JP2013508423A - Catalyst for producing ethanol by hydrogenation of acetic acid comprising platinum-tin on a siliceous support - Google Patents

Abstract

A method for selectively forming ethanol from acetic acid comprises contacting a feed stream comprising acetic acid and hydrogen with a catalyst comprising platinum and tin on high surface area silica promoted by calcium metasilicate at elevated temperature. Including. At 280 ° C., selectivity to ethanol of greater than 85% is achieved with a catalyst life of several hundred hours.
[Selection] Figure 1

Description

This application claims priority to US application 12 / 588,727 filed Oct. 26, 2009, which is hereby incorporated by reference in its entirety.
The present invention generally relates to a tunable catalyst for hydrogenating carboxylic acids, in particular acetic acid, and ethanol to ethyl acetate and acetaldehyde using variations of each catalyst to adapt to changing commercial conditions. It relates to a flexible method of acetic acid dehydrogenation, which can be varied in proportion. More specifically, the present invention relates to catalysts for the gas phase hydrogenation of carboxylic acids, particularly acetic acid, to produce various products such as the corresponding alcohols, esters, and aldehydes, particularly ethanol. The catalyst exhibits excellent activity and selectivity over a range of products.

  Acetic acid can be used in ethanol (which can be used by itself or converted to vinyl acetate and / or ethyl acetate or a wide range of other chemical products, which is an important commercial feed, ethylene. There has long been a need for an economically viable process for conversion to (which can then be converted). For example, ethylene can be converted to a number of polymer and monomer products. Fluctuating natural gas and crude oil prices contribute to fluctuations in the cost of conventionally produced oil or ethylene from natural gas, and the need for another source of ethylene when the price of oil is rising Is even larger.

  Catalytic processes for reducing alkanoic acids and other carbonyl group-containing compounds have been extensively studied, and various combinations of catalysts, supports, and operating conditions are mentioned in the literature. The reduction of various carboxylic acids on metal oxides is reviewed by T. Yokoyama et al., “Fine chemicals through heterogeneous catalysis. Carboxylic acids and derivatives”. Chapter 8.3.1 summarizes some of the development efforts for hydrogenation catalysts for various carboxylic acids (Yokoyama, T .; Setoyama, T., "Carboxylic acids and derivatives": "Fine chemicals through heterogeneous catalysis, 2001, 370-379).

A series of studies by MA Vannice et al. Relates to the conversion of acetic acid over various heterogeneous catalysts (Rachmady, W .; Vannice, MA; J. Catal. 2002, 207, 317-330).
Gas phase reduction of acetic acid with H ₂ on both supported and unsupported iron was reported in another study (Rachmady, W .; Vannice, MA, J. Catal., 2002, 208, 158-169). .

More information on catalyst surface species and organic intermediates is given in Rachmady, W .; Vannice, MA, J. Catal. 2002, 208, 170-179.
Gas phase hydrogenation is described in Rachmady, W .; Vannice, MA, J. Catal. 2002, 209, 87-98 and Rachmady, W .; Vannice, MA, J. Catal. 2000, 192, 322-334. Furthermore, a group of supported Pt-Fe catalysts were studied.

  Various related publications on the selective hydrogenation of unsaturated aldehydes are (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, EL; Bueno, JMC, 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, DY; Touroude, R., J. Catal. 1999, 188, 165-175; Nitta, Y .; Ueno, K .; Imanaka, T .; Applied Catal. 1989, 56, 9- 22).

  Studies reporting activity and selectivity for cobalt, platinum, and tin containing catalysts in the selective hydrogenation of crotonaldehyde to unsaturated alcohols have been reported by R. Touroude et al. (Djerboua, F .; 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 K. Lazar et al. (Lazar, K. Rhodes, WD; Borbath, I .; Hegedues, M .; Margitfalvi, 1.L., Hyperfine Interactions, 2002, 1391140, 87-96).

  In M. Santiago et al. (Santiago, MAN; Sanchez-Castillo, MA; Cortright, RD; Dumesic, 1.A., J. Catal. 2000, 193, 16-28), microcaloric combined with quantum chemical calculations Measurement, infrared spectroscopy, and reaction rate measurement are discussed.

  Catalytic activity in acetic acid hydrogenation has also been reported for heterogeneous systems with rhenium and ruthenium (Ryashentseva, MA; Minachev, KM; Buiychev, BM; Ishchenko, VM, Bull. Acad. Sci. USSR1988, 2436-2439 ).

  Kitson et al., US Pat. No. 5,149,680, describes a process for catalytic hydrogenation of carboxylic acids and their anhydrides to alcohols and / or esters using a platinum group metal alloy catalyst. Kitson et al., U.S. Pat. No. 4,777,303, describes a process for producing alcohols by hydrogenation of carboxylic acids. Kitson et al., U.S. Pat. No. 4,804,791, describes another method for producing alcohols by hydrogenation of carboxylic acids. See also USP-5,061,671; USP-4,990,655; USP-4,985,572; and USP-4,826,795.

In Malinowski et al. (Bull. Soc. Chim. Belg. (1985), 94 (2), 93-5), it is made heterogeneous on a support material such as silica (SiO ₂ ) or titania (TiO ₂ ). The catalytic reaction of acetic acid on low-valent titanium is discussed.

  The bimetallic ruthenium-tin / silica catalyst is produced by reacting tetrabutyltin with ruthenium dioxide supported on silica (Loessard et al., Studies in Surface Science and Catalysis (1989), 1988, 48). (Struct. React. Surf.), 591-600).

  Catalytic reduction of acetic acid has also been studied, for example in Hinderman et al. (Hindermann et al., J. Chem. Res., Synopses (1980), (11), 373), where acetic acid on iron and alkali promoted iron is studied. The catalytic reduction of is disclosed.

US Patent 5,149,680 US Pat. No. 4,777,303 US Patent 4,804,791 USP-5,061,671 USP-4,990,655 USP-4,985,572 USP-4,826,795

Yokoyama, T; Setoyama, T, "Carboxylic acids and derivatives" of "Fine chemicals through heterogeneous catalysis", 2001, 370-379 Rachmady W .; Vannice, M.A .; J. Catal. 2002, 207, 317-330 Rachmady, W .; Vannice, M.A., J. Catal., 2002, 208, 158-169 Rachmady, W .; Vannice, M.A., J. Catal. 2002, 208, 170-179 Rachmady, W .; Vannice, M.A., J. Catal. 2002, 209, 87-98 Rachmady, W .; Vannice, M.A., J. Catal. 2000, 192, 322-334 Djerboua, F .; Benachour, D .; Touroude, R., Applied Catalysis A: General 2005, 282, 123-133 Liberkova, K .; Touroude, R., J. Mol. Catal. 2002, 180, 221-230 Rodrigues, E.L .; Burno, 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 Djerboua, F .; Benachour, D .; Touroude, R., Applied Catalysis A: General 2005, 282, 123-133 Liberkova, K .; Touroude, R .; J. Mol. Catal. 2002, 180, 221-230 Lazar, K .; Rhodes, W.D .; Borbath, I .; Hegedues, M .; Margitfalvi, 1.L., Hyperfine Interactions, 2002, 1391140, 87-96 Santiago, M.A.N .; Sanchez-Castillo, M.A .; Cortright, R.D .; Dumesic, 1.A., J. Catal. 2000, 193, 16-28 Ryashentseva, M.A .; Minachev, K.M .; Buiychev, B.M .; Ishchenko, V.M., Bull. Acad. Sci. USSR1988, 2436-2439 Malinowski et al., Bull. Soc. Chim. Belg. (1985), 94 (2), 93-5 Loessard et al., Studies in Surface Science and Catalysis (1989), 1988, 48 (Struct. React.Surf.), 591-600 Hindermann et al., J. Chem. Res., Synopses (1980), (11), 373

  Existing processes are (i) catalysts that do not have the required selectivity to ethanol; (ii) are sometimes prohibitively expensive and / or non-selective for the formation of ethanol and are undesirable side effects. There are various problems that hinder commercial viability, such as catalysts that produce products; (iii) excessive operating temperatures and pressures; and / or (iv) insufficient catalyst life.

  We have a gaseous stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 between about 125 ° C and 350 ° C, more preferably between about 225 ° C and 300 ° C. Acetic acid is passed through the catalyst at a temperature between about 250 ° C. and 300 ° C., more preferably between (i) an alkaline earth oxide, (ii) an alkali metal oxide, and (iii) an alkaline earth Metasilicates, (iv) alkali metal metasilicates, (v) zinc oxide, (vi) zinc metasilicates, and (vii) precursors for any of (i)-(vi), and (i)-(vii) The amount and oxidation of platinum and tin when reduced over a platinum-tin catalyst dispersed on a modified stabilized siliceous support comprising an effective amount of a support modifier selected from the group consisting of any of State, line It found that it is possible to obtain a high selectivity ratio between platinum and tin, as well as the controls to describe the denaturation stabilized siliceous support here in the conversion to ethanol. In one form of the invention, we neutralize the effect of Bronsted acid sites present on the surface of the siliceous carrier with a carrier modifier selected as described above. In other forms, the carrier modifiers described above are catalytically active and selective in the presence of flowing acetic acid vapor at 275 ° C. for a period of up to 168 hours, 336 hours, or even 500 hours. It is effective in suppressing excessive loss. In another form of the invention, the carrier modifier suppresses the production of ethyl acetate with low selectivity to the conversion of acetic acid to highly undesirable by-products such as alkanes if desired. It is effective to give high selectivity to ethanol production. Preferably, the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures of any of the above.

We have a gaseous stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 between about 125 ° C and 350 ° C, more preferably between about 225 ° C and 300 ° C. And even more preferably, by passing acetic acid over the catalyst at a temperature between about 250 ° C. and 300 ° C. over a platinum-tin catalyst dispersed on a substantially basic calcium metasilicate / silica support. High selectivity in the conversion to ethanol by controlling the amount and oxidation state of platinum and tin, as well as the ratio of platinum to tin, and the acidity of the calcium metasilicate / silica support as described herein Found that you can get. In particular, using the preferred catalyst and method of the present invention, at least 80% of the converted acetic acid is converted to ethanol and less than 4% of the acetic acid is from the group consisting of ethanol, acetaldehyde, ethyl acetate, ethylene, and mixtures thereof. Convert to a compound other than the selected compound. In a preferred method, platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; while tin is present in an amount of at least 0.5-10% by weight of the catalyst; preferably the surface area of the support. Is at least about 100 m ² / g, more preferably about 150 m ² / g, even more preferably at least about 200 m ² / g, most preferably at least about 250 m ² / g; the molar ratio of tin to platinum group metal Is preferably about 1: 2 to about 2: 1, more preferably about 2: 3 to about 3: 2, even more preferably about 5: 4 to about 4: 5, and most preferably about 9:10 to about 10: 9. In many cases, the support comprises an amount of calcium silicate effective to neutralize Bronsted acid sites arising from residual alumina in the silica; typically from about 1% to about 10% by weight. Calcium silicate is sufficient to ensure that the carrier is substantially neutral or basic. In one particularly preferred embodiment, the platinum is present in the hydrogenation catalyst in an amount of at least about 0.75 wt%, more preferably 1 wt%; the molar ratio of tin to platinum is from about 5: 4 to about 4: 5; the carrier comprises at least about 2.5 wt% to 10 wt% calcium silicate.

One feature of many embodiments of the present invention is about ^{1000hr -1, 2500hr} -1, more can be used 5000 hr ^-1 larger space velocity of at least 90% of the converted acetic acid is converted to ethanol, acetic acid Less than 2% is to convert to a compound other than a compound selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, and ethylene, and mixtures thereof. In many embodiments of the invention, alkane formation is low, typically less than 2%, often less than 1%, and often less than 0.5% of the acetic acid passed over the catalyst is fuel or syngas. The alkane is converted to an alkane having little value other than that.

In another aspect of the invention, a gaseous stream comprising vapor phase hydrogen and alkanoic acid in a molar ratio of at least about 2: 1 hydrogen to alkanoic acid at a temperature between about 125 ° C. and 350 ° C., silica, Platinum group metals selected from the group consisting of platinum, palladium, and mixtures thereof selected from the group consisting of calcium metasilicate and calcium metasilicate promoted silica, and tin, rhenium, and these The alkanoic acid is hydrogenated by passing over a hydrogenation catalyst comprising a promoter selected from the group consisting of a mixture, wherein the siliceous support is optionally an alkali metal in an amount of 1-5% by weight of the catalyst. , accelerator selected alkaline earth elements, and from the group consisting of zinc; _WO 3 of 1 to 50% by weight of the amount of _catalyst, MoO _{3, Fe} 2 _O 3 and, redox promoter is selected from the group consisting of r ₂ O _3; and, from 1 to 50% by weight of the catalyst _{TiO 2, ZrO 2, Nb 2} O 5, Ta 2 O 5, and _Al 2 _{O 3} An acid modifier selected from the group consisting of; an acid selected from the group consisting of; an acidity of the carrier is less than 4%, preferably less than 2%, most preferably about 1% of the alkanoic acid Control that less than is converted to alkanes. In many cases, at least one of platinum and palladium is present in an amount of 0.25% to 5% of the weight of the catalyst; the total amount of platinum and palladium present is at least 0.5% by weight of the catalyst; The total amount of rhenium and tin present is at least 0.5 to 10% by weight. In this process, using a catalyst comprising platinum and tin on a basic silica support, the amount and oxidation state of the platinum group metal, rhenium and tin promoter, and the total moles of rhenium and tin present with the platinum group metal and And the acidity of the siliceous support is converted to a compound wherein at least 80% of the converted acetic acid is selected from the group consisting of alkanol and alkyl acetate, while less than 4% of the alkanoic acid corresponds to the corresponding alkanol And control to convert to a compound other than a compound selected from the group consisting of alkyl acetate, and mixtures thereof. Preferably, at least one of platinum and palladium is present in an amount of 0.5% to 5% of the weight of the catalyst; the total amount of platinum and palladium present is at least 0.75% to 5% of the weight of the catalyst . Preferably, the alkanoic acid is acetic acid and the total amount of tin and rhenium present is at least 1.0% by weight of the catalyst, while the amount and oxidation state of the platinum group metal, rhenium and tin promoter, and the platinum group The ratio of metal to rhenium and tin promoter; and the siliceous support acidity to convert at least 80% of the converted acetic acid to ethanol or ethyl acetate and less than 4% of acetic acid to ethanol, acetaldehyde, ethyl acetate, Control is made to convert to a compound other than the compound selected from the group consisting of ethylene and mixtures thereof. Preferably, the total weight of rhenium and tin present is about 1-10% by weight of the catalyst, while the molar ratio of platinum group metal to the total moles of rhenium and tin is about 1: 2 to about 2: 1.

In another aspect, the present invention provides a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 at a temperature between about 225 ° C. and 300 ° C. Consists essentially of a metal component dispersed on the composition:
_{Pt v Pd w Re x Sn y} Ca p Si q O r
Where the ratio of v: y is between 3: 2 and 2: 3 and / or the ratio of w: x is between 1: 3 and 1: 5, and p and q are p: q is selected to be from 1:20 to 1: 200, r is selected to satisfy valence requirements, and v and w are

Selected to be)
A method for hydrogenating acetic acid comprising passing over a hydrogenation catalyst having
In this form, the process conditions and the values of v, w, x, y, p, q, and r are preferably selected from the group wherein at least 90% of the converted acetic acid consists of ethanol and ethyl acetate While converting less than 4% of acetic acid to alkanes. In many aspects of the invention, p is selected to ensure that the surface of the support is substantially free of active Bronsted acid sites, taking into account any minor impurities present.

Still another aspect of the present invention provides a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 at a temperature between about 225 ° C. and 300 ° C. on the oxide support. Consisting essentially of a metal component dispersed in a composition:
_{Pt v Pd w Re x Sn y} Al z Ca p Si q O r
Where v and y are between 3: 2 and 2: 3, w and x are between 1: 3 and 1: 5, p and z, and the relative positions of the aluminum and calcium atoms present. Is controlled such that Bronsted acid sites present on its surface are neutralized by calcium silicate; p and q are selected such that p: q is from 1:20 to 1: 200; Are selected to satisfy valence requirements, and v and w are

Selected to be)
To produce ethanol by reduction of acetic acid comprising passing over a hydrogenation catalyst having Preferably, in this form, the hydrogenation catalyst has a surface area of at least about 100 m ² / g and z and p ≧ z. In many embodiments of the present invention, p also takes into account any minor impurities present and the surface of the support substantially contains active Bronsted acid sites that are believed to promote the conversion of ethanol to ethyl acetate. Selected to ensure that they are not included.

Another aspect of the invention is to provide a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 at a temperature between about 225 ° C. and 300 ° C., and about 7 A platinum group metal selected from the group consisting of platinum and a mixture of platinum and palladium on a siliceous support selected from the group consisting of silica promoted by .5 or less calcium metasilicate The amount of platinum present is at least about 1.5%); and from the group consisting of rhenium and tin in an amount of about 1% to 2% by weight of the catalyst. A metal promoter selected; the platinum to metal promoter molar ratio is between about 3: 1 to 1: 2; the siliceous support is optionally 1 to 5% by weight of the catalyst Amount of alkali metals, alkaline earth elements, and Donor promoter is selected from the group consisting of zinc; 1-50% by weight of the _{catalyst, WO 3, MoO 3, Fe} 2 O 3, and redox promoter selected from the group consisting of _Cr 2 _{O 3} An acid modifier selected from the group consisting of TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and Al ₂ O _{3 in} an amount of 1 to 50% by weight of the catalyst; and combinations thereof; It relates to a process for producing ethanol and ethyl acetate by reduction of acetic acid comprising passing over a hydrogenation catalyst promoted by a second promoter selected from the group consisting of:

In a preferred form of the invention, the molar ratio of metal promoter to platinum group metal is from about 2: 3 to about 3: 2, more preferably from about 5: 4 to about 4: 5, and most preferably about 9: 10 to about 10: 9, while the surface area of the siliceous support is at least about 200 m ² / g and the amount of sodium silicate is sufficient to make the support surface substantially basic. . In some cases, the use of calcium silicate results in the number of moles of Bronsted acid sites present on the surface being less than or equal to the number of moles of Bronsted acid sites present on the surface of Saint-Gobain NorPro SS61138 silica. In other cases, the silica used may be high purity calcined silica with a low content of alumina or other impurities. In many cases, such silica comprises greater than 99% silica, more preferably greater than 99.5% silica, and most preferably greater than 99.7% silica. In many embodiments of the present invention, the silica purity is controlled, or the Bronsted acid sites present on the surface of the support are calcium silicate or one of the other suitable stabilizer-modifiers discussed herein. The available moles of Bronsted acid sites present on the surface by either neutralizing with one of the two is less than or equal to the number of moles of Bronsted acid sites present on the surface of Saint-Gobain NorPro SS61138 silica, Preferably, it is less than half the number of moles of Bronsted acid sites present on the surface of Saint-Gobain NorPro SS61138 silica, more preferably less than 25%, even more preferably less than 10%. The number of acid sites present on the surface of the support is
(1) F. Delannay, “Characterization of Heterogeneous Catalysts”, Chapter III: Measurement of Acidity of Surfaces, p.370-404; Marcel Dekker, Inc., NY, 1984;
(2) CR Brundle, CA Evans, Jr., S. Wilson, LE Fitzpatrick, "Encyclopedia of Materials Characterization", Chapter 12.4: Physical and Chemical Adsorption Measurements of Solid Surface Areas, p.736-744, Butterworth-Heinemann, MA 1992;
(3) GA Olah, GK Sura Prakask, “Superacids”; John Wiley & Sons, NY 1985;
Can be determined using pyridine titration according to the procedure described in.

  Throughout the specification and claims, unless otherwise stated, when measuring surface acidity or the number of acid sites thereon, F. Delannay, "Characterization of Heterogeneous Catalysts ", Chapter III: Measurement of Acidity of Surfaces, p. 370-404; Marcel Dekker, Inc., NY 1984.

In a more preferred case, the surface area of the siliceous support is at least about 250 m ² / g and the number of moles of available Bronsted acid sites present on the surface is present on the surface of Saint-Gobain NorPro HSA SS61138 silica. The hydrogenation is carried out at a temperature between about 250 ° C and 300 ° C.

  As will be appreciated by those skilled in the art upon review of the discussion herein, catalyst supports other than the siliceous supports described above are preferably active, selective, under the process conditions used by the catalyst system, And if the ingredients are selected to be tough, they can be used in some embodiments. Suitable supports include stable metal oxide based supports, or ceramic based supports, and molecular sieves such as zeolites. In some embodiments, it is described in Kitson et al., US Pat. No. 5,149,680, column 2, line 64 to column 4, line 22 (the disclosure of which is incorporated herein by reference). Such a carbon support can be used.

  When preparing a mixture of ethanol and ethyl acetate simultaneously, in many embodiments of the invention, the hydrogenation catalyst is from the group consisting of silica and silica promoted by about 7.5 or less calcium metasilicate. Palladium on the selected siliceous support may be included (the amount of palladium present is at least about 1.5%), while the metal promoter is between about 1% and 10% by weight of the catalyst. The molar ratio of rhenium to palladium is between about 4: 1 to 1: 4, preferably between 2: 1 to 1: 3.

If it is desired to produce primarily ethanol, in many embodiments of the invention the catalyst is substantially comprised of silica promoted by about 3 to about 7.5% calcium silicate. Consisting essentially of platinum on a siliceous support (the amount of platinum present is at least about 1.0%) and a tin promoter in an amount between about 1% and 5% by weight of the catalyst. The platinum to tin molar ratio can be between about 9:10 and 10: 9 in many embodiments of the present invention. In some cases, small amounts of other platinum group metals, most often palladium, can be included in the catalyst metal of the formulation. In many embodiments of the invention, the amount of platinum group metal present is at least about 2.0% and the amount of platinum present is at least about 1.5%, preferably 2.5-3.5% by weight. The platinum promoter is present in an amount between about 2% and 5% by weight of the catalyst, while the process is at least about 1000 hr ⁻¹ at temperatures between about 250 ° C. and 300 ° C. At a pressure of at least 2 atmospheres. The ratio of tin to platinum is preferably between 2: 3 and 3: 2, more preferably between 4: 5 and 5: 4, most preferably between 9:10 and 10: 9. In yet another embodiment where it is desired to produce primarily ethanol, the catalyst is platinum on a siliceous support substantially composed of silica promoted by about 3 to about 7.5% calcium silicate. (The amount of platinum present is at least about 1.0%), and a tin promoter in an amount between about 1% and 5% by weight of the catalyst can be included, and the molar ratio of platinum to tin. Is between about 9:10 and 10: 9 in many embodiments of the invention.

