CN102300635B - Platinum for the production of ethanol by hydrogenating acetic acid contained in the silicon-containing support - tin catalyst - Google Patents

Platinum for the production of ethanol by hydrogenating acetic acid contained in the silicon-containing support - tin catalyst Download PDF

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CN102300635B
CN102300635B CN201080006216.9A CN201080006216A CN102300635B CN 102300635 B CN102300635 B CN 102300635B CN 201080006216 A CN201080006216 A CN 201080006216A CN 102300635 B CN102300635 B CN 102300635B
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molybdenum
tin
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acetic acid
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CN102300635A (en
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H·魏纳
V·J·约翰斯顿
J·L·波茨
R·耶夫蒂奇
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国际人造丝公司
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/62Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/64Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656Manganese, technetium or rhenium
    • B01J23/6567Rhenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0207Pretreatment of the support
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16Clays or other mineral silicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

由乙酸选择性形成乙醇的方法包括在提高的温度下使含有乙酸和氢气的进料流与催化剂接触,所述催化剂包含在用偏硅酸钙促进的高表面积二氧化硅上的铂和锡。 The method of selective formation of ethanol from acetic acid comprising contacting a feed stream containing acetic acid and hydrogen with a catalyst at elevated temperatures, said catalyst comprising platinum and tin on a high surface area silica with a calcium metasilicate promoted. 在280℃下以数百小时的催化剂寿命获得高于85%的乙醇选择性。 At 280 deg.] C to obtain a catalyst life of hundreds of hours greater than 85% selectivity to ethanol.

Description

用于通过将乙酸加氢生产乙醇的包含在含硅载体上的铂-锡的催化剂 Platinum for the production of ethanol by hydrogenating acetic acid contained in the silicon-containing support - tin catalyst

[0001] 优先权要求 [0001] PRIORITY CLAIM

[0002] 本申请要求2009年10月26日提交的美国申请No 12/588,727的优先权,通过引用将其全文并入本文。 [0002] This application claims the United States October 26, 2009, filed No No. 12 / 588,727, and incorporated by reference herein in its entirety. 发明领域 Field of the Invention

[0003] 本发明总体上涉及用于将羧酸、特别是乙酸加氢的可调变催化剂和使乙酸脱氢的灵活方法,其中乙醇相对于乙酸乙酯和乙醛的比例可以随各种催化剂改变而变化以适合改变的商业条件。 Relates to [0003] of the present invention is generally used carboxylic acid, especially acetic acid and the hydrogenation catalyst becomes adjustable flexible dehydrogenation acetic acid, wherein the proportion of ethanol, ethyl acetate and acetaldehyde with respect to various catalysts may be with changes varied to suit changing business conditions. 更具体地,本发明涉及用于将羧酸、特别是乙酸气相加氢以生产包括相应的醇、酯和醛,特别是乙醇的各种产物的催化剂。 More particularly, the present invention relates to a carboxylic acid, especially a gas phase comprising hydrogenating acetic acid to produce the corresponding alcohols, esters and aldehydes, in particular, various products of the catalyst for the alcohol. 所述催化剂在产物范围内表现出优异的活性和选择性。 The catalyst exhibits excellent activity and selectivity in the product range.

背景技术 Background technique

[0004] 存在对将乙酸转化为乙醇的经济上可行的方法的长期需要,所述乙醇可以按其自身使用或随后转化为乙烯,所述乙烯是重要的商品原料,因为可将其转化为乙酸乙烯酯和/ 或乙酸乙酯或任何许多其它化学产品。 [0004] there is a long felt need to convert acetic acid economically viable method of ethanol, the ethanol may be used in its own or subsequently converted to ethylene, the ethylene is an important commodity feedstock as it can be converted to acid vinyl acetate and / or ethyl acetate, or any number of other chemical products. 例如,还可将乙烯转化为许多聚合物和单体产品。 For example, ethylene can also be converted into a number of polymer and monomer products. 波动的天然气和原油价格有助于使按照常规生产的以石油或天然气为来源的乙烯的成本波动,从而当油价上升时使得对可供选择的乙烯来源的需要比以往更大。 Fluctuating natural gas and crude oil prices contribute to fluctuations in the cost of oil or gas according to a conventional source of ethylene production, so that the need for alternative sources of ethylene all the greater when oil prices rise.

[0005] 用于还原链烷酸和其它含羰基化合物的催化方法已得到广泛研究,在文献中已提及催化剂、载体和操作条件的各种组合。 [0005] for reducing alkanoic acids and other carbonyl-containing compound catalyzed methods have been widely studied, various combinations of the catalyst have been mentioned, the carrier and operating conditions in the literature. T.Yokoyama等在"Fine chemicals through heterogeneous catalysis. Carboxylic acids and derivatives"中评述了各种羧酸在金属氧化物上的还原。 T.Yokoyama et al "Fine chemicals through heterogeneous catalysis. Carboxylic acids and derivatives" reviewed in various carboxylic acids on the reduction of the metal oxide. 第8. 3. 1章中概述了用于各种羧酸的加氢催化剂的开发尝试中的一些。 Chapter 1 of 8. 3. outlined some attempts to develop a hydrogenation catalyst for a variety of carboxylic acids. (Yokoyama,T. ;Setoyama,T. "Carboxylic acids and derivatives.,' in :"Fine chemicals through heterogeneous catalysis.,' 2001,370-379.)。 (Yokoyama, T; Setoyama, T "Carboxylic acids and derivatives, 'in: Fine chemicals through heterogeneous catalysis,.."'.. 2001,370-379.).

[0006] MA Vannice等的一系列研究涉及乙酸在各种非均相催化剂上的转化(Rachmady W. ;Vannice,MA ;J.Catal. 2002, 207,317-330)。 [0006] MA Vannice like a series of studies involving conversion of acetic acid on a variety of heterogeneous catalysts (Rachmady W.; Vannice, MA;. J.Catal 2002, 207,317-330).

[0007] 在不同研究中报导了在负载和非负载的铁上用H2将乙酸气相还原。 [0007] reported a reduction with H2 in the vapor phase acetic acid and unsupported iron load in the different studies. (Rachmady, ff. ;Vannice, MAJ Catal. 2002,208,158-169) 〇 (Rachmady, ff;.. Vannice, MAJ Catal 2002,208,158-169) square

[0008] 在Rachmady, W. ;Vannice,MA,J. Catal. 2002,208,170-179 中给出了关于催化剂表面物质和有机中间体的其它信息。 [0008] In Rachmady, W.;. 2002,208,170-179 given additional information about the surface of the catalyst and an organic substance intermediates Vannice, MA, J Catal..

[0009] 在Rachmady,W. ;Vannice,MAJ Catal. 2002,209,87-98 和Rachmady,W.; Vannice,MAJ Catal. 2000,192, 322-334 中进一步研究了在一系列负载型Pt-Fe 催化剂上的气相乙酸加氢。 [0009] In Rachmady, W;... Vannice, MAJ Catal 2002,209,87-98 and Rachmady, W .; Vannice, MAJ Catal 2000,192, 322-334 is further investigated in a series of supported Pt- Fe catalyst on gas-phase hydrogenation of acetic acid.

[0010] 涉及不饱和醛的选择性加氢的各种相关出版物可以在以下中找到:(Djerb 〇ua, F. ;Benachour, D. ;Touroude, R. Applied Catalysis A:General 2005,282,123-133.; Liberkova, K. ;Tourounde, RJ Mol. Catal. 2002,180,221-230. ;Rodrigues, EL; Bueno, JMC Applied Catalysis A:General 2004,257,210-211. ;Ammari , F.; Lamotte, J. ;Touroude, RJ Catal. 2004,221,32-42 ;Ammari, F. ;Milone, C ;Touroude, RJ Catal. 2005,235,1-9. ;Consonni, M. ;Jokic, D. ;Murzin, DY ;Touroude, RJ Catal. 1999,188,165-175. ;Nitta, Y. ;Ueno, K. ;Imanaka, T. ;Applied Catal. 1989, 56,9-22.)。 [0010] relates to selective hydrogenation of the unsaturated aldehyde can be found in various publications of the following: (Djerb 〇ua, F.; Benachour, D.; Touroude, R. Applied Catalysis A: General 2005,282,123- . 133 .; Liberkova, K.; Tourounde, RJ Mol Catal 2002,180,221-230; Rodrigues, EL; Bueno, JMC Applied Catalysis A:... General 2004,257,210-211; Ammari, F .; Lamotte, J. ; Touroude, RJ Catal 2004,221,32-42;. Ammari, F.; Milone, C; Touroude, RJ Catal 2005,235,1-9;.. Consonni, M.; Jokic, D.; Murzin, DY ; Touroude, RJ Catal 1999,188,165-175;.. Nitta, Y.; Ueno, K.; Imanaka, T.; Applied Catal 1989, 56,9-22)...

[0011] 报导了含有钴、钼和锡的催化剂在将巴豆醛选择性加氢为不饱和醇中的活性和选择性的研究在以下中找到:R.Touroude 等的(Djerboua,F. ;Benachour,D. ;Touroude, R.Applied Catalysis A:General 2005,282,123-133 和Liberkova, K. ;Tourounde, R.; J. Mol. Catal. 2002,180, 221-230)以及K. Lazar 等的(Lazar,K. ;Rhodes,WD ;Borbath, I. ;Hegedues, M. ;Margitfalvi, 1. L. Hyperfine Interactions 2002,1391140,87-96.)。 [0011] reported a catalyst containing cobalt, molybdenum and tin as an active unsaturated alcohol and selectivity in the research found in the selective hydrogenation of crotonaldehyde:. R.Touroude like (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 like ( Lazar, K;. Rhodes, WD; Borbath, I.; Hegedues, M.; Margitfalvi, 1. L. Hyperfine Interactions 2002,1391140,87-96)..

[0012] M. Santiago 等(Santiago, Μ· AN ;Sanchez_Castillo,MA ;Cortright,RD; Dumesic,1. A. J Catal. 2000,193,16-28.)讨论了与量子化学计算组合的微量热法测量、红外光谱法测量和反应动力学测量。 [0012] M. Santiago et (Santiago, Μ · AN; Sanchez_Castillo, MA; Cortright, RD;... Dumesic, 1 A. J Catal 2000,193,16-28) discussed the composition of the quantum chemical calculation microcalorimetry measurement, infrared Spectroscopy measurements and reaction kinetics.

[0013] 还就具有铼和钌的非均相体系报导了对于乙酸加氢的催化活性。 Heterogeneous system [0013] further having rhenium and ruthenium on the catalytic activity reported for the hydrogenation of acetic acid. (Ryashentseva, MA ;Minachev, KM ;Buiychev, Β. Μ. ;Ishchenko, V. Μ. Bui 1. Acad Sci. USSR1988, 2436-2439)。 (Ryashentseva, MA; Minachev, KM; Buiychev, Β Μ;... Ishchenko, V. Μ Bui 1. Acad Sci USSR1988, 2436-2439.).

[0014] Kitson等的美国专利No. 5, 149, 680描述了一种利用钼族金属合金催化剂将羧酸及它们的酸酐催化加氢为醇和/或酯的方法。 [0014] Kitson et al. U.S. Pat. No. 5, 149, 680 describes a method using a molybdenum group metal alloy catalyst carboxylic acids and their anhydrides to alcohols and catalytic hydrogenation / or esters. Kitson等的美国专利No. 4, 777, 303描述了一种通过羧酸加氢生产醇的方法。 Kitson et al. U.S. Pat. No. 4, 777, 303 describes a process for the production of alcohols by hydrogenation of carboxylic acids. Kitson等的美国专利No. 4, 804, 791描述了另一种通过羧酸加氢生产醇的方法。 Kitson et al. U.S. Pat. No. 4, 804, 791 describes another method for the production of alcohols by hydrogenation of carboxylic acids. 还参见USP 5, 061,671 ;USP 4, 990, 655 ;USP 4, 985, 572 ;和USP 4, 826, 795。 See also USP 5, 061,671; USP 4, 990, 655; USP 4, 985, 572; and USP 4, 826, 795.

[0015] Malinowski 等(Bull. Soc. Chim. Belg. (1985),94 (2),93-5)讨论了乙酸在多相化于载体材料例如二氧化硅(Si02)或二氧化钛(Ti02)上的低价钛上的反应催化。 [0015] Malinowski et (Bull. Soc. Chim. Belg. (1985), 94 (2), 93-5) is discussed on a carrier of acid in a multiphase material such as silica (Si02) or titania (Titania and) catalyzed reaction on the low-valent titanium.

[0016] 双金属钌-锡/二氧化硅催化剂通过使四丁基锡与负载在二氧化硅上的二氧化钌反应制得。 [0016] Ruthenium bis - tin / silica catalysts by reacting tetrabutyl tin supported on silica with a ruthenium dioxide reaction. (Loessard 等,Studies in Surface Science and Catalysis (1989),Volume Date 1988,48 (Struct. React. Surf),591-600.) 〇 (Loessard etc., Studies in Surface Science and Catalysis (1989), Volume Date 1988,48 (Struct. React. Surf), 591-600.) Square

[0017] 例如,Hindermann 等的(Hindermann 等,J. Chem. Res. , Synopses (1980), (11), 373)中也研究了乙酸的催化还原,公开了乙酸在铁上和在碱促进的铁上的催化还原。 [0017] For example, Hindermann like (Hindermann like, J. Chem. Res., Synopses (1980), (11), 373) was also studied acetate catalytic reduction disclosed acetic acid on iron and on alkali-promoted catalytic reduction of iron.

[0018] 现有方法遭受到阻碍商业可行性的各种问题,包括:(i)催化剂不具有对乙醇的必要选择性;(ii)催化剂有可能过于昂贵和/或对乙醇的生成呈非选择性并且产生不需要的副产物;(iii)过度的操作温度和压力;以及/或者(iv)不足的催化剂寿命。 [0018] Existing methods suffer from various problems hindering commercial viability, including: (i) a catalyst not have the necessary selectivity to ethanol; (ii) may be too expensive catalysts and / or formation of ethanol as a non-selection and generating of undesired by-products; (iii) excessive operating temperatures and pressures; and / or (iv) insufficient catalyst life.

[0019] 发明概述 [0019] Summary of the Invention

[0020] 已发现当在分散于改性的稳定化含硅载体上的钼锡催化剂之上还原乙酸时,其中所述含硅载体包括有效量的选自如下的载体改性剂:(i)碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏娃酸盐,(iv)碱金属偏娃酸盐,(v)氧化锌,(vi)偏娃酸锌和(vii) (i)-(vi)中任一种的前体,以及(i)-(vii)的任意混合物,通过在气相中以至少约4 : 1的氢气与乙酸摩尔比在约125°C _350°C,更优选约225-300°C,还更优选约250°C _300°C的温度下使包含氢气和乙酸的气态料流穿过所述催化剂,当如本文所述控制钼和锡的量和氧化态以及钼与锡的比率和改性的稳定化含硅载体时,可在转化中获得对乙醇的高选择性。 [0020] When the reduction of acetic acid has been found that over a tin catalyst dispersed on a molybdenum modified stabilized silicaceous support, wherein the silicon-containing vectors include an effective amount of a modifier selected from: (i) alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal partial salts baby, (iv) an alkali metal salt of the partial baby, (v) zinc oxide, (vi) vinylidene baby zinc and (vii) (i) - (vi) any one of the precursor, and (i) - (vii) any mixture, by gas phase of at least about 4: 1 molar ratio of hydrogen to acetic acid at about 125 ° C _350 ° C, more preferably about 225-300 ° C, the gaseous stream further comprising hydrogen and acetic acid at a temperature of more C _300 ° C preferably about 250 ° through the catalyst, as described herein, when the amount of tin and molybdenum control and the oxidation state of the tin and the ratio of molybdenum and silicon-modified stabilized carrier, may be obtained in a high selectivity to ethanol transformation. 在本发明的一方面,抵消了存在于具有如上述所选择的载体改性剂的含硅载体表面上的布朗斯台德酸位的影响。 In one aspect of the present invention counteract the effect of the presence of having Bronsted acid sites such as silicon-containing surface of the support the support modifier is selected. 在另一方面,上述载体改性剂对于防止在流动的乙酸蒸气存在下催化剂于275°C下在高达168、336或甚至500小时的时间段内活性和选择性的过度损失是有效的。 Meanwhile, the support modifier for preventing the flow of vapor in the presence of a catalyst in acetic acid at 275 ° C and even up to 168,336 to 500 hours over a period of loss of activity and selectivity or to be effective in. 在本发明的另一方面,当希望伴随有对乙酸向高度不期望的副产物例如烷烃转化的低选择性时,载体改性剂对抑制乙酸乙酯生成是有效的从而产生对于乙醇生产的高选择性。 In another aspect of the present invention, when it is desired to acetic acid is accompanied by highly undesirable by-products such as low selectivity of transformation of alkanes, ethyl support modifier generation inhibition is effective to produce a high ethanol production selectivity. 优选地,载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 Preferably selected from sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and precursors thereof and mixtures of any of the foregoing support modifier. 最优选的载体改性剂是偏硅酸钙。 The most preferred support modifier is calcium metasilicate.

[0021] 已发现当在分散于基本上碱性偏硅酸钙/二氧化硅载体上的钼锡催化剂之上还原乙酸时,其中通过在气相中以至少约4 : 1的氢气与乙酸摩尔比在约125°C_350°C,更优选约225-300°C,还更优选约250°C _300°C的温度下使包含氢气和乙酸的气态料流穿过所述催化剂,当如本文所述控制钼和锡的量和氧化态以及钼与锡的比率和偏硅酸钙/二氧化硅载体的酸度时,可在转化中获得对乙醇的高选择性。 [0021] It has been found when dispersed in an alkaline metasilicate is substantially above the tin catalyst on the molybdenum / silica support reduction acetate, wherein in the gas phase by at least about 4: 1 molar ratio of hydrogen to acetic acid at about 125 ° C_350 ° C, more preferably from about 225-300 ° C, and even more so at a temperature of about 250 ° C _300 ° C is preferably a gaseous stream comprising hydrogen and acetic acid through the catalyst, as described herein, when molybdenum, tin and control acidity amounts and oxidation states of molybdenum and tin, and the ratio of calcium metasilicate and / silica support may be obtained in a high selectivity to ethanol transformation. 特别地,使用本发明的优选催化剂和方法,使所转化乙酸的至少80%转化为乙醇,使小于4%的乙酸转化为除选自乙醇、乙醛、 乙酸乙酯、乙烯及其混合物的化合物以外的化合物。 In particular, using the preferred catalyst and process of the present invention, so that the conversion of acetic acid is converted to ethanol at least 80%, less than 4% of acetic acid is converted to other compounds selected from ethanol, acetaldehyde, ethyl acetate, ethylene and mixtures thereof other than the compound. 在优选的方法中,钼以催化剂重量的0. 5% -5 %的量存在;同时锡以催化剂重量的至少0. 5 -直到10 %的量存在;优选地,载体表面积为至少约l〇〇m2/g,更优选约150m2/g,还更优选至少约200m 2/g,最优选至少约250m2/ g;锡与钼族金属的摩尔比优选为约1 : 2-约2 : 1,更优选约2 : 3-约3 : 2;还更优选约5 : 4-约4 : 5;最优选约9 : 10-10 : 9。 In a preferred method, the molybdenum in an amount of 0.5% to 5% by weight of the catalyst; while the tin catalyst of at least 0.5 weight - present in an amount up to 10%; preferably, support surface area is at least about l〇 〇m2 / g, more preferably from about 150m2 / g, still more preferably at least about 200M 2 / g, most preferably at least about 250m2 / g; tin group metal and molybdenum molar ratio is preferably from about 1: 2 to about 2: 1, more preferably about 2: 3 to about 3: 2; and still more preferably from about 5: 4 to about 4: 5; most preferably about 9: 10-10: 9. 在许多情形中,载体包含以有效平衡布朗斯台德酸位从而在二氧化娃中产生残留氧化错(residual alumina)的量的娃酸|丐;典型地, 约1重量% -直到约10重量%的硅酸钙足以确保所述载体的特性呈基本上中性或碱性。 In many cases, in order to effectively balance the vector comprises Bronsted acid sites resulting oxidation amount of residual error (residual alumina) of the baby doll acid dioxide | cai; Typically, from about 1 wt% - up to about 10 wt. % of calcium sufficient to ensure that the characteristics of the carrier in a substantially neutral or basic. 在一个特别优选的实施方案中,钼以至少约〇. 75重量%,更优选1重量%的量存在于加氢催化剂中;锡与钼的摩尔比为约5 : 4-约4 : 5;并且载体包含至少约2. 5重量% -约10重量%的硅酸钙。 In a particularly preferred embodiment, molybdenum is at least about 75 square wt%, more preferably from 1% by weight is present in the hydrogenation catalyst; and the molar ratio of tin to molybdenum is from about 5: 4 to about 4: 5; and the carrier comprises at least about 2.5 wt% - about 10% by weight of calcium silicate.

[0022] 本发明许多实施方案的一个方面是可使用高于约lOOOhr'ZSOOhf1和甚至高于SOOOhf1的空速,并同时使所转化乙酸的至少90%转化为乙醇,且使小于2%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯和乙烯及其混合物的化合物以外的化合物。 [0022] An aspect of many embodiments of the present invention can be used, and even higher than about lOOOhr'ZSOOhf1 SOOOhf1 airspeed, and while the conversion of acetic acid is converted to ethanol at least 90%, and less than 2% of acetic acid converted to ethanol, acetaldehyde, vinyl acetate and mixtures and compounds other than the compound selected in addition. 在本发明的许多实施方案中,烷烃的形成是低的,通常低于2%,经常低于1%,并且在许多情形中使穿过催化剂的乙酸的0. 5%以下转化为烷烃,该烷烃除作为燃料或合成气外具有很小价值。 In many embodiments of the present invention, the formation of alkane is low, typically less than 2%, often less than 1%, and the acid catalyst through manipulation of many cases 0.5% or less is converted to alkanes, the alkanes having little value except as fuel or synthetic gas outside.

[0023] 在本发明的另一方面,通过在气相中以至少约2 : 1的氢气与链烷酸的摩尔比在约125°C _350°C的温度下使包含氢气和链烷酸的气态料流穿过加氢催化剂将链烷酸进行加氢,所述加氢催化剂包含:在选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属;和选自锡、铼及其混合物的促进剂,其中含硅载体任选用促进剂促进,促进剂选自:催化剂重量的1-5%的量的选自碱金属、碱土元素和锌的促进剂;催化剂重量的1-50%的量的选自103、11〇03、? [0023] In another aspect of the present invention, in the gas phase by at least about 2: 1 molar ratio of hydrogen to an alkanoic acid at a temperature of about 125 ° C _350 ° C to make alkanoic acids comprising hydrogen and gaseous is selected from the silicon-containing carrier selected from silica, calcium metasilicate and calcium metasilicate promoted silica: stream through the hydrogenation catalyst alkanoic acid is hydrogenated, the hydrogenation catalyst comprising since molybdenum metals molybdenum, palladium, and mixtures thereof; and selected from tin, rhenium promoters and mixtures thereof, wherein any one of silicon-containing carrier selection accelerating agent, promoter is selected from: an amount of 1-5% of the weight of the catalyst selected from alkali metal, alkaline earth elements and zinc promoter; an amount of 1-50% by weight of a catalyst selected 103,11〇03 ,? 620 3和(>203的氧化还原型〇^(1(«)促进剂;以及催化剂重量的1-50%量的选自110 2、21〇2、他2053&20 5和41203的酸性改性剂,其中控制所述载体的酸度以使小于4,优选小于2,最优选小于约1 %的链烷酸转化为烷烃。在许多情形中,钼和钯中的至少一种以催化剂重量的0. 25% -5%的量存在;存在的钼和钯的总量为催化剂重量的至少0. 5% ;存在的铼和锡的总量为至少0. 5-10重量%。 在该方法中,对于包含在碱性二氧化硅载体上的钼和锡的催化剂,控制钼族金属、铼和锡促进剂的量和氧化态,以及钼族金属与存在的铼和锡的总摩尔数的摩尔比;和含硅载体的酸度使得所转化乙酸的至少80%转化为选自烷醇和乙酸烷基酯的化合物,并同时使小于4% 的链烷酸转化为除选自相应的烷醇、乙酸烷基酯及其混合物的化合物以外的化合物。优选地,钼和钯中的至少一种以催化剂重量的0. 5% And 6203 (> 203 oxidation reduction square ^ (1 ( «) promoter; and 1-50% by weight of the catalyst is selected from 2,21〇2 110, 2053 & his acidic modifier 205 and 41,203, and wherein said control is such that the acidity of the support is less than 4, preferably less than 2, most preferably less than about 1% of the alkanoic acid is converted to alkanes. in many cases, molybdenum and palladium catalyst in at least one of 0.25 wt. is present in an amount of 5 percent; the total amount of molybdenum present and palladium catalyst is at least 0.5% by weight; the total amount of rhenium and tin present is at least 0.5 to 10% by weight in the process, for. the catalyst comprises molybdenum and tin on a basic silica support, molybdenum metal control, the amount of rhenium and tin, and the oxidation state of the promoter, and molybdenum metal and the molar ratio of the total number of moles of rhenium and tin present; and silicon-containing carrier such that the acidity of the acetic acid conversion of at least 80% conversion to a compound selected from alcohol and acetic acid alkyl ester, alkanoic acids, while less than 4% of selected converted to the corresponding alkanols, in addition to an alkyl acetate 0.5% compound other than the compound esters and mixtures thereof. preferably, molybdenum and palladium, at least one of the catalyst weight -5%的量存在;存在的钼和钯的总量为催化剂重量的至少0.75%至5%。优选地,链烷酸为乙酸,存在的锡和铼的总量为催化剂重量的至少1. 0%,并同时控制钼族金属、铼和锡促进剂的量和氧化态,以及钼族金属与铼和锡促进剂的比率;和含硅载体的酸度使得所转化乙酸的至少80%转化为乙醇或乙酸乙酯,使小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯及其混合物的化合物以外的化合物。优选地,存在的铼和锡的总重量为催化剂重量的约1-10%,并同时钼族金属与铼和锡的总摩尔数的摩尔比为约1 : 2-约2 : 1。 Is present in an amount of 5%; the total amount of molybdenum and palladium present is at least 0.75 to 5% by weight of the catalyst Preferably, the alkanoic acid is acetic acid, the total amount of tin and rhenium present is at least 1 weight of the catalyst. 0%, while controlling the metals molybdenum, rhenium and tin promoter amounts and oxidation states, and the ratio of molybdenum and rhenium and tin metal promoter; acidity and silicon-containing carrier such that at least 80% of the converted acetic acid is converted ethanol or ethyl acetate, acetic acid less than 4% is converted to a compound selected from compounds other than ethanol, acetaldehyde, ethyl acetate, ethylene and mixtures thereof. preferably the total weight, the presence of rhenium and tin to a catalyst weight about 1-10%, while the molar ratio of the molybdenum metal and the total number of moles of rhenium and tin is about 1: 2 to about 2: 1.

[0024] 在另一方面,本发明涉及将乙酸加氢的方法,该方法包括在气相中以至少约4 : 1 的氢气与乙酸摩尔比在约225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,所述加氢催化剂基本上由分散在氧化物类载体上的金属组分构成,所述加氢催化剂具有如下组成: [0024] In another aspect, the present invention relates to a method of hydrogenating acetic acid, the method comprising in the gas phase of at least about 4: 1 molar ratio of hydrogen to acetic acid contained so that at about 225 ° C -300 ° C in acetic acid and a gaseous hydrogen stream through the hydrogenation catalyst, the hydrogenation catalyst consists essentially of a metal component dispersed on oxidic support, said hydrogenation catalyst has the following composition:

[0025] PtvPdwRexSnyCapSi qOr, [0025] PtvPdwRexSnyCapSi qOr,

[0026] 其中:v : y之比为3 : 2-2 : 3;和/或w : X之比为1 : 3-1 : 5,对p和q进行选择使得P : q为1 : 20-1 : 200,其中r的选择满足化合价要求,并且¥和《的选择使得: rtA_^(3,25v4l,75w)^Anc Γ00271 0-005 < --- < 0.05 f ο [0026] wherein: v: y ratio of 3: 2-2: 3; and / or w: X ratio is 1: 3-1: 5, p and q are selected such that the P: q is 1:20 -1: 200, wherein the selection of r satisfy valence requirements, and ¥ and "selected so that: rtA _ ^ (3,25v4l, 75w) ^ Anc Γ00271 0-005 <--- <0.05 f ο

[0028] 在该方面,优选对工艺条件以及v、w、x、y、p、q和r的值进行选择以使所转化乙酸的至少90%转化为选自乙醇和乙酸乙酯的化合物,并同时小于4%的乙酸转化为烷烃。 [0028] In this aspect, preferably the process conditions, and v, w,,, p value x y, q and r are chosen such that the conversion of acetic acid is at least 90% conversion to a compound selected from ethanol and ethyl acetate, while less than 4% of acetic acid is converted to alkanes. 在本发明的许多实施方案中,考虑到存在的任何较少的杂质,对P进行选择以确保载体表面基本上不含活性布朗斯台德酸位。 In many embodiments of the present invention, taking into account any minor impurities present, for P is selected to ensure that the support surface is substantially free of active Bronsted acid sites.

[0029] 本发明的又一方面涉及通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C_300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,所述加氢催化剂基本上由分散在氧化物类载体上的金属组分构成,所述加氢催化剂具有如下组成: [0029] Yet another aspect of the present invention relates to the process for producing acetic acid to ethanol, the method comprising in the gas phase of at least about 4: 1 molar ratio of hydrogen to acetic acid at a temperature of about 225 ° C_300 ° C causes hydrogen comprising acetic acid and gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst consists essentially of a metal component dispersed on oxidic support, said hydrogenation catalyst has the following composition:

[0030] PtvPdwRexSnyAlzCa pSiqOr, [0030] PtvPdwRexSnyAlzCa pSiqOr,

[0031] 其中:v和y为3 : 2-2 : 3 ;w和X为1 : 3-1 : 5,其中控制p和z以及存在的铝原子和钙原子的相对位置使得存在于其表面的布朗斯台德酸位通过硅酸钙进行平衡;对P和q进行选择使得P : q为1 : 20-1 : 200,其中r的选择满足化合价要求,并且v和w 的选择使得: [0031] where: v and y is 3: 2-2: 3; w and X 1: 3-1: 5, wherein the control and p and z aluminum atoms present in the relative position and such that the calcium atoms present on the surface thereof Bronsted acid sites by calcium balance; the P-P and q are selected such that: q is 1: 20-1: 200, with r being selected to satisfy valence requirements, v and w and selected such that:

[0032] < ---<0J5 € O [0032] <--- <0J5 € O

[0033] 优选地,在该方面,所述加氢催化剂具有至少约100m2/g的表面积,并且z和p >z。 [0033] Preferably, in this aspect, the hydrogenation catalyst having a surface area of ​​at least about 100m2 g /, and z and p> z. 在本发明的许多实施方案中,考虑到存在的任何较少的杂质,对P进行选择以同样确保载体表面基本上不含似乎促进乙醇转化为乙酸乙酯的活性布朗斯台德酸位。 In many embodiments of the present invention, taking into account any minor impurities present, on the same P are selected to ensure that the support surface is substantially free of alcohol appears to facilitate the conversion of active Bronsted acid sites ethyl acetate.

[0034] 本发明的另一方面涉及通过将乙酸还原生产乙醇和乙酸乙酯的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C_300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,所述加氢催化剂包含:在选自二氧化硅和用至多约7. 5偏硅酸钙促进的二氧化硅的含硅载体上的选自钼以及钼和钯的混合物的钼族金属,存在的钼族金属的量为至少约2. 0%,存在的钼的量为至少约1. 5% ;和催化剂重量的约1% -2%的量的选自铼和锡的金属促进剂,钼与金属促进剂的摩尔比为约3 : 1-1 : 2;任选用第二促进剂促进的含硅载体,所述第二促进剂选自:催化剂重量的1-5%的量的选自碱金属、碱土元素和锌的给体((1〇11〇1〇促进剂;催化剂重量的1-50%的量的选自103、1〇03、?620 3和(>203 的氧化还原型促进剂;以及催化剂重量的1-50%量的选自1102、21<)2、他205、1& [0034] Another aspect of the present invention relates to a process for producing acetic acid to ethanol and ethyl acetate, the method comprising in the gas phase of at least about 4: 1 molar ratio of hydrogen to acetic acid to a temperature of about 225 ° C_300 ° C in under the gaseous stream comprising hydrogen and acetic acid through hydrogenation catalyst, said hydrogenation catalyst comprising: a support selected from silica and silicon-containing silica up to about 7.5 in the calcium metasilicate promoted molybdenum metals molybdenum and palladium, and mixtures selected from molybdenum, molybdenum metal is present in an amount of at least about 2.0%, molybdenum is present in an amount of at least about 1.5%; and about 1% by weight of the catalyst molar ratio of an amount of 2% of a metal selected from rhenium and tin promoter, and molybdenum promoter metal is from about 3: 1 to 1: 2; the second silicon-containing carrier optionally the accelerating agent, wherein the first two promoter is selected from: an amount of 1-5% by weight of the catalyst selected from alkali metal, alkaline earth elements and zinc donor ((1〇11〇1〇 promoter; an amount of 1-50% by weight of the catalyst is selected from since 103,1〇03, 6203, and (> 203 reduced oxidation promoting agent; and 1-50% by weight of the catalyst selected 1102,21 <)? 2, he & 205,1 205和4120 3 的酸性改性剂;以及它们的组合。 Acidic modifier 205 and 41,203; and combinations thereof.

[0035] 在本发明的优选方面中,金属促进剂与钼族金属的摩尔比为约2 : 3-约3 : 2,更优选约5 : 4-约4 : 5,最优选约9 : 10-约10 : 9,并同时含硅载体表面积为至少约200m2/ g,硅酸钠的量足以使所述载体的表面呈基本上碱性。 [0035] In a preferred aspect of the present invention, the molar ratio of molybdenum metal promoter metal is from about 2: 3 to about 3: 2, more preferably from about 5: 4 to about 4: 5, most preferably from about 9:10 - about 10: 9, while the silicon-containing support surface area of ​​at least about 200m2 / g, an amount of silicate sufficient to form the surface of the carrier is substantially basic. 在一些情形中,可控制硅酸钙的使用使得存在于其表面上的布朗斯台德酸位的摩尔数不大于存在于Saint-Gobain NorPro SS61138二氧化硅表面上的布朗斯台德酸位的摩尔数。 In some cases, the use of calcium silicate may be controlled such that the number of acid sites present on the molar Brønsted its surface is no greater than present in the Saint-Gobain NorPro Bronsted acid sites on the surface of the silica SS61138 the number of moles. 在其它情形中,所使用的二氧化硅可以是具有低含量的氧化铝或其它杂质的高纯度热解二氧化硅。 In other cases, the silica may be used with a low content of impurities, alumina or other high-purity fumed silica. 在许多情形中,这类二氧化硅可包含高于99%的二氧化硅,更优选高于99. 5%的二氧化硅,最优选高于99. 7%的二氧化硅。 In many cases, such silica may comprise more than 99% of silica, more preferably higher than 99.5% silica, and most preferably greater than 99.7 percent silica. 在本发明的许多实施方案中,或者通过控制二氧化硅纯度,或者通过用硅酸钙或本文所论述的其它合适的稳定剂改性剂中的一种平衡存在于载体表面上的布朗斯台德酸位,存在于其表面上的布朗斯台德酸位的可用摩尔数不大于存在于Saint-Gobain NorPro SS61138二氧化硅表面上的布朗斯台德酸位的摩尔数,优选小于一半,更优选小于25%,还更优选小于10%的存在于Saint-Gobain NorPro SS61138二氧化娃表面上的布朗斯台德酸位的摩尔数。 In many embodiments of the invention, the support or present on the surface of silica by controlling the purity, or by other suitable stabilizer a balanced modifier with calcium or discussed herein Bronsted German molar number of available acid sites, the presence of Bronsted acid sites on the surface thereof is not larger than the number of moles present in the Saint-Gobain NorPro Bronsted acid sites on the surface of the silica SS61138, preferably less than half, more preferably less than 25%, still more preferably less than 10% of the number of moles present in Saint-Gobain Bronsted acid sites on the surface of the doll NorPro SS61138 dioxide. 存在于载体表面上的酸位数可以使用吡啶滴定法按如下文献中描述的操作进行测定: An acid number of bits present on the surface of the support may be determined according to the following operation described in the literature using pyridine titration method:

[0036] (1) F. Delannay,编辑,"Characterization of Heterogeneous Catalysts "; Chapter III :Measurement of Acidity of Surfaces, 370-404 页;Marcel Dekker, Inc., NY 1984。 [0036] (1) F. Delannay, editor, "Characterization of Heterogeneous Catalysts"; Chapter III: Measurement of Acidity of Surfaces, 370-404 pages; Marcel Dekker, Inc., NY 1984.

[0037] (2)CR Brundle,CA Evans, Jr. , S. Wilson, LE Fitzpatrick,编辑, "Encyclopedia of Materials Characterization " ;Chapter 12. 4 :Physical and Chemical Adsorption Measurements of Solid Surface Areas, 736-744 页; Butterworth-Heinemann, MA 1992。 [0037] (2) CR Brundle, CA Evans, Jr., S. Wilson, LE Fitzpatrick, editor, "Encyclopedia of Materials Characterization"; Chapter 12. 4: Physical and Chemical Adsorption Measurements of Solid Surface Areas, 736-744 pages ; Butterworth-Heinemann, MA 1992.

[0038] (3)GA Olah,GK Sura Prakask,编辑,"Superacids John Wiley & Sons, NY 1985。 [0038] (3) GA Olah, GK Sura Prakask, editing, "Superacids John Wiley & Sons, NY 1985.

[0039] 在整个本说明书和权利要求,除非上下文另外指出,当测量表面酸度或其上的酸位数时,应使用F.Delannay,编辑,"Characterization of Heterogeneous Catalysts"; Chapter III :Measurement of Acidity ofSurfaces,370-404 页;Marcel Dekker, Inc., NY 1984中所描述的技术。 [0039] Throughout the present specification and claims, unless the context indicates otherwise, when the acid number of bits or on the measuring surface acidity should be used F.Delannay, editor, "Characterization of Heterogeneous Catalysts"; Chapter III: Measurement of Acidity ofSurfaces, 370-404 pages; Marcel Dekker technology Inc., NY 1984 described.

[0040] 在更优选的情形中,含硅载体的表面积为至少约250m2/g,存在于其表面上的可用布朗斯台德酸位的摩尔数不大于存在于Saint-Gobain NorPro HSA SS61138二氧化娃表面上的布朗斯台德酸位摩尔数的一半,并且可在约250°C -300°C的温度下进行加氢。 [0040] In a more preferred case, the surface area of ​​the siliceous support is at least about 250m2 / g, the number of moles thereof present available Bronsted acid site on the surface is not greater than present in the Saint-Gobain NorPro HSA SS61138 dioxide half the number of moles of acid sites on the surface of Bronsted baby, and can be hydrogenated at a temperature of about 250 ° C -300 ° C is.

[0041] 回顾本文讨论,如本领域技术人员可意识到的,在一些实施方案中,可以使用除上述含硅载体外的催化剂载体,条件是对其组分进行选择以使该催化剂体系在所使用的工艺条件下具有合适的活性、选择性和稳健性(robust)。 [0041] Recalling the discussion herein, as those skilled in the art can appreciate, in some embodiments, the catalyst carrier may be used in addition to the silicon-containing carrier, with the proviso that its components are selected such that the catalyst system in the having suitable activity, selectivity, and robustness (robust) at the process conditions used. 合适的载体可以包括稳定的金属氧化物基载体或陶瓷基载体以及包括沸石的分子筛。 Suitable carriers may include stabilizing metal oxide-based or ceramic-based carrier and a support comprising a molecular sieve zeolite. 因此同样,在一些实施方案中,如Kitson 等的上述美国专利No. 5, 149, 680在2栏,64行-4栏,22行中所描述可以使用碳载体,通过引用将该美国专利的公开内容并入本文。 Accordingly Also, in some embodiments, such as the Kitson et al U.S. Patent No. 5, 149, 680 at column 2, line 64 -4 column, line 22 can be described using a carbon support, by reference to U.S. Pat. the disclosure of which is incorporated herein.

[0042] 在本发明的许多实施方案中,在其中将同时生产乙醇和乙酸乙酯的混合物的情形中,加氢催化剂可以包含:在选自二氧化硅和用至多约7. 5偏硅酸钙促进的二氧化硅的含硅载体上的钯,存在的钯的量为至少约1.5% ;并同时金属促进剂是催化剂重量的约1 %-10%的量的铼,铼与钯的摩尔比为约4 : 1-1 : 4,优选2 : 1-1 : 3。 Case [0042] In many embodiments of the present invention, in which the simultaneous production of a mixture of ethanol and ethyl acetate, the hydrogenation catalyst may comprise: selected from silica and up to about 7.5 with metasilicate palladium on a siliceous support to promote calcium silica, palladium is present in an amount of at least about 1.5%; and also an amount of metal promoter is from about 1% to about 10% by weight of the catalyst of rhenium, rhenium to palladium molar ratio of about 4: 1 to 1: 4, preferably 2: 1 to 1: 3.

[0043] 在本发明的许多实施方案中,在其中期望主要生产乙醇的情形中,催化剂可以基本上由如下构成:在基本上由用约3 -直到约7. 5%硅酸钙促进的二氧化硅构成的含硅载体上的钼,其中存在的钼的量为至少约1.0%,和催化剂重量的约1%-5%的量的锡促进齐[J,在本发明的许多实施方案中钼与锡的摩尔比为约9 : 10-10 : 9。 [0043] In many embodiments of the present invention, in the case where it is desired mainly in the production of ethanol, the catalyst may be consisting essentially of: a substantially by about 3 - promoted up to about 7.5% calcium silicate two silicon-containing molybdenum on a carrier of silicon oxide, wherein the amount of molybdenum present is at least about 1.0%, by weight, and the amount of tin catalyst is from about 1% to 5% promote homogeneous [J, many embodiments of the present invention molybdenum molar ratio of tin is from about 9: 10-10: 9. 在一些情形中,可以包括次要量的另一种钼族金属,最通常的是属于配方中的催化金属的钯。 In some cases, it may further comprise a minor amount of molybdenum metal, most typically a metal belonging to palladium catalyzed formulation. 在本发明的许多实施方案中,存在的钼族金属的量为至少约2. 0%,存在的钼的量为至少约1. 5%,优选2. 5-3. 5重量%的钼,锡促进剂以催化剂重量的约2% -5%的量存在,并同时所述方法在约250°C _300°C的温度下以至少约lOOOhr-1的GHSV在至少2atm的压力下进行。 In many embodiments of the present invention, the amount of molybdenum group metal present is at least about 2.0%, molybdenum is present in an amount of at least about 1.5%, preferably from 2. 5-3. 5 wt.% Of molybdenum, tin promoter in an amount of from about 2% to 5% by weight of the catalyst is present, while the method at a temperature of about 250 ° C _300 ° C of at least about lOOOhr-1 GHSV carried out at a pressure of at least 2atm. 锡与钼的比率优选为2 : 3-3 : 2,更优选4 : 5-5 : 4,最优选9 : 10-10 : 9。 Molybdenum ratio of tin is preferably 2: 3-3: 2, more preferably 4: 5-5: 4, most preferably 9: 10-10: 9. 在其中期望主要生产乙醇的仍其它实施方案中,催化剂可以包含在基本上由用约3 -直到约7. 5%硅酸钙促进的二氧化硅构成的含硅载体上的钼,其中存在的钼的量为至少约1. 0%,锡促进剂以催化剂重量的约1%-5%的量存在,在本发明的许多实施方案中钼与锡的摩尔比为约9 : 10-10 : 9。 Where intended primarily for producing ethanol still other embodiments, the catalyst may comprise a substantially by about 3 - molybdenum silicon-containing support comprising silica promoted up to about 7.5 percent calcium silicate, present therein amount of molybdenum of at least about 1.0%, tin promoter in an amount of from about 1% to 5% by weight of the catalyst, in many embodiments of the present invention, the molar ratio of molybdenum to tin is from about 9: 10-10: 9.

[0044] 本发明的另一方面涉及用于将链烷酸加氢为相应的烷醇的颗粒催化剂,该颗粒催化剂包含:在选自二氧化硅和用约3. 0 -直到约7. 5偏硅酸钙促进的二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属,含硅载体的表面积为至少约150m2/g ;锡促进剂为催化剂重量的约1%-3%的量,钼与锡的摩尔比为约4 : 3-3 : 4;对所述含硅载体的组成和结构进行选择使得其表面呈基本上碱性。 [0044] Another aspect of the present invention for hydrogenation of the corresponding alkanoic acid alkanol of particulate catalyst, the particulate catalyst comprises: in a selected from silica and from about 3.0 - up to about 7.5 silicon-containing carrier is selected from molybdenum on silica-promoted calcium metasilicate, palladium, and molybdenum metal, the surface area of ​​the silicon-containing carrier mixture is at least about 150m2 / g; tin accelerator is about 1% by weight of the catalyst molar ratio of an amount of 3% molybdenum and tin is from about 4: 3-3: 4; the composition and structure of the silicon-containing carrier is selected such that its surface was substantially basic.

