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

doi:10.11949/0438-1157.20211523

Abstract

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

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

CLC Number:

TQ 423.1

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.

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.

Figures/Tables 13

Fig.1 Experimental device of continuous sulfonation

Fig.2 Experimental device of continuous synthesis of sulfonates

Fig.3 Liquid chromatogram of heavy alkyl benzene

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

Fig. 4 Titration of color change by programmed titration

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

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

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

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

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

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

Fig.9 Laboratory scale test for continuous synthesis of sulfonates

Fig.10 Sample active substance concentration at different times

References 34

1	张松山, 柯昌美, 邱德芬,等. 煤焦油加氢制备可燃油的研究进展[J]. 炭素, 2014(4): 4.
	Zhang S S, Ke C M, Qiu D F, et al. Research progress of the preparation of the combustible oil by coal tar hydrogenation[J]. Carbon, 2014(4): 4.
2	Xie K, Li W, Wei Z. Coal chemical industry and its sustainable development in China[J]. Energy, 2010, 35(11): 4349-4355.
3	袁华, 董永花, 袁炜. 低温费-托合成轻油加工利用[J]. 炼油技术与工程, 2016, 46(12): 5.
	Yuan H, Dong Y H, Yuan W. Processing and utilization of low-tempreature Fischer-Tropsch light syncrude oil[J]. Petroleum Refinery Engineering, 2016, 46(12): 5.
4	张国华, 支林轩, 赵东睿, 等. 多产品品种SO₃磺化装置的工程设计[J]. 日用化学品科学, 2021, 44(5): 36-39.
	Zhang G H, Zhi L X, Zhao D R, et al. Engineering design of multi-product SO₃ sulfonation plant[J]. Detergent & Cosmetics, 2021, 44(5): 36-39.
5	Kordoghli B, Khiari R, Mhenni M F, et al. Sulfonation of polyester fabrics by gaseous sulfur oxide activated by UV irradiation[J]. Applied Surface Science, 2012, 258(24): 9737-9741.
6	Kucera F, Jancar J. Sulfonation of solid polystyrene using gaseous sulfur trioxide[J]. Polymer Engineering & Science, 2009, 49(9): 1839-1845.
7	Pu X, Li G X, Song Y, et al. Droplet coalescence phenomena during liquid–liquid heterogeneous reactions in microreactors[J]. Industrial & Engineering Chemistry Research, 2017, 56(43): 12316-12325.
8	汪宝和, 吴金川, 张德利, 等. 喷射环流反应器中甲苯气相三氧化硫磺化[J]. 化工学报, 1997, 48(3): 378-381.
	Wang B H, Wu J C, Zhang D L, et al. Sulfonation of toluene by gaseous sulphur trioxide in a jet loop reactor[J]. Journal of Chemical Industry and Engineering (China), 1997, 48(3): 378-381.
9	Hajipour A R, Mirjalili B B F, Zarei A, et al. A novel method for sulfonation of aromatic rings with silica sulfuric acid[J]. Tetrahedron Letters, 2004, 45(35): 6607-6609.
10	Gilbert E E, Veldhuis B, Carlson E J, et al. Sulfonation and sulfation with sulfur trioxide[J]. Industrial & Engineering Chemistry, 1953, 45(9): 2065-2072.
11	Gerhart K R, Popova D O. Sulfonation with sulfur trioxide[J]. Journal of the American Oil Chemists’ Society, 1954, 31(5): 200-203.
12	Morley J O, Roberts D W, Watson S P. Experimental and molecular modelling studies on aromatic sulfonation[J]. Journal of the Chemical Society, Perkin Transactions 2, 2002(3): 538-544.
13	Roberts D W. Optimisation of the linear alkyl benzene sulfonation process for surfactant manufacture[J]. Organic Process Research & Development, 2003, 7(2): 172-184.
14	Zaı̈d T A, Benmaza K, Chitour C E. Sulfonation of linear alkyl benzene (LAB) in a corrugated wall falling film reactor[J]. Chemical Engineering Journal, 2000, 76(2): 99-102.
15	Roberts D W. Sulfonation technology for anionic surfactant manufacture[J]. Organic Process Research & Development, 1998, 2(3): 194-202.
