CN103785414A - Carboxylic acid hydrogenation catalyst, preparation method and application thereof - Google Patents

Carboxylic acid hydrogenation catalyst, preparation method and application thereof Download PDF

Info

Publication number
CN103785414A
CN103785414A CN201210429720.0A CN201210429720A CN103785414A CN 103785414 A CN103785414 A CN 103785414A CN 201210429720 A CN201210429720 A CN 201210429720A CN 103785414 A CN103785414 A CN 103785414A
Authority
CN
China
Prior art keywords
catalyst
according
carboxylic acid
hydrogenation catalyst
hydrogenation
Prior art date
Application number
CN201210429720.0A
Other languages
Chinese (zh)
Other versions
CN103785414B (en
Inventor
黄龙
王国清
田保亮
戴伟
李宝芹
杨溢
唐国旗
彭晖
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to CN201210429720.0A priority Critical patent/CN103785414B/en
Publication of CN103785414A publication Critical patent/CN103785414A/en
Application granted granted Critical
Publication of CN103785414B publication Critical patent/CN103785414B/en

Links

Abstract

The invention relates to a carboxylic acid hydrogenation catalyst which comprises a carrier, cobalt elements, and VIB-group elements, wherein the cobalt element accounts for 15 wt%-50 wt% of the total weight of the catalyst; the VIB-group element is at least one selected from molybdenum, tungsten, and chromium, and accounts for 0.5 wt%-15 wt% of the total weight of the catalyst; the carrier is at least one selected from silica, diatomite, calcium silicate, zirconia, and titanium oxide, and accounts for 20 wt%-80 wt% of the total weight of the catalyst. The catalyst is high in activity, high in selectivity of target products, low in manufacturing cost, and mild in reaction conditions.

Description

羧酸加氢催化剂、制备方法及其应用 Carboxylic hydrogenation catalyst preparation method and application

技术领域 FIELD

[0001] 本发明属于石化领域,更具体地说,涉及一种能将羧酸高收率加氢转化为醇的催化剂及其制备方法和应用。 [0001] The present invention belongs to petrochemical industry, and more particularly, relates to a catalyst and its preparation method and application in high yield carboxylic acids can hydrogenated to an alcohol.

背景技术 Background technique

[0002] 羧酸加氢制备醇的研究由来已久,早在1950年Ford等就申请了使用钌催化剂将羧酸转化为醇的方法。 [0002] Hydrogenation of the preparation of alcohols carboxylic acids long, as early as 1950 Ford applied for other methods using a ruthenium catalyst converting the carboxylic acid to an alcohol. 但是由于上世纪石油资源成本较为低廉以及人类对可持续发展重视程度较低,因此醇类的生产多采用烯烃水合、氧化-水合等技术。 However, due to oil resources and relatively low cost of the last century, mankind lower emphasis on sustainable development, and therefore use more alcohol producing olefin hydration, oxidation - hydration techniques. 进入21世纪后,随着对可再生体系和石油替代资源(煤炭、天然气、页岩气、煤层气)等的大规模开发,羧酸加氢制备醇成为更具经济性和可持续的方法。 In the 21st century, along with alternative sources (coal, natural gas, shale gas, coal bed methane) large-scale development of such systems and renewable petroleum, hydrogenation of carboxylic acids The method of the preparation of alcohols become more economical and sustainable.

[0003] 羧酸加氢制备醇的主要的技术难度在于开发出具有高活性和选择性的催化剂,降低所需的反应压力,并且催化剂需要具备有长时间使用的稳定性;另外催化剂的成本需要在合理的范围内,以保证其商业价值。 [0003] The main technical difficulty of the hydrogenation of carboxylic acids alcohols is to develop a catalyst having high activity and selectivity of the desired reaction pressure is reduced, and the catalyst has stability requires prolonged use; requires additional catalyst cost within reasonable limits, in order to ensure its commercial value.

[0004] US4104478公开了一种羧酸加氢催化剂及其应用方法,使用的催化剂为M-铼双金属催化剂,M为钌、铑、钼和钯中的一种,在170~250°C和2.0~14.0MPa的条件下,将相应的羧酸转化为脂肪醇。 [0004] US4104478 discloses a hydrogenation catalyst and a carboxylic acid application methods, the catalyst used is rhenium bimetallic catalyst M-, M being ruthenium, rhodium, palladium, and molybdenum, in and 170 ~ 250 ° C 2.0 ~ 14.0MPa under the conditions of the corresponding carboxylic acid to a fatty alcohol. 但在公开的实施例中反应压力都非常地高,均大于7.0MPa0 However, in this embodiment the reaction pressure is very high disclosed embodiments, greater than 7.0MPa0

[0005] US4517391公开了一种醋酸气相加氢制备乙醇的催化剂,催化剂含有不少于50wt%的钴,以及铜、锰、钥、铬和磷酸中的一种或者多种。 [0005] US4517391 discloses a gas-phase hydrogenation of ethanol acetate catalyst, the catalyst containing not less than 50wt% cobalt, and copper, manganese, keyhole, chromium, and phosphoric acid or more. 在唯一的实施例中,钴含量更高达70%,使用的反应压力为300bar,乙醇收率为97%。 In the only embodiment, the cobalt content as high as 70%, a reaction pressure of 300bar is used, the ethanol yield was 97%. 该专利催化剂钴金属含量极高,但是由于不使用贵金属,成本具有一定的优势,不过该催化剂活性较低,乙醇收率仅0.09kg/kg Cat/h,综合考虑催化剂成本依然较高,并且反应器将会非常庞大,因此并不具有商业化价值。 The high content of cobalt metal catalyst patent, but does not use the noble metal, the cost has certain advantages, but the low activity of the catalyst, the ethanol yield was only 0.09kg / kg Cat / h, still considering the high cost of the catalyst, and the reaction It is to be huge, and therefore does not have commercial value. 同时实施例未公开尾气中不凝性气相的含量,而物料收率低于理论值。 Example exhaust gas while the non-condensable gas content is not disclosed, but the yield of the material is lower than the theoretical value.

[0006] CN1008088公开了一种羧酸加氢制备醇的负载型催化剂,催化剂的第一组分为钨和钥,第二组分为钯、钌和钼中的一种,载体为活性炭。 [0006] CN1008088 discloses a supported catalyst for producing alcohols from the hydrogenation of a carboxylic acid, tungsten, and a first key component of the catalyst, a second component is palladium, ruthenium, and molybdenum, the carrier is activated carbon. 该催化剂含有I~10wt%的贵金属,成本高昂;并且反应空速较低,实施例中的LHSV仅为0.3511~1,意味着时空收率低于0.26kg/m3Cat/h,在实施例中的反应压力为1.0Mpa左右。 The catalyst comprises a noble metal I ~ 10wt%, costly; and the lower reaction space velocity, LHSV embodiment only 0.3511 to 1, which means space-time yield is less than 0.26kg / m3Cat / h, in the embodiment The reaction pressure is approximately 1.0Mpa.

[0007] CN201110104763.7和CN201110103802.1公开了一种醋酸加氢催化剂及其应用方法,催化剂的第一活性组分为钨和钥,第二组分为钌、铑、钼和钯中的一种,载体为活性炭或者石墨,在其公开的实施例中,反应压力为7.0~10.0MPa0 [0007] CN201110104763.7 and CN201110103802.1 disclose a hydrogenation catalyst and a method for application of acetic acid, the active component of the catalyst of the first tungsten and key, a second component of ruthenium, rhodium, palladium, molybdenum, and a species, the carrier is activated carbon or graphite, in which embodiments of the disclosed embodiment, reaction pressure 7.0 ~ 10.0MPa0

[0008] 在Aqueous-phase hydrogenation of lactic acid to propyleneglycol, Applied Catalysis A:General 219 (2001) 89 - 98 中,Zhang 等研究了乳酸水相加氢制备丙二醇,使用负载的钌催化剂和滴流床反应器,其中水含量一般为40~80%的水。 [0008] In Aqueous-phase hydrogenation of lactic acid to propyleneglycol, Applied Catalysis A: General 219 (2001) 89 - 98 were studied, Zhang et acid aqueous phase hydrogenation of propylene glycol, and the supported ruthenium catalyst using a trickle bed reactor , wherein the water content is generally 40 to 80% water. 在该方法中,较高含量的水无疑会大幅增加分离时的能耗;使用的催化剂为5wt%的Ru/C,高昂的催化剂成本使得其不适应于商业化操作。 In this process, the higher the water content will undoubtedly greatly increase the energy consumption during separation; 5wt% of the catalyst used is Ru / C, the high cost of the catalyst such that it is not suited for commercial operations.

