CN101829571A - Method for preparing Cu/SiO2 catalyst - Google Patents
Method for preparing Cu/SiO2 catalyst Download PDFInfo
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Abstract
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技术领域technical field
本发明涉及一种催化剂,尤其是涉及一种适用于烯烃聚合所需的催化剂组合物,以SiO2为载体,Cu为活性组分的负载型催化剂的制备方法。The invention relates to a catalyst, in particular to a catalyst composition suitable for olefin polymerization, a method for preparing a supported catalyst with SiO2 as a carrier and Cu as an active component.
背景技术Background technique
硅胶的化学成分为SiO2,室温下硅胶表面有一层物理吸附水,表面上同时存在硅烷醇[-SiOH]结构,在423~473K时,大部分吸附的水被脱附,表面上主要留下[-SiOH]。在更高温度下,相邻的[-OH]脱水形成[Si-O-Si]结构。硅胶具有特殊的孔结构、大比表面积和优良的热稳定性,被广泛用作吸附剂、干燥剂、增稠剂、色谱柱载体和催化剂载体等。The chemical composition of silica gel is SiO 2 . At room temperature, there is a layer of physically adsorbed water on the surface of silica gel, and there is a silanol [-SiOH] structure on the surface. At 423-473K, most of the adsorbed water is desorbed, leaving mainly [-SiOH]. At higher temperatures, the adjacent [-OH] dehydrates to form a [Si-O-Si] structure. Silica gel has special pore structure, large specific surface area and excellent thermal stability, and is widely used as adsorbent, desiccant, thickener, chromatographic column support and catalyst support, etc.
硅胶作为烯烃聚合所需催化剂的载体在催化剂组分中具有十分重要的地位,它的形态、粒径及其分布、比表面、孔径分布等参数对聚合物的形态及性能可产生极大的影响。20世纪80年代初,我国已开始进行适用于聚烯烃催化剂硅胶载体的国产化研究,但目前聚烯烃工业中所用催化剂硅胶载体仍大多依靠进口。因此,开发新的聚烯烃催化剂硅胶载体对打破国外长期在催化剂载体硅胶领域对市场的垄断具有重要的实际应用意义。As the carrier of the catalyst required for olefin polymerization, silica gel plays a very important role in the catalyst components. Its shape, particle size and distribution, specific surface area, pore size distribution and other parameters can have a great impact on the shape and performance of the polymer. . In the early 1980s, my country began to carry out research on the localization of silica gel carriers suitable for polyolefin catalysts. However, most of the catalyst silica gel carriers used in the polyolefin industry still rely on imports. Therefore, the development of new silica gel carriers for polyolefin catalysts has important practical significance for breaking the long-term monopoly of foreign countries in the field of catalyst carrier silica gel.
催化剂常用的制备方法主要有浸渍法、沉淀法、溶胶-凝胶法、离子交换法等。溶胶-凝胶法是指金属有机或无机化合物经过溶液、溶胶和凝胶而固化,再经过热处理而形成氧化物或其他化合物固体的方法。溶胶是介质中分散了1~100nm粒子(基本单元)的体系,凝胶是含有亚微米孔和聚合链相互连接的坚实的网络,凝胶结构可分为有序层状结构、无序共聚网络、无序控制聚合的网络和粒子无序结构等。溶胶凝胶法具有很多优点:反应温度低,反应过程易于控制;制品的均匀度和纯度高(均匀性可达分子或原子水平);化学计量准确,易于改性,掺杂的范围宽(包括掺杂的量和种类);从同一种原料出发,改变工艺过程即可获得不同的产品;工艺简单,不需要昂贵的设备。The commonly used preparation methods of catalysts mainly include impregnation method, precipitation method, sol-gel method, ion exchange method and so on. The sol-gel method refers to the method in which metal organic or inorganic compounds are solidified through solutions, sols and gels, and then heat-treated to form oxides or other compound solids. Sol is a system in which 1-100nm particles (basic units) are dispersed in the medium. Gel is a solid network containing submicron pores and interconnected polymer chains. The gel structure can be divided into ordered layered structure and disordered copolymerization network. , disordered controlled aggregated networks and particle disordered structures, etc. The sol-gel method has many advantages: the reaction temperature is low, and the reaction process is easy to control; the uniformity and purity of the product are high (the uniformity can reach the molecular or atomic level); the stoichiometry is accurate, easy to modify, and the range of doping is wide (including The amount and type of doping); starting from the same raw material, different products can be obtained by changing the process; the process is simple and does not require expensive equipment.
