Chinese Journal of Catalysis
Volume 41, Issue 7,
, Pages 1039-1047
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This article mainly summarizes various aspects of hydrogen peroxide (H2O2) production through the anthraquinone route, including hydrogenation catalysts, working solution, regeneration technique, hydrogenation reactors, and environmental protection. The advances and breakthrough of SINOPEC in the production of H2O2 through the anthraquinone route is presented in this review, highlighting recent innovative technology on these aspects developed independently. The technical prospect and scientific challenges associated with the direct synthesis method from hydrogen and oxygen are also briefly discussed.
This review summarizes the breakthroughs of the H2O2 production technology through anthraquinone auto-oxidation, as well as technical prospect and scientific challenges associated with the direct synthesis of H2O2.
Hydrogen peroxide is widely used as an oxidant, a bleaching agent, disinfectant, and polymer initiator and crosslinker in various fields, such as papermaking, textile, chemical synthesis, military, electronics, food, drugs, cosmetics, environment protection, and metallurgy. The global consumption of hydrogen peroxide as of 2018 was about 6.5 million metric tons and the value has been increasing rapidly since then, with a domestic market share of more than 50%.
Electrolysis, anthraquinone (AQ) auto-oxidation (AO), isopropanol oxidation, and electrochemical cathode reduction of oxygen [1, 2, 3] are commonly used in the production of hydrogen peroxide. The AO method has prominent advantages, including its low consumption, low cost, and convenience for equipment scale-up. Thus far, hydrogen peroxide production through the AO method accounts for 95% and 99% of global and domestic production, respectively . This method will remain prevalent for some time before the emergence of more advanced technology.
The main procedures of the AO method include AQ hydrogenation, anthrahydroquinone (AHQ) oxidation, hydrogen peroxide extraction, and working solution purification and recycling (Fig. 1). The working solution is obtained by dissolving AQ in organic solvents (see the third section), where AQ is converted to AHQ in the presence of a hydrogenation catalyst. Subsequently, after separation of the catalyst, AHQ is oxidized back to AQ with the formation of equimolar hydrogen peroxide. Crude hydrogen peroxide obtained through water extraction must be further purified to meet the market demand. In addition, the degradation of AQ is inevitable in both the hydrogenation and oxidation processes, and it negatively affects industrial production. Therefore, the working solution must be post-treated before recycling [5, 6] in the AO method.
Hydrogenation of AQ is the key process in the production of hydrogen peroxide through the AO method, directly affecting the product yield and production efficiency of the equipment. Domestic and foreign experts have conducted extensive research on the catalyst, working solution, and reaction technologies. Several companies with the largest production capacity of hydrogen peroxide in the world also have their original technologies and related production plants. SINOPEC Research Institute of Petroleum Processing (RIPP) studied and developed core technologies in the AO method, particularly for catalysts, regeneration of the working solution, hydrogenation reactor, and environmental protection. In addition, RIPP has made significant breakthroughs in the AO method and done a great deal of work on the basic research and technique planning of future technology in the production of hydrogen peroxide, namely the direct synthesis from hydrogen and oxygen.
Anthraquinone hydrogenation catalyst
In the AO method, the hydrogenation catalyst is the key factor, directly affecting the economics and product quality of hydrogen peroxide. The catalysts should exhibit good selectivity and stability in both fixed-bed and slurry-bed technologies. Low selectivity of the catalyst will increase the production cost, exert a negative effect on continuous production, and reduce the project economics greatly. On the one hand, low selectivity aggravates side reactions, which produces additional
For hydrogen peroxide production by the AO method, the selectivity depends not only on the hydrogenation catalyst but also on the reaction medium system. This reaction medium, called the working solution in hydrogen peroxide industries, is a kind of homogenous organic solution prepared from AQ dissolved in a mixed solvent.
For industrial production, there is rarely only one kind of AQ used in the working solution . With the increase in the carbon chain length, AQs have relatively high
The large-scale production of hydrogen peroxide has been in urgent demand in recent years, due to the successful application of green manufacturing technology for caprolactam and propylene oxide developed independently. The annual productivity of a hydrogen peroxide plant should be about 120 kilo metric tons of 100% product to meet the demand of a caprolactam unit with a capacity of 300 kt/a, and about 220 kilo metric tons for a propylene oxide unit with 300 kilo metric tons per year.
