神府煤液化油加氢精制过程中硫氮化合物分布的变化

黄澎; 张晓静; 毛学锋; 李伟林

神府煤液化油加氢精制过程中硫氮化合物分布的变化

黄澎^{1, 2, ,},
张晓静^{1, 2},
毛学锋^{1, 2},
李伟林^{1, 2}

1.
煤炭科学研究总院北京煤化工研究分院, 北京 100013
2.
煤炭资源开采与洁净利用国家重点实验室, 北京 100013

基金项目:

国家自然科学基金 U1261117

国家国际科技合作计划项目 2013DFA61660

国家科技支撑计划 2012BAA04B04

详细信息

通讯作者:
黄澎, Tel: 010-84262962, E-mail: squallok@qq.com

中图分类号: TQ536
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- HTML全文浏览量: 22
- PDF下载量: 9
- 被引次数: 0
出版历程
- 收稿日期: 2015-07-28
- 修回日期: 2015-09-08
- 网络出版日期: 2022-03-23
- 刊出日期: 2016-01-01

Change of sulfur and nitrogen compounds in the direct liquefaction oil from Shenfu coal upon the hydrofining process

HUANG Peng^{1, 2
, ,},
ZHANG Xiao-jing^{1, 2},
MAO Xue-feng^{1, 2},
LI Wei-lin^{1, 2}

1.
Beijing Coal Chemistry Research Institute, China Coal Research Institute, Beijing 100013, China
2.
State Key Laboratory of Coal Mining and Clean Utilization, Beijing 100013, China

Funds:

The project was supported by the National Science Foundation of China U1261117

the International S & T Cooperation Program of China 2013DFA61660

the National Key Technology R & D Program 2012BAA04B04

More Information

Corresponding author: HUANG Peng, Tel: 010-84262962, E-mail: squallok@qq.com

摘要

摘要: 采用实沸点蒸馏对神府煤液化油及其加氢精制油做了馏分切割, 并采用GC-PFPD与GC-NCD对液化油与精制油中的硫氮化合物类型进行了分析, 研究了液化油加氢精制过程中硫氮化合物分布的变化。结果表明, 液化油中硫含量随窄馏分的馏程由低到高呈现"U"型分布, 氮的分布基本上随窄馏分沸点温度的升高而增大, 氮的含量远高于硫的含量; 经过固定床加氢精制后, 97%的硫和98.9%的氮得到脱除。液化油中苯并噻吩和二苯并噻吩等二环和三环化合物占93.25%;经过加氢处理之后, 硫醇、硫醚、噻吩类等低沸点含硫化合物基本消失, 难脱除组分主要以苯并噻吩类、二苯并噻吩类为主。液化油中含氮化合物主要以五元杂环中性氮化物为主, 占54.96%;碱性氮化物主要以苯胺类为主, 占23.22%, 喹啉类相对较少; 经过加氢处理之后, 脂肪胺类含氮化合物被完全脱除, 精制油中残留的氮主要以碱性氮化物喹啉类与苯胺类含氮化合物存在。
- 煤直接液化油 /
- 含硫化合物 /
- 含氮化合物 /
- 窄馏分 /
- 加氢精制
Abstract: The direct liquefaction oil from Shenfu coal and the refined oil through hydrofining were cut into different fractions by true boiling point distillation and the sulfur and nitrogen compounds in each fraction were analyzed by GC-PFPD and GC-NCD; the change in the sulfur and nitrogen compounds in the direct liquefaction oil upon the hydrofining process was then investigated. The results illustrated that the sulfur content in the direct liquefaction oil takes a 'U' type distribution with the distillation range from low to high boiling point, whereas the content of nitrogen is far higher than that of sulfur, which increases with the rising of the fraction boiling point. After hydrofining, the sulfur and nitrogen contents are removed by 97% and 98.9%, respectively. Bicyclic and tricyclic compounds such as benzothiophene and dibenzothiophene account for 93.25% of the sulfur compounds in the coal liquefaction oil; after the hydrofining, low boiling point sulfur compounds such as mercaptan, sulfoether and thiophene almost disappear, with benzothiophene and dibenzothiophene as the main sulfur compounds that are difficult to remove. In the coal liquefaction oil, five-membered heterocycle neutral compounds account for 54.96% nitrogen and the portion of basic nitrogen compounds, including mainly anilines with a relatively small amount of quinolones, is 23.22%. After hydrofining, fatty amines are removed completely and the residual nitrogen in the refined oil exists mainly as the basic nitrogen compounds such as quinolones and anilines.
- direct coal liquefaction oil /
- sulfur compounds /
- nitrogen compounds /
- narrow fractions /
- hydrofining

