CN103084186A - Catalyst for preparing ethanol directly by acetic acid as well as preparation method and use thereof - Google Patents

Catalyst for preparing ethanol directly by acetic acid as well as preparation method and use thereof Download PDF

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CN103084186A
CN103084186A CN2013100534767A CN201310053476A CN103084186A CN 103084186 A CN103084186 A CN 103084186A CN 2013100534767 A CN2013100534767 A CN 2013100534767A CN 201310053476 A CN201310053476 A CN 201310053476A CN 103084186 A CN103084186 A CN 103084186A
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catalyst
ko
acid
alcohol
molybdenum
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CN2013100534767A
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CN103084186B (en
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蒋建明
常俊石
苏海兰
高珠
张建祥
史立杰
马超
高丽
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新地能源工程技术有限公司
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Abstract

The invention provides a catalyst for preparing ethanol directly by acetic acid as well as a preparation method and use thereof. More specific, the invention provides the catalyst for preparing ethanol directly by acetic acid. The catalyst comprises an active ingredient composition loaded on a carrier. The active ingredient composition comprises platinum and stannum as well as any one base metal in a group formed by free copper, molybdenum, tungsten, nickel, rhenium, chromium, vanadium and zinc. The content of platinum in the catalyst is 0.01-0.09wt%, and the weight ratio of platinum and stannum is Pt/Sn=1. The content of the base metal is 0.01-20wt%. Ethanol can be selectively prepared by the catalyst at a lower temperature, and the loading amount of noble metal platinum in the catalyst is lower, so that the catalyst is lower in cost and is equivalent or better than similar products in level.

Description

用于由こ酸直接制备こ醇的催化剂及其制备方法和用途 The catalyst used in its preparation and use by the alcohol ko ko acid prepared directly

技术领域 FIELD

[0001] 本发明属于催化化学领域,更具体地,本发明涉及用于由こ酸直接制备こ醇的催化剂、及其制备方法和用途。 [0001] The present invention belongs to the field of chemistry, and more particularly, the present invention relates to a catalyst for the production directly from alcohols ko ko acid, its preparation method and uses.

背景技术 Background technique

[0002] こ醇作为ー种基本有机化工原料,在化工和其它エ业领域的用途广泛,可作为消毒剂、溶剤,还可作为有机化工原料,用于油漆、涂料、染料、油墨和药品等的生产制造,另外还主要作为车用燃料。 [0002] ko ー alcohol as basic organic chemicals, widely used in the chemical industry and other fields Ester, as a disinfectant, Ji solvent, can be used as the organic chemical raw materials for paints, coatings, dyes, inks and drugs manufacturing, also primarily as a vehicle fuel. 目前,中国化工用こ醇市场年需求量在300万吨左右,每年增长率为8%-10%。 At present, China's chemical market by ko alcohol annual demand of 300 million tons, the annual growth rate of 8% -10%. 在燃料こ醇领域,中国市场目前需求约为150万吨/年,业内预计将迎来快速增长,2020年有望达1000万吨。 In the field of alcohol fuel ko, Chinese market demand is currently about 150 million tons / year, the industry is expected to usher in rapid growth in 2020 is expected to reach 10 million tons.

[0003] こ醇的生产方法有こ烯水合法和粮食发酵法,我国的エ业こ醇70%以上以粮食发酵法生产为主,毎年需要消耗大量的粮食,为了避免与民争粮,2006年底,国家发改委下达紧急通知,我国燃料こ醇项目的原料应坚持以非粮为主。 [0003] production methods ko alcohols have ko-en-hydration and food fermentation, our Ester industry ko alcohol more than 70% in order to produce food fermentation-based, every year need to consume large amounts of food in order to avoid competing with the public grain, 2006 late last year, the national Development and Reform Commission issued an emergency notice, the raw material of alcohol fuel ko projects should adhere to the non-grain-oriented.

[0004] 近几年中国新建醋酸(即,こ酸)装置陆续投产,国内醋酸产能急剧增加,而醋酸的表观消费量趋于平稳,造成产能严重过剩,醋酸加氢制こ醇エ艺,既可以充分利用过剩的醋酸资源,又可以为燃料こ醇的发展提供新的原料来源。 [0004] In recent years, Chinese New acetic acid (ie, ko acid) device gradually put into operation, domestic acetic acid production capacity increased dramatically, while the apparent consumption of acetic acid is stabilized, resulting in serious excess capacity, acetic acid hydrogenation ko alcohol Ester Arts, you can make full use of excess acetic resources, but also provide a new source of raw materials for the development of fuel ko alcohol. 经济方面,醋酸制こ醇エ艺1.5吨醋酸可生产I吨こ醇,エ艺过程简単,产品纯度高,和当前的粮食发酵法制こ醇相比,具有较大的成本优势。 Economically, Acetic Acid Ester alcohol ko Arts 1.5 tons of acetic acid to produce I t ko alcohol, Ester Jane radiolabeling arts process, high product purity, and the current food law ko alcohol fermentation compared with a large cost advantage.

[0005]目前,国内尚且没有由醋酸直接制こ醇的专利报道,国外已经有公开的专利报道,但大多数缺乏商业操作性。 [0005] At present, the country has not yet reported directly by the patent system ko alcohol acetate, foreign countries have published patent coverage, but most lack of commercial operability. 例如,专利US 2,607, 807报道了在钌催化剂上,在700〜950巴的压カ下醋酸制こ醇的收率可以达到88%,而在200巴的压カ下こ醇的收率仅为40%。 For example, the patent US 2,607, 807 reported on the ruthenium catalyst, the pressure of 700~950 bar ko ka lower alcohol to acetic acid yield can reach 88%, while the yield of alcohol ko ka pressure of 200 bar only 40%.

