CN116020474A - Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by hydrogenation of maleic anhydride - Google Patents
Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by hydrogenation of maleic anhydride Download PDFInfo
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Abstract
本发明涉及催化剂技术领域,具体地,涉及一种加氢催化剂及其制备方法与应用以及顺酐加氢制丁二酸酐的方法,所述加氢催化剂包括载体以及负载在载体上的活性组分,所述活性组分含有:Ni元素、Sn元素、Ca元素和/或Ba元素;所述载体含有SiO2;所述加氢催化剂中,以所述加氢催化剂的总重量为基准,以氧化物计,Ni元素含量为10‑40wt%,Sn元素含量为5‑15wt%、Ca元素和/或Ba元素含量为0.5‑5wt%、载体含量为20‑80wt%。本发明的加氢催化剂在低温反应下仍具有高的催化活性和丁二酸酐选择性,且制备工艺简单,能够应用于连续的大规模生产。The present invention relates to the technical field of catalysts, in particular to a hydrogenation catalyst, its preparation method and application, and a method for producing succinic anhydride by hydrogenation of maleic anhydride. The hydrogenation catalyst includes a carrier and an active component loaded on the carrier , the active component contains: Ni element, Sn element, Ca element and/or Ba element; the carrier contains SiO 2 ; in the hydrogenation catalyst, the total weight of the hydrogenation catalyst is based on the oxidation In terms of material, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, the content of Ca element and/or Ba element is 0.5-5wt%, and the content of carrier is 20-80wt%. The hydrogenation catalyst of the invention still has high catalytic activity and succinic anhydride selectivity under low-temperature reaction, and the preparation process is simple, and can be applied to continuous large-scale production.
Description
技术领域technical field
本发明涉及催化剂技术领域,具体地,涉及一种用于顺酐液相加氢制丁二酸酐的催化剂及其制备方法,该用于顺酐液相加氢制丁二酸酐的催化剂的应用,以及一种顺酐液相加氢制丁二酸酐的方法。The present invention relates to the technical field of catalysts, in particular, to a catalyst for the production of succinic anhydride by liquid-phase hydrogenation of maleic anhydride and a preparation method thereof, and the application of the catalyst for the production of succinic anhydride by liquid-phase hydrogenation of maleic anhydride, And a method for preparing succinic anhydride by liquid-phase hydrogenation of maleic anhydride.
背景技术Background technique
丁二酸酐,又名琥珀酸酐,是一种重要的有机合成中间体和精细化工原料,被广泛地应用于食品、表面活性剂、涂料、医药、农业、塑料等领域。并且,丁二酸酐的水解产物丁二酸,是聚丁二酸丁二醇酯类生物可降解材料的主要原料。随着国家对环保政策的重视及发展,丁二酸的需求量与日俱增。因此,对于丁二酸酐的需求量也在逐年增加,特别是高纯度的丁二酸酐,对外依存度较高。Succinic anhydride, also known as succinic anhydride, is an important organic synthesis intermediate and fine chemical raw material, and is widely used in food, surfactant, paint, medicine, agriculture, plastics and other fields. Moreover, succinic acid, the hydrolysis product of succinic anhydride, is the main raw material of polybutylene succinate biodegradable materials. With the emphasis and development of the country's environmental protection policy, the demand for succinic acid is increasing day by day. Therefore, the demand for succinic anhydride is also increasing year by year, especially for high-purity succinic anhydride, which has a high degree of external dependence.
目前,工业上采用的丁二酸酐的生产方法有:生物发酵法、电化学法和顺酐催化加氢法。其中,生物发酵法虽然环境友好,但该方法生产成本高、产品纯度较低,很难满足工业生产的需要;电化学法生产规模小,难以满足与日俱增的市场需求;顺酐加氢法具有工艺流程简单、操作方便、设备利用率高、运行成本低以及产品纯度高的优点,是目前最为高效的生产丁二酸酐的工艺。At present, the production methods of succinic anhydride used in industry include: biological fermentation method, electrochemical method and catalytic hydrogenation method of maleic anhydride. Among them, although the biological fermentation method is environmentally friendly, the production cost of this method is high and the product purity is low, which is difficult to meet the needs of industrial production; the production scale of the electrochemical method is small, and it is difficult to meet the growing market demand; the maleic anhydride hydrogenation method has a process The advantages of simple process, convenient operation, high equipment utilization rate, low operating cost and high product purity are currently the most efficient process for producing succinic anhydride.
顺酐分子具有一个C=C键以及两个C=O键,在一定催化条件下,对C=C键的选择性加氢可以合成丁二酸酐;继续对其中一个C=O键加氢,可以合成γ-丁内酯;接着对另一个C=O键加氢,则可合成四氢呋喃。由此可见,深度加氢会降低丁二酸酐的选择性,如何控制加氢反应在C=C键加氢阶段是顺酐加氢制备丁二酸酐最主要的问题,需要寻找合适的催化剂来提高丁二酸酐的选择性。The maleic anhydride molecule has a C=C bond and two C=O bonds. Under certain catalytic conditions, the selective hydrogenation of the C=C bond can synthesize succinic anhydride; continue to hydrogenate one of the C=O bonds, γ-butyrolactone can be synthesized; followed by hydrogenation of another C=O bond, tetrahydrofuran can be synthesized. It can be seen that deep hydrogenation will reduce the selectivity of succinic anhydride, how to control the hydrogenation reaction in the C=C bond hydrogenation stage is the most important problem of maleic anhydride hydrogenation to prepare succinic anhydride, and it is necessary to find a suitable catalyst to improve Selectivity of succinic anhydride.
US5616730公开了一种用于催化顺酐加氢制备丁二酸酐的催化剂及连续生产丁二酸酐的方法,该催化剂以SiO2负载镍,添加了Pd或Pt作为助剂,该工艺条件中,反应条件较为苛刻,反应压力高达15MPa,需要对反应器的设置和材质有特殊要求,限制了其的大规模应用。US5616730 discloses a kind of catalyst and the method for continuous production of succinic anhydride that are used to catalyze the hydrogenation of maleic anhydride to prepare succinic anhydride, this catalyst is with SiO Loaded nickel, added Pd or Pt as auxiliary agent, in this processing condition, reaction The conditions are relatively harsh, and the reaction pressure is as high as 15 MPa, which requires special requirements for the reactor settings and materials, which limits its large-scale application.
