高品质O,O-二甲基硫代磷酰氯的合成

以五硫化二磷为起始原材料,经醇解、催化条件下氯化得到高品质O,O-二甲基硫代磷酰氯.优化条件下,产品含量达99％,总收率迭80％.该方法无需碱解、通氯量少、废水量少.适合于工业化生产.     

O,O-二甲基硫代磷酰氯的合成进展

介绍了O,O-二甲基硫代磷酰氯的合成方法,并进行了分析比较。     

O,O-二甲基硫代磷酰氯的合成研究

发现了反应稳定剂,考察了各因素对反应的影响,提出了适宜的工艺条件,使O,O—二甲基硫代磷酰氨基于三氯硫磷的收率得到了较大的提高。     

O,O-二乙基硫代磷酰氯的合成工艺优化

对O,O-二乙基硫代磷酰氯的生产工艺进行了优化。利用第一步五硫化二磷与无水乙醇反应中产生的硫化氢副产物通入到第二步硫代磷酰酯(乙基硫化物)的氯化母液中,以硫化氢替代传统工艺中的硫化碱消除反应母液中的氯化硫,达到精制O,O-二乙基硫代磷酰氯的目的。相比传统工艺,该路线不仅缩短了工艺流程,同时废水量大幅减少为0.2t/t产品,且高收率得到了易于回收的疏松颗粒物单质硫,提高了目标化合物O,O-二乙基硫代磷酰氯的含量。     

O，O-二甲基硫代磷酰氯的合成进展

介绍了O ,O 二甲基硫代磷酰氯的合成方法 ,并对主要的 3种O ,O 二甲基硫代磷酰氯的合成方法在工艺和成本上进行了分析比较 ,同时描述了该产品在国内的生产现状和发展趋势。     

O,O-二乙基硫代磷酰氯精制工艺的改进

在吡啶催化作用下,五硫化二磷与无水乙醇反应生成O,O-二乙基二硫代磷酸酯,其再与氯气反应得到O,O-二乙基硫代磷酰氯粗品。所得粗品分别经清水预处理,硫化钠和氢氧化钠混合碱液处理,得到质量分数在99%以上的O,O-二乙基硫代磷酰氯,总收率达到88%。该工艺废水量大大减少,降低了环保压力。     

气相色谱内标法测定O,O-二甲基硫代磷酰胺含量

建立了以苯甲酸乙酯为内标物,气相色谱内标法定量测定O,O-二甲基硫代磷酰胺含量的新方法。线性回归方程y=0.6837x+0.0186,相关系数r为0.9994,加标回收率达到96.28％,相对标准偏差为1.09％。该方法简便、准确、可靠,适用于O,O-二甲基硫代磷酰胺的质量检验。     

O,O-二烷基硫代磷酰氯制备过程中一氯化硫处理进展

O,O-二烷基硫代磷酰氯是一种重要的农药中间体,可用于制备多种有机磷类杀虫剂。基于五硫化二磷合成O,O-二烷基硫代磷酰氯是目前研究热点,综述了以五硫化二磷为原料合成O,O-二烷基硫代磷酰氯过程中一氯化硫的处理方法,并分析了各种方法的优缺点。     

O，O-二甲基硫代磷酰胺工艺改进

O ,O 二甲基硫代磷酰胺是一种重要农药中间体 ,其传统合成工艺是O ,O 二甲基硫代磷酰氯与氨水反应制取。该工艺存在废水污染、副产品不易回收、成本高等缺点。东营胜利电化有限责任公司采用气氨代替氨水、饱和氯化铵水溶液循环利用替代溶剂反应 ,成功地解决了废水污染、副产品回收问题 ,降低了生产成本     

异构反应-分子蒸馏分离合成O,S-二甲基硫代磷酰胺

对O,O-二甲基硫代磷酰胺催化异构-分子蒸馏合成O,S-二甲基硫代磷酰胺的工艺进行了研究。得到了异构反应-分子蒸馏分离的优化工艺条件:反应温度40~50℃,反应时间3 h,蒸馏温度90~100℃,操作压力20~40 Pa。10 t/a中试装置运行表明:将分子蒸馏分离得到的原料重新异构得到O,S-二甲基硫代磷酰胺的质量分数与总收率分别为92.8%、94.2%。     

