In the long run, the crude oil would become heavier and poorer in quality. Hydrocracking technologies are regarded as one of the key techniques in efficient and clean conversion of residuum, and have become a major upgrading process in the refineries. In this paper, the application status of residuum ebullated bed and slurry bed hydrocracking technologies were introduced. The technical characteristics and technical-economic indicator were also compared. And then, the new progress and future trend were reviewed. The ebullated bed technology is the most mature residuum high-efficient conversion technology currently, and will continue to play an important role in residuum utilization. In the future, the research is focused on combined technology and unconverted tail-oil processing technology. Although the slurry bed technology is far from mature compared with ebullated bed technology, it has its advantage of high conversion rate and great potential for future development. The technology development should resolve equipment coking problem and develop high-active and high-dispersible catalyst.

Ethylene propylene diene monomer(EPDM)has wide applications in the auto industry,construction industry,oil additives,plastic runway etc. due to its unique performance. This article summarizes the production technology of EPDM,and its grades,performance and applications. Based on the existing EPDM researches,the development of catalyst for EPDM,core-shell structure spherical EPDM,long chain branched EPDM by situ polymerization,and the copolymer by ethylene and propylene and other dienes are expounded. Meanwhile,the polymerization technology,monomer recovery technology,deactivation washing technology,and flash concentration technology in the solution polymerization of EPDM and the plant production technology of a foreign company in China are studied in detail. It puts forward that the key in the production of EPDM is the polymerization catalyst system. By the upgrading of catalysts,we could produce EPDM with different functions so as to meet the demand of high-performance materials. So,it points out that the development of new catalytic system will become one research focus in the future.

As a potential platform compound,2,3-butanediol is used widely and can replace the traditional platforms——four carbon hydrocarbons. With the requirements of energy security and environmental protection,biological refinery of 2,3-butanediol have gained substantial interest due to its obvious advantages over the chemical method. However,due to the high boiling point and hydrophilicity of 2,3-butanediol,it is very difficult to be recovered from fermentation broth,which has become the bottle-neck of industrial production of 2,3-butanediol. Therefore,it is important to develop cost effective process to separate 2,3-butanediol. The progress is reviewed on the downstream processing of 2,3-butanediol fermentation. The process contains mainly three steps:solid-liquid separation,deep treatment of broth and purification of 2,3-butanediol. Many technologies have been involved,such as centrifugation,flocculation,membrane filtration,ion exchange,electrodialysis,extraction,distillation and so on,and their optimization and combinations. In the future,researchers should focus on the effective integration of existing technologies and development of new separation process.

The solubility of valsartan in ethyl acetate was measured by a static equilibrium method at temperatures from 278.15K to 323.15K. The solubility data were correlated by the modified Apelblat equation,the NRTL equation,and the λh equation. In addition,the thermodynamic parameters (including the enthalpy,entropy and Gibbs energy) were calculated by the van't Hoff analysis. The results showed that the solubility of valsartan obviously increased with an increase of temperature. The experimental data were well correlated with the above models because the mean deviation values of these three models were 1.03%,3.87%,and 1.7%,respectively. Therefore,the modified Apelblat equation was the best choice in the correlation of the solubility data of valsartan. The values of thermodynamic parameters proved that the dissolution process of valsartan in ethyl acetate was endothermic,spontaneous and entropy-driven. The main contributor to the standard molar Gibbs energy of solution was the enthalpy change during the dissolution process. Furthermore,the supersolubility of valsartan in ethyl acetate was measured at different stirring rates and cooling rates by the laser method. The results indicated that the metastable zone was wider under the condition of low stirring rate,high temperature and large cooling rate. Meanwhile,the temperature effect was remarkable but the cooling rate had little effect on the metastable zone.

In this paper,comprehensive performance of impinging jet cooling system heat exchanger was experimentally studied using nanofluids. The heat transfer efficiencies were compared for nanofluids of different flow rates,jet height and types. The results revealed that heat transfer efficiency significantly increased with the introduction of nanofluids in jet,but,when the mass percentage of nanofluids exceeded of 0.5%,the heat transfer coefficient did not change significantly. For different types of nanofluids:Cu- water,Al₂O₃-water,Al-water nanofluids,the highest heat transfer efficiency was observed for Cu- water. In addition,there was a particular jet height,where the maximum heat transfer coefficient could be reached. The results would be practically valuable in designing and manufacturing light and efficient heat exchanger.

A calculation method of the overall heat transfer coefficient of concentric internally heat integrated distillation column(HIDiC)is proposed in this study. The method is based on the physical property data of experimental system. The ethanol-water mixture is used as a case to study the self-made pilot-plant concentric HIDiC under different pressure ratio experimentally(1.4—2.6,step is 0.1). The phase transformation to the coefficient of heat is calculated by measured temperature distribution. The overall heat transfer coefficient and heat exchange amount between the two columns sections are computed through experimental temperature in this column. The calculated value of the overall heat transfer coefficient decreases with the increase of the pressure ratio and is shown to be between 300W/(m²·K) and 800W/(m²·K). In the case of operating conditions and product purity consistent with the experimental value,the heat transfer calculation value between rectifying and stripping sections is substituted into software to simulate. The temperature distribution simulated by the calculated value in simulation software is correlated with the experimental temperature. The method of calculating the overall heat transfer coefficient of HIDiC is proved to be practical and effective.

The solubility and supersolubility determines the width of the metastable state and the crystallization process is operated in the metastable zone. Therefore,the solubility and supersolubility are an important basic data in industrial crystallization process. In this study,lithium carbonate was used as solute and the solubility of lithium carbonate in water was measured at (283.15 to 318.15) K and atmospheric pressure by using a gravimetric method. The supersolubility was measured by using a laser dynamic method. It was obviously showed that the solubility and supersolubility of lithium carbonate in water and the width of the metastable zone decreased with increasing temperature. The solubility data was correlated by Van't Hoff equation and modified Apelblat equation. The results indicated that the solubility of calculated values was in good agreement with the experimental values. The average relative deviation of the Van't Hoff equation and the modified Apelblat equation were 0.54% and 0.20%,respectively. The changes of enthalpy(ΔH_d),entropy(ΔS_d)and Gibbs free energy (ΔG_d)of the dissolving process were obtained by the thermodynamic calculation. The dissolving process was a non-spontaneous process of exothermic and Entropy. The entropy change was the main influencing factor in the dissolution process.