[0045] 本发明的另一方面涉及基本上由如下物质构成的颗粒加氢催化剂:上面分散有选自钼、钯及其混合物的钼族金属与选自锡、钴和铼的促进剂的含硅载体,该含硅载体具有至少约175m2/g表面积并且选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅(具有位于其表面上的偏硅酸钙),所述含硅载体的表面由于未被钙平衡的氧化铝而基本上不含布朗斯台德酸位。 [0045] Another aspect of the present invention is directed to hydrogenation catalyst particles substantially consisting of the following materials: The above dispersion of metal selected from molybdenum, tin, cobalt and rhenium promoter selected from molybdenum, palladium, and mixtures containing silicon carrier, the silicon-containing carrier having at least about 175m2 / g and a surface area selected from silica, calcium metasilicate and calcium metasilicate promoted silica (calcium metasilicate having positioned on a surface thereof), the Since the silicon surface of the carrier is not calcium balance substantially free of alumina, Bronsted acid sites. 在最适合于同时生产乙醇和乙酸乙酯的那些变型中,存在的钼族金属的总重量为0.5% -2%,存在的钯的量为至少0.5%,促进剂是铼,铼与钯的重量比为10 : 1-2 : 1,偏硅酸钙的量为3-90%。 In the most suitable for the simultaneous production of ethanol and ethyl acetate to those variations, the total weight of the molybdenum metal is present from 0.5% to 2%, the palladium is present in an amount of at least 0.5%, the promoter is rhenium, palladium and rhenium a weight ratio of 10: 1-2: 1, the amount of calcium metasilicate is 3-90%.

[0046] 在最适合于以高选择性生产乙醇的那些方面中,存在的钼族金属的总重量为0.5-2%,存在的钼的量为至少0.5%,促进剂是钴,钴与钼的重量比为20 : 1-3 : 1,硅酸钙的量为3-90%,而对于用具有延长寿命的催化剂生产乙醇时,加氢催化剂包含2. 5-3. 5 重量%的钼,3重量% -5重量%的分散在表面积为至少200m2/g的高表面积热解所得二氧化硅上的锡,所述高表面积二氧化硅用有效量的偏硅酸钙促进以确保其表面基本上不含未被偏硅酸钙平衡的布朗斯台德酸位,钼与锡的摩尔比为4 : 5-5 : 4。 [0046] In those aspects best suited to the production of ethanol with high selectivity, the total weight of the molybdenum metal in the presence of 0.5-2%, molybdenum is present in an amount of at least 0.5%, the promoter is cobalt, molybdenum and cobalt weight ratio of 20: 1 to 3: 1, the amount of calcium silicate is 3-90%, while with respect to the production of a catalyst having a longer life ethanol, 2. the hydrogenation catalyst comprises 5-35 wt% molybdenum. , 3% by weight of 5% by weight of tin dispersed on a surface area of ​​at least 200m2 / resulting fumed silica g of high surface area, a high surface area silica with an effective amount of a calcium metasilicate facilitate to ensure that its surface substantially free of non-balanced calcium metasilicate Bronsted acid sites, molybdenum molar ratio of tin is 4: 5-5: 4.

[0047] 在本发明的另一种催化剂中,存在的钼族金属的总重量为0. 5-2%,存在的钯的量为至少0.5%,促进剂是钴,钴与钯的重量比为20 : 1-3 : 1,硅酸钙的量为3-90%。 [0047] In another catalyst of the present invention, the total weight of the molybdenum metal in the presence of 0. 5-2%, the palladium is present in an amount of at least 0.5%, the promoter is cobalt, the weight ratio of cobalt to palladium 20: 1-3: 1, the amount of calcium silicate 3-90%.

[0048] 本发明的又一种催化剂是包含如下物质的加氢催化剂:0. 5-2. 5重量%钯,2重量% -7重量%铼,铼与钯的重量比为至少1. 5 : 1. 0,其中铼和钯都分散在含硅载体上,所述含硅载体包含至少80 %偏硅酸钙。 [0048] The present invention is further a catalyst comprising a hydrogenation catalyst of the following materials: 05-25 wt% palladium, 2 wt% to 7 wt% rhenium, rhenium to palladium weight ratio of at least 1.5 : 1.0, wherein the palladium and rhenium dispersed on a siliceous support, the silicon-containing carrier comprises at least 80% calcium metasilicate.

[0049] 已发现对于将乙酸加氢为乙醇,由选自如下的催化剂获得出人意料地高的活性和寿命且兼具有优异的选择性: [0049] It has been found for the hydrogenation of acetic acid to ethanol to obtain a surprisingly high activity and life of catalyst selected from the following and have excellent selectivity and:

[0050] (i)兼具有在选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属与锡或铼的催化剂; [0050] (i) selected from silica and has, on the molybdenum metal is selected from molybdenum and silicon-containing carrier metasilicate calcium metasilicate promoted silica, tin and palladium, and mixtures thereof or rhenium;

[0051] (ii)兼具有负载在包含选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的含娃载体上的钮和铼的催化剂,其中含娃载体任选用1% -5%选自碱金属、碱土兀素和锌的促进剂进行促进;促进剂优选以这些促进剂(特别优选钾、铯、钙、镁和锌)各自的硝酸盐或乙酸盐形式加入到催化剂配方中; [0051] (ii) and having a load comprising silica selected, the button on the baby carrier containing calcium metasilicate and calcium metasilicate promoted silica and rhenium, wherein the carrier optionally containing baby with 1% to 5% is selected from alkali metals, alkaline Wu promoting hormone and zinc promoting agent; preferably, the promoter of these accelerators (particularly preferably potassium, cesium, calcium, magnesium and zinc) the respective nitrates or acetates in the form of catalyst added to the formulation;

[0052] (iii)在选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的高表面积含硅载体上用钴促进的钼;以及 [0052] (iii) promoted with cobalt on a high surface area siliceous support is selected from silica, calcium metasilicate and calcium metasilicate promoted molybdenum silica; and

[0053] (iv)在选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的高表面积含硅载体上用钴促进的钯。 [0053] (iv) selected from silicon dioxide, the silicon-containing high surface area support metasilicate and calcium metasilicate promoted silica palladium promoted with cobalt.

[0054] 本发明的另一方面涉及将链烷酸加氢的方法,该方法包括在气相中以至少约2 : 1的氢气与链烷酸的摩尔比在约125°C_350°C的温度下使包含氢气和链烷酸的气态料流穿过加氢催化剂,该加氢催化剂包含: [0054] Another aspect relates to alkanoic acids hydrogenation process of the present invention, the method comprising the gas phase in at least about 2: 1 molar ratio of hydrogen to an alkanoic acid at a temperature of about 125 ° C_350 ° C of the gaseous hydrogen and an alkanoic acid containing stream through the hydrogenation catalyst, the hydrogenation catalyst comprising:

[0055] a.在选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属;和 . [0055] a is selected from molybdenum, palladium, and molybdenum metal on a siliceous support selected from silica, calcium metasilicate and calcium metasilicate promoted silica mixture; and

[0056] b.选自锡和铼的促进剂, [0056] b. Selected from tin and rhenium promoter,

[0057] c.其中含硅载体任选用选自如下的促进剂促进: . [0057] c wherein the siliceous support is optionally selected from the accelerating agent:

[0058] i.催化剂重量的1-5%的量的选自碱金属、碱土元素和锌的促进剂; . [0058] i a catalytic amount of 1-5% by weight selected from alkali metal, alkaline earth elements and zinc accelerators;

[0059] ii.催化剂重量的1-50%的量的选自W03、M〇03、Fe20 3和Cr203的氧化还原型促进剂;以及 . [0059] ii an amount of 1-50% by weight of the catalyst is selected from the group W03, M〇03, Fe20 3 Cr203 and the redox promoters; and

[0060] iii.催化剂重量的1-50%的量的选自1102、21〇2、他20 5、了&205和41203的酸性改性剂。 [0060] iii. An amount of 1-50% by weight of the catalyst is selected 1102,21〇2, he 205, the & acidic modifier 205 and the 41203.

[0061] 优选地,链烷酸为乙酸,钼(如果存在)以催化剂重量的0. 5% -5%的量存在;钯(如果存在)以催化剂重量的0. 25% -5%的量存在;存在的钼和钯的总量为催化剂重量的至少0. 5% ;锡以至少0. 5-5%的量存在,且钼与锡的比率如先前所述。 An amount of 0.25% -5% palladium (if present) to the weight of the catalyst; [0061] Preferably, the alkanoic acid is acetic acid, molybdenum (if present) in an amount of 0.5% to 5% by weight of the catalyst of the present present; the presence of the total amount of molybdenum and palladium catalyst is at least 0.5% by weight; tin in an amount of at least 0.5 in the presence of 5-5%, and the ratio of molybdenum and tin as previously described.

[0062] 在本发明的另一方面,含硅载体的表面积为至少约150m2/g,更优选至少约200m 2/ g,最优选至少约250m2/g。 [0062] In another aspect of the present invention, the surface area of ​​the silicon-containing support is at least about 150m2 / g, more preferably at least about 200m 2 / g, most preferably at least about 250m2 / g. 在更优选的实施方案中,含硅载体包含至多约7. 5%偏硅酸钙。 In a more preferred embodiment, the silicon-containing carrier comprises up to about 7.5% calcium metasilicate. 在另外的实施方案中,含硅载体包含至多约90%偏硅酸钙。 In further embodiments, the silicon-containing carrier comprises up to about 90% calcium metasilicate. 在所有实施方案中,特别是当将生产基本上纯的乙醇时,控制载体酸度可以是相当有利的。 In all embodiments, particularly when a substantially pure ethanol production, control the acidity can be quite advantageous. 在其中二氧化硅单独用作载体的情形中,相当有利地是确保氧化铝(其是二氧化硅的常见污染物)的量是低的,优选低于1% ;更优选低于0. 5% ;最优选低于0. 3重量%。 In the case where silica is used alone as the carrier, rather advantageous to ensure that the amount of alumina (which is a common contaminant of silica) is low, preferably less than 1%; more preferably less than 0.5 %; and most preferably less than 0.3 wt%. 就此而言,极大地优选所谓的热解二氧化硅,因为它一般以高于99. 7%的纯度获得。 In this regard, a so-called greatly preferred fumed silica, since it is generally a purity higher than 99.7% is obtained. 在本申请中,当提及高纯度二氧化硅时,其是指其中酸性污染物例如氧化铝以小于〇. 3重量%的水平存在的二氧化硅。 In the present application, when referring to the high purity silica, which means that contaminants such as silica-alumina wherein the acid level is less than square. Of 3% by weight. 在其中使用偏硅酸钙促进的二氧化硅的情形中,关于用作载体的二氧化硅的纯度通常不必十分严格,尽管氧化铝是不期望的并且将通常不是有意加入。 In the case where calcium metasilicate promoted silica, the silica is used as carrier on the purity is usually not necessary to very strictly, although alumina is undesirable and typically not intentionally added.

[0063] 在本发明的更优选实施方案中,钼(如果存在)以催化剂重量的1% -5%的量存在;钯(如果存在)以催化剂重量的〇. 5%-5%的量存在;以及存在的钼和钯的总量为催化剂重量的至少1%。 [0063] In a more preferred embodiment of the invention, the molybdenum (if present) in an amount of 1% to 5% of the weight of the catalyst; palladium (if present) is present in an amount of 5 billion catalyst weight% to 5% ; the presence and the amount of molybdenum and palladium is at least 1% of the weight of the catalyst.

[0064] 在其中载体是基本上纯的高表面积二氧化硅,优选热解形成的二氧化硅的本发明另一个优选实施方案中,锡以催化剂重量的1% -3%的量存在,更优选地,锡与钼族金属的摩尔比为约1 : 2-约2 : 1;还更优选地,锡与钼的的摩尔比为约2 : 3-约3 : 2;同时最优选地,锡与钼的摩尔比为约5 : 4-约4 : 5。 [0064] In a preferred embodiment wherein the carrier is substantially pure another embodiment of the present invention, a high surface area silica, preferably fumed silica formed of tin in an amount of 1% -3% by weight of the catalyst, more preferably the molar ratio of tin and molybdenum metal is from about 1: 2 to about 2: 1; still more preferably, the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2; and most preferably simultaneously, the molar ratio of tin to molybdenum is from about 5: 4 to about 4: 5. 在其中载体还包含次要量的CaSi03或约2% -约10%的其它稳定剂改性剂的情形中,可容许较大量的酸性杂质,只要通过适当量的基本上碱性的稳定剂改性剂使它们平衡(counter-balance)。 Wherein the carrier further comprises minor amounts of CaSi03 or about 2% - about 10% of other situations stabilizer modifier may be allowed a larger amount of acidic impurities, through proper change amount of the alkaline stabilizer substantially agent so that they balance (counter-balance).

[0065] 在本发明的另一方面,优选在约225°C _300°C,更优选250°C _300°C的温度下进行所述方法,其中所述加氢催化剂包含:在选自二氧化硅和用至多约7. 5偏硅酸钙促进的二氧化硅的含硅载体上的选自钼以及钼和钯的混合物的钼族金属,存在的钼族金属的量为至少约2. 0%,存在的钼的量为至少约1. 5%;锡促进剂的量为催化剂重量的约1 % -2%,钼与锡的摩尔比为约3 : 1-1 : 2,其中含硅载体任选用选自如下的促进剂促进:催化剂重量的1-5 %的量的选自碱金属、碱土元素和锌的促进剂;催化剂重量的1-50 %的量的选自W03、 1〇03、? [0065] In another aspect of the present invention, preferably at about 225 ° C _300 ° C, the method is more preferably at a temperature of 250 ° C _300 ° C, wherein the hydrogenation catalyst comprises: in the selected dioxide metals selected from molybdenum and molybdenum mixture of molybdenum and palladium on a carrier of silicon and silicon-promoted with up to about 7.5 metasilicate silica, molybdenum metal is present in an amount of at least about 2.0 %, molybdenum is present in an amount of at least about 1.5%; the amount of tin promoter is from about 1% to about 2% by weight of the catalyst, the molar ratio of molybdenum to tin is about 3: 1 to 1: 2, wherein the silicon-containing vector optionally selected from the following promoters facilitate: an amount of 1-5% by weight of the catalyst selected from alkali metal, alkaline earth elements and zinc promoter; an amount of 1-50% by weight of the catalyst is selected from the group W03, 1 〇03 ,? 6203和0 203的氧化还原型促进剂;以及催化剂重量的1-50%的量的选自1102、21〇2、 Nb205、Ta205和A120 3的酸性改性剂。 6203 and 0203 are reduced oxidation promoting agent; and an amount of 1-50% by weight of a catalyst selected from 1102,21〇2, Nb205, Ta205 acidic modifier and the A120 3.

[0066] 在用于将链烧酸加氢的本发明特别优选的方法中,催化剂包含:在选自高表面积高纯度二氧化硅和用至多约7. 5偏硅酸钙促进的高表面积二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属,存在的钼族金属的量为至少约2.0%,存在的钼的量为至少约1.5%;锡促进剂的量为催化剂重量的约1%-5%,钼与锡的摩尔比为约3 : 2-2 : 3。 [0066] In a particularly preferred chain according to the present invention for the hydrogenation of an acid burn, the catalyst comprising: the high surface area high purity silica selected and promoted with up to about 7.5 metasilicate two high surface area molybdenum metal is selected from molybdenum on a carrier containing silicon oxide, silicon, palladium, and mixtures thereof, present in an amount of molybdenum metal is at least about 2.0% molybdenum is present in an amount of at least about 1.5%; the amount of accelerator is tin from about 1% to 5% by weight of the catalyst, the molar ratio of molybdenum to tin is from about 3: 2-2: 3. 优选地,高纯度二氧化硅是热解产生的,然后将其压片或造粒为足以在固定床催化剂中使用的致密形式。 Preferably, the high purity silica is a pyrogenically produced, and then tableted or pelletized sufficient to use a fixed bed catalyst in densified form. 然而,甚至在高纯度二氧化硅的情形中,对于在乙酸蒸气存在下于大约275°C 的温度以2500hr4或更高空速的延长到数周、甚至数月的延长时段的商业可行操作,稳定剂改性剂、特别是硅酸钙的存在似乎使催化剂的活性和选择性延长或稳定。 However, even in the case of high purity silica, with respect to the presence of acetic acid vapor at a temperature of about 275 ° C or higher space velocity 2500hr4 to extend to several weeks, or even extended periods of several months commercial viable, stable modifier agents, especially in the presence of calcium seems to prolong the activity and selectivity of the catalyst or stabilization. 特别地,可达到在1周(168小时)或2周(336小时)或甚至超过500小时的时间段内催化剂活性可下降小于10%这样的稳定度。 In particular, up to 1 week (168 hours) or two weeks (336 hours) or even more than 500 hours time period the catalyst activity can be decreased by less than 10% of such stability. 因此,可认识到的是,本发明的催化剂完全能够用于将乙酸加氢、 特别是生产高纯度乙醇以及乙酸乙酯和乙醇的混合物的商业规模的工业应用。 Thus, it can be appreciated that the catalysts of the invention can be used to complete hydrogenation of acetic acid, particularly industrial scale production of commercial applications of high purity ethanol, and a mixture of ethyl acetate and ethanol.

[0067] 本发明的另一方面涉及基于在氧化物类载体上的VIII族金属(Fe、Co、Ni、Ru、Rh、 Pd、Ir、Pt和Os)或其它过渡金属(特别是Ti、Zn、Cr、Mo和W)的加氢催化剂,所述氧化物类载体以足够的量在载体本身的表面上或内部引入碱土金属、碱金属、锌、钪、钇的氧化物和偏硅酸盐形式,这些氧化物和偏硅酸盐的前体形式,以及它们的混合物形式的碱性非挥发性稳定剂-改性剂,从而:抵消其表面上存在的酸位;赋予在遭遇乙酸加氢的温度下抗形状改变性(形状改变尤其主要归因于烧结、晶粒生长、晶界迁移、缺陷和位错迁移、塑性变形和/或其它温度诱导显微结构改变);或这两者。 [0067] Another aspect of the present invention, a Group VIII metal (Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt and Os) based on the oxidic support directed or other transition metal (in particular Ti, Zn , Cr, Mo and W) of the hydrogenation catalyst, the oxidic support in a sufficient amount of an alkaline earth metal or is introduced in the interior surface of the carrier itself, an alkali metal, zinc, scandium, yttrium oxide and metasilicates form, these oxides and metasilicates precursor form thereof, and a mixture of non-volatile stabilizers basic - modifiers, such that: canceling acid sites present on the surface thereof; in the event of imparting the hydrogenation of acetic acid (mainly due to the particular shape changing sintering, grain growth, grain boundary migration, migration of defects and dislocations, plastic deformation and / or other temperature-induced structural changes in the microstructure) of the anti-shape change temperature; or both.

[0068] 在本发明方法的另一个实施方案中,催化剂选自: [0068] In another embodiment of the method of the present invention, the catalyst is selected from:

[0069] (i)兼具有在选自二氧化娃、偏娃酸I丐以及用偏娃酸I丐稳定和通过偏娃酸I丐改性的二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属与锡或铼的催化剂; [0069] (i) and selected from a silicon-containing carrier is selected from the baby dioxide, metaphosphoric acid I Hack and baby doll with an acid partial I and I hack Hack stable modified by the partial acid silica doll molybdenum metal and the rhenium or molybdenum, tin, palladium, and mixtures thereof;

[0070] (ii)兼具有负载在包含选自偏硅酸钙和偏硅酸钙促进的二氧化硅的含硅载体上的钯和铼的催化剂,其中含硅载体任选用1% -5%选自碱金属、碱土元素和锌的促进剂进行促进; [0070] (ii) and having a catalyst loading of palladium and rhenium on a support comprising silicon selected from calcium metasilicate and calcium metasilicate promoted silica, wherein the silicon-containing carrier optionally 1% - 5% selected from alkali metal, alkaline earth elements and zinc promote promoting agent;

[0071] (iii)在选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的含硅载体上用钴促进的钼;以及 [0071] (iii) promoted with cobalt on a siliceous support selected from silica, calcium metasilicate and calcium metasilicate promoted molybdenum silica; and

[0072] (iv)在选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的含硅载体上用钴促进的钯。 [0072] (iv) selected from silicon dioxide, silicon-containing carrier metasilicate and calcium metasilicate promoted silica palladium promoted with cobalt.

[0073] -般而言,含娃载体引入选自如下物质的促进剂:以催化剂重量的1-5%的量的包含碱金属、碱土元素和锌的氧化物和偏硅酸盐以及它们的前体的稳定剂-改性剂;催化剂重量的1-50%的量的选自W0 3、M〇03、Fe203和Cr20 3的氧化还原型促进剂;和催化剂重量的1-50%的量的选自Ti02、Zr02、Nb 205、Ta205和A120 3的酸性改性剂,酸性改性剂的存在有利于生产乙酸乙酯兼乙醇。 [0073] - In general, the introduction of vectors containing baby promoter substance selected from: an amount of 1-5% by weight of the catalyst comprises an alkali metal, alkaline earth elements and zinc oxides and silicates and their partial stabilizer precursor - modifier; an amount of 1-50% by weight of the catalyst is selected from W0 3, M〇03, Fe203 oxide Cr20 3 further reduced promoting agent; and 1-50% by weight of the catalyst in an amount selected from Ti02, Zr02, Nb 205, Ta205 and acidic modifier A120 3, the presence of an acidic modifier is conducive to the production of ethanol and ethyl acetate.

[0074] 本发明的另一方面涉及用于将链烷酸加氢为相应的烷醇的颗粒催化剂,该颗粒催化剂包含:在选自二氧化硅、用至多约7. 5偏硅酸钙促进的二氧化硅及其混合物的含硅载体上的选自钼、钯及其混合物的钼族金属,含硅载体的表面积为至少约150m2/g ;锡促进剂的量为催化剂重量的约1%-2%,钼与锡的摩尔比为约3 : 2-3 : 2,含硅载体任选用选自如下的促进剂进行促进:催化剂重量的1-5%的量的选自碱金属、碱土元素和锌的促进剂; 催化剂重量的1-50%的量的选自10 3、11〇03、? [0074] Another aspect of the present invention for hydrogenation of the corresponding alkanoic acid alkanol of particulate catalyst, the catalyst particle comprises: selected from silica, with up to about 7.5 promote calcium metasilicate of silica, and selected from molybdenum, palladium, and molybdenum metal, the surface area of ​​the silicon-containing mixture on a support siliceous carrier mixture is at least about 150m2 / g; the amount of tin as a catalyst promoter of about 1% by weight -2%, molar ratio of molybdenum to tin is from about 3: 2-3: 2, optionally selected from a silicon-containing carrier accelerator for promoting: an amount of 1-5% of the weight of the catalyst selected from alkali metal, alkaline earth elements and zinc promoter; an amount of 1-50% by weight of a catalyst selected from 10 3,11〇03 ,? 6203和(>20 3的氧化还原型促进剂;和催化剂重量的1-50%的量的选自1102、21〇2、他205、了&205和41 203的酸性改性剂。 6203 and oxidation (> 203 are reduced promoting agent; and an amount of 1-50% by weight of a catalyst selected from 1102,21〇2, he 205 & 205 and the acidic modifier of 41,203.

[0075] 本发明的可供选择的实施方案涉及颗粒加氢催化剂,该颗粒加氢催化剂基本上由如下构成:上面分散有选自钼、钯及其混合物的钼族金属与选自锡、钴和铼的促进剂的含硅载体,该含娃载体具有至少约175m2/g的表面积并且选自二氧化娃、偏娃酸興和偏娃酸|丐促进的二氧化硅;含硅载体任选用如下物质促进:催化剂重量的1-5%的量的1% -5%的选自碱金属、碱土元素和锌的促进剂;催化剂重量的1-50%的量的选自103、11〇0 3、? [0075] The alternative embodiment of the present invention relates to a particulate hydrogenation catalyst, the hydrogenation catalyst particles consisting essentially of: molybdenum dispersed above metals selected from molybdenum, palladium, and mixtures thereof and selected from tin, cobalt and a silicon carrier rhenium promoter, containing baby carrier has / g and a surface area of ​​at least about 175m2 selected baby dioxide, vinylidene baby doll acid and metaphosphoric acid Xing | Hack promoted silica; optionally siliceous carrier promotion of the following materials: 1% to 5% of an amount of 1-5% by weight of the catalyst selected from alkali metal, alkaline earth elements and zinc promoter; an amount of 1-50% by weight of the catalyst is selected 103,11〇0 3 ,? 6203和(>203 的氧化还原型促进剂;和催化剂重量的1-50%的量的选自1102、21〇2、他20 53&205和41203的酸性改性剂。在本发明一个更优选的实施方案中,存在的钼族金属的总重量为2-4%,存在的钼的量为至少2%,促进剂是锡,钼与锡的摩尔比为2 : 3-3 : 2,偏硅酸钙的量为3-7%。 在本发明另一个更优选的实施方案中,存在的钼族金属的总重量为〇. 5% -2%,存在的钯的量为至少0.5%,促进剂是铼,铼与钯的重量比为10 : 1-2 : 1,偏硅酸钙的量为3-90%。 在本发明第三个更优选的实施方案中,存在的钼族金属的总重量为〇. 5-2%,存在的钼的量为至少0.5%,促进剂是钴,钴与钼的重量比为20 : 1-3 : 1,硅酸钙的量为3-90%。在本发明第四个更优选的实施方案中,存在的钼族金属的总重量为〇. 5-2%,存在的钯的量为至少0.5%,促进剂是钴,钴与钯的重量比为20 : 1-3 : 1,硅酸钙的量为3-90% 6203 and oxidation (> 203 reduction promoter; and a quantity of 1-50% by weight of the catalyst selected 1102,21〇2 his acidic modifier 205 and 2053 & 41203 In a further preferred embodiment of the present invention. embodiment, the total weight of the molybdenum metal present is 2-4%, the amount of molybdenum present is at least 2%, the promoter is tin, molybdenum and tin molar ratio of 2: 3-3: 2, metasilicate 3-7% the amount of calcium. in another embodiment of the present invention, more preferred embodiment, the total weight of the molybdenum metal present is square. 5% -2%, the palladium is present in an amount of at least 0.5%, accelerator rhenium, rhenium to palladium weight ratio is 10: 1-2: 1, the amount of calcium metasilicate is 3-90% of the total in a third more preferred embodiment of the invention, the presence of molybdenum metal. square 5-2% by weight, molybdenum present in an amount of at least 0.5%, the promoter is cobalt, the cobalt to molybdenum weight ratio of 20: 1 to 3: 1, the amount of calcium silicate 3-90%. in a fourth more preferred embodiment of the present invention, the total weight of the molybdenum metal present is square. 5-2%, the palladium is present in an amount of at least 0.5%, the promoter is cobalt, the weight ratio of cobalt to palladium 20: 1-3: 1, the amount of calcium silicate 3-90%

[0076] 附图简要描述 [0076] BRIEF DESCRIPTION OF THE

[0077] 下面参考附图详细地描述本发明,其中相同的数字指示类似的部分。 [0077] The present invention will be described in detail with reference to the accompanying drawings, wherein like numerals designate similar parts. 在这些附图中: In these drawings:

[0078] 图1和2描述了本发明催化剂的选择性和产率性能。 [0078] FIGS. 1 and 2 describe the selectivity and yield performance of the catalyst of the present invention.

[0079] 图3A-3C描述了随着当在225°C下于在225°C活化的催化剂上将乙酸加氢时获得的性能变化,本发明催化剂的选择性和产率的相对温度不敏感性。 [0079] Figures 3A-3C as described in vary with the properties at 225 ° C obtained at 225 ° C an activated acid on the hydrogenation catalyst, the selectivity and yield of the relative temperature of the catalyst is not sensitive to the present invention sex.

[0080] 图4A-4C描述了选择性、转化率和产率随着(incumbent upon)本发明优选的钼锡催化剂的钼与锡之比改变而变化。 [0080] Figures 4A-4C described in selectivity, conversion and yield with (incumbent upon) to change the ratio of tin and molybdenum present invention preferably molybdenum tin catalyst varies.

[0081] 图5A和5B描述了负载在高表面积二氧化硅上的本发明最优选的催化剂对于乙醇生产的选择性以及用其获得的高产率。 [0081] Figures 5A and 5B describes the most preferred catalysts supported on high surface area silica of the present invention is ethanol production with high yield and selectivity with respect to their access.

[0082] 图6A和6B以及图7A和7B描述了在低温下使用基于偏硅酸钙促进的高表面积二氧化硅的本发明最优选的催化剂获得的优异的选择性。 [0082] FIGS. 6A and 6B and Figures 7A and 7B describe the use of an excellent selectivity at a low temperature of the present invention is based on the most calcium metasilicate high surface area silica promoted catalysts preferably obtained. 可认识到的是对乙醇的选择性是高的。 It is appreciated that the selectivity to ethanol is high.

[0083] 图8、9和10描述了在使用本发明的二氧化硅上钯铼催化剂时铼的质量分数对乙酸加氢的影响。 [0083] Figures 8, 9 and 10 describes the effect of rhenium content of acetic acid palladium hydrogenation catalyst is rhenium on silica using the present invention.

[0084] 图11和12描述了负载在二氧化硅上的钼和钴催化剂的性能。 [0084] FIGS. 11 and 12 describe the performance of molybdenum and cobalt catalysts supported on silica.

[0085] 发明详述 [0085] DETAILED DESCRIPTION

[0086] 即使市场状况不断波动,但是对于大规模操作,将乙酸催化加氢为乙醇的文献中所报导的选择性、活性和催化剂寿命暗示着需要与其它乙醇生产方法竞争的这些通常是经济上不利的。 [0086] Even fluctuating market conditions, but for large scale operations, acetic acid as catalytic hydrogenation in ethanol literature reported selectivity, activity and catalyst life implies the need to compete with other manufacturing methods which are generally economically ethanol Adverse. 商业可行性所需要的一个产率估算得出,对于约200g乙醇/kg催化剂/小时的产率,将需要超过约50%的乙醇选择性。 A yield of the desired commercial viability estimated from, for about 200g of ethanol / kg of catalyst / hour yield, selectivity to ethanol would need more than about 50%. 本发明的催化剂远远超出了这些要求。 The catalyst of the present invention far exceed these requirements.

[0087] 在下面的描述中,本文公开的所有数值皆为近似值,无论它们是否与措词"约"或"大致"连用。 [0087] In the following description, all numbers disclosed herein are all approximate values, regardless whether they are the word "about" or "approximately" used in conjunction. 这些数值可变化1<%、2%、5(%,或者有时可变化10-20(%。只要公开了具有下限矿和上限R u的一个数值范围,那么落入该范围内的任意数值以及子范围也被具体公开。 特别地,该范围内的以下数值被具体公开:R =妒+k* (Ru-R》,其中k从1%变动到100%, 且增量为1%,即k为1%、2%、3%、4%、5%,· . ·、50%、51%、52%、· . ·、95%、96%、97%、 98%、99%或100%。而且,由两个上面定义的R数值限定的任一数值范围也被具体公开。 These values ​​may vary 1 <%, 2%, 5 (%, or sometimes may vary 10-20 (% whenever a numerical range with a lower limit and an upper limit R u mine, then any number falling within the range, and sub-range is also specifically disclosed in particular, the following numbers within the range are specifically disclosed:. R = jealous + k * (Ru-R ", where k changes from 1% to 100%, and a 1 percent increment, i.e., k is 1%, 2%, 3%, 4%, 5%, · ·, 50%, 51%, 52%, · ·, 95%, 96%, 97%, 98%, 99%, or 100 %. Further, R value defined by any one of two defined above numerical range is also specifically disclosed.

[0088] 图1和2描述了本发明催化剂的选择性和产率性能,以图解形式显示了在各种操作温度下用这些催化剂可得到的很大改善的选择性和产率。 [0088] FIGS. 1 and 2 describe the selectivity and yield performance of the catalyst of the present invention, shown at various operating temperatures obtainable with these catalysts greatly improved selectivity and yields in graphical form. 特别地,在280°C和296°C下, 乙醇选择性为约60%。 In particular, at 280 ° C and 296 ° C, the ethanol selectivity as 60%. 在对此评价中,重要的是要应记得乙酸乙酯也是具有相当大经济重要性和价值的商品,即使主要目的是生产乙醇,转化为乙酸乙酯的任何乙酸也保持相当大的价值,而作为副产物产生的任何烷烃通常比原料价值低很多。 In this evaluation, it is important to recall that ethyl acetate is also of considerable economic importance and value of the goods, even if the main purpose is the production of ethanol, ethyl acetate into any remains of considerable value, and any alkane produced as a byproduct is usually much lower than the value of raw materials. 在图1中,作为时间(以小时计)函数的按每千克催化剂每小时运行所产生的乙醇克数计的产率用正方形表示,并同时乙酸乙酯的产率用圆形表示,乙醛的产率用菱形表示。 In Figure 1, the number of grams of ethanol as the time (in hours) per kilogram of catalyst per hour running count of the generated function yields represented by squares, while the yield of ethyl acetate represented by a circular, acetaldehyde yield represented by diamonds. 明显地,在该运行期间,在运行期间如所示提高操作温度以证明操作温度对产率和选择性的影响。 Obviously, during this operation, the operating temperature increase during operation as shown to demonstrate the influence of operating temperature on the yield and selectivity. 在图2中,作为运行时间函数的如下文所定义的乙醇选择性用圆形表示,并同时如下文所定义的乙酸乙酯选择性用正方形表示,乙醛选择性用菱形表示。 In FIG. 2, below operating ethanol selectivity as a function of time is represented by a circle defined, while selectivity to ethyl acetate as defined below, is represented by squares, and acetaldehyde selectivity represented by diamonds.

[0089] 图3A-3C描述了本发明催化剂的选择性对金属前体还原温度的相对温度不敏感性。 [0089] Figures 3A-3C of the present invention is described with selective catalyst reduction temperature of the metal precursor of relative temperature insensitivity. 这种特性对于商业可行性而言是显著的,因为可在没有经特殊构造以维持整体均匀温度的容器中进行反应,通常这些容器称作"绝热反应器",因为很少为适应伴随着反应过程的温度变化而预先采取措施,尽管通常用石英碎片或其它惰性颗粒"稀释"催化剂以调节反应。 For commercial viability such a characteristic is significant, since the reaction may be conducted without specially configured to maintain a uniform temperature the entire container, these containers generally referred to as "adiabatic reactor", since little to adapt to the reaction along with temperature change processes to take measures in advance, although generally "diluted" with inert quartz chips or other particulate catalyst to moderate the reaction. 图3A报导了如下实验的结果,在该实验中在以°C显示的温度下用氢气还原催化剂并然后在所述催化剂上于250°C下将乙酸加氢。 FIG 3A reported the results of experiments in this experiment reduction catalyst with hydrogen at a temperature shown in ° C and then the catalyst at 250 ° C the hydrogenation of acetic acid. 上线表示所述特定催化剂对乙醇的选择性,而下线表示对乙酸乙酯的选择性。 The line represents a specific catalyst selectivity to ethanol, and the selectivity to ethyl acetate expressed offline. 在图3B中,给出了实验的产率结果,其中上线记录了乙醇的产率而下线记录了乙酸乙酯产率。 In Figure 3B, the yield is given results of experiments in which the line is recorded on ethanol yield and the yield of ethyl recorded offline. 在图3C中,作为还原温度函数显示了该实验的转化率(如下文所定义)结果。 In Figure 3C, as a function of temperature shows a reduction conversion of the experiment (as defined below) results. 此外,也在225°C的温度下于在225°C还原或活化的催化剂上将乙酸加氢。 In addition, also at 225 ° C in the hydrogenation or reduction catalysts on an activated acid at a temperature of 225 ° C. 图3B和3C上的点还包括其中在225°C下于在225°C还原的催化剂上将乙酸加氢的该实验的本结果。 3B and 3C on the point at which further comprises 225 ° C to 225 ° C in the present results on the reduction of the acetic acid hydrogenation catalyst experiment. 可意识到的是,在225°C的温度下在这种催化剂上加氢导致降低的乙醇选择性和降低的转化率。 It is appreciated that at a temperature of 225 ° C in this hydrogenation catalyst results in the conversion of ethanol and reduced selectivity decreased.

[0090] 图4A-4C描述了在如下条件下将乙酸催化加氢中选择性、转化率和产率随着本发明优选的钼锡催化剂中钼与锡之比改变而变化,所述改变是关于Pt在Si0 2-PtxSn(1_x) (Σ [Pt] + [Sn] = 1. 20mmol)中的摩尔分数:使用2. 5ml固体催化剂(14/30目,1 : 1稀释(v/v,用石英碎片,14/30目);在p = 200psig(14bar)的操作压力下;乙酸、氢气和氮气稀释剂的进料速率分别为〇. 〇9g/min HOAc ;160sccm/min H2 ;和60sccm/min N2 ;在12小时的反应时间内总空速(GHSV)为65701^。可意识到的是,在该实验中,对于负载在基本上纯的高表面积二氧化硅上的那些催化剂,以约1比1的摩尔比使对于乙醇生产的选择性最大化。 (在本说明书通篇中,小写字母"1"是用于升以避免在许多字体中用于数字1和罗马字母表小写第12个字母的符号的相似或甚至相同所产生的歧义)。在图4A-4C中的每一个中,水平方向轴(horizont [0090] Figures 4A-4C describes the catalytic hydrogenation of acetic acid selectivity, conversion and yield ratio changing with the present invention preferably molybdenum, tin and tin molybdenum catalyst under conditions vary, the alteration is mole fraction of Pt on the Si0 2-PtxSn (1_x) (Σ [Pt] + [Sn] = 1. 20mmol) of: 2. 5ml using the solid catalyst (14/30 mesh, diluted 1: 1 (v / v, with quartz chips, 14/30 mesh); at p = 200psig (14bar) operating pressures; feed rate of acetic acid, hydrogen and nitrogen diluent were square 〇9g / min HOAc;. 160sccm / min H2; and 60sccm / min N2; within 12 hours of reaction time the total space velocity (a GHSV) of 65701 ^ be appreciated that, in this experiment, those catalysts supported on high surface area substantially pure silica, in order. that the molar ratio of about 1 to 1. maximize selectivity for ethanol production. (throughout this specification, the lowercase letter "a" is a number for 1 to avoid the rise and Roman-alphabet lowercase fonts of many similar or even the same ambiguity generated symbols 12 letters). each one of the horizontal direction (Horizont axis in FIG. 4A-4C al access axis)上的XjPt)表示钼在催化剂中的质量分数,其为0-1, 并同时选择性、转化率和产率如前文所示,如图4A中所示表示催化剂对乙醇和乙酸乙酯的选择性,如图4B中所示对乙醇的选择性在50%的质量分数处达到峰值,如图4C中所示乙酸转化率随着乙醇产率达到峰值而也达到峰值。 XjPt the al access axis)) represents the mass fraction of molybdenum in the catalyst, which is 0-1, while the selectivity, conversion and yield are as indicated above, FIG. 4A shows the catalyst and acetic acid in ethanol as shown ethyl selectivity, as shown in FIG selectivity to ethanol of 50% in the peak fraction at a mass 4B, conversion of acetic acid in ethanol as shown in Figure 4C but may also yield peak to peak.

[0091] 图5A和B描述了负载在高表面积二氧化硅上的本发明最优选的催化剂用于乙醇生产的选择性和产率以及用其获得的高产率。 [0091] FIGS. 5A and B depict the most supported on high surface area silica of the present invention, preferred catalyst for ethanol production yields and selectivity and a high yield which is obtained with the. 在图5A中,在纵轴上显示了按每千克催化剂每小时运行的克数计的产率,其中乙醇产率用正方形表示,乙酸乙酯产率用圆形表示,乙醛产率用菱形表示。 In Figure 5A, the vertical axis shows the yield in grams per kilogram of catalyst per hour running meter, wherein the ethanol yield represented by squares, represented by a circular ethyl acetate yield, yield acetaldehyde by diamonds representation. 类似地,在图5B中,在纵轴上显示了作为横轴上运行时间(以小时计)函数的如下文所定义的选择性,乙酸乙酯选择性再次用圆形表示,乙醇选择性用正方形表示, 乙醛选择性用菱形表示。 Similarly, in FIG. 5B, on the vertical axis shows the operating time as described below selectively (in hours) on the horizontal axis defined by a function, represented by a circular selectivity to ethyl acetate again, with selectivity to ethanol squares represent acetaldehyde selectivity represented by diamonds.

[0092] 图6A和B以及图7A和B使用与图5A和B相同的格式描述了在低温下使用基于偏硅酸钙促进的高表面积二氧化硅的本发明优选催化剂获得的选择性。 [0092] FIGS. 6A and B and 7A and B in FIG. 5A and use the same B-format is described to promote selective use of high surface area silica based calcium metasilicate at a low temperature catalyst of the invention is preferably obtained. 可认识到的是,在整个运行中乙醇选择性高于90%。 Be appreciated that, throughout the run of ethanol selectivity higher than 90%.

[0093] 关于有关实施例讨论图8-12。 [0093] For the embodiment discussed in regard to FIGS. 8-12.

[0094] 下面仅仅出于例示和说明目的而参考许多实施方案详细描述了本发明。 [0094] The following merely for purposes of illustration and description with reference to a number of embodiments of the present invention is described in detail. 对本发明的精神和范围内以及所附权利要求书中给出的具体实施方案进行修饰,对于本领域技术人员而言将是显见的。 Within the spirit and scope of the invention and the appended claims set forth specific embodiments modifications, those skilled in the art will be apparent.

[0095] 除非下文加以更具体地限制,本文所使用的术语取其普通含义,除非另外指明, " % "和类似术语参照重量%。 [0095] More particularly be limited unless Hereinafter, terms used herein takes its ordinary meaning, unless otherwise specified, "%" and like terms refer to weight percent. 一般而言,当讨论载体组成时,组成中的百分数包括氧以及与其连接的离子或金属,而当讨论催化金属的重量时,忽略与其连接的氧的重量。 Generally, when discussing the composition of the carrier, the percentage composition comprises metal ions or oxygen, and connected thereto, when discussing the weight of catalytic metal, ignoring the weight of oxygen attached thereto. 因此,在包含95%二氧化硅和5%氧化铝的载体中,这种组成是基于具有101. 94式量的氧化铝和具有60. 09式量的二氧化硅。 Thus, the carrier comprising 95% silica and 5% alumina, such a composition is based on alumina having a formula weight of 101.94 and the silica has a formula weight 60.09. 然而,当是指具有2%钼和3%锡的催化剂时,忽略可以与其连接的任何氧的重量。 However, when the means having 2% and 3% molybdenum, tin catalyst, oxygen may ignore any weight attached thereto.

[0096] "转化率"按基于进料中乙酸的摩尔百分数表示。 [0096] "conversion" represents a mole percent based on the feed acetic acid.

[0097] A OH转化率ί*/、_100 X mmo1流入的Ac〇H(进料流)_ mmol流出的AcOH(GC) ' () mmol流入的AcOH(进料流) [0097] A OH conversion ί * /, _ 100 X mmo1 Ac〇H inflow (feed stream) flowing _ mmol AcOH (GC) '() mmol flows in AcOH (feed stream)

[0098] "选择性"按基于转化的乙酸的摩尔百分数表示。 [0098] "selective" indicates mole percent based on converted acetic acid. 例如,如果转化率为50摩尔%并且所转化的乙酸的50摩尔%转化为乙醇,则是指乙醇选择性为50%。 For example, if the conversion is 50 mole% and 50 mole% of the converted acetic acid is converted to ethanol, it refers to the ethanol selectivity as 50%. 乙醇选择性由气相色谱(GC)数据按如下来计算: Ethanol selectivity is calculated from gas chromatography (GC) data as follows:

[0099] Eton 选择性(%) =100 X ^〇i^^Et〇H(GC)- 流出的心i^molC(GC)_mm〇1 流出的Ac0H(;GC) [0099] Eton selectivity (%) = 100 X ^ ^^ 〇i Et〇H (GC) - Heart effluent i ^ molC (GC) _mm〇1 flowing Ac0H (; GC)

[0100] 不意欲受理论束缚,认为根据本发明乙酸转化为乙醇涉及如下反应中的一个或多个: [0100] Without being bound by theory, that in accordance with the present invention, acetic acid is converted to ethanol involving one or more of the following reactions:

[0101] 乙酸加氢得到乙醇。 [0101] hydrogenation of acetic acid to give ethanol.

[0102] error ! objects cannot be created from editing field codes。 [0102] error! Objects can not be created from editing field codes.

[0103] 错误! [0103] Error! 对象不能创建编辑域代码。 Objects can not be created from editing field codes.

[0104] 乙酸加氢得到乙酸乙酯 [0104] hydrogenation of ethyl acetate to give

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[0106] 乙酸乙酯裂化得到乙烯和乙酸 [0106] acetate cracked to produce ethylene and acetic acid

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[0108] 乙醇脱水得到乙烯 [0108] dehydration of ethanol to obtain an ethylene

[0109] 错误! [0109] Error! 对象不能创建编辑域代码。 Objects can not be created from editing field codes.

[0110] 用于乙酸催化加氢得到乙醇的选择性催化剂选自如下那些: [0110] The catalyst for the selective catalytic hydrogenation of acetic acid to give those selected from ethanol:

[0111] (i)兼具有在选自二氧化硅、偏硅酸钙和用偏硅酸钙促进的二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属与锡或铼的催化剂 [0111] (i) selected from silica and having a molybdenum metal is selected from molybdenum and silicon-containing carrier on the calcium metasilicate and calcium metasilicate promoted with silica, palladium, and mixtures thereof tin or rhenium

[0112] (ii)兼具有上文所描述的任选用1% -5%选自碱金属、碱土元素和锌的第一促进剂进行促进的负载在含硅载体上的钯和铼的催化剂,促进剂优选以这些促进剂(特别优选钾、铯、钙、镁和锌)各自的硝酸盐或乙酸盐形式加入到催化剂配方中; [0112] (ii) described above and having optionally 1% to 5%, selected from alkali metal, alkaline earth elements and zinc primary accelerator is promoted palladium supported on a siliceous support and rhenium the catalyst, the promoter is preferably added to these accelerators (particularly preferably potassium, cesium, calcium, magnesium and zinc) are each in the form of nitrates or acetates to the catalyst formulation;

[0113] (iii)在含硅载体上用钴促进的钼;以及 [0113] (iii) cobalt promoted molybdenum on a silicon containing carrier; and

[0114] (iv)在含硅载体上用钴促进的钯。 [0114] (iv) a silicon-containing carrier on the palladium promoted with cobalt.