Waste minimization through optimal plant retrofit

A problem for optimal plant retrofitting, aiming to minimize the acrylonitrile released in the atmosphere from a Gas Treatment Department at Acrylic Fibre Plant, is considered. The applied retrofit policy involves (i) substitution of a used solvent with an appropriate selected mixture; (ii) flowsheet superstructure definition; and (iii) process parameters and mixture composition determination, so as the environmental regulations at minimum total retrofit cost to be reached. The pointed steps are described and the results obtained are discussed.     

Decomposable crosslinking paint: Waste minimization

A paint film crosslinked by a reaction between a carbonyl group and a hydrazide group could be easily decomposed by dipping it in a solution containing water, solvents, and acids. The method was studied to minimize the waste produced by the elimination of the decomposable paint film. This was performed in two steps: a dipping in aqueous solution containing solvents and acids, and a successive wash with solvents. Decomposition of the crosslinking bonds and the elution of the decomposed free crosslinker took place in the first dipping process, and the elimination of the decomposed resins in the second washing process. The aqueous solution could be used for a long time without contamination by the decomposed resins, and the decomposed resin could easily be recovered from the resin solution containing no other contaminants. 17-1 Higashi Yawata 4-Chome, Hiratsuka-Shi, Kanagawa-Ken 254-8562, Japan.     

氯乙酸氨解法甘氨酸合成工艺的研究

研究了氯乙酸氨解法制备甘氨酸的工艺条件,讨论了反应温度、催化剂用量和氨水浓度对氨解过程中氯乙酸转化率和甘氨酸产率的影响;研究了甲醇加入量和醇析温度对醇析过程中甘氨酸得率和纯度的影响。结果表明,氨解反应适宜温度为70～80℃,催化剂适宜用量为氯乙酸添加量的15%左右,氨水质量分数高有利于反应,在此工艺条件下氯乙酸的转化率达99.0%以上,反应液中甘氨酸的产率达98.0%以上;醇析过程中甲醇适宜加入量为氨解反应液体积的4.0～4.5倍,醇析温度选择在70～75℃之间,醇析过程中甘氨酸的得率大于79.0%,析出甘氨酸的纯度大于90.0%。     

氨解沉淀法白炭黑的研究进展

氨解沉淀法白炭黑的合成方法是以氨水溶液或液氨等氨化剂为主要原料与磷肥工业产生的含氟硅副产物（如氟硅酸、氟硅酸铵、含氟硅胶、含氟硅渣等）进行氨化沉淀反应合成白炭黑的一种方法。它是近年来随着磷肥工业含氟硅废弃物的产生而形成的一种特殊的沉淀法白炭黑的合成方法。介绍了氨解沉淀法白炭黑的反应原理、研究进展。从反应原理、生产成本、工艺控制、产品质量以及对环境的影响等方面,对氨解沉淀法和传统沉淀法进行了对比,突出了氨解沉淀法的优势。对中国沉淀法白炭黑的发展方向提出了建议。     

钯催化卤代芳烃氨解反应的研究进展

钯催化卤代芳烃进行氨解反应是构建C-N键的重要方法,由于该方法所需的催化剂量少、反应条件温和、应用范围广和操作简单,因而被广泛应用于芳香胺类化合物的制备与生产。本文对该反应机理进行了简介,对近年来钯催化卤代芳烃与氨、伯胺、仲胺和其他含氮化合物的氨解反应研究进展进行了综述。指出迄今为止高活性和高选择性的催化剂依然有限,氨作为氨解剂和低廉的氯代芳烃作为氨解底物的使用都还不够广泛。寻找新的配体、设计新的催化体系、提高反应选择性和改善反应对敏感官能团的容忍性,是钯催化卤代芳烃氨解反应领域未来的发展方向。另外,仔细研究反应机理将会加深对反应的理解。     