烯烃聚合在石油化工中占有较大的比重,而聚烯烃催化剂载体作为烯烃聚合工业的一个重要组成部分对聚烯烃的发展产生巨大的影响。20世纪80年代以后,国内外关于聚烯烃催化剂硅胶载体的研究已申请了许多专利,并有许多相关理论研究方面的报道。姚培洪等在中国专利CN1403486中公开了一种硅胶载体的制备方法,即在制备硅凝胶时将稀硅酸盐和无机酸同时加入装有以部分稀硅酸盐溶液为母液的反应釜中,待溶胶及部分凝胶出现时,调节反应釜中母液pH值至5~8.5,待水溶胶全部转化为硅凝胶后,经老化、洗涤、处理和干燥得到比表面积为200~400m2/g,孔径分布为8~15nm,堆密度为0.2~0.4g/ml,孔容为1.0~1.2ml/g的硅胶载体。聚烯烃工业上使用的聚烯烃催化剂要求硅胶载体的孔体积1.00~2.00ml/g,比表面积为280~555m2/g,孔径分布为9~18nm。Olefin polymerization occupies a large proportion in petrochemical industry, and polyolefin catalyst support, as an important part of olefin polymerization industry, has a huge impact on the development of polyolefin. Since the 1980s, many patents have been applied for research on silica gel carriers for polyolefin catalysts at home and abroad, and there have been many reports on related theoretical research. Yao Peihong etc. disclose a kind of preparation method of silica gel carrier in Chinese patent CN1403486, promptly when preparing silica gel, dilute silicate and inorganic acid are simultaneously added in the reactor that is housed with part dilute silicate solution as mother liquor, When the sol and part of the gel appear, adjust the pH value of the mother liquor in the reactor to 5-8.5, and after the hydrosol is completely converted into silica gel, the specific surface area is 200-400m 2 /g after aging, washing, treatment and drying , the pore size distribution is 8-15nm, the bulk density is 0.2-0.4g/ml, the pore volume is 1.0-1.2ml/g silica gel carrier. The polyolefin catalyst used in the polyolefin industry requires a silica gel carrier with a pore volume of 1.00-2.00ml/g, a specific surface area of 280-555m 2 /g, and a pore size distribution of 9-18nm.
Cu由于具有良好的催化氧化和催化还原性能而被广泛地应用于氧化、加氢及碳氢化合物的催化燃烧、NOx催化还原等化学工程、环境保护及燃料电池等领域。铜系催化剂以活性高、价廉易得等优点使其在催化领域中得到普遍应用。Cu/SiO2催化剂由于具有较好的加氢选择性且无环境污染问题,深受关注。国外对Cu/SiO2催化剂的研究起步较早,到20世纪80~90年代进行了详细研究。国内对Cu/SiO2催化剂的研究兴起于20世纪90年代,李竹霞等(李竹霞,钱志刚,赵秀阁,等.载体对草酸二甲酯加氢铜基催化剂的影响[J].华东理工大学学报,2005,31(1):27-31;李竹霞.草酸二甲酯催化加氢合成乙二醇过程的研究[D].上海:华东理工大学,2004.)研究各种氧化物载体(γ一Al2O3、SiO2、TiO2和ZrO2)时发现,Cu/SiO2活性最好,并研究了助剂的影响(Ni、Zn和Ca)。黄维杰等(黄维杰,文峰,康文国,等.草酸二甲酯加氢制乙二醇Cu/SiO2催化剂的制备与改性[J].工业催化,2008,16(6):13-17.)和文峰等在(文峰,黄维杰,肖文德.草酸二甲酯加氢催化剂Cu/SiO2的制备研究[J].广东化工,2008,35(4):5-11)分别研究了蒸氨法和尿素沉淀沉积法制备Cu/SiO2催化剂各制备因素的影响。Due to its good catalytic oxidation and catalytic reduction properties, Cu is widely used in chemical engineering, environmental protection, fuel cells and other fields such as oxidation, hydrogenation, catalytic combustion of hydrocarbons, catalytic reduction of NOx , etc. Copper-based catalysts have been widely used in the field of catalysis due to their high activity, low cost and easy availability. Cu/SiO 2 catalyst has attracted much attention due to its good hydrogenation selectivity and no environmental pollution. The