生物质焦油催化转化新型催化剂研究
摘要
生物质能作为一种环境友好型的可再生能源，是目前唯一有望能在将来替代传统化石能源的新能源。生物质气化技术是生物质能转化的最有效途径之一。但是在生物质气化过程中，不可避免的产生生物质焦油。生物质焦油不仅能堵塞传输管道，影响气化系统的正常运行，而且对环境及人体健康都有严重的威胁。因此，生物质焦油是影响生物质气化技术推广应用的致命弱点。
本文对国内外生物质焦油脱除技术做了详细的阐述及比较，从中得出结论，催化转化法是生物质焦油脱除的最有效途径。而催化剂的选择是生物质焦油催化转化的重要因素，催化剂的催化活性和寿命是催化剂性能的重要标志。从经济和技术的角度考虑，镍基催化剂被认为是生物质焦油催化转化的最理想催化剂。
本文以筛选催化活性高，抗积炭能力强的新型催化剂为主要目的，对生物质焦油的催化转化做了一系列的实验研究，获得了充实的数据，并对数据进行整理和详细的分析。在对真实生物质焦油催化转化之前，先以甲苯和苯作为生物质焦油模拟化合物，在微型反应装置上对自制的两类镍基镁橄榄石催化剂进行性能测试。首先考察了活性中心镍和助剂铈的负载量对催化剂性能的影响，同时考察了反应条件温度及水碳比对甲苯催化转化的影响。结果显示，CeO_2促进的镍基镁橄榄石催化剂有较好的催化性能，在测试条件下，1％Ce-3％Ni／Olivine催化剂有最好的催化活性，在反应温度为800℃，水碳摩尔比为5的条件下，对甲苯的转化率为88.2％。在此催化剂的基础上，考察了碱性助剂镁的添加对催化剂的催化活性和抗积炭能力的改善情况，同时考察了助剂添加次序的不同所带来的影响。结果显示，镁的添加能显著提高催化剂的抗积炭能力，不同的浸渍次序对催化剂的活性有较大影响；在同等条件下，依次浸渍镁、铈、镍的催化剂有最高的催化活性，在测试条件下，1％Mg-1％Ce-3％Ni／Olivine在反应温度为800℃，水碳摩尔比为3.5时有最好的催化活性，对甲苯和苯的转化率分别为93.8％和76.9％。
为了进一步提高生物质燃气中焦油的催化脱除水平，设计了一套生物质气化和相配套的燃气整体催化净化实验装置，对自行合成的催化剂性能作进一步的验证。实验是以松木锯末为原料，考察了不同的气化条件对气化气中气体组分及焦油含量的影响。同时，以生物质气化产生的整体燃气作为生物质焦油的来源，对自制的1％Ce-3％Ni／Olivine催化剂进行性能测试，并对催化剂的添加以及催化转化过程中蒸气的添加对生物质焦油催化转化前后的气体成分和生物质焦油含量的影响进行分析。结果显示，在催化床温度为750℃，有蒸汽加入的条件下此催化剂对重焦油的脱除效率能达到90％，并且能使H_2的浓度增加6～7％。
As an environment-friendly and renewable resource, biomass is only one of the promising substitutions of fossil fuels at present. The gasification is one of the effective technologies for its conversion. However, the gasification process is inevitably accompanied by the formation of tar. The condensable compounds that present in tar not only cause conglomeration and sediment in the gasification equipment and gas transporting line, but also threat the environment and health of man. Therefore, the tar affects the extensive utilization of the technology of the biomass gasification.
A review of current researches and development of biomass tar destruction is given in this thesis, from which the conclusion can be drew that the catalytic steam reforming of tar is the most effective method to suppress the problem. The choice of catalysts is the important factor of the catalytic reforming of biomass tar, and the reaction activity and life span are the chief performance factors of catalyst. From economical and technical considerations, nickel-containing catalyst appears to be the most appropriate choice.
In the aim of the choice for the new catalysts possessing higher reaction activity and better function to prevent coking, a series of experiments were carried out, from which the useful and systematical data were studied. At first, the performance of two series of synthesized nickel-containing olivine catalysts was investigated using toluene and benzene as model biomass tar. The effects of the content of Nickel and Cerium impregnated olivine and the reaction condition on toluene catalytic reforming were investigated. The results showed: for 1 % Ce-3 % Ni/Olivine catalyst, the conversion efficiency of toluene is 88.2% at the temperature of 800℃and the steam to carbon (s/c) of 5. And then on the basis, the effects of the addition of the basic promoter Mg and the different impregnating order of promoter were examined. The results showed that the catalysts of adding the basic promoter possessed better function to prevent coking. Impregnating order of promoter affected the reaction activity seriously. The catalyst of sequentially impregnating Mg, Ce, Ni exhibited higher catalytic activity under the same condition. For 1%Mg-1%Ce-3%Ni/Olivine catalyst, the conversion efficiencies of toluene and benzene were 93.8% and 76.9% respectively at the temperature of 800°C and the steam to carbon (s/c) of 3.5.
