comprise unreacted acetate, ethyl acetate and optional ethanol.In some exemplary, crude product comprises based on this crude product gross weight meter 5wt.%-70wt.%, for example ethyl acetate of the amount of 15wt.%-50wt.% or 20wt.%-35wt.%.Crude product can comprise based on this crude product gross weight meter 5wt.%-70wt.%, for example ethanol of the amount of 15wt.%-50wt.% or 20wt.%-35wt.%.Depend on conversion ratio, crude product typically also will comprise unreacted acetate, for example 5-75wt.%, for example amount of 10-60wt.% or 20-50wt.%.Because form water in course of reaction, water also will be for example with 5-50wt.%, is present in the crude product as the amount of 10-45wt.% or 15-35wt.%.Other component is aldehyde, ketone, alkane and carbon dioxide for example, if can detect, can be altogether with less than 10wt.%, for example exist less than 6wt.% or less than the amount of 4wt.%.With regard to scope, other component can be by 0.1-10wt.%, and for example the amount of 0.1-6wt.% or 0.1-4wt.% exists.

In preferred embodiments, depend on concrete catalyst and employed process conditions, thick ethyl acetate product can have any composition that shows in the following table 2.The crude mixture of ethyl acetate and ethanol can have any composition that shows in the following table 3.

Relevant employed raw material with the inventive method can comprise natural gas, oil, coal, living beings etc. derived from any suitable source.Produce acetate by carbonylation of methanol, oxidation of acetaldehyde, ethene oxidation, oxidative fermentation and anaerobic fermentation as everyone knows.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, may become favourable by producing acetate derived from the forming gas (" synthesis gas ") of any available carbon source.For example, the U.S. Patent No. 6,232,352 (incorporating its disclosure into this paper by reference) of Vidalin has been instructed and has been transformed methanol device in order to make the method for acetate.By transforming methanol device, for new acetate device, the substantial contribution expense relevant with the CO generation is significantly reduced or eliminates to a great extent.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 also can be used for preparing the available hydrogen of relevant the present invention.

It is a kind of by making for example method of oil, coal, natural gas and conversion of biomass material production methyl alcohol of carbonaceous material that the U.S. Patent No. RE 35,377 (also incorporating it into this paper by reference) of Steinberg etc. 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.Also referring to the U.S. Patent No. 6,685,754 of the U.S. Patent No. 5,821,111 of Grady etc. and Kindig etc., it discloses a kind of living beings of will giving up and has been converted into the method for synthesis gas by gasification, incorporates their disclosure into this paper by reference.

Perhaps, can be directly the flash chamber of a class carbonylation of methanol unit described in the U.S. Patent No. 6,657,078 (incorporating it into this paper in full by reference) of Scates etc. take out the acetate of steam form as crude product.For example, thick vapor product directly can be given to enter ethanol synthetic reaction district of the present invention and do not need condensation acetate and light fraction or remove to anhydrate, thereby save the overall craft expense.

The ethyl acetate that is obtained by the present invention can use by himself, carries out polymerization or be converted into ethene by cleavage method.Shown that below ethyl acetate is cracked into ethene.

Cracking can be a catalytic reaction of utilizing catalyst for cracking.Suitable catalyst for cracking comprises U.S. Patent No. 4,399, and disclosed sulfonate resin perfluorinated sulfonic resin for example as mentioned above, is incorporated its disclosure into this paper by reference in 305.As U.S. Patent No. 4,620, described in 050 (incorporating its disclosure into this paper by reference), zeolite also is suitable as catalyst for cracking.

Any ethanol in the mixture of the present invention can be used as fuel or be converted into ethene subsequently by himself, and ethene is the important goods raw material, because can be translated into polyethylene, vinyl acetate and/or ethyl acetate or any many other chemical products.For example, can be many polymer and monomer product also with conversion of ethylene.Shown that below ethanol dehydration obtains ethene.

