CN102300635B - 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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CN102300635B
CN102300635B CN201080006216.9A CN201080006216A CN102300635B CN 102300635 B CN102300635 B CN 102300635B CN 201080006216 A CN201080006216 A CN 201080006216A CN 102300635 B CN102300635 B CN 102300635B
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platinum
tin
catalyst
acetic acid
weight
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CN102300635A (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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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
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    • 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
    • B01J23/62—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
    • 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
    • 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
    • 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
    • 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
    • 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
    • B01J37/08—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
    • C—CHEMISTRY; METALLURGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • 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 the catalyst containing the platinum-Xi on silicon carrier that is included in by acetic acid hydrogenation being produced to ethanol
Priority request
The application requires the priority of the U. S. application No 12/588,727 submitting on October 26th, 2009, by reference it is incorporated to herein in full.
Invention field
Present invention relates in general to for by carboxylic acid, particularly acetic acid hydrogenation can regulating catalyst and make the flexible way of acetic acid dehydrogenation, wherein ethanol can change to be applicable to the commercial terms changing with various catalyst with respect to the ratio of ethyl acetate and acetaldehyde.More specifically, the present invention relates to the catalyst for carboxylic acid, particularly acetic acid gas phase hydrogenation are comprised to the various products of corresponding alcohol, ester and aldehyde, particularly ethanol with production.Described catalyst shows excellent activity and selectivity within the scope of product.
Background technology
There are the long-term needs of the economically feasible method to acetic acid being 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, also ethene can be converted into many polymer and monomer product.The cost fluctuation taking oil or natural gas as the ethene in source that the natural gas of fluctuation and crude oil price contribute to make to produce according to routine, thus when oil price rises, make alternative ethene to originate need to be than in the past larger.
Obtain broad research for reducing the catalysis process of alkanoic acid and other carbonyl containing compound, mentioned in the literature the various combinations of catalyst, carrier and operating condition.T.Yokoyama etc. have commented the reduction of various carboxylic acids on metal oxide in " Fine chemicals through heterogeneous catalysis.Carboxylic acids and derivatives ".Some of attempting for the exploitation of the hydrogenation catalyst of various carboxylic acids in 8.3.1 chapter, are summarized.(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 acetic acid on various heterogeneous catalysis; Vannice, M.A.; J.Catal.2002,207,317-330).
In difference research, report on load and unsupported iron and used H 2by acetic acid vapour phase reduction.(Rachmady，W.；Vannice，M.A.J.Catal.2002，208，158-169)。
At Rachmady, W.; Vannice, M.A., J.Catal.2002, has provided the out of Memory about catalyst surface material and organic intermediate in 208,170-179.
At Rachmady, W.; Vannice, M.A.J.Catal.2002,209,87-98 and Rachmady, W.; Vannice, M.A.J.Catal.2000, has further studied the vapor phase acetic acid hydrogenation on a series of support type Pt-Fe catalyst in 192,322-334.
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 finds in the following in the research that by crotonaldehyde selective hydrogenation is the activity and selectivity in unsaturated alcohol: (Djerboua, the F. of R.Touroude etc.; 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, the M.A.N. such as M.Santiago; Sanchez-Castillo, M.A.; Cortright, R.D.; Dumesic, 1.A.J Catal.2000,193,16-28.) discuss with microcalorimetric method measurement, ft-ir measurement and the kinetics of quantum chemistry calculation combination and measured.
Also report the catalytic activity for acetic acid hydrogenation with regard to thering is the heterogeneous system of 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 method that platinum group metal Au catalyst is alcohol and/or ester by carboxylic acid and their acid anhydrides catalytic hydrogenation of utilizing.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 4,990,655; USP 4,985,572; With USP 4,826,795.
Malinowski etc. (Bull.Soc.Chim.Belg. (1985), 94 (2), 93-5) discussed acetic acid in heterogeneousization in for example silica (SiO of carrier material 2) or titanium dioxide (TiO 2) on Low-valent Titanium on catalytic reaction.
Bimetallic ruthenium-Xi/SiO 2 catalyst is by making tetrabutyltin and loading on ruthenic oxide on silica and react and make.(Loessard etc., Studies in Surface Science and Catalysis (1989), Volume Date 1988,48 (Struct.React.Surf), 591-600.).
For example, (Hindermann etc., the J.Chem.Res. of Hindermann etc., Synopses (1980), (11), 373), also study the catalytic reduction of acetic acid, disclose the catalytic reduction on the iron that acetic acid promotes on iron and at alkali.
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 likely 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
Find in the time that the stabilisation that is being scattered in modification is gone back ortho-acetic acid on containing the platinum-tin catalyst on silicon carrier, 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) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) any precursor in (i)-(vi), and (i)-any mixture (vii), by in gas phase with the hydrogen at least about 4: 1 and acetic acid mol ratio at approximately 125 DEG C-350 DEG C, more preferably from about 225-300 DEG C, also more preferably from about at the temperature of 250 DEG C-300 DEG C, make the gaseous stream that comprises hydrogen and acetic acid through described catalyst, when the amount of control platinum as described herein and tin and oxidation state and the ratio of platinum and tin and the stabilisation of modification are during containing silicon carrier, can in conversion, obtain the high selectivity to ethanol.In one aspect of the invention, offset and be present in the impact having 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 under mobile acetic acid vapor exists catalyst at 275 DEG C up to 168,336 or time period of even 500 hours in the excessive loss of activity and selectivity be effective.In another aspect of this invention, when hope is attended by, to acetic acid, to highly less desirable accessory substance, for example alkane transforms when low selective, thereby support modification agent is effectively to produce the high selectivity for alcohol production to suppressing that ethyl acetate generates.Preferably, 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 calcium metasilicate.
While having found to go back ortho-acetic acid on the platinum-tin catalyst being scattered on alkaline calcium metasilicate/silica supports substantially, wherein by gas phase with the hydrogen at least about 4: 1 and acetic acid mol ratio at approximately 125 DEG C-350 DEG C, more preferably from about 225-300 DEG C, also more preferably from about at the temperature of 250 DEG C-300 DEG C, make the gaseous stream that comprises hydrogen and acetic acid through described catalyst, in the time of the amount of control platinum as described herein and tin and oxidation state and the ratio of platinum and tin and the acidity of calcium metasilicate/silica supports, can in conversion, obtain the high selectivity to ethanol.Especially, use preferred catalyst of the present invention and method, make at least 80% of transformed acetic acid be converted into ethanol, make to be less than 4% acetic acid and be converted into the compound except being selected from the compound of 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; Tin exists up to 10% amount with at least 0.5 of catalyst weight simultaneously; Preferably, carrier surface area is at least about 100m 2/ g, more preferably from about 150m 2/ g, also more preferably at least about 200m 2/ g, most preferably at least about 250m 2/ g; The mol ratio of tin and platinum group metal is preferably approximately 1: 2-approximately 2: 1, more preferably from about 2: 3-approximately 3: 2; Also more preferably from about 5: 4-approximately 4: 5; 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, approximately 1 % by weight is substantially neutral or alkaline up to the characteristic of carrier described in the calcium silicates sufficient to guarantee of approximately 10 % by weight.In an especially preferred embodiment, platinum is with at least about 0.75 % by weight, and more preferably the amount of 1 % by weight is present in hydrogenation catalyst; The mol ratio of tin and platinum is approximately 5: 4-approximately 4: 5; And carrier comprises the calcium silicates at least about 2.5 % by weight-Yue 10 % by weight.
An aspect of the many embodiments of the present invention is can use higher than about 1000hr -1, 2500hr -1even higher than 5000hr -1air speed, and make at least 90% of transformed acetic acid be converted into ethanol simultaneously, and make to be less than 2% acetic acid and be converted into the compound except being selected from the compound of 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 lower than 1%, and in many situations, make through the acetic acid of catalyst below 0.5%, be converted into alkane, this alkane is except as having very little value fuel or synthesis gas.
In another aspect of this invention, the gaseous stream that makes to comprise hydrogen and alkanoic acid at the temperature of approximately 125 DEG C-350 DEG C by the mol ratio with the hydrogen at least about 2: 1 and alkanoic acid in gas phase is carried out hydrogenation through hydrogenation catalyst by alkanoic acid, and described hydrogenation catalyst comprises: be selected from silica that silica, calcium metasilicate and calcium metasilicate promote containing the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier; With the promoter that is selected from tin, rhenium and composition thereof, wherein optionally promote with promoter containing silicon carrier, 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 3acid modification agent, wherein control the acidity of described carrier so that be less than 4, be preferably less than 2, be most preferably less than approximately 1% alkanoic acid and be converted into alkane.In many situations, at least one in platinum and palladium exists with the amount of the 0.25%-5% of catalyst weight; The platinum existing and the total amount of palladium are catalyst weight at least 0.5%; The rhenium existing and the total amount of tin are 0.5-10 % by weight at least.In the method, for being included in platinum on alkaline silicon dioxide carrier and the catalyst of tin, control amount and the oxidation state of platinum group metal, rhenium and tin promoter, and the mol ratio of the rhenium of platinum group metal and existence and the total mole number of tin; With make at least 80% of transformed acetic acid be converted into the compound that is selected from alkanol and alkyl acetate containing the acidity of silicon carrier, and make to be less than 4% alkanoic acid simultaneously and be converted into the compound except being selected from the compound of corresponding alkanol, alkyl acetate and composition thereof.Preferably, at least one in platinum and palladium exists with the amount of the 0.5%-5% of catalyst weight; The platinum existing and the total amount of palladium are catalyst weight at least 0.75% to 5%.Preferably, alkanoic acid is acetic acid, and the tin of existence and the total amount of rhenium are catalyst weight at least 1.0%, and controls 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; With make at least 80% of transformed acetic acid be converted into ethanol or ethyl acetate containing the acidity of silicon carrier, make to be less than 4% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof.Preferably, the approximately 1-10% that the rhenium of existence and the gross weight of tin are catalyst weight, and the mol ratio of the total mole number of while platinum group metal and rhenium and tin is approximately 1: 2-approximately 2: 1.
On the other hand, the present invention relates to the method for acetic acid hydrogenation, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, described hydrogenation catalyst is made up of the metal component being dispersed on oxide-based carrier substantially, 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, and it is 1 that p and q are selected to make p: q: 20-1: 200, wherein the selection of r meets chemical valence requirement, 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 acetic acid that transforms at least 90% be converted into the compound that is selected from ethanol and ethyl acetate, and be less than 4% acetic acid simultaneously and be converted into alkane.In many embodiments of the present invention, consider any less impurity of existence, p is selected to guarantee that carrier surface does not basically contain active Bronsted acid position.
Another aspect of the present invention relates to by by the also method of original production ethanol of acetic acid, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, described hydrogenation catalyst is made up of the metal component being dispersed on oxide-based carrier substantially, 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 to be present in its surperficial Bronsted acid position and carry out balance by calcium silicates; It is 1 that p and q are selected to make p: q: 20-1: 200, and wherein the selection of r meets chemical valence requirement, 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, p is selected to guarantee equally that carrier surface does not basically contain seems to promote that ethanol conversion is the active Bronsted acid position of ethyl acetate.
Another aspect of the present invention relates to by by the also method of original production ethanol and ethyl acetate of acetic acid, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, described hydrogenation catalyst comprises: be selected from silica and the platinum group metal containing the mixture that is selected from platinum and platinum and palladium on silicon carrier with the silica that approximately 7.5 calcium metasilicates promote at the most, the amount of the platinum group metal existing is at least about 2.0%, the amount of the platinum existing is at least about 1.5%, with the metallic promoter agent that is selected from rhenium and tin of the amount of the approximately 1%-2% of catalyst weight, the mol ratio of platinum and metallic promoter agent is approximately 3: 1-1: 2, optional promote with the second promoter containing silicon carrier, described the 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 3acid modification agent, and their combination.
In preferred aspects of the invention, the mol ratio of metallic promoter agent and platinum group metal is approximately 2: 3-approximately 3: 2, and more preferably from about 5: 4-approximately 4: 5, most preferably from about 9: 10-approximately 10: 9, 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 substantially.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 Saint-Gobain NorPro SS61138 silica surface.In other situation, the silica using 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 the silica higher than 99%, more preferably higher than 99.5% silica, most preferably higher than 99.7% silica.In many embodiments of the present invention, or by controlling silica purity, or be present in Bronsted acid position carrier surface on by a kind of balance with calcium silicates or in other suitable stabilizing agent modifier of discussing herein, 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 Saint-Gobain NorPro SS61138 silica surface, preferably be 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 Saint-Gobain NorPro SS61138 silica surface.The sour figure place being present on carrier surface can be used pyridine titration by measuring as the operation of describing in Publication about Document:
(1) F.Delannay, editor, " Characterization of Heterogeneous Catalysts "; Chapter III:Measurement of Acidity of Surfaces, 370-404 page; 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, 736-744 page; Butterworth-Heinemann, MA 1992.
(3) G.A.Olah, G.K.Sura Prakask, editor, " Superacids "; John Wiley & Sons, N.Y.1985.
In whole description and claim, unless context point out in addition, in the time 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, 370-404 page; Marcel Dekker, Inc., the technology described in N.Y.1984.
In preferred situation, be at least about 250m containing the surface area of silicon carrier 2/ g, the molal quantity that is present in its lip-deep available Bronsted acid position is not more than the half that is present in the Bronsted acid position molal quantity on Saint-Gobain NorPro HSA SS61138 silica surface, and can at the temperature of approximately 250 DEG C-300 DEG C, carry out hydrogenation.
Look back herein and discuss, as those skilled in the art will appreciate that, in some embodiments, can use except above-mentioned containing the catalyst carrier silicon carrier, condition is that its component is selected under used process conditions, have suitable activity, selective and robustness (robust) so that this caltalyst ties up to.Suitable carrier can comprise stable metal oxide base carrier or ceramic base carrier and comprise the molecular sieve of zeolite.Therefore same, in some embodiments, if the above-mentioned U.S. Patent No. 5,149,680 of Kitson etc. is on 2 hurdles, 64 hurdles, row-4, can use carbon carrier described in 22 row, by reference the disclosure of this United States Patent (USP) are incorporated to herein.
In many embodiments of the present invention, to produce in the situation of mixture of ethanol and ethyl acetate therein simultaneously, hydrogenation catalyst can comprise: be selected from silica and with approximately 7.5 calcium metasilicates promote at the most silica containing the palladium on silicon carrier, the amount of the palladium of existence is at least about 1.5%; And simultaneously metallic promoter agent is the rhenium of the amount of the approximately 1%-10% of catalyst weight, the mol ratio of rhenium and palladium is approximately 4: 1-1: 4, preferably 2: 1-1: 3.
In many embodiments of the present invention, expect therein in main situation of producing ethanol, catalyst can be substantially by forming as follows: substantially by with approximately 3 until the silica that approximately 7.5% calcium silicates promotes form containing the platinum on silicon carrier, the amount of the platinum wherein existing is at least about 1.0%, with the tin promoter of the amount of the approximately 1%-5% of catalyst weight, in many embodiments of the present invention, the mol ratio of platinum and tin is approximately 9: 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 formula.In many embodiments of the present invention, the amount of the platinum group metal existing is at least about 2.0%, the amount of the platinum existing is at least about 1.5%, the preferably platinum of 2.5-3.5 % by weight, tin promoter exists with the amount of the approximately 2%-5% of catalyst weight, and simultaneously described method at the temperature of approximately 250 DEG C-300 DEG C 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.Expect therein in main still other embodiment of producing ethanol, catalyst can be included in substantially by the platinum on silicon carrier that contains forming with approximately 3 silica that promote up to approximately 7.5% calcium silicates, the amount of the platinum wherein existing is at least about 1.0%, tin promoter exists with the amount of the approximately 1%-5% of catalyst weight, and in many embodiments of the present invention, the mol ratio of platinum and tin is approximately 9: 10-10: 9.
Another aspect of the present invention relates to the beaded catalyst for alkanoic acid being hydrogenated to corresponding alkanol, this beaded catalyst comprises: being selected from silica and the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier that contains with approximately 3.0 silica that promote up to approximately 7.5 calcium metasilicates, be at least about 150m containing the surface area of silicon carrier 2/ g; Tin promoter is the amount of the approximately 1%-3% of catalyst weight, and the mol ratio of platinum and tin is approximately 4: 3-3: 4; Select to make its surface to be alkalescence substantially to the described the Nomenclature Composition and Structure of Complexes containing silicon carrier.
Another aspect of the present invention relates to the particle hydrogenation catalyst being substantially made up of following material: be dispersed with above the platinum group metal that is selected from platinum, palladium and composition thereof be selected from tin, cobalt and rhenium promoter containing silicon carrier, should have at least about 175m containing silicon carrier 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 containing silicon carrier is owing to not basically contained Bronsted acid position by the aluminium oxide of calcium balance.Being best suited in those modification of producing ethanol and ethyl acetate simultaneously, the gross weight of the platinum group metal existing 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 best suited for those that produce ethanol with high selectivity, the gross weight of the platinum group metal existing is 0.5-2%, the amount of the platinum existing 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 thering is life-extending Catalyst Production ethanol, the platinum that hydrogenation catalyst comprises 2.5-3.5 % by weight, 3 % by weight-5 % by weight be dispersed in surface area for 200m at least 2tin on the high surface pyrolysis gained silica of/g, described high surface area silica promotes to guarantee that with the calcium metasilicate of effective dose its surface does not basically contain not by the Bronsted acid position of calcium metasilicate balance, the mol ratio of platinum and tin is 4: 5-5: 4.
