CN102333588A

CN102333588A - Be used for preparing the catalyst of ethanol by acetate

Info

Publication number: CN102333588A
Application number: CN2010800039266A
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: 2012-01-25
Anticipated expiration: 2030-02-02
Also published as: CN102333588B; WO2011056247A2; MX337472B; WO2011056247A3; AU2010315899A2; MX2012004839A; AU2010315899A1; BR112012009792A2; EP2493606A2; CA2778767A1

Abstract

Catalyst and the method that is used to form catalyst, said catalyst is used for acetic acid hydrogenation is formed ethanol.In one embodiment, this catalyst comprises first metal, contains silicon carrier and the agent of at least a metasilicate support modification.Preferably, said first metal is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten.This catalyst can comprise second metal that is preferably selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel in addition.

Description

Be used for preparing the catalyst of ethanol by acetate

Priority request

The exercise question that the application requires to submit on October 26th, 2009 is incorporated it into this paper by reference in full for the priority of No. 12/588,727, the U. S. application of " Tunable CatalystGas Phase Hydrogenation of Carboxylic Acids ".

Invention field

Present invention relates in general to employed catalyst in the method that acetic acid hydrogenation is formed ethanol, this catalyst has high selectivity to ethanol.

Background of invention

Existence is to the economically feasible method that acetate is converted into ethanol and the long-term needs of catalyst; Said ethanol can use or be converted into subsequently ethene by himself; Said ethene is important commodity raw material, because can be translated into 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.It is the cost fluctuation of the ethene in source with oil or natural gas that natural gas and the crude oil price of fluctuation helps to make what produce according to routine, thus when oil price rises feasible to alternative ethene originate need be bigger than in the past.

The catalysis process of alkanoic acid and other carbonyl containing compound of being used to reduce has obtained broad research, in document, has mentioned the various combinations of catalyst, carrier and operating condition.T.Yokoyama etc. have commented the reduction of various carboxylic acids on metal oxide in " Fine chemicals through heterogeneous catalysis.Carboxylicacids and derivatives ".Some that the exploitation of the hydrogenation catalyst that is used for various carboxylic acids is attempted have been summarized in the 8.3.1 chapter.(Yokoyama，T.；Setoyama，T.“Carboxylic?acids?and?derivatives.”in：“Fine?chemicals?through?heterogeneous?catalysis.”2001，370-379.)。

A series of researchs of M.A.Vannice etc. relate to conversion (the Rachmady W. of acetate on various heterogeneous catalysis; Vannice, M.A.; J Catal. (2002) Vol.207, the 317-330 page or leaf).In difference research, reported on load and unsupported iron and used H ₂With the acetate vapour phase reduction.(Rachmady, W.; Vannice, M.A.J.Catal. (2002) Vol.208,158-169 page or leaf).At Rachmady, W.; Vannice, M.A., J.Catal. (2002) Vol.208,170-179 page or leaf) in provided out of Memory about catalyst surface material and organic intermediate.At Rachmady, W.; Vannice, M.A.J Catal. (2002) Vol.209,87-98 page or leaf) and Rachmady, W.; Vannice, M.A.J Catal. (2000) Vol.192,322-334 page or leaf) in further studied the vapor phase acetic acid hydrogenation on a series of support type Pt-Fe catalyst.

The various relevant publication that relates to the selective hydrogenation of unsaturated aldehyde can find in following: (Djerboua, F.; Benachour, D.; Touroude, R.Applied Catalysis A:General 2005,282,123-133.; Liberkova, K.; Tourounde, R.J.Mol.Catal.2002,180,221-230.; Rodrigues, E.L.; Bueno, J.M.C.AppliedCatalysis A:General 2004,257,210-211.; Ammari, F.; Lamotte, J.; Touroude, R.J.Catal.2004,221,32-42; Ammari, F.; Milone, C; Touroude, R.J.Catal.2005,235,1-9.; Consonni, M.; Jokic, D.; Murzin, D.Y.; Touroude, R.J.Catal.1999,188,165-175.; Nitta, Y.; Ueno, K.; Imanaka, T.; Applied Catal.1989,56,9-22.).

Having reported the catalyst that contains cobalt, platinum and tin is being that activity and Study on Selectivity in the unsaturated alcohol finds in following: (Djerboua, the F. of R.Touroude etc. with crotonaldehyde selective hydrogenation; Benachour, D.; Touroude, R.Applied Catalysis A:General 2005,282,123-133 and Liberkova, K.; Tourounde, R.; J.Mol.Catal.2002,180,221-230) and (Lazar, the K of K.Lazar etc.; Rhodes, W.D.; Borbath, I.; Hegedues, M.; Margitfalvi, 1.L.HyperfineInteractions 2002,1391140,87-96.).

(Santiago, M.A.N. such as M.Santiago; Sanchez-Castillo, M.A.; Cortright, R.D.; Dumesic, 1.A.J Catal.2000,193,16-28.) the microcalorimetric method measurement, ft-ir measurement and the kinetics that make up with quantum chemistry calculation have been discussed and have been measured.

Also reported catalytic activity for acetic acid hydrogenation with regard to heterogeneous system with rhenium and ruthenium.(Ryashentseva，M.A.；Minachev，K.M.；Buiychev，B.M.；Ishchenko，V.M.Bull.Acad?Sci.USSR1988，2436-2439)。

The United States Patent(USP) No. 5,149,680 of Kitson etc. has been described a kind of platinum group metal Au catalyst that utilizes with carboxylic acid and their the acid anhydrides catalytic hydrogenation method for alcohol and/or ester.The United States Patent(USP) No. 4,777,303 of Kitson etc. has been described a kind of method of producing alcohol through hydrogenation of carboxylic acids.The United States Patent(USP) No. 4,804,791 of Kitson etc. has been described another kind of method of producing alcohol through hydrogenation of carboxylic acids.Also referring to USP 5,061,671; USP 4,990, and 655; USP 4,985, and 572; With USP 4,826,795.

Malinowski etc. (Bull Soc.Chim.Belg. (1985), 94 (2), 93-5) discussed acetate in heterogeneousization in carrier material silica (SiO for example ₂) or titanium dioxide (TiO ₂) on the low price titanium on catalytic reaction.

Bimetallic ruthenium-Xi/SiO 2 catalyst makes through making tetrabutyltin and the ruthenic oxide reaction that loads on the silica.(Loessard etc., Studies in Surface Science andCatalysis (1989), Volume Date 1988,48 (Struct.React.Surf), 591-600.).

For example, also studied the catalytic reduction of acetate in Hindermann etc. (Hindermann etc., J.Chem.Res., Synopses (1980), (11), 373), disclose acetate on the iron and the catalytic reduction on the iron that alkali promotes.

Existing method is subjected to hinder the variety of issue of commercial viability, comprising: (i) catalyst does not have the necessary choice property to ethanol; (ii) catalyst is might be too expensive and/or the generation of ethanol is non-selective and produces unwanted accessory substance; And/or (iii) not enough catalyst life.Therefore, need have high selectivity, conversion ratio and and productive rate and have the novel hydrogenation catalyst of the catalyst life that is suitable for commercial hydrogenation technique to ethanol.

Summary of the invention

The present invention relates to catalyst and the method that is used to prepare catalyst, said catalyst is applicable to that with high selectivity be the method for ethanol with acetic acid hydrogenation.

For example, in one embodiment, the present invention relates to comprise first metal, contain silicon carrier, the catalyst of at least a metasilicate (metasilicate) support modification agent and optional second metal.In another embodiment, catalyst comprises first metal, second metal, contains silicon carrier and at least a support modification agent.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.More preferably; First metal can be selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten, and second metal is selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, rhenium and nickel.First metal can exist by the amount based on total catalyst weight 0.1-25 weight %.

