還原性氣氛下可燃固體廢棄物熱解油高值利用途徑

仲兆平

摘 要：在管式爐內進行單組分熱解制油試驗，獲得了各組分的熱解油產率與組分數據。利用主成分分析法分析NaOH、HY-51、凹凸棒土（凹土）原土OA和純化凹土（PA）對廢輪胎熱解油的影響，發現PA在催化廢輪胎熱解制取芳香烴等方面具有巨大潛力。對三種組分的混合熱解制油試驗結果表明，混合組分最佳產油率溫度與單組分較一致，且三組分混合比例較平均時，混合熱解相互影響較小。采用支持向量機方法，建立了熱解油產率預測模型，達到了較好的預測效果。 柱層析試驗結果表明，二氯甲烷和丙酮對熱解油中的烴類有較好的分離效率，達到37.63%，淋洗液具有潛在的用于化工原料或液體燃料的價值。催化酯化試驗結果表明，固體超強酸La3+-SO42-/TiO2能達到較好的催化效果，熱解油中酯類從10.71%增加到24.94%，縮醛類含量增加，降低了熱解油酸性、腐蝕性，提高了熱解油品質。 在PY-GC/MS試驗臺上進行廢紙板催化熱解機理研究，結果表明：HZSM-5具有催化低聚物裂解、增加烴類含量、降低醛類和酸類含量；HY-51能夠降低醛類含量，增加烴類含量，但不能促進低聚物裂解、增加了酸類含量，且易結焦失活，雖催化活性高但用于廢紙板催化熱解還需改性；ReY對廢紙板熱解產物的催化效果有限；PA則基本不具有催化廢紙板熱解產物改善的效果。利用HZSM-5負載各種活性金屬離子對催化劑進行改性，結果表明：0.5wt% Ni-HZ大幅度提高了BTX的產量，具有催化大分子難裂解物質分解的效果；0.5wt% Ca-HZ能夠催化LG通過C-O鍵斷裂反應生成BTX，并脫除大量O元素；0.5wt% Al-HZ能夠催化LG通過C-C鍵斷裂反應生成呋喃類組分，但更容易引起結焦；增加活性組分負載量至2wt%均可能由于活性組分過量而導致堵塞HZ表面孔道，阻礙反應物的進入與溢出，降低催化劑的催化效果。 在PY-GC/MS試驗臺上進行廢輪胎催化熱解機理研究，結果表明：HY-51與ReY對廢輪胎裂解產物具有相近的提質效果，二者能夠有效催化產物中的脂肪烴向芳香烴的轉化，但一些茚族、萘族、菲族等多環芳烴也有增加；HZSM-5對廢輪胎裂解產物也具有較好的重整效果；PA對廢輪胎裂解產物的品質提升效果不佳。 在PY-GC/MS試驗臺上進行廢PE催化熱解機理研究，結果表明：HSZM-5、HY-51和ReY三種分子篩對廢PE的裂解行為影響相似，均降低了裂解產物中烯烴的含量，增加了烷烴和芳香烴的含量；PA對廢PE的催化效果較溫和，促進部分烯烴轉化為烷烴。

關鍵詞：固體廢棄物 熱解 品質提升 裂解-氣相色譜/質譜聯用

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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