CN102300635A - Catalyst for the production of ethanol by hydrogenation of acetic acid comprising platinum-tin on silicaceous support - Google Patents

Catalyst for the production of ethanol by hydrogenation of acetic acid comprising platinum-tin on silicaceous support Download PDF

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CN102300635A
CN102300635A CN2010800062169A CN201080006216A CN102300635A CN 102300635 A CN102300635 A CN 102300635A CN 2010800062169 A CN2010800062169 A CN 2010800062169A CN 201080006216 A CN201080006216 A CN 201080006216A CN 102300635 A CN102300635 A CN 102300635A
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platinum
tin
catalyst
acetate
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CN102300635B (en
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H·魏纳
V·J·约翰斯顿
J·L·波茨
R·耶夫蒂奇
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Celanese International Corp
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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    • B01J21/16—Clays or other mineral silicates
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

A process for selective formation of ethanol from acetic acid includes contacting a feed stream containing acetic acid and hydrogen at an elevated temperature with catalyst comprising platinum and tin on a high surface area silica promoted with calcium metasilicate. Selectivities to ethanol of over 85% are achieved at 280 DEG C with catalyst life in the hundreds of hours.

Description

Be used for by acetic acid hydrogenation being produced the catalyst that being included in of ethanol contains the platinum-Xi on the silicon carrier
Priority request
The application requires the priority of the U. S. application No 12/588,727 of submission on October 26th, 2009, incorporates it into this paper in full by reference.
Invention field
But present invention relates in general to be used for the regulating catalyst of carboxylic acid, particularly acetic acid hydrogenation and make the flexible way of acetate dehydrogenation, wherein ethanol can change the commercial terms that changes to be fit to various catalyst with respect to the ratio of ethyl acetate and acetaldehyde.More specifically, the present invention relates to be used for carboxylic acid, particularly acetate gas phase hydrogenation are comprised with production the catalyst of the various products of corresponding alcohol, ester and aldehyde, particularly ethanol.Described catalyst shows excellent activity and selectivity in the product scope.
Background technology
Existence is to the long-term needs of the economically feasible method that acetate is converted into ethanol, described ethanol can use or be converted into subsequently ethene by himself, described 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 the natural gas of fluctuation and crude oil price help to make what produce according to routine, thus when oil price rises feasible to alternative ethene originate need be than bigger in the past.
The catalysis process of alkanoic acid and other carbonyl containing compound of being used to reduce has obtained broad research, has mentioned the various combinations of catalyst, carrier and operating condition in the literature.T.Yokoyama etc. have commented the reduction of various carboxylic acids on metal oxide in " Fine chemicals through heterogeneous catalysis.Carboxylic acids 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.2002,207,317-330).
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.2002，208，158-169)。
At Rachmady, W.; Vannice, M.A., J.Catal.2002,208, provided out of Memory among the 170-179 about catalyst surface material and organic intermediate.
At Rachmady, W.; Vannice, M.A.J.Catal.2002,209,87-98 and Rachmady, W.; Vannice, M.A.J.Catal.2000,192, further studied the vapor phase acetic acid hydrogenation on a series of support type Pt-Fe catalyst among the 322-334.
The various relevant publication that relates to the selective hydrogenation of unsaturated aldehyde can find in the 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.Applied Catalysis 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 the 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.Hyperfine Interactions 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 U.S. Patent 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 U.S. Patent No. 4,777,303 of Kitson etc. has been described a kind of method of producing alcohol by hydrogenation of carboxylic acids.The U.S. Patent No. 4,804,791 of Kitson etc. has been described another kind of method of producing alcohol by 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 by making tetrabutyltin and the ruthenic oxide reaction that loads on the silica.(Loessard etc., Studies in Surface Science and Catalysis (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 to ethanol; (ii) catalyst is might be too expensive and/or the generation of ethanol is non-selective and produces unwanted accessory substance; (iii) excessive operating temperature and pressure; And/or (iv) not enough catalyst life.
Summary of the invention
When having found on the stabilisation that is being scattered in modification contains platinum-tin catalyst on the silicon carrier, to go back ortho-acetic acid, the wherein said silicon carrier that contains includes the following support modification agent of being selected from of effect amount: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) (i)-(any precursor vi), and (i)-(any mixture vii), by in gas phase with at least about 4: 1 hydrogen and acetate mol ratio at about 125 ℃-350 ℃, more preferably from about 225-300 ℃, also more preferably from about make the gaseous stream that comprises hydrogen and acetate pass described catalyst under 250 ℃-300 ℃ the temperature, when the stabilisation of the ratio of the amount of control platinum as described herein and tin and oxidation state and platinum and tin and modification contains silicon carrier, can in conversion, obtain high selectivity to ethanol.In one aspect of the invention, offset and be present in the influence that has as the Bronsted acid position on the siliceous carrier surface of above-mentioned selected support modification agent.On the other hand, above-mentioned support modification agent for prevent catalyst in the presence of the acetic acid vapor that flows under 275 ℃ up to 168,336 or even time period of 500 hours in activity and optionally excessive loss be effective.In another aspect of this invention, when hope be attended by to acetate to the accessory substance of highly not expecting for example alkane transform low selectivity the time, thereby the support modification agent is the high selectivity that effectively produces for alcohol production to suppressing that ethyl acetate generates.Preferably, the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.Most preferred support modification agent is a calcium metasilicate.
When having found to go back ortho-acetic acid on the platinum-tin catalyst on being scattered in alkaline basically calcium metasilicate/silica supports, wherein by in gas phase with at least about 4: 1 hydrogen and acetate mol ratio at about 125 ℃-350 ℃, more preferably from about 225-300 ℃, also more preferably from about make the gaseous stream that comprises hydrogen and acetate pass described catalyst under 250 ℃-300 ℃ the temperature, when the acidity of the ratio of the amount of control platinum as described herein and tin and oxidation state and platinum and tin and calcium metasilicate/silica supports, can in conversion, obtain high selectivity to ethanol.Especially, use preferred catalyst of the present invention and method, make at least 80% of the acetate that transforms be converted into ethanol, make less than 4% acetate and be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof.In a preferred method, platinum exists with the amount of the 0.5%-5% of catalyst weight; Simultaneously tin with catalyst weight at least 0.5 until 10% amount exist; Preferably, carrier surface area is at least about 100m 2/ g, more preferably from about 150m 2/ g is also more preferably at least about 200m 2/ g is most preferably at least about 250m 2/ g; The mol ratio of tin and platinum group metal is preferably about 1: about 2: 1 of 2-, more preferably from about 2: about 3: 2 of 3-; Also more preferably from about 5: about 4: 5 of 4-; Most preferably from about 9: 10-10: 9.In many situations, thereby carrier comprises the calcium silicates that produces the amount of residual aluminium oxide (residual alumina) with active balance Bronsted acid position in silica; Typically, about 1 weight % is until the characteristic of the described carrier of calcium silicates sufficient to guarantee of about 10 weight % is neutral or alkaline basically.In an especially preferred embodiment, platinum is with at least about 0.75 weight %, and more preferably the amount of 1 weight % is present in the hydrogenation catalyst; The mol ratio of tin and platinum is about 5: about 4: 5 of 4-; And carrier comprises the calcium silicates at least about the about 10 weight % of 2.5 weight %-.
An aspect of the many embodiments of the present invention is can use to be higher than about 1000hr -1, 2500hr -1With in addition be higher than 5000hr -1Air speed, and make at least 90% of the acetate that transforms be converted into ethanol simultaneously, and make less than 2% acetate and be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate and ethene and composition thereof.In many embodiments of the present invention, the formation of alkane is low, is usually less than 2%, often is lower than 1%, and what make the acetate that passes catalyst in many situations is converted into alkane below 0.5%, this alkane except that act as a fuel or synthesis gas have very little value.
In another aspect of this invention, by making the gaseous stream that comprises hydrogen and alkanoic acid pass hydrogenation catalyst with the mol ratio at least about 2: 1 hydrogen and alkanoic acid under about 125 ℃-350 ℃ temperature in gas phase alkanoic acid is carried out hydrogenation, described hydrogenation catalyst comprises: in the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier of containing that is selected from silica that silica, calcium metasilicate and calcium metasilicate promote; With the promoter that is selected from tin, rhenium and composition thereof, it is optional with the promoter promotion wherein to contain silicon carrier, and promoter is selected from: the promoter that is selected from alkali metal, alkaline earth element and zinc of the amount of the 1-5% of catalyst weight; The amount of the 1-50% of catalyst weight be selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type (redox) promoter; And the 1-50% of catalyst weight amount be selected from TiO 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent, the acidity of wherein controlling described carrier is so that less than 4, preferably less than 2, most preferably is converted into alkane less than about 1% alkanoic acid.In many situations, the amount of at least a 0.25%-5% with catalyst weight in platinum and the palladium exists; The platinum that exists and the total amount of palladium are at least 0.5% of catalyst weight; The rhenium that exists and the total amount of tin are 0.5-10 weight % at least.In the method, for being included in the platinum on the alkaline silica supports and the catalyst of tin, the amount and the oxidation state of control platinum group metal, rhenium and tin promoter, and the mol ratio of the total mole number of the rhenium of platinum group metal and existence and tin; Make at least 80% of the acetate that transforms be converted into the compound that is selected from alkanol and alkyl acetate with the acidity that contains silicon carrier, and make simultaneously less than 4% alkanoic acid and be converted into compound except that the compound that is selected from corresponding alkanol, alkyl acetate and composition thereof.Preferably, the amount of at least a 0.5%-5% with catalyst weight in platinum and the palladium exists; The platinum that exists and the total amount of palladium are at least 0.75% to 5% of catalyst weight.Preferably, alkanoic acid is an acetate, and the tin of existence and the total amount of rhenium are at least 1.0% of catalyst weight, and controls the amount and the oxidation state of platinum group metal, rhenium and tin promoter simultaneously, and the ratio of platinum group metal and rhenium and tin promoter; Make at least 80% of the acetate that transforms be converted into ethanol or ethyl acetate with the acidity that contains silicon carrier, make less than 4% acetate and be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof.Preferably, the rhenium of existence and the gross weight of tin are about 1-10% of catalyst weight, and the mol ratio of the total mole number of while platinum group metal and rhenium and tin is about 1: about 2: 1 of 2-.
On the other hand, the present invention relates to method with acetic acid hydrogenation, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, described hydrogenation catalyst is made of the metal component that is dispersed on the oxide-based carrier basically, and described hydrogenation catalyst has following composition:
Pt vPd wRe xSn yCa pSi qO r，
Wherein: v: the ratio of y is 3: 2-2: 3; The ratio of and/or w: x is 1: 3-1: 5, p and q are selected to make that p: q is 1: 20-1: and 200, wherein the chemical valence requirement is satisfied in the selection of r, and the selection of v and w makes:
0.005 ≤ ( 3.25 v + 1.75 w ) q ≤ 0.05 .
Aspect this, preferably the value of process conditions and v, w, x, y, p, q and r is selected so that the acetate that transforms at least 90% be converted into the compound that is selected from ethanol and ethyl acetate, and be converted into alkane less than 4% acetate simultaneously.In many embodiments of the present invention, consider any less impurity of existence, p is selected to guarantee that carrier surface is substantially free of active Bronsted acid position.
Another aspect of the present invention relates to by with the acetate method of original production ethanol also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, described hydrogenation catalyst is made of the metal component that is dispersed on the oxide-based carrier basically, and described hydrogenation catalyst has following composition:
Pt vPd wRe xSn yAl zCa pSi qO r，
Wherein: v and y are 3: 2-2: 3; W and x are 1: 3-1: 5, and wherein control the aluminium atom of p and z and existence and the relative position of calcium atom and make that being present in its surperficial Bronsted acid position carries out balance by calcium silicates; 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 ≤ ( 3.25 v + 1.75 w ) q ≤ 0.05 .
Preferably, aspect this, described hydrogenation catalyst has at least about 100m 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 selected to promote that to guarantee that equally carrier surface is substantially free of ethanol conversion is the active Bronsted acid position of ethyl acetate.
Another aspect of the present invention relates to by with the acetate method of original production ethanol and ethyl acetate also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, described hydrogenation catalyst comprises: in the platinum group metal that contains the mixture that is selected from platinum and platinum and palladium on the silicon carrier of the silica that is selected from silica and promotes with about 7.5 calcium metasilicates at the most, the amount of the platinum group metal that exists is at least about 2.0%, and the amount of the platinum of existence is at least about 1.5%; With the metallic promoter agent that is selected from rhenium and tin of the amount of about 1%-2% of catalyst weight, the mol ratio of platinum and metallic promoter agent is about 3: 1-1: 2; Optional contain silicon carrier with what second promoter promoted, described second promoter is selected from: the amount of the 1-5% of catalyst weight be selected from alkali metal, alkaline earth element and zinc to body (donor) promoter; The amount of the 1-50% of catalyst weight be selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type promoter; And the 1-50% of catalyst weight amount be selected from TiO 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent; And their combination.
In preferred aspects of the invention, the mol ratio of metallic promoter agent and platinum group metal is about 2: about 3: 2 of 3-, and more preferably from about 5: about 4: 5 of 4-, most preferably from about 9: about 10: 9 of 10-, and siliceous carrier surface area is at least about 200m simultaneously 2/ g, the amount of sodium metasilicate is enough to make the surface of described carrier to be alkalescence basically.In some cases, the use of controllable silicon acid calcium makes the molal quantity that is present in its lip-deep Bronsted acid position be not more than the molal quantity that is present in the Bronsted acid position on the Saint-Gobain NorPro SS61138 silica surface.In other situation, employed silica can be to have the aluminium oxide of low content or the high-purity pyrolytic silicon dioxide of other impurity.In many situations, this class silica can comprise and be higher than 99% silica, more preferably is higher than 99.5% silica, most preferably is higher than 99.7% silica.In many embodiments of the present invention, perhaps by control silica purity, perhaps by be present in the Bronsted acid position on the carrier surface with a kind of balance in other suitable stabilizers modifier that calcium silicates or this paper discussed, the available molal quantity that is present in its lip-deep Bronsted acid position is not more than the molal quantity that is present in the Bronsted acid position on the Saint-Gobain NorPro SS61138 silica surface, preferably less than half, be more preferably less than 25%, also be more preferably less than 10% the molal quantity that is present in the Bronsted acid position on the Saint-Gobain NorPro SS61138 silica surface.The sour figure place that is present on the carrier surface can use the pyridine titration to measure by the operation of describing in the following document:
(1) F.Delannay, editor, " Characterization of Heterogeneous Catalysts "; Chapter III:Measurement of Acidity of Surfaces, the 370-404 page or leaf; Marcel Dekker, Inc., N.Y.1984.
(2) C.R.Brundle, C.A.Evans, Jr., S.Wilson, L.E.Fitzpatrick, editor, " Encyclopedia of Materials Characterization "; Chapter 12.4:Physical and Chemical Adsorption Measurements of Solid Surface Areas, the 736-744 page or leaf; Butterworth-Heinemann, MA 1992.
(3) G.A.Olah, G.K.Sura Prakask, editor, " Superacids "; John Wiley ﹠amp; Sons, N.Y.1985.
In whole specification and claim, unless context point out in addition, when measuring surface acidity or the sour figure place on it, should use F.Delannay, editor, " Characterization of Heterogeneous Catalysts "; Chapter III:Measurement of Acidity ofSurfaces, the 370-404 page or leaf; Technology described in the Marcel Dekker, Inc., N.Y.1984.
In preferred situation, the surface area that contains silicon carrier is at least about 250m 2/ g, the molal quantity that is present in its lip-deep available Bronsted acid position is not more than half of the Bronsted acid position molal quantity that is present on the Saint-Gobain NorPro HSA SS61138 silica surface, and can carry out hydrogenation under about 250 ℃-300 ℃ temperature.
Review this paper discusses, as those skilled in the art will appreciate that, in some embodiments, can use the catalyst carrier that contains the silicon carrier except that above-mentioned, condition is that its component is selected to have suitable activity, selectivity and robustness (robust) under the employed process conditions so that this caltalyst ties up to.Suitable carriers can comprise stable metal oxide base carrier or ceramic base carrier and the molecular sieve that comprises zeolite.Therefore same, in some embodiments, on 2 hurdles, can use carbon carrier described in 64 row-4 hurdles, 22 row as the above-mentioned U.S. Patent No. 5,149,680 of Kitson etc., incorporate the disclosure of this United States Patent (USP) into this paper by reference.
In many embodiments of the present invention, to produce simultaneously therein in the situation of mixture of ethanol and ethyl acetate, hydrogenation catalyst can comprise: at the palladium on the silicon carrier of containing of the silica that is selected from silica and promotes with about 7.5 calcium metasilicates at the most, the amount of the palladium of existence is at least about 1.5%; And simultaneously metallic promoter agent is the rhenium of amount of about 1%-10% of catalyst weight, and the mol ratio of rhenium and palladium is about 4: 1-1: 4, preferred 2: 1-1: 3.
In many embodiments of the present invention, in the situation of the ethanol of the main production of expectation therein, catalyst can be made of following basically: basically by with about 3 until the silica that about 7.5% calcium silicates promotes constitute contain platinum on the silicon carrier, wherein the amount of the platinum of Cun Zaiing is at least about 1.0%, with the tin promoter of the amount of about 1%-5% of catalyst weight, the mol ratio of platinum and tin is about 9 in many embodiments of the present invention: 10-10: 9.In some cases, can comprise the another kind of platinum group metal of minor amount, the most common is the palladium that belongs to the catalytic metal in the prescription.In many embodiments of the present invention, the amount of the platinum group metal that exists is at least about 2.0%, the amount of the platinum that exists is at least about 1.5%, the platinum of preferred 2.5-3.5 weight %, tin promoter exists with the amount of about 2%-5% of catalyst weight, and simultaneously described method under about 250 ℃-300 ℃ temperature with at least about 1000hr -1GHSV under the pressure of 2atm at least, carry out.The ratio of tin and platinum is preferably 2: 3-3: 2, more preferably 4: 5-5: 4, most preferably 9: 10-10: 9.In still other embodiment of the ethanol of the main production of expectation therein, catalyst can be included in basically by with about 3 until the silica that about 7.5% calcium silicates promotes constitute contain platinum on the silicon carrier, wherein the amount of the platinum of Cun Zaiing is at least about 1.0%, tin promoter exists with the amount of about 1%-5% of catalyst weight, and the mol ratio of platinum and tin is about 9 in many embodiments of the present invention: 10-10: 9.
Another aspect of the present invention relates to the beaded catalyst that is used for alkanoic acid is hydrogenated to corresponding alkanol, this beaded catalyst comprises: be selected from silica and with about 3.0 until the silica that about 7.5 calcium metasilicates promote contain the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier, the surface area that contains silicon carrier is at least about 150m 2/ g; Tin promoter is the amount of about 1%-3% of catalyst weight, and the mol ratio of platinum and tin is about 4: 3-3: 4; Select to make its surface to be alkalescence basically to the described The Nomenclature Composition and Structure of Complexes that contains silicon carrier.
Another aspect of the present invention relates to the particle hydrogenation catalyst that is made of following material basically: the top silicon carrier that contains that is dispersed with platinum group metal that is selected from platinum, palladium and composition thereof and the promoter that is selected from tin, cobalt and rhenium, this contains silicon carrier has at least about 175m 2/ g surface area and be selected from silica, calcium metasilicate and silica (have and be positioned at its lip-deep calcium metasilicate) that calcium metasilicate promotes, the described surface of silicon carrier that contains is owing to not being substantially free of the Bronsted acid position by the aluminium oxide of calcium balance.Be suitable for most producing simultaneously in those modification of ethanol and ethyl acetate, the gross weight of the platinum group metal that exists is 0.5%-2%, and the amount of the palladium of existence is at least 0.5%, and promoter is rhenium, the weight ratio of rhenium and palladium is 10: 1-2: 1, and the amount of calcium metasilicate is 3-90%.
