固定床过氧化氢生产工艺后处理工序的应用探讨

doi:10.19964/j.issn.1006-4990.2024-0192

Abstract

Abstract:

In view of the application effect of vacuum dehydration technology and alkali tower technology in hydrogen peroxide post-treatment process，it was analyzed and discussed from four aspects：dehydration of working fluid，degradation regeneration，decomposition of hydrogen peroxide in working fluid and comparison of operating costs.Among them，the removal water of alkali tower was 0.65 g/L，and the removal water of vacuum was 0.83 g/L.The content of hydrogen peroxide was decreased from 0.25 g/L to 0.03 g/L when the working liquid was treated by alkali tower.The hydrogen peroxide content in the working liquid of vacuum dehydration treatment remained unchanged.The increment of total available anthraquinone was 1.62~2.12 g/L and the regeneration rate of anthraquinone was 1.43%~1.90%.The vacuum technology adopted physical water removal without regenerative effect.The operating cost of vacuum dehydration was about 1/4 of the operating cost of alkali towers.The data results showed that the dehydration capacity and operating cost of vacuum dehydration technology were better than the latter，but the alkali tower technology had a certain capacity of working fluid regeneration and decomposition of hydrogen peroxide in the working fluid.Finally，the research progress of the regeneration of biodegradants in working fluids was summarized from two aspects：the improvement of regenerant and the improvement of regeneration process.

Key words: anthraquinone method fixed bed, hydrogen peroxide, vacuum dehydration, alkali tower, degradation regeneration

CLC Number:

TQ115

CHENG Xiaoqiang, MA Jun, FENG Bin, BAI Liguang, ZHAO Xiaodong. Discussion on application of post-treatment process in fixed bed hydrogen peroxide production process[J]. Inorganic Chemicals Industry, 2025, 57(2): 98-104.