[0006] 美国塞拉尼斯公司近年来一直致カ于醋酸制こ醇催化剂和エ艺的研究,公开了ー系列专利。 [0006] Celanese Corporation of America in recent years has been the study of Acetic Acid Induced ka ko Ester alcohol and catalyst arts, there is disclosed a series of patents ー.

[0007] 例如,专利US 2011/0245546 Al,以Pt-Co或Pd-Co为活性组分,以石墨、高纯SiO2和硅酸钙等为载体制备负载型催化剂,こ醇收率最高可达68.2%,此时的催化剂组成为PtIwt % -Co IOwt % /SiO2。 [0007] For example, Patent No. US 2011/0245546 Al, to Pt-Co or Pd-Co as the active component, graphite, calcium silicate and SiO2 as the high purity prepared carrier-supported catalyst, an alcohol yield of up ko 68.2%, in this case the catalyst composition PtIwt% -Co IOwt% / SiO2.

[0008] 专利US 2010/0029995 Al,以Pt-Sn为活性组分,以石墨、高纯SiO2和硅酸钙等为载体制备负载型催化剂,こ醇收率最高可达79.4%,此时的催化剂组成为Pt Iwt % -SnIwt% /Si02。 [0008] Patent US 2010/0029995 Al, Pt-Sn to as the active component, graphite, calcium silicate, and high purity SiO2 as the carrier-supported catalyst was prepared, ko up 79.4% yield of the alcohol, in this case The catalyst composition of Pt Iwt% -SnIwt% / Si02.

[0009] 专利US 2011/0098501 Al,以Pt-Sn或Re-Pd为活性组分,以高纯SiO2为载体制备负载型催化剂,こ醇收率最高可达54%,此时的催化剂组成为Pt 0.5wt%-Sn 0.5wt%/Si02。 [0009] Patent US 2011/0098501 Al, or Pt-Sn to Re-Pd as the active component, for the preparation of high purity SiO2 carrier-supported catalyst, the yield ko up to 54% alcohol, in this case the catalyst composition pt 0.5wt% -Sn 0.5wt% / Si02.

[0010]专利 US 2011/0082322 Al,以Pt 1.6wt % -Sn Iwt % 为活性组分,当以高纯SiO2-TiO2 (IOwt% )为载体,こ醇收率最高可达73.6%,当以高纯Si02-Al203(7wt% )为载体,こ醇收率最高可达86.8%。 [0010] Patent US 2011/0082322 Al, to Pt 1.6wt% -Sn Iwt% of active ingredient, when high purity SiO2-TiO2 (IOwt%) as a carrier, an alcohol ko up 73.6% yield, as to high purity Si02-Al203 (7wt%) as a carrier, ko alcohol yield of up to 86.8%.

[0011] 此外,还有在SiO2载体中加入硅酸钙、硅酸镁、氧化锌等载体改进剂的报道,其こ醇的收率均较低。 [0011] In addition, there was added calcium silicate, magnesium silicate, zinc oxide, a carrier such as SiO2 carrier modifiers reported in a low yield rate thereof ko alcohol.

[0012] 塞拉尼斯公司的醋酸制こ醇エ艺简单,操作压カ一般约为2.2MPa,操作压カ低,商业操作性大。 [0012] manufactured by Celanese Acetate Ester alcohol ko simple process, the operating pressure is generally about 2.2MPa ka, ka low operating pressure, large commercial operability. 然而,塞拉尼斯公司的催化剂中,贵金属钼(Pt)的负载量(即,含量)高,均在0.1wt %以上,大多数在0.5〜2wt%以上,这使得制备的催化剂成本高。 However, Celanese catalyst, noble metals molybdenum (Pt) loading amount (i.e., content) high, were more than 0.1wt%, most more than 0.5~2wt%, which makes the high cost of catalyst preparation. 同时,现有的采用非贵金属的催化剂虽可降低成本,但其反应温度和反应压カ要求高,条件苛刻,商业操作性大大降低。 Meanwhile, conventional non-noble metal catalyst, although the cost may be reduced, but the reaction temperature and pressure demanding grades, harsh conditions, commercial operability is greatly reduced.

发明内容 SUMMARY

[0013] 为了克服用于こ酸直接制备こ醇的反应的现有催化剂的上述问题,本发明的目的是提供一种用于こ酸直接制备こ醇的低成本且可商业化的催化剂。 [0013] In order to overcome the above problems of the prior reaction of the acid catalyst used for the preparation of ko ko direct alcohol, object of the present invention to provide a method for the direct preparation of acid ko ko alcohol may be low cost and commercial catalysts.

[0014] 在一方面,本发明提供一种用于由こ酸直接制备こ醇的催化剂,所述催化剂包括负载在载体上的活性成分组合物,所述活性成分组合物包含钼和锡,以及选自由铜、钥、钨、镍、铼、铬、钒和锌组成的组中的任ー种的非贵金属组分,其中所述催化剂中的钼的含量为0.01〜0.09wt%并且钼和锡的重量比Pt/Sn为1,并且其中所述非贵金属组分的含量为0.01 〜20wt%。 [0014] In one aspect, the present invention provides a method for the direct preparation of an acid catalyst ko ko alcohol, the catalyst supported on a carrier comprising the active ingredient compositions, the active ingredient composition comprises molybdenum and tin, and selected from the group consisting of copper, keyhole, tungsten, nickel, rhenium, chromium, vanadium, and zinc according to any of the group consisting of non-noble metal component ー thereof, wherein the content of molybdenum in the catalyst is molybdenum and tin and 0.01~0.09wt% the weight ratio of Pt / Sn is 1, and wherein the content of said non-noble metal component is 0.01 ~20wt%.

