技术领域technical field
本发明涉及生物柴油催化剂技术领域，尤其是涉及一种E-ZrP@SO3H固体酸催化剂的制备方法。The invention relates to the technical field of biodiesel catalysts, in particular to a preparation method of an E-ZrP@SO3 H solid acid catalyst.
背景技术Background technique
石油资源的日渐枯竭和石化产品带来的严重污染促使研究人员寻找其他的绿色可替代能源，用可再生的长链脂肪酸与短链醇(如甲醇、乙醇)通过酯化反应制备的脂肪酸甲酯(或脂肪酸乙酯)是一种可再生的绿色可替代能源，即生物柴油。生物柴油在一定程度上具备替代石油能源的能力，其主要成分是碳链长度在C12-C22的脂肪酸单酯，具有与石化柴油相似的物理化学性质，且拥有可再生、零硫排放、可生物降解、无毒等优点。The depletion of petroleum resources and the serious pollution caused by petrochemical products have prompted researchers to look for other green alternative energy sources, using renewable long-chain fatty acids and short-chain alcohols (such as methanol, ethanol) to prepare fatty acid methyl esters through esterification (or fatty acid ethyl ester) is a renewable green alternative energy source, namely biodiesel. To a certain extent, biodiesel has the ability to replace petroleum energy. Its main component is fatty acid monoester with a carbon chain length of C12 -C22. It has similar physical and chemical properties to petrochemical diesel, and has renewable, zero-sulfur emissions, Biodegradable, non-toxic and other advantages.
生物柴油一般由动植物油脂(如月桂酸、肉豆蔻酸、棕榈酸等)与短链醇(如甲醇、乙醇)通过酸或碱催化酯交换或酯化反应制得。碱催化，条件温和，但需对原料进行预处理，工艺复杂；酸性催化剂在工业上应用较多的通常为同质酸，如硫酸，虽催化活性高，副反应少，但对设备的腐蚀大，难以回收利用，产物需中和水洗，产生大量的污染；固体酸催化剂可以消除同质酸催化剂引起的许多技术和环境问题，但催化活性较低。因此，近年来研究人员重点关注合成生物柴油的新型高效固体酸催化剂的研发。Biodiesel is generally produced from animal and vegetable oils (such as lauric acid, myristic acid, palmitic acid, etc.) and short-chain alcohols (such as methanol, ethanol) through acid or base-catalyzed transesterification or esterification. Alkali catalysis, with mild conditions, but the raw materials need to be pretreated, and the process is complex; acid catalysts are usually used in industry with homogeneous acids, such as sulfuric acid, although they have high catalytic activity and few side reactions, but they are more corrosive to equipment. , It is difficult to recycle, and the product needs to be neutralized and washed with water, resulting in a lot of pollution; solid acid catalyst can eliminate many technical and environmental problems caused by homogeneous acid catalyst, but the catalytic activity is low. Therefore, in recent years, researchers have focused on the development of new high-efficiency solid acid catalysts for biodiesel synthesis.
磷酸锆具备许多优良的特性：首先磷酸锆本身就是较为优良的固体酸；其次拥有较大的比表面积，用作催化剂时，有利于提高催化活性；而且磷酸锆拥有层状结构方便制备各种磷酸锆有机衍生物；此外磷酸锆性质稳定，能耐强酸和一定强度的碱。这些特性使得磷酸锆成为制备固体酸的优良材料。Zirconium phosphate has many excellent characteristics: firstly, zirconium phosphate itself is a relatively good solid acid; secondly, it has a large specific surface area, which is conducive to improving catalytic activity when used as a catalyst; and zirconium phosphate has a layered structure to facilitate the preparation of various phosphoric acids Zirconium organic derivatives; in addition, zirconium phosphate is stable and resistant to strong acids and alkalis of a certain strength. These characteristics make zirconium phosphate an excellent material for the preparation of solid acids.