Second metal can be selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel.Based on the total catalyst weight meter, first metal can exist by the amount of 0.1-10 weight %, and second metal can exist by the amount of 0.1-10 weight %.On the one hand, catalyst can comprise the 3rd metal, and the 3rd metal can be selected from cobalt, palladium, ruthenium, copper, zinc, platinum, tin and rhenium and/or it can exist by the amount based on total catalyst weight 0.05 and 4 weight %.

Preferably, first metal is a platinum, and second metal is a tin, and the mol ratio of platinum and tin is 0.4: 0.6-0.6: 0.4.In another preferably made up, first metal was a palladium, and second metal is a rhenium, and the mol ratio of rhenium and palladium is 0.7: 0.3-0.85: 0.15.As stated, catalyst can be adapted at that acetate is converted into and is used as in the ethanol hydrogenation catalyst and produce at least 10% acetate conversion ratio.In addition, catalyst can have the selectivity of at least 80% pair of ethanol and/or less than the selectivity of 4% pair of 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%.

Containing silicon carrier can choose wantonly and be selected from silica, silica/alumina, calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture and can be by existing based on the amount of total catalyst weight 25 weight %-99 weight %.Contain silicon carrier and have 50m ²/ g-600m ²The surface area of/g.

Support modification agent for example metasilicate support modification agent can be chosen wantonly and is selected from: (i) alkaline-earth metal metasilicate, (ii) alkali metal silicate, (iii) IIB family metal metaphosphate silicate, (iv) IIIB family metal metaphosphate silicate and their mixture.As a kind of selection, the support modification agent can be selected from the metasilicate of metal, and said metal is selected from sodium, potassium, magnesium, scandium, yttrium and zinc, preferred CaSiO ₃The support modification agent can exist by the amount based on total catalyst weight 0.1 weight %-50 weight %.

In another embodiment, catalyst satisfies following formula:

Pt _vPd _wRe _xSn _yCa _pSi _qO _r，

Wherein: the ratio of (i) v: y is 3: 2-2: 3, and/or (ii) the ratio of w: x is 1: 3-1: 5; The selection of p and q makes that p: q is 1: 20-1: 200, and wherein the chemical valence requirement is satisfied in the selection of r, and the selection of v and w makes:

0.005 \leq \frac{(3.25 v + 1.75 w)}{q} \leq 0.05 .

Select as another kind, catalyst can satisfy following formula:

Pt _vPd _wRe _xSn _yAl _zCa _pSi _qO _r，

Wherein: (i) v and y are 3: 2-2: 3; And/or (ii) w and x are 1: 3-1: 5; The aluminium atom of control p and z and existence and the relative position of calcium atom make

acid position that is present in its surface carry out balance through the support modification agent; The selection of p and q makes that p: q is 1: 20-1: 200, and wherein the chemical valence requirement is satisfied in the selection of r, and the selection of v and w makes:

0.005 \leq \frac{(3.25 v + 1.75 w)}{q} \leq 0.05 .

Except that catalyst, the invention still further relates to the method for preparing catalyst.Embodiment preferred relates to the method for preparing catalyst; This method may further comprise the steps: first metal precursor of first metal is contacted with modified silicon-contained carrier to form the carrier of dipping, and wherein said modified silicon-contained carrier comprises siliceous (silicaceous) material and the agent of at least a metasilicate support modification; (b) at effective said first metal of reduction and form the said impregnated carrier of heating under the condition of catalyst.Preferably, said heating is carried out under reducing atmosphere at least in part.Randomly, this method can also may further comprise the steps: the agent of at least a metasilicate support modification or its precursor are contacted with material to form the precursor carrier of modification; (d) precursor carrier of the said modification of heating under the condition that effectively forms modified support, and can comprise calcined catalyst.On the one hand, this method is further comprising the steps of: in step (a) and (b) before, afterwards or simultaneously, dipping and reduction are different from second metal precursor of second metal of said first metal on carrier.Aspect another, this method is further comprising the steps of: in step (a) and (b) before, afterwards or simultaneously, dipping and reduction are different from the 3rd metal precursor of the 3rd metal of said first metal and second metal on carrier.

In addition; Another embodiment of the invention relates to the method that may further comprise the steps: first metal precursor of first metal is contacted with the modified silicon-contained carrier that comprises at least a support modification agent, and wherein said first metal is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten; (b) second metal precursor of second metal that is different from said first metal is contacted with modified silicon-contained carrier, wherein said second metal is selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, rhenium and nickel; (c) at effective reduction said first metal and second metal and form the said modified silicon-contained carrier of heating under the condition of catalyst.On the one hand, said heating is carried out in step (a) with (b) afterwards.Perhaps, said heating is carried out (optional at least in part under reducing atmosphere) to reduce first metal and carry out afterwards to reduce second metal in step (a) with (b) in step (a) with (b).Randomly, this method can also may further comprise the steps: the agent of at least a metasilicate support modification or its precursor are contacted with material to form the precursor carrier of modification; (d) precursor carrier of the said modification of heating under the condition that effectively forms modified support, and can comprise calcined catalyst.Said calcining can be in step (a) and (b) is carried out afterwards or in step (a) with (b).Aspect another, this method is further comprising the steps of: in step (a) and (b) before, afterwards or simultaneously, dipping and reduction are different from the 3rd metal precursor of the 3rd metal of first metal and second metal on carrier.

About method of the present invention; Catalyst that utilizes in the inventive method and component thereof; For example first metal, second metal, the 3rd metal (optional), (siliceous) carrier and the agent of (metasilicate) support modification can be described about catalyst of the present invention like preceding text.

Accompanying drawing is briefly described

Describe the present invention in detail with reference to accompanying drawing below, 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 A be 15 hours whens test catalyst for the coordinate diagram of ethanol yield;

Fig. 3 B is that the catalyst of Fig. 3 A is for ethanol coordinate diagram optionally;

Fig. 4 A be according to another embodiment of the invention in test in 100 hours catalyst for the coordinate diagram of ethanol yield;

Fig. 4 B is the optionally coordinate diagram of the catalyst of Fig. 4 A for ethanol;

Fig. 5 A be according to another embodiment of the invention in test in 20 hours catalyst for the coordinate diagram of ethanol yield;

Fig. 5 B is the optionally coordinate diagram of the catalyst of Fig. 5 A for ethanol;

Fig. 6 A is the coordinate diagram of conversion ratio of the catalyst of embodiment 18;

Fig. 6 B is the coordinate diagram of productive rate of the catalyst of embodiment 18;

Fig. 6 C is the optionally coordinate diagram of catalyst under 250 ℃ of embodiment 18; And

Fig. 6 D is the optionally coordinate diagram of catalyst under 275 ℃ of embodiment 18.

Detailed Description Of The Invention

The present invention relates to be used for through in the presence of catalyst, acetic acid hydrogenation being produced the catalyst of the method for ethanol.Employed catalyst comprises at least a metal, contains silicon carrier and at least a support modification agent, preferred metasilicate support modification agent.The invention still further relates to the method that is used to prepare these catalyst.

Acetic acid hydrogenation is formed ethanol can be represented by following reaction:

Unexpected and unexpectedly find, catalyst of the present invention provides when being used for acetic acid hydrogenation the ethoxylate high selectivity of ethanol and ethyl acetate, particularly ethanol for example.Embodiment of the present invention can be advantageously used in commercial Application with by economically feasible large-scale production ethanol.

Catalyst of the present invention comprises first metal and optional and comprises second metal, the 3rd metal or one or more in the metal in addition on carrier.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.The gross weight that is present in all carried metals in the catalyst is preferably 0.1-25 weight %, for example 0.1-15 weight % or 0.1 weight %-10 weight %.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 metal oxides.With regard to the percetage by weight of metal in confirming catalyst, ignore the weight of any oxygen that combines with metal.