Another aspect of the present invention is a siliceous support selected from the group consisting of silica and silica promoted by about 3.0 to about 7.5 calcium metasilicate, wherein the surface area of the siliceous support is at least about 150 m. on ² a ^/ g), platinum, palladium, and platinum group metal selected from the group consisting of mixtures thereof; and, the amount of tin promoter between about 1 wt% to 3 wt% of the catalyst; the The molar ratio of platinum to tin is between about 4: 3 to 3: 4, and the composition and structure of the siliceous support is selected such that its surface is substantially basic. It relates to a particulate catalyst for hydrogenation to the corresponding alkanol.

In another aspect of the invention, a platinum group metal selected from the group consisting of platinum, palladium, and mixtures thereof is dispersed thereon with an accelerator selected from the group consisting of tin, cobalt, and rhenium. A siliceous support, wherein the siliceous support has a surface area of at least about 175 m ² / g, silica, calcium metasilicate, and calcium metasilicate disposed on the surface thereof. The surface of the siliceous support selected from the group consisting of promoted silica relates to a particulate hydrogenation catalyst that is substantially free of Bronsted acid sites due to alumina that is not neutralized by calcium. In these variants, which are most suitable for the simultaneous production of ethanol and ethyl acetate, the total weight of platinum group metals present is between 0.5% and 2% and the amount of palladium present is at least 0. 0.5%, the promoter is rhenium, the weight ratio of rhenium to palladium is between 10: 1 and 2: 1 and the amount of calcium metasilicate is between 3 and 90%.

In the most suitable form for producing ethanol with high selectivity, the total weight of platinum group metals present is between 0.5-2% and the amount of platinum present is at least 0.5%. The promoter is cobalt, the weight ratio of cobalt to platinum is between 20: 1 and 3: 1 and the amount of calcium silicate is between 3 and 90%, while the catalyst has a long lifetime In the most suitable form for producing ethanol, the hydrogenation catalyst is between 2.5 and 3.5% by weight dispersed on high surface area calcined derived silica having a surface area of at least 200 m ² / g. High surface area silica containing between 3% and 5% by weight of platinum to ensure that the surface is substantially free of Bronsted acid sites that are not neutralized by calcium metasilicate. Effective amount Are promoted by calcium metasilicate, the molar ratio of platinum and tin is 4: 5 to 5: is between 4.

  In other catalysts of the invention, the total weight of platinum group metals present is between 0.5-2%, the amount of palladium present is at least 0.5%, the promoter is cobalt, The weight ratio of cobalt to palladium is between 20: 1 to 3: 1 and the amount of calcium silicate is between 3 to 90%.

  Yet another catalyst of the present invention comprises between 0.5 and 2.5 wt% palladium, between 2 wt% and 7 wt% rhenium, and the rhenium to palladium weight ratio is at least 1.5: 1.0, rhenium and palladium are dispersed on a siliceous support, which is a hydrogenation catalyst comprising at least 80% calcium metasilicate.

The inventors have
(I) a platinum group metal selected from the group consisting of platinum, palladium, and mixtures thereof on a siliceous support selected from the group consisting of silica, calcium metasilicate, and calcium metasilicate promoted silica; and tin or Catalyst combined with rhenium;
(Ii) Palladium and rhenium supported on a siliceous carrier selected from the group consisting of silica, calcium metasilicate, and calcium metasilicate promoted silica are mixed, and the siliceous carrier may be an alkali in some cases. Promoted by 1% to 5% promoter selected from the group consisting of metals, alkaline earth elements, and zinc, the promoter preferably being in the form of the nitrate or acetate salt of each of these promoters Added to the catalyst formulation, particularly preferably potassium, cerium, calcium, magnesium, and zinc;
(Iii) cobalt promoted platinum on a high surface area siliceous support selected from the group consisting of silica, calcium metasilicate, and calcium metasilicate promoted silica; and (iv) silica, calcium metasilicate, and calcium. Platinum promoted by cobalt on a high surface area siliceous support selected from the group consisting of metasilicate-promoted silica;
It has been found that surprisingly high activity and lifetime are obtained from a catalyst selected from the group consisting of in combination with excellent selectivity for the hydrogenation of acetic acid to ethanol.

Another aspect of the present invention provides a gas stream comprising vapor phase hydrogen and alkanoic acid in a molar ratio of at least about 2: 1 hydrogen to alkanoic acid at a temperature between about 125 ° C. and 350 ° C.
a. A platinum group metal selected from the group consisting of platinum, palladium, and mixtures thereof on a siliceous support selected from the group consisting of silica, calcium metasilicate, and calcium metasilicate promoted silica; and b. An accelerator selected from the group consisting of tin and rhenium;
Including
c. The siliceous support is optionally i. A promoter selected from the group consisting of alkali metals, alkaline earth elements, and zinc, in an amount of 1-5% by weight of the catalyst;
ii. 1-50% by weight of the _{catalyst, WO 3, MoO 3, Fe} 2 O 3, and _Cr 2 redox promoter is selected from the group consisting of _{O 3;} and iii. 1-50% by weight of the _catalyst, acidic denaturing agent selected from the group consisting of _{TiO 2, ZrO 2, Nb 2} O 5, Ta 2 O 5, and _Al 2 _{O 3;}
Promoted by an accelerator selected from the group consisting of:
The invention relates to a process for hydrogenating alkanoic acids comprising passing over a hydrogenation catalyst.

  Preferably, the alkanoic acid is acetic acid and platinum, if present, is present in an amount of 0.5% to 5% of the weight of the catalyst; palladium, if present, is 0.25 of the weight of the catalyst. Present in an amount of from 5% to 5%; the total amount of platinum and palladium present is at least 0.5% by weight of the catalyst; tin is present in an amount of at least 0.5 to 5%; The ratio is as described above.

In another form of the invention, the surface area of the siliceous support is at least about 150 m ² / g, more preferably at least about 200 m ² / g, and most preferably at least about 250 m ² / g. In a more preferred embodiment, the siliceous support contains no more than about 7.5% calcium metasilicate. In other embodiments, the siliceous support comprises no more than about 90% calcium metasilicate. In all embodiments, control of the acidity of the carrier can be very beneficial, especially when producing substantially pure ethanol. When silica alone is used as the support, the amount of alumina, which is a normal contaminant for silica, is low, preferably less than 1 wt%, more preferably less than 0.5 wt%, most preferably 0.3 wt%. It is very beneficial to ensure that it is lower than%. In this regard, so-called calcined silica is very preferred because it is usually available in a purity of over 99.7%. In this application, reference to high purity silica refers to silica in which acidic contaminants such as alumina are present at a level of less than 0.3% by weight. When using calcium metasilicate-promoted silica, it is usually not necessary to be very strict about the purity of the silica used as the support, but alumina is not desirable and usually is not intentionally added.

  In a more preferred embodiment of the invention, platinum is present in an amount from 1% to 5% of the weight of the catalyst, if present; palladium, if present, from 0.5% to 5% of the weight of the catalyst. The total amount of platinum and palladium present is at least 1% by weight of the catalyst.

In another preferred embodiment of the invention where the support is substantially pure high surface area silica, preferably calcined silica, the tin is present in an amount of 1% to 3% by weight of the catalyst, more preferably tin. The mole ratio of platinum to platinum group metal is about 1: 2 to about 2: 1; even more preferably, the mole ratio of tin to platinum is about 2: 3 to about 3: 2; Has a molar ratio of tin to platinum of about 5: 4 to about 4: 5. If the support also contains a small amount of CaSiO ₃ or other stabilizer-modifier in the range of about 2% to about 10%, they are neutralized by a suitable amount of a substantially basic stabilizer-modifier. As long as this is done, large amounts of acidic impurities can be tolerated.

In another form of the invention, the process is preferably carried out at a temperature between about 225 ° C. and 300 ° C., more preferably between 250 ° C. and 300 ° C., wherein the hydrogenation catalyst is silica, and about 7. A platinum group metal selected from the group consisting of platinum and a mixture of platinum and palladium on a siliceous support selected from the group consisting of silica promoted by 5 or less calcium metasilicates (of platinum group metals present) The amount of platinum present is at least about 1.5%); and a tin promoter in an amount between about 1% and 2% by weight of the catalyst; The molar ratio of platinum to tin is between about 3: 1 to 1: 2, and the siliceous support is optionally an alkali metal, alkaline earth element, and zinc in an amount of 1-5% by weight of the catalyst. Selected from the group consisting of Accelerators; 1 to 50 wt% of the amount of _WO 3 _{catalyst, MoO 3, Fe 2 O 3} , and redox promoter is selected from the group consisting of _Cr 2 _{O 3;} and 1 to 50 wt% of the catalyst An amount of acidic modifier selected from the group consisting of TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and Al ₂ O ₃ ;

In a particularly preferred embodiment of the present invention for hydrogenating alkanoic acids, the catalyst is selected from the group consisting of high surface area high purity silica and high surface area silica promoted by about 7.5 or less calcium metasilicate. A platinum group metal selected from the group consisting of platinum, palladium, and mixtures thereof, wherein the amount of platinum group metal present is at least about 2.0%, and the amount of platinum present Is at least about 1.5%, the amount of tin promoter is between about 1% and 5% by weight of the catalyst, and the molar ratio of platinum to tin is between about 3: 2 to 2: 3. is there. Preferably, the high purity silica is calcined and then tableted or pelletized into a sufficiently dense form for use in a fixed bed catalyst. However, even in the case of high purity silica, in the presence of stabilizer-modifiers, especially calcium silicate, in the presence of acetic acid vapor, a temperature near 275 ° C. and a space velocity of 2500 hr ⁻¹ and higher It is clear that the activity and selectivity of the operation of a viable operation is extended or stabilized over a long period of time extending to weeks and even months. In particular, it is possible to achieve a degree of stability such that the catalytic activity decreases by less than 10% over a period of one week (168 hours) or two weeks (336 hours) or even over 500 hours. Thus, it can be appreciated that the catalyst of the present invention is completely capable of being used in commercial scale industrial applications for hydrogenating acetic acid, particularly in the production of high purity ethanol and mixtures of ethyl acetate and ethanol. it can.

  Other forms of the invention neutralize the acidic sites present on the surface; shape changes at temperatures encountered in acetic acid hydrogenation (mainly sintering, grain growth, grain boundary migration, defects and Resistance to dislocation migration, plastic deformation, and / or other temperature-induced changes in microstructure); or an amount of alkaline earth metal, alkali metal, zinc, scandium sufficient to do both, Oxide supports and metabolites in the form of yttrium oxides and metasilicates, precursors for oxides and metasilicates, and basic non-volatile stabilizers-modifiers in the form of mixtures thereof introduced on the surface or in the support itself Group VIII metals (Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, and Os) or other transition metals (especially Ti, Zn, Cr, Mo, and ) It relates to the hydrogenation catalyst based on.

In another embodiment of the process of the invention, the catalyst is
(I) selected from the group consisting of platinum, palladium, and mixtures thereof on a siliceous support selected from the group consisting of silica, calcium metasilicate, and silica stabilized and modified by calcium metasilicate Catalyst combining platinum group metal and tin or rhenium;
(Ii) selected from the group consisting of calcium metasilicate and calcium metasilicate promoted silica, optionally accelerated by 1-5% promoter selected from the group consisting of alkali metals, alkaline earth elements, and zinc. A catalyst comprising a combination of palladium and rhenium supported on a siliceous support;
(Iii) cobalt promoted platinum on a siliceous support selected from the group consisting of silica, calcium metasilicate, and calcium metasilicate promoted silica; and (iv) silica, calcium metasilicate, and calcium metasilicate. Palladium promoted by cobalt on a siliceous support selected from the group consisting of promoted silica;
Selected from.

Generally, the siliceous support is a stabilizer-modifier comprising an alkali metal, alkaline earth element, and zinc oxides and metasilicates, and precursors therefor in amounts of 1-5% by weight of the catalyst; A redox promoter selected from the group consisting of WO ₃ , MoO ₃ , Fe ₂ O ₃ , and Cr ₂ O _{3 in} an amount of ˜50 wt%; and TiO ₂ in an amount of 1-50 wt% of the catalyst, An acidic modifier selected from the group consisting of ZrO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and Al ₂ O ₃ ; an accelerator selected from the group consisting of: It favors the production of combined ethyl acetate.

Another aspect of the invention is a siliceous support selected from the group consisting of silica, silica promoted by calcium metasilicate of not more than about 7.5, and mixtures thereof (the surface area of the siliceous support is at least about 150 m). comprises; on ² a ^/ g), platinum, palladium, and these platinum group metal selected from the group consisting; the amount of tin promoter between about 1% to 2% by weight and a catalytic The molar ratio of platinum to tin is between about 3: 2 to 3: 2 and the siliceous support is optionally an alkali metal, alkaline earth element, and an amount of 1 to 5% by weight of the catalyst, and A promoter selected from the group consisting of zinc; a redox promoter selected from the group consisting of WO ₃ , MoO ₃ , Fe ₂ O ₃ , and Cr ₂ O _{3 in} an amount of 1-50% by weight of the catalyst; and , 1-50 layers of catalyst Promoted by an accelerator selected from the group consisting of: an acid modifier selected from the group consisting of TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and Al ₂ O _{3 in} an amount of%. Relates to a particulate catalyst for hydrogenating alkanoic acids to the corresponding alkanols.

In another aspect of the invention, a platinum group metal selected from the group consisting of platinum, palladium, and mixtures thereof is dispersed thereon with an accelerator selected from the group consisting of tin, cobalt, and rhenium. Wherein the siliceous support has a surface area of at least about 175 m ² / g and is selected from the group consisting of silica, calcium metasilicate, and calcium metasilicate promoted silica; Optionally 1% to 5% promoter selected from the group consisting of alkali metals, alkaline earth elements and zinc in an amount of 1 to 5% by weight of the catalyst; of _{WO 3, MoO 3, Fe 2} O 3, and redox promoter is selected from the group consisting of _Cr 2 _{O 3;} and, 1 to 50% by weight of the catalyst TiO , Acidic denaturing agent selected from the group consisting of _{ZrO 2, Nb 2 O 5,} Ta 2 O 5, and _Al 2 _{O 3;} are facilitated by relates particulate hydrogenation catalyst. In one more preferred embodiment of the present invention, the total weight of platinum group metal present is between 2-4%, the amount of platinum present is at least 2%, the promoter is tin, The molar ratio with tin is between 2: 3 and 3: 2, and the amount of calcium metasilicate is between 3 and 7%. In another more preferred embodiment of the invention, the total weight of platinum group metal present is between 0.5% and 2%, the amount of palladium present is at least 0.5% and the promoter is rhenium. And the weight ratio of rhenium to palladium is between 10: 1 and 2: 1 and the amount of calcium metasilicate is between 3 and 90%. In a third more preferred embodiment of the present invention, the total weight of platinum group metal present is between 0.5-2%, the amount of platinum present is at least 0.5% and the promoter is cobalt. The weight ratio of cobalt to platinum is between 20: 1 to 3: 1 and the amount of calcium silicate is between 3 to 90%. In a fourth more preferred embodiment of the present invention, the total weight of platinum group metal present is between 0.5-2%, the amount of palladium present is at least 0.5% and the promoter is cobalt. The weight ratio of cobalt to palladium is between 20: 1 to 3: 1 and the amount of calcium silicate is between 3 to 90%.

  The present invention will now be described in detail with reference to the accompanying drawings. Like numbers indicate like parts.

FIG. 1 shows the selectivity and productivity performance of the catalyst of the present invention. FIG. 2 shows the selectivity and productivity performance of the catalyst of the present invention. FIGS. 3A-3C show the relative temperature insensitivity of the selectivity and productivity of the catalyst of the present invention, the variation in properties obtained when acetic acid is hydrogenated at 225 ° C. over a catalyst activated at 225 ° C. Shown with. 4A-4C show the variation in selectivity, conversion, and productivity with changes in the ratio of platinum to tin in the preferred platinum-tin catalyst of the present invention. FIGS. 5A and 5B show the selectivity for ethanol production of the most preferred catalyst of the present invention supported on high surface area silica and the high productivity obtained using this. 6A and 6B show the excellent selectivity obtained at low temperatures using the most preferred catalysts of the present invention based on high surface area silica promoted by calcium metasilicate. It can be seen that the selectivity for ethanol is high. FIGS. 7A and 7B show the excellent selectivity obtained at low temperatures using the most preferred catalysts of the present invention based on high surface area silica promoted by calcium metasilicate. It can be seen that the selectivity for ethanol is high. FIG. 8 shows the effect of rhenium mass fraction on the hydrogenation of acetic acid using the palladium-rhenium catalyst on silica of the present invention. FIG. 9 shows the effect of rhenium mass fraction on the hydrogenation of acetic acid using the palladium-rhenium catalyst on silica of the present invention. FIG. 10 shows the effect of rhenium mass fraction on the hydrogenation of acetic acid using the palladium-rhenium catalyst on silica of the present invention. FIG. 11 shows the performance of a platinum-cobalt catalyst supported on silica. FIG. 12 shows the performance of a platinum-cobalt catalyst supported on silica.

  While market conditions are steadily changing, for large-scale operations, the selectivity, activity, and catalyst life reported in the literature for the catalytic hydrogenation of acetic acid to ethanol are the other methods of ethanol production. Give a generally unfavorable economy to what it takes to compete with. One estimate of the productivity required for commercialization was concluded that a selectivity for ethanol higher than about 50% was required, as well as a productivity of about 200 g ethanol per hour per kg of catalyst. The catalyst of the present invention far exceeds such requirements.

In the following description, all numerical values disclosed herein are approximate values regardless of whether the word “about” or “approximately” is used in connection therewith. These may vary 1%, 2%, 5%, or sometimes 10-20%. Whenever a numerical range with a lower limit, R ^L and an upper limit R ^U, is disclosed, any number and any sub-ranges within this range is specifically disclosed. In particular, the following numbers within this range are specifically disclosed: R = R ^L + k × (R ^U −R ^L ), where k is in the range of 1% to 100% in 1% increments. I.e., k is 1%, 2%, 3%, 4%, 5%, ... 50%, 51%, 52%, ... 95%, 96%, 97%, 98 %, 99%, or 100% In addition, any numerical range defined by the two R values defined above is also specifically disclosed.

  Figures 1 and 2 show the selectivity and productivity performance of the catalysts of the present invention, and graphically illustrate the greatly improved selectivity and productivity that can be obtained using these catalysts at various operating temperatures. In particular, at 280 ° C. and 296 ° C., the selectivity for ethanol is about 60%. In this evaluation, ethyl acetate is also an economically important and valuable commodity, so the initial objective is the production of ethanol, but all acetic acid converted to ethyl acetate retains great value. On the other hand, it is important to remember that alkanes produced as by-products are generally much less valuable than the feedstock. In FIG. 1, the productivity in grams of ethanol produced per hour of operation per kg of catalyst is represented by a square as a function of time (hours), while the productivity of ethyl acetate is represented by a circle, and acetaldehyde The productivity of is represented by diamonds. Significantly during this experiment, the operating temperature increases during operation as shown, indicating the effect of operating temperature on productivity and selectivity. In FIG. 2, the selectivity for ethanol defined below is represented by a circle as a function of operating time, while the selectivity for ethyl acetate defined below is represented by a square and the selectivity for acetaldehyde is represented by a diamond.

  3A-3C show the relative temperature insensitivity of the selectivity of the catalyst of the present invention to the temperature at which the metal precursor is reduced. The reaction may occur in vessels that are not specifically configured to maintain a uniform temperature throughout (usually these vessels will contain the catalyst in quartz pieces or other inert particles to suppress the reaction. This property is important for commercialization because it is called “adiabatic reactors” because it is usually “diluted” but has little provision for adapting to temperature changes associated with the reaction process. is there. FIG. 3A reports the results of an experiment in which the catalyst is reduced at the temperature indicated in ° C., followed by hydrogenation of hydrogen and acetic acid at 250 ° C. over the catalyst. The upper line represents the selectivity of this particular catalyst with respect to ethanol, while the lower line represents the selectivity with respect to ethyl acetate. In FIG. 3B, the productivity results for this experiment are shown, with the top line reporting ethanol productivity and the bottom line reporting ethyl acetate productivity. In FIG. 3C, the conversion rate results (defined below) for this experiment are expressed as a function of the reduction temperature. Furthermore, acetic acid was also hydrogenated at a temperature of 225 ° C. over a catalyst reduced or activated at 225 ° C. The points on FIGS. 3B and 3C also include the results of experiments where acetic acid was hydrogenated at 225 ° C. over a catalyst reduced at 225 ° C. It can be seen that hydrogenation over this catalyst at a temperature of 225 ° C. results in reduced selectivity to ethanol and reduced conversion.

4A-4C show 2.5 mL solid catalyst (14/30 mesh, 1: 1 dilution (v / v, diluted with 14/30 mesh quartz pieces), p = 200 psig (14 bar) operating pressure. At 0.09 g / min-HOAc, 160 sccm / min-H ₂ , and 60 sccm / min-N ₂ acetic acid, hydrogen, and nitrogen diluent feed rates respectively; 6570 hr ⁻¹ total space velocity: GHSV; This correlates with the molar fraction of Pt in SiO ₂ —Pt _x Sn _(1-x) (Σ [Pt] + [Sn] = 1.20 mmol) in the catalytic hydrogenation of acetic acid over a reaction time of hours. Figure 4 shows the variation in selectivity, conversion, and productivity with changes in the ratio of platinum to tin in the preferred platinum-tin catalyst of the invention, in which the selectivity for ethanol production is substantially pure. It can be seen that for these catalysts supported on high surface area silica, the maximum is about a 1: 1 molar ratio (throughout this specification "L" is the number 1 and many typefaces. In order to avoid ambiguity arising from the similarity or even the ambiguity arising from the identity of the 12th letter of the roman alphabet in roman alphabets.) For each of FIGS. _i (Pt) represents the mass fraction of platinum in the catalyst in the range between 0 and 1, while selectivity, conversion and productivity are shown as above, FIG. 4A shows ethanol and ethyl acetate. The selectivity for ethanol is a peak at 50% mass fraction, where acetic acid conversion is also peaked as shown in FIG. 4B. A click, the same productivity of ethanol, as shown in FIG. 4C.