US1541210和EP0691335公开的方法中,均选择了贵金属Pd作为主要活性组分制备催化剂,虽然加氢选择性较高,但贵金属的用量占到了催化剂总重量的3.0-10.0重量%,大大增加了生产成本,难以实现工业化。In the methods disclosed in US1541210 and EP0691335, the precious metal Pd is selected as the main active component to prepare the catalyst. Although the hydrogenation selectivity is high, the amount of the precious metal accounts for 3.0-10.0% by weight of the total weight of the catalyst, which greatly increases the production cost. , it is difficult to achieve industrialization.
CN109529850A公开了一种SiO2负载Ni的顺酐加氢制备丁二酸酐的催化剂的制备方法及其应用,该催化剂用于液相加氢反应中的压力较高(5.0MPa),并且只能用于间歇式合成反应用,无法应用于连续的大规模生产。CN109529850A discloses a kind of SiO The preparation method and the application of the catalyst for preparing succinic anhydride by the hydrogenation of maleic anhydride supported Ni, the pressure of this catalyst in the liquid phase hydrogenation reaction is higher (5.0MPa), and can only be used It is used for batch synthesis reactions and cannot be applied to continuous large-scale production.
发明内容Contents of the invention
本发明的目的是克服现有技术中存在的催化剂的活性和丁二酸酐选择性低,且催化剂成本高、工艺流程复杂,无法应用于连续的大规模生产的问题,提供加氢催化剂及其制备方法与应用以及顺酐加氢制丁二酸酐的方法。所述加氢催化剂具有催化剂活性和选择性高,制备工艺简单以及催化剂价格低廉的特点,能够应用于连续的大规模工业化生产。The purpose of the present invention is to overcome the catalyst activity and the selectivity of succinic anhydride existing in the prior art are low, and catalyst cost is high, technological process is complicated, can't be applied to the problem of continuous large-scale production, provide hydrogenation catalyst and its preparation Method and application and method of hydrogenation of maleic anhydride to succinic anhydride. The hydrogenation catalyst has the characteristics of high catalyst activity and selectivity, simple preparation process and low catalyst price, and can be applied to continuous large-scale industrial production.
为了实现上述目的,本发明第一方面提供一种加氢催化剂,其特征在于,所述加氢催化剂包括载体以及负载在载体上的活性组分,所述活性组分含有:Ni元素、Sn元素、Ca元素和/或Ba元素;所述载体含有SiO2;In order to achieve the above object, the first aspect of the present invention provides a hydrogenation catalyst, which is characterized in that the hydrogenation catalyst includes a carrier and an active component loaded on the carrier, and the active component contains: Ni element, Sn element , Ca element and/or Ba element; the carrier contains SiO 2 ;
所述加氢催化剂中,以所述加氢催化剂的总重量为基准,以氧化物计,Ni元素含量为10-40wt%,Sn元素含量为5-15wt%、Ca元素和/或Ba元素含量为0.5-5wt%、载体含量为20-80wt%。In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, in terms of oxides, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, and the content of Ca element and/or Ba element 0.5-5wt%, and the carrier content is 20-80wt%.
本发明第二方面提供一种制备加氢催化剂的方法,其特征在于,所述方法为共沉淀法,包括以下步骤:The second aspect of the present invention provides a method for preparing a hydrogenation catalyst, characterized in that the method is a co-precipitation method, comprising the following steps:
(1)将含Ni前体化合物、载体的前体化合物和第一溶剂进行第一混合,得到第一混合液,所述载体的前体化合物含有SiO2;将含Sn前体化合物溶液与所述第一混合液进行第二混合,得到第二混合液;(1) The precursor compound containing Ni, the precursor compound of the carrier and the first solvent are first mixed to obtain the first mixed solution, and the precursor compound of the carrier contains SiO 2 ; the solution of the precursor compound containing Sn is mixed with the The first mixed solution is mixed for the second time to obtain the second mixed solution;
(2)将第二混合液和碱溶液进行第一接触反应,得到沉淀物;(2) carrying out the first contact reaction with the second mixed solution and the alkali solution to obtain a precipitate;
(3)所述沉淀物经过滤、洗涤、干燥、粉碎后,得到粉末基体催化剂;(3) After the precipitate is filtered, washed, dried and pulverized, a powder matrix catalyst is obtained;
(4)将粉末基体催化剂与含Ca前体化合物和/或含Ba前体化合物进行混合成型,焙烧后得到加氢催化剂;(4) mixing and molding the powder base catalyst with the Ca-containing precursor compound and/or the Ba-containing precursor compound, and obtaining a hydrogenation catalyst after roasting;
其中,所述加氢催化剂中,以所述加氢催化剂的总重量为基准,以氧化物计,Ni元素含量为10-40wt%,Sn元素含量为5-15wt%、Ca元素和/或Ba元素含量为0.5-5wt%、载体含量为20-80wt%。Wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the Ni element content is 10-40wt%, the Sn element content is 5-15wt%, and the Ca element and/or Ba The element content is 0.5-5wt%, and the carrier content is 20-80wt%.
本发明第三方面提供一种由上述方法制备得到的加氢催化剂。The third aspect of the present invention provides a hydrogenation catalyst prepared by the above method.
本发明第四方面提供一种上述加氢催化剂和/或所述的加氢催化剂的制备方法在顺酐加氢制丁二酸酐中的应用。The fourth aspect of the present invention provides an application of the above-mentioned hydrogenation catalyst and/or the preparation method of the hydrogenation catalyst in the hydrogenation of maleic anhydride to succinic anhydride.
本发明第五方面提供一种顺酐液相加氢制丁二酸酐的方法,其特征在于,该方法包括:在活化催化剂存在下,氢气和顺酐进行第二接触反应,得到所述丁二酸酐;The fifth aspect of the present invention provides a method for producing succinic anhydride by liquid-phase hydrogenation of maleic anhydride, characterized in that the method comprises: in the presence of an activated catalyst, hydrogen and maleic anhydride are subjected to a second contact reaction to obtain the succinic anhydride ;
其中,所述活化催化剂为上述加氢催化剂和/或上述制备方法得到的加氢催化剂经包含氢气的气体进行还原活化得到。Wherein, the activated catalyst is obtained by reducing and activating the above-mentioned hydrogenation catalyst and/or the hydrogenation catalyst obtained by the above-mentioned preparation method by a gas containing hydrogen.
所述还原活化的条件包括:温度为300-600℃,时间为0.5-20h。The conditions for the reductive activation include: the temperature is 300-600°C, and the time is 0.5-20h.