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 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 availability of platinum, preferred catalyst comprised less than 5 weight %, for example less than 3 weight % or less than the platinum of the amount of 1 weight %.

As implied above, optional second metal that also comprises of catalyst, this second metal typical ground can play promoter.If exist, second metal is preferably selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold and nickel.More preferably, second metal is selected from copper, tin, cobalt, rhenium and nickel.More preferably, second metal is selected from tin and rhenium.

When catalyst comprised two kinds or more kinds of metal, 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 following catalytic activity mechanism.

If catalyst comprises two kinds or more kinds of metal, for example first metal and second metal, then first metal is optional with 0.1-10 weight %, and for example the amount of 0.1-5 weight % or 0.1-3 weight % is present in the catalyst.Second metal is preferably with 0.1-20 weight %, and for example the amount of 0.1-10 weight % or 0.1-5 weight % exists.For the catalyst that comprises two kinds or more kinds of metals, said two kinds or more kinds of metal be alloying or can comprise non-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 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.Reveal that the people expects and unexpectedly find, shown in Figure 1A, 1B and 1C, for platinum/tin catalyst, especially preferred about 0.4: 0.6-0.6: platinum of 0.4 (or about 1: 1) and tin mol ratio are to form ethanol by acetate with high selectivity, conversion ratio and productive rate.The selectivity of ethanol can be further improved through introducing modified support as herein described.

For the catalyst that comprises different metal, the preferred mol ratio except that 1: 1.For example, for rhenium/palladium catalyst, when the rhenium carrying capacity is higher than palladium carrying capacity, can obtain higher ethanol selectivity.Shown in Fig. 2 A, 2B and 2C, form ethanol, with regard to selectivity, conversion ratio and productive rate, preferred rhenium and palladium mol ratio are about 0.7: 0.3-0.85: 0.15 or about 0.75: 0.25 (3: 1).Again, the ethanol selectivity can be further improved through introducing modified support as herein described.

In the embodiment when catalyst comprises the 3rd metal, the 3rd metal can be selected from preceding text about the listed any metal of first or second metal, as long as said the 3rd metal is different from said 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 0.05-4 weight %, for example 0.1-3 weight % or 0.1-2 weight %.

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 0.1-10 weight %.In another embodiment, catalyst comprises two kinds or the combination of more kinds of metals on the carrier.The concrete preferable alloy combination of the various catalyst of the embodiment of the present invention is provided in the following table 1.When catalyst comprised first metal and second metal, first metal preferably exists with the amount of 0.1-5 weight % and second metal preferably exists with the amount of 0.1-5 weight %.When catalyst comprised first metal, second metal and the 3rd metal, first metal preferably existed with the amount of 0.1-5 weight %, and second metal preferably exists with the amount of 0.1-5 weight %, and the 3rd metal preferably exists with the amount of 0.1-2 weight %.In an exemplary, first metal is platinum and exists with the amount of 0.1-5 weight % that second metal exists with the amount of 0.1-5 weight %, and the 3rd metal, if exist, preferably the amount with 0.05-2 weight % 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 one or more metals, catalyst of the present invention also comprises modified support, and modified support is meant the carrier that comprises carrier material and support modification agent, and the acidity of carrier material is regulated in said support modification agent.For example, the acid position on the carrier material as acid position can be regulated during acetic acid hydrogenation, to help the selectivity to ethanol through the support modification agent.Carrier material by reducing the acidity of the carrier material

or decrease the number of acid sites of the carrier material

acid site availability to be adjusted.Carrier material can also be regulated through the pKa that makes the support modification agent change carrier material.Only if context indicates in addition, surface acidity on it or sour bit quantity can be edited " Characterization of Heterogeneous Catalysts " through F.Delannay; 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.The existing discovery, except that employed metal precursor and preparation condition, metal-carrier interacts can have strong influence to the ethanol selectivity.Especially, carrier acidity is regulated in use so that carrier has the modified support of less acidity or big alkalescence, reveals people's expectation and unexpectedly proves with other hydrogenation products and compare the formation that more helps ethanol.

Those of skill in the art would recognize that carrier material selected to make caltalyst tie up to and be used to generate under the process conditions of ethanol and have suitable activity, selectivity and robustness (robust).The suitable carriers material can comprise for example stable metal oxide base carrier or ceramic base carrier.Preferred carrier comprises and contains silicon carrier, for example silica, silica/alumina, IIA family silicate such as calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.Other carrier can be used in embodiments more of the present invention, includes but not limited to graphitized carbon, active carbon and their mixture of ferriferous oxide, aluminium oxide, titanium dioxide, zirconia, magnesia, carbon, graphite, high surface.

In preferred embodiments, carrier comprises the basic supports modifier with 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).The alkaline modifier of this type for example can be selected from: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) IIB family metal oxide, (vi) IIB family metal metaphosphate silicate, (vii) IIIB family metal oxide, (viii) IIIB family metal metaphosphate silicate and their mixture.Except that oxide and metasilicate, can in embodiment of the present invention, use the modifier that comprises nitrate, nitrite, acetate and Lactated other type.Preferably, the support modification agent is selected from the oxide and the metasilicate of arbitrary element in sodium, potassium, magnesium, calcium, scandium, yttrium and the zinc, and aforementioned mixture arbitrarily.Preferably, the support modification agent is a calcium silicates, more preferably calcium metasilicate (CaSiO ₃).If the support modification agent comprises calcium metasilicate, then at least a portion of preferred calcium metasilicate is with crystal form.

The modified support gross weight that comprises carrier material and support modification agent is preferably 75 weight %-99.9 weight % based on the total catalyst weight meter, for example 78 weight %-97 weight % or 80 weight %-95 weight %.The support modification agent that q.s preferably is provided is to regulate acidity; For example through quantity that reduces the sour position of activity

or the availability that reduces active

sour, more preferably to guarantee that carrier surface does not have activity acid position basically.In preferred embodiments, the support modification agent is in based on total catalyst weight 0.1 weight %-50 weight %, and for example the amount of 0.2 weight %-25 weight %, 0.5 weight %-15 weight % or 1 weight %-8 weight % exists.In preferred embodiments, carrier material is with 25 weight %-99 weight %, and for example the amount of 30 weight %-97 weight % or 35 weight %-95 weight % exists.

In one embodiment, carrier material is 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 guarantees advantageously that as containing in the situation of silicon carrier the amount of aluminium (it is the common pollutant of silica) is low therein, is preferably based on modified support gross weight meter below 1 weight %, for example below the 0.5 weight % or below the 0.3 weight %.Thus, preferred pyrolytic silicon dioxide is because it generally obtains with the purity that surpasses 99.7 weight %.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 0.3 weight %, for example less than 0.2 weight % or the silica that exists less than the level of 0.1 weight %.When calcium metasilicate as the support modification agent, needn't be very strict about purity as the silica of carrier material, although aluminium remain do not expect and will not be to have a mind to add usually.The aluminium content of this silica for example can be less than 10 weight %, for example less than 5 weight % or less than 3 weight %.Carrier comprises in the situation of support modification agent of 2 weight %-10 weight % therein, can allow for example aluminium of more a large amount of acid impurities, as long as they are offset by the support modification agent of appropriate amount basically.

The siliceous carrier material for example surface area of silica is preferably 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 is perhaps most preferably at least about 250m ²/ g.With regard to scope, siliceous carrier material for example silica 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 like the application, high surface area silica is meant to have at least about 250m ²The silica 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 through ASTM D6556-04 (incorporating it into this paper in full by reference).

Siliceous carrier material also preferably has like the 5-100nm through 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 through 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 the certain exemplary embodiment; 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, siliceous carrier material has 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, silica support materials 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 for example 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 95 weight % that have an appointment; About 250m ²The surface area of/g; The mean pore sizes of about 12nm; Through the about 1.0cm that presses mercury hole mensuration to measure ³The average pore volume of/g and about 0.352g/cm ³(22lb/ft ³) bulk density.