但是磷酸锆用作酯化反应的催化剂时，其酸强不足，催化产率不高，并不适合作为制备生物柴油的理想催化剂。所以为了解决这个问题，关键在于提高磷酸锆的催化活性，即提高其酸强。但是一般的浸渍法并不适合提高磷酸锆催化活性，这是因为磷酸锆是层状结构，通过浸渍法附着在磷酸锆表面的酸性物质易于流失，在酯化反应中，经过高温搅拌之后，酸性物质会大量流失，导致催化活性降低。所以提高磷酸锆催化活性的最佳方案是将酸性基团通过化学键连接在磷酸锆表面，使其难以流失，这就是本专利的重点和特色。However, when zirconium phosphate is used as a catalyst for the esterification reaction, its acid strength is insufficient and the catalytic yield is not high, so it is not suitable as an ideal catalyst for the preparation of biodiesel. Therefore, in order to solve this problem, the key is to improve the catalytic activity of zirconium phosphate, that is, to increase its acid strength. However, the general impregnation method is not suitable for improving the catalytic activity of zirconium phosphate. This is because zirconium phosphate has a layered structure, and the acidic substances attached to the surface of zirconium phosphate by impregnation are easy to lose. A large amount of material will be lost, resulting in a decrease in catalytic activity. Therefore, the best solution to improve the catalytic activity of zirconium phosphate is to connect acidic groups on the surface of zirconium phosphate through chemical bonds, making it hard to lose. This is the focus and feature of this patent.
发明内容Contents of the invention
针对现有技术存在的上述问题，本发明申请人提供了一种E-ZrP@SO3H固体酸催化剂及其制备方法。本发明固体酸催化剂具有较大的比表面积，有利于提高催化活性，且本发明催化剂易分离回收，可重复利用，节约成本，降低污染。In view of the above-mentioned problems in the prior art, the applicant of the present invention provides an E-ZrP@SO3 H solid acid catalyst and a preparation method thereof. The solid acid catalyst of the invention has a larger specific surface area, which is beneficial to improving catalytic activity, and the catalyst of the invention is easy to separate and recycle, can be reused, saves cost and reduces pollution.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种E-ZrP@SO3H固体酸催化剂，所述催化剂的制备方法包括如下步骤：A kind of E-ZrP@SO3 H solid acid catalyst, the preparation method of described catalyst comprises the steps:
(1)α-ZrP的合成；(1) Synthesis of α-ZrP;
(2)α-ZrP的剥层处理；(2) Delamination of α-ZrP;
(3)E-ZrP-SH的制备；(3) Preparation of E-ZrP-SH;
(4)E-ZrP@SO3H的制备。(4) Preparation of E-ZrP@SO3 H.
所述α-ZrP的合成方法为：将ZrOCl2﹒8H2O与H3PO4溶液混合，之后置于反应釜中，180～220℃油浴温度条件下反应18～30h，反应结束后，经离心分离，α-ZrP粗产品，经过水洗3～5次，在50～80℃的干燥箱中干燥8～16h，制得α-ZrP中间体。所述ZrOCl2﹒8H2O与H3PO4的Zr:P摩尔比为1:250～350；所述H3PO4溶液的浓度为5～7mol/L；The synthesis method of the α-ZrP is: ZrOCl2 . Mix 8H2 O and H3 PO4 solution, then put it in the reaction kettle, and react for 18-30 hours under the temperature of 180-220°C oil bath. After the reaction, the crude product of α-ZrP is washed with water for 3- 5 times, drying in a drying oven at 50-80°C for 8-16 hours to obtain the α-ZrP intermediate. The ZrOCl2 . The Zr:P molar ratio of 8H2 O and H3 PO4 is 1:250-350; the concentration of the H3 PO4 solution is 5-7 mol/L;
所述α-ZrP的剥层处理方法为：The peeling treatment method of the α-ZrP is:
①将α-ZrP置于去离子水中超声分散5～30min，之后在室温下向分散液中加入四正丁基氢氧化铵溶液，冰浴10～30min；① Put α-ZrP in deionized water and ultrasonically disperse for 5-30 minutes, then add tetra-n-butylammonium hydroxide solution to the dispersion at room temperature, and ice-bath for 10-30 minutes;
②再向反应体系中加入HCl溶液，室温下持续搅拌10min，形成悬浊液；② Add HCl solution to the reaction system, and continue stirring at room temperature for 10 minutes to form a suspension;
③对悬浊液进行离心，收集固体，之后依次经过3～5次水洗，3～5次丙酮洗，3～5次甲苯洗，最终制得E-ZrP-OH，并存于甲苯中备用。③ Centrifuge the suspension to collect the solids, and then wash them with water 3-5 times, acetone 3-5 times, and toluene 3-5 times in order to finally obtain E-ZrP-OH, and store them in toluene for later use.
