Front. Chem. Sci. Eng. 2018, 12(1): 124 – 131 131 https://doi.org/10.1007/s11705-017-1676-5
REVIEW REVIE W AR ARTICLE TICLE
Advances in the slurry reactor technology of the anthraquinone process for H2O2 production Hongbo Li1, Bo Zheng1, Zhiyong Pan1, Baoning Baoning Zon Zong g (✉)1, Minghua Qiao2 1 Research Institute of Petroleum Processing, Sinopec, Beijing 100083, China 2 Department of Chemistry, Fudan University, Shanghai 200433, China
© Higher Education Press and Springer-Verlag GmbH Germany 2017
Abstract This paper paper overviews overviews the develo developmen pmentt of the anthraqui anth raquinone none auto auto-oxid -oxidatio ation n (AO) process for the production of hydrogen peroxide in China and abroad. The characteristics and differences between the xed-bed and uidized-bed reactors for the AO process are presented.
peroxide include H2O2 for propyl propylene ene oxide oxide (HPPO) (HPPO),, textile (bleaching of cotton and wool fabrics), food (aseptic packaging of milk and fruit juice) and aquaculture (antiparasite for salmon farming), mining (detoxi cation of cyanide tailings, enhanced recovery of metal), water and
The detailed comparison indicates that the production of hydrogen peroxide with the uidized-bed reactor has many advant adv antage ages, s, such such as lower lower ope operat ration ion cost cost and cataly catalyst st consumpti consu mption, on, less anthraqui anthraquinone none degr degradati adation, on, highe higher r catalyst cata lyst utilizat utilization ion ef cienc ciency y, and high higher er hydrogena hydrogenation tion ef ciency ciency.. The key charac character terss of the pro produc ductio tion n techno technolog logy y of hydrogen peroxide based on the uidized-bed reactor developed by the Research Institute of Petroleum Processi sing ng,, Sino Sinope pecc are are also also disc disclo lose sed. d. It is appa appare rent nt that that substitu subs tituting ting the uidi uidizedzed-bed bed reactor reactor for the xed-bed reac reacto torr is a majo majorr dire direct ctio ion n of brea breakt kthr hrou ough gh for for the the production technology of hydrogen peroxide in China.
wastew was tewate aterr treatm treatment ent (advan (advanced ced oxidati oxidation on proces processes) ses),, semiconductors (cleaning silicon wafers in the manufacture of printed circuit boards), chemical industry (reactant), and pulp and paper paper (ble (bleachi aching ng wood pulp) pulp) [2]. The consumption of hydrogen peroxide (based on 100 % H2O2) in China has boosted from 0.25 million tons per year in 2000 to 1.15 million tons per year in 2009. The annual ann ual growt growth h percen percentag tagee of the con consum sumpti ption on in thi thiss decade is approximately 20% [3]. The domestic capacity (based on 100% H2O2) had reached 3.07 million tons per ye year ar in 20 2016 16,, whic which h acco accoun unte ted d fo forr ha half lf of th thee gl glob obal al capacity of hydrogen peroxide. It is estimated that the rapid growth of the capacity will continue, eventually feeding back into higher production scales, system integration and optimization, and lower production costs. Several commercial processes have been developed for the the prod produc ucti tion on of hy hydr drog ogen en pe pero roxi xide de,, such such as th thee anthraquinone auto-oxidation (AO), primary and secondary alcohol oxidation [4 [4,5], and electrochemical process [6]. New synthesis processes for hydrogen peroxide are still still bei being ng explor explored, ed, e.g., e.g., the dir direct ect syn synthe thesis sis fro from m hydrogen and oxygen in the presence of a catalyst [7 [ 7 – 11 11], ], photocata photocatalyti lyticc reactions reactions over semi semicond conductor uctor oxides oxides [12 12], ], and synthe synthesis sis fro from m CO CO/O /O2/H2O mi mixt xtur ures es in th thee presence presen ce of metal complexes comple xes [13 13]. ]. Howeve However, r, thes thesee processes are plagued by high explosion risk and/or low concentration of the resulting hydrogen peroxide. Owing to the mild reaction temperatures, lower production costs and energy consumption, and larger production scales, the
Keywords anthraquinon anthraquinonee process, process, xed-be xed-bed d reactor, reactor, slurry-bed reactor, hydrogen peroxide
1
Intro Introdu ducti ction on
Hydrogen peroxide is widely used in almost all industrial areas, particularly in chemical industry and environmental protection. Hydrogen peroxide is a versatile oxidant with a high oxidation potential and effectiveness in a wide range of pH. Owing to the high active oxygen content (47.1 % w/w), hydrogen peroxide is a more ef cient oxidant than othe otherr on ones es [1]. The The de dema mand nd of hy hydr drog ogen en pe pero roxi xide de is growing dramatically due to its green character: the only byproduct from it is water water.. It has played an important role in the enviro environme nmenta ntally lly fri friend endly ly proces processes ses in chemi chemical cal “