Preferred silica/alumina carrier material is KA-160 (Sud Chemie) silica spheres, and it has the nominal diameter of about 5mm, the density of about 0.562g/ml, about 0.583gH ₂The absorptivity of O/g carrier, about 160-175m ²The surface area of/g and the pore volume of about 0.68ml/g.

Expect therein in the embodiment of catalyst with high selectivity production ethanol; As implied above, can be quite favourable through

acidity of introducing support modification agent control carrier material.A kind of possible accessory substance of acetic acid hydrogenation is an ethyl acetate.According to the present invention, carrier preferably includes the support modification agent that effective inhibition ethyl acetate produces, thereby makes carbon monoxide-olefin polymeric have high selectivity to ethanol.Therefore, carbon monoxide-olefin polymeric preferably for acetate is converted into ethyl acetate and highly unwanted accessory substance for example alkane have low selectivity.The acidity of preferred control carrier makes less than 4%, preferably less than 2%, most preferably is converted into methane, ethane and carbon dioxide less than about 1% acetate.In addition, the acidity of carrier can be controlled through the pyrolytic silicon dioxide or the high-purity silicon dioxide that use as above institute's articles and opinions to state.

In one embodiment, modified support comprises the calcium metasilicate as the support modification agent of the amount of acid position that carrier material and active balance produce by residual aluminium oxide in the silica for example.Preferably, calcium metasilicate exists in the amount based on total catalyst weight 1 weight %-10 weight %, so that guarantee that the character of carrier is neutral or alkaline for basically.

As the support modification agent; Calcium metasilicate for example; Possibly trend towards having lower surface area than the for example siliceous carrier material of carrier material, in one embodiment, carrier material comprises and contains at least about 80 weight %; For example at least about 85 weight % or at least about the siliceous carrier material of the high surface area silica of 90 weight %, to offset owing to comprising this influence that the support modification agent causes.

On the other hand, carbon monoxide-olefin polymeric can be expressed from the next:

Pt _vPd _wRe _xSn _yCa _pSi _q?O _r，

Wherein: the ratio of (i) v: y is 3: 2-2: 3; And/or (ii) the ratio of w: x is 1: 3-1: 5.Therefore, in this embodiment, said catalyst can comprise (i) platinum and tin; (ii) palladium and rhenium; Or (iii) platinum, tin, palladium and rhenium.Preferably p and q are selected to make that p: q is 1: 20-1: 200, wherein the chemical valence requirement is satisfied in the selection of r, and the selection of v and w makes:

0.005 \leq \frac{(3.25 v + 1.75 w)}{q} \leq 0.05 .

Aspect this; Preferably the value of process conditions and v, w, x, y, p, q and r is selected so that 70% of the acetate that transforms at least; For example at least 80% or at least 90% be converted into the compound that is selected from ethanol and ethyl acetate, and simultaneously be converted into alkane less than 4% acetate.More preferably, preferably the value of process conditions and v, w, x, y, p, q and r is selected so that 70% of the acetate that transforms for example at least 80% or 90% is converted into ethanol at least at least, and simultaneously be converted into alkane less than 4% acetate.In many embodiments of the present invention; Consider any less impurity of existence, p is selected to guarantee that carrier surface does not have activity

acid position basically.

On the other hand, carbon monoxide-olefin polymeric comprises:

Pt _vPd _wRe _xSn _yAl _zCa _pSi _qO _r，

Wherein: (i) v and y are 3: 2-2: 3; And/or (ii) w and x are 1: 3-1: 5.The aluminium atom of preferred control p and z and existence and the relative position of calcium atom make

of being present in its surface sour through the support modification agent for example calcium metasilicate carry out balance; The selection of p and q makes that p: q is 1: 20-1: 200, and wherein the chemical valence requirement is satisfied in the selection of r, and the selection of v and w makes:

0.005 \leq \frac{(3.25 v + 1.75 w)}{q} \leq 0.05 .

Preferably, aspect this, said catalyst has at least about 100m ²/ g is for example at least about 150m ²/ g, at least about 200m ²/ g or most preferably at least about 250m ²The surface area of/g, and z and p>=z.In many embodiments of the present invention; Consider any less impurity of existence, as if p is selected to guarantee that equally carrier surface does not promote that basically ethanol conversion is activity

the acid position of ethyl acetate.Therefore; As for previous embodiment; Preferably the value of process conditions and v, w, x, y, p, q and r is selected so that 70% of the acetate that transforms for example at least 80% or 90% is converted into ethanol at least at least, and simultaneously be converted into alkane less than 4% acetate.

Therefore; Though do not accept the opinion constraint; The oxide carrier material that is used for catalyst of the present invention carries out modification and stabilisation through introducing the agent of non-volatility support modification; Said modifier has effect of offsetting the acid position be present on the carrier surface or the effect that makes the surface heat stabilisation, makes it possible to obtain catalyst life that desired ethanol optionally improves, prolongs or the two.Generally speaking, based on be in its support modification agent of the oxide of stable valence state will have low vapour pressure and therefore have low volatility or even non-volatility.Therefore, the support modification that q.s preferably is provided with: (i) offset the acid position that is present on the surfaces of carrier materials; (ii) give anti-alteration of form property under hydrogenation temperature; Or (iii) the two.Though do not accept the opinion constraint, give anti-alteration of form property and be meant the resistance of giving to for example sintering, grain growth, crystal boundary migration, defective and dislocation migration, plastic deformation and/or other temperature-induced microstructure change.

Catalyst of the present invention is being not that to be similar to that automobile catalyst and diesel oil cigarette ash capturing device that kind be impregnated in the brush applied coating on only stone carrier be pellet type catalyst on this meaning; Be particle preferably with shaped catalyst of the present invention; Sometimes be also referred to as pearl or pill; Have the arbitrary shape in the different shape, place reactor and catalytic metal is provided to reaction zone through catalyst with a lot of these moulding.Common shape comprises the extrudate with any cross section, the bus (generator) that limits extrudate surface 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.

An advantage of catalyst of the present invention is that this catalyst is used to produce the stable or active of ethanol.Therefore, what can recognize is that catalyst of the present invention can be used in the commercial size commercial Application, particularly alcohol production 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 obtains limit, just measure the productive rate fall off rate.

In one embodiment, when catalyst carrier comprises high-purity silicon dioxide and with calcium metasilicate during as the support modification agent, catalyst activity can enlarge or be stable, under 125 ℃-350 ℃ temperature in the presence of acetic acid vapor with greater than 2500hr ^-1The long-term productive rate of catalyst and the selectivity of operation of viable commercial of air speed extend to and surpassed for 1 week, surpassed for 2 week and even several months.

Preferably the metal impregnation through modified support forms carbon monoxide-olefin polymeric of the present invention, although can also use the for example chemical vapour deposition (CVD) of other method.Before impregnating metal, expectation for example forms modified support through the step with support modification agent impregnated carrier material usually.Can use the precursor of support modification agent, for example acetate or nitrate.On the one hand, with support modification agent CaSiO for example ₃Join for example SiO of carrier material ₂In.For example, can be through 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 said beginning profit dipping technique, the support modification agent joined in the pore volume carrier material identical with the volume of support modification agent solution.Capillarity sucks the support modification agent in the hole in the carrier material then.Can form modified support on the carrier material with calcining to remove water and any volatile component in the support modification agent solution and the support modification agent is deposited on through dry then.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.Can carrier 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 to modified support.The precursor of first metal (first metal precursor) is preferred for the metal impregnation step, and said precursor for example comprises the water dissolvable compound or the water-dispersible compound/complex compound of relevant first metal.Depend on employed metal precursor, can preferably use the for example solvent of water, glacial acetic acid or organic solvent.Second metal also preferably is impregnated in the modified support by second metal precursor.If desired, the 3rd metal or the 3rd metal precursor are impregnated in the modified support.

