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Chinese Journal of Catalysis
2013, Vol. 34, No. 1
Online: 23 January 2013


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This special issue is dedicated to Professor Enze Min in honor of his 90th birthday. He won the National Supreme Science and Technology Award in 2007, and he has received wide recognition as “the founder of applied catalysis for petroleum refining, the forerunner of independent innovation of petrochemical technology, and the pioneer in the area of green chemistry in China”.

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Table of Contents for Vol. 34 No. 1 2013, 34 (1):  0-0.  Abstract ( 814 )   PDF (1487KB) ( 567 )

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Preface to Special Issue of Chinese Journal of Catalysis in honor of the 90th birthday of Professor Enze Min HE Ming-Yuan, LIU Hai-Chao 2013, 34 (1):  1-3.  DOI: 10.1016/S1872-2067(11)60511-1 Abstract ( 1710 )   [Full Text(HTML)] () PDF (421KB) ( 669 )

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Biography for Mr. Enze MIN  ZHANG Xiao-Xin 2013, 34 (1):  4-9.  DOI: 10.3724/SP.J.1088.2013.21254 Abstract ( 1646 )   [Full Text(HTML)] () PDF (890KB) ( 669 )

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Devoted in 50 years to national economy via catalytic technology innovations-on major scientific achievements and contributions of Dr. Enze Min HE Ming-Yuan 2013, 34 (1):  10-21.  DOI: 10.3724/SP.J.1088.2013.30108 Abstract ( 1624 )   [Full Text(HTML)] () PDF (443KB) ( 495 )   This article introduces the major scientific achievements and contributions made by academician Dr. Enze Min, recipient of the 2007 National Supreme Science and Technology Award, covering: (1) the founder of applied catalysis science to develop petroleum refining catalysts and to laid the technical foundation for manufacturing China’s petroleum processing catalysts; (2) the forerunner of independent innovation for developing new catalytic materials and novel reaction engineering; (3) the pioneering explorer in the field of green chemistry and green technologies to support nation’s sustainable development.

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Synthesis and applications of hierarchically porous catalysts LI Xiao-Yun, SUN Ming-Hui, ROOKE Joanna Claire, CHEN Li-Hua, SU Bao-Lian 2013, 34 (1):  22-47.  DOI: 10.1016/S1872-2067(11)60507-X Abstract ( 4105 )   [Full Text(HTML)] () PDF (2171KB) ( 1684 )   Hierarchically porous materials that can be used as catalysts or catalyst supports have garnered much attention due to their enhanced mass transport and multiple functionalities. Hierarchically porous catalysts integrate at least two levels of porosity and present the advantages associated with each level of porosity, from selectivity to mass transport. For example, hierarchically porous zeolites offer an effective solution to the mass transport problem associated with conventional zeolites in catalyzed reactions, because they combine the catalytic features of micropores and the improved accessibility and increased molecular transport related to the addition of several porosities within a single body. This review thoroughly summarizes recent developments that have been made in the field of hierarchically porous catalysts, with the main focus on the synthesis strategies that are available as well as their application in catalysis. It is the intent of this work to stimulate intuition into the optimal design of related hierarchically porous catalysts with desired characteristics.

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Crucial technologies supporting future development of petroleum refining industry LI Da-Dong 2013, 34 (1):  48-60.  DOI: 10.1016/S1872-2067(11)60508-1 Abstract ( 2178 )   [Full Text(HTML)] () PDF (724KB) ( 1528 )   The primary tasks of refineries in the future are to improve the yield of light oil and to produce clean fuels and high-quality chemical raw materials. The efficient conversion of heavy oil is necessary to improve the yield of light oil. This conversion requires some crucial technologies, including: (1) residue hydrotreating technology, (2) the research institute of petroleum processing’s (RIPP’s) integrated combination process for residue hydroprocessing, (3) the integration of selective hydrogenation of fluid catalytic cracking gas oil with selective catalytic cracking process, and (4) the combination of superficial solvent deasphalting, hydrotreatment of deasphalted oil, and fluid catalytic cracking technology. The most important technologies for producing clean fuels such as qualified gasoline and diesel include the RIPP’s selective hydrodesulfurization technology, the RIPP’s hydrogenation technology for producing ultra-low-sulfur diesel fuel, and catalysts for producing RS-1000 and RS-2000 (grades of ultra-low-sulfur diesel). To produce high quality chemical raw materials, the Sinopec hydroprocessing for maximum propylene of fluid catalytic cracking process is of vital importance. The characteristics and effects of these technologies are summarized in this article.