[0115] 如本领域技术人员将容易地意识到的,本发明的方法可以在使用固定床反应器或流化床反应器的各种构造中进行。 [0115] As those skilled in the art will readily appreciate, the method of the present invention may be used in a variety of configurations for a fixed bed reactor or a fluidized reactor. 在本发明的许多实施方案中,可以使用"绝热"反应器; 艮P,具有很少或不需要穿过反应区的内部管道装置(plumbing)来加入或除去热。 In many embodiments of the present invention may be used "adiabatic" reactor; Gen P, with little or no need through the interior of conduit means (plumbing) the reaction zone to add or remove heat. 或者,可以使用配设有热传递介质的管壳式反应器。 Alternatively, a shell and tube reactor provided with the heat transfer medium. 在许多情形中,反应区可以容纳在单个容器中或之间具有换热器的系列容器中。 In many cases, the reaction zone may be housed in a heat exchanger having a series of vessels in a single vessel or in between. 明显认为的是,使用本发明催化剂的乙酸还原方法可以在绝热反应器中进行,因为这种反应器构造与管壳式构造相比资本密集程度通常小很多。 Is considered significant that the use of acid catalysts of the invention the reduction process may be performed in an adiabatic reactor, this reactor is configured as a shell and tube configuration with capital intensive than is generally much smaller.

[0116] 可使用本领域已知的各种催化剂载体来负载乙酸加氢催化剂。 [0116] The catalyst may be used various carriers known in the art to acid supported hydrogenation catalyst. 这类载体的实例无任何限制地包括铁氧化物、二氧化硅、氧化铝、二氧化钛、氧化锆、氧化镁、硅酸钙、碳、石墨和它们的混合物。 Examples of such supports include without any limitation, iron oxide, silica, alumina, titania, zirconia, magnesium oxide, calcium silicate, carbon, graphite, and mixtures thereof. 对于本发明,优选使用选自二氧化硅、偏硅酸钙和用硅酸钙促进的二氧化硅的含硅载体,当造粒为对在固定床反应器中使用足够致密的形式时,特别期望的是Si0 2 含量为至少99. 7%的热解二氧化硅。 For the present invention, preferably selected from silica, calcium metasilicate and calcium silicate with silicon containing carrier is silica promoted, when the granulation is sufficiently dense for use in the form of a fixed bed reactor, especially Si0 2 is desirable that the content of at least 99.7% fumed silica. 已发现任选用偏硅酸钙促进的高纯度、高表面积二氧化娃,特别是来自Saint-Gobain NorPro的HSA SS 61138等级,意想不到地优于用于本发明催化剂的其它载体。 It has been found metasilicate optionally high purity, high surface area to promote the baby dioxide, particularly from Saint-Gobain NorPro of HSA SS 61138 levels, unexpectedly superior to other supported catalysts of the present invention. 用作本发明载体的二氧化硅优选具有至少l〇〇m2/g,更优选至少150m 2/ g,更优选至少200m2/g,最优选约250m2/g的表面积。 Silica used as the carrier of the present invention preferably has at least l〇〇m2 / g, more preferably at least 150m 2 / g, more preferably at least 200m2 / g, most preferably from about 250m2 / g surface area. 在本说明书通篇中,术语"高表面积二氧化硅"应理解为表示具有至少250m 2/g表面积的二氧化硅。 Throughout this specification, the term "high surface area silica" is understood to mean having a surface area of ​​at least 250m 2 g silica /. 含硅载体的活性/稳定性可以通过如下文所述纳入次要量的其它组分进行改性。 Other components activity / stability of the silicon-containing carrier may be incorporated into a minor amount by modification described below. 可以使用任何便利的颗粒型状,包括丸粒、挤出物、球、喷雾干燥的、环、五辐轮状物(pentaring)、三叶形物和四叶形物,尽管对于本申请通常优选使用圆柱形丸粒。 Particles may be using any convenient shape, including pellets, extrudates, spheres, spray drying, cyclic, pentarings (pentarings), trefoil and quatrefoil composition thereof, although it is generally preferred for this application using a cylindrical pellet.

[0117] 催化剂载体的影响。 Effect [0117] Catalyst support.

[0118] 除对金属前体(即卤素,Cr相对于(vs.)无卤素,NCV)和制备条件进行选择以夕卜,所产生的金属-载体相互作用强烈地取决于下面(underlying)载体的结构和性能。 [0118] In addition to the metal precursor (i.e. halogen, Cr with respect to the (FC vs.) halogen-free, NCV) and the preparation conditions are selected to Xi Bu, the resulting metal - support interaction strongly depends on the following (the underlying) support the structure and properties.

[0119] 对于各种二氧化硅负载Pt-Sn材料,研究碱性和酸性改性剂的影响。 [0119] For the various impact silica-supported Pt-Sn material, study of basic and acidic modifiers. 对于所有材料,除非另有说明,Pt和Sn之间的摩尔比保持处于1 : 1,还使总金属载量保持不变。 For all materials, unless otherwise indicated, the molar ratio between the Pt and Sn maintained at 1: 1, further total metal loading remains the same. 特别地,在酸性载体例如Si02、Si02-Ti0 2、KA160(即Si02-Al203)和H-ZSM5上制备的催化剂产生高的乙酸转化率,但是产生较低的乙醇选择性。 In particular, in an acidic carrier such as Si02, Si02-Ti0 2, KA160 (i.e., Si02-Al203) and the catalyst prepared on the H-ZSM5 produce high conversion of acetic acid, but resulting in lower selectivity to ethanol. 引起注意的是,H-ZSM5催化剂实际上产生作为主要产物的二乙醚,其最可能是通过乙醇脱水形成。 Attention is, H-ZSM5 catalyst is actually produced as a main product in diethyl ether, which most likely formed by dehydration of ethanol. 基于Si0 2-Ti02和基于KA160 (即Si02-Al203)的催化剂均产生高的转化率和类似的对EtOH和EtOAc的选择性,在两种情形中EtOAc是主要产物。 Si0 2-Ti02 and based on the KA160 (i.e., Si02-Al203) both catalysts produced high conversions and similar selectivity to EtOH and EtOAc, EtOAc in both cases is the major product. 下面催化剂载体中存在的Lewis酸度似乎可有益于较高的乙酸转化率。 Present in the catalyst support below appears to be beneficial Lewis acidity high conversions of acetic acid. 虽然Si0 2-Ti02中的酸度主要基于Lewis酸度,但是KA160 (二氧化硅-氧化铝)材料还具有强的布朗斯台德酸位,这可催化由残余乙酸和EtOH形成EtOAc。 Although Si0 2-Ti02 mainly based on the Lewis acidity of the acidity, but the KA160 (silica - alumina) material also has a strong Bronsted acid sites which can catalyze the formation of acetic acid from the residue EtOAc and EtOH. 基于H-ZSM5的催化剂具有甚至更强的酸性沸石类(zeolytic)布朗斯台德酸位和择形性,这是由于小的孔隙还可有助于通过乙醇脱水而酸催化形成二乙醚。 Based on H-ZSM5 catalysts having even more acidic zeolites (zeolytic) Bronsted acid sites and shape selectivity, which is also due to the small pores contribute to the formation of ethanol diethyl ether by acid-catalyzed dehydration. 将碱性改性剂加入到所研究的任何载体通常产生对乙醇的选择性的提高,伴随着乙酸转化率的明显降低。 Any vector alkaline modifier to enhance studied generally produce the selectivity to ethanol, acetic acid conversion is accompanied by significantly reduced. 发现对于表A中条目2 的5丨0 24&5丨03(5)-?以3)-511(1.8),对于乙醇的最高选择性为92%,用0 &5丨03促进的甚至纯的Ti02以约20%的选择性产生乙醇。 Found that for Table A, entry 5 Shu 024 & 5 Shu 03 (5) 2 -? In 3) -511 (1.8), for the highest selectivity to ethanol is 92%, with even pure Ti02 0 & 5 Shu 03 promoted to about 20% selectivity to produce ethanol. Si0 2-Ti02和Ti02-CaSi03之间的对比暗示着酸位(Lewis)的位置密度还可以具有重要性,并且可最有可能通过与具体制备方法结合仔细地改变碱性和酸性促进剂而实现催化剂载体的酸性性能进一步最优化。 Comparison between the Si0 2-Ti02 and Ti02-CaSi03 suggests acid sites (Lewis) The site density may also be of importance, and may be most likely to alter the basic and acidic carefully promoter by binding to specific preparation method implemented acidic properties of the catalyst support is further optimized.

[0120] 表A.在乙酸的气相加氢中催化剂载体改性剂的催化剂活性数据的汇总。 [0120] Table A. catalytic activity data are summarized in the gas-phase hydrogenation of the catalyst support of modifier acid. 反应条件:2.5ml固体催化剂(14/30目,1 : 1稀释(v/v,用石英碎片,14/30目);p = 200psig(14bar) ;0.09g/minH0Ac ;160sccm/minH2 ;60sccm/minN2 ;GHSV = 657011-1 ;反应时间为12小时。 Reaction conditions: 2.5ml solid catalyst (14/30 mesh, diluted 1: 1 (v / v, with quartz chips, 14/30 mesh); p = 200psig (14bar); 0.09g / minH0Ac; 160sccm / minH2; 60sccm / minN2; GHSV = 657011-1; the reaction time was 12 hours.

[0121] 奈::1 f;t it ^1 产场选择·,¾ (%f HOAC3 No, :H紅Ac H EtOH ElOAc :.· - - -V^^:r:-::::::::::::::::::::.^ri^===n=: : . .- ......r"-.-.........................................- 1 SiCVPtxSrih; x = 0.S0 ^ 74 26 73 2 SiOrCaSiOs(5}-Pt ⑶-Sn(lS} 2 92 6 24 3 Si02-W03(10)-Pt(3)-Sn(1.8) - 77 23 17 4 Si02-Ti02(10)-Pt(3)-Sn(1.8) - 47 53 73 5 Ti02-CaSi03(5)-Pt(3)-Sn(1.8) - 22 78 38 6 KA160-Pt(3)-Sn(1.8) 1 47 52 61 7 KA160-CaSi03(8)-Pt(3)-Sn(1.8) 1 84 15 43 8 (H-ZSM-5)-Pt(3)-Sn(1.8)4 4 78 4 9 Si02-RexPdi.x; x = 0.75 - 56 44 9 10 Si02-CaSi03(5)-Re(4.5)-Pd(l) 83 17 8 [0121] Nye :: 1 f; t it ^ 1 production field selection ·, ¾ (% f HOAC3 No,: H red Ac H EtOH ElOAc: · - - -V ^^: r: - :::::. ::::::::::::::: ^ ri ^ === n =:.:. .- ...... r "-.-.......... ...............................- 1 SiCVPtxSrih; x = 0.S0 ^ 74 26 73 2 SiOrCaSiOs (5} - pt ⑶-Sn (lS} 2 92 6 24 3 Si02-W03 (10) -Pt (3) -Sn (1.8) - 77 23 17 4 Si02-Ti02 (10) -Pt (3) -Sn (1.8) - 47 53 73 5 Ti02-CaSi03 (5) -Pt (3) -Sn (1.8) - 22 78 38 6 KA160-Pt (3) -Sn (1.8) 1 47 52 61 7 KA160-CaSi03 (8) -Pt ( 3) -Sn (1.8) 1 84 15 43 8 (H-ZSM-5) -Pt (3) -Sn (1.8) 4 4 78 4 9 Si02-RexPdi.x; x = 0.75 - 56 44 9 10 Si02- CaSi03 (5) -Re (4.5) -Pd (l) 83 17 8

[0122] 1本文详细地描述了单独催化剂的制备。 [0122] a catalyst prepared separately described herein in detail. 括号内的数字表示以重量%计的实际组分(金属、金属氧化物)的量。 The numbers in parentheses indicates the amount in weight% of the actual component (metal, metal oxide).

[0123] 2产物选择性(重量% )通过由GC分析校正的可靠样品进行计算。 [0123] 2 product selectivity (wt%) was calculated by GC analysis to an authentic sample by a correction.

[0124] 3乙酸转化率(% )通过如下进行计算:[HOAc]转化率,%= {[HOAc](进料,mmol/ min)-[H0Ac](流出物,mmol/min)/[H0Ac](进料,mmol/min)} * 100。 [0124] 3 acetic acid conversion (%) by the following calculation: [HOAc] conversion,% = {[HOAc] (feed, mmol / min) - [H0Ac] (effluent, mmol / min) / [H0Ac ] (feed, mmol / min)} * 100.

[0125] 4用该催化剂获得的主要产物是二乙醚(EtOEt),同时具有96%的选择性和2646g/kg/h 的产率。 [0125] 4 with the major product obtained is a catalyst in diethyl ether (EtOEt), while 96% of the selectivity and yield of 2646g / kg / h of.

[0126] 对比KA160 (Si02_5 % A1203)与KA160_CaSi03促进的催化剂观测到选择性向乙醇的明显转移。 [0126] Comparative (Si02_5% A1203) promoted catalyst KA160_CaSi03 KA160 observed a marked shift in selectivity to ethanol. 参见表A中条目2、6和7,虽然在84 %时,该催化剂的选择性仍低于Si02-CaSi03基材料所观测到的选择性,但乙酸转化率保持处于43 %,是关于Si02-CaSi03(5)-Pt(3)-Sn(l. 8)看到的乙酸转化率的几乎两倍。 Entries in Table A, 6 and 7, although at 84%, the selectivity of the catalyst is still lower than the Si02-CaSi03 based material selectivity observed, but the conversion of acetic acid maintained at 43%, about Si02- CaSi03 (5) -Pt (3) -Sn (l. 8) is almost twice that seen in the acetic acid conversion. 除"酸性改性剂"性能外, 所有CaSi03促进的材料似乎显示出改善的较长时期稳定性(虽然是在较低的转化率下)。 In addition to the properties of "acidic modifier", all the materials appear to promote CaSi03 shows improved stability during a long (though at lower conversion rate). 具体地,在各种反应条件下在大于220小时的反应时间内Si0 2-CaSi03 (5)-Pt (3)-Sn (1. 8) 催化剂表现出小于10 %的活性降低。 Specifically, under various reaction conditions in the reaction time of more than 220 hours Si0 2-CaSi03 (5) -Pt (3) -Sn (1. 8) the catalyst exhibits reduced activity of less than 10%. 关于选择性,在Si02和Si02-CaSi03上制备的两种Re-Pd催化剂也显示出类似趋势。 Selectivity on both Re-Pd catalyst prepared in Si02 and Si02-CaSi03 also showed a similar trend. 表A中条目9和10,对于这两种材料,虽然转化率保持低于10%,但对于CaSi03促进的材料观测到向乙醇选择性的明显转移。 A table entries 9 and 10, for these two materials, although the conversion remained below 10%, but the material obviously observed CaSi03 promote transfer to the ethanol selectivity. 表4中提供了关于产率的另外信息。 Table 4 provides additional information about the yield.

[0127] 因此,不受理论束缚,用于乙酸加氢催化剂的氧化物类载体通过引入非挥发性稳定剂-改性剂加以改性和稳定具有以下作用中的任一种:抵消存在其表面的上的酸位;或者使其表面热稳定使得能够获得期望的乙醇选择性改善,延长的催化剂寿命;或这二者。 [0127] Thus, without being bound by theory, for acetic acid hydrogenation catalyst oxidic support by introduction of a non-volatile stabilizer - have been modified modifiers and stabilizers have any of the following effects: the presence of a surface offset acid sites on; thermally stable such that its surface or improved selectivity of ethanol to obtain a desired, extended catalyst life; or both. 一般而言,基于处于其最稳定价态的氧化物的改性剂可具有低蒸气压力,且因此具有呈相当非挥发性。 In general, based on the modifier oxide is at its most stable valence state may have a low vapor pressure, and thus have the form of relatively non-volatile. 因此,基于在氧化物类载体上的VIII族金属(Fe、Co、Ni、Ru、Rh、Pd、Ir、Pt和〇s)或其它过渡金属(特别是Ti、Zn、Cr、Mo和W)的加氢催化剂,优选以足够的量在载体本身的表面上或内部引入碱土金属、碱金属、锌、钪、钇的氧化物和偏硅酸盐形式,这些氧化物和偏硅酸盐的前体形式,以及它们的混合物形式的碱性非挥发性稳定剂-改性剂,从而:抵消其表面上存在的酸位;赋予在遭遇乙酸加氢的温度下抗形状改变性(形状改变尤其主要归因于烧结、晶粒生长、晶界迁移、缺陷和位错迁移、塑性变形和/或其它温度诱导显微结构改变);或这两者。 Accordingly, VIII metals (Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt and 〇s) based on support oxides or other transition metals (in particular Ti, Zn, Cr, Mo and W) the hydrogenation catalyst, preferably a sufficient amount on the surface of the support itself or is introduced inside alkaline earth metals, alkali metals, zinc, scandium, yttrium oxide and metasilicate forms, and these oxides before metasilicate forms and mixtures thereof in the form of a basic non-volatile stabilizers - modifiers, such that: its offset acid sites present on the surface; imparting (shape change of the shape change of the anti-acetic acid hydrogenation at temperatures encountered in particular major attributed to sintering, grain growth, grain boundary migration, migration of defects and dislocations, plastic deformation and / or other temperature-induced changes microstructure); or both.

[0128] 在本发明中,载体上的金属载量的量并非关键并且可在约0. 3重量% -约10重量%的范围内变化。 [0128] In the present invention, the amount of metal loading on the support is not critical and may range from about 0.3 wt% - in the range of about 10 weight percent of the variation. 特别优选基于催化剂重量计约〇. 5重量% -约6重量%的金属载量。 Particularly preferably from about 5 billion% by weight based on the weight of the catalyst - to about 6 wt% metal loading. 由于极其昂贵,典型地以相当仔细控制的量使用钼族金属,通常小于整个催化组合物的10 重量%。 Because it is extremely expensive, typically in an amount of relatively carefully controlled molybdenum metal, generally less than 10 wt% of the entire catalytic composition. 低至〇. 25-5%的钼,当与如本文所述的其它催化元素组合时,可提供优异的选择性,寿命和活性。 Image square. 25-5% molybdenum, when combined with other elements, such as the catalytic composition described herein, can provide excellent selectivity, life and activity. 典型地,在本发明的含钼催化剂中优选使用〇. 5-5%,更优选1-3%的钼。 Typically, the molybdenum-containing catalyst used according to the present invention is preferably square. 5-5%, more preferably 1-3% molybdenum. 在钼锡催化剂的情形中,当在高表面积二氧化硅/偏硅酸钙上负载时优选使用0. 10-5% 锡,更优选〇. 25-3%锡,还更优选0. 5-2. 5%锡,最优选约3%钼和约1. 5%锡的组合(相当接近地对应于钼与锡的1 : 1摩尔比),或者基于较低重量百分数的钼的不太成比例的量。 In the case of tin-molybdenum catalyst when supported on high surface area silica / calcium metasilicate is preferred to use 0.5 10-5% tin, and more preferably square. 25-3% tin, still more preferably 0. 5- 2.5% tin, most preferably a combination of from about 3% molybdenum, and about 1.5% of tin (fairly closely corresponds to 1 molybdenum and tin: 1 molar ratio), or less proportional to the low based weight percent of molybdenum amount. 对于该催化剂,优选使用选自如上所述的高纯度高表面积二氧化硅、偏硅酸钙和用偏硅酸钙促进的高表面积二氧化硅的含硅载体。 For the catalyst, it is preferred to use high purity and high surface area silica is selected as described above, and calcium metasilicate siliceous support is high surface area silica promoted with calcium metasilicate. 因此,可认识到的是,偏硅酸钙的量可以从〇-直至IJ 100重量%宽泛地变化。 Thus, it can be appreciated that the amount of calcium metasilicate may vary widely from up to 100 wt 〇- IJ%. 因为偏硅酸钙趋向于具有较低的表面积,所以对于该催化剂,在本发明的载体中优选包括至少约10%高表面积二氧化硅,更优选作为本发明的载体,优选使用约95%高表面积二氧化娃,即来自Saint-GobainNorPro的SS61138高表面积(HSA)二氧化硅催化剂载体,其具有250m 2/g的表面积;12nm的中值孔径;通过压汞孔隙测量法测量的1. 0cm3/g的总孔体积和约221bs/ft3的堆积密度。 Because calcium metasilicate tends to have lower surface area, so for this catalyst carrier in the present invention preferably comprises at least about 10% high surface area silica, and more preferably as a carrier of the invention, preferably using about 95% higher baby dioxide surface area, i.e., from Saint-GobainNorPro SS61138 high Surface Area (HSA) silica catalyst support, having a surface area of ​​250m 2 / g; the median pore diameter of 12nm; measured by mercury porosimetry 1. 0cm3 / g, a total pore volume of about 221bs / ft3 bulk density.

[0129] 本发明的催化剂在并不是类似于汽车催化剂和柴油烟灰捕集装置那样浸渍到独石载体上的洗涂层中这种意义上是颗粒状催化剂,本发明的催化剂成形为颗粒,有时也称作珠或丸粒,具有各种形状中的任意形状,通过将很多这些成型的催化剂置于反应器中而将催化金属提供到反应区。 [0129] The catalyst of the present invention is not similar to that in the impregnation automotive catalysts and diesel soot trapped on a monolithic carrier means washcoat is the sense that the particulate catalyst, the catalyst of the present invention is formed into granules, sometimes also referred to as beads or pellets of any shape having a variety of shapes, formed by many of these catalysts in a reactor the catalytic metals are supplied to the reaction zone. 常见的形状包括具有任意横截面的挤出物,在限定出挤出物表面的母线(generator)是平行线的意义上所述形状为广义柱体。 Common shapes include extrudates any cross section, defining a busbar (Generator) extrudate surface are the parallel lines in the sense of a generalized cylinder shape. 球、喷雾干燥的微球、环、 五辐轮状物和多叶形物均是可用的。 Spheres, spray dried microspheres, cycloalkyl, pentarings and multilobal thereof are available. 典型地,根据所认知到的使气相与催化剂有效接触的能力按照经验对形状进行选择。 Typically, according to the cognitive ability to make effective contact of the gas phase with the catalyst shapes are chosen empirically.

[0130] 高度合适的钼锡催化剂包含负载在表面积为约250m2/g的用约0. 5% -7. 5%偏硅酸钙促进的高表面积二氧化硅上的约3重量%钼、1. 5重量%锡。 [0130] Highly suitable tin catalyst comprising molybdenum supported on a surface area of ​​about 3% by weight of molybdenum on high surface area silica from about 250m2 / g with about 0.5% -7. 5% calcium metasilicate promoted, 1 5 wt% tin. 用这种组合物在于280°C 下已经实现数百小时运行时间的催化剂寿命。 This composition was used that has been achieved at 280 ° C catalyst life of hundreds of hours of operation. 在许多情形中,在上文提及的组合物中将能够用钯部分地替代钼。 In many cases, in the composition mentioned above was able to partially substitute molybdenum with palladium.

[0131] 类似于前面段落中描述的那些但含有较少量的用相当大量钴促进的极其昂贵的钼的催化剂提供了良好的初始催化活性但倾向于不表现出与上述钼锡催化剂一样的延长催化剂寿命。 [0131] However, those with a smaller amount of a catalyst containing a relatively large amount of very expensive cobalt-molybdenum-promoted similar to that described in the preceding paragraph provides a good initial catalytic activity but does not tend to exhibit the above-described molybdenum tin catalysts like extension catalyst life. 该催化剂的含娃载体的优选级别(hierarchy)与钼锡催化剂基本上相同。 Preferably level (Hierarchy) baby carrier containing the molybdenum catalyst and a tin catalyst is substantially the same. 优选的这类催化剂包括与约1% -约20%钴,更优选约2% -约15%钴,更优选约8-12%钴组合的0. 25-5%钼,更优选0. 3-3%钼,最优选0. 5-1. 5%钼。 Preferred such catalysts include from about 1% - about 20% cobalt, more preferably about 2% - about 15% cobalt, 8-12%, more preferably from about 0. 25-5% of cobalt molybdenum composition, more preferably 0.3 -3% molybdenum, most preferably 0. 5-1. 5% molybdenum. 即使这些催化剂不如上述钼锡催化剂耐久,但在许多情形中,这可被极大地减少的所需钼的量、钴与钼族金属相比较低的成本和优异的初始选择性而在很大程度上得到抵消。 The amount of cobalt and molybdenum as compared to lower metal cost and excellent initial desired selectivity of these catalysts is better even though molybdenum Mo above tin catalyst durability, but in many cases, this can be greatly reduced while largely get the offset. 当然,应理解的是,在许多情形中,可通过适当的再循环料流或使用较大的反应器弥补活性缺乏,但是较难以弥补差的选择性。 Of course, it should be understood that, in many cases, by appropriate recycle streams or use of larger reactors to compensate for the lack of activity, but more difficult to compensate for poor selectivity.

[0132] 基于用铼或钴促进的钯的催化剂提供了优异的催化活性和稍微较低的选择性,这种选择性丧失在高于280°C的反应温度下加剧从而导致形成提高量的乙醛、二氧化碳和甚至烃。 [0132] Providing the excellent catalytic activity and somewhat lower selectivity rhenium promoted catalyst based on cobalt or palladium, such selective loss increased at a reaction temperature above 280 ° C resulting in formation of increased amounts of B aldehydes, carbon dioxide and hydrocarbons even. 含钴催化剂与相应的铼催化剂相比典型地表现出稍微较好的选择性;但是,虽然这二者都提供了出人意料的长寿命催化活性,却都提供不了与最优选的在用偏硅酸钙稳定和改性的高纯度氧化铝上的钼/锡催化剂一样突出的催化剂寿命。 Typically the cobalt catalyst-containing surface as compared to the corresponding rhenium catalysts exhibit slightly better selectivity; however, although it provides both the catalytic activity unexpectedly long life, but had not provided with the most preferred metasilicate and the molybdenum-modified calcium stable high purity alumina / tin catalyst as catalyst life projections. 此外可以将这种催化剂负载在用上述I族、II族和锌的氧化物和偏硅酸盐以及它们的前体和它们的混合物稳定和改性的含硅载体上。 In addition, this catalyst may be supported on the above Group I, II and Group metasilicates and zinc oxide, and precursors thereof and mixtures thereof and stabilizing the modified silicon-containing carrier. 高度合适的前体包括锌、碱金属和碱土金属的乙酸盐和硝酸盐,可以任选将它们以基于除乙酸根和/或硝酸根部分外的金属重量计约1-5%的量纳入到含硅载体中。 Highly suitable precursors include zinc, alkali metal acetates and alkaline earth metals and nitrates, which can optionally be based on an amount of acetate addition and / or root nitric exceptionally about 1-5% by weight of metal into the silicon-containing carrier.

[0133] 在本发明的其它实施方案中,上述催化剂可以通过将选自氧化还原型活性改性齐IJ、酸性改性剂和它们的混合物的改性剂纳入到含硅载体中进行改性从而改变在乙醇、 乙酸乙酯和乙醛之间的相对选择性。 [0133] In other embodiments of the present invention, the above catalyst may be selected from a redox reactive modifier together IJ, acidic modifier modifiers, and mixtures thereof into the vector is modified so that the silicon-containing changing the relative selectivity among ethanol, ethyl acetate and acetaldehyde. 合适的氧化还原型活性改性剂包括W0 3、M〇03、Fe203 和Cr203,而酸性改性剂包括Ti02、Zr02、Nb 205、Ta205和A120 3。 Suitable redox active modifiers include W0 3, M〇03, Fe203 and Cr203, and the acidic modifier include Ti02, Zr02, Nb 205, Ta205 and A120 3. 通过将这些改性剂合理地(judicious)纳入到含硅载体中,可以调变催化剂的活性以生产与市场波动和对各种产物的要求一致的更加期望的催化加氢产物相对量分布。 By reasonably These modifiers (judicious) into the silicon-containing carrier may be modulated with a more desired activity of the catalyst of catalytic hydrogenation and product production and market volatility consistent with the requirements of the various products relative amount distribution. 典型地,这些材料可按含硅载体重量的约1-50 %的量包括在含娃载体中。 Typically, these materials may be an amount of about 1-50% by weight of silicon-containing carrier comprises a baby carrier.

[0134] 可使用本领域任何已知的方法进行金属浸渍。 [0134] metal impregnation may be carried out using any method known in the art. 典型地,在浸渍之前,将载体在120°C下干燥并成型为具有约0. 2-0. 4_的尺寸分布的颗粒。 Typically, before impregnation, the carrier was dried at 120 ° C for molding and having a particle size distribution of about 0. 2-0. 4_ of. 任选地,可以将载体压制、压碎和筛分为所需尺寸分布。 Optionally, the carrier may be pressed, crushed and sieved to a desired size distribution. 可使用任何使载体材料成型为所需尺寸分布的已知方法。 Using any known method the carrier material is molded into a desired size distribution. 在制备催化剂的优选方法中,可使用钼族金属组分例如钼族金属的合适化合物和/或络合物获得催化组分在载体例如载体颗粒上的分散体。 In a preferred method of preparing the catalyst, the molybdenum metal component may be used such as a suitable metal compounds of molybdenum and / or complexes of catalytic components obtained in the dispersion on a carrier, for example, carrier particles. 可使用钼族金属的水可溶性化合物或水可分散性化合物或络合物将催化金属化合物浸渍到或沉积到载体颗粒上。 Molybdenum metal may be used water-soluble compounds or water dispersible compounds or complexes of the catalytic metal compound is impregnated into or deposited onto the carrier particles. 在加热和/或施加真空时钼族金属组分分解。 Molybdenum metal component decomposition in the heating and / or applying a vacuum while. 在一些情形中,没有进行液体的完全去除直到催化剂投入使用并且经受在操作期间所遭受的高温。 In some cases, no complete removal of the liquid until the catalyst is placed into use and subjected to high temperatures during operation suffered. 通常,从经济和环境方面的观点来看,优选钼族金属可溶性化合物的水溶液。 Typically, from the viewpoint of economic and environmental point of view, preferably an aqueous solution of a soluble molybdenum metal compound. 例如,合适的化合物为氯钼酸、胺溶解的氢氧化钼、硝酸钯或氯化钯、氯化钠钯、氯化钠钼等,尽管当乙醇是所需产物时优选避免使用卤素。 For example, suitable compounds are molybdic acid chloride, amine solubilized molybdenum hydroxide, palladium nitrate or palladium chloride, sodium palladium chloride, molybdenum chloride and the like, although when ethanol is the desired product are preferably avoided halogen. 在煅烧步骤期间,或至少在使用催化剂的初始阶段期间,将这些化合物转化为钼族金属的催化活性形式或其催化活性氧化物。 During the calcination step, or at least during the initial stage of use of the catalyst, such compounds are converted into a catalytically active molybdenum group metal oxide or a catalytically active form. 然而一般而言,优选使用不含氯化物的钼族金属前体,因为已发现由Pt (NH3) 4 (N04) 2制备的催化剂似乎表现出提高的乙醇选择性。 In general, however, it is preferable to use chloride-free molybdenum metal precursor, it has been found by the Pt (NH3) (N04) of the catalyst prepared in 42 seems to exhibit improved selectivity to ethanol.

[0135] 由于通常认为本发明的催化剂是双金属,在这样的情形中,一种金属充当促进剂金属而另一种金属为主金属。 [0135] Since the catalyst of this invention generally considered bimetal, in such cases, one metal acts as a promoter metal and another metal is the main metal. 例如,在钼锡催化剂的情形中,钼可以被认为是用于制备本发明加氢催化剂的主金属,而锡可被认为是促进剂金属。 For example, in the case of a tin catalyst of molybdenum, the molybdenum may be considered to be main metal for preparing hydrogenation catalysts of the present invention, the tin can be considered as promoter metal. 然而,应注意的是,有时这样的区别可能具有误导性,特别是在其中钼锡催化剂对乙醇的选择性的这种情形下,在不存在锡和不存在钼的情况下所需的产物均接近为0。 However, it should be noted that such a distinction may be misleading, especially in the case where such a tin-molybdenum catalyst selectivity to ethanol, in the absence of the desired absence of tin and molybdenum products were close to zero. 出于便利,优选将钼族金属指代为主要催化剂而将其它金属指代为促进剂。 For convenience, the molybdenum metal is preferably referenced as the primary catalyst metal fingers on behalf of the other promoter. 这不应该看作是催化活性根本机理的指示。 This should not be seen as indicative of a fundamental mechanism of the catalytic activity.

[0136] 经常分两个步骤中浸渍双金属催化剂。 [0136] in two steps often immersed bimetallic catalyst. 首先,加入"促进剂"金属,接着是"主"金属。 First, add the metal "promoter", followed by a "master" of metal. 每个浸渍步骤后接着进行干燥和煅烧。 Followed by drying and calcination after each impregnation step. 双金属催化剂还可以通过共浸渍进行制备。 The bimetallic catalysts may also be prepared by co-impregnation. 在如上所述促进的双金属催化剂的情形中,可以使用相继浸渍,开始加入"促进剂金属接着是包括两种主要金属即Pt和Sn的共浸渍的第二浸渍步骤。例如,Si0 2上的PtSn/CaSi03可以通过如下进行制备:首先将CaSi03浸渍到Si0 2上,接着用氯钼酸、胺溶解的氢氧化钼、硝酸钯或氯化钯、氯化钠钯、氯化钠钼、Pt(NH3)4(N04)2等的稀混合物进行共浸渍。再次地,每个浸渍后接着进行干燥和煅烧。在大多数情形中,可以使用金属硝酸盐溶液进行浸渍。然而, 还可使用在煅烧时释放金属离子的各种其它可溶盐。用于浸渍的其它合适金属盐的实例包括金属酸,例如高铼酸溶液、金属草酸盐等。在其中产生基本上纯的乙醇的那些情形中,通常优选避免使用钼族金属的卤化前体,而是使用含氮的胺和/或硝酸盐基前体。 In the case of the bimetallic catalyst promoted as described above, a sequential impregnation may be used, the addition of "metal promoter followed by two principal metals, i.e., Pt, and the second impregnation step co-impregnation of Sn. For example, the Si0 2 PtSn / CaSi03 may be prepared by: first CaSi03 impregnated onto Si0 2, followed by chlorine molybdic acid, amine solubilized molybdenum hydroxide, palladium nitrate or palladium chloride, sodium palladium chloride, molybdenum chloride, Pt ( NH3) 4 (N04) 2 or the like co-impregnation lean mixture. again, each impregnation followed by drying and calcination. in most cases, a metal nitrate solution impregnation, however, can also be used in the calcination when the metal ion release various other soluble salts. examples of other suitable metal salts for impregnation include metal acids, such as perrhenic acid solution, metal oxalate, etc. in those instances wherein produce substantially pure ethanol It is generally preferable to avoid the use of halogenated molybdenum precursor metal, but prior to use of the amine nitrogen and / or nitrate based precursors.

[0137] 可以在许多条件下于蒸气状态中进行反应。 [0137] The reaction can be carried out in the vapor state under many conditions. 优选地,在气相中进行反应。 Preferably, the reaction is carried out in the gas phase. 可以使用例如为约125°C _350°C,更常见约200°C -约325°C,优选约225°C -约300°C,最优选约250°C_约300°C的反应温度。 It may be used from about 125 ° C _350 ° C, more usually from about 200 ° C, for example - to about 325 ° C, preferably from about 225 ° C - about 300 ° C, most preferably from about 250 ° C_ to 300 ° C to about the reaction temperature. 压力对于反应通常并非关键,可以使用低于大气压、大气压或超过大气压的压力。 For the reaction pressure is generally not critical, it may be used subatmospheric, atmospheric or superatmospheric pressure. 然而,在大多数情形中,反应压力可为约1-30个绝对大气压。 However, in most cases, the reaction pressure may range from about 1 to 30 atmospheres absolute. 在本发明方法的另一方面,典型地可在刚刚足以克服穿过催化床的压降的压力下以所选择的总时空速度("GHSV")进行加氢,尽管不限制使用较高的压力,但应理解,对于本发明的催化剂在易于使用5000hf 1和6, 500hf1的空速下可能经历通过反应器床的相当大的压降。 In another aspect hydrogenation, typically it may be just sufficient to overcome the pressure drop across the catalytic bed at the selected pressure to the total hourly space velocity of the process according to the invention ( "GHSV"), although there is no use of higher pressures , it is to be understood that the catalyst of the present invention is easy to use airspeed 5000hf 1 and 6, 500hf1 may be experienced by a considerable pressure drop in the reactor bed.

[0138] 虽然该反应每摩尔乙酸消耗2摩尔氢气从而产生1摩尔乙醇,但进料流中氢气与乙酸的实际摩尔比可以在宽范围之间变化,例如为约100 : 1-1 : 100。 [0138] Although the reaction consumes two moles of acid per mole of hydrogen to produce a mole of ethanol, the actual molar ratio of hydrogen to the feed stream of acetic acid may vary widely between, for example, about 100: 1 to 1: 100. 然而这样的比率优选为约1 : 20-1 : 2。 However, such a ratio is preferably from about 1: 20-1: 2. 最优选地,氢气与乙酸的摩尔比为约5 : 1。 Most preferably, the molar ratio of hydrogen to acetic acid is from about 5: 1.

[0139] 有关本发明方法所使用的原料可以衍生自任何合适的来源,包括天然气、石油、 煤、生物质等。 [0139] For the raw material used in the method according to the present invention may be derived from any suitable source including natural gas, petroleum, coal, biomass, and the like. 众所周知通过甲醇羰基化、乙醛氧化、乙烯氧化、氧化发酵和厌氧发酵等生产乙酸。 Well it is known in the methanol carbonylation, acetaldehyde oxidation, ethylene oxidation, oxidative fermentation, and anaerobic fermentation for producing acetic acid. 由于石油和天然气波动,或多或少变得昂贵,所以由替代碳源生产乙酸和中间体例如甲醇和一氧化碳的方法已逐渐引起关注。 As petroleum and natural gas fluctuate more or less becomes expensive, so the production of acetic acid from alternate carbon sources and intermediates such as methanol and carbon monoxide have drawn increasing attention. 特别地,当石油与天然气相比相对昂贵时,由衍生自任何合适碳源的合成气体("合成气")生产乙酸可能变得有利。 In particular, when a relatively expensive compared to oil and gas, a carbon source derived from any suitable synthesis gas ( "syngas") may become advantageous to produce acetic acid. 例如,Vidalin的美国专利No. 6, 232, 352(通过引用将其公开内容并入本文)教导了改造甲醇装置用以制造乙酸的方法。 For example, Vidalin U.S. Patent No. 6, 232, 352 (the disclosure of which is incorporated by reference herein) teaches a method of retrofitting a methanol plant for the manufacture of acetic acid. 通过改造甲醇装置,对于新的乙酸装置,与C0产生有关的大量资金费用得到显著降低或在很大程度上消除。 By retrofitting a methanol plant for a new acetic acid plant, with a large amount of C0 capital costs associated significantly reduced or largely eliminated. 使所有或部分合成气从甲醇合成环路发生转向并供给到分离器单元以回收C0和氢气,然后将它们用于生产乙酸。 All or part of the syngas from the methanol synthesis loop shift occurs and supplied to a separator unit to recover hydrogen and C0, are then used to produce acetic acid. 除乙酸外,这种方法还可用于制备有关本发明所可利用的氢气。 In addition to acetic acid, this method can also be used hydrogen gas which may be utilized according to the present invention was prepared.

[0140] Steinberg等的美国专利No. RE 35, 377 (也通过引用将其并入本文)提供了一种通过使含碳材料例如油、煤、天然气和生物质材料转化生产甲醇的方法。 U.S. Patent No. [0140] Steinberg like No. RE 35, 377 (also incorporated herein by reference) provides a method of oil, coal, natural gas and biomass materials produced by the carbonaceous material, for example, methanol. 该方法包括使固体和/或液体含碳材料加氢气化以获得工艺气体,用另外的天然气将该工艺气体蒸汽热解以形成合成气。 The method comprises contacting a solid and / or liquid carbonaceous materials to obtain hydrogasification process gas which is steam pyrolized with additional natural gas the process gas to form synthesis gas. 将该合成气转化为可以羰基化为乙酸的甲醇。 The synthesis gas can be converted to a carbonyl group to acetic acid in methanol. 该方法同样产生如上述有关本发明所可使用的氢气。 The method likewise produces hydrogen which may be used above in relation to the present invention. 还参见Grady等的美国专利No. 5, 821,111以及Kindig等的美国专利No. 6, 685, 754,其公开了一种将废生物质通过气化转化为合成气的方法,通过引用将它们的公开内容并入本文。 Grady et al. See also U.S. Patent No. 5, 821,111 and U.S. Pat. Kindig like No. 6, 685, 754, which discloses a process for the conversion of waste biomass through gasification into synthesis gas, by reference the disclosures of which are incorporated herein.

[0141] 可以使乙酸在反应温度下气化,然后可将气化乙酸随同未稀释状态或用相对惰性的载气例如氮气、氩气、氦气、二氧化碳等稀释的氢气一起给进。 [0141] acetic acid may be vaporized at the reaction temperature, and acetic acid may be vaporized along with undiluted state or diluted with a relatively inert carrier gas, such as nitrogen fed together, argon, helium, carbon dioxide diluted hydrogen.

[0142] 或者,可以直接从Scates等的美国专利No. 6, 657, 078 (通过引用将其全文并入本文)中所描述的一类甲醇羰基化单元的闪蒸容器取出蒸气形式的乙酸作为粗产物。 [0142] Alternatively, from U.S. Pat. Scates like No. 6, 657, 078 (incorporated by reference in its entirety herein) for a class of flash vessel of a methanol carbonylation unit as described in the extraction of acetic acid in vapor form as a direct The crude product was. 可以将粗蒸气产物直接给进到本发明的反应区而不需要冷凝乙酸和轻馏分或者除去水,从而节省总体工艺费用。 The crude vapor product may be fed directly to the reaction zone of the present invention without the need for condensing the acetic acid and light ends or removing water, saving overall processing costs.

[0143] 接触或停留时间也可以宽泛地变化,这些变量取决于乙酸的量、催化剂、反应器、 温度和压力。 [0143] Contact or residence time can also vary widely, depending upon such variables amount of acetic acid, catalyst, reactor, temperature and pressure. 当使用除固定床外的催化剂系统时,典型的接触时间为几分之一秒到大于若干小时,至少对于气相反应,优选的接触时间为约0. 5-100秒。 When a fixed bed catalyst systems in addition to, the contact time is typically fraction of a second to more than several hours, at least for vapor phase reactions, preferred contact time is about 0.5 seconds 5-100.

[0144] 典型地,催化剂在例如形状为伸长的管道或导管的固定床反应器中使用,其中典型地为蒸气形式的反应物穿过或通过所述催化剂。 [0144] Typically, the catalyst is used in a fixed bed reactor, for example, the shape of an elongated pipe or conduit, which is typically passed over or through the catalyst is in the form of vapor reactants. 如果需要,可使用其它反应器,例如流化床或沸腾床反应器。 If desired, other reactors may be used, such as fluid or ebullient bed reactors. 在一些情形中,加氢催化剂可以与惰性材料例如玻璃棉结合使用以调节反应物料流通过催化剂床的压降和反应物化合物与催化剂颗粒的接触时间。 In some cases, the hydrogenation catalyst may be used in combination, for example, glass wool and the pressure drop of the reactant compounds with the catalyst particles to regulate the reactant stream through the catalyst bed contact time with the inert material.

[0145] 下面的实施例描述了用于制备本发明方法所使用的各种催化剂的操作。 [0145] The following examples describe the operation of the method for the preparation of various catalysts used in the present invention. 在所有这些制备和实施例中,在使用小写字体或草写体"1"时,其用于避免小写字体字母"1"、数字"1 "以及大写字体或大写字母"I"之间在许多字体和/或字样中固有的含混不清,因为语言的含义由常见用法产生,应理解其是指代"升",尽管其缺乏任何国际承认。 In all of these preparation examples and embodiments, when using lowercase cursive or "1", which is used to avoid lowercase letters "a", many numbers between "1" and the uppercase or capital letters "I" font and / or character inherent ambiguity, because the meaning of the language generated by common usage, it is to be understood to refer to "up", despite its lack of any international recognition.

[0146] 催化剂制备(一般) [0146] Catalyst Preparation (General)

[0147] 催化剂载体在使用之前在循环空气下于120°C下干燥过夜。 [0147] In the catalyst carrier prior to use at 120 ° C for circulating air dried overnight. 除非另外提及,所有商业载体(即Si0 2、Zr02)以14/30目或以其原始形状(1/16英寸或1/8英寸丸粒)使用。 Unless mentioned otherwise, all commercial vector (i.e. Si0 2, Zr02) or 14/30 mesh to its original shape (1/16 inch or 1/8 inch pellets). 在加入金属之后将粉末状材料(即CaSi0 3)粒化、压碎和筛分。 After the addition of the powdered metal material (i.e. CaSi0 3) pelletized, crushed and sieved. 在下面章节中更为详细地描述每种催化剂的制备。 Each catalyst was prepared in the following sections described in more detail.

[0148] 催化剂制备A [0148] Preparation of Catalyst A

[0149] 高纯度低表面积二氧化硅上0. 5重量%钼和5重量%锡的制备 Preparation of high-purity low surface area silica 0.5 wt% of molybdenum and 5 wt% of tin [0149]

[0150] 在氮气氛围下的烘箱中于120°C下将均匀粒径分布为约0. 2mm的粉末化和过筛的高表面积二氧化硅NPSGSS61138(100g)干燥过夜,并然后将其冷却至室温。 [0150] In an oven under a nitrogen atmosphere at 120 ° C for uniform particle size distribution of about 0. 2mm and powder sieved high surface area silica NPSGSS61138 (100g) was dried overnight and then cooled to at room temperature. 向其中加入硝酸钼(Chempur) (0· 82g)在蒸馈水(8ml)中的溶液和草酸锡(Alfa Aesar) (8. 7g)在稀硝酸(1Ν,43· 5ml)中的溶液。 Solution of tin oxalate in the fed distilled water (8ml) was added thereto in a molybdenum nitrate (Chempur) (0 · 82g) (Alfa Aesar) (8. 7g) (1Ν, 43 · 5ml) was in dilute nitric acid. 在逐渐加热到110°C ( > 2小时,10°C /min)的烘箱中干燥所得浆料。 Drying the resulting slurry was gradually heated to 110 ° C (> 2 hours, 10 ° C / min) in an oven. 然后在500°C (6小时,1°C/min)下煅烧经浸渍的催化剂混合物。 The impregnated catalyst mixture was then calcined at 500 ° C (6 hours, 1 ° C / min).