16	Xie T M, Zeng C F, Wang C Q, et al. Preparation of methyl ester sulfonates based on sulfonation in a falling film microreactor from hydrogenated palm oil methyl esters with gaseous SO₃ [J]. Industrial & Engineering Chemistry Research, 2013, 52(10): 3714-3722.
17	王晓立, 田桂芝, 孟兆海. 合成高纯对甲苯磺酸新工艺[J]. 当代化工, 2002, 31(4): 206-208.
	Wang X L, Tian G Z, Meng Z H. New technology on synthesizing high purification toluene-P-sulfonic acid[J]. Shenyang Chemical Industry, 2002, 31(4): 206-208.
18	Sun B C, Zhang L L, Weng Z, et al. Sulfonation of alkylbenzene using liquid sulfonating agent in rotating packed bed: experimental and numerical study[J]. Chemical Engineering and Processing: Process Intensification, 2017, 119: 93-100.
19	Wu J, Wang B, Zhang D, et al. Production of p-toluenesulfonic acid by sulfonating toluene with gaseous sulfur trioxide[J]. Journal of Chemical Technology & Biotechnology, 2001, 76(6): 619-623.
20	陈光文. 微化工技术研究进展[J]. 现代化工, 2007, 27(10): 8-13.
	Chen G W. Advance and prospect of microchemical engineering and technology[J]. Modern Chemical Industry, 2007, 27(10): 8-13.
21	Roberge D M, Ducry L, Bieler N, et al. Microreactor technology: a revolution for the fine chemical and pharmaceutical industries? [J]. Chemical Engineering & Technology, 2005, 28(3): 318-323.
22	陈光文, 袁权. 微化工技术[J]. 化工学报, 2003, 54(4): 427-439.
	Chen G W, Yuan Q. Micro-chemical technology[J]. Journal of Chemical Industry and Engineering (China), 2003, 54(4): 427-439.
23	陈光文, 赵玉潮, 乐军, 等. 微化工过程中的传递现象[J]. 化工学报, 2013, 64(1): 63-75.
	Chen G W, Zhao Y C, Yue J, et al. Transport phenomena in micro-chemical engineering[J]. CIESC Journal, 2013, 64(1): 63-75.
24	Tuvell M E, Kuehnhanss G O, Heidebrecht G D, et al. AOS—An anionic surfactant system: its manufacture, composition, properties, and potential application[J]. Journal of the American Oil Chemists’ Society, 1978, 55(1): 70-80.
25	Zhao Y C, Su Y H, Chen G W, et al. Effect of surface properties on the flow characteristics and mass transfer performance in microchannels[J]. Chemical Engineering Science, 2010, 65(5): 1563-1570.
26	Lin X Y, Wang K, Zhang J S, et al. Process intensification of the synthesis of poly(vinyl butyral) using a microstructured chemical system[J]. Industrial & Engineering Chemistry Research, 2015, 54(14): 3582-3588.
27	主凯, 赵玉潮, 张博宇, 等. 微反应器中十二烷基苯液相SO₃磺化过程[J]. 化学反应工程与工艺, 2015, 31(3): 201-207.
	Zhu K, Zhao Y C, Zhang B Y, et al. Process performance of dodecylbenzene sulfonation with liquid SO₃ in a microreactor[J]. Chemical Reaction Engineering and Technology, 2015, 31(3): 201-207.
28	陈彦全, 韩梅, 焦凤军, 等. 微反应器中甲苯液相SO₃磺化工艺研究[J]. 化学反应工程与工艺, 2013, 29(3): 253-259.
	Chen Y Q, Han M, Jiao F J, et al. Study on the sulfonation of toluene with SO₃ in microreactor[J]. Chemical Reaction Engineering and Technology, 2013, 29(3): 253-259.
29	Geng Y H, Huang J P, Tan B, et al. Efficient synthesis of dodecylbenzene sulfonic acid in microreaction systems[J]. Chemical Engineering and Processing - Process Intensification, 2020, 149: 107858.
30	Xu Y M, Liu S L, Meng W J, et al. Continuous sulfonation of hexadecylbenzene in a microreactor[J]. Green Processing and Synthesis, 2021, 10(1): 219-229.
31	Epton S R. A new method for the rapid titrimetric analysis of sodium alkyl sulphates and related compounds[J]. Trans Faraday Soc, 1948, 44: 226-230.
32	李之平, 巩效牧, 李庆莹. 用百里酚蓝-次甲基蓝混合指示剂测定阴离子表面活性剂[J]. 分析化学, 1984, 12(12): 1058-1061.
	Li Z P, Gong X M, Li Q Y. A mixed indicator of thymol blue-methylene blue for determination of anionic surfactants[J]. Analytical Chemistry, 1984, 12(12): 1058-1061.
33	唐凯, 俞稼镛. 阴离子表面活性剂的测定方法: 混合指示剂程序加入法[J]. 兰州大学学报, 2000, 36(4): 61-65.
	Tang K, Yu J Y. An improved method to determine anionic surfactant in complex system[J]. Journal of Lanzhou University, 2000, 36(4): 61-65.
34	魏鑫, 王延安, 杨广彬. 烷基苯磺酸色泽与磺化反应条件控制[J]. 河南化工, 2003, 20(8): 28-29.
	Wei X, Wang Y A, Yang G B. Color control of alkyl benzenesulfonic acid and sulfonation reaction conditions [J]. Henan Chemical Industry, 2003, 20(8): 28-29.