Can use any known dehydration catalyst to make ethanol dehydration, described dehydration catalyst is for example at common pending application U. S. application No.12/221,137 and 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.Though can use the aperture to be at least about any zeolite of 0.6nm, 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.Zeolite catalyst can be used for making simultaneously ethanol dehydration to obtain ethene in height effective method of the present invention and make the ethyl acetate decomposition obtain ethene.

Form therein in the embodiment of mixture of ethyl acetate and ethanol, can expect to make described mixture further reaction so that described mixture is rich in ethyl acetate or ethanol.For example, if desired, thereby the concentration of alcohol that can improve in the mixture by the hydrolysis of ethyl acetate in the presence of acid catalyst prepares extra ethanol and acetate.Acetate recirculation can be got back in the hydrogenation process then.

Following examples have been described the program that is used for preparing the various catalyst that the inventive method uses.

Embodiment

Preparation of Catalyst (generally)

Catalyst carrier before using under circulating air in 120 ℃ of following dried overnight.Unless otherwise mentioned, all commercial carriers (are SiO ₂, TiO ₂) use with 14/30 order or with its original-shape (1/16 inch or 1/8 inch pill).After adding metal with dusty material granulation, crushing and screening.Detailed hereafter the various Preparation of catalysts of the present invention and Comparative Examples.

Embodiment 1-SiO ₂-CaSiO ₃(5)-Pt (3)-Sn (1.8)

This catalyst passes through at first with CaSiO ₃(Aldrich) join SiO ₂Catalyst carrier then adds Pt/Sn and is prepared.At first, CaSiO ₃The waterborne suspension of (≤200 order) then adds 1.0ml colloid SiO by this solid of 0.52g is joined in the 13ml deionized water ₂(15wt.% solution NALCO) is prepared.At room temperature stir this suspension 2 hours, and use beginning profit dipping technique to add 10.0g SiO then ₂Catalyst carrier (14/30 order).After leaving standstill 2 hours, this material is evaporated to dried, then under circulating air in 120 ℃ of following dried overnight and 500 ℃ of calcinings 6 hours down.Then with all SiO ₂-CaSiO ₃Material is used for the Pt/Sn metal impregnation.

This catalyst passes through at first with Sn (OAc) ₂(tin acetate is from the Sn (OAc) of Aldrich ₂) (0.4104g 1.73mmol) joins in the bottle (vial) of glacial acetic acid (Fisher) of dilution in contain 6.75ml 1: 1 and is prepared.At room temperature stir this mixture 15 minutes, and added 0.6711g (1.73mmol) solid Pt (NH then ₃) ₄(NO ₃) ₂(Aldrich).At room temperature stir this mixture other 15 minutes, and then it was added drop-wise to the 5.0gSiO in the 100ml round-bottomed flask ₂-CaSiO ₃In the carrier.This metallic solution of continuous stirring is up to all Pt/Sn mixtures are joined SiO ₂-CaSiO ₃In the carrier and simultaneously each add metallic solution after rotary flask.After the adding of this metallic solution was finished, the flask that will contain impregnated catalyst was kept and is at room temperature left standstill 2 hours.Then this flask is connected to rotary evaporator (bathing 80 ℃ of temperature), finds time until drying and slow simultaneously this flask of rotation.Then under 120 ℃ with the further dried overnight of this material, use following temperature operation to calcine then: 25 → 160 ℃/slope is 5.0deg/min; Kept 2.0 hours; 160 → 500 ℃/slope is 2.0deg/min; Kept 4 hours.Output (yield): 11.21g Dark grey material.

Embodiment 2-KA160-CaSiO ₃(8)-Pt (3)-Sn (1.8)

This material passes through at first with CaSiO ₃Join KA160 catalyst carrier (SiO ₂-(0.05) Al ₂O ₃, Sud Chemie, 14/30 order), then add Pt/Sn and be prepared.At first, CaSiO ₃The waterborne suspension of (≤200 order) then adds 0.8ml colloid SiO by this solid of 0.42g is joined in the 3.85ml deionized water ₂(15wt.% solution NALCO) is prepared.At room temperature stir this suspension 2 hours, and use beginning profit dipping technique to add 5.0g KA160 catalyst carrier (14/30 order) then.After leaving standstill 2 hours, this material is evaporated to dried, then under circulating air in 120 ℃ of following dried overnight and 500 ℃ of calcinings 6 hours down.Then with all KA160-CaSiO ₃Material is used for the Pt/Sn metal impregnation.

