论文总字数：26873字

摘 要

燃料油中的硫是大气污染物的主要来源，为了治理大气污染带来的一系列问题，对燃料油进行深度脱硫是至关重要的。过渡金属离子Cu 能与有机硫化物形成π络合作用，在吸附脱硫领域有良好的应用前景，但Cu(I)络合吸附剂仍存在稳定性低的问题。为解决这一问题，本文用聚苯乙烯修饰Cu(I)吸附剂，考察其吸附脱硫性能，并在水气条件下对其进行稳定性测试。

本文首先合成Cu(I)络合吸附剂，利用聚苯乙烯对其表面修饰，合成具有疏水性的吸附剂Cu(I)MCr-PS。将制得的Cu(I)吸附剂进行噻吩类硫化物的脱除实验，原吸附剂Cu(I)MCr对模型油中硫的饱和吸附量为0.241 mmol/g，Cu(I)MCr-PS饱和吸附量为0.239 mmol/g，两者吸附性能基本相同。在含有微量水的模型油中，Cu(I)MCr的饱和吸附量为0.093 mmol/g，明显降低，而Cu(I)MCr-PS饱和吸附量为0.237 mmol/g，基本保持不变。在湿气条件下处理25天后，Cu(I)MCr-PS依然稳定存在，而Cu(I)MCr则完全失活。对修饰前后的Cu(I)吸附剂进行4次循环再生测试，Cu(I)MCr的饱和吸附量为原先的7.1 %，Cu(I)MCr-PS的饱和吸附量基本不变。

关键词：Cu(I)络合吸附 MIL-101(Cr) 吸附脱硫 稳定性

Hydrophobic Cu (I) MCr on polystyrene surface and used in fuel oil desulfurization

ABSTRACT

Sulfur in fuel oil is the main source of atmospheric pollutants. In order to control a series of problems caused by atmospheric pollution, deep desulfurization of fuel oil is critical.The transition metal ion Cu has good application prospect in the field of adsorption desulfurization because it can form π complexation with organic sulfide, but Cu(I) complex adsorbent still has the problem of low stability. In order to solve this problem, this paper modified Cu(I) adsorbent with polystyrene to investigate its adsorption and desulfurization performance and tested its stability under water and gas conditions.

In this paper, first,Cu(I) complex adsorbent is synthesized, and its surface is modified with polystyrene to synthesize the hydrophobic adsorbent Cu(I)MCr-PS. The prepared Cu(I)adsorbent was applied to the thiophene sulfide removal experiment. The saturated adsorption capacity of the original adsorbent Cu(I)MCr to sulfur in the model oil is 0.241 mmol/g, the saturation adsorption capacity of Cu(I)MCr-PS is 0.239 mmol/g, the adsorption performance of the two is basically the same. In the model oil containing trace water, the adsorption capacity of Cu(I)MCr is 0.093 mmol/g, which has been significantly reduced, while the adsorption capacity of Cu(I)MCr-PS is 0.237 mmol/g, which basically remains unchanged. After 25 days of treatment under moisture,Cu(I)MCr-PS remained stable, but Cu(I)MCr was completely inactivated. The Cu(I) adsorbent before and after modification was subjected to 4 cycles of regeneration tests. The adsorption capacity of Cu(I)MCr was 7.1 %, and the adsorption capacity of Cu(I)MCr-PS was basically unchanged.

KEYWORDS: Cu(I)-complexing adsorbents; MIL-101(Cr); adsorption desulfurization; stability

目录

摘要 I

ABSTRACT II

第一章 绪论 1

1.1 引言 1

1.2 脱硫研究进展 1

1.2.1 吸附脱硫 1

1.2.2 加氢脱硫 2

1.2.3 氧化脱硫 2

1.2.4 其他脱硫方法 3

1.3 Cu(I)络合吸附剂 3

1.3.1 Cu(I)络合吸附剂的制备 3

1.3.2 Cu(I)络合吸附剂机理 4

1.3.3 Cu(I)络合吸附剂应用 4

1.3.4 Cu(I)络合吸附剂稳定性 5

1.4 固体多孔材料疏水改性方法 5

1.4.1 引入疏水性基团 5

1.4.2 与其他材料杂化 6

1.4.3 聚合物表面修饰 6

1.5 论文研究目的与内容 6

第二章 实验部分 7

2.1 实验材料 7

2.2 样品制备 7

2.2.1 水热法合成MIL-101(Cr) 7

2.2.2 双溶剂法合成Cu(II)MCr 8

2.2.3 蒸汽诱导法合成Cu(I)MCr 8

2.2.4 聚苯乙烯表面修饰合成Cu(I)MCr-PS 8

2.3 样品表征 9

2.3.1 X射线衍射 9

2.3.2 红外光谱 9

2.3.3 固体紫外-可见漫反射光谱 9

2.3.4 77K N₂吸附等温线 9

2.3.5 Cu(I)含量测定 9

2.3.6 水接触角 9

2.4 吸附剂脱硫性能测试 10

第三章 聚苯乙烯（PS）涂层稳定Cu(I)MCr中Cu(I) 12

3.1 引言 12

3.2 MIL-101(Cr)的载铜以及还原 12

3.3 Cu(I)MCr-PS的结构与表面性质 14

3.4 Cu(I)MCr-PS中Cu(I)稳定性 17

3.5 Cu(I)MCr-PS的吸附脱硫性能 19

第四章 结论与展望 24

4.1 结论 24

4.2 展望 24

参考文献 25

致谢 29

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