固体酸催化剂在烷基化反应中的应用
发布时间：2019-05-15 03:48
【摘要】：甲酚与异丁烯烷基化反应分离纯化间对甲酚是目前获取高纯间对甲酚单体的重要手段,十二烷基萘、十二烷基酚是两类重要的工业反应中间体,它们是现代合成基础润滑油及阴离子表面活性剂的重要中间体,同时也是增塑剂、稳定剂等的主要成分。为适应当代环境保护的要求,所有的化学反应必须走绿色可持续发展道路,这就要求这三类工业烷基化反应采用环境友好型催化剂以取代传统污染极大的液体酸催化剂,同时提高反应的催化活性,延长催化剂的使用寿命,降低工业生产成本。目前取代传统液体酸的途径主要是采用固体酸材料,但目前这些固体酸催化剂存在反应条件苛刻、转化率不高、催化剂寿命短、催化产品质量不高等缺陷。本论文的工作选取了强酸型阳离子交换树脂、HUSY、超稳Y型分子筛封装磷钨酸三种类型催化材料加以研究,考察催化剂制备过程中各种因素的作用,并对制备的催化剂进行傅里叶变换红外光谱、差热-热重、比表面积与孔径分布、X-射线粉末衍射、氨气吸附程序升温脱附手段对固体酸催化剂进行了表征；将所制备固体酸催化剂应用于甲酚与异丁烯、十二烯与萘、十二烯与苯酚的烷基化反应中,研究反应过程中各种参数的影响,以达到提高反应转化率和产品质量、优化反应条件的研究目的。研究的主要结论如下：1.强酸型阳离子交换树脂催化剂对甲酚与异丁烯、十二烯与苯酚的烷基化反应具有较好的催化活性,但催化剂寿命较短；强酸型阳离子交换树脂对十二烯与萘的烷基化反应催化活性较低。2.硝酸铵浓度0.5mol/L,离子交换温度353 K,焙烧温度773 K,焙烧时间4小时能得到烷基化催化活性较好的HUSY分子筛；HUSY分子筛对甲酚与异丁烯反应、十二烯与萘反应、十二烯与苯酚反应的催化活性较强酸型阳离子交换树脂好,但使用5次活性明显下降。3.优化并确定了原位法合成超稳Y型分子筛封装磷钨酸的条件,通过BET、FT-IR、氨气吸附程序升温脱附、XRD、SEM等表征,结果表明在USY超笼中实现了磷钨杂多酸的合成。PW-USY在烷基化反应中表现出了相当优越的催化活性,且使用6次后催化活性无明显下降。并进一步在小型固定床上考察十二烯与萘进行烷基化反应时PW-USY催化剂的使用寿命,连续烷基化720 h,催化剂的活性无明显下降,与HUSY相比具有更好的重复使用性能,催化剂寿命更长,能较好地解决活性流失的问题,显示出很好的工业应用前景。4.对失活的]HUSY、PW-USY催化剂分子筛残留物质分析,并通过对失活前后的分子筛催化剂进行BET、FT-IR、XRD、TG-DSC、NH3-TPD表征分析,结果表明,来不及扩散出去的反应原料间对甲酚、间对甲酚原料经高温炭化形成的炭化产物以及多烷基化物产物等覆盖在活性中心或沉积在孔道,造成分子筛失活。
[Abstract]:The separation and purification of m-p-cresol by alkylation of cresol with isobutene is an important method to obtain high purity m-p-cresol monomer. Dodecyl Naphthalene and Dodecyl Phenol are two kinds of important industrial reaction intermediates. They are important intermediates of modern synthetic basic lubricating oil and anionic surfactants, as well as the main components of plasticizers and stabilizers. In order to meet the requirements of contemporary environmental protection, all chemical reactions must take the road of green and sustainable development, which requires these three kinds of industrial alkylation reactions to use environment-friendly catalysts to replace the traditional highly polluted liquid acid catalysts. At the same time, the catalytic activity of the reaction is improved, the service life of the catalyst is prolonged, and the industrial production cost is reduced. At present, the main way to replace traditional liquid acid is to use solid acid material, but at present, these solid acid catalysts have some defects, such as harsh reaction conditions, low conversion, short catalyst life and low quality of catalytic products. In this paper, three types of catalytic materials, strong acid cation exchange resin and HUSY, super stable Y molecular sieves, were selected to encapsulate phosphotungstate acid, and the effects of various factors in the preparation of the catalyst were investigated. The solid acid catalysts were characterized by Fourier transform infrared spectroscopy, differential thermogravimetric analysis, specific surface area and pore size distribution, X-ray powder diffraction and ammonia adsorption temperature programmed desorption. The prepared solid acid catalysts were applied to the alkylation of cresol with isobutene, Dodecene with Naphthalene and Dodecene with Phenol. The effects of various parameters in the reaction process were studied in order to improve the conversion and product quality. The purpose of optimizing reaction conditions. The main conclusions of the study are as follows: 1. The strong acid cation exchange resin catalyst has good catalytic activity for alkylation of cresol with isobutene and Dodecene with phenol, but the catalyst life is short. The catalytic activity of strong acid cation exchange resin for alkylation of Dodecene with Naphthalene is low. 2. The HUSY molecular sieves with good alkylation catalytic activity can be obtained when the concentration of ammonium nitrate is 0.5 mol 路L, the ion exchange temperature is 353K, the calcination temperature is 773K, and the calcination time is 4 hours. The catalytic activity of HUSY molecular sieves for the reaction of p-cresol with isobutene, the reaction of Dodecene with Naphthalene and the reaction of Dodecene with phenol is better than that of acid cation exchange resin, but the activity decreases obviously for 5 times. The conditions for the synthesis of ultra-stable Y-type molecular sieves by in-situ synthesis of phosphotungstic acid were optimized and determined. The conditions were characterized by BET,FT-IR, ammonia adsorption temperature programmed desorption and XRD,SEM. The results showed that the synthesis of phosphotungstate heteropoly acid was realized in Usy supercage. PW-USY showed superior catalytic activity in alkylation, and the catalytic activity did not decrease obviously after 6 times of use. The service life of PW-USY catalyst for alkylation of Dodecene with Naphthalene was further investigated in a small fixed bed. The activity of the catalyst did not decrease significantly during continuous alkylation for 720 h, and the catalyst had better reuse performance than HUSY. The catalyst life is longer, which can solve the problem of activity loss, and shows a good industrial application prospect. 4. The residual matter of molecular sieves of deactivated] HUSY,PW-USY catalyst was analyzed, and the molecular sieves catalyst before and after deactivation was characterized by BET,FT-IR,XRD,TG-DSC,NH3-TPD. The results showed that: The reaction materials m-p-cresol, m-p-cresol formed by high temperature carbonation and polyalkyl compounds were covered in the active center or deposited in the pore, resulting in the inactivation of the molecular sieves.
