利用工业废气中高浓度磷化氢合成四羟甲基氯化磷的研究
摘要
经济全球化在给各国经济发展带来重大机遇的同时,也对各国经济发展战略,尤其对发展中国家传统的工业化道路提出严峻的挑战。随着人类消费需求增加及全球磷化工进程的加速,对磷矿的大量开发和利用造成的磷矿资源短缺现象日益严重,我国国土资源部已将磷矿列为2010年后不能满足中国经济发展需求的矿种之一。云南省的磷矿储量及产量均在全国前列,磷化工同时又是云南省的重要的经济支柱之一,黄磷总产量大量增加,产生的固体废物泥磷也在增加。如何在资源开发利用的同时,依法保护和合理使用资源,提高资源利用率,实现资源的永续利用是重要的课题。课题组前期研究表明利用泥磷与碱液反应制取次磷酸钠是一种有效的资源综合利用及污染治理手段,但此过程中有20%的单质以磷以磷化氢的形式排出,因此对于产生的高浓度磷化氢气体仍需要妥善处理。
本文以泥磷资源化利用过程中产生的磷化氢为研究对象,利用高浓度磷化氢废气合成阻燃剂四羟甲基氯化磷(THPC).但由于传统的高浓度磷化氢合成THPC未采用催化剂,磷化氢的转化率较低,因此反应中需要筛选高效的催化剂,以提高在反应时间内的磷化氢综合利用率。本研究设计出利用催化剂高效制备阻燃剂THPC的的实验方案,采用无载体催化剂氯化铜催化氧化磷化氢,不仅可以无害化处理PH3废气,更可变废为宝实现废气资源化制得产品阻燃剂THPC,有效地提高磷资源的综合利用率。
研究的内容主要有：在前期研究工作的基础上,合理进行流程设计,优化实验方案；根据磷化工常用催化剂的分类及用途,查阅相关文献选取氧化铝、氧化锌、氯铂酸钾、氯化铜作为本研究的催化剂筛选类型,用单因素实验方式考察各种工艺条件：空速、反应时间、反应温度、原料配比等因素对合成工艺磷化氢转化率的影响,确定最佳合成工艺条件,根据单因素实验结果,进行4因素3水平的正交实验,并进行磷化氢转化率方差分析,确定影响磷化氢转化率的因素和最佳工艺方案,并对产品含量和反应机理和动力学过程进行相关分析。
确定了单组分催化剂的筛选、工艺条件的单因素实验的最佳实验条件：选取CuCl2为最适宜催化剂；制备THPC反应条件为空速150h-1,反应温度60℃,催化剂用量0.75g,甲醛和盐酸摩尔比4：1。磷化氢的转化率可达到95%。产品阻燃剂水溶液THPC含量81%,符合工业商品THPC要求。
通过正交实验确定了THPC合成实验,确定响磷化氢转化率的因素从主到次的顺序：空速、反应温度、催化剂用量、甲醛和盐酸摩尔比；筛选出工艺参数最优方案：n(HCHO)/n(HCl)4:1;空速150h-1,反应温度60℃,催化剂用量0.75g。并发现反应温度对磷化氢合成THPC有极显著影响,空速对磷化氢转化率有显著影响。研究表明催化剂样中含有大量的活性成分氯化亚铜,主要由于氯化铜的催化氧化氧化作用加速了合成反应的进行,使得磷化氢的转化率大大的提高。对高浓度废气磷化氢合成阻燃剂THPC的宏观动力学进行研究表明：在催化剂作用下,磷化氢与盐酸和甲醛合成阻燃剂的反应是一级反应。
Economic globalization has brought significant opportunities in the economic development of countries, but it also has posed serious challenges to national economic development strategy, in particular, the traditional path of industrialization in the developing countries. With the increase of human consumption and the acceleration of global phosphorus chemical process, the shortage phenomenon of phosphate resources is worsening with the development and utilization of the phosphate. China's Ministry of Land and Resources has set phosphate as one of minerals that it can not meet China's economic development demand after2010. Phosphate reserves and production in Yunnan Province is the most in the nation, and the phosphorus chemical industry is one of the important economic pillar of Yunnan Province, the total output of yellow phosphorus increase in the enterprises, while the mount of phosphorus sludge is also increasing. How to protect with the law and use resources rationally, improve resource utilization of resources, and use sustainably is an important issue, at the same time of resource development and utilization, in accordance, Group preliminary studies showed that a process of phosphoric sludge to the sodium hypophosphite is an effective comprehensive utilization of resources and means of pollution control, but in the process20%elemental phosphorus discharge in the form of phosphine and produce the high concentration of phosphine gas which still need to be addressed.