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Magnetically stabilized bed reactors ZONG Bao-Ning, MENG Xiang-Kun, MU Xu-Hong, ZHANG Xiao-Xin 2013, 34 (1):  61-68.  DOI: 10.1016/S1872-2067(11)60476-2 Abstract ( 2215 )   [Full Text(HTML)] () PDF (680KB) ( 862 )   The first commercial application of the magnetically stabilized bed (MSB) reactor is discussed. The MSB reactor uses a magnetic catalyst in a uniform magnetic field to combine the many advantages of the fixed bed, slurry bed, moving bed, and fluidized bed reactors. An industrial MSB reactor requires a large and uniform magnetic field, which was obtained by optimizing the coil installation spacing and inserting magnetic grids in the reactor. It was used for the intensification of the hydrogenation processes by operating in the chain mode. By utilizing the excellent hydrogenation activity and magnetism of an amorphous Ni catalyst, a MSB reactor was developed for the hydrorefining of caprolactam. Five industrial units of 200–400 kt/a production capacity have been built since 2003. The use of the appropriate magnetic catalyst in the MSB reactor also enhanced activities in CO methanation, selective acetylene hydrogenation and olefin oligomerization. This technology gives new opportunities for process intensification.

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Nanosized molecular sieves as petroleum refining and petrochemical catalysts MU Xu-Hong, WANG Dian-Zhong, WANG Yong-Rui, LIN Min, CHENG Shi-Biao, SHU Xing-Tian 2013, 34 (1):  69-79.  DOI: 10.1016/S1872-2067(11)60462-2 Abstract ( 3148 )   [Full Text(HTML)] () PDF (1190KB) ( 1046 )   Nanosized ZSM-5 was synthesized and used for straight run gasoline reforming. Nanosized β was synthesized and used for the alkylation of benzene and ethylene in ethylbenzene production. Nanosized titanosilicate molecular sieve with a hollow structure (HTS) was synthesized and used for the oximation of cyclohexanone. Nanosized silicalite-1 was synthesized and used for the gas phase Beckmann rearrangement of cyclohexanone oxime in caprolactam production. Recent progress in the synthesis and application of nanosized ZSM-5, β, TS-1, and silicalite-1 were reviewed. The catalyst lifetimes were prolonged when nanosized molecular sieves were used as petroleum refining and petrochemical catalysts.

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Factors in mass cultivation of microalgae for biodiesel ZHU Jun-Ying, RONG Jun-Feng, ZONG Bao-Ning 2013, 34 (1):  80-100.  DOI: 10.1016/S1872-2067(11)60497-X Abstract ( 2564 )   [Full Text(HTML)] () PDF (897KB) ( 1048 )   Biofuel from microalgae is a long term strategy to solve the energy crisis. It is a new area of biological engineering and process engineering that consists of the isolation and characterization of microalgae species, mass cultivation of microalgae, harvesting and post-processing. The successful mass cultivation of microalgae is one of its main challenges. Several factors influencing the mass cultivation of microalgae are discussed, such as microalgae species, metabolic mechanism, culture conditions and the photobioreactor. This paper will help the development of biofuels from microalgae and its photobioreactor.

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Research and development of a sub-critical methanol alcoholysis process for producing biodiesel using waste oils and fats DU Ze-Xue, TANG Zhong, WANG Hai-Jing, ZENG Jian-Li, CHEN Yan-Feng, MIN En-Ze 2013, 34 (1):  101-115.  DOI: 10.1016/S1872-2067(11)60490-7 Abstract ( 2178 )   [Full Text(HTML)] () PDF (635KB) ( 1100 )   Waste oils and fats (WOFs) are non-edible oils generated in amounts of more than 30 million and 10 million tons/year in China, respectively, from the production and consumption of cooking oil, and which would pollute the environment if disposed of improperly. Due to its poor quality, it is very difficult to transform WOFs to biodiesel by base catalyzed transesterification, especially when these have high free fatty acids and impurities. A new technology, sub-critical methanol alcoholysis process (SRCA process), was developed by SINOPEC Research Institute of Petroleum Processing for producing biodiesel from WOFs. The technical problems that were solved included how to dissolve WOFs in methanol, how to moderate the reaction conditions, how to transform WOFs into more biodiesel, and how to improve product quality. The first industrial demonstration unit of SRCA process with a scale of 60 kton/year biodiesel was set up in 2009, and it had been operated continuously to produce biodiesel from soybean acid oil, palm acid oil, and cooking oil. The biodiesel product quality fulfil the requirements of National Standard (GB/T 20828-2007).