所述α-ZrP与去离子水的质量比为1:60；所述四正丁基氢氧化铵溶液的浓度0.1mol/L；所述HCl溶液的浓度为0.1mol/L。The mass ratio of α-ZrP to deionized water is 1:60; the concentration of the tetra-n-butylammonium hydroxide solution is 0.1mol/L; the concentration of the HCl solution is 0.1mol/L.
所述E-ZrP-SH的制备方法为：The preparation method of the E-ZrP-SH is:
将制得的E-ZrP-OH与γ-巯丙基三乙氧基硅烷KH-580、甲苯混合，在N2保护下，水浴加热至80～95℃，搅拌反应18～30h，反应结束后，固体沉淀在烧瓶底部，用吸管缓慢移除甲苯溶液，再将产物置于40～60℃的干燥箱中干燥8～16h，得到所述E-ZrP-SH。所述E-ZrP-OH与γ-巯丙基三乙氧基硅烷KH-580的质量比为1:10～20；所述甲苯的用量为KH-580体积的20倍。Mix the prepared E-ZrP-OH with γ-mercaptopropyltriethoxysilane KH-580 and toluene, heat it in a water bath to 80-95°C under the protection ofN2 , and stir the reaction for 18-30 hours. After the reaction , the solid precipitated at the bottom of the flask, and the toluene solution was slowly removed with a pipette, and then the product was dried in a drying oven at 40-60° C. for 8-16 hours to obtain the E-ZrP-SH. The mass ratio of E-ZrP-OH to γ-mercaptopropyltriethoxysilane KH-580 is 1:10-20; the amount of toluene is 20 times the volume of KH-580.
所述E-ZrP@SO3H的制备方法为：The preparation method of the E-ZrP@SO3 H is:
将E-ZrP-SH加入去离子水中，之后再加入过硫酸铵，室温下静置反应18～30h，经离心分离，收集固体产物，再将得到固体产物置于浓度为37wt％的盐酸溶液中进行质子化处理，最后将质子化处理过的产物置于40～60℃干燥箱中干燥18～30h，最终得到所述E-ZrP@SO3H固体酸催化剂。Add E-ZrP-SH to deionized water, then add ammonium persulfate, let it stand at room temperature for 18-30 hours, collect the solid product by centrifugation, and then place the solid product in a hydrochloric acid solution with a concentration of 37wt% Protonation treatment is carried out, and finally the protonation-treated product is dried in a 40-60°C drying oven for 18-30 hours to finally obtain the E-ZrP@SO3 H solid acid catalyst.
所述E-ZrP-SH与去离子水的质量比为1:10；所述过硫酸铵的用量与去离子水的质量比为1:10；所述盐酸溶液的用量为5mL。The mass ratio of E-ZrP-SH to deionized water is 1:10; the mass ratio of the amount of ammonium persulfate to deionized water is 1:10; the amount of hydrochloric acid solution is 5mL.