[0015] 在ー个优选实施方式中,所述非贵金属组分是铜、钥或镍。 [0015] In ー preferred embodiment, the non-noble metal component is copper, nickel key.

[0016] 在ー个优选实施方式中,所述载体选自由ニ氧化硅、氧化铝、硅酸钙、碳、氧化锆和氧化钛组成的组中的任ー种,更优选是ニ氧化硅。 [0016] In embodiments ー preferred embodiment, the carrier is selected from the group consisting of Ni according to any species ー silica, alumina, calcium silicate, carbon, zirconia and titania in the composition, and more preferably is Ni silica.

[0017] 在另一方面,本发明提供一种制备上述催化剂的方法,所述方法包括:将钼盐溶液、锡盐溶液和所述非贵金属组分的盐溶液混合以得到浸溃液;将所述浸溃液浸溃到所述载体上以得到催化剂前体;和将所述催化剂前体进行干燥并焙烧而得到所述催化剂。 [0017] In another aspect, the present invention provides a method of preparing the catalyst, the method comprising: molybdenum salt solution, a tin salt solution and the salt solution of the non-noble metal component is impregnated to give a mixed solution; and the dipping liquid prior to dipping to obtain a catalyst precursor on the support; and before the catalyst precursor was dried and calcined to obtain the catalyst.

[0018] 在ー个优选实施方式中,所述浸溃液通过等体积浸溃法浸溃到所述载体上。 [0018] In ー preferred embodiment, the liquid impregnated by an equal volume impregnation method impregnated onto the carrier.

[0019] 在ー个优选实施方式中,所述浸溃液是氯钼酸的水溶液、草酸锡的稀硝酸溶液和所述非贵金属组分的硝酸盐水溶液的混合液。 [0019] In ー preferred embodiment, the dipping solution is an aqueous solution of molybdic acid chloride, a mixture of dilute nitric acid solution of tin oxalate and nitrate aqueous solution of the non-precious metal component.

[0020] 在ー个优选实施方式中,所述催化剂前体在100〜130°C下干燥0.5〜5小时并在400〜600°C下焙烧I〜8小时。 [0020] In ー preferred embodiment, the catalyst precursor was dried 0.5~5 hours at 100~130 ° C and calcined at 400~600 ° C I~8 hours.

[0021] 在另ー个方面,本发明提供上述催化剂在由こ酸直接制备こ醇中的用途,其中こ酸通过与氢气反应而被选择性加氢还原为こ醇。 [0021] In another ー aspect, the present invention provides the catalyst is prepared by the direct acid ko ko use alcohol, wherein the acid ko ko reduced to an alcohol by reaction with hydrogen are selectively hydrogenated.

[0022] 在ー个优选实施方式中,所述由こ酸直接制备こ醇的反应在气相中并且在200〜300°C的温度下进行。 [0022], by the reaction of the acid prepared directly ko ko alcohol and at a temperature of 200~300 ° C in ー preferred embodiment in the gas phase.

[0023] 在一个进ー步的优选实施方式中,作为反应物的こ酸和氢气的摩尔比为100:1〜1: 100,并且所述气相中的压カ为0.1〜3MPa。 Molar ratio [0023] In a further preferred embodiment the intake ー embodiment, as ko acid and hydrogen reactant 100: 1~1: 100, ka and the pressure in the gas phase 0.1~3MPa.

[0024] 在ー个优选实施方式中,所述由こ酸直接制备こ醇的反应在225〜280°C的温度下进行。 [0024], by the reaction of the acid prepared directly ko ko alcohol at a temperature of 225~280 ° C in the preferred embodiment ー.

[0025] 在一个进ー步的优选实施方式中,作为反应物的こ酸和氢气的摩尔比为1: 2〜I: 100,并且所述气相中的压カ为1.0〜2.5MPa。 Molar ratio [0025] In a further preferred embodiment the intake ー embodiment, as ko acid and hydrogen reactants is 1: 2~I: 100, ka and the pressure in the gas phase 1.0~2.5MPa.

[0026] 本发明的催化剂通过使用一定比例的Pt和Sn与另外的非贵金属组分的组合物作为活性成分,将催化剂中的Pt含量降低至0.01〜0.09wt%,不仅降低了所获得的催化剂的成本,而且本发明的催化剂可以以高转化率和高收率由こ酸选择性地制备こ醇,其催化效率优于或相当于现有的高成本贵金属催化剂。 [0026] The catalyst of the present invention, by using a certain proportion of Pt with Sn, and the composition further non-noble metal component as an active ingredient, the Pt content in the catalyst is reduced to 0.01~0.09wt%, not only the catalyst was reduced cost, and the catalyst of the present invention may be implemented in a high conversion rate and a high yield by the selective acid prepared ko ko alcohol, or the equivalent of its catalytic efficiency than the conventional high-cost noble metal catalyst.

具体实施方式 Detailed ways

[0027] 本发明目的是提供一种用于こ酸直接制备こ醇的低成本且可商业化的催化剂。 [0027] The object of the present invention is to provide a low-cost catalyst prepared directly ko ko acid and alcohol used may be commercial. 本发明的目的通过这样的催化剂而实现:所述催化剂包括负载在载体上的活性成分组合物,所述活性成分组合物包含钼和锡以及选自由铜、钥、钨、镍、铼、铬、钒和锌组成的组中的任ー种的非贵金属组分,其中所述催化剂中的钼的含量为0.01〜0.09wt%并且钼和锡的重量比Pt/Sn为1,并且其中所述非贵金属组分的含量为0.01〜20wt%。 Object of the present invention is achieved by providing a catalyst: the catalyst comprising supported on a carrier of the active ingredient composition, the active ingredient comprising a composition selected from the group consisting of molybdenum and tin, and copper, keyhole, tungsten, nickel, rhenium, chromium, vanadium and zinc group consisting of any kind of non-noble metal component ー, wherein the content of molybdenum in the catalyst is 0.01~0.09wt% by weight of molybdenum and the ratio of tin and Pt / Sn is 1, and wherein said non- the content of the noble metal component is 0.01~20wt%.