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Advances in bifunctional catalysis for higher alcohol synthesis from syngas XIAO Kang, BAO Zheng-Hong, QI Xing-Zhen, WANG Xin-Xing, ZHONG Liang-Shu, FANG Ke-Gong, LIN Ming-Gui, SUN Yu-Han 2013, 34 (1):  116-129.  DOI: 10.1016/S1872-2067(11)60496-8 Abstract ( 2449 )   [Full Text(HTML)] () PDF (663KB) ( 1179 )   Bifunctional catalysis on dual sites plays an important role in higher alcohol synthesis from syngas. It makes use of two types of active sites of which one type dissociates CO and forms surface alkyl species and the other type catalyzes non-dissociative CO adsorption for CO insertion and alcohol formation. To improve catalytic activity for higher alcohol synthesis, it is necessary to design dual sites on the atomic scale to give them high stability. The recent advances in higher alcohol synthesis using bifunctional catalysts are reviewed. The design of the dual sites, the structure of the dual sites on several typical catalyst systems, and the structural evolution of the dual sites during reaction are discussed using our latest research results.

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The development and application of catalysts for ultra-deep hydrodesulfurization of diesel FANG Xiang-Chen, GUO Rong, YANG Cheng-Min 2013, 34 (1):  130-139.  DOI: 10.1016/S1872-2067(11)60506-8 Abstract ( 1955 )   [Full Text(HTML)] () PDF (561KB) ( 859 )   The history and current status of research concerning preparation and application technology for diesel ultra-deep hydrodesulfurization (HDS) catalysts were summarized. As a result of systematic research aimed at understanding the fundamental mechanism of ultra-deep HDS catalysis, various technology for the preparation of HDS catalysts have been developed, including novel alumina supports, as well as methods for tuning the surface properties of catalysts and otherwise modifying these materials so as to improve alkyl transfer performance. The result of these improvements is that a number of ultra-deep HDS catalysts with excellent performance, such as FHUDS-5 and FHUDS-6, have been developed. In addition, parallel research work investigating the interactions between different types of HDS catalysts and different hydrotreatment reactor zones has developed stacked catalyst technology that allows for the optimization of catalytic performance, so as to meet the demands of commercial production facilities for ultra-low-sulfur diesel.

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Improvement of adsorptive desulfurization performance of Ni/ZnO adsorbent by doping with Mn additive ZHANG Yu-Liang, YANG Yong-Xing, LIN Feng, YANG Min, LIU Tie-Feng, JIANG Zong-Xuan, LI Can 2013, 34 (1):  140-145.  DOI: 10.1016/S1872-2067(11)60513-5 Abstract ( 2151 )   [Full Text(HTML)] () PDF (575KB) ( 794 )   The effect of Mn doping on the adsorptive desulfurization performance of 5%Ni/ZnO adsorbents was investigated in model gasoline, with thiophene as a sulfur-containing compound, using a fixed-bed reactor. The 5%Ni/MnO-ZnO adsorbents with different levels of Mn doping were prepared using an incipient wetness impregnation method and characterized by powder X-ray diffraction (XRD). It was found that the adsorption performances of the 5%Ni/MnO-ZnO adsorbents were considerably improved after Mn doping compared with that of 5%Ni/ZnO. Moreover, the 5%NiO/MnO-ZnO adsorbents showed high desulfurization activities after regeneration. Sulfur removal by a 5%NiO/8%MnO-ZnO adsorbent after three reaction-regeneration cycles was 4% higher than that by a 5%NiO/ZnO adsorbent without Mn doping. The excellent performance of the 5%NiO/8%MnO-ZnO adsorbent in desulfurization, and its regenerability, were attributed to formation of a new compound, ZnMnO3, in the adsorbent; this compound was characterized using XRD.

