TY - JOUR
AU - Jin, Zhonghao
AB - Abstract Progressing green chemical technologies is significant to the sustainable development of chemical industry in China, as the energy and environment problems increasingly became great challenges to the whole society. The scientific connotation of sustainable energy chemical engineering can be generalized as green carbon/hydrogen science which means optimization of carbon/hydrogen atom economics based on high efficient catalysis and low-carbon emission. This review illustrated recent advances in developing sustainable technologies for applied catalysis in chemical industry of China, including the fields of high efficient conversion of heavy oil, green petrochemical catalytic technologies, clean utilization of coal and natural gas, promoting sustainable resources and clean energy, etc. Moreover, from the view of industrial point, some important common scientific problems were discussed and summarized, such as the relation between molecular diffusion and catalyzing efficiency, homogeneous catalysis in heterogeneous catalysts, in situ or operando characterization of industrial catalysis, etc., aiming to supplying a forward roadmap to academia and/or industry. applied catalysis, catalytic efficiency, green carbon/hydrogen science, green petrochemical technology, coal chemical technology, biomass energy technology INTRODUCTION At present, there are many challenges on sustainable development of energy chemical industry in China, including inferior energy structure, shortage of high-quality resources such as oil and natural gas, low-energy consuming efficiency and severe environmental pollution, etc. Therefore, the efforts devoted to green technique, low-carbon emission and improving resource utilization efficiency have become a current social consensus, which is also desired for sustainable development of the energy and chemical industry. Since the concept of green chemistry proposed in the early 1990s, it has received extensive attention and become firmly entrenched both in academia and industry during recent two decades [1,2]. The general principles of green chemistry guide the design of environmentally benign products and processes. It is known that the efficient utilization of carbon/hydrogen resources and carbon recycling are of great importance for the sustainable development of chemical industry, and there are many related challenging scientific issues to be solved. A simplistic carbon cycle relating the utilization of fossil resources, the conversion of biomass and the recycling of CO2 is shown in Fig. 1. Actually, however, the real carbon cycle has not achieved because efficiencies of most steps in the scheme were still low, leading to the tremendous net emission of CO2 to the environment. Therefore, devoting to realizing entire carbon cycle, He et al. [3,4] recently put forward the concept of green carbon science, which was defined as the study and optimization of the transformation of carbon-containing compounds in relevant processes, involving in the entire carbon cycle from carbon resource processing, carbon energy utilization, CO2 fixation and carbon recycling to utilize carbon resources efficiently and minimize net CO2 emission. On the latest 485th Xiangshan-Science conferences 2014, this concept was further discussed as one of theme reports, coupling with concept of green hydrogen science [5] which refers to the low-carbon production of hydrogen, as well as its highly efficient storage, etc. Figure 1. Open in new tabDownload slide The simplified carbon cycle and related processes for green carbon science. Adapted from [4] © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Figure 1. Open in new tabDownload slide The simplified carbon cycle and related processes for green carbon science. Adapted from [4] © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Five main feasible ways can be summarized as follows for implementation of sustainable development of chemical industry: (1) developing higher efficient catalytic technologies for petroleum processing and petrochemical industry, including higher efficient catalytic materials, process coupling, combination and intensification; (2) developing green processes with higher atom economy and low emission or pollution; (3) developing catalytic technologies based on diversification of raw materials other than oil; (4) developing technologies of carbon capture, utilization and storage (CCUS) and solar energy conversion technologies; (5) developing technologies for green energies, such as low-carbon hydrogen production and highly efficient storage of hydrogen. Since most of the processes in energy chemical industry involving catalysis process, it is a key issue on developing catalysis science and technology to achieve the goal of efficient utilization of resources and green production. Herein, we will review recent progress on applied catalysis for sustainable development of chemical industry in China, including five main aspects such as the high efficient utilization of oil resources, green petrochemical catalytic processes, coal chemical catalysis technologies, catalysis on syngas and natural gas resources and catalysis on renewable, clean energy and carbon dioxide utilization, and so on. RECENT PROGRESS IN APPLIED CATALYSIS ON GREEN CHEMICAL INDUSTRY IN CHINA Catalysis on high efficient utilization of oil resources Refinery catalytic technology needs continuous upgrading and innovation, with the trends of increasingly heavier crude oil resources and desires of cleaner fuel products. Besides, lots of measures on refining and green products have been taken, such as new desulfurization and denitration techniques to meet the demands of oil products of high quality. There are two important methods in converting heavy oil into light fuel and diesel, fluid catalytic cracking (FCC) and residue fluid catalytic cracking (RFCC) followed with hydrocracking processes [6]. As for FCC or RFCC technologies, the main challenge is to improve the catalytic conversion of heavy oil and maximize light oil production. Recently, Zhou et al. synthesized a Nest Shape Y zeolite (called NSY) with hierarchical porosity by in situ growth of NaY zeolites on grains of Kaolin clay [7]. This NSY zeolite catalyst has higher gasoline production and lower diesel production than the conventional ones. Shen et al. synthesized a kind of mesoporous ZSM-5 by desilication with base treatment. They found that more yield of light olefins could be obtained in catalyzing heavy oil from Daqing oil field [8]. Bao et al. reported the synthesis of Kaolin/NaY/MCM-41 composite [9], by which higher yield of gasoline and diesel oil, and lower tail gas and coke than conventional catalysts were found in the catalytic conversion of heavy oil, because of the obvious improvement of hierarchical porosity. It is worth noting that better catalytic performances of all of the above-mentioned catalysts should mostly attribute to their richer porosity than that of conventional catalysts. Except for developing hierarchical porous structure, employing larger microporous zeolites as additives in catalysts may be another choice to improve the catalytic performance. As shown in Fig. 2, we can find more and more zeolitic with larger micropores have been employed as additives in the FCC catalysts [10]. In a word, developing applicable FCC catalysts should pay close attention to hierarchical zeolites and/or larger microporous zeolites in the future. Figure 2. Open in new tabDownload slide Trend on pore sizes of zeolitic additives for FCC catalysts. Reproduced with author's permission from [10]. Figure 2. Open in new tabDownload slide Trend on pore sizes of zeolitic additives for FCC catalysts. Reproduced with author's permission from [10]. In the field of hydrocracking of heavy oil, Zong et al. have carried out systematic researches aiming to high efficient utilization of carbon resources. Based on the analysis of heavy oil on molecular level, they invented novel hydroprocessing catalysts on selective hydrogenation of polycyclic aromatic hydrocarbons (PAHs), developed slurry bed hydrocracking technologies, performed coupling and intensification of catalytic distillation and separation processes, and integrated coupling of heavy oil cracking with biological refining process of micro algae and CO2 CCUS [11–13]. Moreover, basic scientific problems on colloid stability control, hydrodynamic and mass transfer characteristics of slurry bed reactor etc. have also been studied. In the area of desulfurization of gasoline, application of S-Zorb technology is a big advance to be mentioned, which was first developed by Conoco Phillips Company and then became an acquisition technology of Sinopec including a new generation of special adsorbent and fluidized bed process [14]. This special adsorbent is composed of zinc oxide, nickel oxide and silica–alumina. By S-Zorb technology, sulfur can be transferred from oil molecules onto the adsorbent and the remaining hydrocarbon fragments can be released out. Because sulfur components are removed in time, chemical equilibrium will continue moving to desulfurization side, which would result in yield of fuel oil high to 99.5%. Therefore, S-Zorb technology by adsorption-desulfurization method can achieve deeper desulfurization than traditional hydrodesulfurization technologies [15]. And after the adsorption and catalytic process, the adsorbent or catalyst can be regenerated under enriched oxygen environment in the reactor. Moreover, it takes other advantages such as lower loss of octane number (less than 1%), lower consumption of hydrogen and energy, lower requirement on purity of hydrogen, and so on [16]. The products by this technology can reach the National IV and V standard for gasoline of which S content is less than 50 and 10 ppm, respectively. By the way, there are other new catalytic technologies developed for hydrodesulfurization of gasoline, e.g. Li et al. has successfully developed a fixed-bed catalytic technology for ultradeep desulfurization of gasoline, which would possess advantages for easier operation and regeneration procedure, as well as lower operation cost [17]. Then, with the increase of processing capacity of FCC units and more heavy oil components in the feedstock, large amount of low-quality diesel distillates, especially the light cycle oil (LCO) has been produced. Since it has high sulfur, nitrogen and aromatic content, low cetane number and poor stability, it needs further processing such as by hydrofining or hydroupgrading processes to maximize the diesel production [18]. In recent years, MCI technology, a novel hydrotreating process for upgrading low-quality diesel distillates, has been successfully developed by Fang et al. This process can perform hydrotreating reactions (HDS and HDN), which would greatly improve cetane number of diesel product under nearly the same operating conditions of hydrotreating process [19,20]. On the other hand, maximizing the production of BTX aromatics is another feasible way of processing LCO, which includes three main steps, hydrofining, selective hydrogenation cracking and transformation of middle distillate. Nie et al. referred that one of the difficulties for this way was the selectively hydrocracking of PAHs i.e. tetralin, of which optimizing the coordination of acid sites and metal sites on catalysts, as well as reducing the distance between this two sites could be a potential approach to further promote the reaction activity and to improve objective product selectivity [21]. Zheng et al. also carried out some studies and got some positive results on selective catalytic conversion of PAHs components in LCO to BTX aromatics [22]. Besides, alkylate gasoline, which is an important component of reformulated gasoline with high octane number, has received the widespread attention in recent years. Alkylate gasoline can be produced by alkylation of isobutane with butane from refinery by-products. However, current alkylation processes use concentrated sulfuric acid or hydrofluoric acid as catalysts, which would inevitably bring equipment corrosion and environment pollution. Chemists are looking for environmental friendly alternatives instead of the conventional catalysts. Recently, ionic liquid-catalyzed alkylation has aroused much attention because of their clean catalytic properties in alkylation processes. However, common acidic ionic liquids such as aluminum chloride acid ionic liquids have a lower selectivity of alkylate gasoline than conventional liquid acids [23]. Xu et al. found that the selectivity of alkylate gasoline can be improved by adding certain metal chlorides to the aluminum chloride-based ionic liquids [24]. The main challenge is the miscibility and stability of the added components in the ionic liquids. Therefore, they invented a novel multicenter composite ionic liquid, [Et3NH]+[AlCuCl5]−, which presented high selectivity of favorable products, long life of catalysts, and importantly without any problem of self-phase separation aroused from miscibility [25,26]. Based on such new ionic liquids catalyst and alkylation process, a 100 kt/a scale industrial plant has been built up recently. Catalysis on green petrochemical processes It is known that basic organic raw materials such as olefins, aromatics and organic monomers containing oxygen/nitrogen elements are mainly produced from petrochemical industry. However, many current petrochemical processes still suffered from high-energy consumption and/or large amount of wastes or pollutions. Sustainability in petrochemical industry is desired all over the world, which is especially significant in China, encouraging more researchers to develop innovative technologies on energy saving, green processes, environmental safety, etc. One typical example is the green production process of caprolactam developed by Sinopec, which consisted of three main innovations (Table 1) [27]. For the oximation process of cyclohexanone, the traditional process contains four steps: ammoxidation, hydroxylamine, oximation and ammonium decomposition, while only one step was needed in new green process by TS-1 zeolite catalyst. Unfortunately, conventional TS-1 zeolite catalyst cannot reach the conversion and stability requirement in industry. Lin et al. invented a new hollow structured TS-1 zeolite (called HTS) by using a so-called multistage crystallization method [28] which exhibited higher conversion and stability than conventional TS-1 zeolite catalyst. The second innovation is on the rearrangement process of cyclohexanone oxime. By employing radial flow moving-bed reactor as well as zeolite catalyst consisted of pure silica, a gas-phase Beckmann rearrangement process has been developed in absence of ammonia sulfate, in advantage of environmental benign and low cost. The third innovation is on the purification process of caprolactam. Amorphous Ni alloy integrated with magnetically stabilized bed reactor has been used to dramatically improve the efficiency of hydrogenation and catalysis utilization. Based on the commercial application results, the investment of caprolactam production plant decreased 70%, 10% operation costs was saved and atom utilization rate increased from 60 to 90%, respectively, and more importantly, waste-free was realized. Since green caprolactam production technology practiced green chemistry concepts and gained great economic and social benefits, it can be considered as a successful example of green chemistry. Table 1. Three generations of green production technologies of caprolactam developed by Sinopec. Adapted from [27] © 2013 Science China Press. Open in new tab Table 1. Three generations of green production technologies of caprolactam developed by Sinopec. Adapted from [27] © 2013 Science China Press. Open in new tab Selective oxidation is another important subject in green chemical technologies. Among them, new green technologies of olefin epoxidation have attracted great attention for recent decades. One of the green and efficient routes for preparation of propylene oxide (PO) is hydrogen peroxide-propylene oxide (HPPO) process with hydrogen peroxide as oxidant and titanium silicates as catalytic materials. A HPPO technology based on a new titanium silicate catalyst called HTS has been developed by Sinopec [29]. Pilot test has been carried on for more than 4000 h, approving excellent stability of the catalyst [30]. Employing cumene hydroperoxide (CHP) solution as oxidation regent, another route for PO production was developed by Jin et al. in China. The reported Ti/HMS catalysts possessed typical mesoporous structure and tetracoordinated Ti species in the framework [31]. After treating with silane, they found that the hydrophobicity of Ti/HMS was obviously improved, leading to excellent catalytic activity and stability and PO selectivity. Pilot test as long as 2400 h showed the high CHP conversion over 99.0% and the selectivity of PO as high as 97.0% [32]. Of course, there are other potential routes for green technologies of olefin epoxidation, for example, Xi et al. ever reported a novel heteropolyphosphatotungstate catalysts which performed special reaction controlled phase transfer function [33] and can be coupled with direct production of hydrogen peroxide by ethyl-anthraquinone/ethyl-anthracene hydroquinone method. New processes based on this special catalyst are under development, such as in the production of propylene epoxide and epoxy chloropropane [34] which will be discussed in the following section. There is another example on green technology which involves in the production of monoethylene glycol (MEG) by catalytic hydration of ethylene oxide (EO). Many heterogeneous catalysts with ion-exchanged resin (IER) immobilized with quaternary phosphonium halides, polymeric organosilane ammonium salt and macrocyclic chelating compounds, have been studied to reduce energy consumption. However, the major challenge is stability of catalyst, because of the easy swelling of resins under reaction conditions. He et al. has designed resin/carbon nanotuble (CNT) composite catalyst to overcome this problem [35]. Adding CNT into resin could greatly enhance thermo stability and anti-swelling capability during the reaction of hydration of EO. It was found that the glass transition temperature (Tg) of this composite catalyst increased from 125 to 132°C. And the swelling quality of the composite could be reduced to almost half of PS-DVB. Furthermore, the normal reaction temperature of hydration of EO can be increased from 60 to 100°C. The enhanced thermal stability of the polymer composite facilitated the reaction operation at higher temperature, leading to reduction of the feedstock/water ratio to almost half (from 20–25 to less than 12), and greatly cutting down the energy consumption in the whole process. The obtained polymer/MWNTs composite performed very well in the life test of catalytic hydration of EO, in which there was no obvious decline in conversion or selectivity after 2200 h. Very recently, they reported a kind of graphene-reinforced nanocomposite IERs which also exhibited excellent anti-swelling property, thermal stability of the materials and good catalytic performances [36]. Catalysis on coal-based methanol conversion technologies For the sustainable development of energy chemical industry, catalytic technologies based on diversification of raw materials other than oil should attract more and more attentions. Since coal is one of the main energy resources in China, it is a good choice to develop chemical industry involving coal conversion as important supplement to the petrochemical industry. For example, by methanol-to-olefins (MTO) or methanol-to-propylene (MTP) process, methanol can be converted into ethylene, propylene and other light olefins which correlated petrochemical with coal chemical industry. Now in China, MTO technique has been successfully industrialized by Dalian Institute of Chemical Physics of Chinese Academy of Sciences (DICP) and Sinopec Shanghai Research Institute of Petrochemical Technology (Sinopec SRIPT), successively. One of the main challenges in MTO or MTP is how to maximize the yield of light olefins and prolong the lifetime of catalyst. A great deal of research about catalytic materials, reaction mechanism as well as chemical process has been carried out in the last years. Many mechanism studies have demonstrated that the reaction of methanol conversion to light olefins is controlled by molecular diffusion and possesses a complex hydrocarbon pools mechanism. Liu et al. developed the DMTO process which was based on SAPO-34 zeolite catalysts and fluidized bed reactor [37]. They first observed the existence of hepta