Currently,fluid-structure optimization of hydrocyclone has been mainly limited to single-parameter size optimization. Generally,the optimization process is dependent upon the method of separate simulation with multiple sets of grid. Nevertheless,the approach is time-consuming and not capable of controlling the micro size deformation. Besides,further improvement on the separation efficiency of cyclone is rather difficult once a certain maximum optimization is achieved. To solve this problem,mesh deformation-based shape optimization method was proposed. Aimed at improving the hydrocyclone separation efficiency with ANSYS Fluent mesh deformation method,the hydrocyclone sharp structure was optimized and the hydrocyclone separation efficiency was increased from 95.69% to 99.18%. A comparative analysis involved with pressure drop,velocity and oil phase volume distributions before and after optimization was then conducted. The results indicated that the smoothing mesh deformation driven grid nodes by Fluent mesh morpher could concurrently contribute to the optimal combination of structural parameters in the deformation zone,and the optimization of the automation and intelligentization of the iteration process. Besides,it had a considerable capability of global searching and strong robustness. Fluent mesh morphing optimization algorithm can shorten CAD modeling time,avoid mesh reconstruction and further improve the separation efficiency of hydrocyclone within a certain range on the basis of single-parameter size optimization.

At present,researches on coiled tube,about internal flow and heat transfer characteristics,are only limited under the condition of uniformly heated,at the same time,non-uniform heating are rarely reported. But in practice,spiral tube is heated non-uniformly most of the time. To solve the problem,flow boiling heat transfer characteristics in horizontal helically coiled tube with circumferentially non-uniform heating,under the range of system pressure 0.7—1.0MPa,mass flux 181—364kg/(m²·s) and mass quality 0.07—0.69,were experimentally studied in this paper. The in-tube flow boiling heat transfer coefficient variations with surface heat flux,fluid mass flux,and mass quality were examined under two different non-uniform heating modes and also compared with the data of circumferentially uniform heating condition. Results showed that the in-tube flow boiling heat transfer coefficient was the highest under the condition of the inner half wall heated and outer half wall adiabatic,while it was the lowest with the inner wall heated and outer wall adiabatic.

A new three dimensional pulsating heat pipe was formed by improving traditional pulsating heat pipe cooling segment into a double helix structure. An experimental platform of a new three-dimensional pulsating heat pipe was established. In this paper,the influence for the start performance and heat transfer performance of the new type of three-dimensional pulsating heat pipe at various heating powers (20W to 700W)and various inclination angles(0°,50°,90°) were investigated. Acetone was used as working fluid with 54% fill ratio. The temperature of cooling water was 22℃. The start running features of pulsating heat pipe by temperature changes at heating period and cooling period were judged. Heat transfer effect of heat pipe by total thermal resistance was evaluated. Experimental results showed that the pulsating heat pipe could start up at 0°,50°and 90°. It was more conducive for the new type of pulsating heat pipe to start up and operate stably at 90°. At angle 90°,pulsating heat pipe started up at heat power 40W. Stable operation status at 100W as well as heat transfer limit at 700W were achieved. The tendency of the thermal resistance decreased first and then increased. The minimum heat resistance could reach 0.117℃/W. There was no significant difference for the heat resistance of pulsating heat pipe between the angle 90°and 50°. But at angle 0°,in the whole progress,it was easy to achieve heat transfer limit and the thermal resistance was much higher than that of 50°and 90°. Heat limit at 180W was achieved.

Molten salt frozen-wall is proposed as an option for protecting the metallic walls from corrosion by a layer of frozen salt which can prevent gas and liquid medium contacting with metallic wall. Accurate monitoring and controlling the thickness of frozen wall is the key for its successful application. Different on-line thickness detection methods were studied in the condition of frozen-wall forming and maintaining,and results were compared and analyzed with the thickness measured by mechanical caliper. For temperature gradient calculation method the result is more accurately in a state of balance than that in the unsteady condition,but it need to layout applicable thermocouples. The thickness of frozen wall also could be detected by cooling heat calculation method,which using outside heat exchange amount and metal wall temperature,its advantage is that there is no need for additional equipment,but its stability and accuracy depends on the amount of cooling heat,Online image can reflect thickness of frozen wall visual,but it need to be equipped with stable and reliable high temperature camera system. Because molten salt frozen-wall will be used in airtight condition which there is no water and oxygen,these on-line methods should be further researched and evaluated in the real system.

Heat transfer performance of nanofluids in nucleate pool boiling was experimentally investigated in 6 mm copper beads. The nanofluid was prepared by dispersing the 40nm CuO nanoparticles in the base fluid water by using sodium dodecyl benzene sulphate(SDBS) as the surfactants,and both the proportion of the mass fraction were different. Experimental results showed that the nanofluid is in stability and has a good heat transfer performance at the same concentration ranges from 0.01% to 0.03% of nanoparticles and surfactants. The nanofluid could transfer heat more effectively at the slightly higher concentration of surfactants. The best heat transfer coefficient from the range above was 41670 W/(m²·K),where the concentration of CuO and SDBS were 0.02% and 0.03%,respectively. The sedimentation occurred obviously at the larger proportion of nanoparticles,which could enhance or weaken the boiling heat transfer at the different grade. The visualization research of nanofluid pool boiling was also investigated. It could interpret experimental results by analyzing the detachment characteristics of boiling bubble. All these results in this paper can be supplied for the research of nanofluid pool boiling on porous bead-packed structures with useful experimental data.

The classify-impact mill possesses the advantage of high output. It is also widely used in crushing industry. However,the study of classify- impact mill is still insufficient. The grinding experiment of LNI-66A classify-impact mill was finished in this paper. The results showed that its production was higher than 4 beaters or 8 beaters when 2 beaters were used in classify-impact mill. As for the height of beaters,the production was higher than 10mm,20mm,40mm and even 50mm when the height of beaters was 30mm. Ansys Workbench 15.0 was used for numerical simulation of crushing cavity in this study. The distribution of the crushing cavity flow field presented by its velocity field and pressure field,and the influence of the flow field in grinding area caused by the parameters of beaters were discussed in this paper. Simulation results showed that the radial velocity of grinding area changed little while the pressure increased with the increase of the number of beaters. The crushing efficiency and powder production decreased on account of the increase of the number of beaters. The velocity of rising air near beaters and the crushing areas of beaters would be affected by the height of beaters. The velocity of rising air near beaters could reduce the crushing efficiency, while the crushing areas of beaters could increase the crushing efficiency,showing that there was a better choice between the two aspects. As a result,the height of beaters cannot be higher or lower and there was a better value in it.