通过上述技术方案,本发明提供的加氢催化剂及其制备方法与应用以及顺酐加氢制丁二酸酐的方法获得以下有益的效果:Through the above technical scheme, the hydrogenation catalyst provided by the present invention and its preparation method and application and the method for hydrogenating maleic anhydride to succinic anhydride obtain the following beneficial effects:
本发明提供的加氢催化剂具有较高的活性和选择性,顺酐转化率≥95%,丁二酸酐选择性≥90%;The hydrogenation catalyst provided by the invention has high activity and selectivity, the conversion rate of maleic anhydride is ≥ 95%, and the selectivity of succinic anhydride is ≥ 90%;
进一步地,所述加氢催化剂制备工艺简单,催化剂价格低廉,节约成本。Further, the preparation process of the hydrogenation catalyst is simple, the price of the catalyst is low, and the cost is saved.
具体实施方式Detailed ways
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
本发明第一方面提供一种加氢催化剂,其特征在于,所述加氢催化剂包括载体以及负载在载体上的活性组分,所述活性组分含有:Ni元素、Sn元素、Ca元素和/或Ba元素;所述载体含有SiO2;The first aspect of the present invention provides a hydrogenation catalyst, characterized in that the hydrogenation catalyst includes a carrier and an active component loaded on the carrier, and the active component contains: Ni element, Sn element, Ca element and/or or Ba element; the carrier contains SiO 2 ;
所述加氢催化剂中,以所述加氢催化剂的总重量为基准,以氧化物计,Ni元素含量为10-40wt%,Sn元素含量为5-15wt%、Ca元素和/或Ba元素含量为0.5-5wt%、载体含量为20-80wt%。In the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, in terms of oxides, the content of Ni element is 10-40wt%, the content of Sn element is 5-15wt%, and the content of Ca element and/or Ba element 0.5-5wt%, and the carrier content is 20-80wt%.
本发明中,所述加氢催化剂满足上述范围时,具有较高的催化活性和选择性。In the present invention, when the hydrogenation catalyst satisfies the above range, it has higher catalytic activity and selectivity.
根据本发明,所述加氢催化剂中,以所述加氢催化剂的总重量为基准,以氧化物计,Ni元素含量为17-28wt%,Sn元素含量为7-12wt%、Ca和/或Ba元素含量为1-3wt%、载体含量为40-75wt%。According to the present invention, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, in terms of oxides, the Ni element content is 17-28wt%, the Sn element content is 7-12wt%, Ca and/or The Ba element content is 1-3wt%, and the carrier content is 40-75wt%.
本发明第二方面提供一种制备加氢催化剂的方法,其特征在于,所述方法为共沉淀法,包括以下步骤:The second aspect of the present invention provides a method for preparing a hydrogenation catalyst, characterized in that the method is a co-precipitation method, comprising the following steps:
(1)将含Ni前体化合物、载体的前体化合物和第一溶剂进行第一混合,得到第一混合液,所述载体的前体化合物含有SiO2;将含Sn前体化合物溶液与所述第一混合液进行第二混合,得到第二混合液;(1) The precursor compound containing Ni, the precursor compound of the carrier and the first solvent are first mixed to obtain the first mixed solution, and the precursor compound of the carrier contains SiO 2 ; the solution of the precursor compound containing Sn is mixed with the The first mixed solution is mixed for the second time to obtain the second mixed solution;
(2)将第二混合液和碱溶液进行第一接触反应,得到沉淀物;(2) carrying out the first contact reaction with the second mixed solution and the alkali solution to obtain a precipitate;
(3)所述沉淀物经过滤、洗涤、干燥、粉碎后,得到粉末基体催化剂;(3) After the precipitate is filtered, washed, dried and pulverized, a powder matrix catalyst is obtained;
(4)将粉末基体催化剂与含Ca前体化合物和/或含Ba前体化合物混合成型,焙烧后得到加氢催化剂;(4) mixing the powder base catalyst with a Ca-containing precursor compound and/or a Ba-containing precursor compound, and obtaining a hydrogenation catalyst after roasting;
其中,所述加氢催化剂中,以所述加氢催化剂的总重量为基准,以氧化物计,Ni元素含量为10-40wt%,Sn元素含量为5-15wt%、Ca元素和/或Ba元素含量为0.5-5wt%、载体含量为20-80wt%。Wherein, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, the Ni element content is 10-40wt%, the Sn element content is 5-15wt%, and the Ca element and/or Ba The element content is 0.5-5wt%, and the carrier content is 20-80wt%.
本发明中,利用共沉淀法制备的加氢催化剂能够使催化活性和丁二酸酐选择性更高,且制备工艺简单。In the present invention, the hydrogenation catalyst prepared by the co-precipitation method can have higher catalytic activity and succinic anhydride selectivity, and the preparation process is simple.
本发明中,步骤(1)中,对所述第一混合的具体条件没有特别限制,只要使得所述含Ni前体化合物与载体的前体化合物能够充分均匀混合即可。In the present invention, in step (1), the specific conditions for the first mixing are not particularly limited, as long as the Ni-containing precursor compound and the carrier precursor compound can be fully and uniformly mixed.
本发明中,对所述第一溶剂没有任何限制,优选为水、去离子水或蒸馏水中的至少一种。In the present invention, there is no limitation on the first solvent, and it is preferably at least one of water, deionized water or distilled water.
本发明中,优选后加入含Sn前体化合物溶液,能够使得含Sn前体化合物溶液充分分散于第一混合液中,进而使得制备的加氢催化剂中各组分混合得更均匀。In the present invention, it is preferable to add the Sn-containing precursor compound solution later, so that the Sn-containing precursor compound solution can be fully dispersed in the first mixed liquid, and then the components in the prepared hydrogenation catalyst can be mixed more uniformly.
根据本发明,所述加氢催化剂中,以所述加氢催化剂的总重量为基准,以氧化物计,Ni元素含量为17-28wt%,Sn元素含量为7-12wt%、Ca和/或Ba元素含量为1-3wt%、载体含量为40-75wt%。According to the present invention, in the hydrogenation catalyst, based on the total weight of the hydrogenation catalyst, in terms of oxides, the Ni element content is 17-28wt%, the Sn element content is 7-12wt%, Ca and/or The Ba element content is 1-3wt%, and the carrier content is 40-75wt%.
根据本发明,所述含Ni前体化合物为可溶性镍盐,优选为硝酸镍、硫酸镍、氯化镍和醋酸镍中的至少一种。According to the present invention, the Ni-containing precursor compound is a soluble nickel salt, preferably at least one of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate.
进一步地,所述含Sn前体化合物为可溶性锡盐,优选为锡酸钾和/或锡酸钠。Further, the Sn-containing precursor compound is a soluble tin salt, preferably potassium stannate and/or sodium stannate.