MB+/HMMC in the MTO process by using extra large cage of novel molecular sieve material, DNL-6 [38], which confirmed the rationality of hydrocarbon pools mechanism. In addition, 13C isotope tracer experiments further verified the important role of the intermediate in the conversion of methanol and the formation pathway of light olefins from carbon cation intermediate (Fig. 3). Figure 3. Open in new tabDownload slide Methylbenzenes carbenium ions as intermediates and the likely path for olefin generation. Adapted from [38] © 2012 American Chemical Society. Figure 3. Open in new tabDownload slide Methylbenzenes carbenium ions as intermediates and the likely path for olefin generation. Adapted from [38] © 2012 American Chemical Society. Xie et al. has carried out systematic studies on catalytic technologies of methanol conversion to light olefins and aromatics for many years. They have prepared a low wear industrial fluidized MTO catalyst with high yield of olefins by adjusting acidity, crystal morphology and multiscale porosity of SAPO-34 zeolite [39–41]. And a new chemical process including the fast fluidized bed reaction-regeneration technology has also been developed into application. In addition, they have conducted molecular simulation studies on reaction mechanism of hydrocarbon pools. Except for the side-chain and paring mechanism based on methylbenzenes carbenium ions intermediates [42,43], they put forward a new mechanism involving the olefin-derived carbenium ions intermediates (Fig. 4) [44]. Furthermore, they are also developing zeolitic catalyst for MTP process. By adjusting porosity, crystal morphology and sizes, they have successfully prepared a kind of full crystalline hierarchical zeolite catalyst with better diffusion and higher catalytic performance than conventional catalysts [45]. It is reported that the life of the catalyst has exceeded 2000 h. The MTP pilot test with 5 kt/a scale has already been completed recently. Figure 4. Open in new tabDownload slide Reaction network of the MTO conversion in acidic zeolites based on olefin derived carbenium ions intermediates mechanism. Adapted from [44] © 2013 Elsevier Inc. Figure 4. Open in new tabDownload slide Reaction network of the MTO conversion in acidic zeolites based on olefin derived carbenium ions intermediates mechanism. Adapted from [44] © 2013 Elsevier Inc. Methanol can also be directly converted to aromatics (MTA technology). Recently, Wei et al. has developed a Zn/Ag-modified ZSM-5 catalyst [46], and realized a continuous reaction-regeneration process by integrating fluidized bed of aromatization with the catalyst regeneration process, and controlling the amount of coke on catalysts in aromatization reactor [47]. A pilot test with 10 kt/a showed that the single-pass yield of aromatics arrived at 55∼65% and the total yield of aromatics reached about 80%. Alkylation of toluene with methanol to xylene (MTX) technology has been successfully developed by Sinopec SRIPT, which employed a kind of nanozeolite catalyst [48,49] and a new MTX catalytic process [50,51]. It has been reported that the world's first industrial plant with 200 kt/a scale was run up at 2013, in which the lifetime of catalyst exceeded 3 months with the conversion of toluene and methanol to 30 and 100%, respectively, and the selectivity of xylene reaching up to 70%. On the other hand, Liu et al. from DICP has developed a fluidized bed catalyst to solve the fast deactivation problem of zeolite catalysts [52], and a pilot test had been taken on a fluidized bed reactor. Catalysis of syngas and natural gas resources Fischer–Tropsch synthesis (FTS) is a key technology for converting the syngas derived from non-petroleum carbon resources, such as coal and natural gas, into valuable fuels and chemicals ranging from C1 to C120. Since then, FTS has revived great interest of many researchers. High-performance catalyst, reactor, procedure and their optimal integration are the most important features of a high-performance FTS process. Recently, combined with the theory calculation, process simulation and experimental studies, Li and co-workers investigated the structure and its transition of iron-based catalyst in the process of FTS [53]. Especially by identifying the effects of CO pretreatment and K promoter [54] on the surface structure of FexCy active phase and catalytic performance [55], a new perspective for understanding the CO dissociation, CH4 formation and chain growth was received, as shown in Fig. 5. Additionally, an inherent relationship between the preparation method and reaction conditions-catalyst structure-catalytic performance has also been revealed [56]. Based on these research findings, a unique FTS catalyst and complete technological process for high-temperature slurry phase reactor has been developed [57–59], which has been successfully practiced at industrial scale for 100 kt/a. This innovative FTS process effectively achieved a heat balance and improved the energy utilization efficiency of whole system due to the coproduction of high-grade steam and power generation by raising of the reaction temperature from 200–250°C to 260–290°C. Figure 5. Open in new tabDownload slide (a) Potassium promoter (K2O) modifies the crystallographic orientation in catalysts. Adapted from [54] © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) Morphology of χ-Fe5C2 investigated under CO and H2/CO pretreatment. Adapted from [53] © 2012 Elsevier Inc. Figure 5. Open in new tabDownload slide (a) Potassium promoter (K2O) modifies the crystallographic orientation in catalysts. Adapted from [54] © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) Morphology of χ-Fe5C2 investigated under CO and H2/CO pretreatment. Adapted from [53] © 2012 Elsevier Inc. There are still some scientific challenges in the research area of FTS, among which the selectivity control is one of the most attractive and difficult challenges. Over conventional FT catalysts, the hydrocarbon products generally follow the Anderson–Schulz–Flory (ASF) distribution, owing to a polymerization model of the chain growth process. The ASF distribution of FTS imposes a limit to the maximum selectivity of 45 and 30% attainable for gasoline-range and diesel-range products, respectively. Moreover, the yield of CH4 and heavy hydrocarbons are usually significantly higher than that predicted by the ASF distribution. Therefore, the development of novel FTS catalyst for optimizing the product distribution and improving the selectivity for gasoline-range and diesel-range products has acquired more and more attentions. Recently, Wang et al. reported an encouraging progress to overcome the ASF distribution by employing bifunctional FTS catalyst based on zeolite and metals [60]. During the FTS process over these catalysts, FTS products catalyzed by the active metal (i.e. cobalt) phase are hydrocarbons with wide distribution and then the acid sites in zeolites can catalyze the secondary conversions of these heavy hydrocarbons, such as hydrocracking and isomerization. Employing the designed Ru/meso-ZSM-5 composite as catalyst, the selectivity of CH4 decreased to about 5%, while the selectivity for C5–C11 increased to about 81% with a ratio of isoparaffins to n-paraffins of about 2.7, indicating the significantly higher selectivity for gasoline-range products than the ASF distribution (maximum ca. 45%). Furthermore, a high selectivity for C10–C20 to reach about 60–65% was found over Ru/CNT [61]. With the rise of coal chemical industry, techniques of ethylene glycol (EG) production with syngas that derived from coal or natural gas have drawn much attention. Compared with traditional route via vapor phase oxidation of ethylene into epoxide and followed by consequent hydration, better atom economic value can be achieved by the syngas route. In recent years, a research team from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences has developed a series of Cu-Cr supported catalysts for the vapor phase catalytic synthesis of oxalate ester and the corresponding process flow, and investigation on the NO production has also been carried out [62,63]. The process of vapor phase catalytic synthesis of oxalate ester by CO and hydrogenation of dimethyl oxalate into EG has been fully tested in a pilot plant with a capacity of 300 t/a demo plant with a capacity of 10 kt/a in succession. Moreover, an industrial scale plants with 200 kt/a capacity has been built in Tongliao, Inner Mongolia [64]. There are also other accessible reports about this technology, for example, an oxidative dehydrogenation catalyst with low noble metal content for the CO refining and a coupling catalyst of CO and methyl nitrite into dimethyl oxalate (DMO) has developed by Sinopec SRIPT [65], by combining the CO coupling and NO oxidative esterification. A pilot plant with a capacity of 1000 t/a has been completed by this process, with the CO single-pass conversion to more than 80% and the selectivity of DMO reaches more than 99%. Then an industrial scale plants with 200 kt/a capacity has been built in succession. It is also reported that a team from Tianjin university had completed a pilot plant with a capacity of 200 t/a recently [66]. Besides, Zhao et al. recently reported a Pd catalyst supported by nanocarbon fiber which showed high catalytic performance with the methyl nitrite single-pass conversion of more than 85% and the selectivity of EG close to 100%, indicating an alternative route on the choice of catalyst support [66]. In a word, massive research studies and many pilot tests have been made on the vapor phase synthesis of oxalate ester in recent years, which indicates that this technology becomes more and more mature in China. In the future, more attentions will be paid on the optimum of process flow and the NO cyclic utilization, etc. In the conversion of natural gas resources, converting natural gas to high-valued chemicals and liquid fuels through C1 chemistry is a challenge to catalysis science. Currently, indirect route is the method used widely in the conversion of methane. Methane is firstly transformed into syngas by reforming with H2O, O2 and CO2; then the syngas was converted into higher hydrocarbons or lower olefins by corresponding chemical routes, such as FTS and MTO. Unfortunately, these multistep processes usually exhibited low efficiency, high costs