Through with first metal precursor and/or second metal precursor and/or any in the metal precursor (preferably in suspension or solution) or two kinds of adding (the optional dropping) are flooded in dried modified support in addition.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 situations, before catalyst comes into operation and calcines the high temperature that for example stands to meet with during operation, can not accomplish the 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.

First and second metals (and optional other metal) are immersed in the modified support and can (flood altogether) simultaneously or carry out in succession.When flooding at the same time, first and second metal precursors (and optional other metal precursor) are mixed and it is joined in the modified support together, then carry out drying and calcine to form final carbon monoxide-olefin polymeric.For simultaneously the dipping, if for example water is incompatible for said 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 said first and second metal precursors.

When flooding in succession, at first first metal precursor is joined in 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 hydroxides, metal nitrate or the metal oxalate of metal halide, 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.Though do not accept the opinion constraint, think that this type non-(metal halide) precursor has improved the ethanol selectivity.The preferred especially precursor of platinum is the ammino platinum nitrate, i.e. Pt (NH ₃) ₄(NO ₄) ₂

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.

As an example, SiO ₂On PtSn/CaSiO ₃Can pass through at first with CaSiO ₃Be impregnated into SiO ₂On, then with Pt (NH ₃) ₄(NO ₄) ₂And Sn (AcO) ₂Dipping prepares altogether.In addition, after each impregnation steps can then be drying and calcining step.In most of situations, can use metal-nitrate solutions to flood.Yet, also can use various other soluble-salts in when calcining release metal ions.The instance of other suitable metal salt that is used to flood comprises metal acid for example perrhenic acid solution, metal oxalate etc.To generate therein in those situations of straight alcohol basically, preferably avoid the use of the precursor of halogenation usually for the platinum group metal, and be to use based on the nitrogenous amine and/or the precursor of nitrate.

To easily recognize like those skilled in the art, the method that acetic acid hydrogenation forms ethanol can be carried out in the various structures that use fixed bed reactors or fluidized-bed reactor according to one embodiment of the invention.In many embodiments of the present invention, can use " thermal insulation " reactor; That is, have seldom or the internal pipe arrangements (plumbing) that need not pass reaction zone adds or removes and reduce phlegm and internal heat.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 through said catalyst.If, can use other reactor, for example fluid bed or fluidized bed reactor as wanting.In some situations, hydrogenation catalyst can be used in combination with inert material with the conditioned reaction streams through the pressure drop of catalyst bed and the time of contact of reactant compound and catalyst granules.

Can in liquid phase or gas phase, carry out hydrogenation reaction.Preferably, in gas phase, under following condition, carry out this reaction.Reaction temperature can be 125 ℃-350 ℃, for example 200 ℃-325 ℃, 225 ℃-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

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

Thereby produce 1 mole of ethanol though the every mole of acetic acid of this reaction consumes 2 mol of hydrogen, the actual mol ratio of hydrogen and acetate can be about 100 in the incoming flow: 1-1: 100, for example 50: 1-1: 50,20: 1-1: 2 or 12: 1-1: 1.Most preferably, the mol ratio of hydrogen and acetate is greater than 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 these variablees depend on amount, catalyst, reactor, the temperature and pressure of acetate.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.

Can make acetate in the reaction temperature gasified, then can with the acetate of gasification in company with undiluted state or with the carrier gas of relative inertness for example the hydrogen of dilutions such as nitrogen, argon gas, helium, carbon dioxide feed together.Move for making to be reflected in the gas phase, the temperature in should the control system makes it not drop to the dew point that is lower than acetate.

Especially, use catalyst of the present invention can obtain the favourable conversion ratio of acetate and to the favourable selectivity and the productive rate of ethanol.With regard to the present invention, term " conversion ratio " is meant the amount of the acetate that is converted into the compound except that acetate in the charging.Conversion ratio is by representing based on the mole percent of acetate in the charging.

Use the conversion ratio of following equation by gas-chromatography (GC) data computation acetate (AcOH):

With regard to the present invention, said conversion ratio can be at least 10%, for example at least 20%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%.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 ethanol is high.Certainly, should make much of, in many situations, can or use bigger reactor to remedy conversion ratio through 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 ethanol, then the ethanol selectivity is 50%.The selectivity of ethanol (EtOH) uses following equality 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 through gc analysis.

With regard to the present invention, catalyst is at least 60%, for example at least 70% or at least 80% for the selectivity of ethoxylate.As used herein, term " ethoxylate " specifically is meant compound ethanol, acetaldehyde and ethyl acetate.Preferably, the selectivity of ethanol is at least 80%, for example at least 85% or at least 88%.Hope also that in embodiments of the invention for example methane, ethane and carbon dioxide have low selectivity to the product do not expected.These do not expect that product selectivity is 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, and what make the acetate that passes catalyst is converted into alkane below 0.5%, and this alkane has very little value except that acting as a fuel.

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

Catalyst more of the present invention can be realized at least 10% acetate conversion ratio, and at least 80% ethanol selectivity and every kg catalyst be 200g ethanol yield at least per hour.Catalyst in the scope of the invention can be realized at least 50% acetate conversion ratio, at least 80% ethanol selectivity, and the selectivity of not expecting compound less than 4% and every kg catalyst be 600g ethanol yield at least per hour.

The coarse ethanol product that the catalyst of the application of the invention is produced by method of hydrotreating, any for example handle purifying subsequently and separate before, will mainly comprise unreacted acetate and ethanol usually.In the certain exemplary embodiment, the coarse ethanol product comprises based on this coarse ethanol product gross weight meter 15 weight %-70 weight %, the for example ethanol of the amount of 20 weight %-50 weight % or 25 weight %-50 weight %.Preferably, the coarse ethanol product contains at least 22 weight % ethanol, at least 28 weight % ethanol or at least 44 weight % ethanol.Depend on conversion ratio, the coarse ethanol product typically also will comprise unreacted acetate, for example 0-80 weight %, the for example amount of 5-80 weight %, 20-70 weight %, 28-70 weight % or 44-65 weight %.Because in course of reaction, form water, water also will be for example with 5-30 weight %, is present in the coarse ethanol product like the amount of 10-30 weight % or 10-26 weight %.Other component is ester, ether, aldehyde, ketone, alkane and carbon dioxide for example, if can detect, can be altogether with less than 10 weight %, for example exist less than 6 weight % or less than the amount of 4 weight %.With regard to scope, other component can be by 0.1-10 weight %, and for example the amount of 0.1-6 weight % or 0.1-4 weight % exists.Therefore, the compositing range of exemplary coarse ethanol is provided in the following table 2.

On the one hand, for example using CaSiO ₃Generate the coarse ethanol product on platinum/tin catalyst on the improved silica carrier of modification.Depend on concrete catalyst and employed process conditions, the coarse ethanol product can have any composition that shows in the following table 3.

Employed raw material can comprise natural gas, oil, coal, living beings etc. derived from any suitable source in the method for hydrotreating.Produce acetate through 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, possibly become favourable by producing acetate derived from the forming gas (" synthesis gas ") of any available carbon source.For example, the United States Patent(USP) 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.Through transforming methanol device,, be significantly reduced or elimination to a great extent with the relevant substantial contribution expense of CO generation for new acetate device.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 through making the for example method of oil, coal, natural gas and conversion of biomass material production methyl alcohol of carbonaceous material that the United States Patent(USP) 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 United States Patent(USP) No. 6,685,754 of the United States Patent(USP) 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 through gasification, incorporates their disclosure into this paper by reference.

