双酚A酚胺树脂嵌段聚醚的合成及破乳性能研究

doi:10.3969/j.issn.1001-1803.2020.12.004

摘要/Abstract

摘要：

以双酚A和多乙烯多胺为原料,制备了酚胺树脂BPA。以BPA为起始剂,固定PO/EO质量比为3:1,合成了8种不同BPA/PO质量比的二嵌段聚醚破乳剂。结果表明,当BPA/PO质量比为1:99时,二嵌段聚醚破乳剂的脱水速率和脱水量均最大。当固定BPA/PO质量比为1:99时,合成了不同PO/EO质量比的二嵌段聚醚破乳剂,以及不同嵌段方式的多嵌段聚醚破乳剂。采用瓶试法,在50 ℃,破乳剂质量浓度为50 mg/L条件下,对上述原油破乳剂的破乳性能进行了评价。结果表明,当PO/EO质量比等于1.5:1时,BPA99系列破乳剂的破乳性能最好。随着EO含量的增加,破乳剂分子的亲水性逐渐增加,在油水两相会有合适的分配系数,这有利于水滴的聚并和油/水界面膜强度的降低。动态界面张力曲线说明上述破乳剂分子具有较强的扩散能力。随着EO含量的增加,破乳剂分子的界面活性逐渐增强,置换界面活性物质的能力更强。对于不同嵌段顺序的聚醚破乳剂,BPA-PO-EO结构的BPA9915和BPA9910具有较好的破乳性能,而具有BPA-EO-PO结构的BPA9915R和BPA9910R的破乳性能最差。与二嵌段破乳剂BPA9915和BPA9910相比,三嵌段和四嵌段破乳剂分子的脱水速率明显低,最终的脱水率也更低。四嵌段聚醚尾端的EO含量越高,破乳性能越好。与现场在用破乳剂TS-P100A和DM-4002相比,BPA9915的破乳性能更好。

关键词: 低温破乳剂, 酚胺树脂, 双酚A, 嵌段聚醚

Abstract:

Phenol-amine resin （BPA） was synthesized from bisphenol A and polyethylene polyamine. At the PO/EO mass ratio of 3:1, eight kinds of bi-block polyethers with different BPA/PO mass ratios were synthesized. The results showed that the drainage rate and drainage volume for the bi-block polyether with the BPA/PO mass ratio of 1:99 were higher than others. Then, at the BPA/PO mass ratio of 1:99, bi-block polyethers with different PO/EO mass ratios and multi-block polyethers with different PO/EO orders were synthesized. The properties of these oil demulsifiers were evaluated using bottle-testing method at 50 ℃ with the demulsifier mass concentration of 50 mg/L. The results showed that the demulsifying properties of BPA99 demulsifiers reached a maximum at the PO/EO mass ratio of 1.5:1. With the increase of EO content, the hydrophilicity of the demulsifier increased gradually, and thus these molecules would have an appropriate partition coefficient between the oil and aqueous phases. This would benefit the coalescence of water droplets and the decrease of strength of oil-water interfacial film. Dynamic interfacial tension curves indicated that these demulsifiers exhibited rapid interfacial diffusion. With the increase of EO content, the interfacial activity and the ability of interfacial displacement of the demulsifier increased gradually. For the multi-block polyethers with different PO/EO orders, the demulsifying properties of BPA9915 and BPA9910 with the structure of BPA-PO-EO were higher than others. The demulsifiers with the structure of BPA-EO-PO had harmful demulsifying properties. Compared with the bi-block polyethers （BPA9915 and BPA9910）, the tri-block polyethers and tetra-block polyethers showed a low drainage volume and a slow drainage rate. When the EO content in the terminal block was increased （the total number of EO units was fixed）, the demulsifying properties of the tetra-block polyether became excellent. Compared with TS-P100A and DM-4002 used in the oilfield, BPA9915 showed better demulsifying properties.

