废塑料裂解制取液体燃料技术的研究
摘要
废塑料来源广泛、危害极大且难于处理，利用其裂解制备液体燃料作为废塑料的解决办法已受到广泛关注。由于技术落后，在以往的裂解过程中存在着不能连续进料、不能连续釜底清渣、管道容易结胶和产生二次污染等问题。为此，本文开展了塑料裂解行为和催化改质特性和改质催化剂的研究，进行了废塑料、废塑料与废油、废塑料与废油及重油的裂解制取液体燃料技术的研究。
本文通过实验证实，各种塑料均有自己的热裂解温度特性，研究其热裂解温度特性，有助于研究其它影响因素对其热裂解的影响。研究了不同的塑料在不同的温度下裂解的液体收率、残渣收率、不凝气体收率以及汽油溜分、柴油溜分和重油溜分的量。
研究了各种反应影响条件对废塑料裂解气催化改质过程的影响，比较了各种催化剂的催化性能；实验证明，热裂解未经催化改质的产物与裂解气经催化改质后的产物组成有明显的区别。
本文以硝酸铝、硝酸锆、尿素为原料，用共沉淀法制得以Al_2O_3为载体的ZrO_2改质催化剂；在最佳条件下，用这种催化剂所得液体油品产率高，汽油质量明显提高，且催化剂积碳率低。
在塑料的热裂解过程中，重油的加入可以显著地改善传热传质条件，减少残渣的生成，不仅充分利用了重油，减少了结焦，而且改善了汽油的品质，汽油辛烷值大大增加。在此基础上研究了废塑料、废油及重油混合裂解制取燃料油的方法，设计了固定床反应器的裂解工艺流程。
研究了带连续进料装置和连续出渣装置的移动床反应器技术，并以此为基础设计了整套工艺流程，建立了处理废塑料规模达1吨／小时的示范装置；该示范装置实现了废塑料裂解制备液体燃料的连续生产，得到了符合国家标准的汽、柴油产品，生产中的二次污染问题得到了较好的处理。
Waste plastic originated widely is much hazardous and difficult to dispose. As a solution for waste plastic pollution, production of liquid fuel oil by pyrolysis of waste plastics has been paid much attention. Because of old and simple technology, the problem of un-continue feed, un-continue clear the residue at the bottom of reactor, apt to coke in the pipe and the secondary pollution are existed in the production process. So the pyrolysis of waste plastic, the characteristics of catalytic reforming and reforming catalyst were studied in this thesis, the technologies of manufacture fuel oil from waste plastics, the mixture of waste plastics and used oil, and the mixture of waste plastics, used oil and heavy oil were studied, too.
Experiment demonstrated that every kind of waste plastic has its own special characteristic of thermal pyrolysis versus temperature. Research on the characteristic is helpful to study the effect of other factors on the thermal pyrolysis of the waste plastic. The yields of liquid, carbon residue and gas, and the quantity of gasoline, diesel and heavy oil generated by pyrolysis of different kinds of waste plastic at different temperature were studied.
Effects of variety of condition on the process of catalytic reforming were studied in the thesis, the performance of kinds of catalyst were compared to each other, too. Experiment showed that the product components of catalytic reforming are distinctively different from that of thermal pyrolysis.
Taken Al (NO3)3, Zr(NO3)4, and (NH2)2 CO as material, the reforming catalyst with Al2O3 as carrier and ZrO2 as main component was prepared. Research demonstrated that, in the course of catalytic reforming of the product from the pyrolysis of waste plastics, with this catalyst used, the yield of oil is high, the quality of gasoline is improved obviously, and what's more, the coking rate is low.
In the course of thermal pyrolysis of waste plastics, addition of heavy oil can obviously improve the heat transfer and mass transfer and decrease the residue production. So this technology can make better use of heavy oil, decrease the coking, and improve the quality of gasoline with the great increase of RON. On the basis of this research, the technique of production fuel oil from the mixture of waste plastic,
waste oil and heavy oil was studied, and the pyrolysis process with fixed bed as reactor was designed.
