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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

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Front. Chem. Sci. Eng.    2018, Vol. 12 Issue (1) : 124-131    https://doi.org/10.1007/s11705-017-1676-5
REVIEW ARTICLE
Advances in the slurry reactor technology of the anthraquinone process for H2O2 production
Hongbo Li1, Bo Zheng1, Zhiyong Pan1, Baoning Zong1(), Minghua Qiao2
1. Research Institute of Petroleum Processing, Sinopec, Beijing 100083, China
2. Department of Chemistry, Fudan University, Shanghai 200433, China
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Abstract

This paper overviews the development of the anthraquinone auto-oxidation (AO) process for the production of hydrogen peroxide in China and abroad. The characteristics and differences between the fixed-bed and fluidized-bed reactors for the AO process are presented. The detailed comparison indicates that the production of hydrogen peroxide with the fluidized-bed reactor has many advantages, such as lower operation cost and catalyst consumption, less anthraquinone degradation, higher catalyst utilization efficiency, and higher hydrogenation efficiency. The key characters of the production technology of hydrogen peroxide based on the fluidized-bed reactor developed by the Research Institute of Petroleum Processing, Sinopec are also disclosed. It is apparent that substituting the fluidized-bed reactor for the fixed-bed reactor is a major direction of breakthrough for the production technology of hydrogen peroxide in China.
Keywords anthraquinone process      fixed-bed reactor      slurry-bed reactor      hydrogen peroxide     
Corresponding Author(s): Baoning Zong   
Just Accepted Date: 07 July 2017   Issue Date: 26 February 2018
 Cite this article:   
Hongbo Li,Bo Zheng,Zhiyong Pan, et al. Advances in the slurry reactor technology of the anthraquinone process for H2O2 production[J]. Front. Chem. Sci. Eng., 2018, 12(1): 124-131.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1676-5
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I1/124
Fig.1  The production routes of the AO process
Item First generation technology Second generation technology
Reactor Slurry stirring tank reactor Trickle-bed reactor
Catalyst Raney Ni leached from 30?50 mesh of Ni-Al alloy; easy to prepare; self-ignition 0.3±0.02% Pd/Al2O3; 3 mm in diameter extrudate
Hydrogenation activity ≥9 g H2O2/L of working solution 6–7 g H2O2/L of working solution
Selectivity Acceptable High
Filtration Inside back-washable primary filters; outside safety filter Safety filter
Structure Complicated; carefully designed mechanical stirrer and seal Simple; gas and liquid distributors
Tab.1  Highlights of the characteristics of the hydrogenation steps in the first generation technology and second generation technology for the production of hydrogen peroxide via the AO process
Fig.2  Block diagram of the AO process for the production of hydrogen peroxide
Item Domestic companies FMC MGC Solvay Degussa Arkema
Working solution Solvent 1 AR AR AR AR AR AR
Solvent 2 TOP TOP TOP
Solvent 3 TBU TBU 2-MCHA
AQ EAQ EAQ AAQ EAQ EAQ EAQ
Solubility of AQ /(g?L−1) 125–140 160–180 250–300 160–180 160–180 160–180
Pd mass fraction /% 0.3 0.3 1–2 1–2 1–2 1–2
Hydrogenation Reactor Fixed bed Fixed bed Fluidized bed Fluidized bed Fluidized bed Fluidized bed
Hydrogenation efficiency/(g?L−1) 7–8 10–12 15–18 12–15 11–15 11–14
Extraction H2O2 /% 27.5–35 27.5–35 45–48 43–46 40–45 40–45
Tab.2  The comparison of the technological parameters of main companies
Item Fluidized-bed reactor (a foreign company) Fixed-bed reactor (China) Fixed-bed reactor (China) optimized
Main material EAQ /(kg?tH2O2−1) 0.7 1.8 1.1
AR /(kg?tH2O2−1) 0.8 10.9 9
TOP /(kg?tH2O2−1) 0.8 (TBU) 1.3 0.54
H2 /(Nm3?tH2O2−1) 720 737 720
H3PO4/(kg?tH2O2−1) 0.6 0.9 0.8
Al2O3 /(kg?tH2O2−1) 3.5 12.8 9
Pd-based catalyst /(kg?tH2O2−1) 0.02 (Pd 2%) 0.4 (Pd 0.3%) 0.252 (Pd 0.3%)
Utilities Cooling water /(t?tH2O2−1) 228
Electricity /(kWh?tH2O2−1) 700 742
Steam /(t?tH2O2−1) 1.6
Capacity/(t?a−1) 30000 22000 30000
Tab.3  The consumption of the processes using the fluidized- or fixed-bed reactor
Fig.3  Pilot plant of hydrogen peroxide production in Shijiazhuang
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[3] CHENG Yongxi, LI Hongtao, WANG Li, LÜ Shuxiang. Reactive extraction for preparation of hydrogen peroxide under pressure[J]. Front. Chem. Sci. Eng., 2008, 2(3): 335-340.
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