改良西门子法热氢化反应模拟及工艺参数优化

介绍了改良西门子法多晶硅生产工艺。利用Aspen Plus对改良西门子法中的热氢化反应进行模拟,研究了反应温度、反应压力和进料配比对三氯氢硅收率的影响,得出进料配比是影响三氯氢硅收率最重要的因素,并运用正交设计的方法找出最优工艺参数,从而指导实际生产。

In situ synthesis of Fe-N-C catalysts from cellulose for hydrogenation of nitrobenzene to aniline

Owing to Fe being the most abundant and least expensive transition metal on the earth,the utilization of Fe-based catalysts for catalytic hydrogenation has attracted worldwide attention.In this work,a series of N-doped C supported Fe catalysts(Fe-N-C)were prepared by co-pyrolysis of cellulose and ferric chloride under ammonia atmosphere.Characterization methods such as elemental analysis,atomic absorption spectroscopy,nitrogen adsorption-desorption isotherms,transmission electron microscopy,high-resolution transmission electron microscopy,X-ray diffraction,and X-ray photoelectron spectroscopy were carried out to explore the physicochemical properties of the catalysts.Using hydrogenation of nitrobenzene as a model reaction,the catalysts prepared at different pyrolysis temperatures displayed different activities.Fe-N-C-700 exhibited the best activity among these catalysts,with the yield of aniline being up to 98.0%under 5 MPa H2 at 120℃ after 12 h.Combined with the results of catalyst characterization and comparative tests,the transformation of Fe species and the generation of N-doped C,especially graphitized N-doped C,in the catalyst may be the main factors affecting the activity.A kinetic study was carried out and the apparent activation energy was obtained as 31.53 kJ/mol.The stability of the catalyst was also tested and no significant decrease in the activity was observed after 5 runs.

Quantum Chemistry of PAHs Thermal Cracking with Different Hydrogenation Degree

In order to investigate the influence of hydrogenation degree and structural variety on reaction trend of polyaro- matic hydrocarbons (PAHs) in resins and asphaltenes portion of heavy oil, a series of PAHs with different hydrogenation degree were selected as model compounds to simulate their different hydrogenation stage, and the PAHs thermal cracking reaction was simulated based on free radical mechanism by the density functional theory (DFT) to search for reactions'transition state. By comparing the dynamic data obtained from reaction simulation, it is showed that processing difficulty could rise with increasing condensed aromatic ring number, and hydrogenation could promote ring cleavage reaction, but excessive hydrogenation would decrease the oil conversion rate to reduce light-end products. In conclusion, proper hydrogenation was quite critical in promoting light-end products conversion efficiency and saving the processing cost as well. Operational instructions were given based on both PAHs hydrogenation performance and conclusions were drawn up from reaction simulation results.

Hydrogenation reaction characteristics and properties of its hydrides for magnetic regenerative material HoCu_2

The hydrogenation reaction characteristics and the properties of its hydrides for the magnetic regenerative material HoCu_2(CeCu_2-type) of a cryocooler were investigated. The XRD testing reveals that the hydrides of HoCu_2 were a mixture of Cu, unknown hydride Ⅰ, and unknown hydride Ⅱ. Based on the PCT(pressure-concentration-temperature) curves under different reaction temperatures, the relationships among reaction temperature, equilibrium pressure, and maximum hydrogen absorption capacity were analyzed and discussed. The enthalpy change ΔH and entropy change ΔS as a result of the whole hydrogenation process were also calculated from the PCT curves. The magnetization and volumetric specific heat capacity of the hydride were also measured by SQUID magnetometer and PPMS, respectively.

Theoretical Studies on Dehydrogenation Reactions in Mg2（BH4）2（NH2）2 Compounds

Borohydrides have been recently hightlighted as prospective new materials due to their high gravimetric capacities for hydrogen storage. It is, therefore, important to under- stand the underlying dehydrogenation mechanisms for further development of these ma- terials. We present a systematic theoretical investigation on the dehydrogenation mecha- nisms of the Mg2（BH4）2（NH2）2 compounds. We found that dehydrogenation takes place most likely via the intermolecular process, which is favorable both kinetically and thermo- dynamically in comparison with that of the intramolecular process. The dehydrogenation of Mg2（BH4）2（NH2）2 initially takes place via the direct combination of the hydridie H in BH4 and the protie H in NH2-, followed by the formation of Mg-H and subsequent ionic recombination of Mg-Hδ-…Hδ＋-N.

Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory

The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products(C6H6,HC≡C—C≡N,C6H5C≡N and HC≡CH)to be the same,and also decides the total disappearance rates of the reactants to be the same,for both original reactants quinoline and isoquinoline during the pyrolysis reaction.The results indicate that the intramolecular hydrogen migration is an important reaction step,which often appears in the paths of the pyrolysis mechanism.The activation energies of the rate determining steps are obtained.The calculated results are in good agreement with the experimental results.

Effect of hydrogen combustion reaction on the dehydrogenation of ethane in a fixed-bed catalytic membrane reactor

A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction,removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production.For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used.Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogenation method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and signi ficant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.

Converting of MSW into Valuable Hydrocarbons by Pyrolysis： Effect of Paper/Plastic Ratio and Reaction Time

Municipal solid wastes from industrial plants were pyrolyzed in a fixed bed reactor to evaluate the influence of paper/plastic ratio and reaction time both on product quantity and quality. Raw materials have been pyrolyzed under nitrogen in a 3.0 dm^3 autoclave. Results show considerable differences in yields and quality of products obtained by pyrolysis of wastes with different paper content. Light and heavy oils were mixtures of organic compounds containing valuable hydrocarbons and oxygenated chemicals, while chars were rather composed of inorganic compounds from the raw materials. Longer reaction time of pyrolysis had produced higher non-condensable gas, water and light oil. Gases contained CO, CO2 and hydrocarbons, but the concentrations were very function of reaction time and paper/plastic ratio. Light and heavy oils showed similarities with middle distillates and heavy oils in refinery, the high paper content of the raw materials was unfavourable for longer storage of waste derived oils.

Study on Preparation of Porous ZnO Microspheres and Photocatalytic Performance

This paper introduces the method of porous ZnO microspheres by sodium citrate assisted hydrothermal synthesis with a mild, economy： first, basic synthesis globose precursor of Zinc Carbonate Hydroxide, then followed by thermal decompose the precursor to obtain porous Zinc Oxide microspheres. The morphology and structure of the precursor and synthesized porous microspheres were characterize by a series of methods, and did a series of experiments by changing dosage and reaction time of the sodium citrate and urea, finally the paper discussed the formation mechanism of porous ZnO microspheres.

High Temperature Catalytic Hydrogenation of Acetone over Raney Ni for Chemical Heat Pump

Exothermic hydrogenation reaction of acetone is an important part of an IAH-CHP, and the performance of IAH-CHP is affected directly by this reaction. This paper studies the influence of space velocity, temperature, hydrogen flow rate and pressure on conversion and selectivity experimentally. The byproducts are analyzed and classified into three types: hydrogenation product, cracking products and condensation products. Both the conversion and selectivity of this reaction have the same trend with the change of space velocity, temperature and hydrogen flow rate, and has the opposite trend with the change of pressure. As the space velocity increases, the conversion curve is a gradual decline parabola but the selectivity curve is close to a straight line. Hydrogen flow rate has a more obvious influence on conversion than temperature, whereas on selectivity the situation is opposite. High pressure increases the conversion of acetone to all products, but the increment of byproducts is more than that of isopropanol, so the selectivity decreases as pressure increases.

Thermodynamic analysis for a chemically recuperated scramjet

Endothermic hydrocarbon fuel is regarded as an optimal fuel for a scramjet with regenerative cooling,which provides extra cooling through endothermic chemical conversion to avoid the severly limited cooling capacity when conventional fuels are adopted for cooling.Although endothermic cooling is proposed from the view point that the heat sink of a conventional fuel is insufficient,the heat-absorbing through endothermic chemical reaction is actually a chemical recuperation process because the wasted heat dissipated from the engine thermal structure is recovered through the endothermic chemical reaction.Therefore,the working process of a scramjet with endothermic hydrocarbon fuel cooling is a chemical recuperative cycle.To analyze the chemical recuperative cycle of a chemically recuperated scramjet engine,we defined physical and chemical recuperation effectivenesses and heating value increment rate,and derived engine performance parameters with chemical recuperation.The heat value benefits from both physical and chemical recuperations,and it increases with the increase in recuperation effectiveness.The scramjet performance parameters also increase with the increase in chemical recuperation effectiveness.The increase in chemical recuperation effectiveness improves both the performances of the fuel cooling system and the combustion system.The results of analysis prove that the existence of a chemical recuperation process greatly improves the performance of the whole scramjet.