[0028] 利用本发明的催化剂,在氢气气氛下,可以将こ酸直接选择性加氢生成こ醇。 [0028] With the catalyst of the invention, under a hydrogen atmosphere, the acid may be directly ko ko selective hydrogenation alcohol. こ酸加氢生成こ醇的反应方程式如下: Scheme hydrogenation ko ko acid alcohol as follows:

[0029] CH3C00H+2H2--- CH3CH20H+H20 [0029] CH3C00H + 2H2 --- CH3CH20H + H20

[0030] 本发明的催化剂可以使用已知的各种用于催化剂的载体,其实例包括但不局限干:沸石、氧化铁、ニ氧化硅、氧化铝、氧化钛、氧化锆、氧化镁、硅酸钙、碳、石墨及其混合物。 [0030] The catalyst of the present invention can be used for various carriers known catalyst, examples of which include but are not limited to dry: zeolite, iron oxide, Ni silica, alumina, titania, zirconia, magnesia, silicon calcium, carbon, graphite, and mixtures thereof. 本发明优选使用的载体是ニ氧化硅、氧化铝、硅酸钙、碳、氧化锆和氧化钛,更优选使用ニ氧化硅作为本发明的催化剂的载体。 Preferred vectors of the present invention are ni silica, alumina, calcium silicate, carbon, zirconia and titania, the support is more preferably used as silica Ni catalyst according to the present invention.

[0031] 优选地,用于本发明催化剂的所述非贵金属组分可以选自以下金属构成的组:铜、钥、钨、镍、铼、铬、钒和锌,更优选地,所述非贵金属组分是铜、钥或镍。 [0031] Preferably, the non-noble metal component of the catalyst used in the present invention may be selected from the group consisting of the following metals: copper, keyhole, tungsten, nickel, rhenium, chromium, vanadium, and zinc, more preferably, the non- noble metal component is copper, nickel key.

[0032] 在本发明的催化剂中,锡的含量通常參考钼的含量,由于重量比Pt/Sn为1,所以如果催化剂中钼的含量为0.01或0.09wt%,则锡的含量也为0.01或0.09wt%。 [0032] In the catalyst of the present invention, the content of tin is generally referenced content of molybdenum, since the weight ratio of Pt / Sn is 1, if the molybdenum content in the catalyst is 0.01 or 0.09wt%, the tin content is 0.01 or 0.09wt%.

[0033] 本发明的催化剂可以通过本领域已知的方法制备。 [0033] The catalyst of the present invention can be prepared by methods known in the art. 优选地,本发明的催化剂通过以下方法制备,所述方法包括:将钼盐溶液、锡盐溶液和所述非贵金属组分的盐溶液混合以得到浸溃液;将所述浸溃液浸溃到所述载体上以得到催化剂前体;和将所述催化剂前体进行干燥并焙烧而得到所述催化剂。 Preferably, the catalyst of the present invention is prepared by the following method, the method comprising: molybdenum salt solution, a tin salt solution and the salt solution of the non-noble metal component is impregnated to give a mixed solution; the liquid impregnated Impregnated to the support to obtain a catalyst body front; and said catalyst precursor prior to drying and calcining to obtain said catalyst.

[0034] 在本发明的催化剂制备过程中,可以使用本领域内已知的任何方法进行金属浸溃。 [0034] During the preparation of the catalyst of the present invention, any method known in the art of metal impregnation. 优选地,所述浸溃液通过等体积浸溃法浸溃到所述载体上,例如但不限于,通过使用氯钼酸的水溶液、草酸锡的稀硝酸溶液和所述非贵金属组分的硝酸盐水溶液的混合液作为浸溃液进行浸溃,例如通过等体积浸溃法进行浸溃。 Preferably, the impregnated liquid volume impregnation method and the like by dipping onto the carrier, such as, but not limited to, nitric acid chloride by using an aqueous solution of molybdic acid, a dilute nitric acid solution of tin oxalate and the non-noble metal component a mixture of saline solution as a dipping solution for dipping, for example by dipping an equal volume impregnation method.

[0035] 优选地,在本发明的催化剂制备过程中,通过所述催化剂前体在100〜130°C下干燥0.5〜5小时并在400〜600°C下焙烧I〜8小时而获得期望的催化剂。 [0035] Preferably, during the preparation of the catalyst of the present invention, the catalyst precursor was dried by 0.5~5 hours and calcined at 400~600 ° C to obtain the desired I~8 hours at 100~130 ° C catalyst.

[0036] 本发明的催化剂可以应用于许多应用,尤其可以用于こ酸通过与氢气反应而被选择性加氢还原为こ醇的由こ酸直接制备こ醇的反应中。 Catalyst [0036] The present invention can be used in many applications, in particular for an acid ko reduced by reaction with hydrogen is selectively hydrogenated to alcohols by ko ko ko prepared directly from the acid alcohol. 由こ酸直接制备こ醇的反应可以在气相或液相条件下进行。 Prepared by the direct reaction of the acid ko ko alcohol may be carried out in the gas phase or liquid phase conditions. 优选地,该反应在气相(即所有反应物到达反应器时均为气态)中进行。 Preferably, the reaction in the vapor phase (i.e., all of the reactants are gaseous arrival reactor) is carried out. 可以使用的反应温度优选在约200〜300°C,更优选为225〜280°C。 The reaction temperature may be used preferably at from about 200~300 ° C, more preferably 225~280 ° C. 反应压カ通常对该反应不是关键影响因素,因此该反应压カ可以低于大气压、大气压或高于大气压。 The reaction pressure is not critical and the reaction is usually ka factors, so that the reaction pressure may ka subatmospheric, atmospheric or above atmospheric pressure. 然而,优选地,将该反应的压力控制在0.1〜3MPa的压カ范围内,优选在约1.0〜2.5MPa的范围内。 However, the pressure is preferably the pressure of reaction was controlled in the range 0.1~3MPa grades, preferably in the range of about 1.0~2.5MPa.