research on Cu/SiO 2 catalyst started earlier abroad, and detailed research was carried out in the 1980s and 1990s. Domestic research on Cu/SiO 2 catalysts started in the 1990s. Li Zhuxia et al. , 2005, 31(1): 27-31; Li Zhuxia. Study on the catalytic hydrogenation of dimethyl oxalate to ethylene glycol [D]. Shanghai: East China University of Science and Technology, 2004.) Research on various oxide supports (γ- Al 2 O 3 , SiO 2 , TiO 2 and ZrO 2 ), it was found that Cu/SiO 2 had the best activity, and the influence of additives (Ni, Zn and Ca) was studied. Huang Weijie et al. (Huang Weijie, Wenfeng, Kang Wenguo, et al. Preparation and modification of Cu/SiO 2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol [J]. Industrial Catalysis, 2008, 16(6): 13-17 .) and Wenfeng etc. in (Wenfeng, Huang Weijie, Xiao Wende. Preparation of Cu/SiO 2 catalyst for hydrogenation of dimethyl oxalate [J]. Guangdong Chemical Industry, 2008, 35 (4): 5-11) respectively studied the steam Influence of preparation factors on Cu/SiO 2 catalyst prepared by ammonia method and urea precipitation deposition method.
目前的研究表明,Cu/SiO2催化剂作为选择性加氢催化剂具有广泛的用途,制备方法也有多种,但都有一定的局限性,比如载体浸渍法容易发生活性组分在载体的细颗粒边缘的不均匀团聚;离子交换法虽能较好地分散活性组分,但活性组分负载量却很低;沉淀沉积法制备的Cu/SiO2催化剂Cu含量较低,提高铜的含量会导致表面铜晶粒长大,易烧结。The current research shows that Cu/ SiO2 catalyst has a wide range of uses as a selective hydrogenation catalyst, and there are many preparation methods, but all of them have certain limitations, such as the carrier impregnation method, which is prone to the occurrence of active components on the edge of the fine particles of the carrier uneven agglomeration; although the ion exchange method can disperse the active components well, the loading capacity of the active components is very low; the Cu/SiO 2 catalyst prepared by the precipitation deposition method has a low Cu content, and increasing the copper content will lead to surface The copper grain grows up and is easy to sinter.
发明内容Contents of the invention
本发明的目的是提供一种制备Cu/SiO2催化剂的方法,所制备的Cu/SiO2催化剂具有较高的比表面积、Cu负载量、分散性和稳定性等优点。The object of the present invention is to provide a method for preparing Cu/ SiO2 catalyst, the prepared Cu/ SiO2 catalyst has advantages such as higher specific surface area, Cu loading capacity, dispersibility and stability.
本发明的技术方案是采用晶核增长技术及有效控制粒径控制方法,通过溶胶-凝胶法将催化剂有效地分散负载到硅溶胶中,从而获得一种具有较高的比表面积、Cu负载量、分散性和稳定性等优点的Cu/SiO2催化剂。The technical scheme of the present invention adopts crystal nucleus growth technology and effective particle size control method, and effectively disperses and loads the catalyst into the silica sol through the sol-gel method, thereby obtaining a high specific surface area and Cu loading capacity. Cu/SiO 2 catalyst with advantages such as , dispersibility and stability.
