仲兆平

摘 要：在管式炉内进行单组分热解制油试验，获得了各组分的热解油产率与组分数据。利用主成分分析法分析NaOH、HY-51、凹凸棒土（凹土）原土OA和纯化凹土（PA）对废轮胎热解油的影响，发现PA在催化废轮胎热解制取芳香烃等方面具有巨大潜力。对三种组分的混合热解制油试验结果表明，混合组分最佳产油率温度与单组分较一致，且三组分混合比例较平均时，混合热解相互影响较小。采用支持向量机方法，建立了热解油产率预测模型，达到了较好的预测效果。 柱层析试验结果表明，二氯甲烷和丙酮对热解油中的烃类有较好的分离效率，达到37.63%，淋洗液具有潜在的用于化工原料或液体燃料的价值。催化酯化试验结果表明，固体超强酸La3+-SO42-/TiO2能达到较好的催化效果，热解油中酯类从10.71%增加到24.94%，缩醛类含量增加，降低了热解油酸性、腐蚀性，提高了热解油品质。 在PY-GC/MS试验台上进行废纸板催化热解机理研究，结果表明：HZSM-5具有催化低聚物裂解、增加烃类含量、降低醛类和酸类含量；HY-51能够降低醛类含量，增加烃类含量，但不能促进低聚物裂解、增加了酸类含量，且易结焦失活，虽催化活性高但用于废纸板催化热解还需改性；ReY对废纸板热解产物的催化效果有限；PA则基本不具有催化废纸板热解产物改善的效果。利用HZSM-5负载各种活性金属离子对催化剂进行改性，结果表明：0.5wt% Ni-HZ大幅度提高了BTX的产量，具有催化大分子难裂解物质分解的效果；0.5wt% Ca-HZ能够催化LG通过C-O键断裂反应生成BTX，并脱除大量O元素；0.5wt% Al-HZ能够催化LG通过C-C键断裂反应生成呋喃类组分，但更容易引起结焦；增加活性组分负载量至2wt%均可能由于活性组分过量而导致堵塞HZ表面孔道，阻碍反应物的进入与溢出，降低催化剂的催化效果。 在PY-GC/MS试验台上进行废轮胎催化热解机理研究，结果表明：HY-51与ReY对废轮胎裂解产物具有相近的提质效果，二者能够有效催化产物中的脂肪烃向芳香烃的转化，但一些茚族、萘族、菲族等多环芳烃也有增加；HZSM-5对废轮胎裂解产物也具有较好的重整效果；PA对废轮胎裂解产物的品质提升效果不佳。 在PY-GC/MS试验台上进行废PE催化热解机理研究，结果表明：HSZM-5、HY-51和ReY三种分子筛对废PE的裂解行为影响相似，均降低了裂解产物中烯烃的含量，增加了烷烃和芳香烃的含量；PA对废PE的催化效果较温和，促进部分烯烃转化为烷烃。

关键词：固体废弃物 热解 品质提升 裂解-气相色谱/质谱联用

Abstract：The main components of solid waste as waste cardboard， waste tire and waste PVC were chosen for the experiment in a tube reactor to produce pyrolysis oil. The yield and components data of each pyrolysis oil were obtained. Principal component alalysis was used to analyze the influence of NaOH， HY-51， original attapulgite （OA） and purified attapulgite （PA） on the pyrolysis oil of waste tire. It can be concluded that PA has great potential on catalyzing the pyrolysis of waste tire to produce aromatic hydrocarbons. Study on mixed pyrolysis of the three components shows that the optimized temperature of pyrolysis oil yield is the same as single component， and that when the blending rate of three mixed components is mean， their influence to each other is minimised. Column chromatography and catalytic esterification were chosen for upgrade research of pyrolysis oil of solid waste. The column chromatography experiment result shows that dichloromethane and acetone have good separation efficiency for hydrocarbons， which reaches 37.63%. The catalytic pyrolysis mechanism research of waste cardboard was carried out on a PY-GC/MS platform. The results show that HZSM-5 （HZ） has a good ability for cracking the oligomers， increasing the hydrocarbons and lowering the aldehydes and scids， which is being proved to be a good- performance catalyst. HY-51 would decrease the content of aldehydes and increase the yield of hydrocarbons， while do not promote the crack of oligomers， increase the content of acids， and get coking leading to inactivation. It indicates that HY-51 needs further modification for the using in the catalytic pyrolysis of waste cardboard despite its high catalytic activity. ReY shows a limited catalytic effect for the pyrolysis of waste cardboard， while PA performances an ignorable effect. Various active metal ions were loaded on catalyst HZSM-5 for modification. The catalytic pyrolysis mechanism research of waste tire was carried out on a PY-GC/MS platform. The catalytic pyrolysis mechanism research of waste PE was carried out on a PY-GC/MS platform. HZSM-5， HY-51 and ReY show alike influence on the catalytic pyrolysis of waste PE. All of them decrease the content of olefins and increase that of the alkanes and aromatic hydrocarbons. PA performs a mild effect， which promotes some olefins transfer to alkanes.

Key word：Solid waste； Pyrolysis； Quality improvement； PY-GC/MS

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