本发明所述E-ZrP@SO3H固体酸催化剂用于生物柴油合成的应用，应用方法如下：将脂肪酸与短链醇以油醇摩尔比1:10～40的比例置于烧瓶中，再加入基于脂肪酸质量1～8％的E-ZrP@SO3H固体酸催化剂，在70～120℃下反应1～6h，反应结束后，离心分离出固体催化剂继续循环利用，所得反应混合液再静置分层，下层为水和过量的甲醇，上层液体为生物柴油和未反应的脂肪酸，分液后减压蒸馏得生物柴油。The E-ZrP@SO3 H solid acid catalyst of the present invention is used in the application of biodiesel synthesis, and the application method is as follows: the fatty acid and the short-chain alcohol are placed in a flask at a molar ratio of oleyl alcohol to 1:10-40, and then Add E-ZrP@SO3 H solid acid catalyst based on 1-8% fatty acid mass, and react at 70-120°C for 1-6 hours. After the reaction, the solid catalyst is separated by centrifugation and continued to be recycled. Set the layers, the lower layer is water and excess methanol, the upper liquid is biodiesel and unreacted fatty acid, and after liquid separation, the biodiesel is obtained by vacuum distillation.
上述脂肪酸为月桂酸、肉豆蔻酸、棕榈酸、硬脂酸或油酸的任何一种，短链醇是甲醇、乙醇或丙醇的一种。The above-mentioned fatty acid is any one of lauric acid, myristic acid, palmitic acid, stearic acid or oleic acid, and the short-chain alcohol is one of methanol, ethanol or propanol.
本发明有益的技术效果在于：The beneficial technical effects of the present invention are:
本发明采用的γ-巯丙基三乙氧基硅烷KH-580是一种硅烷偶联剂，带有一个巯基基团，易于氧化成磺酸基，可以被各种强氧化物氧化，但是本身是液体，作为催化剂使用时，难以与反应液分离，会增加生产成本和技术难度，因此采用KH-580做为酸性基团的供体，而磷酸锆作为载体，可制备本发明的固体酸催化剂；The γ-mercaptopropyltriethoxysilane KH-580 used in the present invention is a silane coupling agent with a mercapto group, which is easily oxidized into a sulfonic acid group and can be oxidized by various strong oxides, but itself It is a liquid, and when used as a catalyst, it is difficult to separate from the reaction liquid, which will increase production costs and technical difficulties. Therefore, using KH-580 as the donor of acidic groups, and zirconium phosphate as a carrier, the solid acid catalyst of the present invention can be prepared ;
本发明采用的四正丁基氢氧化铵水溶液TBA，将磷酸锆进行剥层处理，得到剥层处理的磷酸锆标记为E-ZrP，极大地扩大了磷酸锆的比表面积，使得磷酸锆可以与更多的KH-580反应，明显提高其酸强。再通过盐酸溶液处理E-ZrP，使得E-ZrP表面羟基化，得到羟基化的E-ZrP标记为E-ZrP-OH，这样可以载体更加易于与KH-580发生取代反应，使得更多KH-580连接在载体表面，这样也能提高催化剂的酸强。The tetra-n-butyl ammonium hydroxide aqueous solution TBA that the present invention adopts, zirconium phosphate is carried out exfoliation treatment, the zirconium phosphate that obtains the exfoliation treatment is marked as E-ZrP, has enlarged the specific surface area of zirconium phosphate greatly, makes zirconium phosphate can be combined with more The reaction of KH-580 significantly increases its acid strength. Then E-ZrP is treated with hydrochloric acid solution to make the surface of E-ZrP hydroxylated, and the hydroxylated E-ZrP is labeled as E-ZrP-OH, so that the carrier can be more easily substituted with KH-580, making more KH- 580 is connected to the surface of the carrier, which can also improve the acid strength of the catalyst.
将E-ZrP-OH与KH-580混合加入烧瓶中，加入甲苯作为溶剂，在90℃下，通入氮气，搅拌反应24h，得到目标产物，标记为E-ZrP-SH。Mix E-ZrP-OH and KH-580 into a flask, add toluene as a solvent, blow nitrogen at 90°C, and stir for 24 hours to obtain the target product, marked as E-ZrP-SH.