  FIGS. 5A and B show the selectivity and productivity for ethanol production of the most preferred catalyst of the present invention supported on high surface area silica and the high productivity obtained using it. In FIG. 5A, the productivity in grams per hour of operation per kg of catalyst is shown on the vertical axis, where the productivity for ethanol is represented by a square, the productivity of ethyl acetate is represented by a circle, and acetaldehyde The productivity of is represented by diamonds. Similarly, in FIG. 5B, the selectivity defined below is represented on the vertical axis as a function of operating time (hours), again, the selectivity to ethyl acetate is represented by a circle, and the selectivity to ethanol is represented by a square. And the selectivity to acetaldehyde is represented by diamonds.

  FIGS. 6A and B and FIGS. 7A and B show the selectivity obtained at low temperatures using the same format as FIGS. 5A and B using the preferred catalyst of the present invention based on calcium metasilicate promoted high surface area silica. It can be seen that the selectivity for ethanol is higher than 90% throughout the run.

8-12 will be discussed in connection with related embodiments.
In the following, the present invention will be described in detail with reference to several embodiments for purposes of illustration and illustration only. Modifications to particular embodiments within the spirit and scope of the invention as set forth in the claims will be readily apparent to those skilled in the art.

  Unless defined more specifically below, terms used herein are given their ordinary meaning, and terms such as “%” refer to weight percent unless otherwise indicated. In general, when discussing the composition of the support, the percentage in the composition includes oxygen and the ions or metals bound to it, whereas when discussing the weight of the catalytic metal, the percentage of oxygen bound to it. Ignore the weight. Thus, in a support comprising 95% silica and 5% alumina, the composition is based on alumina having a formula weight of 101.94 and silica having a formula weight of 60.09. However, if the catalyst is shown as having 2% platinum and 3% tin, the weight of oxygen that may be bound to it is ignored.

  “Conversion” is expressed in mole percent based on acetic acid in the feed stream.

  “Selectivity” is expressed in mole percent based on converted acetic acid. For example, when the conversion is 50 mol% and 50 mol% of the converted acetic acid is converted to ethanol, the ethanol selectivity is called 50%. The ethanol selectivity is calculated from gas chromatography (GC) data as follows.

While not intending to be bound by theory, it is believed that the conversion of acetic acid to ethanol according to the present invention involves one or more of the following reactions.
Hydrogenation of acetic acid to ethanol;
Hydrogenation of acetic acid to ethyl acetate;
Decomposition of ethyl acetate to ethylene and acetic acid;
Dehydration of ethanol to ethylene.

The selective catalyst for catalytic cracking of acetic acid to ethanol is
(I) a platinum group metal selected from the group consisting of platinum, palladium, and mixtures thereof on a siliceous support selected from the group consisting of silica, calcium metasilicate, or silica promoted by calcium metasilicate. And a catalyst combining tin or rhenium;
(Ii) optionally 1 to 5% of a first promoter selected from the group consisting of alkali metals, alkaline earth elements and zinc (the promoter is preferably the nitrate of each of these promoters Or added to the catalyst formulation in the form of acetate), particularly preferably palladium and rhenium supported on a siliceous support as described above, promoted by potassium, cesium, calcium, magnesium and zinc. Combined catalyst;
(Iii) platinum promoted by cobalt on a siliceous support; and (iv) palladium promoted by cobalt on a siliceous support;
Selected from the group consisting of

  The process of the invention can be carried out in various configurations using a fixed bed reactor or a fluidized bed reactor, as can be readily appreciated by those skilled in the art. In many aspects of the invention, an "adiabatic" reactor can be used, i.e. little or no need to use internal piping through the reaction zone to add or remove heat. Alternatively, a shell and tube reactor with a heat transfer medium can be used. In many cases, the reaction zone can be housed in a single vessel or in a series of multiple vessels with heat exchange therebetween. Since the adiabatic reactor configuration is usually much less expensive than the tube and shell configuration, it is considered important that the acetic acid reduction process using the catalyst of the present invention can be performed in the adiabatic reactor.

A variety of catalyst carriers known in the art can be used to support the hydrogen acetate catalyst. Examples of such carriers include, without limitation, iron oxide, silica, alumina, titania, zirconia, magnesium oxide, calcium silicate, carbon, graphite, and mixtures thereof. Preferably, a siliceous support selected from the group consisting of silica, calcium metasilicate, and silica promoted by calcium silicate is used for the present invention and has a SiO ₂ content of at least 99.7%. Is particularly desirable when pelletized to a sufficiently dense form for use in a fixed bed reactor. We have unexpectedly reported that high-purity high surface area silica, in particular grade HSA SS61138 from Saint-Gobain NorPro, promoted by calcium metasilicates, is unexpected for other catalysts for the present invention. It was found to be superior to the other carrier. The silica used as a support in the present invention preferably has a surface area of at least 100 m ² / g, more preferably at least 150 m ² / g, more preferably at least 200 m ² / g, and most preferably about 250 m ² / g. Throughout this specification, the term “high surface area silica” should be understood to mean silica having a surface area of at least 250 m ² / g. The activity / stability of the siliceous support can be varied by including small amounts of other ingredients as described below. Any convenient particle shape can be used, such as pellets, extrudates, spheroids, spray-dried, annular, pentaring, trefoil, and four-leaf, but for this application, generally cylindrical It is preferable to use pellets.

Effect of catalyst support:
In addition to the selection of the metal precursor (ie, halogen: Cl ⁻ and halogen-free NO ₃ ⁻ ) and production conditions, the resulting metal-support interaction is strongly dependent on the structure and properties of the underlying support.

The effect of basic and acidic modifiers was studied on various silica-supported Pt-Sn materials. The molar ratio between Pt and Sn was kept 1: 1 for all materials and the total metal loading was kept constant unless otherwise indicated. In _{particular, SiO 2, SiO 2 -TiO 2} , KA160 ( i.e. _SiO 2 _-Al 2 _O 3), and an acidic carrier on catalysts produced in like H-ZSM5 is giving a high acid conversions, ethanol The selectivity to is lower. Interestingly, the H-ZSM5 catalyst actually produces diethyl ether as the main product, possibly formed by dehydration from ethanol. Both catalysts based on SiO ₂ —TiO ₂ and KA160 (ie SiO ₂ —Al ₂ O ₃ ) give high conversions and equivalent selectivities for EtOH and EtOAc, in which case the main production of EtOAc It is a thing. It is clear that the presence of Lewis acidity in the underlying catalyst support may be beneficial due to the higher conversion of acetic acid. Is based on the acidity primarily Lewis acidity in SiO ₂ -TiO _2, KA160 (silica - alumina) material has also strongly Bronsted sites capable of catalyzing the formation of EtOAc from residual acetic acid and EtOH. Catalysts based on H-ZSM5 have more strongly acidic zeolite Bronsted sites, and shape selectivity due to small pores may also contribute to the formation of an acid catalyst for diethyl ether by ethanol dehydration. Adding a basic modifier to any carrier being studied generally resulted in a significant decrease in acetic acid conversion and increased selectivity to ethanol. The highest selectivity for 92% ethanol is seen for the second SiO ₂ —CaSiO ₃ (5) -Pt (3) —Sn (1.8) in Table A, and pure TiO promoted by CaSiO ₃ . ₂ also produced ethanol with a selectivity of about 20%. By comparing between SiO ₂ —TiO ₂ and TiO ₂ —CaSiO ₃ , the site density of acidic (Lewis) sites may also be important, and further optimization of the acidic properties of the catalyst support is probably It is suggested that basic and acidic accelerators can be achieved by careful changes in combination with specific manufacturing methods.

KA160 Comparing _{(SiO 2 -5% Al 2 O} 3) and KA160-CaSiO ₃ promoted catalyst, large shifts in selectivity to ethanol was observed. In 84%, selectivity of this catalyst is still lower than that observed with respect to _SiO 2 -CaSiO ₃ based materials, the conversion of acetic _{acid, SiO 2 -CaSiO 3 (5)} -Pt (3) - It is maintained at 43%, which is almost double that seen for Sn (1.8). See Table A, 2nd, 6th and 7th. In addition to the “acid modifier” properties, it is clear that all CaSiO ₃ promoted materials exhibit improved long-term stability (albeit at lower conversion). _{Specifically, SiO 2 -CaSiO 3 (5)} -Pt (3) -Sn (1.8) catalyst, in various reaction conditions, less than 10% over longer reaction times 220 hours reduced activity Indicated. Also, the two types of Re—Pd catalysts produced on SiO ₂ and SiO ₂ —CaSiO ₃ show similar trends with respect to selectivity. Although the conversion was kept below 10% for all materials, a large shift in selectivity to ethanol was observed for the CaSiO ₃ -promoting material (9th and 10th in Table A). Further information on productivity is given in Table 4.

  Thus, without being bound by theory, the introduction of a non-volatile stabilizer-modifier having either the effect of neutralizing acid sites present on the surface; or the effect of thermally stabilizing the surface By modifying and stabilizing the oxide support for the acetic acid hydrogenation catalyst, it is possible to achieve the desired improvement in selectivity to ethanol, long catalyst life, or both. In general, modifiers based on their most stable valence state oxides have low vapor pressures and are therefore rather non-volatile. Thus, Group VIII metals (Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, and Os) or other transition metals (especially Ti, Zn, Cr, Mo, and W) on oxide supports The hydrogenation catalyst based on NF neutralizes acidic sites present on its surface or changes shape at temperatures encountered in acetic acid hydrogenation (mainly sintering, grain growth, grain boundary migration, defects, among others). And an amount of alkaline earth metal, alkali metal, zinc, scandium sufficient to provide resistance to, or both, resistance to dislocation migration, plastic deformation, and / or other temperature-induced changes in microstructure A basic non-volatile stabilizer-modifier in the form of yttrium oxides and metasilicates, precursors for oxides and metasilicates, and mixtures thereof; Preferably it includes into the carrier itself.

The metal loading on the support is not critical in the present invention and can vary from about 0.3% to about 10% by weight. Particularly preferred is a metal loading of about 0.5% to about 6% by weight, based on the weight of the catalyst. Due to their extreme cost, platinum group metals are usually used in rather carefully controlled amounts, often less than 10% by weight of the total catalyst composition. Combining small amounts of platinum, such as 0.25-5%, with other catalytic elements described herein can provide excellent selectivity, lifetime, and activity. Usually, it is preferable to use 0.5 to 5%, more preferably 1 to 3% of platinum in the platinum-containing catalyst of the present invention. In the case of a platinum-tin catalyst, 0.10 to 5% tin, more preferably 0.25 to 3% tin, even more preferably 0.5 to 2.5% tin, most preferably high surface area When supported on silica / calcium metasilicate, a combination of about 3% platinum and about 1.5% tin, corresponding somewhat closer to the 1: 1 molar ratio of platinum to tin, or lower It is preferred to use smaller corresponding amounts based on weight percent platinum. For this catalyst, it is preferable to use a siliceous support selected from the group consisting of the high purity high surface area silica described above, calcium metasilicate, and high surface area silica promoted by calcium metasilicate. Thus, it can be seen that the amount of calcium metasilicate can be varied over a wide range in the range of 0-100% by weight. Since calcium metasilicate tends to have a lower surface area, it is preferred to include at least about 10% high surface area silica in our support for this catalyst, more preferably about 95% as high as our support. Saint- having a surface area of silica, 250 m ² / g surface area; a median pore size of 12 nm; a total pore volume of 1.0 cm ³ / g as measured by mercury intrusion porosimetry; and a packing density of about 22 lbs / ft ³ It is preferred to use SS61138 high surface area (HSA) silica catalyst support from Gobain NorPro.

  Rather than impregnating within a cleaning coating on a monolithic support similar to automotive catalysts and diesel soot traps, our catalysts are shaped into particles, also called beads or pellets, when they have any variety of shapes, The catalyst of the present invention is a particulate catalyst in the sense that the catalyst metal is fed to the reaction zone by placing these shaped catalysts in the reactor. Shapes commonly found include extrudates of any cross-section that take the form of a general cylinder in the sense that the origin defining the extrudate surface is parallel lines. Spheroids, spray-dried microspheres, rings, pentarings, and multi-leaf shapes can all be used. Usually, the shape is selected experimentally based on the perceived ability to effectively contact the vapor phase with the catalytic reagent.

Highly preferred platinum - tin catalyst is from about 3 weight being supported on high surface area silica with a surface area of about 250 meters 2 / ^g, which is promoted by calcium metasilicate of from about 0.5% to 7.5% % Platinum and 1.5 wt% tin. We have already achieved a catalyst life of 100 hours of operation time at 280 ° C. with this composition. In many cases, it is possible to partially replace platinum with palladium in the composition described above.

  A catalyst that is similar to that described in the previous paragraph, but with a lower amount of very costly platinum promoted by a higher amount of cobalt, gives good initial catalytic activity. , There is a tendency not to show a catalyst life as long as the platinum-tin catalyst described above. The priorities for the siliceous support for this catalyst are substantially the same as for the platinum-tin catalyst. Preferred catalysts of this type include 0.25-5% platinum, more preferably 0.3-3% platinum, most preferably 0.5-1.5% platinum, about 1% to about 20%. Of cobalt, more preferably about 2% to about 15% cobalt, more preferably about 8-12% cobalt. These catalysts are not as durable as the platinum-tin catalysts described above, but in many cases this is a greatly reduced platinum requirement, a lower cost of cobalt compared to platinum group metals, and Greatly offset by excellent initial selectivity. Of course, in many cases, it is possible to compensate for the lack of activity by appropriately recycling the stream or using a larger reactor, but it is more difficult to compensate for poor selectivity. Is well understood.

  Palladium-based catalysts promoted by rhenium or cobalt provide excellent catalytic activity with somewhat lower selectivity, and this selectivity loss is further exacerbated at reaction temperatures higher than 280 ° C. with increased amounts of Causes the formation of acetaldehyde, carbon dioxide, and even hydrocarbons. Cobalt-containing catalysts usually show slightly better selectivity than the corresponding rhenium catalysts. However, both give surprisingly long-lived catalytic activity, but both are as excellent as those of the most preferred platinum / tin catalysts on high purity alumina that are stabilized and modified by calcium metasilicate. Does not give life. Again, this catalyst is on siliceous supports stabilized and modified by the Group I, Group II, and zinc oxides and metasilicates described above, and precursors therefor, and mixtures thereof. It can be supported on. Very suitable precursors include zinc, alkali metal, and alkaline earth metal acetates and nitrates, which in some cases may be about about 50% by weight of the metal excluding the acetate and / or nitrate moieties. It can be included in the siliceous support in an amount of 1-5%.

In another aspect of the invention, a modifier selected from the group consisting of a redox active modifier, an acidic modifier, and mixtures thereof is introduced into a siliceous carrier, thereby producing ethanol, ethyl acetate, and acetaldehyde. The catalysts described above can be modified by changing the relative selectivity between the two. Suitable redox active modifiers include WO ₃ , MoO ₃ , Fe ₂ O ₃ , and Cr ₂ O ₃ , while acidic modifiers include TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ and Al ₂ O ₃ are mentioned. By carefully introducing these modifiers into the siliceous support, the activity of the catalyst can be adjusted so that the relative amounts of products of catalytic hydrogenation meet market fluctuations and demands for various products. A more desirable distribution can be generated. Typically, these materials are included in the siliceous carrier in amounts ranging from about 1 to 50% by weight.

Metal impregnation can be performed using any method known in the art. Usually, prior to impregnation, the support is dried at 120 ° C. and formed into particles having a size distribution in the range of about 0.2-0.4 mm. In some cases, the support can be pressed, crushed and sieved to the desired size distribution. Any known method of shaping the support material to the desired size distribution can be used. In a preferred method of preparing the catalyst, dispersion of the catalyst component on a support, such as support particles, can be achieved using a platinum group metal component, such as a suitable compound and / or complex of a platinum group metal. The catalytic metal compound can be impregnated or deposited on the carrier particles using a water-soluble compound or water-dispersible compound or complex of a platinum group metal. The platinum group metal component is decomposed by heating and / or applying a vacuum. In some cases, liquid removal does not complete until the catalyst is placed in service and subjected to the high temperatures encountered during operation. In general, an aqueous solution of a platinum group metal soluble compound is preferred from both an economic and environmental standpoint. For example, suitable compounds are chloroplatinic acid, amine solubilized platinum hydroxide, palladium nitrate or palladium chloride, sodium chloride palladium, sodium chloride platinum, etc., but the use of halogens when ethanol is the desired product It is preferable to avoid. During the calcination process or at least during the initial use phase of the catalyst, such compounds are converted to the catalytically active form of the platinum group metal or its catalytically active oxide. In general, however, the inventors have found that catalysts made from Pt (NH ₃ ) ₄ (NO ₄ ) ₂ appear to exhibit increased selectivity to ethanol, so chlorides are used. It is preferable to use a platinum group metal precursor not contained.

  As long as the catalyst of the present invention is a binary metal, it is generally considered that one metal functions as the promoter metal and the other metal is the main metal. For example, in the case of a platinum-tin catalyst, platinum can be considered the main metal for producing the hydrogenation catalyst of the present invention, while tin is considered the promoter metal. However, sometimes this distinction is not true, especially when the selectivity of the platinum-tin catalyst with respect to the desired product ethanol is close to zero both in the absence of tin and in the absence of platinum. Note that there is a possibility. For reasons of convenience, it is preferable to call one or more platinum group metals as the main catalyst and other metals as promoters. This should not be taken as an indication of the basic mechanism of catalytic activity.

Bimetallic catalysts are often impregnated in two steps. First add the “promoter” metal and then the “main” metal. Drying and calcination are performed after each impregnation step. Bimetallic catalysts can also be produced by co-impregnation. In the case of a promoted bimetallic catalyst as described above, a second impregnation starts with the addition of a “promoter” metal and then involves the co-impregnation of two main metals, namely Pt and Sn. Sequential impregnation that performs the process can be used. For example, PtSn / CaSiO ₃ on SiO ₂ causes the first impregnated and CaSiO ₃ on SiO _2, then chloroplatinic acid, amine solubilized platinum hydroxide, palladium nitrate or palladium chloride, sodium palladium chloride, sodium platinum , Pt (NH ₃ ) ₄ (NO ₄ ) _{2 and the} like. Again, drying and calcination are performed after each impregnation. In most cases, impregnation can be performed using a metal nitrate solution. However, various other soluble salts that release metal ions upon calcination can also be used. Examples of other metal salts suitable for impregnation include metal acids such as perrhenic acid solution, metal oxalate and the like. When producing substantially pure ethanol, it is generally preferred to avoid the use of halogenated precursors for platinum group metals, and instead use nitrogen containing amine and / or nitrate based precursors. .

The reaction can be carried out in the vapor state under a wide range of conditions. Preferably the reaction is carried out in the vapor phase. For example, using a reaction temperature in the range of about 125 ° C to about 350 ° C, more usually about 200 ° C to about 325 ° C, preferably about 225 ° C to about 300 ° C, and most preferably about 250 ° C to 300 ° C. it can. The pressure is generally not critical to the reaction, and pressures below atmospheric pressure, atmospheric pressure, or above atmospheric pressure can be used. However, in most cases, the reaction pressure is in the range of about 1-30 absolute atmospheric pressure. In another form of the process of the present invention, the hydrogenation can be carried out at just enough pressure to overcome the pressure drop across the catalyst bed, usually at the total hourly space velocity (GHSV) selected, but more There are no restrictions on the use of high pressures, and at 5000 hr ^-1 and 6,500 hr ^-1 space velocities, a significant pressure drop through the reactor bed can be encountered, which is easily achieved with the catalyst of the present invention. It is understood that can be used.

  The reaction consumes 2 moles of hydrogen per mole of acetic acid to produce 1 mole of ethanol, but the actual mole ratio of hydrogen to acetic acid in the feed stream is between a wide range of limits, for example about 100: It can be varied between 1-1: 100. However, this ratio is preferably in the range of about 1:20 to 1: 2. More preferably, the molar ratio of hydrogen to acetic acid is about 5: 1.

  The raw materials used in connection with the method of the present invention can be derived from any suitable source including natural gas, petroleum, coal, biomass and the like. It is well known to produce acetic acid by methanol carbonylation, acetaldehyde oxidation, ethylene oxidation, oxidative fermentation, anaerobic fermentation, and the like. As oil and natural gas fluctuate and become more expensive or cheaper, there is an increasing interest in methods of producing intermediates such as acetic acid and methanol and carbon monoxide from alternative carbon sources. In particular, if petroleum is relatively expensive compared to natural gas, it may be advantageous to produce acetic acid from synthesis gas (syngas) derived from any suitable carbon source. For example, U.S. Pat. No. 6,232,352 to Vidalin (the disclosure of which is incorporated herein by reference) teaches a method for retrofitting a methanol plant to produce acetic acid. By remodeling the methanol plant, the large equipment costs associated with CO production for the new acetic acid plant are greatly reduced or largely eliminated. All or part of the syngas is bypassed from the methanol synthesis loop and fed to the separator unit to recover CO and hydrogen, which is then used to produce acetic acid. In addition to acetic acid, this process can also be used to produce the hydrogen used in connection with the present invention.

  In Steinberg et al., US Pat. No. RE 35,377, which is also incorporated herein by reference, a process for producing methanol by converting carbonaceous materials such as petroleum, coal, natural gas, and biomass materials. Is given. This process involves hydrogenating a solid and / or liquid carbonaceous material to obtain a process gas, which is steam pyrolyzed with additional natural gas to form a synthesis gas. Syngas can be converted to methanol, which can be carbonylated to acetic acid. This process also produces hydrogen that can be used in connection with the present invention as described above. Grady et al., US Pat. No. 5,821,111 (a method for converting waste biomass to syngas by gasification is disclosed), and Kindig et al. US Pat. No. 6,685,754 (the disclosures of which are hereby incorporated by reference) See also (included in the specification).

