费托蜡热裂解制线性α-烯烃工艺研究

李镇伶; 程嵩鹏; 安良成; 刘素丽; 韩婷婷; 孙功成; 吕俊敏; 范素兵; 赵天生

doi:10.1016/S1872-5813(22)60056-2

费托蜡热裂解制线性α-烯烃工艺研究

doi: 10.1016/S1872-5813(22)60056-2

李镇伶^{1, #,},
程嵩鹏^{1, #,},
安良成^2,,
刘素丽^2,,
韩婷婷^1,,
孙功成^1,,
吕俊敏^1, ,,
范素兵^1, ,,
赵天生^1,

1.
宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室, 宁夏银川 750021
2.
国家能源集团宁夏煤业集团有限责任公司, 宁夏银川 750411

基金项目: 宁夏自然科学基金（2020AAC03012）和宁夏重点研发计划（2018BDE02057）资助

详细信息

通讯作者:
E-mail: lvjunmin@nxu.edu.cn

fansb@nxu.edu.cn

# These authors contributed equally to this work
中图分类号: TQ203.8;TQ645.9^{+ 3};TQ649.4^{+ 2}
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出版历程
- 收稿日期: 2022-04-30
- 修回日期: 2022-07-12
- 录用日期: 2022-07-13
- 网络出版日期: 2022-08-04
- 刊出日期: 2022-12-28

Cracking of F-T refined wax for producing linear α-olefin

LI Zhen-ling^{1, #
,},
CHENG Song-peng^{1, #
,},
AN Liang-cheng^2
,,
LIU Su-li^2
,,
HAN Ting-ting^1
,,
SUN Gong-cheng^1
,,
LÜ Jun-min^{1
, ,},
FAN Su-bing^{1
, ,},
ZHAO Tian-sheng^1
,

1.
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China
2.
Ningxia Coal Industry Co., Ltd., National Energy Group, Yinchuan 750411, China

Funds: The project was supported by Ningxia Natural Science Foundation (2020AAC03012) and the Key R&D Program of Ningxia (2018BDE02057).

摘要

摘要: 以煤制油工艺费托精制蜡为原料，在固定床反应器上进行了热裂解制线性α-烯烃（LAO）的实验，考察了原料组成、裂解温度、停留时间、水蜡比及循环工艺对转化率及裂解产物分布的影响，优化了工艺条件。结果表明，裂解温度及停留时间对原料转化率及LAO收率有显著影响，循环工艺可进一步提高LAO收率。过高的裂解温度或过长的停留时间均会导致生成的LAO的二次反应，对反应不利。在适合的工艺条件下可获得53%的LAO收率。
- 费托精制蜡 /
- 热裂解 /
- 线性α-烯烃 /
- 液烃 /
- 工艺优化
Abstract: The steam cracking of Fischer-Tropsch refined wax from the coal-to-oil process for producing linear α-olefin (LAO) was carried out on a fixed bed reactor. The effects of feedstock composition, cracking temperature, contact time, water-to-wax ratio and cyclic process on the feed conversion and products distribution were investigated and optimized. The factors such as cracking temperature and contact time have significant influence on conversion and LAO yield, and cyclic process can further improve the LAO yield. However, excess high cracking temperature and longer contact time result in the second reactions, which are unfavorable for the LAO production. Under the suitable process conditions 53% of LAO yield are obtained.
- Fischer-Tropsch refined wax /
- thermal cracking /
- linear α-olefin /
- liquid hydrocarbon /
- optimization
注释:

1) # These authors contributed equally to this work

HTML全文

FIG. 2029. FIG. 2029.

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图 1 不同费托蜡碳数分布对比

Figure 1 Carbon number distribution of F-T wax

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图 2 不同原料蜡的单程转化率、α-烯烃选择性及收率

Figure 2 Conversion, selectivity and yield of LAO for different wax

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图 3 不同原料裂解的液相产物分布（a）和LAO碳数分布（b）

Figure 3 Liquid product distribution (a) and carbon number distribution of LAO (b) for different wax

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图 4 反应后填料的TG分析

Figure 4 TG analysis of quartz sand after reaction

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图 5 不同裂解温度下转化率、选择性及收率变化

Figure 5 Conversion, selectivity and yield at different thermal cracking temperatures

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图 6 不同温度裂解气液产物组成(a)和LAO碳数分布(b)

Figure 6 Composition of gas/liquid product (a) and carbon number distribution of LAO (b) at different thermal cracking temperatures

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图 7 不同停留时间的转化率、选择性及收率

Figure 7 Conversion, LAO selectivity and yield at different contact time(a): 500 ℃; (b): 550 ℃; (c): 600 ℃; (d): 650 ℃

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图 8 不同温度条件下不同停留时间裂解产物分布

Figure 8 Products distribution under different contact time and temperature(a): 500 ℃; (b): 550 ℃; (c): 600 ℃; (d): 650 ℃

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图 9 裂解产物LAO的碳数分布

(a)550 ºC；(b)600 ℃

Figure 9 Carbon number distribution of LAO at 550 ℃ (a) and 600 ℃ (b)

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图 10 不同水蜡比裂解的转化率、选择性和收率

Figure 10 Conversion, selectivity and yield at different water-wax ratios

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图 11 不同水蜡比（a）液相产物分布和（b）LAO碳数分布

Figure 11 Liquid product distribution (a) and Carbon number distribution of LAO (b) at different water-wax ratios

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图 12 不同循环原料对LAO收率的影响

Figure 12 Effect of cyclic feedstock on LAO yield

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表 1 费托蜡基本组成

Table 1 Composition of F-T wax

Fischer-Tropsch refined wax		1#	2#	3#	4#	5#
Composition w/%	n-paraffin	95.56	93.49	87.96	95.11	99.11
	i-paraffin	4.44	6.51	12.04	4.89	0.89
	other	0	0	0	0	0
	heavy hydrocarbon (>C₂₅)	−	−	0.34	32.34	44.10

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表 2 不同原料蜡的裂解气组成

Table 2 Composition of cracking gas for different wax

Feedstock		1#	2#	3#	4#	5#
Yield /%		2.3	3.1	4.9	10.1	7.4
Selectivity /%	methane	24.2	24.0	22.2	22.4	22.5
	ethane	14.8	14.8	13.6	13.3	11.3
	ethylene	39.3	39.2	36.1	38.0	39.8
	propylene	14.4	14.6	17.1	15.3	15.4
	propane	1.3	1.2	1.5	1.5	1.0
	isobutene	0.0	0.0	0.0	3.8	0.0
	n-butene	3.2	3.4	4.0	1.6	3.6
	n-butane	1.0	1.0	2.0	0.5	1.9
	maleic	0.1	0.1	0.3	0.3	0.3
	C₅₊	1.6	1.7	3.2	3.3	4.1

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表 3 不同循环原料的基本组成

Table 3 Composition of cyclic feedstock

Composition /%	Feedstock
Composition /%	4#	4#-1	4#-2	4#-3
n -paraffin	95.1	95.2	91.8	90.6
iso-paraffin	4.9	3.0	3.5	3.4
LAO	0	1.7	4.6	5.8
Total olefins	0	1.7	4.8	6.0
Heavy hydrocarbon（C₂₅₊）	32.3	30.8	29.9	30.9

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