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Partial oxidation of methane to syngas over mesoporous Co-Al2O3 catalysts LIU Rui-Yan, YANG Mei-Hua, HUANG Chuan-Jing, WENG Wei-Zheng, WAN Hui-Lin 2013, 34 (1):  146-151.  DOI: 10.1016/S1872-2067(11)60481-6 Abstract ( 2062 )   [Full Text(HTML)] () PDF (692KB) ( 699 )   Mesoporous Co-Al2O3 catalysts were prepared by one-pot synthesis and, for the first time, used in the partial oxidation of methane to synthesis gas. Compared with the catalysts prepared by impregnation methods, the catalysts prepared by one-pot synthesis showed superior catalytic performance for this reaction. The results showed that mesoporous Co-Al2O3 catalysts have high surface areas, large pore volumes, and an ordered hexagonal mesostructure. In the catalysts, Co species are highly dispersed, resulting in high dispersion of the metal after reduction. A confinement effect, provided by the mesopores, on metal nanoparticles could effectively enhance resistance to metal sintering.

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Hydrodenitrogenation of porphyrin on Ni-Mo based catalysts Eika W. QIAN, Satoshi ABE, Yusaku KAGAWA, Hiroyuki IKEDA 2013, 34 (1):  152-158.  DOI: 10.1016/S1872-2067(11)60514-7 Abstract ( 1677 )   [Full Text(HTML)] () PDF (492KB) ( 542 )   The hydrodenitrogenation (HDN) of porphyrins was carried out over a series of phosphorus containing NiMo/Al2O3 catalysts using a fixed-bed flow reaction system. A method of quantitative analysis of the porphyrin and its derivatives produced by HDN was established. In HDN of porphyrin, four types of hydrocarbons: C8 alkanes, C8 alkenes, C9 alkanes, and C10 alkanes, and two groups of nitrogen-containing compounds: alkyl substituted bipyrrolidines (alkylbipyrrolidines) and alkyl substituted tripyrrolidines (alkyltripyrrolidines) were identified. The hydrogenolysis of porphyrins occurred rapidly at lower temperature but higher temperatures were required for the HDN of porphyrins. The NiMoP3 catalyst showed the highest catalytic activity for the HDN of porphyrins. Based on the characterization of the supports and catalysts, it is suggested that the dispersion of Mo is improved and the number of weak acidic sites on the NiMoP catalysts increases with the addition of phosphorus.

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Synthesis of Ni/Mo/N catalyst and its application in benzene hydrogenation in the presence of thiophene CHU Qi, FENG Jie, LI Wen-Ying, XIE Ke-Chang 2013, 34 (1):  159-166.  DOI: 10.1016/S1872-2067(11)60509-3 Abstract ( 1888 )   [Full Text(HTML)] () PDF (1269KB) ( 900 )   Ni/Mo/N catalysts made to have an interstitial structure gave high catalytic activity and sulfur tolerance in the hydrotreating of coal liquid fuel to produce high performance jet fuel. The dissolving of N atoms into the metal lattices to make the interstitial structure is difficult to control, and the preparation conditions of the precursor synthesis and the crystallinity of the precursors were changed to monitor how N atoms were inserted into the metal lattice. Ni/Mo/N catalysts were prepared by a one pot synthesis using ammonium molybdate [(NH4)6Mo7O24?4H2O] and nickel acetate [Ni(CH3COO)2?4H2O] and the decomposition of hexamine under an argon atmosphere at 650 °C. Benzene hydrogenation was used as a model reaction to evaluate catalytic activity. Benzene was hydrogenated over the Ni/Mo/N catalyst at 250 °C and 3 MPa in a fixed bed reactor in the absence and presence of thiophene to also test the Ni/Mo/N catalysts for sulfur tolerance. X-ray diffraction analysis showed that the formation of different precursors and use of different aging times affected the composition of the Ni/Mo/N catalysts, and also determined the crystal phases in the Ni/Mo/N catalysts. Ni2Mo3N, Mo2C, and Ni metal phases were present in the most active Ni/Mo/N catalyst which gave a conversion of benzene of 93% and selectivity to cyclohexane of almost 100%. The atomic ratio of Ni/Mo in the most active Ni/Mo/N catalyst was 5/4 as determined by energy dispersive X-ray spectroscopy. Benzene hydrogenation over the Ni/Mo/N catalyst in the presence of thiophene led to a decline in benzene conversion from 72% to 50% due to the formation of MoS2.