and enormous CO2 emission. Reversely, the direct route is a promising method in term of possessing simple process flow, low-energy consumption and CO2 emission. To achieve the direct conversion of CH4 efficiently, the challenges lie in cleaving of the first C–H bond, while suppressing further catalytic dehydrogenation, and avoiding both CO2 generation and coke deposition, which initiated a worldwide research surge to explore the selective activation and orient transition of methane. Very recently, Bao et al. have made a significant progress on the direct conversion of methane, in which carbon atom efficiency is close to 100% [67]. They found that the synthesized single iron sites embedded in a silica matrix enable direct, non-oxidative conversion of methane, exclusively to ethylene and aromatics (benzene and naphthalene) via initiating methyl radicals and a series of vapor phase reactions under high temperature (Fig. 6). This finding anticipated that the direct conversion of methane is possible to be commercialized based on the development of catalysis science. Figure 6. Open in new tabDownload slide High efficient catalyst with single iron sites embedded in a silica matrix for direct, non-oxidative conversion of methane to ethylene, aromatics, and hydrogen. Adapted from [67] © 2014 American Association for the Advancement of Science. Figure 6. Open in new tabDownload slide High efficient catalyst with single iron sites embedded in a silica matrix for direct, non-oxidative conversion of methane to ethylene, aromatics, and hydrogen. Adapted from [67] © 2014 American Association for the Advancement of Science. Catalysis on renewable, clean energy and carbon dioxide utilization As the rapid decrease of fossil fuel reservoir, the utilization of renewable feedstock attracts more and more attentions in recent years. It is expected that the industrialization of some emerging biomass energy technology will be achieved in the next 10 or 20 years. Up to date, however, the development of the biomass energy technologies is still unbalanced and far from blooming [68]. Few of them, such as march gas technology, has been found commercial applications; the others, for instance biomass power, biomass briquettes combustion, bioethanol and biodiesel, are still difficult to reach the commercial requirement and need more state support; more researches are still in the lab scale. Enze Min is the founder in the field of biomass conversion in China [69]. A ‘Min Enze Energy Chemical Industry Award’ has been jointly set by the Chinese Academy of Engineering (CAE) and Sinopec groups to promote the progresses of biomass energy technology and encourage the outstanding contributors in this field. In the biomass fuel field, Du et al. successfully developed a new biodiesel technology, named as SRCA biomass green technology [68], which was based on the near-critical/supercritical methanolysis reaction. Most kind of the oil such as swill-cooked oil, acidic oil, animal fat, vegetable oil can be used as feedstock. Reducing the reaction temperature and pressure increases the conversion of the feedstock but promotes the separation of the products. This process has been applied in the national biodiesel demonstration project (60 kt/a) and gone into operation in 2009. In addition, Sinopec has developed a new technology, which converts the waste cooking oil and seaweed to aviation fuel. In April of 2013, the home-developed biomass aviation fuel 1# completed its maiden flight successfully [70]. Compared with traditional aviation fuel, biomass aviation fuel reduces the CO2 emission by 55–92%. What is more, the modification of the engine is not necessary. Moreover, some researchers propose the second-generation biodiesel synthesis route, which is based on the catalytic hydrogenation. Generally speaking, it is feasible to transform animal fat and vegetable oil to unbranched alkanes by hydrodeoxygenation and isomerization reactions [71]. A biodiesel process based on the hydrodeoxygenation of vegetable oil has been developed and industrialized by Sakatehewan Science Research Council in Canada [72]. In China, a team from Tsinghua University put forward the process which integrates the hydrofining and hydrocracking process for preparing biodiesel from bio oil and petroleum distillates [73]. Yao et al. designed a supercritical solvent for the fatty acid methyl ester hydrogenation reaction. The reaction pressure and the feed ratio of H2 and fatty acid methyl ester were greatly reduced keeping the conversion and selectivity as high as 99% [74]. The exploitation of cellulose plays a very important part in the biomass development. A lot of chemicals, such as synthesis gas, pyrolysis oil, glucose, ethanol and aromatics, can be produced from cellulose. Increasing the selectivity of the products coming from cellulose is a challenge work because of the complex chemical bonds in the cellulose (C–O, C–C, C–H, O–H, etc.). Some progresses have been achieved in the other countries. For instance, Anellotech company developed a biomass pyrolysis technology to produce aromatic; Virent company realized producing xylene by the aqueous reforming reaction. In China, Zhang et al. designed a Ni-W2C/AC difunctional catalyst for the transformation of cellulose to EG with the yield up to 50–74% [75,76]. Liu's group reported the conversion of cellulose to polyhydric alcohols via green and energy efficient approaches [77,78], developing a new route to produce propylene glycol, lactic acid, in which the WO3-Ru/C catalyst selectively broke the C–C bond and increased the selectivity of the product [79]. Wang et al. reported that Pb(II) can effectively catalyze the transformation of cellulose to lactic acid, the yield reached to above 60% when the microcrystalline cellulose was used as feedstock [80]. The unpurified cellulose, such as sugarcane and grass, can be directly fed in this catalytic system. As an ideal and clean energy carrier, interest in hydrogen is rising due to alleviating the dependence on fossil fuels and reducing pollution and greenhouse gas emissions [81]. However, current utilizing of hydrogen energy is still hindered by several key issues, in particular current unsustainable production and storage process with high greenhouse gas emissions, low-energy efficiency and atom economy. Therefore, improving the sustainability of product and efficiency of storage is crucial for building hydrogen infrastructure if considering the increasing demand in energy sector. Xie and co-workers recently proposed a concept of ‘green hydrogen science’ [5], which can be intended to design and construct the hydrogen energy system with a high degree of atom economy and sustainability. By putting forward a theoretical view of  ‘design and construction of a hydrogen energy system covering low-carbon production and highly efficient storage based on the concept of green hydrogen science’, a technology roadmap of ‘low-carbon hydrogen production and highly efficient storage’ was used to identify the strategic goals, barriers and key activities, attempting to solve many related challenging scientific issues (Fig. 7). For the purpose of a sustainable and green production process, catalysis science also plays an extremely important role. During the hydrogen production, highly value-added chemical coproducts such as coal and aromatic can be obtained via increasing the degree of unsaturation of carbon containing products from the cleaving of the first C–H bond by methane decomposition and non-oxidative dehydroaromatization. These production processes show high atom economy and relative greenness, according to the demand of ‘low-carbon production’. In the course of non-oxidative reaction, the carbon containing products with a high degree of unsaturation is notoriously difficult to control. A sharp reduction of production efficiency is usually observed because of a rapid deactivation of catalyst caused by coke accumulation. In this respect, many intense research efforts on fabricating a high-performance catalyst have been devoted to inhibit a fast deactivation caused by the build-up of carbon deposits [82]. Besides, a promising long-term strategy of hydrogen production is photocatalytic water splitting by utilizing solar energy. Through understanding the photoexcited charge separation and recombination behavior and the mechanism of hydrogen production, the preparation of a high effective visible-light-driven photocatalyst is the key to a breakthrough for the improvement of the solar energy conversion efficiency [83,84]. Figure 7. Open in new tabDownload slide Roadmap of low-carbon hydrogen production technologies. Adapted from [5] © 2014 Science China Press. Figure 7. Open in new tabDownload slide Roadmap of low-carbon hydrogen production technologies. Adapted from [5] © 2014 Science China Press. Carbon emission reduction policy is one of the core contents of green chemical engineering, in which the CO2 emission reduction, trapping, storage and chemical utilization are key measures. CO2 is one of the ‘chemical blocks’ and can be used for the production of hydrocarbon, methanol, formic acid, aldehyde, ether, ester, acrylic acid, salicylic acid, organic carbonates and a series of organic chemicals and high-value-added fine products. Currently, the processes of transformation of CO2 to urea, ammonium carbonate, carbonate, CO, carbonic ester are partly or fully industrialized. On the other hand, some approaches, such as CO2 hydrogenation to methanol, reforming of CO2 and methane to synthesis gas, are not mature yet. Mitsui Chemicals Inc. has set up the first demonstration plant in the world (100 t/a) for the hydrogenation of CO2 to methanol. But in China, this process is still in the stage of laboratory research. The technologies of reforming of CO2 and methane to synthesis gas is mostly in the laboratory scale or just a few pilot tests were ever reported such as the SPARG process by Haldor Topsoe [85] and the CALCOR process in Germany [86]. In China, it was reported that a mesoporous zirconia supported metal catalyst with excellent catalytic activity and stability developed by China Petroleum University (Hua Dong) [87]. In addition, it is also reported by Sinopec SRIPT [88] and Shanghai Advanced Research Institute [89] respectively that novel non-noble metal catalysts can be employed as effective catalysts in