进一步地,所述载体的前体化合物选自酸性硅溶胶和/或碱性硅溶胶,优选为酸性硅溶胶。Further, the precursor compound of the carrier is selected from acidic silica sol and/or alkaline silica sol, preferably acidic silica sol.
本发明中,所述加氢催化剂中含有含Ca前体化合物和/或含Ba前体化合物,能够有效降低催化剂的酸性中心,抑制反应过程中副反应的发生,使得反应具有顺酐转化率高、丁二酸酐选择性高的特点。In the present invention, the hydrogenation catalyst contains a Ca-containing precursor compound and/or a Ba-containing precursor compound, which can effectively reduce the acid center of the catalyst, suppress the occurrence of side reactions in the reaction process, and make the reaction have a high conversion rate of maleic anhydride , High selectivity of succinic anhydride.
进一步地,含Ca前体化合物为CaCO。Further, the Ca-containing precursor compound is CaCO.
进一步地,含Ba前体化合物为BaCO3。Further, the Ba-containing precursor compound is BaCO 3 .
根据本发明,步骤(1)中,所述第二混合的条件包括:温度40-90℃,搅拌时间0.5-10h。According to the present invention, in step (1), the conditions for the second mixing include: a temperature of 40-90° C., and a stirring time of 0.5-10 h.
根据本发明,步骤(2)中,控制第一接触反应体系的pH值为5-8。According to the present invention, in step (2), the pH value of the first contact reaction system is controlled to 5-8.
根据本发明,所述碱溶液为氨水、碳酸铵溶液和碳酸氢铵溶液中的至少一种。According to the present invention, the alkaline solution is at least one of ammonia water, ammonium carbonate solution and ammonium bicarbonate solution.
根据本发明,步骤(2)中,所述第一接触反应的条件包括:温度为40-90℃,反应时间为0.5-10h。According to the present invention, in step (2), the conditions of the first contact reaction include: a temperature of 40-90° C., and a reaction time of 0.5-10 h.
根据本发明,步骤(3)中,所述干燥条件包括:温度为100-120℃,时间为10-20h。According to the present invention, in step (3), the drying conditions include: the temperature is 100-120°C, and the time is 10-20h.
根据本发明,步骤(4)中,所述焙烧条件包括:温度为300-600℃,时间为10-20h。According to the present invention, in step (4), the calcination conditions include: the temperature is 300-600°C, and the time is 10-20h.
进一步地,步骤(4)中,所述焙烧条件包括:温度为450-550℃,时间为2-6h。Further, in step (4), the calcination conditions include: the temperature is 450-550°C, and the time is 2-6h.
根据本发明的一种优选的实施方式:According to a preferred embodiment of the present invention:
(1)在去离子水的存在下,将硝酸镍和硅溶胶进行第一混合,得到第一混合液;并在40-90℃下,将锡酸钾水溶液与所述第一混合液进行第二混合,搅拌1-4h后得到第二混合液;(1) In the presence of deionized water, nickel nitrate and silica sol are mixed for the first time to obtain the first mixed solution; and at 40-90° C., the potassium stannate aqueous solution is mixed with the first mixed solution Two mixing, after stirring for 1-4h, the second mixed solution is obtained;
(2)将第二混合液和碱溶液在40-90℃下进行第一接触反应0.5-3h,得到沉淀物;(2) performing the first contact reaction with the second mixed solution and the alkali solution at 40-90° C. for 0.5-3 hours to obtain a precipitate;
(3)所述沉淀物经过滤、洗涤,并在100-120℃下干燥10-20h干燥后粉碎,得到粉末基体催化剂;(3) The precipitate is filtered, washed, dried at 100-120°C for 10-20 hours, and then pulverized to obtain a powder matrix catalyst;
(4)将粉末基体催化剂与CaCO3和/或BaCO3进行混合成型后,在450-600℃下焙烧10-20h,得到加氢催化剂。(4) After mixing and molding the powder matrix catalyst with CaCO 3 and/or BaCO 3 , calcining at 450-600° C. for 10-20 h to obtain a hydrogenation catalyst.
本发明第三方面提供一种由上述方法制备得到的加氢催化剂。The third aspect of the present invention provides a hydrogenation catalyst prepared by the above method.
本发明中,利用上述制备方法得到的加氢催化剂有更高的催化活性和选择性,更有利于应用到大规模工业化生产中。In the present invention, the hydrogenation catalyst obtained by the above-mentioned preparation method has higher catalytic activity and selectivity, and is more favorable to be applied in large-scale industrial production.
本发明第四方面提供一种上述加氢催化剂和/或所述的加氢催化剂的制备方法在顺酐加氢制丁二酸酐中的应用。The fourth aspect of the present invention provides an application of the above-mentioned hydrogenation catalyst and/or the preparation method of the hydrogenation catalyst in the hydrogenation of maleic anhydride to succinic anhydride.
本发明第五方面提供一种顺酐液相加氢制丁二酸酐的方法,其特征在于,该方法包括:在活化催化剂存在下,氢气和顺酐进行第二接触反应,得到所述丁二酸酐;The fifth aspect of the present invention provides a method for producing succinic anhydride by liquid-phase hydrogenation of maleic anhydride, characterized in that the method comprises: in the presence of an activated catalyst, hydrogen and maleic anhydride are subjected to a second contact reaction to obtain the succinic anhydride ;
其中,所述活化催化剂为上述加氢催化剂和/或上述制备方法得到的加氢催化剂经包含氢气的气体进行还原活化得到。Wherein, the activated catalyst is obtained by reducing and activating the above-mentioned hydrogenation catalyst and/or the hydrogenation catalyst obtained by the above-mentioned preparation method by a gas containing hydrogen.
本发明中,所述第二接触反应所采用的设备没有限制,只要能实现发生所述反应即可,例如可以在浆态床或悬浮床反应器中进行。In the present invention, the equipment used for the second contact reaction is not limited, as long as the reaction can be realized, for example, it can be carried out in a slurry bed or a suspension bed reactor.
根据本发明,所述还原活化的条件包括:温度为300-600℃,时间为0.5-20h。According to the present invention, the reductive activation conditions include: the temperature is 300-600°C, and the time is 0.5-20h.
本发明中,对所述加氢催化剂的还原活化的环境没有限制,只要能够进行活化即可。In the present invention, there is no limitation on the environment for the reductive activation of the hydrogenation catalyst, as long as the activation can be performed.
根据本发明,所述第二接触反应的条件包括:所述氢气和所述顺酐的用量摩尔比为10-30:1,温度为40-70℃,时间为1-6h,压力为1-5MPa。According to the present invention, the conditions of the second contact reaction include: the molar ratio of the hydrogen to the maleic anhydride is 10-30:1, the temperature is 40-70°C, the time is 1-6h, and the pressure is 1-6h. 5MPa.