硅烷偶联剂的偶联机理虽然存在不同的观点，但是主流认为化学键合模型是比较成功的一种理论。化学键合理论认为硅烷偶联剂的烷氧基Si-O-C在适当条件下会水解形成Si-OH，再与偶联的对象表面的O-H发生缩合反应，从而连接在一起。所以为了保证偶联的效果，不同的硅烷偶联剂会采用不同的溶剂，而KH-580有巯基，巯基S-H特性类似于O-H，而且在水溶液中比O-H更容易断裂，所以KH-580在高温下，容易形成共聚化合物，所以反应中要严格去除水分，所以采用了甲苯作为溶剂，并且在反应之前用丙酮和甲苯反复洗涤。此外巯基易于氧化，在高温反应中比较脆弱，在高温和空气氛围中会生成二硫化物，因此通过不断通入N2保证反应体系处于惰性氛围，这一步对于制备出正确的产品中间物是至关重要的。Although there are different views on the coupling mechanism of silane coupling agents, the mainstream believes that the chemical bonding model is a relatively successful theory. The chemical bonding theory believes that the alkoxy Si-OC of the silane coupling agent will be hydrolyzed under appropriate conditions to form Si-OH, and then undergo a condensation reaction with the OH on the surface of the coupling object, thereby connecting together. Therefore, in order to ensure the coupling effect, different silane coupling agents will use different solvents, and KH-580 has mercapto groups. Under the conditions, it is easy to form a copolymer compound, so the water must be strictly removed during the reaction, so toluene is used as a solvent, and it is washed repeatedly with acetone and toluene before the reaction. In addition, mercapto groups are easy to oxidize, relatively fragile in high-temperature reactions, and disulfides will be generated in high-temperature and air atmospheres, so by constantly feedingN2 to ensure that the reaction system is in an inert atmosphere, this step is crucial for preparing the correct product intermediate important.
本发明E-ZrP@SO3H固体酸催化剂具有较大的比表面积，有利于提高催化活性，可使生物柴油收率达95％以上。The E-ZrP@SO3 H solid acid catalyst of the invention has a large specific surface area, which is beneficial to improving the catalytic activity, and can make the biodiesel yield reach more than 95%.
附图说明Description of drawings
图1为本发明示意图。Fig. 1 is a schematic diagram of the present invention.
图2是实施例1催化剂制备过程中的红外监测图谱。Fig. 2 is the infrared monitoring spectrum during the catalyst preparation process of embodiment 1.
具体实施方式Detailed ways
下面结合附图和实施例，对本发明进行具体描述。The present invention will be specifically described below in conjunction with the accompanying drawings and embodiments.