CH4/CO2 reforming, with lifetime of catalysts exceeding 1000 h. The photocatalytic conversion of CO2 is one of the ideal ways for removing CO2 fundamentally on a long view. In nature, plants convert CO2 and water into glucose by using solar energy. Therefore, the scientists are making great efforts to convert CO2 to CO, methane, methanol, formic acid and formaldehyde as fuel or chemicals by photocatalysis processes. The main challenge of these processes is the limitation of photocatalytic efficiency. Li's group have researched a lot about the photoelectric, photothermal and photocatalytic conversion of CO2 and gained plentiful achievements. They found that a suitable promoter catalyst greatly reduces the overpotential of the reduction reaction, and improves the photocatalytic efficiency [90]. This result prompts a new research climax in this field. DISCUSSION ON SOME SCIENTIFIC PROBLEMS FROM INDUSTRIAL POINT OF VIEW From the industrial point of view, high efficiency and green low carbon will be more emphasized in the future energy chemical catalysis. Therefore, more attentions should be paid to the basic scientific problems including catalysis efficiency, homogenous catalysis in heterogonous system and catalyst design directed by in situ characterization. Catalytic efficiency related with diffusion The improvement method of catalysis property was usually focused on the adjustment of active sites, such as their types, amounts, activity and stability. However, out of active sites, diffusion is another critical factor impacting catalyst performance and the efficiency of active sites. As mentioned above, zeolites were employed as catalysts in lots of chemical processes, like heavy oil refining, MTO/MTP, toluene disproportionation and alkylation of aromatics, etc. The accessibility of reactant molecules to active sites was usually restricted by the diffusion limit, leading to low efficiency in catalysis. Therefore, improving diffusion to promote the catalysis efficiency by modulating pore structure and morphology will be a considerable scientific problem. To improve catalysis efficiency, the trends for zeolitic catalysts should be noticed as follows: the first is synthesis and application of zeolite materials with larger pores, such as large or super microporous zeolite, mesoporous and macroporous materials, which were synthesized to meet the demand in catalysis conversion of heavy oil, heavy aromatics and biological macromolecules. Lots of new type zeolites with large or superlarge micropores, including VPI-5, UTP-1, ECR-34, ITQ-21, ITQ-33, SSZ-35, SSZ-44 etc. [91] and mesoporous materials, M41-S and SBA-15 [92] etc. were found or synthesized in recent years. At present, however, low hydrothermal stability for the inherent amorphous pore wall hindered the industrial applications of mesoporous materials. Secondly, the miniaturization of zeolites by constructing nanocrystals and nanofilms [93] was usually considered as another method to improve utilization efficiency of active sites, in which diffusion length in micropores was shortened by reducing crystal size. However, there are still some unavoidable challenges in the application of nanomaterials, such as high synthesizing cost, low stability for easy aggregation. Moreover, the catalyst/product separation problem emerged in the heterogeneous reaction, leading to the recycle problem of catalyst in industry, especially in the solid/liquid phase system involving nanozeolites. The third measure which may be taken to improve diffusion in zeolite catalyst is constructing multiple pore structure to develop hierarchical porous materials [94]. Based on such concept, Xie's group have developed lots of synthesis methods and industrial applications of hierarchical zeolites [95]. Hierarchical ZSM-5, Silicalite-1, Beta and SAPO-34 zeolites have been successively developed by templating method, steam-assisted-crystallization, post-alkaline treatment, etc. Moreover, outstanding performances have been found in the catalyzing supercritical toluene disproportionation [96], conversion of heavy aromatics [97], alkylation of benzene with ethylene [98], transalkylation of multi-isopropyl benzene [99], methanol conversion to olefin/propylene [41] etc., some of which have found applications in industry. Moreover, a determination strategy for diffusivity was developed via thiele modulus analysis which providing direct experimental evidence for the remarkable improvement of utilization efficiency in hierarchical MFI zeolites catalyst [100] (Fig. 8). Construction of hierarchical porous structure is considered an important method to promote diffusion and utilization efficiency of zeolite catalysts which indicated a meaningful direction for catalysis research. Many other groups such as Shi's group [101], Tang's group [102] and Xiao's group [103], etc. in China have also done many innovative works on the hierarchical porous zeolite materials in recent years. Figure 8. Open in new tabDownload slide (A) The scheme (adapted from [104] ©2008 The Royal Society of Chemistry) and (B) the real determinations of catalytic effectiveness with Thiele Modulus for conventional zeolite (filled triangles) and hierarchical zeolite (filled asterisks). Adapted from [100] © 2014 The Royal Society of Chemistry. Figure 8. Open in new tabDownload slide (A) The scheme (adapted from [104] ©2008 The Royal Society of Chemistry) and (B) the real determinations of catalytic effectiveness with Thiele Modulus for conventional zeolite (filled triangles) and hierarchical zeolite (filled asterisks). Adapted from [100] © 2014 The Royal Society of Chemistry. Homogeneous catalysis within heterogeneous catalysts It is known that the efficiency of homogeneous catalyst is much higher than heterogeneous catalyst in liquid phase. However, unsustainable homogeneous catalysts often suffered from separation problem and led to environmental hazard. Therefore, developing high efficient heterogeneous catalyst with homogeneous catalysis property is still challenging in green chemistry. Homogeneous catalysis in heterogeneous system, especially the development of nanoreactor based on the characteristic of enzyme structure, has drawn lots of attentions in recent years. Mn (Salen) molecular catalyst which demonstrated high activity in selective oxidation reaction was constructed in the micropores of zeolite by Jacobsen et al. [105]. Subsequently, chiral molecular catalyst assembled in nanopores of mesoporous materials was found possessing higher chiral selectivity and subsequently, the concept of space confinement effect was also proposed [106]. Lots of innovative progresses about nanoreactor have been reported by Yang and Li's group. They designed a heterogeneous asymmetric catalyst by confining nanoparticles within nanotubes and found the promotion of reactant concentration and accelerative effect of dual-centered activated coupling in confined space of nanoreator [107]. Such dual-centered activated coupling effect can even be observed in the low catalyst content which demonstrated even higher performance than homogeneous catalysts. A non-acid molecular catalyst was then developed and employed for hydration of epoxide in which the yield of MEG can result up to 96% even at the condition of H2O/EO molar ratio as low as 2 under mild reaction conditions [108]. Because of synergic coupling effect, the significant promotion of MEG, from 10 to 74 wt%, remarkably reduced energy cost in distils procedure. Therefore, the cooperation activation effect of the molecular catalysts in the nanoreactors resulted in enormous enhancement of catalytic activity, offering a new strategy of  homogeneous catalysis in heterogeneous system and will prompt potential applications in green catalysis. Reaction controlled phase transfer catalyst is also a heterogeneous catalysis system with homogeneous characteristics [33,109], such as heteropolyphosphatotungstate catalysts Q3[PW4O16] (Q represents quaternary ammonium cationic). Such catalysts are usually insoluble in reactant system at first, but become soluble under the presence of H2O2. Therefore, in fact, the propylene epoxidation reaction is a homogeneous catalysis process with this kind of catalyst. Along with the consumption of H2O2 after reaction, catalyst becomes insoluble again and gradually precipitates from the reaction system, and can be conveniently recycled. Such special catalyst/procedure has been employed in process of producing epoxy chlorohexane [34,110] and is now being developed for application in other green processes, such as the production of propylene epoxide and epoxy chloropropane, etc. The combination of nanocatalysis with membrane separation is a green feasible technique by which the efficiency of heterogeneous catalysis may be significantly promoted. Membranes separation techniques have experienced rapid expansion recently [111]. Recently, a new kind of slurry reaction procedure was successfully developed by employing nanosized hollow Ti-Silicalite zeolite (HTS) as oxidation catalyst [27] and combining membrane separation technique [112–114]. On the basis of keeping high catalysis performance, separation and recycle problem was overcome by such method. Development of in situ or operando techniques for characterization of heterogeneous catalysts or mechanism Considered as important techniques for catalysis, advanced operando or in situ characterization studies demonstrated direct evidences in observing and researching structure, active sites and reaction mechanism information, providing theoretical guidance for design and optimization of catalyst. Early in the 1950s, in situ IR spectra have been employed in the study of NH3 absorbance on Pd/SiO2-Al2O3 catalyst by Eischens [115]. With the development of in situ or operando characterization technique, the studies of active sites have been deep into the atomic level and intermediate state in catalysis now. It is found that just tiny structure conversion of catalyst often significantly impacted reaction performance which was uncovered by in situ characterization studies [116]. The status of active sites in catalysis can be only characterized by in situ techniques by which the fundamental insight made the rational design of catalysts possible. Besides, some advanced in situ imaging techniques such as transmission X-ray microscope, combined μ-XRD-CT and