In aspect being suitable for most producing those of ethanol with high selectivity, the gross weight of the platinum group metal that exists is 0.5-2%, the amount of the platinum that exists is at least 0.5%, promoter is cobalt, the weight ratio of cobalt and platinum is 20: 1-3: 1, and the amount of calcium silicates is 3-90%, and for when having the Catalyst Production ethanol of life-saving, hydrogenation catalyst comprises the platinum of 2.5-3.5 weight %, and the surface area that is dispersed in of 3 weight %-5 weight % is 200m at least 2Tin on the high surface pyrolysis gained silica of/g, described high surface area silica promotes that with the calcium metasilicate of effective dose the mol ratio of platinum and tin is 4: 5-5: 4 to guarantee that its surface is substantially free of not by the Bronsted acid position of calcium metasilicate balance.
In another kind of catalyst of the present invention, the gross weight of the platinum group metal of existence is 0.5-2%, and the amount of the palladium of existence is at least 0.5%, and promoter is cobalt, and the weight ratio of cobalt and palladium is 20: 1-3: 1, and the amount of calcium silicates is 3-90%.
Another catalyst of the present invention is the hydrogenation catalyst that comprises following material: 0.5-2.5 weight % palladium, 2 weight %-7 weight % rheniums, the weight ratio of rhenium and palladium is at least 1.5: 1.0, and wherein rhenium and palladium all are dispersed in and contain on the silicon carrier, and the described silicon carrier that contains comprises at least 80% calcium metasilicate.
Found for being ethanol acetic acid hydrogenation, by being selected from that following catalyst obtains unexpectedly high activity and life-span and with excellent selectivity:
(i) with containing the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier and the catalyst of tin or rhenium what be selected from silica that silica, calcium metasilicate and calcium metasilicate promote;
(ii) with load on comprise be selected from silica that silica, calcium metasilicate and calcium metasilicate promote contain the palladium on the silicon carrier and the catalyst of rhenium, wherein contain the optional promoter that is selected from alkali metal, alkaline earth element and zinc with 1%-5% of silicon carrier and promote; Promoter preferably joins in the catalyst formulation with these promoter (preferred especially potassium, caesium, calcium, magnesium and zinc) nitrate or acetate form separately;
(iii) the high surface at the silica that is selected from silica, calcium metasilicate and calcium metasilicate promotion contains the platinum that promotes with cobalt on the silicon carrier; And
(iv) the high surface at the silica that is selected from silica, calcium metasilicate and calcium metasilicate promotion contains the palladium that promotes with cobalt on the silicon carrier.
Another aspect of the present invention relates to the method with the alkanoic acid hydrogenation, this method is included in the gas phase to make the gaseous stream that comprises hydrogen and alkanoic acid pass hydrogenation catalyst at least about 2: 1 the hydrogen and the mol ratio of alkanoic acid under about 125 ℃-350 ℃ temperature, and this hydrogenation catalyst comprises:
A. in the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier of containing that is selected from silica that silica, calcium metasilicate and calcium metasilicate promote; With
B. be selected from the promoter of tin and rhenium,
C. it is optional with being selected from the promotion of following promoter wherein to contain silicon carrier:
I. the promoter that is selected from alkali metal, alkaline earth element and zinc of the amount of the 1-5% of catalyst weight;
Ii. the amount of the 1-50% of catalyst weight is selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type promoter; And
Iii. the amount of the 1-50% of catalyst weight is selected from TiO 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent.
Preferably, alkanoic acid is an acetate, and platinum (if existence) exists with the amount of the 0.5%-5% of catalyst weight; Palladium (if existence) exists with the amount of the 0.25%-5% of catalyst weight; The platinum that exists and the total amount of palladium are at least 0.5% of catalyst weight; Tin exists with the amount of 0.5-5% at least, and the ratio of platinum and tin is as discussed previously.
In another aspect of this invention, the surface area that contains silicon carrier is at least about 150m 2/ g is more preferably at least about 200m 2/ g is most preferably at least about 250m 2/ g.In a more preferred embodiment, contain silicon carrier and comprise about at the most 7.5% calcium metasilicate.In other embodiments, contain silicon carrier and comprise about at the most 90% calcium metasilicate.In all embodiments, particularly when when producing pure basically ethanol, control carrier acidity can be quite favourable.Silica is used alone as in the situation of carrier therein, guarantees that quite advantageously the amount of aluminium oxide (it is the common pollutant of silica) is low, preferably is lower than 1%; More preferably less than 0.5%; Most preferably be lower than 0.3 weight %.Thus, greatly preferred so-called pyrolytic silicon dioxide is because it generally obtains to be higher than 99.7% purity.In this application, when mentioning high-purity silicon dioxide, it is meant for example silica that exists with the level less than 0.3 weight % of aluminium oxide of acid contaminant wherein.Use therein in the situation of the silica that calcium metasilicate promotes, usually needn't be very strict about purity as the silica of carrier, although aluminium oxide be do not expect and will not be to have a mind to add usually.
In more preferred of the present invention, platinum (if existence) exists with the amount of the 1%-5% of catalyst weight; Palladium (if existence) exists with the amount of the 0.5%-5% of catalyst weight; And the platinum that exists and the total amount of palladium are at least 1% of catalyst weight.
Carrier is pure basically high surface area silica therein, in another preferred embodiment of the present invention of the silica that preferred pyrolysis forms, tin exists with the amount of the 1%-3% of catalyst weight, and more preferably, the mol ratio of tin and platinum group metal is about 1: about 2: 1 of 2-; Also more preferably, tin and platinum mol ratio be about 2: about 3: 2 of 3-; Simultaneously most preferably, the mol ratio of tin and platinum is about 5: about 4: 5 of 4-.Carrier also comprises the CaSiO of minor amount therein 3Or in the situation of other stabilizing agent modifier of about 2%-about 10%, the acid impurities that tolerable is relatively large is as long as make their balances (counter-balance) by the stabilizing agent modifier of alkalescence basically of appropriate amount.
In another aspect of this invention, preferably at about 225 ℃-300 ℃, more preferably carry out described method under 250 ℃-300 ℃ the temperature, wherein said hydrogenation catalyst comprises: in the platinum group metal that contains the mixture that is selected from platinum and platinum and palladium on the silicon carrier of the silica that is selected from silica and promotes with about 7.5 calcium metasilicates at the most, the amount of the platinum group metal that exists is at least about 2.0%, and the amount of the platinum of existence is at least about 1.5%; The amount of tin promoter is about 1%-2% of catalyst weight, the mol ratio of platinum and tin is about 3: 1-1: 2, and it is optional with being selected from the promotion of following promoter wherein to contain silicon carrier: the promoter that is selected from alkali metal, alkaline earth element and zinc of the amount of the 1-5% of catalyst weight; The amount of the 1-50% of catalyst weight be selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type promoter; And the amount of the 1-50% of catalyst weight be selected from TiO 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent.
Be used for particularly preferred method with the present invention of alkanoic acid hydrogenation, catalyst comprises: in the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier of containing of the high surface area silica that is selected from the high surface high-purity silicon dioxide and promotes with about 7.5 calcium metasilicates at the most, the amount of the platinum group metal that exists is at least about 2.0%, and the amount of the platinum of existence is at least about 1.5%; The amount of tin promoter is about 1%-5% of catalyst weight, and the mol ratio of platinum and tin is about 3: 2-2: 3.Preferably, high-purity silicon dioxide is that pyrolysis produces, and is the fine and close form that is enough to use in fixed bde catalyst with its compressing tablet or granulation then.Yet, even in the situation of high-purity silicon dioxide, in the presence of acetic acid vapor in about 275 ℃ temperature with 2500hr -1Or the more commericially feasible operation of the prolongation period that extends to several weeks even several months of high-speed, as if the existence of stabilizing agent modifier, particularly calcium silicates make activity of such catalysts and selectivity prolong or be stable.Especially, can reach in 1 week (168 hours) or 2 weeks (336 hours) or even surpass 500 hours time period inner catalyst activity and can descend less than 10% such stability.Therefore, what can recognize is that catalyst of the present invention can be used in the commercial-scale commercial Application of the mixture of with acetic acid hydrogenation, particularly producing high purity ethanol and ethyl acetate and ethanol fully.
Another aspect of the present invention relates to based on the metal (Fe of VIII family on oxide-based carrier, Co, Ni, Ru, Rh, Pd, Ir, Pt and Os) or other transition metal (Ti particularly, Zn, Cr, Mo and W) hydrogenation catalyst, described oxide-based carrier with enough amounts on the surface of carrier itself or the inner alkaline-earth metal of introducing, alkali metal, zinc, scandium, the oxide of yttrium and metasilicate form, the precursor forms of these oxides and metasilicate, and the alkaline non-volatile stabilizing agent-modifier of their form of mixtures, thereby: offset its surface and go up the acid position that exists; Give anti-alteration of form under the temperature that meets with acetic acid hydrogenation (alteration of form especially mainly changes owing to sintering, grain growth, crystal boundary migration, defective and dislocation migration, plastic deformation and/or other temperature-induced microstructure); Or the two.
In another embodiment of the inventive method, catalyst is selected from:
(i) be selected from silica, calcium metasilicate and and silica by calcium metasilicate modification stable with calcium metasilicate contain the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier and the catalyst of tin or rhenium;
(ii) with load on comprise be selected from silica that calcium metasilicate and calcium metasilicate promote contain the palladium on the silicon carrier and the catalyst of rhenium, wherein contain the optional promoter that is selected from alkali metal, alkaline earth element and zinc with 1%-5% of silicon carrier and promote;
(iii) be selected from the platinum that promotes with cobalt on the silicon carrier that contains of silica that silica, calcium metasilicate and calcium metasilicate promote; And
(iv) be selected from the palladium that promotes with cobalt on the silicon carrier that contains of silica that silica, calcium metasilicate and calcium metasilicate promote.
Generally speaking, contain silicon carrier and introduce the promoter be selected from following material: with the oxide that comprises alkali metal, alkaline earth element and zinc of the amount of the 1-5% of catalyst weight and the stabilizing agent-modifier of metasilicate and their precursor; The amount of the 1-50% of catalyst weight be selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type promoter; The TiO that is selected from the amount of the 1-50% of catalyst weight 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent, the having of acid modification agent is beneficial to produces the ethyl acetate ethanol of holding concurrently.
Another aspect of the present invention relates to the beaded catalyst that is used for alkanoic acid is hydrogenated to corresponding alkanol, this beaded catalyst comprises: in the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier of containing of silica that is selected from silica, promotes with about 7.5 calcium metasilicates at the most and composition thereof, the surface area that contains silicon carrier is at least about 150m 2/ g; The amount of tin promoter is about 1%-2% of catalyst weight, the mol ratio of platinum and tin is about 3: 2-3: 2, contain that silicon carrier is optional to be promoted with being selected from following promoter: the promoter that is selected from alkali metal, alkaline earth element and zinc of the amount of the 1-5% of catalyst weight; The amount of the 1-50% of catalyst weight be selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type promoter; The TiO that is selected from the amount of the 1-50% of catalyst weight 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent.
Alternative embodiment of the present invention relates to the particle hydrogenation catalyst, this particle hydrogenation catalyst is made of following basically: the top silicon carrier that contains that is dispersed with platinum group metal that is selected from platinum, palladium and composition thereof and the promoter that is selected from tin, cobalt and rhenium, this contains silicon carrier has at least about 175m 2The surface area of/g and be selected from silica, calcium metasilicate and silica that calcium metasilicate promotes; It is optional with following material promotion to contain silicon carrier: the promoter that is selected from alkali metal, alkaline earth element and zinc of the 1%-5% of the amount of the 1-5% of catalyst weight; The amount of the 1-50% of catalyst weight be selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type promoter; The TiO that is selected from the amount of the 1-50% of catalyst weight 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent.In preferred embodiment of the present invention, the gross weight of the platinum group metal of existence is 2-4%, and the amount of the platinum of existence is at least 2%, and promoter is tin, and the mol ratio of platinum and tin is 2: 3-3: 2, and the amount of calcium metasilicate is 3-7%.In another preferred embodiment of the present invention, the gross weight of the platinum group metal of existence is 0.5%-2%, and the amount of the palladium of existence is at least 0.5%, and promoter is rhenium, and the weight ratio of rhenium and palladium is 10: 1-2: 1, and the amount of calcium metasilicate is 3-90%.In the 3rd preferred embodiment of the present invention, the gross weight of the platinum group metal of existence is 0.5-2%, and the amount of the platinum of existence is at least 0.5%, and promoter is cobalt, and the weight ratio of cobalt and platinum is 20: 1-3: 1, and the amount of calcium silicates is 3-90%.In the 4th preferred embodiment of the present invention, the gross weight of the platinum group metal of existence is 0.5-2%, and the amount of the palladium of existence is at least 0.5%, and promoter is cobalt, and the weight ratio of cobalt and palladium is 20: 1-3: 1, and the amount of calcium silicates is 3-90%.
Accompanying drawing is briefly described
Describe the present invention in detail below with reference to accompanying drawing, wherein identical numeral is indicated similar part.In these accompanying drawings:
Fig. 1 and 2 has described selection of catalysts of the present invention and productive rate performance.
Fig. 3 A-3C described along with when under 225 ℃ in the performance variation that on the catalyst of 225 ℃ of activation, obtains during with acetic acid hydrogenation, the relative temperature insensitivity of selection of catalysts of the present invention and productive rate.
Fig. 4 A-4C has described selectivity, conversion ratio and productive rate along with the platinum of (incumbent upon) preferred platinum-tin catalyst of the present invention ratio with tin changes and changes.
Fig. 5 A and 5B have described the most preferred catalyst of the present invention who loads on the high surface area silica for the selectivity of alcohol production and with the high yield of its acquisition.
Fig. 6 A and 6B and Fig. 7 A and 7B have described the excellent selectivity that the most preferred catalyst of the present invention who uses the high surface area silica that promotes based on calcium metasilicate at low temperatures obtains.What can recognize is that selectivity to ethanol is high.
The mass fraction of rhenium was to the influence of acetic acid hydrogenation when Fig. 8,9 and 10 had described on using silica of the present invention palladium rhenium catalyst.
Figure 11 and 12 has described the platinum that loads on the silica and the performance of Co catalysts.
Detailed Description Of The Invention
Even market situation constantly fluctuates, but for large-scale operation, acetic acid catalysis is hydrogenated to that selectivity, activity and the catalyst life reported in the document of ethanol hinting need be normally disadvantageous economically with these of other method ethanol production competition.The needed productive rate estimation of commercial viability draws, for about 200g ethanol/kg catalyst/hour productive rate, with needs above about 50% ethanol selectivity.Catalyst of the present invention head and shoulders above these requirements.
In the following description, all numerical value disclosed herein are all approximation, no matter they whether with word " pact " or " roughly " logotype.These numerical value can change 1%, 2%, 5%, perhaps can change 10-20% sometimes.As long as disclose and had lower limit R LWith upper limit R UA number range, fall into any number in this scope and subrange so also by specifically open.Especially, the following numerical value in this scope is by specifically open: R=R L+ k ★(R U-R L), wherein k varies to 100% from 1%, and increment is 1%, promptly k is 1%, 2%, 3%, 4%, 5% ..., 50%, 51%, 52% ..., 95%, 96%, 97%, 98%, 99% or 100%.And, by arbitrary number range of two R numerical definitenesses defined above also by specifically open.
Fig. 1 and 2 has described selection of catalysts of the present invention and productive rate performance, has shown under various operating temperatures selectivity and productive rate with the available very big improvement of these catalyst with schematic form.Especially, under 280 ℃ and 296 ℃, the ethanol selectivity is about 60%.In this is estimated, to remember that importantly ethyl acetate also is the commodity with suitable large economy importances and value, even main purpose is to produce ethanol, the any acetate that is converted into ethyl acetate also keeps sizable value, and is worth much lower than raw material usually as any alkane that accessory substance produces.In Fig. 1, represent with square as the productive rate that per hour moves the ethanol gram number that is produced by every kg catalyst of time (in hour) function, and the productive rate of ethyl acetate represents that with circle the productive rate of acetaldehyde is represented with rhombus simultaneously.Significantly, at this run duration, run duration improve as shown operating temperature with the justification function temperature to productive rate and optionally the influence.In Fig. 2, as the representing with circle as defined ethanol selectivity hereinafter of function running time, and simultaneously as hereinafter defined ethyl acetate selectivity represents that with square the acetaldehyde selectivity is represented with rhombus.
Fig. 3 A-3C has described the relative temperature insensitivity of selection of catalysts of the present invention to the metal precursor reduction temperature.This specific character is significant for commercial viability, because can not react in the container of keeping whole uniform temperature through special tectonic, usually these containers are called " adiabatic reactor ", because seldom the variations in temperature that is accompanied by course of reaction for adaptation is taken measures in advance, although usually with quartz chips or other inert particle " dilution " catalyst with conditioned reaction.Fig. 3 A has reported following result of experiment, in this experiment under with ℃ temperature displayed with the hydrogen reducing catalyst and then on the described catalyst under 250 ℃ with acetic acid hydrogenation.Reach the standard grade and represent the selectivity of described special catalyst ethanol, and the selectivity of expression to ethyl acetate that roll off the production line.In Fig. 3 B, provided the yield results of experiment, wherein reach the standard grade and to have write down ethanol yield and roll off the production line and write down the ethyl acetate productive rate.In Fig. 3 C, as the reduction temperature function shown this experiment conversion ratio (such as hereinafter definition) result.In addition, also under 225 ℃ the temperature in 225 ℃ the reduction or the activation catalyst on acetic acid hydrogenation.Point on Fig. 3 B and the 3C also comprise wherein under 225 ℃ on the catalyst of 225 ℃ of reduction with this result of this experiment of acetic acid hydrogenation.Can will be appreciated that, under 225 ℃ the temperature on this catalyst hydrogenation cause the ethanol selectivity that reduces and the conversion ratio of reduction.
Fig. 4 A-4C has described under the following conditions selectivity, conversion ratio and productive rate in the acetic acid catalysis hydrogenation along with the ratio of platinum in the preferred platinum-tin catalyst of the present invention with tin changes and change, and described change is at SiO about Pt 2-Pt xSn (1-x)(the molar fraction among ∑ [Pt]+[Sn]=1.20mmol): use 2.5ml solid catalyst (14/30 order, dilution (v/v uses quartz chips, 14/30 order) in 1: 1; Under the operating pressure of p=200psig (14bar); The feed rate of acetate, hydrogen and nitrogen dilution agent is respectively 0.09g/min HOAc; 160sccm/min H 2With 60sccm/min N 2Total air speed (GHSV) is 6570h in 12 hours reaction time -1Can will be appreciated that in this experiment, for those catalyst that load on the pure basically high surface area silica, the mol ratio with about 1 to 1 makes the selectivity maximization for alcohol production.(this specification in the whole text in, lowercase " l " is to be used for rising to avoid being used in many fonts similar or even the identical ambiguity that is produced of the symbol of numeral 1 and the 12nd letter of Roman alphabet small letter).In in Fig. 4 A-4C each, the X on the horizontal direction axle (horizontal access axis) i(Pt) mass fraction of expression platinum in catalyst, it is 0-1, and while selectivity, conversion ratio and productive rate are as indicated earlier, the expression catalyst is to the selectivity of ethanol and ethyl acetate as shown in Fig. 4 A, selectivity to ethanol as shown in Fig. 4 B reaches peak value at 50% mass fraction place, and the acetate conversion ratio reaches peak value and also reaches peak value along with alcohol yied as shown in Fig. 4 C.
Fig. 5 A and B have described that the most preferred catalyst of the present invention who loads on the high surface area silica is used for the selectivity of alcohol production and productive rate and with the high yield of its acquisition.In Fig. 5 A, on the longitudinal axis, shown the productive rate of the gram number that per hour moves by every kg catalyst, wherein alcohol yied is represented with square, the ethyl acetate productive rate represents that with circle the acetaldehyde productive rate is represented with rhombus.Similarly, in Fig. 5 B, running time on having shown on the longitudinal axis as transverse axis (in hour) function as defined selectivity hereinafter, the ethyl acetate selectivity is represented with circle once more, the ethanol selectivity represents that with square the acetaldehyde selectivity is represented with rhombus.
