Microreaction continuous synthesis and application of bromine chloride

doi:10.16085/j.issn.1000-6613.2022-2234

Abstract

Abstract:

Bromine chloride is an important halogenating reagent in industry. Its synthesis has many challenges such as high heat release, low production efficiency and serious potential safety hazards. The continuity and miniaturization of producing equipment is an important development direction of bromine chloride synthesis technology. To develop microreaction technology for preparing bromine chloride via absorbing chlorine by means of dichloromethane solution of bromine, the mass transfer performances of Corning G1 reactor, Jinde C1 reactor and self-made micromixer + micro packed reactor were investigated. Continuous and stable preparation of bromine chloride was realized and the space-time yield of the microreactors reached 2.25g/(min∙mL). Bromination of polystyrene was implemented using the bromine chloride prepared from microreactors, and brominated polystyrene products with mass percentage >66% bromine content and 5% thermogravimetric temperature >370℃ were obtained.

Key words: bromine chloride, microreactor, continuous synthesis, brominated polystyrene

摘要：

氯化溴是工业上重要的卤化试剂，其合成过程具有放热量大、生产效率低、存在安全隐患重等问题，生产装备的连续化和小型化是氯化溴合成技术的重要发展方向。本文针对通过溴素的二氯甲烷溶液吸收氯气制备氯化溴的微反应技术开发，考察了康宁G1反应器、金德C1反应器和自制的微混合器+微填充床反应器的传质性能，实现了氯化溴的连续稳定制备，反应器的时空收率达到2.25g/(min∙mL)。利用微反应器所制得的氯化溴实施聚苯乙烯的溴化反应，取得了溴质量分数>66%和5%热失重温度>370℃的溴化聚苯乙烯产品。

关键词: 氯化溴, 微反应器, 连续合成, 溴化聚苯乙烯

CLC Number:

TQ025.5

WANG Deqiang, LI Jinzhong, WANG Kai, LUO Guangsheng. Microreaction continuous synthesis and application of bromine chloride[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5585-5591.

王德强, 李金忠, 王凯, 骆广生. 氯化溴的微反应连续合成与应用[J]. 化工进展, 2023, 42(11): 5585-5591.

Figures/Tables 8

反应器体积V/mL	心形宽度/通道宽度/mm·mm^-1	$Q B r 2 - D C M$ / mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	τ/min	STY/ g·min^-1∙mL^-1	T₁/℃	T₂/℃	反应模块1 出口状态	反应模块2 出口状态
16	15/1	20	20%	1.30	0.90	0.460	-9	-3	大量气泡	无气泡
16	15/1	20	20%	1.23	0.90	0.465	-10	-5	大量气泡	无气泡
16	15/1	20	20%	1.07	0.90	0.449	-10	-5	大量气泡	无气泡
16	15/1	21	20%	0.97	0.86	0.470	-8	-3	大量气泡	无气泡
16	15/1	21	20%	0.96	0.86	0.460	-9	-3	大量气泡	无气泡
16	15/1	21	20%	0.96	0.86	0.465	-9	-5	大量气泡	无气泡

反应器体积V/mL	心形宽度/通道宽度/mm·mm^-1	$Q B r 2 - D C M$ / mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	τ/min	STY/ g·min^-1∙mL^-1	T₁/℃	T₂/℃	反应模块1 出口状态	反应模块2 出口状态
16	15/1	20	20%	1.30	0.90	0.460	-9	-3	大量气泡	无气泡
16	15/1	20	20%	1.23	0.90	0.465	-10	-5	大量气泡	无气泡
16	15/1	20	20%	1.07	0.90	0.449	-10	-5	大量气泡	无气泡
16	15/1	21	20%	0.97	0.86	0.470	-8	-3	大量气泡	无气泡
16	15/1	21	20%	0.96	0.86	0.460	-9	-3	大量气泡	无气泡
16	15/1	21	20%	0.96	0.86	0.465	-9	-5	大量气泡	无气泡

反应器体积V/mL	心形宽度/通道宽度/mm·mm^-1	$Q B r 2 - D C M$ /mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	τ/min	STY/ g·min^-1∙mL^-1	T₁ /℃	T₂ /℃	反应模块1 出口状态	反应模块2 出口状态
16	15/1	20	42%	1.14	0.90	1.062	-12	-3	大量气泡	无气泡
16	15/1	20	42%	1.05	0.90	1.069	-10	-1	大量气泡	无气泡
16	15/1	25	42%	1.08	0.72	1.333	-10	-1	大量气泡	微量气泡
16	15/1	26	42%	1.05	0.69	1.375	-10	-1	大量气泡	微量气泡

反应器体积V/mL	心形宽度/通道宽度/mm·mm^-1	$Q B r 2 - D C M$ /mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	τ/min	STY/ g·min^-1∙mL^-1	T₁ /℃	T₂ /℃	反应模块1 出口状态	反应模块2 出口状态
16	15/1	20	42%	1.14	0.90	1.062	-12	-3	大量气泡	无气泡
16	15/1	20	42%	1.05	0.90	1.069	-10	-1	大量气泡	无气泡
16	15/1	25	42%	1.08	0.72	1.333	-10	-1	大量气泡	微量气泡
16	15/1	26	42%	1.05	0.69	1.375	-10	-1	大量气泡	微量气泡