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 % by weight palladium, 2 % by weight-7 % by weight rheniums, the weight ratio of rhenium and palladium is at least 1.5: 1.0, and wherein rhenium and palladium are all dispersed in containing on silicon carrier, and the described silicon carrier that contains comprises at least 80% calcium metasilicate.
Find for being ethanol by acetic acid hydrogenation, obtained unexpectedly high activity and life-span and selective with excellence by being selected from following catalyst:
(i) be selected from silica that silica, calcium metasilicate and calcium metasilicate promote containing the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier and the catalyst of tin or rhenium;
(ii) with load on comprise be selected from silica that silica, calcium metasilicate and calcium metasilicate promote containing the palladium on silicon carrier and the catalyst of rhenium, wherein optionally promote with the promoter that 1%-5% is selected from alkali metal, alkaline earth element and zinc containing silicon carrier; Promoter preferably joins in catalyst formulation with these promoter (particularly preferably potassium, caesium, calcium, magnesium and zinc) nitrate or acetate form separately;
(iii) contain at the high surface of the silica that is selected from silica, calcium metasilicate and calcium metasilicate promotion the platinum promoting with cobalt on silicon carrier; And
(iv) contain at the high surface of the silica that is selected from silica, calcium metasilicate and calcium metasilicate promotion the palladium promoting with cobalt on silicon carrier.
Another aspect of the present invention relates to the method for alkanoic acid hydrogenation, the method is included in the mol ratio with the hydrogen at least about 2: 1 and alkanoic acid in gas phase makes the gaseous stream that comprises hydrogen and alkanoic acid through hydrogenation catalyst at the temperature of approximately 125 DEG C-350 DEG C, and this hydrogenation catalyst comprises:
A. be selected from silica that silica, calcium metasilicate and calcium metasilicate promote containing the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier; With
B. be selected from the promoter of tin and rhenium,
C. wherein optional with being selected from the promotion of following promoter containing 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 be 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 be selected from TiO 2, ZrO 2, Nb 2o 5, Ta 2o 5and Al 2o 3acid modification agent.
Preferably, alkanoic acid is acetic acid, 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 existing and the total amount of palladium are catalyst weight at least 0.5%; 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, be at least about 150m containing the surface area of silicon carrier 2/ g, more preferably at least about 200m 2/ g, most preferably at least about 250m 2/ g.In a more preferred embodiment, comprise approximately 7.5% calcium metasilicate at the most containing silicon carrier.In other embodiments, comprise approximately 90% calcium metasilicate at the most containing silicon carrier.In all embodiments, particularly, when when producing substantially pure ethanol, it can be quite favourable controlling carrier acidity.Silica is used alone as in the situation of carrier therein, quite advantageously guarantees that the amount of aluminium oxide (it is the common pollutant of silica) is low, preferably lower than 1%; More preferably less than 0.5%; Most preferably lower than 0.3 % by weight.Thus, greatly preferred so-called pyrolytic silicon dioxide, because it generally obtains with the purity higher than 99.7%.In this application, in the time mentioning high-purity silicon dioxide, it refers to the wherein acid contaminant silica that for example aluminium oxide exists to be less than the level of 0.3 % by weight.Use therein in the situation of silica of calcium metasilicate promotion, conventionally needn't be very strict about the purity of the silica as carrier, although aluminium oxide is less desirable and will will not be to have a mind to add conventionally.
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 existing and the total amount of palladium are catalyst weight at least 1%.
Carrier is substantially pure high surface area silica therein, in another preferred embodiment of the present invention of the silica that preferably 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 approximately 1: 2-approximately 2: 1; Also more preferably, tin and platinum mol ratio be approximately 2: 3-approximately 3: 2; Most preferably, the mol ratio of tin and platinum is approximately 5: 4-approximately 4: 5 simultaneously.Carrier also comprises the CaSiO of minor amount therein 3or in the situation of other stabilizing agent modifier of about 2%-approximately 10%, the acid impurities that tolerable is relatively large, as long as make their balances (counter-balance) by the stabilizing agent modifier of alkalescence substantially of appropriate amount.
In another aspect of this invention, preferably at approximately 225 DEG C-300 DEG C, more preferably at the temperature of 250 DEG C-300 DEG C, carry out described method, wherein said hydrogenation catalyst comprises: be selected from silica and the platinum group metal containing the mixture that is selected from platinum and platinum and palladium on silicon carrier with the silica that approximately 7.5 calcium metasilicates promote at the most, the amount of the platinum group metal existing 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 the approximately 1%-2% of catalyst weight, the mol ratio of platinum and tin is approximately 3: 1-1: 2, and wherein optional with being selected from the promotion of following promoter containing 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 3acid modification agent.
For by method that is particularly preferred the present invention of alkanoic acid hydrogenation, catalyst comprises: be selected from high surface high-purity silicon dioxide and with approximately 7.5 calcium metasilicates promote at the most high surface area silica containing the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier, the amount of the platinum group metal existing 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 the approximately 1%-5% of catalyst weight, and the mol ratio of platinum and tin is approximately 3: 2-2: 3.Preferably, high-purity silicon dioxide is that pyrolysis produces, and is then the fine and close form that is enough to use in fixed bde catalyst by its compressing tablet or granulation.But, even in the situation of high-purity silicon dioxide, under existing in acetic acid vapor in the temperature of about 275 DEG C with 2500hr -1or more high-speed extend to several weeks, the even commericially feasible operation of the prolongation period of several months, the existence of stabilizing agent modifier, particularly calcium silicates seems to make the activity and selectivity of catalyst to extend or is stable.Especially, can reach in 1 week (168 hours) or 2 weeks (336 hours) or even exceed the time period inner catalyst activity of 500 hours and can decline and be less than 10% such stability.Therefore, can recognize, catalyst of the present invention can be used in acetic acid hydrogenation completely, particularly produce the commercial-scale commercial Application of the mixture of high purity ethanol and ethyl acetate and ethanol.
Another aspect of the present invention relates to the metal (Fe of VIII family based on oxide-based carrier, Co, Ni, Ru, Rh, Pd, Ir, Pt and Os) or other transition metal (particularly Ti, 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 non-volatile stabilizing agent-modifier of the alkalescence of their form of mixtures, thereby: offset the upper acid position existing, its surface, give anti-alteration of form at the temperature that meets with acetic acid hydrogenation (alteration of form especially mainly changes owing to sintering, grain growth, crystal boundary migration, defect 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 containing the platinum group metal that is selected from platinum, palladium and composition thereof on 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 containing the palladium on silicon carrier and the catalyst of rhenium, wherein optionally promote with the promoter that 1%-5% is selected from alkali metal, alkaline earth element and zinc containing silicon carrier;
(iii) be selected from silica that silica, calcium metasilicate and calcium metasilicate promote containing the platinum promoting with cobalt on silicon carrier; And
(iv) be selected from silica that silica, calcium metasilicate and calcium metasilicate promote containing the palladium promoting with cobalt on silicon carrier.
Generally speaking, introduce and be selected from the promoter of following material containing silicon carrier: with the oxide that comprises alkali metal, alkaline earth element and zinc of amount and the stabilizing agent-modifier of metasilicate and their precursor 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 3acid 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 for alkanoic acid being hydrogenated to corresponding alkanol, this beaded catalyst comprises: in the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier that contains that is selected from silica, use silica that approximately 7.5 calcium metasilicates promote at the most and composition thereof, be at least about 150m containing the surface area of silicon carrier 2/ g; The amount of tin promoter is the approximately 1%-2% of catalyst weight, the mol ratio of platinum and tin is approximately 3: 2-3: 2, promote with being selected from following promoter containing silicon carrier is optional: 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 3acid modification agent.
Alternative embodiment of the present invention relates to particle hydrogenation catalyst, this particle hydrogenation catalyst is substantially by forming as follows: be dispersed with above the platinum group metal that is selected from platinum, palladium and composition thereof be selected from tin, cobalt and rhenium promoter containing silicon carrier, should have at least about 175m containing silicon carrier 2the surface area of/g and be selected from silica, calcium metasilicate and silica that calcium metasilicate promotes; Optionally promote with following material containing 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 3acid 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 the selective and productive rate performance of catalyst of the present invention.
Fig. 3 A-3C described along with when at 225 DEG C in the performance change obtaining during by acetic acid hydrogenation on the catalyst of 225 DEG C of activation, the relative temperature insensitivity of the selective and productive rate of catalyst of the present invention.
Fig. 4 A-4C has described selectively, conversion ratio and productive rate be along with the platinum of (incumbent upon) preferred platinum-tin catalyst of the present invention and the ratio of tin change and change.
Fig. 5 A and 5B have described the most preferred catalyst of the present invention who loads on high surface area silica for the selective of alcohol production and by the high yield of its acquisition.
Fig. 6 A and 6B and Fig. 7 A and 7B have described use at low temperatures that the most preferred catalyst of the present invention of high surface area silica who promotes based on calcium metasilicate obtains excellent selective.What can recognize is to be selectively high to ethanol.
The impact of the mass fraction that Fig. 8,9 and 10 has described rhenium in the time using palladium rhenium catalyst on silica of the present invention on acetic acid hydrogenation.
Figure 11 and 12 has described the platinum that loads on silica and the performance of Co catalysts.
Detailed Description Of The Invention
Even if market situation constantly fluctuates, but for large-scale operation, acetic acid catalysis being hydrogenated to report in the document of ethanol selective, activity and catalyst life implying need to 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, need to exceed approximately 50% ethanol selective.Catalyst of the present invention is far beyond these requirements.
In the following description, all numerical value disclosed herein is all approximation, and no matter whether they are used in conjunction with word " approximately " or " roughly ".These numerical value can change 1%, 2%, 5%, or sometimes can change 10-20%.As long as disclose and there is lower limit R lwith upper limit R ua number range, fall into so any number within the scope of this and subrange also by specifically open.Especially, the following numerical value within the scope of this is by specifically open: R=R l+ k ★(R u-R l), wherein k varies to 100% from 1%, and increment is 1%, k is 1%, 2%, 3%, 4%, 5% ..., 50%, 51%, 52% ..., 95%, 96%, 97%, 98%, 99% or 100%.And, also specifically disclosed by arbitrary number range of two R numerical definitenesses defined above.
Fig. 1 and 2 has described the selective and productive rate performance of catalyst of the present invention, has shown the selective and productive rate with the available very large improvement of these catalyst under various operating temperatures with schematic form.Especially, at 280 DEG C and 296 DEG C, ethanol is selectively approximately 60%.In this is evaluated, importantly to remember that ethyl acetate is also the commodity with quite large Economic Importance and value, even if main purpose is to produce ethanol, the any acetic acid that is converted into ethyl acetate also keeps sizable value, and any alkane producing as accessory substance is worth much lower than raw material conventionally.In Fig. 1, represent as the productive rate square of the ethanol grams being produced by the operation per hour of every kg catalyst of time (in hour) function, and the productive rate of ethyl acetate represents by circle simultaneously, the productive rate of acetaldehyde represents with rhombus.Significantly, at this run duration, run duration improve as shown operating temperature with justification function temperature on productive rate and optionally impact.In Fig. 2, as selectively the representing by circle as defined ethanol below of function running time, and simultaneously as below defined ethyl acetate selectively represents with square, and acetaldehyde selectively represents with rhombus.
Fig. 3 A-3C has described the selective relative temperature insensitivity to metal precursor reduction temperature of catalyst of the present invention.This specific character is significant for commercial viability, because can not react in maintaining the container of overall uniform temperature through special tectonic, conventionally these containers are called " adiabatic reactor ", because seldom for the variations in temperature that adapts to be accompanied by course of reaction is taken measures in advance, although conventionally react to regulate with quartz chips or other inert particle " dilution " catalyst.Fig. 3 A has reported the result of following experiment, in this experiment at the temperature with DEG C demonstration with hydrogen reducing catalyst and then on described catalyst at 250 DEG C by acetic acid hydrogenation.Reach the standard grade and represent selective to ethanol of described special catalyst, represent selective to ethyl acetate and roll off the production line.In Fig. 3 B, provide the yield results of experiment, wherein reach the standard grade and recorded the productive rate of ethanol and roll off the production line and recorded ethyl acetate productive rate.In Fig. 3 C, show conversion ratio (as the below defined) result of this experiment as reduction temperature function.In addition, also at the temperature of 225 DEG C in 225 DEG C reduction or activation catalyst on by acetic acid hydrogenation.Point on Fig. 3 B and 3C also comprises wherein at 225 DEG C on the catalyst 225 DEG C of reduction this result of this experiment of acetic acid hydrogenation.Can will be appreciated that, at the temperature of 225 DEG C, on this catalyst, hydrogenation causes the selective conversion ratio with reducing of ethanol reducing.
Fig. 4 A-4C has described under the following conditions selective in acetic acid catalysis hydrogenation, conversion ratio and productive rate along with the ratio of platinum in the preferred platinum-tin catalyst of the present invention and tin changes and changes, and described change is at SiO about Pt 2-Pt xsn (1-x)molar fraction in (∑ [Pt]+[Sn]=1.20mmol): use 2.5ml solid catalyst (14/30 order, dilution in 1: 1 (v/v uses quartz chips, 14/30 order); Under the operating pressure of p=200psig (14bar); The feed rate of acetic acid, hydrogen and nitrogen dilution agent is respectively 0.09g/min HOAc; 160sccm/min H 2; With 60sccm/min N 2; Within the reaction time of 12 hours, total air speed (GHSV) is 6570h -1.Can will be appreciated that, in this experiment, for those catalyst that load on substantially pure high surface area silica, make the selective maximization for alcohol production with approximately 1 to 1 mol ratio.(this description in the whole text in, lowercase " l " is for rising to avoid similar or even identical the produced ambiguity for numeral 1 and the 12nd alphabetical symbol of Roman alphabet small letter in many fonts).In each in Fig. 4 A-4C, the X on horizontal direction axle (horizontal access axis) i(Pt) represent the mass fraction of platinum in catalyst, it is 0-1, and simultaneously selective, conversion ratio and productive rate be as indicated earlier, represent as shown in Figure 4 A selective to ethanol and ethyl acetate of catalyst, as shown in Figure 4 B the selective of ethanol reached to peak value at 50% mass fraction place, as shown in Fig. 4 C, acetic acid conversion ratio is along with alcohol yied reaches peak value and also reaches peak value.
Fig. 5 A and B have described the most preferred catalyst of the present invention who loads on high surface area silica for the selective and productive rate of alcohol production and by the high yield of its acquisition.In Fig. 5 A, on the longitudinal axis, show that wherein alcohol yied represents with square by the productive rate of the grams of every kg catalyst operation per hour, ethyl acetate productive rate represents by circle, acetaldehyde productive rate represents with rhombus.Similarly, in Fig. 5 B, on the longitudinal axis, shown as running time on transverse axis (in hour) function as below defined selective, ethyl acetate selectively represents by circle again, ethanol selectively represents with square, and acetaldehyde selectively represents with rhombus.
Fig. 6 A and B and Fig. 7 A use the format description identical with B with Fig. 5 A with B use at low temperatures that the preferred catalyst of the present invention of the high surface area silica promoting based on calcium metasilicate obtains selectively.Can recognize, in whole service, ethanol is selectively higher than 90%.
About relevant embodiment, Fig. 8-12 are discussed.
Only describe the present invention for illustration and illustration purpose in detail with reference to many embodiments below.The specific embodiments providing in the spirit and scope of the present invention and in appended claims is modified, and will be obvious to those skilled in the art.
Unless below more specifically limit, term as used herein is got its its ordinary meaning, except as otherwise noted, " % " and similar terms are with reference to % by weight.Generally speaking, in the time that carrier composition is discussed, the percentage in composition comprises oxygen and connected ion or metal, and in the time that the weight of catalytic metal is discussed, ignores the weight of connected oxygen.Therefore,, in the carrier that comprises 95% silica and 5% aluminium oxide, this composition is the aluminium oxide and the silica with 60.09 formula weights based on having 101.94 formula weights.But, in the time referring to the catalyst with 2% platinum and 3% tin, ignore can connected any oxygen weight.
" conversion ratio " represents by the mole percent based on acetic acid in charging.
" selectively " represents by the mole percent of the acetic acid based on transforming.For example, if 50 % by mole that conversion ratio is 50 % by mole and the acetic acid that transforms are converted into ethanol, refer to that ethanol is selectively 50%.Ethanol selectively by gas-chromatography (GC) data by as the calculating of getting off:
Be not intended to bound by theoryly, think that according to the present invention acetic acid is converted into ethanol and relates to one or more in following reaction:
Acetic acid hydrogenation obtains ethanol.