Fig. 6 A and B and Fig. 7 A and B have used the format description identical with B with Fig. 5 A and have used the selectivity of the preferred catalyst acquisition of the present invention of the high surface area silica that promotes based on calcium metasilicate at low temperatures.What can recognize is that the ethanol selectivity is higher than 90% in whole service.
About relevant embodiment Fig. 8-12 is discussed.
Only describe the present invention in detail with reference to many embodiments below for illustration and illustration purpose.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.
Unless hereinafter more specifically limit, term as used herein is got its its ordinary meaning, except as otherwise noted, " % " and similar terms are with reference to weight %.Generally speaking, when the carrier composition was discussed, the percentage in the composition comprised oxygen and connected ion or metal, and when the weight of catalytic metal is discussed, ignored the weight of connected oxygen.Therefore, in the carrier that comprises 95% silica and 5% aluminium oxide, this composition is based on the aluminium oxide with 101.94 formula weights and has the silica of 60.09 formula weights.Yet, when being meant catalyst with 2% platinum and 3% tin, ignore can connected any oxygen weight.
" conversion ratio " is by representing based on the mole percent of acetate in the charging.
Figure BDA0000080408810000181
" selectivity " is by representing based on the mole percent of the acetate that transforms.For example, be converted into ethanol, be meant that then the ethanol selectivity is 50% if conversion ratio is 50 moles of % of 50 moles of % and the acetate that transformed.The ethanol selectivity by gas-chromatography (GC) data by as the calculating of getting off:
Figure BDA0000080408810000191
Be not intended to bound by theoryly, think that according to the present invention acetate is converted into ethanol and relates to one or more in the following reaction:
Acetic acid hydrogenation obtains ethanol.
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Acetic acid hydrogenation obtains ethyl acetate
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The ethyl acetate cracking obtains ethene and acetate
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Ethanol dehydration obtains ethene
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Be used for catalysts selective that the acetic acid catalysis hydrogenation obtains ethanol be selected from following those:
(i) with containing the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier and the catalyst of tin or rhenium at the silica that is selected from silica, calcium metasilicate and promotes with calcium metasilicate
(ii) with the optional palladium that contains on the silicon carrier with 1%-5% loading on of being selected from that first promoter of alkali metal, alkaline earth element and zinc promotes as described above and the catalyst of rhenium, promoter preferably joins in the catalyst formulation with these promoter (preferred especially potassium, caesium, calcium, magnesium and zinc) nitrate or acetate form separately;
(iii) containing the platinum that promotes with cobalt on the silicon carrier; And
(iv) containing the palladium that promotes with cobalt on the silicon carrier.
To recognize easily that as those skilled in the art method of the present invention can be carried out in the various structures that use fixed bed reactors or fluidized-bed reactor.In many embodiments of the present invention, can use " thermal insulation " reactor; That is, the internal pipe arrangements (plumbing) that has seldom or do not need to pass a reaction zone adds or removes and reduce phlegm and internal heat.Perhaps, can use the shell-and-tube reactor that is equipped with heat transmission medium.In many situations, reaction zone can be contained in the single container or between have in the series containers of heat exchanger.Obviously recognize in order that the acetate method of reducing of use catalyst of the present invention can carry out in adiabatic reactor, and is little usually a lot of because this reactor structure is compared capital intensity with the shell-and-tube structure.
Can use various catalyst carrier known in the art to come load acetic acid hydrogenation catalyst.The example of this class carrier does not have any ferriferous oxide, silica, aluminium oxide, titanium dioxide, zirconia, magnesia, calcium silicates, carbon, graphite and their mixture of restrictedly comprising.For the present invention, the preferred silicon carrier that contains that uses the silica that is selected from silica, calcium metasilicate and promotes with calcium silicates, when granulation be when using enough fine and close form in fixed bed reactors, that expect especially is SiO 2Content is at least 99.7% pyrolytic silicon dioxide.Found optional high-purity, the high surface area silica that promotes with calcium metasilicate,, unexpectedly be better than being used for other carrier of catalyst of the present invention particularly from HSA SS 61138 grades of Saint-Gobain NorPro.Silica as carrier of the present invention preferably has 100m at least 2/ g, more preferably 150m at least 2/ g, more preferably 200m at least 2/ g, most preferably from about 250m 2The surface area of/g.This specification in the whole text in, term " high surface area silica " is interpreted as expression and has a 250m at least 2The silica of/g surface area.Activity/the stability that contains silicon carrier can be carried out modification by other component of including minor amount in as mentioned below.Any shape of granular pattern easily be can use, pill, extrudate, ball, spray-dired, ring, five spoke wheels (pentaring), trilobal thing and quatrefoil thing comprised, although for the preferred usually cylindrical pellets of using of the application.
The influence of catalyst carrier.
Remove to metal precursor (be halogen, Cl -Halogen-free with respect to (vs.), NO 3 -) and beyond preparation condition selects, the metal that is produced-carrier interact depend on consumingly below the structure and the performance of (underlying) carrier.
For various silicon dioxide carried Pt-Sn materials, the influence of research alkalescence and acid modification agent.For all material, except as otherwise noted, the mol ratio between Pt and the Sn remains in 1: 1, and total metal carrying capacity is remained unchanged.Especially, at acid carrier SiO for example 2, SiO 2-TiO 2, KA160 (is SiO 2-Al 2O 3) and the H-ZSM5 catalyst of going up preparation produce high acetate conversion ratio, but produce lower ethanol selectivity.What arouse attention is, in fact the H-ZSM5 catalyst produces the diethyl ether as primary product, and it most likely forms by ethanol dehydration.Based on SiO 2-TiO 2With (be SiO based on KA160 2-Al 2O 3) catalyst all produce high conversion ratio and similarly to the selectivity of EtOH and EtOAc, EtOAc is a primary product in two kinds of situations.As if the Lewis acidity that exists in the following catalyst carrier can be of value to higher acetate conversion ratio.Though SiO 2-TiO 2In acidity mainly based on Lewis acidity, but KA160 (silica-alumina) material also has strong Bronsted acid position, but this catalysis forms EtOAc by remaining acetate and EtOH.Catalyst based on H-ZSM5 has even stronger acid zeolite class (zeolytic) Bronsted acid position and shape selectivity, and this is that acid catalysis forms diethyl ether by ethanol dehydration because little hole also can help.Alkaline modifier is joined the common optionally raising that produces ethanol of any carrier of being studied, be accompanied by the obvious reduction of acetate conversion ratio.Discovery is for the SiO of clauses and subclauses in the Table A 2 2-CaSiO 3(5)-and Pt (3)-Sn (1.8), be 92% for the high selectivity of ethanol, use CaSiO 3That promote even pure TiO 2Selectivity with about 20% produces ethanol.SiO 2-TiO 2And TiO 2-CaSiO 3Between contrast hinting that the position density of acid position (Lewis) can also have importance, and can be most possibly realize the further optimization of acid performance of catalyst carrier by combine the alkaline and acid accelerator of change carefully with concrete preparation method.
Table A. the catalyst activity data of catalyst carrier modifier gathers in the gas phase hydrogenation of acetate.Reaction condition: 2.5ml solid catalyst (14/30 order, dilution (v/v uses quartz chips, 14/30 order) in 1: 1; P=200psig (14bar); 0.09g/min HOAc; 160sccm/min H 260sccm/min N 2GHSV=6570h -1Reaction time is 12 hours.
Figure BDA0000080408810000221
1This paper has described independent Preparation of catalysts in detail.Numeral in the bracket is in the amount of the real composition (metal, metal oxide) of weight %.
2Selectivity of product (weight %) is by being calculated by the reliable sample of GC analysis correction.
3Acetate conversion ratio (%) calculates by following: [HOAc] conversion ratio, %={[HOAc] (charging, mmol/min)-[HOAc] (effluent, and mmol/min)/[HOAc] (charging, mmol/min) } * 100.
4The primary product that obtains with this catalyst is diethyl ether (EtOEt), has 96% selectivity and the productive rate of 2646g/kg/h simultaneously.
Contrast KA160 (SiO 2-5%Al 2O 3) and KA160-CaSiO 3The catalyst that promotes observes the obvious transfer of selectivity to ethanol.Referring to clauses and subclauses in the Table A 2,6 and 7, though at 84% o'clock, this selection of catalysts still is lower than SiO 2-CaSiO 3The selectivity that sill observed, but the acetate conversion ratio remains in 43%, is about SiO 2-CaSiO 3(5)-almost twice of Pt (3)-acetate conversion ratio that Sn (1.8) sees.Except that " acid modification agent " performance, all CaSiO 3As if the material that promotes demonstrate the long term stability (though being under lower conversion ratio) of improvement.Particularly, under the various reaction conditions in greater than 220 hours reaction time SiO 2-CaSiO 3(5)-Pt (3)-Sn (1.8) catalyst shows less than 10% activity and reduces.About selectivity, at SiO 2And SiO 2-CaSiO 3Two kinds of Re-Pd catalyst of last preparation also demonstrate similar trend.Clauses and subclauses 9 and 10 in the Table A are for these two kinds of materials, though conversion ratio keeps below 10%, for CaSiO 3The material that promotes observes to ethanol and optionally obviously shifts.Other information about productive rate is provided in the table 4.
Therefore, not bound by theory, the oxide-based carrier that is used for the acetic acid hydrogenation catalyst by introduce non-volatile stabilizing agent-modifier in addition modification and stable have following active any: offset exist its surface on the acid position; Perhaps make the stable ethanol selectivity that makes it possible to obtain to expect of its surface heat improve the catalyst life of prolongation; Or these two.Generally speaking, based on be in its modifier of the oxide of stable valence state can have low vapor pressure, and therefore have and be quite non-volatile.Therefore, hydrogenation catalyst based on the VIII family metal (Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt and Os) on oxide-based carrier or other transition metal (particularly Ti, Zn, Cr, Mo and W), preferably with enough amounts on the surface of carrier itself or inner oxide and the metasilicate form of introducing alkaline-earth metal, alkali metal, zinc, scandium, yttrium, the precursor forms of these oxides and metasilicate, and the alkaline non-volatile stabilizing agent-modifier of their form of mixtures, thereby: offset its surface and go up the acid position that exists; Give anti-alteration of form under the temperature that meets with acetic acid hydrogenation (alteration of form especially mainly changes owing to sintering, grain growth, crystal boundary migration, defective and dislocation migration, plastic deformation and/or other temperature-induced microstructure); Or the two.
In the present invention, the amount of the metal carrying capacity on the carrier and non-key and can in the scope of the about 10 weight % of about 0.3 weight %-, change.Be preferably based on the metal carrying capacity of the about 6 weight % of the about 0.5 weight %-of catalyst weight meter especially.Owing to extremely expensive, typically use the platinum group metal, common 10 weight % less than whole catalyst composition with the amount of quite careful control.Be low to moderate the platinum of 0.25-5%, when with as described herein other catalytic elements combination, can provide excellent selectivity, life-span and activity.Typically, preferred 0.5-5%, the more preferably platinum of 1-3% of using in catalyst made from platonic of the present invention.In the situation of platinum-tin catalyst, when load on high surface area silica/calcium metasilicate, preferably use 0.10-5% tin, more preferably 0.25-3% tin, more preferably 0.5-2.5% tin also, the most preferably from about combination of 3% platinum and about 1.5% tin 1: 1 mol ratio of platinum and tin (quite closely corresponding to) is perhaps based on the not too proportional amount than the platinum of low weight percentage.For this catalyst, the preferred silicon carrier that contains that uses the high surface area silica that is selected from aforesaid high-purity high surface area silica, calcium metasilicate and promotes with calcium metasilicate.Therefore, what can recognize is that the amount of calcium metasilicate can vary widely from 0 up to 100 weight %.Because calcium metasilicate trends towards having lower surface area, so for this catalyst, in carrier of the present invention, preferably include at least about 10% high surface area silica, more preferably as carrier of the present invention, about 95% high surface area silica of preferred use, promptly from SS61138 high surface (HSA) the SiO 2 catalyst carrier of Saint-GobainNorPro, it has 250m 2The surface area of/g; The mean pore sizes of 12nm; By the 1.0cm that presses mercury hole mensuration to measure 3The total pore volume of/g and about 22lbs/ft 3Bulk density.
Catalyst of the present invention is being not that to be similar to that automobile catalyst and diesel oil cigarette ash capturing device be impregnated in the washcoated layer on only stone carrier like that be pellet type catalyst on this meaning, shaped catalyst of the present invention is a particle, 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 by catalyst with a lot of these moulding.Common shape comprises the extrudate with any cross section, the bus that limits the extrudate surface (generator) be parallel lines meaning the above be shaped as the broad sense cylinder.Ball, spray-dried microspheres, ring, five spoke wheels and leafy shape thing all are available.Typically, according to cognition to the gas phase that makes shape is selected according to experience with the ability that catalyst effectively contacts.
Highly suitable platinum-tin catalyst comprises that to load on surface area be about 250m 2About 3 weight % platinum, 1.5 weight % tin on the high surface area silica of using about 0.5%-7.5% calcium metasilicate promotion of/g.Be to have realized under 280 ℃ the catalyst life of hundreds of hours running times with this composition.In many situations, in composition mentioned above, can partly substitute platinum by enough palladiums.
Be similar to describe in the earlier paragraphs those but contain the extremely catalyst of expensive platinum that the quite a large amount of cobalts of more a spot of usefulness promote and good initial catalytic activity be provided but tended to not show the prolongation catalyst life the same with above-mentioned platinum-tin catalyst.The preferred rank (hierarchy) that contains silicon carrier of this catalyst is substantially the same with platinum-tin catalyst.Preferably this class catalyst comprises and about 20% cobalt of about 1%-, more preferably from about about 15% cobalt of 2%-, more preferably from about the 0.25-5% platinum of 8-12% cobalt combination, more preferably 0.3-3% platinum, most preferably 0.5-1.5% platinum.Even these catalyst are durable not as above-mentioned platinum-tin catalyst, but in many situations, the amount of the required platinum that this can greatly be reduced, cobalt are compared low cost and excellent initial selectivity and are obtained counteracting to a great extent with the platinum group metal.Certainly, it should be understood that in many situations, can or use bigger reactor to remedy active the shortage by suitable recycle stream, but be difficult to remedy poor selectivity.
Catalyst based on the palladium that promotes with rhenium or cobalt provides excellent catalytic activity and lower a little selectivity, thereby the forfeiture of this selectivity is being higher than acetaldehyde, carbon dioxide and even the hydrocarbon that aggravates to cause forming the raising amount under 280 ℃ the reaction temperature.Cobalt-containing catalyst is compared typical earth surface with corresponding rhenium catalyst and is revealed selectivity a little preferably; But,, all do not provide the same outstanding catalyst life with most preferred platinum/tin catalyst on the high-purity alpha-alumina of and modification stable with calcium metasilicate though these two all provides beat all long life catalytic activity.In addition can be with this catalyst cupport with above-mentioned I family, II family and the oxide of zinc and containing on the silicon carrier of metasilicate and their precursor and their stabilized with mixture and modification.The height suitable precursor comprises the acetate and the nitrate of zinc, alkali metal and alkaline-earth metal, can choose wantonly they are contained in the silicon carrier to bring into based on the amount of the about 1-5% of weight metal except that acetate and/or nitrate anion part.
In other embodiments of the present invention, thus above-mentioned catalyst can bring into to contain by the modifier that will be selected from oxidation-reduction type active modifier, acid modification agent and their mixture and carry out modification in the silicon carrier and change relative selectivity between ethanol, ethyl acetate and acetaldehyde.Suitable oxidation-reduction type active modifier comprises WO 3, MoO 3, Fe 2O 3And Cr 2O 3, and the acid modification agent comprises TiO 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3By with these modifier reasonably (judicious) bring into and contain in the silicon carrier, activity that can regulating catalyst distributes with production and market fluctuation with to the catalytic hydrogenation product relative quantity of the consistent expectation more of the requirement of various products.Typically, these materials can be included in by the amount of about 1-50% of siliceous vehicle weight and contain in the silicon carrier.
Can use any known method in this area to carry out metal impregnation.Typically, before dipping, that carrier is down dry and be shaped to the particles of the Size Distribution with about 0.2-0.4mm at 120 ℃.Randomly, carrier can be suppressed, crushed and sieve and be that required size distributes.Can use any carrier material that makes to be shaped to the known method that required size distributes.In the method for optimizing of preparation catalyst, for example the suitable combination thing of platinum group metal and/or complex compound obtain catalyst component in the carrier dispersion on the carrier granular for example can to use platinum group metal component.Can use the water dissolvable compound of platinum group metal or water-dispersible compound or complex compound that catalytic metal compound is impregnated into or deposits on the carrier granular.Platinum group metal component is decomposed when heating and/or applying vacuum.That in some cases, does not carry out liquid removes the high temperature that comes into operation and stand during operation to be suffered up to catalyst fully.Usually, from the viewpoint of economy and environment aspect, the aqueous solution of preferred platinum group metal soluble compound.For example, suitable compound is platinic hydroxide, palladium nitrate or palladium bichloride, sodium chloride palladium, sodium chloride platinum of chloroplatinic acid, amine solvent etc., although preferably avoid using halogen when ethanol is required product.During calcining step, or at least during using the starting stage of catalyst, these compounds are converted into catalytic activity form or its catalytic activity oxide of platinum group metal.Yet generally speaking, preferably use the not platinum group metal precursor of chloride, because found (NH by Pt 3) 4(NO 4) 2As if the catalyst of preparation show the ethanol selectivity of raising.
Owing to it has been generally acknowledged that catalyst of the present invention is a bimetallic, in such circumstances, a kind of metal serves as promoter metals and another kind of metal is main metal.For example, in the situation of platinum-tin catalyst, platinum can be considered to be used to prepare the main metal of hydrogenation catalyst of the present invention, and tin can be considered to promoter metals.Yet, it should be noted that so sometimes difference may have misleading, particularly therein under the optionally this situation of platinum-tin catalyst to ethanol, there is not tin and do not existing product required under the situation of platinum all to be close to 0.For facility, preferably the platinum group metal is referred to as main catalyst and with other metal finger on behalf of promoter.This should not be viewed as the indication of the basic mechanism of catalytic activity.
Often divide in two steps and flood bimetallic catalyst.At first, adding " promoter " metal, then is " master " metal.Then carry out drying and calcining after each impregnation steps.Bimetallic catalyst can also be prepared by flooding altogether.In the situation of the bimetallic catalyst that promotes as mentioned above, can use dipping in succession, begin to add that " promoter metals then is second impregnation steps of the common dipping that comprises that two kinds of major metals are Pt and Sn.For example, SiO 2On PtSn/CaSiO 3Can be prepared by following: at first with CaSiO 3Be impregnated into SiO 2On, then with chloroplatinic acid, platinic hydroxide, palladium nitrate or the palladium bichloride of amine solvent, sodium chloride palladium, sodium chloride platinum, Pt (NH 3) 4(NO 4) 2Deng lean mixture carry out common dipping.Again, then carry out drying and calcining behind each dipping.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 example of other suitable metal salt that is used to flood comprises metal acid, for example perrhenic acid solution, metal oxalate etc.Produce in those situations of pure basically ethanol therein, preferably avoid using the halogenation precursor of platinum group metal usually, and be to use nitrogenous amine and/or nitrate-based precursor.
Can under many conditions, in vapor state, react.Preferably, in gas phase, react.For example can use to be about 125 ℃-350 ℃, more common about 200 ℃-Yue 325 ℃, preferred about 225 ℃-Yue 300 ℃, most preferably from about 250 ℃-Yue 300 ℃ reaction temperature.Pressure is also non-key usually for reaction, can use to be lower than atmospheric pressure, atmospheric pressure or superatmospheric pressure.Yet in most of situations, reaction pressure can be about 1-30 absolute atmosphere.In the inventive method on the other hand, typically can carry out hydrogenation with selected total space-time speed (" GHSV ") just being enough to overcome under the pressure of the pressure drop of passing catalytic bed, do not use higher pressure although do not limit, should be understood that for catalyst of the present invention be easy to use 5000hr -1With 6,500hr -1Air speed under may experience sizable pressure drop by 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 change between wide region in the incoming flow, for example is about 100: 1-1: 100.Yet such ratio is preferably about 1: 20-1: 2.Most preferably, the mol ratio of hydrogen and acetate is about 5: 1.
