净化黄磷尾气和合成气一步法制二甲醚

【作者】 任占冬；

【导师】 陈樑；

【作者基本信息】 昆明理工大学 ， 应用化学， 2004， 硕士

【摘要】 黄磷尾气是黄磷生产过程中的副产物，其直接排放对空气造成极大的污染。黄磷尾气中含有大量的CO及一些有害杂质，其中CO是碳一化工的基本原料。如何除去尾气中的有害杂质，得到高纯度的CO，生产高附加值的化工产品是黄磷尾气综合利用的基本方向。利用CO合成气一步法制二甲醚就是一条很好的线路。 二甲醚是一种用途较广的化工产品。可以用作制冷剂，气雾剂、发泡剂等，还可用作民用清洁燃料和汽车燃料。另外二甲醚还有好多化学应用，如制甲醛、二甲胺、乙酸、乙酸酐等。 本研究论文综述了国内外黄磷尾气的应用和二甲醚的利用现状，全面分析了黄磷尾气净化研究和二甲醚合成研究的国内外进展及研究动态。针对黄磷尾气中有害杂质（PH₃、H₂S）净化的难题和合成气一步法制二甲醚工艺及双功能催化剂的选择进行了较全面的研究。其主要研究内容的成果有： （1）对黄磷尾气的主要成分和有害杂质进行了分析，建立快速准确的分析黄磷尾气中磷、硫含量的方法。 （2）研究出以活性碳为载体，制备出四种不同型号的JC系列催化剂，并进行了JC系列催化剂对PH₃、H₂S净化能力、寿命等的研究。通过优化催化剂和净化工艺，获得优秀的JC-4型催化剂。该催化剂能完全净化除去黄磷尾气中PH₃、H₂S等杂质，使其含量在1ppm以下。 制备的JC～4型催化剂性能优良、稳定，其吸附容量大约为300 m³／kg。另外，还研究了尾气中氧含量对JC—4型催化剂性能的影响。 在小试试验中，JC—4型催化剂寿命长达195小时；并可以再生，新的再生方法可靠，再生后的催化剂基本达到新鲜催化剂的净化效果。应用JC—4型催化剂到处理50m³／h黄磷尾气中试实验中，得到了较佳的中试效果。中试连续72小时，PH₃、H₂S等杂质的含量始终在1ppm以下 （3）通过三相浆态床中，对三种甲醇合成催化剂（C301、C207、XNC98）性能和工艺条件的考察，选择出在合成工艺条件为压力3.0MPa、温度240℃、转速1500n／min、进气流量0.07L.min^-1、CO：H₂=1：2（摩尔比）下，合成甲醇效果最好的催化剂----国产C301。其CO转化率为63.68％，甲醇的选择性达到91.68昆明理工大学硕士学位论文摘要%。另外，还对C301在三相床中受温度，压力等工艺条件的影响效果进行了考察。 （4）在三相浆态床中，利用C301为甲醇合成催化剂，分别以Hp、HY、ZSM一5为甲醇脱水催化剂，制备出双功能催化剂c301一Hp、c301一HY、c301一ZSM一5，并研究了双功能催化剂一步法合成二甲醚的催化效果。 在压力3.OMPa、温度290，C、转速1500可min、进气流量0.07L.min一’、Co:H2=l:2（摩尔比）工艺条件下。虽然C301一ZSM一5型双功能催化剂二甲醚的收率最好（42.24%），但其总有机物选择性太低（78.40%），又有甲烷生成（21名1%），产物又比较复杂，不利于后续产品的分离利用。C301一HY型双功能催化剂和C301一Hp型双功能催化剂的催化效果较好，他们二甲醚的收率分别为33.“%、31.81%，总有机物的选择性分别为93.94%、93.99%，适于一步法合成二甲醚。 在三相浆态床中对c301一 Hp型双功能催化剂制备二甲醚的工艺条件（温度、压力）进行了优化，得到CO转化率、二甲醚收率等随温度、压力变化的规律。以及双功能催化剂中甲醇合成催化剂和甲醇脱水催化剂的配比对反应的影响。 （5）论文还通过一步法合成二甲醚的试验研究和理论研究，对合成气一步法制二甲醚的反应机理进行了初步的探讨以及动力学和热力学分析。 总之，本论文对黄磷尾气的净化和合成气一步法制二甲醚的双功能催化剂及工艺两方面内容进行了研究，得到了比较满意的结果。为净化黄磷尾气一步法合成二甲醚的课题做了基础性研究，解决了黄磷尾气综合利用的瓶颈问题和合成气一步法制二甲醚双功能催化剂的合成及工艺选择等关键性问题。更多还原

