A safe and efficient process for the preparation of difluoromethane in continuous flow

Difluoromethane is typically produced vialiquid-phase fluorination as performed in a batch reactor. However,this process suffers from some problems, e.g., severe corrosion of the reactor, high safety risk, and the regeneration of the catalyst. In this paper, a flow process as performed in the tubular reactor was designed. The optimum conditions for continuous synthesis of difluoromethane were obtained as follows: the reaction temperature was 100℃, the molar ratio of dichloromethane to hydrogen fluoride was 1.6:1 and the reaction time was 300 s. The operation of the cyclic process was stable for 24 h with the conversion per pass of hydrogen fluoride up to 16.2%.The unreacted raw materials were easily reused. The deactivation of the common catalyst, antimony pentachloride, was investigated by catalyst concentration curve and XPS analysis. The approach proposed in this work is proven to be safe, efficient and low amount of catalyst.     

Computational design of heterogeneous catalysts and gas separation materials for advanced chemical processing

Functional materials are widely used in chemical industry in order to reduce the process cost while simultaneously increase the product quality.Considering their significant effects,systematic methods for the optimal selection and design of materials are essential.The conventional synthesis-and-test method for materials development is inefficient and costly.Additionally,the performance of the resulting materials is usually limited by the designer’s expertise.During the past few decades,computational methods have been significantly developed and they now become a very important tool for the optimal design of functional materials for various chemical processes.This article selectively focuses on two important process functional materials,namely heterogeneous catalyst and gas separation agent.Theoretical methods and representative works for computational screening and design of these materials are reviewed.     

Simulation and assessment of manufacturing ethylene carbonate from ethylene oxide in multiple process routes

Ethylene oxide(EO) is an important raw material for producing ethylene carbonate(EC). However, the traditional method for the separation of EO from mixture gas by water in the refining process is high energy consumption. In this paper, two processes of manufacturing EC from EO mixture gas were studied by process simulation. Two processes for producing EC from EO mixture as raw materials without EO purification, called the OSAC process and the Modified OSAC process, were developed and assessed systematically. Both processes use EC as the absorbent to capture EO, avoiding the separation process of EO from solution. For comparisons, the EC producing process containing EO absorption by water, EO refinement and carbonylation process were also modeled, which was called the ERC process. Three schemes were designed for the EO absorber using EC as absorbent. Compared with the initial absorber scheme,the optimal liquid–vapor ratio is reduced from 1.66 to 1.45(mass). Moreover, the mass distribution analysis for the three processes were carried out in the form of the material chain. It was found that, compared with the ERC process, the energy consumption of the OSAC and the Modified OSAC process is reduced by 56.89% and 30.03%, respectively. This work will provide helpful information for the industrialization of the OSAC process.     

微波辅助萃取中药刺五加中有效成分的研究

Microwave-assisted extraction (MAE) for active ingredients in Ciwujia was studied by using ethanol as the extractant. Comparing MAE with conventional methods, the former can save the extracting time and increase the content of the active ingredients in product. As to the operation in MAE, the continuous radiation process is more convenient for the extraction for traditional Chinese medicine than the intermittent radiation process. Optimized by uniform design, MAE was proved to be an effective and novel process for extracting active ingredients in Ciwujia. The optimized MAE conditions are as follows: the microwave power is 510W, the radiation time 30min, the alcohol concentration at 80%, the ratio of solvent to solid material being 5:1, the soaking time 0.5h, and the herbal particle size is (520±19)μm.     

面向可持续发展的半导体制造的集成产品和过程控制

Semiconductor fabrication is a manufacturing sequence with hundreds of sophisticated unit operations and it is always challenged by strategy development for ensuring the yield of defect-free products. In this paper, an advanced control strategy through integrating product and process control is established. The proposed multiscale scheme contains three layers for coordinated equipment control, process control and product quality control. In the upper layer, online control performance assessment is applied to reduce the quality variation and maximize the overall product performance (OPP). It serves as supervisory control to update the recipe of the process controller in the middle layer. The process controller is designed as an exponentially weighted moving average (EWMA) run-to-run controller to reject disturbances, such as process shift, drift and tool worn out, that are exerted to the op-eration. The equipment in the process is individually controlled to maintain its optimal operational status and maximize the overall equipment effectiveness (OEE), based on the set point given by the process controller. The ef-ficacy of the proposed integrated control scheme is demonstrated through case studies, where both the OPP (for product) and the OEE (for equipment) are enhanced.     

英文摘要

The upstream materials for industry of liquid crystal display are mainly six kinds as follows, liquid crystal materials, color filter film, photoresist, polarizer, touch screen and backlight module. Liquid crystal material is the upstream material with top technology and best industrial base in China The main raw materials for color filter film produced by pigment dispersion method are color photoresist, indium tin oxide based target materials and black matrix materiala There is no production capacity of photoresist yet for TFT-LCD in China mainland. The polarizer was manufactured by dyeing with dichroic organic dyestuff, and the technology for producing polarizer was depended mostly （80%） on the technique of the Japanese enterprises.     