  Acetic acid is vaporized at the reaction temperature and then fed with hydrogen either undiluted or diluted with a relatively inert carrier gas such as nitrogen, argon, helium, carbon dioxide, etc. be able to.

  Alternatively, as a crude product from a flash vessel of a methanol carbonylation unit of the type described in Scates et al., US Pat. No. 6,657,078, the disclosure of which is incorporated herein by reference, the vapor form Of acetic acid can be recovered directly. The crude vapor product can be fed directly to the reaction zone of the present invention without the need to condense acetic acid and light fractions or remove water, thereby saving overall processing costs.

  Contact or residence time can also vary widely depending on variables such as the amount of acetic acid, catalyst, reactor, temperature, and pressure. Typical contact times range from less than 1 second to more than several hours when using catalyst systems other than fixed bed, and preferred contact times are between about 0.5 and 100 seconds, at least for vapor phase reactions. is there.

  Typically, the catalyst is used in a fixed bed reactor, for example in the form of an elongated pipe or tube through which reactants, usually in vapor form, pass over or through the catalyst. If desired, other reactors such as fluidized bed or ebullated bed reactors can be used. In some cases, the hydrogenation catalyst is used in combination with an inert material such as glass wool to control the pressure drop of the reactant stream through the catalyst bed and the contact time between the reactant compound and the catalyst particles. be able to.

  The following examples describe the procedures used to produce the various catalysts used in the process of the present invention. Throughout these manufacturing examples and examples, when “L” is used, this means that the lowercase “l”, the number “1”, and the uppercase “I” are unique in many fonts and / or typefaces. It is used to avoid uncertainties in between, and since the meaning of the term arises from a common usage, it should be understood as "liter" although there are no international restrictions on it.

Catalyst production (basic procedure)
The catalyst support was dried overnight at 120 ° C. under circulating air before use. All commercially available carriers (ie, SiO ₂ , ZrO ₂ ) are in 14/30 mesh or in their original form (1/16 inch or 1/8 inch pellets) unless otherwise stated. Using. After adding the metal, the powder material (ie CaSiO ₃ ) was pelletized, crushed and sieved. In the following sections, the preparation of the individual catalysts is described in detail.

Catalyst production example A
Production of 0.5 wt% platinum and 5 wt% tin on high purity low surface area silica:
A powdered and screened high surface area silica NPSG SS61138 (100 g) with a uniform particle size distribution of about 0.2 mm was dried in an oven at 120 ° C. overnight under a nitrogen atmosphere and then cooled to room temperature. To this was added a solution of platinum nitrate (Chempur) (0.82 g) in distilled water (8 mL) and a solution of tin oxalate (Alfa Aesar) (8.7 g) in dilute nitric acid (1N, 43.5 mL). added. The resulting slurry was dried by gradually heating to 110 ° C. (> 2 hours, 10 ° C./min) in an oven. The impregnated catalyst mixture was then calcined at 500 ° C. (6 hours, 1 ° C./min).

Catalyst production example B
Production of 1 wt% platinum and 1 wt% tin on high surface area silica:
Others using a solution of platinum nitrate (Chempur) (1.64 g) in distilled water (16 mL) and a solution of tin oxalate (Alfa Aesar) (1.74 g) in dilute nitric acid (1 N, 8.5 mL) Substantially repeated the procedure of Catalyst Preparation Example A.

Catalyst production example C
Production of 1 wt% platinum and 1 wt% tin on calcium metasilicate:
Using a solution of platinum nitrate (Chempur) (1.64 g) in distilled water (16 mL) and a solution of tin oxalate (Alfa Aesar) (1.74 g) in dilute nitric acid (1 N, 8.5 mL), the catalyst The procedure of Catalyst Preparation Example B was substantially repeated except that calcium metasilicate was used as the support.

Catalyst production example D
Production of 0.5 wt% platinum, 0.5 wt% tin, and 0.2 wt% cobalt on high surface area silica:
Powdered and screened high surface area silica (100 g) with a uniform particle size distribution of about 0.2 mm was dried in an oven at 120 ° C. overnight under a nitrogen atmosphere and then cooled to room temperature. To this was added a solution of platinum nitrate (Chempur) (0.82 g) in distilled water (8 mL) and a solution of tin oxalate (Alfa Aesar) (0.87 g) in dilute nitric acid (1 N, 4.5 mL). added. The resulting slurry was dried by gradually heating to 110 ° C. (> 2 hours, 10 ° C./min) in an oven. The impregnated catalyst mixture was then calcined at 500 ° C. (6 hours, 1 ° C./min). To this calcined and cooled material was added a solution of cobalt nitrate hexahydrate (0.99 g) in distilled water (2 mL). The resulting slurry was dried by gradually heating to 110 ° C. (> 2 hours, 10 ° C./min) in an oven. The impregnated catalyst mixture was then calcined at 500 ° C. (6 hours, 1 ° C./min).

Catalyst production example E
Production of 0.5 wt% tin on high purity low surface area silica:
Powdered and screened high purity low surface area silica (100 g) with a uniform particle size distribution of about 0.2 mm was dried in an oven overnight at 120 ° C. under a nitrogen atmosphere and then cooled to room temperature. To this was added a solution of tin oxalate (Alfa Aesar) (1.74 g) in dilute nitric acid (1N, 8.5 mL). The resulting slurry was dried by gradually heating to 110 ° C. (> 2 hours, 10 ° C./min) in an oven. The impregnated catalyst mixture was then calcined at 500 ° C. (6 hours, 1 ° C./min).

Catalyst production example F
Production of 2 wt% platinum and 2 wt% tin on high surface area silica:
A powdered and screened high surface area silica NPSG SS61138 (100 g) of uniform particle size distribution of about 0.2 mm was dried overnight at 120 ° C. in a circulating air oven atmosphere and then cooled to room temperature. To this was added a solution of nitrate hexahydrate (Chempur). The resulting slurry was dried by heating gradually to 110 ° C. (> 2 hours, 10 ° C./min) in an oven and then calcined. To this was added a solution of platinum nitrate (Chempur) in distilled water and a solution of tin oxalate (Alfa Aesar) in dilute nitric acid. The resulting slurry was dried by gradually heating to 110 ° C. (> 2 hours, 10 ° C./min) in an oven. The impregnated catalyst mixture was then calcined at 500 ° C. (6 hours, 1 ° C./min).

Catalyst production example G
Production of 1 wt% platinum and 1 wt% tin on high surface area silica promoted by 5% ZnO:
The procedure of Catalyst Preparation Example F was substantially repeated except that a solution of zinc nitrate hexahydrate was added to the high surface area silica described in Catalyst Preparation Example F. The resulting slurry was dried by heating gradually to 110 ° C. (> 2 hours, 10 ° C./min) in an oven and then calcined. Thereafter, a solution of platinum nitrate (Chempur) in distilled water and a solution of tin oxalate (Alfa Aesar) (1.74 g) in dilute nitric acid (1N, 8.5 mL) to high surface area silica promoted by zinc. added.

Catalyst production example H
5% 1 wt% platinum and 1 wt% zinc production on high surface area silica promoted with SnO _2:
In place of zinc nitrate hexahydrate, a solution of tin acetate (Sn (OAc) ₂ ), and a solution of platinum nitrate in distilled water: Pt (NH ₃ ) ₄ (NO ₃ ) ₂ (Aldrich), and in dilute nitric acid The procedure of Catalyst Preparation Example G was substantially repeated except that a solution of tin oxalate (Alfa Aesar) was added to the high surface area silica.

Catalyst production example I
Production of 1.5 wt% platinum, 0.5 wt% tin on calcium metasilicate:
The procedure of Catalyst Preparation Example C above was repeated except that a solution of platinum nitrate (Chempur) in distilled water and a solution of tin oxalate (Alfa Aesar) in dilute nitric acid were used.

Catalyst production example J
Production of 1.5 wt% platinum, 10 wt% cobalt on high surface area silica:
Using the solution of platinum nitrate (Chempur) in distilled water and the solution of cobalt nitrate (II) hexahydrate (1.74 g) instead of stannous octoate, the procedure of Catalyst Preparation Example H was repeated. It was.
A summary of the composition of the catalyst produced and the composition of other catalysts produced and tested by similar procedures is shown in Table 1.

Catalyst production examples K to O
SiO ₂ —Pt _x Sn _1-x (0 <x <1): Five materials were prepared by changing the molar fraction of Pt while maintaining the total metal amount (Pt + Sn) of 1.20 mmol. The following preparation example describes the procedure for catalyst preparation example K: SiO ₂ —Pt _0.5 Sn _0.5 (ie x = 0.5; equimolar ratio of both metals). The remaining preparations (ie, x = 0, 0.25, 0.75, and 1.00; catalyst preparations L, M, N, and O, respectively) are prepared with an appropriate amount of metal precursor: Pt ( was carried out in the same manner by using a _{NH 3) 4 (NO 3)} 2 and Sn _{(OAc) 2.} The catalyst was initially Sn (OAc) ₂ (tin acetate, Sn (OAc) ₂ from Aldrich) (0.1421 g, 0.60 mmol) in a glass bottle containing 6.75 mL of 1: 1 diluted glacial acetic acid (Fisher). It was prepared by adding to The mixture was stirred at room temperature for 15 minutes, then 0.2323 g (0.60 mmol) of solid Pt (NH ₃ ) ₄ (NO ₃ ) ₂ (Aldrich) was added. The mixture is stirred for an additional 15 minutes at room temperature and then in a 100 mL round bottom flask, 5.0 g dry SiO ₂ catalyst support (high purity silica catalyst support: HSA SS # 61138, SA = 250 m ² / g; SZ # 61152, SA = 156 m ² / g; Saint-Gobain NorPro). After all the metal solution was added, the metal solution was continuously stirred while rotating the flask until all the Pt / Sn mixture was added to the SiO ₂ catalyst support. After the addition of the metal solution was complete, the flask containing the impregnated catalyst was left at room temperature for 2 hours. Next, the flask was attached to a rotary evaporator (bath temperature 80 ° C.), and the flask was drained until it was dried while rotating slowly. The material is then further dried at 120 ° C. overnight before the following temperature program: 25 ° C. → 160 ° C./5.0° C./min; temperature rise for 2.0 hours; 160 → 500 ° C./2.0 Calcination was carried out using a temperature rising at 0 ° C./min; holding for 4 hours. Yield: 5.2 g dark gray material.

Catalyst production example P
SiO ₂ —CaSiO ₃ (5) —Pt (3) —Sn (1.8): This material is first added CaSiO ₃ (Aldrich) to the SiO ₂ catalyst support and then Pt / P as described above. Prepared by adding Sn. First, 0.52 g of solid is added to 13 mL of deionized H ₂ O and then 1.0 mL of colloidal SiO ₂ (15 wt% solution, NALCO) is added to the aqueous solution of CaSiO ₃ (≦ 200 mesh). A suspension was prepared. The suspension was stirred at room temperature for 2 hours and then added to 10.0 g SiO ₂ catalyst support (14/30 mesh) using the incipient wetness method. After standing for 2 hours, the material was evaporated to dryness, then dried overnight at 120 ° C. under circulating air and calcined at 500 ° C. for 6 hours. Next, following the procedure described above for the SiO ₂ —Pt _x Sn _1-x material, 0.6711 g (1.73 mmol) of Pt (NH ₃ ) ₄ (NO ₃ ) ₂ and 0.4104 g (1. All of the SiO ₂ —CaSiO ₃ material was used for Pt / Sn metal impregnation using 73 mmol) Sn (OAc) ₂ . Yield: 11.21 g of dark gray material.

Catalyst production example Q
_{CaSiO 3 -Pt (1) -Sn (} 1): To a round bottom flask 100mL containing Teflon-coated magnetic stirrer, was added 1.0 M-NHO ₃ of 40 mL, then 0.2025g of (0.52 mmol) Solid Pt (NH ₃ ) ₄ (NO ₃ ) ₂ was added. The Pt complex was dissolved with stirring and then 0.2052 g (0.87 mmol) of solid Sn (OAc) ₂ was added. Next, 10.0 g CaSiO ₃ (≦ 200 mesh) was added with stirring, then the mixture was heated to 80 ° C. and stirred at this temperature for 2 hours. The suspension was then drained to dryness using a rotary evaporator (bath temperature 80 ° C.), the solid was transferred into a porcelain dish and dried overnight at 120 ° C. under circulating air. After calcination (temperature rise at 25 ° C. → 160 ° C./5.0° C./min; hold for 2.0 hours; temperature rise at 160 → 500 ° C./2.0° C./min; hold for 4 hours), press the material And pelletized under pressure (our particular press applies 40,000 pounds of force for 15 minutes), crushed and sieved to 14/30 mesh. Yield: 9.98 g wheat material.

Catalyst production example R
_{SiO 2 -TiO 2 (10) -Pt} (3) -Sn (1.8): was as follows preparing TiO ₂ modified silica carrier. A solution of 4.15 g (14.6 mmol) of Ti {OCH (CH ₃ ) ₂ } ₄ in 2-propanol (14 mL) was placed in a 100 mL round bottom flask with 10.0 g of SiO ₂ catalyst support (1 / 16 inch extrudate). The flask was left at room temperature for 2 hours and then drained to dryness using a rotary evaporator (bath temperature 80 ° C.). Next, 20 mL of deionized H ₂ O was slowly added to the flask and the material was left for 15 minutes. The resulting water / 2-propanol was then removed by filtration and the addition of H ₂ O was repeated two more times. The final material was dried overnight at 120 ° C. under circulating air and then calcined at 500 ° C. for 6 hours. Then, follow the procedure described above for SiO2-PtxSn1-x materials, 0.6711G of (1.73 mmol) _Pt of _{(NH 3) 4 (NO 3} ) 2 and 0.4104G (1.73 mmol) All of the SiO ₂ —TiO ₂ material was used for Pt / Sn metal impregnation using Sn (OAc) ₂ . Yield: 11.98 g dark gray 1/16 inch extrudate.

Catalyst production example S
_{SiO 2 -WO 3 (10) -Pt} (3) -Sn (1.8): to prepare a WO ₃ modified silica support in the following manner. A solution of 1.24 g (0.42 mmol) (NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ · nH ₂ O (AMT) in deionized H ₂ O (14 mL) was placed in a 100 mL round bottom flask. 10.0 g SiO ₂ : NPSGSS 61138 catalyst support (SA = 250 m ² / g, 1/16 inch extrudate) was added dropwise. The flask was left at room temperature for 2 hours and then drained to dryness using a rotary evaporator (bath temperature 80 ° C.). The resulting material was dried overnight at 120 ° C. under circulating air and then calcined at 500 ° C. for 6 hours. Next, following the procedure described above for the SiO ₂ —Pt _x Sn _1-x material, 0.6711 g (1.73 mmol) of Pt (NH ₃ ) ₄ (NO ₃ ) ₂ and 0.4104 g (1. All of the (light yellow) SiO ₂ —WO ₃ material was used for Pt / Sn metal impregnation with (73 mmol) Sn (OAc) ₂ . Yield: 12.10 g dark gray 1/16 inch extrudate.

Catalyst production example T
(H-ZSM-5) -Pt (3) -Sn (1.8): slurry of H-ZSM-5 (prepared from NH ₄ -ZSM-5 by calcination at 550 ° C. for 8 hours in air) The material was prepared by impregnation. In a 100 mL round bottom flask, the ingredients were added to 40 mL of 1: 1 dilute acetic acid and the mixture was stirred at room temperature for 15 minutes to give 0.6711 g (1.73 mmol) of Pt (NH ₃ ) ₄ (NO ₃ ). An aqueous solution of ₂ and 0.4104 g (1.73 mmol) Sn (OAc) ₂ was prepared. Next, 10.0 g of solid fine powder H-ZSM-5 was added to the solution with stirring and the mixture was stirred at room temperature for another 2 hours. The flask was then drained to dryness using a rotary evaporator (bath temperature 80 ° C.) and the resulting material was dried overnight at 120 ° C. under circulating air. After calcination (heated at 250 ° C. → 160 ° C./5.0° C./min; held for 2.0 hours; heated at 160 → 500 ° C./2.0° C./min; held for 4 hours), the material was pressed And pelletized, crushed and sieved to 14/30 mesh. Yield: 9.55 g of gray material.

Catalyst production example U
SiO ₂ —Re _x Pd _1-x (0 <x <1): Five materials were prepared by changing the molar fraction of Re while maintaining the total metal amount (Re + Pd) of 1.20 mmol. The following preparation example describes the procedure for SiO ₂ —Re _0.5 Pd _0.5 (ie, x = 0.5; equimolar amounts of both metals). The remaining preparation examples (ie, x = 0, 0.25, 0.75, and 1.00) are similarly performed using appropriate amounts of metal precursors: NH ₄ ReO ₄ and Pd (NO ₃ ) _2. went. First, a metal solution was prepared by adding NH ₄ ReO ₄ (0.1609 g, 0.60 mmol) to a glass bottle containing 6.75 mL of deionized H ₂ O. The mixture was stirred at room temperature for 15 minutes and then 0.1154 g (0.60 mmol) of solid Pd (NO ₃ ) ₂ was added. The mixture was stirred at room temperature for an additional 15 minutes and then added dropwise to 5.0 g dry SiO ₂ catalyst support (14/30 mesh) in a 100 mL round bottom flask. After the addition of the metal solution was complete, the flask containing the impregnated catalyst was left at room temperature for 2 hours. Next, the flask was attached to a rotary evaporator (bath temperature: 80 ° C.) and drained to dryness. All other operations (drying, calcination) _was performed as described above with respect to SiO ₂ -Pt _{x Sn 1-x} material (see above). Yield: 5.1 g brown material.

Catalyst production example V
SiO ₂ —CaSiO ₃ (5) —Re (4.5) —Pd (1): SiO ₂ —CaSiO ₃ (5) —Pt (3) —Sn (1.8) as described for SiO ₂ -CaSiO ₃ (5) A modified catalyst support was prepared (see above). Next, a Re / Pd catalyst was prepared by impregnating SiO ₂ —CaSiO ₃ (5) (1/16 inch extrudate) with an aqueous solution containing NH ₄ ReO ₄ and Pd (NO ₃ ) ₂ . First, a metal solution was prepared by adding NH ₄ ReO ₄ (0.7237 g, 2.70 mmol) to a glass bottle containing 12.0 mL of deionized H ₂ O. The mixture was stirred at room temperature for 15 minutes and then 0.1756 g (0.76 mmol) of solid Pd (NO ₃ ) ₂ was added. The mixture was stirred for an additional 15 minutes at room temperature and then added dropwise to 10.0 g of dry SiO _2- (0.05) CaSiO ₃ catalyst support in a 100 mL round bottom flask. After the addition of the metal solution was complete, the flask containing the impregnated catalyst was left at room temperature for 2 hours. All other operations (drying, calcination) _was performed as described above with respect to SiO ₂ -Re _{x Pd 1-x} material (see above). Yield: 10.9 g brown material.

Catalyst production example W
_{CaSiO 3 -Re (5) -Pd (} 2.5): CaSiO 3 ( powder, ≦ 200 mesh) material was prepared by slurry impregnation of. In a 100 mL round bottom flask, the ingredients were added to 40 mL of deionized H ₂ O and the mixture was stirred at room temperature for 15 minutes to give 0.6169 g (2.30 mmol) NH ₄ ReO ₄ and 0.5847 g (2 .53 mmol) of an aqueous solution of Pd (NO ₃ ) ₂ was prepared. Next, 10.0 g of solid fine powdered CaSiO ₃ was added to the solution with stirring and the mixture was stirred at room temperature for an additional 2 hours. The flask was then drained to dryness using a rotary evaporator (bath temperature 80 ° C.) and the resulting material was dried overnight at 120 ° C. under circulating air. All other operations (drying, calcination) _was performed as described above with respect to SiO ₂ -Re _{x Pd 1-x} material (see above). The final material was pressed and pelletized using a press applying 40,000 pounds of force for 15 minutes, ground and sieved to 14/30 mesh. Yield: 10.65 g of brown material.

Catalyst production example X
SiO ₂ —Co (10) —Pt (1): an aqueous solution containing Co (NO ₃ ) ₂ .H ₂ O and Pt (NH ₃ ) ₄ (NO ₃ ) ₂ in HSA-SiO ₂ (14/30 mesh). The material was prepared by impregnating. First, a metal solution was prepared by adding Co (NO ₃ ) ₂ .6H ₂ O (5.56 g, 19.1 mmol) to a glass bottle containing 12.0 mL of deionized H ₂ O. The mixture was stirred at room temperature for 15 minutes and then 0.2255 g (0.58 mmol) of solid Pt (NH ₃ ) ₄ (NO ₃ ) ₂ was added. The mixture was stirred at room temperature for an additional 15 minutes and then added dropwise to 10.0 g dry SiO ₂ catalyst support (14/30 mesh) in a 100 mL round bottom flask. After the addition of the metal solution was complete, the flask containing the impregnated catalyst was left at room temperature for 2 hours. All other operations (drying, calcination) _was performed as described above with respect to SiO ₂ -Pt _{x Sn 1-x} material (see above). Yield: 11.35 g of black material.

Catalyst production example Y
_{CaSiO 3 -Co (10) -Pt (} 1): CaSiO 3 ( powder, ≦ 200 mesh) material was prepared by slurry impregnation of. The ingredients were added to 40 mL deionized H ₂ O in a 100 mL round bottom flask and the mixture was stirred at room temperature for 15 minutes to allow 5.56 g (19.1 mmol) Co (NO ₃ ) ₂ · 6H ₂ O. And 0.2255 g (0.58 mmol) of an aqueous solution of Pt (NH ₃ ) ₄ (NO ₃ ) ₂ . Next, 10.0 g of solid fine powder CaSiO ₃ was added to the solution with stirring. The mixture was then heated to 65 ° C. and stirred at this temperature for an additional 2 hours. The flask was then drained to dryness using a rotary evaporator (bath temperature 80 ° C.) and the resulting material was dried overnight at 120 ° C. under circulating air. All other operations (drying, calcination) _was performed as described above with respect to SiO 2 -Co (10) -Pt ( 1) material (see above). The final material was pressed, pelletized under pressure, crushed and sieved to 14/30 mesh. Yield: 10.65 g of black material.