进一步地,所述活化催化剂和所述顺酐的质量比为0.01-0.05:1。Further, the mass ratio of the activated catalyst to the maleic anhydride is 0.01-0.05:1.
根据本发明,所述顺酐溶液中含有第二溶剂,所述第二溶剂为四氢呋喃、1.4-二氧六环和γ-丁内酯中的至少一种。According to the present invention, the maleic anhydride solution contains a second solvent, and the second solvent is at least one of tetrahydrofuran, 1.4-dioxane and γ-butyrolactone.
根据本发明的一种优选的实施方式:According to a preferred embodiment of the present invention:
(a)在浆态床反应器内,将上述加氢催化剂在400-600℃下用氮气和氢气的混合物(混合物中氢气含量为50体积%,氢气空速为100h-1)还原3-10h进行活化,得到活化催化剂;(a) In a slurry bed reactor, reduce the above-mentioned hydrogenation catalyst with a mixture of nitrogen and hydrogen (the hydrogen content in the mixture is 50% by volume, and the hydrogen space velocity is 100h -1 ) at 400-600°C for 3-10h Activating to obtain an activated catalyst;
(b)在所述活化催化剂存在下,将氢气和顺酐溶液(溶剂选自四氢呋喃、1.4-二氧六环和γ-丁内酯中的至少一种,顺酐溶液浓度为10-30重量%),在60-150℃,压力1-5MPa下进行第二接触反应,活化催化剂和顺酐的用量摩尔比0.01-0.05:1;(b) In the presence of the activated catalyst, hydrogen and maleic anhydride solution (solvent is selected from at least one of tetrahydrofuran, 1.4-dioxane and γ-butyrolactone, the maleic anhydride solution concentration is 10-30% by weight ), the second contact reaction is carried out at 60-150°C under a pressure of 1-5MPa, and the molar ratio of activated catalyst to maleic anhydride is 0.01-0.05:1;
(c)将步骤(b)反应后的产物经冷凝得到液体产品,通过气相色谱分析液体产品中各组分的含量。其中,所述顺酐转化率和所述丁二酸酐的选择性通过以下公式计算得到:(c) condensing the reacted product in step (b) to obtain a liquid product, and analyzing the contents of each component in the liquid product by gas chromatography. Wherein, the selectivity of described maleic anhydride conversion rate and described succinic anhydride is calculated by following formula:
顺酐转化率=(Mo-Ma)/Mo×100%Maleic anhydride conversion=(Mo-Ma)/Mo×100%
丁二酸酐的选择性=Mi/(Mo-Ma)×100%Selectivity of succinic anhydride=Mi/(Mo-Ma)×100%
其中,Mo—原料顺酐的物质的量,mol;Wherein, Mo—the amount of substance of raw material maleic anhydride, mol;
Ma—反应后顺酐剩余的物质的量,mol;Ma—the amount of the remaining material of maleic anhydride after the reaction, mol;
Mi—反应后生成的丁二酸酐的物质的量,mol。Mi—the amount of succinic anhydride generated after the reaction, mol.
以下将通过实例对本发明进行详细描述。The present invention will be described in detail below by way of examples.
本发明中所用压力均为绝对压力。All pressures used in the present invention are absolute pressures.
以下使用的硅溶胶中SiO2的含量为25重量%。The content of SiO2 in the silica sol used below was 25% by weight.
在没有特别说明的情况下,以下各实施例和对比例中所用原料均为市售品。Unless otherwise specified, the raw materials used in the following examples and comparative examples are commercially available.
以下制备例和对比制备例中,所述加氢催化剂组成及其含量通过XRF测试获得。In the following preparation examples and comparative preparation examples, the composition and content of the hydrogenation catalyst were obtained through XRF testing.
以下制备例用于说明本发明的加氢催化剂及其制备方法。The following preparation examples are used to illustrate the hydrogenation catalyst of the present invention and its preparation method.
制备例1Preparation Example 1
(1)称取233.55g Ni(NO3)2·6H2O、828g酸性硅溶胶混溶于2000mL去离子水中,得到第一混合溶液;53.56g K2Sn(OH)6溶于250mL去离子水中;将第一混合溶液放入反应釜中,在70℃搅拌下,将K2Sn(OH)6加入到第一混合溶液中,搅拌2h,得到第二混合液;(1) Weigh 233.55g Ni(NO 3 ) 2 ·6H 2 O, 828g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 53.56g K 2 Sn(OH) 6 is dissolved in 250mL deionized water; put the first mixed solution into a reaction kettle, and add K 2 Sn(OH) 6 into the first mixed solution under stirring at 70°C, and stir for 2 hours to obtain the second mixed solution;
(2)向步骤(1)的第二混合液中加入10wt%的碳酸氢铵溶液,控制pH值为7.2,在65℃下搅拌1小时,得到沉淀物;(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;
(3)将步骤(2)中的沉淀物过滤,洗涤,120℃干燥12小时,然后与10.71g CaCO3混合成型,在马弗炉中550℃焙烧4小时,即得加氢催化剂S1。(3) The precipitate in step (2) was filtered, washed, dried at 120°C for 12 hours, then mixed with 10.71g of CaCO 3 and baked in a muffle furnace at 550°C for 4 hours to obtain hydrogenation catalyst S1.
以所述加氢催化剂S1的总重量计,该加氢催化剂S1中含有NiO 20wt%、SnO29wt%、SiO2 69wt%、CaO 2wt%。Based on the total weight of the hydrogenation catalyst S1, the hydrogenation catalyst S1 contains 20 wt% of NiO, 9 wt% of SnO 2 , 69 wt% of SiO 2 and 2 wt% of CaO.
制备例2Preparation example 2
(1)称取315.3g Ni(NO3)2·6H2O、696g酸性硅溶胶混溶于2000mL去离子水中,得到第一混合溶液;71.41g K2Sn(OH)6溶于250mL去离子水中;将第一混合溶液放入反应釜中,在70℃搅拌下,将锡酸钾水溶液加入到第一混合溶液中,搅拌2h,得到第二混合液;(1) Weigh 315.3g Ni(NO 3 ) 2 ·6H 2 O, 696g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 71.41g K 2 Sn(OH) 6 is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;
(2)向步骤(1)的第二混合液中加入10wt%的碳酸氢铵溶液,控制pH值为7.2,在65℃下搅拌1小时,得到沉淀物;(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;
(3)将步骤(2)中的沉淀物过滤,洗涤,120℃干燥12小时,然后与16.07g CaCO3混合成型,在马弗炉中550℃焙烧4小时,即得加氢催化剂S2。(3) The precipitate in step (2) was filtered, washed, dried at 120°C for 12 hours, then mixed with 16.07g of CaCO 3 to shape, and calcined in a muffle furnace at 550°C for 4 hours to obtain hydrogenation catalyst S2.