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Acetic acid hydrogenation obtains ethyl acetate
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Ethyl acetate cracking obtains ethene and acetic acid
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Ethanol dehydration obtains ethene
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The catalysts selective that obtains ethanol for acetic acid catalysis hydrogenation be selected from following those:
(i) with the silica being selected from silica, calcium metasilicate and promote with calcium metasilicate containing the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier and the catalyst of tin or rhenium
(ii) be optionally selected from 1%-5% loading on containing the palladium on silicon carrier and the catalyst of rhenium that the first promoter of alkali metal, alkaline earth element and zinc promotes with as described above, promoter preferably joins in catalyst formulation with these promoter (particularly preferably potassium, caesium, calcium, magnesium and zinc) nitrate or acetate form separately;
(iii) at the platinum containing promoting with cobalt on silicon carrier; And
(iv) at the palladium containing promoting with cobalt on silicon carrier.
As the skilled person will be readily appreciated, 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; , have seldom or do not need internal pipe arrangements (plumbing) through reaction zone to add or remove heat.Or, can use the shell-and-tube reactor that is equipped with heat transmission medium.In many situations, reaction zone can be contained in single container or between have in the series containers of heat exchanger.Obviously recognize in order that use the acetic acid method of reducing of catalyst of the present invention to carry out in adiabatic reactor, because this reactor structure capital intensity compared with shell-and-tube structure is conventionally little a lot.
Can carry out load acetic acid hydrogenation catalyst by various catalyst carriers known in the art.The example of this class carrier comprises ferriferous oxide, silica, aluminium oxide, titanium dioxide, zirconia, magnesia, calcium silicates, carbon, graphite and their mixture without any restrictionsly.For the present invention, preferably use the silica that is selected from silica, calcium metasilicate and promote with calcium silicates containing silicon carrier, when granulation is to use enough fine and close form in fixed bed reactors time, special expectation be SiO 2content is at least 99.7% pyrolytic silicon dioxide.Find the high-purity, the high surface area silica that optionally promote with calcium metasilicate, particularly, from HSA SS 61138 grades of Saint-Gobain NorPro, be unexpectedly better than other carrier for catalyst of the present invention.Silica as carrier of the present invention preferably has at least 100m 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 description in the whole text in, term " high surface area silica " is interpreted as representing to have an at least 250m 2the silica of/g surface area.Activity/stability containing silicon carrier can be carried out modification by other component of including as mentioned below minor amount in.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 conventionally preferably use cylindrical pellets for the application.
The impact of catalyst carrier.
Except to metal precursor (be halogen, Cl -halogen-free with respect to (vs.), NO 3 -) and beyond preparation condition selects, the metal-carrier producing interact depend on consumingly below structure and the performance of (underlying) carrier.
For various silicon dioxide carried Pt-Sn materials, the impact of research alkalescence and acid modification agent.For all material, except as otherwise noted, the mol ratio between Pt and Sn remains in 1: 1, also makes total metal carrying capacity remain unchanged.Especially, at such as SiO of acid carrier 2, SiO 2-TiO 2, KA160 (is SiO 2-Al 2o 3) and the catalyst of the upper preparation of H-ZSM5 produce high acetic acid conversion ratio, but it is selective to produce lower ethanol.Arouse attention, in fact 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 similar selective to EtOH and EtOAc, in two kinds of situations, EtOAc is primary product.The Lewis acidity existing in catalyst carrier below seems to be of value to higher acetic acid conversion ratio.Although SiO 2-TiO 2in acidity mainly based on Lewis acidity, but KA160 (silica-alumina) material also has strong Bronsted acid position, this can catalysis form EtOAc by remaining acetic acid and EtOH.Catalyst based on H-ZSM5 has even stronger acid zeolite class (zeolytic) Bronsted acid position and shape selectivity, and this is to form diethyl ether because little hole also can contribute to the acid catalysis by ethanol dehydration.Alkaline modifier is joined to studied any carrier and conventionally produce the optionally raising to ethanol, be accompanied by the obvious reduction of acetic acid conversion ratio.Find the SiO for entry in Table A 2 2-CaSiO 3(5)-Pt (3)-Sn (1.8), is 92% for the high selectivity of ethanol, uses CaSiO 3the even pure TiO promoting 2with approximately 20% selective generation ethanol.SiO 2-TiO 2and TiO 2-CaSiO 3between contrast implying 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 be combined the alkaline and acid accelerator of carefully change with concrete preparation method.
Table A. in the gas phase hydrogenation of acetic acid, the catalyst activity data of catalyst carrier modifier gathers.Reaction condition: 2.5ml solid catalyst (14/30 order, dilution in 1: 1 (v/v, by quartz chips, 14/30 order); P=200psig (14bar); 0.09g/min HOAc; 160sccm/min H 2; 60sccm/min N 2; GHSV=6570h -1; Reaction time is 12 hours.
1describe the preparation of independent catalyst herein in detail.Numeral in bracket is in the amount of the real composition (metal, metal oxide) of % by weight.
2selectivity of product (% by weight) is by being calculated by the reliable sample of GC analysis correction.
3acetic acid conversion ratio (%) is by calculating as follows: [HOAc] conversion ratio, %={[HOAc] (charging, mmol/min)-[HOAc] (effluent, mmol/min)/[HOAc] (charging, mmol/min) } * 100.
4with the primary product that this catalyst obtains be diethyl ether (EtOEt), there is the productive rate of 96% selective and 2646g/kg/h simultaneously.
Contrast KA160 (SiO 2-5%Al 2o 3) and KA160-CaSiO 3the catalyst promoting observes the selectively obvious transfer to ethanol.Referring to entry in Table A 2,6 and 7, although 84% time, this catalyst selectively still lower than SiO 2-CaSiO 3it is selective that sill observes, but acetic acid conversion ratio remains in 43%, is about SiO 2-CaSiO 3(5) almost twice of the acetic acid conversion ratio that-Pt (3)-Sn (1.8) sees.Except " acid modification agent " performance, all CaSiO 3the material promoting seems to demonstrate the long term stability (although being under lower conversion ratio) of improvement.Particularly, under various reaction conditions, be greater than SiO in reaction time of 220 hours 2-CaSiO 3(5)-Pt (3)-Sn (1.8) catalyst shows the activity decreased that is less than 10%.About selectively, at SiO 2and SiO 2-CaSiO 3two kinds of Re-Pd catalyst of upper preparation also demonstrate similar trend.Entry 9 and 10 in Table A, for this bi-material, although conversion ratio keeps below 10%, for CaSiO 3the material promoting observes to ethanol and optionally obviously shifts.Other information about productive rate is provided in table 4.
Therefore, not bound by theory, for the oxide-based carrier of acetic acid hydrogenation catalyst by introduce non-volatile stabilizing agent-modifier in addition modification and stable have following active any: offset the upper acid position that has its surface; Or the stable ethanol that makes it possible to acquisition expectation of its surface heat is selectively improved, the catalyst life of prolongation; Or these two.Generally speaking, based in its modifier of the oxide of stable valence state can there is low vapor pressure, and therefore have and be quite non-volatile.Therefore, the hydrogenation catalyst of the VIII family metal (Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt and Os) based 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 non-volatile stabilizing agent-modifier of the alkalescence of their form of mixtures, thereby: offset the upper acid position existing, its surface; Give anti-alteration of form at the temperature that meets with acetic acid hydrogenation (alteration of form especially mainly changes owing to sintering, grain growth, crystal boundary migration, defect 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 carrier non-key and can change in the scope of approximately 0.3 % by weight-Yue 10 % by weight.The particularly preferably metal carrying capacity based on catalyst weight meter approximately 0.5 % by weight-Yue 6 % by weight.Due to extremely expensive, typically use platinum group metal with the amount of quite carefully controlling, be conventionally less than 10 % by weight of whole catalyst composition.Be low to moderate the platinum of 0.25-5%, when with other catalytic elements combination as described herein, can provide excellent selective, life-span and activity.Typically, in catalyst made from platonic of the present invention, preferably use 0.5-5%, the more preferably platinum of 1-3%.In the situation of platinum-tin catalyst, in the time of load on high surface area silica/calcium metasilicate, preferably use 0.10-5% tin, more preferably 0.25-3% tin, also more preferably 0.5-2.5% tin, the most preferably from about combination of 3% platinum and approximately 1.5% tin 1: 1 mol ratio of platinum and tin (quite closely corresponding to), or based on compared with not too proportional amount of the platinum of low weight percentage.For this catalyst, preferably use the high surface area silica that is selected from high-purity high surface area silica as above, calcium metasilicate and promote with calcium metasilicate containing silicon carrier.Therefore, can recognize, the amount of calcium metasilicate can vary widely up to 100 % by weight from 0.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, preferably use approximately 95% high surface area silica, 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 automobile catalyst and diesel oil cigarette ash capturing device be pellet type catalyst in this meaning in being impregnated into like that the washcoated layer on only stone carrier, shaped catalyst of the present invention is particle, sometimes also referred to as pearl or pill, there is the arbitrary shape in various shapes, by the catalyst of a lot of these moulding is placed in to reactor and catalytic metal is provided to reaction zone.Common shape comprises the extrudate with arbitrary cross section, the bus (generator) that limits extrudate surface be parallel lines meaning the above be shaped as For Generalized Cylinders.Ball, spray-dired microballoon, ring, five spoke wheels and multi-leaf-shaped thing are all 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 2approximately 3 % by weight platinum, 1.5 % by weight tin on the high surface area silica that the about 0.5%-7.5% calcium metasilicate of use of/g promotes.Be to have realized at 280 DEG C the catalyst life of hundreds of hours running times with this composition.In many situations, in composition mentioned above, can partly substitute platinum with palladium.
Being similar to those but the extremely catalyst of expensive platinum that the suitable Large Amount of Co of the use that contains small amount promotes in earlier paragraphs, described provides good initial catalytic activity but has tended to and do not shown the extending catalyst life-span the same with above-mentioned platinum-tin catalyst.The preferred rank (hierarchy) containing silicon carrier of this catalyst is substantially the same with platinum-tin catalyst.Preferred this class catalyst comprises approximately 20% cobalt with about 1%-, more preferably from about 2%-approximately 15% cobalt, the more preferably from about 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 not as above-mentioned platinum-tin catalyst durable, but in many situations, the amount of this required platinum that can greatly be reduced, cobalt compare with platinum group metal low cost and excellence initial selectivity and offset to a great extent.Certainly, it should be understood that in many situations, can or use larger reactor make up active shortage by suitable recycle stream, but be difficult to make up poor selective.
The catalyst of the palladium based on promoting with rhenium or cobalt provide excellent catalytic activity and lower a little selectively, thereby this selective forfeiture aggravates to cause forming the acetaldehyde, carbon dioxide of raising amount and hydrocarbon even under the reaction temperature higher than 280 DEG C.Cobalt-containing catalyst typical earth surface compared with corresponding rhenium catalyst reveals selective a little preferably; But, although these two all provides beat all long life catalytic activity, all do not provide and the most preferred the same catalyst life of giving prominence to of platinum/tin catalyst on the high-purity alpha-alumina of and modification stable with calcium metasilicate.In addition can by this catalyst cupport the oxide with above-mentioned I family, II family and zinc and metasilicate and their precursor and their stabilized with mixture and modification containing on silicon carrier.Highly suitable precursor comprises acetate and the nitrate of zinc, alkali and alkaline earth metal ions, can optionally they be brought into containing in silicon carrier in the amount of the about 1-5% of weight metal based on except acetate and/or nitrate anion part.
In other embodiments of the present invention, thus above-mentioned catalyst can change the relative selectivity between ethanol, ethyl acetate and acetaldehyde by the modifier that is selected from oxidation-reduction type active modifier, acid modification agent and their mixture being brought into containing carrying out modification in silicon carrier.Suitable oxidation-reduction type active modifier comprises WO 3, MoO 3, Fe 2o 3and Cr 2o 3, and acid modification agent comprises TiO 2, ZrO 2, Nb 2o 5, Ta 2o 5and Al 2o 3.By by these modifier reasonably (judicious) bring into containing in silicon carrier, activity that can regulating catalyst distributes with production and market fluctuation with to the consistent catalytic hydrogenation product relative quantity of more expecting of the requirement of various products.Typically, these materials can be included in containing in silicon carrier by the amount of the approximately 1-50% of siliceous vehicle weight.
Can use any known method in this area to carry out metal impregnation.Typically, before dipping, carrier is dried and is shaped at 120 DEG C the particle of the distribution of sizes with about 0.2-0.4mm.Optionally, carrier can be suppressed, crush and sieve as required size distribution.Can use any carrier material that makes to be shaped to the known method that required size distributes.In the method for optimizing of Kaolinite Preparation of Catalyst, can use the suitable combination thing of for example platinum group metal of platinum group metal component and/or complex compound to obtain catalyst component in for example dispersion on carrier granular of carrier.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 is deposited on carrier granular.In the time heating and/or apply vacuum, platinum group metal component is decomposed.In some cases, do not carry out removing until the high temperature that catalyst comes into operation and stands suffered during operation completely of liquid.Conventionally, 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 in the time that ethanol is required product.During calcining step, or at least during using starting stage of catalyst, these compounds are converted into catalytic activity form or its catalytic activity oxide of platinum group metal.But generally speaking, preferably use the not platinum group metal precursor of chloride, because found (the NH by Pt 3) 4(NO 4) 2it is selective that the catalyst of preparation seems to show the ethanol of raising.
Owing to it has been generally acknowledged that catalyst of the present invention is 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 the main metal for the preparation of hydrogenation catalyst of the present invention, and tin can be considered to promoter metals.But, it should be noted, such difference sometimes may have misleading, and particularly platinum-tin catalyst is under the optionally this situation of ethanol therein, and product required in the situation that not having tin and not having platinum is all close to 0.For facility, preferably platinum group metal is referred to as to main catalyst and by other metal finger on behalf of promoter.This should not be viewed as the instruction of the basic mechanism of catalytic activity.
Often in point two steps, flood bimetallic catalyst.First, adding " promoter " metal, is then " master " metal.After each impregnation steps, be then dried and calcine.Bimetallic catalyst can also be steeped and is prepared by total immersion.In the situation of the bimetallic catalyst promoting as mentioned above, can use dipping in succession, start to add that " promoter metals is then the second impregnation steps of the total immersion stain that comprises that two kinds of major metals are Pt and Sn.For example, SiO 2on PtSn/CaSiO 3can be by being prepared as follows: first by CaSiO 3be impregnated into SiO 2upper, 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 total immersion stain.Again, each dipping is then dried afterwards and calcines.In most of situations, can use metal-nitrate solutions to flood.But, also can use various other soluble salts in when calcining release metal ions.The example that is used for other suitable metal salt flooding comprises metal acid, such as perrhenic acid solution, metal oxalate etc.Produce therein substantially in those situations of pure ethanol, conventionally preferably avoid using the halogenated precursors of platinum group metal, but 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 and be approximately 125 DEG C-350 DEG C, more common approximately 200 DEG C-Yue 325 DEG C, preferably approximately 225 DEG C-Yue 300 DEG C, the reaction temperature of most preferably from about 250 DEG C-Yue 300 DEG C.Pressure is conventionally also non-key for reaction, can use lower than atmospheric pressure, atmospheric pressure or superatmospheric pressure.But in most of situations, reaction pressure can be an about 1-30 absolute atmosphere.In the inventive method on the other hand, typically can under the pressure that is just enough to overcome through the pressure drop of catalytic bed, carry out hydrogenation with selected total space-time speed (" GHSV "), although do not limit the higher pressure of use, but should be understood that for catalyst of the present invention and be easy to use 5000hr -1with 6,500hr -1air speed under may experience the sizable pressure drop by reactor beds.
Thereby produce 1 mole of ethanol although the every mole of acetic acid of this reaction consumes 2 mol of hydrogen, in incoming flow, the actual mol ratio of hydrogen and acetic acid can change between wide region, for example, be approximately 100: 1-1: 100.But such ratio is preferably approximately 1: 20-1: 2.Most preferably, the mol ratio of hydrogen and acetic acid is approximately 5: 1.
The raw material using about the inventive method can, derived from any suitable source, comprise natural gas, oil, coal, living beings etc.Produce acetic acid by carbonylation of methanol, oxidation of acetaldehyde, ethylene, oxidative fermentation and anaerobic fermentation etc. as everyone knows.Due to oil and natural gas fluctuation, more or less become expensive, so cause gradually concern by the method that substitutes carbon source production acetic acid and for example methyl alcohol of intermediate and carbon monoxide.Especially, when oil and gas is compared when relatively costly, produce acetic acid by the forming gas derived from any suitable carbon source (" synthesis gas ") and may become favourable.For example, the U.S. Patent No. 6,232,352 of Vidalin (by reference its disclosure being incorporated to herein) has instructed transformation methanol device in order to manufacture the method for acetic acid.By transformation methanol device, for new acetic acid device, produce with CO that relevant substantial contribution expense is significantly reduced or eliminate to a great extent.Make all or part synthesis gas turn to and be supplied to separator unit with recovery CO and hydrogen from the synthetic loop of methyl alcohol, then by them for the production of acetic acid.Except acetic acid, this method also can be used for preparing the available hydrogen of relevant the present invention.