Key words: low-temperature demulsifier, phenol-amine resin, bisphenol A, block polyether

中图分类号:

TE868

曾浩见,常振,冀文雄,铁磊磊,李翔. 双酚A酚胺树脂嵌段聚醚的合成及破乳性能研究[J]. 日用化学工业, 2020, 50(12): 833-841.

ZENG Hao-jian,CHANG Zhen,JI Wen-xiong,TIE Lei-lei,LI Xiang. Study on the synthesis and demulsification of phenol-amine resin block polyether based on bisphenol A[J]. China Surfactant Detergent & Cosmetics, 2020, 50(12): 833-841.

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物质	w/%
饱和烃	48.0
芳香烃	17.4
蜡	5.8
胶质	25.2
沥青质	2.8

产品名称	BPA/PO质量比	PO/EO质量比
BPA4930	1: 49	3.0:1.0
BPA6930	1: 69	3.0:1.0
BPA9930	1: 99	3.0:1.0
BPA12930	1:129	3.0:1.0
BPA16930	1:169	3.0:1.0
BPA19930	1:199	3.0:1.0
BPA24930	1:249	3.0:1.0
BPA29930	1:299	3.0:1.0
BPA9935	1: 99	3.5:1.0
BPA9930	1: 99	3.0:1.0
BPA9925	1: 99	2.5:1.0
BPA9920	1: 99	2.0:1.0
BPA9915	1: 99	1.5:1.0
BPA9910	1: 99	1.0:1.0

原油破乳剂		50 ℃不同时间脱水量/mL					界面状况	水相清洁度	挂壁程度
名称	加药质量浓度/（mg·L^-1）	5 min	10 min	15 min	20 min	30 min	界面状况	水相清洁度	挂壁程度
BPA4930	50	1	2	3	3	3	齐	清	微挂
BPA6930	50	2	4	7	7	19	齐	清	微挂
BPA9930	50	3	5	10	10	24	齐	清	严重
BPA12930	50	2	4	6	7	12	齐	清	微挂
BPA16930	50	1	2	3	4	7	齐	清	微挂
BPA19930	50	2	2	3	4	6	齐	清	微挂
BPA24930	50	2	2	3	4	5	齐	清	微挂
BPA29930	50	1	2	3	3	4	齐	清	微挂
空白	0	0	0	0	0	0	—	—	—

原油破乳剂		50 ℃不同时间脱水量/mL					界面状况	水相清洁度	挂壁程度
名称	加药质量浓度/（mg·L^-1）	5 min	10 min	15 min	20 min	30 min	界面状况	水相清洁度	挂壁程度
BPA9935	50	4	4	4	4	11	齐	清	微挂
BPA9930	50	3	3	4	4	15	齐	清	微挂
BPA9925	50	4	4	4	5	19	齐	清	微挂
BPA9920	50	5	9	11	16	30	齐	清	微挂
BPA9915	50	8	16	20	25	31	齐	清	微挂
BPA9910	50	6	10	13	18	29	齐	清	微挂
空白	0	0	0	0	0	0	—	—	—

产品名称	嵌段方式	嵌段质量比例
BPA9915	BPA-PO-EO	1.5 :1.0
BPA9910	BPA-PO-EO	1.0 :1.0
BPA9915R	BPA-EO-PO	1.0 :1.5
BPA9910R	BPA-EO-PO	1.0 :1.0
BPA115	BPA-PO-EO-PO	1.0 :1.0 :0.5
BPA717	BPA-PO-EO-PO	0.75:1.0 :0.75
BPA511	BPA-PO-EO-PO	0.5 :1.0 :1.0
BPA1653	BPA-PO-EO-PO-EO	1.0 :0.67:0.5 :0.33
BPA1555	BPA-PO-EO-PO-EO	1.0 :0.5 :0.5 :0.5
BPA1356	BPA-PO-EO-PO-EO	1.0 :0.33:0.5 :0.67