【Abstract】 Yellow phosphorous tail gas is byproduct produced during yellow phosphorous production progress, it will pollute atmosphere seriously if it is discharged directly. Yellow phosphorous tail gas contains large numbers of CO and some of deleterious impurities,. CO is the basic material of one carbon chemistry engineering. How to get rid of deleterious impurities in the tail gas and get the high pure CO which can produce the high value chemistry engineering products is the basic way of the integrative utilize of yellow phosphorous tail gas. Using the synthetical gas CO synthesize dimethyl ether in one step is a good way.Dimethyl ether is a kind of chemistry engineering product been used in many fields. It can be used as refrigeration, aerosol, vesicant, clean fuel and automobile fuel. In addition, dimethyl ether is used in many chemical fields, for example, the synthesis of formaldehyde, dimethylamine, acetic acid, acetic anhydride etc.This paper summarizes the use of yellow phosphorous tail gas and dimethyl ether, analyzes entirely the studying developments of the yellow phosphorous tail gas’s purity and the dimethyl ether’s synthesis in the world. The difficult problem of the purity of deleterious impurities(PH3 , H2S) in yellow phosphorous tail gas, the choices of the arts and the double-fuction catalyst of the dimethyl ether’s synthesis in one step was studied. The main research achievement include:(1) The paper analyzes the main ingredients and deleterious impurities in the yellow phosphorous tail gas, and establishes the fast and exact analysis method to inspect the content of sulphur, phosphorus.(2) Using active carbon as carrier, the four types JC series catalysts were made. The ability and longevity of catalysts to purify the PH3 and H2S was studied, and get the excellent JC-4 catalyst through optimized the catalyst and the purity arts. The JC-4 catalyst can remove the most PH3 and H2S from the yellow phosphorous tail gas to less than 1ppm.The quality of JC-4 catalyst is excellent and stable, and it’s adsorption quantity is about 300 m3/kg. In addition, the effect of the oxygen’s quantity in the tail gas on thepurity capability of the JC-4 catalyst is studied.In the experiment, the longevity of JC-4 catalyst is 195 hours, and can be renewed. The new method of renewal is reliable, the renewed catalyst has the same purity effect as the new catalyst. Using this JC-4 catalyst to purify 50m3/h yellow phosphorous tail gas in the middle experiment, there is also good effect. During the 72 consecutive hours, the contents of PH3 and H2S are less than 1ppm in all the time.(3) The performance and art condition of three kinds of catalysts being used to synthesize methanol was studied in the three phase bed. In the condition of pressure 3.0MPa, temperature 240C, rotate speed 1500n/min, gas current 0.07L.min-1, CO:H2=l:2(mol), the best synthesizing methanol catalyst - C301 was gained. The convert rate of CO is 63.68%, the selectivity reaches 91.68% . Otherwise, the effect of the technical conditions such as temperature and pressure on C301 in the three phase bed was studied.(4) Using C301 as the synthesizing methanol catalyst, and HP, HY and ZSM-5 as the dehydration catalyst of methanol, the double-function catalysts C301 - HP, C301 - HY and C301 -ZSM-5 were made, and the effect on synthesizing dimethyl ether in one step using double-function catalyst in the three phase serous bed.In the condition of pressure 3.0MPa, temperature 2406, rotate speed 1500n/min, gas current 0.07L.min-1, CO:H2=1:2(mol), although the yield of dimethyl ether is the highest(42.24%) using the double-function catalyst C301 -ZSM-5, the total selectivity of organization is too low(78.4%), at the same time, methane is produced (21.81 % ) , the products are complex, and the separation and utilization of products are difficult. The catalysis effect of double-catalyst C301- HY and C301- Hp are good, the yield of dimethyl ether are 33.66% and 31.81%, and the total selectivity of the organization are 93.94% and 93.99%, so the double-ca更多还原