Catalyst production example Z
_{ZrO 2 -Co (10) -Pt (} 1): ZrO 2 (SZ61152, Saint-Gobain NorPro, 14/30 mesh) _{to, Co (NO 3) 2 ·} 6H 2 O and _{Pt (NH 3) 4 (NO} 3 ) The material was prepared by impregnating an aqueous solution containing ₂ . First, a metal solution was prepared by adding Co (NO ₃ ) ₂ .6H ₂ O (5.56 g, 19.1 mmol) to a glass bottle containing 5.0 mL of deionized H ₂ O. The mixture was stirred at room temperature for 15 minutes and then 0.2255 g (0.58 mmol) of solid Pt (NH ₃ ) ₄ (NO ₃ ) ₂ was added. The mixture was stirred at room temperature for an additional 15 minutes and then added dropwise to 10.0 g dry ZrO ₂ catalyst support (14/30 mesh) in a 100 mL round bottom flask. After the addition of the metal solution was complete, the flask containing the impregnated catalyst was left at room temperature for 2 hours. All other operations (drying, calcination) _was performed as described above with respect to SiO 2 -Co (10) -Pt ( 1) material (see above). Yield: 11.35 g of black material.

Catalyst production example AA
_{SiO 2 -CaSiO 3 (2.5) -Pt} (1.5) -Sn (0.9):
0.26 g CaSiO ₃ , 0.5 mL colloidal SiO ₂ (15 wt% solution, NALCO), 0.3355 g (0.86 mmol) Pt (NH ₃ ) ₄ (NO ₃ ) ₂ , and 0.2052 g with Sn _{(OAc) 2} in (0.86 _mmol), was prepared materials as described above with respect to _{SiO 2 -CaSiO 3 (5) -Pt} (3) -Sn (1.8). Yield: 10.90 g of dark gray material.

Catalyst production example BB
_{TiO 2 -CaSiO 3 (5) -Pt} (3) -Sn (1.8):
The material was prepared by first adding CaSiO ₃ to a TiO ₂ catalyst (Anatase, 14/30 mesh) support and then adding Pt / Sn as described above. First, 0.52 g of solid is added to 7.0 mL of deionized H ₂ O and then 1.0 mL of colloidal SiO ₂ (15 wt% solution, NALCO) is added to form CaSiO ₃ (≦ 200 mesh). An aqueous suspension of was prepared. The suspension was stirred at room temperature for 2 hours and then added to 10.0 g TiO ₂ catalyst support (14/30 mesh) using the incipient wetness method. After standing for 2 hours, the material was evaporated to dryness, then dried overnight at 120 ° C. under circulating air and calcined at 500 ° C. for 6 hours. Next, following the procedure described above for the SiO ₂ —Pt _x Sn _1-x material, 0.6711 g (1.73 mmol) of Pt (NH ₃ ) ₄ (NO ₃ ) ₂ and 0.4104 g (1. All of the TiO ₂ —CaSiO ₃ material was used for Pt / Sn metal impregnation using 73 mmol) Sn (OAc) ₂ . Yield: 11.5 g light gray material.

Catalyst production example CC
KA160-Pt (3) -Sn (1.8):
The material was prepared by incipient wetness impregnation of _{- ((0.05) Al 2 O} 3, Sud Chemie, 14/30 -mesh SiO 2) KA160 catalyst support as described above with respect to SiO ₂ -Pt _x Sn _1-x (See above). First, a metal solution was prepared by adding Sn (OAc) ₂ (0.2040 g, 0.86 mmol) to a glass bottle containing 4.75 mL of 1: 1 diluted glacial acetic acid. The mixture was stirred at room temperature for 15 minutes and then 0.3350 g (0.86 mmol) of solid Pt (NH ₃ ) ₄ (NO ₃ ) ₂ was added. The mixture was stirred at room temperature for an additional 15 minutes and then added dropwise to 5.0 g of dry KA160 catalyst support (14/30 mesh) in a 100 mL round bottom flask. All other operations (drying, calcination) _was performed as described above with respect to _{SiO 2 -Pt x Sn 1-x} ( see above). Yield: 5.23 g wheat material.

Catalyst production example DD
KA160-CaSiO ₃ (8) -Pt (3) -Sn (1.8):
The material was prepared by first adding CaSiO ₃ to the KA160 catalyst support and then adding Pt / Sn as described above for KA160-Pt (3) -Sn (1.8). First, 0.42 g of solid was added to 3.85 mL of deionized H ₂ O, followed by addition of 0.8 mL of colloidal SiO ₂ (15 wt% solution, NALCO) to produce CaSiO ₃ (≦ 200 mesh). An aqueous suspension of was prepared. The suspension was stirred at room temperature for 2 hours and then added to 5.0 g KA160 catalyst support (14/30 mesh) using the incipient wetness method. After standing for 2 hours, the material was evaporated to dryness, then dried overnight at 120 ° C. under circulating air and calcined at 500 ° C. for 6 hours. _Then, follow the procedure described above for the SiO ₂ -Pt _{x Sn 1-x material, Pt (NH 3) 4 (} NO 3) of 0.3350g (0.86 mmol) ₂ and 0.2040g (0. for Pt / Sn metal impregnation using Sn _{(OAc) 2} in 86 mmol) was used all the KA160-CaSiO ₃ material. Yield: 5.19 g wheat material.

Gas chromatographic (GC) analysis of the product:
The product was analyzed by on-line GC. Reactants and products were analyzed using a three-channel miniature GC equipped with one flame ionization detector (FID) and two thermal conductivity detectors (TCD).

  FID and CP-Sil 5 (20 m) + WaxFFap (5 m) are attached to the front channel, and are used with acetaldehyde; ethanol; acetone; methyl acetate; vinyl acetate; ethyl acetate; acetic acid; ethylene glycol diacetate; Ethylidene diacetate; and paraaldehyde;

The middle channel was fitted with TCD and Porabond Q columns and used to quantify CO ₂ ; ethylene; and ethane.
The back channel was fitted with a TCD and Molsieve 5A column and used to quantify helium; hydrogen; nitrogen; methane; and carbon monoxide.

  Prior to the reaction, the retention times of the different components were determined by spiking the individual compounds and the GC was calibrated using either a calibration gas of known composition or a liquid solution of known composition. As a result, response coefficients for various components could be obtained.

Example 1
A 50 mL catalyst prepared as described in Catalyst Preparation Example C above was placed in a stainless steel tubular reactor having an internal diameter of 30 mm and capable of raising the temperature to a controlled temperature. The total catalyst bed length after packing was about 70 mm.

The feed solution contained substantially acetic acid. The reaction feed was evaporated and charged to the reactor at a temperature of 250 ° C. and a pressure of 100 psig using an average total gas space velocity (GHSV) of 2500 hr ⁻¹ with hydrogen and helium as the carrier gas. The feed stream contained about 6.1% to about 7.3% mol% acetic acid and about 54.3% to about 61.5% mol% hydrogen. A portion of the vapor effluent from the reactor was passed through a gas chromatograph for analysis of the contents of the effluent. At 85% acetic acid conversion, the selectivity to ethanol was 93.4%.

The catalyst used was 1 wt% platinum and 1 wt% tin on silica prepared according to the procedure of Catalyst Preparation Example A.
Example 2
The catalyst used was 1 wt% platinum and 1 wt% tin on calcium silicate prepared according to the procedure of Example C.

The procedure shown in Example 1 was substantially repeated using a feed stream of vaporized acetic acid and hydrogen with an average total gas space velocity (GHSV) of 2,500 hr ⁻¹ at a temperature of 250 ° C. and a pressure of 22 bar. A portion of the vapor effluent was passed through a gas chromatograph for analysis of the effluent contents. The acetic acid conversion was greater than 70% and the ethanol selectivity was 99%.

Comparative Example 1
The catalyst used was 1 wt% tin on low surface area high purity silica prepared according to the procedure of Example E.

The procedure shown in Example 1 was substantially repeated using a feed stream of vaporized acetic acid and hydrogen with an average total gas space velocity (GHSV) of 2,500 hr ⁻¹ at a temperature of 250 ° C. and a pressure of 22 bar. A portion of the vapor effluent was passed through a gas chromatograph for analysis of the effluent contents. The acetic acid conversion was less than 10% and the ethanol selectivity was less than 1%.

Example 3
Using various catalysts, the percent of carbon monoxide (CO), acetaldehyde (AcH), and ethane in the product, and the selectivity to ethyl acetate (EtOAc); ethanol (EtOH) and its productivity, and acetic acid ( The procedure of Example 2 was repeated at the temperatures shown in Table 2 showing the conversion of HOAc) (MCD p.4). During the reaction, the molar ratio of H ₂ to acetic acid was kept at 5: 1. For convenience, the results of Examples 1 and 2 and Comparative Example 1 are also included in Table 2. Generally speaking, if it is desired to produce ethanol as the main product, a selectivity to ethanol of greater than 80% is desirable and a choice for ethyl acetate of less than 5%, preferably less than 3%. Rate is desirable.

Example 4
About 250 meters ² / g high surface area silica with a surface area of (NPSG SS61138) 2 wt% on Pt; and 2 wt% Sn; on the hydrogenation catalyst of the present invention including the vaporized acetic acid and hydrogen, about 160 sccm / min -H _2: the ratio of the 0.09 g / min -HOAc hydrogen and acetic acid, hydrogen diluted with about 60 sccm / min of _{N 2,} was passed at a pressure in the space velocity and 200psig about 6570hr ^-1. As shown in FIGS. 1 and 2, the temperature was increased at about 50, 70, and 90 hours. Here, the productivity (g) of the indicated products (ethanol, acetaldehyde, and ethyl acetate) per hour per kg of catalyst is shown in FIG. 1, and the catalyst selectivity for various products is shown in FIG. The upper line shows the productivity or selectivity to ethyl acetate, the middle line shows ethanol and the lower line shows acetaldehyde. It is considered particularly important that the productivity of acetaldehyde and the selectivity related thereto were low. The results are summarized in the data summary below.

Example 5
Vaporized acetic acid with an average total gas space velocity (GHSV) of 2500 hr ⁻¹ using a catalyst loaded with 2 wt% Pt; 2 wt% Sn on a catalyst containing pellets of high surface area silica SS61138 from Saint-Gobain NorPro The procedure shown in Example 1 was substantially repeated using feed streams of hydrogen, helium, and helium at the indicated temperatures and pressures of 100 psig shown in Table 2. The resulting feed stream contained about 7.3% mol% acetic acid and about 54.3% mol% hydrogen. A portion of the vapor effluent was passed through a gas chromatograph for analysis of the effluent contents. The results are shown in Table 1.

  The results of Example 5 are summarized in FIG. This is because in the so-called adiabatic reactor where the relative insensitivity of the catalyst to changes in temperature can cause the catalyst to change greatly in temperature on the catalyst bed due to the low and uneven rate of heat removal from the reactor. Indicates that it is appropriate to use.

Example 6
(I) Varying the mole fraction of Pt at a constant metal loading ([Pt] + [Sn] = 1.20 mmol), and (ii) SiO ₂ —Pt _x Sn _{(1 -X)} The effect of the [Sn] / [Pt] molar ratio in the catalyst was studied. A clear maximum was observed at a Pt mole fraction of 0.5 (ie, [Sn] / [Pt] = 1.0) for both acetic acid conversion and ethanol selectivity. The selectivity to ethyl acetate changed sharply with ethanol predominance at [Sn] / [Pt] = 1.0. Ethyl acetate was observed as the main product at either 25% or 75% Pt mole fraction. It is clear that the presence of equimolar ratios of Pt and Sn is favorable for increasing both acetic acid conversion and selectivity to ethanol (see FIGS. 4A-C).

A book containing vaporized acetic acid (0.09 g / min HOAc) and hydrogen (160 sccm / min H ₂ ; 60 sccm / min N ₂ ) with Pt and Sn on high surface area silica having a surface area of about 250 m ² / g. It was passed over the inventive hydrogenation catalyst at a temperature of 250 ° C .; a GHSV of 6570 hr ⁻¹ ; a reaction time of 12 hours. In Example 6, the amount of metal (Pt + Sn) was kept constant, and the mass fraction of platinum was changed between 0 and 1. 4A-4C show catalyst selectivity, activity, and productivity in each. From this example, the maximum value appears in selectivity, activity, and productivity when the mass fraction of platinum is about 0.5, ie, when the weight of platinum in the catalyst is substantially equal to the amount of tin. I can admit that.

Example 7
A book containing vaporized acetic acid and hydrogen on high purity high surface area silica with a surface area of about 250 m ² / g, 3 wt% Pt, 1.5 wt% Sn, and 5 wt% CaSiO ₃ as promoter. It was passed over the inventive hydrogenation catalyst at a temperature of about 225 ° C. with about 5: 1 moles of hydrogen and acetic acid. Figures 5A and 5B show catalyst selectivity and productivity as a function of operating time during the initial portion of the catalyst life. From the results of this example reported in FIGS. 6A and 6B, it can be seen that over 90% ethanol selectivity activity and over 500 g ethanol productivity per hour per kg of catalyst can be achieved.

Example 8
The procedure of Example 8 was repeated at the temperature of about 250 ° C. (same catalyst?). 7A-7B show catalyst selectivity and productivity as a function of operating time during the initial portion of the catalyst life. From the results of this example reported in FIGS. 7A and 7B, at this temperature, it is possible to achieve more than 90% ethanol selectivity activity with more than 800 g of ethanol productivity per hour per kg of catalyst. I can admit that there is.

Example 9
In order to investigate the sensitivity of the temperature used to reduce the binary platinum-tin precursor to the catalytic species, SiO _2- (Pt _0.5 Sn ₀ optimized Pt / Sn in an independent experiment at 225 to 500 ° C. _.5 ) The effect of reduction temperature was investigated by activating the catalyst (see below). In four experiments, the material was activated at 280, 350, 425, and 500 ° C. under flowing hydrogen for 4 hours and then acetic acid reduced at a reaction temperature of 250 ° C. (catalytic activation was 10 mol% H _2. / N ₂ mixture (275 sccm / min) and under atmospheric pressure the following temperature program: room temperature → reduction temperature (225-500 ° C.), temperature rise at 2 ° C./min; hold for 4.0 hours; then HOAc Reduced to 250 ° C. for reduction (or increased temperature if necessary): In addition, materials activated at 225 ° C. were studied at both 225 and 250 ° C. reaction temperatures in HOAc hydrogenation. Both reaction temperatures: for 225 and 250 ° C, a selection for ethanol and ethyl acetate over the entire temperature range, including for the catalyst activated at 225 ° C. No significant change in rate was observed, interestingly, for catalysts activated at lower reduction temperatures of 225 and 280 ° C., a large increase in conversion (and productivity) was observed. The decrease in the conversion at may be due to the sintering of the metal particles (see Figures 7A and 7B) Since no change in selectivity was observed, the composition of the metal particles (ie PtSn alloy) is It is clear that it is held unchanged, the results of this example are shown in FIGS.

  In these examples, various other products such as acetaldehyde, ethanol, ethyl acetate, ethane, carbon monoxide, carbon dioxide, methane, isopropanol, acetone, and water were detected.

Example 10
Using 2.5 mL solid catalyst of the catalyst shown in Table 4, the catalytic properties of various catalysts were evaluated in the catalytic hydrogenation of acetic acid. In each case, the catalyst particles had a size of 14/30 mesh and were diluted 1: 1 v / v with 14/30 mesh quartz pieces. In each experiment, the operating pressure was 200 psig (14 bar), 0.09 g / min acetic acid; 120 sccm / min of hydrogen; 60 sccm / min nitrogen; feed rate of; a total hourly space velocity of 6570hr ^-1, 24 Performed over a period of time running time (TOS). The results are shown in Table 4.

Example 11
Catalyst _{Stability: SiO 2 -CaSiO 3 (5)} -Pt (3) -Sn (1.8): catalyst performance and initial SiO 2 -CaSiO 3 (5) -Pt (3) -Sn (1.8) Stability was evaluated over a 100 hour reaction time at a constant temperature (260 ° C.). Only small changes in catalyst performance and selectivity were observed over the entire reaction time of 100 hours. Acetaldehyde appeared to be the only by-product and its concentration (about 3% by weight) was kept unchanged throughout the experiment. An overview of catalyst productivity and selectivity is given in FIGS. 5A and 5B. The effect of reaction temperature on product selectivity was investigated over a total reaction time of 125 hours in another experiment. See above.

Example 12
Productivity and selectivity in the hydrogenation of 3% Pt: 1.5% Sn acetic acid on high purity high surface area SiO ₂ stabilized by 5% CaSiO ₃ , hydrogenation and esters in the normal range of operating conditions Using a fixed bed continuous reactor system that mainly produces acetaldehyde, ethanol, and ethyl acetate by the hydration reaction, 2.5 mL of solid catalyst (14/30 mesh, 1: 1 diluted (v / v, 14/30 mesh quartz) At a pressure of 200 psig; 0.09 g / min-HOAc; 160 sccm / min-H ₂ ; 60 sccm / min-N ₂ ; feed rate; and 6570 hr ⁻¹ GHSV; The test was conducted at 225 ° C. with an operation time of 15 hours. The results are shown in FIGS. 6A and 6B.

Example 13
Using 2.5 mL of solid catalyst (14/30 mesh, 1: 1 dilution (v / v, diluted by 14/30 mesh quartz pieces)) at 200 psig (14 bar) pressure; 0.09 g / min Acetic acid was supplied at 160 sccm / min-hydrogen and 60 sccm / min-nitrogen as a diluent; at a temperature of 250 ° C .; at 6570 hr ⁻¹ GHSV; + [Sn] = 1.20 mmol) of the catalyst containing Re and Pd in SiO ₂ in which the molar ratio of Re _x Pd _(1-x) was changed between the catalysts by changing the molar fraction of Re. Productivity and selectivity were investigated. A maximum conversion of acetic acid was observed at a Re mole fraction of about 0.6, but only ethanol was the main product at a Re mole fraction of about 0.78. At this molar ratio between Re and Pd (denoted “Re ₇ Pd ₂ ”), the selectivity to ethyl acetate varied narrowly to ethanol predominance. Importantly, as shown for the Pd / Sn series above, the presence of two metals in a specific ratio may be a major structural requirement for the selectivity of a specific product. it is obvious. That is, the selectivity is shifted towards ethanol at [Re] / [Re + Pd] = 0.78 (FIGS. 8, 9, and 10: this is the mass fraction of rhenium in the catalyst where X _i (Re) is Except in the same manner as in FIGS. 4A-C). However, in contrast to Pt / Sn materials, the maximum conversion of acetic acid and selectivity to ethanol is not consistent with these materials, and preferential selectivity to ethanol is only observed at low HOAc conversion. There wasn't. Thus, maximum productivity is seen with ethyl acetate, not with ethanol. See FIG. Furthermore, with a CaSiO ₃ —Re (5) —Pd (2.5) catalyst, hydrocarbons (methane and ethane; 5.3 and 2 respectively) at about 30% acetic acid conversion and a reaction temperature of only 225 ° C. .4 wt%) formation was observed. Although higher acetic acid conversions can probably be obtained by increasing the reaction temperature, the amount of hydrocarbons will probably increase as well, thus limiting the overall efficiency of the Re / Pr-based catalyst system.

Example 14
Initial catalyst screening with silica-supported platinum (1%) cobalt catalyst on SiO ₂ (Co loading = 10 wt%) resulted in high acetic acid conversion and about 80% selectivity to ethanol. See FIGS. 11 and 12 (where selectivity and activity are as defined above, results for ethanol are represented by squares, results for ethyl acetate are represented by circles, acetaldehyde is represented by diamonds, ethane is represented by triangles). . However, it is clear that the catalyst deteriorates because the acetic acid selectivity dropped from about 80% to 42% during the reaction time of 9 hours. In addition, large changes in productivity were observed as well, increasing selectivity to ethyl acetate and acetaldehyde and decreasing ethanol selectivity. Similar results were observed with 10% cobalt supported on silica.

Example 15
Vaporized acetic acid (0.09 g / min-HOAc) and hydrogen (160 sccm / min-H ₂ ; 60 sccm / min-N ₂ ) at a pressure of 200 psig, 3% by weight on a support containing ZSM-5 molecular sieve in hydrogen form It was passed over a hydrogenation catalyst of the invention containing Pt and 1.8 wt% Sn at a temperature of 250 ° C .; GHSV of 6570 hr ⁻¹ ; with a reaction time of 12 hours. With 4% ethyl acetate, diethyl ether was observed with a selectivity of 96% and a productivity of 2646 g / kg / hr, with 78% acetic acid remaining unreacted.

Example 16
Vaporized acetic acid (0.09 g / min-HOAc) and hydrogen (160 sccm / min-H ₂ ; 60 sccm / min-N ₂ ) at a pressure of 200 psig, 2 wt% Pt and 1 wt% on a support comprising high surface area graphite. It was passed over a hydrogenation catalyst of the invention containing Sn at 275 ° C .; 6570 hr ⁻¹ GHSV; with a reaction time of 12 hours. The selectivity to ethyl acetate is 43%, the selectivity to ethanol is 57%, the productivity of ethyl acetate is 66 g / kg / hour, the productivity of ethanol is 88 g / kg / hour, The conversion rate was 12%.

  Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be readily apparent to those skilled in the art. In view of the above discussion, relevant knowledge in the art, and references discussed above in connection with background and detailed description (the disclosures of which are all incorporated herein by reference), further An illustration is considered unnecessary. Further, it should be understood that the forms of the present invention as set forth below and / or the claims, as well as the various aspects and portions of the various features, can be combined or exchanged in whole or in part. is there. Moreover, those skilled in the art will recognize that the above description is for illustrative purposes only and is not intended to limit the invention.

