Synthesis and Application of a Novel Polyurethane Demulsifier

doi:10.12422/j.issn.1006-396X.2023.04.011

Abstract

Abstract:

After the application of a non?ionic polyether clear water agent in an oilfield in the Bohai Sea,the difficulty of dewatering crude oil in the downstream terminal treatment plant increased,and the water content of the outgoing crude oil frequently exceeded the standard.The Effect of nonionic polyether water clarifier on crude oil dehydration was researched,the reasons of difficulty in dewatering were analysed,and the emulsion could not be treated by conventional polyether demulsifier.Polyamines were synthesised from dimethylamine,dodecyl dimethyl tertiary amine and epichlorohydrin,while polyethylene?polyamines were used as cross?linking agents to synthesise polyamine copolymer emulsion breakers.The emulsion breaker can reduce the water content of the external crude oil to less than 0.5% at a concentration of 80 mg/L,and reduce the static dewatering time of the crude oil from more than 120 h to less than 48 h.This effectively solves the problem of excessive water content in the external crude oil of the terminal treatment plant.

Key words: Polyamine demulsifier, Nonionic polyether water clarifier, Zeta potential, Emulsion, Adsorption, Heary oil

摘要：

渤海某油田应用非离子聚醚清水剂后，下游终端处理厂原油脱水难度增大，外输原油含水率频繁超标。通过探究非离子聚醚清水剂对原油脱水效果的影响，分析了终端处理厂原油脱水困难的原因。结果表明，常规聚醚类破乳剂无法处理此类原油；以二甲胺、十二烷基二甲基叔胺、环氧氯丙烷为原料合成聚胺，以多乙烯多胺为交联剂合成聚胺破乳剂，加注该破乳剂80 mg/L后，可将外输原油含水率降至0.5%以内，原油静置脱水时间从大于120 h降至48 h以内，有效解决了终端处理厂外输原油含水超标的问题。

关键词: 聚胺破乳剂, 非离子聚醚清水剂, Zeta电位, 乳化液, 吸附, 稠油

CLC Number:

TQ325

Qiang Wei, Shaopeng Liu, Chao Xu, Jing Wang, Jun Li. Synthesis and Application of a Novel Polyurethane Demulsifier[J]. Journal of Petrochemical Universities, 2023, 36(4): 75-80.

魏强, 刘少鹏, 徐超, 王晶, 李军. 新型聚胺破乳剂的合成与应用[J]. 石油化工高等学校学报, 2023, 36(4): 75-80.

Figures/Tables 8

Table 1 The Zeta potential of emulsion

序号	油样	药剂名称	$ρ$ （药剂）/（mg $⋅$ L^-1）	Zeta电位/mV
1	未加药		0	-64.60
2	未加药	清水剂A	50	-48.85
3	未加药	清水剂A	100	-40.40
4	未加药	清水剂A	150	-72.25
5	未加药	清水剂A	200	-82.65
6	未加药	清水剂A	250	-96.50
7	未加药	清水剂A	300	-106.80
8	回收老化油		0	-115.70
9	海管出口油样		0	-80.45
10	海管出口油样	破乳剂SP169	100	-86.20
11	海管出口油样	破乳剂BP169	100	-80.75
12	海管出口油样	破乳剂AE8051	100	-78.60
13	海管出口油样	破乳剂PR⁃7525	100	-82.50
14	海管出口油样	破乳剂TA⁃1031	100	-76.60

Table 1 The Zeta potential of emulsion

序号	油样	药剂名称	$ρ$ （药剂）/（mg $⋅$ L^-1）	Zeta电位/mV
1	未加药		0	-64.60
2	未加药	清水剂A	50	-48.85
3	未加药	清水剂A	100	-40.40
4	未加药	清水剂A	150	-72.25
5	未加药	清水剂A	200	-82.65
6	未加药	清水剂A	250	-96.50
7	未加药	清水剂A	300	-106.80
8	回收老化油		0	-115.70
9	海管出口油样		0	-80.45
10	海管出口油样	破乳剂SP169	100	-86.20
11	海管出口油样	破乳剂BP169	100	-80.75
12	海管出口油样	破乳剂AE8051	100	-78.60
13	海管出口油样	破乳剂PR⁃7525	100	-82.50
14	海管出口油样	破乳剂TA⁃1031	100	-76.60

