超支化聚酰胺-胺的合成及其在O/W型乳状液的破乳应用

doi:10.16085/j.issn.1000-6613.2022-0532

化工进展 ›› 2023, Vol. 42 ›› Issue (1): 401-408.DOI: 10.16085/j.issn.1000-6613.2022-0532

超支化聚酰胺-胺的合成及其在O/W型乳状液的破乳应用

李松涛¹(), 赵谨², 张丽锋²^,³()

^1.中海石油化学股份有限公司，北京 100029
^2.中海油天津化工研究设计院有限公司，天津 300131
^3.天津大学化工学院，天津 300072

收稿日期:2022-03-31 修回日期:2021-07-06 出版日期:2023-01-25 发布日期:2023-02-20
通讯作者: 张丽锋
作者简介:李松涛（1971—），男，高级工程师，研究方向为智慧水务体系及智能工厂建设。E-mail：list@cnooc.com.cn
基金资助:
中国博士后科学基金(2019M661034);中海油集团公司科研项目(CNOOC-KJ145FZDXM00TJY002TJY 2021)

Preparation of hyperbranched poly(amido amine) and its application to demulsification of oil-in-water emulsions

LI Songtao¹(), ZHAO Jin², ZHANG Lifeng²^,³()

^1.China BlueChemical Ltd. , Beijing 100029, China
^2.CNOOC Tianjin Chemical Research and Design Institute Company Limited, Tianjin 300131, China
^3.School of Chemical Engineering & Technology, Tianjin University, Tianjin 300072, China

Received:2022-03-31 Revised:2021-07-06 Online:2023-01-25 Published:2023-02-20
Contact: ZHANG Lifeng

摘要/Abstract

摘要：

采用“一锅法”，通过Michael加成法以及逐步升温缩聚法，调节起始剂和丙烯酸甲酯的比例，合成了一系列超支化聚酰胺-胺（h-PAMAM）破乳剂，并应用数字化技术控制产品质量更加稳定，考察了添加量、破乳温度及沉降时间对破乳性能的影响，并探究界面张力和破乳过程中乳状液透射率与粒径的变化，分析其破乳机理。结果表明，在60℃、沉降时间为30min、破乳剂的添加量为40mg/L时，其脱油率达到95%。与商用破乳剂相比，超支化聚酰胺-胺因具有独特的超支化多位点以及酰胺基团和伯胺基团结构，用作破乳剂时界面活性高、沉降时间短。

关键词: 超支化聚合物, 破乳剂, 破乳机理, 数字化

Abstract:

In this work, with the application of one-pot synthesis based on Michael addition and temperature-programmed reaction, a series of h-PAMAM samples were successfully synthesized through adjusting the ratio of methyl acrylate(MA) to initiator. Moreover, the application of digital technology made the quality of product more reliable. The effects of demulsifier concentration, temperature and settling time on the performance of demulsifier were systematically investigated. Meanwhile, the research of interfacial tension, the real-time size and transmittance changes of oil droplets in the demulsification were also explored to analyze its demulsification mechanism. The results indicated that the oil removal rate could reach 95% with condition of 40mg/L, 30min and 60℃. Compared with commercial demulsifiers, h-PAMAM exhibited high interfacial activity and short settling time because of the unique hyperbranched multipoint structures, amido and amine groups.

Key words: hyperbranched polymer, demulsifier, demulsification mechanism, digital

中图分类号:

TE39

李松涛, 赵谨, 张丽锋. 超支化聚酰胺-胺的合成及其在O/W型乳状液的破乳应用[J]. 化工进展, 2023, 42(1): 401-408.

LI Songtao, ZHAO Jin, ZHANG Lifeng. Preparation of hyperbranched poly(amido amine) and its application to demulsification of oil-in-water emulsions[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 401-408.

图/表 15

图1 超支化聚酰胺-胺（h-PAMAM）分子结构示意图

图2 超支化聚酰胺-胺（h-PAMAM）合成示意图

图3 h-PAMAM的1H NMR谱图及其归属

图4 h-PAMAM的红外谱图

表1 h-PAMAM样品的相对分子质量及相关物性参数

n_TEPA∶n_MA	聚合物	$M n ¯$ ^①	—NH₂数目	D	R_h^② /nm
1∶2	h-PAMAM-2	4500	13.12	1.41	5.00
1∶1	h-PAMAM-3	9200	15.18	1.79	9.30
2∶1	h-PAMAM-1	4100	65.24	1.26	4.90

表1 h-PAMAM样品的相对分子质量及相关物性参数

n_TEPA∶n_MA	聚合物	$M n ¯$ ^①	—NH₂数目	D	R_h^② /nm
1∶2	h-PAMAM-2	4500	13.12	1.41	5.00
1∶1	h-PAMAM-3	9200	15.18	1.79	9.30
2∶1	h-PAMAM-1	4100	65.24	1.26	4.90

图5 系统功能和逻辑架构

表2 不同批次h-PAMAM样品的相关物性参数

聚合物样品	n_TEPA∶n_MA	$M n ¯$	D	R_h/nm
批次1（0.1t/釜）	1∶1	9200	1.79	9.30
批次2（1t/釜）	1∶1	9300	1.80	9.35
批次3（5t/釜）	1∶1	9300	1.81	9.36

表2 不同批次h-PAMAM样品的相关物性参数

聚合物样品	n_TEPA∶n_MA	$M n ¯$	D	R_h/nm
批次1（0.1t/釜）	1∶1	9200	1.79	9.30
批次2（1t/釜）	1∶1	9300	1.80	9.35
批次3（5t/釜）	1∶1	9300	1.81	9.36

图6 h-PAMAM破乳剂的破乳性能（沉降时间30min，温度60℃）

图7 不同沉降时间下破乳剂h-PAMAM-3添加量对脱油率的影响

图8 不同沉降时间下温度对h-PAMAM-3脱油率的影响

图9 不同破乳温度下沉降时间对h-PAMAM-3脱油率的影响

表3 添加不同起始剂的破乳剂的油水界面张力

破乳剂	浓度/mg·L^-1	界面张力/mN·m^-1
无	0	37.67
h-PAMAM-1	10	27.05
	20	26.55
	30	25.53
	40	25.09
h-PAMAM-2	10	24.49
	20	22.38
	30	21.94
	40	20.75
h-PAMAM-3	10	11.44
	20	10.23
	30	9.55
	40	8.59

图10 添加h-PAMAM-3破乳剂对乳状液透射率的影响

图11 h-PAMAM破乳剂对乳状液平均粒径的影响

图12 不同类型破乳剂的脱油率（沉降时间60min，温度45℃）

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超支化聚酰胺-胺的合成及其在O/W型乳状液的破乳应用

Preparation of hyperbranched poly(amido amine) and its application to demulsification of oil-in-water emulsions

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