[1]	Xin YANG, Xiao PENG, Kairu XUE, Mengwei SU, Yan WU. Preparation of molecularly imprinted-TiO₂ and its properties of photoelectrocatalytic degradation of solubilized PHE [J]. CIESC Journal, 2023, 74(8): 3564-3571.
[2]	Yuntong GE, Wei WANG, Kai LI, Fan XIAO, Zhipeng YU, Jing GONG. AFM study of the interaction forces between micro-oil droplets and modified silica surfaces in multiphase dispersion systems [J]. CIESC Journal, 2023, 74(4): 1651-1659.
[3]	Chenghao ZHANG, Jing LUO, Jisong ZHANG. Advances in continuous aerobic oxidation based on nitroxyl radical catalyst in microreactors [J]. CIESC Journal, 2023, 74(2): 511-524.
[4]	Yu XIE, Min ZHANG, Weiguo HU, Yujun WANG, Guangsheng LUO. Study on efficient dissolution of D-7-ACA using membrane dispersion microreactor [J]. CIESC Journal, 2023, 74(2): 748-755.
[5]	Jiawei FU, Shuaishuai CHEN, Kailun FANG, Xin JIANG. Advantage of microreactor on the synthesis of high-activity Cu-Mn catalyst by co-precipitation [J]. CIESC Journal, 2023, 74(2): 776-783.
[6]	Xingyu YANG, You MA, Chunying ZHU, Taotao FU, Youguang MA. Study on liquid-liquid distribution in comb parallel microchannels [J]. CIESC Journal, 2023, 74(2): 698-706.
[7]	Yuehui HOU, Xuan LIU, Yingjiang LIAN, Mei HAN, Chaoqun YAO, Guangwen CHEN. Synthesis process of trinitrophloroglucinol in an ultrasonic microreactor [J]. CIESC Journal, 2022, 73(8): 3597-3607.
[8]	Jingwei ZHANG, Yiwei ZHOU, Zhuo CHEN, Jianhong XU. Advances in frontiers of organic synthesis in microreactor [J]. CIESC Journal, 2022, 73(8): 3472-3482.
[9]	Renjie GU, Jiawei ZHANG, Xueyang JIN, Lixiong WEN. Synthesis of nickel-cobalt hydroxide composites as supercapacitor materials by micro-impinging stream reactors and their performance study [J]. CIESC Journal, 2022, 73(8): 3749-3757.
[10]	Feishi XU, Lixia YANG, Guangwen CHEN. Mesoscale enhancement mechanism of gas-liquid mass transfer in ultrasonic microreactor [J]. CIESC Journal, 2022, 73(6): 2552-2562.
[11]	Xiaohui SU, Chi ZHANG, Zhifeng XU, Hui JIN, Zhiguo WANG. Study on particle settling behavior in viscoelastic surfactant solutions [J]. CIESC Journal, 2022, 73(5): 1974-1985.
[12]	Yifei WANG, Qingqiang WANG, Desheng JI, Shenfang LI, Nan JIN, Yuchao ZHAO. Effects of the wall wettability of microchannel on the gas-liquid two-phase flow hydrodynamics [J]. CIESC Journal, 2022, 73(4): 1501-1514.
[13]	Chuxin CHANG, Liting XU, Jialun YIN, Xian LUO, Hongwei JIA. Study on low voltage electrowetting behavior under immersion state [J]. CIESC Journal, 2022, 73(4): 1673-1682.
[14]	Liang XIANG, Zihao ZHONG, Yuanhai SU. Advances on continuous synthesis of topological polymers in microreactors [J]. CIESC Journal, 2022, 73(12): 5275-5288.
[15]	Kailun FANG, Shuaishuai CHEN, Jiawei FU, Xin JIANG. Effect of aging process on copper manganese composite catalyst [J]. CIESC Journal, 2022, 73(10): 4438-4447.