本发明包括以下步骤:The present invention comprises the following steps:
1)配制含有表面活性剂的硅酸乙酯溶液;1) preparing an ethyl silicate solution containing a surfactant;
2)配制无机酸溶液;2) preparing inorganic acid solution;
3)将步骤1)配制好的含有表面活性剂的硅酸乙酯溶液加到反应釜中,同时向反应釜中加入步骤2)配制好的无机酸溶液,搅拌,恒温老化,得混合溶液;3) adding the surfactant-containing ethyl silicate solution prepared in step 1) into the reaction kettle, and simultaneously adding the inorganic acid solution prepared in step 2) into the reaction kettle, stirring, and aging at constant temperature to obtain a mixed solution;
4)将步骤3)所得的混合溶液溶入无水乙醇,搅拌,再加入催化剂、乙醇,再搅拌,得混合液;4) Dissolving the mixed solution obtained in step 3) into absolute ethanol, stirring, then adding catalyst and ethanol, and stirring again to obtain a mixed solution;
5)将含有2%~5%Cu计算量的铜盐溶液加入步骤4)所得的混合液中,再用氨水调节pH值,搅拌,室温老化,再恒温水浴干燥后焙烧,研磨过筛,得Cu/SiO2催化剂。5) adding copper salt solution containing 2% to 5% Cu in calculated amount to the mixed solution obtained in step 4), adjusting the pH value with ammonia water, stirring, aging at room temperature, drying in a constant temperature water bath, roasting, grinding and sieving to obtain Cu/ SiO2 catalyst.
在步骤1)中,所述表面活性剂可选自十二烷基苯磺酸钠等,所述十二烷基苯磺酸钠的浓度可为0.01~0.02mol/L;所述硅酸乙酯溶液的浓度可为0.5~1.0mol/L。In step 1), the surfactant can be selected from sodium dodecylbenzenesulfonate, etc., and the concentration of the sodium dodecylbenzenesulfonate can be 0.01-0.02mol/L; The concentration of the ester solution may be 0.5-1.0 mol/L.
在步骤2)中,所述无机酸溶液的浓度可为0.5~1.0mol/L;所述无机酸可选自盐酸、硫酸和硝酸等中的一种。In step 2), the concentration of the inorganic acid solution may be 0.5-1.0 mol/L; the inorganic acid may be selected from one of hydrochloric acid, sulfuric acid and nitric acid.
在步骤3)中,所述将步骤1)配制好的含有表面活性剂的硅酸乙酯溶液加到反应釜中的流速可为2~5ml/min;所述向反应釜中加入步骤2)配制好的无机酸溶液,最好使反应釜中溶液的pH值为8.5~10;所述搅拌的速度可为2000~3000r/min;所述恒温老化的温度可为65~85℃,恒温老化的时间可为1~2h。In step 3), the flow rate of adding the surfactant-containing ethyl silicate solution prepared in step 1) to the reactor can be 2 to 5ml/min; adding step 2) to the reactor The prepared inorganic acid solution should preferably have a pH value of 8.5 to 10 in the reaction kettle; the stirring speed can be 2000 to 3000r/min; the constant temperature aging temperature can be 65 to 85°C, and the constant temperature aging The time can be 1 ~ 2h.
在步骤4)中,所述将步骤3)所得的混合溶液溶入无水乙醇,按体积比,混合溶液∶无水乙醇可为11∶(18~20);所述催化剂、乙醇,按体积比,催化剂∶乙醇可为1∶(2.5~10),所述乙醇的醇水体积比可为7∶11;所述催化剂可选自HNO3或NH4OH等。In step 4), the mixed solution obtained in step 3) is dissolved into absolute ethanol, and the mixed solution: absolute ethanol can be 11: (18~20) by volume; the catalyst, ethanol, by volume The catalyst:ethanol ratio can be 1:(2.5-10), and the alcohol-water volume ratio of the ethanol can be 7:11; the catalyst can be selected from HNO 3 or NH 4 OH and the like.