[0009] CN102149662公开一种用于醋酸加氢的钴催化剂,钴的负载量低于20wt%,并且催化剂中还含有lwt%&右的钯和钼。 [0009] CN102149662 discloses a cobalt catalyst for the hydrogenation of acetic acid, the cobalt loading is less than 20wt%, and the catalyst also contains a right lwt% & palladium and molybdenum. 在公开的实施例中钴含量均低于10wt%。 In the disclosed embodiment, a cobalt content of less than 10wt%. [0010] US7863489公开一种醋酸加氢催化剂,催化剂活性组分为钼,助剂为锡。 [0010] US7863489 discloses a hydrogenation catalyst acid activity of the catalyst component is molybdenum, tin aid. 催化剂可以将乙酸以较高的收率转化为乙醇,但是钼含量较高,在公布的实施例中,钼含量超过lwt%。 The catalyst may be acetic acid is converted to ethanol in good yield, but high molybdenum content, in the embodiment of the publication, the molybdenum content of more than lwt%. 众所周知,钼的价格非常昂贵而且储量非常有限,因此在商业化应用中将会使得催化剂的成本极高。 As we all know, the price of molybdenum reserves are very limited and very expensive, so in commercial applications will make the high cost of the catalyst. 同样的问题也存在于另一专利US7608744中,钴催化剂含量较低,约为10wt%,同时催化剂需要使用贵金属助剂,如钼和钯,助剂含量高于lwt%。 The same problem also exists in another patent US7608744, a lower cobalt content of the catalyst, about 10wt%, while the need to use a noble metal catalyst additives, such as molybdenum and palladium, aid content greater than lwt%.

[0011] 综上所述,现有技术中存在一些技术和商业化问题:催化剂成本高昂而且生产催化剂的原料供给量有限、时空收率低、选择性较低、反应压力较高使得操作条件过于苛刻、能耗过高。 [0011] In summary, there are some technical issues and commercial prior art: the catalyst is costly and of limited supplies of the raw materials of the catalyst, low space-time yield, selectivity is low, the reaction pressure is too high so that the operating conditions harsh, high energy consumption.

发明内容 SUMMARY

[0012] 本发明要解决的技术问题是提供一种含有VIB族元素的钴金属催化剂及其制备方法和其在一元羧酸加氢中的应用,该催化剂活性较高,目的产物选择性高,制造成本较为低廉,反应条件较温和。 [0012] The present invention is to solve the technical problem is to provide a catalyst and its preparation method and use thereof containing a group VIB element is cobalt metal in the hydrogenation of a monocarboxylic acid, the higher the catalytic activity, high selectivity of the desired product, relatively low manufacturing cost, relatively mild reaction conditions.

[0013] 本发明的目的之一是提供一种羧酸加氢催化剂,该催化剂含有载体、钴元素、VIB族元素,其中钴元素的含量占催化剂总重的15wt%〜50wt%,VIB族元素选自钥、钨、铬中的至少一种,其含量占催化剂总重的0.5wt%〜15wt%,所述的载体选自氧化娃、娃藻土、娃酸隹丐、氧化错、氧化钛的至少一种,其含量占催化剂总重的20wt%〜80wt%。 [0013] One object of the present invention is to provide a carboxylic acid hydrogenation catalyst, the catalyst comprising a carrier, the content of cobalt, VIB group elements, cobalt accounts for 15wt% ~50wt% of the total weight of the catalyst, VIB group elements key is selected, tungsten, chromium, at least one of an amount of from 0.5wt% ~15wt% of the total weight of the catalyst, the carrier is selected baby oxide, diatomaceous earth baby, baby acid short-tailed Hack, wrong oxide, titanium oxide at least one of an amount of from 20wt% ~80wt% of the total weight of the catalyst.

[0014] 本发明的详细说明: [0014] Detailed Description of the Invention:

[0015] 本发明的催化剂主活性组分为钴,其中钴金属含量占催化剂总重的15wt%〜50wt%,更优选的含量为20wt%〜40wt%。 Primary active catalyst component [0015] of the present invention is cobalt, wherein the cobalt metal content accounts for 15wt% ~50wt% of the total weight of the catalyst, more preferably in an amount of 20wt% ~40wt%. 所述的钴金属含量是指元素钴的含量。 The cobalt metal content refers to the content of elemental cobalt. 本技术领域的技术人员往往认为提高主活性组分的含量会提高催化剂的活性,但发明人意外地发现:在较低钴含量时催化剂的活性较低,而更高含量的钴不仅使得催化剂的成本上升,而且并不能够提高催化剂的活性,甚至有所下降,在较高含量时候有明显的下降;在钴含量高于50wt%时候催化剂的制备难度增加,如成型过程等,这将会使得催化剂的商业化较为困难。 Those skilled in the art that tend to increase the content of the main active components will increase the activity of the catalyst, the inventors surprisingly found that: lower activity of the catalyst at lower cobalt content, higher levels of the cobalt catalyst not only makes costs, but is not able to improve the catalytic activity, even decreased, significantly decreased when higher levels; the cobalt content is higher than 50wt% when catalyst increases the difficulty of preparation, such as molding processes, etc., which will make commercial catalyst more difficult.

[0016] 钴金属的来源可选自水溶性的硝酸盐、硫酸盐、氯盐、醋酸盐、草酸盐和溴盐,具体地说,选自硝酸钴、氯化钴、草酸钴、硫酸钴、醋酸钴中的一种或者多种,更优选为硝酸钴、醋酸钴和草酸钴中的一种或者多种。 [0016] The cobalt metal source selected from water-soluble nitrate, sulfate, chloride, acetate, oxalate and bromide salts, in particular, is selected from cobalt nitrate, cobalt chloride, cobalt oxalate, sulfate , cobalt acetate in one or more, and more preferably as a cobalt nitrate, cobalt acetate and cobalt oxalate or more.

[0017] 所述的催化剂还含有VIB族元素,所述的VIB族元素为钥、钨和铬中的至少一种,占催化剂总重的0.5wt%〜15.0wt%,优选的重量范围为1.0wt%〜10.Wt%。 Catalyst [0017] further comprises said group VIB element, the Group VIB element is key, tungsten, chromium, and at least one, accounting for 0.5wt% ~15.0wt% of the total weight of the catalyst, preferably in the range of 1.0 wt. wt% ~10.Wt%. 钥的来源可选自水溶性钥酸盐,如钥酸铵、钥酸钠、钥酸钾、钥酸镁中的一种,或者钥的络合物,如柠檬酸钥等。 Key key source selected from water soluble salts, such as ammonium key, key, sodium, potassium key a key of magnesium, key or complexes, such as citric acid and other keys.

[0018] 钨的来源可选择水溶性盐或者添加碱性助溶剂后可溶的盐,如钨酸铵、偏钨酸铵、钨酸锌、钨酸钠、钨酸钾等。 After Source [0018] Alternatively the water-soluble salts of tungsten or adding a basic co-solvent-soluble salts, such as ammonium tungstate, ammonium meta tungstate, zinc tungstate, sodium tungstate, potassium tungstate and the like.

[0019] 铬的来源可选择自水溶性盐或者加入酸性助溶剂后可溶的盐,如重铬酸铵、重铬酸钠、重铬酸钾、铬酸钡、铬酸酐、铬酸钠、铬酸钾、铬酸镁、硝酸铬、醋酸铬、草酸铬等。 After [0019] The source of chromium from water soluble salts or optionally adding an acidic co-solvent-soluble salts, such as ammonium dichromate, sodium dichromate, potassium dichromate, barium chromate, chromic anhydride, sodium chromate, potassium chromate, magnesium chromate, chromium nitrate, chromium acetate, chromium oxalate and the like.