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Catalytic activity of immobilized Ru nanoparticles in a porous metal-organic framework using supercritical fluid WU Tian-Bin, ZHANG Peng, MA Jun, FAN Hong-Lei, WANG Wei-Tao, JIANG Tao, HAN Bu-Xing 2013, 34 (1):  167-175.  DOI: 10.1016/S1872-2067(11)60475-0 Abstract ( 2084 )   [Full Text(HTML)] () PDF (599KB) ( 888 )   A Zr-based metal-organic framework (Zr-MOF) with both micropores and mesopores was prepared by the reaction of 1,4-benzenedicarboxylic acid (H2BDC) and ZrOCl2·8H2O with the aid of a citric acid (CA) chelating agent and a cetyltrimethylammonium bromide (CTAB) surfactant. This was followed by formation of a Ru@Zr-MOF catalyst from RuCl3·3H2O in a supercritical CO2-methanol solution. The catalyst was characterized by Fourier transform infrared spectroscopy, power X-ray diffraction, transmission electron microscopy, thermo-gravimetric analysis, N2 adsorption-desorption, X-ray photoelectron spectroscopy, and inductively coupled plasma-atomic emission spectroscopy. Ru particles with an average diameter of 2.3 nm were uniformly supported in the Zr-MOF. The catalytic performance of Ru@Zr-MOF for the hydrogenation of benzene and its derivatives was investigated and was found to be active and stable.

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Preparation and formation mechanism of Al-YNU-1 using highly acid-treated Fe-YNU-1 molecular sieve as a silica source WANG Peng-Fei, LI Jun-Fen, DONG Mei, QIN Zhang-Feng, WANG Jian-Guo, FAN Wei-Bin 2013, 34 (1):  176-184.  DOI: 10.1016/S1872-2067(11)60510-X Abstract ( 1789 )   [Full Text(HTML)] () PDF (903KB) ( 519 )   Al-YNU-1 molecular sieve was synthesized through the post-synthesis method from highly acid-treated Fe-YNU-1 in the presence of piperidine. The effects of silica sources, structure-directing agents, composition of raw materials, and crystallization conditions on the structure and Al content of Al-YNU-1 were investigated. Optimizing the Al and H2O amounts in the synthesis mixture, as well as the crystallization time and the acid treatment conditions applied to the as-synthesized lamellar precursors, produced a large increase in the content of Al in the Al-YNU-1 framework, to nearly double that of a sample prepared using deborated MWW as the silica source. To form Al-YNU-1, it is essential to remove most of the template molecules and framework Al species from the lamellar Al-MWW precursor by acid treatment, and to have a large number of defect sites within the Si source.

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Palladium-catalyzed synthesis of indole-3-alkynones via direct carbonylation of indoles LI Deng-Feng, DAN Shang, SHI Li-Jun, LANG Rui, XIA Chun-Gu, LI Fu-Wei 2013, 34 (1):  185-192.  DOI: 10.1016/S1872-2067(11)60491-9 Abstract ( 2134 )   [Full Text(HTML)] () PDF (550KB) ( 549 )   A new method has been developed for the Pd-catalyzed direct carbonylation of indoles with phenylacetylenes. The process involved the initial iodination of the indole to afford the corresponding 3-iodo-indole, which was subsequently carbonylated with a variety of different alkynes using Pd(0) to yield the indole-3-alkynones. In contrast to the traditional Pd-catalyzed oxidative carbonylation strategy, which involves the Pd(II)-mediated activation of the aromatic C–H bonds, the aromatic C–H bonds in the current process were activated by iodine oxidation, eliminating the problems associated with the reduction of Pd(II) to Pd(0) under the CO atmosphere. Following an extensive screening process, Pd(OAc)2/CuI was identified as the most efficient catalyst system for the reaction in the presence of a base and iodine as an oxidant under mild conditions (0.2 MPa CO, 90 oC). The reaction provided the desired products in moderate to excellent isolated yields (up to 94%) and good tolerance to a variety of different functional groups. The structure of a representative alkynone product (3he) was unambiguously verified by X-ray single crystal structure analysis. Furthermore, the carbonylation products underwent a three-component reaction with sodium azide and benzyl bromide to give the corresponding 1,2,3-triazole analogues in the absence of any catalyst, thus expanding the synthetic application of the current methodology.