在步骤5)中,所述氨水的浓度可为2mol/L,所述焙烧的温度可为400℃,焙烧的时间可为4h;所述铜盐可选自Cu(NO3)2、CuCl2、Cu(CH3COO)2等中的一种,最好为Cu(NO3)2;所述再用氨水调节pH值,最好是pH值为6~8;所述恒温水浴的温度可为60~70℃,所述焙烧的温度可为400℃。In step 5), the concentration of the ammonia water can be 2mol/L, the temperature of the calcination can be 400°C, and the calcination time can be 4h; the copper salt can be selected from Cu(NO 3 ) 2 , CuCl 2 , Cu(CH 3 COO) 2 , etc., preferably Cu(NO 3 ) 2 ; the pH value is adjusted with ammonia water, preferably the pH value is 6-8; the temperature of the constant temperature water bath can be 60-70°C, and the calcination temperature may be 400°C.
由于本发明采用晶核增长技术及有效控制粒径控制方法,通过溶胶-凝胶法将催化剂均匀有效地分散负载到硅溶胶中,因此本发明具有以下突出优点:工艺过程简单,工艺条件易控制,所得催化剂的比表面积高、铜负载量高、分散性和稳定性优良,是一种很有应用前景的聚烯烃用催化剂。经试验,本发明制得的催化剂其催化效率比普通催化剂明显高,便于产业化推广。Since the present invention adopts crystal nucleus growth technology and effective particle size control method, the catalyst is evenly and effectively dispersed and loaded into the silica sol by the sol-gel method, so the present invention has the following outstanding advantages: the process is simple and the process conditions are easy to control , the obtained catalyst has high specific surface area, high copper loading capacity, excellent dispersion and stability, and is a very promising catalyst for polyolefins. Tests show that the catalytic efficiency of the catalyst prepared by the invention is significantly higher than that of common catalysts, which is convenient for industrial promotion.
具体实施方式Detailed ways
实施例1Example 1
1)在安装有温度计、pH计和搅拌器的反应釜中加入200ml去离子水,开动搅拌器速度3000r/min,使反应釜温度为80℃。1) Add 200ml of deionized water to the reactor equipped with a thermometer, a pH meter and a stirrer, and start the stirrer at a speed of 3000r/min, so that the temperature of the reactor is 80°C.
2)配制浓度为1.0mol/L硅酸乙酯溶液,再向此溶液中加入十二烷基苯磺酸钠,使十二烷基苯磺酸钠浓度为0.01mol/L。配制浓度为0.5mol/L的硝酸溶液。2) Prepare an ethyl silicate solution with a concentration of 1.0 mol/L, and then add sodium dodecylbenzenesulfonate to the solution so that the concentration of sodium dodecylbenzenesulfonate is 0.01mol/L. Prepare a nitric acid solution with a concentration of 0.5mol/L.
3)以3ml/min的流速将硅酸乙酯溶液加入反应釜中,同时滴加硝酸溶液,使反应釜中溶液的pH值为8.5,在反应中保持恒定搅拌速度和恒定温度,滴加完后,在搅拌下恒温老化1~2h。3) Add ethyl silicate solution in the reaction kettle at a flow rate of 3ml/min, and simultaneously add nitric acid solution dropwise, so that the pH value of the solution in the reaction kettle is 8.5, keep constant stirring speed and constant temperature in the reaction, and dropwise add Afterwards, aging at constant temperature for 1 to 2 hours under stirring.
4)取11ml步骤3)所得溶液溶入18.5ml无水乙醇,搅拌均匀。将1ml的HNO3、8ml乙醇混合倒入混合物中,搅拌均匀。4) Dissolve 11ml of the solution obtained in step 3) into 18.5ml of absolute ethanol, and stir evenly. 1ml of HNO 3 and 8ml of ethanol were mixed and poured into the mixture, and stirred evenly.
5)将含有2%Cu计算量的Cu(NO3)2溶液50ml缓慢滴入步骤4)所得混合液中,再用浓度为2mol/L的氨水调节pH值为7,强力搅拌1h,室温老化12h,在60℃恒温水浴干燥20h,110℃烘箱干燥15h,400℃焙烧4h。研磨,过筛,备用。5) Slowly drop 50 ml of Cu(NO 3 ) 2 solution containing 2% Cu into the mixed solution obtained in step 4), adjust the pH value to 7 with ammonia water with a concentration of 2 mol/L, stir vigorously for 1 hour, and age at room temperature 12h, dry in a constant temperature water bath at 60°C for 20h, oven dry at 110°C for 15h, and bake at 400°C for 4h. Grind, sieve, and set aside.