Figures/Tables 10

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References 21

1	杨盟飞，冯彬，白立光，等.蒽醌法制过氧化氢技术研究进展［J］.化学推进剂与高分子材料，2024，22（1）：25-32.
	YANG Mengfei， FENG Bin， BAI Liguang，et al.Research progress in technology preparing hydrogen peroxide by anthraquinone process［J］.Chemical Propellants & Polymeric Materials，2024，22（1）：25-32.
2	成小强，李鹏翔，冯彬，等.蒽醌法制备过氧化氢用钯催化剂的再生及科学使用探讨［J］.化学推进剂与高分子材料，2022，20（6）：25-30.
	CHENG Xiaoqiang， LI Pengxiang， FENG Bin，et al.Discussion on regeneration and scientific use of palladium catalysts for preparation of hydrogen peroxide by anthraquinone process［J］.Chemical Propellants & Polymeric Materials，2022，20（6）：25-30.
3	潘智勇，邢定峰.过氧化氢市场现状和技术发展趋势［J］.现代化工，2021，41（4）：11-16.
	PAN Zhiyong， XING Dingfeng.Market status and technology development trend of hydrogen peroxide［J］.Modern Chemical Industry，2021，41（4）：11-16.
4	沈冲，庞飞，柴春玲，等.磷酸三辛酯的合成工艺概况［J］.化学推进剂与高分子材料，2021，19（6）：1-7.
	SHEN Chong， PANG Fei， CHAI Chunling，et al.Overview of synthesis process of trioctyl phosphate［J］.Chemical Propellants & Polymeric Materials，2021，19（6）：1-7.
5	刘向来.真空脱水在双氧水生产中的应用［J］.无机盐工业，2014，46（7）：47-50.
	LIU Xianglai.Application of vacuum dehydration in hydrogen peroxide production［J］.Inorganic Chemicals Industry，2014，46（7）：47-50.
6	陈四海，蔡志伟，龚凌，等.四丁基脲代替磷酸三辛酯用于过氧化氢生产［J］.石油化工，2003，32（6）：470-473.
	CHEN Sihai， CAI Zhiwei， GONG Ling，et al.Tetra-n-butyl urea substituted for tri-iso-octyl phosphate to manufacture H₂O₂ ［J］.Petrochemical Technology，2003，32（6）：470-473.
7	许颖睿，庞飞，申敬敬，等.一种过氧化氢生产用萃取塔：中国，116236813A［P］.2023-06-09.
8	初铭玥，吴美岩，唐春，等.过氧化氢工作液中蒽醌降解物再生剂研究现状［J］.无机盐工业，2018，50（11）：7-10.
	CHU Mingyue， WU Meiyan， TANG Chun，et al.Recent advances in regenerant of anthraquinone degradation products in working solution of hydrogen peroxide［J］.Inorganic Chemicals Industry，2018，50（11）：7-10.
9	邓明杨，张晓昕，宗保宁.蒽醌加氢法生产过氧化氢工业催化剂中的科学问题［J］.中国科学：化学，2021，51（7）：896-904.
	DENG Mingyang， ZHANG Xiaoxin， ZONG Baoning.Scientific issues in industrial catalysts for anthraquinone hydrogenation to produce hydrogen peroxides［J］.Scientia Sinica Chimica，2021，51（7）：896-904.
10	庞飞，许颖睿，柴春玲，等.蒽醌法过氧化氢生产工艺中废弃活性氧化铝的回收利用研究概况［J］.无机盐工业，2023，55（6）：1-7，49.
	PANG Fei， XU Yingrui， CHAI Chunling，et al.Overview on recycling of waste activated alumina in production of hydrogen peroxide by anthraquinone process［J］.Inorganic Chemicals Industry，2023，55（6）：1-7，49.
11	周伟，王红琴，安霓虹，等.过氧化氢生产中新型氧化铝再生剂工业应用实验［J］.无机盐工业，2018，50（12）：44-46.
	ZHOU Wei， WANG Hongqin， AN Nihong，et al.Industrial application of new alumina regenerant for hydrogen peroxide working solution［J］.Inorganic Chemicals Industry，2018，50（12）：44-46.
12	庞飞，许颖睿，柴春玲，等.蒽醌法过氧化氢生产工艺中废弃活性氧化铝的回收利用研究概况［J］.无机盐工业，2023，55（6）：1-7，49.
	PANG Fei， XU Yingrui， CHAI Chunling，et al.Overview on recycling of waste activated alumina in production of hydrogen peroxide by anthraquinone process［J］.Inorganic Chemicals Industry，2023，55（6）：1-7，49.
13	赵珒，袁恩先，王莅.氧化镁/γ-氧化铝催化蒽醌法工艺降解物再生过程研究［J］.无机盐工业，2015，47（6）：70-73.
	ZHAO Jin， YUAN Enxian， WANG Li.Regenerations of degradation products in anthraquinone process of hydrogen peroxide production over MgO/γ-Al₂O₃ catalysts［J］.Inorganic Chemicals Industry，2015，47（6）：70-73.
14	陈振.蒽醌降解物再生固体碱催化剂制备及性能研究［D］.北京：北京化工大学，2019.
15	程义，梁希慧，朱朝莹，等.CaO和MnO₂双修饰的γ-Al₂O₃催化再生乙基蒽醌工作液［J］.化学反应工程与工艺，2018，34（5）：431-439.
	CHENG Yi， LIANG Xihui， ZHU Chaoying，et al.CaO and MnO₂-modified γ-Al₂O₃catalyzed the regeneration of ethyl anthraquinone working solution［J］.Chemical Reaction Engineering and Technology，2018，34（05）：431-439.
16	李亚北.新型固体镁基催化剂的构筑及其蒽醌降解物再生催化性能研究［D］.北京：北京化工大学，2021.
17	史振宇，孙小惠，张旭旺，等.一种用于蒽醌法制备双氧水工作液的再生剂及其应用：中国，112551541B［P］.2022.10.11.
18	H·堺谷，井浦克弘，萩原猪佐夫，等.过含工作液再生工序的过氧化氢制造方法：中国，101421184B［P］.2011-04-13.
19	庞飞，许颖睿，马俊，等.一种蒽醌法生产过氧化氢用工作液的后处理新工艺：中国，114180773A［P］.2022-03-15.
20	卿光宗，杨华，刘光昌，等.蒽醌法全酸性工作液体系制备双氧水的方法：中国，103496674B［P］.2015-02-18.
21	张永泽，王珂.高效2-乙基蒽醌催化再生系统：中国，113045396A［P］.2021-06-29.

物质	饱和蒸气压（50 ℃）/kPa	相对分子质量	质量浓度/ （g·L^-1）	浓度/ （mol·L^-1）	物质的量分数	蒸气分压/Pa	蒸气总压/Pa	气相物质的量分数	气相质量分数
AR	1.29	120	696.36	5.80	0.83	1 070.7	1 317.5	0.81	0.97
TOP	0	602	124.35	0.21	0.03	0		0	0
TBU	0	284	61.36	0.22	0.03	0		0	0
H₂O	12.34	18	2.90	0.16	0.02	246.8		0.18	0.03
AQ	0	237	152.76	0.64	0.09	0		0	0

时间/d	回收的芳烃/mL	回收的水相/mL	凝液中水相体积分数/%	凝液中水相质量分数/%
1	1 550	1 775	53.4	56.7
2	1 280	1 640	56.2	59.4
3	965	1 410	59.4	62.5
4	1 520	1 280	45.7	49.0
5	1 400	1 615	53.6	56.9

