高分子醇醚羧酸盐表面活性剂活性物含量的测定

doi:10.3969/j.issn.1001-1803.2022.04.001

摘要/Abstract

摘要：

高分子醇醚羧酸盐具有优良的耐温耐盐性能,是理想的三次采油用表面活性剂。然而其定量分析仍是一个难题,例如采用溴甲酚绿指示剂两相滴定法所得结果严重偏低,从而给相关产品的质量控制、配方研制等带来困难。本文在系统考察了溴甲酚绿指示剂两相滴定法对羧酸盐类表面活性剂适用性的基础上,提出了改进的比色法。以具体产品的纯化产物作为基准物,以海明1622作为阳离子表面活性剂,溴甲酚绿作为显色剂,氯仿作为颜色萃取剂,通过两相萃取并测定氯仿相的吸光度,得到了线性关系优良的标准曲线,进而能够定量测定合成产品中醇醚羧酸盐的含量和转化率,灵敏度达到10^-6 mol/L数量级,回收率达到97%以上。

关键词: 醇醚羧酸盐, 两相滴定, 溴甲酚绿指示剂, 比色法, 三次采油

Abstract:

Fatty alcohol polyoxypropylene （PO）-polyoxyethylene （EO） ether carboxylates （APEC） with relatively large molecular weight （1 500~3 000） are excellent surfactants for enhanced oil recovery due to their good tolerance to high temperature and high salinity. However, the quantitative analysis of this type of surfactants is still a problem. For example, using the typical two-phase titration in alkaline media with bromcresol green as indicator gives significantly underestimated results. The lack of an accurate and precise analytic method has brought difficulty to relevant formulation and quality control in industrial production. Herein, the applicability of the typical two-phase titration method in alkaline media with bromcresol green as indicator to the high-molecular-weight APEC was examined and a new method based on colorimetry was proposed. For the high-molecular-weight APEC synthesized, a linear calibration curve indicative of the relationship between the surfactant concentration in aqueous phase and the absorbance of chloroform phase at 630 nm equilibrated with the aqueous phase after two-phase extraction could be obtained, in which the purified product was used as standard sample, Hyamine 1622 was used as cationic surfactant, bromcresol green was used as indicator, and chloroform was used as extraction agent of the color. By these means, the content of APEC in industrial products can be determined and the conversion can also be obtained. Specifically, the minimum concentration detectable of the APEC in aqueous phase can be as low as 10^-6 mol/L, and the recovery can be higher than 97%.

Key words: alcohol ether carboxylate, two-phase titration, bromcresol green indicator, colorimetry, enhanced oil recovery

中图分类号:

TQ423

冉立君,陈琪,陈钊,崔正刚. 高分子醇醚羧酸盐表面活性剂活性物含量的测定[J]. 日用化学工业, 2022, 52(4): 345-354.

Ran Lijun,Chen Qi,Chen Zhao,Cui Zhenggang. Determination of high-molecular-weight fatty alcohol polyoxypropylene-polyoxyethylene ether carboxylates[J]. China Surfactant Detergent & Cosmetics, 2022, 52(4): 345-354.