Fluidized bed technology with equipment of continuous feed and residue removal was studied. On the basi
s of this research, the whole process for the technology was designed, and demonstration production facility was established, which dispose of the mixed waste plastics at the rate of 1 t/h. Through the facility, the continuous production of fuel oil by pyrolysis of waste plastic was achieved, the gasoline and diesel met national standard were produced, and the problem of the secondary pollution met in the product was properly solved.
本文通过实验证实，各种塑料均有自己的热裂解温度特性，研究其热裂解温度特性，有助于研究其它影响因素对其热裂解的影响。研究了不同的塑料在不同的温度下裂解的液体收率、残渣收率、不凝气体收率以及汽油溜分、柴油溜分和重油溜分的量。
研究了各种反应影响条件对废塑料裂解气催化改质过程的影响，比较了各种催化剂的催化性能；实验证明，热裂解未经催化改质的产物与裂解气经催化改质后的产物组成有明显的区别。
本文以硝酸铝、硝酸锆、尿素为原料，用共沉淀法制得以Al_2O_3为载体的ZrO_2改质催化剂；在最佳条件下，用这种催化剂所得液体油品产率高，汽油质量明显提高，且催化剂积碳率低。
在塑料的热裂解过程中，重油的加入可以显著地改善传热传质条件，减少残渣的生成，不仅充分利用了重油，减少了结焦，而且改善了汽油的品质，汽油辛烷值大大增加。在此基础上研究了废塑料、废油及重油混合裂解制取燃料油的方法，设计了固定床反应器的裂解工艺流程。
研究了带连续进料装置和连续出渣装置的移动床反应器技术，并以此为基础设计了整套工艺流程，建立了处理废塑料规模达1吨／小时的示范装置；该示范装置实现了废塑料裂解制备液体燃料的连续生产，得到了符合国家标准的汽、柴油产品，生产中的二次污染问题得到了较好的处理。
Waste plastic originated widely is much hazardous and difficult to dispose. As a solution for waste plastic pollution, production of liquid fuel oil by pyrolysis of waste plastics has been paid much attention. Because of old and simple technology, the problem of un-continue feed, un-continue clear the residue at the bottom of reactor, apt to coke in the pipe and the secondary pollution are existed in the production process. So the pyrolysis of waste plastic, the characteristics of catalytic reforming and reforming catalyst were studied in this thesis, the technologies of manufacture fuel oil from waste plastics, the mixture of waste plastics and used oil, and the mixture of waste plastics, used oil and heavy oil were studied, too.
Experiment demonstrated that every kind of waste plastic has its own special characteristic of thermal pyrolysis versus temperature. Research on the characteristic is helpful to study the effect of other factors on the thermal pyrolysis of the waste plastic. The yields of liquid, carbon residue and gas, and the quantity of gasoline, diesel and heavy oil generated by pyrolysis of different kinds of waste plastic at different temperature were studied.
Effects of variety of condition on the process of catalytic reforming were studied in the thesis, the performance of kinds of catalyst were compared to each other, too. Experiment showed that the product components of catalytic reforming are distinctively different from that of thermal pyrolysis.
Taken Al (NO3)3, Zr(NO3)4, and (NH2)2 CO as material, the reforming catalyst with Al2O3 as carrier and ZrO2 as main component was prepared. Research demonstrated that, in the course of catalytic reforming of the product from the pyrolysis of waste plastics, with this catalyst used, the yield of oil is high, the quality of gasoline is improved obviously, and what's more, the coking rate is low.
In the course of thermal pyrolysis of waste plastics, addition of heavy oil can obviously improve the heat transfer and mass transfer and decrease the residue production. So this technology can make better use of heavy oil, decrease the coking, and improve the quality of gasoline with the great increase of RON. On the basis of this research, the technique of production fuel oil from the mixture of waste plastic,
waste oil and heavy oil was studied, and the pyrolysis process with fixed bed as reactor was designed.
Fluidized bed technology with equipment of continuous feed and residue removal was studied. On the basi
s of this research, the whole process for the technology was designed, and demonstration production facility was established, which dispose of the mixed waste plastics at the rate of 1 t/h. Through the facility, the continuous production of fuel oil by pyrolysis of waste plastic was achieved, the gasoline and diesel met national standard were produced, and the problem of the secondary pollution met in the product was properly solved.
引文
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