As a kind of green chemical, hydrogen peroxide decomposes into water and oxygen without secondary pollution. However, the production of H2O2 through the AQ method is not eco-friendly. Apart from the tons of solid waste produced in the regeneration process of the working solution, quite a significant amount of exhaust waste containing aromatics is discharged as air is compressed into the system to offer enough oxygen in the oxidation process .
Decreasing the temperature of the exhaust gas can
Direct synthesis of hydrogen peroxide
As the mainstream route for the production of hydrogen peroxide, the AO method is a mature industrial technology, whose high efficiency and high safety are attributed to the absence of direct contact between hydrogen and oxygen [47, 48]. However, the technology still faces several challenges, such as high energy consumption, high equipment input, and environmental pollution caused by the large amount of organic solvents used in the process mentioned above. Compared with the traditional process,
Hydrogen peroxide production through AQ is applied in almost all domestic industries. Despite the high technical maturity, many aspects of this process have not been optimized, including the hydrogenation catalysts, working solution system, hydrogenation reactor, and environmental protection, which require effective solutions to scale up the process. With original innovation on every aspect mentioned above, different technologies for hydrogen peroxide production by the AQ process have been
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We report an approach of direct production of H2O2 from water by applying altering potential in the electrocatalysis. By switching potentials periodically between positive to negative, oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) occurs sequentially on a single electrode loaded catalysts, which leads to the reduction of the newly-formed OER active species, forming H2O2 directly. The H2O2 production is dependent on the time and potentials of OER and ORR, which is optimized in this study. Besides, a waiting time is set after each period to let H2O2 diffusion from the catalyst surface. Different catalysts are employed to test the feasibility of this approach, including glassy carbon, graphene oxide, nickel particles, nickel foam, and palladium particles. All these catalysts result in the production of H2O2 at various reaction rates. Ni offers the highest H2O2 productivity. With the prolonging of the reaction time, the decomposition of H2O2 occurs on the surface of Ni catalysts, which is inhibited by the addition of Zn into the catalysts. The in-situ generated H2O2 is used for partial oxidation of propylene by passing propylene into the porous electrode during the reaction, which lead to the formation of dimethyl ether and adipic acid. This study shows a new route of the direct synthesis and utilization of H2O2 for the generation of valuable chemicals.
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Highly dispersed Pd/SiO2/cordierite monolith catalysts (PSC) were prepared to investigate the influence of support alkalinity on 2-ethyl-anthraquinone (eAQ) hydrogenation. The support alkalinity was adjusted by the MgO content in SiO2 washcoat. The behavior of the PSC catalysts was tested by liquid phase hydrogenation of eAQ in a continuous trickle bed reactor. PSC catalyst with 2wt.% MgO (Mg-2 sample) exhibited excellent for hydrogenation of eAQ. The support alkalinity directly influenced the electronic properties of the Pd nanoparticles as proved by Fourier transformed infrared spectroscopy with CO probe molecule and X-ray photoelectron spectroscopy. The electron density at lower binding energy of the supported Pd particles increased with the increasing alkalinity. PSC catalysts with alkali modifiers exhibited higher hydrogenation efficiency for benefiting the activation of CO group in eAQ and the adsorption of eAQ via the enhanced interaction of lone pair of CO electrons. However, increased support alkalinity contributed to higher Pd loss due to the weak coating strength. Besides, the active quinone selectivity decreased with the progressive MgO addition due to the tautomerization of 2-ethylanthrahydroquinone to 2-ethyloxoanthrone, which is the precursor of other degradations. Consequently, a volcano shape curve between hydrogenation efficiency (H2O2 yield) and MgO content was obtained.