Aviation gasoline is an important member of aviation fuels. This article discusses the progress of aviation gasoline at home and abroad,which undergoes a course from mobile gasoline to leaded and unleaded aviation gasoline and that from low octane number to high octane number. Comparing the leaded and unleaded aviation gasoline standards,we find that there are several different technical indexes,including octane number,lead content,net heat of combustion,aromatic content etc. The analysis shows the differences in the two standards are because various base oils have been used to blend avgas. Simultaneously,this article points out it is possible to observe lead deposit,valve ablation and cylinder sealing reduction in piston engine when using Chinese 100 aviation gasoline. Unleaded 102 avgas produced by 12 manufactures have already been approved by the Federal Aviation Administration and is planned to replace the leaded avgas in 2018. Because of the demands of environment protection,energy-saving and emission-reduction,unleaded and bio-gasoline should be the development directions of aviation gasoline.

Biodiesel is a clean and renewable energy,which has drawn more and more attention in recent years. However,the high production cost of biodiesel has hindered its industrial applications. Many strategies including adopting cheap raw materials,efficient catalysts,new technologies and equipments have been developed to solve this problem,among which the development of cheap raw materials should be preferred. The spent bleaching clay from oil plants has a large oil content ranged from 20% to 40%,by recycling which to produce biodiesel can reduce the raw material costs as well as achieve resource utilization of factory waste. This article reviews the current research progress about biodiesel production from spent bleaching clay including the one-step and two-step processes. The two-step process is well developed but is complicated and a large amount of solvent is required. In contrast,the one-step process is simpler and less costly,while the reaction time is longer and the separation of catalysts is more difficult. Therefore,it is necessary to explore a one-step process featured with high reaction rate,high efficiency and easily recycled catalysts in the future.

The aged oil in treatment station and oil tank has increased dramatically as the exploitation of main domestic oilfields has entered their middle and late periods. It has become not only a waste resource and huge burden for the gathering system,but also one key factor in potential environmental pollution and safety risks if not timely treated. In this paper,we start with emulsion and sludge,the two main physical forms of aged oil,and conclude with the commonly used processes in aging oil treatment including extra electric treatment,thermal gravity settling,centrifugation separation,ultrasonic treatment,biological treatment and oxidative emulsion-three phases separation processes. We review the biological technology in aging oil demulsification through the mechanism of microbial cells and biosurfactant to achieve oil-water separation. In aging oil desulfurization,microbes directly consume sulfide compounds to reduce the sulphide content and thereby reduce the electrical conductivity,making the dehydration treatment and recovery and purification of crude oil easier. In oil sludge degradation,high hydrocarbon oils are treated by biological compost method. In oiled soil remediation,microbes degrade total petroleum hydrocarbons and PAHs to meet the landfill disposal standards after remediation of contaminated soils. Biotechnology has the advantages of low cost,low power consumption,remarkable effect and no secondary pollution,compared with some traditional physical and chemical methods,and therefore has a broad and promising development and application future. Moreover,we propose new research ideas and development directions for the oil aging process,and positively explore innovative strategies for oilfield gathering system.

Polyoxymethylene dimethyl ether(PODE_n) are ideal novel green oxygenated diesel blending compounds,which can not only utilize the excess methanol in China but also relieve the air pollution of haze. The present work provided an overview of the progress of PODE_n research in China and abroad,with the focus on the research background and significance,advantages of PODE_n,properties and quantitatively analysis methods,synthesis methods,process and reactor instruments. Meanwhile,the industrialization status of PODE_n were introduced followed by a summarization of the characteristics of different technologies and processes. Finally,potential applications of PODE_n were analyzed,and it is prospected that they are favorable to be used as diesel blending compounds,solvents or low temperature flow improver for diesel fuel.

Pyrolysis experiments of high sulfur petroleum coke under N₂ atmosphere at different temperatures were conducted in a tube furnace. TG-FTIR test was carried out to analyze the pyrolysis process and the transformation of sulfur species during the pyrolysis process was characterized by XPS. TG/DTG resulted show that the pyrolysis process experienced dehydration,decomposition of long chain aliphatic hydrocarbon and fused ring aromatic hydrocarbon stages,with the maximum rate of weight loss at 430℃ and 635℃ respectively. The FTIR analysis showed that the gas-phase products from the pyrolysis process mainly included CO₂,CH₄,H₂O,SO₂,aromatic compounds,aliphatic compounds and so on. In addition,the gas components that released at different temperatures showed great difference. The XPS analysis showed that the total sulfur content and the species on the surface of high sulfur petroleum coke were associated with the pyrolysis temperature. To be specific,the total sulfur content on the surface increased with the temperature,reaching a maximum value at 700℃,and the mutual conversion among different sulfur species occurred during the pyrolysis process.

This paper presents a modeling method for the coal gasification process proceeding in GSP pulverized coal gasification,GE coal-water slurry gasification and Opposed Multiple-Burner gasification based on the thermodynamic equilibrium with the aid of Aspen Plus. In the light of thermal conversion procedure of fine coal particles,the coal gasification was interpreted as consisting of four stages including pyrolysis,volatile combustion,char decomposition and gasification reaction. Then,the pyrolysis stage was calculated by the David Merrick model and the effect of pressure on the coal pyrolysis was corrected by means of Beath model. The volatile combustion stage was simulated by using Rstoic reactor and the yield of char decomposition products was calculated via compiling Fortran program. And finally,the gasification reaction stage was simulated based on the Gibbs free energy minimization. The results revealed that the simulated values from the developed simulation model of gasification processes were in good consistent with the industrial field data. The deviation of simulated results of volume fraction of the effective gas (CO+H₂) of these three typical entrained-flow gasifiers were all less than 2%,which can validate the reliability of the coal gasification model.