μ-absorption-CT (CT = computed tomography) technique by focusing hard X-ray were developed and applied in syngas conversion which realized the 3D tracing of composition and structure in Fe-based catalyst by Weckhuysen et al. [117]. They also studied the revolution of pore structure, composition, coking in the gradual inactivation process of refining catalyst by in situ imaging technique [118]. The development of powerful spectra characterization technique in micro-nanometer scale makes it possible to reveal the relevance between macroscopic and submicroscopic domains. Big progresses have been made also in China in the field of in situ characterization technique. Li et al. [119,120] studied the synthesis and reaction theory of Fe-, V- and Mo- catalyst by in situ ultraviolet Raman spectra and realized the in situ detecting of zeolite under hydrothermal condition using self-developed Raman spectrometer. Lots of related reports, including the design, synthesis, identification of active species and catalysis mechanism of heteroatomic zeolite can also be found in recent years [121,122]. By in situ synchrotron radiation technique, Bao et al. studied the confined space catalysis in carbon nanotubes [123,124] and interface-confined ferrous centers on nano Pt particles [125]. And by operando IR or Raman spectra, Wan et al. studied the catalysts for C1–C3 alkane conversion [126,127]. As the representative of the advanced research level in catalysis field, more attentions should be paid to develop in situ and operando characterization techniques at present and in future. CONCLUSION AND OUTLOOK The scientific connotation for sustainable development of energy chemical engineering is involved in green carbon science, which means optimization of carbon atom economics based on high efficient catalysis and carbon emission reduction. Centered on the concept of green and low carbon, lots of innovations on catalytic techniques have been progressed on higher efficient or green processes as well as alternative non-oil routes in China, which include high efficient conversion of oil, clean utilization of coal and natural gas, development of sustainable resources and clean energy, etc. From the view of industry, fundamental researches on scientific problems such as diffusion and efficiency of catalysts, homogeneous catalysis in heterogeneous system, in situ characterization in industrial catalysis, etc., are definitely helpful to develop new catalytic techniques for sustainable energy chemical industry. It is believed that environmental friendly and low-carbon catalysis will play an important role leading to sustainable development of energy chemical industry in China. FUNDING This work was supported by the National Natural Science Foundation of China (91434102). REFERENCES 1. Anastas PT , Warner J . , Green Chemistry Theory and Practice , 1998 Oxford Oxford University Press Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 2. Anastas PT , Kirchhoff MM . Origins, current status, and future challenges of green chemistry , Acc Chem Res , 2002 , vol. 35 (pg. 686 - 94 ) Google Scholar Crossref Search ADS PubMed WorldCat 3. He MY , Sun YH . Green carbon science: scientific basis for the efficient utilization of fossil energy with low emission , Sci China Chem , 2011 , vol. 41 (pg. 925 - 32 ) Google Scholar OpenURL Placeholder Text WorldCat 4. He MY , Sun YH , Han BX . Green carbon science: scientific basis for integrating carbon resource processing, utilization, and recycling , Angew Chem Int Ed , 2013 , vol. 52 (pg. 9620 - 33 ) Google Scholar Crossref Search ADS WorldCat 5. Xie ZK , Jin ZH , Wang YD . Design and construction of a hydrogen energy system covering low-carbon production and highly efficient storage based on the concept of green hydrogen science , Sci China Chem , 2014 , vol. 44 (pg. 6 - 12 ) Google Scholar OpenURL Placeholder Text WorldCat 6. Simanzhenkov V , Oballa MC , Kim G , et al. Technology for producing petrochemical feedstock from heavy aromatic oil fractions , Ind Eng Chem Res , 2010 , vol. 49 (pg. 953 - 63 ) Google Scholar Crossref Search ADS WorldCat 7. Zhou JH , Min EZ , Shu XT , et al. A zeolite Y material with dual porosity and its preparation method , 2008 China Patent: CN200810227657.6 8. Zhao L , Shen BJ , Gao JS , et al. Investigation on the mechanism of diffusion in mesopore structured ZSM-5 and improved heavy oil conversion , J Catal , 2008 , vol. 258 (pg. 228 - 34 ) Google Scholar Crossref Search ADS WorldCat 9. Tan QF , Bao XJ , Song TC , et al. Synthesis, characterization, and catalytic properties of hydrothermally stable macro–meso–micro-porous composite materials synthesized via in situ assembly of preformed zeolite Y nanoclusters on kaolin , J Catal , 2007 , vol. 251 (pg. 69 - 79 ) Google Scholar Crossref Search ADS WorldCat 10. Tatsumi T , Nishimura Y . , Development Technology of Zeolite Catalyst , 2010 Japan CMC Publishing Co., Ltd pg. 39 Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 11. Liu YD , Gao L , Zong BN , et al. Recent advances in heavy oil hydroprocessing technologies , Recent Pat Chem Eng , 2009 , vol. 2 (pg. 22 - 36 ) Google Scholar Crossref Search ADS WorldCat 12. Liu YD , Gao L , Zong BN , et al. Development of slurry bed technologies for upgrading heavy oils , Chem Ind Eng Prog , 2010 , vol. 29 (pg. 1589 - 96 ) Google Scholar OpenURL Placeholder Text WorldCat 13. Gao L , Liu YD , Wen LY , et al. The effect of supercritical water on the hydroconversion of Tahe residue , AIChE J , 2010 , vol. 56 (pg. 3236 - 42 ) Google Scholar Crossref Search ADS WorldCat 14. Zhu YX , Xu H . Improvemant and development of S-Zorb process , Pet Refin Eng , 2009 , vol. 39 (pg. 7 - 12 ) Google Scholar OpenURL Placeholder Text WorldCat 15. Long J , Lin W , Dai Z . From detailed desulfurization mechanism to successful commercial application I. Features and adcantages of S Zorb technology , Acta Pet Sin (Petro Proc Sect) , 2015 , vol. 31 (pg. 1 - 6 ) Google Scholar OpenURL Placeholder Text WorldCat 16. Liu L . Comparison of FCC naphtha desulfurization process schemes and application analysis , Pet Refin Eng , 2008 , vol. 38 (pg. 11 - 5 ) Google Scholar OpenURL Placeholder Text WorldCat 17. Yang YX , Zhang YL , Li C , et al. Ultra deep adsorptive desulfurization of solvent oils by Ni/ZnO adsorbent , Petrochem Tech , 2008 , vol. 37 (pg. 243 - 6 ) Google Scholar OpenURL Placeholder Text WorldCat 18. Corma A , Martinez C , Sauvanaud L . New materials as FCC active matrix components for maximizing diesel (light cycle oil, LCO) and minimizing its aromatic content , Catal Today , 2007 , vol. 127 (pg. 3 - 16 ) Google Scholar Crossref Search ADS WorldCat 19. Guo R , Shen BX , Fang XC , et al. Study on performances of diesel deep hydrodesulfurization catalyst , Pet Refin Eng , 2011 , vol. 41 (pg. 31 - 4 ) Google Scholar OpenURL Placeholder Text WorldCat 20. Jing DH , Guo R , Yao B , et al. Study on production of clean diesel oil of Euro-specifications in high space velocity conditions , Pet Refin Eng , 2011 , vol. 41 (pg. 1 - 3 ) Google Scholar OpenURL Placeholder Text WorldCat 21. Yang P , Xin J , Nie H , et al. Research advances in the hydroconversion of tetralin , Pet Proc Petrochem , 2011 , vol. 42 (pg. 1 - 6 ) Google Scholar OpenURL Placeholder Text WorldCat 22. Zheng JL , Qian B , Qi XL , et al. Research on direct production of BTX aromatic from light cycle oil , Petrochem Tech , 2014 , vol. 43 (pg. 124 - 5 ) Google Scholar OpenURL Placeholder Text WorldCat 23. Chauvin Y , Hirschauer A , Olivier H . Alkylation of isobutane with 2-butene using 1-butyl-3-methylimidazolium chloride-aluminium chloride molten salts as catalysts , J Mol Catal , 1994 , vol. 92 (pg. 155 - 65 ) Google Scholar Crossref Search ADS WorldCat 24. Huang CP , Liu ZC , Xu CM , et al. Effects of additives on the properties of chloroaluminate ionic liquids catalyst for alkylation of isobutane and butene , Appl Catal A , 2004 , vol. 277 (pg. 41 - 3 ) Google Scholar Crossref Search ADS WorldCat 25. Liu Y , Hu RS , Xu CM , et al. Alkylation of isobutene with 2-butene using composite ionic liquid catalysts , Appl Catal A , 2008 , vol. 346 (pg. 189 - 93 ) Google Scholar Crossref Search ADS WorldCat 26. Cui J , With JD , Klusener PAA , et al. Identification of acidic species in chloroaluminate ionic liquid catalysts , J Catal , 2014 , vol. 320 (pg. 26 - 32 ) Google Scholar Crossref Search ADS WorldCat 27. Su B , Chen SB , Meng XK , et al. Green production technology of caprolactam , Sci China Chem , 2014 , vol. 44 (pg. 40 - 5 ) Google Scholar OpenURL Placeholder Text WorldCat 28. Lin M , Shu XT , Wang XQ , et al. Titanium-silicalite molecular sieve and the method for its preparation US Patent: 6475465, Nov 05, 2002 Google Scholar 29. Zhu B . Study on catalytic material used in HPPO process , Acta Pet Sin (Petro Proc Sect) , 2013 , vol. 29 (pg. 223 - 7 ) Google Scholar OpenURL Placeholder Text WorldCat 30. Shi CF , Lin M , Long J , et al. Deactivation and regeneration of titanosilicate catalyst used in HPPO pilot test , Acta Pet Sin (Petro Proc Sect) , 2013 , vol. 29 (pg. 864 - 9 ) Google Scholar OpenURL Placeholder Text WorldCat 31. Li XF , Gao HX , Jin GJ , et al. Influence of silylation on catalytic performance of Ti/HMS molecular sieve , Chin J Catal , 2007 , vol. 28 (pg. 551 - 6 ) Google Scholar OpenURL Placeholder Text WorldCat 32. Jin GJ , Gao HX , Yang HY , et al. Study on characterization and catalytic performance for propylene epoxidation of Ti/HMS catalyst prepared by grafting technology , J Mol Catal , 2010 , vol. 24 (pg. 6 - 12 ) Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 33. Xi ZW , Zhou N , Sun Y , et al. Reaction-controlled phase-transfer catalysis for propylene epoxidation to propylene oxide , Science , 2001 , vol. 292 (pg. 1139 - 41 ) Google Scholar Crossref Search ADS PubMed WorldCat 34. Gao S , Xi ZW . Oyama ST . Reaction-Controlled Phase-Transfer Catalysts for Epoxidation of Olefins , Mechanisms in Homogeneous and Heterogeneous Epoxidation Catalysis , 2007 Amsterdam Elsevier pg. 429 Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 35. Yu FP , Cai H , He WJ , et al. Synthesis and characterization of a polymer/multiwalled carbon nanotube composite and its application in the hydration of ethylene oxide , J Appl Polym Sci , 2010 , vol. 115 (pg. 2946 - 54 ) Google Scholar Crossref Search ADS WorldCat 36. Li YN , Yu