The U.S. Patent No. RE 35,377 (being also incorporated to by reference herein) of Steinberg etc. provides a kind of by making for example method of oil, coal, natural gas and conversion of biomass material methanol of carbonaceous material.The method comprises makes solid and/or the hydrogasification of liquid carbon-containing material to obtain process gas, with other natural gas by this process gas steam pyrolysis with formation synthesis gas.This synthesis gas is converted into the methyl alcohol that can carbonyl turns to acetic acid.The method is same to be produced as the above-mentioned relevant spendable hydrogen of the present invention.Also, referring to the U.S. Patent No. 6,685,754 of U.S. Patent No. 5,821,111 and the Kindig etc. of Grady etc., it discloses a kind of method that useless living beings is converted into synthesis gas by gasification, by reference their disclosure is incorporated to this paper.
Can make acetic acid gasify under reaction temperature, then gasification acetic acid can be fed together in company with undiluted state or with the hydrogen of the dilutions such as carrier gas such as nitrogen, argon gas, helium, the carbon dioxide of relative inertness.
Or the acetic acid that can be directly takes out steam form from the flash chamber of the class carbonylation of methanol unit described in the U.S. Patent No. 6,657,078 (by reference it being incorporated to herein in full) of Scates etc. is as crude product.Thick vapor product directly can not needed to condensation acetic acid and light fraction or removes and anhydrate to entering reaction zone of the present invention, thereby saving overall craft expense.
Contact or the time of staying also can vary widely, and these variablees depend on amount, catalyst, reactor, the temperature and pressure of acetic acid.In the time using antigravity system except fixed bed, typical time of contact is for part is second to being greater than some hours, and at least for gas-phase reaction, be preferably about 0.5-100 second time of contact.
Typically, catalyst uses being for example shaped as in the pipeline of elongation or the fixed bed reactors of conduit, the reactant that typically wherein is steam form through or by described catalyst.For example, if need, can use other reactor, fluid bed or fluidized bed reactor.In some cases, the pressure drop that hydrogenation catalyst can be combined with for example mineral wool of inert material to regulate reactant streams to pass through catalyst bed and the time of contact of reactant compound and catalyst granules.
The following examples have been described the operation of the various catalyst that use for the preparation of the inventive method.In all these preparations and embodiment, in the time using small letters or cursive " l ", its for avoid small letters letter " l ", numeral " 1 " and between uppercase or 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.
Catalyst preparation (generally)
Catalyst carrier use before under circulated air at 120 DEG C dried overnight.Unless otherwise mentioned, all business carriers (are SiO 2, ZrO 2) use with 14/30 order or with its original-shape (1/16 inch or 1/8 inch of pill).After adding metal, (be CaSiO by dusty material 3) granulation, crushing and screening.The preparation of every kind of catalyst is described in chapters and sections below in more detail.
Catalyst is prepared A
The preparation of 0.5 % by weight platinum and 5 % by weight tin in high-purity low-surface area silica
In the baking oven under nitrogen atmosphere, uniform grading is distributed as to the powdered of about 0.2mm and high surface area silica NPSG SS61138 (100g) dried overnight of sieving at 120 DEG C, and is then cooled to room temperature.Add wherein (0.82g) solution in distilled water (8ml) and (8.7g) solution in rare nitric acid (1N, 43.5ml) of tin oxalate (Alfa Aesar) of platinum nitrate (Chempur).Dry gained slurry in the baking oven that is heated to gradually 110 DEG C (> 2 hours, 10 DEG C/min).Then the catalyst mixture through dipping in 500 DEG C (6 hours, 1 DEG C/min) lower calcining.
Catalyst is prepared B
The preparation of 1 % by weight platinum and 1 % by weight tin on high surface area silica
Substantially repeat catalyst and prepare the operation of A, difference is to utilize (1.64g) solution in distilled water (16ml) and (1.74g) solution in rare nitric acid (1N, 8.5ml) of tin oxalate (Alfa Aesar) of platinum nitrate (Chempur).
Catalyst is prepared C
The preparation of 1 % by weight platinum and 1 % by weight tin on calcium metasilicate
Substantially repeat catalyst and prepare the operation of 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, solution 8.5ml), and utilize calcium metasilicate as catalyst carrier.
Catalyst is prepared D
The preparation of 0.5 % by weight platinum, 0.5 % by weight tin and 0.2 % by weight cobalt on high surface area silica
In the baking oven under nitrogen atmosphere, uniform grading is distributed as to the powdered of about 0.2mm and the high surface area silica sieving (100g) dried overnight at 120 DEG C, and is then cooled to room temperature.Add wherein (0.82g) solution in distilled water (8ml) and (0.87g) solution in rare nitric acid (1N, 4.5ml) of tin oxalate (Alfa Aesar) of platinum nitrate (Chempur).Dry gained slurry in the baking oven that is heated to gradually 110 DEG C (> 2 hours, 10 DEG C/min).Then the catalyst mixture through dipping in 500 DEG C (6 hours, 1 DEG C/min) lower calcining.In calcining and cooling material, add the solution of cabaltous nitrate hexahydrate (0.99g) in distilled water (2ml) to this.Dry gained slurry in the baking oven that is heated to gradually 110 DEG C (> 2 hours, 10 DEG C/min).Then the catalyst mixture through dipping in 500 DEG C (6 hours, 1 DEG C/min) lower calcining.
Catalyst is prepared E
The preparation of 0.5 % by weight tin in high-purity low-surface area silica
In the baking oven under nitrogen atmosphere, uniform grading is distributed as to the powdered of about 0.2mm and high-purity low-surface area silica (100g) dried overnight of sieving at 120 DEG C, and is then cooled to room temperature.Add wherein (1.74g) solution in rare nitric acid (1N, 8.5ml) of tin oxalate (Alfa Aesar).Dry gained slurry in the baking oven that is heated to gradually 110 DEG C (> 2 hours, 10 DEG C/min).Then the catalyst mixture through dipping in 500 DEG C (6 hours, 1 DEG C/min) lower calcining.
Catalyst is prepared F
The preparation of 2 % by weight platinum and 2 % by weight tin on high surface area silica
In circulated air oven atmosphere, uniform grading is distributed as to the powdered of about 0.2mm and high surface area silica NPSG SS61138 (100g) dried overnight of sieving at 120 DEG C, and is then cooled to room temperature.Add wherein six nitric hydrate salt (Chempur) solution.Dry gained slurry in the baking oven that is heated to gradually 110 DEG C (> 2 hours, 10 DEG C/min), then by its calcining.Add wherein solution and tin oxalate (Alfa Aesar) solution in rare nitric acid of platinum nitrate (Chempur) in distilled water.Dry gained slurry in the baking oven that is heated to gradually 110 DEG C (> 2 hours, 10 DEG C/min).Then the catalyst mixture through dipping in 500 DEG C (6 hours, 1 DEG C/min) lower calcining.
Catalyst is prepared G
The preparation of 1 % by weight platinum and 1 % by weight tin on the high surface area silica promoting with 5%ZnO
Substantially repeat catalyst and prepare the operation of F, difference is: zinc nitrate hexahydrate solution is joined to catalyst and prepare in the described high surface area silica of F.Dry gained slurry in the baking oven that is heated to gradually 110 DEG C (> 2 hours, 10 DEG C/min).Then, solution by platinum nitrate (Chempur) in distilled water and tin oxalate (Alfa Aesar) (1.74g) solution in rare nitric acid (1N, 8.5ml) join in the high surface area silica of zinc promotion subsequently.
Catalyst is prepared H
Use 5%SnO 2the preparation of 1 % by weight platinum and 1 % by weight Zn on the high surface area silica promoting
Substantially repeat catalyst and prepare the operation of G, difference is: by tin acetate (Sn (OAC) 2) solution instead of 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 high surface area silica.
Catalyst is prepared I
The preparation of 1.5 % by weight platinum, 0.5 % by weight tin on calcium metasilicate
Utilize solution and tin oxalate (Alfa Aesar) solution in rare nitric acid of platinum nitrate (Chempur) in distilled water to repeat the operation that above-mentioned catalyst is prepared C.
Catalyst is prepared J
The preparation of 1.5 % by weight platinum, 10 % by weight cobalts on 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 that above-mentioned catalyst is prepared H.Other catalyst composition that has shown the catalyst composition of preparation in table 1 and prepared by similar operation herein and test.
Catalyst is prepared K-O
SiO 2-Pt xSn 1-x(0＜x＜1)。The molar fraction of change Pt also maintains total amount of metal (Pt+Sn) of 1.20mmol simultaneously and prepares five kinds of materials.Preparation has below been described catalyst and has been prepared K, i.e. SiO 2-Pt 0.5sn 0.5(be x=0.5; Two kinds of metal equimolar ratios) 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; Respectively that catalyst is prepared L, M, N and O).Described catalyst is by being prepared as follows: first by Sn (OAc) 2(from the tin acetate of Aldrich, Sn (OAc) 2) (0.1421g, 0.60mmol) join in the bottle of glacial acetic acid (Fisher) of dilution in contain 6.75ml 1: 1.At room temperature stir this mixture 15 minutes, then add 0.2323g (0.60mmol) solid Pt (NH 3) 4(NO 3) 2(Aldrich).At room temperature stir this mixture other 15 minutes, be then added dropwise to the dry SiO of 5.0g in 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 until join SiO by all Pt/Sn mixtures 2in catalyst carrier, also after adding metallic solution, rotate this flask simultaneously at every turn.After having added of this metallic solution, the flask that contains impregnated catalyst is maintained at room temperature and leaves standstill 2 hours.Then this flask is connected to rotary evaporator (bathing 80 DEG C of temperature), finds time until dry and while this flask of slow circumvolve.Then at 120 DEG C by further this material dried overnight, then use following temperature program(me) to calcine: 25 → 160 DEG C/slope is 5.0deg/min; Keep 2.0 hours; 160 → 500 DEG C/slope is 2.0deg/min; Keep 4 hours.Output: 5.2g Dark grey material.
Catalyst is prepared P
SiO 2-CaSiO 3(5)-Pt(3)-Sn(1.8)。This material passes through first by CaSiO 3(Aldrich) join SiO 2catalyst carrier then added Pt/Sn to be prepared described in previously.First, CaSiO 3the waterborne suspension of (≤200 order), by this solid of 0.52g is joined in 13ml deionized water, then adds 1.0ml colloid SiO 2(15 % by weight solution, NALCO) is prepared.At room temperature stir this suspension 2 hours, and then use the profit dipping technique that begins to add 10.0g SiO 2catalyst carrier (14/30 order).Leave standstill after 2 hours, this material is evaporated to dry, then under circulated air at 120 DEG C dried overnight calcining at 500 DEG C 6 hours.Then use the Pt (NH of 0.6711g (1.73mmol) 3) 4(NO 3) 2and the Sn (OAc) of 0.4104g (1.73mmol) 2according to above with regard to SiO 2-Pt xsn 1-xoperation described in material is by all SiO 2-CaSiO 3material is for Pt/Sn metal impregnation.Output: 11.21g Dark grey material.
Catalyst is prepared Q
CaSiO 3-Pt(1)-Sn(1)。In the round-bottomed flask that contains teflon-coating magnetic stirring bar to 100ml, add the 1.0M NHO of 40ml 3, then add 0.2025g (0.52mmol) solid Pt (NH 3) 4(NO 3) 2.Along with then stirring and dissolving Pt complex compound also adds 0.2052g (0.87mmol) solid Sn (OAc) 2.Next, add the CaSiO of 10.0g along with stirring 3(≤200 order); Then this mixture is heated to 80 DEG C and at this temperature, stir 2 hours.Then use rotary evaporator (bathe temperature 80 DEG C) this suspension to be found time until dry, by solid transfer in porcelain evaporating dishes, and under circulated air at 120 DEG C dried overnight.In calcining, (25 DEG C → 160 DEG C/slope is 5.0deg/min; Keep 2.0 hours; 160 → 500 DEG C/slope is 2.0deg/min; Keep 4 hours) after, under pressure, the power that particularly applies 40,000lbs is suppressed 15 minutes, and by material compacting, granulation, and crushing and screening are 14/30 order.The sepia material of output: 9.98g.
Catalyst is prepared R
SiO 2-TiO 2(10)-Pt(3)-Sn(1.8)。By being prepared as follows TiO 2the silica supports of-modification.By the Ti{OCH (CH of 4.15g (14.6mmol) 3) 2} 4solution in 2-propyl alcohol (14ml) is added drop-wise to the 10.0g SiO in 100ml round-bottomed flask 2in catalyst carrier (1/16 inch of extrudate).Allow this flask at room temperature leave standstill 2 hours, then use rotary evaporator (bathing 80 DEG C of temperature) to find time until dry.Next, 20ml deionized water is slowly joined to this flask, and allow this material maintain standing 15 minutes.Then by removing by filter produced water/2-propyl alcohol, then repeat to add H 2o 2 times.Under circulated air at 120 DEG C by final material dried overnight, then at 500 DEG C, calcine 6 hours.Then use the Pt (NH of 0.6711g (1.73mmol) 3) 4(NO 3) 2and the Sn (OAc) of 0.4104g (1.73mmol) 2according to above with regard to SiO 2-Pt xsn 1-xoperation described in material is by all SiO 2-TiO 2material is for Pt/Sn metal impregnation.Output: 1/16 inch of extrudate of 11.98g Dark grey.
Catalyst is prepared S
SiO 2-WO 3(10)-Pt(3)-Sn(1.8)。By being prepared as follows WO 3the silica supports of-modification.By (the NH of 1.24g (0.42mmol) 4) 6h 2w 12o 40nH 2the solution of O (AMT) in deionized water (14ml) is added drop-wise to the 10.0g SiO in 100ml round-bottomed flask 2nPSGSS61138 catalyst carrier (SA=250m 2/ g, 1/16 inch of extrudate) in.This flask is maintained at room temperature and leaves standstill 2 hours, then use rotary evaporator (bathing 80 DEG C of temperature) to find time until dry.Under circulated air at 120 DEG C by resulting materials dried overnight, then at 500 DEG C, calcine 6 hours.Then use the Pt (NH of 0.6711g (1.73mmol) 3) 4(NO 3) 2and the Sn (OAc) of 0.4104g (1.73mmol) 2according to above with regard to SiO 2-Pt xsn 1-xoperation described in material will own (light yellow) SiO 2-WO 3material is for Pt/Sn metal impregnation.Output: 1/16 inch of extrudate of 12.10g Dark grey.
Catalyst is prepared T
(H-ZSM-5)-Pt(3)-Sn(1.8)。This material passes through H-ZSM-5 (by NH 4-ZSM-5 by calcining and make for 8 hours in air at 550 DEG C) slurry dipping be prepared.Pt (the NH of 0.6711g (1.73mmol) 3) 4(NO 3) 2and the Sn (OAc) of 0.4104g (1.73mmol) 2the aqueous solution within 15 minutes, be prepared by described component being joined in the acetic acid of 40ml in 100ml round-bottomed flask dilution in 1: 1 and at room temperature stirring this mixture.Next, along with stirring, 10.0g solid fines powder H-ZSM-5 is joined in described solution, at room temperature stir this mixture other 2 hours.Then use rotary evaporator (bathe temperature 80 DEG C) this flask to be found time until dry, and under circulated air at 120 DEG C by resulting materials dried overnight.In calcining, (250 DEG C → 160 DEG C/slope is 5.0deg/min; Keep 2.0 hours; 160 → 500 DEG C/slope is 2.0deg/min; Keep 4 hours) after, be 14/30 order by this material compacting, granulation, crushing and screening.Output: 9.55g grey material.
Catalyst is prepared U
SiO 2-Re xPd 1-x(0＜x＜1)。The molar fraction of change Re also maintains total amount of metal (Re+Pd) of 1.20mmol simultaneously and prepares five kinds of materials.SiO has been described in preparation below 2-Re 0.5pd 0.5(be x=0.5; Two kinds of metal equimolar ratios) 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 by being prepared as follows: first by NH 4reO 4(0.1609g, 0.60mmol) joins in the bottle that contains 6.75ml deionized water.At room temperature stir this mixture 15 minutes, then add 0.1154g (0.60mmol) solid Pd (NO 3) 2.At room temperature stir this mixture other 15 minutes, be then added dropwise to the dry SiO of 5.0g in 100ml round-bottomed flask 2in catalyst carrier (14/30 order).After having added of this metallic solution, the flask that contains impregnated catalyst is maintained at room temperature and leaves standstill 2 hours.Then this flask is connected to rotary evaporator (bathing 80 DEG C of temperature), finds time until dry.Press above with regard to SiO 2-Pt xsn 1-xdescribed in material, carry out all other operations (dry, calcining), see above.The brown material of output: 5.1g.
Catalyst is prepared 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) describes preparation SiO 2-CaSiO 3(5) catalyst carrier of modification, sees above.Then contain NH by use 4reO 4and Pd (NO 3) 2aqueous solution dipping SiO 2-CaSiO 3(5) (1/16 inch of extrudate) prepares Re/Pd catalyst.This metallic solution passes through first by NH 4reO 4(0.7237g, 2.70mmol) joins in the bottle that contains 12.0ml deionized water and is prepared.At room temperature stir this mixture 15 minutes, then add 0.1756g (0.76mmol) solid Pd (NO 3) 2.At room temperature stir this mixture other 15 minutes, be then added dropwise to the dry SiO of 10.0g in 100ml round-bottomed flask 2-(0.05) CaSiO 3in catalyst carrier.After having added of this metallic solution, the flask that contains impregnated catalyst is maintained at room temperature and leaves standstill 2 hours.Press above with regard to SiO 2-Re xpd 1-xdescribed in material, carry out all other and process (dry, calcining), see above.The brown material of output: 10.9g.