[0020] 钥、钨和铬同属于VIB族元素,作为催化剂的第二组分可明显地提高催化剂的活性、选择性和稳定性等催化剂的性能指标,其中的原因可能是多方面的:抑制了钴晶粒的长大或者活化了羧酸。 [0020] Key, tungsten and chromium belong to group VIB element, as a second component of the catalyst can significantly improve the performance of the catalyst activity of the catalyst, selectivity and stability and the like, which may be due to many reasons: inhibition cobalt grain growth or activated carboxylic acid. 另外,相对于浸溃法,通过共沉淀、沉积-沉淀或者溶胶-凝胶方法制备的钴催化剂,其性能改善的效果更加明显,更加体现本发明方案的优越性。 Further, with respect to the dipping method, by co-precipitation, deposition - precipitation or sol - gel method for preparing a cobalt catalyst, its performance improvement effect is more obvious, and more reflects the superiority of the present invention. [0021] 所述的催化剂中含有氧化物组分,其含量占催化剂总重的20wt%〜80wt%。 [0021] The oxide component contained in the catalyst, an amount of from 20wt% ~80wt% of the total weight of the catalyst. 所述的氧化物组分选自氧化硅、氧化锆、氧化钛中的一种或多种,优选氧化硅。 The oxide component selected from silicon oxide, zirconium oxide, one or more, preferably silicon oxide, titanium oxide. 这些氧化物主要起到载体的作用,不仅起到支撑作用,还能够协助活性组分的分散或羧酸的活化。 These oxides are mainly functions as a carrier, not only play a supporting role, but also to assist in the activation of dispersed active ingredient or a carboxylic acid. 因此这些载体影响着催化剂的结构性能、产物和原料在其中的扩散、机械强度、活性和稳定性等关键性指标。 These vectors thus affecting the structure of the catalyst performance, and product diffusion material therein, mechanical strength, stability and activity of key indicators.

[0022] 所述的氧化硅载体可以选自水玻璃沉淀法、二氧化硅粉末、正硅酸乙酯水解、硅溶胶等。 Silica support according to [0022] can be selected from precipitated silicate, silica powder, TEOS hydrolysis, such as silica sol. 所述的水玻璃沉淀法是指以水玻璃为原料,在水玻璃中加入酸性沉淀剂或者离子沉淀剂,如硫酸、盐酸、硝酸、醋酸、硝酸钙、硝酸氧锆、氧氯化锆、硝酸镁、硝酸钴等。 The precipitation method is a sodium silicate water glass as raw material, or the addition of an acidic ion precipitating agent in water glass precipitating agent, such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, calcium nitrate, zirconyl nitrate, zirconium oxychloride, zirconium nitrate magnesium, cobalt nitrate. 沉淀剂加入后形成白色胶状物,洗涤数次后使用或者在此基础之上进行其他组分的沉淀法加入。 A white gum after precipitation agent is added, after washing several times or by using other components precipitated on this basis was added. 所述的二氧化硅粉末可以通过化学沉积法、水玻璃沉淀干燥后球磨获得、或者是硅溶胶喷雾干燥等方法获得,其尺寸选自IOnm〜500 μ m ;如青岛海洋化工厂生产的粗孔微球二氧化硅,平均孔径为8.0〜12.0nm,比表面积为300〜600m2/g,孔容为0.8〜1.lml/g ;又如广州人民化工厂生产的沉淀二氧化硅,二氧化硅含量95.0,细度(325目筛余物)%< 1.8,比表面积为400〜600m2/g或者活性白炭黑;又如德固赛公司的气相二氧化硅AER0SIL200,其比表面为200m2/g ;又如自制喷雾干燥获得的二氧化硅微球,比表面为400〜500m2/g,尺寸为2〜30 μ m。 The silicon dioxide powder by a chemical deposition method, waterglass precipitate was dried to obtain milling, spray drying or the like to obtain silica, which size is selected IOnm~500 μ m; Qingdao Ocean Chemical Plant as coarse pores silica microspheres, average pore diameter 8.0~12.0nm, specific surface area 300~600m2 / g, a pore volume of 0.8~1.lml / g; and if people Guangzhou chemical Plant precipitated silica, silica content 95.0, fineness (325 mesh sieve residue)% <1.8, a specific surface area 400~600m2 / g or activity of white carbon; and if Degussa fumed silica AER0SIL200, the specific surface of 200m2 / g ; spray drying and if self-silica microspheres, specific surface area 400~500m2 / g, a size of 2~30 μ m. 二氧化硅粉末可以在沉淀或者沉积-沉淀法中作为载体加入。 Silica powder may be precipitated or deposited - precipitation method was added as a carrier. 正硅酸乙酯是在溶胶-凝胶法制备本发明的催化剂中使用。 TEOS is a sol - gel method using the catalyst of the present invention. 硅溶胶作为液态硅源,可直接使用进入沉淀、沉积-沉淀法的沉淀物系中。 Silica as a liquid silicon source, can be used directly into the precipitation, deposition - precipitation method based precipitate in.

[0023] 所述的硅藻土是一种天然的多孔材料,主要由无定形的SiO2组成并含有少量Fe203、CaO、Mg0、Al203及有机杂质,具有特殊多孔性构造。 [0023] The diatomaceous earth is a naturally porous material, mainly composed of amorphous SiO2 and containing a small amount of Fe203, CaO, Mg0, Al203 and organic impurities, having a specific porous structure. 如吉林省长白县青山源娃藻土公司生产的娃藻土。 Jilin Changbai County Aoyama source as diatomaceous earth produced baby doll diatomaceous earth.

[0024] 所述的氧化锆载体选自粉体氧化锆材料或者通过锆盐的沉淀获得。 Zirconia support the [0024] material selected from zirconium oxide powder is obtained by precipitation or zirconium salt. 粉体氧化锆尺寸选自IOnm〜500 μ m,比表面大于20m2/g。 Zirconia powder size selected IOnm~500 μ m, a specific surface area greater than 20m2 / g. 锆盐的沉淀物可按照以下途径实现:首先将氧氯化锆溶解在水中,随后加入苛性钠等强碱,最后将沉淀物洗涤过滤得到的凝胶;或者使用硝酸氧锆作为锆源,加入苛性钠沉淀后洗涤过滤获得的凝胶。 Precipitate zirconium salt may be implemented in the following ways: First, zirconium oxychloride was dissolved in water, followed by addition of a strong base such as caustic soda, and finally the obtained precipitate was filtered and washed gel; using zirconyl nitrate or a zirconium source were added after the precipitate was washed with caustic soda obtained gel filtration. 将上述的凝胶加入到其他沉淀物中,或者将上述的凝胶经过干燥后磨成粉体后作为沉积-沉淀的载体加入。 The above gel was added to precipitate the other, or the above-mentioned gel after drying the milled powder is deposited as a - added to the precipitated carrier.

[0025] 本发明中的氧化钛载体可以是市售二氧化钛,如德固赛公司的P25,也可以采用液相沉淀的方法制备,如采用四氯化钛或者硫酸钛作为钛源,加入尿素、氨水、碳酸钠或者苛性钠等作为沉淀剂,也可以采用有机钛酸如钛酸丁酯水解制备。 [0025] In the present invention, the titania support may be a commercially available titanium dioxide, such as Degussa's P25, may also be prepared using a liquid phase precipitation method, such as titanium tetrachloride or titanium sulfate as a titanium source, addition of urea, ammonia, such as caustic soda or sodium carbonate as a precipitating agent, an organic titanate such as tetrabutyl titanate prepared hydrolysis may also be employed.

[0026] 所述催化剂的制备方法选自共沉淀法、沉积-沉淀法和溶胶-凝胶法中的至少一种。 [0026] The preparation of a catalyst selected from the coprecipitation method, a deposition - at least one gel process - precipitation method and sol. 共沉淀法、沉积-沉淀法和溶胶-凝胶法制备催化剂作为现有成熟技术为本领域技术人员所熟知,在本领域书籍中均有详细的介绍,如黄仲涛所著的《工业催化剂设计与开发》,Gerhard Ertl 教授等所著的《Preparation of Solid Catalysts》。 Coprecipitation, deposition - precipitation method and sol - gel method as a catalyst mature prior art known to the person skilled in the art are described in detail in the book, such as the Huang Zhongtao book "Industrial Design and catalyst development ", Professor Gerhard Ertl book" Preparation of Solid Catalysts ".

[0027] 本发明的催化剂还可以含有银盐作为助剂,银元素含量占催化剂总重的 [0027] The catalyst of the present invention may also contain as additives a silver salt, the silver content of the total weight of the catalyst accounted

0.1wt %〜IOwt 更优先的范围为0.2wt%〜2wt%,进一步优选的范围为0.2wt %〜 0.1wt% ~IOwt more preferred in the range of 0.2wt% ~2wt%, more preferably in the range of 0.2wt% ~

0.5wt%;银元素的来源为硝酸银。 0.5wt%; the silver source is silver nitrate. 银盐的添加方式可以是多样的,如在沉淀、沉积-沉淀或者溶胶-凝胶过程中与钴盐一起溶解后加入;在催化剂前驱体中加入,如沉淀、沉积-沉淀或者溶胶-凝胶中获得的干燥后滤饼或干凝胶中,或者焙烧分解后的材料中;或者在打片或者挤条等成型阶段加入。 Manner of adding the silver salt may be varied, such as precipitation, deposition - precipitation or sol - gel process after the dissolution of the cobalt salt was added together; added catalyst precursor, such as precipitation, deposition - precipitation or sol - gel after drying the filter cake or the dry gel obtained or calcined material decomposition; or added in a tabletting or extrusion molding strips stage. 在通过共沉淀、沉积-沉淀或者溶胶-凝胶方法制备的钴催化剂中,加入银盐改善催化剂反应性能的效果更加明显。 By co-precipitation, deposition - precipitation or sol - gel effect cobalt catalyst prepared in the method, silver salt was added to improve catalyst performance is more pronounced.