Thus, according to the present invention, a novel process and catalyst for providing a hydrogenation product based on acetic acid is provided.
For example, the first embodiment disperses a gaseous stream comprising vapor phase hydrogen and acetic acid in a molar ratio of at least about 4: 1 hydrogen to acetic acid on a siliceous support at a temperature between about 225 ° C. and 300 ° C. A method of producing ethanol by reduction of acetic acid comprising passing over a platinum and tin-containing hydrogenation catalyst, wherein the amount and oxidation state of platinum and tin, and the ratio of platinum to tin, and silica The carrier is (i) at least 80% of the converted acetic acid is converted to ethanol; (ii) less than 4% of the acetic acid is selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, ethylene, and mixtures thereof. Conversion to compounds other than compounds; and the activity of the catalyst is reduced to a vapor mixture of acetic acid and hydrogen in a 10: 1 molar ratio to a pressure of 2 atm and a temperature of 275 ° C. and a GH of 2500 hr ⁻¹ . The above method of selecting, configuring and controlling such that it decreases by less than 10% upon exposure for 168 hours in SV.

  In the second aspect, the hydrogenation catalyst is substantially composed of platinum and tin dispersed on a siliceous support, the siliceous support is a modified siliceous support, and the modified siliceous support is (i) alkaline earth. Oxides, (ii) alkali metal oxides, (iii) alkaline earth metasilicates, (iv) alkali metal metasilicates, (v) zinc oxide, (vi) zinc metasilicates, and (vii) (i)- The method of the first aspect, comprising an effective amount of a carrier modifier selected from the group consisting of a precursor for any of (vi) and a mixture of any of (i) to (vii).

  In a third aspect, the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures of any of the above. A method of an embodiment.

The fourth embodiment is that of (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The fifth aspect is the method of the third aspect, wherein the molar ratio of platinum and tin is between 4: 5 and 5: 4.

  In a sixth aspect, the method of the second aspect, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc metasilicates, and precursors therefor, and mixtures of any of the above. It is.

The seventh embodiment is that of (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst, and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The eighth aspect is the method according to the sixth aspect, wherein the molar ratio of platinum and tin is between 4: 5 and 5: 4.

  A ninth aspect is the method of the second aspect, wherein the carrier modifier is selected from the group consisting of magnesium, calcium, and zinc oxides and metasilicates, precursors related thereto, and mixtures of any of the above. is there.

The tenth embodiment is the embodiment of the ninth embodiment, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst, and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The eleventh aspect is the method of the tenth aspect, wherein the molar ratio of platinum and tin is between 4: 5 and 5: 4.

  The twelfth aspect is the method of the second aspect, wherein the carrier modifier is selected from the group consisting of magnesium, calcium, and zinc metasilicates, precursors related thereto, and mixtures of any of the above.

The thirteenth embodiment is the one of the twelfth embodiment, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst, and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The fourteenth aspect is the method according to the twelfth aspect, wherein the molar ratio of platinum and tin is between 4: 5 and 5: 4.

  The fifteenth aspect is the method of the second aspect, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor for calcium metasilicate, and a mixture of calcium metasilicate and a precursor related thereto.

The sixteenth embodiment is the one of the fifteenth embodiment, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The seventeenth aspect is the method of the sixteenth aspect, wherein the molar ratio of platinum and tin is between 4: 5 and 5: 4.

The eighteenth embodiment is that of (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst, and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The nineteenth aspect is the method of the sixteenth aspect, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.

The twentieth embodiment is the method of the eighteenth embodiment, wherein the support has a surface area of at least about 100 m ² / g.
The twenty-first aspect is the method of the twentieth aspect, wherein the molar ratio of tin to platinum group metal is from about 1: 2 to about 2: 1.

The twenty-second aspect is the method of the twentieth aspect, wherein the molar ratio of tin to platinum is about 2: 3 to about 3: 2.
The twenty third aspect is the method of the twentieth aspect, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5.

The twenty-fourth aspect is the method of the second aspect, wherein the support has a surface area of at least about 150 m ² / g.
The twenty-fifth embodiment is that of (24) wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-5%. Is the way.

A twenty-sixth embodiment is the method of the twenty-fourth embodiment, wherein the carrier comprises at least about 1 wt% to about 10 wt% calcium silicate.
The twenty-seventh aspect is the method of the twenty-fourth aspect, wherein the molar ratio of tin to platinum is about 1: 2 to about 2: 1.

The twenty-eighth aspect is the method of the twenty-fourth aspect, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.
The twenty-ninth aspect is the method of the twenty-fourth aspect, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5.

The thirtieth aspect is the method of the second aspect, wherein the support has a surface area of at least about 200 m ² / g.
The thirty-first aspect is the method of the thirty aspect, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.

The thirty second aspect is the method of the thirty aspect, wherein the molar ratio of tin to platinum is from about 5: 4 to about 4: 5.
The thirty third aspect is the method of the thirty aspect, wherein the molar ratio of tin to platinum is from about 9:10 to about 10: 9.

A thirty fourth aspect is the method of the thirty third aspect, wherein the modified siliceous support has a surface area of at least about 250 m ² / g.
The thirty-fifth embodiment is performed at a temperature between about 250 ° C. and 300 ° C .; (a) the modified siliceous support has a surface area of at least about 250 m ² / g; (b) platinum is at least about 0.75 wt%. Present in the hydrogenation catalyst in an amount; (c) a molar ratio of tin to platinum is from about 5: 4 to about 4: 5; and (d) the modified siliceous support is at least about 2.5% by weight. A method according to the second embodiment, comprising silica having a purity of at least about 95% modified with about 10% by weight calcium metasilicate.

A thirty sixth aspect is the method of the thirty fifth aspect, wherein the amount of platinum present is at least 1% by weight.
The thirty-seventh embodiment is performed at a temperature between about 250 ° C. and 300 ° C .; (a) the surface area of the modified siliceous support is at least about 100 g / m; and (b) the molar ratio of tin to platinum is about 2: 3 to about 3: 2; and (c) silica having a purity of at least about 95%, wherein the modified siliceous support is modified with at least about 2.5% to about 10% by weight of calcium metasilicate. The method of the second aspect.

The thirty eighth aspect is the method of the thirty seventh aspect, wherein the amount of platinum present is at least 0.75 wt%.
A thirty-ninth aspect is the method of the thirty-eighth aspect, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 1000 hr ⁻¹ .

The 40th embodiment is the method of the 38th embodiment, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 2500 hr ⁻¹ .
A forty-first embodiment comprises: (i) at least 90% of the converted acetic acid is converted to ethanol; (ii) the amount and oxidation state of platinum and tin, and the ratio of platinum to tin, and the modified siliceous support; Less than 2% is converted to a compound other than a compound selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, and ethylene, and mixtures thereof; and (iii) the activity of the catalyst is at a molar ratio of 10: 1 40. The method of the 40th aspect, wherein the method is controlled such that it is reduced to less than 10% upon exposure to a vapor mixture of acetic acid and hydrogen at a pressure of 2 atmospheres and a temperature of 275 ° C. and a GHSV of 2500 hr ⁻¹ for 336 hours.

A forty-second embodiment is the method of the thirty-eighth aspect, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 5000 hr ⁻¹ .
A forty-third embodiment comprises the amount and oxidation state of platinum and tin, and the ratio of platinum to tin, and the modified siliceous support: (i) at least 90% of the converted acetic acid is converted to ethanol; Less than 2% converted to alkanes; (iii) The activity of the catalyst was increased to a vapor mixture of acetic acid and hydrogen in a 10: 1 molar ratio at a pressure of 2 atmospheres and a temperature of 275 ° C. at 168 SVH at 2500 hr ⁻¹ The method of the forty-second embodiment, wherein the method is controlled such that it decreases by less than 10% upon exposure to time.

The forty-fourth embodiment is carried out at a temperature between about 250 ° C. and 300 ° C .; (a) the surface area of the modified siliceous support is at least about 200 m ² / g; (b) the molar ratio of tin to platinum is about 5 (C) the modified siliceous support comprises silica having a purity of at least about 95%, and the modifying agent comprises at least about 2.5 wt% to about 10 wt% calcium silicate. The method of the 43rd aspect.

In a forty-fifth aspect, a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 is dispersed on an oxide support at a temperature between about 225 ° C. and 300 ° C. A method for producing ethanol by reduction of acetic acid comprising passing over a hydrogenation catalyst comprising platinum and tin, wherein the amount and oxidation state of platinum and tin, and the ratio of platinum to tin, and oxide support (I) at least 80% of the converted acetic acid is converted to ethanol; (ii) less than 4% of the acetic acid is a compound selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, ethylene, and mixtures thereof And the activity of the catalyst was reduced to a vapor mixture of acetic acid and hydrogen in a 10: 1 molar ratio at a pressure of 2 atm and a temperature of 275 ° C. and a GHSV of 2500 hr ⁻¹ . Reduced by less than 10% when exposed for 500 hours; selected, configured and controlled.

  In a 46th aspect, the hydrogenation catalyst is substantially composed of platinum and tin dispersed on an oxide support, the oxide support is a modified oxide support, and the modified oxide support is (i) alkaline earth. Oxides, (ii) alkali metal oxides, (iii) alkaline earth metasilicates, (iv) alkali metal metasilicates, (v) zinc oxide, (vi) zinc metasilicates, and (vii) (i)- 45. The method of the 45th aspect, comprising a precursor relating to any of (vi) and an effective amount of a carrier modifier selected from the group consisting of any mixture of (i) to (vii).

  A forty-seventh aspect is the forty-sixth aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of sodium, potassium, magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. A method of an embodiment.

The 48th aspect is the aspect of the 47th aspect, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The 49th aspect is the method of the 47th aspect, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.

  A 50th aspect is the method of the 46th aspect, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc metasilicates, and precursors therefor, and mixtures of any of the above. It is.

The fifty-first embodiment is that of (50) wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The 52nd aspect is the method of the 51st aspect, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.

  A 53rd aspect is the method of the 46th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. is there.

The 54th embodiment is the embodiment of 53rd embodiment, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The 55th aspect is the method of the 54th aspect, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.

  The 56th aspect is the method of the 46th aspect, wherein the carrier modifier is selected from the group consisting of magnesium, calcium, and zinc metasilicates, precursors related thereto, and mixtures of any of the above.

The 57th embodiment is the embodiment of the 56th embodiment, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The 58th aspect is the method of the 57th aspect, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.

  The 59th aspect is the method of the 46th aspect, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor for calcium metasilicate, and a mixture of calcium metasilicate and a precursor related thereto.

The 60th embodiment of the 59th embodiment, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst, and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The 61st aspect is the method of the 60th aspect, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.

The 62nd embodiment is the embodiment of 46, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The 63rd aspect is the method of the 62nd aspect, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.

The 64th embodiment is the method of the 62nd embodiment, wherein the surface area of the support is at least about 100 m ² / g.
The 65th embodiment is the method of the 64th embodiment, wherein the molar ratio of tin to platinum group metal is from about 1: 2 to about 2: 1.

The 66th aspect is the process of the 64th aspect, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.
The 67th aspect is the method of the 64th aspect, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5.

The 68th aspect is the method of the 46th aspect, wherein the surface area of the support is at least about 150 m ² / g.
The 69th embodiment is the embodiment of 68th embodiment, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-5%. Is the method.

The 70th embodiment is the method of the 68th embodiment, wherein the carrier comprises at least about 1 wt% to about 10 wt% calcium silicate.
The 71st embodiment is the method of the 68th embodiment, wherein the molar ratio of tin to platinum is from about 1: 2 to about 2: 1.

The 72nd embodiment is the method of the 68th embodiment, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.
The 73rd aspect is the method of the 68th aspect, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5.

The 74th embodiment is the method of the 46th embodiment, wherein the support has a surface area of at least about 200 m ² / g.
The 75th embodiment is the method of the 74th embodiment, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.

The 76th embodiment is the method of the 74th embodiment, wherein the molar ratio of tin to platinum is from about 5: 4 to about 4: 5.
The 77th embodiment is the method of the 74th embodiment, wherein the molar ratio of tin to platinum is from about 9:10 to about 10: 9.

  A 78th aspect provides a gaseous stream comprising vapor phase hydrogen and acetic acid in a molar ratio of at least about 4: 1 hydrogen to acetic acid on a modified stabilized siliceous support at a temperature between about 225 ° C. and 300 ° C. A process for producing ethanol by reduction of acetic acid comprising passing over a hydrogenation catalyst consisting essentially of dispersed platinum and tin, wherein the modified stabilized siliceous support comprises (i) alkaline earth Oxides, (ii) alkali metal oxides, (iii) alkaline earth metasilicates, (iv) alkali metal metasilicates, (v) zinc oxide, (vi) zinc metasilicates, and (vii) (i)- A purity of at least about 95% by weight modified by a stabilizer-modifier selected from the group consisting of a precursor for any of (vi), and a mixture of any of (i)-(vii) The amount and oxidation state of platinum and tin, the ratio of platinum and tin, and the stabilizer in the modified stabilized siliceous support-the relative proportion of modifier and silica, and in the modified stabilized siliceous support. A compound other than a compound wherein at least 80% of the converted acetic acid is converted to ethanol and less than 4% of the acetic acid is selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, ethylene, and mixtures thereof It is the said method controlled to convert into.

The 79th embodiment is the embodiment of 78th embodiment, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-10%. Is the method.
The 80th embodiment is the method of the 79th embodiment, wherein the modified stabilized siliceous support has a surface area of at least about 100 m ² / g.

The 81st aspect is the process of the 80th aspect, wherein the molar ratio of tin to platinum group metal is from about 1: 2 to about 2: 1.
The 82nd embodiment is the method of the 80th embodiment, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.

The 83rd aspect is the method of the 79th aspect, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5.
The 84th embodiment is the method of the 78th embodiment, wherein the modified stabilized siliceous support has a surface area of at least about 150 m ² / g.

The 85th embodiment is the embodiment of 84, wherein (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst and (b) tin is present in an amount of at least 0.5-5%. Is the method.
The 86th embodiment is the method of the 84th embodiment, wherein the modified stabilized siliceous support comprises at least about 1 wt% to about 10 wt% calcium silicate.

The 87th embodiment is the method of the 84th embodiment, wherein the molar ratio of tin to platinum is from about 1: 2 to about 2: 1.
The 88th embodiment is the method of the 84th embodiment, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.

The 89th aspect is the method of the 84th aspect, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5.
The 90th embodiment is the method of the 87th embodiment, wherein the modified stabilized siliceous support has a surface area of at least about 200 m ² / g.

The 91st aspect is the method of the 90th aspect, wherein the molar ratio of tin to platinum is from about 9:10 to about 10: 9.
The 92nd embodiment is the method of the 90th embodiment, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.

The 93rd embodiment is the method of the 90th embodiment, wherein the molar ratio of tin to platinum is from about 5: 4 to about 4: 5.
The 94th embodiment is the method of the 90th embodiment, wherein the modified stabilized siliceous support has a surface area of at least about 250 m ² / g.

The 95th embodiment is performed at a temperature between about 250 ° C. and 300 ° C .; (a) the surface area of the modified stabilized siliceous support is at least about 250 m ² / g; (b) platinum is at least about 0.75 wt. % In the hydrogenation catalyst; (c) a molar ratio of tin to platinum is from about 5: 4 to about 4: 5; and (d) the modified stabilized siliceous support is at least about 2 78. The method of the 78th embodiment, comprising from 5 wt% to about 10 wt% calcium silicate;

The 96th embodiment is the method of the 95th embodiment, wherein the amount of platinum present is at least 1% by weight.
The 97th embodiment is carried out at a temperature between about 250 ° C. and 300 ° C .; (a) the surface area of the modified stabilized siliceous support is at least about 100 g / m; (b) the molar ratio of tin to platinum is about 78. The method of embodiment 78, wherein from 2: 3 to about 3: 2, and (c) the modified stabilized siliceous support comprises at least about 2.5 wt% to about 10 wt% calcium silicate;

The 98th embodiment is the method of the 97th embodiment, wherein the amount of platinum present is at least 0.75 wt%.
The 99th embodiment is the method of the 98th embodiment, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 1000 hr ⁻¹ .

The 100th embodiment is the method of the 98th embodiment, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 2500 hr ⁻¹ .
The 101st aspect is that the amount and oxidation state of platinum and tin, as well as the ratio of platinum and tin, and the composition of the modified stabilized siliceous support are such that at least 90% of the converted acetic acid is converted to ethanol and 2% of acetic acid. Less than is the method of the 100th aspect, wherein the conversion is controlled to convert to a compound other than a compound selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, and ethylene, and mixtures thereof.

The 102nd embodiment is the method of the 98th embodiment, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 5000 hr ⁻¹ .
The 103rd aspect is that the amount and oxidation state of platinum and tin, as well as the ratio of platinum and tin, and the composition of the modified stabilized siliceous support are such that at least 90% of the converted acetic acid is converted to ethanol and 2% of acetic acid. The method of the 79th aspect, wherein less than is controlled to convert to alkane.

The 104th embodiment is performed at a temperature between about 250 ° C. and 300 ° C .; (a) the amount and oxidation state of platinum and tin, and the ratio of platinum to tin, and the acidity of the modified stabilized siliceous support, Control that at least 90% of the converted acetic acid is converted to ethanol and less than 1% of the acetic acid is converted to alkanes; (b) the surface area of the modified stabilized siliceous support is at least about 200 m ² / g; c) the molar ratio of tin to platinum is from about 5: 4 to about 4: 5; (d) the modified stabilized siliceous support comprises at least about 2.5 wt% to about 10 wt% calcium silicate. The method of the 79th aspect.

A 105th aspect comprises a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 and dispersed on a suitable support at a temperature between about 225 ° C and 300 ° C. Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Re, Os, Ti, Zn, Cr, Mo, and in an amount of about 0.1 wt% to about 10 wt% A process for producing ethanol by reduction of acetic acid comprising passing over a hydrogenation catalyst consisting essentially of W, and a catalytic metal selected from the group consisting of these; and optionally a promoter; Wherein the amount and oxidation state of one or more catalytic metals and the composition of the support and optional promoter and reaction conditions are: (i) at least 80% of the converted acetic acid is converted to ethanol; 4) not acetic acid Is converted to a compound other than a compound selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, ethylene, diethyl ether, and mixtures thereof; and the activity of the catalyst is 10: 1 molar ratio of acetic acid and hydrogen The above-mentioned method is controlled so as to decrease by less than 10% when exposed to a vapor mixture of 2 at atmospheric pressure and a temperature of 275 ° C. and GHSV of 2500 hr ⁻¹ for 500 hours.

  A 106th aspect is a modification wherein the support is selected from the group consisting of oxides and metasilicates of sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc, and precursors therefor, and mixtures of any of the above. The method according to the 105th aspect, wherein the oxide support is modified with an agent.

The 107th aspect is the method of the 105th aspect, wherein the support is a carbon support and the catalytic metal comprises platinum and tin.
The 108th aspect is the method of the 107th aspect, wherein the carbon support is modified with a reducing metal oxide.

A 109th aspect is that a gaseous stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 is dispersed on an oxide support at a temperature between about 225 ° C. and 300 ° C. Consists essentially of a metal component that has a composition:
_{Pt v Pd w Re x Sn y} Al z Ca p Si q O r
(Wherein v and y are between 3: 2 and 2: 3, w and x are between 1: 3 and 1: 5, and the relative positions of p and z and the aluminum and calcium present are The Bronsted acid sites present on the surface are controlled to be neutralized by calcium silicate, p and q are selected such that p: q is from 1:20 to 1: 200, and r is the valence And v and w are selected to satisfy the requirements of

Selected to be)
A process for producing ethanol by reduction of acetic acid comprising passing over a hydrogenation catalyst having

The 110th embodiment is the method of the 109th embodiment, wherein the hydrogenation catalyst has a surface area of at least about 100 m ² / g and z and p are controlled such that p ≧ z.
The 111th aspect is the method of the 110th aspect, wherein p is selected to ensure that the surface of the support is substantially free of Bronsted acid sites, taking into account any minor impurities present. is there.

A 112th aspect comprises a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 and dispersed on a suitable support at a temperature between about 225 ° C. and 300 ° C. Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Re, Os, Ti, Zn, Cr, Mo, and in an amount of about 0.1 wt% to about 10 wt% A process for hydrogenating acetic acid comprising passing over a hydrogenation catalyst consisting essentially of W, and a catalytic metal selected from the group consisting of these; and optionally a promoter; Or the amount and oxidation state of a plurality of catalytic metals, and the composition of the support and optional promoter, and the reaction conditions, wherein less than 4% of acetic acid is ethanol, acetaldehyde, ethyl acetate, ethylene, diethyl ether, and mixtures thereof Converted to compounds other than a compound selected from Ranaru group; and, the activity of the catalyst is 10: vapor mixture of 1 molar ratio of acetic acid and hydrogen pressure and 275 ° C. for 2 atm Temperature and 2500Hr ^-1 And less than 10% when exposed to 500 hours of exposure to GHSV; and (i) the carrier is an oxide and metasilicate of sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc, and A precursor related thereto, and an oxide support modified with a modifier selected from the group consisting of any of the above mixtures; (ii) the support is a carbon support, and the catalyst metal comprises platinum and tin. Or (iii) the above process provided that the support is a carbon support modified with a reducing metal oxide; A.

A 113th aspect provides a gas stream comprising vapor phase hydrogen and alkanoic acid in a molar ratio of at least about 2: 1 hydrogen to alkanoic acid at a temperature between about 125 ° C. and 350 ° C., silica, calcium metasilicate, And a platinum group metal selected from the group consisting of platinum, palladium, rhenium, and mixtures thereof on a siliceous support selected from the group consisting of calcium metasilicate promoted silica; and tin, rhenium, and mixtures thereof A process for hydrogenating an alkanoic acid comprising passing over a hydrogenation catalyst comprising a promoter selected from the group consisting of: (a) 1 to 5% by weight of the catalyst, optionally alkali metal, alkaline earth element in an amount, and promoters are selected from the group consisting of zinc; (b) _WO of 1 to 50 wt% of the amount of the catalyst 3, _MoO 3, Fe _{2 3,} and redox promoter is selected from the group consisting of _Cr 2 _{O 3;} and, (c) _TiO 2 1 to 50% by weight of the _{catalyst, ZrO 2, Nb 2 O 5} , Ta 2 O 5, And an acid modifier selected from the group consisting of Al ₂ O ₃ ; and the above method being promoted by an accelerator selected from the group consisting of:

  In a fourteenth embodiment, the alkanoic acid is acetic acid, (a) at least one of platinum and palladium is present in an amount of 0.25% to 5% of the weight of the catalyst; (b) the total amount of platinum and palladium present The method of the 113th embodiment, wherein is at least 0.5% by weight of the catalyst; (c) the total amount of rhenium and tin present is at least 0.5 to 10% by weight.