实施例1Example 1
一种E-ZrP@SO3H固体酸催化剂，所述催化剂的制备方法包括如下步骤：A kind of E-ZrP@SO3 H solid acid catalyst, the preparation method of described catalyst comprises the steps:
(1)α-ZrP的合成：将6.0g的ZrOCl2﹒8H2O与60.0mL浓度为6.0mol/L的H3PO4溶液混合、搅拌均匀，再将混合液倒入特氟龙水热反应釜中，于200℃油浴温度条件下反应24h，反应结束后，经离心分离，α-ZrP粗产品，经过水洗3次，在60℃的干燥箱中干燥12h，制得α-ZrP中间体；(1) Synthesis of α-ZrP: 6.0g of ZrOCl2 . Mix 8H2 O with 60.0 mL of H3 PO4 solution with a concentration of 6.0 mol/L, stir evenly, then pour the mixed solution into a Teflon hydrothermal reaction kettle, and react for 24 hours at the temperature of an oil bath at 200°C. After the end, after centrifugation, the crude α-ZrP product was washed 3 times with water, and dried in a drying oven at 60°C for 12 hours to obtain the α-ZrP intermediate;
(2)α-ZrP的剥层处理：①称量1.0g的α-ZrP与60mL的去离子水置于烧杯中，超声10min，使其混合均匀，然后向烧杯中缓慢加入33mL浓度为0.1mol/L的四正丁基氢氧化铵TBA，冰浴10min；②再向烧杯中加入33mL浓度为0.1mol/L的HCl溶液，室温下，连续搅拌10min后，形成悬浊液；③将得到的悬浊液离心分离，收集固体，然后依次用去离子水洗涤3次，丙酮洗涤3次，甲苯洗涤3次，将水分彻底去除后，将E-ZrP-OH保存在3mL的甲苯中。(2) Stripping treatment of α-ZrP: ①Weigh 1.0g of α-ZrP and 60mL of deionized water into a beaker, ultrasonicate for 10min to mix evenly, then slowly add 33mL of 0.1mol into the beaker /L tetra-n-butylammonium hydroxide TBA, ice bath for 10min; ② Add 33mL HCl solution with a concentration of 0.1mol/L to the beaker, and stir continuously for 10min at room temperature to form a suspension; ③The obtained suspension The liquid was centrifuged to collect the solid, and then washed three times with deionized water, three times with acetone, and three times with toluene. After the water was completely removed, E-ZrP-OH was stored in 3 mL of toluene.
(3)E-ZrP-SH的制备：取1.0g E-ZrP-OH与10mL的γ-巯丙基三乙氧基硅烷KH-580，置于500mL的三颈烧瓶中，再向三颈烧瓶中倒入300mL的甲苯，在N2保护下，水浴加热至90℃，搅拌反应24h，反应完毕收集固体产物，再将产物置于50℃的干燥箱中干燥12h，得到E-ZrP-SH；(3) Preparation of E-ZrP-SH: Take 1.0g of E-ZrP-OH and 10mL of γ-mercaptopropyltriethoxysilane KH-580, put them in a 500mL three-necked flask, and then add Pour 300mL of toluene into the mixture, under the protection of N2 , heat it in a water bath to 90°C, stir and react for 24h, collect the solid product after the reaction, and dry the product in a drying oven at 50°C for 12h to obtain E-ZrP-SH;
(4)E-ZrP@SO3H的制备：取0.3g的E-ZrP-SH置于烧杯中，再向烧杯中加入10mL去离子水，再加入1g过硫酸铵，室温下静置反应24h，经离心分离，再将得到固体产物置于5mL浓度为37wt％的盐酸溶液中进行质子化处理，最后将质子化处理过的产物置于50℃干燥箱中干燥24h，最终得到剥层磷酸锆@磺酸基E-ZrP@SO3H固体酸催化剂。(4) Preparation of E-ZrP@SO3 H: Take 0.3g of E-ZrP-SH in a beaker, add 10mL of deionized water to the beaker, then add 1g of ammonium persulfate, and let it stand for 24 hours at room temperature , after centrifugation, the solid product was placed in 5 mL of 37 wt% hydrochloric acid solution for protonation treatment, and finally the protonated product was placed in a 50°C drying oven for 24 hours to finally obtain exfoliated zirconium phosphate @sulfonic acid group E-ZrP@SO3 H solid acid catalyst.