Catalyst is prepared W
CaSiO 3-Re(5)-Pd(2.5)。This material passes through CaSiO 3the slurry dipping of (powder ,≤200 orders) is prepared.The NH of 0.6169g (2.30mmol) 4reO 4and the Pd (NO of 0.5847g (2.53mmol) 3) 2the aqueous solution within 15 minutes, be prepared by described component being joined in the 40ml deionized water in 100ml round-bottomed flask and at room temperature stirring this mixture.Next, along with stirring 10.0g solid fines powder CaSiO 3join in described solution, at room temperature stir this mixture other 2 hours.Then use rotary evaporator (bathe temperature 80 DEG C) this flask to be found time until dry, and under circulated air at 120 DEG C by resulting materials dried overnight.Press above with regard to SiO 2-RexPd 1-xdescribed in material, carry out all other and process (dry, calcining), see above.The power press of 15 minutes that use applies 40,000lbs by final material suppress, granulation, and crushing and screening are 14/30 order.The brown material of output: 10.65g.
Catalyst is prepared X
SiO 2-Co(10)-Pt(1)。This material contains Co (NO by use 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 first by Co (NO 3) 26H 2o (5.56g, 19.1mmol) joins in the bottle that contains 12.0ml deionized water and is prepared.At room temperature stir this mixture 15 minutes, then add 0.2255g (0.58mmol) solid Pt (NH 3) 4(NO 3) 2.At room temperature stir this mixture other 15 minutes, be then added dropwise to the dry SiO of 10.0g in 100ml round-bottomed flask 2in catalyst carrier (14/30 order).After having added of this metallic solution, the flask that contains impregnated catalyst is maintained at room temperature and leaves standstill 2 hours.Press above with regard to SiO 2-Pt xsn 1-xdescribed in material, carry out all other and process (dry, calcining), see above.Output: 11.35g black material.
Catalyst is prepared Y
CaSiO 3-Co(10)-Pt(1)。This material passes through CaSiO 3the slurry dipping of (powder ,≤200 orders) is prepared.Co (the NO of 5.56g (19.1mmol) 3) 26H 2pt (the NH of O and 0.2255g (0.58mmol) 3) 4(NO 3) 2the aqueous solution within 15 minutes, be prepared by described component being joined in the 40ml deionized water in 100ml round-bottomed flask and at room temperature stirring this mixture.Next, along with stirring 10.0g solid fines powder CaSiO 3join in described solution.Then this mixture is heated to 65 DEG C, and at this temperature, stirs other 2 hours.Then use rotary evaporator (bathe temperature 80 DEG C) this flask to be found time until dry, and under circulated air at 120 DEG C by resulting materials dried overnight.Press above with regard to SiO 2described in-Co (10)-Pt (1) material, carry out all other and process (dry, calcining), see above.By final material under pressure, suppress, granulation, and crushing and screening are 14/30 order.The black material of output: 10.65g.
Catalyst is prepared Z
ZrO 2-Co(10)-Pt(1)。This material contains Co (NO by use 3) 26H 2o and Pt (NH 3) 4(NO 3) 2aqueous solution dipping ZrO 2(SZ 61152, Saint-Gobain NorPro, 14/30 order) is prepared.This metallic solution passes through first by Co (NO 3) 26H 2o (5.56g, 19.1mmol) joins in the bottle that contains 5.0ml deionized water and is prepared.At room temperature stir this mixture 15 minutes, then add 0.2255g (0.58mmol) solid Pt (NH 3) 4(NO 3) 2.At room temperature stir this mixture other 15 minutes, be then added dropwise to the dry ZrO of 10.0g in 100ml round-bottomed flask 2in catalyst carrier (14/30 order).After having added of this metallic solution, the flask that contains impregnated catalyst is maintained at room temperature and leaves standstill 2 hours.Press above with regard to SiO 2described in-Co (10)-Pt (1), carry out all other and process (dry, calcining), see above.Output: 11.35g black material.
Catalyst is prepared 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) the described use of-Pt (3)-Sn (1.8) 0.26gCaSiO 3, 0.5ml colloid SiO 2(15 % by 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.
Catalyst is prepared BB
TiO 2-CaSiO 3(5)-Pt(3)-Sn(1.8)。
This material passes through first by CaSiO 3join TiO 2catalyst (anatase, 14/30 order) carrier then added Pt/Sn to be prepared described in previously.First, CaSiO 3the waterborne suspension of (≤200 order), by this solid of 0.52g is joined in 7.0ml deionized water, then adds 1.0ml colloid SiO 2(15 % by weight solution, NALCO) is prepared.At room temperature stir this suspension 2 hours, and then use the profit dipping technique that begins to add 10.0g TiO 2catalyst carrier (14/30 order).Leave standstill after 2 hours, this material is evaporated to dry, then under circulated air at 120 DEG C dried overnight calcining at 500 DEG C 6 hours.Then use the Pt (NH of 0.6711g (1.73mmol) 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 by all TiO 2-CaSiO 3material is for Pt/Sn metal impregnation.The light grey material of output: 11.5g.
Catalyst is prepared CC
KA160-Pt(3)-Sn(1.8)。
This material is pressed previously 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 first by 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, then add 0.3350g (0.86mmol) solid Pt (NH 3) 4(NO 3) 2.At room temperature stir this mixture other 15 minutes, be then added dropwise in the dry KA160 catalyst carrier (14/30 order) of 5.0g in 100ml round-bottomed flask.Press SiO above 2-Pt xsn 1-xdescribedly carry out that all other processed, dry and calcining.Output: 5.23g sepia material.
Catalyst is prepared DD
KA160-CaSiO 3(8)-Pt(3)-Sn(1.8)。
This material passes through first by CaSiO 3join KA160 catalyst carrier, then by adding Pt/Sn to be prepared above described in KA160-Pt (3)-Sn (1.8).First, CaSiO 3the waterborne suspension of (≤200 order), by this solid of 0.42g is joined in 3.85ml deionized water, then adds 0.8ml colloid SiO 2(15 % by weight solution, NALCO) is prepared.At room temperature stir this suspension 2 hours, and then use the profit dipping technique that begins to add 5.0g KA160 catalyst carrier (14/30 order).Leave standstill after 2 hours, this material is evaporated to dry, then under circulated air at 120 DEG C dried overnight calcining at 500 DEG C 6 hours.Then use the Pt (NH of 0.3350g (0.86mmol) 3) 4(NO 3) 2and the Sn (OAc) of 0.2040g (0.86mmol) 2according to above with regard to SiO 2-Pt xsn 1-xdescribed in material, operation is by all KA160-CaSiO 3material is for Pt/Sn metal impregnation.Output: 5.19g sepia material.
The gas chromatography (gc) of product 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 for quantizing: acetaldehyde; Ethanol; Acetone; Methyl acetate; Vinyl acetate; Ethyl acetate; Acetic acid; Ethylene acetate; Ethylene glycol; Oxalic acid ethyl; And para-acetaldehyde.
Center-aisle is equipped with TCD and Porabond Q pillar and for quantizing: CO 2; Ethene; And ethane.
Rear passage is equipped with TCD and Molsieve 5A pillar and for quantizing: helium; Hydrogen; Nitrogen; Methane; And carbon monoxide.
Before reaction, by form the retention time of spike mensuration different component with individually oriented compound, and with the calibration gas of known composition or by the liquid solution of known composition, GC is calibrated.This allows to measure the response factor of each component.
Embodiment 1
Be that 30mm and can rising to controls in the tubular reactor of temperature at the internal diameter of being made by stainless steel, settle 50ml to prepare the catalyst of preparing described in C by catalyst above.The total length of charging rear catalyst bed is approximately about 70mm.
Feed liquid is made up of acetic acid substantially.Under the pressure of the temperature of 250 DEG C 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 reactor.Incoming flow is containing having an appointment the acetic acid of 6.1%-approximately 7.3% mole percent and the hydrogen of about 54.3%-approximately 61.5% mole percent.The part of steam effluent that makes autoreactor by gas-chromatography in order to analyze the content of this effluent.Under 85% acetic acid conversion ratio, ethanol is selectively 93.4%.
The catalyst utilizing is to prepare 1 % by weight platinum and 1 % by weight tin on silica prepared by the operation of A according to catalyst.
Embodiment 2
The catalyst utilizing is 1 % by weight platinum and 1 % by weight tin on the calcium silicates of preparing according to the operation of Embodiment C.
Under the pressure of the temperature of 250 DEG C and 22bar with 2,500hr -1average total gasification acetic acid of gas hourly space velocity (GHSV) and the incoming flow of hydrogen repeat the operation providing in embodiment 1 substantially.A part that makes steam effluent by gas-chromatography in order to analyze the content of this effluent.Acetic acid conversion ratio is greater than 70%, and ethanol is selectively 99%.
Comparative example 1
The catalyst utilizing is 1 % by weight tin on the low surface area high-purity silicon dioxide of preparing according to the operation of embodiment E.
Under the pressure of the temperature of 250 DEG C and 22bar with 2,500hr -1average total gasification acetic acid of gas hourly space velocity (GHSV) and the incoming flow of hydrogen repeat the operation providing in embodiment 1 substantially.A part that makes steam effluent by gas-chromatography in order to analyze the content of this effluent.Acetic acid conversion ratio is less than 10%, and ethanol is selectively less than 1%.
Embodiment 3
At the temperature that uses various catalyst to provide, repeat the operation of embodiment 2 in table 2, in table 2, provided percentage and the ethyl acetate (EtOAc) of the carbon monoxide in product (CO), acetaldehyde (AcH) and ethane; The percentage conversion ratio (MCD p.4) of selective and productive rate and the acetic acid (HOAc) of ethanol (EtOH).All the time H, 2maintain 5: 1 with the mol ratio of acetic acid.For facility, in table 2, also comprise the result of embodiment 1,2 and comparative example 1.Generally speaking in the time expecting to produce ethanol as primary product, that expects ethanol is selectively approximately higher than greatly 80%; That expects ethyl acetate is selectively less than 5%, is preferably less than 3%.
Embodiment 4
At about 6570hr -1air speed and the pressure of 200psig under with about 160sccm/minH 2: ratio (the about 60sccm/min N for hydrogen of the hydrogen of 0.09g/min HOAc and acetic acid 2dilution) make to gasify acetic acid and hydrogen are through hydrogenation catalyst of the present invention, and it is about 250m that this hydrogenation catalyst is included in surface area 22 % by weight Pt and 2 % by weight Sn on the high surface area silica (NPSG SS61138) of/g.Press shown in Fig. 1 and 2 approximately 50 hours, 70 hours and 90 hours raising temperature, wherein in Fig. 1, shown in shown in product (ethanol, acetaldehyde and ethyl acetate) grams/kg catalyst/hour productive rate, in Fig. 2, show selective to various products of catalyst, wherein reach the standard grade and represent the productive rate of ethyl acetate or selective, medium line represents ethanol, and expression acetaldehyde rolls off the production line.Think and be apparent that especially, the productive rate of acetaldehyde and selectively low.The results are summarized in during data below gather.
Data gather
Embodiment 5
Use has and loads on the 2 % by weight Pt that comprise from the catalyst of the high surface area silica SS61138 pill of Saint-Gobain NorPro; The catalyst of 2 % by weight Sn, uses 2500hr under the institute's temp. displaying function providing and the pressure of 100psig in table 2 -1the incoming flow of gasification acetic acid, hydrogen and the helium of average total gas hourly space velocity (GHSV), repeats the operation providing in embodiment 1 substantially.Gained incoming flow is containing the hydrogen of the have an appointment acetic acid of 7.3% mole percent and approximately 54.3% mole percent.A part that makes steam effluent by gas-chromatography in order to analyze the content of this effluent.Result is presented in table 1.
Table 3
Embodiment 5 the results are summarized in 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, in adiabatic reactor, causes that owing to removing hot low and inhomogeneous speed from reactor the temperature catalyst bed can alter a great deal.
Embodiment 6
By following research SiO 2-Pt xsn 1-xthe impact of [Sn]/[Pt] mol ratio in catalyst: (i) in the lower molar fraction that changes Pt of constant metal carrying capacity ([Pt]+[Sn]=1.20mmol), and (ii) as the function of reduction temperature.Observe in the time that Pt molar fraction is 0.5 (i.e. [Sn]/[Pt]=1.0) for acetic acid conversion ratio and be obvious maximum to the selective of ethanol.In [Sn]/[Pt]=1.0) selectively sharply changing ethyl acetate while being conducive to ethanol.In the time that Pt molar fraction is 25% or 75%, observe ethyl acetate as primary product.The Pt of equimolar ratio and the existence of Sn seem for acetic acid conversion ratio and ethanol is optionally improved is preferred, with reference to figure 4A-C.
In temperature=250 DEG C; GHSV=6570h -1; Reaction time is under 12 hours, make to gasify acetic acid (0.09g/min HOAc) and hydrogen (160sccm/min H 2; 60sccm/min N 2) through 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 selective, activity and productive rate separately.By this embodiment, can recognize, when the mass fraction of platinum is approximately 0.5 when the amount of platinum is by weight substantially equal to the amount of tin in this catalyst, there is the maximum of selective, activity and productive rate.
Embodiment 7
At the temperature of approximately 225 DEG C, make to gasify acetic acid and hydrogen through hydrogenation catalyst of the present invention with the hydrogen of approximately 5: 1 and acetic acid mol ratio, it is about 250m that this hydrogenation catalyst is included in surface area 23 % by weight Pt, 1.5 % by weight Sn on the high-purity high surface area silica of/g and 5 % by weight are as the CaSiO of promoter 3.Fig. 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 reporting in Fig. 6 A and 6B, can recognize, can obtain selective active and every kg catalyst productive rate higher than 500g ethanol per hour higher than 90%.
Embodiment 8
At the temperature of approximately 250 DEG C, 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 being reported by Fig. 7 A and 7B, can recognize, still can obtain higher than 90% selective active but obtain every kg catalyst productive rate higher than 800g ethanol per hour simultaneously at this temperature.
Embodiment 9
In order to study the temperature control for bimetallic platinum and tin precursor being reduced to catalytic specie, in the independent experiment of 225-500 DEG C, by making optimized Pt/Sn, SiO 2-(Pt 0.5sn 0.5) catalyst activation studied the impact of reduction temperature, see below.In 4 experiments, make material under flowing hydrogen, activate 4 hours at 280,350,425 and 500 DEG C, then under the reaction temperature of 250 DEG C, carry out acetic acid reduction.(use 10mol%H 2/ N 2mixture (275sccm/min) uses following temperature program(me) to carry out catalyst activation under environmental pressure: RT-reduction temperature (225-500 DEG C), and slope is 2deg/min; Keep 4.0 hours, then for the reduction of HOAc reduces (or promoting where necessary) to 250 DEG C).In addition the material that, research activates at 225 DEG C under the reaction temperature of 225 and 250 DEG C in HOAc hydrogenation.Run through whole temperature range and do not observe the optionally significant change to ethanol and ethyl acetate, comprise the catalyst for activation at 225 DEG C with regard to 225 and 250 DEG C of reaction temperatures.Arouse attention, observe the obvious raising of conversion ratio (and productive rate) for the catalyst activating under lower, the reduction temperature of 225 and 280 DEG C.Under higher reduction temperature, conversion ratio reduction may be owing to the sintering of metallic particles.(referring to Fig. 7 A and 7B), because do not observe optionally variation, the composition (being PtSn alloy) of metallic particles seems to remain unchanged.The result of this embodiment has been described in Fig. 3 A-3C.
Various other products detected in these embodiments, comprise acetaldehyde, ethanol, ethyl acetate, ethane, carbon monoxide, carbon dioxide, methane, isopropyl alcohol, acetone and water.
Embodiment 10
In acetic acid catalysis hydrogenation, use the solid catalyst in catalyst shown in 2.5ml table 4 to evaluate the catalytic performance of various catalyst.In every kind of situation, catalyst granules has 14/30 object size, and by 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) while feed rate are 0.09g/min acetic acid; 120sccm/min hydrogen; 60sccm/min nitrogen, with 6570h -1total gas hourly space velocity.In table 4, show result.
The catalytic activity of table 4. various load type metal catalysts in HOAc catalytic hydrogenation.Reaction condition: 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 2; 60sccm/min N 2; GHSV=6570h -1; The running time (TOS) of 24 hours.
Embodiment 11
Catalyst stability: SiO 2-CaSiO 3(5)-Pt (3)-Sn (1.8).Under constant temperature (260 DEG C), exceed in reaction time of 100 hours and evaluate SiO 2-CaSiO 3(5) catalytic performance and the initial stability of-Pt (3)-Sn (1.8).In the total reaction time that exceedes 100 hours, observe catalyst performance and very little variation selectively only occurs.Seemingly unique accessory substance of acetaldehyde, and its concentration (approximately 3 % by weight) remains unchanged to a great extent in the process of experiment.Catalyst production is provided in Fig. 5 A and 5B and has optionally gathered.In independent experiment, in exceeding the total reaction time of 125 hours, study the impact of reaction temperature on selectivity of product, seen above.