[0037] 尽管理论上,上述反应中每摩尔こ酸消耗2摩尔的氢气,但优选地,作为反应物的こ酸和氢气的进料摩尔比为约100:1〜1: 100,更优选地为1: 2〜1: 100,例如こ酸与氢气的进料摩尔比为1: 5,以提高こ酸的转化率。 [0037] Although in theory, the above reaction of acid per mole of ko consumes two moles of hydrogen, but preferably, a molar ratio ko acid and hydrogen feed of reactants is from about 100: 1~1: 100, more preferably 1: 2~1: 100, e.g. ko molar ratio of acid to hydrogen feed is 1: 5, in order to improve the conversion rate ko acid. [0038] 对于由こ酸直接制备こ醇的反应,可以采用常规方法例如采用安捷伦-6890气相色谱对产物进行定性和定量分析。 [0038] For the reaction of the acid prepared directly ko ko alcohols may be employed conventional methods such as gas chromatography with Agilent -6890 were qualitatively and quantitatively analyzed. 分析之前,用已知组成的标准气体和标准液体标定气相色谱。 Prior to analysis, the calibration gas and the standard gas chromatography using a standard liquid of known composition. 其中,前通道FID检测器和PLOT Q毛细管色谱柱用于分析反应中可能的以下产物:甲烷、こ烯、こ烷、丙烯、丙烷、甲醇、こ醇、こ醛、丙酮、こ酸甲酷、こ酸こ酯以及こ酸。 Wherein the front channel FID detector and a capillary column PLOT Q may be used to analyze the reaction product of the following: methane, ko alkenyl, alkoxy ko, propylene, propane, methanol, ko alcohols, aldehydes ko, acetone, methanesulfonic acid ko cool, acid esters and ko ko ko acid. 后通道TCD检测器和5A分子筛色谱柱用于分析可能的以下产物:ニ氧化碳等。 After passage TCD detector and a molecular sieve 5A column for an analysis of the possible products: carbon dioxide and the like Ni.

[0039] 采集的数据按以下方法处理: [0039] The data acquisition processing according to the following method:

[0040] 转化率X:表示发生转化的こ酸占作为原料的こ酸的摩尔百分比。 [0040] Conversion of X: represents the generation of transformed ko ko acid comprises the mole percent of the acid feed. こ酸的转化率 Ko conversion of the acid

是根据气相色谱数据按以下公式计算: According to gas chromatography data is calculated as follows:

[0041] [0041]

Figure CN103084186AD00061

[0042] 选择性S:表示某一产物基于转化掉的こ酸的摩尔百分比。 [0042] Selective S: represents the mole percent based on conversion of a product out ko acid. 选择性是根据气相色谱数据按以下公式计算,以こ醇为例: Selectivity is gas chromatography data is calculated according to the following formula to an alcohol ko Example:

[0043] [0043]

Figure CN103084186AD00062

[0044] 收率Y:表示某ー产物基于原料こ酸的摩尔百分数。 [0044] Yield Y: represents a mole percent based on the starting acid ko ー a product. 某ー产物的收率按以下公式计算:ー yield a product calculated by the following formula:

[0045] [0045]

Figure CN103084186AD00063

[0046] 以下实施例描述了用于制备在本发明的方法中使用的各种催化剂的程序。 [0046] The following examples describe various procedures for the preparation of the catalyst used in the process of the present invention.

[0047] 实施例A [0047] Example A

[0048] 制备Pt 0.01% -Sn0.01% /SiO2催化剂(无非贵金属组分,用于比较) [0048] Preparation of Pt 0.01% -Sn0.01% / SiO2 catalyst (nothing more precious metal components, for comparison)

[0049] 将氯钼酸(0.027g)的水溶液(0.67ml)和草酸锡(0.017g)的稀硝酸溶液(Iml)混合并加水配成72.6ml的浸溃液,加入到IOOg ニ氧化硅中,边加边搅拌,将得到的物料在逐渐加热到110°C的烘箱中干燥2小时,然后在马弗炉中500°C (升温速率,2°C /min)焙烧4小时,既得催化剂样品。 [0049] The aqueous solution of molybdic acid chloride (0.027 g) of (0.67 ml) and tin oxalate (0.017 g of) a dilute nitric acid solution (of Iml) were mixed and water was added 72.6ml of solution impregnated dubbed, Ni added to the silicon oxide IOOg , while adding while stirring, the resulting material was dried in an oven gradually heated to 110 ° C for 2 hours, and then in a muffle furnace 500 ° C (rate of temperature increase, 2 ° C / min) and baked for 4 hours, the catalyst sample vested .

[0050] 实施例B [0050] Example B

[0051] 制备Pt 0.09% -Sn0.09% /SiO2催化剂(无非贵金属组分,用于比较) [0051] Preparation of Pt 0.09% -Sn0.09% / SiO2 catalyst (nothing more precious metal components, for comparison)

[0052] 将氯钼酸(0.243g)的水溶液(6.03ml)和草酸锡(0.153g)的稀硝酸溶液(Iml)混合并加水配成72.6ml的浸溃液,加入到IOOg ニ氧化硅中,边加边搅拌,将得到的物料在逐渐加热到120°C的烘箱中干燥3小时,然后在马弗炉中500°C (升温速率,2°C /min)焙烧4小时,既得催化剂样品。 [0052] The aqueous solution of molybdic acid chloride (0.243 g) of (6.03 mL) and tin oxalate (0.153 g) in dilute nitric acid solution (of Iml) were mixed and water was added 72.6ml of solution impregnated dubbed, Ni added to the silicon oxide IOOg , while adding while stirring, the resultant material in an oven gradually heated to 120 ° C and dried for 3 hours in a muffle furnace and then 500 ° C (rate of temperature increase, 2 ° C / min) and baked for 4 hours, the catalyst sample vested .