Catalytic effects in the ammonolysis of vegetable oils

Catalysts for the ammonolysis of soybean oil are, in order of decreasing overall effectiveness, ammonium acetate, sodium methoxide, 9-amino-nonanoic acid, sodium soyate, ammonium nitrate, alanine, sodium acetate and glycerol. At 125 C, a reaction time of 1 hr and a 30:1 mole ratio of ammonia to ester, ammonium acetate achieved ammonolysis in 16%, 61% and 84% conversions at the respective concentrations of 0.0, 0.1 and 1.0 mole per mole ester groups. Conversion was 98% complete in 4 hr with 1.0 mole. The ammonolysis generally exhibited the expected first order kinetics up to about 80% reaction. Presented at the ISF-AOCS Meeting, Chicago, September 1970. No. Market. Nutr. Res. Div., ARS, USDA.     

影响臭氧化污泥减量工艺的因子

采用臭氧作为剩余污泥的细胞裂解剂,并与淹没式生物膜工艺相结合进行污泥减量的实验研究,臭氧化后的污泥上清液回流入曝气池与污水合并处理。结果表明:在每kgMLSS臭氧投量为0.05 kg,臭氧化污泥体积流量为进水量的5%条件下,淹没式生物膜系统对SCOD和NH3-N的平均去除率分别为87.06%和84.80%,出水水质同对比实验相当;同时获得了去除1 g SCOD得到0.054 gMLSS的剩余污泥产率,与对比实验相比降低了78.4%。     

Conversion of a polysilazane-modified cellulose-based paper into a C/SiFe(N,C)O ceramic paper via thermal ammonolysis

Cellulose-based paper samples were surface-modified by a polymeric single-source precursor prepared from perhydropolysilazane (PHPS) and iron(III)acetylacetonate (Fe(acac)₃) and ammonolyzed at 500°C, 700°C, 900°C, and 1000°C, leading to C/SiFe(N,C)O-based ceramic papers with in situ-generated hierarchical micro/nano-morphology. As reference, cellulose-free samples were prepared under the same conditions. Upon thermal treatment, the microstructure evolutions of the resulting ceramic paper and the reference sample were comparatively investigated. Scanning electron microscopy (SEM) showed that for all temperatures, the ceramic papers exhibit the same morphology as the template, however, with noticeable shrinkage and curling, particularly evident at higher temperatures. X-ray diffraction (XRD) measurements of the reference samples and the ceramic papers showed a similar crystallization behavior and phase evolution in both materials. In the ceramic paper, the crystallization process seems to occur at a later time. The results provide a comprehensive understanding of the investigated C/SiFe(N,C)O-based ceramic system. It was shown that use of the cellulose-based paper template has the benefit of retaining the microstructure and furthermore, apart from transforming the cellulose fibers into turbostratic carbon, does not change the phase evolution during the polymer-to-ceramic transformation, allowing at the same time the manufacturing of novel morphologically complex parts by a convenient one-pot synthesis approach.     

Integration of electroplating process design and operation for simultaneous productivity maximization,energy saving,and freshwater minimization

Electroplating industry annually produces numerous plated workpieces for U.S. pillar industries. However, it is also a major environment polluter in forms of wastewater, sludge, and spent solution. Thus, waste source reduction for the electroplating industry is a must. In practice, when productivity and energy use efficiency are also taken into account, the design and operation of an electroplating process become very complicated and need an in-depth study. In this paper, productivity maximization, energy saving, and freshwater/wastewater minimization are simultaneously addressed for the optimal design and operation of electroplating processes, which generates a triple-objective mixed-integer dynamic optimization (MIDO) model. The MIDO model is iteratively solved by a developed methodology to obtain the 3D Pareto frontier of the optimization problem, which provides important technical supports for the design and operation of electroplating processes. The efficacy has been demonstrated with a case study on an electroplating process.