以所述加氢催化剂S2的总重量计,该加氢催化剂S2中含有NiO 27wt%、SnO212wt%、SiO2 58wt%、CaO 3wt%。Based on the total weight of the hydrogenation catalyst S2, the hydrogenation catalyst S2 contains 27wt% NiO, 12wt% SnO2 , 58wt% SiO2 and 3wt% CaO.
制备例3Preparation example 3
(1)称取210.2g Ni(NO3)2·6H2O、888g酸性硅溶胶混溶于2000mL去离子水中,得到第一混合溶液;41.66g K2Sn(OH)6溶于250mL去离子水中;将第一混合溶液放入反应釜中,在70℃搅拌下,将锡酸钾水溶液加入到第一混合溶液中,搅拌2h,得到第二混合液;(1) Weigh 210.2g Ni(NO 3 ) 2 ·6H 2 O, 888g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 41.66g K 2 Sn(OH) 6 is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;
(2)向步骤(1)的第二混合液中加入10wt%的碳酸氢铵溶液,控制pH值为7.2,在65℃下搅拌1小时,得到沉淀物;(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;
(3)将步骤(2)中的沉淀物过滤,洗涤,120℃干燥12小时,然后与5.35g CaCO3混合成型,在马弗炉中550℃焙烧4小时,即得加氢催化剂S3。(3) The precipitate in step (2) was filtered, washed, dried at 120°C for 12 hours, then mixed with 5.35g of CaCO 3 to shape, and calcined in a muffle furnace at 550°C for 4 hours to obtain hydrogenation catalyst S3.
以所述加氢催化剂S3的总重量计,该加氢催化剂S3中含有NiO 18wt%、SnO27wt%、SiO2 74wt%、CaO1 wt%。Based on the total weight of the hydrogenation catalyst S3, the hydrogenation catalyst S3 contains 18 wt% of NiO, 7 wt% of SnO 2 , 74 wt% of SiO 2 and CaO1 wt%.
制备例4Preparation Example 4
与制备例1一致,不同的是将CaCO3替换为BaCO3,得到加氢催化剂S4。Consistent with Preparation Example 1, the difference is that CaCO 3 is replaced by BaCO 3 to obtain hydrogenation catalyst S4.
以所述加氢催化剂S4的总重量计,该加氢催化剂S4中含有:NiO20wt%、SnO29wt%、SiO268wt%、BaO 3wt%。Based on the total weight of the hydrogenation catalyst S4, the hydrogenation catalyst S4 contains: NiO 20wt%, SnO 2 9wt%, SiO 2 68wt%, BaO 3wt%.
制备例5Preparation Example 5
(1)称取128.45g Ni(NO3)2·6H2O、984g酸性硅溶胶混溶于2000mL去离子水中,得到第一混合溶液;35.70g K2Sn(OH)6溶于250mL去离子水中;将第一混合溶液放入反应釜中,在70℃搅拌下,将锡酸钾水溶液加入到第一混合溶液中,搅拌2h,得到第二混合液;(1) Weigh 128.45g Ni(NO 3 ) 2 ·6H 2 O, 984g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 35.70g K 2 Sn(OH) 6 is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;
(2)向步骤(1)的第二混合液中加入10wt%的碳酸氢铵溶液,控制pH值为7.2,在65℃下搅拌1小时,得到沉淀物;(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;
(3)将步骤(2)中的沉淀物过滤,洗涤,120℃干燥12小时,然后与5.35gCaCO3混合成型,在马弗炉中550℃焙烧4小时,即得加氢催化剂S5。(3) The precipitate in step (2) was filtered, washed, dried at 120°C for 12 hours, then mixed with 5.35g of CaCO 3 to shape, and calcined in a muffle furnace at 550°C for 4 hours to obtain hydrogenation catalyst S5.
以所述加氢催化剂S5的总重量计,该加氢催化剂S5中含有NiO 11wt%、SnO26wt%、SiO2 82wt%、CaO1 wt%。Based on the total weight of the hydrogenation catalyst S5, the hydrogenation catalyst S5 contains 11 wt% of NiO, 6 wt% of SnO 2 , 82 wt% of SiO 2 and CaO1 wt%.
制备例6Preparation example 6
(1)称取443.75g Ni(NO3)2·6H2O、516g酸性硅溶胶混溶于2000mL去离子水中,得到第一混合溶液;83.32g K2Sn(OH)6溶于250mL去离子水中;将第一混合溶液放入反应釜中,在70℃搅拌下,将锡酸钾水溶液加入到第一混合溶液中,搅拌2h,得到第二混合液;(1) Weigh 443.75g Ni(NO 3 ) 2 ·6H 2 O, 516g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 83.32g K 2 Sn(OH) 6 is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;
(2)向步骤(1)的第二混合液中加入10wt%的碳酸氢铵溶液,控制pH值为7.2,在65℃下搅拌1小时,得到沉淀物;(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;
(3)将步骤(2)中的沉淀物过滤,洗涤,120℃干燥12小时,然后与26.78g CaCO3混合成型,在马弗炉中550℃焙烧4小时,即得加氢催化剂S6。(3) The precipitate in step (2) was filtered, washed, dried at 120°C for 12 hours, then mixed with 26.78g of CaCO 3 to shape, and calcined in a muffle furnace at 550°C for 4 hours to obtain hydrogenation catalyst S6.
以所述加氢催化剂S6的总重量计,该加氢催化剂S6中含有NiO 38wt%、SnO214wt%、SiO2 43wt%、CaCO3 5wt%。Based on the total weight of the hydrogenation catalyst S6, the hydrogenation catalyst S6 contains 38 wt% of NiO, 14 wt% of SnO 2 , 43 wt% of SiO 2 and 5 wt% of CaCO 3 .
制备例7Preparation Example 7
与制备例1一致,不同的是,步骤(1)中,在50℃搅拌下,将K2Sn(OH)6加入到第一混合溶液中,搅拌3h,得到第二混合液,其他步骤与制备例1一致,制备得到加氢催化剂S7。Consistent with Preparation Example 1, the difference is that in step (1), under stirring at 50°C, K 2 Sn(OH) 6 was added to the first mixed solution, and stirred for 3 hours to obtain the second mixed solution, and the other steps were the same as Consistent with Preparation Example 1, the hydrogenation catalyst S7 was prepared.