6)将步骤5)所得催化剂样品在300℃真空条件下预处理3h,以高纯氮作吸附质,在液氮温度下使用BET法进行测定。测得催化剂比表面积为716.5m2/g,孔容为0.696cc/g。6) The catalyst sample obtained in step 5) was pretreated under vacuum conditions at 300°C for 3 hours, and high-purity nitrogen was used as the adsorbate, and the BET method was used for determination at liquid nitrogen temperature. The measured specific surface area of the catalyst was 716.5m 2 /g, and the pore volume was 0.696cc/g.
7)将步骤5)所得催化剂样品0.2mol与同等粒径和体积的石英砂混合后置于泵型反应器中部,控制草酸二乙酯溶液的进料量为0.01ml/min,经预热器预热为气态后,与氢气混合进行反应。反应温度220-250℃,压力0.5~4MPa,氢/酯摩尔比170~290.液相产物用美国Varian公司生产的3700型气相色谱仪分析,采用校正因子法计算各物质的百分含量,得草酸二乙酯转化率为94.5%和乙二醇收率为81%。7) Mix 0.2 mol of the catalyst sample obtained in step 5) with quartz sand of the same particle size and volume and place it in the middle of the pump reactor, control the feed rate of the diethyl oxalate solution to 0.01ml/min, After preheating to a gaseous state, it is mixed with hydrogen to react. The reaction temperature is 220-250° C., the pressure is 0.5-4 MPa, and the hydrogen/ester molar ratio is 170-290. The liquid phase product is analyzed by a 3700 gas chromatograph produced by Varian Company of the United States, and the percentage content of each substance is calculated by the correction factor method to obtain The conversion of diethyl oxalate was 94.5% and the yield of ethylene glycol was 81%.
实施例2Example 2
制备过程同实施例1。反应釜温度为80℃,硅酸乙酯溶液浓度为1.0mol/L,十二烷基苯磺酸钠浓度为0.01mol/L,硅酸乙酯溶液加入反应釜中流速为3ml/min,反应釜中溶液的pH值为8.5,Cu(NO3)2溶液中Cu计算量为2%,氨水调节pH值为7.2,恒温水浴温度为65℃,催化剂比表面积为715.5m2/g,孔容为0.689cc/g,将所得催化剂用于草酸二乙酯加氢制备乙二醇的反应中,草酸二乙酯转化率为93.8%和乙二醇收率为79.8%。The preparation process is the same as in Example 1. The temperature of the reaction kettle is 80°C, the concentration of the ethyl silicate solution is 1.0mol/L, the concentration of sodium dodecylbenzenesulfonate is 0.01mol/L, the flow rate of the ethyl silicate solution into the reaction kettle is 3ml/min, and the reaction The pH value of the solution in the kettle is 8.5, the calculated amount of Cu in the Cu(NO 3 ) 2 solution is 2%, the pH value adjusted by ammonia water is 7.2, the temperature of the constant temperature water bath is 65°C, the specific surface area of the catalyst is 715.5m 2 /g, and the pore volume was 0.689cc/g, and the obtained catalyst was used in the reaction of hydrogenating diethyl oxalate to prepare ethylene glycol. The conversion rate of diethyl oxalate was 93.8% and the yield of ethylene glycol was 79.8%.