Polylactide(PLA)is a new biodegradable and biocompatible polymer,and can be prepared by ring-opening polymerization of lactides. Metal complexes are attractive catalysts for polylactide production,due to their rich structural availability,remarkable catalytic properties and stereoselectivity. In recent years,the low-toxic metal complexes have attracted growing interest. The progress in preparation of polylactide by low-toxic metal complexes is summarized and reviewed in this paper. The influences of the steric structure of ligands and the electronic effect of substituted groups on catalysis performance of complex catalysts are mainly explained. The effects of solvent on the existing state of complex in solution,the coordination-inserting of monomer and the ring-opening polymerization of lactide are analyzed. The development trends are proposed as well. With the knowledge of the mechanism of ring-opening polymerization of lactides by low-toxic metal complexes,new ligands will be designed and synthesized. Complex catalysts with high catalysis activity will be developed,and polylactide with improved properties will be produced in the future.

As a promising non-oil route technology with obvious advantages,light olefins production from syngas through one step has not been industrialized owing to the low selectivity of the catalyst. Research progress on the catalyst in past decade was introduced,and influences of active components,additives,carriers and preparation technology on the structure and properties of the catalyst were analyzed in this paper. The Fe-based and Co-based catalysts were considered as the most promising catalysts,and alkali metal,alkaline earth metal,transition metal,rare earth metal and non-metal showed different positive effects in modulating acid-base properties and electrical properties of the catalyst,which prevented light olefins from secondary hydrogenation reaction. Carriers,such as molecular sieve,had controllable pore structure and surface area,and were convenient for the diffusion and removal of light olefins from the catalyst. Improvements and combinations of the technologies of impregnation,precipitation,sol-gel,melting,hydro-thermal,microwave,supercritical and vacuum drying are all favored for the dispersion of active components and formation of ultra-fine particles. It pointed out that only with an appropriate combination of the catalyst,process and reactor could it obtain the maximum efficiency,break the ASF rule of light olefins yield limitations in F-T synthesis,and achieve its industrialization promotion.

TiO₂ has such advantages as excellent photocatalytic performance,high chemical stability,low toxicity and price. However,it only responds to UV light due to its wide forbidden band,and the electrons and holes are prone to recombination,leading to a decrease of catalytic activity and efficiency. This paper introduced the latest research progress on several main modification methods of TiO₂. Surface deposition of noble metal,semiconductor composite and dye sensitization can reduce the width of the forbidden band,increase the response wavelength and make full use of the sunlight. Ion doping can make TiO₂ crystal surface generate the defects,restrain the recombination of photoproduction electrons and holes,and increase the number of surface active centers. Carbon nanotube and graphene modification can improve light absorption of TiO₂ to the visible,extend the response range, speed up the electronic transmission,reduce the carrier recombination,and upgrade the catalytic efficiency. As a new doping material graphene has great potentials,and TiO₂-based multi-components composite photocatalysts are promising to achieve better catalytic properties than single-component surface modified or doped TiO₂. Finally,research progress on hydrophilic/hydrophobic surface modification of TiO₂ was reviewed.

The research status of isomerization process for producing clean gasoline is introduced. The domestic and foreign application and development of light naphtha isomerization and its catalyst in recent years are reviewed. From two sides of active metal and support,the research and development of metal-acid bifunctional catalyst are briefly introduced. The characteristic of solid superacid is mainly expounded. The research progress in modification of SO₄^2-/ZrO₂ solid superacid isomerization catalyst by introducing promoter,support,active metal elements are described in detail. Through the comparison of commercial isomerization process,the problems of isomerization catalyst are discussed. In the future,isomerization process will become the major technology for the production of clean gasoline. Inexpensive,environmental-friendly and efficient solid superacid catalyst will be widely applied in the industrial isomerization process.

The calcination procedures affected the state and the distribution of Cu species in the one-pot synthesized Cu-SSZ-13,which then influenced their catalytic performance greatly. In order to investigate the effect of calcination procedure on the Cu-SSZ-13 in the selective catalytic reduction of NO_x by ammonia(NH₃-SCR),we prepared the catalysts with different temperatures and ramp rates. The catalytic activity and hydrothermal stability and state of active species of the catalysts were tested. The calcination temperature did not change the structure of the catalyst,but affected the state and the stability of the active species. When the temperature was set at 600℃,all Cu species in the catalyst were isolated Cu²⁺ with excellent stability,and the catalyst showed the best catalytic performance and hydrothermal stability. When the temperature was fixed at 600℃,the activity and hydrothermal stability of the catalysts decreased with the increase of ramp rate. Considering the cost,we had better set the ramp rate as 1℃/min. Thus,the optimal procedure was to calcine sample at 600℃ for 6h with a ramp rate of 1℃/min,and the catalyst showed the best NH₃-SCR activity and the highest hydrothermal stability.

A series of CuZnAlTi catalysts were prepared by sol-gel method and characterized by X-ray diffraction,N₂-adsorption,H₂ temperature-programmed reduction and NH₃ temperature-programmed desorption. The catalytic performance of CO hydrogenation of catalyst was evaluated in a fixed bed reactor. The effects of Al/Ti molar ratio on the catalysts' structure and performance were investigated. Al and Ti in the catalyst were in the form of amorphous or highly fragmented. After Ti was introduced to CuZnAl catalyst,the dispersion of CuO,surface area and the amount of surface acid increased,while the average pore diameter decreased,and the reduction ability of CuO in the catalyst was weakened,therefore the product distribution of the CO hydrogenation reaction was changed accordingly. With the increase of Ti/Al ratio,the size of CuO grain and the average pore diameter in the catalyst showed a tendency of increasing firstly but decreasing subsequently,while the specific surface area and reduction peak temperature of the catalyst show an opposite tendency,and the conversion of CO showed no certain corresponding relationship with Ti/Al ratio.