[0053] 实施例C [0053] Example C

[0054] 制备Pt 0.09% -Sn0.09% -Ni 15% /SiO2催化剂(根据本发明的催化剂) [0054] Preparation of Pt 0.09% -Sn0.09% -Ni 15% / SiO2 catalyst (catalyst according to the invention)

[0055] 将氯钼酸(0.243g)的水溶液(6.03ml)、草酸锡(0.153g)的稀硝酸溶液(Iml)和硝酸镍(74.17g)的水溶液(50ml)混合并加水配成72.6ml的浸溃液,加入到IOOg ニ氧化硅中,边加边搅拌,将得到的物料在逐渐加热到110°C的烘箱中干燥2小时,然后在马弗炉中600°C (升温速率,2°C /min)焙烧3小时,既得催化剂样品。 [0055] The aqueous solution of molybdic acid chloride (0.243 g) of (6.03ml), tin oxalate (0.153 g) in dilute nitric acid solution (of Iml) and nickel nitrate (74.17g) (50ml) was mixed and water was added 72.6ml dubbed the dipping solution was added to the silicon oxide IOOg ni,, with stirring, and the resulting dried material was heated gradually to 110 ° C in an oven for 2 hours in a muffle furnace and then 600 ° C (heating rate, 2 ° C / min) was calcined for 3 hours, the catalyst samples acquired. [0056] 实施例D [0056] Example D

[0057] 制备Pt 0.09% -Sn0.09% -Cul5% /SiO2催化剂(根据本发明的催化剂) [0057] Preparation of Pt 0.09% -Sn0.09% -Cul5% / SiO2 catalyst (catalyst according to the invention)

[0058] 将氯钼酸(0.243g)的水溶液(6.03ml)、草酸锡(0.153g)的稀硝酸溶液(Iml)和硝酸铜(56.98g)的水溶液(50ml)混合并加水配成72.6ml的浸溃液,加入到IOOg ニ氧化硅中,边加边搅拌,将得到的物料在逐渐加热到110°C的烘箱中干燥2小时,然后在马弗炉中400°C (升温速率,2°C/min)焙烧4小时,既得催化剂样品。 [0058] The aqueous solution of molybdic acid chloride (0.243 g) of (6.03ml), tin oxalate (0.153 g) in dilute nitric acid solution (of Iml) and copper nitrate (56.98g) (50ml) was mixed and water was added 72.6ml dubbed the dipping solution was added to the silicon oxide IOOg ni,, with stirring, and the resulting dried material was heated gradually to 110 ° C in an oven for 2 hours in a muffle furnace and then 400 ° C (heating rate, 2 ° C / min) and baked for 4 hours, the catalyst samples acquired.

[0059] 实施例E [0059] Example E

[0060] 制备Pt 0.09% -Sn0.09% -Mol5% /SiO2催化剂(根据本发明的催化剂) [0060] Preparation of Pt 0.09% -Sn0.09% -Mol5% / SiO2 catalyst (catalyst according to the invention)

[0061] 将氯钼酸(0.243g)的水溶液(6.03ml)、草酸锡(0.153g)的稀硝酸溶液(Iml)和钥酸铵(193.24g)的水溶液(50ml)混合并加水配成72.6ml的浸溃液,加入到IOOg ニ氧化硅中,边加边搅拌,将得到的物料在逐渐加热到130°C的烘箱中干燥2小时,然后在马弗炉中500°C (升温速率,20C /min)焙烧4小时,既得催化剂样品。 [0061] The aqueous solution of molybdic acid chloride (0.243 g) of (6.03ml), a dilute nitric acid solution of tin oxalate (0.153 g) of (of Iml) and ammonium key (193.24g) (50ml) was mixed and water was added 72.6 dubbed ml of the dipping solution was added to Ni IOOg silicon oxide, while adding while stirring, the resulting material was dried in an oven gradually heated to 130 ° C for 2 hours and then in a muffle furnace 500 ° C (heating rate, 20C / min) and baked for 4 hours, the catalyst samples acquired.

[0062] 催化剂样品评价 [0062] Evaluation of catalyst sample

[0063] 所用的反应器为不锈钢管式反应器,将实施例A〜E制得的催化剂和前面提及的塞拉尼斯公司的催化剂(分别编号为塞拉尼斯I〜5)置于反应器恒温区中部,上下用不锈钢网和石英砂做支撑物。 [0063] The reactor used is a stainless steel tubular reactor, the catalyst and Celanese aforementioned catalyst prepared in Example A~E the embodiment (respectively numbered Celanese I~5) placed in the reactor middle temperature zone, vertical support made of stainless steel net and quartz sand. 反应原料为こ酸和氢气,こ酸由计量泵输送和计量,氢气由高压钢瓶输出并用质量流量计计量,こ酸和氢气的摩尔比为1: 5,こ酸和氢气在反应器之前混合并一起进入反应器中,在275°C和2.2MPa的压カ下进行反应,采出一部分反应流出物经过气相色谱分析组成及含量。 The reaction raw material ko acid and hydrogen ko acid, hydrogen output by the metering pump delivery and metered by a high pressure cylinder and measurement of the mass flow, molar ratio ko acid and hydrogen of 1: 5, ko acid and hydrogen mixed before the reactor and together into the reactor, reaction was performed at 275 ° C and a pressure of 2.2MPa ka, taken through a portion of the reaction effluent was analyzed by gas chromatography and the content of the composition.