实施例3Example 3
制备过程同实施例1。反应釜温度为85℃,硅酸乙酯溶液浓度为0.5mol/L,十二烷基苯磺酸钠浓度为0.01mol/L,硅酸乙酯溶液加入反应釜中流速为3ml/min,反应釜中溶液的pH值为9.0,Cu(NO3)2溶液中Cu计算量为2%,氨水调节pH值为7.5,恒温水浴温度为65℃,催化剂比表面积为714.9m2/g,孔容为0.690cc/g,将所得催化剂用于草酸二乙酯加氢制备乙二醇的反应中,草酸二乙酯转化率为93.5%和乙二醇收率为80%。The preparation process is the same as in Example 1. The temperature of the reaction kettle is 85°C, the concentration of the ethyl silicate solution is 0.5mol/L, the concentration of sodium dodecylbenzenesulfonate is 0.01mol/L, the flow rate of the ethyl silicate solution into the reaction kettle is 3ml/min, and the reaction The pH value of the solution in the kettle is 9.0, the calculated amount of Cu in the Cu(NO 3 ) 2 solution is 2%, the pH value is adjusted by ammonia water to 7.5, the temperature of the constant temperature water bath is 65°C, the specific surface area of the catalyst is 714.9m 2 /g, and the pore volume The obtained catalyst was used in the reaction of diethyl oxalate hydrogenation to prepare ethylene glycol, the conversion rate of diethyl oxalate was 93.5% and the yield of ethylene glycol was 80%.
实施例4Example 4
制备过程同实施例1。反应釜温度为80℃,硅酸乙酯溶液浓度为1.0mol/L,十二烷基苯磺酸钠浓度为0.02mol/L,硅酸乙酯溶液加入反应釜中流速为4ml/min,反应釜中溶液的pH值为9.0,Cu(NO3)2溶液中Cu计算量为3%,氨水调节pH值为7.5,恒温水浴温度为60℃,催化剂比表面积为717.1m2/g,孔容为0.693cc/g,将所得催化剂用于草酸二乙酯加氢制备乙二醇的反应中,草酸二乙酯转化率为95.3%和乙二醇收率为83%。The preparation process is the same as in Example 1. The temperature of the reaction kettle is 80°C, the concentration of the ethyl silicate solution is 1.0mol/L, the concentration of sodium dodecylbenzenesulfonate is 0.02mol/L, the flow rate of the ethyl silicate solution into the reaction kettle is 4ml/min, and the reaction The pH value of the solution in the kettle is 9.0, the calculated amount of Cu in the Cu(NO 3 ) 2 solution is 3%, the pH value is adjusted by ammonia water to 7.5, the temperature of the constant temperature water bath is 60°C, the specific surface area of the catalyst is 717.1m 2 /g, and the pore volume was 0.693cc/g, and the obtained catalyst was used in the reaction of hydrogenating diethyl oxalate to prepare ethylene glycol, the conversion rate of diethyl oxalate was 95.3% and the yield of ethylene glycol was 83%.
实施例5Example 5
制备过程同实施例1。反应釜温度为85℃,硅酸乙酯溶液浓度为1.0mol/L,十二烷基苯磺酸钠浓度为0.01mol/L,硅酸乙酯溶液加入反应釜中流速为3ml/min,反应釜中溶液的pH值为9.0,Cu(NO3)2溶液中Cu计算量为3%,氨水调节pH值为7,恒温水浴温度为70℃,催化剂比表面积为716.8m2/g,孔容为0.701cc/g,将所得催化剂用于草酸二乙酯加氢制备乙二醇的反应中,草酸二乙酯转化率为94.7%和乙二醇收率为81.6%。The preparation process is the same as in Example 1. The temperature of the reaction kettle is 85°C, the concentration of the ethyl silicate solution is 1.0mol/L, the concentration of sodium dodecylbenzenesulfonate is 0.01mol/L, the flow rate of the ethyl silicate solution into the reaction kettle is 3ml/min, and the reaction The pH value of the solution in the kettle is 9.0, the calculated amount of Cu in the Cu(NO 3 ) 2 solution is 3%, the pH value is adjusted by ammonia water, the temperature of the constant temperature water bath is 70°C, the specific surface area of the catalyst is 716.8m 2 /g, and the pore volume was 0.701cc/g, and the obtained catalyst was used in the reaction of hydrogenating diethyl oxalate to prepare ethylene glycol, the conversion rate of diethyl oxalate was 94.7% and the yield of ethylene glycol was 81.6%.