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参考文献 33

[1]	Mikael Höök, Tang Xu, Pang Xiongqi, et al. Development journey and outlook of Chinese giant oilfields[J]. Petrol Explor Develop, 2010, 37 (2) : 237-249. doi: 10.1016/S1876-3804(10)60030-4
[2]	Zhu Youyi, Hou Qingfeng, Jian Guoqing, et al. Current development and application of chemical combination flooding technique[J]. Petrol Explore Develop, 2013, 40 (1) : 90-96.
[3]	Zhu Youyi, Zhang Yi, Niu Jialing, et al. The research progress in the alkali-free surfactant-polymer combination flooding technique[J]. Petrol Explore Develop, 2012, 39 (3) : 371-376.
[4]	Abass A Olajire. Review of ASP EOR (alkaline surfactant polymer enhanced oil recovery) technology in the petroleum industry: Prospects and challenges[J]. Energy, 2014, 77: 963-982. doi: 10.1016/j.energy.2014.09.005
[5]	Wang Bin, Zhou Xun, Wang Min, et al. Application of tertiary oil recovery technology in Zhongyuan oilfield[J]. Oilfield Chemistry, 2020, 37 (3) : 552-556.
[6]	Wang Chengqi, Li Yihui, Zhang Jinshan, et al. Development of enhanced oil recovery by chemical flooding in Daqing oilfield[J]. Chemical Engineer, 2021, 35 (6) : 61-64.
[7]	Zhang Miao, Yang Mingda. Experimental study on improving recovery of low permeability reservoir with high temperature and high salinity by surfactant[J]. Chemical Engineering Design Communications, 2017, 43 (8) : 143-146.
[8]	Huang Yajie, Zhou Ming, Zhang Meng, et al. Displacement oil performance evaluation of polymer enhanced foam flooding in high-temperature and high-salinity reservoirs[J]. Chemical Engineering of Oil ＆ Gas, 2016, 45 (6) : 70-74.
[9]	Shi Jing, Cao Xulong, Wang Hongyan, et al. Combination flooding technology used in high-temperature, high-salinity heavy oil reservoirs of Shengli oil field[J]. Special Oil and Gas Reservoirs, 2018, 25 (4) : 129-133.
[10]	Qin Huibo, Sun Xiaochao, Sun Changyu, et al. Applicability of nonionic surfactant alkyl polyglucoside in preparation of liquid CO₂ emulsion[J]. Journal of CO₂ Utilization, 2018, 26: 503-510.
[11]	Joohyung Lee. Charge carriers created by interaction of a nonionic surfactant with water in a nonpolar medium[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 554: 211-217. doi: 10.1016/j.colsurfa.2018.06.050
[12]	Gao Chun. Current situation and development of surfactants used in tertiary oil recovery[J]. Chemical Engineering Design Communications, 2021, 47 (7) : 92-93.
[13]	Tang Hongjiao, Hou Jirui, Zhao Fenglan. Application progress of nonionic and anionic-nonionic surfactants used in oilfield[J]. Oilfield Chemistry, 2011, 28 (1) : 115-118.
[14]	Xiao Sa, Sun Yongtao, Wang Shaohua, et al. Study on polyether carboxylate surfactant as viscosity reducing agent for heavy oil recovery[J]. Energy Chemical Industry, 2018, 39 (6) : 49-54.
[15]	Puerto M C, Lopez-Salinas J L, Jian Guoqing, et al. Laboratory studies of ternary surfactant formulation for EOR in oil-wet, high-temperature carbonate formations[C]. In SPE Improved Oil Recovery Conference. Tulsa, Oklahoma, USA, 2018.
[16]	Pinnawala Gayani, Davidson, Taylor Isbell, et al. Characterization of carboxylate surfactant retention in high temperature, hard brine sandstone reservoirs[C]. In SPE Improved Oil Recovery Conference. Virtual, 2020.
[17]	Jürgenson G A, Bittner C, Kurkal-Siebert V, et al. Alkyl ether carboxylate surfactants for chemically enhanced oil recovery in harsh field conditions[C]. In SPE Asia Pacific Enhanced Oil Recovery Conference. Kuala Lumpur, Malaysia, 2015.
[18]	Song Xinwang, Zhang Lei, Wang Xiaochun, et al. Study on foaming properties of polyoxyethylene alkyl ether carboxylic salts with different structures[J]. Journal of Dispersion Science and Technology, 2011, 32 (2) : 247-253. doi: 10.1080/01932691003657001
[19]	Zulkifli N N, Mahmood S M, Akbari S, el al. Evaluation of new surfactants for enhanced oil recovery applications in high-temperature reservoirs[J]. Journal of Petroleum Exploration and Production Technology, 2020, 10 (2) : 283-296. doi: 10.1007/s13202-019-0713-y
[20]	Wang Licheng, Wang Xusheng, Zhang Jichao, et al. Synthesis and interfacial activity of nonyl phenol polyoxyethylene ether carboxylate[J]. Journal of Dispersion Science and Technology, 2014, 35 (5) : 641-646. doi: 10.1080/01932691.2013.802653
[21]	Chen Xirong, Huang Fengxing. Research progress of temperature-resistant and salt-tolerant surfactants for enhanced oil recovery[J]. Petrochemical Technology, 2010, 39 (12) : 1307-1312.
[22]	Bao Xinning, Zhang Weidong, Sha Ou, et al. Synthesis and application of coconut acid polyether carboxylate anionic-nonionic surfactant for EOR[J]. Applied Chemical Industry, 2015, 44 (7) : 1230-1232.
[23]	Liu Xiaochen, Huo Yueqing, Niu JinPing. Research progress of extended surfactants[J]. Detergent & Cosmetics, 2018, 41 (10) : 18-23.
[24]	Lv M D, Luo C, Yang J, et al. Effect of number of oxypropylene on dynamic interfacial tensions of extended surfactants[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2019, 570: 429-437. doi: 10.1016/j.colsurfa.2019.03.054
[25]	Thomas Anthony C. Process for making alkyl ethoxy carboxylate: EP0399751A2 [P]. 1996-01-17.
[26]	Leinweber D. Processes for the solvent-free preparation of ether carboxylic acids having a low residual salt content: US7208118B2 [P]. 2007-04-24.
[27]	Akira M. Process for production of ether carboxylate: US8304575B2 [P]. 2012-10-06.
[28]	Lu Xuejun, Tao Huadong, Zhang Yiyong, et al. Research progress in alcohol ether carboxylate surfactant[J]. Detergent & Cosmetics, 2014, 37 (11) : 21-23.
[29]	Xu Fuli, Shen Qiongxia, Fan Wei, et al. Research progress of syntheses and applications of AEC[J]. Detergent & Cosmetics, 2016, 39 (2) : 35-41.
[30]	Mao Peikun. Industrial analysis of synthetic detergents[M]. Beijing: China Light Industry Press, 1998.
[31]	Reid V W, Longman G F, Heinerth E. Determination of anionic-active detergents by two-phase titration[J]. Tenside, 1967, 4 (9) : 292-304.
[32]	The Ministry of Health of the PRC. Standard test method for domestic and drinking water, disinfection by-product Index: GB/T 5750.10-2006 [S]. BeiJing: Standards Press of China, 2006.
[33]	Wang Feng, Wang Xin, Cui Zhenggang. Quantitative determination of trace anionic sufactant with visible spectrophotometry[J]. China Surfactant Detergent ＆Cosmetics, 2002 (1) : 65-67.