Table 2 The dehydration effect of conventional demulsifier

药剂名称	$ρ$ （药剂）/（mg $⋅$ L^-1）	含水率/%
未加药	0	1.45
BH⁃01	100.0	1.35
SP169	100.0	1.72
BP169	100.0	1.68
AE8051	100.0	1.38
PR⁃7525	100.0	1.42
TA⁃1031	100.0	1.50

Table 2 The dehydration effect of conventional demulsifier

药剂名称	$ρ$ （药剂）/（mg $⋅$ L^-1）	含水率/%
未加药	0	1.45
BH⁃01	100.0	1.35
SP169	100.0	1.72
BP169	100.0	1.68
AE8051	100.0	1.38
PR⁃7525	100.0	1.42
TA⁃1031	100.0	1.50

Table 3 The effect of the mass ratio of dimethylamine and di-methyl-dodecyl amine on dehydration rate

序号	质量比	表面张力/（mN·m^-1）	$ρ$ （药剂）/（mg $⋅$ L^-1）	上层原油净化油含水率/%
序号	质量比	表面张力/（mN·m^-1）	$ρ$ （药剂）/（mg $⋅$ L^-1）	24 h	48 h	72 h	96 h	120 h
1	未加药	0	0	3.62	2.25	1.45	1.22	1.10
2	加注BH⁃01	45.8	100.0	3.48	2.16	1.35	1.16	1.05
3	1 $∶$ 0	37.4	100.0	2.85	1.85	1.14	0.92	0.76
4	6 $∶$ 1	32.5	100.0	1.45	0.92	0.65	0.54	0.48
5	5 $∶$ 1	29.2	100.0	1.25	0.65	0.42	0.30	0.26
6	4 $∶$ 1	30.7	100.0	1.38	0.75	0.58	0.44	0.35
7	3 $∶$ 1	34.8	100.0	1.85	1.15	0.82	0.75	0.64
8	2 $∶$ 1	36.5	100.0	2.64	1.74	1.04	0.87	0.70
9	1 $∶$ 1	39.4	100.0	2.95	1.90	1.20	1.02	0.96

Table 3 The effect of the mass ratio of dimethylamine and di-methyl-dodecyl amine on dehydration rate

序号	质量比	表面张力/（mN·m^-1）	$ρ$ （药剂）/（mg $⋅$ L^-1）	上层原油净化油含水率/%
序号	质量比	表面张力/（mN·m^-1）	$ρ$ （药剂）/（mg $⋅$ L^-1）	24 h	48 h	72 h	96 h	120 h
1	未加药	0	0	3.62	2.25	1.45	1.22	1.10
2	加注BH⁃01	45.8	100.0	3.48	2.16	1.35	1.16	1.05
3	1 $∶$ 0	37.4	100.0	2.85	1.85	1.14	0.92	0.76
4	6 $∶$ 1	32.5	100.0	1.45	0.92	0.65	0.54	0.48
5	5 $∶$ 1	29.2	100.0	1.25	0.65	0.42	0.30	0.26
6	4 $∶$ 1	30.7	100.0	1.38	0.75	0.58	0.44	0.35
7	3 $∶$ 1	34.8	100.0	1.85	1.15	0.82	0.75	0.64
8	2 $∶$ 1	36.5	100.0	2.64	1.74	1.04	0.87	0.70
9	1 $∶$ 1	39.4	100.0	2.95	1.90	1.20	1.02	0.96

Fig.1 Infrared spectrogram of polyamine demulsifier

Table 4 The effect of polyamine on Zeta potential of emulsion

破乳剂	$ρ$ （药剂）/（mg $⋅$ L^-1）	Zeta电位/mV
未加药		-90.45
BH⁃01	100.0	-85.64
聚胺破乳剂	100.0	-12.50

Table 4 The effect of polyamine on Zeta potential of emulsion

破乳剂	$ρ$ （药剂）/（mg $⋅$ L^-1）	Zeta电位/mV
未加药		-90.45
BH⁃01	100.0	-85.64
聚胺破乳剂	100.0	-12.50

Fig.2 The change curve of water cut of purified oil with polyamine demulsifier concentration after standing for 72 hours

Fig.3 The flow chart of crude oil technological process of production

Fig.4 The curve of water cut of output crude oil

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