This catalyst passes through at first with Sn (OAc) ₂(tin acetate is from the Sn (OAc) of Aldrich ₂) (0.2040g 0.86mmol) joins in the bottle of glacial acetic acid (Fisher) of dilution in contain 6.75ml 1: 1 and is prepared.At room temperature stir this mixture 15 minutes, and added 0.3350g (0.86mmol) solid Pt (NH then ₃) ₄(NO ₃) ₂(Aldrich).At room temperature stir this mixture other 15 minutes, and then it was added drop-wise to the 5.0g SiO in the 100ml round-bottomed flask ₂-CaSiO ₃In the carrier.After the adding of this metallic solution was finished, the flask that will contain impregnated catalyst was kept and is at room temperature left standstill 2 hours.Then this flask is connected to rotary evaporator (bathing 80 ℃ of temperature), finds time until drying and slow simultaneously this flask of rotation.Then under 120 ℃ with the further dried overnight of this material, use following temperature operation to calcine then: 25 → 160 ℃/slope is 5.0deg/min; Kept 2.0 hours; 160 → 500 ℃/slope is 2.0deg/min; Kept 4 hours.Output: 5.19g sepia material.

Embodiment 3-SiO ₂-CaSiO ₃(2.5)-Pt (1.5)-Sn (0.9)

Use following parent material, by with embodiment 1 in identical mode prepare this catalyst: 0.26g CaSiO ₃As the support modification agent; 0.5ml colloid SiO ₂(15wt.% solution, NALCO), the Pt (NH of 0.3355g (0.86mmol) ₃) ₄(NO ₃) ₂And the Sn (OAc) of 0.2052g (0.86mmol) ₂Output: 10.90g Dark grey material.

Embodiment 4-SiO ₂+ MgSiO ₃-Pt (1.0)-Sn (1.0)

Use following parent material, by with embodiment 1 in identical mode prepare this catalyst: 0.69g Mg (AcO) is as the support modification agent; 1.3g colloid SiO ₂(15wt.% solution, NALCO), the Pt (NH of 0.2680g (0.86mmol) ₃) ₄(NO ₃) ₂And the Sn (OAc) of 0.1640g (0.86mmol) ₂Output: 8.35g.With Mg (AcO) solution and colloid SiO ₂Dipping SiO ₂Carrier.This carrier drying also is fired to 700 ℃ then.

Embodiment 5-SiO ₂-CaSiO ₃(5)-Re (4.5)-Pd (1)

Described in embodiment 1, prepare SiO ₂-CaSiO ₃(5) catalyst carrier of modification.Then by with containing NH ₄ReO ₄And Pd (NO ₃) ₂Aqueous solution dipping SiO ₂-CaSiO ₃(5) (1/16 inch extrudate) preparation Re/Pd catalyst.Metallic solution passes through at first with NH ₄ReO ₄(0.7237g 2.70mmol) joins in the bottle that contains the 12.0ml deionized water and is prepared.At room temperature stir this mixture 15 minutes, and added 0.1756g (0.76mmol) solid Pd (NO then ₃) ₂At room temperature stir this mixture other 15 minutes, and then it was added drop-wise to the dry SiO of 10.0g in the 100ml round-bottomed flask ₂-(0.05) CaSiO ₃In the catalyst carrier.After the adding of this metallic solution was finished, the flask that will contain impregnated catalyst was kept and is at room temperature left standstill 2 hours.By carrying out all other processing (dry, calcining) described in the embodiment 1.Output: 10.9g brown materials.