A series of Pd/γ-Al₂O₃ hybrid catalysts with different promoters were prepared by impregnation. The catalysts were used for syngas-to-dimethyl(STD)reaction and the influence of the promoters on the catalysts' stability has been investigated. Then,the surface physic-chemical properties and crystal structure of the samples before and after the stability test and coke-burning regeneration test were characterized by a variety of physical techniques,such as N₂ adsorption、XRD、H₂-TPR and TG. Good correlation was observed between the promoters and the stability of Pd/γ-Al₂O₃ catalysts for STD reaction. Compared to the original Pd/Al₂O₃ catalyst,the addition of promoter CeO₂ had increased Pd dispersion,covered partial acid sites and inhibited carbon deposition to a certain degree,resulting in improvements on the activity and stability of the catalyst. The Ce-O-Zr crystal structure was formed when the compound promoters CeO₂-ZrO₂ were added,which was responsible for the increase of Pd dispersity and anti-carbon and anti-sintering ability,and therefore increased the activity and stability of the catalyst. Catalyst modified by SO₄^2- would deactivate quickly because of serious carbon deposition,medium strong acid reduction and sulfur loss.After 20h stability test,the CO conversion and DME selectivity of CeO₂-ZrO₂-Pd/γ-Al₂O₃ were above 59% and 65%,respectively. The catalytic activity of the regenerated catalyst recovered to 91.83% of that of the fresh one.

Polyvinylidene fluoride(PVDF),due to its excellent mechanical and chemical properties,has been widely used to prepare microfiltration,ultrafiltration,nanofiltration and reverse osmosis membranes for water treatment. However,its strong hydrophobicity makes it easy get fouled and poor permeability in the water treating process,so it is beneficial to improve the hydrophilic properties by modification. This paper summarized the researches of PVDF hydrophilic modification in recent years from the aspects of blending,co-polymerization,surface grafting and surface coating. By comparing the influence of hydrophilicity,permeability and anti-fouling among various modification methods,we introduced the modification effect and the advantages and disadvantages of various methods. Finally,the trends of PVDF hydrophilic modification research and its industrialization were prospected.

Ionic self-assembly(ISA)is a powerful tool to create functional supramolecular materials. In this context,the ISA between oppositely charged small molecular ions has attracted enormous attention because of the designable structure and tunable function of small ions. In this paper,the characteristics of ISA technique are briefly introduced,and the developments of small molecular ions based ISA in preparation of functional supramolecular materials are summarized,including the ISA between dye and surfactant,the ISA based on planar charged species and the ISA based on polyoxometallate. So far,great efforts have been made in developing charged building blocks and multi-functional materials. However,there is still a great need in further developing techniques for the practical applications of functional supramolecular materials by the ISA between oppositely charged small molecular ions.

Double perovskite-type composite oxides have attracted considerable attentions as a new inorganic non-metallic materials owing to their superiority in electromagnetism and catalysis recently.This paper describes the structure and the traditional and new synthesis methods of double perovskite-type composite oxides A₂B'B''O₆ at home and abroad.The structures of single and double perovskite composite oxides have both similarities and differences. They both have stable skeleton structure,while the main difference is that octahedral structure of B atoms is formed by arranging alternately of B'O₆ and B''O₆ for double perovskite,resulting in the forming of B'-O-B" and the superexchange effect.The traditional synthesis methods mainly include high-temperature solid phase method,sol-gel method and hydrothermal synthesis method,whereas the new synthesis methods mainly include microwave sintering method,sol-gel spontaneous combustion method,chemical solution deposition method,electrostatic spinning method,freeze drying method,amorphous alloy method and pulsed laser deposition method.The synthesis procedures and main features of each method are described in detail. The future development of synthesis method is also proposed,and exploring better synthesis method is still a hot spot in the future.

Non-silica mesoporous materials have been widely used in many fields owing to their outstanding structural characteristics and unique optical,electrical,magnetic properties,so the synthesis of these materials has gradually become the research focus. This work reviewed the recent research progress in surfactant initiated synthesis of non-silica mesoporous materials,such as mesoporous carbon,mesoporous metal oxides,and summarized the optimum synthesis conditions and the advantages of different materials. It also compared the performance and applications of the synthesized materials,and provided some prospections about their future development. Green surfactants,functional materials and co-template are main directions for the synthesis process.

The high concentration of poly(vinyl alcohol) hydrogels possesses self-healing property. However,its self-healing mechanism and the effects of the preparation conditions on the self-healing property of the hydrogel were rarely studied. In this paper,the high concentration PVA hydrogel was prepared by the freezing and thawing method. The optimum conditions were obtained by changing the preparation conditions(the PVA molecular weight,PVA concentration,freezing time,thawing time,numbers of freezing and thawing cycles,healing time,freezing temperature,etc.) and the self-healing mechanism was analyzed. The multiple self-healing performance of the hydrogel was also investigated. The results showed that the larger the molecular weight of the PVA,the better the self-healing performance of the hydrogels. The hydrogels prepared under 2h freezing and 1h thawing in only one cycle showed the best self-healing performance,and the best healing time was 12h. The PVA hydrogel could self-heal for many times. The self-healing property of the hydrogel was due to the interaction of reversible hydrogen bond,which was mainly influenced by the content of hydroxyl group and the mobility of the PVA molecules in the hydrogel.

Polystyrene@ZnO nanocomposites were synthesized by chemical bath precipitation method with well-dispersed polystrene microspheres as the template. The morphology,structure,composition and optical property of the as-prepared nanocomposites were characterized by the SEM,TEM,XRD,FTIR and DRS. The photocatalytic properties of the as-prepared samples were evaluated by photocatalytic degradation of methylene blue aqueous solution under UV light irradiation. The results showed that the prepared PS@ZnO nanocomposites was of core-shell structure and mono-dispersed. The core of the nanoparticles was typically spherical with an average diameter of ca. 200nm and the shell thickness was ca. 20nm. In addition,the degradation rate of PS@ZnO core-shell nanocomposites was 13% more than that of pure ZnO and they can be reused.

The ultrafine ZrO₂ nanocrystals with high surface area have been synthesized by the solvent-assisted vapor hydrolysis method. The effects of solvent and precursor concentration on the crystal structure of the ZrO₂ nanocrystals were investigated. The structural properties of the samples were characterized by X-ray diffraction(XRD),N₂ adsorption-desorption,scanning electron microscope(SEM),transmission electron microscope(TEM) and corresponding selected area electron diffraction(SAED). The experimental results demonstrated that the synthesized ZrO₂ nanocrystals had an average crystal size below 5nm and specific surface areas in the range of 237—450m²/g. Moreover,the synthesized samples possessed tetragonal phase and even higher specific surface areas using precursor of low concentration and in the presence of solvent,while,the samples with the monoclinic and tetragonal phase coexisted and lower specific surface areas were also obtained when we increased the precursor concentration or did not use solvent. These findings indicated that the precursor concentration and the solvent both exhibited excellent controllability over the properties of ZrO₂ nanocrystals such as crystal structure,specific surface area and crystal size.

