Advances in the production technology of hydrogen peroxide

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.

Green Production Technology of the Monomer of Nylon-6： Caprolactam

After two decades＇ endeavor, the Research Institute of Petroleum Processing （RIPP） has successfully de- veloped a green caprolactam （CPL） production technology. This technology is based on the integration of titanium silicate （TS）-I zeolite with the slurry-bed reactor for the ammoximation of cyclohexanone, the integration of silicalite-1 zeolite with the moving-bed reactor for the gas-phase rearrangement of cyclohex- anone oxime, and the integration of an amorphous nickel （Ni） catalyst with the magnetically stabilized bed reactor for the purification of caprolactam. The world＇s first industrial plant based on this green CPL produc- tion technology has been built and possesses a capacity of 200 kt·a-1. Compared with existing technologies, the plant investment is pronouncedly reduced, and the nitrogen （N） atom utilization is drastically improved. The waste emission is reduced significantly; for example, no ammonium sulfate byproduct is produced. As a result, the price difference between CPL and benzene drops. In 2015, the capacity of the green CPL produc- tion technology reached 3 ×10-6 t·a-1, making China the world＇s largest CPL producer, with a global market share exceeding 50%.

Hydrogen peroxide and applications in green hydrocarbon nitridation and oxidation

Basic organic chemicals and high value–added products are mainly produced by hydrocarbon nitridation and oxidation.However,several drawbacks limit the application of the traditional oxidation and nitridation technologies in the future,such as complex processes,poor intrinsic safety,low atom utilization,and serious environmental pollution.The green nitridation and oxidation technologies are urgently needed.Hydrogen peroxide,a well–known green oxidant,is widely used in green hydrocarbon oxidation and nitridation.But its industrial production in China adopts fixed–bed technology,which is fall behind slurry–bed technology adopted by advanced foreign chemical companies,limiting the development of hydrogen peroxide industry and green hydrocarbon nitridation or oxidation industry.This article reviews the industrial production technologies of hydrogen peroxide and basic organic chemicals such as caprolactam,aniline,propene oxide,epichlorohydrin,phenol,and benzenediol,especially introduces the green production technologies of basic organic chemicals related with H_(2)O_(2).The article also emphasis on the efforts of Chinese researchers in developing its own slurry–bed technology of hydrogen peroxide production,and corresponding green hydrocarbon nitridation or oxidation technologies with hydrogen peroxide.Compared with traditional nitridation or oxidation technologies,green production technologies of caprolactam,propene oxide,epichlorohydrin,and benzenediol with hydrogen peroxide promote the nitrogen atom utilization from 60%to near 100%and the carbon atom utilization from 80%to near 100%.The waste emissions and environmental investments are reduced dramatically.Technological blockade against the green chemical industry of China are partially broken down,and technological upgrade in the chemical industry of China is guaranteed.

A sustainable integration of removing CO_(2)/NO_(x) and producing biomass with high content of lipid/protein by microalgae

Due to the boost of CO_(2)/NO_(x)emissions which cause environmental pollution,processes that remove such pollutants from flue gas have attracted increasing attention in recent years.Among these technologies,biological CO_(2)/NO_(x)emission reduction has received more interest.Microalgae,a kind of photosynthetic microorganism,offer great promise to convert CO_(2)/NO_(x)to biomass with high content of lipid and protein,which can be used as feedstock for various products such as biodiesel,health products,feedstuff and biomaterials.In this paper,biological CO_(2)/NO_(x)removing technologies by microalgae,together with the products(such as biofuel and protein)and their economic viability are discussed.Although commercial applications of microalgae for biodiesel and protein products are hampered by the high production cost of biomass,the use of CO_(2)/NO_(x)from flue gas as carbon and nitrogen sources can reduce the cost of biomass production,which makes these technologies more competent for real-life applications.Moreover,it is projected that the increasing in CO_(2)allowances will lead to further reduction in the cost of biomass production,which especially favors related products with lower values such as biodiesel.Furthermore,by combining various process optimization and integration,biorefinery is proposed and considered as the crucial component for the sustainable and economically feasible bulk applications of microalgae biomass.

Phosphate modified carbon nanotubes for oxidative dehydrogenation of n-butane

Catalytic performance of phosphate-modified carbon nanotube（PoCNT） catalysts for oxidative dehydrogenation（ODH） of n-butane has been systematically investigated. The Po CNT catalysts are characterized by SEM, TEM, XPS and TG techniques. We set the products selectivity as a function of butane conversion over various phosphate loading, and it is found that the PoCNT catalyst with the 0.8% phosphate weight loading（0.8PoCNT） exhibits the best catalytic performance. When the phosphate loading is higher than 0.8 wt%, the difference of catalytic activity among the PoCNT catalysts is neglectable. Consequently, the ODH of n-butane over the 0.8PoCNT catalyst is particularly discussed via changing the reaction conditions including reaction temperatures, residence time and n-butane/O;ratios. The interacting mechanism of phosphate with the oxygen functional groups on the CNT surface is also proposed.

Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents:A Direct Approach to Anilines

The structure of Montelukast-derivatives(12)in Table 2 and the structure of its product 25 in page s24 are wrong,and they should be Montelukast-derivatives(12)methyl(R,E)-2-(1-(1-(3-(2-(7-chloroquinolin-2-yl)vinyl)phenyl)-3-(2-(2-hydroxypropan-2-yl)phenyl)propyl)thio)methyl)cyclopropyl)acetate and methyl(R,E)-2-(1-(3-(2-aminophenyl)-1-(3-(2-(7-chloroquinolin-2-yl)vinyl)phenyl)propyl)thio)-methyl)cyclopropyl)acetate(25).

Advances in the slurry reactor technology of the anthraquinone process for H2O2 production

This paper overviews the development of the anthraquinone auto-oxidation （AO） process for the pro- duction of hydrogen peroxide in China and abroad. The characteristics and differences between the fixed-bed and fiuidized-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 Proces- sing, 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.

Efficient aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid on Ru/C catalysts

2,5-Furandicarboxylic(FDCA) is a potential substitute for petroleum-derived terephthalic acid, and aerobic oxidation of5-hydroxymethylfurfural(HMF) provides an efficient route to synthesis of FDCA. On an activated carbon supported ruthenium(Ru/C) catalyst(with 5 wt% Ru loading), HMF was readily oxidized to FDCA in a high yield of 97.3% at 383 K and 1.0 MPa O_2 in the presence of Mg(OH)_2 as base additive. Ru/C was superior to Pt/C and Pd/C and also other supported Ru catalysts with similar sizes of metal nanoparticles(1–2 nm). The Ru/C catalysts were stable and recyclable, and their efficiency in the formation of FDCA increased with Ru loadings examined in the range of 0.5 wt%–5.0 wt%. Based on the kinetic studies including the effects of reaction time, reaction temperature, O_2 pressure, on the oxidation of HMF to FDCA on Ru/C, it was confirmed that the oxidation of HMF to FDCA proceeds involving the primary oxidation of HMF to 2,5-diformylfuran(DFF) intermediate, and its sequential oxidation to 5-formyl-2-furancarboxylic acid(FFCA) and ultimately to FDCA, in which the oxidation of FFCA to FDCA is the rate-determining step and dictates the overall formation rate of FDCA. This study provides directions towards efficient synthesis of FDCA from HMF, for example, by designing novel catalysts more efficient for the involved oxidation step of FFCA to FDCA.

L-S mass transfer in G-L-S countercurrent magnetically stabilized bed with amorphous alloy SRNA-4 catalyst

Liquid-solid （L-S） mass transfer coefficients （Ks） were characterized in a gas-liquid-solid （G-L-S） three-phase countercurrent magnetically stabilized bed （MSB） using amorphous alloy SRNA-4 as the solid phase. Effects of superficial liquid velocity, superficial gas velocity, magnetic field strength, liquid viscosity and surface tension were investigated. Experimental results indicated that the external magnetic field increased Ks in three-phase MSB, as compared to those in conventional G-L-S fluidized beds; that Ks increased with magnetic field strength, superficial gas and liquid velocities and decreased with liquid viscosity and surface tension; and that Ks showed uniform axial and radial distributions except for small increases close to the wall. Dimensionless correlations were established to estimate Ks of the G-L-S countercurrent MSB using SRNA-4 catalyst, with an average error of 3.6%.

Local heat transfer properties in co- and counter-current G-L-S magnetically stabilized fluidized beds

Heat transfer coefficients were measured by immersed probes in co- and counter-current G-L-S magnetically stabilized fluidized beds （MSFBs） using air, water and nickel-alloy particles as the gas, liquid and solid phases. Influences of major factors, including magnetic field intensity, superficial gas and liquid velocities, liquid viscosity and surface tension, on heat-transfer properties were studied experimentally, indicating that both co- and counter-current G-L-S MSFB can provide relatively uniform radial distribution of heat transfer coefficients under appropriate operation conditions, thus controlling operation temperature for highly exothermic multi-phase reaction systems. Two correlations were provided to estimate accurately heat transfer properties in both co- and counter-current G-L-S MSFB systems, with an average error of less than 10%.

Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents:A Direct Approach to Anilines

Amines are among the most fundamental motifs in chemical synthesis,and the introduction of amine building blocks via selective C-C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification.Herein,we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents,which are easily prepared from hydroxylamine.Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions.Good compatibility and valuable applications of the transformation were also displayed.