本文旨在通过对煤热催化氧化降解特性的研究，为煤基降解复合材料的制备提供理论基础。利用盐酸脱灰处理的神府煤（ASFC）为原料，采用重液分离方法得到不同密度级神府超细煤粉（d2:1.35~1.375g.cm-3 d3: 1.375~1.4g.cm-3 d4:1.4g.cm-3以上）。应用离子交换方法，制得了以煤为载体的担载有过渡金属离子和纳米TiO2催化剂的热氧化降解反应样品。在热重分析仪和自制的固定床反应器上，研究了神府煤不同密度级组分热氧化反应性的差异及其不同催化剂对其热氧化降解反应性的影响，并进一步探讨了其热氧化反应动力学。 应用FTIR，元素分析及TG分析和固定床反应器，研究了不同密度级煤样的结构及其热氧化反应性。TG分析表明不同密度级煤样的热氧化失重反应活性不同，热氧化失重活性顺序依次为d2>d3～d4。在固定床反应器中，热氧化失重活性顺序依次为d2>d3>d4而CO2释放的反应活性顺序为：d4>>d3～d2。这主要归因于d2和d3组分相对于d4和ASFC具有较高脂肪结构，H/C元素比较高，矿物质含量低。d2与d3组分由于H/C比高，热氧化活性主要表现为分解产生CO2的同时，还有其它低分子烃类产生，d4组分由于矿物质含量高，矿物质在这些组分的热氧化反应中对CO2的生成起到一定的催化作用，导致其有较高的CO2产率。 分别采用液相离子交换方法和固相力化学离子交换方法制得担载有不同过渡金属离子和TiO2的ASFC及其不同密度级煤样研究样品，TG分析研究表明：就这些离子交换样的热氧化失重活性而言，机械力固相交换法优于液相离子交换法。在所研究的温度范围内，在液相离子交换法制得的担载有金属离子和TiO2的研究煤样的热氧化反应性研究结果表明：钴离子对于不同组分热氧化降解失重活性的阻化作用最大；机械力固相离子交换法制得的担载的TiO2＋Ni复配的催化剂的d3组分表现出较高的热氧化降解失重活性；固定床反应器热氧化降解反应研究表明：机械力固相离子交换法制得的担载有TiO2的d3组分热氧化失重催化活性最好。 利用红外光谱、溶胀度和腐植酸含量等测试方法对固定床反应器中氧化前后煤样结构和性质进行了表征，结果表明：ASFC及不同密度级组分中的与芳香环相连的亚甲基官能团具有较高的氧化降解反应活性。ASFC的溶胀度随氧化反应时间的变化规律与氧化反应温度有关，60℃时，随氧化反应进行，15h后溶胀度明显下降，而80℃时溶胀度在15h之前略有增加，随后也开始下降，但下降趋势较为平缓，并且总体上具有较高的溶胀度。60℃时,氧化煤中腐植酸含量随氧降解时间的变化在26h时呈现出一个最大值，并且不同密度组分氧化产物中腐植酸净增加量的大小顺序为：d4>d3>ASFC，这与此温度下CO2的释放量是一致的。因此，可以推断腐植酸是煤低温氧化的中间产物和CO2释放的主要来源。 假设煤的低温热氧化降解反应为简单反应，对在TG和固定床反应器中煤的热氧化降解反应进行了动力学分析，建立了相应的动力学方程。在TG中，对d3组分和利用机械力担载TiO2+Ce离子的d3组分在120℃处分为两个阶段分别利用Coast-Redfern法计算了反应的活化能，结果说明反应活化能在120℃以前差别不大，在120℃以后d3组分大于担载离子的d3组分活化能。在固定床反应器中，通过对ASFC、d2和d4组分在60和80℃下反应的活化能计算，得出活化能的大小顺序为：d2>ASFC>d4，与在这两个温度下的热氧化降解失重量活性相同。

This article intended to provide theoretical foundation for the preparation of coal-based dergradable composites through the investigation of characteristics of the low temperature thermal oxidation reaction(LTTOR) of coal. Using acid-washed SF Coal(ASFC), the different coal samples(d2:1.35~1.375g.cm-3 d3: 1.375~1.4g.cm-3 d4:+1.4g.cm-3) was obtained by means of sink-float method. The research samples loaded with transition metal ions and nano-TiO2 as catalyst, were prepared by using ion exchange method. The thermal oxidation degradation reactivities of AFSF, its differenct density components were studied, and the effect of transition metal and nano-TiO2 on their thermal oxidation degradation reactivities were also investigated in TG, fixed bed reactor，The oxidaton reaction kinetics were further studied based on the results from TG analysis and test of oxidative degradation reaction in fixed bed reactor. The structure and thermal oxidation reactivity of AFSF, its differenct density components were studied by FTIR, element analysis, TG analysis and test of oxidative degradation reation in fixed bed reactor. TG analysis show that different density samples have different thermal oxidation mass loss reactivity, the reactivity order is in the sequence of d2>d3～d4.In fixed bed reactor, the order is d2>d3>d4,but the CO2 released amount is in the order of d4>> d3~d2. That is because d2 and d3 samples have higher aliphatic structure uinit and higher H/C ratio, but have lower mineral matter. It can be guessed that gas producs of oxidation of d2 and d3 samples contain other small molecule hydrocarbon beside