[0064] 催化剂评价结果參见表I。 [0064] Catalyst evaluation are summarized in Table I.

[0065]表 I [0065] TABLE I

[0066] [0066]

Figure CN103084186AD00071

[0067] 从表I的催化剂评价结果可以看出:⑴根据实施例A〜E的催化剂(其中钼的含量为0.01〜0.09wt%并且钼和锡的重量比Pt/Sn为I)都可以催化こ酸制备こ醇;然而活性成分中不含根据本发明的非贵金属组分的催化剂(实施例A〜B)无论是在こ酸转化率方面还是在こ醇收率方面都大大低于根据本发明的催化剂(实施例D〜E的催化剂,其活性成分中含有根据本发明的非贵金属组分);(2)根据本发明的催化剂(实施例D〜E的催化剂)在由こ酸选择性地制备こ醇反应中,こ酸的转化率高(96%以上),こ醇的收率高(82%以上);(3)根据本发明的催化剂(实施例D〜E的催化剂)在こ醇收率方面与现有的塞拉尼斯公司的高贵金属含量催化剂(塞拉尼斯I〜5)的水平相当或更高。 [0067] As can be seen from the evaluation results of Table I Catalyst: ⑴ A~E of the catalyst according to Example (in which the content of molybdenum is molybdenum and tin 0.01~0.09wt% and the weight ratio of Pt / Sn is I) can catalyze acid preparation ko ko-ol; however, the active ingredient does not contain non-noble metal component of the catalyst according to the present invention (Example A~B) both in terms of conversion of the acid ko ko or in an alcohol yields are significantly lower than the present the catalyst of the invention (catalyst of Example D~E, which contains the active ingredient in accordance with the present invention, the non-noble metal components); (2) a selective catalyst according ko acid (Example D~E of catalyst) of the present invention. preparation of alcohol to ko, the conversion rate ko acid (96%), high yield ko alcohol (82%); (3) the catalyst according to the invention (catalyst of Example D~E embodiment) in ko yield aspect alcohol Celanese conventional high precious metal content of the catalyst (Celanese I~5) level comparable to or higher.

[0068] 另外,从催化剂成本来看,塞拉尼斯的催化剂中钼的负载量为0.5wt%以上,粗略地按I %钼负载量计算,每克钼按400元(人民币)计算,则每吨催化剂的成本至少为400万元。 [0068] Further, the catalyst costs, the Celanese molybdenum catalyst loading of less than 0.5wt%, calculated roughly I% Mo loading, per gram of molybdenum calculated as 400 yuan (RMB), each tons of catalyst cost at least 400 million yuan. 而在根据本发明的催化剂中,由于贵金属Pt的含量低(最高为整个催化剂的 In the catalyst according to the present invention, due to the low content of noble metal of Pt (up to the entire catalyst

0.09wt% ),同时负载量较高的非贵金属成本本身较低,对催化剂成本不会造成太大影响,这里以钼的负载量为0.09wt%计算,则每吨催化剂的成本不到40万元,低于塞拉尼斯催化剂成本的十分之一,因此具有较大成本优势,从经济角度来说更适合エ业化应用。 0.09wt%), while higher loadings of non-precious metal itself is low cost, the cost of the catalyst will not cause much impact, here to load 0.09wt% molybdenum is calculated, the cost per ton of catalyst less than 400,000 yuan, less than one-tenth the cost of Celanese catalyst, and therefore has a large cost advantage, from an economic point of view is more suitable for Ester industry applications.

[0069] 以上已对本发明进行了详细描述,但本发明并不局限于本文所描述具体实施方式。 [0069] The present invention has above been described in detail, but the present invention is not limited to the specific embodiments described herein. 本领域技术人员理解,在不背离本发明范围的情况下,可以作出其他更改和变形。 Those skilled in the art understand, without departing from the scope of the present invention, other changes and variations may be made. 本发明的范围由所附权利要求限定。 Scope of the invention defined by the appended claims.

Claims (13)

