论文总字数：19550字

摘 要

目前，大多数炼油厂仍采用加氢脱硫技术生产超低硫柴油，其需要高温、高压以及高氢气消耗，经济成本较高。非加氢脱硫技术能够在温和的条件下实现超低硫柴油的生产，具有较好的工业应用前景。本文分析了加氢柴油中的硫化物和烃类组成；对水热法合成的MIL-101采用XRD、BET和TG-DTA表征并考察了其对低硫加氢柴油的静态吸附脱硫性能和动态吸附脱硫性能。主要研究内容和结论如下：

1. 采用微库仑仪、GC-SCD和GC-MS对加氢柴油中的硫化物和烃类组成进行分析。结果表明，加氢柴油的总硫含量为14.82 μg/g，主要是带有C1-C3烷基支链的二苯并噻吩类化合物，链烷烃、环烷烃和芳烃的含量分别约为47.0 wt%、37.6 wt%和15.4 wt%。
2. MIL-101静态吸附脱硫性能考察。分别考察吸附温度、固液比对MIL-101静态吸附脱硫性能的影响。结果表明，初始硫浓度为14.82 μg/g，吸附温度为50 ℃，固液比为1/25（g/mL）时，MIL-101对加氢柴油的平衡吸附硫容为0.11 mg S/g_ads。
3. MIL-101动态吸附脱硫性能考察。分别考察吸附温度、原料体积空速对MIL-101动态吸附脱硫性能的影响。结果表明，初始硫浓度为14.82 μg/g，吸附温度为30 ℃，原料体积空速为16.26 h^-1时，MIL-101对加氢柴油的动态吸附硫容为0.40 mg S/g_ads。

关键词：MIL-101 加氢柴油 脱硫 吸附硫容

Study on Adsorptive Desulfurization Process of MIL-101 for Hydrocracking Diesel Oil

Abstract

In refineries, ultra-low sulfur diesel oil is obtained by hydrodesulfurization technology. The process needs high economic cost because of the strict conditions in temperature, pressure and hydrogen consumption. However, qualified diesel fuel can be obtained in a mild condition through non-hydrodesulfurization technology which is widely concerned and has high value of application.

In this paper, the sulfur components and hydrocarbon compositions of hydrocracking diesel oil were analyzed. MIL-101 was synthesized by hydrothermal method and characterized by XRD, BET and TG-DTA. The static and dynamic desulfurization performance of MIL-101 were studied. Main contents and results are as follows:

1. Sulfur components and hydrocarbon compositions in hydrocracking diesel oil were analyzed by microcoulometry instrument, GC-SCD, and GC-MS. Result shows that total sulfur content is 14.82 μg/g, which contains dibenzothiophene derivatives with less than four alkyl groups. The contents of paraffins, cycloparaffins and aromatics are about 47.0 wt%, 37.6 wt% and 15.4 wt%.
2. Equilibrium adsorption performance of MIL-101 for hydrocracking diesel oil was investigated. Influence of temperature and solid to liquid ratio on equilibrium adsorption capacity of MIL-101 was measured. Results indicate that the initial concentration of sulfur is 14.82 μg/g, equilibrium adsorption capacity is 0.11 mg S/g_ads at the conditions of 50 ℃ and 1/25(g/mL).
3. Dynamic adsorption performance of MIL-101 for hydrocracking diesel oil was investigated. Effects of temperature and liquid hourly space velocity on adsorptive capacity of MIL-101 were measured. Results indicate that the initial concentration of sulfur is 14.82 μg/g, the dynamic adsorption capacity is 0.40 mg S/g_ads at the conditions of 30 ℃ and 16.26 h^-1.

Key Words: MIL-101; Hydrocracking diesel oil; Desulfurization; Adsorption capacity

目 录

摘 要 I

ABSTRACT II

第一章 概述 1

1.1 课题背景研究 1

1.2 柴油脱硫技术研究现状 1

1.2.1 加氢脱硫 1

1.2.2 非加氢脱硫 2

1.3 柴油脱硫吸附剂研究进展 3

1.3.1 活性炭 3

1.3.2 金属氧化物 3

1.3.3 分子筛 3

1.3.4 金属有机骨架材料 4

1.4 本文主要内容 5

第二章 实验 6

2.1 主要试剂和仪器 6

2.2 柴油组分分析方法 6

2.2.1 柴油总硫含量测定 6

2.2.2 柴油硫形态分析 7

2.2.3 柴油中烃类组成分析 7

2.3 MIL-101的制备方法 8

2.4 吸附脱硫实验 8

2.4.1 静态吸附脱硫性能测定 8

2.4.2 动态吸附脱硫性能测定 8

2.5 吸附剂表征方法 9

2.5.1 XRD表征物相 9

2.5.2 BET表征孔结构 10

2.5.3 TG-DTA 10

第三章 结果与讨论 11

3.1 加氢柴油中烃类及硫化物组成分析 11

3.1.1 烃类组成分析 11

3.1.2 硫化物成分分析 12

3.2 MIL-101结构表征 12

3.2.1 XRD 12

3.2.2 BET 13

3.2.3 TG-DTA 14

3.3 MIL-101对加氢柴油的静态吸附脱硫性能 14

3.3.1 吸附温度 14

3.3.2 固液比 15

3.3.3 MIL-101对加氢柴油的吸附脱硫速率 16

3.4 MIL-101对加氢柴油的动态吸附脱硫性能 16

3.4.1 吸附温度 16

3.4.2 原料体积空速 17

第四章 结论与展望 19

4.1 结论 19

4.2 展望 19

参考文献 20

致 谢 22

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