The employed raw material of relevant the inventive method can comprise natural gas, oil, coal, living beings etc. derived from any suitable source.Produce acetate by carbonylation of methanol, oxidation of acetaldehyde, ethene oxidation, oxidative fermentation and anaerobic fermentation etc. as everyone knows.Because oil and natural gas fluctuation more or less becomes expensive, thus by substitute carbon source produce acetate and intermediate for example the method for methyl alcohol and carbon monoxide cause concern gradually.Especially, when oil is compared with natural gas when relatively costly, may become favourable by producing acetate derived from the forming gas (" synthesis gas ") of any suitable carbon source.For example, the U.S. Patent No. 6,232,352 (incorporating its disclosure into this paper by reference) of Vidalin has been instructed and has been transformed methanol device in order to make the method for acetate.By transforming methanol device, for new acetate device, the substantial contribution expense relevant with the CO generation is significantly reduced or eliminates to a great extent.Make all or part synthesis gas turn to and supply to separator unit to reclaim CO and hydrogen, then they are used to produce acetate from the synthetic loop of methyl alcohol.Except that acetate, this method also can be used for preparing the available hydrogen of relevant the present invention.
It is a kind of by making for example method of oil, coal, natural gas and conversion of biomass material production methyl alcohol of carbonaceous material that the U.S. Patent No. RE 35,377 (also incorporating it into this paper by reference) of Steinberg etc. provides.This method comprises makes solid and/or the hydrogasification of liquid carbon-containing material to obtain process gas, with other natural gas with this process gas steam pyrolysis with the formation synthesis gas.This synthesis gas is converted into the methyl alcohol that can carbonyl turns to acetate.This method is same to be produced as the above-mentioned relevant spendable hydrogen of the present invention.Also referring to the U.S. Patent No. 6,685,754 of the U.S. Patent No. 5,821,111 of Grady etc. and Kindig etc., it discloses a kind of living beings of will giving up and has been converted into the method for synthesis gas by gasification, incorporates their disclosure into this paper by reference.
Acetate is gasified under reaction temperature, then can with gasification acetate 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.
Perhaps, can be directly the flash chamber of a class carbonylation of methanol unit described in the U.S. Patent No. 6,657,078 (incorporating it into this paper in full by reference) of Scates etc. take out the acetate of steam form as crude product.Thick vapor product directly can be given to enter reaction zone of the present invention and do not need condensation acetate and light fraction or remove to anhydrate, thereby save the overall craft expense.
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, typical time of contact be part second to greater than some hrs, at least for gas-phase reaction, preferably be about 0.5-100 second time of contact.
Typically, catalyst uses in the fixed bed reactors of pipeline that for example is shaped as elongation or conduit, and the reactant that wherein typically is the steam form passes or by described catalyst.If desired, can use other reactor, for example fluid bed or fluidized bed reactor.In some cases, hydrogenation catalyst can with inert material for example mineral wool be used in combination with the conditioned reaction material flow by catalyst bed pressure drop and the time of contact of reactant compound and catalyst granules.
The following examples have been described the operation that is used to prepare the employed various catalyst of the inventive method.In all these preparations and embodiment, when using small letters or cursive " l ", its be used for avoiding small letters letter " l ", the numeral " 1 " and between uppercase or the capitalization " I " at many fonts and/or the intrinsic ambiguous of printed words, because the implication of language is produced by common usage, should understand it is to refer to " liter ", although it lacks any international recognition.
Preparation of Catalyst (generally)
Catalyst carrier before using under circulating air in 120 ℃ of following dried overnight.Unless otherwise mentioned, all commercial carriers (are SiO 2, 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 in the chapters and sections below in more detail.
Preparation of Catalyst A
The preparation of 0.5 weight % platinum and 5 weight % tin on the high-purity low-surface area silica
In the baking oven under the nitrogen 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 add platinum nitrate (Chempur) (0.82g) solution in distilled water (8ml) and tin oxalate (Alfa Aesar) (8.7g) at rare nitric acid (1N, 43.5ml) solution in.Be heated to gradually 110 ℃ (＞2 hours, dry gained slurry in 10 ℃/min) the baking oven.Then 500 ℃ (6 hours, 1 ℃/min) down calcining through the catalyst mixture of dipping.
Preparation of Catalyst B
The preparation of 1 weight % platinum and 1 weight % tin on the high surface area silica
Basically repeat the operation of Preparation of Catalyst A, difference be to utilize platinum nitrate (Chempur) (1.64g) solution in distilled water (16ml) and tin oxalate (Alfa Aesar) (1.74g) at rare nitric acid (1N, 8.5ml) solution in.
Preparation of Catalyst C
The preparation of 1 weight % platinum and 1 weight % tin on calcium metasilicate
Basically repeat the operation of Preparation of Catalyst B, difference be to utilize platinum nitrate (Chempur) (1.64g) solution in distilled water (16ml) and tin oxalate (Alfa Aesar) (1.74g) at rare nitric acid (1N, 8.5ml) in solution, and utilize calcium metasilicate as catalyst carrier.
Preparation of Catalyst D
The preparation of 0.5 weight % platinum, 0.5 weight % tin and 0.2 weight % cobalt on the high surface area silica
In the baking oven under the nitrogen atmosphere, under 120 ℃, uniform grading is distributed as the powdered of about 0.2mm and the high surface area silica that sieves (100g) dried overnight, and then it is cooled to room temperature.To wherein add platinum nitrate (Chempur) (0.82g) solution in distilled water (8ml) and tin oxalate (Alfa Aesar) (0.87g) at rare nitric acid (1N, 4.5ml) solution in.Be heated to gradually 110 ℃ (＞2 hours, dry gained slurry in 10 ℃/min) the baking oven.Then 500 ℃ (6 hours, 1 ℃/min) down calcining through the catalyst mixture of dipping.In the material of calcining and cooling, add the solution of cabaltous nitrate hexahydrate (0.99g) in distilled water (2ml) to this.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.
Preparation of Catalyst E
The preparation of 0.5 weight % tin on the high-purity low-surface area silica
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 rare nitric acid (1N, 8.5ml) solution in.Be heated to gradually 110 ℃ (＞2 hours, dry gained slurry in 10 ℃/min) the baking oven.Then 500 ℃ (6 hours, 1 ℃/min) down calcining through the catalyst mixture of dipping.
Preparation of Catalyst F
The preparation of 2 weight % platinum and 2 weight % tin on the high surface area silica
In circulated air oven atmosphere, under 120 ℃, uniform grading is distributed as the powdered of about 0.2mm and high surface area silica NPSG SS61138 (100g) dried overnight of sieving, and then it is cooled to room temperature.To wherein adding six nitric hydrate salt (Chempur) solution.(＞2 hours, dry gained slurry in 10 ℃/min) the baking oven was then with its calcining being heated to 110 ℃ gradually.To wherein adding solution and tin oxalate (Alfa Aesar) the solution in rare 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.
Preparation of Catalyst G
Preparation with 1 weight % platinum and 1 weight % tin on the high surface area silica of 5%ZnO promotion
Basically repeat the operation of Preparation of Catalyst F, difference is: zinc nitrate hexahydrate solution is joined in the described high surface area silica of Preparation of Catalyst F.Be heated to gradually 110 ℃ (＞2 hours, dry gained slurry in 10 ℃/min) the baking oven.Then, with platinum nitrate (Chempur) in distilled water solution and tin oxalate (Alfa Aesar) (1.74g) (1N, 8.5ml) solution in joins in the high surface area silica that zinc promotes subsequently at rare nitric acid.
Preparation of Catalyst H
Use 5%SnO 2The preparation of 1 weight % platinum and 1 weight %Zn on the high surface area silica that promotes
Basically repeat the operation of Preparation of Catalyst G, difference is: with tin acetate (Sn (OAC) 2) solution rather than zinc nitrate hexahydrate; And platinum nitrate Pt (NH 3) 4(NO 3) 2(Aldrich) solution in distilled water and tin oxalate (Alfa Aesar) solution in rare nitric acid joins in the high surface area silica.
Preparation of Catalyst I
The preparation of 1.5 weight % platinum, 0.5 weight % tin on the calcium metasilicate
Utilize solution and tin oxalate (Alfa Aesar) the solution in rare nitric acid of platinum nitrate (Chempur) in distilled water to repeat the operation of above-mentioned Preparation of Catalyst C.
Preparation of Catalyst J
The preparation of 1.5 weight % platinum, 10 weight % cobalts on the high surface area silica
Utilize the solution of platinum nitrate (Chempur) in distilled water, cabaltous nitrate hexahydrate (II) solution (1.74g) replaces stannous octoate to repeat the operation of above-mentioned Preparation of Catalyst H.The catalyst that has shown preparation in the table 1 is formed and is formed by other catalyst of similar operation preparation and test herein.
Preparation of Catalyst K-O
SiO 2-Pt xSn 1-x(0＜x＜1)。Total amount of metal (Pt+Sn) that the molar fraction of change Pt is also kept 1.20mmol simultaneously prepares five kinds of materials.Preparation of Catalyst K, i.e. SiO have been described in following preparation 2-Pt 0.5Sn 0.5(be x=0.5; Two kinds of mol ratios such as metal) operation.Similarly use the metal precursor Pt (NH of appropriate amount 3) 4(NO 3) 2And Sn (OAc) 2Carrying out all the other preparations (is x=0,0.25,0.75 and 1.00; Be respectively Preparation of Catalyst L, M, N and O).Described catalyst is prepared by following: at first with Sn (OAc) 2(from the tin acetate of Aldrich, Sn (OAc) 2) (0.1421g 0.60mmol) joins in the bottle of the glacial acetic acid (Fisher) that dilutes at 1: 1 that contains 6.75ml.At room temperature stir this mixture 15 minutes, and added 0.2323g (0.60mmol) 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 dry SiO of 5.0g in the 100ml round-bottomed flask 2Catalyst carrier (high-purity silicon dioxide catalyst carrier HSA SS#61138, SA=250m 2/ g; SZ#61152, SA=156m 2/ g; Saint-Gobain NorPro) in.This metallic solution of continuous stirring is up to all Pt/Sn mixtures are joined SiO 2Behind each adding metallic solution, rotate this flask in the catalyst carrier and simultaneously.After the adding of this metallic solution was finished, the flask that will contain impregnated catalyst was kept and is at room temperature left standstill 2 hours.Then this flask is connected to rotary evaporator (bathing 80 ℃ of temperature), finds time until drying and slow simultaneously this flask of rotation.Then under 120 ℃ with the further dried overnight of this material, use following temperature program(me) 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: 5.2g Dark grey material.
Preparation of Catalyst P
SiO 2-CaSiO 3(5)-Pt(3)-Sn(1.8)。This material passes through at first with CaSiO 3(Aldrich) join SiO 2Catalyst carrier then is prepared by previous described adding Pt/Sn.At first, CaSiO 3The waterborne suspension of (≤200 order) then adds 1.0ml colloid SiO by this solid of 0.52g is joined in the 13ml deionized water 2(15 weight % solution NALCO) are prepared.At room temperature stir this suspension 2 hours, and use beginning profit dipping technique to add 10.0g SiO then 2Catalyst carrier (14/30 order).After leaving standstill 2 hours, this material is evaporated to dried, then under circulating air in 120 ℃ of following dried overnight and 500 ℃ of calcinings 6 hours down.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 above with regard to SiO 2-Pt xSn 1-xThe described operation of material is with all SiO 2-CaSiO 3Material is used for the Pt/Sn metal impregnation.Output: 11.21g Dark grey material.
Preparation of Catalyst Q
CaSiO 3-Pt(1)-Sn(1)。Contain the 1.0M NHO that adds 40ml in the round-bottomed flask of teflon-coating magnetic stirring bar to 100ml 3, then add 0.2025g (0.52mmol) solid Pt (NH 3) 4(NO 3) 2Along with stirring and dissolving Pt complex compound also adds 0.2052g (0.87mmol) solid Sn (OAc) then 2Next, along with stirring the CaSiO that adds 10.0g 3(≤200 order); Then this mixture is heated to 80 ℃ and under this temperature, stirred 2 hours.Use rotary evaporator (bathe temperature 80 ℃) that this suspension is found time until drying then, with solid transfer in porcelain evaporating dishes, and under circulating air in 120 ℃ of following dried overnight.(25 ℃ → 160 ℃/slope is 5.0deg/min in calcining; Kept 2.0 hours; 160 → 500 ℃/slope is 2.0deg/min; Kept 4 hours) after, under pressure, particularly applying 40, the power of 000lbs was suppressed 15 minutes, and with material compacting, granulation, and crushing and screening are 14/30 order.The sepia material of output: 9.98g.
Preparation of Catalyst R
SiO 2-TiO 2(10)-Pt(3)-Sn(1.8)。By being prepared as follows TiO 2The silica supports of-modification.Ti{OCH (CH with 4.15g (14.6mmol) 3) 2} 4Drips of solution in 2-propyl alcohol (14ml) is added to the 10.0g SiO in the 100ml round-bottomed flask 2In the catalyst carrier (1/16 inch extrudate).Allow this flask at room temperature leave standstill 2 hours, use rotary evaporator (bathing 80 ℃ of temperature) to find time then until drying.Next, the 20ml deionized water is slowly joined this flask, and allow this material keep to leave standstill 15 minutes.The water that produces by removing by filter then/2-propyl alcohol repeats to add H again 2 O 2 times.Under circulating air under 120 ℃ with final material dried overnight, then 500 ℃ of calcinings 6 hours down.Use the Pt (NH of 0.6711g (1.73mmol) then 3) 4(NO 3) 2And the Sn (OAc) of 0.4104g (1.73mmol) 2According to above with regard to SiO 2-Pt xSn 1-xThe described operation of material is with all SiO 2-TiO 2Material is used for the Pt/Sn metal impregnation.Output: 1/16 inch extrudate of 11.98g Dark grey.
Preparation of Catalyst S
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 ℃ with gained material dried overnight, then 500 ℃ of calcinings 6 hours down.Use the Pt (NH of 0.6711g (1.73mmol) then 3) 4(NO 3) 2And the Sn (OAc) of 0.4104g (1.73mmol) 2According to above with regard to SiO 2-Pt xSn 1-xThe described operation of material will own (light yellow) SiO 2-WO 3Material is used for the Pt/Sn metal impregnation.Output: 1/16 inch extrudate of 12.10g Dark grey.
Preparation of Catalyst T
(H-ZSM-5)-Pt(3)-Sn(1.8)。This material passes through H-ZSM-5 (by NH 4-ZSM-5 by in air in 550 ℃ down calcining made in 8 hours) the slurry dipping be prepared.0.6711g Pt (NH (1.73mmol) 3) 4(NO 3) 2And the Sn (OAc) of 0.4104g (1.73mmol) 2The aqueous solution by in the acetate that described component is joined 40ml 1: 1 dilution in the 100ml round-bottomed flask and at room temperature stir this mixture and be prepared in 15 minutes.Next, 10.0g solid fines powder H-ZSM-5 is joined in the described solution, at room temperature stirred this mixture other 2 hours along with stirring.Use rotary evaporator (bathe temperature 80 ℃) that this flask is found time until drying then, and under circulating air under 120 ℃ with gained material dried overnight.(250 ℃ → 160 ℃/slope is 5.0deg/min in calcining; Kept 2.0 hours; 160 → 500 ℃/slope is 2.0deg/min; Kept 4 hours) after, be 14/30 order with this material compacting, granulation, crushing and screening.Output: 9.55g grey material.
Preparation of Catalyst U
SiO 2-Re xPd 1-x(0＜x＜1)。Total amount of metal (Re+Pd) that the molar fraction of change Re is also kept 1.20mmol simultaneously prepares five kinds of materials.SiO has been described in following preparation 2-Re 0.5Pd 0.5(be x=0.5; Two kinds of mol ratios such as metal) operation.Similarly use the metal precursor NH of appropriate amount 4ReO 4And Pd (NO 3) 2Carry out all the other preparations (being x=0,0.25,0.75 and 1.00).Described metallic solution is prepared by following: at first with NH 4ReO 4(0.1609g 0.60mmol) joins in the bottle that contains the 6.75ml deionized water.At room temperature stir this mixture 15 minutes, and added 0.1154g (0.60mmol) 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 5.0g in the 100ml round-bottomed flask 2In the catalyst carrier (14/30 order).After the adding of this metallic solution was finished, the flask that will contain impregnated catalyst was kept and is at room temperature left standstill 2 hours.Then this flask is connected to rotary evaporator (bathing 80 ℃ of temperature), finds time until drying.Press above with regard to SiO 2-Pt xSn 1-xMaterial is described to carry out all other operations (dry, calcining), sees above.The brown material of output: 5.1g.
Preparation of Catalyst V
SiO 2-CaSiO 3(5)-Re(4.5)-Pd(1)。Press with regard to SiO 2-CaSiO 3(5)-Pt (3)-Sn (1.8) describe the preparation SiO 2-CaSiO 3(5) catalyst carrier of modification sees above.Then by with containing NH 4ReO 4And Pd (NO 3) 2Aqueous solution dipping SiO 2-CaSiO 3(5) (1/16 inch extrudate) preparation Re/Pd catalyst.This metallic solution passes through at first with NH 4ReO 4(0.7237g 2.70mmol) joins in the bottle that contains the 12.0ml deionized water and is prepared.At room temperature stir this mixture 15 minutes, and added 0.1756g (0.76mmol) solid Pd (NO then 3) 2At room temperature stir this mixture other 15 minutes, and then it was added drop-wise to the dry SiO of 10.0g in the 100ml round-bottomed flask 2-(0.05) CaSiO 3In the catalyst carrier.After the adding of this metallic solution was finished, the flask that will contain impregnated catalyst was kept and is at room temperature left standstill 2 hours.Press above with regard to SiO 2-Re xPd 1-xMaterial is described to carry out all other processing (dry, calcining), sees above.The brown material of output: 10.9g.
Preparation of Catalyst W
CaSiO 3-Re(5)-Pd(2.5)。This material passes through CaSiO 3The slurry dipping of (powder ,≤200 orders) is prepared.0.6169g NH (2.30mmol) 4ReO 4And the Pd (NO of 0.5847g (2.53mmol) 3) 2The aqueous solution be prepared in 15 minutes by described component being joined in the 40ml deionized water in the 100ml round-bottomed flask and at room temperature stirring this mixture.Next, along with stirring with 10.0g solid fines powder CaSiO 3Join in the described solution, at room temperature stirred this mixture other 2 hours.Use rotary evaporator (bathe temperature 80 ℃) that this flask is found time until drying then, and under circulating air under 120 ℃ with gained material dried overnight.Press above with regard to SiO 2-RexPd 1-xMaterial is described to carry out all other processing (dry, calcining), sees above.Use applies 40,15 minutes the press of power of 000lbs with final material suppress, granulation, and crushing and screening are 14/30 order.The brown material of output: 10.65g.
Preparation of Catalyst X
SiO 2-Co(10)-Pt(1)。This material is by with containing Co (NO 3) 26H 2O and Pt (NH 3) 4(NO 3) 2Aqueous solution dipping HSA SiO 2(14/30 order) is prepared.This metallic solution passes through at first with Co (NO 3) 26H 2(5.56g 19.1mmol) joins in the bottle that contains the 12.0ml deionized water and is prepared O.At room temperature stir this mixture 15 minutes, and added 0.2255g (0.58mmol) solid Pt (NH then 3) 4(NO 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 2In the catalyst carrier (14/30 order).After the adding of this metallic solution was finished, the flask that will contain impregnated catalyst was kept and is at room temperature left standstill 2 hours.Press above with regard to SiO 2-Pt xSn 1-xMaterial is described to carry out all other processing (dry, calcining), sees above.Output: 11.35g black material.