Now,efficient utilization of aluminum and aluminum alloy slag(aluminum dross)is an important problem in solving environmental pollution,and a new method was presented which can realize convenient,economical and environmentally use of aluminum dross. Aluminum dross was firstly ground,screened and washed,then directly calcinated under high temperature to prepare alumina. The chemical composition and phase of aluminum dross,pretreatment aluminum dross and alumina products were analyzed by X-ray fluorescence(XRF)and X-ray diffraction(XRD). Results showed that washing aluminum dross could remove the soluble salt such as NaCl and improve the purity of alumina,and the higher the temperature,the higher the purity. After calcinated for 4 hours at 1600℃,the alumina had a purity of 95.86% and a whiteness of 87.2,and the specific surface was 38.98m²/g,allowing it to be used for abrasive and catalyst support etc. High temperature calcination of aluminum dross can remove most impurities of aluminum dross,and is a convenient,green method to prepare alumina.

The flavone compounds were extracted from citruspeels with a modified ethanol extraction method. The optimum extraction conditions were determined by orthogonal tests as:70% ethanol as extractant with solid to liquid ratio 1︰20(g/mL) at 70℃ for 2 hours. The concentration of the flavone compounds were determined with a spectrophotometer at λ=510nm. The results showed that the yield of flavone compounds to the raw materials reached 2.938mg/g,and the ethanol recovery could be up to 94%. The antimicrobial features were also studied. The inhibition of the extracted flavonoids against the growth of Staphylococcus aureus,E. coli,Botrytis cinere,and Cladosporiumfulvum was found,and copper and magnesium ions could enhance the inhibition function on bacteria and fungus respectively. In addition,pH and temperature of the flavonoids could affect the inhibition efficiency. The minimum inhibition concentration(MIC)was reduced by 20% with the ideal formulation of the extracted flavonoids,and the inhibition capabilities against Staphylococcus aureus,E. coli,Aspergillus niger,Botrytis cinere,and Cladosporiumfulvum were increased by 17%,27%,25%,28%,19% respectively under acidic pH and suitable temperature. The inhibition capabilities of the extracted flavonoids against bacteria and fungus,particularly against bacteria,were higher than those of chloro 3,5-dimethylphenol p-chloro-m-xylenol and thiophanate-methyl at the equivalent concentration.

The conventional synthesis of 2-fluoroadenine suffers from dangerous diazo reaction,expensive starting materials,low total yields and small scales,which limit the further application of 2-fluoroadenine. In order to overcome the preceding problems,a new method for the synthesis of 2-fluoroadenine from more commercially available 6-chloropurine was developed. The key intermediate 6-chlro-2-nitro-9-pyranylpurine was obtained from N9-pyranyl protected 6-chloropurine with a yield of 85% in butyl ammonium nitrate and trifluoroacetic anhydride and using CH₂Cl₂ as solvent. Then,6-chlro-2-nitro-9-pyranylpurine reacted with NH₄F with a yield of 82% in DMF followed by the ammonolysis in NH₃/CH₃OH solution. Finally,2-Fluoroadenine was obtained with a total yield of 58% through such a 4-step process. Chromatography was not necessary in the separating and purifying steps. The effects of protecting groups and reaction scales were investigated. The presented method avoided the toxic regents and expensive substrates and was simpler and safer,showing better practical application prospect.

Mitiglinide acid and its isomer by-product acid were prepared by the reaction of cis-hexahydroisoindoline with acid anhydride which was prepared firstly from (S)-2-benzylsuccinic acid via dehydration. Isomer by-product acid was separated and isomerizated to mitiglinide acid,with which mitiglinide calcium was obtained by salification reaction. The effects of process conditions were studied. It has been shown that the yield of acid anhydride could reach 90.49% with 0.03mol (S)-2-benzyl succinic acid as raw material,10mL toluene as solvent,5mL acetic anhydride as dehydrating agent,and reaction temperature 110℃,reaction time 1h,while the yield of the reaction of acid anhydride with cis-hexahydroisoindoline can reach 97.60%. The HPLC contents of mitiglinide acid and its isomer were both higher than 98% after separated with ethyl acetate. The isomerization conversion rate can reach 57.65% using toluene as solvent and refluxed for 3h. The overall yield of product mitiglinide calcium was up to 67.49% with a HPLC content of 99.25%. The structure of the intermediates and products were characterized by ¹H NMR.

As alkaline pH regulators,sodium hydroxide and calcium hydroxide are widely applied in fermentation industry. In the fermentation process,these two pH regulators produce organic acid salts with significantly different solubility,which can indirectly affect the fermentation process. This study focused on investigating the effects of two alkaline pH regulators on the 1,3-propanediol fermentation process. Through laboratory investigations on the process parameters (including osmotic pressure of the fermentation liquor,composition of tail gas,fermentation period and production intensity),the negative effect of using soluble strong alkali as pH regulator in 1,3-propanediol fermentation has been analyzed. The feasibility of interval anaerobic fermentation has also been examined using sodium hydroxide as pH regulator,and the fermentation grows into its end stage after about 21 hours within one period. So,the active stage of fermentation is relatively short,and shortening the fermentation period should be helpful to raise the production intensity. In addition,by ventilation during the interval anaerobic fermentation,the use of nitrogen can be further reduced to improve the economical efficiency of this process.

In view of the application and development of W-FGD technology of our country in recent years,this paper discusses the research progress of W-FGD sulfite oxidation control.The related research results of sulfite oxidation kinetics was introduced in detail,pointing out the major defects in the engineering practice of current power plant oxidation control,aiming at the defect analysis of the issue,and putting forward the slurry pH and ORP oxidation double control strategy.The theoretical feasibility of the plan was analyzed emphatically.Meanwhile,under the ideal state,the potential-pH model of the S(Ⅳ)-S(Ⅵ)-H₂O system was established.Results showed that the scheme has dual advantages of SO₂ gas absorption and the control of the CaSO₃ oxidation,and could effectively alleviate desulfurization system scaling,reduce energy consumption of the oxidation fan,optimize the control system of calcium sulfite oxidation,raise the quality of gypsum. The research indicates that the proposed scheme in sulfite oxidation control has a good application prospect.

