典型可燃固体废弃物热解制油及生物油品质提升试验研究

论文总字数：35171字

摘 要

之后，通过采用配比的模化物（乙酸：丁醛：丙酮：苯酚：甲醇=1:1:1:1:5）于高压反应釜内进行一步加氢催化酯化反应（OHE）。实验设计采用正交实验，研究了催化剂种类、催化剂数量、温度、压力4因素4水平，综合分析比较16个工况从而得出模化物OHE反应的最优工况。最优工况下反应后的模化物的酸值由79.19mgNaOH/g 大大降至于22.57mgNaOH/g，乙酸被消耗完全，酯类产物的选择性由反应前的6.16%增加到21.08%，酯化效率达48%，同时丁醛发生加氢反应生成丁醇，加氢效率达到37.9%，催化酯化效果良好。

最后，采用MSW热解油在上述最优工况下进行加氢催化酯化反应，产物酸值6.57mgNaOH/g，远远小于初始热解油的164.84mgNaOH/g，热解油的酸类物质被消耗，酯类化合物含量提升了2倍。 高温高压的条件下，部分多环芳烃发生裂解生成单环芳烃，多环芳烃含量降低，单环芳烃含量上升；部分芳香族化合物（含苯环的酸类）与甲醇发生酯化反应生成酯类。 酮类物质发生缩醛反应含量降低。 脂肪烃类物质基本含量不变，但由于加氢，存在着一些不饱和烃加氢向饱和烃的转化以及原有的带支链的烷烃转变成直链烷烃的情况。

关键词：城市固体废弃物热解油，模化物，一步加氢催化酯化，酸值，GC-MS

Production of oil by pyrolysis of municipal solid waste and the test research on the promotion of oil equality

03211712 Da Kang

Supervised by Zhaoping Zhong

Abstract： Recently, the production of solid waste is growing fast in major cities, while the study on making liquid oil by the pyrolysis technology has become a hot spot to be expected to replace the industrial oil. In this paper, we make oil by pyrolysis of municipal solid waste in the tube furnace. The production rate of oil is 42.17%, the carbon is 38.43% and the gas is 19.40%. The oil has high acid numbers with 164.84mgNaOH/g and high moisture contents with 25.30% after preprocessing. Analyzing by GC-MS instrument, the main eight components are monocyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons, acids, esters, fatty hydrocarbons, alcohols, sulfur and ketone from more to less.

Then, we do the one-step hydrogenation-esterification experiment in the high-pressure reaction kettle with the model compound (acetic acid: butyl aldehyde: acetone: phenol: methanol=1:1:1:1:5). The experiment is using orthogonal experiment to study the influence of the types of catalyst, catalyst quantity, temperature and pressure. Studying four factors at four levels, we got the optimal reaction condition by analyzing and comparing among the total 16 cases. Under the optimal condition, the acid numbers of model compound lowers to 22.57mgNaOH/g from the original 79.19mgNaOH/g. The acetic acid ran out and the proportion of ester products adds to 21.08% from 6.16%. At the same time, butyl aldehyde generated butanol by hydrogenation reaction and the yield reached 37.9% which prove the good effect of catalytic esterification.

At last, we do the OHE experiment with the MSW pyrolysis oil under the optimal condition. The acid numbers of the product is 6.57mgNaOH/g, far less than the original 164.84mgNaOH/g. The acid chemicals ran out and the ester compounds increase two times. Under the high temperature and pressure, some polycyclic aromatic hydrocarbons crack to monocyclic aromatics, leading to the decline of polycyclic aromatic hydrocarbons and the increase of monocyclic aromatics. Also, some aromatic compounds like the acids containing benzene ring esterify with methanol. Ketone is decreased with the ketalation. The total quantity of aliphatic hydrocarbons is stable, but it has the conversion of unsaturated hydrocarbons to saturated hydrocarbons due to hydrogenation and branched-chain alkanes to the straight alkanes.

Key words: municipal solid waste pyrolysis oil, model compound, one-step hydrogenation esterification, acid number, GC-MS

目 录

第一章 绪 论 1

1.1 引言 1

1.2 城市固体废弃物现状 1

1.3 热解技术 1

1.3.1 热解原理 1

1.3.2 热解技术影响因素 2

1.3.3 热解工艺 2

1.4 固体废弃物热解制油现状 3

1.4.1国内现状 3

1.4.2国外现状 3

1.4.3热解液化反应器 3

1.5 热解油理化性质 7

1.6 热解油的精制 10

1.7 课题研究目的和主要内容 10

第二章 MSW热解制油实验 12

2.1 实验部分 12

2.1.1 实验原料 12

2.1.2 实验方法 12

2.1.3 实验操作流程 12

2.2 分析方法 13

2.2.1热解产率分析 13

2.2.2热解油预处理 13

2.2.3酸值测定 13

2.2.4水分测定 14

2.2.5GC-MS分析 15

2.3 分析结果 16

2.3.1热解产率 16

2.3.2物理性质 16

2.3.3GC-MS 17

第三章 模化物提质正交实验 19

3.1 提质方案的确定 19

3.2 模化物的选取与配比 19

3.3 催化剂的选取与制备 19

3.3.1 Pt-SO42-/TiO2(Pt-ST)的制备 19

3.3.2 Pt-732树脂(Pt-732)的制备 20

3.3.3 Pt-montmorillonite(Pt-M)的制备 20

3.3.4催化剂的还原 20

3.4 高压反应釜 20

3.5 正交实验设计 21

3.6 实验流程 22

3.7 产物分析及结果 22

3.7.1模化物提质后效果 22

3.7.2物理性质分析 23

3.7.3GC-MS分析 24

3.7.4模化物最优工况 29

3.8 最优工况下OHE实验 30

第四章 MSW热解油提质实验 35

4.1 实验流程 35

4.2 实验结果 35

4.2.1物理性质分析 35

4.2.2GC-MS分析 35

第五章 结论及建议 40

5.1 结论 40

5.2 建议 41

致谢 42

参考文献 43

绪 论

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