Preparation of Catalyst Y
CaSiO 3-Co(10)-Pt(1)。This material passes through CaSiO 3The slurry dipping of (powder ,≤200 orders) is prepared.5.56g Co (NO (19.1mmol) 3) 26H 2Pt (the NH of O and 0.2255g (0.58mmol) 3) 4(NO 3) 2The aqueous solution be prepared in 15 minutes by described component being joined in the 40ml deionized water in the 100ml round-bottomed flask and at room temperature stirring this mixture.Next, along with stirring with 10.0g solid fines powder CaSiO 3Join in the described solution.Then this mixture is heated to 65 ℃, and under this temperature, stirred other 2 hours.Use rotary evaporator (bathe temperature 80 ℃) that this flask is found time until drying then, and under circulating air under 120 ℃ with gained material dried overnight.Press above with regard to SiO 2-Co (10)-Pt (1) material is described to carry out all other processing (dry, calcining), sees above.With final material under pressure, suppress, granulation, and crushing and screening are 14/30 order.The black material of output: 10.65g.
Preparation of Catalyst Z
ZrO 2-Co(10)-Pt(1)。This material is by with containing Co (NO 3) 26H 2O and Pt (NH 3) 4(NO 3) 2Aqueous solution dipping ZrO 2(SZ 61152, Saint-Gobain NorPro, 14/30 order) are prepared.This metallic solution passes through at first with Co (NO 3) 26H 2(5.56g 19.1mmol) joins in the bottle that contains the 5.0ml deionized water and is prepared O.At room temperature stir this mixture 15 minutes, and added 0.2255g (0.58mmol) solid Pt (NH then 3) 4(NO 3) 2At room temperature stir this mixture other 15 minutes, and then it was added drop-wise to the dry ZrO of 10.0g in the 100ml round-bottomed flask 2In the catalyst carrier (14/30 order).After the adding of this metallic solution was finished, the flask that will contain impregnated catalyst was kept and is at room temperature left standstill 2 hours.Press above with regard to SiO 2-Co (10)-Pt (1) is described to carry out all other processing (dry, calcining), sees above.Output: 11.35g black material.
Preparation of Catalyst AA
SiO 2-CaSiO 3(2.5)-Pt(1.5)-Sn(0.9)。
This material is pressed above with regard to SiO 2-CaSiO 3(5)-Pt (the 3)-described use of Sn (1.8) 0.26gCaSiO 3, 0.5ml colloid SiO 2(15 weight % solution, NALCO), 0.3355g (0.86mmol) Pt (NH 3) 4(NO 3) 2And 0.2052g (0.86mmol) Sn (OAc) 2Be prepared.Output: 10.90g Dark grey material.
Preparation of Catalyst BB
TiO 2-CaSiO 3(5)-Pt(3)-Sn(1.8)。
This material passes through at first with CaSiO 3Join TiO 2Catalyst (anatase, 14/30 order) carrier then is prepared by previous described adding Pt/Sn.At first, CaSiO 3The waterborne suspension of (≤200 order) then adds 1.0ml colloid SiO by this solid of 0.52g is joined in the 7.0ml deionized water 2(15 weight % solution NALCO) are prepared.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 above with regard to SiO 2-Pt xSn 1-xThe described operation of material is with all TiO 2-CaSiO 3Material is used for the Pt/Sn metal impregnation.The light grey material of output: 11.5g.
Preparation of Catalyst CC
KA160-Pt(3)-Sn(1.8)。
This material is pressed before with regard to SiO 2-Pt xSn 1-xDescribed by KA160 catalyst carrier (SiO 2-(0.05) Al 2O 3, Sud Chemie, 14/30 order) beginning profit infusion process dipping be prepared, see above.This metallic solution passes through at first with Sn (OAc) 2(0.2040g 0.86mmol) joins in the bottle of glacial acetic acid of dilution in contain 4.75ml 1: 1 and is prepared.At room temperature stir this mixture 15 minutes, and added 0.3350g (0.86mmol) solid Pt (NH then 3) 4(NO 3) 2At room temperature stirred this mixture other 15 minutes, and then it was added drop-wise in the dry KA160 catalyst carrier of 5.0g (14/30 order) in the 100ml round-bottomed flask.Press above SiO 2-Pt xSn 1-xDescribedly carry out all other processing, drying and calcining.Output: 5.23g sepia material.
Preparation of Catalyst DD
KA160-CaSiO 3(8)-Pt(3)-Sn(1.8)。
This material passes through at first with CaSiO 3Join the KA160 catalyst carrier, then by above being prepared with regard to KA160-Pt (the 3)-described adding of Sn (1.8) Pt/Sn.At first, CaSiO 3The waterborne suspension of (≤200 order) then adds 0.8ml colloid SiO by this solid of 0.42g is joined in the 3.85ml deionized water 2(15 weight % solution NALCO) are prepared.At room temperature stir this suspension 2 hours, and use beginning profit dipping technique to add 5.0g KA160 catalyst carrier (14/30 order) then.After leaving standstill 2 hours, this material is evaporated to dried, then under circulating air in 120 ℃ of following dried overnight and 500 ℃ of calcinings 6 hours down.Use the Pt (NH of 0.3350g (0.86mmol) then 3) 4(NO 3) 2And the Sn (OAc) of 0.2040g (0.86mmol) 2According to above with regard to SiO 2-Pt xSn 1-xThe described operation of material is with all KA160-CaSiO 3Material is used for the Pt/Sn metal impregnation.Output: 5.19g sepia material.
Figure BDA0000080408810000391
Figure BDA0000080408810000401
The gas chromatography of product (gc) is analyzed
Carry out the analysis of product by online GC.Use is equipped with the integrated GC of triple channel of 1 flame ionization detector (FID) and 2 thermal conductivity detector (TCD)s (TCD) to come analytical reactions thing and product.
Prepass is equipped with FID and CP-Sil 5 (20m)+WaxFFap (5m) pillar and is used for quantizing: acetaldehyde; Ethanol; Acetone; Methyl acetate; Vinyl acetate; Ethyl acetate; Acetate; Ethylene acetate; Ethylene glycol; The oxalic acid ethyl; And para-acetaldehyde.
Center-aisle is equipped with TCD and Porabond Q pillar and is used for quantizing: CO 2Ethene; And ethane.
Back passage is equipped with TCD and Molsieve 5A pillar and is used for quantizing: helium; Hydrogen; Nitrogen; Methane; And carbon monoxide.
Before reaction, by forming the retention time of spike mensuration different component with independent compound, and GC is calibrated with the calibration gas of known composition or with the liquid solution of known composition.This allows to measure the response factor of each component.
Embodiment 1
Be 30mm and can rise in the tubular reactor of control temperature at the internal diameter of making by stainless steel, settle 50ml to press the above catalyst of the described preparation of Preparation of Catalyst C.The total length of charging rear catalyst bed is approximately about 70mm.
Feed liquid is made up of acetate basically.Under the pressure of 250 ℃ temperature and 100psig, make reaction feed liquid evaporation and with hydrogen and as the helium of carrier gas with 2500hr -1Average total gas hourly space velocity (GHSV) be encased in the reactor.Incoming flow contains the acetate of about 7.3% mole percent of the 6.1%-that has an appointment and the hydrogen of about 61.5% mole percent of about 54.3%-.The part of steam effluent that makes autoreactor by gas-chromatography in order to analyze the content of this effluent.The selectivity of ethanol is 93.4% under 85% acetate conversion ratio.
The catalyst that is utilized is according to 1 weight % platinum and 1 weight % tin on the silica of the operation preparation of Preparation of Catalyst A.
Embodiment 2
The catalyst that is utilized is according to 1 weight % platinum and 1 weight % tin on the calcium silicates of the operation preparation of Embodiment C.
Under the pressure of 250 ℃ temperature and 22bar with 2,500hr -1The gasification acetate of average total gas hourly space velocity (GHSV) and the incoming flow of hydrogen repeat the operation that provides among the embodiment 1 basically.A part that makes the steam effluent by gas-chromatography in order to analyze the content of this effluent.The acetate conversion ratio is greater than 70%, and the ethanol selectivity is 99%.
Comparative Examples 1
The catalyst that is utilized is according to 1 weight % tin on the low surface area high-purity silicon dioxide of the operation preparation of embodiment E.
Under the pressure of 250 ℃ temperature and 22bar with 2,500hr -1The gasification acetate of average total gas hourly space velocity (GHSV) and the incoming flow of hydrogen repeat the operation that provides among the embodiment 1 basically.A part that makes the steam effluent by gas-chromatography in order to analyze the content of this effluent.The acetate conversion ratio is less than 10%, and the ethanol selectivity is less than 1%.
Embodiment 3
Repeat the operation of embodiment 2 under the temperature of using various catalyst in table 2, to provide, provided the percentage and the ethyl acetate (EtOAc) of the carbon monoxide in the product (CO), acetaldehyde (AcH) and ethane in the table 2; The percentage conversion ratio of the selectivity of ethanol (EtOH) and productive rate and acetate (HOAc) (MCD p.4).All the time, H 2Maintain 5: 1 with the mol ratio of acetate.For facility, also comprised the result of embodiment 1,2 and Comparative Examples 1 in the table 2.Generally speaking when expectation produced ethanol as primary product, the selectivity of expectation ethanol was approximately higher than 80% greatly; The selectivity of expectation ethyl acetate is less than 5%, preferably less than 3%.
Figure BDA0000080408810000441
Figure BDA0000080408810000451
Embodiment 4
At about 6570hr -1Air speed and the pressure of 200psig under with about 160sccm/minH 2: (hydrogen is with about 60sccm/min N for the ratio of the hydrogen of 0.09g/min HOAc and acetate 2Dilution) make gasification acetate and hydrogen pass hydrogenation catalyst of the present invention, it is about 250m that this hydrogenation catalyst is included in surface area 22 weight %Pt on the high surface area silica of/g (NPSG SS61138) and 2 weight %Sn.Press shown in Fig. 1 and 2 about 50 hours, 70 hours and 90 hours raising temperature, wherein shown among Fig. 1 in shown in product (ethanol, acetaldehyde and ethyl acetate) gram number/kg catalyst/hour productive rate, shown among Fig. 2 that catalyst is to various product selectivity, wherein reach the standard grade and represent the productive rate or the selectivity of ethyl acetate, medium line is represented ethanol, and expression acetaldehyde rolls off the production line.Think to be apparent that especially that the productive rate and the selectivity of acetaldehyde are low.The results are summarized in during following data gather.
Data gather
Embodiment 5
Use has and loads on the 2 weight %Pt that comprise from the catalyst of the high surface area silica SS61138 pill of Saint-Gobain NorPro; The catalyst of 2 weight %Sn is used 2500hr under the pressure of temperature and 100psig shown in providing in table 2 -1The incoming flow of gasification acetate, hydrogen and the helium of average total gas hourly space velocity (GHSV) repeats the operation that provides among the embodiment 1 basically.The gained incoming flow contains the acetate of 7.3% mole percent of having an appointment and the hydrogen of about 54.3% mole percent.A part that makes the steam effluent by gas-chromatography in order to analyze the content of this effluent.The result is presented in the table 1.
Table 3
Figure BDA0000080408810000471
Embodiment 5 the results are summarized among Fig. 3, this figure has proved that catalyst makes this catalyst fully be suitable for so-called adiabatic reactor to the relative insensitivity of variations in temperature, causes owing to removing the low and uneven speed of reducing phlegm and internal heat from reactor that the temperature on the catalyst bed can alter a great deal in adiabatic reactor.
Embodiment 6
By following research SiO 2-Pt xSn 1-xThe influence of [Sn]/[Pt] mol ratio in the catalyst: (i) ([Pt]+[Sn]=1.20mmol) changes down the molar fraction of Pt and (ii) as the function of reduction temperature in constant metal carrying capacity.Observe when the Pt molar fraction is 0.5 (i.e. [Sn]/[Pt]=1.0) for the acetate conversion ratio and be obvious maximum the selectivity of ethanol.In [Sn]/[Pt]=1.0) selectivity to ethyl acetate when helping ethanol sharply changes.In the Pt molar fraction is 25% or 75% o'clock, observes ethyl acetate as primary product.As if optionally to improve for the acetate conversion ratio with to ethanol be preferred etc. the existence of the Pt of mol ratio and Sn, with reference to figure 4A-C.
In temperature=250 ℃; GHSV=6570h -1Reaction time is to make gasification acetate (0.09g/min HOAc) and hydrogen (160sccm/min H under 12 hours 260sccm/min N 2) passing hydrogenation catalyst of the present invention, it is about 250m that this hydrogenation catalyst is included in surface area 2Pt on the high surface area silica of/g and Sn.In this embodiment 6, the amount of metal (Pt+Sn) keeps mass fraction constant and platinum to change between 0-1.Fig. 4 A-4C has described catalyst selectivity, activity and productive rate separately.By this embodiment, what can recognize is, when the mass fraction of platinum is about 0.5 when promptly by weight the amount of platinum is substantially equal to the amount of tin in this catalyst, the maximum of selectivity, activity and productive rate occurs.
Embodiment 7
Make gasification acetate and hydrogen pass hydrogenation catalyst of the present invention with about 5: 1 hydrogen and acetate mol ratio under about 225 ℃ temperature, it is about 250m that this hydrogenation catalyst is included in surface area 23 weight %Pt on the high-purity high surface area silica of/g, 1.5 weight %Sn and 5 weight % are as the CaSiO of promoter 3Fig. 5 A and 5B have described during the starting stage of catalyst life catalyst selectivity and the productive rate as the function of running time.By the result of this embodiment that is reported among Fig. 6 A and the 6B, what can recognize is, can obtain to be higher than 90% selective active and every kg catalyst and per hour be higher than the 500g ethanol yield.
Embodiment 8
Under about 250 ℃ temperature, repeat the operation (same catalyst of embodiment 8?).Fig. 7 A-7B has described during the starting stage of catalyst life catalyst selectivity and the productive rate as the function of running time.The result of this embodiment that is reported by Fig. 7 A and 7B, what can recognize is, still can obtain to be higher than 90% selective active but obtain every kg catalyst simultaneously per hour to be higher than the 800g ethanol yield under this temperature.
Embodiment 9
In order to study the temperature control that is used for bimetallic platinum and tin precursor are reduced to catalytic specie, in 225-500 ℃ independent experiment, by making optimized Pt/Sn, SiO 2-(Pt 0.5Sn 0.5) catalyst activation studied the influence of reduction temperature, see below.In 4 experiments, make material under flowing hydrogen, activate 4 hours under 280,350,425 and 500 ℃, then under 250 ℃ reaction temperature, carry out the acetate reduction.(use 10mol%H 2/ N 2Mixture (275sccm/min) uses following temperature program(me) to carry out the catalyst activation under environmental pressure: RT-reduction temperature (225-500 ℃), and slope is 2deg/min; Kept 4.0 hours, the reduction for HOAc reduces (or promoting where necessary) to 250 ℃ then).In addition, the materials that research activates under 225 ℃ under 225 and 250 ℃ reaction temperature in the HOAc hydrogenation.Run through whole temperature range and do not observe optionally significant change, comprise with regard to reaction temperature 225 and 250 ℃ at 225 ℃ of catalyst of activation down ethanol and ethyl acetate.What arouse attention is, observes the obvious raising of conversion ratio (and productive rate) for the catalyst that activates under lower, 225 and 280 ℃ reduction temperature.The conversion ratio reduction may be owing to the sintering of metallic particles under higher reduction temperature.(referring to Fig. 7 A and 7B) as if because do not observe optionally variation, the composition of metallic particles (being the PtSn alloy) remains unchanged.The result of this embodiment has been described among Fig. 3 A-3C.
Detect various other products in these embodiments, comprise acetaldehyde, ethanol, ethyl acetate, ethane, carbon monoxide, carbon dioxide, methane, isopropyl alcohol, acetone and water.
Embodiment 10
In the acetic acid catalysis hydrogenation, use the solid catalyst in the catalyst shown in the 2.5ml table 4 to estimate the catalytic performance of various catalyst.In every kind of situation, catalyst granules has 14/30 purpose size, and with 14/30 order quartz chips 1: 1v/v dilutes.In service separately, in the scope (span) of 24 hour running time (TOS), operating pressure is that 200psig (14bar) and while feed rate are 0.09g/min acetate; 120sccm/min hydrogen; 60sccm/min nitrogen is with 6570h -1Total gas hourly space velocity.Shown the result in the table 4.
The catalytic activity of table 4. various load type metal catalysts in the HOAc catalytic hydrogenation.Reaction condition: the 2.5ml solid catalyst (14/30 order, dilution in 1: 1 (v/v, with quartz chips, 14/30 order); P=200psig (14bar); 0.09g/min HOAc; 120sccm/min H 260sccm/min N 2GHSV=6570h -124 hours running time (TOS).
Figure BDA0000080408810000511
Embodiment 11
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. 5 A and the 5B and has optionally gathered.In surpassing 125 hours total reaction time, having studied the influence of reaction temperature in the experiment separately, see above to selectivity of product.
Embodiment 12
Use 2.5ml solid catalyst (14/30 order, dilution in 1: 1 (v/v, with quartz chips, 14/30 order); Under the pressure of 200psig; Feed rate is 0.09g/min HOAc; 160sccm/minH 260sccm/min N 2GHSV=6570h -1In typical operating condition scope, use the fixed bed continuous reactor system mainly to produce acetaldehyde, ethanol, ethyl acetate by hydrogenation and esterification and study and in acetic acid hydrogenation, use 5%CaSiO 225 ℃ of following 15 hour duration in service 3Stable high-purity high surface SiO 2On productive rate and the selectivity of 3%Pt:1.5%Sn.Provided the result among Fig. 6 A and the 6B.
Embodiment 13
Use 2.5ml solid catalyst (14/30 order, dilution (v/v uses quartz chips, 14/30 order) in 1: 1; Under the pressure of 200psig (14bar); Be accompanied by 160sccm/min hydrogen and 60sccm/min and feed 0.09g/min acetate as the nitrogen of diluent (diulent); Under 250 ℃ temperature; GHSV=6570h -1Or 12 hours reaction time, ([Pt]+[Sn]=1.20mmol) the molar fraction research of Re down is included in SiO in constant metal carrying capacity by changing 2In Re and the productive rate and the selectivity of the catalyst of Pd (wherein between catalyst, revise Re xPd (1-x)Mol ratio).Though in the Re molar fraction is about maximum conversion rate that observed acetate at 0.6 o'clock, be that about 0.78 o'clock ethanol becomes primary product only in the Re molar fraction.Mol ratio (is expressed as " Re between this Re and Pd 7Pd 2") under, thereby the selectivity close limit ground variation of ethyl acetate is helped ethanol.Importantly, and shown in above-mentioned Pd/Sn series, the existence of two kinds of metals of concrete ratio is the key structure requirement of concrete selectivity of product seemingly, promptly in of the transfer of [Re]/[Re+Pd]=0.78 o'clock selectivity to ethanol, with reference to the Fig. 8,9 and 10 that provides by the form identical with Fig. 4 A-C, difference is X i(Re) mass fraction of rhenium in the expression catalyst.Yet, be that the maximum conversion rate of acetate does not conform to these materials with selectivity to ethanol, and only observes the favourable selectivity to ethanol when low HOAc conversion ratio with the Pt/Sn material forms contrast.Therefore, with reference to figure 8, observe maximum yield to ethyl acetate rather than for ethanol.In addition, use CaSiO 3-Re (5)-Pd (2.5) catalyst is at about 30% acetate conversion ratio and only observe hydrocarbon (methane and ethane under 225 ℃ the reaction temperature; They are respectively 5.3 and 2.4 weight %) formation.Though the higher conversion of acetate can most possibly obtain by improving reaction temperature, also may improve the amount of hydrocarbon, therefore limited the overall efficiency of Re/Pd base catalysis system.