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

Use catalyst of the present invention can be used as fuel or be converted into ethene subsequently by himself by the ethanol that method of hydrotreating obtains; 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; Said dehydration catalyst is for example at common pending application U. S. application No.12/221; 137 with U. S. application No.12/221, those described in 138 are incorporated their full content and disclosure into this paper by reference at this.For example, zeolite catalyst can be used as dehydration catalyst.Though can use the aperture to be at least about all zeolites 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 United States Patent(USP) No. 2,882, and in 244, zeolite Y is described in United States Patent(USP) No. 3,130, in 007, incorporates them into this paper in full by reference at this.

Ethanol can also be used as fuel, is used for drug products, cleaning agent, disinfectant, hydro-conversion or consumption.Ethanol can also be as the source material in order to preparation ethyl acetate, aldehyde and higher alcohol, particularly butanols.In addition, can with any ester that during the process of ethanol produced according to the present invention, forms for example ethyl acetate and acid catalyst further reaction can they be recycled in the hydrogenation process to form other ethanol and acetate.

Only start from illustration and illustration purpose below and describe the present invention in detail with reference to many embodiments.To in the spirit and scope of the present invention and the specific embodiments that provides in the appended claims modify, will be obvious to those skilled in the art.

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.Only if mention in addition, all commercial carriers (are SiO ₂, ZrO ₂) use with 14/30 order or with its original-shape (1/16 inch or 1/8 inch pill).After adding metal, (be CaSiO with dusty material ₃) granulation, crushing and screening.Every kind of Preparation of catalysts is described below in more detail.

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

This catalyst passes through at first with CaSiO ₃(Aldrich) join SiO ₂Catalyst carrier then adds Pt/Sn and prepares.At first, CaSiO ₃The waterborne suspension of (≤200 order) then adds 1.0ml colloid SiO through this solid of 0.52g is joined in the 13ml deionized water ₂(15 weight % solution MALCO) prepare.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 prepares.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 at each rotary flask when adding metallic solution.After the adding of this metallic solution was accomplished, 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 prepare.At first, CaSiO ₃The waterborne suspension of (≤200 order) then adds 0.8ml colloid SiO through this solid of 0.42g is joined in the 3.85ml deionized water ₂(15 weight % solution NALCO) prepare.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 prepares.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 accomplished, 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(15 weight % solution, MALCO), 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(15 weight % solution, MALCO), 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 through 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 prepares.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 accomplished, 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.The brown material of output: 10.9g.

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.To wherein adding solution and the tin oxalate (Alfa Aesar) of platinum nitrate (Chempur) in distilled water (1.74g) at dilution nitric acid (1N, the solution in 8.5ml).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.

In addition, also prepare following comparative catalyst.

Embodiment 7-contrast

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 prepares by adding Pt/Sn described in the embodiment 1.At first, CaSiO ₃The waterborne suspension of (≤200 order) then adds 1.0ml colloid SiO through this solid of 0.52g is joined in the 7.0ml deionized water ₂(15 weight % solution NALCO) prepare.At room temperature stir this suspension 2 hours, and use beginning profit dipping technique to add 10.0g TiO 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.

Embodiment 8-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, the solution in 8.5ml).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.

Embodiment 9-contrast

Pt on high surface area silica (2)-Sn (2).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 mixture of dipping.

Embodiment 10-contrast

KA160-Pt(3)-Sn(1.8)。This material is pressed described in the embodiment 16 through KA 160 catalyst carrier (SiO ₂-(0.05) Al ₂O ₃, Sud Chemie, 14/30 order) beginning profit infusion process dipping prepare.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 prepares.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 11-contrast

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 NPSGSS61138 (100g) dried overnight of sieving, and then it is cooled to room temperature.To wherein adding tin acetate (Sn (OAc) ₂Solution.(＞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 mixture of dipping.

Embodiment 12-contrast

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).Let 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 let this material keep to leave standstill 15 minutes.The water that produces through removing by filter then/2-propyl alcohol repeats to add H ₂O 2 times.Under circulating air, under 120 ℃, final drying of materials is spent the night, then calcined 6 hours down at 500 ℃.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 13-contrast

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 ₂The drips of solution of O (AMT) in deionized water (14ml) is added to the 10.0g SiO in the 100ml round-bottomed flask ₂NPSGSS61138 catalyst carrier (SA=250m ²/ g, 1/16 inch extrudate) in.This flask kept 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 ℃, the gained drying of materials is spent the night, then calcined 6 hours down at 500 ℃.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 14-analyzes in the gas chromatography (GC) from acetic acid hydrogenation on the catalyst of embodiment 1-13 and coarse ethanol product

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

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.Said incoming flow contains the mol ratio of hydrogen and acetate as shown in table 4.

Carry out the analysis of product (coarse ethanol composition) through 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, through forming the retention time that spike is measured different component, and perhaps GC is calibrated with the liquid solution of known composition with the calibration gas of known composition with independent compound.This allows to measure the response factor of each component.

Embodiment 15-catalyst stability (15 hours)

Pressure and GHSV=6570h at about 225 ℃ temperature, 200psig (about 1400KPag) ^-1Down (feed rate is 0.09g/min HOAc with the mol ratio of about 5: 1 hydrogen and acetate; 160sccm/min H ₂60sccm/min N ₂) make the acetate of gasification and hydrogen pass hydrogenation catalyst of the present invention, it is about 250m that this hydrogenation catalyst is included in surface area ²3 weight %Pt on the high-purity of/g, the high surface area silica, 1.5 weight %Sn and 5 weight % are as the CaSiO of promoter ₃Use 2.5ml solid catalyst (14/30 order; 1: 1 (v/v of dilution; With quartz chips; 14/30 order) in typical operating condition scope, uses the fixed bed continuous reactor system mainly to produce ethanol, acetaldehyde and ethyl acetate through hydrogenation and esterification and study and in acetic acid hydrogenation, use 5%CaSiO 225 ℃ of following 15 hour duration in service ₃Stable SiO ₂Fig. 3 A has described selectivity, and Fig. 3 B has described during the starting stage of catalyst life the catalyst production as the function of running time.By the result like this embodiment of being reported among Fig. 3 A and Fig. 3 B, what can recognize is, can obtain to surpass 90% selectivity and every kg catalyst and per hour surpass the 500g ethanol yield.

Embodiment 16-catalyst stability (above 100 hours)

Catalyst stability: SiO ₂-CaSiO ₃(5)-Pt (3)-Sn (1.8).Estimate SiO above in 100 hours reaction time down at constant temperature (260 ℃) ₂-CaSiO ₃(5)-catalytic performance and the initial stability of Pt (3)-Sn (1.8).In surpassing 100 hours total reaction time, observe catalyst performance and very little variation only takes place selectivity.Acetaldehyde is unique side product seemingly, and its concentration (about 3 weight %) remains unchanged in the process of experiment to a great extent.Catalyst production is provided among Fig. 4 A and the 4B and has optionally gathered.

Embodiment 17-catalyst stability

The operation of repetition embodiment 16 under about 250 ℃ temperature.Fig. 5 A and 5B have described during the starting stage of catalyst life catalyst production and the selectivity as the function of running time.By the result like this embodiment of being reported among Fig. 5 A and the 5B, what can recognize is, still can obtain to surpass 90% selective active, per hour surpasses the 800g ethanol yield but under this temperature, have every kg catalyst.

Embodiment 18

The catalyst of embodiment 3 is with the support modification agent CaSiO of different carrying capacity ₃Prepare, and produced following catalyst: (i) SiO ₂-Pt (1.5)-Sn (0.9); (ii) SiO ₂-CaSiO ₃(2.5)-Pt (1.5)-Sn (0.9); (iii) SiO ₂-CaSiO ₃(5.0)-Pt (1.5)-Sn (0.9); (iv) SiO ₂-CaSiO ₃(7.5)-Pt (1.5)-Sn (0.9); (v) SiO ₂-CaSiO ₃(10)-Pt (1.5)-Sn (0.9).At conditions of similarity i.e. 1400 crust (200psig) and 10: 1 hydrogen and the acetate molar feed ratio (H of 683sccm/min ₂To 0.183g/min AcOH) under under 250 ℃ and 275 ℃, every kind of catalyst is used for acetic acid hydrogenation.Show conversion ratio among Fig. 6 A, shown productive rate among Fig. 6 B, shown the selectivity under 250 ℃ among Fig. 6 C, shown the selectivity under 275 ℃ among Fig. 6 D.

