【作者】 潘琦琨；

【导师】 张秋民；

【作者基本信息】 大连理工大学 ， 化学工艺， 2007， 硕士

【摘要】 煤在碱性溶液中控制氧化，可以直接得到以水溶芳香羧酸为主的混合物，称为煤酸(CA)，其中大部分是各种苯多羧酸(BPCA)同系物异构体，煤酸异构化可制得对苯二甲酸(TPA)。本文对霍林河褐煤氧化规律及煤酸在浆态床下异构化制取对苯二甲酸的最佳反应条件进行了研究。霍林河褐的煤氧化实验在1L的摇动式高压釜中进行。采取单因素法进行实验分析，分别考察温度、氧气初压、碱煤比和恒温时间，对煤酸产率的影响。进而得到了霍林河褐煤碱氧氧化的最佳条件。霍林河褐煤在KOH介质中氧化的最佳条件是：反应温度240℃，碱煤比3∶1，恒温时间0.5小时，氧气初压5.5MPa，在最佳条件下煤酸收率为35.21％(对daf煤)，煤酸中苯羧酸含量为63.97％。TPA(对苯二甲酸)理论产率计算为68.56％，折合对煤酸计的理论产率为43.86％，折合对霍林河褐煤的理论产率为15.44％。以霍林河褐煤、咋子焦煤和太西无烟煤的混合媒酸为原料，在分别使用有机高沸点分散剂联苯和联三苯的条件下，以苯甲酸锌为催化剂，在容量100mL的高压反应釜中进行了煤氧化产物煤酸(水溶酸WSA)钾异构化制对苯二甲酸(TPA)的研究。主要考察了反应温度、催化剂用量、分散剂用量、二氧化碳初压和反应时间对TPA产率的影响。结果表明，在催化剂存在下煤酸可以转化成TPA。单独煤酸钾异构化时，以联苯为分散剂时较佳反应条件：温度420℃，压力3MPa，催化剂苯甲酸锌用量3％，分散剂用量60％，反应时间1h，TPA收率24.1％，TPA纯度为92％。以联三苯为分散剂时较佳反应条件：温度380℃，压力1MPa，催化剂苯甲酸锌用量3％，分散剂用量60％，TPA收率25.2％，TPA纯度为94％。煤酸钾与苯甲酸(BA)钾混合异构化时，以联苯为分散剂TPA产率可达60％，TPA纯度为93％。以联三苯为分散剂TPA产率可达62％，TPA纯度为96％。为对比催化剂氧化锌和苯甲酸锌在煤酸异构化反应中的催化活性，本文对这两种催化剂进行了对照实验，实验结果证明，苯甲酸锌作催化剂时煤酸异构化的对苯二甲酸收率略高于氧化锌催化剂时的收率，说明更易于回收的苯甲酸锌可以取代氧化锌作为煤酸异构化的催化剂。本文采用红外光谱、气相色谱等分析方法，对反应产物进行了定性和定量分析。更多还原

【Abstract】 This investigation relates to a method of producing terephthalic acid（TPA） from coal, including oxidation of coal for producing coal acids, followed by isomerization of the coal acids. Huolinhe lignite was subjected to alkali-oxygen oxidation in an aqueous solution of potassium hydroxide, then to make terephthalic acid by isomerization of potassium salt of coal acid in organic dispersant.In order to investigate the formation of aromatic polycarboxylic acids from coals, Huo linhe lignite oxygen-oxidation in aqueous alkali was studied. The coal oxidation was performed in an one-liter autoclave and the initial oxygen pressure, reaction time, reaction temperature and the alkali/coal ratio were changed respectively to study the influence on the yield of coal acids. The highest yield of coal acid under the optimum reaction conditions was 35.21％（daf）, which contains 63.97％benzene polycarboxylic acids（BPCA）. The theoretical yield of TPA are 68.56％（to BPCA）、43.86％（to coal acids） and 15.44％（to coal daf）. The optimum actions are: reaction temperature: 240℃, oxygen initial pressure 5.5Mpa, alkali/coal ratio: 3: 1, reaction time: 0.5h.Terephthalic acid can be obtained in the presence of a catalyst Zn（Bzo）₂ by isomerization of potassium salt of coal acid（which is a mixture of Huolinhe lignite coal acids, Zazi coal acids and Taxi anthracite coal acids）in organic dispersant have the high boil. The initial CO₂ pressure、amount of catalyst、reaction time, reaction temperature and the amount of dispersant were changed respectively to study the influence on the yield of TPA. The optimum conditions of isomerization use biphenyl as the dispersant were: temperature 420℃, initial CO₂ pressure 4MPa, catalyst Zn（Bzo）₂ 3％, dispersant 60％and reaction time 1h, TPA yield 24.1％, with a purity 92％. The optimum conditions of isomerization use p-Terphenyl as the dispersant were: temperature 380℃, initial CO₂ pressure 1MPa, catalyst Zn（Bzo）₂ 3％, dispersant 60％, TPA yield 25.2％, with a purity 94％. The yield of TPA by isomerization a mixture of potassium Salts of coal acid and benzoic acid were 60％, with a purity 93％（use biphenyl as the dispersant）and 62％, with a purity 96％（use p-Terphenyl as the dispersant）.The products were analyzed by gas chromatograghy.更多还原