Phosphine generated in the process of phosphoric sludge utilization is viewed as the this research object, with use of of high concentration of phosphine emissions flame retardants (THPC) is composited. However due to synthesis of THPC did not use catalyst in Traditional research,so the conversion rate of phosphine is the low. The reaction need to be screened in a highly efficient catalyst, in order to improve the comprehensive utilization rate of phosphine in the reaction time. In this study, the catalyst for efficient preparation of flame retardants THPC, using carrier-free catalyst copper chloride catalyzed and oxidated of phosphine gas.It is not only harmless treatment of phosphine, but also change the waste to the resources of the system and get the products flame retardants THPC, effectively improving the comprehensive utilization rate of phosphorus resources.
The content of the study:on the basis of preliminary studies, a reasonable process is designed, and the experimental program is optimizated too; According to the classification and use of commonly catalyst in phosphorus chemistry, select the alumina, zinc oxide, chloroplatinic potassium copper chloride as a catalyst for this study, single factor experiments to examine the impact of a variety of conditions:space velocity, reaction time, reaction temperature, the ratio of raw materials and other factors on the synthesis process at phosphine conversion rate, to determine the optimum conditions.4factors and3levels of orthogonal experiment is conducted according to the results of single factor experiments, and phosphine conversion rate variance analysis to determine the phosphine conversion rate factors and the best of the process plan, and also product content and the reaction mechanism and analysis of dynamic process.
Single-component catalyst screening and the optimal experimental conditions of the process conditions is determined, the single factor experiment:select CuC12as the optimal catalyst; airspeed in preparation of THPC conditions150h-1,the reaction temperature of60℃, the amount of catalyst0.75g, formaldehyde and andhydrochloric acid molar ratio of4:1. Phosphine conversion rate can reach95%. Product of flame retardant solution content is80%, which is in line with THPC requirements of industrial commodities.
the THPC synthesis experiments is determined by orthogonal experiments, the factors that ring the rate of phosphine conversion from the main to order: airspeed, the reaction temperature, amount of catalyst, formaldehyde and hydrochloric acid molar ratio; optimal solution of screening process parameters:n(HCHO)/n (HC1)4:1, space velocity150h-1, the reaction temperature of60℃, the amount of catalyst0.75g. The research found that the reaction temperature had very significant effects on the synthesis of THPC with phosphine, and the airspeed also have a significant effect on phosphine conversion rate. The study showed that the catalyst samples contained a large number of active ingredients cuprous chloride which accelerated the synthesis reaction, this mainly due to the catalytic oxidation of copper chloride oxidation, making the conversion rate of phosphine greatly improve. Studies the macroscopic dynamics of the synthesis of flame retardants THPC have shown that reaction of synthetic flame retardants with phosphine, hydrochloric acid and formaldehyde under catalyst is first-order reaction.
本文以泥磷资源化利用过程中产生的磷化氢为研究对象,利用高浓度磷化氢废气合成阻燃剂四羟甲基氯化磷(THPC).但由于传统的高浓度磷化氢合成THPC未采用催化剂,磷化氢的转化率较低,因此反应中需要筛选高效的催化剂,以提高在反应时间内的磷化氢综合利用率。本研究设计出利用催化剂高效制备阻燃剂THPC的的实验方案,采用无载体催化剂氯化铜催化氧化磷化氢,不仅可以无害化处理PH3废气,更可变废为宝实现废气资源化制得产品阻燃剂THPC,有效地提高磷资源的综合利用率。
研究的内容主要有：在前期研究工作的基础上,合理进行流程设计,优化实验方案；根据磷化工常用催化剂的分类及用途,查阅相关文献选取氧化铝、氧化锌、氯铂酸钾、氯化铜作为本研究的催化剂筛选类型,用单因素实验方式考察各种工艺条件：空速、反应时间、反应温度、原料配比等因素对合成工艺磷化氢转化率的影响,确定最佳合成工艺条件,根据单因素实验结果,进行4因素3水平的正交实验,并进行磷化氢转化率方差分析,确定影响磷化氢转化率的因素和最佳工艺方案,并对产品含量和反应机理和动力学过程进行相关分析。
确定了单组分催化剂的筛选、工艺条件的单因素实验的最佳实验条件：选取CuCl2为最适宜催化剂；制备THPC反应条件为空速150h-1,反应温度60℃,催化剂用量0.75g,甲醛和盐酸摩尔比4：1。磷化氢的转化率可达到95%。产品阻燃剂水溶液THPC含量81%,符合工业商品THPC要求。
通过正交实验确定了THPC合成实验,确定响磷化氢转化率的因素从主到次的顺序：空速、反应温度、催化剂用量、甲醛和盐酸摩尔比；筛选出工艺参数最优方案：n(HCHO)/n(HCl)4:1;空速150h-1,反应温度60℃,催化剂用量0.75g。并发现反应温度对磷化氢合成THPC有极显著影响,空速对磷化氢转化率有显著影响。研究表明催化剂样中含有大量的活性成分氯化亚铜,主要由于氯化铜的催化氧化氧化作用加速了合成反应的进行,使得磷化氢的转化率大大的提高。对高浓度废气磷化氢合成阻燃剂THPC的宏观动力学进行研究表明：在催化剂作用下,磷化氢与盐酸和甲醛合成阻燃剂的反应是一级反应。