【学位授予单位】：广东工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251
[Abstract]:The separation and purification of m-p-cresol by alkylation of cresol with isobutene is an important method to obtain high purity m-p-cresol monomer. Dodecyl Naphthalene and Dodecyl Phenol are two kinds of important industrial reaction intermediates. They are important intermediates of modern synthetic basic lubricating oil and anionic surfactants, as well as the main components of plasticizers and stabilizers. In order to meet the requirements of contemporary environmental protection, all chemical reactions must take the road of green and sustainable development, which requires these three kinds of industrial alkylation reactions to use environment-friendly catalysts to replace the traditional highly polluted liquid acid catalysts. At the same time, the catalytic activity of the reaction is improved, the service life of the catalyst is prolonged, and the industrial production cost is reduced. At present, the main way to replace traditional liquid acid is to use solid acid material, but at present, these solid acid catalysts have some defects, such as harsh reaction conditions, low conversion, short catalyst life and low quality of catalytic products. In this paper, three types of catalytic materials, strong acid cation exchange resin and HUSY, super stable Y molecular sieves, were selected to encapsulate phosphotungstate acid, and the effects of various factors in the preparation of the catalyst were investigated. The solid acid catalysts were characterized by Fourier transform infrared spectroscopy, differential thermogravimetric analysis, specific surface area and pore size distribution, X-ray powder diffraction and ammonia adsorption temperature programmed desorption. The prepared solid acid catalysts were applied to the alkylation of cresol with isobutene, Dodecene with Naphthalene and Dodecene with Phenol. The effects of various parameters in the reaction process were studied in order to improve the conversion and product quality. The purpose of optimizing reaction conditions. The main conclusions of the study are as follows: 1. The strong acid cation exchange resin catalyst has good catalytic activity for alkylation of cresol with isobutene and Dodecene with phenol, but the catalyst life is short. The catalytic activity of strong acid cation exchange resin for alkylation of Dodecene with Naphthalene is low. 2. The HUSY molecular sieves with good alkylation catalytic activity can be obtained when the concentration of ammonium nitrate is 0.5 mol 路L, the ion exchange temperature is 353K, the calcination temperature is 773K, and the calcination time is 4 hours. The catalytic activity of HUSY molecular sieves for the reaction of p-cresol with isobutene, the reaction of Dodecene with Naphthalene and the reaction of Dodecene with phenol is better than that of acid cation exchange resin, but the activity decreases obviously for 5 times. The conditions for the synthesis of ultra-stable Y-type molecular sieves by in-situ synthesis of phosphotungstic acid were optimized and determined. The conditions were characterized by BET,FT-IR, ammonia adsorption temperature programmed desorption and XRD,SEM. The results showed that the synthesis of phosphotungstate heteropoly acid was realized in Usy supercage. PW-USY showed superior catalytic activity in alkylation, and the catalytic activity did not decrease obviously after 6 times of use. The service life of PW-USY catalyst for alkylation of Dodecene with Naphthalene was further investigated in a small fixed bed. The activity of the catalyst did not decrease significantly during continuous alkylation for 720 h, and the catalyst had better reuse performance than HUSY. The catalyst life is longer, which can solve the problem of activity loss, and shows a good industrial application prospect. 4. The residual matter of molecular sieves of deactivated] HUSY,PW-USY catalyst was analyzed, and the molecular sieves catalyst before and after deactivation was characterized by BET,FT-IR,XRD,TG-DSC,NH3-TPD. The results showed that: The reaction materials m-p-cresol, m-p-cresol formed by high temperature carbonation and polyalkyl compounds were covered in the active center or deposited in the pore, resulting in the inactivation of the molecular sieves.
【学位授予单位】：广东工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251
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