Embodiment 14
Use is at SiO 2On the primary catalyst screening of silicon dioxide carried platinum (1%) Co catalysts (the Co carrying capacity is 10 weight %) produce the high acetate conversion ratio and the selectivity of about 80% pair of ethanol.Referring to Figure 11 and 12, wherein selectivity and activity are represented with square for the result of ethanol as previously defined, represent with circle that for the result of ethyl acetate acetaldehyde represents that with rhombus ethane is represented with triangle.Yet, as if in 9 hours reaction time process catalyst along with acetic acid selectivity drops to 42% and deterioration from about 80%.In addition, also observe the significant change of productive rate, and along with the ethanol selectivity that is accompanied by that optionally improves to ethyl acetate and acetaldehyde descends.Obtain similar result with 10% cobalt that loads on the silica.
Embodiment 15
In temperature=250 ℃; GHSV=6570h -1Under 12 hours reaction time, under the pressure of 200psig, make gasification acetate (0.09g/min HOAc) and hydrogen (160sccm/min H 260sccm/min N 2) passing hydrogenation catalyst of the present invention, this hydrogenation catalyst is included in 3 weight %Pt and the 1.8 weight %Sn on the carrier that comprises Hydrogen ZSM-5 molecular sieve.Selectivity with 96% and the productive rate of 2646g/kg/h obtain diethyl ether, and with 4% ethyl acetate, 78% acetate keeps unreacted.
Embodiment 16
At 275 ℃; GHSV=6570h -1Under 12 hours reaction time, under the pressure of 200psig, make gasification acetate (0.09g/min HOAc) and hydrogen (160sccm/min H 260sccm/min N 2) passing hydrogenation catalyst of the present invention, this hydrogenation catalyst is included in 2 weight %Pt and the 1 weight %Sn on the carrier that comprises high surface graphite.The selectivity of ethyl acetate is 43%, the selectivity 57% of ethanol, and the productive rate of ethyl acetate is 66g/kg/hr, and ethanol yield is 88g/kg/hr, and the conversion ratio of acetate is 12%.
Though describe the present invention in detail, various modifications within the spirit and scope of the present invention will be conspicuous to those skilled in the art.In view of the above discussion, above this area relevant knowledge and the list of references of being discussed about background technology and detailed description all incorporated their disclosure into this paper by reference, and thinks that other illustration is unnecessary.In addition, should understand hereinafter and/or the various aspects of the present invention quoted from appended claims and the various piece of a plurality of embodiment and a plurality of features can partly or entirely make up or exchange.In 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.
Therefore for the hydrogenation products based on acetate is provided, according to the invention provides novel method and catalyst.
For example embodiment #1 is by with the acetate method of original production ethanol also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, this hydrogenation catalyst is included in and contains platinum and the tin that disperses on the silicon carrier, wherein to the amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and contain silicon carrier and select, constitute and control and make: (i) make at least 80% of the acetate that transforms be converted into ethanol; (ii) be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof less than 4% acetate; And work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 168 hours time period, this catalyst activity reduction is less than 10%.
Embodiment #2 is the method for embodiment #1, wherein hydrogenation catalyst basically by be dispersed in the platinum that contains on the silicon carrier and tin constitutes and this to contain silicon carrier be modified silicon-contained carrier, described modified silicon-contained carrier comprises the support modification agent that being selected from of effective dose is following: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) (i)-(any precursor vi), and (i)-(any mixture vii).
Embodiment #3 is the method for embodiment #2, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #4 is the method for embodiment #2, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #5 is the method for embodiment #3, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #6 is the method for embodiment #2, and wherein the support modification agent is selected from metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #7 is the method for embodiment #5, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #8 is the method for embodiment #6, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #9 is the method for embodiment #2, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #10 is the method for embodiment #9, and wherein: (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #11 is the method for embodiment #10, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #12 is the method for embodiment #2, and wherein the support modification agent is selected from metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #13 is the method for embodiment #12, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #14 is the method for embodiment #12, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #15 is the method for embodiment #2, and wherein the support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
Embodiment #16 is the method for embodiment #15, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #17 is the method for embodiment #16, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #18 is the method for embodiment #2, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #19 is the method for embodiment #16, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #20 is the method for embodiment #18, and wherein carrier surface area is at least about 100m 2/ g.
Embodiment #21 is the method for embodiment #20, and wherein the mol ratio of tin and platinum group metal is about 1: about 2: 1 of 2-.
Embodiment #22 is the method for embodiment #20, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #23 is the method for embodiment #20, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
Embodiment #24 is the method for embodiment #2, and wherein carrier surface area is at least about 150m 2/ g.
Embodiment #25 is the method for embodiment #24, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-5% at least.
Embodiment #26 is the method for embodiment #24, and wherein carrier comprises the calcium silicates at least about the about 10 weight % of 1%-.
Embodiment #27 is the method for embodiment #24, and wherein the mol ratio of tin and platinum is about 1: about 2: 1 of 2-.
Embodiment #28 is the method for embodiment #24, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #29 is the method for embodiment #24, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
Embodiment #30 is the method for embodiment #2; Wherein carrier surface area is at least about 200m 2/ g.
Embodiment #31 is the method for embodiment #30, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #32 is the method #30 of embodiment, and wherein the mol ratio of tin and platinum is about 5: about 4: 5 of 4-.
Embodiment #33 is the method for embodiment #30, and wherein the mol ratio of tin and platinum is about 9: about 10: 9 of 10-.
Embodiment #34 is the method for embodiment #33, and wherein the surface area of modified silicon-contained carrier is at least about 250m 2/ g.
Embodiment #35 is the method for embodiment #2, and this method is carried out under about 250 ℃-300 ℃ temperature, and wherein the surface area of (a) modified silicon-contained carrier is at least about 250m 2/ g; (b) platinum is present in the hydrogenation catalyst with the amount at least about 0.75 weight %; (c) mol ratio of tin and platinum is about 5: about 4: 5 of 4-; (d) modified silicon-contained carrier comprises purity and is at least about 95% the silica at least about the calcium metasilicate modification of the about 10 weight % of 2.5 weight %-used.
Embodiment #36 is the method for embodiment #35, and wherein the amount of the platinum of Cun Zaiing is at least 1 weight %.
Embodiment #37 is the method for embodiment #2, and this method is carried out under about 250 ℃-300 ℃ temperature, and wherein the surface area of (a) modified silicon-contained carrier is at least about 100g/m; (b) wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-; (c) modified silicon-contained carrier comprises purity and is at least about 95% the silica at least about the calcium metasilicate modification of the about 10 weight % of 2.5 weight %-used.
Embodiment #38 is the method for embodiment #37, and wherein the amount of the platinum of Cun Zaiing is at least 0.75 weight %.
Embodiment #39 is the method for embodiment #38, and wherein catalyst occupies reactor volume, and in gas phase with at least about 1000hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
Embodiment #40 is the method for embodiment #38, and wherein catalyst occupies reactor volume, and in gas phase with at least about 2500hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
Embodiment #41 is the method for embodiment #40, wherein control the amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and modified silicon-contained carrier make: (i) make at least 90% of the acetate that transforms be converted into ethanol: (ii) be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate and ethene and composition thereof less than 2% acetate; (iii) work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 336 hours time period, catalyst activity reduction is less than 10%.
Embodiment #42 is the method for embodiment #38, and wherein catalyst occupies reactor volume, and in gas phase with at least about 5000hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
Embodiment #43 is the method for embodiment #42, wherein controls the amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and modified silicon-contained carrier make: (i) make at least 90% of the acetate that transforms be converted into ethanol; (ii) be converted into alkane less than 2% acetate; (iii) work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 168 hours time period, catalyst activity reduction is less than 10%.
Embodiment #44 is the method for embodiment #43, and this method is carried out under about 250 ℃-300 ℃ temperature, and wherein the surface area of (a) modified silicon-contained carrier is at least about 200m 2/ g; (b) mol ratio of tin and platinum is about 5: about 4: 5 of 4-; (c) modified silicon-contained carrier comprises purity and is at least about 95% the silica at least about the calcium silicates modification of the about 10 weight % of 2.5 weight %-used.
Embodiment #45 is by with the acetate method of original production ethanol also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, this hydrogenation catalyst is included in platinum and the tin that disperses on the oxide-based carrier, wherein to the amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and oxide-based carrier are selected, are constituted and control and make: (i) make at least 80% of the acetate that transforms be converted into ethanol; (ii) be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof less than 4% acetate; And work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 500 hours time period, this catalyst activity reduction is less than 10%.
Embodiment #46 is the method for embodiment #45, wherein hydrogenation catalyst is basically by being dispersed in the platinum on the oxide-based carrier and tin constitutes and this oxide-based carrier is a modified oxide class carrier, described modified oxide class carrier comprises the support modification agent that being selected from of effective dose is following: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) (i)-(any precursor vi), and (i)-(any mixture vii).
Embodiment #47 is the method #46 of embodiment, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #48 is the method for embodiment #47, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #49 is the method for embodiment #47, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #50 is the method for embodiment #46, and wherein the support modification agent is selected from metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #51 is the method for embodiment #50, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #52 is the method for embodiment #51, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #53 is the method for embodiment #46, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #54 is the method for embodiment #53, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #55 is the method for embodiment #54, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #56 is the method for embodiment #46, and wherein the support modification agent is selected from metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #57 is the method for embodiment #56, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #58 is the method for embodiment #57, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #59 is the method for embodiment #46, and wherein the support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
Embodiment #60 is the method for embodiment #59, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #61 is the method for embodiment #60, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #62 is the method for embodiment #46, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #63 is the method for embodiment #62, and wherein the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #64 is the method for embodiment #62, and wherein carrier surface area is at least about 100m 2/ g.
Embodiment #65 is the method for embodiment #64, and wherein the mol ratio of tin and platinum group metal is about 1: about 2: 1 of 2-.
Embodiment #66 is the method for embodiment #64, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #67 is the method for embodiment #64, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
Embodiment #68 is the method for embodiment #46, and wherein carrier surface area is at least about 150m 2/ g.
Embodiment #69 is the method for embodiment #68, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-5% at least.
Embodiment #70 is the method for embodiment #68, and wherein carrier comprises the calcium silicates at least about the about 10 weight % of 1%-.
Embodiment #71 is the method for embodiment #68, and wherein the mol ratio of tin and platinum is about 1: about 2: 1 of 2-.
Embodiment #72 is the method for embodiment #68, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #73 is the method for embodiment #68, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
Embodiment #74 is the method for embodiment #46, and wherein carrier surface area is at least about 200m 2/ g.
Embodiment #75 is the method #74 of embodiment, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #76 is the method for embodiment #74, and wherein the mol ratio of tin and platinum is about 5: about 4: 5 of 4-.
Embodiment #77 is the method for embodiment #74, and wherein the mol ratio of tin and platinum is about 9: about 10: 9 of 10-.
Embodiment #78 is by with the acetate method of original production ethanol also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, this hydrogenation catalyst contains the platinum and the tin that disperse on the silicon carrier by the stabilisation in modification basically and constitutes, the stabilisation of described modification contains silicon carrier and comprises the silica that usefulness that purity is at least about 95 weight % is selected from following stabilizing agent-modifier modification: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) (i)-(any precursor vi), and (i)-(any mixture vii), wherein control the amount and the oxidation state of platinum and tin, the ratio of platinum and tin, the purity that the stabilisation that stabilizing agent-modifier and silica contain relative scale in the silicon carrier and modification in the stabilisation of modification contains silica in the silicon carrier makes at least 80% of the acetate that transforms be converted into ethanol, and the acetate less than 4% is converted into except that being selected from ethanol, acetaldehyde, ethyl acetate, compound beyond the compound of ethene and composition thereof.
Embodiment #79 is the method for embodiment #78, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-10% at least.
Embodiment #80 is the method for embodiment #79, and wherein the stabilisation of the modification surface area that contains silicon carrier is at least about 100m 2/ g.
Embodiment #81 is the method for embodiment #80, and wherein the mol ratio of tin and platinum group metal is about 1: about 2: 1 of 2-.
Embodiment #82 is the method for embodiment #80, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #83 is the method for embodiment #79, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
Embodiment #84 is the method for embodiment #78, and wherein the stabilisation of the modification surface area that contains silicon carrier is at least about 150m 2/ g.
Embodiment #85 is the method for embodiment #84, and wherein (a) platinum exists with the amount of the 0.5%-5% of catalyst weight; (b) tin exists with the amount of 0.5-5% at least.
Embodiment #86 is the method for embodiment #84, and wherein the stabilisation of modification contains silicon carrier and comprises calcium silicates at least about the about 10 weight % of 1 weight %-.
Embodiment #87 is the method for embodiment #84, and wherein the mol ratio of tin and platinum is about 1: about 2: 1 of 2-.
Embodiment #88 is the method for embodiment #84, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #89 is the method for embodiment #84, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
Embodiment #90 is the method for embodiment #87, and wherein the stabilisation of the modification surface area that contains silicon carrier is at least about 200m 2/ g.
Embodiment #91 is the method for embodiment #90, and wherein the mol ratio of tin and platinum is about 9: about 10: 9 of 10-.
Embodiment #92 is the method for embodiment #90, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #93 is the method for embodiment #90, and wherein the mol ratio of tin and platinum is about 5: about 4: 5 of 4-.
Embodiment #94 is the method for embodiment #90, and wherein the stabilisation of the modification surface area that contains silicon carrier is at least about 250m 2/ g.
Embodiment #95 is the method for embodiment #78, and this method is carried out under about 250 ℃-300 ℃ temperature, and wherein the stabilisation of (a) modification surface area that contains silicon carrier is at least about 250m 2/ g; (b) platinum is present in the hydrogenation catalyst with the amount at least about 0.75 weight %; (c) mol ratio of tin and platinum is about 5: about 4: 5 of 4-; (d) stabilisation of modification contains silicon carrier and comprises calcium silicates at least about the about 10 weight % of 2.5 weight %-.
Embodiment #96 is the method for embodiment #95, and wherein the amount of the platinum of Cun Zaiing is at least 1 weight %.
Embodiment #97 is the method for embodiment #78, and this method is carried out under about 250 ℃-300 ℃ temperature, and wherein the stabilisation of (a) modification surface area that contains silicon carrier is at least about 100g/m; (b) wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-; (c) stabilisation of modification contains silicon carrier and comprises calcium silicates at least about the about 10 weight % of 2.5 weight %-.
Embodiment #98 is the method for embodiment #97, and wherein the amount of the platinum of Cun Zaiing is at least 0.75 weight %.
Embodiment #99 is the method for embodiment #98, and wherein catalyst occupies reactor volume, and in gas phase with at least about 1000hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
Embodiment #100 is the method for embodiment #98, and wherein catalyst occupies reactor volume, and in gas phase with at least about 2500hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
Embodiment #101 is the method for embodiment #100, wherein control the amount and the oxidation state of platinum and tin, and the composition that the stabilisation of the ratio of platinum and tin and modification contains silicon carrier makes at least 90% of the acetate that transforms be converted into ethanol, and the acetate less than 2% is converted into the compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate and ethene and composition thereof.
Embodiment #102 is the method for embodiment #98, and wherein catalyst occupies reactor volume, and in gas phase with at least about 5000hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
Embodiment #103 is the method for embodiment #79, wherein control the amount and the oxidation state of platinum and tin, and the composition that the stabilisation of the ratio of platinum and tin and modification contains silicon carrier makes: make at least 90% of the acetate that transforms be converted into ethanol, the acetate less than 2% is converted into alkane.
Embodiment #104 is the method for embodiment #79, this method is carried out under about 250 ℃-300 ℃ temperature, wherein (a) wherein controls the amount and the oxidation state of platinum and tin, and the acidity that the stabilisation of the ratio of platinum and tin and modification contains silicon carrier makes at least 90% of the acetate that transforms be converted into ethanol, and the acetate less than 1% is converted into alkane; (b) stabilisation of the modification surface area that contains silicon carrier is at least about 200m 2/ g; (c) mol ratio of tin and platinum is about 5: about 4: 5 of 4-; (d) stabilisation of modification contains silicon carrier and comprises calcium silicates at least about the about 10 weight % of 2.5 weight %-.
Embodiment #105 is by with the acetate method of original production ethanol also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, and this hydrogenation catalyst is made of following basically: with the catalytic metal that is selected from Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Re, Os, Ti, Zn, Cr, Mo and W and their mixture of the amount of the about 10 weight % of about 0.1%-; With the optional promoter of on suitable carrier, disperseing, wherein control the amount and the oxidation state of catalytic metal, the composition of carrier and optional promoter and reaction condition make: (i) make at least 80% of the acetate that transforms be converted into ethanol; (ii) be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene, diethyl ether and composition thereof less than 4% acetate; And work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 500 hours time period, this catalyst activity reduction is less than 10%.
Embodiment #106 is the method for embodiment #105, and wherein carrier is with the oxide-based carrier that is selected from following modifier modification: the oxide of sodium, potassium, magnesium, calcium, scandium, yttrium and zinc and metasilicate and their precursor and aforesaid any mixture.
Embodiment #107 is the method for embodiment #105, and wherein carrier is a carbon carrier, and catalytic metal comprises platinum and tin.
Embodiment #108 is the method for embodiment #107, wherein the reducible metal oxide modified of carbon carrier.
Embodiment #109 is by acetic acid hydrogenation being produced the method for ethanol, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, this hydrogenation catalyst is made of the metal component that disperses on oxide-based carrier basically, and described hydrogenation catalyst has following composition:
Pt vPd wRe xSn yAl zCa pSi qO r，
Wherein v and y are 3: 2-2: 3; W and x are 1: 3-1: 5, and wherein control the aluminium atom of p and Z and existence and the relative position of calcium atom and make that being present in its surperficial Bronsted acid position carries out balance by calcium silicates; 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 ≤ ( 3.25 v + 1.75 w ) q ≤ 0.05 .
Embodiment #110 is the method for embodiment #109, and wherein hydrogenation catalyst has at least about 100m 2The surface area of/g, and wherein control z and p and make p 〉=z.
Embodiment #111 is the method for embodiment #110, wherein considers any less impurity of existence, and p is selected to guarantee that carrier surface is substantially free of the Bronsted acid position.
Embodiment #112 is the method with acetic acid hydrogenation, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, and this hydrogenation catalyst is made of following basically: with the catalytic metal that is selected from Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Re, Os, Ti, Zn, Cr, Mo and W and their mixture of the amount of the about 10 weight % of about 0.1%-; With the optional promoter of on suitable carrier, disperseing, wherein control the amount and the oxidation state of catalytic metal, the feasible acetate less than 4% of the composition of carrier and optional promoter and reaction condition is converted into the compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene, diethyl ether and composition thereof; And work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be that the mixture of vaporous of 10: 1 acetate and hydrogen is during 500 hours time period, this catalyst activity reduction is less than 10%, and other condition is: (i) wherein said carrier is with the oxide-based carrier that is selected from following modifier modification: the oxide of sodium, potassium, magnesium, calcium, scandium, yttrium and zinc and metasilicate and their precursor and aforesaid any mixture; (ii) described carrier is a carbon carrier, and catalytic metal comprises that platinum and tin or (iii) described carrier are the carbon carriers with reducible metal oxide modified.
Embodiment #113 is the method with the alkanoic acid hydrogenation, this method is included in the gas phase to make the gaseous stream that comprises hydrogen and alkanoic acid pass hydrogenation catalyst at least about 2: 1 the hydrogen and the mol ratio of alkanoic acid under about 125 ℃-350 ℃ temperature, and this hydrogenation catalyst comprises: in the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier of containing that is selected from silica that silica, calcium metasilicate and calcium metasilicate promote; With the promoter that is selected from tin, rhenium and composition thereof, it is optional with the promoter promotion wherein to contain silicon carrier, and promoter is selected from: (a) promoter that is selected from alkali metal, alkaline earth element and zinc of the amount of the 1-5% of catalyst weight; (b) amount of the 1-50% of catalyst weight is selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type promoter; And (c) catalyst weight 1-50% amount be selected from TiO 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent.
Embodiment #114 is the method for embodiment #113, and wherein said alkanoic acid is an acetate, and wherein the amount of at least a 0.25%-5% with catalyst weight in (a) platinum and the palladium exists; (b) total amount of platinum of Cun Zaiing and palladium is at least 0.5% of a catalyst weight; And the total amount of rhenium that (c) exists and tin is 0.5-10 weight % at least.