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indust ind ustry ry.. Curren Currently tly,, the main main market marketss for hyd hydrog rogen en Received April 28, 2017; accepted July 29, 2017 E-mail:
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AO process has supplanted all its commercial competitors. The share of the AO process in the production of H2O2 is above 95% in the world and above 99% in domestic. The rst commercial AO process (one ton H2O2 per day)
Hongbo Li et al. Advances in the slurry reactor technology
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production routes routes of the AO process Fig. 1 The production
was developed by IG Farbenindustrie in Germany in the 1940s. All the plants based on the AO process follow the
peroxide usually contains trace organic impurities, which requir req uiree to be fur furthe therr pur puriied [16 16]. ]. Theref Therefore ore,, it is still still
original orig inal concept composed composed of four major step steps: s: hydrohydrogenation, oxidation genation, oxidation,, hydrogen hydrogen peroxide peroxide extracti extraction, on, and treatment of the working solution. The working solution refers refe rs to the organic organic solution solution diss dissolvi olving ng anthraqui anthraquinone none during the AO process. A simplied production route of this process is showed in Fig. 1. In genera general, l, 2-alky 2-alkylan lanthr thraqu aquino inone ne (AQ; (AQ; usuall usually y, 2ethyla eth ylantr ntraqu aquino inone) ne) dis dissol solved ved in a mixtu mixture re of org organi anicc solvents solv ents (includi (including ng nonpolar nonpolar and polar polar solvents solvents)) is rst catalytically hydrogenated to the corresponding anthrahydroquinone (AHQ) over a Pd/Al2O3 catalyst at temperature of 40 – 70 70 °C and under H2 pressure of 4 atm. The resulting solution of AHQ is sent to an oxidation reactor, where AHQ AH Q is ox oxid idiz ized ed with with air air to the the orig origin inal al AQ and an equimolar hydrogen peroxide is simultaneously produced with with a co conc ncen entr trat atio ion n of 0. 0.6 6 – 1.8 1 .8 wtwt-% [14 14,,15 15]. ]. Th Thee produced hydrogen peroxide is extracted by demineralized water wat er in an extrac extractio tion n col column umn to produc producee a hydrog hydrogen en peroxide solution of usually 27.5% by weight. The mixture of organic solvent and AQ is recycled. Hydrogen peroxide is subsequently puried and concentrated through distillation (with steam, the perox peroxide ide does not form a azeotrop azeotropic ic mixture with water and can be completely separated by distillation) to different commercial grades, typically up to 70%. The concentr concentrated ated hydrogen peroxide is stabiliz stabilized ed agains aga instt decomp decomposi ositio tion n by adding adding stabil stabilize izers rs and then then pumped into product storage tanks. The AO process has advantages such as the very high yield yie ld of hydrog hydrogen en peroxi peroxide de per cycle cycle and remark remarkabl ablee
highly hig hly desir desirabl ablee to impro improve ve the ef ci cien ency cy of th thee AO process. In this paper, we reviews the progresses on the research and development of the AO process in China and abroad. The main focus is the characteristics and differences of the hydrogenation reactors for the AO process. The trend for the further development of the AO process in China is also suggested.
In Ch Chin ina, a, th thee rese resear arch ch on th thee te tech chno nolo logy gy to pr prod oduc ucee hydrogen peroxide via the AO process developed by IG Farbenindustrie in Germany can be traced back to the year of 1958. Due to the limitation of the research conditions, a batchwise operation was adopted and did not afford satisfactory results. Another bench test was carried out and succeeded in 1961. The parameters such as the temperature, pressure, residence time, operation method, analytical method, meth od, and catalyst catalyst preparati preparation on method method were investiinvestigated. However, the road from the bench test to a largescale implementation is long. A pilot plant with a scale of 7 tons per year was established in 1964. It took three years to obtain the satisfactory result in the pilot test. The rst plant with an industrial scale of 300 tons per year was established in Beijing in 1971. Then, another eight similar factories had been set up since 1976, indicating the success
economic benets. However, it still has some drawbacks. Both the working solution and hydrogenation catalyst need to be re rege gene nera rate ted d beca becaus usee of side side reac reacti tion onss in th thee hydrogenation step. Furthermore, the produced hydrogen
of this technology in industrial application in China. The larges largestt uni unitt locate located d in Zunyi Zunyi could could produc producee 200 2000 0 tons tons H2O2 per year [3 [3]. The technology used in the above plants is regarded as
2 The The deve devellopm opmen entt of the the AO pr proc oces ess s in China