of CO2 , mineral matter may has catalysis on production of CO2 from thermal oxidation of d4 due to deep catalytic decdomposing of them. Ion exchange of ASFC and different density components with with transition metal cation and TiO2 were conducted by impregnating method and mechanical chemistry method.The TG analysis have proved that mechanical chemistry method is more effective than impregnating method for the catalytic oxidation of the coals. In the range of research temperature, Co3+in ion exchanged ASFC and its different density components by impregnating method has the most negative catalysis on the mass loss reactivity of them in thermal oxidation, whereas d3 loaded TiO2＋Ni by mechanical chemistry method has more effective catalysis on mass loss reativity than d3. The results of oxidative degradation reaction of d3 loaded transition metal cation and TiO2 by mechanical chemistry method show that TiO2 has the most effective catalyst for mass loss reativity of d3. FTIR analysis showed the methylene group, connected with the aromatic ring in ASFC and differernt density components, have higher reactivity during the LTTOR in fixed bed reactor. The degree of equillibrium swelling of oxidized ASFC, varied with the change of its oxidation time and temperature, arrived maximum at 80℃ while oxidation time at 15h , and then decreased sharply with oxidation time, but slow decreased at 60℃ with oxidation time, and that of oxidized ASFC at 80℃ is larger than that at 60℃ at any oxidation time. The content of humid acids of oxidized ASFC, d3and d4 appeared a maximum while the oxidation time arrived 26h at 60℃, and increase extent of their humid acids content at this condation is in the sequence of: d4>d3>ASFC. This is consistent with the order of CO2 released amount at the same oxidation temperature. This results showed that humid acids is the intermediate products and the major source of CO2 for LTTOR of the coals. The kinetics of LTTOR of the coals was disscussed and the kinetic equations were established with hypothesis that LTTOR of the coals in TG and fixed bed reactor is a simple oxidaton decomposing reaction. The kinetics of LTTOR of d3 and d3 loaded TiO2＋Ce by mechanical chemistry method(J-d3-TiO2＋Ce) was divided into two period at 120℃, and their activate reaction energy in LTTOR were calculated by using Coast-Redfern.method according to the results of their TG analysis. The results show that in the first period( below 120℃) , difference of the activation energy of d3 and J-TiO2＋Ce-d3 in LTTOR is very small, but become larger in the second period (above 120℃), and that of d3 is small than that of J-d3-TiO2＋Ce. The kinetics of ASFC, d2 and d4 in LTTOR at 60℃ and 80℃were further analyzed by according to the results of their LTTOR in fixed bed reactor. The calculated results show that the magnitude of activate reaction energy of LTTOR of ASFC and its defferent density components in fixed bed reactor is in the sequence of d2>ASFC>d4, which was consistent with change role of their mass loss reactivity at the same temperature.