Embodiment #115 is the method for embodiment #114, and the surface area that wherein contains silicon carrier is at least about 150m 2/ g.
Embodiment #116 is the method for embodiment #115, the wherein amount and the oxidation state of control (a) platinum group metal, rhenium and tin promoter, and (b) mol ratio of the total mole number of the rhenium of platinum group metal and existence and tin; And the number that (c) contains the Bronsted acid position on the silicon carrier makes at least 80% of the acetate that transforms be converted into the compound that is selected from ethanol and ethyl acetate, and makes simultaneously less than 4% acetate and be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof.
Embodiment #117 is the method for embodiment #115, and wherein the amount of at least a 0.5%-5% with catalyst weight in (a) platinum and the palladium exists; (b) total amount of platinum of Cun Zaiing and palladium is the 0.75%-5% at least of catalyst weight; And the tin that (c) exists and the total amount of rhenium are at least 1.0% of catalyst weight.
Embodiment #118 is the method for embodiment #117, wherein (a) control (i) platinum group metal, the (ii) amount and the oxidation state of rhenium and tin promoter, and the (iii) ratio of platinum group metal and rhenium and tin promoter; The acidity that (iv) contains silicon carrier makes at least 80% of the acetate that transforms be converted into ethanol, and the acetate less than 4% is converted into the compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof.
Embodiment #119 is the method for embodiment #118, and wherein the gross weight of rhenium of Cun Zaiing and tin is about 1-10% of catalyst weight.
Embodiment #120 is the method for embodiment #119, and wherein the mol ratio of the total mole number of platinum group metal and rhenium and tin is about 1: about 2: 1 of 2-.
Embodiment #121 is the method with acetic acid hydrogenation, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, described hydrogenation catalyst is made of the metal component that is dispersed on the oxide-based carrier basically, and described hydrogenation catalyst has following composition:
Pt vPd wRe xSn yCa pSi qO r，
Wherein the ratio of v: y is 3: 2-2: 3; The ratio of w: x is 1: 3-1: 5, p and q are selected to make that p: q is 1: 20-1: and 200, wherein the chemical valence requirement is satisfied in the selection of r, and the selection of v and w makes:
0.005 ≤ ( 3.25 v + 1.75 w ) q ≤ 0.05 .
Embodiment #122 is the method for embodiment #121, wherein the value of process conditions and v, w, x, y, p, q and r is selected so that the acetate that transforms at least 90% be converted into the compound that is selected from ethanol and ethyl acetate, and be converted into alkane less than 4% acetate simultaneously.
Embodiment #123 is the method #122 of embodiment, wherein the value of process conditions and v, w, x, y, p, q and r is selected so that the acetate that transforms at least 90% be converted into ethanol, the acetate less than 2% is converted into alkane.
Embodiment #124 is the method for embodiment #122, wherein considers any less impurity of existence, and p is selected to guarantee that carrier surface is alkalescence basically.
Embodiment #125 is the method with acetic acid hydrogenation, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, described hydrogenation catalyst is made of the metal component that is dispersed on the oxide-based carrier basically, and described hydrogenation catalyst has following composition:
Pt vPd wRe xSn yAl zCa pSi qO r，
Wherein v and y are 3: 2-2: 3; W and x are 1: 3-1: 5, and wherein control the aluminium atom of p and z and existence and the relative position of calcium atom and make that being present in its surperficial Bronsted acid position carries out balance by calcium silicates; 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 ≤ ( 3.25 v + 1.75 w ) q ≤ 0.05 .
Embodiment #126 is the method for embodiment #125, and wherein hydrogenation catalyst has at least about 100m 2The surface area of/g, and wherein control z and p and make p 〉=z.
Embodiment #127 is the method for embodiment #125, wherein considers any less impurity of existence, and p is selected to guarantee that carrier surface is substantially free of the Bronsted acid position.
Embodiment #128 is the method with the alkanoic acid hydrogenation, this method be included in the gas phase with at least about the mol ratio of 5: 1 hydrogen and alkanoic acid under about 125 ℃-350 ℃ temperature with at least about 1000hr -1GHSV under the pressure of 2atm at least, make the gaseous stream that comprises hydrogen and alkanoic acid pass hydrogenation catalyst, this hydrogenation catalyst comprises: (a) in the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier of containing that is selected from silica that silica, calcium metasilicate and calcium metasilicate promote; (b) be selected from the metallic promoter agent of tin, rhenium and composition thereof, (c) optionally contain silicon carrier with what second promoter promoted, described second promoter is selected from: (i) amount of the 1-5% of catalyst weight be selected from alkali metal, alkaline earth element and zinc to body promoter; (ii) the amount of the 1-50% of catalyst weight is selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type promoter; (iii) the 1-50% of catalyst weight amount is selected from TiO 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent; And the (iv) combination of i, ii and iii.
Embodiment #129 is the method for embodiment #128, and wherein said alkanoic acid is an acetate, and wherein (a) platinum (if exist) exists with the amount of the 0.5%-5% of catalyst weight; (b) palladium (if existence) exists with the amount of the 0.5%-5% of catalyst weight; And (c) metallic promoter agent exists with the amount of 0.5-10% at least.
Embodiment #130 is the method for embodiment #129, and the surface area that wherein contains silicon carrier is at least about 150m 2/ g.
Embodiment #131 is the method for embodiment #130, and wherein (a) platinum exists with the amount of the 1%-5% of catalyst weight; (b) palladium (if existence) exists with the amount of the 0.25%-5% of catalyst weight; And the platinum that (c) exists and the total amount of palladium are at least 1.25% of catalyst weight.
Embodiment #132 is the method for embodiment #131, and wherein tin exists with the amount of catalyst weight 1-3%.
Embodiment #133 is the method #132 of embodiment, and wherein the mol ratio of tin and platinum group metal is about 1: about 2: 1 of 2-.
Embodiment #134 is the method for embodiment #132, and wherein the mol ratio of tin and platinum is about 5: about 4: 5 of 4-.
Embodiment #135 is the method for embodiment #132, wherein contain silicon carrier and be substantially free of the Bronsted acid position of not offset by calcium metasilicate, and its surface area is at least about 200m 2/ g.
Embodiment #136 is the method #132 of embodiment, and wherein the weight ratio of tin and platinum group metal is about 2: about 3: 2 of 3-.
Embodiment #137 is the method for embodiment #128, and wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
Embodiment #138 is the method with acetic acid hydrogenation, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, and this hydrogenation catalyst is made of following basically: with the catalytic metal that is selected from Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Os, Ti, Zn, Cr, Mo and W and their mixture of the amount of the about 10 weight % of about 0.1%-; With the optional promoter of on suitable carrier, disperseing, wherein control the amount and the oxidation state of catalytic metal, the feasible acetate less than 4% of the composition of carrier and optional promoter and reaction condition is converted into the compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene, diethyl ether and composition thereof; And work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 500 hours time period, this catalyst activity reduction is less than 10%.
Embodiment #139 is the method for embodiment #138, and wherein carrier is selected from: molecular sieve carrier; With the modified silicon-contained carrier of modifier modification, described modifier is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium, scandium, yttrium and zinc, and carbon carrier.
Embodiment #140 is the method for embodiment #139, and wherein catalytic metal comprises platinum and tin, and the selectivity of diethyl ether is higher than 80%.
Embodiment #141 is the method for embodiment #107, and wherein carrier is a Zeolite support, and the selectivity of diethyl ether is higher than 90%.
Embodiment #142 is by with the acetate method of original production ethanol and ethyl acetate also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, this hydrogenation catalyst comprises: (a) in the platinum group metal that contains the mixture that is selected from platinum and platinum and palladium on the silicon carrier of the silica that is selected from silica and promotes with about 7.5 calcium metasilicates at the most, the amount of the platinum group metal that exists is at least about 2.0%, and the amount of the platinum of existence is at least about 1.5%; (b) metallic promoter agent that is selected from rhenium and tin of the amount of about 1%-2% of catalyst weight, the mol ratio of platinum and metallic promoter agent is about 3: 1-1: 2; (c) optionally contain silicon carrier with what second promoter promoted, described second promoter be selected from (i) catalyst weight 1-5% amount be selected from alkali metal, alkaline earth element and zinc to body promoter; (ii) the amount of the 1-50% of catalyst weight is selected from WO 3, MoO 3, Fe 2O 3And Cr 2O 3Oxidation-reduction type promoter; (iii) the 1-50% of catalyst weight amount is selected from TiO 2, ZrO 2, Nb 2O 5, Ta 2O 5And Al 2O 3The acid modification agent; And the (iv) combination of i, ii and iii.
Embodiment #143 is the method for embodiment #142, and wherein the mol ratio of metallic promoter agent and platinum group metal is about 2: about 3: 2 of 3-.
Embodiment #144 is the method for embodiment #142, and wherein the mol ratio of metallic promoter agent and platinum group metal is about 5: about 4: 5 of 4-.
Embodiment #145 is the method for embodiment #142, and the surface area that wherein contains silicon carrier is at least about 200m 2/ g, and the amount of calcium metasilicate is enough to make the surperficial essentially no broensted acidity that contains silicon carrier.
Embodiment #146 is the method for embodiment #145, and wherein the mol ratio of metallic promoter agent and platinum group metal is about 2: about 3: 2 of 3-.
Embodiment #147 is the method for embodiment #146, and the surface area that wherein contains silicon carrier is at least about 200m 2/ g, and the molal quantity that is present in its lip-deep Bronsted acid position is not more than the molal quantity that is present in the Bronsted acid position on the Saint-Gobain NorPro SS61138 silica surface.
Embodiment #148 is the method for embodiment #142, and the surface area that wherein contains silicon carrier is at least about 250m 2/ g, and the molal quantity that is present in its lip-deep Bronsted acid position is not more than the molal quantity that is present in the Bronsted acid position on the Saint-Gobain NorPro HSA SS61138 silica surface half.
Embodiment #149 is the method for #142 embodiment, this method is carried out under about 250 ℃-300 ℃ temperature, wherein (a) hydrogenation catalyst is included in the palladium on the silicon carrier of containing of the silica that is selected from silica and promotes with about 7.5 calcium metasilicates at the most, and the amount of the palladium of existence is at least about 1.5%; (b) the metallic promoter agent amount of being is the rhenium of about 1%-10% of catalyst weight, and the mol ratio of rhenium and palladium is about 3: 1-5: 1.
Embodiment #150 is the method for the acetate reduction of embodiment #142, wherein hydrogenation catalyst is made of platinum basically, its basically by with about 3 until the silica that about 7.5% calcium silicates promotes containing on the silicon carrier of constituting, the amount of the platinum that exists is at least about 1.0%, tin promoter is with the amount of about 1%-5% of catalyst weight, and the mol ratio of platinum and tin is about 9: 10-10: 9.
Embodiment #151 is the method for the acetate reduction of embodiment #142, wherein the amount of the platinum group metal of Cun Zaiing is at least about 2.0%, the amount of the platinum that exists is at least about 1.5%, and tin promoter is the amount of about 1%-5% of catalyst weight, and the mol ratio of platinum and tin is about 9: 10-10: 9.
Embodiment #152 is the method for embodiment #151, and this method is carried out under about 250 ℃-300 ℃ temperature, and wherein said hydrogenation catalyst comprises: be 200m at least at surface area 2The 2.5-3.5 weight % platinum that disperses on the high surface area silica of/g, 2 weight %-5 weight % tin, described high surface area silica promotes with the 4-7.5% calcium metasilicate.
Embodiment #153 be by with acetate also original production comprise ethanol and at least about the method for the materials flow of 40% ethyl acetate, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, described hydrogenation catalyst is made of the metal component that disperses on oxide-based carrier basically, and described hydrogenation catalyst has following composition:
Pt vPd wRe xSn yAl zTi nCa pSi qO r，，
Wherein the ratio of v and y is 3: 2-2: 3; The ratio of w and x is 1: 3-1: 5, and wherein to p, z and p, q and n select to make:
0.005 ≤ 2 p q + 1.33 n + 1.77 z ≤ 0.2
Wherein the chemical valence requirement is satisfied in the selection of r, and the selection of v and w makes:
0.005 ≤ ( 3.25 v + 1.75 w ) q + 1.33 n + 1.77 z ≤ 0.05 .
Embodiment #154 is the method for embodiment #153, and wherein hydrogenation catalyst has at least about 100m 2The surface area of/g.
Embodiment #155 is the method with acetic acid hydrogenation, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, and this hydrogenation catalyst is made of following basically: with the catalytic metal that is selected from Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Os, Ti, Zn, Cr, Mo and W and their mixture of the amount of the about 10 weight % of about 0.1%-; With the optional promoter of on suitable carrier, disperseing, wherein control the amount and the oxidation state of catalytic metal, the composition of carrier and optional promoter and reaction condition make: what i) make the acetate that transforms is converted into ethyl acetate greater than 50%; (ii) be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene, diethyl ether and composition thereof less than 4% acetate; And work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 500 hours time period, this catalyst activity reduction is less than 10%.
Embodiment #156 is the beaded catalyst that alkanoic acid is hydrogenated to corresponding alkanol, this beaded catalyst comprises: (a) be selected from silica and with about 3.0 until the silica that about 7.5 calcium metasilicates promote contain the platinum group metal that is selected from platinum, palladium and composition thereof on the silicon carrier, the surface area that contains silicon carrier is at least about 150m 2/ g; (b) tin promoter is the amount of about 1%-3% of catalyst weight, and the mol ratio of platinum and tin is about 4: 3-3: 4; (c) the described The Nomenclature Composition and Structure of Complexes that contains silicon carrier is selected to make that its surface is substantially free of the Bronsted acid position of not offset by calcium metasilicate.
Embodiment #157 is the hydrogenation catalyst of embodiment #156, and wherein the gross weight of the platinum group metal of Cun Zaiing is 2-4%, and the amount of the platinum of existence is at least 2%, and the weight ratio of platinum and tin is 4: 5-5: 4, and the amount of the calcium silicates that exists is 3-7.5%.
Embodiment #158 is basically by the following particle hydrogenation catalyst that constitutes: the top silicon carrier that contains that is dispersed with platinum group metal that is selected from platinum, palladium and composition thereof and the promoter that is selected from tin, cobalt and rhenium, this contains silicon carrier has at least about 175m 2/ g surface area and be selected from silica, calcium metasilicate and silica (have and be positioned at its lip-deep calcium metasilicate) that calcium metasilicate promotes, the described surface of silicon carrier that contains is owing to not being substantially free of the Bronsted acid position by the aluminium oxide of calcium balance.
Embodiment #159 is the hydrogenation catalyst of embodiment #158, wherein the gross weight of the platinum group metal of Cun Zaiing is 0.5%-2%, and the amount of the palladium of existence is at least 0.5%, and promoter is rhenium, the weight ratio of rhenium and palladium is 10: 1-2: 1, and the amount of calcium metasilicate is 3-90%.
Embodiment #160 is the hydrogenation catalyst of embodiment #159, wherein the gross weight of the platinum group metal of Cun Zaiing is 0.5-2%, and the amount of the platinum of existence is at least 0.5%, and promoter is cobalt, the weight ratio of cobalt and platinum is 20: 1-3: 1, and the amount of calcium silicates is 3-90%.
Embodiment #161 is the hydrogenation catalyst of embodiment #158, wherein the gross weight of the platinum group metal of Cun Zaiing is 0.5-2%, and the amount of the palladium of existence is at least 0.5%, and promoter is cobalt, the weight ratio of cobalt and palladium is 20: 1-3: 1, and the amount of calcium silicates is 3-90%.
Embodiment #162 is the hydrogenation catalyst that comprises following material: be 200m at least at surface area 2The 2.5-3.5 weight % platinum that disperses on the high surface pyrolytic silicon dioxide of/g, 3 weight %-5 weight % tin, described high surface area silica promotes that with the calcium metasilicate of 4-6% the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #163 is the hydrogenation catalyst that comprises following material: 0.5-2.5 weight % palladium, 2 weight %-7 weight % rheniums, the weight ratio of rhenium and palladium is at least 1.5: 1.0, and wherein rhenium and palladium all are dispersed in and contain on the silicon carrier, and the described silicon carrier that contains comprises at least 80% calcium metasilicate.
Embodiment #164 is the beaded catalyst that alkanoic acid is hydrogenated to corresponding alkanol, this beaded catalyst comprises: the platinum that is selected from the silicon carrier of containing that (a) contains silicon carrier in the stabilisation that is selected from modification, the platinum group metal of palladium and composition thereof, the described silicon carrier that contains is with being selected from following stabilizing agent-modifier modification and stable: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) (i)-(any precursor vi), and (i)-(any mixture vii), the surface area that the stabilisation of described modification contains silicon carrier is at least about 150m 2/ g; (b) with the tin promoter of the amount of about 1%-3% of catalyst weight, the mol ratio of platinum and tin is about 4: 3-3: 4.
Embodiment #165 is the hydrogenation catalyst of embodiment #164, and wherein the gross weight of the platinum group metal of Cun Zaiing is 2-4%, and the amount of the platinum of existence is at least 2%, and the weight ratio of platinum and tin is 4: 5-5: 4, and the amount of the stabilizing agent-modifier that exists is 3-7.5%.
Embodiment #166 is the hydrogenation catalyst of embodiment #165, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #167 is the hydrogenation catalyst of embodiment #165, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #168 is the hydrogenation catalyst of embodiment #165, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #169 is the hydrogenation catalyst of embodiment #165, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #170 is the hydrogenation catalyst of embodiment #165, and wherein the support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
Embodiment #171 is the hydrogenation catalyst of embodiment #164, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #172 is the hydrogenation catalyst of embodiment #164, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #173 is the hydrogenation catalyst of embodiment #164, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #174 is the hydrogenation catalyst of embodiment #164, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #175 is the hydrogenation catalyst of embodiment #164, and wherein the support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
Embodiment #176 is basically by the following particle hydrogenation catalyst that constitutes: the top stabilisation that is dispersed with the platinum group metal that is selected from platinum, palladium and composition thereof and the modification of the promoter that is selected from tin, cobalt and rhenium contains silicon carrier, and this contains silicon carrier and comprises and have at least 95% purity and at least about 175m 2The surface area of/g and with being selected from following stabilizing agent-modifier modification and stable silica: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) (i)-(any precursor vi), and (i)-(any mixture vii), the described surface of silicon carrier that contains is owing to the aluminium oxide that is not stabilized agent-modifier balance is substantially free of the Bronsted acid position.
Embodiment #177 is the hydrogenation catalyst of embodiment #176, wherein the gross weight of the platinum group metal of Cun Zaiing is 0.5%-2%, and the amount of the palladium of existence is at least 0.5%, and promoter is rhenium, the weight ratio of rhenium and palladium is 10: 1-2: 1, and the amount of carrier-modifier is 3-90%.
Embodiment #178 is the hydrogenation catalyst of embodiment #177, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #179 is the hydrogenation catalyst of embodiment #177, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #180 is the hydrogenation catalyst of embodiment #177, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #181 is the hydrogenation catalyst of embodiment #177, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #182 is the hydrogenation catalyst of embodiment #177, and wherein the support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
Embodiment #183 is the hydrogenation catalyst of embodiment #176, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #184 is the hydrogenation catalyst of embodiment #176, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #185 is the hydrogenation catalyst of embodiment #176, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #186 is the hydrogenation catalyst of embodiment #176, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #187 is the hydrogenation catalyst of embodiment #176, and wherein the support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
Embodiment #188 is the hydrogenation catalyst of embodiment #176, wherein the gross weight of the platinum group metal of Cun Zaiing is 0.5-2%, and the amount of the platinum of existence is at least 0.5%, and promoter is cobalt, the weight ratio of cobalt and platinum is 20: 1-3: 1, and the amount of support modification agent is 3-90%.
Embodiment #189 is the hydrogenation catalyst of embodiment #188, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #190 is the hydrogenation catalyst of embodiment #188, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #191 is the hydrogenation catalyst of embodiment #188, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #192 is the hydrogenation catalyst of embodiment #188, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #193 is the hydrogenation catalyst of embodiment #188, and wherein the support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
Embodiment #194 is the hydrogenation catalyst of embodiment #176, wherein the gross weight of the platinum group metal of Cun Zaiing is 0.5-2%, and the amount of the palladium of existence is at least 0.5%, and promoter is cobalt, the weight ratio of cobalt and palladium is 20: 1-3: 1, and the amount of support modification agent is 3-90%.