Automobile exhaust leads to serious pollution,a mixture of organic solvent and ionic liquid(IL)was proposed as the mixed extractant to produce clean gasoline whose sulfur content below 10μg/g. The composition and property of model gasoline neared real FCC gasoline during the simulation. The selectivity and solubility of 30 kinds of normal ILs to cyclohexane-thiophene system were calculated by COSMO-RS model,and [EMIM][BF₄] might be the most suitable IL as entrainer with N-formylmorphol(NFM). Then simulation and optimization of extractive distillation process were carried out by Aspen Plus,which used NFM and [EMIM][BF₄] as mixed extractant. The optimized results showed the extractant was composed of NFM(98wt%) and [EMIM][BF₄](2wt%),reflux mass ratio was 0.4 for extractive distillation column,recovery ratio was 70% and the mass flow ratio of solvent to feed was 1. The method of extractive distillation could remove benzothiophene,thioether and thiophenes effectively,and the content of these sulfides could be decreased from 1581μg/g to 5.37μg/g in model gasoline,desulfurization efficiency was 98.1%,the distillate could reach up to mass yield 70% and volume yield 75%. Moreover,the prediction accuracy of COSMO-RS model in thermodynamics of IL,UNIFAC model in vapor-liquid equilibrium of organic sulfur compounds -hydrocarbon system and the reliability of simulation process were tested by comparing calculated value and experimental value in literature.

The wet flue gas desulfurization(WFGD) system occupies a heavy water consumption,and large amounts of water get loss with net gas. This study can decrease the desulfurization serosity temperature and reuse moisture and latent heat of flue gas by the way of vacuum distillation to achieve the multiple purposes including energy and water conservation and improving the desulfurization efficiency. In this experiment,we studied distillation characteristics,the condensate water quality and release characteristics of the non-condensable gas under different evaporation temperature difference,cooling water temperature and evaporation pressure by whirling evaporator. Under the experimental conditions of this paper,results showed that the evaporation rate was between 0.07 and 0.77. It increased with an increase in the evaporation temperature difference and decreased with an increase in the cooling water temperature and evaporation pressure. For the condensing water,pH was between 8.14 and 8.33 and its change was small which did not present obvious rules with evaporation pressure,evaporation temperature difference and cooling water temperature rising. The effect of ammonia co concentration becomed weak which was just between 1.25mg/L and 5.26mg/L. It increased with the increase of evaporation pressure and evaporation temperature difference. It becomed weak with the increase of cooling water temperature. S^IV ncentration was between 6.13×10^-4mol/L and 7.78×10^-4mol/L. It increased with the increase of the evaporation temperature difference and evaporation pressure. It decreased with an increase in the cooling water temperature. Total alkalinity existed in the form of HCO₃^-,changing from10.3mg/L to 20.7mg/L,which has the same regular pattern with ammonia. NH₃ producing each unit condensate water,increased with evaporation pressure and cooling water temperature rising. It decreased with evaporation temperature difference increase.

The Fe(II)(EDTA)/O₃ process was used to degrade polymer-contained wastewater. The effects of influencing factors such as EDTA concentration,Fe²⁺ concentration,hydraulic retention time (HRT) and initial pH on removal rate of polyacrylamide (PAM) and degradation efficiency of COD were studied. Moreover,the kinetic characteristics and mechanism of Fe (Ⅱ) complexing and catalysis reaction of ozone were discussed. Results showed that the PAM removal rate reached at 75% when the EDTA concentration was 0.050mmol/L,Fe²⁺ concentration was 0.050mmol/L and HRT was 120min. The increase of initial pH was in favor of PAM removal rate. At the same time,the pH of the wastewater decreased slowly along with the HRT. In addition,the COD values of the wastewater gradually increased to maximum when the HRT was during 30min and then decreased with the time gradually to a stable value. Furthermore,the degradation of polymer-contained wastewater conformed to the second-order kinetics whose rate constant was 2.35×10^-4—3.35×10^-4L/(mg·min) when the initial PAM concentration was 50—100mg/L.

Membrane bioreactor(MBR) has been widely used in the field of wastewater treatment. The addition of carriers has partly effect on the wastewater treatment efficiency and membrane fouling of MBR. In this work,different dosages of soft and hard carriers were added into MBR. Impact of suspended carriers on the treatment efficiency and membrane fouling of the MBR was studied. Results showed that the treatment efficiency of MBR for COD,ammonia nitrogen and total phosphorus was improved. The process of membrane fouling was obviously slowed down after adding carriers. The improvement effect of soft carrier on MBR was better than that of hard carrier. The removal rates of COD,ammonia nitrogen and total phosphorus were 96.53%,52.75% and 98.21%,respectively. Membrane fouling was mitigated by 41.43% of the original system after 30 days operation. According to the comparison,soft carrier supplied more living room for microorganism and the microbial biomass of reactor could be improved,so that the wastewater treatment efficiency of MBR was improved and membrane fouling was mitigated. The soft carrier was a kind of suitable carrier to enhance the MBR system,and the optimum dosage was 20% of effective volume of reactor.

The content of cobalt in the waste cobalt and manganese catalyst in the production of PTA was low and the content of manganese was high. The common cobalt and manganese separation methods generally were not suitable for this material and would make cobalt and manganese mixed with each other,leading to incomplete separation. Ammonia - carbonate method was used in the separation of the cobalt and manganese from lixivium of the waste residue of PTA in this paper. As the surplus rate of cobalt and the precipitation rate of manganese were used as assessment indicators,the effects of the carbonates' types,reaction time,temperature,stirring speed,the amount of ammonia and the amount of carbonate on the separation effect of cobalt and manganese were studied on the basis of orthogonal experiments. Experimental results show that,in the solutions of ammonia-sodium carbonate,ammonium carbonate and ammonium bicarbonate,the best reaction condition is: stirring rate 200r/min,reaction time 8 hours and temperature 20℃. The amount of ammonia is 1.9,1.4 and 1.7 times of chemical stoichiometric coefficient, respectively, and the amount of carbonate is 1.0,1.3 and 1.3 times. The surplus rate of cobalt in these three solutions can reach to 96.0%,99.8% and 99.5%,respectively,and the precipitation rate of manganese can all reach 100%.