Embodiment 6-SiO ₂-ZnO (5)-Pt (1)-Sn (1)

In circulated air oven atmosphere, under 120 ℃, uniform grading is distributed as the powdered of about 0.2mm and high surface area silica NPSG SS61138 (100g) dried overnight of sieving, and then it is cooled to room temperature.To wherein adding zinc nitrate hexahydrate solution.(＞2 hours, dry gained slurry in 10 ℃/min) the baking oven was then with its calcining being heated to 110 ℃ gradually.(1.74g) diluting nitric acid (1N, 8.5ml) solution in to wherein adding the solution and the tin oxalate (Alfa Aesar) of platinum nitrate (Chempur) in distilled water.Be heated to gradually 110 ℃ (＞2 hours, dry gained slurry in 10 ℃/min) the baking oven.Then 500 ℃ (6 hours, 1 ℃/min) down calcining through the catalyst compounds of dipping.

Embodiment 7-TiO ₂-CaSiO ₃(5)-Pt (3)-Sn (1.8)

This material passes through at first with CaSiO ₃Join TiO ₂Catalyst (anatase, 14/30 order) carrier then is prepared by adding Pt/Sn described in the embodiment 1.At first, CaSiO ₃The waterborne suspension of (≤200 order) then adds 1.0ml colloid SiO by this solid of 0.52g is joined in the 7.0ml deionized water ₂(15wt.% solution NALCO) is prepared.At room temperature stir this suspension 2 hours, and use beginning profit dipping technique to add 10.0gTiO then ₂Catalyst carrier (14/30 order).After leaving standstill 2 hours, this material is evaporated to dried, then under circulating air in 120 ℃ of following dried overnight and 500 ℃ of calcinings 6 hours down.Use the Pt (NH of 0.6711g (1.73mmol) then ₃) ₄(NO ₃) ₂And the Sn (OAc) of 0.4104g (1.73mmol) ₂According to the operation described in the embodiment 1 with all TiO ₂-CaSiO ₃Material is used for the Pt/Sn metal impregnation.The light grey material of output: 11.5g.

Pt (the 2)-Sn (2) of embodiment 8-on high surface area silica

In circulated air oven atmosphere, under 120 ℃, uniform grading is distributed as the powdered of about 0.2mm and high surface area silica NPSG SS61138 (100g) dried overnight of sieving, and then it is cooled to room temperature.To wherein adding six nitric hydrate salt (Chempur) solution.(＞2 hours, dry gained slurry in 10 ℃/min) the baking oven was then with its calcining being heated to 110 ℃ gradually.To wherein adding solution and tin oxalate (Alfa Aesar) the solution in dilution nitric acid of platinum nitrate (Chempur) in distilled water.Be heated to gradually 110 ℃ (＞2 hours, dry gained slurry in 10 ℃/min) the baking oven.Then 500 ℃ (6 hours, 1 ℃/min) down calcining through the catalyst compounds of dipping.

Embodiment 9-KA160-Pt (3)-Sn (1.8)

This material is pressed described in the embodiment 1 by KA 160 catalyst carrier (SiO ₂-(0.05) Al ₂O ₃, Sud Chemie, 14/30 order) beginning profit infusion process dipping be prepared.Metallic solution passes through at first with Sn (OAc) ₂(0.2040g 0.86mmol) joins in the bottle of glacial acetic acid of dilution in contain 4.75ml 1: 1 and is prepared.At room temperature stir this mixture 15 minutes, and added 0.3350g (0.86mmol) solid Pt (NH then ₃) ₄(NO ₃) ₂At room temperature stirred this mixture other 15 minutes, and then it was added drop-wise in the dry KA160 catalyst carrier of 5.0g (14/30 order) in the 100ml round-bottomed flask.By carrying out all other processing, drying and calcining described in the embodiment 16.Output: 5.23g sepia material.