Comparison of Dissolved Air Flotation and Sedimentation in Treatment of Typical North China Source Water

The treatment of typical north China water by dissolved air flotation (DAF) and sedimentation process was examined. A pilot plant with a water treatment capacity of 120 m3/d constructed in the Jieyuan Water Treatment Plant (JWTP) of Tianjin, China, was utilized for the comparison of the two processes. The results show that during the pilot test, DAF process can remove particles and organic mater more efficiently than sedimentation process. The removal rate for turbidity by DAF process is 5.5% higher than that by sedimentation in normal turbidity period, and 40% higher in low turbidity period, it is 5%~10% higher for removals of algae, total organic carbon (TOC), trihalomethane formation potential (THMFP) and bacteria in all periods. The removal rates for turbidity, TOC, THMFP, algae and bacteria by DAF process can reach 95%, 30%, 20%, 94% and 97% respectively. From the results of the pilot test, it can be concluded that DAF is a feasible clarification process, especially for source water with low turbidity and high algal blooming.     

An improved theoretical procedure for the pore-size analysis of activated carbon by gas adsorption

Amorphous carbon materials play a vital role in adsorbed natural gas (ANG) storage.One of the key issues in themore prevalent use of ANG is the limited adsorption capacity,which is primarily determined by the porosity and surface characteristics of porous materials.To identify suitable adsorbents,we need a reliable computational tool for pore characterization and,subsequently,quantitative prediction of the adsorption behavior.Within the framework of adsorption integral equation (AIE),the pore-size distribution (PSD) is sensitive to the adopted theoretical models and numerical algorithms through isotherm fitting.In recent years,the classical density functional theory (DFT) has emerged as a common choice to describe adsorption isotherms for AIE kernel construction.However,rarely considered is the accuracy of the mean-field approximation (MFA) commonly used in commercial software.In this work,we calibrate four versions of DFT methods with grand canonical Monte Carlo (GCMC) molecular simulation for the adsorption of CH4 and CO2 gas in slit pores at 298 K with the pore width varying from 0.65 to 5.00 nm and pressure from 0.2 to 2.0 MPa.It is found that a weighted-density approximation proposed by Yu (WDA-Yu) is more accurate than MFA and other non-local DFT methods.In combination with the trapezoid discretization of AIE,the WDA-Yu method provides a faithful representation of experimental data,with the accuracy and stability improved by 90.0％ and 91.2％,respectively,in comparison with the corresponding results from MFA for fitting CO2 isotherms.In particular,those distributions in the feature pore width range (FPWR)are proved more representative for the pore-size analysis.The new theoretical procedure for pore characterization has also been tested with the methane adsorption capacity in seven activated carbon samples.     

Thermochemical Treatment--Technologies for Recovery and Utilisation of Materials

The arc furnace technology is an ideally suited process for the treatment of hazardous and problematic waste. The operation conditions of the arc furnace can be adapted for optimal transformation of the waste material input into raw materials and usable products. The process can significantly reduce the impact of contaminated wastes and industrial residues, and enable material conversion and separation. Thus, the products of the process have various applications. The capability of the process is illustrated with three examples, the treatment of bottom ash and filter ash from waste incineration plants, of stainless steel slags and of chromium containing residues from the refractory industry.     

对称四取代钯酞菁的合成及其对氯苯气相加氢脱氢的催化作用

1 INTRODUCTION Catalytic hydrodechlorination is an elegant reaction for disposal of environmentally hazardous chlorocarbons,such as chloro-benzene[1].Development of a new catalyst with excellent stability is necessary due to the deactivation of supported noble metal catalysts[1].However the modification of catalytic properties of catalysts in hydrodechlorination reaction by introducing stable ligands to noble metals has been the least studied.Here the synthesis of Pd(Ⅱ) 2,9,16,23-symetrically tetrasubstituted phthalocyanines PdPTX4 (where X=-H,-NO2,-NH2 respectively) from phthalimide derivatives is reported,and their application as catalysts in hydrodechlorination of chlorobenzene,which is a representative environmentally hazardous materials is discussed.     

Preparation of bis(chloroformate)s for use in cyclization reactions

Cyclic oligomeric carbonates are prepared by a hydrolysis/condensation reaction from aromatic bis(chloroformate)s. Three methods for convenient preparation of bis(chloroformate)s have been developed: (1) use of diethylaniline to scavenge HCl, in a modification of an earlier procedure; (2) low pH, low temperature interfacial condensation of bisphenols with phosgene; and (3) use of Ca(OH)₂ in interfacial condensation with phosgene. Reaction parameters which control formation of monomeric bis(chloroformate)s versus higher oligomerization include temperature, pH, and rate of phosgene addition. For water-soluble bisphenols such as hydroquinone, the phase ratio of water to CH₂Cl₂ can also be important.     