洗涤程序	洗涤时间/min	m（甲醇）: m（水）	混合溶剂流量/（mL/min）
1	0~9	60:40	0.5
1	10~20	90:10	0.5
2	0~9	30:70	0.5
2	10~20	30:70	0.5

羧酸钠	含量/%		平均值/%
羧酸钠	平行实验（1）	平行实验（2）	平均值/%
C₁₂羧酸钠	83.4	83.5	83.5±0.05
C₁₄羧酸钠	96.9	96.5	96.7±0.2
C₁₆羧酸钠	97.9	98.0	97.9±0.05

脂肪酸	含量/%		平均值/%
脂肪酸	平行实验（1）	平行实验（2）	平均值/%
C₁₂脂肪酸	99.7	99.1	99.4±0.3
C₁₄脂肪酸	99.0	99.1	99.1±0.05
C₁₆脂肪酸	97.8	98.3	98.1±0.25

V（氯仿） : V（异丙醇）/ （mL:mL）	含量/%		平均值/%
V（氯仿） : V（异丙醇）/ （mL:mL）	平行实验（1）	平行实验（2）	平均值/%
10:0	95.1	95.2	95.1±0.05
9:1	96.9	97.2	97.1±0.1
8:2	99.0	98.8	98.9±0.1
7:3	97.0	97.5	97.3±0.25
6:4	90.9	91.0	90.9±0.05
5:5	83.2	83.4	83.3±0.1

V（氯仿） : V（异丙醇）/ （mL:mL）	含量/%		平均值/%
V（氯仿） : V（异丙醇）/ （mL:mL）	平行实验（1）	平行实验（2）	平均值/%
9:1	85.9	86.6	86.3±0.35
8:2	90.8	90.0	90.4±0.4
7:3	91.4	91.2	91.3±0.1
6:4	86.3	86.8	86.6±0.25