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 2; 60sccm/min N 2; GHSV=6570h -1within the scope of typical operating condition, mainly produce acetaldehyde, ethanol, ethyl acetate with fixed bed continuous reactor system 15 hour duration in service at 225 DEG C by hydrogenation and esterification and study and in acetic acid hydrogenation, use 5%CaSiO 3stable high-purity high surface SiO 2on the productive rate of 3%Pt:1.5%Sn and selective.In Fig. 6 A and 6B, provide result.
Embodiment 13
Use 2.5ml solid catalyst (14/30 order, dilution in 1: 1 (v/v uses quartz chips, 14/30 order); Under the pressure of 200psig (14bar); Be accompanied by 160sccm/min hydrogen and 60sccm/min and feed 0.09g/min acetic acid as the nitrogen of diluent (diulent); At the temperature of 250 DEG C; GHSV=6570h -1; Or the reaction time of 12 hours, be included in SiO by changing in the molar fraction research of the lower Re of constant metal carrying capacity ([Pt]+[Sn]=1.20mmol) 2in Re and the productive rate of the catalyst of Pd and selectively (wherein between catalyst, revise Re xpd (1-x)mol ratio).Although be to observe the maximum conversion rate of acetic acid at approximately 0.6 o'clock in Re molar fraction, be only that approximately 0.78 o'clock ethanol becomes primary product in Re molar fraction.Between this Re and Pd, mol ratio (is expressed as " Re 7pd 2") under, thereby the selective close limit to ethyl acetate change and be conducive to ethanol.Importantly, and as 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, the i.e. o'clock selectively transfer to ethanol in [Re]/[Re+Pd]=0.78, with reference to the Fig. 8,9 and 10 providing by the form identical with Fig. 4 A-C, difference is X i(Re) mass fraction of rhenium in expression catalyst.But, form and contrast with Pt/Sn material, the maximum conversion rate of acetic acid with the selective of ethanol do not conformed to these materials, and only in the time of low HOAc conversion ratio, observe to ethanol favourable selectively.Therefore,, with reference to figure 8, observe maximum yield to ethyl acetate instead of for ethanol.In addition, use CaSiO 3-Re (5)-Pd (2.5) catalyst is at approximately 30% acetic acid conversion ratio and only under the reaction temperature of 225 DEG C, observe hydrocarbon (methane and ethane; They are respectively 5.3 and 2.4 % by weight) formation.Although the higher conversion of acetic acid can most possibly obtain by improving reaction temperature, also may improve the amount of hydrocarbon, has therefore limited the overall efficiency of Re/Pd base catalysis system.
Embodiment 14
Use at SiO 2on the primary catalyst screening of silicon dioxide carried platinum (1%) Co catalysts (Co carrying capacity is 10 % by weight) produce the selective of high acetic acid conversion ratio and approximately 80% pair of ethanol.Referring to Figure 11 and 12, wherein selective and activity as previously defined, represents with square for the result of ethanol, represents by circle for the result of ethyl acetate, and acetaldehyde represents with rhombus, and ethane represents with triangle.But, seem in the reaction time process of 9 hours catalyst along with acetic acid selectivity drops to 42% and deteriorated from approximately 80%.In addition, also observe the significant change of productive rate, and along with the ethanol being accompanied by that optionally improves to ethyl acetate and acetaldehyde selectively declines.Obtain similar result with 10% cobalt loading on silica.
Embodiment 15
In temperature=250 DEG C; GHSV=6570h -1; Under the reaction time of 12 hours, acetic acid (0.09g/min HOAc) and hydrogen (160sccm/min H make to gasify under the pressure of 200psig 2; 60sccm/min N 2) through hydrogenation catalyst of the present invention, this hydrogenation catalyst is included in 3 % by weight Pt and the 1.8 % by weight Sn on the carrier that comprises Hydrogen ZSM-5 molecular sieve.The productive rate of selective and 2646g/kg/h with 96% obtains diethyl ether, and with 4% ethyl acetate, 78% acetic acid keeps unreacted.
Embodiment 16
At 275 DEG C; GHSV=6570h -1; Under the reaction time of 12 hours, acetic acid (0.09g/min HOAc) and hydrogen (160sccm/min H make to gasify under the pressure of 200psig 2; 60sccm/min N 2) through hydrogenation catalyst of the present invention, this hydrogenation catalyst is included in 2 % by weight Pt and the 1 % by weight Sn on the carrier that comprises high surface graphite.Ethyl acetate be selectively 43%, ethanol selective 57%, the productive rate of ethyl acetate is 66g/kg/hr, the productive rate of ethanol is 88g/kg/hr, the conversion ratio of acetic acid is 12%.
Although describe the present invention in detail, various amendments within the spirit and scope of the present invention will be apparent to those skilled in the art.In view of the above discussion, this area relevant knowledge and the bibliography above discussed about background technology and detailed description, be all incorporated to their disclosure herein by reference, and think that other illustration is unnecessary.In addition, should understand below and/or the various piece of the various aspects of the present invention of quoting from appended claims and multiple embodiment and multiple features can partly or entirely combine or exchange.In addition, those skilled in the art will recognize that aforementioned description is only way of example, and be not intended to limit the present invention.
Therefore for the hydrogenation products based on acetic acid is provided, according to the invention provides novel method and catalyst.
For example embodiment #1 is by by the also method of original production ethanol of acetic acid, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, this hydrogenation catalyst is included in containing the platinum disperseing on silicon carrier and tin, the wherein amount to platinum and tin and oxidation state, and the ratio of platinum and tin, and select, form and control makes containing silicon carrier: (i) make at least 80% of transformed acetic acid be converted into ethanol; (ii) be less than 4% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof; And work as at the pressure of 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 168 hours of vaporous of the acetic acid of 10: 1 and hydrogen, this catalyst activity reduction is less than 10%.
Embodiment #2 is the method for embodiment #1, wherein hydrogenation catalyst substantially by be dispersed in containing the platinum on silicon carrier and tin forms and should containing 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) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) any precursor in (i)-(vi), and (i)-any mixture (vii).
Embodiment #3 is the method for embodiment #2, and wherein 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 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 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, 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 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 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 approximately 1: 2-approximately 2: 1.
Embodiment #22 is the method for embodiment #20, and wherein the mol ratio of tin and platinum is approximately 2: 3-approximately 3: 2.
Embodiment #23 is the method for embodiment #20, wherein tin and platinum weight ratio be approximately 5: 4-approximately 4: 5.
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 1%-approximately 10 % by weight.
Embodiment #27 is the method for embodiment #24, and wherein the mol ratio of tin and platinum is approximately 1: 2-approximately 2: 1.
Embodiment #28 is the method for embodiment #24, and wherein the mol ratio of tin and platinum is approximately 2: 3-approximately 3: 2.
Embodiment #29 is the method for embodiment #24, wherein tin and platinum weight ratio be approximately 5: 4-approximately 4: 5.
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 approximately 2: 3-approximately 3: 2.
Embodiment #32 is the method #30 of embodiment, and wherein the mol ratio of tin and platinum is approximately 5: 4-approximately 4: 5.
Embodiment #33 is the method for embodiment #30, and wherein the mol ratio of tin and platinum is approximately 9: 10-approximately 10: 9.
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 the method is carried out at the temperature of approximately 250 DEG C-300 DEG C, and wherein the surface area of (a) modified silicon-contained carrier is at least about 250m 2/ g; (b) platinum is to be present in hydrogenation catalyst at least about the amount of 0.75 % by weight; (c) mol ratio of tin and platinum is approximately 5: 4-approximately 4: 5; (d) modified silicon-contained carrier comprises purity and is at least about 95% the silica at least about the calcium metasilicate modification of 2.5 % by weight-Yue 10 % by weight of using.
Embodiment #36 is the method for embodiment #35, and the amount of the platinum wherein existing is at least 1 % by weight.
Embodiment #37 is the method for embodiment #2, and the method is carried out at the temperature of approximately 250 DEG C-300 DEG C, 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 approximately 2: 3-approximately 3: 2; (c) modified silicon-contained carrier comprises purity and is at least about 95% the silica at least about the calcium metasilicate modification of 2.5 % by weight-Yue 10 % by weight of using.
Embodiment #38 is the method for embodiment #37, and the amount of the platinum wherein existing is at least 0.75 % by weight.
Embodiment #39 is the method for embodiment #38, and wherein catalyst occupies reactor volume, and in gas phase with at least about 1000hr -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through 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 -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
Embodiment #41 is the method for embodiment #40, wherein control 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 transformed acetic acid be converted into ethanol: (ii) be less than 2% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate and ethene and composition thereof; (iii) as the pressure at 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 336 hours of vaporous of the acetic acid of 10: 1 and hydrogen, 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 -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
Embodiment #43 is the method for embodiment #42, wherein controls 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 transformed acetic acid be converted into ethanol; (ii) be less than 2% acetic acid and be converted into alkane; (iii) as the pressure at 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 168 hours of vaporous of the acetic acid of 10: 1 and hydrogen, catalyst activity reduction is less than 10%.
Embodiment #44 is the method for embodiment #43, and the method is carried out at the temperature of approximately 250 DEG C-300 DEG C, 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 approximately 5: 4-approximately 4: 5; (c) modified silicon-contained carrier comprises purity and is at least about 95% the silica at least about the calcium silicates modification of 2.5 % by weight-Yue 10 % by weight of using.
Embodiment #45 is by by the also method of original production ethanol of acetic acid, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, this hydrogenation catalyst is included in the platinum and the tin that on oxide-based carrier, disperse, the wherein amount to platinum and tin and oxidation state, and the ratio of platinum and tin, and oxide-based carrier is selected, is formed and control makes: (i) make at least 80% of transformed acetic acid be converted into ethanol; (ii) be less than 4% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof; And work as at the pressure of 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 500 hours of vaporous of the acetic acid of 10: 1 and hydrogen, this catalyst activity reduction is less than 10%.
Embodiment #46 is the method for embodiment #45, wherein hydrogenation catalyst is substantially by being dispersed in the platinum on oxide-based carrier and tin forms and this oxide-based carrier is 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) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) any precursor in (i)-(vi), and (i)-any mixture (vii).
Embodiment #47 is the method #46 of embodiment, and wherein 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 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 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 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 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 approximately 1: 2-approximately 2: 1.
Embodiment #66 is the method for embodiment #64, and wherein the mol ratio of tin and platinum is approximately 2: 3-approximately 3: 2.
Embodiment #67 is the method for embodiment #64, wherein tin and platinum weight ratio be approximately 5: 4-approximately 4: 5.
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 1%-approximately 10 % by weight.
Embodiment #71 is the method for embodiment #68, and wherein the mol ratio of tin and platinum is approximately 1: 2-approximately 2: 1.
Embodiment #72 is the method for embodiment #68, and wherein the mol ratio of tin and platinum is approximately 2: 3-approximately 3: 2.
Embodiment #73 is the method for embodiment #68, wherein tin and platinum weight ratio be approximately 5: 4-approximately 4: 5.
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 approximately 2: 3-approximately 3: 2.
Embodiment #76 is the method for embodiment #74, and wherein the mol ratio of tin and platinum is approximately 5: 4-approximately 4: 5.
Embodiment #77 is the method for embodiment #74, and wherein the mol ratio of tin and platinum is approximately 9: 10-approximately 10: 9.
Embodiment #78 is by by the also method of original production ethanol of acetic acid, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, this hydrogenation catalyst is made up of containing the platinum and the tin that disperse on silicon carrier the stabilisation in modification substantially, the stabilisation of described modification comprises use that purity is at least about 95 % by weight and is selected from the silica of following stabilizing agent-modifier modification containing silicon carrier: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) any precursor in (i)-(vi), and (i)-any mixture (vii), wherein control amount and the oxidation state of platinum and tin, the ratio of platinum and tin, stabilizing agent-modifier and silica make at least 80% of transformed acetic acid be converted into ethanol containing the stabilisation of the relative scale in silicon carrier and modification containing the purity of silica in silicon carrier in the stabilisation of modification, being less than 4% acetic acid is converted into except 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 modification is at least about 100m containing the surface area of silicon carrier 2/ g.
Embodiment #81 is the method for embodiment #80, and wherein the mol ratio of tin and platinum group metal is approximately 1: 2-approximately 2: 1.
Embodiment #82 is the method for embodiment #80, and wherein the mol ratio of tin and platinum is approximately 2: 3-approximately 3: 2.
Embodiment #83 is the method for embodiment #79, wherein tin and platinum weight ratio be approximately 5: 4-approximately 4: 5.
Embodiment #84 is the method for embodiment #78, and wherein the stabilisation of modification is at least about 150m containing the surface area of silicon carrier 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 comprises the calcium silicates at least about 1 % by weight-Yue 10 % by weight containing silicon carrier.
Embodiment #87 is the method for embodiment #84, and wherein the mol ratio of tin and platinum is approximately 1: 2-approximately 2: 1.
Embodiment #88 is the method for embodiment #84, and wherein the mol ratio of tin and platinum is approximately 2: 3-approximately 3: 2.
Embodiment #89 is the method for embodiment #84, wherein tin and platinum weight ratio be approximately 5: 4-approximately 4: 5.
Embodiment #90 is the method for embodiment #87, and wherein the stabilisation of modification is at least about 200m containing the surface area of silicon carrier 2/ g.
Embodiment #91 is the method for embodiment #90, and wherein the mol ratio of tin and platinum is approximately 9: 10-approximately 10: 9.
Embodiment #92 is the method for embodiment #90, and wherein the mol ratio of tin and platinum is approximately 2: 3-approximately 3: 2.
Embodiment #93 is the method for embodiment #90, and wherein the mol ratio of tin and platinum is approximately 5: 4-approximately 4: 5.
Embodiment #94 is the method for embodiment #90, and wherein the stabilisation of modification is at least about 250m containing the surface area of silicon carrier 2/ g.
Embodiment #95 is the method for embodiment #78, and the method is carried out at the temperature of approximately 250 DEG C-300 DEG C, and wherein the stabilisation of (a) modification is at least about 250m containing the surface area of silicon carrier 2/ g; (b) platinum is to be present in hydrogenation catalyst at least about the amount of 0.75 % by weight; (c) mol ratio of tin and platinum is approximately 5: 4-approximately 4: 5; (d) stabilisation of modification comprises the calcium silicates at least about 2.5 % by weight-Yue 10 % by weight containing silicon carrier.
Embodiment #96 is the method for embodiment #95, and the amount of the platinum wherein existing is at least 1 % by weight.
Embodiment #97 is the method for embodiment #78, and the method is carried out at the temperature of approximately 250 DEG C-300 DEG C, and wherein the stabilisation of (a) modification is at least about 100g/m containing the surface area of silicon carrier; (b) wherein the mol ratio of tin and platinum is approximately 2: 3-approximately 3: 2; (c) stabilisation of modification comprises the calcium silicates at least about 2.5 % by weight-Yue 10 % by weight containing silicon carrier.
Embodiment #98 is the method for embodiment #97, and the amount of the platinum wherein existing is at least 0.75 % by weight.
Embodiment #99 is the method for embodiment #98, and wherein catalyst occupies reactor volume, and in gas phase with at least about 1000hr -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through 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 -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
Embodiment #101 is the method for embodiment #100, wherein control amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and the stabilisation of modification make at least 90% of transformed acetic acid be converted into ethanol containing the composition of silicon carrier, be less than 2% acetic acid and be converted into the compound except being selected from the compound of 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 -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
Embodiment #103 is the method for embodiment #79, wherein control amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and the stabilisation of modification make containing the composition of silicon carrier: make at least 90% of transformed acetic acid be converted into ethanol, be less than 2% acetic acid and be converted into alkane.
Embodiment #104 is the method for embodiment #79, the method is carried out at the temperature of approximately 250 DEG C-300 DEG C, wherein (a) wherein controls amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and the stabilisation of modification make at least 90% of transformed acetic acid be converted into ethanol containing the acidity of silicon carrier, be less than 1% acetic acid and be converted into alkane; (b) stabilisation of modification is at least about 200m containing the surface area of silicon carrier 2/ g; (c) mol ratio of tin and platinum is approximately 5: 4-approximately 4: 5; (d) stabilisation of modification comprises the calcium silicates at least about 2.5 % by weight-Yue 10 % by weight containing silicon carrier.
Embodiment #105 is by by the also method of original production ethanol of acetic acid, the method is included in gas phase with the hydrogen at least about 4: 1 and acetic acid mol ratio and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst, and this hydrogenation catalyst is substantially by forming as follows: 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 about 0.1%-approximately 10 % by weight; With the optional promoter of disperseing on suitable carrier, wherein control amount and the oxidation state of catalytic metal, composition and the reaction condition of carrier and optional promoter make: (i) make at least 80% of transformed acetic acid be converted into ethanol; (ii) be less than 4% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene, diethyl ether and composition thereof; And work as at the pressure of 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 500 hours of vaporous of the acetic acid of 10: 1 and hydrogen, 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 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 the method by acetic acid hydrogenation being produced to ethanol, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, this hydrogenation catalyst is made up of the metal component disperseing on oxide-based carrier substantially, 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 to be present in its surperficial Bronsted acid position and carry out balance by calcium silicates; It is 1 that p and q are selected to make p: q: 20-1: 200, and wherein the selection of r meets chemical valence requirement, 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 makes 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 does not basically contain Bronsted acid position.