1.一种用于由こ酸直接制备こ醇的催化剂,所述催化剂包括负载在载体上的活性成分组合物,所述活性成分组合物包含钼和锡,以及选自由铜、钥、钨、镍、铼、铬、钒和锌组成的组中的任ー种的非贵金属组分, 其中所述催化剂中的钼的含量为0.01〜0.09wt%并且钼和锡的重量比Pt/Sn为1,并且其中所述非贵金属组分的含量为0.01〜20wt%。 A catalyst was prepared directly from the acid ko ko alcohol, said catalyst comprising a carrier supported on active ingredient compositions, the active ingredient composition comprises molybdenum and tin, and selected from the group consisting of copper, keyhole, tungsten, any group of nickel, rhenium, chromium, vanadium and zinc in the non-noble metal component ー thereof, wherein the content of molybdenum in the catalyst is 0.01~0.09wt% tin and molybdenum and the weight ratio of Pt / Sn 1 and wherein the content of said non-noble metal component is 0.01~20wt%.
2.根据权利要求1所述的催化剂,其特征在于,所述非贵金属组分是铜、钥或镍。 2. The catalyst according to claim 1, wherein said non-noble metal component is copper, nickel key.
3.根据权利要求1所述的催化剂,其特征在于,所述载体选自由ニ氧化硅、氧化铝、硅酸钙、碳、氧化锆和氧化钛组成的组中的任ー种。 3. The catalyst according to claim 1, characterized in that the carrier is selected from the group consisting of any one kind of Ni ー silica, alumina, calcium silicate, carbon, zirconia and titania in the composition.
4.根据权利要求3所述的催化剂,其特征在于,所述载体是ニ氧化硅。 4. A catalyst according to claim 3, wherein said support is silica ni.
5.一种制备根据权利要求1-4中任一项所述的催化剂的方法,所述方法包括: 将钼盐溶液、锡盐溶液和所述非贵金属组分的盐溶液混合以得到浸溃液; 将所述浸溃液浸溃到所述载体上以得到催化剂前体;和将所述催化剂前体进行干燥并焙烧而得到所述催化剂。 A method for preparing a catalyst as claimed in any one of the preceding claims, said method comprising: molybdenum salt solution, a tin salt solution and the salt solution mixed non-precious metal component is impregnated to give liquid; the dipping solution impregnated into the carrier to obtain a catalyst body front; and said catalyst precursor prior to drying and calcining to obtain said catalyst.
6.根据权利要求5所述的方法,其特征在干,所述浸溃液通过等体积浸溃法浸溃到所述载体上。 6. The method according to claim 5, characterized in that the dry, the impregnated liquid impregnated to the carrier by an equal volume impregnation method.
7.根据权利要求5所述的方法,其特征在于,所述浸溃液是氯钼酸的水溶液、草酸锡的稀硝酸溶液和所述非贵金属组分的硝酸盐水溶液的混合液。 7. The method as claimed in claim 5, wherein said immersion liquid is an aqueous solution collapse of molybdic acid chloride, a mixture of dilute nitric acid solution of tin oxalate and nitrate aqueous solution of the non-precious metal component.
8.根据权利要求5所述的方法,其特征在于,所述催化剂前体在100〜130°C下干燥0.5〜5小时并在400〜600°C下焙烧I〜8小时。 8. The method as claimed in claim 5, wherein the catalyst precursor is dried 0.5~5 hours at 100~130 ° C and calcined at 400~600 ° C I~8 hours.
9.根据权利要求1-4中任一项所述的催化剂在由こ酸直接制备こ醇中的用途,其中こ酸通过与氢气反应而被选择性加氢还原为こ醇。 9. The catalyst according to any one of claims 1-4 in claim acid directly produced by ko ko use alcohol, wherein the acid ko ko reduced to an alcohol by reaction with hydrogen are selectively hydrogenated.
10.根据权利要求9所述的用途,其特征在于,所述由こ酸直接制备こ醇的反应在气相中并且在200〜300°C的温度下进行。 10. Use according to claim 9, wherein the reaction of the acid prepared directly from the ko ko alcohol and at a temperature of 200~300 ° C in the gas phase.
11.根据权利要求10所述的用途,其特征在于,作为反应物的こ酸和氢气的摩尔比为100:1〜1: 100,并且所述气相中的压カ为0.1〜3MPa。 11. The use of claim 10, wherein the molar ratio of the acid and hydrogen gas as a reactant ko of 100: 1~1: 100, ka and the pressure in the gas phase 0.1~3MPa.
12.根据权利要求9所述的用途,其特征在干,所述由こ酸直接制备こ醇的反应在225〜280°C的温度下进行。 12. Use according to claim 9, characterized in that the dry, direct reaction of the acid prepared by the ko ko alcohol is performed at a temperature of 225~280 ° C.
13.根据权利要求12所述的用途,其特征在于,作为反应物的こ酸和氢气的摩尔比为1: 2〜1: 100,并且所述气相中的压カ为1.0〜2.5MPa。 13. Use according to claim 12, wherein the molar ratio of the acid and hydrogen gas as ko reactants is 1: 2~1: 100, ka and the pressure in the gas phase 1.0~2.5MPa.
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CN103691440A (en) * 2014-01-06 2014-04-02 神华集团有限责任公司 Catalyst for preparing ethanol through acetic acid hydrogenation and preparation method thereof
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CN104557453A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Method for preparing ethanol through hydrogenating acetic acid
CN104557454A (en) * 2013-10-23 2015-04-29 中国石油化工股份有限公司 Method for preparing high-quality ethanol through hydrogenating acetic acid
CN104557453B (en) * 2013-10-23 2017-03-29 中国石油化工股份有限公司 Hydrogenation of ethanol having an acetic acid method
CN103691450B (en) * 2014-01-06 2015-11-11 神华集团有限责任公司 One kind of acid ethanol hydrogenation catalyst and preparation method
CN103691440A (en) * 2014-01-06 2014-04-02 神华集团有限责任公司 Catalyst for preparing ethanol through acetic acid hydrogenation and preparation method thereof
US9353035B2 (en) 2014-04-28 2016-05-31 Celanese International Corporation Process for producing ethanol with zonal catalysts
US9073815B1 (en) 2014-04-28 2015-07-07 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol
US9024088B1 (en) 2014-04-28 2015-05-05 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide comprising nickel
US9458072B2 (en) 2014-04-28 2016-10-04 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol
US9382177B2 (en) 2014-04-28 2016-07-05 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal
CN105566064A (en) * 2014-10-14 2016-05-11 中国石油化工股份有限公司 Method for preparation of ethanol by acetic acid hydrogenation
CN105566064B (en) * 2014-10-14 2017-12-19 中国石油化工股份有限公司 Hydrogenation of ethanol having an acetic acid method
CN105709729A (en) * 2014-12-03 2016-06-29 神华集团有限责任公司 Catalyst for preparing ethanol through acetic acid hydrogenation, preparation method of catalyst and method for preparing ethanol through acetic acid hydrogenation
CN105709766A (en) * 2014-12-03 2016-06-29 神华集团有限责任公司 Catalyst for preparing ethanol through acetic acid hydrogenation, preparation method of catalyst and method for preparing ethanol through acetic acid hydrogenation

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