[0151] 催化剂制备B [0151] Preparation of Catalyst B

[0152] 高表面积二氧化硅上1重量%钼和1重量%锡的制备 Prepared on high surface area silica 1% wt of molybdenum and 1 wt% of tin [0152]

[0153] 基本上重复催化剂制备A的工序,不同之处在于利用硝酸钼(Chempur) (1. 64g)在蒸馏水(16ml)中的溶液和草酸锡(AlfaAesar) (1.74g)在稀硝酸(1N,8. 5ml)中的溶液。 [0153] A procedure for preparing the catalyst was substantially repeated, except that a molybdenum nitrate (Chempur) (1. 64g) and a solution of tin oxalate in distilled water (16ml) of (AlfaAesar) (1.74g) in dilute nitric acid (1N , in 8. 5ml) was added.

[0154] 催化剂制备C [0154] Catalyst C Preparation

[0155] 在偏硅酸钙上1重量%钼和1重量%锡的制备 Preparation 1 wt% of molybdenum and 1 wt% of tin [0155] In the calcium metasilicate

[0156] 基本上重复催化剂制备B的工序,不同之处在于利用硝酸钼(Chempur) (1. 64g)在蒸馏水(16ml)中的溶液和草酸锡(AlfaAesar) (1. 74g)在稀硝酸(1N,8. 5ml)中的溶液,并利用偏硅酸钙作为催化剂载体。 [0156] The procedure for preparing Catalyst B was substantially repeated, except that a molybdenum nitrate (Chempur) (1. 64g) in dilute nitric acid (16ml) and a solution of tin oxalate in distilled water (AlfaAesar) (1. 74g) ( 1N, the 8. 5ml) was added and the use of metasilicate as a catalyst support.

[0157] 催化剂制备D [0157] Catalyst D Preparation

[0158] 高表面积二氧化硅上0. 5重量%钼、0. 5重量%锡和0. 2重量%钴的制备 High surface area silica prepared 0.5 wt [0158]% molybdenum, 0.5 wt% tin and 0.2 wt% cobalt

[0159] 在氮气氛围下的烘箱中于120°C下将均匀粒径分布为约0. 2mm的粉末化和过筛的高表面积二氧化硅(l〇〇g)干燥过夜,并然后将其冷却至室温。 [0159] at 120 ° C for uniform particle size distribution of about 0. 2mm and powder sieved high surface area silica (l〇〇g) was dried overnight in an oven under a nitrogen atmosphere, and then cooled to room temperature. 向其中加入硝酸钼(Chempur) (0· 82g)在蒸馈水(8ml)中的溶液和草酸锡(AlfaAesar) (0· 87g)在稀硝酸(1N, 4. 5ml)中的溶液。 To this was added the molybdenum nitrate (Chempur) (0 · 82g) solution of tin oxalate in the fed distilled water (8ml) in (AlfaAesar) (0 · 87g) in dilute nitric acid (1N, 4. 5ml) was added. 在逐渐加热到110°C (> 2小时,10°C /min)的烘箱中干燥所得浆料。 Drying the resulting slurry was gradually heated to 110 ° C (> 2 hours, 10 ° C / min) in an oven. 然后在500°C (6小时,1°C/min)下煅烧经浸渍的催化剂混合物。 The impregnated catalyst mixture was then calcined at 500 ° C (6 hours, 1 ° C / min). 向这种经煅烧和冷却的材料中加入六水合硝酸钴(〇. 99g)在蒸馏水(2ml)中的溶液。 Solution (2ml) in distilled water was added cobalt nitrate hexahydrate (square. 99 g of) To this calcined and cooled material. 在逐渐加热到110°C (> 2小时,10°C/min)的烘箱中干燥所得浆料。 Drying the resulting slurry was gradually heated to 110 ° C (> 2 hours, 10 ° C / min) in an oven. 然后在500°C (6小时,l°C/min)下煅烧经浸渍的催化剂混合物。 The impregnated catalyst mixture was then calcined at 500 ° C (6 hours, l ° C / min).

[0160] 催化剂制备E [0160] Catalyst Preparation E

[0161] 高纯度低表面积二氧化硅上0. 5重量%锡的制备 Preparation of high-purity low surface area silica 0.5 wt% of tin [0161]

[0162] 在氮气氛围下的烘箱中于120°C下将均匀粒径分布为约0. 2mm的粉末化和过筛的高纯度低表面积二氧化硅(l〇〇g)干燥过夜,并然后将其冷却至室温。 [0162] In an oven under a nitrogen atmosphere at 120 ° C for a low uniform particle size distribution of from about 0. 2mm Powdered and meshed high purity silica surface area (l〇〇g) overnight, and then it was cooled to room temperature. 向其中加入草酸锡(Alfa Aesar) (1. 74g)在稀硝酸(1N,8. 5ml)中的溶液。 To this was added tin oxalate (Alfa Aesar) (1. 74g) in dilute nitric acid (1N, 8. 5ml) in. 在逐渐加热到110°C ( > 2小时, 10°C/min)的烘箱中干燥所得浆料。 Drying the resulting slurry was gradually heated to 110 ° C (> 2 hours, 10 ° C / min) in an oven. 然后在500°C (6小时,l°C/min)下煅烧经浸渍的催化剂混合物。 The impregnated catalyst mixture was then calcined at 500 ° C (6 hours, l ° C / min).

[0163] 催化剂制备F [0163] Catalyst Preparation F

[0164] 高表面积二氧化硅上2重量%钼和2重量%锡的制备 Prepared on high surface area silica 2 wt% Mo and 2 wt% of tin [0164]

[0165] 在循环空气烘箱气氛中于120°C下将均匀粒径分布为约0. 2mm的粉末化和过筛的高表面积二氧化硅NPSGSS61138(100g)干燥过夜,并然后将其冷却至室温。 [0165] In an atmosphere of a circulating air oven at 120 ° C for uniform particle size distribution of about 0. 2mm and powder sieved high surface area silica NPSGSS61138 (100g) was dried overnight and then cooled to room temperature . 向其中加入六水合硝酸盐(Chempur)溶液。 To this was added nitrate hexahydrate (Chempur) was added. 在逐渐加热到110°C ( > 2小时,10°C /min)的烘箱中干燥所得浆料,然后将其煅烧。 Drying the resulting slurry was gradually heated to 110 ° C (> 2 hours, 10 ° C / min) in an oven, then calcined. 向其中加入硝酸钼(Chempur)在蒸馏水中的溶液和草酸锡(Alfa Aesar)在稀硝酸中的溶液。 Solution in distilled water and a solution of tin oxalate (Alfa Aesar) in dilute nitric acid was added thereto molybdenum nitrate (Chempur). 在逐渐加热到110°C (> 2小时,10°C /min)的烘箱中干燥所得浆料。 Drying the resulting slurry was gradually heated to 110 ° C (> 2 hours, 10 ° C / min) in an oven. 然后在500°C (6小时,1°C/min)下煅烧经浸渍的催化剂混合物。 The impregnated catalyst mixture was then calcined at 500 ° C (6 hours, 1 ° C / min).

[0166] 催化剂制备G [0166] Preparation of Catalyst G

[0167] 用5% ZnO促进的高表面积二氧化硅上1重量%钼和1重量%锡的制备 Prepared on high surface area silica promoted with 5% ZnO 1% by weight of molybdenum and 1 wt% of tin [0167]

[0168] 基本上重复催化剂制备F的工序,不同之处在于:将六水合硝酸锌溶液加入到催化剂制备F所描述的高表面积二氧化硅中。 [0168] Preparation F is substantially repeated step catalyst, except that: the solution of zinc nitrate hexahydrate was added to high surface area silica catalyst as described in Preparation F. 在逐渐加热到110°C ( > 2小时,10°C /min)的烘箱中干燥所得浆料。 Drying the resulting slurry was gradually heated to 110 ° C (> 2 hours, 10 ° C / min) in an oven. 然后,将硝酸钼(Chempur)在蒸馏水中的溶液和草酸锡(Alfa Aesar) (1.74g)在稀硝酸(1N,8. 5ml)中的溶液随后加入到锌促进的高表面积二氧化硅中。 Then, the molybdenum nitrate (Chempur) in distilled water and a solution of tin oxalate (Alfa Aesar) (1.74g) in dilute nitric acid (1N, 8. 5ml) was then added to the high surface area silica in zinc promoted.

[0169] 催化剂制备Η [0169] Catalyst Preparation Η

[0170] 用5% Sn02促进的高表面积二氧化硅上1重量%钼和1重量% Ζη的制备 [0170] promoted on high surface area silica with 5% Sn02 1 wt% of molybdenum and 1 wt% Ζη prepared

[0171] 基本上重复催化剂制备G的工序,不同之处在于:将乙酸锡(Sn(0AC)2)溶液而不是六水合硝酸锌;以及硝酸钼Pt(NH 3)4(N03) 2 (Aldrich)在蒸馏水中的溶液和草酸锡(Alfa Aesar)在稀硝酸中的溶液加入到高表面积二氧化硅中。 [0171] A procedure substantially catalyst G was prepared, except that: the tin acetate (Sn (0AC) 2) instead of a solution of zinc nitrate hexahydrate; molybdenum nitrate and Pt (NH 3) 4 (N03) 2 (Aldrich ) solution of tin oxalate (Alfa Aesar) in distilled water in a dilute nitric acid solution was added to high surface area silica.

[0172] 催化剂制备I [0172] I Catalyst Preparation

[0173] 偏娃酸I丐上1. 5重量%钼、0. 5重量%锡的制备 Partial Acid I hack the baby 1.5 wt% molybdenum, 0.5 wt% of tin was prepared [0173]

[0174] 利用硝酸钼(Chempur)在蒸馏水中的溶液和草酸锡(Alfa Aesar)在稀硝酸中的溶液重复上述催化剂制备C的工序。 [0174] using a molybdenum nitrate (Chempur) solution of tin oxalate (Alfa Aesar) in distilled water was repeated in dilute nitric acid in step C the above prepared catalyst.

[0175] 催化剂制备J [0175] Catalyst J was prepared

[0176] 高表面积二氧化硅上1. 5重量%钼、10重量%钴的制备 High surface area silica prepared 1.5 wt [0176]% molybdenum, 10 wt% cobalt

[0177] 利用硝酸钼(Chempur)在蒸馏水中的溶液,六水合硝酸钴(II) (1. 74g)的溶液代替辛酸亚锡重复上述催化剂制备Η的工序。 [0177] using a molybdenum nitrate (Chempur) solution in distilled water, cobalt nitrate hexahydrate (II) (1. 74g) was used instead of stannous octoate was repeated Η step of the catalyst preparation. 表1中显示了制备的催化剂组成以及本文中通过类似工序制备和测试的其它催化剂组成。 Table 1 shows the composition of the catalyst described herein and by other catalyst prepared in a similar procedure were prepared and tested composition.

[0178] 催化剂制备Κ-0 [0178] Catalyst Preparation Κ-0

[0179] SiC^-PtxSrvJO < X < 1)。 [0179] SiC ^ -PtxSrvJO <X <1). 改变Pt的摩尔分数并同时维持1. 20mmol的总金属量(Pt+Sn)来制备五种材料。 Changing the mole fraction of Pt prepared five kinds of materials while maintaining a total amount of metal (Pt + Sn) 1. 20mmol of. 下面的制备描述了催化剂制备K,即Si02-PtQ.5Sn Q.5(即x = 0. 5 ; 两种金属等摩尔比)的工序。 The following describes the preparation of preparation of catalyst K, i.e., Si02-PtQ.5Sn Q.5 (i.e. x = 0. 5; molar ratio of the two metals, etc.) processes. 同样地使用适当量的金属前体Pt(NH3)4(N03) 2和511((^(:)2进行其余制备(即X = 〇、〇. 25、0. 75和1. 00 ;分别是催化剂制备L、M、N和0)。所述催化剂通过如下进行制备:首先将Sn(0Ac)2 (来自Aldrich的乙酸锡,Sn(0Ac)2) (0. 1421g,0. 60mmol) 加入到含有6. 75ml的1 : 1稀释的冰乙酸(Fisher)的小瓶中。在室温下搅拌该混合物15 分钟,然后加入〇. 2323g (0. 60mmol)固体Pt (NH3) 4 (N03) 2 (Aldrich)。在室温下搅拌该混合物另外15分钟,然后将其滴加到在100ml圆底烧瓶内的5. 0g干燥Si02催化剂载体(高纯度二氧化硅催化剂载体HSA SS#61138, SA = 250m2/g ;SZ#61152, SA = 156m2/g ;Saint-Gobain NorPro)中。连续搅拌该金属溶液直到将所有Pt/Sn混合物加入到Si02催化剂载体中并同时在每次加入金属溶液后旋转该烧瓶。在该金属溶液的加入完成之后,将含有浸渍催化剂的烧瓶维持在室温下静置2小时。然后将该烧瓶连接到 Similarly using the appropriate amount of the metal precursor Pt (NH3) 4 (N03) 2 and 511 ((^ (:) Preparation of 2 remaining (i.e. X = square, and 1.00 billion 25,0 75;.. Are preparation of the catalyst L, M, N and 0) as the catalyst is prepared by: first Sn (0Ac) 2 (tin acetate from Aldrich, Sn (0Ac) 2) (0. 1421g, 0 60mmol) was added to containing 6. 75ml of 1: 1 diluted glacial acetic acid (Fisher) in a vial and the mixture was stirred at room temperature for 15 minutes and then square 2323g (0. 60mmol) of solid Pt (NH3) 4 (N03) 2 (Aldrich. ). the mixture was stirred at room temperature for another 15 minutes and then added dropwise in the round bottom flask 100ml 5. 0g dried Si02 catalyst support (catalyst support is high purity silica HSA SS # 61138, SA = 250m2 / g ; SZ # 61152, SA = 156m2 / g;. Saint-Gobain NorPro) solution was continuously stirred until all the metal Pt / Sn mixture was added to Si02 catalyst support while rotating the flask after each addition of the metal solution. after the addition of the metal solution, the flask containing the impregnated catalyst was allowed to stand at room temperature for 2 hours. the flask was then ligated to 转蒸发器(浴温80°C ),抽空直至干燥并同时缓慢旋转该烧瓶。然后在120°C下将该材料进一步干燥过夜,然后使用如下温度程序进行煅烧:25 - 160°C /斜率为5. Odeg/min ;保持2. 0小时;160 - 500°C /斜率为2. Odeg/min ;保持4小时。产量:5. 2g深灰色材料。 Rotations of the evaporator (bath temperature 80 ° C), dried and evacuated until the flask while slowly rotating the material was then further dried overnight at 120 ° C, and then calcined using the following temperature program:. 25 - 160 ° C / slope 5. Odeg / min; retention 2.0 hours; 160 - 500 ° C / slope 2. Odeg / min; 4 hours yield: 5 2g dark gray material.

[0180] 催化剂制备P [0180] Catalyst Preparation P

[0181] Si02-CaSi03(5)-Pt(3)-Sn(l. 8)。 [0181] Si02-CaSi03 (5) -Pt (3) -Sn (l. 8). 该材料通过首先将CaSi03(Aldrich)加入到Si02催化剂载体,接着按先前所述加入Pt/Sn进行制备。 The first material CaSi03 (Aldrich) was added to the catalyst support by Si02, followed by addition of the previously Pt / Sn prepared. 首先,CaSi03(< 200目)的水性悬浮液通过将0. 52g该固体加入到13ml去离子水中,接着加入1. 0ml胶体Si02(15重量%溶液,NALC0)进行制备。 First, CaSi03 (<200 mesh) by adding an aqueous suspension of 0. 52g of the solid was added to 13ml of deionized water, followed by addition of 1. 0ml colloidal Si02 (15 wt% solution, NALC0) was prepared. 在室温下搅拌该悬浮液2小时,并然后使用始润浸渍技术加入10. 0g Si02催化剂载体(14/30目)。 It was stirred at room temperature for 2 hours the suspension and using the incipient wetness technique and then added 10. 0g Si02 catalyst support (14/30 mesh). 静置2小时之后,将该材料蒸发至干,接着在循环空气下于120°C下干燥过夜并在500°C下煅烧6小时。 After standing for 2 hours, the material was evaporated to dryness and then dried overnight in the circulating air at 120 ° C for and calcined at 500 ° C 6 hours. 然后使用0. 6711g(1.73mmol)的Pt (NH3) 4 (N03) 2 和0. 4104g (1. 73mmol)的Sn (OAc) 2 按照上文就Si02-PtxSni_x 材料所述的工序将所有Si02-CaSi03材料用于Pt/Sn金属浸渍。 Then 0. 6711g (1.73mmol) of Pt (NH3) 4 (N03) 2 and 0. 4104g (1. 73mmol) of Sn (OAc) 2 in accordance with the above procedure the Si02-PtxSni_x material on all Si02- CaSi03 material for the Pt / Sn metal impregnation. 产量:11. 21g深灰色材料。 Yield:. 11 21g dark gray material.

[0182] 催化剂制备Q [0182] Catalyst Preparation Q

[0183] CaSi03-Pt(l)-Sn(l)。 [0183] CaSi03-Pt (l) -Sn (l). 向100ml含有聚四氟乙烯涂覆的磁性搅拌棒的圆底烧瓶中加入40ml的1.0MNH0 3,接着加入0.2025g(0.52mmol)固体Pt(NH3)4(N0 3)2。 Round bottom flask containing a Teflon coated magnetic stir bar to 100ml 40ml of added 1.0MNH0 3, followed by 0.2025g (0.52mmol) of solid Pt (NH3) 4 (N0 3) 2. 随着搅拌溶解Pt络合物并然后加入0. 2052g(0.87mmol)固体Sn(0Ac)2。 Pt complex was dissolved with stirring and then added 0. 2052g (0.87mmol) solid Sn (0Ac) 2. 接下来,随着搅拌加入10.0g 的CaSi03 (彡200目);然后将该混合物加热到80°C并在该温度下搅拌2小时。 Next, was added with stirring 10.0g of CaSi03 (San 200 mesh); the mixture was then heated to 80 ° C and stirred at this temperature for 2 hours. 然后使用旋转蒸发器(浴温80°C )将该悬浮液抽空直至干燥,将固体转移到瓷蒸发皿中,并在循环空气下于120°C下干燥过夜。 Using a rotary evaporator (bath temperature 80 ° C) and the suspension was evacuated to dryness, the solid was transferred to a porcelain evaporating dish, and dried overnight at 120 ° C for circulating air. 在煅烧(25°C- 160°C /斜率为5. Odeg/min ;保持2. 0小时; 160 - 500°C /斜率为2. Odeg/min ;保持4小时)后,在压力下,特别是施加40, OOOlbs的力进行压制15分钟,将材料压制、粒化,并且压碎和筛分为14/30目。 Calcination (25 ° C- 160 ° C / slope 5. Odeg / min; retention 2.0 hours; 160 - 500 ° C / slope 2. Odeg / min; hold for 4 hours), under pressure, in particular is applied 40, OOOlbs force pressed for 15 minutes, the material is pressed, pelletized, crushed and sieved to 14/30 mesh and. 产量:9. 98g的棕褐色材料。 Yield:. 9 98g of brown material.

[0184] 催化剂制备R [0184] Catalyst Preparation R

[0185] Si02-Ti02(10)-Pt(3)-Sn(1.8)。 [0185] Si02-Ti02 (10) -Pt (3) -Sn (1.8). 按如下制备Ti02-改性的二氧化硅载体。 Ti02- prepared as follows modified silica support. 将4. 15g(14. 6mmol)的Ti {0CH(CH3)2}4在2-丙醇(14ml)中的溶液滴加到在100ml圆底烧瓶内的10. 0gSi02催化剂载体(1/16英寸挤出物)中。 The 4. 15g (14. 6mmol) of Ti {0CH (CH3) 2} 4 solution in 2-propanol (14ml) was added dropwise in a 100ml round bottom flask 10. 0gSi02 catalyst carrier (1/16 inch extrudates) was. 让该烧瓶在室温下静置2小时,然后使用旋转蒸发器(浴温80°C )抽空直至干燥。 The flask was let stand for 2 hours at room temperature, and then using a rotary evaporator (bath temperature 80 ° C) evacuated to dryness. 接下来,将20ml去离子水缓慢加入到该烧瓶,并让该材料维持静置15分钟。 Next, 20ml of deionized water was slowly added to the flask, and the material was left standing for 15 minutes. 然后通过过滤除去所产生的水/2-丙醇,再重复加入H 20 2次。 Was then removed by filtration and the resulting aqueous / 2-propanol, was added H 20 2 was repeated twice. 在循环空气下于120°C下将最终材料干燥过夜,接着在500°C下煅烧6小时。 Under circulating air to 120 ° C for final material was dried overnight, followed by calcination at 500 ° C 6 hours. 然后使用0· 6711g(l. 73mmol)的Pt(NH3)4(N03)2 和0· 4104g(l. 73mmol)的Sn(OAc)2 按照上文就Si02-PtxSni_x材料所述的工序将所有Si0 2-Ti02材料用于Pt/Sn金属浸渍。 Then 0 · 6711g (l. 73mmol) of Pt (NH3) 4 (N03) 2 and 0 · 4104g (l. 73mmol) of Sn (OAc) 2 in accordance with the above procedure Si02-PtxSni_x material on all of the Si0 2-Ti02 material for the Pt / Sn metal impregnation. 产量:11. 98g深灰色1/16英寸挤出物。 Yield:. 11 98g dark gray 1/16 inch extrudates.

[0186] 催化剂制备S [0186] Catalyst Preparation S

[0187] Si02-W03(10)-Pt(3)_Sn(1.8)。 [0187] Si02-W03 (10) -Pt (3) _Sn (1.8). 按如下制备W03_改性的二氧化硅载体。 W03_ modified silica support was prepared as follows. 将1. 24g (0· 42mmol)的(NH4) 6H2W1204Q · nH20 (AMT)在去离子水(14ml)中的溶液滴加到在100ml圆底烧瓶内的10. 0g Si02NPSGSS61138催化剂载体(SA = 250m2/g,1/16英寸挤出物)中。 The 1. 24g (0 · 42mmol) of (NH4) 6H2W1204Q · nH20 (AMT) in deionized water (14ml) was added dropwise in a 100ml round bottom flask 10. 0g Si02NPSGSS61138 catalyst support (SA = 250m2 / g, 1/16 inch extrudates) was. 将该烧瓶维持在室温下静置2小时,然后使用旋转蒸发器(浴温80°C )抽空直至干燥。 The flask was left standing at room temperature for 2 hours and then using a rotary evaporator (bath temperature 80 ° C) evacuated to dryness. 在循环空气下于120°C下将所得材料干燥过夜,接着在500°C下煅烧6小时。 Under circulating air to 120 ° C for overnight The resulting material was dried, followed by calcination at 500 ° C 6 hours. 然后使用0· 671 lg (1. 73mmol)的Pt (NH3) 4 (N03) 2 和0· 4104g (1. 73mmol)的Sn (OAc) 2 按照上文就Si02-PtxSni_x材料所述的工序将所有(浅黄色)Si0 2-W03材料用于Pt/Sn金属浸渍。 Then 0 · 671 lg (1. 73mmol) of Pt (NH3) 4 (N03) 2 and 0 · 4104g (1. 73mmol) of Sn (OAc) 2 in accordance with the above procedure Si02-PtxSni_x material on all the (pale yellow) Si0 2-W03 material for the Pt / Sn metal impregnation. 产量: 12. 10g深灰色1/16英寸挤出物。 Yield: 12. 10g dark gray 1/16 inch extrudates.

[0188] 催化剂制备T [0188] Catalyst Preparation T

[0189] (H-ZSM-5) -Pt (3) -Sn (1. 8)。 [0189] (H-ZSM-5) -Pt (3) -Sn (1. 8). 该材料通过H-ZSM-5 (由NH4-ZSM-5 通过在空气中于550°C下煅烧8小时制得)的浆料浸渍进行制备。 This material is prepared (by the NH4-ZSM-5 was obtained by calcination of 8 hours at 550 ° C in air) by the slurry impregnated H-ZSM-5. 0.6711g(1.73mm〇l)的Pt(NH 3)4(N03)2和0. 4104g(l. 73mmol)的Sn(0Ac)2的水溶液通过将所述组分加入到在100ml圆底烧瓶内的40ml 1 : 1稀释的乙酸中并在室温下搅拌该混合物15分钟进行制备。 0.6711g (1.73mm〇l) of Pt (NH 3) 4 (N03) 2 and 0. 4104g (l. 73mmol) of Sn (0Ac) 2 by adding an aqueous solution of the components into a 100ml round bottom flask at in 40ml 1: 1 diluted acetic acid and the mixture was stirred at room temperature for 15 minutes was prepared. 接下来,随着搅拌将10. 0g固体细粉末状H-ZSM-5加入到所述溶液中,在室温下搅拌该混合物另外2小时。 Next, with stirring the solid fine powder 10. 0g H-ZSM-5 was added to the solution, and the mixture was stirred at room temperature for an additional 2 hours. 然后使用旋转蒸发器(浴温80°C )将该烧瓶抽空直至干燥,并在循环空气下于120°C下将所得材料干燥过夜。 Using a rotary evaporator (bath temperature 80 ° C) The flask was evacuated to dryness, and at 120 ° C for overnight The resulting material was dried in circulating air. 在煅烧(250°C - 160°C /斜率为5. Odeg/min ;保持2. 0小时;160 - 500°C / 斜率为2. Odeg/min ;保持4小时)后,将该材料压制、粒化、压碎且筛分为14/30目。 Calcination (250 ° C - 160 ° C / slope 5. Odeg / min; retention 2.0 hours; 160 - 500 ° C / slope 2. Odeg / min; hold for 4 hours), the material is pressed, pelletized, crushed and sieved to 14/30 mesh. 产量: 9. 55g灰色材料。 Yield: 9. 55g gray material.

[0190] 催化剂制备U [0190] Catalyst Preparation U

[0191] SiC^-RexPUO < X < 1)。 [0191] SiC ^ -RexPUO <X <1). 改变Re的摩尔分数并同时维持1. 20mmol的总金属量(Re+Pd)来制备五种材料。 Re changing mole fraction prepared five kinds of materials and simultaneously to maintain the total amount of metal (Re + Pd) 1. 20mmol of. 下面的制备描述了Si02-Rea5Pda5(即X = 0. 5 ;两种金属等摩尔比)的工序。 The following describes the preparation of Si02-Rea5Pda5 (i.e. X = 0. 5; molar ratio of the two metals, etc.) processes. 同样地使用适当量的金属前体順4此04和? Likewise before an appropriate amount of this metal body 04 and the cis 4? (1(勵3)2进行其余制备(即X = 0、0. 25、0. 75和1. 00)。所述金属溶液通过如下进行制备:首先将NH4Re04(0. 1609g, 0. 60mmol)加入到含有6. 75ml去离子水的小瓶中。在室温下搅拌该混合物15分钟,然后加入0. 1154g(0. 60mmol)固体Pd(N03)2。在室温下搅拌该混合物另外15分钟,然后将其滴加到在100ml圆底烧瓶内的5. 0g干燥Si02催化剂载体(14/30目)中。在该金属溶液的加入完成之后,将含有浸渍催化剂的烧瓶维持在室温下静置2小时。然后将该烧瓶连接到旋转蒸发器(浴温80°C ),抽空直至干燥。按上文就Si02-PtxSni_x材料所述进行所有其它操作(干燥、煅烧),见上文。产量:5. lg棕色材料。 (1 (Lai 3) Preparation of 2 remaining (i.e., X = 0,0 25,0 75 and 1.00) of the metal solution is prepared by as follows:.... First NH4Re04 (0 1609g, 0. 60mmol) 6. 75ml was added to a vial containing deionized water. the mixture was stirred at room temperature for 15 minutes, then added 0. 1154g (0. 60mmol) solid Pd (N03) 2. the mixture was stirred at room temperature for another 15 min and then was added dropwise to the flask in a 100ml round bottom flask 5. 0g dried Si02 catalyst support (14/30 mesh). after the addition of the metal solution, containing the impregnated catalyst was standing for 2 hours at room temperature . the flask is then connected to a rotary evaporator (bath temperature 80 ° C), evacuated to dryness by other operations, as described above (drying, calcination) on Si02-PtxSni_x material, supra yield: 5. lg brown material.

[0192] 催化剂制备V [0192] Catalyst Preparation V

[0193] Si02-CaSi03(5)-Re(4. 5)-Pd(l)。 [0193] Si02-CaSi03 (5) -Re (4. 5) -Pd (l). 按就Si02-CaSi03(5)-Pt(3)-Sn(l. 8)所描述制备Si02-CaSi03(5)改性的催化剂载体,见上文。 (5) modified catalyst support prepared as described Si02-CaSi03 on Si02-CaSi03 (5) -Pt (3) -Sn (l. 8) Press, supra. 然后通过用含有NH 4Re04和Pd(N03)2的水溶液浸渍Si0 2-CaSi03 (5) (1/16英寸挤出物)制备Re/Pd催化剂。 NH 4Re04 and then Pd (N03) 2 was impregnated Si0 2-CaSi03 (5) (1/16 inch extrudates) prepared Re / Pd catalyst is prepared by containing. 该金属溶液通过首先将NH4Re04(0 . 7 2 3 7g,2. 70mmol)加入到含有12. 0ml去离子水的小瓶中进行制备。 The metal was added by first NH4Re04 (0. 7 2 3 7g, 2. 70mmol) 12. 0ml to a vial containing deionized water was prepared. 在室温下搅拌该混合物15分钟,然后加入0. 1756g(0. 76mmol)固体Pd(N03)2。 The mixture was stirred at room temperature for 15 minutes, then added 0. 1756g (0. 76mmol) solid Pd (N03) 2. 在室温下搅拌该混合物另外15分钟,然后将其滴加到在100ml圆底烧瓶内的10. 0g干燥Si02-(0 . 05)CaSi03催化剂载体中。 The mixture was stirred at room temperature for another 15 minutes and then added dropwise in a 100ml round bottom flask 10. 0g dried Si02- (0. 05) CaSi03 catalyst support. 在该金属溶液的加入完成之后,将含有浸渍催化剂的烧瓶维持在室温下静置2 小时。 After the addition of the metal solution, the flask containing the impregnated catalyst was allowed to stand at room temperature for 2 hours. 按上文就SiC^-RexPdh材料所述进行所有其它处理(干燥、煅烧),见上文。 All performed as described above for the other processing (drying, calcination) on SiC ^ -RexPdh material, supra. 产量: 10. 9g棕色材料。 Yield: 10. 9g brown material.

[0194] 催化剂制备W [0194] Catalyst Preparation W

[0195] CaSi03-Re(5)-Pd(2. 5)。 [0195] CaSi03-Re (5) -Pd (2. 5). 该材料通过CaSi03(粉末,彡200目)的浆料浸渍进行制备。 The material is prepared by impregnating a slurry CaSi03 (powder, San 200 mesh). 0. 6169g(2. 30mmol)的NH4Re04 和0. 5847g(2. 53mmol)的Pd(N03)2 的水溶液通过将所述组分加入到在l〇〇ml圆底烧瓶内的40ml去离子水中并在室温下搅拌该混合物15分钟进行制备。 0. 6169g (2. 30mmol) and an aqueous solution of NH4Re04 Pd (N03) 2 is 0. 5847g (2. 53mmol) was added to deionized water in a 40ml round bottom flask and l〇〇ml by the components the prepared mixture was stirred for 15 minutes at room temperature. 接下来,随着搅拌将10. 〇g固体细粉末状CaSi03加入到所述溶液中,在室温下搅拌该混合物另外2小时。 Next, with stirring the solid was finely powdered 10. 〇g CaSi03 added to the solution, and the mixture was stirred at room temperature for an additional 2 hours. 然后使用旋转蒸发器(浴温80°C )将该烧瓶抽空直至干燥,并在循环空气下于120°C下将所得材料干燥过夜。 Using a rotary evaporator (bath temperature 80 ° C) The flask was evacuated to dryness, and at 120 ° C for overnight The resulting material was dried in circulating air. 按上文就SiO^RexPdh材料所述进行所有其它处理(干燥、煅烧),见上文。 All performed as described above for the other processing (drying, calcination) on SiO ^ RexPdh material, supra. 使用施加40, OOOlbs的力15分钟的压机将最终材料压制、 粒化,并且压碎和筛分为14/30目。 40 is applied using, for 15 minutes OOOlbs press pressing force to the final material, granulating, and crushed and sieved to 14/30 mesh. 产量:10. 65g的棕色材料。 Yield:. 10 65g brown material.

[0196] 催化剂制备X [0196] Catalyst Preparation X

[0197] Si02-Co(10)-Pt(l)。 [0197] Si02-Co (10) -Pt (l). 该材料通过用含有C〇(N03)2 · 6H20 和Pt(NH3)4(N03)2 的水溶液浸渍HSA Si02(14/30目)进行制备。 This material is prepared containing C〇 (N03) 2 · 6H20 and Pt (NH3) solution (N03 is) immersed in the 42 HSA Si02 (14/30 mesh) pass. 该金属溶液通过首先将C〇(N03)2 · 6Η20(5· 56g, 19. lmmol)加入到含有12. 0ml去离子水的小瓶中进行制备。 The metal solution was prepared by first C〇 (N03) 2 · 6Η20 (5 · 56g, 19. lmmol) was added to a vial containing 12. 0ml of deionized water was prepared. 在室温下搅拌该混合物15分钟,然后加入〇. 2255g(0. 58mmol)固体Pt(NH3)4(N03)2。 The mixture was stirred at room temperature for 15 minutes and then square. 2255g (0. 58mmol) solid Pt (NH3) 4 (N03) 2. 在室温下搅拌该混合物另外15分钟,然后将其滴加到在l〇〇ml圆底烧瓶内的10. 0g干燥Si02催化剂载体(14/30目)中。 10. 0g Si02 catalyst support is dried and the mixture was stirred at room temperature for another 15 minutes and then added dropwise in the round bottom flask l〇〇ml (14/30 mesh). 在该金属溶液的加入完成之后,将含有浸渍催化剂的烧瓶维持在室温下静置2小时。 After the addition of the metal solution, the flask containing the impregnated catalyst was allowed to stand at room temperature for 2 hours. 按上文就Si0 2-PtxSni_x材料所述进行所有其它处理(干燥、煅烧),见上文。 All performed as described above for the other processing (drying, calcination) on Si0 2-PtxSni_x material, supra. 产量:11.35g黑色材料。 Yield: 11.35g black material.

[0198] 催化剂制备Y [0198] Catalyst Preparation Y

[0199] CaSi03-Co(10)-Pt(l)。 [0199] CaSi03-Co (10) -Pt (l). 该材料通过CaSi03 (粉末,彡200目)的浆料浸渍进行制备。 The material is prepared by impregnating a slurry CaSi03 (powder, San 200 mesh). 5. 56g(19. lmmol)的C〇(N03)2 · 6H20 和0· 2255g(0. 58mmol)的Pt(NH3)4(N03)2 的水溶液通过将所述组分加入到在l〇〇ml圆底烧瓶内的40ml去离子水中并在室温下搅拌该混合物15分钟进行制备。 5. 56g (19. Lmmol) of C〇 (N03) 2 · 6H20 and 0 · 2255g (0. 58mmol) of Pt (NH3) solution (N03) 2 to 4 by adding the components to the l〇〇 ml round bottom flask in 40ml of deionized water and the mixture was stirred at room temperature for 15 minutes was prepared. 接下来,随着搅拌将10. 0g固体细粉末状CaSi03加入到所述溶液中。 Next, with stirring the 10. 0g CaSi03 finely powdered solid was added to the solution. 然后将该混合物加热到65°C,并在该温度下搅拌另外2小时。 The mixture was then heated to 65 ° C, and stirred at this temperature for an additional 2 hours. 然后使用旋转蒸发器(浴温80°C )将该烧瓶抽空直至干燥,并在循环空气下于120°C下将所得材料干燥过夜。 Using a rotary evaporator (bath temperature 80 ° C) The flask was evacuated to dryness, and at 120 ° C for overnight The resulting material was dried in circulating air. 按上文就Si02-Co(10)-Pt(l)材料所述进行所有其它处理(干燥、煅烧),见上文。 All performed as described above for the other processing (drying, calcination) on Si02-Co (10) -Pt (l) material, supra. 将最终材料在压力下压制、粒化,并且压碎和筛分为14/30目。 The final material is pressed under pressure, granulating, and crushed and sieved to 14/30 mesh. 产量:10. 65g的黑色材料。 Yield:. 10 65g of black material.

[0200] 催化剂制备Z [0200] Catalyst Preparation Z

[0201] Zr02-Co (10) -Pt (1)。 [0201] Zr02-Co (10) -Pt (1). 该材料通过用含有Co (Ν03) 2 · 6H20 和Pt (NH3) 4 (N03) 2 的水溶液浸渍Zr02(SZ 61152, Saint-Gobain NorPro, 14/30目)进行制备。 The material was impregnated with an aqueous solution prepared Zr02 4 (N03) 2 in (SZ 61152, Saint-Gobain NorPro, 14/30 mesh) containing Co (Ν03) 2 · 6H20 and Pt (NH3) through. 该金属溶液通过首先将C〇(N03)2 · 6Η20(5· 56g,19. lmmol)加入到含有5. 0ml去离子水的小瓶中进行制备。 The solution was first C〇 metal (N03) 2 · 6Η20 (5 · 56g, 19. Lmmol) was added to a vial containing 5. 0ml deionized water prepared by. 在室温下搅拌该混合物15分钟,然后加入0. 2255g(0. 58mmol)固体Pt(NH3)4(N03)2。 The mixture was stirred at room temperature for 15 minutes, then added 0. 2255g (0. 58mmol) solid Pt (NH3) 4 (N03) 2. 在室温下搅拌该混合物另外15分钟,然后将其滴加到在100ml圆底烧瓶内的10. 0g干燥Zr02催化剂载体(14/30目)中。 10. 0g Zr02 catalyst support is dried at room temperature and the mixture was stirred an additional 15 minutes and then added dropwise in a 100ml round bottom flask (14/30 mesh). 在该金属溶液的加入完成之后,将含有浸渍催化剂的烧瓶维持在室温下静置2小时。 After the addition of the metal solution, the flask containing the impregnated catalyst was allowed to stand at room temperature for 2 hours. 按上文就Si02-Co(10)-Pt(l)所述进行所有其它处理(干燥、煅烧),见上文。 All performed as described above for the other processing (drying, calcination) on Si02-Co (10) -Pt (l), supra. 产量:11. 35g黑色材料。 Yield:. 11 35g black material.

[0202] 催化剂制备AA [0202] Catalyst Preparation AA

[0203] Si02-CaSi03 (2. 5) -Pt (1. 5) -Sn (0· 9)。 [0203] Si02-CaSi03 (2. 5) -Pt (1. 5) -Sn (0 · 9).

[0204] 该材料按上文就Si02-CaSi03 (5) -Pt (3) -Sn (L 8)所述使用0· 26gCaSi03,0· 5ml 胶体Si02(15 重量%溶液,NALCO),0· 3355g(0. 86mmol)Pt(NH3)4(N03) 2 和0· 2〇52g(0. 86臟〇1) Sn(0Ac)2进行制备。 [0204] The material according to above for Si02-CaSi03 (5) -Pt (3) -Sn (L 8) using the 0 · 26gCaSi03,0 · 5ml colloidal Si02 (15 wt% solution, NALCO), 0 · 3355g (0. 86mmol) Pt ​​(NH3) 4 (N03) 2 and 0 · 2〇52g (0.86 dirty 〇1) Sn (0Ac) 2 were prepared. 产量:10. 90g深灰色材料。 Yield:. 10 90g dark gray material.

[0205] 催化剂制备BB [0205] Catalyst Preparation BB

[0206] Ti02-CaSi03 (5) -Pt (3) -Sn (1. 8)。 [0206] Ti02-CaSi03 (5) -Pt (3) -Sn (1. 8).

[0207] 该材料通过首先将CaSi03加入到Ti02催化剂(锐钛矿,14/30目)载体,接着按先前所述加入Pt/Sn进行制备。 [0207] This material was added to CaSi03 by first Ti02 catalyst (anatase, 14/30 mesh) support, followed by addition of the previously Pt / Sn prepared. 首先,CaSi0 3(< 200目)的水性悬浮液通过将0. 52g该固体加入到7. 0ml去离子水中,接着加入1. 0ml胶体Si02 (15重量%溶液,NALC0)进行制备。 First, CaSi0 3 (<200 mesh) by adding an aqueous suspension of 0. 52g of the solid to 7. 0ml of deionized water, followed by addition of 1. 0ml colloidal Si02 (15 wt% solution, NALC0) was prepared. 在室温下搅拌该悬浮液2小时,并然后使用始润浸渍技术加入10. 0g Ti02催化剂载体(14/30 目)。 It was stirred at room temperature for 2 hours the suspension and using the incipient wetness technique and then added 10. 0g Ti02 catalyst support (14/30 mesh). 静置2小时之后,将该材料蒸发至干,接着在循环空气下于120°C下干燥过夜并在500°C下煅烧6 小时。 After standing for 2 hours, the material was evaporated to dryness and then dried overnight in the circulating air at 120 ° C for and calcined at 500 ° C 6 hours. 然后使用0· 6711g(l. 73mmol)的Pt(NH3)4(N03)2和0· 4104g(l. 73mmol) 的Sn(0Ac)2按照上文就Si02-PtxS ni_x材料所描述的工序将所有Ti02-CaSi03材料用于Pt/ Sn金属浸渍。 Then 0 · 6711g (l. 73mmol) of Pt (NH3) 4 (N03) 2 and 0 · 4104g (l. 73mmol) of Sn (0Ac) 2 in accordance with the above procedure Si02-PtxS ni_x materials described on all Ti02-CaSi03 material for the Pt / Sn metal impregnation. 产量:11. 5g浅灰色材料。 Yield:. 11 5g light gray material.

[0208] 催化剂制备CC [0208] Catalyst Preparation CC

[0209] KA160_Pt (3) -Sn (1. 8)。 [0209] KA160_Pt (3) -Sn (1. 8).

[0210] 该材料按先前就Si02-PtxSni_ x所述通过KA160催化剂载体(Si02-(0 . 05)A1203, SudChemie,14/30目)的始润浸渍法浸渍进行制备,见上文。 [0210] The material as previously (A1203, SudChemie, 14/30 mesh Si02- (0. 05)) is immersed incipient wetness impregnation prepared Si02-PtxSni_ x on the catalyst support by KA160, supra. 该金属溶液通过首先将Sn(0Ac)2(0. 2040g,0. 86mmol)加入到含有4. 75ml的1 : 1稀释的冰乙酸的小瓶中进行制备。 Glacial acetic acid diluted 1 vial prepared: This solution was added to a metal-containing 4. 75ml by first Sn (0Ac) 2 (0 2040g, 0 86mmol..). 在室温下搅拌该混合物15分钟,然后加入0. 3350g(0. 86mmol)固体Pt(NH3)4(N03)2。 The mixture was stirred at room temperature for 15 minutes, then added 0. 3350g (0. 86mmol) solid Pt (NH3) 4 (N03) 2. 在室温下搅拌该混合物另外15分钟,然后将其滴加到在100ml圆底烧瓶内的5. 0g干燥KA160 催化剂载体(14/30目)中。 5. 0g KA160 catalyst support is dried at room temperature and the mixture was stirred an additional 15 minutes and then added dropwise in a 100ml round bottom flask (14/30 mesh). 按上文Si02-PtxS ni_x所述进行所有其它处理、干燥和煅烧。 For all other processing, drying and calcination according to the Si02-PtxS ni_x above. 产量:5. 23g棕褐色材料。 Yield:. 5 23g brown material.

[0211] 催化剂制备DD [0211] Catalyst Preparation DD

[0212] KA160_CaSi03 (8) -Pt (3) -Sn (1. 8)。 [0212] KA160_CaSi03 (8) -Pt (3) -Sn (1. 8).

[0213] 该材料通过首先将CaSi03加入到KA160催化剂载体,接着按上文就KA160-Pt(3)-Sn(1.8)所述加入Pt/Sn进行制备。 [0213] This material was added to CaSi03 by first KA160 catalyst support, followed by the above for KA160-Pt (3) -Sn (1.8) was added to the Pt / Sn prepared. 首先,CaSi03(彡200目)的水性悬浮液通过将0. 42g该固体加入到3. 85ml去离子水中,接着加入0. 8ml胶体Si02 (15重量% 溶液,NALC0)进行制备。 First, CaSi03 (San 200 mesh) by adding an aqueous suspension of 0. 42g of the solid to 3. 85ml of deionized water, followed by addition of 0. 8ml colloidal Si02 (15 wt% solution, NALC0) was prepared. 在室温下搅拌该悬浮液2小时,并然后使用始润浸渍技术加入5.0gKA160催化剂载体(14/30目)。 It was stirred at rt the suspension for 2 hours and then added to incipient wetness technique 5.0gKA160 catalyst support (14/30 mesh). 静置2小时之后,将该材料蒸发至干,接着在循环空气下于120°C下干燥过夜并在500°C下煅烧6小时。 After standing for 2 hours, the material was evaporated to dryness and then dried overnight in the circulating air at 120 ° C for and calcined at 500 ° C 6 hours. 然后使用0. 3350g(0. 86mmol)的Pt (NH3) 4 (N03) 2 和0· 2040g (0· 86mmol)的Sn (OAc) 2 按照上文就Si02-PtxSni_x 材料所述工序将所有KA160-CaSi03材料用于Pt/Sn金属浸渍。 Then 0. 3350g (0. 86mmol) of Pt (NH3) 4 (N03) 2 and 0 · 2040g (0 · 86mmol) of Sn (OAc) 2 in accordance with the above, the material on the Si02-PtxSni_x step all KA160- CaSi03 material for the Pt / Sn metal impregnation. 产量:5. 19g棕褐色材料。 Yield:. 5 19g brown material.