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Catalytic epoxidation of cyclohexene over mesoporous-silica immobilized Keggin-type tungstophosphoric acid CAI Wen-Jia, ZHOU Yan, BAO Ren-Lie, YUE Bin, HE He-Yong 2013, 34 (1):  193-199.  DOI: 10.1016/S1872-2067(11)60459-2 Abstract ( 2254 )   [Full Text(HTML)] () PDF (572KB) ( 787 )   A series of aminosilylated mesoporous silica (SBA-15) samples with different contents of (3-aminopropyl)triethoxysilane (APTES), synthesized using a simple one-pot method, were used as hosts for immobilization of Keggin-type 12-phosphotungstic acid (H3PW12O40). The loading of H3PW12O40 increased with increasing content of grafted APTES. The obtained materials were calcined at different temperatures, and the tungsten species were highly dispersed inside the SBA-15 channels. The catalytic activities of these samples were tested in heterogeneous oxidation of cyclohexene using H2O2 as the oxidant. The effects of different loadings and treatment temperatures on the activities of the catalysts were also investigated. The catalysts calcined at 400 °C showed high catalytic activities and reusabilities.

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Enhanced phenol hydroxylation with oxygen using a ceramic membrane distributor CHEN Ri-Zhi, BAO Yao-Hui, XING Wei-Hong, JIN Wan-Qin, XU Nan-Ping 2013, 34 (1):  200-208.  DOI: 10.1016/S1872-2067(11)60512-3 Abstract ( 1817 )   [Full Text(HTML)] () PDF (727KB) ( 570 )   A CuO/TiO2 catalyst was prepared by impregnation and characterized by X-ray diffraction, transmission electron microscopy, and temperature-programmed reduction. Two types of dispersed species formed on the TiO2 surface, which were possibly isolated and polymeric CuO species. The CuO catalyst interacted strongly with the TiO2 support. A porous ceramic membrane was used as a distributor to control the supply of oxygen in phenol hydroxylation over the CuO/TiO2 catalyst. Compared to a direct feed of oxygen without a membrane, the yield of dihydroxybenzene (DHB) increased by 13% using a porous ceramic membrane with a pore size of 0.5 µm as an oxygen distributor. This is because the membrane distributor produced numerous small oxygen bubbles, increasing the volumetric oxygen transfer coefficient and gas-liquid mass transfer. Optimizing reaction conditions resulted in a yield of DHB of 2.5%. Scanning electron microscope observation of the used ceramic membrane showed that it possessed excellent thermal and chemical stability.

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Some innovation ideas and practices on progresses from catalytic directional fundamental research to industrial applications —to celebrate the 90 birthday of Mr. Min Enze XIE Zai-Ku 2013, 34 (1):  209-216.  DOI: 10.3724/SP.J.1088.2013.20926 Abstract ( 1975 )   [Full Text(HTML)] () PDF (399KB) ( 1001 )   Mr. Min Enze ever said that it was very important to carry on directional fundamental research during the development and application of new industrial technology. Under the guidance of Mr. Min’s thoughts on innovation, we keep on making exploration and practice on new technology in recent years. One of the important and effective ways for innovation on petrochemical technology is to combine advanced catalytic materials with chemical engineering processes. It would promote the development of petrochemical technology by introduction and integration of new materials, new technology and new processes into the conventional petrochemical area. In this paper, we summarize some of our innovation practices on development of new porous catalytic materials and new petrochemical technology during recent years, such as the application of new porous composite materials on conventional industrial processes, new green reaction process via advanced catalysts, several progresses on process coupling and intensification, etc. We intend to stimulate thought and creative ideas on combination of material science and chemical engineering as well as their applications.

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Recent advances in coal to chemicals technology developed by SINOPEC CHEN Qing-Ling, YANG Wei-Min, TENG Jia-Wei 2013, 34 (1):  217-224.  DOI: 10.3724/SP.J.1088.2013.21056 Abstract ( 2173 )   [Full Text(HTML)] () PDF (597KB) ( 1061 )   Coal to chemicals technology has made a breakthrough in recent years in China, mainly driven by high crude oil price and strong market demand for chemicals. The latest advances in coal to chemicals technology developed by SINOPEC were reviewed. SINOPEC methanol to olefins (S-MTO) technology has been commercialized successfully in 2011. Industrial demo tests of SINOPEC methanol to propylene (S-MTP), syngas to ethylene glycol, methanol to xylene (MTX) and SNG processes are being carried out. A great progress has been made in the research area of methanol to aromatics (MTA), syngas to olefins (GTO) and acetic acid hydrogenation technology etc. in laboratory scale.

