固體酸催化劑在烷基化反應中的應用
發(fā)布時間：2019-05-15 03:48
【摘要】：甲酚與異丁烯烷基化反應分離純化間對甲酚是目前獲取高純間對甲酚單體的重要手段,十二烷基萘、十二烷基酚是兩類重要的工業(yè)反應中間體,它們是現(xiàn)代合成基礎潤滑油及陰離子表面活性劑的重要中間體,同時也是增塑劑、穩(wěn)定劑等的主要成分。為適應當代環(huán)境保護的要求,所有的化學反應必須走綠色可持續(xù)發(fā)展道路,這就要求這三類工業(yè)烷基化反應采用環(huán)境友好型催化劑以取代傳統(tǒng)污染極大的液體酸催化劑,同時提高反應的催化活性,延長催化劑的使用壽命,降低工業(yè)生產(chǎn)成本。目前取代傳統(tǒng)液體酸的途徑主要是采用固體酸材料,但目前這些固體酸催化劑存在反應條件苛刻、轉(zhuǎn)化率不高、催化劑壽命短、催化產(chǎn)品質(zhì)量不高等缺陷。本論文的工作選取了強酸型陽離子交換樹脂、HUSY、超穩(wěn)Y型分子篩封裝磷鎢酸三種類型催化材料加以研究,考察催化劑制備過程中各種因素的作用,并對制備的催化劑進行傅里葉變換紅外光譜、差熱-熱重、比表面積與孔徑分布、X-射線粉末衍射、氨氣吸附程序升溫脫附手段對固體酸催化劑進行了表征；將所制備固體酸催化劑應用于甲酚與異丁烯、十二烯與萘、十二烯與苯酚的烷基化反應中,研究反應過程中各種參數(shù)的影響,以達到提高反應轉(zhuǎn)化率和產(chǎn)品質(zhì)量、優(yōu)化反應條件的研究目的。研究的主要結(jié)論如下：1.強酸型陽離子交換樹脂催化劑對甲酚與異丁烯、十二烯與苯酚的烷基化反應具有較好的催化活性,但催化劑壽命較短；強酸型陽離子交換樹脂對十二烯與萘的烷基化反應催化活性較低。2.硝酸銨濃度0.5mol/L,離子交換溫度353 K,焙燒溫度773 K,焙燒時間4小時能得到烷基化催化活性較好的HUSY分子篩；HUSY分子篩對甲酚與異丁烯反應、十二烯與萘反應、十二烯與苯酚反應的催化活性較強酸型陽離子交換樹脂好,但使用5次活性明顯下降。3.優(yōu)化并確定了原位法合成超穩(wěn)Y型分子篩封裝磷鎢酸的條件,通過BET、FT-IR、氨氣吸附程序升溫脫附、XRD、SEM等表征,結(jié)果表明在USY超籠中實現(xiàn)了磷鎢雜多酸的合成。PW-USY在烷基化反應中表現(xiàn)出了相當優(yōu)越的催化活性,且使用6次后催化活性無明顯下降。并進一步在小型固定床上考察十二烯與萘進行烷基化反應時PW-USY催化劑的使用壽命,連續(xù)烷基化720 h,催化劑的活性無明顯下降,與HUSY相比具有更好的重復使用性能,催化劑壽命更長,能較好地解決活性流失的問題,顯示出很好的工業(yè)應用前景。4.對失活的]HUSY、PW-USY催化劑分子篩殘留物質(zhì)分析,并通過對失活前后的分子篩催化劑進行BET、FT-IR、XRD、TG-DSC、NH3-TPD表征分析,結(jié)果表明,來不及擴散出去的反應原料間對甲酚、間對甲酚原料經(jīng)高溫炭化形成的炭化產(chǎn)物以及多烷基化物產(chǎn)物等覆蓋在活性中心或沉積在孔道,造成分子篩失活。
[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.
【學位授予單位】：廣東工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：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.
【學位授予單位】：廣東工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O621.251
【相似文獻】
相關(guān)期刊論文 前10條
1 洪關(guān)林;;酰胺的N—烷基化反應[J];火炸藥;1982年02期
2 牛蓉,盧建軍,李凡,朱素渝,謝克昌;煤的烷基化反應研究進展[J];煤炭轉(zhuǎn)化;2000年02期
3 胡q，
本文編號：2477288
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2477288.html
最近更新
教材專著