Economic globalization has brought significant opportunities in the economic development of countries, but it also has posed serious challenges to national economic development strategy, in particular, the traditional path of industrialization in the developing countries. With the increase of human consumption and the acceleration of global phosphorus chemical process, the shortage phenomenon of phosphate resources is worsening with the development and utilization of the phosphate. China's Ministry of Land and Resources has set phosphate as one of minerals that it can not meet China's economic development demand after2010. Phosphate reserves and production in Yunnan Province is the most in the nation, and the phosphorus chemical industry is one of the important economic pillar of Yunnan Province, the total output of yellow phosphorus increase in the enterprises, while the mount of phosphorus sludge is also increasing. How to protect with the law and use resources rationally, improve resource utilization of resources, and use sustainably is an important issue, at the same time of resource development and utilization, in accordance, Group preliminary studies showed that a process of phosphoric sludge to the sodium hypophosphite is an effective comprehensive utilization of resources and means of pollution control, but in the process20%elemental phosphorus discharge in the form of phosphine and produce the high concentration of phosphine gas which still need to be addressed.
Phosphine generated in the process of phosphoric sludge utilization is viewed as the this research object, with use of of high concentration of phosphine emissions flame retardants (THPC) is composited. However due to synthesis of THPC did not use catalyst in Traditional research,so the conversion rate of phosphine is the low. The reaction need to be screened in a highly efficient catalyst, in order to improve the comprehensive utilization rate of phosphine in the reaction time. In this study, the catalyst for efficient preparation of flame retardants THPC, using carrier-free catalyst copper chloride catalyzed and oxidated of phosphine gas.It is not only harmless treatment of phosphine, but also change the waste to the resources of the system and get the products flame retardants THPC, effectively improving the comprehensive utilization rate of phosphorus resources.
The content of the study:on the basis of preliminary studies, a reasonable process is designed, and the experimental program is optimizated too; According to the classification and use of commonly catalyst in phosphorus chemistry, select the alumina, zinc oxide, chloroplatinic potassium copper chloride as a catalyst for this study, single factor experiments to examine the impact of a variety of conditions:space velocity, reaction time, reaction temperature, the ratio of raw materials and other factors on the synthesis process at phosphine conversion rate, to determine the optimum conditions.4factors and3levels of orthogonal experiment is conducted according to the results of single factor experiments, and phosphine conversion rate variance analysis to determine the phosphine conversion rate factors and the best of the process plan, and also product content and the reaction mechanism and analysis of dynamic process.
Single-component catalyst screening and the optimal experimental conditions of the process conditions is determined, the single factor experiment:select CuC12as the optimal catalyst; airspeed in preparation of THPC conditions150h-1,the reaction temperature of60℃, the amount of catalyst0.75g, formaldehyde and andhydrochloric acid molar ratio of4:1. Phosphine conversion rate can reach95%. Product of flame retardant solution content is80%, which is in line with THPC requirements of industrial commodities.
the THPC synthesis experiments is determined by orthogonal experiments, the factors that ring the rate of phosphine conversion from the main to order: airspeed, the reaction temperature, amount of catalyst, formaldehyde and hydrochloric acid molar ratio; optimal solution of screening process parameters:n(HCHO)/n (HC1)4:1, space velocity150h-1, the reaction temperature of60℃, the amount of catalyst0.75g. The research found that the reaction temperature had very significant effects on the synthesis of THPC with phosphine, and the airspeed also have a significant effect on phosphine conversion rate. The study showed that the catalyst samples contained a large number of active ingredients cuprous chloride which accelerated the synthesis reaction, this mainly due to the catalytic oxidation of copper chloride oxidation, making the conversion rate of phosphine greatly improve. Studies the macroscopic dynamics of the synthesis of flame retardants THPC have shown that reaction of synthetic flame retardants with phosphine, hydrochloric acid and formaldehyde under catalyst is first-order reaction.
引文
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