本实施例制备过程中中间产物的红外谱图如图2所示，可以看出3512cm-1和3598cm-1是ZrP夹层中所含水分的特征峰；3176cm-1和1622cm-1是-OH的对称振动峰和弯曲振动峰；968cm-1和1251cm-1则是P-OH的面内和面外振动峰；同样1041cm-1和1128cm-1可以归结为PO2中的P-O的对称和不对称伸缩振动峰，而532cm-1和595cm-1是Zr-O的弯曲振动峰。曲线b是E-ZrP-SH的红外曲线，其中2554cm-1处弱峰则是S-H的特征峰，而2932cm-1是C-H的伸缩振动峰，1120cm-1是Si-O的弯曲振动峰；这说明KH-580顺利地连接到ZrP的纳米片上。曲线c是E-ZrP-SO3H的红外特征峰：与E-ZrP-SH的红外曲线对比，2554cm-1的S-H峰因为氧化消失，而在1041cm-1的峰可以归结于P-O，S＝O的红外吸收峰的重叠，而1125cm-1的峰则是S＝O的红外吸收峰。由此可以看出制备的产品的确是目标产物。The infrared spectrogram of the intermediate product in the preparation process of this embodiment is as shown in Figure 2, and it can be seen that 3512cm-1 and 3598cm-1 are characteristic peaks of moisture contained in the ZrP interlayer; 3176cm-1 and 1622cm-1 are the peaks of -OH Symmetric vibration peak and bending vibration peak; 968cm-1 and 1251cm-1 are the in-plane and out-of-plane vibration peaks of P-OH; similarly, 1041cm-1 and 1128cm-1 can be attributed to the symmetry and asymmetry of PO in PO2 The stretching vibration peaks, while 532cm-1 and 595cm-1 are the bending vibration peaks of Zr-O. Curve b is the infrared curve of E-ZrP-SH, in which the weak peak at 2554cm-1 is the characteristic peak of SH, while 2932cm-1 is the stretching vibration peak of CH, and 1120cm-1 is the bending vibration peak of Si-O; It shows that KH-580 is successfully connected to ZrP nanosheets. Curve c is the infrared characteristic peak of E-ZrP-SO3 H: compared with the infrared curve of E-ZrP-SH, the SH peak at 2554cm-1 disappears due to oxidation, and the peak at 1041cm-1 can be attributed to PO, S= The infrared absorption peak of O overlaps, and the peak at 1125cm-1 is the infrared absorption peak of S=O. It can be seen that the prepared product is indeed the target product.
【实施例2】[Example 2]
本实施例催化剂的制备条件与实施例1完全相同的情况下，只是将步骤(1)中的油浴温度改为180℃，得到E-ZrP@SO3H固体酸催化剂。The preparation conditions of the catalyst in this example were exactly the same as those in Example 1, except that the temperature of the oil bath in step (1) was changed to 180°C to obtain an E-ZrP@SO3 H solid acid catalyst.
【实施例3】[Example 3]
本实施例催化剂的制备条件与实施例1完全相同的情况下，只是将步骤(1)中的油浴温度改为220℃，得到E-ZrP@SO3H固体酸催化剂。The preparation conditions of the catalyst in this example were exactly the same as those in Example 1, except that the temperature of the oil bath in step (1) was changed to 220° C. to obtain an E-ZrP@SO3 H solid acid catalyst.
【实施例4】【Example 4】
本实施例催化剂的制备条件与实施例1完全相同的情况下，只是将步骤(3)中的水浴温度改为80℃，得到E-ZrP@SO3H固体酸催化剂。The preparation conditions of the catalyst in this example were exactly the same as those in Example 1, except that the temperature of the water bath in step (3) was changed to 80° C. to obtain an E-ZrP@SO3 H solid acid catalyst.
【实施例5】【Example 5】
本实施例催化剂的制备条件与实施例1完全相同的情况下，只是将步骤(3)中的水浴温度改为95℃，得到E-ZrP@SO3H固体酸催化剂。The preparation conditions of the catalyst in this example were exactly the same as in Example 1, except that the temperature of the water bath in step (3) was changed to 95° C. to obtain an E-ZrP@SO3 H solid acid catalyst.
【实施例6】[Example 6]
本实施例催化剂的制备条件与实施例1完全相同的情况下，只是将步骤(3)中的γ-巯丙基三乙氧基硅烷用量改为15mL，得到E-ZrP@SO3H固体酸催化剂。The preparation conditions of the catalyst in this example are exactly the same as in Example 1, except that the amount of γ-mercaptopropyltriethoxysilane in step (3) is changed to 15mL to obtain E-ZrP@SO3 H solid acid catalyst.