Embodiment 10-SiO ₂-SnO ₂(5)-Pt (1)-Zn (1)

In circulated air oven atmosphere, under 120 ℃, uniform grading is distributed as the powdered of about 0.2mm and high surface area silica NPSG SS61138 (100g) dried overnight of sieving, and then it is cooled to room temperature.To wherein adding tin acetate (Sn (OAc) ₂) solution.(＞2 hours, dry gained slurry in 10 ℃/min) the baking oven was then with its calcining being heated to 110 ℃ gradually.To wherein adding solution and tin oxalate (Alfa Aesar) the solution in dilution nitric acid of platinum nitrate (Chempur) in distilled water.Be heated to gradually 110 ℃ (＞2 hours, dry gained slurry in 10 ℃/min) the baking oven.Then 500 ℃ (6 hours, 1 ℃/min) down calcining through the catalyst compounds of dipping.

Embodiment 11-SiO ₂-TiO ₂(10)-Pt (3)-Sn (1.8)

By being prepared as follows TiO ₂The silica supports of modification.Ti{OCH (CH with 4.15g (14.6mmol) ₃) ₂} ₄Drips of solution in 2-propyl alcohol (14ml) is added to the 10.0g SiO in the 100ml round-bottomed flask ₂In the catalyst carrier (1/16 inch extrudate).Allow this flask at room temperature leave standstill 2 hours, use rotary evaporator (bathing 80 ℃ of temperature) to find time then until drying.Next, the 20ml deionized water is slowly joined this flask, and allow this material keep to leave standstill 15 minutes.The water that produces by removing by filter then/2-propyl alcohol repeats to add H again ₂ O 2 times.Under circulating air under 120 ℃ with final material dried overnight, then 500 ℃ of calcinings 6 hours down.Use the Pt (NH of 0.6711g (1.73mmol) then ₃) ₄(NO ₃) ₂And the Sn (OAc) of 0.4104g (1.73mmol) ₂According to the operation described in the embodiment 1 with all SiO ₂-TiO ₂Material is used for the Pt/Sn metal impregnation.Output: 1/16 inch extrudate of 11.98g Dark grey.

Embodiment 12-SiO ₂-WO ₃(10)-Pt (3)-Sn (1.8)

By being prepared as follows WO ₃The silica supports of modification.(NH with 1.24g (0.42mmol) ₄) ₆H ₂W ₁₂O ₄₀NH ₂O is (AMT) at deionization H ₂Drips of solution among the O (14ml) is added to the 10.0g SiO in the 100ml round-bottomed flask ₂NPSGSS 61138 catalyst carrier (SA=250m ²/ g, 1/16 inch extrudate) in.Allow this flask at room temperature leave standstill 2 hours, use rotary evaporator (bathing 80 ℃ of temperature) to find time then until drying.Under circulating air under 120 ℃ with gained material dried overnight, then 500 ℃ of calcinings 6 hours down.Use the Pt (NH of 0.6711g (1.73mmol) then ₃) ₄(NO ₃) ₂And the Sn (OAc) of 0.4104g (1.73mmol) ₂To own (light yellow) SiO according to the operation described in the embodiment 1 ₂-WO ₃Material is used for the Pt/Sn metal impregnation.Output: 1/16 inch extrudate of 12.10g Dark grey.

Embodiment 13-contrast

Sn on the high-purity low-surface area silica (0.5).In the baking oven under the nitrogen atmosphere, under 120 ℃, uniform grading is distributed as the powdered of about 0.2mm and high-purity low-surface area silica (100g) dried overnight of sieving, and then it is cooled to room temperature.To wherein adding tin oxalate (Alfa Aesar) (1.74g) at dilution nitric acid (1N, 8.5ml) solution in.Be heated to gradually 110 ℃ (＞2 hours, dry gained slurry in 10 ℃/min) the baking oven.Then 500 ℃ (6 hours, 1 ℃/min) down calcining through the catalyst mixture of dipping.

The gas chromatography (GC) of embodiment 14-crude product hydrogenation is analyzed

The catalyst of test implementation example 1-13 is to determine the ethyl acetate as shown in table 4 and the selectivity and the productive rate of ethanol.

