微通道反应器中工业混合直链烷基苯磺酸盐的连续合成工艺研究

doi:10.11949/0438-1157.20211523

化工学报 ›› 2022, Vol. 73 ›› Issue (3): 1184-1193.DOI: 10.11949/0438-1157.20211523

• 催化、动力学与反应器 • 上一篇下一篇

微通道反应器中工业混合直链烷基苯磺酸盐的连续合成工艺研究

徐一鸣¹(),袁华²,刘素丽²,李平¹(),严佩蓉¹,赵曦¹,卢俊华¹,赵唯¹,张学兰¹

^1.宁夏大学化学化工学院，省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021
^2.国家能源集团宁夏煤业有限责任公司，宁夏银川 750011

收稿日期:2021-10-26 修回日期:2021-12-11 出版日期:2022-03-15 发布日期:2022-03-14
通讯作者: 李平
作者简介:徐一鸣(1994—)，女，硕士研究生，junshaxi@163.com
基金资助:
国家自然科学基金项目(22068030);宁夏回族自治区国内一流学科建设项目(NXYLXK2017A04)

Study on the continuous synthesis process of industrial mixed linear alkyl benzene sulfonates in a microchannel reactor

Yiming XU¹(),Hua YUAN²,Suli LIU²,Ping LI¹(),Peirong YAN¹,Xi ZHAO¹,Junhua LU¹,Wei ZHAO¹,Xuelan ZHANG¹

^1.State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China
^2.Ningxia Coal Industry Group Co. Ltd. , CHN ENERGY, Yinchuan 750011, Ningxia, China

Received:2021-10-26 Revised:2021-12-11 Online:2022-03-15 Published:2022-03-14
Contact: Ping LI

摘要/Abstract

摘要：

直链烷基苯磺酸是一种重要的阴离子表面活性剂，由其合成的直链烷基苯磺酸盐是价格低廉的表面活性剂之一，广泛应用于洗涤和三次采油等领域。以某煤制油企业的工业混合烯烃生产的直链烷基苯为原料，在微通道反应器中连续合成直链烷基苯磺酸，考察磺化温度、原料摩尔比以及磺化剂浓度等工艺条件对磺酸产物的影响规律，并与纯十六烷基苯磺化规律进行对比。研究发现混合直链烷基苯磺化过程中各个工艺条件对产品收率的影响较大。在反应温度为50℃，SO₃与LAB摩尔比为1.0∶1，停留时间为5.09 s条件下，最终产品中活性物含量可达到94.5%(质量)。同时，设计并搭建了微反应器小试平台，实现连续合成混合烷基苯磺酸盐，磺酸盐产品收率在90%以上，可为该工艺的工业应用提供技术支持。

关键词: 微反应器, 磺化, 直链烷基苯磺酸, 液相三氧化硫, 表面活性剂

Abstract:

Linear alkyl benzene sulfonic acid and its derivatives, straight-chain alkyl benzene sulfonates, are a class of inexpensive surfactants that are widely used in washing and tertiary oil recovery. In this experiment, we propose a continuous synthesis process of linear alkylbenzene sulfonic acid using Linear alkylbenzene produced from industrial mixed olefins in a coal-to-oil enterprise in a microreactor, and investigate the influence of process conditions such as sulfonation temperature, molar ratio of raw materials and concentration of sulfonating agent. It was found that the individual process conditions during the mixed straight-chain alkylbenzene sulfonation process had a significant effect on the product yield. Under the conditions of reaction temperature of 50℃, SO₃∶LAB molar ratio of 1.0∶1 and residence time of 5.09 s, the final product could reach 94.5%(mass) of active species. Meanwhile, a microreactor pilot platform was designed and built to realize the continuous synthesis of mixed alkylbenzene sulfonate,and the yield of sulfonate product was over 90%. The study can provide technical support for the industrial application of the process.

Key words: microreactor, sulfonation, linear alkyl benzene sulphonic acid, liquid sulfur trioxide, surfactants

中图分类号:

TQ 423.1

徐一鸣, 袁华, 刘素丽, 李平, 严佩蓉, 赵曦, 卢俊华, 赵唯, 张学兰. 微通道反应器中工业混合直链烷基苯磺酸盐的连续合成工艺研究[J]. 化工学报, 2022, 73(3): 1184-1193.

Yiming XU, Hua YUAN, Suli LIU, Ping LI, Peirong YAN, Xi ZHAO, Junhua LU, Wei ZHAO, Xuelan ZHANG. Study on the continuous synthesis process of industrial mixed linear alkyl benzene sulfonates in a microchannel reactor[J]. CIESC Journal, 2022, 73(3): 1184-1193.

图/表 13

图1 连续磺化实验装置

Fig.1 Experimental device of continuous sulfonation

图2 磺酸盐连续合成实验装置

Fig.2 Experimental device of continuous synthesis of sulfonates

图3 混合烷基苯液相色谱图（1 mAu=1000 mV）

Fig.3 Liquid chromatogram of heavy alkyl benzene

表1 各碳数烷基苯的分子量

Table 1 Relative molecular weight of alkylbenzene at each carbon number

碳数	分子量
10	218
11	232
12	246
13	260
14	274

图4 程序滴定法滴定色泽变化

Fig. 4 Titration of color change by programmed titration

图5 反应温度对HBSA产率和LABSA产率和色泽的影响SO3∶LAB(摩尔比)为0.94∶1, SO3质量分数= 10%,停留时间是5.09 s(绿色部分表明了优质产品色泽的范围)

Fig.5 Effect of reaction temperature on the yield of HBSA and the yield and color of LABSA

表2 不同温度下产品老化前后色泽对比

Table 2 Color comparison of products before and after aging at different temperatures

老化前后	Klett色度
老化前后	30℃	40℃	50℃	60℃	70℃
老化前
老化后

图6 原料摩尔比对HBSA产率以及LABSA产率和色泽的影响反应温度为50℃, SO3质量分数为10%,停留时间是5.09 s(绿色部分表明了优质产品色泽的范围)

Fig.6 Effect of molar ratio of raw materials on the yield of LBSA as well as the yield and color of LABSA

表3 不同原料摩尔比产品色泽对比

Table 3 Comparison of product color under different raw material molar ratio

Klett色度
SO₃/LAB=0.94	SO₃/LAB=1.00	SO₃/LAB=1.05	SO₃/LAB=1.10	SO₃/LAB=1.15	SO₃/LAB=1.21	SO₃/LAB=1.26

图7 磺化剂浓度对HBSA产率以及LABSA产率和色泽的影响反应温度为50℃, SO3∶LAB(摩尔比)为1.0∶1, 停留时间是5.09 s(绿色部分表明了优质产品色泽的范围)

Fig.7 Effect of sulfonation agent concentration on the yield of LBSA as well as the yield and color of LABSA

图8 实验中磺化后产品的不同色泽对比

Fig.8 Comparison of the different colors of the products after sulfonation in the experiment

图9 磺酸盐连续合成小试装置

Fig.9 Laboratory scale test for continuous synthesis of sulfonates

图10 不同时间样品活性物浓度

Fig.10 Sample active substance concentration at different times

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微通道反应器中工业混合直链烷基苯磺酸盐的连续合成工艺研究

Study on the continuous synthesis process of industrial mixed linear alkyl benzene sulfonates in a microchannel reactor

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