【实施例7】[Example 7]
本实施例催化剂的制备条件与实施例1完全相同的情况下，只是将步骤(3)中的γ-巯丙基三乙氧基硅烷用量改为20mL，得到E-ZrP@SO3H固体酸催化剂。The preparation conditions of the catalyst in this example are exactly the same as in Example 1, except that the amount of γ-mercaptopropyltriethoxysilane in step (3) is changed to 20mL to obtain E-ZrP@SO3 H solid acid catalyst.
【实施例8】[Embodiment 8]
本实施例催化剂的制备条件与实施例1完全相同的情况下，只是将步骤(2)中的冰浴时间改为20min，得到E-ZrP@SO3H固体酸催化剂。The preparation conditions of the catalyst in this example were exactly the same as those in Example 1, except that the ice bath time in step (2) was changed to 20 minutes to obtain an E-ZrP@SO3 H solid acid catalyst.
【实施例9】[Example 9]
本实施例催化剂的制备条件与实施例1完全相同的情况下，只是将步骤(2)中的冰浴时间改为30min，得到E-ZrP@SO3H固体酸催化剂。The preparation conditions of the catalyst in this example were exactly the same as those in Example 1, except that the ice bath time in step (2) was changed to 30 minutes to obtain an E-ZrP@SO3 H solid acid catalyst.
测试例test case
1、将4.0g棕榈酸与10.0g甲醇加入到圆底烧瓶中，再分别加入实施例1～9所制得的催化剂0.16g，在80℃下反应5h。生物柴油的收率以脂肪酸甲酯收率Y为指标，本发明实施例催化剂的催化性能如表1所示。1. Add 4.0 g of palmitic acid and 10.0 g of methanol into a round bottom flask, then add 0.16 g of the catalysts prepared in Examples 1 to 9, and react at 80° C. for 5 h. The yield of biodiesel is based on the fatty acid methyl ester yield Y, and the catalytic performance of the catalysts in the examples of the present invention is shown in Table 1.
表1Table 1
2、将3.0g月桂酸与14.4g甲醇加入到圆底烧瓶中，再分别加入实施例1～9所制得的催化剂0.09g，在90℃下反应5h。生物柴油的收率以脂肪酸甲酯收率Y为指标，催化剂的反应性能如表2所示。2. Add 3.0 g of lauric acid and 14.4 g of methanol into a round bottom flask, then add 0.09 g of the catalysts prepared in Examples 1 to 9 respectively, and react at 90° C. for 5 h. The yield of biodiesel is based on the yield Y of fatty acid methyl ester, and the reaction performance of the catalyst is shown in Table 2.
表2Table 2
| Application Number | Priority Date | Filing Date | Title |
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| CN201810442757.4ACN108499583A (en) | 2018-05-10 | 2018-05-10 | A kind of E-ZrP@SO3H solid acid catalysts and preparation method thereof |
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| CN201810442757.4ACN108499583A (en) | 2018-05-10 | 2018-05-10 | A kind of E-ZrP@SO3H solid acid catalysts and preparation method thereof |
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| JPH08268991A (en)* | 1995-03-29 | 1996-10-15 | Nippon Shokubai Co Ltd | Production of n-(1-alkyloxyalkyl)-urethane |
| CN102575301A (en)* | 2010-01-27 | 2012-07-11 | 科学与工业研究委员会 | A one pot and single step hydrolytic process for the conversion of lignocellulose into value added chemicals |
| CN104492493A (en)* | 2014-11-26 | 2015-04-08 | 绍兴文理学院 | Magnetic solid acid material catalyst and preparation method thereof |
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| YINGJIE ZHOU ET AL.: ""Solid Acid Catalyst Based on Single-Layer α-Zirconium Phosphate Nanosheets for Biodiesel Production via Esterification"", 《CATALYSTS》* |
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