以所述加氢催化剂S7的总重量计,该加氢催化剂S7中含有NiO 21wt%、SnO210wt%、SiO267wt%、CaO 2wt%。Based on the total weight of the hydrogenation catalyst S7, the hydrogenation catalyst S7 contains 21wt% NiO, 10wt% SnO2 , 67wt% SiO2 and 2wt% CaO.
制备例8Preparation example 8
与制备例1一致,不同的是,步骤(3)中,焙烧条件替换为450℃焙烧6小时,其他步骤与制备例1一致,制备得到加氢催化剂S8。Consistent with Preparation Example 1, the difference is that in step (3), the calcination condition was replaced by calcination at 450° C. for 6 hours, and other steps were consistent with Preparation Example 1 to prepare hydrogenation catalyst S8.
以所述加氢催化剂S8的总重量计,该加氢催化剂S8中含有NiO 19wt%、SnO28wt%、SiO269 wt%、CaO 2wt%。Based on the total weight of the hydrogenation catalyst S8, the hydrogenation catalyst S8 contains 19 wt% of NiO, 8 wt% of SnO 2 , 69 wt% of SiO 2 and 2 wt% of CaO.
制备例9Preparation Example 9
与制备例1一致,不同的是,步骤(3)中,将CaCO3替换为BaCO3和CaCO3的混合物,保持总用量相同,其中,CaCO3与BaCO3质量比为1:1,其他步骤与制备例1一致,制备得到加氢催化剂S9。Consistent with Preparation Example 1, the difference is that in step (3), CaCO is replaced by a mixture of BaCO and CaCO to keep the total amount the same, wherein the mass ratio of CaCO to BaCO is 1:1 , and the other steps Consistent with Preparation Example 1, hydrogenation catalyst S9 was prepared.
以所述加氢催化剂S9的总重量计,该加氢催化剂S9中含有NiO20wt%、SnO29wt%、SiO269 wt%、CaO 1wt%、BaO 1wt%Based on the total weight of the hydrogenation catalyst S9, the hydrogenation catalyst S9 contains NiO20wt%, SnO2 9wt%, SiO2 69wt%, CaO1wt%, BaO1wt%
对比制备例1Comparative Preparation Example 1
(1)称取233.55g Ni(NO3)2·6H2O、936g酸性硅溶胶混溶于2000mL去离子水中,得到第一混合溶液;(1) Weigh 233.55g of Ni(NO 3 ) 2 ·6H 2 O and 936g of acidic silica sol and dissolve them in 2000mL of deionized water to obtain the first mixed solution;
(2)将第一混合溶液放入反应釜中,在70℃搅拌下,将10wt%的碳酸氢铵溶液加入上述第一混合液中,控制pH值为7.2,在65℃下搅拌1小时,得到沉淀物;(2) Put the first mixed solution into the reaction kettle, under stirring at 70°C, add 10wt% ammonium bicarbonate solution into the first mixed solution, control the pH value to 7.2, and stir at 65°C for 1 hour, get sediment;
(3)将步骤(2)中的沉淀物过滤,洗涤,120℃干燥12小时,然后与10.71gCaCO3混合成型,在马弗炉中550℃焙烧4小时,即得加氢催化剂CS1。(3) The precipitate in step (2) was filtered, washed, dried at 120°C for 12 hours, then mixed with 10.71g of CaCO 3 and baked in a muffle furnace at 550°C for 4 hours to obtain the hydrogenation catalyst CS1.
以所述加氢催化剂CS1的总重量计,该加氢催化剂CS1中含有NiO 20wt%、SiO278wt%、CaO2 wt%。Based on the total weight of the hydrogenation catalyst CS1, the hydrogenation catalyst CS1 contains 20wt% NiO, 78wt% SiO2 and CaO2 wt%.
对比制备例2Comparative Preparation Example 2
(1)称取233.55g Ni(NO3)2·6H2O、852g酸性硅溶胶混溶于2000mL去离子水中,得到第一混合溶液;53.56g K2Sn(OH)6溶于250mL去离子水中;将第一混合溶液放入反应釜中,在70℃搅拌下,将K2Sn(OH)6加入到第一混合溶液中,搅拌2h,得到第二混合液;(1) Weigh 233.55g Ni(NO 3 ) 2 ·6H 2 O, 852g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 53.56g K 2 Sn(OH) 6 is dissolved in 250mL deionized water; put the first mixed solution into a reaction kettle, and add K 2 Sn(OH) 6 into the first mixed solution under stirring at 70°C, and stir for 2 hours to obtain the second mixed solution;
(2)向步骤(1)的第二混合液中加入10wt%的碳酸氢铵溶液,控制pH值为7.2,在65℃下搅拌1小时,得到沉淀物;(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;
(3)将步骤(2)中的沉淀物过滤,洗涤,120℃干燥12小时,在马弗炉中550℃焙烧4小时,即得加氢催化剂CS2。(3) The precipitate in step (2) was filtered, washed, dried at 120°C for 12 hours, and calcined in a muffle furnace at 550°C for 4 hours to obtain the hydrogenation catalyst CS2.
以所述加氢催化剂CS2的总重量计,该加氢催化剂CS2中含有NiO 20wt%、SnO29wt%、SiO2 71wt%。Based on the total weight of the hydrogenation catalyst CS2, the hydrogenation catalyst CS2 contains 20 wt% of NiO, 9 wt% of SnO 2 and 71 wt% of SiO 2 .
制备对比例3Prepare comparative example 3
(1)称取93.42g Ni(NO3)2·6H2O、984g酸性硅溶胶混溶于2000mL去离子水中,得到第一混合溶液;53.56g K2Sn(OH)6溶于250mL去离子水中;将第一混合溶液放入反应釜中,在70℃搅拌下,将锡酸钾水溶液加入到第一混合溶液中,搅拌2h,得到第二混合液;(1) Weigh 93.42g Ni(NO 3 ) 2 ·6H 2 O, 984g acidic silica sol and dissolve in 2000mL deionized water to obtain the first mixed solution; 53.56g K 2 Sn(OH) 6 is dissolved in 250mL deionized In water; put the first mixed solution into a reaction kettle, and under stirring at 70° C., add an aqueous solution of potassium stannate to the first mixed solution, and stir for 2 hours to obtain a second mixed solution;
(2)向步骤(1)的第二混合液中加入10wt%的碳酸氢铵溶液,控制pH值为7.2,在65℃下搅拌1小时,得到沉淀物;(2) Add 10wt% ammonium bicarbonate solution to the second mixed solution in step (1), control the pH value to 7.2, and stir at 65° C. for 1 hour to obtain a precipitate;
(3)将步骤(2)中的沉淀物过滤,洗涤,120℃干燥12小时,然后与5.36g CaCO3混合成型,在马弗炉中550℃焙烧4小时,即得加氢催化剂CS3。(3) The precipitate in step (2) was filtered, washed, dried at 120°C for 12 hours, then mixed with 5.36g of CaCO 3 to form, and calcined in a muffle furnace at 550°C for 4 hours to obtain the hydrogenation catalyst CS3.