FP , He WJ , et al. The preparation and catalytic performance of graphene-reinforced ion-exchange resins , RSC Adv , 2015 , vol. 5 (pg. 2550 - 61 ) Google Scholar Crossref Search ADS WorldCat 37. Liu ZM , Wei YX , Li JZ , et al. Yu JH , Yan WF . Chapter 1: Important progresses on industrial application of zeolitic catalysts and DMTO technologies , Chemistry of Nanoporous Materials: Catalysis and Function , 2013 Beijing Science Press (pg. 21 - 30 ) Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 38. Li JZ , Wei YX , Liu ZM , et al. Observation of heptamethylbenzenium cation over SAPO-type molecular sieve DNL-6 under real MTO conversion conditions , J Am Chem Soc , 2012 , vol. 134 (pg. 836 - 9 ) Google Scholar Crossref Search ADS PubMed WorldCat 39. Liu HX , Xie ZK , Zhang CF , et al. Study on synthesis of SAPO-34 molecular sieve using composite template TEAOH-morpholine , Chin J Catal , 2004 , vol. 25 (pg. 702 - 10 ) Google Scholar OpenURL Placeholder Text WorldCat 40. Xie ZK , Liu ZC , Wang CM , et al. Catalytic conversion of methanol to olefins: some progresses on catalytic materials and reaction mechanism [oral presentation] , Presented at the 15th International Congress on Catalysis, Munich , 2012 Germany Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 41. Yang HQ , Liu ZC , Xie ZK , et al. Synthesis and catalytic performances of hierarchical SAPO-34 monolith , J Mater Chem , 2010 , vol. 20 (pg. 3227 - 31 ) Google Scholar Crossref Search ADS WorldCat 42. Wang CM , Wang YD , Xie ZK , et al. Methanol to olefin conversion on HSAPO-34 zeolite from periodic density functional theory calculations: a complete cycle of side chain hydrocarbon pool mechanism , J Phys Chem C , 2009 , vol. 113 (pg. 4584 - 91 ) Google Scholar Crossref Search ADS WorldCat 43. Wang CM , Wang YD , Xie ZK , et al. Catalytic activity and selectivity of methylbenzenes in HSAPO-34 catalyst for the methanol-to-olefins conversion from first principles , J Catal , 2010 , vol. 271 (pg. 386 - 91 ) Google Scholar Crossref Search ADS WorldCat 44. Wang CM , Wang YD , Xie ZK , et al. Insights into the reaction mechanism of methanol-to-olefins conversion in HSAPO-34 from first principles: are olefins themselves the dominating hydrocarbon pool species? , J Catal , 2013 , vol. 301 (pg. 8 - 19 ) Google Scholar Crossref Search ADS WorldCat 45. Teng JW , Xie ZK . Novel binder-less hierarchical ZSM-5 catalysts for olefins catalytic cracking to produce propylene , Sci China Chem , 2015 doi:10.1360/N032014-00296 Google Scholar OpenURL Placeholder Text WorldCat 46. Tian T , Qian WZ , Sun YJ , et al. Aromatization of methanol on Ag/ZSM-5 catalyst , Mod Chem Ind , 2009 , vol. 29 (pg. 55 - 9 ) Google Scholar OpenURL Placeholder Text WorldCat 47. Jian WF , Wei F , Wei T , et al. An apparatus and process for continuous aromatization and catalyst regeneration , 2008 China Patent: CN 200810102684 48. Zou W , Kong DJ , Zhu ZH , et al. A process for PX production by benzene alkylation with methanol , 2005 China Patent: CN 200510028770 49. Kong DJ , Liu ZC , Fang DY . Epitaxial growth of core-shell ZSM-5/Silicalite-1 with shape selectivity , Chin J Catal , 2009 , vol. 30 (pg. 885 - 90 ) Google Scholar OpenURL Placeholder Text WorldCat 50. Zou W , Yang DQ , Xie ZK , et al. Selective methylation of toluene with methanol over HZSM-5 zeolite modified by chemical liquid deposition , Chem React Eng Tech , 2006 , vol. 22 (pg. 305 - 9 ) Google Scholar OpenURL Placeholder Text WorldCat 51. Zou W , Kong DJ . A process for PX production by toluene alkylation with methanol , 2009 China Patent: CN 200910057232.X 52. Xu L , Liu ZM , Zhang ZX , et al. An online modification method of catalyst for toluene methylation , 2006 China Patent: CN 200610011662.4 53. Zhao S , Liu XW , Huo CF , et al. Surface morphology of Hägg iron carbide (χ-Fe5C2) from ab initio atomistic thermodynamics , J Catal , 2012 , vol. 294 (pg. 47 - 53 ) Google Scholar Crossref Search ADS WorldCat 54. Huo CF , Wu BS , Gao P , et al. The mechanism of potassium promoter: enhancing the stability of active surfaces , Angew Chem Int Ed , 2011 , vol. 50 (pg. 7403 - 6 ) Google Scholar Crossref Search ADS WorldCat 55. Huo CF , Li YW , Wang J , et al. Insight into CH4 formation in iron-catalyzed Fischer-Tropsch synthesis , J Am Chem Soc , 2009 , vol. 131 (pg. 14713 - 21 ) Google Scholar Crossref Search ADS PubMed WorldCat 56. Deng LJ , Huo CF , Li YW , et al. Density functional theory study on surface CxHy formation from CO activation on Fe3C(100) , J Phys Chem C , 2010 , vol. 114 (pg. 21585 - 92 ) Google Scholar Crossref Search ADS WorldCat 57. Li YW , Xu J , Yang Y . , Diesel From Syngas , 2009 New York Wiley Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 58. Li YW , De KA . , Industrial Case Studies , 2013 New York Wiley Google Scholar Crossref Search ADS Google Preview WorldCat COPAC 59. Liu ZY , Shi SD , Li YW . Coal liquefaction technologies-development in China and challenges in chemical reaction engineering , Chem Eng Sci , 2010 , vol. 65 (pg. 12 - 7 ) Google Scholar Crossref Search ADS WorldCat 60. Kang J , Cheng K , Wang Y , et al. Mesoporous zeolite-supported ruthenium nanoparticles ashighly selective Fischer-Tropsch catalysts for the production of C5-C11 isoparaffins , Angew Chem Int Ed , 2011 , vol. 50 (pg. 5200 - 3 ) Google Scholar Crossref Search ADS WorldCat 61. Kang J , Zhang S , Wang Y , et al. Ruthenium nanoparticles supported on carbon nanotubes as efficient catalysts for selective conversion of syngas to diesel fuel , Angew Chem Int Ed , 2009 , vol. 48 (pg. 2565 - 8 ) Google Scholar Crossref Search ADS WorldCat 62. Huang YY , Guo YL , Wang YB . Ethylene glycol electrooxidation on core-shell PdCuBi nanoparticles fabricated via substitution and self-adsorption processes , J Power Sources , 2014 , vol. 249 (pg. 9 - 12 ) Google Scholar Crossref Search ADS WorldCat 63. Lin L , Pan PB , Zhou ZF , et al. Cu/SiO2 catalysts prepared by the sol-gel method for hydrogenation of dimethyl oxalate to ethylene glycol , Chin J Catal , 2011 , vol. 32 (pg. 957 - 69 ) Google Scholar Crossref Search ADS WorldCat 64. Li T . Review on current development of syngas to glycol technologies in China , Fine Chem Ind Raw Mater Intermed , 2012 , vol. 12 (pg. 40 - 3 ) Google Scholar OpenURL Placeholder Text WorldCat 65. Jiang ZH . The composition of syngas to ethylene glycol technical progress abroad and at home , Synth Tech Appl , 2010 , vol. 25 (pg. 27 - 30 ) Google Scholar OpenURL Placeholder Text WorldCat 66. Zhou JF , Liu XQ , Liu DH . Progress and perspective of synthesis of ethylene glycol from syngas via oxalate , Chem Ind Eng Prog , 2009 , vol. 28 (pg. 47 - 50 ) Google Scholar OpenURL Placeholder Text WorldCat 67. Guo XG , Fang GZ , Bao XH , et al. Direct, nonoxidative conversion of methane to ethylene, aromatics, and hydrogen , Science , 2014 , vol. 344 (pg. 616 - 9 ) Google Scholar Crossref Search ADS PubMed WorldCat 68. Wu CZ , Zhou ZQ , Yin XL , et al. Current status of biomass energy development in China , Trans Chin Soc Agri Mach , 2009 , vol. 40 (pg. 91 - 9 ) Google Scholar OpenURL Placeholder Text WorldCat 69. Min EZ , Zhang LX . , Analysis Report of Biomass Refining & Chemical Industry , 2013 Beijing Science Press Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 70. China's no. 1 biological fuel test success , Energy Conserv Emiss Reduct Pet Petrochem Ind , 2013 , vol. 3 pg. 19 OpenURL Placeholder Text WorldCat 71. Stumborg M , Wong A , Hogan E . Hydroprocessed vegetable oils for diesel fuel improvement , Bioresour Technol , 1996 , vol. 56 (pg. 13 - 8 ) Google Scholar Crossref Search ADS WorldCat 72. Zhou JX . Development and future of full green chemical industry , Chem Eng Des , 2010 , vol. 20 (pg. 3 - 7 ) Google Scholar OpenURL Placeholder Text WorldCat 73. Yuan RB , Wang YJ , Piao XL , et al. A process for biodiesel prduction by integrated hydrogenation , 2007 China Patent: CN 200710065393.4 OpenURL Placeholder Text WorldCat 74. Yao ZL . Research on synthesis of fatty alcohols from fatty acid methyl ester by supercritical hydrogenation technology , Doctoral dissertation , 2008 Beijing Sinopec Research Institute of Petroleum Processing Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 75. Ji N , Zhang T , Zheng MY , et al. Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts , Angew Chem Int Ed , 2008 , vol. 47 (pg. 8510 - 3 ) Google Scholar Crossref Search ADS WorldCat 76. Wang AQ , Zhang T . One-pot conversion of cellulose to ethylene glycol with multifunctional tungsten-based catalysts , Acc Chem Res , 2013 , vol. 46 (pg. 1377 - 86 ) Google Scholar Crossref Search ADS PubMed WorldCat 77. Luo C , Wang S , Liu HC . Cellulose conversion to polyols catalyzed by reversibly-formed acids and supported ruthenium clusters in hot water , Angew Chem Int Ed , 2007 , vol. 46 (pg. 7636 - 9 ) Google Scholar Crossref Search ADS WorldCat 78. Yan N , Zhao C , Luo C , et al. One step conversion of cellobiose to C6-alcohols using a ruthenium nanocluster catalyst , J Am Chem Soc , 2006 , vol. 128 (pg. 8714 - 5 ) Google Scholar Crossref Search ADS PubMed WorldCat 79. Liu Y , Luo C , Liu HC . Tungsten trioxide promoted selective conversion of cellulose into propylene glycol and ethylene glycol on a ruthenium catalyst , Angew Chem Int Ed , 2012 , vol. 51 (pg. 3249 - 53 ) Google Scholar Crossref Search ADS WorldCat 80. Wang Y , Wang B , Deng W , et al. Chemical synthesis of lactic acid from cellulose catalysed by lead(II) ions in water , Nat Commun , 2013 , vol. 4 pg. 2141 Google Scholar Crossref Search ADS PubMed WorldCat 81. Navarro RM , Pena MA , Fierro JLG . Hydrogen production reactions from carbon feedstocks: fossil fuels and biomass , Chem Rev , 2007 , vol. 107 (pg. 3952 - 91 ) Google Scholar Crossref Search ADS PubMed WorldCat 82. Jin ZH , Liu S , Xie ZK , et al. Methane dehydroaromatization by Mo-supported MFI-type zeolite with core-shell structure , Appl Catal A-Gen , 2013 , vol. 453 (pg. 295 - 301 ) Google Scholar Crossref Search ADS WorldCat 83. Wen FY , Yang JH , Zong X , et al. Photocatalytic hydrogen production utilizing solar energy , Prog Chem , 2009 , vol. 21 (pg. 2285 - 302 ) Google Scholar OpenURL Placeholder Text WorldCat 84. Maeda K , Domen K . Photocatalytic water splitting: recent progress and future challenges , J Phys Chem Lett , 2010 , vol. 1 (pg. 2655 - 61 ) Google Scholar Crossref Search