To study the effects of different final temperatures to heavy metals volatilization and adsorbent adsorption characteristics,an experiment of Huadian oil shale semi-coke combustion is carried out. Results indicate that the volatilization rate of each element increases along with the raise of temperature,and the volatilization rate of Cd,Te,Co,Sn,Pb and Sb increases distinctly when temperature reaches to 650℃. Cd and Te have higher volatilization rate,while that of Mn,Y and W is relatively lower within each temperature segment. The contents of most elements significantly increase after adding Kaolin and CaO,showing that the adsorbents have good adsorption effects for most elements. As can be seen from the adsorption rate,except W and Te,CaO has good adsorption effects for the metal elements like Co,Mn,Cu,Y,Sn and Cd in especial,while Kaolin has good adsorption effects for the metal elements like Co,Mn,Cu,Y,Sn and Cd except Pb and Te. CaO has better adsorption effects about same certain heavy metal elements than Kaolin.

Environmental and food safety issues caused by cadmium pollution have seriously threatened human health. In this paper,soy protein was loaded on konjac glucomannan(KGM) gel molecular skeleton and the structurally stable soy protein loaded KGM adsorbent were obtained by chemical cross-linking reaction. A detailed characterization of its structure and further study of its adsorption performance for Cd(Ⅱ) were performed. The results showed that soy protein loaded KGM adsorbent with porous structure showed fast adsorption rate for Cd(Ⅱ). The adsorption equilibrium can be reached within 5 min and the adsorption process followed pseudo-second order kinetics. The removal efficiency can be 99.99%. Isotherm results showed that the soy protein loaded KGM adsorption process was well described by the Langmuir isotherm equation,and the maximum adsorption capacity was 52.63mg/g.

Currently,the crop straw was washed by water aquapulper,which has the disadvantages of high power consumption and poor washing effect. In this experiment,a new straw washing device was designed,and the experiment was carried out with wheat straw. Experiments were conducted to study the influences on the wheat straw moisture content,impurity removing efficiency,power consumption per unit,by process parameters like agitator speed,water inflow and feed rate etc. According to single factor experiment results,we analyzed the washing device by response surface optimization. The results showed that power consumption per unit has a minimum value,when the agitator speed is 9.5r/min,water inflow 1.35 times saturated water inflow,feed rate 1400kg/h. The washing device can satisfy the requirement of wheat straw moisture content and impurity removing efficiency,and washing device has the highest comprehensive efficiency.

In the operation and maintenance of ammonia synthesis process with semi-water gas,coking problem of a Guizhou company's compressor heat exchanger is one of the most prominent and urgent problem. Coking not only caused the heat transfer efficiency decrease,increased the resistance,reduced compression ratio,but also seriously affected the normal operation of production. This paper aimed at the compression section of synthetic ammonia coking phenomenon of a Guizhou company. Based on coking mechanism and composition,ultrasonic cleaning method was used. OP-10,sodium dodecyl sulfate were selected as leaning agent. Sodium hydroxide was selected as co-cleaning agent. Optimum composition and concentration of ultrasonic cleaning agent,cleaning temperature and cleaning ability were studied. Experimental results showed that the composition of the cleaning agent is 60g/L OP-10 emulsifier,50g/L sodium dodecyl sulfonate,3g/L sodium hydroxide with the volume ratio of 1∶2∶2. When the ultrasonic cleaning was performed at 50℃,the cleaning result was the best.

To solve the limitations of methanol washing tower efficiency and the problem of excessive amounts of methanol content in the mixed carbon four in a mixed carbon four deep processing project in a petrochemical company,a complete sets of technical equipment of a hybrid micro extraction coupled modular depth of coalescence separation is developed for removal of methanol in the carbon four. The pilot test is performed at a side line of the petrochemical company. The experimental results show that at the inlet and outlet pressure drop of 5kPa,water injection 5%,retention time within 180s and the inlet methanol content of 300—400μL/L,1200—1400μL/L and 40000—50000μL/L in the mixed carbon four,the outlet methanol content is 10—30μL/L,50—100μL/L and 4000—5000μL/L with a separation efficiency higher than 96%,95% and 88%,respectively. The features of deep and quick separation ability of methanol with low pressure drop at a wider range of elasticity of operation show that the technology has a good applicability in the system of water elution of methanol in carbon four,providing a new way of separating the mixed carbon four and methanol.

With the deepening of China's New Normal,the strategy of innovation-driven development is becoming the only way out for future Chinese economy. The industry in Chemical Industry Park is one of the main components among Chinese economy industries. Therefore, how to use intellectual property to promote the innovation and industrial upgrade in Chemical Industry Park is the target of this paper. This paper investigates the development of intellectual property for Chemical Industrial Park according to the national strategy of creative-activated development in industrial upgrading. Domestic petrochemical enterprises own not only less application amount of patent than overseas,but also poorer patent quality and usage. In the aspect of patent layout for Chemical Industry Park,the government should have global view and establish management system of intellectual property accorded with the Park; the manager should plan strategy of patent layout according to industry chain; and the enterprise should pay much more attention to patent technique and industry connection. In the aspect of patent conversion,the patent could be effectively converted by solving the value of patent and bilateral information docking. The industry upgrade for Chemical Industry Park could be motivated.

Low-dimensional carbon nanomaterials,including fullerene,carbon nanotube and grapheme,are the research hotspot in the field of nanomaterial and nanotechnology. In this paper,three kinds of typical low-dimensional carbon nanomaterials were selected as the research object. Patent information about the three kinds of low-dimensional carbon nanomaterials was collected by Derwent innovations index database from 2005 to 2015. Through analyzing the granted patent numbers,country distribution of patent applications,patentee's names,subject category and the international patent classification code,the authors found that in recent years,researchers has gradually paid pay more attention to grapheme,but less to carbon nanotubes and fullerene. By the analysis of the technical innovation status and the development trend of low-dimensional carbon nanomaterials,we also revealed the existing problems in the further development of low-dimensional carbon nanomaterials. The development levels of low-dimensional carbon nanomaterials in different research fields are unbalanced,and there is still lack of comprehensive development strategy. The industrialization of technological achievements and the research outcomes of original innovation is still problematic and the investment for research and development is insufficient. This article also gave the corresponding suggestions about the restrictions of developing low-dimensional carbon nanomaterials. The results will provide references for the technical innovation and strategic development of low-dimensional carbon nanomaterials.