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We studied the hydrogenation of 2-ethylanthraquinone (eAQ) over Pd/SiO2/COR (COR = cordierite) monometallic and Pd-M/SiO2/COR (M = Ni, Fe, Mn, and Cu) bimetallic monolithic catalysts, which were prepared by the co-impregnation method. Detailed investigations showed that the particle sizes and structures of the Pd-M (M = Ni, Fe, Mn, and Cu) bimetallic monolithic catalysts were greatly affected by the second metal M and the mass ratio of Pd to the second metal M. By virtue of the small particle size and the strong interaction between Pd and Ni of Pd-Ni alloy, Pd-Ni bimetallic monolithic catalysts with the mass ratio of Pd/Ni = 2 achieved the highest H2O2 yield (7.5 g/L) and selectivity (95.3%). Moreover, density functional theory calculations were performed for eAQ adsorption to gain a better mechanistic understanding of the molecule-surface interactions between eAQ and the Pd(1 1 1) or PdM(1 1 1) (M = Ni, Fe, Mn, and Cu) surfaces. It was found that the high activity of the bimetallic Pd-Ni catalyst was a result of strong chemisorption between Pd3Ni1 (1 1 1) and the carbonyl group of eAQ.
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Highly dispersed Pd/AlPO-5 catalyst was prepared and tested in the hydrogenation of 2-ethylanthraquinone. Characterization results suggested that the abundant surface P-OH groups of AlPO-5 zeolite substituted NH3 ligands of [Pd(NH3)4]2+ precursor to form [Pd(NH3)3(POH)]2+. After calcination, the latter formed Pd-O-P interfacial linkage between Pd nanoparticles and AlPO-5, benefiting the suppression of Pd sintering. SiO2 and SiO2-AlPO-5 composite were used as supports for comparison. Catalyst supported on SiO2-AlPO-5 composite (25wt% AlPO-5) exhibited improved catalytic activity and stability in consideration of reactant activation as well as the mass transfer of reactant molecules, which is expected to decrease precious metal loading in industrial application.
A current perspective on hydrogen peroxide production in honey. A review
Food Chemistry, Volume 332, 2020, Article 127229
Hydrogen peroxide plays a key role in honey antibacterial activity. The production of H2O2 in honey requires glucose oxidase (GOx) that oxidizes glucose to gluconolactone and reduces molecular oxygen to hydrogen peroxide. The content of GOx of honeybee origin was believed to be the main predictor of H2O2 concentration in honey. The observed variations in H2O2 levels among honeys questioned however the direct GOx-H2O2 relationship and left its absence opened for exploration. Here, we evaluated principal causes underlying the imbalance in the quantitative enzyme-product relationship with respect to: (a) enzyme and the product inactivation or destruction by honey compounds; (b) non-enzymatic pathway of H2O2 formation, and (c) a potential contribution of enzymes with GOx activity originating from nectars and microorganisms inhabiting honey. We also bring new facts on the relationship between honey colloidal structure and H2O2 production that change our traditional understanding of honey function as antimicrobial agent.
Promotional effects of Sb on Pd-based catalysts for the direct synthesis of hydrogen peroxide at ambient pressure
Chinese Journal of Catalysis, Volume 39, Issue 4, 2018, pp. 673-681
TiO2-supported Pd-Sb bimetallic catalysts were prepared and evaluated for the direct synthesis of H2O2 at ambient pressure. The addition of Sb to Pd significantly enhanced catalytic performance, and a Pd50Sb catalyst showed the greatest selectivity of up to 73%. Sb promoted the dispersion of Pd on TiO2, as evidenced by transmission electron microscopy and X-ray diffraction. X-ray photoelectron spectroscopy indicated that the oxidation of Pd was suppressed by Sb. In addition, Sb2O3 layers were formed and partially wrapped the surfaces of Pd catalysts, thus suppressing the activation of H2 and subsequent hydrogenation of H2O2. In situ diffuse reflection infrared Fourier transform spectroscopy for CO adsorption suggested that Sb homogenously located on the surface of Pd-Sb catalysts and isolated contiguous Pd sites, resulting in the rise of the ratio of Pd monomer sites that are favorable for H2O2 formation. As a result, the Sb modified Pd surfaces significantly enhanced the non-dissociative activation of O2 and H2O2 selectivity.
Published 5 July 2020
This work was supported by the National Key Research and Development Program of China (2016YFB0301600).
Copyright © 2020 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.