序号	采样位置	ρ（EAQ）/ （g·L^-1）	ρ（THEAQ）/ （g·L^-1）	ρ（AQ）/ （g·L^-1）	AR含量/ （mL·L^-1）	TOP含量/ （mL·L^-1）	TBU含量/ （mL·L^-1）	总有效蒽醌增量/（g·L^-1）
1	碱塔前	111.21	53.47	164.68	661.64	130.05	54.04	2.08
1	碱塔后	112.21	54.50	166.71	664.51	128.58	54.26	2.08
2	碱塔前	111.12	53.51	164.63	663.73	129.31	52.12	2.12
2	碱塔后	112.18	54.57	166.75	664.69	128.41	52.75	2.12
3	碱塔前	113.57	54.68	168.25	660.43	129.88	54.41	1.62
3	碱塔后	113.44	56.34	169.78	662.67	128.56	54.76	1.62

[1]	QI Guoqing, LI Tong. Research progress of quality improvement plans for industrial hydrogen peroxide [J]. Inorganic Chemicals Industry, 2025, 57(1): 36-41.
[2]	Yang Jie,An Nihong,Wei Jianwei,Wang Hongqin,Xie Jiyang,Dai Yunsheng. Research progress of anthraquinone synthesis catalyst for hydrogen peroxide [J]. Inorganic Chemicals Industry, 2021, 53(4): 20-24.
[3]	Yu Tianhua,Huang Qipeng,Situ Cheng. Synthesis of dihydroxybenzenes by hydroxylation of phenol over Cu/ MS-1 with mesoporous [J]. Inorganic Chemicals Industry, 2021, 53(2): 94-99.
[4]	Zhu Hongwei, Jiang Jie, Sun Bing, Sun Feng, Xu Wei. Strategy on safety of hydrogen peroxide oxidation process [J]. Inorganic Chemicals Industry, 2021, 53(1): 77-81.
[5]	Yao Dongling,Zhang Xiaoping. Development progress and technical process of hydrogen peroxide production by anthraquinone process in China [J]. Inorganic Chemicals Industry, 2020, 52(6): 1-7.
[6]	Zhou Yi,Nie Xiaoyun. Determination method of some trace elements in hydrogen peroxide products [J]. Inorganic Chemicals Industry, 2020, 52(6): 80-82.
[7]	Wang Ben,Chen Mengmeng,Zhang Fan. Research progress on purification technology of hydrogen peroxide [J]. Inorganic Chemicals Industry, 2019, 51(6): 1-4.
[8]	RUAN Heng, WANG Fu-Li, HUANG Shi-Yong, GUO Zi-Tian, HUANG Shang-Shun, HUANG Mei, HUANG Qing-Ze, WANG Qiu-Ping. Regeneration of anthraquinone degradation products with organic alkali as catalyst [J]. INORGANICCHEMICALSINDUSTRY, 2016, 48(6): 75-.
[9]	GUO Zi-Tian, RUAN Heng, WANG Fu-Li, HUANG Shi-Yong, HUANG Mei, HUANG Qing-Ze, WANG Qiu-Ping. Regeneration and physical-chemical properties of inactivated alumina in production of hydrogen peroxide [J]. INORGANICCHEMICALSINDUSTRY, 2016, 48(5): 66-.
[10]	LIANG Yuan, WANG Hong. Determination of nitrate in hydrogen peroxide ion by ion chromatography [J]. INORGANICCHEMICALSINDUSTRY, 2016, 48(12): 78-.
[11]	. Regenerations of degradation products in anthraquinone process of hydrogen peroxide production over MgO/γ-Al2O3 catalysts [J]. INORGANICCHEMICALSINDUSTRY, 2015, 47(6): 70-.
[12]	GAO Yuan, LUO Meng, ZHU Liu. Preparation of high purity boric oxide [J]. INORGANICCHEMICALSINDUSTRY, 2015, 47(2): 46-.
[13]	YAN Shao-Peng, MIAO Jun-Kui, JIANG Peng, LENG Kai-Liang, SUN Wei-Hong, XING Li-Hong, YU Yue-Qin. Study on new oxidation process for iodine ion in kelp soaking liquid [J]. INORGANICCHEMICALSINDUSTRY, 2014, 46(7): 27-.
[14]	LIU Xiang-Lai. Application of vacuum dehydration in hydrogen peroxide production [J]. INORGANICCHEMICALSINDUSTRY, 2014, 46(7): 47-.
[15]	LIU Xi-Xiang, 欧Yang-Hui-Xiang , XIE Yu-Qi, LING Shao-Ming, LAN Cui-Ling. Mimic enzyme catalytic spectrophotometric determination of trace hydrogen peroxide in foodstuff with Fe3O4 nanoparticles [J]. INORGANICCHEMICALSINDUSTRY, 2014, 46(5): 66-.

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Discussion on application of post-treatment process in fixed bed hydrogen peroxide production process

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