Embodiment #195 is the hydrogenation catalyst of embodiment #194, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #196 is the hydrogenation catalyst of embodiment #194, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of sodium, potassium, magnesium, calcium and zinc.
Embodiment #197 is the hydrogenation catalyst of embodiment #194, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #198 is the hydrogenation catalyst of embodiment #194, and wherein the support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid any mixture of magnesium, calcium and zinc.
Embodiment #199 is the hydrogenation catalyst of embodiment #194, and wherein the support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
Embodiment #200 is the hydrogenation catalyst that comprises following material: be 200m at least at surface area 2The 2.5-3.5 weight % platinum that disperses on the high surface pyrolytic silicon dioxide of/g, 3 weight %-5 weight % tin, described high surface area silica promotes that with the calcium metasilicate of 4-6% the mol ratio of platinum and tin is 4: 5-5: 4.
Embodiment #201 is the hydrogenation catalyst that comprises following material: 0.5-2.5 weight % palladium, 2 weight %-7 weight % rheniums, the weight ratio of rhenium and palladium is at least 1.5: 1.0, and wherein said rhenium and palladium all are dispersed in and contain on the silicon carrier, and the described silicon carrier that contains comprises at least 80% calcium metasilicate.
Embodiment #202 is a kind of hydrogenation catalyst of introducing the catalytic metal that is selected from Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Os, Ti, Zn, Cr, Mo and W on the oxide-based carrier of stabilizing modification with the amount of the about 10 weight % of about 0.1 weight %-, described oxide-based carrier is introduced the oxide and the metasilicate form of alkaline-earth metal, alkali metal, zinc, scandium, yttrium with enough amounts, the precursor forms of these oxides and metasilicate, and the alkaline non-volatile stabilizing agent-modifier of their form of mixtures, go up the acid position that exists thereby offset its surface; Give anti-alteration of form under the temperature that meets with acetic acid hydrogenation (alteration of form especially mainly changes owing to sintering, grain growth, crystal boundary migration, defective and dislocation migration, plastic deformation and/or other temperature-induced microstructure); Or the two.
Embodiment #203 is the hydrogenation catalyst of embodiment #202, and the amount of its neutral and alkali modifier-stabilizing agent and position are enough to make on the oxide-based carrier surface number of every square metre of existing acid position to be reduced to be lower than the number that purity is at least about the last every square metre acid position of being found, pyrolytic silicon dioxide surface of 99.7 weight %.
Embodiment #204 is the hydrogenation catalyst of embodiment #202, and the amount of its neutral and alkali modifier-stabilizing agent and position are enough to make on the oxide-based carrier surface number of every square metre of existing acid position to be reduced to be lower than the numbers that purity is at least about the last every square metre acid position of being found, Saint-Gobain NorPro HSA SS 61138 surfaces of 99.7 weight %.
Embodiment #205 is the hydrogenation catalyst of embodiment #202, and the amount of its neutral and alkali modifier-stabilizing agent and position are enough to make on the oxide-based carrier surface number of every square metre of existing acid position to be reduced to be lower than purity to be at least about half of the last every square metre sour bits number of being found in pyrolytic silicon dioxide surface of 99.7 weight %.
Embodiment #206 is the hydrogenation catalyst of embodiment #202, and the amount of its neutral and alkali modifier-stabilizing agent and position are enough to make on the oxide-based carrier surface number of every square metre of existing acid position to be reduced to be lower than purity to be at least about half of the last every square metre sour bits number of being found in Saint-Gobain NorPro HSA SS 61138 surfaces of 99.7 weight %.
Embodiment #207 is the hydrogenation catalyst of embodiment #202, the amount of its neutral and alkali modifier-stabilizing agent and position be enough to make on the oxide-based carrier surface number of every square metre of existing acid position to be reduced to be lower than purity be at least about 99.7 weight % the last every square metre sour bits number of being found in pyrolytic silicon dioxide surface 25%.
Embodiment #208 is the hydrogenation catalyst of embodiment #202, the amount of its neutral and alkali modifier-stabilizing agent and position be enough to make on the oxide-based carrier surface number of every square metre of existing acid position to be reduced to be lower than purity be at least about 99.7 weight % the last every square metre sour bits number of being found in Saint-Gobain NorPro HSA SS 61138 surfaces 25%.
Embodiment #209 is the hydrogenation catalyst of embodiment #202, the amount of its neutral and alkali modifier-stabilizing agent and position be enough to make on the oxide-based carrier surface number of every square metre of existing acid position to be reduced to be lower than purity be at least about 99.7 weight % the last every square metre sour bits number of being found in pyrolytic silicon dioxide surface 10%.
Embodiment #210 is the hydrogenation catalyst of embodiment #202, the amount of its neutral and alkali modifier-stabilizing agent and position be enough to make on the oxide-based carrier surface number of every square metre of existing acid position to be reduced to be lower than purity be at least about 99.7 weight % the last every square metre sour bits number of being found in Saint-Gobain NorPro HSA SS 61138 surfaces 10%.
In the description of aforementioned each embodiment, can recognize that as those skilled in the art the embodiment of quoting another embodiment can suitably make up with other embodiment.

Claims (108)

1. one kind by with the acetate method of original production ethanol also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, this hydrogenation catalyst is included in and contains platinum and the tin that disperses on the silicon carrier, wherein to the amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and contain silicon carrier and select, constitute and control and make: (i) make at least 80% of the acetate that transforms be converted into ethanol; (ii) be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof less than 4% acetate; And work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 168 hours time period, this catalyst activity reduction is less than 10%.
2. the method for claim 1, wherein said hydrogenation catalyst basically by be dispersed in the platinum that contains on the silicon carrier and tin constitutes and this to contain silicon carrier be modified silicon-contained carrier, described modified silicon-contained carrier comprises the support modification agent that being selected from of effective dose is following: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) (i)-(precursor vi), and (i)-(mixture vii).
3. the method for claim 2, wherein said support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid mixture of sodium, potassium, magnesium, calcium and zinc.
4. the method for claim 2, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
5. the method for claim 3, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
6. the method for claim 2, wherein said support modification agent is selected from metasilicate and their precursor and the aforesaid mixture of sodium, potassium, magnesium, calcium and zinc.
7. the method for claim 5, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
8. the method for claim 6, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
9. the method for claim 2, wherein said support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid mixture of magnesium, calcium and zinc.
10. the method for claim 9, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
11. the method for claim 10, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
12. the method for claim 2, wherein said support modification agent are selected from metasilicate and their precursor and the aforesaid mixture of magnesium, calcium and zinc.
13. the method for claim 12, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
14. the method for claim 12, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
15. the method for claim 2, wherein said support modification agent are selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
16. the method for claim 15, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
17. the method for claim 16, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
18. the method for claim 2, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
19. the method for claim 16, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
20. the method for claim 18, the surface area of wherein said carrier is at least about 100m 2/ g.
21. the method for claim 20, wherein the mol ratio of tin and platinum group metal is about 1: about 2: 1 of 2-.
22. the method for claim 20, wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
23. the method for claim 20, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
24. the method for claim 2, the surface area of wherein said carrier is at least about 150m 2/ g.
25. the method for claim 24, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-5% at least.
26. the method for claim 24, wherein said carrier comprises the calcium silicates at least about the about 10 weight % of 1%-.
27. the method for claim 24, wherein the mol ratio of tin and platinum is about 1: about 2: 1 of 2-.
28. the method for claim 24, wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
29. the method for claim 24, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
30. the method for claim 2, the surface area of wherein said carrier is at least about 200m 2/ g.
31. the method for claim 30, wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
32. the method for claim 30, wherein the mol ratio of tin and platinum is about 5: about 4: 5 of 4-.
33. the method for claim 30, wherein the mol ratio of tin and platinum is about 9: about 10: 9 of 10-.
34. the method for claim 33, the surface area of wherein said modified silicon-contained carrier is at least about 250m 2/ g.
35. the method for claim 2, this method is carried out under about 250 ℃-300 ℃ temperature, wherein:
A. the surface area of described modified silicon-contained carrier is at least about 250m 2/ g;
B. platinum is present in the described hydrogenation catalyst with the amount at least about 0.75 weight %;
C. the mol ratio of tin and platinum is about 5: about 4: 5 of 4-; And
D. described modified silicon-contained carrier comprises purity and is at least about 95% the silica at least about the calcium metasilicate modification of the about 10 weight % of 2.5 weight %-used.
36. the method for claim 35, wherein the amount of the platinum of Cun Zaiing is at least 1 weight %.
37. the method for claim 2, this method is carried out under about 250 ℃-300 ℃ temperature, wherein:
A. the surface area of described modified silicon-contained carrier is at least about 100g/m;
B. wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-; And
C. described modified silicon-contained carrier comprises purity and is at least about 95% the silica at least about the calcium metasilicate modification of the about 10 weight % of 2.5 weight %-used.
38. the method for claim 37, wherein the amount of the platinum of Cun Zaiing is at least 0.75 weight %.
39. the method for claim 38, wherein said catalyst occupies reactor volume, and in gas phase with at least about 1000hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
40. the method for claim 38, wherein said catalyst occupies reactor volume, and in gas phase with at least about 2500hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
41. the method for claim 40 is wherein controlled the amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and described modified silicon-contained carrier make: (i) make at least 90% of the acetate that transforms be converted into ethanol; (ii) be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate and ethene and composition thereof less than 2% acetate; And (iii) work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 336 hours time period, this catalyst activity reduction is less than 10%.
42. the method for claim 38, wherein said catalyst occupies reactor volume, and in gas phase with at least about 5000hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
43. the method for claim 42 is wherein controlled the amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and described modified silicon-contained carrier make: (i) make at least 90% of the acetate that transforms be converted into ethanol; (ii) be converted into alkane less than 2% acetate; (iii) work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 168 hours time period, this catalyst activity reduction is less than 10%.
44. the method for claim 43, this method is carried out under about 250 ℃-300 ℃ temperature, wherein:
A. the surface area of described modified silicon-contained carrier is at least about 200m 2/ g;
B. the mol ratio of tin and platinum is about 5: about 4: 5 of 4-;
C. described modified silicon-contained carrier comprises purity and is at least about 95% silica, and modifier comprises the calcium silicates at least about the about 10 weight % of 2.5 weight %-.
45. one kind by with the acetate method of original production ethanol also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, this hydrogenation catalyst is included in platinum and the tin that disperses on the oxide-based carrier, wherein to the amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and oxide-based carrier are selected, are constituted and control and make: (i) make at least 80% of the acetate that transforms be converted into ethanol; (ii) be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof less than 4% acetate; And work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 500 hours time period, this catalyst activity reduction is less than 10%.
46. the method for claim 45, wherein said hydrogenation catalyst is basically by being dispersed in the platinum on the oxide-based carrier and tin constitutes and this oxide-based carrier is a modified oxide class carrier, described modified oxide class carrier comprises the support modification agent that being selected from of effective dose is following: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) (i)-(precursor vi), and (i)-(mixture vii).
47. the method for claim 46, wherein said support modification agent are selected from oxide and metasilicate and their precursor and the aforesaid mixture of sodium, potassium, magnesium, calcium and zinc.
48. the method for claim 47, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
49. the method for claim 47, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
50. 46 methods of claim, wherein said support modification agent are selected from metasilicate and their precursor and the aforesaid mixture of sodium, potassium, magnesium, calcium and zinc.
51. the method for claim 50, wherein:
C. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
D. tin exists with the amount of 0.5-10% at least.
52. the method for claim 51, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
53. the method for claim 46, wherein said support modification agent are selected from oxide and metasilicate and their precursor and the aforesaid mixture of magnesium, calcium and zinc.
54. the method for claim 53, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
55. the method for claim 54, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
56. the method for claim 46, wherein said support modification agent are selected from metasilicate and their precursor and the aforesaid mixture of magnesium, calcium and zinc.
57. the method for claim 56, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
58. the method for claim 57, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
59. the method for claim 46, wherein the support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
60. the method for claim 59, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
61. the method for claim 60, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
62. the method for claim 46, wherein:
E. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
F. tin exists with the amount of 0.5-10% at least.
63. the method for claim 62, wherein the mol ratio of platinum and tin is 4: 5-5: 4.
64. the method for claim 62, wherein said carrier surface area is at least about 100m 2/ g.
65. the method for claim 64, wherein the mol ratio of tin and platinum group metal is about 1: about 2: 1 of 2-.
66. the method for claim 64, wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
67. the method for claim 64, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
68. the method for claim 46, wherein carrier surface area is at least about 150m 2/ g.
69. the method for claim 68, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-5% at least.
70. the method for claim 68, wherein carrier comprises the calcium silicates at least about the about 10 weight % of 1%-.
71. the method for claim 68, wherein the mol ratio of tin and platinum is about 1: about 2: 1 of 2-.
72. the method for claim 68, wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
73. the method for claim 68, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
74. the method for claim 46, wherein carrier surface area is at least about 200m 2/ g.
75. the method for claim 74, wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
76. the method for claim 74, wherein the mol ratio of tin and platinum is about 5: about 4: 5 of 4-.
77. the method for claim 74, wherein the mol ratio of tin and platinum is about 9: about 10: 9 of 10-.
78. one kind by with the acetate method of original production ethanol also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, this hydrogenation catalyst contains the platinum and the tin that disperse on the silicon carrier by the stabilisation in modification basically and constitutes, the stabilisation of described modification contains silicon carrier and comprises the silica that usefulness that purity is at least about 95 weight % is selected from following stabilizing agent-modifier modification: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline-earth metal metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) (i)-(precursor vi), and (i)-(mixture vii), wherein control the amount and the oxidation state of platinum and tin, the ratio of platinum and tin, the purity that the stabilisation that stabilizing agent-modifier and silica contain relative scale in the silicon carrier and modification in the stabilisation of modification contains silica in the silicon carrier makes at least 80% of the acetate that transforms be converted into ethanol, and the acetate less than 4% is converted into except that being selected from ethanol, acetaldehyde, ethyl acetate, compound beyond the compound of ethene and composition thereof.
79. the method for claim 78, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-10% at least.
80. the method for claim 79, the surface area that the stabilisation of wherein said modification contains silicon carrier is at least about 100m 2/ g.
81. the method for claim 80, wherein the mol ratio of tin and platinum group metal is about 1: about 2: 1 of 2-.
82. the method for claim 80, wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
83. the method for claim 79, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
84. the method for claim 78, the surface area that the stabilisation of wherein said modification contains silicon carrier is at least about 150m 2/ g.
85. the method for claim 84, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-5% at least.
86. the method for claim 84, the stabilisation of wherein said modification contain silicon carrier and comprise calcium silicates at least about the about 10 weight % of 1 weight %-.
87. the method for claim 84, wherein the mol ratio of tin and platinum is about 1: about 2: 1 of 2-.
88. the method for claim 84, wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
89. the method for claim 84, wherein tin and platinum weight ratio be about 5: about 4: 5 of 4-.
90. the method for claim 87, the surface area that the stabilisation of wherein said modification contains silicon carrier is at least about 200m 2/ g.
91. the method for claim 90, wherein the mol ratio of tin and platinum is about 9: about 10: 9 of 10-.
92. the method for claim 90, wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-.
93. the method for claim 90, wherein the mol ratio of tin and platinum is about 5: about 4: 5 of 4-.
94. the method for claim 90, the surface area that the stabilisation of wherein said modification contains silicon carrier is at least about 250m 2/ g.
95. the method for claim 78, this method is carried out under about 250 ℃-300 ℃ temperature, wherein:
A. the stabilisation of the described modification surface area that contains silicon carrier is at least about 250m 2/ g;
B. platinum is present in the described hydrogenation catalyst with the amount at least about 0.75 weight %;
C. the mol ratio of tin and platinum is about 5: about 4: 5 of 4-; And
D. the stabilisation of modification contains silicon carrier and comprises calcium silicates at least about the about 10 weight % of 2.5 weight %-.
96. the method for claim 95, wherein the amount of the platinum of Cun Zaiing is at least 1 weight %.
97. the method for claim 78, this method is carried out under about 250 ℃-300 ℃ temperature, wherein:
A. the stabilisation of the described modification surface area that contains silicon carrier is at least about 100g/m;
B. wherein the mol ratio of tin and platinum is about 2: about 3: 2 of 3-; And
C. the stabilisation of described modification contains silicon carrier and comprises calcium silicates at least about the about 10 weight % of 2.5 weight %-.
98. the method for claim 97, wherein the amount of the platinum of Cun Zaiing is at least 0.75 weight %.
99. the method for claim 98, wherein said catalyst occupies reactor volume, and in gas phase with at least about 1000hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
100. the method for claim 98, wherein said catalyst occupies reactor volume, and in gas phase with at least about 2500hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
101. the method for claim 100, wherein control the amount and the oxidation state of platinum and tin, and the composition that the stabilisation of the ratio of platinum and tin and modification contains silicon carrier makes: make at least 90% of the acetate that transforms be converted into ethanol, the acetate less than 2% is converted into the compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate and ethene and composition thereof.
102. the method for claim 98, wherein said catalyst occupies reactor volume, and in gas phase with at least about 5000hr -1Air speed make the gaseous stream that comprises hydrogen and acetate pass described reactor volume.
103. the method for claim 79, wherein control the amount and the oxidation state of platinum and tin, and the composition that the stabilisation of the ratio of platinum and tin and described modification contains silicon carrier makes: make at least 90% of the acetate that transforms be converted into ethanol, the acetate less than 2% is converted into alkane.
104. the method for claim 79, this method is carried out under about 250 ℃-300 ℃ temperature, wherein:
A. wherein control the amount and the oxidation state of platinum and tin, and the acidity that the stabilisation of the ratio of platinum and tin and described modification contains silicon carrier makes: make at least 90% of the acetate that transforms be converted into ethanol, the acetate less than 1% is converted into alkane;
B. the stabilisation of the described modification surface area that contains silicon carrier is at least about 200m 2/ g;
C. the mol ratio of tin and platinum is about 5: about 4: 5 of 4-;
D. the stabilisation of described modification contains silicon carrier and comprises calcium silicates at least about the about 10 weight % of 2.5 weight %-.
105. one kind by with the acetate method of original production ethanol also, this method is included in the gas phase and makes the gaseous stream that comprises hydrogen and acetate pass hydrogenation catalyst with hydrogen and acetate mol ratio at least about 4: 1 under about 225 ℃-300 ℃ temperature, and this hydrogenation catalyst is made of following basically: with the catalytic metal that is selected from Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Re, Os, Ti, Zn, Cr, Mo and W and their mixture of the amount of the about 10 weight % of about 0.1%-; With the optional promoter of on suitable carrier, disperseing, wherein control the amount and the oxidation state of catalytic metal, the composition of carrier and optional promoter and reaction condition make: (i) make at least 80% of the acetate that transforms be converted into ethanol; (ii) be converted into compound except that the compound that is selected from ethanol, acetaldehyde, ethyl acetate, ethene, diethyl ether and composition thereof less than 4% acetate; And work as at the pressure of 2atm, 275 ℃ temperature and 2500hr -1GHSV under to be exposed to mol ratio be the mixture of vaporous of 10: 1 acetate and hydrogen during 500 hours time period, this catalyst activity reduction is less than 10%.
106. the method for claim 105, wherein said carrier are with the oxide-based carrier that is selected from following modifier modification: the oxide of sodium, potassium, magnesium, calcium, scandium, yttrium and zinc and metasilicate and their precursor and aforesaid any mixture.
107. the method for claim 105, wherein said carrier is a carbon carrier, and described catalytic metal comprises platinum and tin.
108. the method for claim 107, the reducible metal oxide modified of wherein said carbon carrier.
CN201080006216.9A 2009-10-26 2010-10-26 Catalyst for the production of ethanol by hydrogenation of acetic acid comprising platinum-tin on silicaceous support Expired - Fee Related CN102300635B (en)

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