[0028] 所述的催化剂还可以含有碱金属或碱土金属元素,所述的碱金属或碱土金属元素含量占催化剂总重的0.lwt%~ 15wt%。 [0028] The catalyst may also contain an alkali metal or alkaline earth metal element, the alkali metal or alkaline earth metal element content accounts 0.lwt% ~ 15wt% of the total weight of the catalyst. 具体地说,所述的碱金属或碱土金属元素选自钾、纳、韩、续、锁中的一种或多种,含量占ί隹化剂总重的0.2wt*%~10wt*%。 In particular, the alkali metal or alkaline earth metal element selected from potassium, sodium, Han, continued a lock or more, the content of the total weight of short-tailed ί agent 0.2wt *% ~ 10wt *%. 喊金属和喊土金属元素的来源可以为水溶性的硝酸盐、碳酸盐、氯盐、磷酸盐、硫酸盐、醋酸盐、氟化物、氢氧化物等。 Call and call metallic earth metal element source may be water soluble nitrate, carbonate, chloride, phosphate, sulfate, acetate, fluoride, hydroxide and the like. 具体地说,其来源选自氢氧化钾、硝酸钾、碳酸钾、醋酸钾、氟化钾、磷酸钾、氢氧化钠、硝酸钠、碳酸钠、碳酸氢钠、氯化钠、硫酸钠、醋酸钠、硝酸钙、磷酸二氢钙、硝酸镁、磷酸镁、硝酸钡中的一种或多种。 Specifically, the source is selected from potassium hydroxide, potassium nitrate, potassium carbonate, potassium acetate, potassium fluoride, potassium phosphate, sodium hydroxide, sodium nitrate, sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate, acetate sodium, calcium nitrate, calcium dihydrogen phosphate, magnesium nitrate, magnesium phosphate, barium nitrate of one or more.

[0029] 含有碱金属和碱土金属兀素的化合物的加入方式可以选自以下方式中的任意一种:在沉淀、沉积-沉淀或者溶胶-凝胶过程中与钴盐一起溶解后加入;在沉淀、沉积-沉淀或者溶胶-凝胶过程中与钴盐分别加入;在催化剂前驱体中加入,如沉淀、沉积-沉淀或者溶胶-凝胶中获得的干燥后滤饼或干凝胶中,或者焙烧分解后的材料中;或者在打片或者挤条等成型阶段加入。 [0029] The addition of the compounds containing alkali and alkaline earth metal element may be selected Wu any one of the following ways: the precipitation, deposition - precipitation or sol - gel process after dissolved together with cobalt salt is added; the precipitated deposition - precipitation or sol - gel process and the cobalt salt were added; added catalyst precursor, such as precipitation, deposition - precipitation or sol - gel after drying the filter cake or dry gel obtained, calcined or material after decomposition; or added in a tabletting or extrusion molding strips stage.

[0030] 所述的催化剂还可以含有稀土金属元素,其氧化物含量占催化剂总重的0.1wt %~8wt% ;所述的稀土金属元素选择镧或者铺中的一种,其氧化物含量优选占催化剂总重的0.5wt%~5wt%。 [0030] The catalyst may also contain rare earth metal elements, the content of which accounts for oxides 0.1wt% ~ 8wt% of the total weight of the catalyst; said rare earth metal element selected in the shop or lanthanum, oxides content is preferably accounting for the total 0.5wt% ~ 5wt% of the weight of the catalyst. 加入微量的稀土元素能够降低不凝性气体含量而使得钴催化剂的选择性得到一定程度的提高。 Adding a trace amount of rare earth elements can be reduced and the non-condensable gas content such that the cobalt catalyst selectivity improved to some extent.

[0031] 所述催化剂还可以含有一种或多种无机非金属元素,含量占催化剂总重的 [0031] The catalyst may further contain one or more inorganic non-metallic elements, the content of the total weight of the catalyst

0.lwt%~5wt%。 0.lwt% ~ 5wt%. 具体地说,所述的无机非金属元素选自磷、硼、氟中的一种,含量占催化剂总重的0.3wt%~ 2wt%。 Specifically, the inorganic non-metallic element selected from phosphorus, boron, fluorine, and content accounts 0.3wt% ~ 2wt% of the total weight of the catalyst. 这些无机非金属元素的加入,有的伴随着其他助剂的加入而进入催化剂体系,如氟化钾。 The addition of inorganic non-metallic elements, along with some other additives added into the catalyst system, such as potassium fluoride. 有的是通过额外的方式加入,如硼的加入可采用将硼酸水溶液加入滤饼中的方式。 By addition of some additional manner, such as boron can be added to an aqueous solution of boric acid was added in such a way the filter cake.

[0032] 本发明的另一个目的是提供一种将上述催化剂应用于羧酸加氢制备醇的方法。 [0032] Another object of the present invention is to provide a catalyst for hydrogenation of carboxylic acids to the above-described method for the preparation of alcohols. 具体地说,是将一元羧酸气化并与氢气混合,或者将一元羧酸在氢气中气化后进入加氢反应器内,并与本发明所述的催化剂接触转化为脂肪醇和水。 More specifically, the monocarboxylic acid is vaporized and mixed with hydrogen, or the monocarboxylic acid into the gasification hydrogen in the hydrogenation reactor, and the conversion catalyst of the present invention with the aliphatic alcohol and water.

[0033] 催化剂装填的反应器为固定床反应器,优选列管式反应器。 [0033] The packing of the catalyst reactor is a fixed bed reactor, preferably a tubular reactor column. 具体地说,是将催化剂装填在管内,而管间充填导热介质,如导热油或者水等,这样更利于反应热的移出。 More specifically, the catalyst is packed in the tube, and the tube is filled between the heat transfer medium, such as water or thermal oil, which is more conducive to the heat of reaction is removed. 本领域的技术人员均熟知该项技术要领,如每根管装填量需保持一致等。 Those skilled in the art are well known to the technical points, such as the amount of each tube loading must be consistent and the like.

[0034] 本发明所述的催化剂在应用于羧酸加氢中时,需要将其充分地还原活化使得绝大部分钴在进行加氢反应前都被还原为零价状态,活化的方式可以是在升温条件下通入氢气、使用还原剂如硼酸钠等、或者采用电离辐照的方法。 [0034] The catalyst of the present invention, when applied to the hydrogenation of carboxylic acids, which needs to be sufficiently reductive activation is performed such that most of the cobalt in the zero valence state are restored before the hydrogenation reaction, the activated mode can be at elevated temperature into hydrogen gas using a reducing agent such as sodium borate, or with ionizing radiation. 这些方法都为本领域的技术人员所熟知。 These methods are known to those skilled in the art.

[0035]本发明所述的加氢方法,反应温度为180~350°C,更优选为220~300°C,在该范围内催化剂的选择性变化较小,维持较高的水平。 [0035] The hydrogenation process of the present invention, the reaction temperature is 180 ~ 350 ° C, more preferably 220 ~ 300 ° C, the catalyst is less selective variation within this range, to maintain a high level. 反应温度较低时,羧酸转化率较低,这使得循环能耗增大;而反应温度继续升高时,副产物尤其是不凝性气体产物如乙烷的量大幅增加。 When the reaction temperature is low, low conversion of carboxylic acid, which makes circulation increased energy consumption; the reaction temperature continues to rise, especially byproducts products such as non-condensable gas a substantial increase in the amount of ethane.

[0036] 对于一元羧酸加氢制备为醇的反应,理论上氢气消耗量与一元羧酸的摩尔比为2,但为维持后续反应压力和催化剂寿命,氢气与一元羧酸的摩尔比例为4:1~40:1,更优比为6:1~25:1,进一步的优化比率为8:1~20:1。 [0036] For the preparation of monocarboxylic acid the hydrogenation reaction of the alcohol, the molar ratio of the theoretical hydrogen consumption with a monocarboxylic acid of 2, but the subsequent reaction pressure and to maintain catalyst life, the molar ratio of hydrogen is 4 monocarboxylic acid : 1 to 40: 1, more preferably ratio of 6: 1 to 25: 1, further optimization ratio of 8: 1 to 20: 1. 从反应器出来的粗产品经过气液分离器后,过量的氢气可以循环使用。 Out of the crude product from the reactor after the gas-liquid separator, the excess hydrogen can be recycled.