In order to eliminate the formation of the tar derived from the gasification of biomass, a set of apparatus that used for the gasification of biomass and the corresponding catalytic reforming of tar was set up. The further tests for synthesized catalysts were conducted in this apparatus. The effects of the reaction condition on the composition of gas and the content of biomass tar were determined. At the same time, the performance of synthesized 1%Ce-3%Ni/Olivine catalyst was researched using the producer gas derived from biomass gasification, and changes in gas composition and the tar content by the addition of catalyst and the steam were also analyzed in this study. The catalyst proved effective and the conversion efficiency of heavy tars was 90% in the presence of steam and at the temperature of 750℃, and hydrogen yield also increased 6～7%
本文对国内外生物质焦油脱除技术做了详细的阐述及比较，从中得出结论，催化转化法是生物质焦油脱除的最有效途径。而催化剂的选择是生物质焦油催化转化的重要因素，催化剂的催化活性和寿命是催化剂性能的重要标志。从经济和技术的角度考虑，镍基催化剂被认为是生物质焦油催化转化的最理想催化剂。
本文以筛选催化活性高，抗积炭能力强的新型催化剂为主要目的，对生物质焦油的催化转化做了一系列的实验研究，获得了充实的数据，并对数据进行整理和详细的分析。在对真实生物质焦油催化转化之前，先以甲苯和苯作为生物质焦油模拟化合物，在微型反应装置上对自制的两类镍基镁橄榄石催化剂进行性能测试。首先考察了活性中心镍和助剂铈的负载量对催化剂性能的影响，同时考察了反应条件温度及水碳比对甲苯催化转化的影响。结果显示，CeO_2促进的镍基镁橄榄石催化剂有较好的催化性能，在测试条件下，1％Ce-3％Ni／Olivine催化剂有最好的催化活性，在反应温度为800℃，水碳摩尔比为5的条件下，对甲苯的转化率为88.2％。在此催化剂的基础上，考察了碱性助剂镁的添加对催化剂的催化活性和抗积炭能力的改善情况，同时考察了助剂添加次序的不同所带来的影响。结果显示，镁的添加能显著提高催化剂的抗积炭能力，不同的浸渍次序对催化剂的活性有较大影响；在同等条件下，依次浸渍镁、铈、镍的催化剂有最高的催化活性，在测试条件下，1％Mg-1％Ce-3％Ni／Olivine在反应温度为800℃，水碳摩尔比为3.5时有最好的催化活性，对甲苯和苯的转化率分别为93.8％和76.9％。
为了进一步提高生物质燃气中焦油的催化脱除水平，设计了一套生物质气化和相配套的燃气整体催化净化实验装置，对自行合成的催化剂性能作进一步的验证。实验是以松木锯末为原料，考察了不同的气化条件对气化气中气体组分及焦油含量的影响。同时，以生物质气化产生的整体燃气作为生物质焦油的来源，对自制的1％Ce-3％Ni／Olivine催化剂进行性能测试，并对催化剂的添加以及催化转化过程中蒸气的添加对生物质焦油催化转化前后的气体成分和生物质焦油含量的影响进行分析。结果显示，在催化床温度为750℃，有蒸汽加入的条件下此催化剂对重焦油的脱除效率能达到90％，并且能使H_2的浓度增加6～7％。
As an environment-friendly and renewable resource, biomass is only one of the promising substitutions of fossil fuels at present. The gasification is one of the effective technologies for its conversion. However, the gasification process is inevitably accompanied by the formation of tar. The condensable compounds that present in tar not only cause conglomeration and sediment in the gasification equipment and gas transporting line, but also threat the environment and health of man. Therefore, the tar affects the extensive utilization of the technology of the biomass gasification.
A review of current researches and development of biomass tar destruction is given in this thesis, from which the conclusion can be drew that the catalytic steam reforming of tar is the most effective method to suppress the problem. The choice of catalysts is the important factor of the catalytic reforming of biomass tar, and the reaction activity and life span are the chief performance factors of catalyst. From economical and technical considerations, nickel-containing catalyst appears to be the most appropriate choice.
In the aim of the choice for the new catalysts possessing higher reaction activity and better function to prevent coking, a series of experiments were carried out, from which the useful and systematical data were studied. At first, the performance of two series of synthesized nickel-containing olivine catalysts was investigated using toluene and benzene as model biomass tar. The effects of the content of Nickel and Cerium impregnated olivine and the reaction condition on toluene catalytic reforming were investigated. The results showed: for 1 % Ce-3 % Ni/Olivine catalyst, the conversion efficiency of toluene is 88.2% at the temperature of 800℃and the steam to carbon (s/c) of 5. And then on the basis, the effects of the addition of the basic promoter Mg and the different impregnating order of promoter were examined. The results showed that the catalysts of adding the basic promoter possessed better function to prevent coking. Impregnating order of promoter affected the reaction activity seriously. The catalyst of sequentially impregnating Mg, Ce, Ni exhibited higher catalytic activity under the same condition. For 1%Mg-1%Ce-3%Ni/Olivine catalyst, the conversion efficiencies of toluene and benzene were 93.8% and 76.9% respectively at the temperature of 800°C and the steam to carbon (s/c) of 3.5.
In order to eliminate the formation of the tar derived from the gasification of biomass, a set of apparatus that used for the gasification of biomass and the corresponding catalytic reforming of tar was set up. The further tests for synthesized catalysts were conducted in this apparatus. The effects of the reaction condition on the composition of gas and the content of biomass tar were determined. At the same time, the performance of synthesized 1%Ce-3%Ni/Olivine catalyst was researched using the producer gas derived from biomass gasification, and changes in gas composition and the tar content by the addition of catalyst and the steam were also analyzed in this study. The catalyst proved effective and the conversion efficiency of heavy tars was 90% in the presence of steam and at the temperature of 750℃, and hydrogen yield also increased 6～7%
引文
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