实施例6Example 6
制备过程同实施例1。反应釜温度为80℃,硅酸乙酯溶液浓度为0.5mol/L,十二烷基苯磺酸钠浓度为0.02mol/L,硅酸乙酯溶液加入反应釜中流速为4ml/min,反应釜中溶液的pH值为8.5,Cu(NO3)2溶液中Cu计算量为2%,氨水调节pH值为7.2,恒温水浴温度为70℃,催化剂比表面积为715.9m2/g,孔容为0.688cc/g,将所得催化剂用于草酸二乙酯加氢制备乙二醇的反应中,草酸二乙酯转化率为94.1%和乙二醇收率为80.5%。The preparation process is the same as in Example 1. The temperature of the reaction kettle is 80°C, the concentration of the ethyl silicate solution is 0.5mol/L, the concentration of sodium dodecylbenzenesulfonate is 0.02mol/L, the flow rate of the ethyl silicate solution into the reaction kettle is 4ml/min, and the reaction The pH value of the solution in the kettle is 8.5, the calculated amount of Cu in the Cu(NO 3 ) 2 solution is 2%, the pH value adjusted by ammonia water is 7.2, the temperature of the constant temperature water bath is 70°C, the specific surface area of the catalyst is 715.9m 2 /g, and the pore volume was 0.688cc/g, and the obtained catalyst was used in the reaction of hydrogenating diethyl oxalate to prepare ethylene glycol, the conversion rate of diethyl oxalate was 94.1% and the yield of ethylene glycol was 80.5%.
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Cited By (5)
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CN102716744A (en) * | 2012-06-18 | 2012-10-10 | 河南煤业化工集团研究院有限责任公司 | Preparation method for synthesizing copper-based catalyst by sol-gel ammonia still process |
CN108393076A (en) * | 2018-03-20 | 2018-08-14 | 扬州大学 | Containing copper adsorbent, preparation method and its in adsorbing water tetracycline application |
CN112830871A (en) * | 2019-11-22 | 2021-05-25 | 中国科学院大连化学物理研究所 | A kind of method for preparing cyclopentanone by catalytic conversion of furan derivative |
CN115212885A (en) * | 2022-05-24 | 2022-10-21 | 天津大学 | Cobalt silicate derived cobalt-based catalyst for directly preparing low-carbon alcohol from synthesis gas, preparation method and pretreatment method |
CN117942998A (en) * | 2023-12-06 | 2024-04-30 | 江苏宏邦化工科技有限公司 | Cu/SiO2Preparation method of catalyst and application of catalyst in preparation of sandalwood 196 by catalytic hydrogenation |
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CN1803600A (en) * | 2005-12-16 | 2006-07-19 | 厦门大学 | Preparation method of silica gel carrier |
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Cited By (8)
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CN102716744A (en) * | 2012-06-18 | 2012-10-10 | 河南煤业化工集团研究院有限责任公司 | Preparation method for synthesizing copper-based catalyst by sol-gel ammonia still process |
CN108393076A (en) * | 2018-03-20 | 2018-08-14 | 扬州大学 | Containing copper adsorbent, preparation method and its in adsorbing water tetracycline application |
CN108393076B (en) * | 2018-03-20 | 2021-06-11 | 扬州大学 | Copper-containing adsorbent, preparation method and application thereof in adsorption of tetracycline in water |
CN112830871A (en) * | 2019-11-22 | 2021-05-25 | 中国科学院大连化学物理研究所 | A kind of method for preparing cyclopentanone by catalytic conversion of furan derivative |
CN112830871B (en) * | 2019-11-22 | 2022-03-08 | 中国科学院大连化学物理研究所 | A kind of method for preparing cyclopentanone by catalytic conversion of furan derivative |
CN115212885A (en) * | 2022-05-24 | 2022-10-21 | 天津大学 | Cobalt silicate derived cobalt-based catalyst for directly preparing low-carbon alcohol from synthesis gas, preparation method and pretreatment method |
CN115212885B (en) * | 2022-05-24 | 2023-08-01 | 天津大学 | A cobalt-based catalyst derived from cobalt silicate used for directly producing low-carbon alcohols from syngas, its preparation method and pretreatment method |
CN117942998A (en) * | 2023-12-06 | 2024-04-30 | 江苏宏邦化工科技有限公司 | Cu/SiO2Preparation method of catalyst and application of catalyst in preparation of sandalwood 196 by catalytic hydrogenation |
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