[0037] 本发明所述的催化剂选择性较高,因此副产物中不凝性气体的选择性低于10%,更优的情况下低于5%,进一步优化情况下低于2%。 The [0037] higher selectivity of the catalyst according to the present invention, therefore by-products selective non-condensable gases is less than 10%, more preferably less than 5% of cases, further optimization is lower than 2%.

[0038] 本发明所述的加氢方法的反应压力为0.3~8.0MPa,更优选的反应压力为0.5~ [0038] The reaction pressure of the hydrogenation process of the present invention is 0.3 ~ 8.0MPa, more preferably 0.5 to reaction pressure

4.0MPa,进一步优化的反应压力为1.0~2.5MPa。 4.0MPa, further optimization of reaction pressure 1.0 ~ 2.5MPa. 本发明使用的反应压力,相对于之前许多加氢技术公开的反应压力低许多,这使得反应条件更加温和,并且降低了成本。 The reaction pressure in the present invention, the reaction pressure relative to many prior art disclosed hydrogenation much lower, which makes the reaction conditions more moderate, and the cost is reduced.

[0039] 在本发明所述的方法中,一元羧酸的体积空速为0.1~5.0h-1,更优选的体积空速为0.2~2.0h—1。 [0039] In the method according to the present invention, the volume space velocity monocarboxylic acid is 0.1 ~ 5.0h-1, and more preferably a volume space velocity of 0.2 ~ 2.0h-1. 空速实际是根据工厂希望采出产品组成和后续分离能力有关,本发明在实施中不作限制,这是由于:在空速较高时,虽然醋酸转化率较低,但是乙醇和醋酸乙酯的产率和反而会增加,特别是醋酸乙酯选择性会提高;在空速较低时,醋酸转化率极高,但是乙醇的产率可能会降低,因此对于有分离能力并且希望多产醋酸乙酯的工厂,可以采用高空速操作模式,而对于后续分离能力较小的工厂,可采用低空速操作。 The actual airspeed is desired recovery plant product composition and subsequent separation capabilities related to the present invention is not limited in the embodiment, since it is: at higher space velocity, although the rate of conversion is low acetic acid, ethanol and ethyl acetate but instead, the yield will increase and, in particular, to improve the selectivity of ethyl acetate; the lower airspeed, a high conversion rate of acetic acid, the ethanol yield may be reduced, and therefore the ability to have separate desired prolific vinyl acetate ester factories, high-speed operation mode may be employed, and subsequent separation ability for smaller plants, low speed operation may be employed. 本发明所述的催化剂,在0.3~1.0h-1内可以保证醋酸的转化率高于50%,更优选的高于75%,进一步优选的高于90%。 The catalyst according to the present invention, in a 0.3 ~ 1.0h-1 can ensure conversion of acetic acid was higher than 50%, more preferably greater than 75%, more preferably greater than 90%.

[0040] 本发明所述的催化剂可广泛应用于一元羧酸加氢制备为醇,具体而言,所述的一元羧酸选自乙酸、丙酸、丁酸、乳酸、3-羟基丙酸、衣康酸中的一种或者混合物。 [0040] The catalyst of the present invention can be widely applied one yuan hydrogenation of carboxylic acids to alcohols, in particular, the monocarboxylic acid is selected from acetic acid, propionic acid, butyric acid, lactic acid, 3-hydroxypropionic acid, itaconic acid or a mixture thereof. 这些羧酸来源于可再生的生物质资源,如乳酸、3-羟基丙酸、苯甲酸、醋酸/丙酸等混合酸液等,也可以来源于其他石油替代资源,如醋酸。 These carboxylic acids from renewable biomass resources, such as lactic acid, 3-hydroxypropionic acid, benzoic acid, acetic acid / propionic acid mixture and the like, can also be derived from other petroleum alternative sources, such as acetic acid. 更优选的,所述的一元羧酸为乙酸和丙酸中的一种或者混合物。 More preferably, the monocarboxylic acid is one or a mixture of acetic acid and propionic acid. 进一步优选的一元羧酸为乙酸。 Further preferred monocarboxylic acid is acetic acid.

[0041] 本发明所述的方法,当一元羧酸和氢气与催化剂接触后,反应产物除醇外,还有微量其他副产物,主要来源于(I)脱羧/脱羰产物包括一氧化碳、二氧化碳、烷烃;(2)酮基化产物;(3)醇酸/醛缩合产物;(4)脱水产物等。 The method of the present invention, [0041], when in contact with a monocarboxylic acid and hydrogen with a catalyst, the reaction product of an alcohol addition, there are trace amounts of other by-products, mainly from (I) decarboxylation / decarbonylation products include carbon monoxide, carbon dioxide, alkanes; (2) a ketone group of product; (3) an alkyd / aldehyde condensation products; (4) dehydration products and the like. 举例而言,对于醋酸加氢制备乙醇,产物除主要由乙醇和醋酸乙酯外,还有乙醛、乙醚、丁醇、丙酮、异丙醇、甲缩醛、甲烷、乙烷、丙烷、一氧化碳、二氧化碳等。 For example, for the hydrogenation of acetic acid in ethanol, addition to the main product from ethanol and ethyl acetate, there acetaldehyde, diethyl ether, butanol, acetone, isopropyl alcohol, methylal, methane, ethane, propane, carbon monoxide , carbon dioxide and so on. 本发明描述的催化剂及其应用可以保证羧酸转化为醇和相应的酯的总选择率大于70%,更优化情况大于85%,进一步优化的情况大于90%。 The catalyst of the present invention is described and its application can ensure that the corresponding carboxylic acid to an alcohol esters overall selectivity greater than 70%, more than 85% optimized case, where more than 90% further optimization.

[0042] 相对于现有技术,本发明所述的羧酸加氢催化剂及其应用具有以下优点: [0042] with respect to the prior art, the present invention is applied hydrogenation catalyst and a carboxylic acid has the following advantages:

[0043] ( 1)催化剂活性较高,目的产物选择性高; High [0043] (1) the catalyst activity, high selectivity of desired product;

[0044] (2)催化剂制造成本较为低廉,使得投资和运行成本降低; [0044] (2) Catalyst for producing relatively inexpensive, so that the investment and operating costs;

[0045] (3)反应条件较温和,可以在较宽的反应操作条件下运行,增宽了操作窗口。 [0045] (3) relatively mild reaction conditions, can operate over a wide reaction operating conditions, broadening the operating window.

具体实施方式 Detailed ways

[0046] 下面以实施例来说明本发明,但并非限制发明范围。 [0046] In the following examples illustrate the invention, but not limit the scope of the invention.

[0047] 实施例1 [0047] Example 1

[0048] 取lmol/L的硝酸钴水溶液I升,在其中加入钥酸铵9.5克和硝酸镧7.5g, [0048] taken lmol / L aqueous solution of cobalt nitrate I liter, to which 9.5 g of ammonium key and lanthanum nitrate 7.5g,

[0049] 加入20wt°M^酸钠溶液进行沉淀至PH值为9.0左右,在加热的条件下搅拌2小时,得到前驱体I。 [0049] Add sodium 20wt ° M ^ PH value of solution was precipitated into about 9.0, stirred under heating for 2 hours to obtain a precursor I.

[0050] 将IOg浓硝酸和6g四水硝酸钙加入300ml水中,缓慢地加入到500g稀释的水玻璃水溶液中(二氧化硅含量约10wt%)中,形成白色沉淀物,使用大功率搅拌器搅拌沉淀物形成浆态物,将这些浆态物质加入到前驱体I中,在搅拌的条件继续老化I小时。 [0050] The concentrated nitric acid and 6g IOg calcium nitrate tetrahydrate was added 300ml of water was slowly added to 500g of the diluted aqueous solution of water glass (silicon dioxide content of about 10wt%), a white precipitate formed, using high-power stirrer the precipitate slurry was formed, the addition of these substances to a slurry precursor I, the aging continued stirring I h. 洗涤过滤,并干燥过夜得到干燥滤饼,在该滤饼中喷入含有0.lwt%的硝酸银溶液15ml后造粒。 Filtered, washed and dried overnight to obtain a dry cake, the cake containing the injected 0.lwt% silver nitrate solution was granulated 15ml. 将粒子焙烧分解后打片成型,得到催化剂CHZ-21。 After firing the particles exploded tableting molding, to obtain a catalyst CHZ-21.