The 115th embodiment is the method of the 114th embodiment, wherein the siliceous support has a surface area of at least about 150 m ² / g.
The 116th aspect comprises (a) the amount and oxidation state of the platinum group metal, rhenium and tin promoter, and (b) the molar ratio of the platinum group metal to the total moles of rhenium and tin present; and (c) silica. Converting the number of Bronsted acid sites on the carbon support to a compound wherein at least 80% of the converted acetic acid is selected from the group consisting of ethanol and ethyl acetate, while less than 4% of acetic acid is ethanol, acetaldehyde, acetic acid The method according to the 115th aspect, wherein the conversion is controlled to a compound other than the compound selected from the group consisting of ethyl, ethylene, and a mixture thereof.

  The 117th embodiment is that (a) at least one of platinum and palladium is present in an amount of 0.5% to 5% of the weight of the catalyst; (b) the total amount of platinum and palladium present is at least 0 of the weight of the catalyst. 115. The method of embodiment 115, wherein (c) the total amount of tin and rhenium present is at least 1.0% by weight of the catalyst.

  The 118th aspect comprises (a) (i) platinum group metal, (ii) amount and oxidation state of rhenium and tin promoter; and (iii) ratio of platinum group metal to rhenium and tin promoter; and (iv) The acidity of the siliceous support is such that at least 80% of the converted acetic acid is converted to ethanol and less than 4% of the acetic acid is selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, ethylene, and mixtures thereof It is the method of the 117th aspect controlled to convert into the compound of this.

The 119th aspect is the process of the 118th aspect, wherein the total weight of rhenium and tin present is about 1-10% by weight of the catalyst.
The 120th embodiment is the method of the 119th embodiment, wherein the molar ratio of the platinum group metal to the total moles of rhenium and tin is from about 1: 2 to about 2: 1.

A 121th aspect comprises a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 and dispersed on an oxide support at a temperature between about 225 ° C. and 300 ° C. Consists essentially of a metal component that has a composition:
_{Pt v Pd w Re x Sn y} Ca p Si q O r
(Wherein the ratio of v: y is between 3: 2 and 2: 3, the ratio of w: x is between 1: 3 and 1: 5, and p and q are p: q is 1: 20 to 1: 200 is selected, r is selected to satisfy the valence requirement, and v and w are

Selected to be)
A process for hydrogenating acetic acid comprising passing over a hydrogenation catalyst having
The 122 th aspect converts the process conditions and the values of v, w, x, y, p, q, and r to a compound wherein at least 90% of the converted acetic acid is selected from the group consisting of ethanol and ethyl acetate. Meanwhile, the method of the 121st aspect, wherein less than 4% of the acetic acid is selected to be converted to alkanes.

  The 123rd aspect is that the process conditions and values of v, w, x, y, p, q, and r are such that at least 90% of the converted acetic acid is converted to ethanol and less than 2% of the acetic acid is converted to alkane. The method of the 122nd aspect, selected as follows.

The 124th aspect is the method of the 122nd aspect, wherein p is selected to ensure that the surface of the support is substantially basic, taking into account any minor impurities present.
In a 125th aspect, a gaseous stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 is dispersed on the oxide support at a temperature between about 225 ° C and 300 ° C. Consists essentially of a metal component that has a composition:
_{Pt v Pd w Re x Sn y} Al z Ca p Si q O r
Where v and y are between 3: 2 and 2: 3, w and x are between 1: 3 and 1: 5, p and z, and the relative positions of the aluminum and calcium atoms present. Is controlled so that the Bronsted acid sites present on its surface are neutralized by calcium silicate; p and q are selected such that p: q is from 1:20 to 1: 200; Selected to satisfy valence requirements, and v and w are

Selected to be)
A process for hydrogenating acetic acid comprising passing over a hydrogenation catalyst having
The 126th embodiment is the method of the 125th embodiment, wherein the hydrogenation catalyst has a surface area of at least about 100 m ² / g and z and p are controlled such that p ≧ z.

  The 127th aspect is the method of the 125th aspect, wherein p is selected to ensure that the surface of the support is substantially free of Bronsted acid sites, taking into account any minor impurities present. is there.

A 128th aspect provides a gaseous stream comprising vapor phase hydrogen and alkanoic acid in a molar ratio of hydrogen to alkanoic acid of at least about 5: 1 at a temperature between about 125 ° C. and 350 ° C. of at least about 1000 hr ⁻¹ . In GHSV, at a pressure of at least 2 atmospheres, (a) from a group consisting of platinum, palladium, and mixtures thereof on a siliceous support selected from the group consisting of silica, calcium metasilicate, and calcium metasilicate promoted silica. A selected platinum group metal; and (b) a metal promoter selected from the group consisting of tin and rhenium and mixtures thereof; (c) a siliceous support, optionally (i) A donor promoter selected from the group consisting of alkali metals, alkaline earth elements, and zinc in an amount of 1-5% by weight; (ii) 1-50 of the catalyst A redox promoter selected from the group consisting of WO ₃ , MoO ₃ , Fe ₂ O ₃ , and Cr ₂ O _{3 in} an amount of% by weight; (iii) TiO _{2 in} an amount of 1-50% by weight of the catalyst. Selected from the group consisting of: ZrO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , and Al ₂ O ₃ ; and (iv) a combination of i, ii, and iii; A process for hydrogenating an alkanoic acid comprising passing over a hydrogenation catalyst promoted by a second promoter.

  The 129th embodiment is when the alkanoic acid is acetic acid, (a) platinum is present in an amount of 0.5% to 5% of the weight of the catalyst, if present, and (b) palladium is present. Is the process of embodiment 128, wherein the catalyst is present in an amount of 0.5% to 5% of the weight of the catalyst, and (c) the metal promoter is present in an amount of at least 0.5 to 10%.

The 130th embodiment is the method of the 129th embodiment, wherein the siliceous support has a surface area of at least about 150 m ² / g.
The thirty-first aspect is that (a) platinum is present in an amount of 1% to 5% of the weight of the catalyst, and (b) palladium, if present, in an amount of 0.25% to 5% of the weight of the catalyst. The method of the thirty-first aspect, wherein (c) the total amount of platinum and palladium present is at least 1.25% by weight of the catalyst.

The 132nd aspect is the process of the 131st aspect, wherein tin is present in an amount of 1-3% by weight of the catalyst.
The 133rd aspect is the method of the 132nd aspect, wherein the molar ratio of tin to platinum group metal is from about 1: 2 to about 2: 1.

The 134th embodiment is the method of the 132nd embodiment, wherein the molar ratio of tin to platinum is from about 5: 4 to about 4: 5.
The 135th embodiment is the method of the 132nd embodiment, wherein the siliceous support is substantially free of Bronsted acid sites that are not neutralized by calcium metasilicate and has a surface area of at least about 200 m ² / g.

The 136th embodiment is the method of the 132nd embodiment, wherein the weight ratio of tin to platinum group metal is from about 2: 3 to about 3: 2.
The 137th embodiment is the method of the 128th embodiment, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.

A 138th embodiment comprises a gaseous stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 and dispersed on a suitable support at a temperature between about 225 ° C and 300 ° C. Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Os, Ti, Zn, Cr, Mo, and W, in an amount of about 0.1 wt% to about 10 wt%. And a catalyst metal selected from the group consisting of these mixtures; and optionally a promoter; a method of hydrogenating acetic acid comprising passing over a hydrogenation catalyst substantially composed of one or more The amount and catalytic state of the catalyst metal, and the composition of the support and optional promoter, and the reaction conditions consisted of less than 4% acetic acid from ethanol, acetaldehyde, ethyl acetate, ethylene, diethyl ether, and mixtures thereof. Converted to compounds other than a compound selected from the group; and, the activity of the catalyst is 10: vapor mixture of 1 molar ratio of acetic acid and hydrogen at a temperature of pressure and 275 ° C. for 2 atm and the 2500hr ^-1 GHSV The above method is controlled to reduce by less than 10% upon exposure for 500 hours.

  A 139th aspect is that the carrier is a molecular sieve carrier; a group consisting of sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc oxides and metasilicates, precursors therefor, and mixtures of any of the above. 138. The method of aspect 138, selected from a modified siliceous support modified with a selected modifying agent; and a carbon support.

The 140th embodiment is the method of the 139th embodiment, wherein the catalytic metal comprises platinum and tin and the selectivity to diethyl ether is higher than 80%.
A 141st aspect is the method of the 107th aspect, wherein the support is a zeolite support and the selectivity to diethyl ether is higher than 90%.

A 142nd embodiment provides a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 at a temperature between about 225 ° C. and 300 ° C., (a) silica, and about 7 A platinum group metal selected from the group consisting of platinum and a mixture of platinum and palladium on a siliceous support selected from the group consisting of silica promoted by .5 or less calcium metasilicate The amount of platinum present is at least about 1.5%); and (b) rhenium in an amount between about 1% and 2% by weight of the catalyst and A metal promoter selected from the group consisting of tin; the molar ratio of platinum to metal promoter is between about 3: 1 to 1: 2; (c) the siliceous support is optionally (I) Alkaline gold in an amount of 1-5% by weight of the catalyst , Donor accelerator selected alkaline earth elements, and from the group consisting of zinc; (ii) 1 to 50% by weight of the _catalyst, from _{WO 3, MoO 3, Fe 2} O 3, and _Cr 2 _{O 3} comprising redox promoter is selected from the group; (iii) 1 to 50% by weight of the _catalyst, from the group consisting of _{TiO 2, ZrO 2, Nb 2} O 5, Ta 2 O 5, and _Al 2 _{O 3} Reduction of acetic acid comprising passing over a hydrogenation catalyst promoted by a second promoter selected from the group consisting of: (iv) a combination of i, ii, and iii; To produce ethanol and ethyl acetate.

The 143rd embodiment is the method of the 142nd embodiment, wherein the molar ratio of metal promoter to platinum group metal is from about 2: 3 to about 3: 2.
The 144th embodiment is the method of the 142nd embodiment, wherein the molar ratio of metal promoter to platinum group metal is from about 5: 4 to about 4: 5.

The 145th embodiment is that the surface area of the siliceous support is at least about 200 m ² / g and the amount of calcium metasilicate is sufficient to make the surface of the siliceous support substantially free of Bronsted acidity. The method according to the 142nd aspect.

The 146th embodiment is the method of the 145th embodiment, wherein the molar ratio of metal promoter to platinum group metal is from about 2: 3 to about 3: 2.
In a 147th embodiment, the surface area of the siliceous support is at least about 200 m ² / g, and the number of moles of Bronsted acid sites present on the surface is Bronsted acid sites present on the surface of Saint-Gobain NorPro SS61138 silica. It is the method of the 146th aspect which is below the mol number of.

In a fourteenth embodiment, the surface area of the siliceous support is at least about 250 m ² / g and the number of moles of Bronsted acid sites present on the surface is Bronsted acid present on the surface of Saint-Gobain NorPro HSA SS61138 silica. It is the method of the 142nd aspect which is 1/2 or less of the number-of-moles of a site | part.

  The 149th embodiment is carried out at a temperature between about 250 ° C. and 300 ° C .; (a) the hydrogenation catalyst is selected from the group consisting of silica and silica promoted by about 7.5 or less calcium metasilicate. Palladium on a siliceous support (the amount of palladium present is at least about 1.5%); and (b) rhenium in an amount between about 1% and 10% by weight of the metal promoter. And the molar ratio of rhenium to palladium is between about 3: 1 to 5: 1.

  The 150th embodiment provides platinum on a siliceous support wherein the hydrogenation catalyst is substantially comprised of silica promoted by about 3 to about 7.5% calcium silicate (the amount of platinum present is at least about 1.0%), and a tin promoter in an amount between about 1% and 5% by weight of the catalyst, wherein the molar ratio of platinum to tin is about 9:10 to 10: 9. It is the reduction method of the acetic acid of the 142nd aspect which is between.

  The 151st embodiment is that the amount of platinum group metal present is at least about 2.0%, the amount of platinum present is at least about 1.5%, and the tin promoter is about 1% to 5% by weight of the catalyst. The method of reducing acetic acid according to the 142nd aspect, wherein the molar ratio of platinum to tin is between about 9:10 and 10: 9.

The 152 th embodiment is carried out at a temperature between about 250 ° C. and 300 ° C .; the hydrogenation catalyst has a surface area of at least 200 m ² / g and is promoted by between 4 and 7.5% calcium metasilicate. 151. The method of embodiment 151, comprising 2.5 to 3.5 wt% platinum, 2 wt% to 5 wt% tin dispersed on a high surface area silica.

A fifteenth aspect is a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 and dispersed on an oxide support at a temperature between about 225 ° C and 300 ° C. Consists essentially of a metal component that has a composition:
_{Pt v Pd w Re x Sn y} Al z Ti n Ca p Si q O r
(Wherein the ratio of v to y is between 3: 2 to 2: 3, the ratio of w to x is between 1: 3 to 1: 5, p and z, and p, q , And n are

, R is selected to satisfy the valence requirement, and v and w are

Selected to be)
Producing a stream comprising ethanol and at least about 40% ethyl acetate by reduction of acetic acid comprising passing over a hydrogenation catalyst having

The 154th embodiment is the method of the 153th embodiment, wherein the hydrogenation catalyst has a surface area of at least about 100 m ² / g.
A 155th embodiment comprises a gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 and dispersed on a suitable support at a temperature between about 225 ° C and 300 ° C. Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Os, Ti, Zn, Cr, Mo, and W, in an amount of about 0.1 wt% to about 10 wt%. And a catalyst metal selected from the group consisting of these mixtures; and optionally a promoter; a method of hydrogenating acetic acid comprising passing over a hydrogenation catalyst substantially composed of one or more The amount and catalytic state of the catalyst metal and the composition of the support and optional promoter and reaction conditions were: (i) greater than 50% of the converted acetic acid was converted to ethyl acetate; (ii) 4% of acetic acid Less than ethanol, acetaldehyde, Conversion to a compound other than a compound selected from the group consisting of ethyl acid, ethylene, diethyl ether, and mixtures thereof; and the activity of the catalyst is 2 to a vapor mixture of acetic acid and hydrogen in a 10: 1 molar ratio. The above method is controlled such that it is reduced by less than 10% upon exposure to 500 hours of atmospheric pressure and a temperature of 275 ° C. and a GHSV of 2500 hr ⁻¹ .

A 156 embodiment is a siliceous support selected from the group consisting of (a) silica and silica promoted by about 3.0 to about 7.5 calcium metasilicate (the surface area of the siliceous support is at least about 150 m). ^{2 /} g and a) on, platinum, palladium, and platinum group metal selected from the group consisting of mixtures thereof; and, (b) tin promoting amount between about 1 wt% to 3 wt% of the catalyst The molar ratio of platinum to tin is between about 4: 3 to 3: 4; (c) the composition and structure of the siliceous support has its surface not neutralized by calcium metasilicate Particulate catalyst for hydrogenating alkanoic acid to the corresponding alkanol, selected to be substantially free of Sted acid sites.

  In a 157th aspect, the total weight of platinum group metals present is between 2-4%, the amount of platinum present is at least 2%, and the weight ratio of platinum to tin is 4: 5-5: 4. A hydrogenation catalyst according to embodiment 156, wherein the amount of calcium silicate present is between 3 and 7.5%.

A fifteenth aspect is a siliceous material in which a platinum group metal selected from the group consisting of platinum, palladium, and mixtures thereof is dispersed thereon with an accelerator selected from the group consisting of tin, cobalt, and rhenium. The siliceous carrier is substantially composed of a carrier and has a surface area of at least about 175 m ² / g and is composed of silica, calcium metasilicate, and calcium metasilicate promoted silica on which calcium metasilicate is disposed. The surface of the siliceous support selected from the group consisting of is a particulate hydrogenation catalyst that is substantially free of Bronsted acid sites due to alumina not neutralized by calcium.

  The 159th aspect is that the total weight of platinum group metal present is between 0.5% and 2%, the amount of palladium present is at least 0.5%, the promoter is rhenium, rhenium and palladium The hydrogenation catalyst of the 158th aspect, wherein the weight ratio is between 10: 1 and 2: 1 and the amount of calcium metasilicate is between 3 and 90%.

  The 160th aspect is that the total weight of platinum group metals present is between 0.5-2%, the amount of platinum present is at least 0.5%, the promoter is cobalt, cobalt and platinum, The hydrogenation catalyst of the 159th aspect, wherein the weight ratio is between 20: 1 and 3: 1 and the amount of calcium silicate is between 3 and 90%.

  The 161st aspect is that the total weight of platinum group metal present is between 0.5-2%, the amount of palladium present is at least 0.5%, the promoter is cobalt, cobalt and palladium, The hydrogenation catalyst of the 158th aspect, wherein the weight ratio is between 20: 1 and 3: 1 and the amount of calcium silicate is between 3 and 90%.

A 162nd embodiment comprises between 2.5 and 3.5 wt% platinum, between 3 wt% and 5 wt% tin dispersed on a high surface area calcined silica having a surface area of at least 200 m ² / g. Including high surface area silica is promoted by between 4-6% calcium metasilicate, and the hydrogenation catalyst is a molar ratio of platinum to tin between 4: 5 and 5: 4.

  The 163rd aspect comprises between 0.5 and 2.5 wt% palladium, between 2 wt% and 7 wt% rhenium, wherein the weight ratio of rhenium to palladium is at least 1.5: 1.0. Rhenium and palladium are dispersed on a siliceous support, which is a hydrogenation catalyst containing at least 80% calcium metasilicate.

A 164th aspect is a siliceous support selected from the group consisting of a modified and stabilized siliceous support (the siliceous support is (i) an alkaline earth oxide, (ii) an alkali metal oxide, (iii) an alkaline earth Metasilicates, (iv) alkali metal metasilicates, (v) zinc oxide, (vi) zinc metasilicates, and (vii) precursors for any of (i)-(vi), and (i)-(vii) The surface area of the modified and stabilized siliceous support is at least about 150 m ² / g) selected from the group consisting of any mixture of: (a) A platinum group metal selected from the group consisting of platinum, palladium, and mixtures thereof; and (b) a tin promoter in an amount between about 1% and 3% by weight of the catalyst; Le ratio of about 4: 3 to 3: is between 4 is a particulate catalyst for hydrogenation alkanols to the corresponding alkanoic acid.

  In a 165th aspect, the total weight of platinum group metal present is between 2-4%, the amount of platinum present is at least 2%, and the molar ratio of platinum to tin is 4: 5-5: 4. The hydrogenation catalyst of aspect 164, wherein the amount of stabilizer-modifier present is between 3 and 7.5%.

  In a 166th aspect, the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, precursors related thereto, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  In a 167th aspect, the carrier modifier is selected from the group consisting of oxides and metasilicates of sodium, potassium, magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  The 168th aspect is the hydrogenation of the 165th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 169th aspect is the hydrogenation of the 165th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 170th aspect is the hydrogenation catalyst of the 165th aspect, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor for calcium metasilicate, and a mixture of calcium metasilicate and a precursor related thereto.

  A 171st aspect is that the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  A 172nd embodiment is that the carrier modifier is selected from the group consisting of oxides and metasilicates of sodium, potassium, magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  The 173rd aspect is the hydrogenation of the 164th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 174th aspect is the hydrogenation of the 164th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 175th aspect is the hydrogenation catalyst of the 164th aspect, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor for calcium metasilicate, and a mixture of calcium metasilicate and a precursor related thereto.

The 176th aspect is a modified stable material in which a platinum group metal selected from the group consisting of platinum, palladium, and a mixture thereof is dispersed thereon with an accelerator selected from the group consisting of tin, cobalt, and rhenium. A siliceous support having a purity of at least 95% and a surface area of at least about 175 m ² / g; (i) an alkaline earth oxide; (ii) an alkali Precursor for metal oxide, (iii) alkaline earth metasilicate, (iv) alkali metal metasilicate, (v) zinc oxide, (vi) zinc metasilicate, and (vii) (i)-(vi) And a silica modified and stabilized by a stabilizer-modifier selected from the group consisting of any mixture of (i) to (vii), Ca protein carrier surface stabilizer - substantially free of Bronsted acid sites for alumina unneutralized by denaturing agent, a particulate hydrogenation catalyst.

  A 177th embodiment is that the total weight of platinum group metal present is between 0.5% and 2%, the amount of palladium present is at least 0.5%, the promoter is rhenium, rhenium and palladium The hydrogenation catalyst of the 176th embodiment, wherein the weight ratio of to is between 10: 1 and 2: 1 and the amount of carrier modifier is between 3 and 90%.

  In a 178th aspect, the carrier modifier is selected from the group consisting of oxides and metasilicates of sodium, potassium, magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  The 179th aspect is that the carrier modifier is selected from the group consisting of oxides and metasilicates of sodium, potassium, magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  The 180th aspect is the hydrogenation of the 177th aspect, wherein the carrier modifier is selected from the group consisting of magnesium, calcium, and zinc oxides and metasilicates, precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 181st aspect is the hydrogenation of the 177th aspect, wherein the carrier modifier is selected from the group consisting of magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures of any of the foregoing. It is a catalyst.

  The 182nd aspect is the hydrogenation catalyst of the 177th aspect, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor related to calcium metasilicate, and a mixture of calcium metasilicate and related precursor.

  A 183rd aspect is the 176th aspect, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  A 184th aspect is the 176th aspect, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  The 185th aspect is the hydrogenation of the 176th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 186th aspect is the hydrogenation of the 176th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 187th aspect is the hydrogenation catalyst of the 176th aspect, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor for calcium metasilicate, and a mixture of calcium metasilicate and a precursor related thereto.