Shown in Fig. 6 A, at CaSiO ₃Carrying capacity during greater than 2.5 weight % the conversion ratio of acetate under 250 ℃ and 275 ℃ unexpectedly be improved.0-2.5 weight %CaSiO ₃The conversion ratio that is shown initially descends and is hinting along with adding more CaSiO ₃Then the conversion ratio expection reduces.Yet this trend unexpectedly is maintained along with adding more support modification agent.Shown in Fig. 6 B, the conversion ratio of raising also produces the productive rate of raising.Selectivity among Fig. 6 C and the 6C shows along with the raising of the amount of support modification agent raising a little.

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

Claims

1. catalyst that comprises first metal, contains silicon carrier and the agent of at least a metasilicate support modification.

2. the catalyst of claim 1; The agent of wherein said at least a metasilicate support modification is selected from: (i) alkaline-earth metal metasilicate, (ii) alkali metal silicate, (iii) IIB family metal metaphosphate silicate; (iv) IIIB family metal metaphosphate silicate and their mixture.

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

4. the catalyst of claim 1, wherein said first metal exists in the amount based on this total catalyst weight 0.1-25 weight %.

5. the catalyst of claim 1, the agent of wherein said at least a metasilicate support modification is selected from the metasilicate of metal, and said metal is selected from sodium, potassium, magnesium, scandium, yttrium and zinc.

6. the catalyst of claim 1, the agent of wherein said at least a metasilicate support modification comprises CaSiO ₃

7. the catalyst of claim 1, the agent of wherein said at least a metasilicate support modification exists in the amount based on this total catalyst weight 0.1 weight %-50 weight %.

8. the catalyst of claim 1, the wherein said silicon carrier that contains exists in the amount based on this total catalyst weight 25 weight %-99 weight %.

9. the catalyst of claim 1, the wherein said silicon carrier that contains has 50m ²/ g-600m ²The surface area of/g.

10. the catalyst of claim 1, the wherein said silicon carrier that contains is selected from silica, silica/alumina, calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.

11. the catalyst of claim 10, the wherein said silicon carrier that contains contains based on the aluminium of this total catalyst weight meter less than 1 weight %.

12. the catalyst of claim 1, 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.

13. the catalyst of claim 12, this catalyst also comprise second metal that is different from said first metal.

14. the catalyst of claim 13, wherein said first metal is a platinum, and second metal is a tin.

15. the catalyst of claim 14, wherein the mol ratio of platinum and tin is 0.4: 0.6-0.6: 0.4.

16. the catalyst of claim 13, wherein said first metal is a palladium, and second metal is a rhenium.

17. the catalyst of claim 16, wherein the mol ratio of rhenium and palladium is 0.7: 0.3-0.85: 0.15.

18. the catalyst of claim 13, 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.

19. the catalyst of claim 13, wherein said second metal exists in the amount based on this total catalyst weight 0.1-10 weight %.

20. the catalyst of claim 13, wherein this catalyst also comprises the 3rd metal that is different from said first metal and second metal.

21. the catalyst of claim 20, wherein said the 3rd metal is selected from cobalt, palladium, ruthenium, copper, zinc, platinum, tin and rhenium.

22. the catalyst of claim 20, wherein said the 3rd metal exists in the amount based on this total catalyst weight 0.05 and 4 weight %.

23. the catalyst of claim 1, wherein this catalyst is converted into acetate to be suitable as in the ethanol hydrogenation catalyst and is producing at least 10% acetate conversion ratio.

24. the catalyst of claim 23, wherein this catalyst has at least 80% ethanol selectivity.

25. the catalyst of claim 24, wherein this catalyst to the selectivity of methane, ethane and carbon dioxide less than 4%.

26. the catalyst of claim 24, wherein this catalyst has per 100 hours catalyst and uses the productive rate that reduces less than 6%.

27. catalyst that satisfies following formula:

Pt _vPd _wRe _xSn _yCa _pSi _qO _r，

Wherein:

(i) ratio of v: y is 3: 2-2: 3, and/or (ii) the ratio of w: x is 1: 3-1: 5; And

The selection of p and q makes that p: q is 1: 20-1: 200, and wherein the chemical valence requirement is satisfied in the selection of r, and the selection of v and w makes:

0.005 \leq \frac{(3.25 v + 1.75 w)}{q} \leq 0.05 .

28. the ratio of the catalyst of claim 27, wherein v: y is 3: 2-2: 3.

29. the ratio of the catalyst of claim 27, wherein w: x is 1: 3-1: 5.

30. catalyst that satisfies following formula:

Pt _vPd _wRe _xSn _yAl _zCa _pSi _qO _r，

Wherein:

(i) v and y are 3: 2-2: 3; And/or (ii) w and x are 1: 3-1: 5; And

The aluminium atom of control p and z and existence and the relative position of calcium atom make that being present in its lip-deep acid position carries out balance through the support modification agent; And

The selection of p and q makes that p: q is 1: 20-1: 200, and wherein the chemical valence requirement is satisfied in the selection of r, and

The selection of v and w makes:

0.005 \leq \frac{(3.25 v + 1.75 w)}{q} \leq 0.05 .

31. the ratio of the catalyst of claim 30, wherein v: y is 3: 2-2: 3.

32. the ratio of the catalyst of claim 30, wherein w: x is 1: 3-1: 5.

33. the catalyst of claim 30, wherein said at least a 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.

34. catalyst; This catalyst comprises first metal, second metal, contains silicon carrier and at least a support modification agent; Said first metal is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten; Said second metal is selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, rhenium and nickel, and wherein said second metal is different with said first metal.

35. the catalyst of claim 34, wherein said at least a support modification agent is selected from: (i) alkaline-earth metal metasilicate, (ii) alkali metal silicate, (iii) IIB family metal metaphosphate silicate, (iv) IIIB family metal metaphosphate silicate and their mixture.

36. the catalyst of claim 34, wherein said first metal exists in the amount based on this total catalyst weight 0.1-25 weight %.

37. the catalyst of claim 34, wherein said at least a support modification agent is selected from the metasilicate of metal, and said metal is selected from sodium, potassium, magnesium, scandium, yttrium and zinc.

38. the catalyst of claim 34, wherein said at least a support modification agent comprises CaSiO ₃

39. the catalyst of claim 34, wherein said at least a support modification agent exists in the amount based on this total catalyst weight 0.1 weight %-50 weight %.

40. the catalyst of claim 34, the wherein said silicon carrier that contains exists in the amount based on this total catalyst weight 25 weight %-99 weight %.

41. the catalyst of claim 34, the wherein said silicon carrier that contains has 50m ²/ g-600m ²The surface area of/g.

42. the catalyst of claim 34, the wherein said silicon carrier that contains is selected from silica, silica/alumina, calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.

43. the catalyst of claim 42, the wherein said silicon carrier that contains contains based on the aluminium of this total catalyst weight meter less than 1 weight %.

44. the catalyst of claim 34, wherein said first metal is a platinum, and second metal is a tin.

45. the catalyst of claim 44, wherein the mol ratio of platinum and tin is 0.4: 0.6-0.6: 0.4.

46. the catalyst of claim 34, wherein said first metal is a palladium, and second metal is a rhenium.

47. the catalyst of claim 46, wherein the mol ratio of rhenium and palladium is 0.7: 0.3-0.85: 0.15.