[0051] 实施例2 [0051] Example 2

[0052]取1.5mol/L的硝酸钴水溶液I升,在其中加入硝酸铈6.0克和硝酸铬4克,充分溶解,在搅拌的情况下,在加入德固赛公司生产的二氧化钛粉末60克(型号为P25,粒子粒径为大于150目),所得的含固体液体称为溶液I。 [0052] Take 1.5mol / L aqueous solution of cobalt nitrate I liter, to which 6.0 g of cerium nitrate and chromium nitrate 4 g, sufficiently dissolved, under stirring, in Jia Rude Degussa titanium dioxide powder produced 60 grams ( model P25, particle diameter larger than 150 mesh), the resulting solids-containing liquid was referred to as I. 溶解于氨水中的偏钨酸铵溶液250ml (钨含量约为1.5wt%)为溶液II ;20wt%的碳酸钠溶液为溶液III。 Aqueous ammonia was dissolved in a solution of ammonium metatungstate 250ml (tungsten content of about 1.5wt%) as a solution II; 20wt% sodium carbonate solution is a solution III. 将溶液II倒入溶液I中后进行沉淀,最后使用溶液III调节PH值至6.7左右。 After precipitation the solution was poured into solution I II, III and finally used to adjust the PH value of the solution to about 6.7. 随后进行洗涤和过滤得到一个较潮湿的滤饼;在该滤饼中喷入含有0.lwt%的硼酸溶液25ml后放置I小时后干燥。 Followed by washing and filtration to obtain a relatively moist cake; the cake is injected into the drying after placing 0.lwt% boric acid solution containing 25ml I h. 将干燥滤饼焙烧分解后成型,得到催化剂CHZ-22。 The dried cake was baked after molding decomposed to obtain a catalyst CHZ-22.

[0053] 实施例3 [0053] Example 3

[0054] 升温条件下将经过干燥处理的硝酸钴和硝酸铬分别为240g和15g溶解于800ml正丙醇中,温度控制在50~60°C,缓慢加入正硅酸乙酯300g,经过纯化后制备得到含钴和铬的正硅酸乙酯。 [0054] The elevated temperature after cobalt nitrate and chromium nitrate were dried 15g and 240g in 800ml of n-propanol were dissolved, the temperature controlled at 50 ~ 60 ° C, was slowly added TEOS 300g, the purified TEOS prepared containing cobalt and chromium. 取上述的含钴和铬正硅酸乙酯100g溶解于乙醇中,加入水600ml和浓硝酸5.0g后,于75°C条件下放置6小时得到凝胶。 After taking the above-mentioned tetraethyl orthosilicate containing cobalt and chromium are dissolved in 100g of ethanol, 600ml of water was added 5.0g of concentrated nitric acid and allowed to stand 6 hours to obtain a gel at 75 ° C for the condition. 在上述凝胶中加入20ml硝酸银水溶液(60mg Ag/ml)并搅拌打浆,将浆体喷雾干燥得到细小微球。 20ml of an aqueous solution of silver nitrate (60mg Ag / ml) stirring the above gel and beating, the slurry is spray dried to obtain fine microspheres. 将上述微球筛分除去300 μ m以上的粒子后,400°C焙烧,将上述粉体打片成型后获得催化剂CHZ-23。 After the above 300 μ m sieve to remove particles of the microspheres, 400 ° C calcination, the powder was molded to obtain a catalyst tableting CHZ-23.

[0055] 对比例I [0055] Comparative Example I

[0056] 取30克二氧化硅载体(青岛海洋化工厂,吸水率约为0.9g/g),将60克硝酸钴和Ig硝酸银溶于水中,通过结合多次浸溃-共浸溃-等体积浸溃的方法制备得到前驱体,并将该前驱体400°C焙烧获得催化剂CHZ-24。 [0056] 30 g of a silica support (Qingdao Ocean Chemical Plant, water absorption of about 0.9g / g), 60 g of cobalt nitrate and silver nitrate was dissolved in water Ig, by combining multiple impregnation - Impregnated co - or the like impregnated volume of the prepared precursor, and the precursor 400 ° C calcined catalyst obtained CHZ-24.

[0057] 对比例2 [0057] Comparative Example 2

[0058] 按照CN200980134837.2公开的方法,制备了一个钙改性的二氧化硅负载钴-钼催化剂,钴负载量为10wt%和钼负载量0.85wt%0该催化剂为CHZ-25。 Molybdenum catalyst cobalt loading is 10wt% and 0.85wt% 0 molybdenum loading of the catalyst is CHZ-25 - [0058] The method disclosed in CN200980134837.2, a modified silica-supported cobalt, a calcium preparation.

[0059] 实施例4 [0059] Example 4

[0060] 将上述催化剂在固定床反应器中进行评价,用于醋酸加氢制备乙醇,装填量为10ml,采用1:1的石英砂稀释,在使用前采用纯氢气还原,还原最高温度为450~500°C,具体反应条件和反应结果如表1中所示。 [0060] The above catalyst was evaluated in a fixed bed reactor for hydrogenation of acetic acid, ethanol, 10ml loading is, using 1: 1 dilution of quartz sand, pure hydrogen reduction prior to use, reducing the maximum temperature of 450 ~ 500 ° C, the specific reaction conditions and reaction results are shown in table 1.

[0061] 在本实施例中,醋酸转化率和乙醇选择性按照各组分的碳摩尔百分含量计算获得。 [0061] In the present embodiment, conversion and selectivity to ethanol acetate obtained by calculation according to carbon molar percentage of each component.

[0062] [0062]

Figure CN103785414AD00091

[0064] 其他产物有:乙醛、乙烷、甲烷、一氧化碳、二氧化碳、乙酸醛、丙酮、丙醇等; [0064] Other products are: acetaldehyde, ethane, methane, carbon monoxide, carbon dioxide, acetic aldehyde, acetone, propanol and the like;

[0065] 表1反应条件和结果 [0065] TABLE 1 Reaction conditions and results

[0066] [0066]

Figure CN103785414AD00101

[0068] 从表1中可以看出,本发明的催化剂活性高,选择性高。 [0068] As can be seen from Table 1, the present invention high catalytic activity, high selectivity.

[0069] 实施例5 [0069] Example 5

[0070] 将上述催化剂在固定床反应器中进行评价,用于乳酸(20wt%水溶液)加氢制备 [0070] The above catalyst was evaluated in a fixed bed reactor, the preparation of lactic acid (20wt% aqueous solution) was hydrogenated for

1,2-丙二醇,装填量为10ml,采用1:1的石英砂稀释,在使用前采用纯氢气还原,还原最高 1,2-propanediol, loading is 10ml, using 1: 1 dilution of quartz sand, pure hydrogen reduction prior to use, reducing the maximum

温度为450~500°C,具体反应条件和反应结果如表2中所示。 Temperature of 450 ~ 500 ° C, specific reaction conditions and reaction results are shown in Table 2.

[0071] 在本实施例中,乳酸转化率和1,2-丙二醇选择性按照各组分的碳摩尔百分含量 [0071] In the present embodiment, the conversion of lactic acid and 1,2-propanediol selectivity according to carbon molar percentages of the components

计算获得。 Calculation available. 其他副产物包括:正丙醇、异丙醇、2-羟基-丙醛、丙烷、乙烷、一氧化碳、二氧化 Other by-products include: n-propanol, isopropanol, 2-hydroxy - propionaldehyde, propane, ethane, carbon monoxide, carbon dioxide

碳、乙醇、戊二酮等。 Carbon, ethanol, pentanedione, and the like.

[0072] 表2反应条件和结果 [0072] Table 2 Reaction conditions and results

[0073] [0073]

Figure CN103785414AD00102

[0074] 从表2可以看出,本发明的催化剂活性高,选择性高。 [0074] As can be seen from Table 2, the present invention high catalytic activity, high selectivity.