[0214] ~ .….… 表1 m丽逐----...: ............................................................................... C^l PGM iililr I'i I 我洛I 3χΜί>ί _______-._j- _______1................................- A 0.5 wt% Pt 5 wt% Sn - HPLSASi02 | i B. lwt% Pt = 1 wt% Sn - HP LSA Si022 C 1 wt% Pt ; 1 wt% Sn - CaSiO+2 ^ D. 0.5 wt% Pt 0.5 wt% Sn 0.2 wt% Co HP LSA Si02 " E - 0.5 wt% Sn - HP LSA Si02CE1 F. 2 wt% Pt 2 wt% Sn ~ HSA Si〇2 G lwt% Pt lwt% Sn 5 wt% ZnO HSA Si024 H lwt% Pt 1 wt%Zn 5Sn02 HSASi0 24 I 1.5 wt% Pt 0.5 wt% Sn - Ca Si024 J. 1 wt% Pt - 10 wt% Co HSA Si024 K Si〇2-PtxSn(ix) (Σ [Pt] + [Sn] = 1.20 mmol __ HSA Si〇2 ___X=0_5___\__ Si〇2-PtxSn(ix) (Σ [Pt] + [Sn] = 1.20 mmol L χ_〇- HSA Si02 Μ Si〇2-PtxSn(ix) (Σ [Pt] + [Sn] = 1.20 mmol .. _ ς._ __X=0.75___b b 2__ M Si〇2-PtxSn(ix) (Σ [Pt] + [Sn] = 1.20 mmol r.^ NX=0.25 - HSAS 丨& q Si〇2-PtxSn(ix) (Σ [Pt] + [Sn] = 1.20 mmol . HSA Si〇2 p 3 wt% Pt 1.8 wt% Sn 5 wt% CaSi03 HSA Si02 Q 1 wt% Pt 1 wt% Sn CaSi . [0214] Table 1 m ... ~ ... Korea by ----...: ............................. .................................................. C ^ l PGM iililr I'i I I Luo I 3χΜί> ί _______-._ j- _______ 1 ............................. ...- A 0.5 wt% Pt 5 wt% Sn - HPLSASi02 | i B. lwt% Pt = 1 wt% Sn - HP LSA Si022 C 1 wt% Pt; 1 wt% Sn - CaSiO + 2 ^ D. 0.5 wt % Pt 0.5 wt% Sn 0.2 wt% Co HP LSA Si02 "E - 0.5 wt% Sn - HP LSA Si02CE1 F. 2 wt% Pt 2 wt% Sn ~ HSA Si〇2 G lwt% Pt lwt% Sn 5 wt% ZnO HSA Si024 H lwt% Pt 1 wt% Zn 5Sn02 HSASi0 24 I 1.5 wt% Pt 0.5 wt% Sn - Ca Si024 J. 1 wt% Pt - 10 wt% Co HSA Si024 K Si〇2-PtxSn (ix) (Σ [ pt] + [Sn] = 1.20 mmol __ HSA Si〇2 ___ X = 0_5 ___ \ __ Si〇2-PtxSn (ix) (Σ [pt] + [Sn] = 1.20 mmol L χ_〇- HSA Si02 Μ Si〇2 -PtxSn (ix) (Σ [Pt] + [Sn] = 1.20 mmol .. _ ς._ __X = 0.75 ___ b b 2__ M Si〇2-PtxSn (ix) (Σ [Pt] + [Sn] = 1.20 mmol . r ^ NX = 0.25 - HSAS & q Si〇2 Shu-PtxSn (ix) (Σ [Pt] + [Sn] = 1.20 mmol HSA Si〇2 p 3 wt% Pt 1.8 wt% Sn 5 wt% CaSi03 HSA. si02 Q 1 wt% Pt 1 wt% Sn CaSi 3 1 R %»»+ 〇/ R 3 wt% Pt * r 10 wt % Ti02 HSA Si〇2? _ Sn s 3 wt°/〇Pt 1.8 wt°/〇w〇3 HSA Si02 __Sn _ T 3 wt% Pt 1.8 wt% Pt H-ZSM-5 y Si〇2-RexPdu-x){I [Re + [Pd] = 1.20 mmol HSA Si〇2 __X=0.5___^_J_ 3 1 R% »» + billion / R 3 wt% Pt * r 10 wt% Ti02 HSA Si〇2? _ Sn s 3 wt ° / 〇Pt 1.8 wt ° / 〇w〇3 HSA Si02 __Sn _ T 3 wt% pt 1.8 wt% pt H-ZSM-5 y Si〇2-RexPdu-x) {I [Re + [Pd] = 1.20 mmol HSA Si〇2 __X = 0.5 ___ ^ _ J_

[0215] 表1 伐化則概述(含量) CP ....................................... PGM - ' --瓦涵「其它| 我佟.....-. y StOa-RexPdi;i->:j(Z [Be] + [Pd] = 1.20 mmol HSA SiO 1 ___ x=o _ …丄: yy SiOz-ReRPda-A){I [Re] + fPd] = 1-20 mmol ; HSA Si〇2 ___X=.25______! 2__ X SiO^-RexPda-^{Σ [Re] + [Pd] = 1.20 mmol HSA Si〇2 __X=.75_____ γ Si〇2-RexPd(ix)(I [Re] + [Pd] = 1.20 mmol HSA SiO __X=1___2 Z 1 mol% Pd 4. 5 mol% Re 5 wt% CaSi03 HSA Si02? AA l_5%Pt 0.9% Sn 2.5°/〇CaSi03 Si〇2 BB 3%Pt 1.8%Sn 5°/〇CaSi0 3 Ti02 cc 3%-Pt 1.8% Sn KA160 DD 3%Pt 1.8% Sn. 8%CaSi03 KA-160 AAA 2.5 wt% Pd 5 wt% Re CaSi〇3 BBB 1 wt°/〇Pt 10 wt% Co HSA Si02 CCC 1 wt°/〇Pt 10 wt% Co CaSi〇3 DDD 1 wt% Pt 10wt°/〇Co Zr〇2 [0215] Table 1 is an overview of cutting (content) CP ..................................... .. PGM - '- W Han "other | I Tong .....- y StOa-RexPdi; i ->:. j (Z [Be] + [Pd] = 1.20 mmol HSA SiO 1 ___ x = o _ ... Shang: yy SiOz-ReRPda-A) {I [Re] + fPd] = 1-20 mmol; HSA Si〇2 ___ X = .25 ______ 2__ X SiO ^ -RexPda - ^ {Σ [Re] + [Pd! ] = 1.20 mmol HSA Si〇2 __X = .75 _____ γ Si〇2-RexPd (ix) (I [Re] + [Pd] = 1.20 mmol HSA SiO __X = 1 ___ 2 Z 1 mol% Pd 4. 5 mol% Re 5 wt% CaSi03 HSA Si02? AA l_5% Pt 0.9% Sn 2.5 ° / 〇CaSi03 Si〇2 BB 3% Pt 1.8% Sn 5 ° / 〇CaSi0 3 Ti02 cc 3% -Pt 1.8% Sn KA160 DD 3% Pt 1.8% sn. 8% CaSi03 KA-160 AAA 2.5 wt% Pd 5 wt% Re CaSi〇3 BBB 1 wt ° / 〇Pt 10 wt% Co HSA Si02 CCC 1 wt ° / 10 wt% Co 〇Pt DDD 1 wt CaSi〇3 % Pt 10wt ° / 〇Co Zr〇2

[0216] 产物的气相色谱法(gc)分析 [0216] The product gas chromatography (GC) analysis

[0217] 通过在线GC进行产物的分析。 [0217] The product was analyzed by online GC. 使用配备有1个火焰离子化检测器(FID)和2个热导检测器(TCD)的三通道集成GC来分析反应物和产物。 Use equipped with a flame ionization detector (FID) and 2 thermal conductivity detector (TCD) A three channel compact GC to analyze the reactants and products.

[0218] 前通道配备有FID和CP-Sil 5(20m)+WaxFFap(5m)柱子并用于量化:乙醛;乙醇; 丙酮;乙酸甲酯;乙酸乙烯酯;乙酸乙酯;乙酸;乙二醇二乙酸酯;乙二醇;二乙酸亚乙酯; 和三聚乙醛。 [0218] front channel was equipped with an FID and a CP-Sil 5 (20m) + WaxFFap (5m) column and was used to quantify: Acetaldehyde; ethanol; acetone; ethyl acetate; vinyl acetate; ethyl acetate; acetic acid; glycol diacetate; ethylene glycol; ethylidene diacetate; and paraldehyde.

[0219] 中间通道配备有T⑶和Porabond Q柱子并用于量化:C02 ;乙烯;和乙烷。 [0219] and the middle channel was equipped with T⑶ Porabond Q column and was used to quantify: C02; ethylene; and ethane.

[0220] 后通道配备有TCD和Molsieve 5A柱子并用于量化:氦气;氢气;氮气;甲烧;和一氧化碳。 [0220] After the channel was equipped with a TCD and Molsieve 5A column and was used to quantify: Helium; Hydrogen; nitrogen; A burning; and carbon monoxide.

[0221] 在反应之前,通过用单独化合物形成尖峰测定不同组分的保留时间,并且用已知组成的校准气体或者用已知组成的液体溶液对GC进行校准。 [0221] Before the reaction, the retention time of the different components is measured by spiking with individual compounds and the GC calibrated with a calibration gas of known composition or with liquid solutions of known compositions. 这允许测定各个组分的响应因子。 This allows the determination of the response factors of the individual components.

[0222] 实施例1 [0222] Example 1

[0223] 在由不锈钢制成的内径为30mm且能够升至控制温度的管式反应器中,安置50ml 按上文催化剂制备C所述制备的催化剂。 [0223] In an inner diameter of 30mm and is made of stainless steel tubular reactor can be raised to a controlled temperature, the catalyst C disposed 50ml Catalyst prepared as described above is prepared. 装料后催化剂床的总长度近似地为约70mm。 The total length of the catalyst bed after charging was approximately from about 70mm.

[0224] 进料液体基本上由乙酸组成。 [0224] Liquid feed consisting essentially of acetic acid. 在250°C的温度和lOOpsig的压力下使反应进料液体蒸发并随氢气和作为载气的氦气一起以2500111^ 1的平均总气时空速(GHSV)装入到反应器中。 The reaction temperature and at a pressure of to 250 ° C lOOpsig feed liquid was evaporated and charged with hydrogen and with an average total gas hourly space velocity (GHSV) 2500111 ^ 1 with helium as a carrier gas into the reactor. 进料流含有约6. 1% -约7. 3%摩尔百分数的乙酸和约54. 3% -约61. 5%摩尔百分数的氢气。 Feed stream contains from about 6.1% - about 7.3% mole percent of acetic acid and about 54.3% - mole percent to about 61.5 percent hydrogen. 使来自反应器的蒸气流出物的一部分通过气相色谱用以分析该流出物的内容物。 Portion of the vapor effluent from the reactor is analyzed by gas chromatography for the contents of the effluents. 在85%的乙酸转化率下乙醇的选择性为93. 4%。 Ethanol at a conversion of 85% acetic acid selectivity of 93.4%.

[0225] 所利用的催化剂是根据催化剂制备A的工序制备的二氧化硅上1重量%钼和1重量%锡。 [0225] The catalyst utilized was tin% silica prepared according to the procedure of Preparation A catalyst 1 wt% of molybdenum and 1 wt.

[0226] 实施例2 [0226] Example 2

[0227] 所利用的催化剂是根据实施例C的工序制备的硅酸钙上1重量%钼和1重量% 锡。 [0227] The use of calcium silicate catalysts are prepared according to the procedure of Example C, 1 wt% of molybdenum and 1 wt% tin.

[0228] 在250°C的温度和22bar的压力下用2, 500hr_1平均总气时空速(GHSV)的气化乙酸和氢气的进料流基本上重复实施例1中给出的工序。 [0228] with temperature at a pressure of 2 to 250 ° C and 22bar, the feed stream 500hr_1 average total gas hourly space velocity (GHSV) of substantially vaporized acetic acid and hydrogen in Example 1 given in the step was repeated. 使蒸气流出物的一部分通过气相色谱用以分析该流出物的内容物。 Portion of the vapor effluent was analyzed by gas chromatography for the contents of the effluents. 乙酸转化率大于70%,乙醇选择性为99%。 Acetic acid conversion is greater than 70% and ethanol selectivity was 99%.

[0229] 对比例1 [0229] Comparative Example 1

[0230] 所利用的催化剂是根据实施例E的工序制备的低表面积高纯度二氧化硅上1重量%锡。 [0230] The catalyst utilized was 1 weight percent tin in accordance with the low surface area high purity silica prepared in Step E of Example.

[0231] 在250°C的温度和22bar的压力下用2, 500hr_1平均总气时空速(GHSV)的气化乙酸和氢气的进料流基本上重复实施例1中给出的工序。 [0231] with temperature at a pressure of 2 to 250 ° C and 22bar, the feed stream 500hr_1 average total gas hourly space velocity (GHSV) of substantially vaporized acetic acid and hydrogen in Example 1 given in the step was repeated. 使蒸气流出物的一部分通过气相色谱用以分析该流出物的内容物。 Portion of the vapor effluent was analyzed by gas chromatography for the contents of the effluents. 乙酸转化率小于10%,乙醇选择性小于1 %。 Acetic acid conversion is less than 10% and ethanol selectivity is less than 1%.

[0232] 实施例3 [0232] Example 3

[0233] 使用各种催化剂在表2中给出的温度下重复实施例2的工序,表2中给出了产物中的一氧化碳(⑶)、乙醛(AcH)和乙烷的百分数以及乙酸乙酯(EtOAc);乙醇(EtOH)的选择性和产率以及乙酸(HOAc)的百分数转化率(MCDp.4)。 The procedure of Example 2 was repeated under the [0233] using various catalyst temperatures are given in Table 2, Table 2 shows the carbon monoxide in the product (⑶), the percentage of acetaldehyde (AcH) and ethyl acetate and ethane ester (EtOAc in); ethanol (EtOH), and the selectivity and yield of acetic acid (HOAc) percent conversion (MCDp.4). 始终,4与乙酸的摩尔比维持在5 : 1。 Always, 4 molar ratio of acetic acid is maintained at 5: 1. 为了便利,表2中还包括了实施例1、2和对比例1的结果。 For convenience, Table 2 also includes the results of Comparative Example 1 and Examples 1 and 2. 一般而言当期望产生乙醇作为主要产物时,期望乙醇的选择性大约高于80% ;期望乙酸乙酯的选择性小于5%,优选小于3%。 Generally speaking when it is desired to produce ethanol as the major product, selectivity to the desired ethanol above about 80%; ethyl acetate in the desired selectivity of less than 5%, preferably less than 3%. .......! i ............ 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I -.......... i 470-I ~~ .: a ::,:.. 6 luxury administered about III I, I -! i-- a really ----------- _-_ _-_ _-_ 678333222 [0 [0 [0 hydrogen the ratio of acetic acid (hydrogen gas around 60SCCm / min N2 dilution) vaporized acetic acid and hydrogen through the present invention 氢催化剂,该加氢催化剂包含在表面积为约250m2/g的高表面积二氧化硅(NPSG SS61138)上的2重量% Pt和2重量% Sn。按图1和2中所示在约50小时、70小时和90小时提高温度, 其中图1中显示了以所示产物(乙醇、乙醛和乙酸乙酯)的克数/千克催化剂/小时计的产率,图2中显示了催化剂对各种产物的选择性,其中上线表示乙酸乙酯的产率或选择性, 中间线表示乙醇,下线表示乙醛。认为特别明显的是,乙醛的产率和选择性低。结果汇总于下面的数据汇总中。 Hydrogenation catalyst, the hydrogenation catalyst comprises 2 wt% Pt and 2 wt% Sn on a surface area of ​​about 250m2 / g of high surface area silica (NPSG SS61138) of Press 1 and shown in Figure 2 at about 50 hours. 70 hours and 90 hours increasing the temperature, wherein FIG. 1 shows the / hour to yield a catalyst shown in figure 2 to the various products (ethanol, acetaldehyde, and ethyl acetate) in grams / kilogram of catalyst shown in FIG. product selectivity, wherein the upper line represents the yield or selectivity of ethyl acetate, the middle line indicates ethanol, acetaldehyde offline represented. This is particularly evident that, acetaldehyde low yields and selectivities. the results are summarized in the following data rollup.

[0239] 数据汇总 [0239] Data Summary

[0240] ^ 細^ 22S°C 250mC 2 麵0C 2166C- HOAc 转化牟(%): 11.15 26.49 36,65 33.77 EtOH · (g/kg/h): 187 JS 380,59 §1?J2 434JT EtOH 选择社(wt%): 41 JS 35.83 35.67 33.07 EtOAc 产-取(g/kg/h): 244.04 §38.20 882,55 835,50 _EtOAc :i 祛性(wt%): 57.08 §2,79 62,36 63.S6 [0240] Fine ^ ^ 22S ° C 250mC 2 Mu conversion surface 0C 2166C- HOAc (%): 11.15 26.49 36,65 33.77 EtOH · (g / kg / h):? 187 JS 380,59 §1 J2 434JT EtOH selection Co. (wt%): 41 JS 35.83 35.67 33.07 EtOAc yield - taking (g / kg / h): 244.04 §38.20 882,55 835,50 _EtOAc: i cured properties (wt%): 57.08 §2,79 62,36 63.S6

[0241] 实施例5 [0241] Example 5

[0242] 使用具有负载在包含来自Saint-Gobain NorPro的高表面积二氧化娃SS61138丸粒的催化剂上的2重量% Pt ;2重量% Sn的催化剂,在表2中给出的所示温度和lOOpsig 的压力下用2500111^1平均总气时空速(GHSV)的气化乙酸、氢气和氦气的进料流,基本上重复实施例1中给出的工序。 [0242] having a catalyst supported on high surface area silica containing pellet baby SS61138 from Saint-Gobain NorPro of 2 wt% Pt; 2 wt% Sn catalyst and lOOpsig temperature shown are given in Table 2 2,500,111 ^ 1 with an average total gas hourly space velocity (GHSV) of vaporized acetic acid, hydrogen and helium feed stream under pressure substantially Example 1 given in the step was repeated. 所得进料流含有约7. 3%摩尔百分数的乙酸和约54. 3%摩尔百分数的氢气。 The resulting feed stream, and about 54.3% mole percent hydrogen gas containing from about 7.3% acetic acid mole percent. 使蒸气流出物的一部分通过气相色谱用以分析该流出物的内容物。 Portion of the vapor effluent was analyzed by gas chromatography for the contents of the effluents. 结果呈现在表1中。 The results are presented in Table 1.

[0243] 表3 [0243] TABLE 3

[0244] 传* k AV .-.4- 在:丨AS i 0:丄* 的2 1M p 1 .-2 --E ;i. .¾ aF ____ 225°c- 296ec; 4 TOS = 115 h. - 〇225X T-_i5CTC ---i-胃-280X --^29TC HOAc 1 接(匕5: % 11-15 26.49 j 36.65 33,77 Eton--~ - r- - 一^ H 187.65 380.59 i 517.62 434,67 g/kg/h.__ EtOH-.~~ - wt, 41.96 35.83 35.67 33,07 _________ EtOAc . 244.04 638.20 8082.55 835.50 g/kg/h_______ EtOAc - -...................................................................................................................................................... 远批! wt, 57.08 62.79 6236 63,56 _ % _J_[_ [0244] * k AV .- 4- passed in: Shu AS i 0:.. * Shang of 2 1M p 1.-2 --E; i .¾ aF ____ 225 ° c- 296ec; 4 TOS = 115 h - T-_i5CTC --- i- 〇225X stomach -280X - ^ 29TC HOAc 1 contact (dagger 5:% 11-15 26.49 j 36.65 33,77 Eton-- ~ - r- - a ^ H 187.65 380.59 i 517.62 434,67 g / kg / h .__ EtOH- ~~ -. wt, 41.96 35.83 35.67 33,07 _________ EtOAc 244.04 638.20 8082.55 835.50 g / kg / h _______ EtOAc -. -.......... .................................................. .................................................. ........................................ far approved! wt, 57.08 62.79 6236 63, 56 _% _J _ [_

[0245] 实施例5的结果汇总于图3中,该图证明了催化剂对温度变化的相对不敏感性使该催化剂充分适合用于所谓的绝热反应器,在绝热反应器中由于从反应器除去热的低且不均匀的速率而引起催化剂床上的温度会变化很大。 [0245] The results of Example 5 are summarized in FIG. 3, which demonstrate the catalyst to temperature changes relative insensitivity that the catalyst well suited for so-called adiabatic reactor, due to removal from the reactor in an adiabatic reactor temperature vary greatly low and uneven heat rate caused by the catalyst bed.

[0246] 实施例6 [0246] Example 6

[0247] 通过如下研究Si02-PtxSni_ x催化剂中[Sn]/[Pt]摩尔比的影响:(i)在恒定金属载量([Pt] + [Sn] = 1.20mmol)下改变Pt的摩尔分数,和(ii)作为还原温度的函数。 [0247] By studying the influence Si02-PtxSni_ x catalyst as in [Sn] / [Pt] molar ratio of: (i) loading of the metal at a constant change in the mole fraction of Pt ([Pt] + [Sn] = 1.20mmol) and (ii) as a function of reduction temperature. 观测到在Pt摩尔分数为0. 5(即[Sn]/[Pt] = 1.0)时对于乙酸转化率和对乙醇的选择性为明显最大值。 Pt observed in the mole fraction of conversion and selectivity to acetic acid to ethanol is clearly the maximum value 0.5 (i.e., [Sn] / [Pt] = 1.0). 在[Sn]/[Pt] = 1.0)有利于乙醇时对乙酸乙酯的选择性急剧变化。 In [Sn] / [Pt] = 1.0) abruptly changes when the selectivity in favor of ethanol in ethyl acetate. 在Pt摩尔分数为25%或75%时,观测到乙酸乙酯作为主要产物。 When Pt molar fraction of 25% or 75%, ethyl acetate was observed as the major product. 等摩尔比的Pt和Sn的存在似乎对于乙酸转化率和对乙醇选择性的提高是优选的,参考图4A-C。 Like the presence of Pt and Sn molar ratio of acetic acid seems to improve conversion and selectivity to ethanol is preferred, with reference to FIGS. 4A-C.

[0248] 在温度=250°C ;GHSV = 65701Γ1 ;反应时间为12小时下使气化乙酸(0. 09g/min HOAc)和氢气(160sccm/minH2 ;60sccm/minN2)穿过本发明的加氢催化剂,该加氢催化剂包含在表面积为约250m2/g的高表面积二氧化硅上的Pt和Sn。 [0248] temperature = 250 ° C; GHSV = 65701Γ1; reaction time is vaporized acetic acid (0. 09g / min HOAc) for 12 hours and hydrogen (160sccm / minH2; 60sccm / minN2) through the hydrogenation of the present invention the catalyst, the hydrogenation catalyst comprises Pt on high surface area silica the surface area of ​​about 250m2 / g and a Sn. 在该实施例6中,金属(Pt+Sn) 的量保持恒定并且钼的质量分数在0-1之间变化。 Example 6 In this embodiment, the amount of metal (Pt + Sn) is kept constant and the molybdenum content varied between 0-1. 图4A-4C描述了催化剂各自的选择性、 活性和产率。 Figures 4A-4C describes their selectivity, catalyst activity and productivity. 由该实施例,可认识到的是,当钼的质量分数为约〇. 5即以重量计的钼的量基本上等于该催化剂中锡的量时,出现选择性、活性和产率的最大值。 Of this embodiment it may be appreciated that, when the molybdenum content is about square. 5 i.e. the amount of molybdenum by weight substantially equal to the amount of tin catalyst, selectivity appears, the maximum activity and productivity value.

[0249] 实施例7 [0249] Example 7

[0250] 在约225°C的温度下以约5 : 1的氢气与乙酸摩尔比使气化乙酸和氢气穿过本发明的加氢催化剂,该加氢催化剂包含在表面积为约250m2/g的高纯度高表面积二氧化硅上的3重量% Pt、l. 5重量% Sn和5重量%作为促进剂的CaSi03。 [0250] at a temperature of about 225 ° C to about 5: 1 of hydrogen to acetic acid mole ratio of vaporized acetic acid and hydrogen through the hydrogenation catalyst of the present invention, the hydrogenation catalyst comprises a surface area of ​​about 250m2 / g of 3 wt% Pt on high purity and high surface area silica, l. 5 wt% Sn and 5% by weight as accelerator CaSi03. 图5A和5B描述了在催化剂寿命的初始阶段期间作为运行时间的函数的催化剂选择性和产率。 5A and 5B describe the yields and selectivity of the catalyst during the initial stage of life of the catalyst as a function of operating time. 由图6A和6B中所报导的该实施例的结果,可认识到的是,可以获得高于90%的选择性活性和每千克催化剂每小时高于500g乙醇的产率。 The results of this embodiment from the embodiment in FIGS. 6A and 6B reported, it can be appreciated that it is possible to obtain more than 90% of the activity and selectivity of higher yield per kilogram of catalyst per hour, 500g ethanol.

[0251] 实施例8 [0251] Example 8

[0252] 在约250°C的温度下重复实施例8的工序(相同催化剂?)。 [0252] at a temperature of about to 250 ° C The procedure of Example 8 was repeated (same catalyst?). 图7A-7B描述了在催化剂寿命的初始阶段期间作为运行时间的函数的催化剂选择性和产率。 Figures 7A-7B describes a catalyst selectivity and productivity of the catalyst during the initial stages of the life as a function of operating time. 由图7A和7B所报导的该实施例的结果,可认识到的是,在该温度下仍可获得高于90%的选择性活性但同时获得每千克催化剂每小时商于800g乙醇的广率。 The results of this embodiment from the embodiment of FIGS. 7A and 7B are reported, it can be appreciated that the still available selective activity higher than 90% but at this temperature to obtain a wide rate per hour per kilogram of catalyst supplier in 800g ethanol .

[0253] 实施例9 [0253] Example 9

[0254] 为了研究用于将双金属钼和锡前体还原为催化物质的温度灵敏度,在225_500°C 的独立实验中,通过使最优化的Pt/Sn,Si02-(PtQ.5Sn Q.5)催化剂活化研究了还原温度的影响,见下文。 [0254] In order to study for the reduction of double molybdenum and tin precursor is the temperature sensitivity of catalytic species, 225_500 ° C in separate experiments, the optimized by Pt / Sn, Si02- (PtQ.5Sn Q.5 ) the effect of the reduction catalyst activation temperature, see below. 在4个实验中,使材料在280、350、425和500°C下于流动氢气下活化4小时, 接着在250°C的反应温度下进行乙酸还原。 In four experiments, the material 280,350,425 and activated at 500 ° C under flowing hydrogen for 4 hours followed by reduction acetate at a reaction temperature to 250 ° C. (使用lOmol% H2/N2混合物(275sccm/min)在环境压力下使用如下温度程序进行催化剂活化:RT-还原温度(225-500°C ),斜率为2deg/ min;保持4.0小时,然后为了HOAc的还原降低(或在必要时提升)到250°C)。 (Using lOmol% H2 / N2 mixture (275sccm / min) at ambient pressure using the following catalyst activation temperature program: RT- reduction temperature (225-500 ° C), slope 2deg / min; held 4.0 hours, then to HOAc reduction reduction (or lift when necessary) to 250 ° C). 此外,在HOAc加氢中于225和250°C的反应温度下研究在225°C下活化的材料。 In addition, the activated materials at 225 ° C and at a reaction temperature of 225 to 250 ° C in HOAc hydrogenation studies. 贯穿整个温度范围没有观测到对乙醇和乙酸乙酯的选择性的明显变化,包括就反应温度225和250°C而言对于在225°C下活化的催化剂。 Throughout the whole temperature range without significant change was observed selectivity of ethanol and ethyl acetate, to the reaction temperature includes 225 and 250 ° C activation at 225 ° C for the catalyst. 引起注意的是,对于在较低、225和280°C的还原温度下活化的催化剂观测到转化率(和产率)的明显提高。 Attention is, for the activation at a low reduction temperature of 225 280 ° C and catalyst was observed conversion (and yield) is significantly improved. 在较高的还原温度下转化率降低可能归因于金属颗粒的烧结。 At higher reduction temperature decrease may be due to the conversion of sintered metal particles. (参见图7A和7B)因为没有观测到选择性的变化,金属颗粒的组成(即PtSn合金)似乎保持不变。 (See FIGS. 7A and 7B) because there is no change in selectivity was observed, the composition of the metal particles (i.e., PtSn alloys) appears unchanged. 图3A-3C中描述了该实施例的结果。 Figures 3A-3C depicts the results of in this embodiment.

[0255] 在这些实施例中检测到各种其它产物,包括乙醛、乙醇、乙酸乙酯、乙烷、一氧化碳、二氧化碳、甲烷、异丙醇、丙酮和水。 [0255] Various other product detected in these embodiments, include acetaldehyde, ethanol, ethyl acetate, ethane, carbon monoxide, carbon dioxide, methane, isopropanol, acetone and water.

[0256] 实施例10 [0256] Example 10

[0257] 在乙酸催化加氢中使用2. 5ml表4中所示催化剂中的固体催化剂评价各种催化剂的催化性能。 [0257] 2. 5ml catalytic performance of the solid catalyst in the catalyst shown in Table 4 Evaluation of various catalysts in catalytic hydrogenation in acetic acid. 在每种情形中,催化剂颗粒具有14/30目的尺寸,并且用14/30目石英碎片1 : lv/v进行稀释。 In each case, the catalyst particles having a mesh size of 14/30, with 14/30 mesh quartz chips and 1: diluted lv / v. 在各自运行中,在24小时运行时间(T0S)的范围(span)内,操作压力为200psig(14bar)并同时进料速率为0· 09g/min 乙酸;120sccm/min 氧气;60sccm/min 氣气,以65701Γ1的总气时空速。 In their operation, in the range of 24 hours run time (the T0S) of (span), an operating pressure of 200 psig (14bar) and at the same feed rate of 0 · 09g / min acetic acid; 120sccm / min oxygen; 60sccm / min Gas Gas , at a total gas hourly space velocity of 65701Γ1. 表4中显示了结果。 Table 4 shows the results.

[0258] 表4.在HOAc催化加氢中各种负载型金属催化剂的催化活性。 [0258] Table 4 in HOAc catalytic hydrogenation of various supported metal catalysts in catalytic activity. 反应条件:2. 5ml固体催化剂(14/30 目,1 : 1稀释(v/v,与石英碎片,14/30 目);p = 200psig(14bar) ;0.09g/ min HOAc ;120sccm/min H2 ;60sccm/min N2 ;GHSV = 65701Γ1 ;24 小时的运行时间(T0S)。 6Γ\ΙσιίηΓΝ9ΐ 6Z S EtNILnδ {Lndpd-qlnarH-dlseu寸1-| 9Ζροσιi oro09rslΙΝ17LO卜Ζo.tcs-odld-o.sovoiseuΓπτ 艺寸PJfNoox Ng 卜- S -Lnzzodld-o.oI-lovoisTOurslT; 00176(Ντ 5 ττ - τ -Lnz.(N{InOcs 乂Sds-OISEUπ ττ Ζ6ΐ sroooooOI - τ 丨oszοΤυςΗΟ-τί-^οιοωΙΛΙ.οΪΛοιηΓΝινίίιsττ τ9ΓνιSσι卜卜τ - t? -ir>LZo.I)us-orH)ld-o!seu6 ετ οοτΓΟ6 8呀5 - L - no.l;)cz-odw-(ous-o!s-oLnrNIlvs}00 ττ 山π 寸009 卜一lrsl,rn_irlr-zodus-o.sd-ocz-ois-oslNIVS} L OS 对sTHt? 6卜9fNsl? pa°l;)id-o.sou-{o!soLn(Nl<s) 9ετ SI Tros Z.IH- -- srvrvlodldlo.so:Ho!so91r<s) s01 srstLn# s ^LnK {Ln^pd-qsQrcc^osoLrlfNIVS) 寸OZ 9Π st-tLO9 8 寸τε00= {s7}pd-oLnary-<ol5o91;-<5)00 τοο寸2VDootN00Γ0卜Lo. -Ln-ipr-τod.us-o<N)w-<o Reaction conditions: 2 5ml solid catalyst (14/30 mesh, diluted 1: 1 (v / v, with quartz chips, 14/30 mesh); p = 200psig (14bar); 0.09g / min HOAc; 120sccm / min H2 ; 60sccm / min N2; GHSV = 65701Γ1;. 24 hours running time (T0S) 6Γ \ ΙσιίηΓΝ9ΐ 6Z S EtNILnδ {Lndpd-qlnarH-dlseu inch 1- | 9Ζροσιi oro09rslΙΝ17LO Bu Ζo.tcs-odld-o.sovoiseuΓπτ Yi inch PJfNoox Ng Bu - S -Lnzzodld-o.oI-lovoisTOurslT;. 00176 (Ντ 5 ττ - τ -Lnz (N {InOcs qe Sds-OISEUπ ττ Ζ6ΐ sroooooOI - τ Shu oszοΤυςΗΟ-τί- ^ οιοωΙΛΙ.οΪΛοιηΓΝινίίιsττ τ9ΓνιSσι pitapat τ - ?! t -ir> LZo.I) us-orH) ld-o seu6 ετ οοτΓΟ6 8 die 5 - L - no.l;) cz-odw- (ous-o s-oLnrNIlvs} 00 ττ 009 mountain π inches! ?? BU lrsl, rn_irlr-zodus-o.sd-ocz-ois-oslNIVS} L OS of sTHt 6 Bu 9fNsl pa ° l;!) id-o.sou- {o soLn (Nl <s) 9ετ SI Tros Z.IH- - srvrvlodldlo.so:Ho!so91r<s) s01 srstLn # s ^ LnK {Ln ^ pd-qsQrcc ^ osoLrlfNIVS) inch OZ 9Π st-tLO9 8 inch τε00 = {s7} pd-oLnary- <ol5o91 ; -. <5) 00 τοο inch 2VDootN00Γ0 Bu Lo -Ln-ipr-τod.us-o <N) w- <o !s-os-vs) Z8S is 一广. s β (519,3-01:)01=505 +HSWWVS3 Hoffl 0<oa«κιI s0Esi i £ .OZ-if i ,sli 3 -l;i i"9125-Q- 时小οο1-Η"^w%ix23VOH】/ciJVOH】-!【3VOH】)}^ii3vow紐。 ! S-os-vs) Z8S is a wide s β (519,3-01:) 01 = 505 + HSWWVS3 Hoffl 0 <oa «κιI s0Esi i £ .OZ-if i, sli 3 -l; ii" 9125. -Q- small οο1-Η "^ w% ix23VOH] / ciJVOH] -! [3VOH])} ^ ii3vow York. 攻祐餐令30客锊餐姹奪媧ht/li#令#<e 下\1/。 Attack woo meal made 30 off Lue meal at Cha Wa wins ht / li # make # <e \ 1 /. (801)叵言^??容言,7 寸ζ ίτΛ9 卜9ζ=Λ8Ηοg VZSUI/UI33S 0OOXW.SUI/UI33S onlrvow.sUI/6x)OQeooi(Jeq 寸I).2fsd 007a.xtnroe/n 广柘贫缽^邶*>/>)(26 4#ί:ϊ ρΕΓοε/η)^^樂姝MIs os :幸^饵^。 (801) made thereupon receiving ^ ?? words, 7 inch ζ ίτΛ9 Bu 9ζ = Λ8Ηοg VZSUI / UI33S 0OOXW.SUI / UI33S onlrvow.sUI / 6x) OQeooi (Jeq inch I) .2fsd 007a.xtnroe / n Zhe wide lean bowl Bei ^ *> />) (26 4 # ί: ϊ ρΕΓοε / η) ^^ Yue Shu MIs os: Fortunately ^ ^ bait. 圮^啕劣眾^锯-0-木攻挺.sumlupsss 彡68;-hj f卜^碱咩本本悻友#^龠¥矣樂<*盔^杷昤毋逄。 ^ ^ Wail destroyed all the bad wood saw -0- attack very .sumlupsss Pie 68; -hj f ^ Bu Xing Friends of the base baa books # ^ ¥ carry flute music <* ^ helmet loquat Ling Wu Pang. (凇%咖制¾)令劫冢孕搫脸铖弈'T价耜客M4-來T1.8)/N----sn-⑶I - 9 οοτ - - " - szz {sovz-ouz-inioro 卜τ3t(ρ±-ΓΝίτ008 99 卜S εΜ-- - - sodus-odldo 9ΓΗ(5)3卜π s τ-vt·9L0, m S.Poduz-odld-oiseoLOT10s一%) Ηοδ IfiΧδ3 Is x«< 8 E ,022-cas、#l€5/asi' ' xi , ' s*:«w<ox 齋1 lE.fli' 一51,0 性' ' 1定rlmt. 1 稳例剂施化实催_-_ _-_ _-_ ο 12 6 6 6 2 2 2[0[0[0 的反应时间中评价Si02-CaSi03(5)-Pt(3)-Sn(1.8)的催化性能和初始稳定性。在超过100 小时的总反应时间中观测到催化剂性能和选择性仅仅发生很小变化。乙醛似乎是唯一的副产物,并且其浓度(约3重量% )在实验的过程中在很大程度上保持不变。图5A和5B* 提供了催化剂产率和选择性的汇总。在单独实验中于超过125小时的总反应时间中研究了反应温度对产物选择性的影响,见上文。 (Song ¾% coffee Ltd.) Order robbery Otsuka face Cheng Yi pregnant Po 'T monovalent plow off M4- to T1.8) / N ---- sn-⑶I - 9 οοτ - - "- szz {sovz-ouz-inioro Bu τ3t (ρ ± -ΓΝίτ008 99 Bu S εΜ-- - - sodus-odldo 9ΓΗ (5) 3 Bu π s τ-vt · 9L0, m S.Poduz-odld-oiseoLOT10s a%) Ηοδ IfiΧδ3 Is x «<8 E, 022-cas, # l € 5 / asi '' xi, 's *: «w <ox fasting 1 lE.fli' of a 51,0 'rlmt 1 1 set of stabilizing agent to the solid catalyst in Example _. -_ _-_ _-_ ο 12 6 6 6 2 2 2 [0 [0 [0 reaction time was evaluated Si02-CaSi03 (5) -Pt (3) -Sn (1.8) of the initial catalytic performance and stability . observed little change in selectivity and catalyst performance only acetaldehyde seems to be the only by-product, and its concentration (about 3% by weight) in a total reaction time exceeds 100 hours in the course of the experiment to a great extent holding constant. FIGS. 5A and 5B * providing the catalyst productivity and selectivity are summarized. in a separate experiment studies the total reaction time exceeds 125 hours in the product of reaction temperature on selectivity, supra.

[0263] 实施例12 [0263] Example 12

[0264] 使用2. 5ml固体催化剂(14/30目,1 : 1稀释(v/v,与石英碎片,14/30目);在200psig 的压力下;进料速率为0· 09g/min HOAc ;160sccm/minH2 ;60sccm/min N2 ;GHSV = 65701^在典型的操作条件范围内,使用固定床连续反应器系统在225°C下15小时持续时间的运行中通过加氢和酯化反应主要产生乙醛、乙醇、乙酸乙酯来研究在乙酸加氢中用5% CaSi03稳定的高纯度高表面积Si02上的3% Pt :1. 5% Sn的产率和选择性。图6A和6B中给出了结果。 [0264] 2. 5ml using the solid catalyst (14/30 mesh, diluted 1: 1 (v / v, with quartz chips, 14/30 mesh); at a pressure of 200psig; feed rate of 0 · 09g / min HOAc ; 160sccm / minH2; 60sccm / min N2; GHSV = 65701 ^ in a typical range of operating conditions, using a fixed bed continuous reactor system operating 15 hours duration is mainly produced by the hydrogenation and esterification reaction at 225 ° C acetaldehyde, ethanol, ethyl acetate, acetic acid studied in the hydrogenation with 5% CaSi03 3% Pt on high purity and high surface area stable Si02: to 1 5% Sn yield and selectivity of FIGS. 6A and 6B. the results.

[0265] 实施例13 [0265] Example 13

[0266] 使用2.5ml固体催化剂(14/30目,1 : 1稀释(v/v,用石英碎片,14/30目);在200psig(14bar)的压力下;伴随着160sccm/min氧气和60sccm/min作为稀释剂(diulent) 的氮气给进〇. 〇9g/min乙酸;在250°C的温度下;GHSV = 65701Γ1 ;或12小时的反应时间,通过改变在恒定金属载量([Pt] + [Sn] = 1. 20mmol)下Re的摩尔分数研究包含在Si02中的Re和Pd的催化剂的产率和选择性(其中在催化剂之间修改RexPd(1_x)的摩尔比)。虽然在Re摩尔分数为约0. 6时观测到乙酸的最大转化率,但是仅仅在Re摩尔分数为约0. 78时乙醇变成主要产物。在该Re和Pd之间摩尔比(表示为"Re7Pd2")下,对乙酸乙酯的选择性窄范围地变化从而有利于乙醇。重要地,且如上述Pd/Sn系列所示,具体比率的两种金属的存在似乎是具体产物选择性的关键结构要求,即在[Re]/[Re+Pd] = 0. 78时选择性向乙醇的转移,参考按与图4A-C相同的 [0266] 2.5ml using the solid catalyst (14/30 mesh, diluted 1: 1 (v / v, with quartz chips, 14/30 mesh); at a pressure of 200 psig (14bar); and accompanied 160sccm / min oxygen gas and 60sccm / min as a diluent (diulent) nitrogen feed square 〇9g / min acetic acid; at a temperature to 250 ° C; GHSV = 65701Γ1; or 12 hours of reaction time, by varying the metal loading a constant ([of Pt] + [Sn] = 1. 20mmol) under study mole fraction of Re contained in the yield and selectivity of the catalyst Si02 Re and Pd (where between the catalyst modified RexPd (1_x) molar ratio). Although Re mole fraction of about 0. 6 to observe the maximum conversion rate of acetic acid, but only becomes a major product of about 0.78 mole fraction of ethanol in Re. between the molar ratio of Re and Pd (denoted as "Re7Pd2") , the selectivity to ethyl acetate in a narrow range of variation to facilitate ethanol. importantly, and as the above-described Pd / Sn series, the presence of two metals seem to be the ratio of the specific key structural requirements of the particular product selectivity, i.e. [Re] / [Re + Pd] = 0. 78 ethanol selectivity for the transfer, with reference to Figures 4A-C by the same 格式给出的图8、9和10,不同之处在于\ (Re)表示催化剂中铼的质量分数。然而,与Pt/Sn材料形成对照的是,乙酸的最大转化率和对乙醇的选择性与这些材料不相符,并且仅仅在低的HOAc转化率时观测到对乙醇的有利选择性。因此,参考图8,对乙酸乙酯而不是对于乙醇观察到最大产率。此外,使用CaSi0 3-Re (5)-Pd (2. 5)催化剂在约30%的乙酸转化率和仅225°C的反应温度下观测到烃(甲烷和乙烷;它们分别为5. 3和2. 4重量% )的形成。虽然乙酸的较高转化率可以最有可能通过提高反应温度获得, 但是也将可能提高烃的量,因此限制了Re/Pd基催化系统的总体效率。 Format given in Figures 8, 9 and 10, except that the \ (Re) represents the mass fraction of the rhenium catalyst. However, in contrast with the Pt / Sn material, the maximum conversion of acetic acid and selectivity to ethanol these materials do not match, and only observed favorable selectivity to ethanol HOAc at low conversion. Thus, referring to Figure 8, instead of ethyl alcohol was observed for the maximum yield. in addition, CaSi0 3- Re (5) -Pd (2. 5) catalyst was observed hydrocarbons (methane and ethane at a reaction temperature of about 30 percent conversion of acetic acid and of only 225 ° C; they are 5.3 and 2.4 wt% respectively ) are formed. Although a high conversion of acetic acid can most likely be obtained by increasing the reaction temperature, it is also possible to increase the amount of hydrocarbons, thus limiting the overall efficiency of Re / Pd-based catalyst system.

[0267] 实施例14 [0267] Example 14

[0268] 使用在Si02上的二氧化硅负载钼(1% )钴催化剂(Co载量为10重量% )的初始催化剂筛选产生高的乙酸转化率和约80%对乙醇的选择性。 [0268] Using a molybdenum supported on silica Si02 (1%) cobalt catalyst (Co loading was 10 wt%) of the initial screening of the catalyst to produce a high conversion of acetic acid and about 80% selectivity to ethanol. 参见图11和12,其中选择性和活性如先前所定义,对于乙醇的结果用正方形表示,对于乙酸乙酯的结果用圆形表示,乙醛用菱形表示,乙烷用三角形表示。 Referring to FIGS. 11 and 12, wherein the selectivity and activity are as previously defined, the results of ethanol represented by squares, the results expressed by a circular ethyl acetate, acetaldehyde represented by diamonds, ethane represented by triangles. 然而,似乎在9小时的反应时间过程中催化剂随着乙酸选择性从约80%下降到42%而劣化。 However, it appears the catalyst as acetic acid selectivity decreased from about 80% to 42% in 9 hours deteriorated during the reaction time. 此外,还观测到产率的明显变化,以及随着对乙酸乙酯和乙醛的选择性的提高所伴随着的乙醇选择性下降。 In addition, significant change was observed in yield, as well as to improve the selectivity to acetaldehyde and ethyl acetate, the selectivity decrease is accompanied ethanol. 用负载在二氧化硅上的10%钴获得类似的结果。 Similar results were obtained with 10% cobalt supported on silica.