48. the catalyst of claim 34, wherein said second metal exists in the amount based on this total catalyst weight 0.1-10 weight %.

49. the catalyst of claim 34, wherein this catalyst also comprises the 3rd metal that is different from said first metal and second metal.

50. the catalyst of claim 49, wherein said the 3rd metal is selected from cobalt, palladium, ruthenium, copper, zinc, platinum, tin and rhenium.

51. the catalyst of claim 49, wherein said the 3rd metal exists in the amount based on this total catalyst weight 0.05 and 4 weight %.

52. the catalyst of claim 34, wherein this catalyst is converted into acetate to be suitable as in the ethanol hydrogenation catalyst and is producing at least 10% acetate conversion ratio.

53. the catalyst of claim 52, wherein this catalyst has at least 80% ethanol selectivity.

54. the catalyst of claim 53, wherein this catalyst to the selectivity of methane, ethane and carbon dioxide less than 4%.

55. the catalyst of claim 53, wherein this catalyst has per 100 hours catalyst and uses the productive rate that reduces less than 6%.

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

(a) first metal precursor of first metal is contacted to form the carrier of dipping with modified silicon-contained carrier, wherein said modified silicon-contained carrier comprises material and the agent of at least a metasilicate support modification; And

(b) at effective said first metal of reduction and form the said impregnated carrier of heating under the condition of catalyst.

57. the method for claim 56, this method is further comprising the steps of:

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

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

58. the method for claim 56, wherein said heating is carried out under reducing atmosphere at least in part.

59. the method for claim 56, this method also comprises the step of calcined catalyst.

60. the method for claim 56; The agent of wherein said at least a metasilicate support modification is selected from: (i) alkaline-earth metal metasilicate, (ii) alkali metal silicate, (iii) IIB family metal metaphosphate silicate; (iv) IIIB family metal metaphosphate silicate and their mixture.

61. the method for claim 56, wherein said first metal is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten.

62. the method for claim 56, wherein said catalyst comprise first metal that exists in the amount based on this total catalyst weight 0.1-25 weight %.

63. the method for claim 56, the agent of wherein said at least a metasilicate support modification is selected from the metasilicate of metal, and said metal is selected from sodium, potassium, magnesium, scandium, yttrium and zinc.

64. the method for claim 56, the agent of wherein said at least a metasilicate support modification comprises CaSiO ₃

65. the method for claim 56, the agent of wherein said at least a metasilicate support modification is present in the catalyst in the amount based on this total catalyst weight 0.1 weight %-50 weight %.

66. the method for claim 56, wherein said modified silicon-contained carrier is present in the catalyst in the amount based on this total catalyst weight 25 weight %-99 weight %.

67. the method for claim 56, wherein said material has 50m ²/ g-600m ²The surface area of/g.

68. the method for claim 56, wherein said material are selected from silica, silica/alumina, calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.

69. the method for claim 68, wherein said material contain based on the aluminium of this total catalyst weight meter less than 1 weight %.

70. the method for claim 56, 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.

71. the method for claim 56, this method is further comprising the steps of: in step (a) and (b) before, afterwards or simultaneously, dipping and reduction are different from second metal precursor of second metal of said first metal on carrier.

72. the method for claim 71, wherein said first metal is a platinum, and second metal is a tin.

73. the method for claim 72, wherein the mol ratio of platinum and tin is 0.4: 0.6-0.6: 0.4.

74. the method for claim 71, wherein said first metal is a palladium, and second metal is a rhenium.

75. the method for claim 74, wherein the mol ratio of rhenium and palladium is 0.7: 0.3-0.85: 0.15.

76. the method for claim 71, 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.

77. the method for claim 71, wherein said second metal is present in the catalyst in the amount based on this total catalyst weight 0.1-10 weight %.

78. the method for claim 71, this method is further comprising the steps of: in step (a) and (b) before, afterwards or simultaneously, dipping and reduction are different from the 3rd metal precursor of the 3rd metal of said first metal and second metal on carrier.

79. the method for claim 78, wherein said the 3rd metal is selected from cobalt, palladium, ruthenium, copper, zinc, platinum, tin and rhenium.

80. the method for claim 78, wherein said the 3rd metal is present in the catalyst in the amount based on this total catalyst weight 0.05 and 4 weight %.

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

(a) first metal precursor of first metal is contacted with the modified silicon-contained carrier that comprises at least a support modification agent, wherein said first metal is selected from copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum and tungsten;

(b) second metal precursor of second metal that is different from said first metal is contacted with modified silicon-contained carrier, wherein said second metal is selected from copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, rhenium and nickel; And

(c) at effective reduction said first metal and second metal and form the said modified silicon-contained carrier of heating under the condition of catalyst.

82. the method for claim 81, wherein said heating is carried out in step (a) with (b) afterwards.

83. the method for claim 81, wherein said heating are carried out in step (a) with (b) to reduce said first metal and carry out afterwards to reduce said second metal in step (a) with (b).

84. the method for claim 81, this method can also may further comprise the steps:

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

(e) precursor carrier of the said modification of heating under the condition that effectively forms modified silicon-contained carrier.

85. the method for claim 81, wherein said heating is carried out under reducing atmosphere at least in part.

86. the method for claim 81, this method is further comprising the steps of:

(d) calcined catalyst.

87. the method for claim 86, wherein said calcining is carried out in step (a) with (b) afterwards.

88. the method for claim 86, wherein said calcining is carried out in step (a) with (b) and in step (a) with (b) afterwards.

89. the method for claim 81, wherein said at least a support modification agent is selected from: (i) alkaline-earth metal metasilicate, (ii) alkali metal silicate, (iii) IIB family metal metaphosphate silicate, (iv) IIIB family metal metaphosphate silicate and their mixture.

90. the method for claim 81, wherein first metal exists in the amount based on this total catalyst weight 0.1-25 weight %.

91. the method for claim 81, wherein said at least a support modification agent is selected from the metasilicate of metal, and said metal is selected from sodium, potassium, magnesium, scandium, yttrium and zinc.

92. the method for claim 81, wherein said at least a support modification agent comprises CaSiO ₃

93. the method for claim 81, wherein said at least a support modification agent exists in the amount based on this total catalyst weight 0.1 weight %-50 weight %.

94. the method for claim 81, wherein said modified silicon-contained carrier exists in the amount based on this total catalyst weight 25 weight %-99 weight %.

95. the method for claim 81, wherein said modified silicon-contained carrier has 50m ²/ g-600m ²The surface area of/g.

96. the method for claim 81, wherein said modified silicon-contained carrier also comprises the carrier material that is selected from silica, silica/alumina, calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide and their mixture.

97. the method for claim 96, wherein said modified silicon-contained carrier contain based on the aluminium of this total catalyst weight meter less than 1 weight %.

98. the method for claim 81, wherein said first metal is a platinum, and second metal is a tin.

99. the catalyst of claim 98, wherein the mol ratio of platinum and tin is 0.4: 0.6-0.6: 0.4.

100. the method for claim 81, wherein said first metal is a palladium, and second metal is a rhenium.

101. the method for claim 100, wherein the mol ratio of rhenium and palladium is 0.7: 0.3-0.85: 0.15.

102. the method for claim 81, wherein said second metal exists in the amount based on this total catalyst weight 0.1-10 weight %.

103. the method for claim 81, this method is further comprising the steps of: dipping and reduction are different from the 3rd metal precursor of the 3rd metal of said first metal and second metal on modified silicon-contained carrier.

104. the method for claim 103, wherein said the 3rd metal is selected from cobalt, palladium, ruthenium, copper, zinc, platinum, tin and rhenium.

105. the method for claim 103, wherein said the 3rd metal exists in the amount based on this total catalyst weight 0.05 and 4 weight %.