Claims (26)

1.一种羧酸加氢催化剂,其特征在于催化剂含有载体、钴元素、VIB族元素,其中钴元素的含量占催化剂总重的15wt%~ 50wt%,VIB族元素选自钥、钨、铬中的至少一种,其含量占催化剂总重的0.5wt%~15wt%,所述的载体选自氧化娃、娃藻土、娃酸钙、氧化错、氧化钛的至少一种,其含量占催化剂总重的20wt%~80wt%。 An acid hydrogenation catalyst, wherein the catalyst comprises a carrier, cobalt, VIB group elements, wherein the content of cobalt accounts for 15wt% ~ 50wt% of the total weight of the catalyst, VIB elements selected key, tungsten, chromium at least one of an amount of from 0.5wt% ~ 15wt% of the total weight of the catalyst, the carrier is selected baby oxide, diatomaceous earth baby, baby, calcium oxide wrong, at least one of titanium oxide, an amount of from total 20wt% ~ 80wt% of the weight of the catalyst.
2.根据权利要求1所述的羧酸加氢催化剂,其特征在于所述的催化剂通过共沉淀法、沉积-沉淀法或者溶胶-凝胶方法制备。 2. A hydrogenation catalyst according to the carboxylic acid according to claim 1, wherein said catalyst is deposited by a coprecipitation method, - precipitation method or the sol - gel process.
3.根据权利要求2所述的羧酸加氢催化剂,其特征在于所述的催化剂含有银元素,其含量占催化剂总重的0.lwt%~10wt%。 3. A hydrogenation catalyst according to the carboxylic acid according to claim 2, characterized in that said silver-containing catalyst, an amount of from 0.lwt% ~ 10wt% of the total weight of the catalyst.
4.根据权利要求3所述的羧酸加氢催化剂,其特征在于所述的银元素来源于硝酸银,银含量占催化剂总重的0.2wt%~2wt%。 The catalyst according to claim hydrogenation of carboxylic acids according to claim 3, wherein said silver element from silver nitrate, silver content representing 0.2wt% ~ 2wt% of the total weight of the catalyst.
5.根据权利要求4所述的羧酸加氢催化剂,其特征在于所述的银元素含量占催化剂总重的0.2wt% ~0.5wt%。 The hydrogenation of carboxylic acids of the catalyst according to claim 4, wherein said silver element content accounted 0.2wt% ~ 0.5wt% of the total weight of the catalyst.
6.根据权利要求1-3之一所述的羧酸加氢催化剂,其特征在于所述的钴元素来源于水溶性的硝酸盐、硫酸盐、氯盐、醋酸盐、草酸盐和溴盐,其含量占催化剂总重的20wt%~40wt%o 6. A hydrogenation catalyst according to the carboxylic acid according to one of claims 1-3, wherein said water-soluble cobalt from nitrate, sulfate, chloride, acetate, oxalate and bromide salt, in an amount accounting for the total weight of the catalyst of 20wt% ~ 40wt% o
7.根据权利要求6所述的羧酸加氢催化剂,其特征在于所述的钴元素的来源选自水溶性的硝酸钴、氯化钴、草酸钴、硫酸钴、醋酸钴中的至少一种。 7. The catalyst of the hydrogenation of carboxylic acids according to claim 6, wherein said source of cobalt is selected from at least one water-soluble cobalt nitrate, cobalt chloride, cobalt oxalate, cobalt sulfate, cobalt acetate in .
8.根据权利要求1-3之一所述的羧酸加氢催化剂,其特征在于所述的钥元素来源于水溶性的钥酸盐或钥的络合物。 Acid hydrogenation catalyst according to claim any one of the claims 1-3, characterized in that the key element from the complex of water-soluble salts of keys or keys.
9.根据权利要求8所述的羧酸加氢催化剂,其特征在于所述的钥元素来源于钥酸铵、钥酸钠、钥酸钾、钥酸镁、柠檬酸钥中的一种。 9. A hydrogenation catalyst according to the carboxylic acid according to claim 8, characterized in that the key element from the key ammonium, sodium key, key, potassium, magnesium key, the key of one citrate.
10.根据权利要求1-3之一所述的羧酸加氢催化剂,其特征在于所述的钨元素来源于水溶性或者添加碱性助溶剂后可溶的盐。 10. The hydrogenation catalyst according to one of the carboxylic acid according to claim 1-3, wherein said tungsten or an element derived from a water-soluble cosolvent after adding the alkaline-soluble salts.
11.根据权利要求10所述的羧酸加氢催化剂,其特征在于所述的钨元素来源于钨酸铵、偏钨酸铵、钨酸锌、钨酸钠、钨酸钾。 11. The hydrogenation catalyst according to the carboxylic acid according to claim 10, wherein said tungsten element from ammonium tungstate, ammonium meta tungstate, zinc tungstate, sodium tungstate, potassium tungstate.
12.根据权利要求1-3之一所述的羧酸加氢催化剂,其特征在于所述的铬元素来源于水溶性的或者加入酸性助溶剂后可溶的盐。 12. The hydrogenation catalyst according to one of the carboxylic acid according to claim 1-3, characterized in that said chromium is added after or derived from acidic water-soluble co-solvent-soluble salt.
13.根据权利要求12所述的羧酸加氢催化剂,其特征在于所述的铬元素来源于重铬酸铵、重铬酸钠、重铬酸钾、铬酸钡、铬酸酐、铬酸钠、铬酸钾、铬酸镁、硝酸铬、醋酸铬、草酸铬中的一种。 13. carboxylic hydrogenation catalyst as claimed in claim 12, wherein the chromium from ammonium dichromate, sodium dichromate, potassium dichromate, barium chromate, chromic anhydride, sodium chromate , potassium chromate, magnesium chromate, chromium nitrate, chromium acetate, chromium oxalate of one.
14.根据权利要求1-3之一所述的羧酸加氢催化剂,其特征在于所述的催化剂还含有稀土金属元素,其氧化物含量占催化剂总重的0.lwt%~8wt%0 14. The hydrogenation catalyst according to one of the carboxylic acid according to claim 1-3, wherein said catalyst further contains rare earth metal elements, the content of which accounts for oxides 0.lwt% ~ 8wt% 0 of the total weight of the catalyst
15.根据权利要求14所述的羧酸加氢催化剂,其特征在于所述的稀土金属元素为镧或者铈,其氧化物含量占催化剂总重的0.5wt%~5wt%。 15. A carboxylic acid of the hydrogenation catalyst according to claim 14, wherein said rare earth element is lanthanum or cerium, oxides amount of from 0.5wt% ~ 5wt% of the total weight of the catalyst.
16.根据权利要求1-3之一所述的羧酸加氢催化剂,其特征在于所述的催化剂还含有至少一种无机非金属元素,其含量占催化剂总重的0.lwt%~5wt%。 16. The hydrogenation catalyst according to one of the carboxylic acid according to claim 1-3, wherein said catalyst further comprises at least one inorganic non-metallic element in an amount accounting for the total 0.lwt% ~ 5wt% of the weight of the catalyst .
17.根据权利要求16所述的羧酸加氢催化剂,其特征在于所述的无机非金属元素选自磷、硼、氟中的一种,其含量占催化剂总重的0.3wt%~2wt%。 17. The hydrogenation catalyst according to the carboxylic acid according to claim 16, wherein said inorganic non-metallic element selected from phosphorus, boron, fluorine kind, an amount of from 0.3wt% ~ 2wt% of the total weight of the catalyst .
18.根据权利要求1-3之一所述的羧酸加氢催化剂,其特征在于所述的催化剂还含有碱金属或碱土金属元素,其含量占催化剂总重的0.lwt%~ 15wt%。 18. The hydrogenation catalyst according to one of the carboxylic acid according to claim 1-3, wherein said catalyst further contains an alkali metal or alkaline earth metal element in an amount accounting for the total 0.lwt% ~ 15wt% of the weight of the catalyst.
19.根据权利要求18所述的羧酸加氢催化剂,其特征在于所述的碱金属或碱土金属元素为钾、钠、钙、镁、钡中的至少一种,其含量占催化剂总重的0.2wt%~ 10wt%。 19. The hydrogenation catalyst according to the carboxylic acid according to claim 18, wherein said alkali metal or alkaline earth metal element is potassium, sodium, calcium, magnesium, at least one of barium, the content thereof based on the total weight of the catalyst 0.2wt% ~ 10wt%.
20.根据权利要求18所述的羧酸加氢催化剂,其特征在于所述的碱金属或碱土金属元素来源于水溶性的硝酸盐、碳酸盐、氯盐、磷酸盐、硫酸盐、醋酸盐、氟化物、氢氧化物。 20. A carboxylic acid of the hydrogenation catalyst according to claim 18, wherein said alkali metal or alkaline earth metal element derived from a water-soluble nitrate, carbonate, chloride, phosphate, sulfate, acetate, salt, fluorides, hydroxides.
21.根据权利要求18所述的羧酸加氢催化剂,其特征在于所述的碱金属或碱土金属元素来源于氢氧化钾、硝酸钾、碳酸钾、醋酸钾、氟化钾、磷酸钾、氢氧化钠、硝酸钠、碳酸钠、碳酸氢钠、氯化钠、硫酸钠、醋酸钠、硝酸钙、磷酸二氢钙、硝酸镁、磷酸镁、硝酸钡中的至少一种。 21. The hydrogenation catalyst according to the carboxylic acid according to claim 18, wherein said alkali metal or alkaline earth metal element derived from potassium hydroxide, potassium nitrate, potassium carbonate, potassium acetate, potassium fluoride, potassium phosphate, hydrogen sodium oxide, sodium nitrate, sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate, sodium acetate, calcium nitrate, calcium dihydrogen phosphate, magnesium nitrate, magnesium phosphate, barium nitrate of at least one.
22.权利要求1-21之一所述的羧酸加氢催化剂在一元羧酸加氢制备醇的反应中的应用。 Acid 1-21 hydrogenation catalyst according to one application in the hydrogenation reaction of one yuan alcohol carboxylic acid prepared according to claim 22..
23.权利要求22所述的羧酸加氢催化剂在乙酸加氢制备醇的反应中的应用。 The hydrogenation catalyst is a carboxylic acid in acetic acid 22 application hydrogenation reaction of an alcohol of claim 23.
24.根据权利要求22或23所述的羧酸加氢催化剂的应用,其特征在于一元羧酸、含氢气体成混合气体后与羧酸加氢催化剂接触,转化为醇和水,氢气和一元羧酸的摩尔比例为4:1~40:1,反应温度为180~350°C,反应压力为0.3~8.0MPa,一元羧酸的体积空速为0.1 ~5.0h 1O 24. Use according to claim 22 or 23 carboxylic hydrogenation catalyst as claimed in claim, wherein the monocarboxylic acid, the hydrogen-containing gas into the mixed gas is contacted with a hydrogenation catalyst carboxylic acid, alcohol and water into hydrogen and monocarboxylic molar ratio of acid is 4: 1 to 40: 1, reaction temperature of 180 ~ 350 ° C, reaction pressure 0.3 ~ 8.0MPa, LHSV monocarboxylic acid is 0.1 ~ 5.0h 1O
25.根据权利要求2 4所述的羧酸加氢催化剂的应用,其特征在于氢气和一元羧酸的摩尔比例为6:1~25:1,反应温度为220~300°C,反应压力为0.5~4.0M Pa,一元羧酸的体积空速为0.2~2.0h' 24 25. The use of carboxylic acid according to claim hydrogenation catalyst, wherein the molar ratio of hydrogen and monocarboxylic acid is 6: 1 to 25: 1, reaction temperature of 220 ~ 300 ° C, a reaction pressure of 0.5 ~ 4.0M Pa, LHSV monocarboxylic acid is 0.2 ~ 2.0h '
26.根据权利要求25所述的羧酸加氢催化剂的应用,其特征在于氢气和一元羧酸的摩尔比例为8:1~20:1,反应压力为1.0~2.5MPa,一元羧酸的体积空速为0.3~LOh' 25 26. The use according to claim acid hydrogenation catalyst, wherein the molar ratio of hydrogen and monocarboxylic acid is 8: 1 to 20: 1, a reaction pressure 1.0 ~ 2.5MPa, the volume of monocarboxylic acids a space velocity of 0.3 ~ LOh '
CN201210429720.0A 2012-10-31 2012-10-31 Carboxylic hydrogenation catalyst preparation method and application CN103785414B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210429720.0A CN103785414B (en) 2012-10-31 2012-10-31 Carboxylic hydrogenation catalyst preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210429720.0A CN103785414B (en) 2012-10-31 2012-10-31 Carboxylic hydrogenation catalyst preparation method and application