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Catalysts with catalytic sites highly dispersed from layered double hydroxide as precursors AN Zhe, HE Jing, DUAN Xue 2013, 34 (1):  225-234.  DOI: 10.3724/SP.J.1088.2013.20870 Abstract ( 2092 )   [Full Text(HTML)] () PDF (792KB) ( 1033 )   Layered double hydroxides (LDHs) refer to a class of clays with diverse brucite-like layers and intercalated anions, which have attracted increasing interest in the field of catalysis. Benefiting from the atomic-scale distribution of metal cations in the brucite-like layers and the ordered arrangement of diversified interlayer anions, the LDHs display great potential as the precursors to prepare catalysts in that the catalytic sites could be highly dispersed. The approaches to prepare catalysts from LDHs as precursors include, but not limited to, exfoliation of the brucite-like layers, confinement by the brucite-like layers, intercalation, and/or nanosheet arrays. The latest development of the catalyst preparation using LDHs as precursors was mainly summarized.

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Support Effects on Properties of Ce-Zr Mixed Oxide-Supported Gold Catalysts in Oxidation of Methanol ZHANG Hong-Peng, LIU Hai-Chao 2013, 34 (1):  235-242.  DOI: 10.3724/SP.J.1088.2012.20543 Abstract ( 2268 )   [Full Text(HTML)] () PDF (415KB) ( 767 )   Ce-Zr oxide-supported nano-sized Au catalysts Au/Ce1-xZrxO2 (x = 0, 0.2, 0.4, 0.6, 0.8) were prepared by a deposition-precipitation method. Their catalytic properties were examined in both the combustion of methanol and the selective oxidation of methanol to methyl formate. The composition and structure of the catalysts were characterized by complementary methods including nitrogen physisorption, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and high resolution transmission electron microscopy. Their acidity and basicity were probed by CO2 and NH3 temperature-programmed desorption and also Fourier transform infrared spectroscopy for CO adsorption. The characterization results showed that the catalysts possessed similar particle size and phase of the Ce1-xZrxO2 supports, and their Au nanoparticles were of around 3.0 nm mainly in the state of Au0. In the CH3OH combustion reaction (1% CH3OH + 14% O2), the activity of the Au/Ce1-xZrxO2 catalysts decreased with decreasing the Ce contents in the Ce1-xZrxO2 supports. Similar change was also found in the methanol selective oxidation (6% CH3OH + 3% O2), while the selectivity to methyl formate increased with decreasing the Ce contents. Such changes in the catalytic activity of the Au/Ce1-xZrxO2 catalysts were in positive parallel with their oxygen storage capacity values, which reflect the number of the lattice oxygen atoms active for the methanol oxidation. The support effects on the selectivity for methyl formate were clear not due to effects of the supports on the acid-base properties of the catalysts but to the effects on the active lattice oxygen atoms on catalyst surfaces and consequently their reducibility. Such understanding on the support effects provides useful information for design of oxide-supported Au catalysts with improved activity or selectivity for the targeted oxidation reactions.

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Highly Efficient Synthesis of Methyl Ethyl Ketone Oxime through Ammoximation over Ti-MOR Catalyst DING Jiang-Hong, XU Le, XU Hao, WU Hai-Hong, LIU Yue-Ming, WU Peng 2013, 34 (1):  243-250.  DOI: 10.3724/SP.J.1088.2013.20860 Abstract ( 2699 )   [Full Text(HTML)] () PDF (489KB) ( 857 )   The liquid-phase ammoximation of methyl ethyl ketone (MEK) to methyl ethyl ketone oxime (MEKO) with ammonia and hydrogen peroxide was conducted over MOR-type titanosilicate (Ti-MOR), which was prepared from highly dealuminated mordenite and TiCl4 vapor by a secondary method of gas-solid phase reaction. The effects of reaction parameters on this reaction were studied systematically in a bath-type reactor. Based on the optimized reaction conditions, Ti-MOR was further employed as the catalyst for the ammoximation of MEK to MEKO in a continuous slurry reactor. This catalyst exhibited good catalytic activity and excellent MEKO selectivity in comparison to TS-1. Moreover, in terms of ketone conversion, oxime selectivity, coke resistance, and lifetime, Ti-MOR possessed the same advantages as the Ti-MWW catalyst prepared by structural rearrangement.