Have the 30mm internal diameter and can rise in the tubular reactor of control temperature making, settle listed catalyst in the 50ml table 2 by stainless steel.The length of charging back total catalyst bed is approximately about 70mm.Make the reaction feed liquid evaporation of acetate and be encased in the reactor with hydrogen with as the helium of carrier gas with the average total gas hourly space velocity (GHSV) shown in the table 4, temperature and pressure.Described incoming flow contains the mol ratio of hydrogen and acetate as shown in table 4.

Carry out the analysis of product by online GC.Use is equipped with the integrated GC of triple channel of 1 flame ionization detector (FID) and 2 thermal conductivity detector (TCD)s (TCD) to come analytical reactions thing and product.Prepass is equipped with FID and CP-Sil 5 (20m)+WaxFFap (5m) pillar and is used for quantizing: acetaldehyde; Ethanol; Acetone; Methyl acetate; Vinyl acetate; Ethyl acetate; Acetate; Ethylene acetate; Ethylene glycol; The oxalic acid ethyl; And para-acetaldehyde.Center-aisle is equipped with TCD and Porabond Q pillar and is used for quantizing: CO ₂Ethene; And ethane.Back passage is equipped with TCD and Molsieve 5A pillar and is used for quantizing: helium; Hydrogen; Nitrogen; Methane; And carbon monoxide.

Before reaction, by forming the retention time of spike mensuration different component with independent compound, and GC is calibrated with the calibration gas of known composition or with the liquid solution of known composition.This allows to measure the response factor of each component.

Embodiment 15

At 6570h ^-1Air speed and the pressure of 200psig (about 1379kPag) under make the acetate of gasification and hydrogen with about 160sccm/min H ₂: the hydrogen of 0.09g/min HOAc passes hydrogenation catalyst of the present invention with the ratio of acetate, and it is about 250m that this hydrogenation catalyst is included in surface area ²2wt.%Pt, 2wt%Sn on the high surface area silica of/g (NPSG SS61138), the about 60sccm/min N of described hydrogen ₂Dilution.Temperature is by improving at about 50 hours, 70 hours and 90 hours shown in Fig. 3 and Fig. 4.Shown among Fig. 3 in the productive rate of the gram number of product shown in every kg catalyst (ethanol, acetaldehyde and ethyl acetate) per hour, shown among Fig. 4 that catalyst is for various product selectivity, top line is represented the productive rate of ethyl acetate or selectivity, middle lines represent that for ethanol yield or selectivity, bottom line is represented the productive rate of acetaldehyde or selectivity.Think to be especially significantly that the productive rate and the selectivity of acetaldehyde are low.Fig. 3 and 4 proofs, described catalyst makes this catalyst fully be suitable for so-called adiabatic reactor to the insensitivity of variations in temperature, in adiabatic reactor owing to low and unevenly remove the speed reduce phlegm and internal heat from reactor and cause that the temperature on the catalyst bed may alter a great deal.

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 quoted from appended claims and the various piece of a plurality of embodiment and a plurality of features can partly or entirely make up or exchange.In the description of aforementioned each embodiment, can recognize that as those skilled in the art 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. catalyst, this catalyst comprises first metal, second metal and carrier, wherein first metal is selected from nickel, palladium and platinum and to exist based on the amount of total catalyst weight greater than 1wt.%, wherein second metal is selected from molybdenum, rhenium, zirconium, copper, cobalt, tin and zinc, and wherein said catalyst has the ethyl acetate selectivity greater than 40%.

2. the catalyst of claim 1, wherein said first metal is to exist greater than 1wt.% and less than the amount of 25wt% based on total catalyst weight.

3. the catalyst of claim 1, wherein said carrier exists in the amount based on total catalyst weight 25wt.%-99wt.%.

4. the catalyst of claim 1, wherein said carrier chosen from Fe oxide, silica, aluminium oxide, silica/alumina, titanium dioxide, zirconia, magnesia, calcium silicates, carbon, graphite, high surface graphitized carbon, active carbon and their mixture.

5. the catalyst of claim 1, this catalyst also comprises at least a support modification agent, described support modification agent is 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.

6. the catalyst of claim 1, this catalyst also comprises at least a support modification agent, and described support modification agent is selected from: IVB family metal oxide, VB family metal oxide, group vib metal oxide, ferriferous oxide, aluminum oxide and their mixture.