以所述加氢催化剂CS3的总重量计,该加氢催化剂CS3中含有NiO8wt%、SnO29wt%、SiO282 wt%、CaO 1wt%。Based on the total weight of the hydrogenation catalyst CS3, the hydrogenation catalyst CS3 contains 8 wt% of NiO, 9 wt% of SnO 2 , 82 wt% of SiO 2 and 1 wt% of CaO.
以下实施例用于说明本发明的加氢催化剂的应用和顺酐加氢制丁二酸酐的方法The following examples are used to illustrate the application of the hydrogenation catalyst of the present invention and the method for the hydrogenation of maleic anhydride to produce succinic anhydride
实施例1Example 1
(a)在浆态床反应器内,称取上述加氢催化剂1.2g在450℃下用氮气和氢气的混合物(混合物中氢气含量为50体积%,氢气空速为400h-1)还原6h进行活化,得到活化催化剂;(a) In a slurry bed reactor, weigh 1.2 g of the above-mentioned hydrogenation catalyst and reduce it with a mixture of nitrogen and hydrogen (the hydrogen content in the mixture is 50% by volume, and the hydrogen space velocity is 400h -1 ) at 450°C for 6h. Activation to obtain an activated catalyst;
(b)在所述活化催化剂存在下,将氢气和500g顺酐溶液(溶剂为四氢呋喃顺酐溶液浓度为20重量%),在60℃,2MPa下进行第二接触反应;(b) In the presence of the activated catalyst, hydrogen and 500g maleic anhydride solution (the solvent is tetrahydrofuran maleic anhydride solution with a concentration of 20% by weight) are carried out at 60°C and 2MPa for the second contact reaction;
(c)将步骤(b)反应后的产物经冷凝得到液体产品,通过气相色谱分析液体产品中各组分的含量。通过下述公式计算得到顺酐的转化率和丁二酸酐的选择性,具体结果见表1。(c) condensing the reacted product in step (b) to obtain a liquid product, and analyzing the contents of each component in the liquid product by gas chromatography. The conversion rate of maleic anhydride and the selectivity of succinic anhydride are calculated by the following formula, and the specific results are shown in Table 1.
其中,所述顺酐转化率和所述丁二酸酐的选择性通过以下公式计算得到:Wherein, the selectivity of described maleic anhydride conversion rate and described succinic anhydride is calculated by following formula:
顺酐转化率=(Mo-Ma)/Mo×100%Maleic anhydride conversion=(Mo-Ma)/Mo×100%
丁二酸酐的选择性=Mi/(Mo-Ma)×100%Selectivity of succinic anhydride=Mi/(Mo-Ma)×100%
其中,Mo—原料顺酐的物质的量,mol;Wherein, Mo—the amount of substance of raw material maleic anhydride, mol;
Ma—反应后顺酐剩余的物质的量,mol;Ma—the amount of the remaining material of maleic anhydride after the reaction, mol;
Mi—反应后生成的丁二酸酐的物质的量,mol。Mi—the amount of succinic anhydride generated after the reaction, mol.
实施例2-9Example 2-9
按照实施例1的方法进行,不同的是,分别采用制备例2-9制得的加氢催化剂代替上述制备例1制得的加氢催化剂,其他与实施例1相同。顺酐的转化率和丁二酸酐的选择性,具体结果见表1。Proceed according to the method of Example 1, except that the hydrogenation catalysts prepared in Preparation Examples 2-9 were used instead of the hydrogenation catalysts prepared in Preparation Example 1 above, and the others were the same as in Example 1. The conversion rate of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1 for specific results.
对比例1-3Comparative example 1-3
按照实施例1的方法进行,不同的是,分别采用对比制备例1-3制备的加氢催化剂代替上述制备例1制得的加氢催化剂,其他与实施例1相同。顺酐的转化率和丁二酸酐的选择性,具体结果见表1。Proceed according to the method of Example 1, except that the hydrogenation catalysts prepared in Comparative Preparation Examples 1-3 were used instead of the hydrogenation catalysts prepared in the above Preparation Example 1, and the others were the same as in Example 1. The conversion rate of maleic anhydride and the selectivity of succinic anhydride are shown in Table 1 for specific results.
表1Table 1
由表1可知,本发明的含Ni-Sn-Si-Ca/Ba元素的加氢催化剂应用于顺酐液相催化加氢制丁二酸酐时,具有较高的催化活性和丁二酸酐的选择性。As can be seen from Table 1, when the hydrogenation catalyst containing Ni-Sn-Si-Ca/Ba element of the present invention is applied to the liquid-phase catalytic hydrogenation of maleic anhydride to produce succinic anhydride, it has higher catalytic activity and the selection of succinic anhydride sex.
由实施例1-3和实施例5、6的数据对比可见,实施例1-3的效果均优于实施例5、6,由此可知,当催化剂中活性组分的含量满足本申请的优选范围时,制备的加氢催化剂的催化活性和丁二酸酐的选择性更好。By the comparison of the data of Examples 1-3 and Examples 5 and 6, it can be seen that the effects of Examples 1-3 are better than Examples 5 and 6, so it can be seen that when the content of active components in the catalyst meets the preferred range, the catalytic activity of the prepared hydrogenation catalyst and the selectivity of succinic anhydride are better.
由实施例1和对比例1可见,对比例1由于未引入Sn元素,在与本发明相同的反应条件下,丁二酸酐选择性明显降低,而实施例1中,丁二酸酐的选择性高达99.6%。As can be seen from Example 1 and Comparative Example 1, Comparative Example 1 is due to not introducing the Sn element, under the same reaction conditions as the present invention, the selectivity of succinic anhydride is significantly reduced, while in Example 1, the selectivity of succinic anhydride is as high as 99.6%.
由实施例1和对比例2可知,对比例由于未引入Ca或Ba元素,在与本发明相同的反应条件下,丁二酸酐选择性明显降低。From Example 1 and Comparative Example 2, it can be seen that the comparative example does not introduce Ca or Ba elements, and under the same reaction conditions as the present invention, the selectivity of succinic anhydride is significantly reduced.
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.
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