固体推进剂用异佛尔酮二异氰酸酯的生产技术

比较了异佛尔酮二异氰酸酯（IPDI）的生产方法和经济性,传统光气法收率高,但毒性大,非光气法特别是DMC法反应条件温和,环境污染小,虽比光气法生产成本增加了5.45%,但仍然具有广泛的工业化应用前景。     

高纯氯甲酸苄酯无溶剂生产工艺的研究

本文以苯甲醇和光气为原料,研究了无溶剂高纯度氯甲酸苄酯的生产工艺。,优化的生产工艺条件为：在干燥的氮气保护下,在10hA左右于-10-5℃向光气中滴加苯甲醇,滴毕再于10℃回流反应10h。产品纯度达到98．5％,收率达99％。该方法反应条件温和、操作方便、后处理简单、成本低,适合于工业化。     

9-芴甲氧羰基氨基保护试剂的合成与分析

研究了9 芴甲基氯甲酸酯(Fmoc Cl)、9 芴甲基叠氮甲酸酯(Fmoc N3)和9 芴甲基琥珀酰亚胺碳酸酯(Fmoc OSu)这3种氨基保护试剂的合成方法。用碳酸二(三氯甲酯)代替光气与芴甲醇反应得到Fmoc Cl;Fmoc Cl可分别与叠氮化钠及N 羟基琥珀酰亚胺反应得到9 芴甲基叠氮甲酸酯(Fmoc N3)以及9 芴甲基琥珀酰亚胺碳酸酯(Fmoc OSu),收率分别为87 9%和86 9%。上述Fmoc保护试剂在碱性条件下分别与甘氨酸反应进行氨基保护得到产品Fmoc 甘氨酸,收率分别为83 1%、73 3%及93 9%,用毛细管电泳仪分析其摩尔分数分别为97 7%、99 5%及大于99 9%,结果表明,Fmoc OSu是甘氨酸Fmoc氨基保护的最佳试剂。     

Polymerization by phase transfer catalysis

Summary Poly(amido-carbonate)s and poly(amido-thiocarbonate)s derived from 1,6-bis(4-hydroxyphenyl-carbamoyl)-hexamethylene I and 1,4-bis(4-hydroxyphenyl-carbamoyl)-phenylene II, and phosgene or thiophosgene, have been synthesized by a phase transfer catalysis process, which was ineffective for polymers derived from monomer I because the best results were obtained without catalyst, but was effective for those derived from monomer II obtaining higher yields when the catalysts were used. The ineffectivity was attributed to a hydrolytic process of the polymeric chains in the reaction media.     

碳酸二甲酯及其下游产品研究进展

介绍了碳酸二甲酯的合成技术及其替代光气合成碳酸二苯酯、异氰酸酯(MDI、HDI等)等的研究进展,对替代光气、硫酸二甲酯等剧毒和重污染化学品的清洁生产工艺具有一定的参考价值。     

A convenient laboratory preparation of aromatic polycarbonate

Summary An experimentally simple method for the synthesis of aromatic polycarbonates is described. Reaction of commercially available p-nitrophenyl chloroformate with bisphenol A afforded BPA polycarbonate in good yields with M _n= 26,000 g/mol. This laboratory procedure avoids the use of phosgene or phosgene equivalents in the laboratory. The process requires the use of 2 equivalents of triethylamine and a catalytic amount of 4-dimethylaminopyridine. Received: 31 July 2001/ Revised version: 16 November 2001/ Accepted: 28 November 2001     

Polymerization by phase transfer catalysis

Summary Polycarbonates and polythiocarbonates from phosgene and thiophosgene respectively, were synthesized from diphenols with chlorinated aromatic side groups under phase transfer conditions using several quaternary ammonium and phosphonium salts and dichloromethane as solvent. Polymers were characterized by IR and ¹H NMR, and the molecular weights estimated by viscosity measurements. The influence of the catalysts and the structure of the diphenols were studied.for part 9, see ref. 9     

芳磺酰基异氰酸酯的合成概述与展望

概述了磺酰脲除草剂关键中间体芳磺酰基异氰酸酯的主要合成方法。对光气法、草酰氯法、双光气法与固体光气法做了详细介绍比较,采用固体光气法合成芳磺酰基异氰酸酯是一条清洁生产工艺路线;同样氰酸盐法因工艺简单,安全环保,也是一种极具推广价值的工艺路线。对于难以直接合成为异氰酸酯的物质可以先与氯化亚砜反应后再与固体光气反应,不失为一种好方法。相比传统磺酰脲除草剂,芳环5位取代的磺酰脲除草剂更具有市场竞争力与潜力。     

氯甲酸烯丙酯的合成及其在阿维菌素结构改造中的羟基保护作用

采用光气法制备氯甲酸烯丙酯,后处理简单,收率高（94%）。对反应条件进行优化。产品用于阿维菌素结构改造时的5-羟基保护,生成的5-烯丙氧基甲酸酯阿维菌素B1衍生物用于后续的结构改造。预试验显示羟基保护反应完全,在一定条件下去保护快速、彻底。具有较高的实用价值。