Publications (2)

Publication Number Publication Date
CN103785414A true CN103785414A (en) 2014-05-14
CN103785414B CN103785414B (en) 2016-03-30

Family

ID=50661720

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210429720.0A CN103785414B (en) 2012-10-31 2012-10-31 Carboxylic hydrogenation catalyst preparation method and application

Country Status (1)

Country Link
CN (1) CN103785414B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9024088B1 (en) 2014-04-28 2015-05-05 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide comprising nickel
US9073815B1 (en) 2014-04-28 2015-07-07 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol
US9353035B2 (en) 2014-04-28 2016-05-31 Celanese International Corporation Process for producing ethanol with zonal catalysts
US9382177B2 (en) 2014-04-28 2016-07-05 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal
CN107349947A (en) * 2017-05-24 2017-11-17 沈阳三聚凯特催化剂有限公司 Acetic acid hydrogenation catalyst and applications thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104478A (en) * 1977-11-23 1978-08-01 Ashland Oil, Inc. Catalytic hydrogenation of fatty acids
CN86102420A (en) * 1985-04-13 1986-10-08 Bp化学有限公司 Alcohols production by hydrogenation of carboxylic acids
CN102149662A (en) * 2008-07-31 2011-08-10 国际人造丝公司 Ethanol production from acetic acid utillizing a cobalt catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104478A (en) * 1977-11-23 1978-08-01 Ashland Oil, Inc. Catalytic hydrogenation of fatty acids
CN86102420A (en) * 1985-04-13 1986-10-08 Bp化学有限公司 Alcohols production by hydrogenation of carboxylic acids
CN86102452A (en) * 1985-04-13 1986-12-03 Bp化学有限公司 Alcohols production by hydrogenation of carboxylic acids
CN102149662A (en) * 2008-07-31 2011-08-10 国际人造丝公司 Ethanol production from acetic acid utillizing a cobalt catalyst

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9024088B1 (en) 2014-04-28 2015-05-05 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide comprising nickel
US9073815B1 (en) 2014-04-28 2015-07-07 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol
US9353035B2 (en) 2014-04-28 2016-05-31 Celanese International Corporation Process for producing ethanol with zonal catalysts
US9382177B2 (en) 2014-04-28 2016-07-05 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal
US9458072B2 (en) 2014-04-28 2016-10-04 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol
CN107349947A (en) * 2017-05-24 2017-11-17 沈阳三聚凯特催化剂有限公司 Acetic acid hydrogenation catalyst and applications thereof

Also Published As

Publication number Publication date
CN103785414B (en) 2016-03-30

Similar Documents

Publication Publication Date Title
Gong et al. Synthesis of ethanol via syngas on Cu/SiO2 catalysts with balanced Cu0–Cu+ sites
CN102272089B (en) Integrated process for the production of vinyl acetate from acetic acid via ethyl acetate
CN102190562B (en) Method for preparing ethylene glycol from polyols
CN101879448B (en) Ordered structure catalyst for hydrogenation of oxalic ester for preparing ethylene glycol and preparation method thereof
CN102093162B (en) Method for preparing ethanol by hydrogenation of acetic ester
CN101954288B (en) Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof
JP5275080B2 (en) Method for producing monohydric alcohol from monocarboxylic acid or its derivative
Wang et al. Catalytic hydrogenolysis of glycerol to propanediols: a review
CN101934228A (en) Catalyst for preparing alcohol by acetic ester hydrogenation as well as preparation method and application thereof
CA2778771A1 (en) Catalysts for making ethyl acetate from acetic acid
CN102247861A (en) Coal gas high-temperature methanation catalyst and preparation method thereof
Yang et al. The conversion of glycerol to lactic acid catalyzed by ZrO2-supported CuO catalysts
CN102120184B (en) Noble metal-carrying titanium dioxide catalyst and preparation method and use thereof
CN101411990B (en) Method for preparing catalyst used in method for preparing ethanediol by dimethyl oxalate hydrogenation
CN102872878B (en) Catalyst for preparing ethanol from acetic ester hydrogenation, preparation method and application thereof
CN102105222B (en) Catalyst for synthesizing methanol from synthesis gas and preparation method thereof
CN101851160B (en) Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst
CN101138730B (en) Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same
CN102350358B (en) Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation
CN101185895A (en) Catalyst for synthesizing low carbon mellow with synthesis gas and preparation method thereof
CN103159589A (en) Process for producing hydrogenolysis products of polyhydric alcohols
CN101791556A (en) Octanol hydrorefining catalyst and preparation method thereof
CN101850273B (en) Structured catalyst for synthesizing oxalate by CO gaseous-phase coupling and preparation method thereof
Yin et al. Hydrothermal conversion of glycerol to lactic acid catalyzed by Cu/hydroxyapatite, Cu/MgO, and Cu/ZrO2 and reaction kinetics
US3579569A (en) Preparation of vinyl acetate

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
C14 Grant of patent or utility model