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图 1 液化油与精制油实沸点蒸馏曲线

Figure 1 True boiling point curves of the direct coal liquefaction (DCL) oil and refined oil through hydrofining

☞: DCL oil; ☞:refined oil

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图 2 液化油加氢精制流程示意图

Figure 2 Flowchart of hydrofining test

1: compressor; 2: feed pump; 3: water pump; 4: fixed-bed reactor; 5: separator; 6: caustic tank; 7: tail gas flowmeter

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图 3 液化油硫含量随窄馏分的变化

Figure 3 Sulfur content changes with the fraction boiling point in DCL oil

☞: sulfur content

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图 4 精制油中硫含量随窄馏分的变化

Figure 4 Sulfur content changes with the fraction boiling point in the refined oil

☞: sulfur content

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图 5 液化油中氮含量随窄馏分的变化

Figure 5 Nitrogen content changes with narrow fractions in DCL oil

☞: nitrogen content

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图 6 精制油中氮含量随窄馏分的变化

Figure 6 Nitrogen content changes with the fraction boiling point in the refined oil

☞: nitrogen content

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图 7 液化油的GC-PFPD谱图

Figure 7 GC-PFPD spectrum of the DCL oil

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图 8 精制油的GC-PFPD谱图

Figure 8 GC-PFPD spectrum of the refined oil

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图 9 液化油的GC-NCD谱图

Figure 9 GC-NCD spectrum of the DCL oil

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图 10 精制油的GC-NCD谱图

Figure 10 GC-NCD spectrum of the refined oil

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表 1 煤液化油和精制油性质

Table 1 Properties of the direct coal liquefaction (DCL) oil and refined oil through hydrofining

Property	DCL oil	Refined oil
Density /(g·cm^-3)	0.948	0.867
H w/%	11.27	12.65
C w/%	87.23	86.44
O w/%	1.174	0.54
S w/(mg·kg^-1)	780	23
N w/(mg·kg^-1)	4 910	55
Alkane w/%	15.12	21.41
Cycloalkane w/%	7.02	75.16
Olefin w/%	2.32	-
Aromatic w/%	73.48	5.43
Polar fraction w/%	3.1	-

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表 2 加氢催化剂性质

Table 2 Properties of the hydrofining catalyst

Composition w/%				Carrier	Surface area A/(m²·g^-1)	Pore volume v/(mL·g^-1)	Mechanical strength /(N·cm^-1)
WO₃	MoO₃	NiO	F	Carrier	Surface area A/(m²·g^-1)	Pore volume v/(mL·g^-1)	Mechanical strength /(N·cm^-1)
13.62	7.82	7.11	2.54	γ-Al₂O₃	＞200	0.45-0.55	＞155

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表 3 液化油及精制油中类型硫含量

Table 3 Contents of sulfur compounds in the DCL oil and refined oil

Sulfur compound	Contents w/(mg·kg^-1)
Sulfur compound	DCL oil	refined oil
MN	10.2	-
SF	5.7	-
T	7.8	＜0.5
Ts	29.0	-
BT	44.1	-
BTs	259.5	9.6
DBT	146.6	5.3
DBTs	278.1	12.6

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表 4 液化油及精制油中类型氮含量

Table 4 Contents of nitrogen compounds in the DCL oil and the refined oil

Nitrogen compound	Contents w/(mg·kg^-1)
Nitrogen compound	DCL oil	refined oil
Basic nitrogen compound
AAs	179.0	-
ANs	1 140.3	34.0
PDs	35.8	-
Q	174.9	5.1
Qs	258.8	9.2
Neutral nitrogen compound
ID	323.7	1.7
IDs	941.4	6.7
CZ	644.8	-
CZs	788.5	3.1

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