Embodiment #112 is by the method for acetic acid hydrogenation, the method is included in gas phase with the hydrogen at least about 4: 1 and acetic acid mol ratio and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst, and this hydrogenation catalyst is substantially by forming as follows: 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 about 0.1%-approximately 10 % by weight; With the optional promoter of disperseing on suitable carrier, wherein control amount and the oxidation state of catalytic metal, the composition of carrier and optional promoter and reaction condition make to be less than 4% acetic acid and are converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene, diethyl ether and composition thereof; And work as at the pressure of 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 500 hours of vaporous of the acetic acid of 10: 1 and hydrogen, 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 carbon carrier, and catalytic metal comprise platinum and tin or (iii) described carrier be the carbon carrier by reducible metal oxide modified.
Embodiment #113 is by the method for alkanoic acid hydrogenation, the method is included in the mol ratio with the hydrogen at least about 2: 1 and alkanoic acid in gas phase makes the gaseous stream that comprises hydrogen and alkanoic acid through hydrogenation catalyst at the temperature of approximately 125 DEG C-350 DEG C, and this hydrogenation catalyst comprises: be selected from silica that silica, calcium metasilicate and calcium metasilicate promote containing the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier; With the promoter that is selected from tin, rhenium and composition thereof, wherein optionally promote with promoter containing silicon carrier, 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 be 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 3acid modification agent.
Embodiment #114 is the method for embodiment #113, and wherein said alkanoic acid is acetic acid, and wherein at least one in (a) platinum and palladium exists with the amount of the 0.25%-5% of catalyst weight; (b) platinum existing and the total amount of palladium are catalyst weight at least 0.5%; And (c) rhenium that exists and the total amount of tin are 0.5-10 % by weight at least.
Embodiment #115 is the method for embodiment #114, is wherein at least about 150m containing the surface area of silicon carrier 2/ g.
Embodiment #116 is the method for embodiment #115, wherein controls amount and the oxidation state of (a) platinum group metal, rhenium and tin promoter, and (b) mol ratio of platinum group metal and the rhenium of existence and the total mole number of tin; And (c) make at least 80% of transformed acetic acid be converted into the compound that is selected from ethanol and ethyl acetate containing the number of the Bronsted acid position on silicon carrier, and make to be less than 4% acetic acid simultaneously and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof.
Embodiment #117 is the method for embodiment #115, and wherein at least one in (a) platinum and palladium exists with the amount of the 0.5%-5% of catalyst weight; (b) at least 0.75%-5% that the platinum existing and the total amount of palladium are catalyst weight; And (c) tin that exists and the total amount of rhenium are catalyst weight at least 1.0%.
Embodiment #118 is the method for embodiment #117, wherein (a) controls amount and the oxidation state of (i) platinum group metal, (ii) rhenium and tin promoter, and (iii) ratio of platinum group metal and rhenium and tin promoter; (iv) make at least 80% of transformed acetic acid be converted into ethanol containing the acidity of silicon carrier, be less than 4% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof.
Embodiment #119 is the method for embodiment #118, the approximately 1-10% that the rhenium wherein existing and the gross weight of tin are 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 approximately 1: 2-approximately 2: 1.
Embodiment #121 is by the method for acetic acid hydrogenation, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, described hydrogenation catalyst is made up of the metal component being dispersed on oxide-based carrier substantially, and described hydrogenation catalyst has following composition:
Pt vPd wRe xSn yCa pSi qO r，
The ratio of wherein v: y is 3: 2-2: 3; The ratio of w: x is 1: 3-1: 5, and it is 1 that p and q are selected to make p: q: 20-1: 200, wherein the selection of r meets chemical valence requirement, 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 acetic acid that transforms at least 90% be converted into the compound that is selected from ethanol and ethyl acetate, and be less than 4% acetic acid simultaneously and be converted into alkane.
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 acetic acid that transforms at least 90% be converted into ethanol, be less than 2% acetic acid and be 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 substantially.
Embodiment #125 is by the method for acetic acid hydrogenation, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, described hydrogenation catalyst is made up of the metal component being dispersed on oxide-based carrier substantially, 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 to be present in its surperficial Bronsted acid position and carry out balance by calcium silicates; It is 1 that p and q are selected to make p: q: 20-1: 200, and wherein the selection of r meets chemical valence requirement, 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 makes 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 does not basically contain Bronsted acid position.
Embodiment #128 is by the method for alkanoic acid hydrogenation, the method be included in gas phase mol ratio with the hydrogen at least about 5: 1 and alkanoic acid at the temperature of approximately 125 DEG C-350 DEG C with at least about 1000hr -1gHSV under the pressure of 2atm at least, make the gaseous stream that comprises hydrogen and alkanoic acid through hydrogenation catalyst, this hydrogenation catalyst comprises: (a) be selected from silica that silica, calcium metasilicate and calcium metasilicate promote containing the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier; (b) be selected from the metallic promoter agent of tin, rhenium and composition thereof, (c) optionally promote with the second promoter containing silicon carrier, described the 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) amount of the 1-50% of catalyst weight be selected from WO 3, MoO 3, Fe 2o 3and Cr 2o 3oxidation-reduction type promoter; (iii) what the 1-50% of catalyst weight measured is selected from TiO 2, ZrO 2, Nb 2o 5, Ta 2o 5and Al 2o 3acid modification agent; And (iv) combination of i, ii and iii.
Embodiment #129 is the method for embodiment #128, and wherein said alkanoic acid is acetic acid, and wherein (a) platinum (if existence) 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, is wherein at least about 150m containing the surface area of silicon carrier 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 (c) platinum that exists and the total amount of palladium are catalyst weight at least 1.25%.
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 approximately 1: 2-approximately 2: 1.
Embodiment #134 is the method for embodiment #132, and wherein the mol ratio of tin and platinum is approximately 5: 4-approximately 4: 5.
Embodiment #135 is the method for embodiment #132, wherein do not basically contain the Bronsted acid position of not offset by calcium metasilicate containing silicon carrier, 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 approximately 2: 3-approximately 3: 2.
Embodiment #137 is the method for embodiment #128, and wherein the mol ratio of tin and platinum is approximately 2: 3-approximately 3: 2.
Embodiment #138 is by the method for acetic acid hydrogenation, the method is included in gas phase with the hydrogen at least about 4: 1 and acetic acid mol ratio and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst, and this hydrogenation catalyst is substantially by forming as follows: 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 about 0.1%-approximately 10 % by weight; With the optional promoter of disperseing on suitable carrier, wherein control amount and the oxidation state of catalytic metal, the composition of carrier and optional promoter and reaction condition make to be less than 4% acetic acid and are converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene, diethyl ether and composition thereof; And work as at the pressure of 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 500 hours of vaporous of the acetic acid of 10: 1 and hydrogen, 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 to diethyl ether selectively higher than 80%.
Embodiment #141 is the method for embodiment #107, and wherein carrier is Zeolite support, and to diethyl ether selectively higher than 90%.
Embodiment #142 is by by the also method of original production ethanol and ethyl acetate of acetic acid, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, this hydrogenation catalyst comprises: (a) be selected from silica and the platinum group metal containing the mixture that is selected from platinum and platinum and palladium on silicon carrier with the silica that approximately 7.5 calcium metasilicates promote at the most, the amount of the platinum group metal existing is at least about 2.0%, the amount of the platinum existing is at least about 1.5%, (b) metallic promoter agent that is selected from rhenium and tin of the amount of the approximately 1%-2% of catalyst weight, the mol ratio of platinum and metallic promoter agent is approximately 3: 1-1: 2, (c) optionally promote with the second promoter containing silicon carrier, described the second promoter be selected from the 1-5% of (i) catalyst weight amount be selected from alkali metal, alkaline earth element and zinc to body promoter, (ii) amount of the 1-50% of catalyst weight be selected from WO 3, MoO 3, Fe 2o 3and Cr 2o 3oxidation-reduction type promoter, (iii) what the 1-50% of catalyst weight measured is selected from TiO 2, ZrO 2, Nb 2o 5, Ta 2o 5and Al 2o 3acid modification agent, and (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 approximately 2: 3-approximately 3: 2.
Embodiment #144 is the method for embodiment #142, and wherein the mol ratio of metallic promoter agent and platinum group metal is approximately 5: 4-approximately 4: 5.
Embodiment #145 is the method for embodiment #142, is wherein at least about 200m containing the surface area of silicon carrier 2/ g, and the amount of calcium metasilicate is enough to make the essentially no broensted acidity in surface containing silicon carrier.
Embodiment #146 is the method for embodiment #145, and wherein the mol ratio of metallic promoter agent and platinum group metal is approximately 2: 3-approximately 3: 2.
Embodiment #147 is the method for embodiment #146, is wherein at least about 200m containing the surface area of silicon carrier 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 Saint-Gobain NorPro SS61138 silica surface.
Embodiment #148 is the method for embodiment #142, is wherein at least about 250m containing the surface area of silicon carrier 2/ g, and the molal quantity that is present in its lip-deep Bronsted acid position is not more than the half of the molal quantity that is present in the Bronsted acid position on Saint-Gobain NorPro HSA SS61138 silica surface.
Embodiment #149 is the method for #142 embodiment, the method is carried out at the temperature of approximately 250 DEG C-300 DEG C, wherein (a) hydrogenation catalyst be included in be selected from silica and with approximately 7.5 calcium metasilicates promote at the most silica containing the palladium on silicon carrier, the amount of the palladium of existence is at least about 1.5%; (b) rhenium of the approximately 1%-10% that the metallic promoter agent amount of being is catalyst weight, the mol ratio of rhenium and palladium is approximately 3: 1-5: 1.
Embodiment #150 is the method for the acetic acid reduction of embodiment #142, wherein hydrogenation catalyst is made up of platinum substantially, its substantially by with approximately 3 until the silica that approximately 7.5% calcium silicates promotes form containing on silicon carrier, the amount of the platinum existing is at least about 1.0%, tin promoter is with the amount of the approximately 1%-5% of catalyst weight, and the mol ratio of platinum and tin is approximately 9: 10-10: 9.
Embodiment #151 is the method for the acetic acid reduction of embodiment #142, the amount of the platinum group metal wherein existing is at least about 2.0%, the amount of the platinum existing is at least about 1.5%, the amount of the approximately 1%-5% that tin promoter is catalyst weight, and the mol ratio of platinum and tin is approximately 9: 10-10: 9.
Embodiment #152 is the method for embodiment #151, and the method is carried out at the temperature of approximately 250 DEG C-300 DEG C, and wherein said hydrogenation catalyst comprises: be 200m at least at surface area 2the 2.5-3.5 % by weight platinum, the 2 % by weight-5 % by weight tin that on the high surface area silica of/g, disperse, described high surface area silica promotes with 4-7.5% calcium metasilicate.
Embodiment #153 be by by acetic acid also original production comprise ethanol and the method at least about the material stream of 40% ethyl acetate, the method is included in gas phase and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst with the hydrogen at least about 4: 1 and acetic acid mol ratio, described hydrogenation catalyst is made up of the metal component disperseing on oxide-based carrier substantially, 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 selection of r meets chemical valence requirement, 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 by the method for acetic acid hydrogenation, the method is included in gas phase with the hydrogen at least about 4: 1 and acetic acid mol ratio and at the temperature of approximately 225 DEG C-300 DEG C, makes the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst, and this hydrogenation catalyst is substantially by forming as follows: 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 about 0.1%-approximately 10 % by weight; With the optional promoter of disperseing on suitable carrier, wherein control amount and the oxidation state of catalytic metal, composition and the reaction condition of carrier and optional promoter make: i) make being greater than of transformed acetic acid 50% be converted into ethyl acetate; (ii) be less than 4% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene, diethyl ether and composition thereof; And work as at the pressure of 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 500 hours of vaporous of the acetic acid of 10: 1 and hydrogen, 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), being selected from silica and the platinum group metal that is selected from platinum, palladium and composition thereof on silicon carrier that contains with approximately 3.0 silica that promote up to approximately 7.5 calcium metasilicates, be at least about 150m containing the surface area of silicon carrier 2/ g; (b) tin promoter, is the amount of the approximately 1%-3% of catalyst weight, and the mol ratio of platinum and tin is approximately 4: 3-3: 4; (c) the Bronsted acid position of the described the Nomenclature Composition and Structure of Complexes containing silicon carrier being selected that its surface is not basically contained and not offset by calcium metasilicate.
Embodiment #157 is the hydrogenation catalyst of embodiment #156, and the gross weight of the platinum group metal wherein existing 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 existing is 3-7.5%.
Embodiment #158 is substantially by the particle hydrogenation catalyst forming as follows: be dispersed with above the platinum group metal that is selected from platinum, palladium and composition thereof be selected from tin, cobalt and rhenium promoter containing silicon carrier, should have at least about 175m containing silicon carrier 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 containing silicon carrier is owing to not basically contained Bronsted acid position by the aluminium oxide of calcium balance.
Embodiment #159 is the hydrogenation catalyst of embodiment #158, the gross weight of the platinum group metal wherein existing 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, the gross weight of the platinum group metal wherein existing 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, the gross weight of the platinum group metal wherein existing 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 % by weight platinum, the 3 % by weight-5 % by weight tin that on the high surface pyrolytic silicon dioxide of/g, disperse, the calcium metasilicate promotion of 4-6% for described high surface area silica, 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 % by weight palladium, 2 % by weight-7 % by weight rheniums, the weight ratio of rhenium and palladium is at least 1.5: 1.0, and wherein rhenium and palladium are all dispersed in containing on 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: (a) be selected from the stabilisation of modification containing the platinum that is selected from silicon carrier that contains of silicon carrier, 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) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) any precursor in (i)-(vi), and (i)-any mixture (vii), the stabilisation of described modification is at least about 150m containing the surface area of silicon carrier 2/ g, (b) with the tin promoter of the amount of the approximately 1%-3% of catalyst weight, the mol ratio of platinum and tin is approximately 4: 3-3: 4.
Embodiment #165 is the hydrogenation catalyst of embodiment #164, and the gross weight of the platinum group metal wherein existing 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 existing is 3-7.5%.
Embodiment #166 is the hydrogenation catalyst of embodiment #165, and wherein 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 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 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 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 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 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 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 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 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 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 substantially by the particle hydrogenation catalyst forming as follows: be dispersed with above the platinum group metal that is selected from platinum, palladium and composition thereof with the stabilisation of modification of promoter that is selected from tin, cobalt and rhenium containing silicon carrier, should comprise and there is at least 95% purity and at least about 175m containing silicon carrier 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) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) any precursor in (i)-(vi), and (i)-any mixture (vii), the described surface containing silicon carrier is owing to not basically contained Bronsted acid position by the aluminium oxide of stabilizing agent-modifier balance.
Embodiment #177 is the hydrogenation catalyst of embodiment #176, the gross weight of the platinum group metal wherein existing 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 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 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 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 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 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 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 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 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 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 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, the gross weight of the platinum group metal wherein existing 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 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 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 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 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 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, the gross weight of the platinum group metal wherein existing 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 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 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 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 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 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 % by weight platinum, the 3 % by weight-5 % by weight tin that on the high surface pyrolytic silicon dioxide of/g, disperse, the calcium metasilicate promotion of 4-6% for described high surface area silica, 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 % by weight palladium, 2 % by weight-7 % by weight rheniums, the weight ratio of rhenium and palladium is at least 1.5: 1.0, and wherein said rhenium and palladium are all dispersed in containing on silicon carrier, and the described silicon carrier that contains comprises at least 80% calcium metasilicate.
Embodiment #202 a kind ofly introduces and is selected from Fe with the amount of approximately 0.1 % by weight-Yue 10 % by weight on the oxide-based carrier of stabilizing modification, Co, Ni, Ru, Rh, Pd, Ir, Pt, Os, Ti, Zn, Cr, the hydrogenation catalyst of the catalytic metal of Mo and W, described oxide-based carrier is introduced alkaline-earth metal with enough amounts, alkali metal, zinc, scandium, the oxide of yttrium and metasilicate form, the precursor forms of these oxides and metasilicate, and the non-volatile stabilizing agent-modifier of the alkalescence of their form of mixtures, thereby offset the upper acid position existing, its surface, give anti-alteration of form at the temperature that meets with acetic acid hydrogenation (alteration of form especially mainly changes owing to sintering, grain growth, crystal boundary migration, defect 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 the number of every square metre of existing acid position on oxide-based carrier surface to be reduced to the number that is at least about upper every square metre of acid position of finding, pyrolytic silicon dioxide surface of 99.7 % by weight lower than purity.
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 the number of every square metre of existing acid position on oxide-based carrier surface to be reduced to the number that is at least about upper every square metre of acid position of finding, Saint-Gobain NorPro HSA SS 61138 surfaces of 99.7 % by weight lower than purity.