[0269] 实施例15 [0269] Example 15

[0270] 在温度=250°C;GHSV = 65701Γ1 ;12小时的反应时间下,于200psig的压力下使气化乙酸(〇· 09g/min HOAc)和氢气(160sccm/min H2 ;60sccm/min N2)穿过本发明的加氢催化齐U,该加氢催化剂包含在包含氢型ZSM-5分子筛的载体上的3重量% Pt和1. 8重量% Sn。 [0270] temperature = 250 ° C; GHSV = 65701Γ1; a reaction time of 12 hours, vaporized acetic acid (square · 09g / min HOAc) at a pressure of 200psig and hydrogen (160sccm / min H2; 60sccm / min N2 ) catalytic hydrogenation of the present invention together through a U, the hydrogenation catalyst comprising a carrier comprising on a hydrogen form of ZSM-5 is 3 wt% Pt and 1.8 wt% Sn. 以96 %的选择性和2646g/kg/h的产率获得二乙醚,伴有4%乙酸乙酯,78%乙酸保持未反应。 96% selectivity and yield of 2646g / kg / h is obtained as diethyl ether, with 4% ethyl acetate, 78% acetic acid remains unreacted.

[0271] 实施例16 [0271] Example 16

[0272] 在275°C ;GHSV = 65701Γ1 ;12小时的反应时间下,于200psig的压力下使气化乙酸(0.09g/min HOAc)和氢气(160sccm/min H2 ;60sccm/min N2)穿过本发明的加氢催化剂,该加氢催化剂包含在包含高表面积石墨的载体上的2重量% Pt和1重量% Sn。 [0272] at 275 ° C; GHSV = 65701Γ1; a reaction time of 12 hours, vaporized acetic acid at a pressure of 200psig (0.09g / min HOAc) and hydrogen (160sccm / min H2; 60sccm / min N2) through the hydrogenation catalyst of the present invention, the hydrogenation catalyst comprises a support comprising a high surface area graphitized 2 wt% Pt and 1 wt% Sn. 乙酸乙酯的选择性为43%,乙醇的选择性57%,乙酸乙酯的产率为66g/kg/hr,乙醇的产率为88g/kg/ hr,乙酸的转化率为12%。 Ethyl acetate selectivity was 43%, 57% selectivity to ethanol and ethyl acetate in a yield of 66g / kg / hr, the ethanol yield was 88g / kg / hr, acetic acid conversion was 12%.

[0273] 虽然详细描述了本发明,但在本发明的精神和范围内的各种修改对于本领域技术人员而言将是显而易见的。 [0273] While the invention has been described in detail, but within the spirit and scope of the invention modifications to those skilled in the art will be apparent. 鉴于上述讨论,上文关于背景技术和详细描述所讨论的本领域相关知识和参考文献,通过引用将它们的公开内容全部并入本文,而认为其它例证并没有必要。 In view of the above discussion, the background art above with respect to the art and discussed in the detailed description and references relevant knowledge, by reference the disclosures of which are all incorporated herein, and the illustration is not necessary that the other. 此外,应理解在下文和/或在所附权利要求书中引述的本发明的各个方面以及多个实施方案和多个特征的各个部分可以部分或全部地进行组合或者互换。 Further, it should be understood that, and / or may be partially or entirely in a plurality of parts of various aspects and embodiments and features of the present invention, a plurality of the appended claims recited hereinafter combined or interchanged. 此外,本领域技术人员将认识到前述描述仅仅是举例方式,并且不意欲限制本发明。 Moreover, those skilled in the art will recognize that the foregoing description is by way of example only, and not intended to limit the present invention.

[0274] 因此为了提供基于乙酸的加氢产物,根据本发明提供了新型的方法和催化剂。 [0274] Therefore, in order to provide acid-based hydrogenation product provides a novel catalyst and a method according to the present invention.

[0275] 例如实施方案#1是通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C_300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂包含在含硅载体上分散的钼和锡,其中对钼和锡的量和氧化态,以及钼与锡的比率,和含硅载体进行选择、构成和控制使得:(i)使所转化乙酸的至少80%转化为乙醇;(ii)小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯及其混合物的化合物以外的化合物;并且当在2atm的压力、275°C的温度和25001^ 1的GHSV下暴露于摩尔比为10 : 1的乙酸和氢气的蒸气状的混合物168小时的时间段时,该催化剂活性下降小于10%。 [0275] For example embodiment # 1 is a process for producing ethanol by acid reduction, the method comprising in the gas phase of at least about 4: hydrogen to acetic acid 1 molar ratio at a temperature from about 225 ° C_300 ° C comprising hydrogen and acetic acid gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst comprising dispersed on a siliceous support and molybdenum, tin, molybdenum, and wherein the amounts and oxidation states of tin, and the ratio of molybdenum and tin, and silicon-vector Alternatively, the control and configuration such that: (i) the conversion of acetic acid is converted to ethanol at least 80%; (ii) less than 4% of acetic acid is converted to other compounds selected from ethanol, acetaldehyde, ethyl acetate, ethylene and mixtures thereof compound other than; and when the pressure 2atm, the temperature of 275 ° C the GHSV and 25001 ^ 1 is exposed to a molar ratio of 10: vaporous acetic acid and hydrogen in a mixture of 168 hours time period the catalyst activity less than 10% decrease.

[0276] 实施方案#2是实施方案#1的方法,其中加氢催化剂基本上由分散在含娃载体上的钼和锡构成并且该含硅载体是改性含硅载体,所述改性含硅载体包括有效量的选自如下的载体改性剂:(i)碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏硅酸盐, (iv)碱金属偏娃酸盐,(v)氧化锌,(vi)偏娃酸锌和(vii) (i)-(vi)中任一种的前体,以及(i)-(vii)的任意混合物。 [0276] Embodiment # 2 # 1 embodiment is a process wherein the hydrogenation catalyst consists essentially of molybdenum, and tin dispersed on the support and containing a silicon-containing baby carrier siliceous support is modified, the modification comprising silicon vectors include an effective amount of a modifier selected from: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal metasilicates, (iv) an alkali metal salt of the partial doll , (v) zinc oxide, (vi) and partial zinc baby (vii) (i) - (vi) according to any one of the precursor, and (i) - (vii) any mixture.

[0277] 实施方案#3是实施方案#2的方法,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0277] Embodiment # 2 # 3 is a process scheme of the embodiment, wherein the support modifier is selected from mixtures of any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0278] 实施方案#4是实施方案#2的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0278] Embodiment # 4 # 2 embodiment is a process, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) at least tin of 0.5 to 10% presence.

[0279] 实施方案#5是实施方案#3的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0279] Embodiment # 5 # 3 embodiment is a process, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0280] 实施方案#6是实施方案#2的方法,其中载体改性剂选自钠、钾、镁、钙和锌的偏硅酸盐以及它们的前体和前述的任意混合物。 [0280] Embodiment # 6 # 2 is a process scheme of the embodiment, wherein the support modifier is selected from mixtures of any of sodium, potassium, magnesium, calcium and zinc as well as their precursors and foregoing.

[0281] 实施方案#7是实施方案#5的方法,其中(a)钼以催化剂重量的0.5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0281] Embodiment # 7 is the method of embodiment # 5 embodiment, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) tin in an amount of at least 0.5 to 10 percent.

[0282] 实施方案#8是实施方案#6的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0282] Embodiment # 8 # The method of embodiment 6, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0283] 实施方案#9是实施方案#2的方法,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0283] Embodiment # 9 # 2 is a process scheme of embodiment, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0284] 实施方案#10是实施方案#9的方法,其中:(a)钼以催化剂重量的0. 5% -5%的量存在;(b)锡以至少0. 5-10%的量存在。 [0284] Embodiment # 10 # The method of embodiment 9, wherein: (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; the amount of (b) at least tin of 0.5 to 10% presence.

[0285] 实施方案#11是实施方案#10的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0285] Embodiment # 11 # 10 embodiment is a process, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0286] 实施方案#12是实施方案#2的方法,其中载体改性剂选自镁、钙和锌的偏硅酸盐以及它们的前体和前述的任意混合物。 [0286] Embodiment 12 is the method of embodiment # 2 # embodiments, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc as well as their precursors and foregoing.

[0287] 实施方案#13是实施方案#12的方法,其中(a)钼以催化剂重量的0.5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0287] Embodiment # 13 # 12 is a process scheme of the embodiment, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) tin in an amount of at least 0.5 to 10 percent.

[0288] 实施方案#14是实施方案#12的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0288] Embodiment 14 is the method of embodiment # 12 # embodiments, wherein the mole ratio of molybdenum and tin is 4: 5-5: 4.

[0289] 实施方案#15是实施方案#2的方法,其中载体改性剂选自偏娃酸|丐、偏娃酸|丐的前体以及偏硅酸钙和其前体的混合物。 [0289] Embodiment 15 is the method of embodiment # 2 # embodiments, wherein the support modifier is selected from partial acid baby | Hack, metaphosphoric acid baby | Hack, and mixtures and precursors thereof metasilicate precursor.

[0290] 实施方案#16是实施方案#15的方法,其中(a)钼以催化剂重量的0.5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0290] Embodiment # 16 # scheme is a method of embodiment 15, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) tin in an amount of at least 0.5 to 10 percent.

[0291] 实施方案#17是实施方案#16的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0291] Embodiment # 17 # scheme is a method of embodiment 16, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0292] 实施方案#18是实施方案#2的方法,其中(a)钼以催化剂重量的0. 5%-5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0292] Embodiment 18 is the method of embodiment # 2 # embodiments, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) at least tin of 0.5 to 10% presence.

[0293] 实施方案#19是实施方案#16的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0293] Embodiment # 19 # scheme is a method of embodiment 16, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0294] 实施方案#20是实施方案#18的方法,其中载体表面积为至少约100m2/g。 [0294] Embodiment # 20 # scheme is a method of embodiment 18, wherein the support surface area of ​​at least about 100m2 / g.

[0295] 实施方案#21是实施方案#20的方法,其中锡与钼族金属的摩尔比为约1 : 2-约2 : 1〇 [0295] Embodiment # 21 # 20 is a process scheme of the embodiments, wherein the mole ratio of tin and molybdenum metal is from about 1: 2 to about 2: 1〇

[0296] 实施方案#22是实施方案#20的方法,其中锡与钼的摩尔比为约2 : 3-约3 : 2。 [0296] Embodiment # 22 is a process scheme of embodiment # 20, wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2.

[0297] 实施方案#23是实施方案#20的方法,其中锡与钼的的重量比为约5 : 4-约4 : 5〇 [0297] Embodiment # 23 # 20 embodiment is a process wherein the weight ratio of tin to molybdenum is from about 5: 4 to about 4: 5〇

[0298] 实施方案#24是实施方案#2的方法,其中载体表面积为至少约150m2/g。 [0298] Embodiment 24 is the method of embodiment # 2 # embodiments, wherein the support surface area of ​​at least about 150m2 / g.

[0299] 实施方案#25是实施方案#24的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;(b)锡以至少0. 5-5%的量存在。 [0299] Embodiment # 25 # 24 embodiment is a process, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; (b) tin in an amount of at least 0.5% by 5-5 .

[0300] 实施方案#26是实施方案#24的方法,其中载体包含至少约1% -约10重量%的硅酸钙。 [0300] Embodiment # 26 # 24 embodiment is a process, wherein the carrier comprises at least about 1% - about 10% by weight of calcium silicate.

[0301] 实施方案#27是实施方案#24的方法,其中锡与钼的摩尔比为约1 : 2-约2 : 1。 [0301] Embodiment # 27 # 24 is a process scheme of the embodiment, wherein the molar ratio of tin to molybdenum is from about 1: 2 to about 2: 1.

[0302] 实施方案#28是实施方案#24的方法,其中锡与钼的摩尔比为约2 : 3-约3 : 2。 [0302] Embodiment # 28 is a process scheme of embodiment # 24, wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2.

[0303] 实施方案#29是实施方案#24的方法,其中锡与钼的的重量比为约5 : 4-约4 : 5〇 [0303] Embodiment # 29 # 24 embodiment is a process wherein the weight ratio of tin to molybdenum is from about 5: 4 to about 4: 5〇

[0304] 实施方案#30是实施方案#2的方法;其中载体表面积为至少约200m2/g。 [0304] Embodiment 30 is the method of embodiment # 2 # Scheme embodiment; wherein the support surface area of ​​at least about 200m2 / g.

[0305] 实施方案#31是实施方案#30的方法,其中锡与钼的摩尔比为约2 : 3-约3 : 2。 [0305] Embodiment # 31 # 30 is a process embodiment, the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2.

[0306] 实施方案#32是实施方案的方法#30,其中锡与钼的摩尔比为约5 : 4-约4 : 5。 [0306] Embodiment # 32 # 30 is a process embodiment, the molar ratio of tin to molybdenum is from about 5: 4 to about 4: 5.

[0307] 实施方案#33是实施方案#30的方法,其中锡与钼的摩尔比为约9 : 10-约10 : 9〇 [0307] Embodiment # 33 # 30 is a process embodiment, the molar ratio of tin to molybdenum is from about 9: 10 to about 10: 9〇

[0308] 实施方案#34是实施方案#33的方法,其中改性含硅载体的表面积为至少约250m 2/g。 [0308] Embodiment # 34 # scheme is a method of embodiment 33, wherein the surface area of ​​the modified silicon-containing support is at least about 250m 2 / g.

[0309] 实施方案#35是实施方案#2的方法,该方法在约250°C _300°C的温度下进行,其中(a)改性含硅载体的表面积为至少约250m2/g ; (b)钼以至少约0. 75重量%的量存在于加氢催化剂中;(c)锡与钼的摩尔比为约5 : 4-约4 : 5 ;(d)改性含硅载体包含纯度为至少约95%的用至少约2. 5重量% -约10重量%的偏硅酸钙改性的二氧化硅。 [0309] Embodiment 35 is the method of embodiment # 2 # embodiments, the process is carried out at a temperature of about 250 ° C _300 ° C, wherein the surface area (a) a silicon-containing modified support is at least about 250m2 / g; (b ) Mo in an amount of at least about 0.75% by weight in the presence of a hydrogenation catalyst; molar ratio of (c) tin and molybdenum is from about 5: 4 to about 4: 5; (d) a carrier comprising a modified silicon purity at least at least about 2.5 wt% to about 95% by - weight to about 10% of calcium metasilicate modified silica.

[0310] 实施方案#36是实施方案#35的方法,其中存在的钼的量为至少1重量%。 [0310] Embodiment # 36 # scheme is a method of embodiment 35, wherein the amount of molybdenum present is at least 1% by weight.

[0311] 实施方案#37是实施方案#2的方法,该方法在约250°C _300°C的温度下进行,其中(a)改性含硅载体的表面积为至少约100g/m;(b)其中锡与钼的摩尔比为约2 : 3-约3 : 2 ; (c)改性含硅载体包含纯度为至少约95 %的用至少约2. 5重量% -约10重量%的偏硅酸钙改性的二氧化硅。 [0311] Embodiment 37 is the method of embodiment # 2 # embodiments, the process is carried out at a temperature of about 250 ° C _300 ° C, wherein the surface area (a) a silicon-containing modified carrier is at least about 100g / m; (b ) wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2; (c) a carrier comprising a modified silicon purity of at least about 95% by weight of at least about 2.5% - to about 10% by weight of vinylidene calcium modified silica.

[0312] 实施方案#38是实施方案#37的方法,其中存在的钼的量为至少0. 75重量%。 [0312] Embodiment # 38 # The method of embodiment 37, wherein the amount of molybdenum present is at least 0.75% by weight.

[0313] 实施方案#39是实施方案#38的方法,其中催化剂占据反应器体积,并且在气相中以至少约lOOOhf 1的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 [0313] Embodiment # 39 # The method of embodiment 38, wherein the volume of the reactor occupied by the catalyst, and the gas phase in a reactor volume of at least about 1 lOOOhf space velocity of the gaseous stream comprising hydrogen and acetic acid through the .

[0314] 实施方案#40是实施方案#38的方法,其中催化剂占据反应器体积,并且在气相中以至少约2500h r4的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 [0314] Embodiment # 40 # 38 embodiment is a method wherein the volume of the reactor occupied by the catalyst, and at a space velocity of at least about 2500h r4 of the gaseous stream comprising hydrogen and acetic acid through the reactor in a gas phase volume .

[0315] 实施方案#41是实施方案#40的方法,其中控制钼和锡的量和氧化态,以及钼与锡的比率和改性含硅载体使得:(i)使所转化乙酸的至少90%转化为乙醇:(ii)小于2% 的乙酸转化为除选自乙醇、乙醛、乙酸乙酯和乙烯及其混合物的化合物以外的化合物;和(iii)当在2atm的压力、275°C的温度和25001^ 1的GHSV下暴露于摩尔比为10 : 1的乙酸和氢气的蒸气状的混合物336小时的时间段时,催化剂活性下降小于10%。 [0315] Embodiment # 41 # scheme is a method of embodiment 40, wherein the molybdenum and the control amounts and oxidation states of tin, molybdenum, and tin and the ratio of the modified silicon-containing carrier such that: (i) the conversion of acetic acid of at least 90 % ethanol is converted to: (ii) less than 2% of acetic acid is converted to compounds other than the compounds selected from ethanol, acetaldehyde, ethyl acetate, and mixtures of ethylene; and (iii) when the pressure 2atm, 275 ° C molar ratio is exposed to a temperature at GHSV 25001 ^ 1 and 10: a mixture of acetic acid and hydrogen vaporous period of 1 336 hours, the catalyst activity decreased less than 10%.

[0316] 实施方案#42是实施方案#38的方法,其中催化剂占据反应器体积,并且在气相中以至少约SOOOhf 1的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 [0316] Embodiment # 42 # 38 embodiment is a method wherein the volume of the reactor occupied by the catalyst, and the gas phase in a reactor volume of at least about 1 SOOOhf space velocity of the gaseous stream comprising hydrogen and acetic acid through the .

[0317] 实施方案#43是实施方案#42的方法,其中控制钼和锡的量和氧化态,以及钼与锡的比率和改性含硅载体使得:(i)使所转化乙酸的至少90%转化为乙醇;(ii)小于2%的乙酸转化为烷烃;(iii)当在2atm的压力、275°C的温度和25001^- 1的GHSV下暴露于摩尔比为10 : 1的乙酸和氢气的蒸气状的混合物168小时的时间段时,催化剂活性下降小于10%。 [0317] Embodiment # 43 # scheme is a method of embodiment 42, wherein the molybdenum and the control amounts and oxidation states of tin, molybdenum, and tin and the ratio of the modified silicon-containing carrier such that: (i) the conversion of acetic acid of at least 90 % converted to ethanol; (ii) acetic acid of less than 2% conversion of alkanes; (iii) when the pressure 2atm, the temperature of 275 ° C and 25001 ^ - exposure at a GHSV 1 in molar ratio of 10: acetic acid 1 and when the time period of a vaporous mixture of hydrogen for 168 hours, the catalyst activity decreased less than 10%.

[0318] 实施方案#44是实施方案#43的方法,该方法在约250°C _300°C的温度下进行,其中(a)改性含硅载体的表面积为至少约200m2/g;(b)锡与钼的摩尔比为约5 : 4-约4 : 5; (c)改性含硅载体包含纯度为至少约95%的用至少约2. 5重量% -约10重量%的硅酸钙改性的二氧化硅。 [0318] Embodiment # 44 # 43 is a process embodiment, the process is carried out at a temperature of about 250 ° C _300 ° C, wherein the surface area (a) a silicon-containing modified support is at least about 200m2 / g; (b ) molar ratio of tin to molybdenum is from about 5: 4 to about 4: 5; (c) a carrier comprising a modified silicon purity of at least about 95% by weight of at least about 2.5% - to about 10% by weight silicic acid calcium modified silica.

[0319] 实施方案#45是通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C_300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂包含在氧化物类载体上分散的钼和锡,其中对钼和锡的量和氧化态,以及钼与锡的比率,和氧化物类载体进行选择、构成和控制使得:(i)使所转化乙酸的至少80%转化为乙醇;(ii)小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯及其混合物的化合物以外的化合物;并且当在2atm的压力、275°C的温度和25001^ 1的GHSV 下暴露于摩尔比为10 : 1的乙酸和氢气的蒸气状的混合物500小时的时间段时,该催化剂活性下降小于ίο%。 [0319] Embodiment # 45 is obtained by acid reduction process for producing ethanol which comprises the gas phase of at least about 4: 1 molar ratio of hydrogen to acetic acid 1 at a temperature of about 225 ° C_300 ° C makes comprising hydrogen and acetic acid the gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst comprising the oxides dispersed in a carrier and molybdenum, tin, molybdenum and tin wherein the amounts and oxidation states, and the ratio of molybdenum and tin, and oxidic support are selected and configured such that the control: (i) the conversion of acetic acid is converted to ethanol at least 80%; (ii) less than 4% of acetic acid is converted to other selected from ethanol, acetaldehyde, ethyl acetate, ethylene and mixtures thereof compound other than the compound; and when the pressure 2atm, the temperature of 275 ° C the GHSV and 25001 ^ 1 is exposed to a molar ratio of 10: vaporous acetic acid and hydrogen in a mixture of 500 hours period, the catalyst activity decreased less than ίο%.

[0320] 实施方案#46是实施方案#45的方法,其中加氢催化剂基本上由分散在氧化物类载体上的钼和锡构成并且该氧化物类载体是改性氧化物类载体,所述改性氧化物类载体包括有效量的选自如下的载体改性剂:(i)碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏娃酸盐,(iv)碱金属偏娃酸盐,(v)氧化锌,(vi)偏娃酸锌和(vii) (i)-(vi)中任一种的前体,以及(i)-(vii)的任意混合物。 [0320] Embodiment # 46 # 45 embodiment is a process wherein the hydrogenation catalyst consists essentially of molybdenum, and tin dispersed on the support oxides and the oxide type of vector is a modified oxidic support, the modified oxidic support comprises a support modifier selected from an effective amount of: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal partial salts baby, (iv) an alkali metal baby partial salts, (v) zinc oxide, (vi) and partial zinc baby (vii) (i) - (vi) any one of the precursor, and (i) - a mixture of any of (vii) a.

[0321] 实施方案#47是实施方案的方法#46,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0321] Embodiment # 47 is a process embodiment # 46, wherein the support modifier is selected from mixtures of any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0322] 实施方案#48是实施方案#47的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0322] Embodiment # 48 # The method of embodiment 47, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) at least tin of 0.5 to 10% presence.

[0323] 实施方案#49是实施方案#47的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0323] Embodiment # 49 # scheme is a method of embodiment 47, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0324] 实施方案#50是实施方案#46的方法,其中载体改性剂选自钠、钾、镁、钙和锌的偏硅酸盐以及它们的前体和前述的任意混合物。 [0324] Embodiment # 50 is the embodiment of embodiment # 46, wherein the support modifier is selected from mixtures of any of sodium, potassium, magnesium, calcium and zinc as well as their precursors and foregoing.

[0325] 实施方案#51是实施方案#50的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0325] Embodiment # 51 # The method of embodiment 50, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) at least tin of 0.5 to 10% presence.

[0326] 实施方案#52是实施方案#51的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0326] Embodiment # 52 # 51 embodiment is a process, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0327] 实施方案#53是实施方案#46的方法,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0327] Embodiment # 53 # The method of embodiment 46, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0328] 实施方案#54是实施方案#53的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0328] Embodiment # 54 # The method of embodiment 53, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) at least tin of 0.5 to 10% presence.

[0329] 实施方案#55是实施方案#54的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0329] Embodiment # 55 # scheme is a method of embodiment 54, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0330] 实施方案#56是实施方案#46的方法,其中载体改性剂选自镁、钙和锌的偏硅酸盐以及它们的前体和前述的任意混合物。 [0330] Embodiment # 56 # scheme is a method of embodiment 46, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc as well as their precursors and foregoing.

[0331] 实施方案#57是实施方案#56的方法,其中(a)钼以催化剂重量的0.5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0331] Embodiment # 57 # 56 is a process scheme of embodiment, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) tin in an amount of at least 0.5 to 10 percent.

[0332] 实施方案#58是实施方案#57的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0332] Embodiment # 58 # The method of embodiment 57, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0333] 实施方案#59是实施方案#46的方法,其中载体改性剂选自偏娃酸|丐、偏娃酸|丐的前体以及偏硅酸钙和其前体的混合物。 [0333] Embodiment # 59 # scheme is a method of embodiment 46, wherein the support modifier is selected from partial acid baby | Hack, metaphosphoric acid baby | Hack, and mixtures and precursors thereof metasilicate precursor.

[0334] 实施方案#60是实施方案#59的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0334] Embodiment # 60 # 59 embodiment is a process, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) at least tin of 0.5 to 10% presence.

[0335] 实施方案#61是实施方案#60的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0335] Embodiment # 61 # 60 embodiment is a process, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0336] 实施方案#62是实施方案#46的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0336] Embodiment # 62 # The method of embodiment 46, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) at least tin of 0.5 to 10% presence.

[0337] 实施方案#63是实施方案#62的方法,其中钼与锡的摩尔比为4 : 5-5 : 4。 [0337] Embodiment # 63 # The method of embodiment 62, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.

[0338] 实施方案#64是实施方案#62的方法,其中载体表面积为至少约100m2/g。 [0338] Embodiment # 64 # 62 embodiment is a process wherein the support surface area of ​​at least about 100m2 / g.

[0339] 实施方案#65是实施方案#64的方法,其中锡与钼族金属的摩尔比为约1 : 2-约2 : 1〇 [0339] Embodiment # 65 # 64 embodiment is a process, wherein the molar ratio of tin to molybdenum metal is from about 1: 2 to about 2: 1〇

[0340] 实施方案#66是实施方案#64的方法,其中锡与钼的摩尔比为约2 : 3-约3 : 2。 [0340] Embodiment # 66 # scheme is a method of embodiment 64, wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2.

[0341] 实施方案#67是实施方案#64的方法,其中锡与钼的的重量比为约5 : 4-约4 : 5〇 [0341] Embodiment # 67 # scheme is a method of embodiment 64, wherein the weight ratio of tin to molybdenum is from about 5: 4 to about 4: 5〇

[0342] 实施方案#68是实施方案#46的方法,其中载体表面积为至少约150m2/g。 [0342] Embodiment # 68 # The method of embodiment 46, wherein the support surface area of ​​at least about 150m2 / g.

[0343] 实施方案#69是实施方案#68的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;和(b)锡以至少0. 5-5%的量存在。 [0343] Embodiment # 69 # 68 embodiment is a process, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) an amount of at least 0.5 tin of 5-5% presence.

[0344] 实施方案#70是实施方案#68的方法,其中载体包含至少约1% -约10重量%的硅酸钙。 [0344] Embodiment # 70 # scheme is a method of embodiment 68, wherein the carrier comprises at least about 1% - about 10% by weight of calcium silicate.

[0345] 实施方案#71是实施方案#68的方法,其中锡与钼的摩尔比为约1 : 2-约2 : 1。 [0345] Embodiment # 71 # scheme is a method of embodiment 68, wherein the molar ratio of tin to molybdenum is from about 1: 2 to about 2: 1.

[0346] 实施方案#72是实施方案#68的方法,其中锡与钼的摩尔比为约2 : 3-约3 : 2。 [0346] Embodiment # 72 # The method of embodiment 68, wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2.

[0347] 实施方案#73是实施方案#68的方法,其中锡与钼的的重量比为约5 : 4-约4 : 5〇 [0347] Embodiment # 73 # The method of embodiment 68, wherein the weight ratio of tin to molybdenum is from about 5: 4 to about 4: 5〇

[0348] 实施方案#74是实施方案#46的方法,其中载体表面积为至少约200m2/g。 [0348] Embodiment # 74 # scheme is a method of embodiment 46, wherein the support surface area of ​​at least about 200m2 / g.

[0349] 实施方案#75是实施方案的方法#74,其中锡与钼的摩尔比为约2 : 3-约3 : 2。 [0349] Embodiment # 75 is a process embodiment # 74, wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2.

[0350] 实施方案#76是实施方案#74的方法,其中锡与钼的摩尔比为约5 : 4-约4 : 5。 [0350] Embodiment # 76 # scheme is a method of embodiment 74, wherein the molar ratio of tin to molybdenum is from about 5: 4 to about 4: 5.

[0351] 实施方案#77是实施方案#74的方法,其中锡与钼的摩尔比为约9 : 10-约10 : 9〇 [0351] Embodiment # 77 # scheme is a method of embodiment 74, wherein the molar ratio of tin to molybdenum is from about 9: 10 to about 10: 9〇

[0352] 实施方案#78是通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C_300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂基本上由在改性的稳定化含硅载体上分散的钼和锡构成,所述改性的稳定化含硅载体包含纯度为至少约95重量%的用选自如下的稳定剂-改性剂改性的二氧化硅:(i)碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏硅酸盐,(iv)碱金属偏娃酸盐,(v)氧化锌,(vi)偏娃酸锌和(vii) (i)-(vi)中任一种的前体,以及(i)-(vii) 的任意混合物,其中控制钼和锡的量和氧化态,钼与锡的比率,稳定剂-改性剂与二氧化硅在改性的稳定化含硅载体中的相对比例以及改性的稳定化含硅载体中二氧化硅的纯度使得所转化乙酸的至少80%转化为乙醇,小于4%的乙酸转化为除选自乙醇 [0352] 78 is a process for producing ethanol by adding acetic acid to embodiment #, the process comprising the gas phase of at least about 4: hydrogen to acetic acid 1 molar ratio at a temperature from about 225 ° C_300 ° C comprising hydrogen and acetic acid the gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst consists essentially of a dispersion of stabilized on the modified silicon-containing molybdenum and tin carrier, said modified silicon-containing carrier comprises a stabilized purity of at least about 95 % by weight of stabilizer selected from - modified silica modifier: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal metasilicates, (iv) alkali metal partial salts baby, (v) zinc oxide, (vi) and partial zinc baby (vii) (i) - (vi) any one of the precursor, and (i) - (vii) any mixture of wherein the ratio of molybdenum and controlling the amounts and oxidation states of tin, molybdenum and tin stabilizers - the relative proportions of modifier to silica stabilized in the modified silicon-containing carrier and modified stabilized silicaceous support purity silica in acetic acid converted such that at least 80% conversion to ethanol, acetic acid less than 4% converted to other selected from ethanol 、乙醛、乙酸乙酯、乙烯及其混合物的化合物以外的化合物。 , And the compound other than the compound mixture of acetaldehyde, ethyl acetate, ethylene.

[0353] 实施方案#79是实施方案#78的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;和(b)锡以至少0. 5-10%的量存在。 [0353] Embodiment # 79 # 78 are embodiments of a method, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; and (b) at least tin of 0.5 to 10% presence.

[0354] 实施方案#80是实施方案#79的方法,其中改性的稳定化含硅载体的表面积为至少约100m2/g。 [0354] Embodiment # 80 is the method of embodiment # 79 embodiment, the surface area of ​​the silicon-containing carrier wherein the stabilized modification is at least about 100m2 / g.

[0355] 实施方案#81是实施方案#80的方法,其中锡与钼族金属的摩尔比为约1 : 2-约2 : 1〇 [0355] Embodiment # 81 # The method of embodiment 80, wherein the molar ratio of tin to molybdenum metal is from about 1: 2 to about 2: 1〇

[0356] 实施方案#82是实施方案#80的方法,其中锡与钼的摩尔比为约2 : 3-约3 : 2。 [0356] Embodiment # 82 # The method of embodiment 80, wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2.

[0357] 实施方案#83是实施方案#79的方法,其中锡与钼的的重量比为约5 : 4-约4 : 5〇 [0357] Embodiment # 83 # 79 embodiment is a process wherein the weight ratio of tin to molybdenum is from about 5: 4 to about 4: 5〇

[0358] 实施方案#84是实施方案#78的方法,其中改性的稳定化含硅载体的表面积为至少约150m2/g。 [0358] Embodiment # 84 # 78, the program is implemented, the surface area of ​​the silicon-containing carrier wherein the stabilized modification is at least about 150m2 / g.

[0359] 实施方案#85是实施方案#84的方法,其中(a)钼以催化剂重量的0. 5% -5%的量存在;(b)锡以至少0. 5-5%的量存在。 [0359] Embodiment # 85 # The method of embodiment 84, wherein (a) molybdenum in an amount of 0.5% to 5% by weight of the catalyst; (b) tin in an amount of at least 0.5% by 5-5 .

[0360] 实施方案#86是实施方案#84的方法,其中改性的稳定化含娃载体包含至少约1 重量% -约10重量%的娃酸隹丐。 [0360] Embodiment # 86 # scheme is a method of embodiment 84, wherein the modified aqueous stabilized baby carrier comprises at least about 1 wt% - about 10 wt% of the baby acid Zhui hack.

[0361] 实施方案#87是实施方案#84的方法,其中锡与钼的摩尔比为约1 : 2-约2 : 1。 [0361] Embodiment # 87 # scheme is a method of embodiment 84, wherein the molar ratio of tin to molybdenum is from about 1: 2 to about 2: 1.

[0362] 实施方案#88是实施方案#84的方法,其中锡与钼的摩尔比为约2 : 3-约3 : 2。 [0362] Embodiment # 88 # The method of embodiment 84, wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2.

[0363] 实施方案#89是实施方案#84的方法,其中锡与钼的的重量比为约5 : 4-约4 : 5〇 [0363] Embodiment 89 is the method of embodiment # 84 # embodiments, wherein the weight ratio of tin to molybdenum is from about 5: 4 to about 4: 5〇

[0364] 实施方案#90是实施方案#87的方法,其中改性的稳定化含硅载体的表面积为至少约200m2/g。 [0364] Embodiment # 90 # 87 is a process embodiment, the surface area of ​​the stabilized silicaceous support modified which is at least about 200m2 / g.

[0365] 实施方案#91是实施方案#90的方法,其中锡与钼的摩尔比为约9 : 10-约10 : 9〇 [0365] Embodiment # 91 # 90 is a process embodiment, the molar ratio of tin to molybdenum is from about 9: 10 to about 10: 9〇

[0366] 实施方案#92是实施方案#90的方法,其中锡与钼的摩尔比为约2 : 3-约3 : 2。 [0366] Embodiment # 92 # scheme is a method of embodiment 90, wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2.

[0367] 实施方案#93是实施方案#90的方法,其中锡与钼的摩尔比为约5 : 4-约4 : 5。 [0367] Embodiment # 93 # scheme is a method of embodiment 90, wherein the molar ratio of tin to molybdenum is from about 5: 4 to about 4: 5.

[0368] 实施方案#94是实施方案#90的方法,其中改性的稳定化含娃载体的表面积为至少约250m2/g。 [0368] Embodiment # 94 # 90 embodiment is a method of stabilizing a surface area wherein the modified vector containing the baby is at least about 250m2 / g.

[0369] 实施方案#95是实施方案#78的方法,该方法在约250°C _300°C的温度下进行,其中(a)改性的稳定化含硅载体的表面积为至少约250m2/g ; (b)钼以至少约0. 75重量%的量存在于加氢催化剂中;(c)锡与钼的摩尔比为约5 : 4-约4 : 5 ;(d)改性的稳定化含硅载体包含至少约2. 5重量% -约10重量%的娃酸隹丐。 [0369] Embodiment # 78, the embodiment 95 is the program #, the process is carried out at a temperature of about 250 ° C _300 ° C, wherein the surface area (a) modified stabilized silicaceous support is at least about 250m2 / g ; (b) in an amount of molybdenum of at least about 0.75% by weight in the presence of a hydrogenation catalyst; molar ratio of (c) tin and molybdenum is from about 5: 4 to about 4: 5; (d) the modified stabilized silicon-containing carrier comprises at least about 2.5 wt% - about 10 wt% of the baby acid Zhui hack.

[0370] 实施方案#96是实施方案#95的方法,其中存在的钼的量为至少1重量%。 [0370] Embodiment # 96 # scheme is a method of embodiment 95, wherein the amount of molybdenum present is at least 1% by weight.

[0371] 实施方案#97是实施方案#78的方法,该方法在约250°C _300°C的温度下进行, 其中(a)改性的稳定化含硅载体的表面积为至少约100g/m;(b)其中锡与钼的摩尔比为约2 : 3-约3 : 2 ; (c)改性的稳定化含硅载体包含至少约2. 5重量% -约10重量%的硅酸钙。 [0371] Embodiment # 97 is a embodiment # 78, the process is carried out at a temperature of about 250 ° C _300 ° C, wherein the surface area (a) modified stabilized silicaceous support is at least about 100g / m ; (b) wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2; (c) modified stabilized silicaceous support comprises at least about 2.5 wt% - about 10% by weight of calcium silicate .

[0372] 实施方案#98是实施方案#97的方法,其中存在的钼的量为至少0. 75重量%。 [0372] Embodiment # 98 # The method of embodiment 97, wherein the amount of molybdenum present is at least 0.75% by weight.

[0373] 实施方案#99是实施方案#98的方法,其中催化剂占据反应器体积,并且在气相中以至少约lOOOhf 1的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 [0373] Embodiment # 99 # 98 are embodiments of a method, wherein the volume of the reactor occupied by the catalyst, and in the gas phase reactor lOOOhf of at least about 1 volume space velocity of the gaseous stream comprising hydrogen and acetic acid through the .

[0374] 实施方案#100是实施方案#98的方法,其中催化剂占据反应器体积,并且在气相中以至少约2500h r4的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 [0374] Embodiment # 100 # 98 are embodiments of a method, wherein the volume of the reactor occupied by the catalyst, and at a space velocity of at least about 2500h r4 of the gaseous stream comprising hydrogen and acetic acid through the reactor in a gas phase volume .

[0375] 实施方案#101是实施方案#100的方法,其中控制钼和锡的量和氧化态,以及钼与锡的比率和改性的稳定化含硅载体的组成使得所转化乙酸的至少90%转化为乙醇,小于2%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯和乙烯及其混合物的化合物以外的化合物。 [0375] Embodiment # 101 # 100 of method embodiments, wherein the composition of molybdenum and the control amounts and oxidation states of tin, silicon and stabilized carrier and the ratio of molybdenum and tin modified so that acetic acid conversion is at least 90 % conversion to ethanol, acetic acid less than 2% conversion of compounds other than the compounds selected from ethanol, acetaldehyde, ethyl acetate, and mixtures of ethylene and.

[0376] 实施方案#102是实施方案#98的方法,其中催化剂占据反应器体积,并且在气相中以至少约SOOOhf 1的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 [0376] Embodiment # 102 is a program of a method embodiment # 98, wherein the volume of the reactor occupied by the catalyst, and the gas phase in a reactor volume of at least about 1 SOOOhf space velocity of the gaseous stream comprising hydrogen and acetic acid through the .

[0377] 实施方案#103是实施方案#79的方法,其中控制钼和锡的量和氧化态,以及钼与锡的比率和改性的稳定化含硅载体的组成使得:使所转化乙酸的至少90%转化为乙醇,小于2%的乙酸转化为烷烃。 [0377] Embodiment # 103 # 79 embodiment is a process, wherein molybdenum and composition control oxidation states and amounts of tin, silicon and stabilized carrier and the ratio of molybdenum and tin modified such that: the conversion of acetic acid to make at least 90% conversion to ethanol, acetic acid less than 2% conversion of alkanes.

[0378] 实施方案#104是实施方案#79的方法,该方法在约250°C _300°C的温度下进行, 其中(a)其中控制钼和锡的量和氧化态,以及钼与锡的比率和改性的稳定化含硅载体的酸度使得所转化乙酸的至少90%转化为乙醇,小于1%的乙酸转化为烷烃;(b)改性的稳定化含硅载体的表面积为至少约200m 2/g ; (c)锡与钼的摩尔比为约5 : 4-约4 : 5 ; (d)改性的稳定化含硅载体包含至少约2. 5重量% -约10重量%的硅酸钙。 [0378] Embodiment # 104 embodiment # 79 embodiment, the process is carried out at a temperature of about 250 ° C _300 ° C, wherein (a) wherein the control molybdenum and tin amounts and oxidation states, as well as molybdenum and tin ratio and the acidity stabilized silicaceous support modified such that at least 90% conversion of acetic acid is converted to ethanol, acetic acid less than 1% is converted to alkanes; Surface area (b) modified stabilized silicaceous support is at least about 200m 2 / g; (c) molar ratio of tin to molybdenum is from about 5: 4 to about 4: 5; (d) the modified stabilized silicaceous support comprises at least about 2.5 wt% - about 10 wt% of silicon calcium.

[0379] 实施方案#105是通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C _300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂基本上由如下构成:以约〇. 1 % -约10重量%的量的选自Fe、 Co、Cu、Ni、Ru、Rh、Pd、Ir、Pt、Sn、Re、Os、Ti、Zn、Cr、Mo 和W 以及它们的混合物的催化金属;和在合适载体上分散的任选促进剂,其中控制催化金属的量和氧化态,载体和任选促进剂的组成以及反应条件使得:(i)使所转化乙酸的至少80%转化为乙醇;(ii)小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯、二乙醚及其混合物的化合物以外的化合物; 并且当在2atm的压力、275°C的温度和25001^ 1的GHSV下暴露于摩尔比为10 : 1的乙酸和氢气的蒸气状的混合物500小时的时间段时,该催化剂活性下降小于10%。 [0379] Embodiment # 105 is a process for producing ethanol by acid reduction, the method comprising in the gas phase of at least about 4: 1 molar ratio of hydrogen to acetic acid 1 at a temperature of about 225 ° C _300 ° C so that contains hydrogen and acetic acid gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst consisting essentially of: square of about 1% - about 10 wt% of an amount selected from Fe, Co, Cu, Ni, Ru, Rh, Pd , catalytic metals Ir, Pt, Sn, Re, Os, Ti, Zn, Cr, Mo and W and mixtures thereof; and dispersed on a suitable carrier optionally promoters, wherein the control amount of the catalytic metal and oxidation states, and the reaction conditions and the composition of the carrier accelerator such optionally: (i) the conversion of acetic acid is converted to ethanol at least 80%; (ii) less than 4% of acetic acid is converted to other selected from ethanol, acetaldehyde, ethyl acetate, vinyl compounds other than those, diethyl ether and mixtures thereof; at a pressure of 2atm and when the temperature of 275 ° C and a GHSV of 25001 ^ 1 is exposed to a molar ratio of 10: 1 mixture of acetic acid and hydrogen vaporous 500 when hour period, the catalyst activity decreased less than 10%.

[0380] 实施方案#106是实施方案#105的方法,其中载体是用选自如下的改性剂改性的氧化物类载体:钠、钾、镁、钙、钪、钇和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0380] Embodiment # 106 # The method of embodiment 105, wherein the support is modified with a modifier selected from oxides of carriers: sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc oxide and any mixture of metasilicates and their precursors, and the foregoing.

[0381] 实施方案#107是实施方案#105的方法,其中载体是碳载体,催化金属包括钼和锡。 [0381] Embodiment # 107 # is the embodiment of a method embodiment 105, wherein the support is a carbon support, the catalytic metals include molybdenum and tin.

[0382] 实施方案#108是实施方案#107的方法,其中碳载体用可还原的金属氧化物改性。 [0382] Embodiment # 108 # is the method of embodiment 107 embodiment, wherein the metal oxide modifying the carbon support with a reducible.

[0383] 实施方案#109是通过将乙酸加氢生产乙醇的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C _300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂基本上由在氧化物类载体上分散的金属组分构成,所述加氢催化剂具有如下组成: [0383] Embodiment # 109 is a process for producing ethanol by hydrogenating acetic acid, the process comprising the gas phase of at least about 4: 1 of hydrogen to acetic acid molar ratio at a temperature from about 225 ° C _300 ° C comprising hydrogen acetic acid and a gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst consists essentially of a dispersion of oxide based on the carrier metal component, a hydrogenation catalyst has the following composition:

[0384] PtvPdwRexSnyAlzCa pSiqOr, [0384] PtvPdwRexSnyAlzCa pSiqOr,

[0385] 其中v和y为3 : 2-2 : 3 ;w和X为1 : 3-1 : 5,其中控制p和Z以及存在的铝原子和钙原子的相对位置使得存在于其表面的布朗斯台德酸位通过硅酸钙进行平衡;对P和q进行选择使得P : q为1 : 20-1 : 200,其中r的选择满足化合价要求,并且v和w 的选择使得: [0385] wherein v and y is 3: 2-2: 3; w and X 1: 3-1: 5, wherein p and Z and controls the relative positions of the aluminum and calcium atoms present in the surface thereof so that the presence of Bronsted acid sites by calcium balance; the P-P and q are selected such that: q is 1: 20-1: 200, with r being selected to satisfy valence requirements, v and w and selected such that:

[0386] 0.005 < imz') <〇,〇5 q ο [0386] 0.005 <imz ') <square, 〇5 q ο

[0387] 实施方案#110是实施方案#109的方法,其中加氢催化剂具有至少约100m2/g的表面积,并且其中控制Z和P使得P > Z。 [0387] Embodiment # 110 # The method of embodiment 109, wherein the hydrogenation catalyst has a surface area of ​​at least about 100m2 g /, and wherein the control Z and P such that P> Z.

[0388] 实施方案#111是实施方案#110的方法,其中考虑到存在的任何较少的杂质,对p 进行选择以确保载体表面基本上不含布朗斯台德酸位。 [0388] Embodiment # 111 is a process scheme of embodiment # 110, taking into account any minor impurities present, p is selected to ensure that the surface of the support is substantially free from Bronsted acid sites.