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A new method for preparation of cylohexanol from benzene LOU Shu-Jie, XIAO Chao-Xian, SUN Geng, KOU Yuan 2013, 34 (1):  251-256.  DOI: 10.3724/SP.J.1088.2013.20949 Abstract ( 1760 )   [Full Text(HTML)] () PDF (435KB) ( 584 )   A new process to prepare cyclohexanol from benzene has been developed by a three-step approach. First, the benzene is selectively hydrogenated to cyclohexene by using soluble Ru nanoparticles as catalyst. Second, the epoxidation of cyclohexene can be achieved by literature methods. Then, in the end, the hydrogenation of cyclohexane oxide was performed by using anhydrous Raney-Ni as catalyst. It was found that in step one and three, the overall yield to produce cylohexanol from benzene reaches 14% under the optimized reaction conditions.

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Rh/CeO2-SiC as a catalyst in partial oxidation of ethanol for hydrogen production LI Xing-Yun, WANG Fa-Gen, PAN Xiu-Lian, BAO Xin-He- 2013, 34 (1):  257-262.  DOI: 10.3724/SP.J.1088.2013.30105 Abstract ( 1798 )   [Full Text(HTML)] () PDF (1293KB) ( 857 )   An Rh catalyst supporting on CeO2-SiC composite has been designed for partial oxidation of ethanol for hydrogen production. X ray diffraction and transmission electron microscopy results show that CeO2 nanoparticles with an average size of 4 nm are well dispersed on SiC surface, which further acts as a support of Rh nanoparticles. The obtained Rh/CeO2-SiC catalyze efficiently partial oxidation of ethanol. At 700 oC, the ethanol conversion is 100%, with a H2 selectivity of 50%, CO selectivity of 13%. No deactivation is observed within 40 h time on stream. Furthermore, the ethanol conversion and the H2 selectivity increase with the rising temperature. No noticeable carbon deposition is observed on the catalyst after reaction. The rather low CO selectivity and little carbon deposition may be attributed to the unique property of good heat conductivity of SiC and the carbon elimination ability of CeO2 with active oxygen species.

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Catalytic hydrogenation of nitrobenzene to p-aminophenol over Ni/SiO2 and SO3H-C/SBA-15 solid acid mixed catalyst BAI Yu-Ting, ZHU Xue-Cheng, ZHANG Li-Xiong, XU Nan-Ping 2013, 34 (1):  263-271.  DOI: 10.3724/SP.J.1088.2013.20846 Abstract ( 1926 )   [Full Text(HTML)] () PDF (551KB) ( 817 )   Mechanical mixed catalysts comprised of 20% Ni/SiO2 and carbon-silica mesoporous composite functionalized with sulfonic acid groups (SO3H-C/SBA-15) were used for hydrogenation of nitrobenzene to p-aminophenol. The effects of the mass ratio of Ni/SiO2 to SO3H-C/SBA-15, reaction pressure, temperature, stirring speed, and reaction time were examined. The catalysts were characterized by X-ray diffraction, H2 temperature-programmed desorption, transmission electron microscopy, infrared spectroscopy, and thermal gravity analysis. The results indicated that Ni is uniformly dispersed on the support, forming a single active center. The SO3H-C/SBA-15 solid acid with 40% carbon content exhibits the highest acid density. The mixed catalyst with a Ni/SiO2 to SO3H-C/SBA-15 mass ratio of 1:6 shows the highest activity. Under optimized reaction conditions of a reaction temperature of 120 ºC, reaction pressure of 0.6 MPa, stirring speed of 1200 r/min, and reaction time of 3 h, the nitrobenzene conversion of 85.1% and p-aminophenol selectivity of 23.8% were obtained. The reaction result is comparable with those on most mixed catalysts containing Pt and solid acid reported in the literature.

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Impact Factor of Chinese Journal of Catalysis increases from 0.752 to 1.171 — congratulations and thanks to the authors of our most cited articles 2013, 34 (1):  272-274.  Abstract ( 1100 )   [Full Text(HTML)] () PDF (183KB) ( 705 )

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Author Guidelines 2013, 34 (1):  278-281.  Abstract ( 837 )   [Full Text(HTML)] () PDF (219KB) ( 408 )