ADS WorldCat 85. Udengaard NR , Hansen JHB , Hanson DC , et al. Sulfur passivated reforming process lowers syngas H2/CO ratio , Oil Gas J , 1992 , vol. 90 (pg. 62 - 7 ) Google Scholar OpenURL Placeholder Text WorldCat 86. Teuner SC , Neumann P , Linde FV . CO through CO2 reforming-the calcor standard and calcor economy processes , Oil Gas Eur Mag , 2001 , vol. 27 (pg. 44 - 6 ) Google Scholar OpenURL Placeholder Text WorldCat 87. Rezaei M , Alavi SM , Yan ZF , et al. Effects of K2O promoter on the activity and stability of nickel catalysts supported on mesoporous nanocrystalline zirconia in CH4 reforming with CO2 , Energy Fuel , 2008 , vol. 22 (pg. 2195 - 202 ) Google Scholar Crossref Search ADS WorldCat 88. Liu ZC , Zhou J , Cao K , et al. Highly dispersed nickel loaded on mesoporous silica: one-spot synthesis strategy and high performance as catalysts for methane reforming with carbon dioxide , Appl Catal B-Environ , 2012 , vol. 125 (pg. 324 - 30 ) Google Scholar Crossref Search ADS WorldCat 89. Sun NN , Wen X , Wang F , et al. Catalytic performance and characterization of Ni-CaO-ZrO2 catalysts for dry reforming of methane , Appl Surf Sci , 2011 , vol. 257 (pg. 9169 - 76 ) Google Scholar Crossref Search ADS WorldCat 90. Yang JH , Wang DG , Li C , et al. Roles of cocatalysts in photocatalysis and photoelectrocatalysis , Acc Chem Res , 2013 , vol. 46 (pg. 1900 - 9 ) Google Scholar Crossref Search ADS PubMed WorldCat 91. Wan Y , Zhao DY . On the controllable soft-templating approach to mesoporous silicates , Chem Rev , 2007 , vol. 107 (pg. 2821 - 60 ) Google Scholar Crossref Search ADS PubMed WorldCat 92. Liu ZC , Wang YD , Xie ZK . Some thoughts on future development of zeolitic catalysts from industrial catalysis point of view , Chin J Catal , 2012 , vol. 33 (pg. 22 - 38 ) Google Scholar Crossref Search ADS WorldCat 93. Zhang H , Ma Y , Song K , et al. Nano-crystallite oriented self-assembled ZSM-5 zeolite and its LDPE cracking properties: effects of accessibility and strength of acid sites , J Catal , 2013 , vol. 302 (pg. 115 - 25 ) Google Scholar Crossref Search ADS WorldCat 94. Su BL , Sanchez C , Yang XY . , Hierarchically Structured Porous Materials: From Nanoscience to Catalysis, Separation, Optics, Energy, and Life Science , 2011 Weinheim Wiley-VCH Google Scholar Crossref Search ADS Google Preview WorldCat COPAC 95. Xie ZK , Liu ZC , Wang YD . Yu JH , Yan WF . Hierarchical construction of porous materials and their catalysis , Chemistry of Nanoporous Materials: Catalysis and Function , 2013 Beijing Science Press (pg. 69 - 123 ) Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 96. Liu ZC , Wang YD , Xie ZK , et al. Wang JK . Frontiers of modern chemical engineering, metallurgy, and material technologies , Proceedings of the 7th Chinese Academy of Engineering Symposium , 2009 Beijing Chem Ind Press pg. 557 Google Scholar OpenURL Placeholder Text WorldCat 97. Zhu HB , Liu ZC , Xie ZK , et al. Synthesis and catalytic performances of mesoporous zeolites templated by polyvinyl butyral gel as the mesopore directing agent , J Phys Chem C , 2008 , vol. 112 (pg. 17257 - 64 ) Google Scholar Crossref Search ADS WorldCat 98. Zhang B , Wang ZD , Ji P , et al. Efficient liquid-phase ethylation of benzene with ethylene over mesoporous MCM-22 catalyst , Microporous Mesoporous Mater , 2013 , vol. 179 (pg. 63 - 8 ) Google Scholar Crossref Search ADS WorldCat 99. Yang HQ , Liu ZC , Xie ZK , et al. Transalkylation of diisopropylbenzenes with benzene over hierarchical beta zeolite , Appl Catal A , 2010 , vol. 379 (pg. 166 - 71 ) Google Scholar Crossref Search ADS WorldCat 100. Zhou J , Liu ZC , Xie ZK , et al. Enhanced accessibility and utilization efficiency of acid sites in hierarchical MFI zeolite catalyst for effective diffusivity improvement , RSC Adv , 2014 , vol. 4 (pg. 43752 - 5 ) Google Scholar Crossref Search ADS WorldCat 101. Hua ZL , Zhou J , Shi JL . Recent advances in hierarchically structured zeolites: synthesis and material performances , Chem Commun , 2011 , vol. 47 (pg. 10536 - 47 ) Google Scholar Crossref Search ADS WorldCat 102. Chen LH , Li XY , Tang Y , et al. Hierarchically structured zeolites: synthesis, masstransport properties and applications , J Mater Chem , 2012 , vol. 22 (pg. 17381 - 403 ) Google Scholar Crossref Search ADS WorldCat 103. Liu FJ , Willhammar T , Xiao FS , et al. ZSM-5 zeolite single crystals with b-axis-aligned mesoporous channels as an efficient catalyst for conversion of bulky organic molecules , J Am Chem Soc , 2012 , vol. 134 (pg. 4557 - 60 ) Google Scholar Crossref Search ADS PubMed WorldCat 104. Pérez-Ramírez J , Christensen CH , Egeblad K , et al. Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design , Chem Soc Rev , 2008 , vol. 37 (pg. 2530 - 42 ) Google Scholar Crossref Search ADS PubMed WorldCat 105. Jacobson RH , Zhang XJ , DuBose RF , et al. Three-dimensional structure of beta-galactosidase from E. coli , Nature , 1994 , vol. 369 (pg. 761 - 6 ) Google Scholar Crossref Search ADS PubMed WorldCat 106. Caplan NA , Hancock FE , Bulman PC , et al. Heterogeneous enantioselective catalyzed carbonyl- and imino-ene reactions using copper bis(oxazoline) zeolite Y , Angew Chem In Ed , 2004 , vol. 43 (pg. 1685 - 8 ) Google Scholar Crossref Search ADS WorldCat 107. Chen ZJ , Guan ZH , Li MR , et al. Enhancement of the performance of a platinum nanocatalyst confined within carbon nanotubes for asymmetric hydrogenation , Angew Chem In Ed , 2011 , vol. 50 (pg. 4913 - 7 ) Google Scholar Crossref Search ADS WorldCat 108. Li B , Bai SY , Wang XF , et al. Sustained water oxidation by a catalyst cage-isolated in a metal-organic framework , Angew Chem In Ed , 2012 , vol. 51 (pg. 11517 - 21 ) Google Scholar Crossref Search ADS WorldCat 109. Li J , Gao S , Li M , et al. Influence of composition of heteropolyphosphatotungstate catalyst on epoxidation of propylene , J Mol Catal A , 2004 , vol. 218 (pg. 247 - 52 ) Google Scholar Crossref Search ADS WorldCat 110. Xie ZK . , Porous Catalytic Materials with New Structure and Improved Performance , 2010 Beijing Sinopec Press Google Scholar Google Preview OpenURL Placeholder Text WorldCat COPAC 111. Xing WH , Wang Y , Chen RZ , et al. Membranes and membrane reactors: state of the art, challenges, and opportunities , Sci China Chem , 2014 , vol. 44 (pg. 1469 - 80 ) Google Scholar OpenURL Placeholder Text WorldCat 112. Zhong ZX , Xing WH , Liu X , et al. Fouling and regeneration of ceramic membranes used in recovering titanium silicalite-1 catalysts , J Membr Sci , 2007 , vol. 301 (pg. 67 - 75 ) Google Scholar Crossref Search ADS WorldCat 113. Lu CJ , Chen RZ , Xing WH , et al. A submerged membrane reactor for continuous phenol hydroxylation over TS-1 , AIChE J , 2008 , vol. 54 (pg. 1842 - 9 ) Google Scholar Crossref Search ADS WorldCat 114. Li ZH , Chen RZ , Xing WH , et al. Continuous acetone ammoximation over TS-1 in a tubular membrane reactor , Ind Eng Chem Res , 2010 , vol. 49 (pg. 6309 - 16 ) Google Scholar Crossref Search ADS WorldCat 115. Mapes JE , Eischens RP . The infrared spectra of ammonia chemisorbed on cracking catalysts , J Phys Chem , 1954 , vol. 58 (pg. 1059 - 62 ) Google Scholar Crossref Search ADS WorldCat 116. Buurmans ILC , Weckhuysen BM . Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy , Nat Chem , 2012 , vol. 4 (pg. 873 - 86 ) Google Scholar Crossref Search ADS PubMed WorldCat 117. Beale AM , Jacques SDM , Weckhuysen BM . Chemical imaging of catalytic solids with synchrotron radiation , Chem Soc Rev , 2010 , vol. 39 (pg. 4656 - 72 ) Google Scholar Crossref Search ADS PubMed WorldCat 118. Groot FMFD , Smit ED , Schooneveld MMV , et al. In-situ scanning transmission X-ray microscopy of catalytic solids and related nanomaterials , Chem Phys Chem , 2010 , vol. 11 (pg. 951 - 62 ) Google Scholar Crossref Search ADS PubMed WorldCat 119. Fan FT , Feng ZC , Li C , et al. In situ UV Raman spectroscopic study on the synthesis mechanism of AlPO-5 , Angew Chem Int Ed , 2009 , vol. 46 (pg. 8899 - 903 ) Google Scholar Crossref Search ADS WorldCat 120. Fan FT , Feng ZC , Li C . UV Raman spectroscopic study on the synthesis mechanism and assembly of molecular sieves , Chem Soc Rev , 2010 , vol. 39 (pg. 4794 - 801 ) Google Scholar Crossref Search ADS PubMed WorldCat 121. Fan FT , Feng ZC , Li C . UV Raman spectroscopic studies on active sites and synthesis mechanisms of transition metal-containing microporous and mesoporous materials , Acc Chem Res , 2010 , vol. 43 (pg. 378 - 87 ) Google Scholar Crossref Search ADS PubMed WorldCat 122. Wang JY , Fan FT , Li C , et al. Influence of extra-framework Al on the structure of the active iron sites in Fe/ZSM-35 , J Catal , 2013 , vol. 300 (pg. 251 - 9 ) Google Scholar Crossref Search ADS WorldCat 123. Pan X , Bao XH . The effects of confinement inside carbon nanotubes on catalysis , Acc Chem Res , 2011 , vol. 44 (pg. 553 - 62 ) Google Scholar Crossref Search ADS PubMed WorldCat 124. Zhang F , Pan XL , Hu YF , et al. Tuning the redox activity of encapsulated metal clusters via the metallic and semiconducting character of carbon nanotubes , Proc Natl Acad Sci USA , 2013 , vol. 110 (pg. 14861 - 6 ) Google Scholar Crossref Search ADS PubMed WorldCat 125. Fu Q , Li WX , Yao YX , et al. Interface-confined ferrous centers for catalytic oxidation , Science , 2010 , vol. 328 (pg. 1141 - 4 ) Google Scholar Crossref Search ADS PubMed WorldCat 126. Fu G , Yi XD , Huang CJ . Developing selective oxidation catalysts of light alkanes: from fundamental understanding to rational design , Surf Rev Lett , 2007 , vol. 14 (pg. 645 - 56 ) Google Scholar Crossref Search ADS WorldCat 127. Wang ML , Zheng HZ , Li JM , et al. In situ Raman and pulse reaction study on the partial oxidation of methane to synthesis gas over a Pt/Al2O3 catalyst , Chem-Asian J , 2011 , vol. 6 (pg. 580 - 9 ) Google Scholar Crossref Search ADS PubMed WorldCat © The Author(s) 2015. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd. All rights reserved. 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TI - Applied catalysis for sustainable development of chemical industry in China
JF - National Science Review
DO - 10.1093/nsr/nwv019
DA - 2015-06-01
UR - https://www.deepdyve.com/lp/oxford-university-press/applied-catalysis-for-sustainable-development-of-chemical-industry-in-k08BucRey9
SP - 167
EP - 182
VL - 2
IS - 2
DP - DeepDyve
ER -