[0389] 实施方案#112是将乙酸加氢的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂, 该加氢催化剂基本上由如下构成:以约〇. 1% -约10重量%的量的选自Fe、Co、Cu、Ni、Ru、 Rh、Pd、Ir、Pt、Sn、Re、Os、Ti、Zn、Cr、Mo和W以及它们的混合物的催化金属;和在合适载体上分散的任选促进剂,其中控制催化金属的量和氧化态,载体和任选促进剂的组成以及反应条件使得小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯、二乙醚及其混合物的化合物以外的化合物;并且当在2atm的压力、275°C的温度和25001^ 1的GHSV下暴露于摩尔比为10 : 1的乙酸和氢气的蒸气状的混合物500小时的时间段时,该催化剂活性下降小于10%,其它条件是:(i)其中所述载体是用选自如下的改性剂改性的氧化 [0389] Embodiment # 112 is a process for hydrogenating acetic acid, the method comprising in the gas phase of at least about 4: 1 of hydrogen to acetic acid molar ratio at a temperature from about 225 ° C -300 ° C and acetic acid containing hydrogen the gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst consisting essentially of: square of about 1% - about 10 wt%, an amount selected from Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, catalytic metal Pt, Sn, Re, Os, Ti, Zn, Cr, Mo and W and mixtures thereof; and dispersed on a suitable carrier optionally promoters, wherein the control amount of the catalytic metal and the oxidation state of the carrier and optionally the composition and the reaction conditions such that the accelerator is less than 4% of acetic acid is converted to compounds other than the compounds selected from ethanol, acetaldehyde, ethyl acetate, ethylene, diethyl ether and mixtures thereof; and when the pressure 2atm, exposed to a molar ratio at a temperature of 275 ° C for GHSV and 25 001 ^ 1 to 10: vaporous acetic acid and hydrogen in a period of time a mixture of 500 hours, the catalyst activity decreased less than 10%, other conditions that: (i ) oxide modified with a modifier, wherein said support is selected from 类载体:钠、 钾、镁、钙、钪、钇和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物;(ii)所述载体是碳载体,并且催化金属包括钼和锡或(iii)所述载体是用可还原的金属氧化物改性的碳载体。 Based carrier: sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc oxides and metasilicates and any mixture thereof and precursors of the foregoing; (ii) the support is a carbon support, and the catalytic metal comprises molybdenum and tin, or (iii) the carrier is a metal oxide reducible modified carbon support.

[0390] 实施方案#113是将链烷酸加氢的方法,该方法包括在气相中以至少约2 : 1的氢气与链烷酸的摩尔比在约125°C -350°C的温度下使包含氢气和链烷酸的气态料流穿过加氢催化剂,该加氢催化剂包含:在选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属;和选自锡、铼及其混合物的促进剂,其中含硅载体任选用促进剂促进,促进剂选自:(a)催化剂重量的1-5%的量的选自碱金属、碱土元素和锌的促进剂;(b)催化剂重量的1-50 %的量的选自W03、Mo03、Fe203和Cr 203的氧化还原型促进剂;以及(〇)催化剂重量的1-50%量的选自1102、21<) 2、他205、了&205和41 203的酸性改性剂。 [0390] Embodiment # 113 is a process of hydrogenation of alkanoic acids, the method comprising in the vapor phase at least about 2: molar ratio of hydrogen to an alkanoic acid at a temperature of about 125 ° C -350 ° C in the gaseous hydrogen and an alkanoic acid containing stream through the hydrogenation catalyst, the hydrogenation catalyst comprises: in selected from silica, silica, calcium metasilicate and calcium metasilicate on silicon-containing support promoted is selected from molybdenum, palladium, and mixtures of the metals molybdenum; and selected from tin, rhenium promoters and mixtures thereof, wherein any one of silicon-containing carrier selection accelerating agent, promoter is selected from: (a) weight of the catalyst 1- an amount of 5% of a metal selected from alkali, alkaline earth elements and zinc promoter; (b) an amount of 1-50% by weight of a catalyst selected from the group W03, Mo03, Fe203 and Cr oxide 203 is reduced promoter; and ( 1-50% by weight of the catalyst of the square) selected 1102,21 <) 2, he 205, 205 and the & acidic modifier of 41,203.

[0391] 实施方案#114是实施方案#113的方法,其中所述链烷酸是乙酸,并且其中(a)钼和钯中的至少一种以催化剂重量的0. 25% -5%的量存在;(b)存在的钼和钯的总量为催化剂重量的至少0. 5% ;以及(c)存在的铼和锡的总量为至少0. 5-10重量%。 [0391] Embodiment # 114 is a process of embodiment # 113, wherein the alkanoic acid is acetic acid, and wherein an amount of 0.25% -5% by weight of at least one of the catalyst (a) of molybdenum, and palladium present; the total amount of (b) the presence of molybdenum and palladium catalyst is at least 0.5% by weight; and the total amount of rhenium and tin presence (c) of at least 0.5 to 10 wt%.

[0392] 实施方案#115是实施方案#114的方法,其中含硅载体的表面积为至少约150m2/ g° [0392] Embodiment # 115 # is the embodiment of a method embodiment 114, wherein the silicon-containing surface area of ​​the carrier is at least about 150m2 / g °

[0393] 实施方案#116是实施方案#115的方法,其中控制(a)钼族金属、铼和锡促进剂的量和氧化态,以及(b)钼族金属与存在的铼和锡的总摩尔数的摩尔比;以及(c)含硅载体上的布朗斯台德酸位的数目使得所转化乙酸的至少80%转化为选自乙醇和乙酸乙酯的化合物,并同时使小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯及其混合物的化合物以外的化合物。 [0393] Embodiment # 116 is a process of embodiment # 115, the total of which controls (a) a molybdenum group metal, rhenium and tin promoter amounts and oxidation states, and (b) molybdenum metal and the presence of rhenium and tin molar ratio of moles; and Bronsted acid sites on a number of (c) a silicon-containing carrier such as acetic acid conversion of at least 80% conversion to a compound selected from ethanol and ethyl acetate, and while less than 4% acid is converted to the compound is selected from compounds other than ethanol, acetaldehyde, ethyl acetate, ethylene and mixtures thereof.

[0394] 实施方案#117是实施方案#115的方法,其中(a)钼和钯中的至少一种以催化剂重量的0. 5% -5%的量存在;(b)存在的钼和钯的总量为催化剂重量的至少0. 75% -5% ; 以及(c)存在的锡和铼的总量为催化剂重量的至少1.0%。 [0394] Embodiment # 117 # 115 is a process embodiments, wherein the at least one in an amount of 0.5% to 5% by weight of the catalyst in the presence of (a) molybdenum and palladium; (b) the presence of molybdenum and palladium the total amount of at least 0.75% to 5% by weight of the catalyst; and (c) the total amount of rhenium and tin is present at least 1.0% by weight of the catalyst.

[0395] 实施方案#118是实施方案#117的方法,其中(a)控制(i)钼族金属、(ii)铼和锡促进剂的量和氧化态,以及(iii)钼族金属与铼和锡促进剂的比率;和(iv)含硅载体的酸度使得所转化乙酸的至少80%转化为乙醇,小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯及其混合物的化合物以外的化合物。 [0395] Embodiment # 118 is a process of embodiment # 117, wherein (a) control (i) molybdenum metal, (ii) rhenium and tin promoter amounts and oxidation states, and (iii) a molybdenum group metal and rhenium and the ratio of tin promoter; and (iv) a silicon-containing carrier such that the acidity of the converted acetic acid is converted to ethanol at least 80%, less than 4% of acetic acid is converted to other selected from ethanol, acetaldehyde, ethyl acetate, ethylene and compound other than the compound mixture.

[0396] 实施方案#119是实施方案#118的方法,其中存在的铼和锡的总重量为催化剂重量的约1-10%。 [0396] Embodiment # 119 # is the embodiment of a method embodiment 118, wherein the total weight of rhenium and tin are present in about 1 to 10% by weight of the catalyst.

[0397] 实施方案#120是实施方案#119的方法,其中钼族金属与铼和锡的总摩尔数的摩尔比为约1 : 2-约2 : 1。 [0397] Embodiment # 120 # 119 is a process embodiments, wherein the molar ratio of the molybdenum metal and the total number of moles of rhenium and tin is about 1: 2 to about 2: 1.

[0398] 实施方案#121是将乙酸加氢的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂, 所述加氢催化剂基本上由分散在氧化物类载体上的金属组分构成,所述加氢催化剂具有如下组成: [0398] Embodiment # 121 acetic acid is hydrogenated, which comprises a gas phase of at least about 4: 1 of hydrogen to acetic acid molar ratio at a temperature from about 225 ° C -300 ° C and acetic acid containing hydrogen the gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst consists essentially of a metal component dispersed on oxidic support, said hydrogenation catalyst has the following composition:

[0399] PtvPdwRexSnyCapSi qOr, [0399] PtvPdwRexSnyCapSi qOr,

[0400] 其中v : y之比为3 : 2-2 : 3 ;w : X之比为1 : 3-1 : 5,对p和q进行选择使得P : q为1 : 20-1 : 200,其中r的选择满足化合价要求,并且¥和《的选择使得: [0401 ] 0-005 < 翌^之<0,05 ο [0400] wherein v: the ratio of y is 3: 2-2: 3; w: X ratio is 1: 3-1: 5, p and q are selected such that the P: q is 1: 20-1: 200 wherein r is selected to satisfy valence requirements, and selection and ¥ "such that: [0401] 0-005 <Yi ^ of <0,05 ο

[0402] 实施方案#122是实施方案#121的方法,其中对工艺条件以及V、W、 X、y、p、q和r 的值进行选择以使所转化乙酸的至少90%转化为选自乙醇和乙酸乙酯的化合物,并同时小于4%的乙酸转化为烷烃。 [0402] Embodiment # 122 # 121 of method embodiments, wherein the process conditions, and V, W, X,, p values ​​of y, q and r are chosen such that the conversion of acetic acid is at least 90% conversion to selected acid compound ethanol and ethyl acetate, while less than 4% is converted to alkanes.

[0403] 实施方案#123是实施方案的方法#122,其中对工艺条件以及V、w、X、y、p、q和r 的值进行选择以使所转化乙酸的至少90%转化为乙醇,小于2%的乙酸转化为烷烃。 [0403] Embodiment # 123 is a process embodiment # 122, wherein the process conditions, and V, w,, p values ​​X, y, q and r are chosen such that the acetic acid conversion of at least 90% conversion to ethanol, less than 2% of acetic acid is converted to alkanes.

[0404] 实施方案#124是实施方案#122的方法,其中考虑到存在的任何较少的杂质,对p 进行选择以确保载体表面呈基本上碱性。 [0404] Embodiment # 124 # The method of embodiment 122, wherein taking into account any minor impurities present, p is selected to ensure that the surface of the support in a substantially basic.

[0405] 实施方案#125是将乙酸加氢的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂, 所述加氢催化剂基本上由分散在氧化物类载体上的金属组分构成,所述加氢催化剂具有如下组成: [0405] Embodiment # 125 acetic acid is hydrogenated, which comprises a gas phase of at least about 4: 1 of hydrogen to acetic acid molar ratio at a temperature from about 225 ° C -300 ° C and acetic acid containing hydrogen the gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst consists essentially of a metal component dispersed on oxidic support, said hydrogenation catalyst has the following composition:

[0406] PtvPdwRexSnyAlzCa pSiqOr, [0406] PtvPdwRexSnyAlzCa pSiqOr,

[0407] 其中v和y为3 : 2-2 : 3 ;w和X为1 : 3-1 : 5,其中控制p和z以及存在的铝原子和钙原子的相对位置使得存在于其表面的布朗斯台德酸位通过硅酸钙进行平衡;对P和q进行选择使得P : q为1 : 20-1 : 200,其中r的选择满足化合价要求,并且v和w 的选择使得: [0407] wherein v and y is 3: 2-2: 3; w and X 1: 3-1: 5, and wherein the control p z relative position of the aluminum and calcium atoms present on the surface thereof so that the presence of Bronsted acid sites by calcium balance; the P-P and q are selected such that: q is 1: 20-1: 200, with r being selected to satisfy valence requirements, v and w and selected such that:

[0408] 0.005 < .趕^土ί:翌<0.05 〇 . [0408] 0.005 <^ catch soil ί: Yi <0.05 billion

[0409] 实施方案#126是实施方案#125的方法,其中加氢催化剂具有至少约100m2/g的表面积,并且其中控制Z和P使得P > Z。 [0409] Embodiment # 126 is a process of embodiment # 125, wherein the hydrogenation catalyst has a surface area of ​​at least about 100m2 g /, and wherein the control Z and P such that P> Z.

[0410] 实施方案#127是实施方案#125的方法,其中考虑到存在的任何较少的杂质,对p 进行选择以确保载体表面基本上不含布朗斯台德酸位。 [0410] Embodiment # 127 is a process scheme of embodiment # 125, taking into account any minor impurities present, p is selected to ensure that the surface of the support is substantially free from Bronsted acid sites.

[0411] 实施方案#128是将链烷酸加氢的方法,该方法包括在气相中以至少约5 : 1的氢气与链烷酸的摩尔比在约125°C _350°C的温度下以至少约lOOOhf1的GHSV在至少2atm的压力下使包含氢气和链烷酸的气态料流穿过加氢催化剂,该加氢催化剂包含:(a)在选自二氧化硅、偏硅酸钙和偏硅酸钙促进的二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属;和(b)选自锡、铼及其混合物的金属促进剂,(c)任选用第二促进剂促进的含硅载体,所述第二促进剂选自:(i)催化剂重量的1-5%的量的选自碱金属、碱土元素和锌的给体促进剂;(ii)催化剂重量的1-50%的量的选自W0 3、M〇03、Fe203和Cr20 3的氧化还原型促进剂;(iii)催化剂重量的1-50%量的选自Ti02、Zr02、Nb 205、Ta205和A120 3的酸性改性齐U ;以及(iv) i、ii和iii的组合。 [0411] 128 is a method of alkanoic acids # hydrogenated embodiments, the method comprises at least about 5 in the gas phase: the molar ratio of hydrogen to alkanoic acid to 1 at a temperature of about 125 ° C _350 ° C of at least about lOOOhf1 gaseous stream comprising hydrogen and a GHSV make alkanoic acid at a pressure of at least 2atm through the hydrogenation catalyst, the hydrogenation catalyst comprising: (a) selected from silica, calcium metasilicate and partial molybdenum metal is selected from molybdenum, palladium, and mixtures of calcium to promote the silicon-containing silica support; and (b) selected from tin, rhenium metal promoter and mixtures thereof, (c) optionally a second silicon-containing carrier of the accelerating agent, the second promoter is selected from: (i) an amount of a promoting agent 1-5% of the weight of the catalyst selected from alkali metal, alkaline earth elements and zinc; (ii) an amount of 1-50% by weight of the catalyst is selected from W0 3, M〇03, Fe203 oxide Cr20 3 further reduced accelerators; (III) 1-50% by weight of the amount of catalyst selected from Ti02, Zr02, Nb 205 , Ta205 acid modified homogeneous and A120 3 U; and combinations of (iv) i, ii and iii of.

[0412] 实施方案#129是实施方案#128的方法,其中所述链烷酸是乙酸,并且其中(a)钼(如果存在)以催化剂重量的0.5%-5%的量存在;(b)钯(如果存在)以催化剂重量的0.5 %-5 %的量存在;以及(c)金属促进剂以至少0.5-10 %的量存在。 [0412] Embodiment # 129 is a process of embodiment # 128, wherein the alkanoic acid is acetic acid, and wherein (a) molybdenum (if present) in an amount of 0.5% to 5% of the weight of the catalyst; (b) palladium (if present) in an amount of 0.5% to 5% by weight of the catalyst; and (c) in an amount of metal promoter present in at least 0.5 to 10%.

[0413] 实施方案#130是实施方案#129的方法,其中含硅载体的表面积为至少约150m2/ g° [0413] Embodiment # 130 # 129 is a process embodiment, the silicon-containing carrier wherein the surface area is at least about 150m2 / g °

[0414] 实施方案#131是实施方案#130的方法,其中(a)钼以催化剂重量的1% -5%的量存在;(b)钯(如果存在)以催化剂重量的0. 25% -5 %的量存在;以及(c)存在的钼和钯的总量为催化剂重量的至少1. 25%。 [0414] Embodiment # 131 # 130 embodiment is a process, wherein (a) molybdenum in an amount of 1% to 5% by weight of the catalyst; (b) palladium (if present) 0.25% by weight of the catalyst - is present in an amount of 5%; and (c) the total amount of molybdenum and palladium presence of at least 1.25% by weight of the catalyst.

[0415] 实施方案#132是实施方案#131的方法,其中锡以催化剂重量1-3%的量存在。 [0415] Embodiment # 132 # 131 of the embodiment is a method, wherein the tin catalyst in an amount of 1-3% by weight.

[0416] 实施方案#133是实施方案的方法#132,其中锡与钼族金属的摩尔比为约1 : 2-约2 : 1。 [0416] Embodiment # 133 # 132 embodiment of the process, wherein the molar ratio of tin to molybdenum metal is from about 1: 2 to about 2: 1.

[0417] 实施方案#134是实施方案#132的方法,其中锡与钼的摩尔比为约5 : 4-约4 : 5〇 [0417] Embodiment # 134 # The method of embodiment 132, wherein the molar ratio of tin to molybdenum is from about 5: 4 to about 4: 5〇

[0418] 实施方案#135是实施方案#132的方法,其中含娃载体基本上不含未被偏娃酸隹丐抵消的布朗斯台德酸位,并且其表面积为至少约200m 2/g。 [0418] Embodiment # 135 # is the embodiment of a method embodiment 132, wherein the carrier is substantially free of non-containing vinylidene baby doll Bronsted acid sites Hack offset short-tailed acid, and a surface area of ​​at least about 200m 2 / g.

[0419] 实施方案#136是实施方案的方法#132,其中锡与钼族金属的重量比为约2 : 3-约3 : 2。 [0419] Embodiment # 136 # 132 embodiment of the method, the weight of tin and molybdenum group metal ratio of about 2: 3 to about 3: 2.

[0420] 实施方案#137是实施方案#128的方法,其中锡与钼的摩尔比为约2 : 3-约3 : 2〇 [0420] Embodiment # 137 # 128 of the embodiment is a method, wherein the molar ratio of tin to molybdenum is from about 2: 3 to about 3: 2〇

[0421] 实施方案#138是将乙酸加氢的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂, 该加氢催化剂基本上由如下构成:以约〇. 1% -约10重量%的量的选自Fe、Co、Cu、Ni、Ru、 Rh、Pd、Ir、Pt、Sn、Os、Ti、Zn、Cr、Mo和W以及它们的混合物的催化金属;和在合适载体上分散的任选促进剂,其中控制催化金属的量和氧化态,载体和任选促进剂的组成以及反应条件使得小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯、二乙醚及其混合物的化合物以外的化合物;并且当在2atm的压力、275°C的温度和2500111^ 1的GHSV下暴露于摩尔比为10 : 1的乙酸和氢气的蒸气状的混合物500小时的时间段时,该催化剂活性下降小于10%。 [0421] Embodiment # 138 acetic acid is hydrogenated, which comprises a gas phase of at least about 4: 1 molar ratio of hydrogen to acetic acid at a temperature of about 225 ° C -300 ° C comprising hydrogen and acetic acid to make the the gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst consisting essentially of: square of about 1% - about 10 wt%, an amount selected from Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, catalytic metal Pt, Sn, Os, Ti, Zn, Cr, Mo and W and mixtures thereof; and dispersed on a suitable carrier optionally promoters, wherein the control amount of the catalytic metal and the oxidation state, and any carrier composition and the reaction conditions selected such that the accelerator is less than 4% of acetic acid is converted to the compound is selected from compounds other than ethanol, acetaldehyde, ethyl acetate, ethylene, diethyl ether and mixtures thereof; and when the pressure 2atm, 275 ° exposure to a temperature of molar ratio of C 1 GHSV and 2,500,111 is ^ 10: vaporous acetic acid and hydrogen mixture of a period of 500 hours, the catalyst activity decreased less than 10%.

[0422] 实施方案#139是实施方案#138的方法,其中载体选自:分子筛载体;用改性剂改性的改性含硅载体,所述改性剂选自钠、钾、镁、钙、钪、钇和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物,以及碳载体。 [0422] Embodiment # 139 # 138 of the embodiment is a method, wherein the carrier is selected from: molecular sieve support; one modified with a modifying agent siliceous support, the modifier is selected from sodium, potassium, magnesium, calcium , scandium, yttrium, and zinc oxides and metasilicates and any mixture thereof and precursors of the foregoing, and the carbon support.

[0423] 实施方案#140是实施方案#139的方法,其中催化金属包括钼和锡,并且对二乙醚的选择性高于80%。 [0423] Embodiment # 140 # 139 is a process embodiment wherein the catalytic metal comprises molybdenum and tin, and the selectivity to diethyl ether higher than 80%.

[0424] 实施方案#141是实施方案#107的方法,其中载体是沸石载体,并且对二乙醚的选择性高于90%。 [0424] Embodiment # 141 of embodiment # 107 embodiment, wherein the carrier is a zeolite support, and the selectivity to diethyl ether higher than 90%.

[0425] 实施方案#142是通过将乙酸还原生产乙醇和乙酸乙酯的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C_300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂包含:(a)在选自二氧化硅和用至多约7. 5偏硅酸钙促进的二氧化硅的含硅载体上的选自钼以及钼和钯的混合物的钼族金属,存在的钼族金属的量为至少约2. 0%,存在的钼的量为至少约1. 5% ;和(b)催化剂重量的约1% -2%的量的选自铼和锡的金属促进剂,钼与金属促进剂的摩尔比为约3 : 1-1 : 2 ;(c)任选用第二促进剂促进的含硅载体,所述第二促进剂选自(i)催化剂重量的1-5%的量的选自碱金属、碱土元素和锌的给体促进剂;(ii)催化剂重量的1-50%的量的选自W0 3、M〇03、Fe203和Cr203的氧化还原型促进剂;(iii)催化剂重量的1-50%量的选自Ti02、Zr0 2、Nb205、Ta2〇dP ΑΙΑ [0425] Embodiment # 142 is a process for the production of ethanol and ethyl acetate by reduction, the method comprising in the gas phase of at least about 4: 1 molar ratio of hydrogen to acetic acid is at a temperature from about 225 ° C_300 ° C of the gaseous stream comprising hydrogen and acetic acid through hydrogenation catalyst, the hydrogenation catalyst comprising: (a) a support selected from silica and silicon-calcium metasilicate promoted silica up to about 7.5 in of molybdenum metal selected from molybdenum and molybdenum and mixtures palladium, molybdenum metal is present in an amount of at least about 2.0%, molybdenum is present in an amount of at least about 1.5%; and (b) weight of the catalyst molar ratio of an amount of from about 1% to 2% of a metal selected from rhenium and tin promoter, and molybdenum promoter metal is from about 3: 1-1: 2; (c) optionally a second accelerating agent containing silicon carrier, the second promoter is selected from (i) a catalytic amount of 1-5% by weight selected from alkali metal, alkaline earth elements and zinc to promoting agent; (ii) 1-50% by weight of the catalyst selected amount of W0 3, M〇03, Fe203 and Cr203 of redox promoters; (iii) 1-50% by weight of the amount of catalyst selected from Ti02, Zr0 2, Nb205, Ta2〇dP ΑΙΑ 酸性改性剂;以及(iv) i、ii和iii的组合。 Acidic modifier; and a composition (iv) i, ii and iii of.

[0426] 实施方案#143是实施方案#142的方法,其中金属促进剂与钼族金属的摩尔比为约2 : 3-约3 : 2。 [0426] Embodiment # 143 of embodiment # 142 embodiment, wherein the molar ratio of the metal and the molybdenum promoter metal is from about 2: 3 to about 3: 2.

[0427] 实施方案#144是实施方案#142的方法,其中金属促进剂与钼族金属的摩尔比为约5 : 4-约4 : 5。 [0427] Embodiment # 144 of embodiment # 142 embodiment, wherein the molar ratio of the metal and the molybdenum promoter metal is from about 5: 4 to about 4: 5.

[0428] 实施方案#145是实施方案#142的方法,其中含硅载体的表面积为至少约200m2/ g,并且偏硅酸钙的量足以使含硅载体的表面基本上无布朗斯台德酸度。 [0428] Embodiment # 145 # The method of embodiment 142, wherein the surface area of ​​the silicon-containing support is at least about 200m2 / g, and the amount of calcium metasilicate sufficient to support substantially free surface of the silicon-containing Bronsted acidity .

[0429] 实施方案#146是实施方案#145的方法,其中金属促进剂与钼族金属的摩尔比为约2 : 3-约3 : 2。 [0429] Embodiment # 146 # is the method of embodiment 145 embodiment, wherein the molar ratio of the metal and the molybdenum promoter metal is from about 2: 3 to about 3: 2.

[0430] 实施方案#147是实施方案#146的方法,其中含硅载体的表面积为至少约200m2/ g,并且存在于其表面上的布朗斯台德酸位的摩尔数不大于存在于Saint-Gobain NorPro SS61138二氧化硅表面上的布朗斯台德酸位的摩尔数。 [0430] Embodiment # 147 # 146 is a process embodiment, the silicon-containing carrier wherein the surface area is at least about 200m2 / g, and the number of moles thereof present Bronsted acid sites on the surface is not greater than exist in Saint- moles of Bronsted acid site on the surface of silica gobain NorPro SS61138.

[0431] 实施方案#148是实施方案#142的方法,其中含硅载体的表面积为至少约250m2/ g,并且存在于其表面上的布朗斯台德酸位的摩尔数不大于存在于Saint-Gobain NorPro HSA SS61138二氧化硅表面上的布朗斯台德酸位的摩尔数的一半。 [0431] Embodiment # 148 # 142 is a process embodiment, the silicon-containing carrier wherein the surface area is at least about 250m2 / g, and the number of moles thereof present Bronsted acid sites on the surface is not greater than exist in Saint- gobain NorPro HSA half Bronsted acid sites of the number of moles of silicon dioxide on the surface SS61138.

[0432] 实施方案#149是#142实施方案的方法,该方法在约250°C _300°C的温度下进行, 其中(a)加氢催化剂包含在选自二氧化硅和用至多约7. 5偏硅酸钙促进的二氧化硅的含硅载体上的钯,存在的钯的量为至少约1.5% ;和(b)金属促进剂是量为催化剂重量的约1%-10%的铼,铼与钯的摩尔比为约3 : 1-5 : 1。 [0432] Embodiment # 149 # 142 is an embodiment of the method is carried out at a temperature of about 250 ° C _300 ° C, wherein (a) comprising a hydrogenation catalyst selected from silica and used in up to about 7. palladium on a siliceous carrier 5 calcium metasilicate promoted silica, palladium is present in an amount of at least about 1.5%; and (b) an amount of metal promoter of the catalyst is from about 1% to about 10 wt% of rhenium the molar ratio of rhenium to palladium is about 3: 1-5: 1.

[0433] 实施方案#150是实施方案#142的乙酸还原的方法,其中加氢催化剂基本上由钼构成,其在基本上由用约3 -直到约7. 5%硅酸钙促进的二氧化硅构成的含硅载体上,存在的钼的量为至少约1.0%,锡促进剂以催化剂重量的约1% -5%的量,钼与锡的摩尔比为约9 : 10-10 : 9。 [0433] embodiment is the method of embodiment # 150 # 142 acetic acid reduction, wherein the hydrogenation catalyst consists essentially of molybdenum, which is essentially a by about 3 - up to about 7.5% calcium oxide promoted silicon-containing carrier composed of silicon, molybdenum present in an amount of at least about 1.0%, tin promoter in an amount of from about 1% to 5% by weight of the catalyst, the molar ratio of molybdenum to tin is from about 9: 10-10: 9 .

[0434] 实施方案#151是实施方案#142的乙酸还原的方法,其中存在的钼族金属的量为至少约2. 0%,存在的钼的量为至少约1. 5%,锡促进剂为催化剂重量的约1% -5%的量,钼与锡的摩尔比为约9 : 10-10 : 9。 [0434] Embodiment # 151 of embodiment # 142 acetic acid reduction, the amount of molybdenum group metal present therein is at least about 2.0%, molybdenum is present in an amount of at least about 1.5%, tin promoter in an amount from about 1% to 5% by weight of the catalyst, the molar ratio of molybdenum to tin is from about 9: 10-10: 9.

[0435] 实施方案#152是实施方案#151的方法,该方法在约250°C _300°C的温度下进行,其中所述加氢催化剂包含:在表面积为至少200m2/g的高表面积二氧化硅上分散的2. 5-3. 5重量%钼、2重量%-5重量%锡,所述高表面积二氧化硅用4-7. 5%偏硅酸钙促进。 [0435] Embodiment # 152 # 151 is a process embodiment, the process is carried out at a temperature of about 250 ° C _300 ° C, wherein the hydrogenation catalyst comprises: a surface area of ​​at least 200m2 / g of high surface area silica dispersed silicon 2. 5-3. 5 wt.% Mo, 2 wt.% to 5 wt% of tin, a high surface area silica with 4-7. 5% calcium metasilicate promoted.

[0436] 实施方案#153是通过将乙酸还原生产包含乙醇和至少约40%乙酸乙酯的料流的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C_300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,所述加氢催化剂基本上由在氧化物类载体上分散的金属组分构成,所述加氢催化剂具有如下组成: [0436] Embodiment # 153 is a reducing process for producing acetic acid by ethanol and a stream comprising at least about 40% ethyl acetate, the method comprising in the gas phase of at least about 4: 1 molar ratio of hydrogen to acetic acid at about 225 the lower temperature ° C_300 ° C a gaseous stream comprising hydrogen and acetic acid through hydrogenation catalyst consists essentially of a hydrogenation catalyst dispersed on a metal oxide based support component, said hydrogenation catalyst has composition:

[0437] PtvPdwRexSnyAlzTi nCapSiqOr,, [0437] PtvPdwRexSnyAlzTi nCapSiqOr ,,

[0438] 其中v和y之比为3 : 2-2 : 3 ;w和X之比为1 : 3-1 : 5,其中对p、z和p,q 和η进行选择使得: [0438] wherein y and v ratio of 3: 2-2: 3; w and X ratio of 1: 3-1: 5, in which p, z, and p, q and η are selected such that:

[0439] 0.005 <---< 0,2 g-X33r- +1^772 - [0439] 0.005 <--- <0,2 g-X33r- + 1 ^ 772 -

[0440] 其中r的选择满足化合价要求,并且v和w的选择使得: [0440] wherein r is selected to satisfy valence requirements, v and w and selected such that:

[0441] 0.005 < -二-HM· < 0,05, q^l.33n^rt,77^ 〇 [0441] 0.005 <- two -HM · <0,05, q ^ l.33n ^ rt, 77 ^ square

[0442] 实施方案#154是实施方案#153的方法,其中加氢催化剂具有至少约100m2/g的表面积。 [0442] Embodiment # 154 # is the method of embodiment 153 embodiment, wherein the hydrogenation catalyst has a surface area of ​​at least about 100m2 / g to.

[0443] 实施方案#155是将乙酸加氢的方法,该方法包括在气相中以至少约4 : 1的氢气与乙酸摩尔比在约225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂, 该加氢催化剂基本上由如下构成:以约〇. 1% -约10重量%的量的选自Fe、Co、Cu、Ni、Ru、 Rh、Pd、Ir、Pt、Sn、Os、Ti、Zn、Cr、Mo和W以及它们的混合物的催化金属;和在合适载体上分散的任选促进剂,其中控制催化金属的量和氧化态,载体和任选促进剂的组成以及反应条件使得:i)使所转化乙酸的大于50%转化为乙酸乙酯;(ii)小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯、二乙醚及其混合物的化合物以外的化合物;并且当在2atm的压力、275°C的温度和2500111^ 1的GHSV下暴露于摩尔比为10 : 1的乙酸和氢气的蒸气状的混合物500小时的时间段时,该催化剂活性下降小于10%。 [0443] Embodiment # 155 acetic acid is hydrogenated, which comprises a gas phase of at least about 4: 1 of hydrogen to acetic acid molar ratio at a temperature from about 225 ° C -300 ° C and acetic acid containing hydrogen the gaseous stream through the hydrogenation catalyst, the hydrogenation catalyst consisting essentially of: square of about 1% - about 10 wt%, an amount selected from Fe, Co, Cu, Ni, Ru, Rh, Pd, Ir, catalytic metal Pt, Sn, Os, Ti, Zn, Cr, Mo and W and mixtures thereof; and dispersed on a suitable carrier optionally promoters, wherein the control amount of the catalytic metal and the oxidation state, and any carrier composition and the reaction conditions such that the accelerator is selected from: i) the conversion of acetic acid of greater than 50% conversion to ethyl acetate; acetic acid (ii) less than 4% is converted to other selected from ethanol, acetaldehyde, ethyl acetate, ethylene, diethyl ether compound other than the compound and mixtures thereof; and when the pressure 2atm, the temperature of 275 ° C and GHSV 2,500,111 ^ 1 is exposed to a molar ratio of 10: 1 acetic acid and hydrogen vaporous mixture of 500 hours when the time period, the catalytic activity will decrease less than 10%.

[0444] 实施方案#156是将链烷酸加氢为相应的烷醇的颗粒催化剂,该颗粒催化剂包含: (a)在选自二氧化硅和用约3. 0 -直到约7. 5偏硅酸钙促进的二氧化硅的含硅载体上的选自钼、钯及其混合物的钼族金属,含硅载体的表面积为至少约150m2/g;和(b)锡促进剂,为催化剂重量的约1%-3%的量,钼与锡的摩尔比为约4 : 3-3 : 4 ;(c)对所述含硅载体的组成和结构进行选择使得其表面基本上不含未被偏硅酸钙抵消的布朗斯台德酸位。 [0444] Embodiment # 156 alkanoic acid is hydrogenated to the corresponding alkanol particulate catalyst, the catalyst particle comprises: (a) selected from silica and with from about 3.0 - 7.5 up to about partial a silicon-containing carrier is selected from molybdenum on silica-promoted calcium, molybdenum, palladium, and mixtures of metals, silicon-containing surface area of ​​the carrier is at least about 150m2 / g; and (b) tin promoter, the catalyst weight molar ratio of an amount of from about 1% to 3% molybdenum and tin is from about 4: 3-3: 4; (c) the composition and structure of the silicon-containing carrier is selected such that its surface is substantially free of non- metasilicate Bronsted acid sites offset.

[0445] 实施方案#157是实施方案#156的加氢催化剂,其中存在的钼族金属的总重量为2-4%,存在的钼的量为至少2%,钼与锡的重量比为4 : 5-5 : 4,并且存在的硅酸钙的量为3-7. 5%。 [0445] Embodiment # 157 # hydrogenation catalyst of embodiment 156, wherein the total weight of the molybdenum metal in the presence of 2-4%, the amount of molybdenum present is at least 2% by weight of molybdenum and tin is 4 : 5-5: 4, and the amount of calcium present is 3-75%.

[0446] 实施方案#158是基本上由如下构成的颗粒加氢催化剂:上面分散有选自钼、钯及其混合物的钼族金属与选自锡、钴和铼的促进剂的含硅载体,该含硅载体具有至少约175m 2/g表面积并且选自二氧化娃、偏娃酸興和偏娃酸興促进的二氧化娃(具有位于其表面上的偏硅酸钙),所述含硅载体的表面由于未被钙平衡的氧化铝而基本上不含布朗斯台德酸位。 [0446] Embodiment # 158 consisting essentially of the particulate hydrogenation catalyst is constructed as follows: The above dispersion of molybdenum metal selected from molybdenum, palladium, and mixtures thereof and selected from tin, cobalt and silicon-containing carrier rhenium promoter, the silicon-containing carrier having at least about 175m 2 / g and a surface area selected baby dioxide, dioxide partial doll baby acid and metaphosphoric acid Xing Xing promoted (calcium metasilicate having positioned on a surface thereof), the silicon support Since the surface of calcium homeostasis is not substantially free of alumina, Bronsted acid sites.

[0447] 实施方案#159是实施方案#158的加氢催化剂,其中存在的钼族金属的总重量为0.5%-2%,存在的钯的量为至少0.5%,促进剂是铼,铼与钯的重量比为10 : 1-2 : 1,并且偏硅酸钙的量为3-90%。 [0447] Embodiment # 159 # 158 of the embodiment is a hydrogenation catalyst, wherein the total weight of the molybdenum metal present is from 0.5% to 2%, the palladium is present in an amount of at least 0.5%, the promoter is rhenium, rhenium palladium weight ratio of 10: 1-2: 1, and the amount of calcium metasilicate is 3-90%.

[0448] 实施方案#160是实施方案#159的加氢催化剂,其中存在的钼族金属的总重量为0.5-2%,存在的钼的量为至少0.5%,促进剂是钴,钴与钼的重量比为20 : 1-3 : 1,并且硅酸钙的量为3-90%。 [0448] Embodiment # 160 # embodiments of the hydrogenation catalyst is 159, the total weight of the metals present therein molybdenum 0.5-2%, molybdenum is present in an amount of at least 0.5%, the promoter is cobalt, molybdenum and cobalt weight ratio of 20: 1 to 3: 1, and the amount of calcium silicate 3-90%.

[0449] 实施方案#161是实施方案#158的加氢催化剂,其中存在的钼族金属的总重量为0.5-2%,存在的钯的量为至少0.5%,促进剂是钴,钴与钯的重量比为20 : 1-3 : 1,并且硅酸钙的量为3-90%。 [0449] Embodiment # 161 # 158 are embodiments of the hydrogenation catalyst, the total weight of the metals present therein molybdenum 0.5-2%, the palladium is present in an amount of at least 0.5%, the promoter is cobalt, cobalt and palladium weight ratio of 20: 1 to 3: 1, and the amount of calcium silicate 3-90%.

[0450] 实施方案#162是包含如下物质的加氢催化剂:在表面积为至少200m2/g的高表面积热解二氧化硅上分散的2. 5-3. 5重量%钼、3重量% -5重量%锡,所述高表面积二氧化硅用4-6%的偏硅酸钙促进,钼与锡的摩尔比为4 : 5-5 : 4。 [0450] Embodiment # 162 is a hydrogenation catalyst comprising the following materials: a surface area of ​​at least 200m2 / dispersible 2. 5-35 wt% of molybdenum, 3% to 5 g on the high surface area fumed silica. wt.% tin, a high surface area silica with 4-6% of the calcium metasilicate promoted molybdenum molar ratio of tin is 4: 5-5: 4.

[0451] 实施方案#163是包含如下物质的加氢催化剂:0. 5-2. 5重量%钯,2重量% -7重量%铼,铼与钯的重量比为至少1.5 : 1.0,其中铼和钯都分散在含硅载体上,所述含硅载体包含至少80%的偏硅酸钙。 [0451] Embodiment # 163 is a hydrogenation catalyst comprising the following materials: 05-25 wt% palladium, 2 wt% to 7 wt% rhenium, rhenium to palladium weight ratio is at least 1.5: 1.0, wherein the rhenium and the palladium dispersed on a siliceous support, the silicon-containing carrier comprises at least 80% of the calcium metasilicate.

[0452] 实施方案#164是将链烷酸加氢为相应的烷醇的颗粒催化剂,该颗粒催化剂包含: (a)在选自改性的稳定化含硅载体的含硅载体上的选自钼、钯及其混合物的钼族金属,所述含硅载体用选自如下的稳定剂-改性剂改性和稳定:(i)碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏娃酸盐,(iv)碱金属偏娃酸盐,(v)氧化锌,(vi)偏娃酸锌和(vii) (i)-(vi)中任一种的前体,以及(i)-(vii)的任意混合物,所述改性的稳定化含娃载体的表面积为至少约150m 2/g;和(b)以催化剂重量的约1% -3%的量的锡促进剂,钼与锡的摩尔比为约4 : 3-3 : 4。 [0452] Embodiment # 164 alkanoic acid is hydrogenated to the corresponding alkanols particulate catalyst, the catalyst particle comprises: (a) a carrier selected from silicon-containing carrier is selected from siliceous stabilized-modified molybdenum metals molybdenum, palladium, and mixtures thereof, the silicon-containing carrier with a stabilizing agent selected from the group of - modified with a modifier and stabilizer: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (III ) alkaline earth metal partial salts baby, (iv) an alkali metal salt of the partial baby, (v) zinc oxide, (vi) and partial zinc baby (vii) (i) - (vi) any one of the precursor, and (i) - (vii) any mixture, stabilized surface area of ​​the modified baby carrier containing at least about 150m 2 / g; and (b) in an amount of from about 1% to 3% by weight of tin catalyst promoter, the molar ratio of molybdenum to tin is from about 4: 3-3: 4.

[0453] 实施方案#165是实施方案#164的加氢催化剂,其中存在的钼族金属的总重量为2-4%,存在的钼的量为至少2%,钼与锡的重量比为4 : 5-5 : 4,并且存在的稳定剂-改性剂的量为3-7. 5%。 [0453] Embodiment # 165 # hydrogenation catalyst of embodiment 164, wherein the total weight of the molybdenum metal in the presence of 2-4%, the amount of molybdenum present is at least 2% by weight of molybdenum and tin is 4 : 5-5: 4, in the presence of a stabilizer and - the amount of modifier is 3-75%.

[0454] 实施方案#166是实施方案#165的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0454] Embodiment # 166 # 165 embodiment of a hydrogenation catalyst, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0455] 实施方案#167是实施方案#165的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0455] Embodiment # 167 is the embodiment of a hydrogenation catalyst # 165, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0456] 实施方案#168是实施方案#165的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0456] Embodiment # 168 # 165 of the embodiment is a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0457] 实施方案#169是实施方案#165的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0457] Embodiment # 169 # 165 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0458] 实施方案#170是实施方案#165的加氢催化剂,其中载体改性剂选自偏硅酸钙、偏硅酸钙的前体以及偏硅酸钙和其前体的混合物。 [0458] Embodiment # 170 # 165 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from a mixture of calcium metasilicate, calcium metasilicate and calcium metasilicate precursors and precursors thereof.

[0459] 实施方案#171是实施方案#164的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0459] Embodiment # 171 # 164 embodiment of a hydrogenation catalyst, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0460] 实施方案#172是实施方案#164的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0460] Embodiment # 172 # hydrogenation catalyst of embodiment 164, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0461] 实施方案#173是实施方案#164的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0461] Embodiment # 173 # 164 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0462] 实施方案#174是实施方案#164的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0462] Embodiment # 174 # 164 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0463] 实施方案#175是实施方案#164的加氢催化剂,其中载体改性剂选自偏娃酸|丐、偏硅酸钙的前体以及偏硅酸钙和其前体的混合物。 [0463] Embodiment # 175 is the embodiment of a hydrogenation catalyst # 164, wherein the support modifier is selected from partial acid baby | Hack, and mixtures of calcium metasilicate and calcium metasilicate precursors precursors thereof.

[0464] 实施方案#176是基本上由如下构成的颗粒加氢催化剂:上面分散有选自钼、钯及其混合物的钼族金属与选自锡、钴和铼的促进剂的改性的稳定化含硅载体,该含硅载体包含具有至少95%的纯度和至少约175m 2/g的表面积且用选自如下的稳定剂-改性剂改性和稳定的二氧化硅:(i)碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏硅酸盐, (iv)碱金属偏娃酸盐,(v)氧化锌,(vi)偏娃酸锌和(vii) (i)-(vi)中任一种的前体,以及(i)-(vii)的任意混合物,所述含硅载体的表面由于未被稳定剂-改性剂平衡的氧化铝而基本上不含布朗斯台德酸位。 [0464] Embodiment # 176 consisting essentially of the particulate hydrogenation catalyst is constructed as follows: The above dispersion selected from molybdenum, molybdenum, palladium, and mixtures of metals selected from tin-modified cobalt and rhenium promoters and stability, silicaceous support, having a surface area of ​​the silicon support comprises at least 95% and a purity of at least about 175m 2 / g and is selected from the following stabilizers - the silica modified with a modifier and stability: (i) an alkaline earth a metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal metasilicates, (iv) an alkali metal salt of the partial baby, (v) zinc oxide, (vi) and partial baby zinc (VII) ( I) - any one of (vi) of one of the precursor, and (I) - any mixture of (vii), the surface of the carrier since the silicon-containing stabilizer is not - the balance being alumina modified agent substantially with Bronsted acid sites.

[0465] 实施方案#177是实施方案#176的加氢催化剂,其中存在的钼族金属的总重量为0.5%-2%,存在的钯的量为至少0.5%,促进剂是铼,铼与钯的重量比为10 : 1-2 : 1,并且载体-改性剂的量为3-90 %。 [0465] Embodiment # 177 # 176 are embodiments of the hydrogenation catalyst, wherein the total weight of the molybdenum metal present is from 0.5% to 2%, the palladium is present in an amount of at least 0.5%, the promoter is rhenium, rhenium palladium weight ratio of 10: 1-2: 1, and the carrier - an amount of modifier is 3-90%.

[0466] 实施方案#178是实施方案#177的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0466] Embodiment # 178 is the embodiment of a hydrogenation catalyst # 177, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0467] 实施方案#179是实施方案#177的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0467] Embodiment # 179 is the embodiment of a hydrogenation catalyst # 177, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0468] 实施方案#180是实施方案#177的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0468] Embodiment # 180 # 177 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0469] 实施方案#181是实施方案#177的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0469] Embodiment # 181 # 177 of the embodiment is a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0470] 实施方案#182是实施方案#177的加氢催化剂,其中载体改性剂选自偏硅酸钙、偏硅酸钙的前体以及偏硅酸钙和其前体的混合物。 [0470] Embodiment # 182 # 177 of the embodiment is a hydrogenation catalyst, wherein the support modifier is selected from a mixture of calcium metasilicate, calcium metasilicate and calcium metasilicate precursors and precursors thereof.