7. the catalyst of claim 1, wherein said second metal exists in the amount based on total catalyst weight 0.1-10wt.%.

8. the catalyst of claim 1, wherein said catalyst has selectivity less than 4% for methane, ethane and carbon dioxide.

9. the catalyst of claim 1, wherein said catalyst have per 100 hours catalyst and use the productive rate that reduces less than 6%.

10. the catalyst of claim 1, wherein said catalyst has 50m ²/ g-600m ²The surface area of/g.

11. a method for preparing catalyst, this method comprises:

(a) first metal precursor of first metal is contacted with carrier, wherein said first metal is selected from nickel, palladium and platinum;

(b) second metal precursor of second metal is contacted with carrier, wherein said second metal is selected from molybdenum, rhenium, zirconium, copper, cobalt, tin and zinc; And

(c) at effective reduction described first metal and second metal and form the described carrier of heating under the condition of catalyst, wherein said catalyst comprises based on first metal of total catalyst weight meter greater than the amount of 1wt%.

12. the method for claim 11, wherein said heating is carried out afterwards in step (a) with (b).

13. the method for claim 11, wherein said heating are carried out in step (a) with (b) to reduce described first metal and carry out afterwards to reduce described second metal in step (a) with (b).

14. catalyst, this catalyst comprises first metal, second metal and silica/alumina carrier, wherein first metal is selected from nickel, palladium and platinum, second metal is selected from molybdenum, rhenium, zirconium, copper, cobalt, tin and zinc, and wherein the silica/alumina carrier comprises based on the gross weight meter of high surface area silica/alumina support greater than the aluminium of the amount of 1wt.% and have 150m at least ²The surface area of/g, wherein catalyst has the ethyl acetate selectivity greater than 40%.

15. a catalyst, this catalyst comprises first metal, second metal and carrier, and wherein first metal is selected from nickel and palladium, and wherein second metal is selected from tin and zinc, and wherein said catalyst has the ethyl acetate selectivity greater than 40%.

16. the catalyst of claim 15, wherein said first metal exists in the amount based on total catalyst weight 0.1-25wt.%.

17. the catalyst of claim 15, wherein said carrier exists in the amount based on total catalyst weight 25wt.%-99.9wt.%.

18. the catalyst of claim 15, wherein said carrier has 50m ²/ g-600m ²The surface area of/g.

19. the catalyst of claim 15, wherein said carrier chosen from Fe oxide, silica, aluminium oxide, silica/alumina, titanium dioxide, zirconia, magnesia, calcium silicates, carbon, graphite, high surface graphitized carbon, active carbon and their mixture.

20. the catalyst of claim 15, this catalyst also comprises at least a support modification agent, and described support modification agent is 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.

21. the catalyst of claim 15, this catalyst also comprise at least a support modification agent, described support modification agent is selected from: IVB family metal oxide, VB family metal oxide, group vib metal oxide, ferriferous oxide, aluminum oxide and their mixture.

22. the catalyst of claim 15, wherein said second metal exists in the amount based on total catalyst weight 0.1-10wt.%.

23. the catalyst of claim 15, wherein said catalyst has selectivity less than 4% for methane, ethane and carbon dioxide and their mixture.

24. having per 100 hours catalyst, the catalyst of claim 15, wherein said catalyst use the productive rate that reduces less than 6%.

25. the catalyst of claim 15, wherein said catalyst have the ethyl acetate selectivity greater than 50%.

26. a method for preparing catalyst, this method comprises:

(a) first metal precursor of first metal is contacted with carrier, wherein said first metal is selected from nickel and palladium;

(b) second metal precursor of second metal is contacted with carrier, wherein said second metal is selected from tin and zinc; And

(c) at effective reduction described first metal and second metal and form the described carrier of heating under the condition of catalyst.

27. the method for claim 26, wherein said heating is carried out afterwards in step (a) with (b).