  In a 188th aspect, the total weight of platinum group metals present is between 0.5-2%, the amount of platinum present is at least 0.5%, the promoter is cobalt, cobalt and platinum, The hydrogenation catalyst of the 176th embodiment, wherein the weight ratio is between 20: 1 and 3: 1 and the amount of carrier modifier is between 3 and 90%.

  The 189th aspect is the 188th aspect, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  The 190th aspect is the 188th aspect, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  The 191st aspect is the hydrogenation of the 188th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 192nd embodiment is the hydrogenation of the 188th embodiment, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 193rd aspect is the hydrogenation catalyst according to the 188th aspect, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor for calcium metasilicate, and a mixture of calcium metasilicate and a precursor related thereto.

  In a 194th aspect, the total weight of platinum group metals present is between 0.5-2%, the amount of palladium present is at least 0.5%, the promoter is cobalt, cobalt and palladium, The hydrogenation catalyst of the 176th embodiment, wherein the weight ratio is between 20: 1 and 3: 1 and the amount of carrier modifier is between 3 and 90%.

  In a 195th aspect, the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  The 196th aspect is that the carrier modifier is selected from the group consisting of oxides and metasilicates of sodium, potassium, magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a hydrogenation catalyst of an aspect.

  The 197th aspect is the hydrogenation of the 194th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 198th aspect is the hydrogenation of the 194th aspect, wherein the carrier modifier is selected from the group consisting of oxides and metasilicates of magnesium, calcium, and zinc, and precursors therefor, and mixtures of any of the above. It is a catalyst.

  The 199th aspect is the hydrogenation catalyst of the 194th aspect, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor for calcium metasilicate, and a mixture of calcium metasilicate and a precursor related thereto.

The 200th aspect comprises between 2.5 and 3.5 wt% platinum, between 3 wt% and 5 wt% tin dispersed on a high surface area calcined silica having a surface area of at least 200 m ² / g. Including high surface area silica is promoted by between 4-6% calcium metasilicate, and the hydrogenation catalyst is a molar ratio of platinum to tin between 4: 5 and 5: 4.

  The 201st embodiment comprises between 0.5 and 2.5 wt% palladium, between 2 wt% and 7 wt% rhenium, wherein the weight ratio of rhenium to palladium is at least 1.5: 1.0. Rhenium and palladium are dispersed on a siliceous support, which is a hydrogenation catalyst containing at least 80% calcium metasilicate.

  The 202nd aspect neutralizes the acidic sites present on the surface or changes in shape at temperatures encountered in acetic acid hydrogenation (mainly sintering, grain growth, grain boundary migration, defect and dislocation migration). A sufficient amount of alkaline earth metal, alkali metal, zinc, scandium, and yttrium to provide resistance to, or both, resistance to, plastic deformation, and / or other temperature-induced changes in microstructure About 0.1 on a stabilized-modified oxide support incorporating a basic non-volatile stabilizer-modifier in the form of oxides and metasilicates, precursors for oxides and metasilicates, and mixtures thereof. Selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Os, Ti, Zn, Cr, Mo, and W in an amount of from about 10% to about 10% by weight. A hydrogenation catalyst obtained by introducing medium metal.

A 203rd embodiment is a calcined silica wherein the amount and location of the basic modifier-stabilizer has a purity of at least about 99.7 wt% of acid sites present per 1 m ² on the surface of the oxide support. The hydrogenation catalyst of aspect 202, which is sufficient to reduce to a number less than the number of acid sites found per m ² on the surface of the catalyst.

The 204th embodiment provides that the amount and position of the basic modifier-stabilizer has a purity of at least about 99.7% by weight of acid sites present per 1 m ² on the surface of the oxide support. The hydrogenation catalyst of aspect 202, which is sufficient to reduce to fewer than the number of acid sites found per m ² on the surface of Gobain NorPro HSA SS61138.

A 205th aspect provides a calcined silica in which the amount and position of the basic modifier-stabilizer has a purity of at least about 99.7% by weight of acid sites present per 1 m ² on the surface of the oxide support. The hydrogenation catalyst of aspect 202, which is sufficient to reduce to less than half the number of acid sites found per m ² on the surface of the catalyst.

The 206 th aspect is that the amount and position of the basic modifier-stabilizer has a purity of at least about 99.7% by weight of acid sites present per 1 m ² on the surface of the oxide support. The hydrogenation catalyst of aspect 202, which is sufficient to reduce to less than half the number of acid sites found per m ² on the surface of Gobain NorPro HSA SS61138.

The 207 th aspect is a calcined silica wherein the amount and position of the basic modifier-stabilizer has a purity of at least about 99.7% by weight of acid sites present per 1 m ² on the surface of the oxide support. The hydrogenation catalyst of aspect 202, which is sufficient to reduce to less than 25% of the number of acid sites found per m ² on the surface of the catalyst.

The 208 th aspect is that the amount and position of the basic modifier-stabilizer has a purity of at least about 99.7% by weight of acid sites present per 1 m ² on the surface of the oxide support. it is sufficient to reduce the number less than 25% of the number of Gobain Norpro HSA acid sites found per 1 m ² on the surface of SS61138, a hydrogenation catalyst of the 202 embodiments.

The 209th aspect is a calcined silica wherein the amount and position of the basic modifier-stabilizer has a purity of at least about 99.7% by weight of acid sites present per 1 m ² on the surface of the oxide support. The hydrogenation catalyst of aspect 202, which is sufficient to reduce to less than 10% of the number of acid sites found per m ² on the surface of the catalyst.

The 210th embodiment provides that the amount and position of the basic modifier-stabilizer has a purity of at least about 99.7% by weight of acid sites present per 1 m ² on the surface of the oxide support. The hydrogenation catalyst of aspect 202, which is sufficient to reduce to less than 10% of the number of acid sites found per m ² on the surface of Gobain NorPro HSA SS61138.

  In the above description of the various embodiments, those embodiments relating to other embodiments can be suitably combined with other embodiments, as will be appreciated by those skilled in the art.

Claims (108)

A gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 and platinum and tin dispersed on the siliceous support at a temperature between about 225 ° C. and 300 ° C. A process for producing ethanol by reduction of acetic acid comprising passing over a hydrogenation catalyst comprising a platinum and tin amount and oxidation state, and a platinum to tin ratio, and a siliceous support, (i) At least 80% of the converted acetic acid is converted to ethanol; (ii) less than 4% of the acetic acid is converted to a compound other than a compound selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, ethylene, and mixtures thereof. And the activity of the catalyst is 168 hours at a pressure of 2 atm and a temperature of 275 ° C. and a GHSV of 2500 hr ^{−1 in} a 10: 1 molar ratio of acetic acid and hydrogen vapor mixture. The above method of selecting, configuring and controlling so that it decreases by less than 10% when exposed for a long time.   The hydrogenation catalyst is substantially composed of platinum and tin dispersed on a siliceous support, the siliceous support is a modified siliceous support, and the modified siliceous support comprises (i) an alkaline earth oxide, ( ii) Alkali metal oxides, (iii) Alkaline earth metasilicates, (iv) Alkali metal metasilicates, (v) Zinc oxide, (vi) Zinc metasilicates, and (vii) Precursors for (i)-(vi) The method of claim 1 comprising an effective amount of a carrier modifier selected from the group consisting of a body and a mixture of (i) to (vii).   The method of claim 2, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures thereof. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
The method of claim 2.   4. The method of claim 3, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.   The method of claim 2, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc metasilicates, and precursors therefor, and mixtures thereof. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
The method of claim 5.   The method of claim 6, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.   3. The method of claim 2, wherein the carrier modifier is selected from the group consisting of magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures thereof. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
The method of claim 9.   The method of claim 10, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.   The method of claim 2, wherein the carrier modifier is selected from the group consisting of magnesium, calcium, and zinc metasilicates, and precursors therefor, and mixtures thereof. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
The method of claim 12.   The method of claim 12, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.   3. The method of claim 2, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor for calcium metasilicate, and a mixture of calcium metasilicate and a precursor related thereto. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
The method of claim 15.   The method of claim 16, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
The method of claim 2.   The method of claim 16, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4. The method of claim 18, wherein the surface area of the support is at least about 100 m ² / g.   21. The method of claim 20, wherein the molar ratio of tin to platinum group metal is from about 1: 2 to about 2: 1.   21. The method of claim 20, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.   21. The method of claim 20, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5. The method of claim 2, wherein the support has a surface area of at least about 150 m ² / g. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5-5%;
25. A method according to claim 24.   25. The method of claim 24, wherein the carrier comprises at least about 1 wt% to about 10 wt% calcium silicate.   25. The method of claim 24, wherein the molar ratio of tin to platinum is about 1: 2 to about 2: 1.   25. The method of claim 24, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.   25. The method of claim 24, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5. The method of claim 2, wherein the surface area of the support is at least about 200 m ² / g.   32. The method of claim 30, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.   32. The method of claim 30, wherein the molar ratio of tin to platinum is from about 5: 4 to about 4: 5.   32. The method of claim 30, wherein the molar ratio of tin to platinum is from about 9:10 to about 10: 9. 34. The method of claim 33, wherein the surface area of the modified siliceous support is at least about 250 m < ² > / g. At a temperature between about 250 ° C. and 300 ° C.,
a. The surface area of the modified siliceous support is at least about 250 m ² / g;
b. Platinum is present in the hydrogenation catalyst in an amount of at least about 0.75% by weight;
c. The molar ratio of tin to platinum is from about 5: 4 to about 4: 5; and d. The modified siliceous support comprises silica having a purity of at least about 95% that has been modified with at least about 2.5% to about 10% by weight of calcium metasilicate;
The method of claim 2.   36. The method of claim 35, wherein the amount of platinum present is at least 1% by weight. At a temperature between about 250 ° C. and 300 ° C.,
a. The surface area of the modified siliceous support is at least about 100 m ² / g;
b. The molar ratio of tin to platinum is from about 2: 3 to about 3: 2;
c. The modified siliceous support comprises silica having a purity of at least about 95% that has been modified with at least about 2.5% to about 10% by weight of calcium metasilicate;
The method of claim 2.   38. The method of claim 37, wherein the amount of platinum present is at least 0.75 wt%. 40. The method of claim 38, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 1000 hr- ¹ . 40. The method of claim 38, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 2500 hr- ¹ . The amount and oxidation state of platinum and tin, and the ratio of platinum to tin, and the modified siliceous support, (i) at least 90% of the converted acetic acid is converted to ethanol; (ii) less than 2% of acetic acid is Conversion to a compound other than a compound selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, and ethylene, and mixtures thereof; and (iii) a catalytic activity of acetic acid and hydrogen vapor in a 10: 1 molar ratio. 41. The method of claim 40, wherein the mixture is controlled to decrease by less than 10% upon exposure to a pressure of 2 atmospheres and a temperature of 275 [deg.] C. and a GHSV of 2500 hr < ^-1 > for 336 hours. 39. The method of claim 38, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 5000 hr- ¹ . The amount and oxidation state of platinum and tin, and the ratio of platinum to tin, and the modified siliceous support, (i) at least 90% of the converted acetic acid is converted to ethanol; (ii) less than 2% of the acetic acid is alkane (Iii) when the activity of the catalyst was exposed to a vapor mixture of acetic acid and hydrogen in a 10: 1 molar ratio at a pressure of 2 atmospheres and a temperature of 275 ° C. in 2500 hr ⁻¹ GHSV for 168 hours. 43. The method of claim 42, wherein the method is controlled to decrease by less than 10%. At a temperature between about 250 ° C. and 300 ° C.,
a. The surface area of the modified siliceous support is at least about 200 m ² / g;
b. The molar ratio of tin to platinum is from about 5: 4 to about 4: 5;
c. The modified siliceous support comprises silica having a purity of at least about 95% and the modifying agent comprises at least about 2.5 wt% to about 10 wt% calcium silicate;
44. The method of claim 43. A gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 and platinum and tin dispersed on the oxide support at a temperature between about 225 ° C. and 300 ° C. A process for producing ethanol by reduction of acetic acid comprising passing over a hydrogenation catalyst comprising a platinum and tin amount and oxidation state, as well as a platinum to tin ratio, and an oxide support, (i) At least 80% of the converted acetic acid is converted to ethanol; (ii) less than 4% of the acetic acid is converted to a compound other than a compound selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, ethylene, and mixtures thereof. And the activity of the catalyst was exposed to a 10: 1 molar ratio of acetic acid and hydrogen vapor mixture for 500 hours at a pressure of 2 atm and a temperature of 275 ° C. and a GHSV of 2500 hr ^−1. Reduced by less than 10% when exposed; the above method of selecting, configuring and controlling.   The hydrogenation catalyst is substantially composed of platinum and tin dispersed on an oxide support, the oxide support is a modified oxide support, the modified oxide support is (i) an alkaline earth oxide, ( ii) Alkali metal oxides, (iii) Alkaline earth metasilicates, (iv) Alkali metal metasilicates, (v) Zinc oxide, (vi) Zinc metasilicates, and (vii) Precursors for (i)-(vi) 46. The method of claim 45, comprising an effective amount of a carrier modifier selected from the group consisting of a body and a mixture of (i)-(vii).   47. The method of claim 46, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc oxides and metasilicates, and precursors therefor, and mixtures thereof. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
48. The method of claim 47.   48. The method of claim 47, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.   47. The method of claim 46, wherein the carrier modifier is selected from the group consisting of sodium, potassium, magnesium, calcium, and zinc metasilicates, and precursors therefor, and mixtures thereof. c. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and d. Tin is present in an amount of at least 0.5 to 10%;
51. The method of claim 50.   52. The method of claim 51, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.   47. The method of claim 46, wherein the carrier modifier is selected from the group consisting of magnesium, calcium, and zinc oxides and metasilicates, and precursors related thereto, and mixtures thereof. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
54. The method of claim 53.   55. The method of claim 54, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.   47. The method of claim 46, wherein the carrier modifier is selected from the group consisting of magnesium, calcium, and zinc metasilicates, and precursors therefor, and mixtures thereof. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
57. The method of claim 56.   58. The method of claim 57, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4.   47. The method of claim 46, wherein the carrier modifier is selected from the group consisting of calcium metasilicate, a precursor for calcium metasilicate, and a mixture of calcium metasilicate and a precursor related thereto. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
60. The method of claim 59.   61. The method of claim 60, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4. e. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and f. Tin is present in an amount of at least 0.5 to 10%;
48. The method of claim 46.   64. The method of claim 62, wherein the molar ratio of platinum to tin is between 4: 5 and 5: 4. 64. The method of claim 62, wherein the support has a surface area of at least about 100 m < ² > / g.   65. The method of claim 64, wherein the molar ratio of tin to platinum group metal is from about 1: 2 to about 2: 1.   65. The method of claim 64, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.   65. The method of claim 64, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5. 47. The method of claim 46, wherein the support has a surface area of at least about 150 m < ² > / g. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5-5%;
69. The method of claim 68.   69. The method of claim 68, wherein the carrier comprises at least about 1 wt% to about 10 wt% calcium silicate.   69. The method of claim 68, wherein the molar ratio of tin to platinum is about 1: 2 to about 2: 1.   69. The method of claim 68, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.   69. The method of claim 68, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5. 48. The method of claim 46, wherein the support has a surface area of at least about 200 m < ² > / g.   75. The method of claim 74, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.   75. The method of claim 74, wherein the molar ratio of tin to platinum is from about 5: 4 to about 4: 5.   75. The method of claim 74, wherein the molar ratio of tin to platinum is from about 9:10 to about 10: 9.   Platinum dispersed on a modified stabilized siliceous support at a temperature between about 225 ° C. and 300 ° C. with a gas stream comprising hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid in a molar ratio of at least about 4: 1 And a method of producing ethanol by reduction of acetic acid comprising passing over a hydrogenation catalyst consisting essentially of tin, wherein the modified stabilized siliceous support comprises (i) an alkaline earth oxide, ( ii) Alkali metal oxides, (iii) Alkaline earth metasilicates, (iv) Alkali metal metasilicates, (v) Zinc oxide, (vi) Zinc metasilicates, and (vii) Precursors for (i)-(vi) And silica having a purity of at least about 95% by weight modified with a stabilizer-modifier selected from the group consisting of a mixture of (i) to (vii); platinum and tin And the oxidation state, the ratio of platinum and tin, and the relative proportion of stabilizer-modifier and silica in the modified stabilized siliceous support, and the purity of the silica in the modified stabilized siliceous support, of the converted acetic acid. The above process wherein at least 80% is converted to ethanol and less than 4% of acetic acid is controlled to convert to a compound other than a compound selected from the group consisting of ethanol, acetaldehyde, ethyl acetate, ethylene, and mixtures thereof. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5 to 10%;
79. The method of claim 78. 80. The method of claim 79, wherein the modified stabilized siliceous support has a surface area of at least about 100 m < ² > / g.   81. The method of claim 80, wherein the molar ratio of tin to platinum group metal is from about 1: 2 to about 2: 1.   81. The method of claim 80, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.   80. The method of claim 79, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5. 79. The method of claim 78, wherein the modified stabilized siliceous support has a surface area of at least about 150 m < ² > / g. a. Platinum is present in an amount of 0.5% to 5% of the weight of the catalyst; and b. Tin is present in an amount of at least 0.5-5%;
85. The method of claim 84.   85. The method of claim 84, wherein the modified stabilized siliceous support comprises at least about 1 wt% to about 10 wt% calcium silicate.   85. The method of claim 84, wherein the molar ratio of tin to platinum is about 1: 2 to about 2: 1.   85. The method of claim 84, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.   85. The method of claim 84, wherein the weight ratio of tin to platinum is from about 5: 4 to about 4: 5. 90. The method of claim 87, wherein the modified stabilized siliceous support has a surface area of at least about 200 m < ² > / g.   92. The method of claim 90, wherein the molar ratio of tin to platinum is from about 9:10 to about 10: 9.   94. The method of claim 90, wherein the molar ratio of tin to platinum is from about 2: 3 to about 3: 2.   94. The method of claim 90, wherein the molar ratio of tin to platinum is from about 5: 4 to about 4: 5. 94. The method of claim 90, wherein the modified stabilized siliceous support has a surface area of at least about 250 m < ² > / g. At a temperature between about 250 ° C. and 300 ° C.,
a. The surface area of the modified stabilized siliceous support is at least about 250 m ² / g;
b. Platinum is present in the hydrogenation catalyst in an amount of at least about 0.75% by weight;
c. The molar ratio of tin to platinum is from about 5: 4 to about 4: 5; and d. The modified stabilized siliceous support comprises at least about 2.5 wt% to about 10 wt% calcium silicate;
79. The method of claim 78.   96. The method of claim 95, wherein the amount of platinum present is at least 1% by weight. At a temperature between about 250 ° C. and 300 ° C.,
a. The surface area of the modified stabilized siliceous support is at least about 100 m ² / g;
b. The molar ratio of tin to platinum is from about 2: 3 to about 3: 2;
c. The modified stabilized siliceous support comprises at least about 2.5 wt% to about 10 wt% calcium silicate;
79. The method of claim 78.   98. The method of claim 97, wherein the amount of platinum present is at least 0.75 wt%. 99. The method of claim 98, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 1000 hr- ¹ . 99. The method of claim 98, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 2500 hr- ¹ .   The amount and oxidation state of platinum and tin, as well as the ratio of platinum to tin, and the composition of the modified stabilized siliceous support, wherein at least 90% of the converted acetic acid is converted to ethanol and less than 2% of acetic acid is ethanol, 101. The method of claim 100, wherein the process is controlled to convert to a compound other than a compound selected from the group consisting of acetaldehyde, ethyl acetate, and ethylene, and mixtures thereof. 99. The method of claim 98, wherein the catalyst fills the reactor volume and a gas stream comprising vapor phase hydrogen and acetic acid is passed through the reactor volume at a space velocity of at least about 5000 hr- ¹ .   The amount and oxidation state of platinum and tin, as well as the ratio of platinum to tin, and the composition of the modified stabilized siliceous support, at least 90% of the converted acetic acid is converted to ethanol and less than 2% of acetic acid is converted to alkane. 80. The method of claim 79, wherein the method is controlled. At a temperature between about 250 ° C. and 300 ° C.,
a. The amount and oxidation state of platinum and tin, as well as the ratio of platinum to tin, and the acidity of the modified stabilized siliceous support, converted at least 90% of the converted acetic acid to ethanol and less than 1% of the acetic acid to alkane. Control to convert;
b. The surface area of the modified stabilized siliceous support is at least about 200 m ² / g;
c. The molar ratio of tin to platinum is from about 5: 4 to about 4: 5;
d. The modified stabilized siliceous support comprises at least about 2.5 wt% to about 10 wt% calcium silicate;
80. The method of claim 79. A gas stream comprising vapor phase hydrogen and acetic acid in a molar ratio of hydrogen to acetic acid of at least about 4: 1 is dispersed on a suitable support at a temperature between about 225 ° C. and 300 ° C. Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, Pt, Sn, Re, Os, Ti, Zn, Cr, Mo, and W in amounts of 1 wt% to about 10 wt%, and these A process for producing ethanol by reduction of acetic acid comprising passing over a hydrogenation catalyst substantially composed of a catalytic metal selected from the group consisting of a mixture; and optionally a promoter; Or the amount and oxidation state of a plurality of catalytic metals, and the composition of the support and optional promoter, and the reaction conditions: (i) at least 80% of the converted acetic acid is converted to ethanol; (ii) 4% of acetic acid Less than ethanol Converted to a compound other than a compound selected from the group consisting of acetaldehyde, ethyl acetate, ethylene, diethyl ether, and mixtures thereof; and the activity of the catalyst is converted to a vapor mixture of acetic acid and hydrogen in a 10: 1 molar ratio. The above method of controlling so that it decreases by less than 10% upon exposure for 500 hours at a pressure of 2 atmospheres and a temperature of 275 ° C. and a GHSV of 2500 hr ⁻¹ .   The carrier is modified with a modifying agent selected from the group consisting of oxides and metasilicates of sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc, and precursors therefor, and mixtures of any of the above. 106. The method of claim 105, wherein the method is an oxide support.   106. The method of claim 105, wherein the support is a carbon support and the catalytic metal comprises platinum and tin.   108. The method of claim 107, wherein the carbon support is modified with a reducing metal oxide.