NPEAA与AEPH共改性苯基含氢硅油的制备及其破乳性能

doi:10.16085/j.issn.1000-6613.2018-2149

摘要/Abstract

摘要：

以氯铂酸为催化剂，异丙醇为溶剂，以自制的丙烯酸壬基酚聚氧乙烯聚氧丙烯酯（NPEAA）与烯丙基聚氧乙烯聚氧丙烯环氧基封端聚醚（AEPH）为原料，共同改性苯基含氢硅油合成了聚硅氧烷稠油破乳剂（NAEPHS），以Si—H转化率和表面张力为衡量指标，探讨不同因素对NAEPHS的影响规律，确定最佳合成条件：温度110℃，n(Si—H)∶n(C—C)为1∶1.10，反应时间5.5h，催化剂用量30μg/g时，NAEPHS的Si—H键的转化率为94.06%、表面张力为26.46mN/m。并用红外光谱、核磁氢谱作结构表征。采用吊片法和荧光光谱仪测得其临界胶束质量浓度CMC为0.6g/L，最低表面张力为26.48mN/m。将其应用于陈庄稠油模拟乳状液破乳，在NAEPHS浓度0.6g/L，破乳温度45℃，破乳时间1.5h的条件下，脱水率为89.7%，脱出水中含油量为189.7mg/L。根据Turbiscan Lab稳定性分析仪谱图和TSI测试结果得出，破乳效果明显优于其他3种市售破乳剂。通过对体系黏度、油水界面张力和破乳过程综合推测，NAEPHS分子的破乳机理为顶替或置换机理。

关键词: 苯基含氢硅油, 硅氢加成, 聚硅氧烷破乳剂, 稠油破乳

Abstract:

Using chloroplatinic acid as catalyst, isopropanol as solvent, self-made nonylphenol polyoxyethylene polyoxypropylene acrylate(NPEAA) and allyl polyoxyethylene propylene epoxy-terminated polyether (AEPH) were used as raw materials. Polysiloxane heavy oil demulsifier (NAEPHS) was synthesized by co-modification of phenyl hydrogen-containing silicone oil. The conversion of Si—H and surface tension were taken as the measurement index. The influence of different factors on NAEPHS was discussed. The optimum synthesis conditions were determined as follows: temperature 110℃. n(Si—H)∶n(C—C) is 1∶1.10, reaction time is 5.5h, amount of catalyst is 30μg/g, the conversion of Si—H bond of NAEPHS is 94.06% and the surface tension is 26.46mN/m. The structure was characterized by FTIR, ¹H NMR, GPC and other methods. The critical micelle mass concentration (CMC) is 0.6g/L and the lowest surface tension is 26.48mN/m. Under the conditions of NAEPHS concentration of 0.6g/L, demulsification temperature of 45℃ and demulsification time of 1.5h, the dehydration rate is 89.7%. The oil content in the water is 189.7mg/L. According to the spectrum of Turbiscan Lab stability analyzer and the results of TSI test, the demulsifying effect is obviously superior to that of the other three kinds of commercially available demulsifiers. According to the system viscosity, oil-water interfacial tension and demulsification process, the mechanism of NAEPHS demulsification is replacement mechanism.

Key words: phenyl hydrosilicon oil, hydrosilylation, polysiloxane demulsifier, heavy oil demulsification

中图分类号:

TQ423

郭睿, 高弯弯, 刘雪艳, 霍文生, 冯文佩, 李秀环. NPEAA与AEPH共改性苯基含氢硅油的制备及其破乳性能[J]. 化工进展, 2019, 38(06): 2922-2932.

Rui GUO, Wanwan GAO, Xueyan LIU, Wensheng HUO, Wenpei FENG, Xiuhuan LI. Preparation and demulsification properties of phenyl hydrosilicon oil modified by NPEAA and AEPHS[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2922-2932.

图/表 20

图1 反应过程

图2 标准油样的最大吸收波长的测定

图 3 不同浓度标准油样在λ max=291.32nm处的吸光度

图4 标准曲线

图 5 苯基含氢硅油与 NAEPHS 的FTIR图

图 6 苯基含氢硅油和NAEPHS 的核磁共振氢谱图

图 7 反应温度对NAEPHS的转化率和表面张力的影响

图8 n(Si—H)∶n(C=C)对NAEPHS的转化率和表面张力的影响

图9 反应时间对NAEPHS的转化率和表面张力的影响

图 10 催化剂用量对NAEPHS的转化率和表面张力的影响

图11 n(NPEAA)∶n(AEPH)对转化率以及表面张力的影响

图 12 不同浓度NAEPHS水溶液的稳态荧光发射光谱

表1 破乳浓度对NAEPHS破乳性能的影响

破乳浓度 /g?L^-1	脱水率/%	脱出水含油量 /mg?L^-1	界面状况	脱出水质清洁度
0.3	46.7	409.2	较整齐	浑浊
0.4	57.8	371.8	整齐	较浑浊
0.5	75.4	314.5	整齐	较清
0.6	87.3	195.8	整齐	清
0.7	87.2	201.6	整齐	清
0.8	87.0	206.7	整齐	清

表2 破乳时间对NAEPHS破乳性能的影响

破乳时间/h	脱水率/%	脱出水含油量 /mg?L^-1	界面状况	脱出水质清洁度
0.5	40.0	470.65	较整齐	浑浊
1.0	70.3	325.74	较整齐	较清
1.5	89.3	191.50	整齐	清
2.0	89.3	191.50	整齐	清
2.5	89.3	191.50	整齐	清
3.0	89.3	191.50	整齐	清

表3 破乳温度对NAEPHS破乳性能的影响

破乳温度/℃	脱水率/%	脱出水含油量 /mg?L^-1	界面状况	脱出水质清洁度
20	21.9	587.5	不整齐	浑浊
30	57.4	373.0	较整齐	较浑浊
40	91.1	184.5	整齐	较清
45	89.7	189.7	整齐	清
50	87.2	194.3	较整齐	清
60	86.6	218.5	较整齐	清

图13 NAEPHS破乳剂与市售AE2010、SP169、N81800破乳剂对陈庄稠油破乳过程中的 Turbiscan Lab谱图

图 14 AE 2010、SP 169、N 81800和NAEPHS破乳剂的不稳定动力指数TSI图

图15 稠乳状液以及投入NAEPHS（0.6g/L）后破乳体系的表观黏度

图16 不同浓度下NAEPHS对油-水界面张力的影响

图 17 NAEPHS的破乳过程

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