28. the method for claim 26, wherein said heating are carried out in step (a) with (b) to reduce described first metal and carry out afterwards to reduce described second metal in step (a) with (b).

29. the method for claim 26, wherein step (b) is carried out before in step (a).

30. a catalyst, this catalyst comprise first metal, carrier and at least a support modification agent, described support modification agent is selected from the IVB family metal oxide, the VB family metal oxide, group vib metal oxide, ferriferous oxide, aluminum oxide and their mixture.

31. the catalyst of claim 30, wherein said first metal is selected from IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII group 4 transition metal, lanthanide series metal, actinide metals, the perhaps metal of any family in IIIA, IVA, VA or the VIA family.

32. the catalyst of claim 30, wherein said first metal is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten.

33. the catalyst of claim 30, wherein said first metal exists in the amount based on total catalyst weight 0.1-25wt.%.

34. the catalyst of claim 30, wherein said at least a support modification agent is selected from WO ₃, MoO ₃, Fe ₂O ₃, Cr ₂O ₃, TiO ₂, ZrO ₂, Nb ₂O ₅, Ta ₂O ₅And Al ₂O ₃

35. the catalyst of claim 30, wherein said at least a support modification agent exists in the amount based on total catalyst weight 0.1wt.%-50wt.%.

36. the catalyst of claim 30, wherein said carrier exists in the amount based on total catalyst weight 25wt.%-99wt.%.

37. the catalyst of claim 30, wherein said carrier chosen from Fe oxide, silica, aluminium oxide, silica/alumina, titanium dioxide, zirconia, magnesia, calcium silicates, carbon, graphite, high surface graphitized carbon, active carbon and their mixture.

38. the catalyst of claim 31, wherein said catalyst also comprise second metal that is different from first metal.

39. the catalyst of claim 38, wherein said first metal is a platinum, and second metal is a tin.

40. the catalyst of claim 39, wherein the mol ratio of platinum and tin is 0.65: 0.35-0.95: 0.05.

41. the catalyst of claim 38, wherein said first metal is a palladium, and second metal is a rhenium.

42. the catalyst of claim 41, wherein the mol ratio of rhenium and palladium is 0.65: 0.35-0.95: 0.05.

43. the catalyst of claim 38, 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.

44. the catalyst of claim 38, wherein said second metal exists in the amount based on total catalyst weight 0.1-10wt.%.

45. the catalyst of claim 38, wherein said catalyst also comprise the 3rd metal that is different from first and second metals.

46. the catalyst of claim 45, wherein said the 3rd metal is selected from cobalt, palladium, ruthenium, copper, zinc, platinum, tin and rhenium.

47. the catalyst of claim 45, wherein said the 3rd metal exists in the amount based on total catalyst weight 0.05 and 4wt.%.

48. the catalyst of claim 30, wherein said catalyst have at least 40% ethyl acetate selectivity.

49. the catalyst of claim 30, wherein said catalyst has selectivity less than 4% for methane, ethane and carbon dioxide and their mixture.

50. having per 100 hours catalyst, the catalyst of claim 30, wherein said catalyst use the productive rate that reduces less than 6%.

51. a method for preparing catalyst, this method may further comprise the steps:

(a) first metal precursor of first metal is contacted with the modified support that comprises at least a support modification agent, described support modification agent is selected from the IVB family metal oxide, the VB family metal oxide, the group vib metal oxide, ferriferous oxide, aluminum oxide and their mixture; And

(b) at effective described first metal of reduction and form the described modified support of heating under the condition of catalyst, wherein said catalyst has the ethyl acetate selectivity greater than 40%.

52. the method for claim 51, wherein said heating is carried out afterwards in step (a) with (b).

53. the method for claim 51, wherein said heating are carried out in step (a) with (b) to reduce described first metal and carry out afterwards to reduce described second metal in step (a) with (b).

54. the method for claim 51, this method is following steps also:

(c) at least a support modification agent or its precursor are contacted to form the precursor carrier of modification with carrier material; And

(d) precursor carrier of the described modification of heating under the condition that effectively forms modified support.