反应器体积V/mL	环形宽度/通道宽度/mm·mm^-1	$Q B r 2 - D C M$ /mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	τ /min	STY/ g·min^-1∙mL^-1	T₁/℃	T₂/℃	反应模块1 出口状态	反应模块2 出口状态
40	9.5/1.58	20	42%	1.02	2.00	0.478	-15	-5	大量气泡	无气泡
40	9.5/1.58	23	42%	1.00	1.74	0.548	-15	-5	大量气泡	无气泡
40	9.5/1.58	24	42%	1.03	1.68	0.570	-10	-2	大量气泡	无气泡
40	9.5/1.58	26	42%	0.99	1.53	0.617	-10	-2	大量气泡	无气泡

反应器体积V/mL	环形宽度/通道宽度/mm·mm^-1	$Q B r 2 - D C M$ /mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	τ /min	STY/ g·min^-1∙mL^-1	T₁/℃	T₂/℃	反应模块1 出口状态	反应模块2 出口状态
40	9.5/1.58	20	42%	1.02	2.00	0.478	-15	-5	大量气泡	无气泡
40	9.5/1.58	23	42%	1.00	1.74	0.548	-15	-5	大量气泡	无气泡
40	9.5/1.58	24	42%	1.03	1.68	0.570	-10	-2	大量气泡	无气泡
40	9.5/1.58	26	42%	0.99	1.53	0.617	-10	-2	大量气泡	无气泡

反应器体积V/mL	微筛孔/填充颗粒直径/mm·mm^-1	$Q B r 2 - D C M$ /mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	τ/min	STY/ g·min^-1∙mL^-1	T₁/℃	T₂/℃	T₃/℃	T₄/℃	微混合器出口状态	微填充床出口状态
12.3	0.3/1.5	22	42%	1.05	0.58	1.67	2	17	22	-5	大量气泡	无气泡
12.3	0.3/1.5	25	42%	1.04	0.51	1.88	3	17	23	-5	大量气泡	无气泡
12.3	0.3/1.5	25	42%	1.03	0.51	1.93	3	19	24	-5	大量气泡	无气泡
12.3	0.3/1.5	27	42%	0.96	0.47	1.94	3	18	22	-6	大量气泡	无气泡
12.3	0.3/1.5	27	42%	1.03	0.47	2.05	3	18	24	-6	大量气泡	无气泡
12.3	0.3/1.5	30	42%	0.99	0.42	2.25	2	18	24	-6	大量气泡	无气泡

反应器体积V/mL	微筛孔/填充颗粒直径/mm·mm^-1	$Q B r 2 - D C M$ /mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	τ/min	STY/ g·min^-1∙mL^-1	T₁/℃	T₂/℃	T₃/℃	T₄/℃	微混合器出口状态	微填充床出口状态
12.3	0.3/1.5	22	42%	1.05	0.58	1.67	2	17	22	-5	大量气泡	无气泡
12.3	0.3/1.5	25	42%	1.04	0.51	1.88	3	17	23	-5	大量气泡	无气泡
12.3	0.3/1.5	25	42%	1.03	0.51	1.93	3	19	24	-5	大量气泡	无气泡
12.3	0.3/1.5	27	42%	0.96	0.47	1.94	3	18	22	-6	大量气泡	无气泡
12.3	0.3/1.5	27	42%	1.03	0.47	2.05	3	18	24	-6	大量气泡	无气泡
12.3	0.3/1.5	30	42%	0.99	0.42	2.25	2	18	24	-6	大量气泡	无气泡

反应器类型	$Q B r 2 - D C M$ / mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	T_B1 /℃	T_B2 /℃	T_B3 /℃	X_Br	X_Cl	5%热失重温度 /℃
康宁G1反应器	26	42%	1.05	-10	-9	8	66.3%	0.8%	377
	25	42%	1.08	-14	-13	5	66.5%	1.1%	376
金德C1反应器	20	42%	1.02	-6	-5	17	66.6%	0.9%	374
	24	42%	1.03	-10	-10	10	66.3%	1.0%	373
	26	42%	0.99	-16	-15	5	66.4%	0.9%	371
微混合器+微填充床反应器	25	42%	0.99	-5	-5	15	66.4%	0.8%	373
	30	42%	0.99	-10	-9	10	66.7%	0.8%	373
	27	42%	1.03	-14	-11	3	66.3%	1.0%	373

反应器类型	$Q B r 2 - D C M$ / mL·min^-1	$W B r 2$	$N C l 2 / N B r 2$	T_B1 /℃	T_B2 /℃	T_B3 /℃	X_Br	X_Cl	5%热失重温度 /℃
康宁G1反应器	26	42%	1.05	-10	-9	8	66.3%	0.8%	377
	25	42%	1.08	-14	-13	5	66.5%	1.1%	376
金德C1反应器	20	42%	1.02	-6	-5	17	66.6%	0.9%	374
	24	42%	1.03	-10	-10	10	66.3%	1.0%	373
	26	42%	0.99	-16	-15	5	66.4%	0.9%	371
微混合器+微填充床反应器	25	42%	0.99	-5	-5	15	66.4%	0.8%	373
	30	42%	0.99	-10	-9	10	66.7%	0.8%	373
	27	42%	1.03	-14	-11	3	66.3%	1.0%	373

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