[0471] 实施方案#183是实施方案#176的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0471] Embodiment # 183 # 176 embodiment of a hydrogenation catalyst, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0472] 实施方案#184是实施方案#176的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0472] Embodiment # 184 is the embodiment of a hydrogenation catalyst # 176, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0473] 实施方案#185是实施方案#176的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0473] Embodiment # 185 # 176 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0474] 实施方案#186是实施方案#176的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0474] Embodiment # 186 # 176 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0475] 实施方案#187是实施方案#176的加氢催化剂,其中载体改性剂选自偏硅酸钙、偏硅酸钙的前体以及偏硅酸钙和其前体的混合物。 [0475] Embodiment # 187 # 176 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from a mixture of calcium metasilicate, calcium metasilicate and calcium metasilicate precursors and precursors thereof.

[0476] 实施方案#188是实施方案#176的加氢催化剂,其中存在的钼族金属的总重量为0.5-2%,存在的钼的量为至少0.5%,促进剂是钴,钴与钼的重量比为20 : 1-3 : 1,并且载体改性剂的量为3-90%。 [0476] Embodiment # 188 # hydrogenation catalyst of embodiment 176, wherein the total weight of the metals present in the molybdenum 0.5-2%, molybdenum is present in an amount of at least 0.5%, the promoter is cobalt, molybdenum and cobalt weight ratio of 20: 1 to 3: 1, and the amount of support modifier is 3-90%.

[0477] 实施方案#189是实施方案#188的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0477] Embodiment # 189 # 188 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0478] 实施方案#190是实施方案#188的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0478] Embodiment # 190 # 188 embodiment of a hydrogenation catalyst, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0479] 实施方案#191是实施方案#188的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0479] Embodiment # 191 # 188 of the embodiment is a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0480] 实施方案#192是实施方案#188的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0480] Embodiment # 192 # 188 are embodiments of a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0481] 实施方案#193是实施方案#188的加氢催化剂,其中载体改性剂选自偏硅酸钙、偏硅酸钙的前体以及偏硅酸钙和其前体的混合物。 [0481] Embodiment # 193 # 188 of the embodiment is a hydrogenation catalyst, wherein the support modifier is selected from a mixture of calcium metasilicate, calcium metasilicate and calcium metasilicate precursors and precursors thereof.

[0482] 实施方案#194是实施方案#176的加氢催化剂,其中存在的钼族金属的总重量为0.5-2%,存在的钯的量为至少0.5%,促进剂是钴,钴与钯的重量比为20 : 1-3 : 1,并且载体改性剂的量为3-90%。 [0482] Embodiment # 194 # hydrogenation catalyst of embodiment 176, wherein the total weight of the metals present in the molybdenum 0.5-2%, the palladium is present in an amount of at least 0.5%, the promoter is cobalt, cobalt and palladium weight ratio of 20: 1 to 3: 1, and the amount of support modifier is 3-90%.

[0483] 实施方案#195是实施方案#194的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0483] Embodiment # 195 # 194 embodiment of a hydrogenation catalyst, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0484] 实施方案#196是实施方案#194的加氢催化剂,其中载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0484] Embodiment # 196 is the embodiment of a hydrogenation catalyst # 194, wherein the support modifier is selected from any of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors and the foregoing mixture.

[0485] 实施方案#197是实施方案#194的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0485] Embodiment # 197 # 194 of the embodiment is a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0486] 实施方案#198是实施方案#194的加氢催化剂,其中载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的任意混合物。 [0486] Embodiment # 198 # 194 of the embodiment is a hydrogenation catalyst, wherein the support modifier is selected from mixtures of any of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.

[0487] 实施方案#199是实施方案#194的加氢催化剂,其中载体改性剂选自偏硅酸钙、偏硅酸钙的前体以及偏硅酸钙和其前体的混合物。 [0487] Embodiment # 199 # 194 of the embodiment is a hydrogenation catalyst, wherein the support modifier is selected from a mixture of calcium metasilicate, calcium metasilicate and calcium metasilicate precursors and precursors thereof.

[0488] 实施方案#200是包含如下物质的加氢催化剂:在表面积为至少200m2/g的高表面积热解二氧化硅上分散的2. 5-3. 5重量%钼、3重量% -5重量%锡,所述高表面积二氧化硅用4-6%的偏硅酸钙促进,钼与锡的摩尔比为4 : 5-5 : 4。 [0488] Embodiment # 200 is a hydrogenation catalyst comprising the following materials: a surface area of ​​at least 200m2 / dispersible 2. 5-35 wt% of molybdenum, 3% to 5 g on the high surface area fumed silica. wt.% tin, a high surface area silica with 4-6% of the calcium metasilicate promoted molybdenum molar ratio of tin is 4: 5-5: 4.

[0489] 实施方案#201是包含如下物质的加氢催化剂:0. 5-2. 5重量%钯,2重量% -7重量%铼,铼与钯的重量比为至少1.5 : 1.0,其中所述铼和钯都分散在含硅载体上,所述含硅载体包含至少80%的偏硅酸钙。 [0489] Embodiment # 201 is a hydrogenation catalyst comprising the following materials: 05-25 wt% palladium, 2 wt% to 7 wt% rhenium, rhenium to palladium weight ratio is at least 1.5: 1.0, wherein said palladium and rhenium are dispersed on a siliceous support, the silicon-containing carrier comprises at least 80% of the calcium metasilicate.

[0490] 实施方案#202是一种在稳定化改性的氧化物类载体上以约0. 1重量% -约10重量%的量引入选自Fe、Co、Ni、Ru、Rh、Pd、Ir、Pt、Os、Ti、Zn、Cr、Mo和W的催化金属的加氢催化剂,所述氧化物类载体以足够的量引入碱土金属、碱金属、锌、钪、钇的氧化物和偏硅酸盐形式,这些氧化物和偏硅酸盐的前体形式,以及它们的混合物形式的碱性非挥发性稳定剂-改性剂,从而抵消其表面上存在的酸位;赋予在遭遇乙酸加氢的温度下抗形状改变性(形状改变尤其主要归因于烧结、晶粒生长、晶界迁移、缺陷和位错迁移、塑性变形和/或其它温度诱导显微结构改变);或这两者。 [0490] Embodiment # 202 is a modification of stabilizing oxides on the support from about 0.1 wt% - about 10% by weight is introduced is selected from Fe, Co, Ni, Ru, Rh, Pd, Ir, hydrogenation catalyst catalytic metal Pt, Os, Ti, Zn, Cr, Mo and W, the oxidic support is introduced in a sufficient amount of alkaline earth metal, alkali metal, zinc, scandium, yttrium oxide and partial silicate form, these oxides and metasilicates precursor form thereof, and a mixture of non-volatile stabilizers basic - modifying agents, so as to counteract the acid sites present on the surface thereof; encountered in imparting acid anti hydrogenated at a temperature of shape change (mainly due to the particular shape changing sintering, grain growth, grain boundary migration, migration of defects and dislocations, plastic deformation and / or other temperature-induced changes microstructure); or both By.

[0491] 实施方案#203是实施方案#202的加氢催化剂,其中碱性改性剂-稳定剂的量和位置足以使氧化物类载体表面上每平方米所存在的酸位的数目降低到低于纯度为至少约99. 7重量%的热解二氧化硅表面上每平方米所发现的酸位的数目。 [0491] Embodiment # 203 # hydrogenation catalyst of embodiment 202, wherein the basic modifiers - stabilizers the amount and location sufficient number of acid sites per square meter of the surface of the oxide present on the carrier is reduced to class purity less than the number of acid sites on the 99.7% by weight of fumed silica per square meter of the surface of at least about found.

[0492] 实施方案#204是实施方案#202的加氢催化剂,其中碱性改性剂-稳定剂的量和位置足以使氧化物类载体表面上每平方米所存在的酸位的数目降低到低于纯度为至少约99. 7重量%的Saint-Gobain NorPro HSA SS 61138表面上每平方米所发现的酸位的数目。 [0492] Embodiment # 204 # 202 embodiment of a hydrogenation catalyst, wherein the alkaline modifier - stabilizers the amount and location sufficient number of acid sites per square meter of the surface of the oxide present on the carrier is reduced to class number below purity of at least about 99.7 wt% of Saint-Gobain NorPro HSA SS on 61,138 per square meter of surface acid sites found.

[0493] 实施方案#205是实施方案#202的加氢催化剂,其中碱性改性剂-稳定剂的量和位置足以使氧化物类载体表面上每平方米所存在的酸位的数目降低到低于纯度为至少约99. 7重量%的热解二氧化硅表面上每平方米所发现的酸位数目的一半。 [0493] Embodiment # 205 # 202 embodiment of a hydrogenation catalyst, wherein the alkaline modifier - stabilizers the amount and location sufficient number of acid sites per square meter of the surface of the oxide present on the carrier is reduced to class less than half of a purity of at least about object acid median 99.7 weight% of fumed silica per square meter of the surface found.

[0494] 实施方案#206是实施方案#202的加氢催化剂,其中碱性改性剂-稳定剂的量和位置足以使氧化物类载体表面上每平方米所存在的酸位的数目降低到低于纯度为至少约99. 7重量%的Saint-Gobain NorPro HSA SS 61138表面上每平方米所发现的酸位数目的一半。 [0494] Embodiment # 206 # hydrogenation catalyst of embodiment 202, wherein the basic modifiers - stabilizers the amount and location sufficient number of acid sites per square meter of the surface of the oxide present on the carrier is reduced to class an acid number of bits per square meter found on the surface of 61138 Saint-Gobain NorPro HSA SS is lower than the purity of at least about 99.7% by weight of one half object.

[0495] 实施方案#207是实施方案#202的加氢催化剂,其中碱性改性剂-稳定剂的量和位置足以使氧化物类载体表面上每平方米所存在的酸位的数目降低到低于纯度为至少约99. 7重量%的热解二氧化硅表面上每平方米所发现的酸位数目的25%。 [0495] Embodiment # 207 # 202 embodiment of a hydrogenation catalyst, wherein the alkaline modifying agent - stabilizer sufficient amount and location of the support surface oxides reduce the number of acid per square meter of the present position to acid purity of at least less than the number of bits about 99.7 weight% of fumed silica per square meter of the surface found 25%.

[0496] 实施方案#208是实施方案#202的加氢催化剂,其中碱性改性剂-稳定剂的量和位置足以使氧化物类载体表面上每平方米所存在的酸位的数目降低到低于纯度为至少约99. 7重量%的Saint-Gobain NorPro HSA SS 61138表面上每平方米所发现的酸位数目的25%。 [0496] Embodiment # 208 # hydrogenation catalyst of embodiment 202, wherein the basic modifiers - stabilizers the amount and location sufficient number of acid sites per square meter of the surface of the oxide present on the carrier is reduced to class an acid number of bits per square meter of 25% found on the surface of 61138 Saint-Gobain NorPro HSA SS is lower than the purity of at least about 99.7% by weight.

[0497] 实施方案#209是实施方案#202的加氢催化剂,其中碱性改性剂-稳定剂的量和位置足以使氧化物类载体表面上每平方米所存在的酸位的数目降低到低于纯度为至少约99. 7重量%的热解二氧化硅表面上每平方米所发现的酸位数目的10%。 [0497] Embodiment # 209 # 202 embodiment of a hydrogenation catalyst, wherein the alkaline modifier - stabilizers the amount and location sufficient number of acid sites per square meter of the surface of the oxide present on the carrier is reduced to class acid purity of at least less than the number of bits about 99.7 weight% of fumed silica per square meter of the surface found 10%.

[0498] 实施方案#210是实施方案#202的加氢催化剂,其中碱性改性剂-稳定剂的量和位置足以使氧化物类载体表面上每平方米所存在的酸位的数目降低到低于纯度为至少约99. 7重量%的Saint-Gobain NorPro HSA SS 61138表面上每平方米所发现的酸位数目的10%。 [0498] Embodiment # 210 # hydrogenation catalyst of embodiment 202, wherein the basic modifiers - stabilizers the amount and location sufficient number of acid sites per square meter of the surface of the oxide present on the carrier is reduced to class an acid number of bits per square meter of 10% found on the surface of 61138 Saint-Gobain NorPro HSA SS is lower than the purity of at least about 99.7% by weight.

[0499] 在前述各个实施方案的描述中,如本领域技术人员所可认识到的,引用另一个实施方案的实施方案可以与其它实施方案适当地组合。 [0499] In the foregoing descriptions of the various embodiments, as those skilled in the art may be appreciated, reference to another embodiment of the embodiment may be appropriately combined with other embodiments.

Claims (88)

1. 一种通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少4:1的氢气与乙酸摩尔比在225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂包含在改性含硅载体上分散的钼和锡,其中钼以催化剂重量的0. 5% -5%的量存在和锡以0.5-10%的量存在,所述改性含硅载体包括有效量的选自如下的载体改性剂:(i) 碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏硅酸盐,(iv)碱金属偏硅酸盐,(v) 氧化锌,(vi)偏硅酸锌和(vii) (i)-(vi)的前体,以及(i)-(vii)的混合物;其中对钼和锡的量和氧化态,以及钼与锡的比率,和含硅载体进行选择、构成和控制使得:(i)使所转化乙酸的至少80%转化为乙醇;(ii)小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯及其混合物的化合物以外的化合物;并且当在2atm的压力、275°C的温度 CLAIMS 1. A method of reducing the production of acetic acid by ethanol, the process comprising the gas phase in at least 4: 1 gaseous hydrogen to acetic acid mole ratio at a temperature of 225 ° C -300 ° C causes hydrogen and acetic acid containing stream through the hydrogenation catalyst, the hydrogenation catalyst comprising dispersed on the modified carrier molybdenum and silicon containing tin, wherein the molybdenum in an amount of 0.5% -5% by weight of the catalyst and the tin is present in an amount of 0.5 to 10% by said modified silicon-containing carrier comprising an effective amount of a support modifier selected from: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) zinc oxide, (vi) zinc metasilicate, and (vii) (i) - a mixture of (vii) a - (vi) of the precursor, and (I); and wherein molybdenum the amounts and oxidation states of tin, and the ratio of molybdenum and tin, and silicon-vector selection, configuration and control such that: (i) the conversion of acetic acid is converted to ethanol at least 80%; (ii) conversion of less than 4% acetic acid is a compound selected from compounds other than ethanol, acetaldehyde, ethyl acetate, ethylene and mixtures thereof in addition; when the pressure 2atm, the temperature of 275 ° C and 和2500111^ 1的GHSV下暴露于摩尔比为10:1的乙酸和氢气的蒸气状的混合物168小时的时间段时,该催化剂活性下降小于10%。 And the lower GHSV 2500111 ^ 1 is exposed to a molar ratio of 10: a mixture of acetic acid and hydrogen vaporous period of 1 168 hours, the catalyst activity decreased less than 10%.
2. 权利要求1的方法,其中所述载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的混合物。 The method of claim 1, wherein the support modifier is selected from a mixture of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.
3. 权利要求2的方法,其中钼与锡的摩尔比为4:5-5:4。 The method of claim 2, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
4. 权利要求1的方法,其中所述载体改性剂选自钠、钾、镁、钙和锌的偏硅酸盐以及它们的前体和前述的混合物。 The method of claim 1, wherein the support modifier is selected from a mixture of sodium, potassium, magnesium, calcium and zinc as well as their precursors and foregoing.
5. 权利要求4的方法,其中钼与锡的摩尔比为4:5-5:4。 The method of claim 4, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
6. 权利要求1的方法,其中所述载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的混合物。 6. The method of claim 1, wherein the support modifier is selected from a mixture of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.
7. 权利要求6的方法,其中钼与锡的摩尔比为4:5-5:4。 The method of claim 6, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
8. 权利要求1的方法,其中所述载体改性剂选自镁、钙和锌的偏硅酸盐以及它们的前体和前述的混合物。 The method of claim 1, wherein the support modifier is selected from a mixture of magnesium, calcium and zinc as well as their precursors and foregoing.
9. 权利要求8的方法,其中钼与锡的摩尔比为4:5-5:4。 9. The method of claim 8, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
10. 权利要求1的方法,其中所述载体改性剂选自偏娃酸I丐、偏娃酸I丐的前体以及偏娃酸钙和其前体的混合物。 10. The method of claim 1, wherein the support modifier is selected from vinylidene baby I Hack acid, metaphosphoric acid, and mixtures partial baby doll and calcium precursors thereof hack I precursor.
11. 权利要求10的方法,其中钼与锡的摩尔比为4:5-5:4。 11. The method of claim 10, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
12. 权利要求1的方法,其中所述载体的表面积为至少100m2/g。 12. The method of claim 1, wherein the surface area of ​​the support is at least 100m2 / g.
13. 权利要求12的方法,其中锡与钼的摩尔比为1:2-2:1。 13. The method of claim 12, wherein the molar ratio of tin to molybdenum is 1: 2-2: 1.
14. 权利要求12的方法,其中锡与钼的摩尔比为2:3-3: 2。 14. The method as claimed in claim 12, wherein the molar ratio of tin to molybdenum is 2: 3-3: 2.
15. 权利要求12的方法,其中锡与钼的重量比为5:4-4:5。 15. The method of claim 12, wherein the weight ratio of tin to molybdenum is 5: 4-4: 5.
16. 权利要求1的方法,其中所述载体的表面积为至少150m2/g。 16. The method of claim 1, wherein the surface area of ​​the support is at least 150m2 / g.
17. 权利要求16的方法,其中: a. 钼以催化剂重量的0. 5% -5 %的量存在;以及b. 锡以0. 5-5 %的量存在。 17. The method of claim 16, wherein: a molybdenum in an amount of 0.5% -5% by weight of the catalyst; and b. An amount of 0. 5-5% of tin is present...
18. 权利要求16的方法,其中所述载体包含1% -10重量%的硅酸钙。 18. The method of claim 16, wherein said carrier comprises from 1% to 10% by weight of calcium silicate.
19. 权利要求16的方法,其中锡与钼的摩尔比为1:2-2:1。 19. The method of claim 16, wherein the molar ratio of tin to molybdenum is 1: 2-2: 1.
20. 权利要求16的方法,其中锡与钼的摩尔比为2:3-3: 2。 20. The method of claim 16, wherein the molar ratio of tin to molybdenum is 2: 3-3: 2.
21. 权利要求16的方法,其中锡与钼的重量比为5:4-4:5。 21. The method of claim 16, wherein the weight ratio of tin to molybdenum is 5: 4-4: 5.
22. 权利要求1的方法,其中所述载体的表面积为至少200m2/g。 22. The method of claim 1, wherein the surface area of ​​the support is at least 200m2 / g.
23. 权利要求22的方法,其中锡与钼的摩尔比为2:3-3:2。 23. The method of claim 22, wherein the molar ratio of tin to molybdenum is 2: 3-3: 2.
24. 权利要求22的方法,其中锡与钼的摩尔比为5:4-4:5。 24. The method of claim 22, wherein the molar ratio of tin to molybdenum is 5: 4-4: 5.
25. 权利要求22的方法,其中锡与钼的摩尔比为9:10-10:9。 25. The method of claim 22, wherein the molar ratio of tin to molybdenum is 9: 10-10: 9.
26. 权利要求25的方法,其中所述改性含娃载体的表面积为至少250m2/g。 26. The method of claim 25, wherein said baby carrier comprising the modified surface area of ​​at least 250m2 / g.
27. 权利要求1的方法,该方法在250°C _300°C的温度下进行,其中: a. 所述改性含娃载体的表面积为至少250m2/g ; b. 钼以0. 75重量% -5重量%的量存在于所述加氢催化剂中; c. 锡与钼的摩尔比为5:4-4:5 ;以及d. 所述改性含硅载体包含纯度为至少95 %的用2. 5重量% -10重量%的偏硅酸钙改性的二氧化硅。 27. The method as claimed in claim 1, which is carried out at a temperature of 250 ° C _300 ° C, wherein:.. A baby carrier comprising the modified surface area of ​​at least 250m2 / g; b 0.75 wt% molybdenum 5% by weight of the amount present in the hydrogenation catalyst; C molar ratio of tin to molybdenum is 5: 4-4: 5; and d the modified silicon-containing carrier comprises a purity of at least 95% by % to 10 wt% by weight of calcium metasilicate 2.5 modified silica.
28. 权利要求27的方法,其中存在的钼的量为1重量% -5重量%。 28. The method of claim 27, wherein the amount of molybdenum is present in 1% to 5% by weight.
29. 权利要求1的方法,该方法在250°C _300°C的温度下进行,其中: a. 所述改性含硅载体的表面积为至少100m2/g ; b. 其中锡与钼的摩尔比为2:3-3:2 ;以及c. 所述改性含硅载体包含纯度为至少95 %的用2. 5重量% -10重量%的偏硅酸钙改性的二氧化硅。 Wherein the molar ratio of tin to molybdenum b; a surface area of ​​the modified silicon-containing support is at least 100m2 / g: 29. The method of claim 1, which is carried out at a temperature of 250 ° C _300 ° C, wherein. 2: 3-3: 2; c and the modified silicon-containing carrier comprises a purity of at least 95% by weight calcium metasilicate 2.5% -10% by weight of the modified silica.
30. 权利要求29的方法,其中存在的钼的量为0. 75重量% -5重量%。 30. The method of claim 29, wherein the amount of molybdenum present is 0.75 wt% to 5 wt%.
31. 权利要求30的方法,其中所述催化剂占据反应器体积,并且在气相中以至少lOOOhf1的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 31. The method of claim 30, wherein the volume of the reactor occupied by the catalyst, and at a space velocity of the gaseous lOOOhf1 comprising at least hydrogen and acetic acid in the vapor phase stream through the reactor volume.
32. 权利要求30的方法,其中所述催化剂占据反应器体积,并且在气相中以至少2500hrH的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 32. The method of claim 30, wherein the volume of the reactor occupied by the catalyst, and at a space velocity of the gaseous 2500hrH comprising at least hydrogen and acetic acid in the vapor phase stream through the reactor volume.
33. -种通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少4:1的氢气与乙酸摩尔比在225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂包含在改性含硅载体上分散的钼和锡,其中钼以催化剂重量的0.5% -5%的量存在和锡以0. 5-10%的量存在,所述改性含硅载体包括有效量的选自如下的载体改性剂: (i)碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏硅酸盐,(iv)碱金属偏硅酸盐, (v)氧化锌,(vi)偏娃酸锌和(vii) (i)-(vi)的前体,以及⑴_(vii)的混合物;其中控制钼和锡的量和氧化态,以及钼与锡的比率和所述改性含硅载体使得:(i)使所转化乙酸的至少90%转化为乙醇;(ii)小于2%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯和乙烯及其混合物的化合物以外的化合物;以及(iii)当在2atm的压力、275°C的温度和25001^- 1的G 33. - species by reducing the acetic acid process for producing ethanol, which comprises at least 4 in the gas phase: 1 gaseous hydrogen to acetic acid mole ratio at a temperature of 225 ° C -300 ° C so that the acetic acid stream comprising hydrogen and through the hydrogenation catalyst, the hydrogenation catalyst comprising dispersed on the modified carrier molybdenum and silicon containing tin, wherein the molybdenum in an amount of 0.5% to 5% by weight of the catalyst and the tin is present in an amount of 0.5 to 10% by said modified silicon-containing carrier comprising an effective amount of a support modifier selected from: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) zinc oxide, (vi) and partial zinc baby (vii) (i) -, and mixtures ⑴_ (vii) (vi) of a precursor; wherein the control amount of molybdenum and tin and the oxidation state of the tin and the ratio of molybdenum and silicon containing carrier and the modified such that: (i) the conversion of acetic acid is converted to ethanol at least 90%; (ii) less than 2% of acetic acid is converted to other selected from ethanol, compound other than the compound acetaldehyde, ethyl acetate, and ethylene and mixtures thereof; and (iii) when the pressure 2atm, the temperature of 275 ° C and 25001 ^ - G 1 is HSV下暴露于摩尔比为10:1的乙酸和氢气的蒸气状的混合物336小时的时间段时,该催化剂活性下降小于10%。 Under exposure to HSV molar ratio of 10: a mixture of acetic acid and hydrogen vaporous period of 1 336 hours, the catalyst activity decreased less than 10%.
34. 权利要求30的方法,其中所述催化剂占据反应器体积,并且在气相中以至少SOOOhf1的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 34. The method of claim 30, wherein the volume of the reactor occupied by the catalyst, and at a space velocity of the gaseous SOOOhf1 comprising at least hydrogen and acetic acid in the vapor phase stream through the reactor volume.
35. 权利要求34的方法,其中控制钼和锡的量和氧化态,以及钼与锡的比率和所述改性含硅载体使得:(i)使所转化乙酸的至少90%转化为乙醇;(ii)小于2%的乙酸转化为烷烃;(iii)当在2atm的压力、275°C的温度和25001^ 1的GHSV下暴露于摩尔比为10:1的乙酸和氢气的蒸气状的混合物168小时的时间段时,该催化剂活性下降小于10%。 35. The method of claim 34, wherein the molybdenum and the control amounts and oxidation states of tin, molybdenum, tin and the ratio of silicon-vector and the modified such that: (i) the conversion of acetic acid is converted to ethanol at least 90%; (ii) acid less than 2% conversion of alkanes; (iii) when at a pressure of 2atm, the temperature of 275 ° C the GHSV and 25001 ^ 1 is exposed to a molar ratio of 10: mixture of acetic acid and hydrogen 1 vaporous 168 hour period, the catalyst activity decreased less than 10%.
36. -种通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少4:1的氢气与乙酸摩尔比在250°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂包含在改性含硅载体上分散的钼和锡,其中钼以催化剂重量的〇. 75重量% -5重量%的量存在和锡以〇. 5-10 %的量存在,锡与钼的摩尔比为5:4-4:5,其中所述改性含硅载体的表面积为至少200m2/g,所述改性含硅载体包含纯度为至少95%的二氧化硅,改性剂包含2. 5重量%-10重量%的硅酸钙;其中控制钼和锡的量和氧化态,以及钼与锡的比率和所述改性含硅载体使得:(i)使所转化乙酸的至少90%转化为乙醇;(ii)小于2%的乙酸转化为烷烃;(iii)当在2atm的压力、275°C的温度和25001^ 1的GHSV下暴露于摩尔比为10:1的乙酸和氢气的蒸气状的混合物168小时的时间段时,该催化剂活性下降小于10%, 其中所 36. - species by reducing the acetic acid process for producing ethanol, which comprises at least 4 in the gas phase: 1 gaseous hydrogen to acetic acid mole ratio at a temperature of 250 ° C -300 ° C so that the acetic acid stream comprising hydrogen and through the hydrogenation catalyst, the hydrogenation catalyst comprising dispersed on the modified carrier molybdenum and silicon containing tin, wherein the molybdenum. an amount of 75 wt.% to 5 wt% of the weight of the catalyst present in the square to square and tin. 5-10 % of the amount present, the molar ratio of tin to molybdenum is 5: 4-4: 5, wherein the modified silicon-containing surface area of ​​the support is at least 200m2 / g, the modified silicon-containing carrier comprises a purity of at least 95% silica, the modifying agent comprises 2.5 wt% to 10 wt% of calcium silicate; molybdenum and tin wherein the control amounts and oxidation states, and the ratio of molybdenum and tin and the modified silicon-containing carrier such :( i) reacting acetic acid conversion of at least 90% conversion to ethanol; (ii) acetic acid of less than 2% conversion of alkanes; (iii) when exposed to a pressure of 2atm, the temperature of 275 ° C the GHSV and 25001 ^ 1 in molar ratio of 10: a mixture of 168 hours period of 1 vaporous acetic acid and hydrogen, the catalyst activity decreased less than 10%, wherein 述催化剂占据反应器体积,并且在气相中以至少sooohf1的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 Said catalyst occupies a reactor volume, and at a space velocity of the gaseous sooohf1 comprising at least hydrogen and acetic acid in the vapor phase stream through the reactor volume.
37. -种通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少4:1的氢气与乙酸摩尔比在225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂包含在改性氧化物类载体上分散的钼和锡,其中钼以催化剂重量的〇. 5% -5%的量存在和锡以0. 5-10 %的量存在,所述改性氧化物类载体包括有效量的选自如下的载体改性剂:(i)碱土金属氧化物,(ii)碱金属氧化物,(iii)碱土金属偏硅酸盐,(iv)碱金属偏娃酸盐,(v)氧化锌,(vi)偏娃酸锌和(vii) (i)-(vi)的前体,以及(i)-(vii)的混合物; 其中对钼和锡的量和氧化态,以及钼与锡的比率,和氧化物类载体进行选择、构成和控制使得:⑴使所转化乙酸的至少80%转化为乙醇;(ii)小于4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯及其混合物的化合物以外的化合物;并且当在2atm的压 37. - species by reducing the acetic acid process for producing ethanol, which comprises at least 4 in the gas phase: 1 gaseous hydrogen to acetic acid mole ratio at a temperature of 225 ° C -300 ° C so that the acetic acid stream comprising hydrogen and through the hydrogenation catalyst, the hydrogenation catalyst comprising dispersed on the modified carrier molybdenum and tin oxides, wherein the molybdenum. square weight of the catalyst is present in an amount of 5% to -5% of tin and 0.5 to 10% present in an amount, based oxide of the modified vectors include an effective amount of a modifier selected from: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal metasilicates , (iv) an alkali metal salt of the partial baby, (v) zinc oxide, (vi) and partial zinc baby (vii) (i) - (vi) of the precursor, and (i) - a mixture of (vii) a; molybdenum and wherein the amounts and oxidation states of tin, and the ratio of molybdenum and tin oxides, and carrier selection, configuration and control such that: ⑴ transformed so that at least 80% acetic acid is converted to ethanol; (ii) less than 4% acetic acid is converted to the compound is selected from compounds other than ethanol, acetaldehyde, ethyl acetate, ethylene and mixtures thereof; and when the pressure 2atm 、275°C的温度和2500hr<的GHSV下暴露于摩尔比为10:1的乙酸和氢气的蒸气状的混合物500小时的时间段时,该催化剂活性下降小于10%。 , At a temperature of 275 ° C and 2500hr <GHSV is exposed to a molar ratio of 10: a mixture of 500 hours period of vaporous acetic acid and hydrogen of 1, the catalyst activity decreased less than 10%.
38. 权利要求37的方法,其中所述载体改性剂选自钠、钾、镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的混合物。 38. The method of claim 37, wherein the support modifier is selected from a mixture of sodium, potassium, magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.
39. 权利要求38的方法,其中钼与锡的摩尔比为4:5-5:4。 39. The method of claim 38, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
40. 权利要求的37方法,其中所述载体改性剂选自钠、钾、镁、钙和锌的偏硅酸盐以及它们的前体和前述的混合物。 40. The method of claim 37, wherein the mixture of support modifier is selected from sodium, potassium, magnesium, calcium and zinc as well as their precursors and foregoing.
41. 权利要求40的方法,其中钼与锡的摩尔比为4:5-5:4。 41. The method of claim 40, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
42. 权利要求37的方法,其中所述载体改性剂选自镁、钙和锌的氧化物和偏硅酸盐以及它们的前体和前述的混合物。 42. The method of claim 37, wherein the support modifier is selected from a mixture of magnesium, calcium and zinc oxides and metasilicates and their precursors, and the foregoing.
43. 权利要求42的方法,其中钼与锡的摩尔比为4:5-5:4。 43. The method of claim 42, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
44. 权利要求37的方法,其中所述载体改性剂选自镁、钙和锌的偏硅酸盐以及它们的前体和前述的混合物。 44. The method of claim 37, wherein the support modifier is selected from a mixture of magnesium, calcium and zinc as well as their precursors and foregoing.
45. 权利要求44的方法,其中钼与锡的摩尔比为4:5-5:4。 45. The method of claim 44, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
46. 权利要求37的方法,其中载体改性剂选自偏娃酸|丐、偏娃酸|丐的前体以及偏娃酸钙和其前体的混合物。 46. ​​The method of claim 37, wherein the support modifier is selected from partial acid baby | Hack, metaphosphoric acid baby | precursors, and mixtures of calcium and hack partial baby precursors thereof.
47. 权利要求46的方法,其中钼与锡的摩尔比为4:5-5:4。 47. The method of claim 46, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
48. 权利要求37的方法,其中钼与锡的摩尔比为4:5-5:4。 48. The method of claim 37, wherein the molar ratio of the molybdenum and tin is 4: 5-5: 4.
49. 权利要求37的方法,其中所述载体表面积为至少100m2/g。 49. The method of claim 37, wherein the support surface area of ​​at least 100m2 / g.
50. 权利要求49的方法,其中锡与钼的摩尔比为1:2-2:1。 50. The method of claim 49, wherein the molar ratio of tin to molybdenum is 1: 2-2: 1.
51. 权利要求49的方法,其中锡与钼的摩尔比为2:3-3:2。 51. The method of claim 49, wherein the molar ratio of tin to molybdenum is 2: 3-3: 2.
52. 权利要求49的方法,其中锡与钼的重量比为5:4-4:5。 52. The method of claim 49, wherein the weight ratio of tin to molybdenum is 5: 4-4: 5.
53. 权利要求37的方法,其中载体表面积为至少150m2/g。 53. The method of claim 37, wherein the support surface area of ​​at least 150m2 / g.
54. 权利要求53的方法,其中: a. 钼以催化剂重量的0. 5% -5 %的量存在;以及b. 锡以0. 5-5 %的量存在。 54. The method of claim 53, wherein: a molybdenum in an amount of 0.5% -5% by weight of the catalyst; and b. An amount of 0. 5-5% of tin is present...
55. 权利要求53的方法,其中载体包含1% -10重量%的娃酸隹丐。 55. The method of claim 53, wherein the carrier comprises from 1% to 10% by weight of the baby acid Zhui hack.
56. 权利要求53的方法,其中锡与钼的摩尔比为1:2-2:1。 56. The method of claim 53, wherein the molar ratio of tin to molybdenum is 1: 2-2: 1.
57. 权利要求53的方法,其中锡与钼的摩尔比为2:3-3: 2。 57. The method of claim 53, wherein the molar ratio of tin to molybdenum is 2: 3-3: 2.
58. 权利要求53的方法,其中锡与钼的重量比为5:4-4:5。 58. The method of claim 53, wherein the weight ratio of tin to molybdenum is 5: 4-4: 5.
59. 权利要求37的方法,其中载体表面积为至少200m2/g。 59. The method of claim 37, wherein the support surface area of ​​at least 200m2 / g.
60. 权利要求59的方法,其中锡与钼的摩尔比为2:3-3: 2。 60. The method of claim 59, wherein the molar ratio of tin to molybdenum is 2: 3-3: 2.
61. 权利要求59的方法,其中锡与钼的摩尔比为5:4-4:5。 61. The method of claim 59, wherein the molar ratio of tin to molybdenum is 5: 4-4: 5.
62. 权利要求59的方法,其中锡与钼的摩尔比为9:10-10:9。 62. The method of claim 59, wherein the molar ratio of tin to molybdenum is 9: 10-10: 9.
63. -种通过将乙酸还原生产乙醇的方法,该方法包括在气相中以至少4:1的氢气与乙酸摩尔比在225°C -300°C的温度下使包含氢气和乙酸的气态料流穿过加氢催化剂,该加氢催化剂基本上由在改性的稳定化含硅载体上分散的钼和锡构成,其中钼以催化剂重量的0. 5% -5%的量存在和锡以0. 5-10%的量存在,所述改性的稳定化含硅载体包含纯度为至少95重量%的用选自如下的稳定剂-改性剂改性的二氧化硅:(i)碱土金属氧化物,(ii) 碱金属氧化物,(iii)碱土金属偏硅酸盐,(iv)碱金属偏硅酸盐,(v)氧化锌,(vi)偏硅酸锌和(vii)(i)-(vi)的前体,以及(i)-(vii)的混合物,其中控制钼和锡的量和氧化态,钼与锡的比率,稳定剂-改性剂与二氧化硅在改性的稳定化含硅载体中的相对比例以及改性的稳定化含硅载体中二氧化硅的纯度使得所转化乙酸的至少80%转化为乙醇,小 63. - species by reducing the acetic acid process for producing ethanol, which comprises at least 4 in the gas phase: 1 gaseous hydrogen to acetic acid mole ratio at a temperature of 225 ° C -300 ° C so that the acetic acid stream comprising hydrogen and through the hydrogenation catalyst, the hydrogenation catalyst consists essentially of dispersing in the modified stabilized silicaceous support molybdenum and tin, wherein the molybdenum in an amount of 0.5% -5% by weight of the catalyst in the presence of tin and 0 . present in an amount of 5-10%, the modified silicon-containing carrier comprises a stabilized purity of at least 95% by weight of a stabilizer selected from the following - modified silica modifier: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal metasilicates, (iv) an alkali metal metasilicates, (v) zinc oxide, (vi) zinc metasilicate, and (vii) (i mixture of (vii), wherein the ratio of molybdenum and controlling the amounts and oxidation states of tin, molybdenum and tin stabilizer - -) - (vi) of the precursor, and (i) modifying agent in the modified silica stabilized relative proportions of siliceous carrier and purity modified stabilized silicaceous support of silica in such converted acetic acid is converted to ethanol at least 80%, small 4%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯、乙烯及其混合物的化合物以外的化合物。 4% acetic acid is converted to the compound is selected from compounds other than ethanol, acetaldehyde, ethyl acetate, ethylene and mixtures thereof.
64. 权利要求63的方法,其中所述改性的稳定化含娃载体的表面积为至少100m2/g。 64. The method of claim 63, wherein the stabilized-modified baby carrier containing a surface area of ​​at least 100m2 / g.
65. 权利要求64的方法,其中锡与钼的摩尔比为1:2-2:1。 65. The method of claim 64, wherein the molar ratio of tin to molybdenum is 1: 2-2: 1.
66. 权利要求64的方法,其中锡与钼的摩尔比为2:3-3:2。 66. The method of claim 64, wherein the molar ratio of tin to molybdenum is 2: 3-3: 2.
67. 权利要求63的方法,其中锡与钼的重量比为5:4-4:5。 67. The method of claim 63, wherein the weight ratio of tin to molybdenum is 5: 4-4: 5.
68. 权利要求63的方法,其中所述改性的稳定化含娃载体的表面积为至少150m2/g。 68. The method of claim 63, wherein the stabilized-modified baby carrier containing a surface area of ​​at least 150m2 / g.
69. 权利要求68的方法,其中: a. 钼以催化剂重量的0. 5% -5 %的量存在;以及b. 锡以0. 5-5 %的量存在。 69. The method of claim 68, wherein: a molybdenum in an amount of 0.5% -5% by weight of the catalyst; and b. An amount of 0. 5-5% of tin is present...
70. 权利要求68的方法,其中所述改性的稳定化含娃载体包含1重量% -10重量%的硅酸钙。 70. The method of claim 68, wherein said modified-containing stabilized baby carrier comprises 1% to 10% by weight of calcium silicate.
71. 权利要求68的方法,其中锡与钼的摩尔比为1:2-2:1。 71. The method of claim 68, wherein the molar ratio of tin to molybdenum is 1: 2-2: 1.
72. 权利要求68的方法,其中锡与钼的摩尔比为2:3-3:2。 72. The method of claim 68, wherein the molar ratio of tin to molybdenum is 2: 3-3: 2.
73. 权利要求68的方法,其中锡与钼的重量比为5:4-4:5。 73. The method of claim 68, wherein the weight ratio of tin to molybdenum is 5: 4-4: 5.
74. 权利要求71的方法,其中所述改性的稳定化含硅载体的表面积为至少200m2/g。 74. The method of claim 71, wherein the surface area of ​​the modified stabilized silicaceous support is at least 200m2 / g.
75. 权利要求74的方法,其中锡与钼的摩尔比为9:10-10:9。 75. The method of claim 74, wherein the molar ratio of tin to molybdenum is 9: 10-10: 9.
76. 权利要求74的方法,其中锡与钼的摩尔比为2:3-3:2。 76. The method of claim 74, wherein the molar ratio of tin to molybdenum is 2: 3-3: 2.
77. 权利要求74的方法,其中锡与钼的摩尔比为5:4-4:5。 77. The method of claim 74, wherein the molar ratio of tin to molybdenum is 5: 4-4: 5.
78. 权利要求74的方法,其中所述改性的稳定化含硅载体的表面积为至少250m2/g。 78. The method of claim 74, wherein the surface area of ​​the modified stabilized silicaceous support is at least 250m2 / g.
79. 权利要求63的方法,该方法在250°C _300°C的温度下进行,其中: a. 所述改性的稳定化含娃载体的表面积为至少250m2/g ; b. 钼以0. 75重量% -5重量%的量存在于所述加氢催化剂中; c. 锡与钼的摩尔比为5:4-4:5 ;以及d. 改性的稳定化含娃载体包含2. 5重量% -10重量%的娃酸隹丐。 79. The method as claimed in claim 63, which is carried out at a temperature of 250 ° C _300 ° C, wherein:.. A stabilized surface area support containing the modified baby is at least 250m2 / g; b molybdenum 0. an amount of 5% by weight of 75% by weight is present in the hydroprocessing catalyst; C molar ratio of tin to molybdenum is 5: 4-4: 5; and d modified stabilized containing baby carrier comprises 2.5 wt% to 10 wt% of an acid-tailed bird baby hack.
80. 权利要求79的方法,其中存在的钼的量为1重量% -5重量%。 80. The method of claim 79, wherein the amount of molybdenum is present in 1% to 5% by weight.
81. 权利要求63的方法,该方法在250°C _300°C的温度下进行,其中: a. 所述改性的稳定化含娃载体的表面积为至少100m2/g ; b. 其中锡与钼的摩尔比为2:3-3:2 ;以及c. 所述改性的稳定化含娃载体包含2. 5重量% -10重量%的娃酸隹丐。 Wherein the tin and molybdenum b; a modification of the stabilized baby carrier comprising a surface area of ​​at least 100m2 / g: 81. The method of claim 63, which is carried out at a temperature of 250 ° C _300 ° C, wherein. the molar ratio of 2: 3-3: 2; and c stabilizing the baby carrier comprising a modified aqueous 2.5 wt% to 10 wt% of the baby acid Zhui hack.
82. 权利要求81的方法,其中存在的钼的量为0.75重量%-5重量%。 82. The method of claim 81, wherein the amount of molybdenum present is 0.75 wt% to 5 wt%.
83. 权利要求82的方法,其中所述催化剂占据反应器体积,并且在气相中以至少lOOOhf1的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 83. The method of claim 82, wherein the volume of the reactor occupied by the catalyst, and at a space velocity of at least lOOOhf1 the gaseous stream comprising hydrogen and acetic acid in the vapor phase through the reactor volume.
84. 权利要求82的方法,其中所述催化剂占据反应器体积,并且在气相中以至少2500hrH的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 84. The method of claim 82, wherein the volume of the reactor occupied by the catalyst, and at a space velocity of at least 2500hrH the gaseous stream comprising hydrogen and acetic acid in the vapor phase through the reactor volume.
85. 权利要求84的方法,其中控制钼和锡的量和氧化态,以及钼与锡的比率和改性的稳定化含硅载体的组成使得:使所转化乙酸的至少90%转化为乙醇,小于2%的乙酸转化为除选自乙醇、乙醛、乙酸乙酯和乙烯及其混合物的化合物以外的化合物。 85. The method of claim 84, wherein the control amount of molybdenum and tin and oxidation states, and the composition ratio of the silicon-containing carrier and stabilizer of molybdenum and tin modified such that: the converted acetic acid is converted to ethanol at least 90%, less than 2% of acetic acid is converted to compounds other than the compounds selected from ethanol, acetaldehyde, ethyl acetate, and mixtures of ethylene and.
86. 权利要求82的方法,其中所述催化剂占据反应器体积,并且在气相中以至少SOOOhf1的空速使包含氢气和乙酸的气态料流穿过所述反应器体积。 86. The method of claim 82, wherein the volume of the reactor occupied by the catalyst, and at a space velocity of at least SOOOhf1 the gaseous stream comprising hydrogen and acetic acid in the vapor phase through the reactor volume.
87. 权利要求63的方法,其中控制钼和锡的量和氧化态,以及钼与锡的比率和所述改性的稳定化含硅载体的组成使得:使所转化乙酸的至少90%转化为乙醇,小于2%的乙酸转化为烷烃。 87. The method of claim 63, wherein the control amount of molybdenum and tin and oxidation states, and the composition ratio of the silicon-containing support and stabilization of the molybdenum and tin modified such that: at least 90% of the converted acetic acid is converted ethanol, acetic acid less than 2% conversion of alkanes.
88. 权利要求63的方法,该方法在250°C _300°C的温度下进行,其中: a. 其中控制钼和锡的量和氧化态,以及钼与锡的比率和所述改性的稳定化含硅载体的酸度使得:使所转化乙酸的至少90%转化为乙醇,小于1%的乙酸转化为烷烃; b. 所述改性的稳定化含娃载体的表面积为至少200m2/g ; c. 锡与钼的摩尔比为5:4-4:5 ; d. 所述改性的稳定化含娃载体包含2. 5重量% -10重量%的娃酸隹丐。 Molybdenum and wherein the control amounts and oxidation states of tin, molybdenum, tin and the ratio of the modified and stabilizing a: 88. A method as claimed in claim 63, which is carried out at a temperature of 250 ° C _300 ° C, wherein. silicaceous support acidity that: the converted acetic acid is converted to ethanol at least 90%, less than 1% of acetic acid is converted to alkanes; b. at stabilized surface area support containing modified baby of at least 200m2 / g; c. tin molybdenum molar ratio is 5: 4-4: 5; d stabilizing the baby carrier comprises modified containing 2.5 wt% to 10 wt% of the baby acid Zhui hack.
CN201080006216.9A 2008-07-31 2010-10-26 Platinum for the production of ethanol by hydrogenating acetic acid contained in the silicon-containing support - tin catalyst CN102300635B (en)

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CN102300635A (en) 2011-12-28
EP2493609A1 (en) 2012-09-05
RU2012121807A (en) 2013-12-10
BR112012009770A2 (en) 2016-05-17

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