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 the number of every square metre of existing acid position on oxide-based carrier surface to be reduced to the half that is at least about the upper every square metre of sour bits number found in pyrolytic silicon dioxide surface of 99.7 % by weight lower than purity.
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 the number of every square metre of existing acid position on oxide-based carrier surface to be reduced to the half that is at least about the Saint-Gobain NorPro HSA SS 61138 upper every square metre of sour bits number found in surface of 99.7 % by weight lower than purity.
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 the number of every square metre of existing acid position on oxide-based carrier surface be reduced to lower than purity be at least about 99.7 % by weight the upper every square metre of sour bits number 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 the number of every square metre of existing acid position on oxide-based carrier surface be reduced to lower than purity be at least about 99.7 % by weight the Saint-Gobain NorPro HSA SS 61138 upper every square metre of sour bits number found in surface 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 the number of every square metre of existing acid position on oxide-based carrier surface be reduced to lower than purity be at least about 99.7 % by weight the upper every square metre of sour bits number 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 the number of every square metre of existing acid position on oxide-based carrier surface be reduced to lower than purity be at least about 99.7 % by weight the Saint-Gobain NorPro HSA SS 61138 upper every square metre of sour bits number found in surface 10%.
In the description of aforementioned each embodiment, as those skilled in the art can recognize, the embodiment of quoting another embodiment can suitably combine with other embodiment.

Claims (88)

1. one kind is passed through the also method of original production ethanol of acetic acid, the method is included in gas phase so that at least hydrogen and the acetic acid mol ratio of 4:1 make the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst at the temperature of 225 DEG C-300 DEG C, this hydrogenation catalyst is included in the platinum and the tin that on modified silicon-contained carrier, disperse, wherein platinum exists with tin and exists with the amount of 0.5-10% with the amount of the 0.5%-5% of catalyst weight, 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) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) precursor of (i)-(vi), and (i)-mixture (vii), the wherein amount to platinum and tin and oxidation state, and the ratio of platinum and tin, and select, form and control makes containing silicon carrier: (i) make at least 80% of transformed acetic acid be converted into ethanol, (ii) be less than 4% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof, and work as at the pressure of 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 168 hours of the acetic acid of 10:1 and the vaporous of hydrogen, this catalyst activity reduction is less than 10%.
2. the process of claim 1 wherein that described support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid mixture of sodium, potassium, magnesium, calcium and zinc.
3. the method for claim 2, wherein the mol ratio of platinum and tin is 4:5-5:4.
4. the process of claim 1 wherein that described support modification agent is selected from metasilicate and their precursor and the aforesaid mixture of sodium, potassium, magnesium, calcium and zinc.
5. the method for claim 4, wherein the mol ratio of platinum and tin is 4:5-5:4.
6. the process of claim 1 wherein that described support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid mixture of magnesium, calcium and zinc.
7. the method for claim 6, wherein the mol ratio of platinum and tin is 4:5-5:4.
8. the process of claim 1 wherein that described support modification agent is selected from metasilicate and their precursor and the aforesaid mixture of magnesium, calcium and zinc.
9. the method for claim 8, wherein the mol ratio of platinum and tin is 4:5-5:4.
10. the process of claim 1 wherein that described support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
The method of 11. claims 10, wherein the mol ratio of platinum and tin is 4:5-5:4.
12. the process of claim 1 wherein that the surface area of described carrier is 100m at least 2/ g.
The method of 13. claims 12, wherein the mol ratio of tin and platinum is 1:2-2:1.
The method of 14. claims 12, wherein the mol ratio of tin and platinum is 2:3-3:2.
The method of 15. claims 12, wherein the weight ratio of tin and platinum is 5:4-4:5.
16. the process of claim 1 wherein that the surface area of described carrier is 150m at least 2/ g.
The method of 17. claims 16, 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%.
The method of 18. claims 16, the calcium silicates that wherein said carrier comprises 1%-10 % by weight.
The method of 19. claims 16, wherein the mol ratio of tin and platinum is 1:2-2:1.
The method of 20. claims 16, wherein the mol ratio of tin and platinum is 2:3-3:2.
The method of 21. claims 16, wherein the weight ratio of tin and platinum is 5:4-4:5.
22. the process of claim 1 wherein that the surface area of described carrier is 200m at least 2/ g.
The method of 23. claims 22, wherein the mol ratio of tin and platinum is 2:3-3:2.
The method of 24. claims 22, wherein the mol ratio of tin and platinum is 5:4-4:5.
The method of 25. claims 22, wherein the mol ratio of tin and platinum is 9:10-10:9.
The method of 26. claims 25, the surface area of wherein said modified silicon-contained carrier is 250m at least 2/ g.
The method of 27. claims 1, the method is carried out at the temperature of 250 DEG C-300 DEG C, wherein:
A. the surface area of described modified silicon-contained carrier is 250m at least 2/ g;
B. platinum is present in described hydrogenation catalyst with the amount of 0.75 % by weight-5 % by weight;
C. the mol ratio of tin and platinum is 5:4-4:5; And
D. described modified silicon-contained carrier comprises the silica that purity is the calcium metasilicate modification of at least 95% use 2.5 % by weight-10 % by weight.
The method of 28. claims 27, the amount of the platinum wherein existing is 1 % by weight-5 % by weight.
The method of 29. claims 1, the method is carried out at the temperature of 250 DEG C-300 DEG C, wherein:
A. the surface area of described modified silicon-contained carrier is 100m at least 2/ g;
B. wherein the mol ratio of tin and platinum is 2:3-3:2; And
C. described modified silicon-contained carrier comprises the silica that purity is the calcium metasilicate modification of at least 95% use 2.5 % by weight-10 % by weight.
The method of 30. claims 29, the amount of the platinum wherein existing is 0.75 % by weight-5 % by weight.
The method of 31. claims 30, wherein said catalyst occupies reactor volume, and in gas phase with 1000hr at least -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
The method of 32. claims 30, wherein said catalyst occupies reactor volume, and in gas phase with 2500hr at least -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
33. 1 kinds are passed through the also method of original production ethanol of acetic acid, the method is included in gas phase so that at least hydrogen and the acetic acid mol ratio of 4:1 make the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst at the temperature of 225 DEG C-300 DEG C, this hydrogenation catalyst is included in the platinum and the tin that on modified silicon-contained carrier, disperse, wherein platinum exists with tin and exists with the amount of 0.5-10% with the amount of the 0.5%-5% of catalyst weight, 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) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) precursor of (i)-(vi), and (i)-mixture (vii), wherein control 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 transformed acetic acid be converted into ethanol, (ii) be less than 2% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate and ethene and composition thereof, and (iii) as the pressure at 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 336 hours of the acetic acid of 10:1 and the vaporous of hydrogen, this catalyst activity reduction is less than 10%.
The method of 34. claims 30, wherein said catalyst occupies reactor volume, and in gas phase with 5000hr at least -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
The method of 35. claims 34, wherein controls 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 transformed acetic acid be converted into ethanol; (ii) be less than 2% acetic acid and be converted into alkane; (iii) as the pressure at 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 168 hours of the acetic acid of 10:1 and the vaporous of hydrogen, this catalyst activity reduction is less than 10%.
36. 1 kinds are passed through the also method of original production ethanol of acetic acid, the method is included in gas phase so that at least hydrogen and the acetic acid mol ratio of 4:1 make the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst at the temperature of 250 DEG C-300 DEG C, this hydrogenation catalyst is included in the platinum and the tin that on modified silicon-contained carrier, disperse, wherein platinum exists with tin and exists with the amount of 0.5-10% with the amount of 0.75 % by weight-5 % by weight of catalyst weight, the mol ratio of tin and platinum is 5:4-4:5, and the surface area of wherein said modified silicon-contained carrier is 200m at least 2/ g, it is at least 95% silica that described modified silicon-contained carrier comprises purity, the calcium silicates that modifier comprises 2.5 % by weight-10 % by weight; Wherein control 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 transformed acetic acid be converted into ethanol; (ii) be less than 2% acetic acid and be converted into alkane; (iii) as the pressure at 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 168 hours of the acetic acid of 10:1 and the vaporous of hydrogen, this catalyst activity reduction is less than 10%,
Wherein said catalyst occupies reactor volume, and in gas phase with 5000hr at least -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
37. 1 kinds are passed through the also method of original production ethanol of acetic acid, the method is included in gas phase so that at least hydrogen and the acetic acid mol ratio of 4:1 make the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst at the temperature of 225 DEG C-300 DEG C, this hydrogenation catalyst is included in the platinum and the tin that on modified oxide class carrier, disperse, wherein platinum exists with tin and exists with the amount of 0.5-10% with the amount of the 0.5%-5% of catalyst weight, 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) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) precursor of (i)-(vi), and (i)-mixture (vii), the wherein amount to platinum and tin and oxidation state, and the ratio of platinum and tin, and oxide-based carrier is selected, is formed and control makes: (i) make at least 80% of transformed acetic acid be converted into ethanol, (ii) be less than 4% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate, ethene and composition thereof, and work as at the pressure of 2atm, temperature and the 2500hr of 275 DEG C -1gHSV under when being exposed to mol ratio and being the mixture time period of 500 hours of the acetic acid of 10:1 and the vaporous of hydrogen, this catalyst activity reduction is less than 10%.
The method of 38. claims 37, 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.
The method of 39. claims 38, wherein the mol ratio of platinum and tin is 4:5-5:4.
37 methods of 40. claims, wherein said support modification agent is selected from metasilicate and their precursor and the aforesaid mixture of sodium, potassium, magnesium, calcium and zinc.
The method of 41. claims 40, wherein the mol ratio of platinum and tin is 4:5-5:4.
The method of 42. claims 37, wherein said support modification agent is selected from oxide and metasilicate and their precursor and the aforesaid mixture of magnesium, calcium and zinc.
The method of 43. claims 42, wherein the mol ratio of platinum and tin is 4:5-5:4.
The method of 44. claims 37, wherein said support modification agent is selected from metasilicate and their precursor and the aforesaid mixture of magnesium, calcium and zinc.
The method of 45. claims 44, wherein the mol ratio of platinum and tin is 4:5-5:4.
The method of 46. claims 37, wherein support modification agent is selected from the precursor of calcium metasilicate, calcium metasilicate and the mixture of calcium metasilicate and its precursor.
The method of 47. claims 46, wherein the mol ratio of platinum and tin is 4:5-5:4.
The method of 48. claims 37, wherein the mol ratio of platinum and tin is 4:5-5:4.
The method of 49. claims 37, wherein said carrier surface area is 100m at least 2/ g.
The method of 50. claims 49, wherein the mol ratio of tin and platinum is 1:2-2:1.
The method of 51. claims 49, wherein the mol ratio of tin and platinum is 2:3-3:2.
The method of 52. claims 49, wherein the weight ratio of tin and platinum is 5:4-4:5.
The method of 53. claims 37, wherein carrier surface area is 150m at least 2/ g.
The method of 54. claims 53, wherein:
A. platinum exists with the amount of the 0.5%-5% of catalyst weight; And
B. tin exists with the amount of 0.5-5%.
The method of 55. claims 53, the calcium silicates that wherein carrier comprises 1%-10 % by weight.
The method of 56. claims 53, wherein the mol ratio of tin and platinum is 1:2-2:1.
The method of 57. claims 53, wherein the mol ratio of tin and platinum is 2:3-3:2.
The method of 58. claims 53, wherein the weight ratio of tin and platinum is 5:4-4:5.
The method of 59. claims 37, wherein carrier surface area is 200m at least 2/ g.
The method of 60. claims 59, wherein the mol ratio of tin and platinum is 2:3-3:2.
The method of 61. claims 59, wherein the mol ratio of tin and platinum is 5:4-4:5.
The method of 62. claims 59, wherein the mol ratio of tin and platinum is 9:10-10:9.
63. 1 kinds are passed through the also method of original production ethanol of acetic acid, the method is included in gas phase so that at least hydrogen and the acetic acid mol ratio of 4:1 make the gaseous stream that comprises hydrogen and acetic acid through hydrogenation catalyst at the temperature of 225 DEG C-300 DEG C, this hydrogenation catalyst is made up of containing the platinum and the tin that disperse on silicon carrier the stabilisation in modification substantially, wherein platinum exists with tin and exists with the amount of 0.5-10% with the amount of the 0.5%-5% of catalyst weight, it is the silica that the use of at least 95 % by weight is selected from following stabilizing agent-modifier modification that the stabilisation of described modification comprises purity containing silicon carrier: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkali earth metasilicate, (iv) alkali metal silicate, (v) zinc oxide, (vi) zinc metasilicate and (vii) precursor of (i)-(vi), and (i)-mixture (vii), wherein control amount and the oxidation state of platinum and tin, the ratio of platinum and tin, stabilizing agent-modifier and silica make at least 80% of transformed acetic acid be converted into ethanol containing the stabilisation of the relative scale in silicon carrier and modification containing the purity of silica in silicon carrier in the stabilisation of modification, being less than 4% acetic acid is converted into except being selected from ethanol, acetaldehyde, ethyl acetate, compound beyond the compound of ethene and composition thereof.
The method of 64. claims 63, the stabilisation of wherein said modification is 100m at least containing the surface area of silicon carrier 2/ g.
The method of 65. claims 64, wherein the mol ratio of tin and platinum is 1:2-2:1.
The method of 66. claims 64, wherein the mol ratio of tin and platinum is 2:3-3:2.
The method of 67. claims 63, wherein the weight ratio of tin and platinum is 5:4-4:5.
The method of 68. claims 63, the stabilisation of wherein said modification is 150m at least containing the surface area of silicon carrier 2/ g.
The method of 69. claims 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%.
The method of 70. claims 68, the calcium silicates that the stabilisation of wherein said modification comprises 1 % by weight-10 % by weight containing silicon carrier.
The method of 71. claims 68, wherein the mol ratio of tin and platinum is 1:2-2:1.
The method of 72. claims 68, wherein the mol ratio of tin and platinum is 2:3-3:2.
The method of 73. claims 68, wherein the weight ratio of tin and platinum is 5:4-4:5.
The method of 74. claims 71, the stabilisation of wherein said modification is 200m at least containing the surface area of silicon carrier 2/ g.
The method of 75. claims 74, wherein the mol ratio of tin and platinum is 9:10-10:9.
The method of 76. claims 74, wherein the mol ratio of tin and platinum is 2:3-3:2.
The method of 77. claims 74, wherein the mol ratio of tin and platinum is 5:4-4:5.
The method of 78. claims 74, the stabilisation of wherein said modification is 250m at least containing the surface area of silicon carrier 2/ g.
The method of 79. claims 63, the method is carried out at the temperature of 250 DEG C-300 DEG C, wherein:
A. the stabilisation of described modification is 250m at least containing the surface area of silicon carrier 2/ g;
B. platinum is present in described hydrogenation catalyst with the amount of 0.75 % by weight-5 % by weight;
C. the mol ratio of tin and platinum is 5:4-4:5; And
D. the calcium silicates that the stabilisation of modification comprises 2.5 % by weight-10 % by weight containing silicon carrier.
The method of 80. claims 79, the amount of the platinum wherein existing is 1 % by weight-5 % by weight.
The method of 81. claims 63, the method is carried out at the temperature of 250 DEG C-300 DEG C, wherein:
A. the stabilisation of described modification is 100m at least containing the surface area of silicon carrier 2/ g;
B. wherein the mol ratio of tin and platinum is 2:3-3:2; And
C. the calcium silicates that the stabilisation of described modification comprises 2.5 % by weight-10 % by weight containing silicon carrier.
The method of 82. claims 81, the amount of the platinum wherein existing is 0.75 % by weight-5 % by weight.
The method of 83. claims 82, wherein said catalyst occupies reactor volume, and in gas phase with 1000hr at least -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
The method of 84. claims 82, wherein said catalyst occupies reactor volume, and in gas phase with 2500hr at least -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
The method of 85. claims 84, wherein control amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and the stabilisation of modification make containing the composition of silicon carrier: make at least 90% of transformed acetic acid be converted into ethanol, be less than 2% acetic acid and be converted into the compound except being selected from the compound of ethanol, acetaldehyde, ethyl acetate and ethene and composition thereof.
The method of 86. claims 82, wherein said catalyst occupies reactor volume, and in gas phase with 5000hr at least -1the air speed gaseous stream that makes to comprise hydrogen and acetic acid through described reactor volume.
The method of 87. claims 63, wherein controls amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and the stabilisation of described modification make containing the composition of silicon carrier: make at least 90% of transformed acetic acid be converted into ethanol, be less than 2% acetic acid and be converted into alkane.
The method of 88. claims 63, the method is carried out at the temperature of 250 DEG C-300 DEG C, wherein:
A. wherein control amount and the oxidation state of platinum and tin, and the ratio of platinum and tin and the stabilisation of described modification make containing the acidity of silicon carrier: make at least 90% of transformed acetic acid be converted into ethanol, be less than 1% acetic acid and be converted into alkane;
B. the stabilisation of described modification is 200m at least containing the surface area of silicon carrier 2/ g;
C. the mol ratio of tin and platinum is 5:4-4:5;
D. the calcium silicates that the stabilisation of described modification comprises 2.5 % by weight-10 % by weight containing silicon 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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