煤直接液化油中混合酚的分离研究

薛怡凡; 李梦瑶; 冯杰; 樊文俊; 李文英

煤直接液化油中混合酚的分离研究

太原理工大学煤科学与技术教育部重点实验室, 煤科学与技术省部共建国家重点实验室培育基地, 山西太原 030024

基金项目:

国家自然科学基金 U161020031

国家重点研发计划 2017YFB0602803

详细信息

中图分类号: TQ424
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- 被引次数: 0
出版历程
- 收稿日期: 2019-07-22
- 修回日期: 2019-09-30
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-11-10

Separation of mixed phenolic compounds from direct coal liquefaction

Key Laboratory of Coal Science and Technology(Taiyuan University of Technology), Ministry of Education and Shanxi Province; Training Base of State Key Laboratory of Coal Science and Technology Jointly Constructed by Shanxi Province and Ministry of Science and Technology, Taiyuan 030024, China

Funds:

the National Natural Science Foundation of China U161020031

National Key Research and Development Program of China 2017YFB0602803

More Information

Corresponding author: FENG Jie, Tel & Fax:+8603516018957, E-mail:fengjie@tyut.edu.cn

摘要

摘要: 利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。
- 煤直接液化油 /
- 混合酚选择性分离 /
- HZSM-5分子筛 /
- 硅铝物质的量比 /
- 化学液相沉积法
Abstract: The shape selection features of molecular sieve were used to efficiently separate the mixed phenols of oil fraction from coal direct liquefaction. In this paper, m-cresol and p-cresol were selected as the model compounds for coal liquified oil fraction. The pore structure of HZSM-5 adsorbent was adjusted by chemical liquid phase deposition method. Influence of ratio of silica to alumina and particle size of molecular sieve on the structural properties after modification were investigated. Considering the modified effect on adsorption and separation properties of cresol and p-cresol, a high-performance solid phase adsorbent was obtained, and was applied to separation of phenols in liquid oil from 180-190℃ fraction. The results show that when the molecular sieve has a silica-alumina ratio of 25 and a particle size of 3-5 μm, the pore structure adjustment effect of the molecular sieve is optimal. When the minimum amount of tetraethyl orthosilicate is 0.2 mL/g, the adsorption capacity of solid phase adsorption is 0.03 g/g, and the selectivity of p-cresol is greater than 95%. The selectivity to p-cresol is increased due to changes in the orifice regulation of the adsorbent on the outer surface deposits. Furthermore, using modified HZSM-5(1) adsorbent to separate the mixed phenols from real coal direct liquefied oil, the selectivity of phenol and p-cresol reached 100%.
- coal liquefied oil /
- separation of the mixed phenols /
- HZSM-5 modification /
- Si/Al molar ratio /
- chemical liquid deposition

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图 1 不同硅铝比分子筛增量随正硅酸乙酯加入量的变化

Figure 1 Relation between the mass increment of molecular sieves with different Si/Al ratio and the addition of ethyl orthosilicate

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图 2 不同硅铝比对间甲酚和对甲酚分离中吸附性能的影响

Figure 2 Effect of Si/Al ratios on adsorption properties of m-cresol and p-cresol separation

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图 3 吸附剂粒径对间甲酚和对甲酚分离中吸附性能的影响

Figure 3 Effects of particle size on the adsorption property during separation of m-cresol and p-cresol

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图 4 HZSM-5和HZSM-5(1)吸附剂的拉曼光谱谱图

Figure 4 Raman spectroscopy of HZSM-5 and HZSM-5(1) adsorbents

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图 5 HZSM-5和HZSM-5(1)吸附剂的XRD谱图

Figure 5 XRD spectroscopy of HZSM-5 and HZSM-5(1) adsorbents

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图 6 HZSM-5(1)吸附剂的表面孔口结构示意图

Figure 6 Orifice structure of HZSM-5(1) adsorbent

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图 7 改性后间甲酚和对甲酚吸附容量随时间的变化

Figure 7 Changes of adsorption capacity for m-cresol and p-cresol with time

(a): HZSM-5 adsorbent; (b): HZSM-5(1) adsorbent

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表 1 HZSM-5和HZSM-5(1)吸附剂的比表面积和孔容

Table 1 Specific surface area and pore volume of HZSM-5 and HZSM-5(1) adsorbents

Adsorption	BET specific surface area A/(m²·g^-1)	Total pore volume v/(cm³·g^-1)
HZSM-5	429.38	0.25
HZSM-5(1)	409.91	0.25

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表 2 180-190 ℃馏分段液化油混合酚组成

Table 2 Composition of mixed phenol in 180-190 ℃ distillate of liquefied oil

Sample	Mixed phenols /%	Experimental value in raffinate /%	Calculated value in raffinate /%
p-cresol	14.57	0.00	0.00
m-cresol	25.81	37.80	40.79
o-cresol	14.24	23.64	22.50
Phenol	22.14	0.00	0.00
2-ethyl phenol	3.26	7.04	5.15
3-ethyl phenol	3.68	7.26	5.82
4-ethyl phenol	7.25	8.10	11.46
2, 4-dimethylphenol	2.80	5.38	4.42
3, 5-dimethylphenol	6.24	10.37	9.86
Total	100	100	100

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参考文献(22)

[1]	YU X Y, LIU C H, CHENG W P, YANG J G, HE M Y. Tert-butylation of p-cresol catalyzed by Al-MCM-41 mesoporous molecular sieves[J]. J Fuel Chem Technol, 2006, 34(6):757-760. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb200606024
[2]	包铁竹, 曾凡礼, 曹贤, 李总成. Inventors络合萃取结晶法分离提纯对甲酚工艺: CN, 1127241A[P]. 1996-07-24. BAO Tie-zhu, ZENG Fan-li, CAO Xian, LI Zong-cheng. Study on separation and purification p-cresol by complexing extraction and crystallization: CN, 1127241A[P]. 1996-07-24.
[3]	侯颖, 眭贤明, 杨立荣, 吴坚平, 徐刚.尿素一溴化钙联用分离制高纯度间甲酚[J].化学反应工程与工艺, 2011, 27(2):178-182. http://www.cnki.com.cn/Article/CJFDTotal-HXFY201102020.htm HOU Ying, KUI Xian-ming, YANG Li-rong, WU Jian-ping, XU Gang. Preparation of high purity m-cresol by separation of urea and calcium bromide[J]. Chem React Eng Technol, 2011, 27(2):178-182. http://www.cnki.com.cn/Article/CJFDTotal-HXFY201102020.htm
[4]	宋晓敏, 陈源光.间甲酚的分离精制[J].现代化工, 1997, 17(6):2829. http://d.old.wanfangdata.com.cn/Periodical/trqhg201601019 SONG Xiao-min, CHEN Yuan-guang. Separation and purification of m-cresol[J]. Mod Chem Ind, 1997, 17(6):2829. http://d.old.wanfangdata.com.cn/Periodical/trqhg201601019
[5]	王春蓉.烃化法分离间/对甲酚的研究[J].应用化工, 2009, 38(8):1196-1198. doi: 10.3969/j.issn.1671-3206.2009.08.033 WANG Chun-rong. Study on the separation of meta-and para-cresol with alkyl product[J]. Appl Chem Ind, 2009, 38(8):1196-1198. doi: 10.3969/j.issn.1671-3206.2009.08.033
[6]	LIU X M, ZHOU J X, GUO X W, LIU M, MA X L, SONG C S, WANG C. SO₃H-functionalized Ionic liquids for selective alkylation of p-cresol with tert-butanol[J]. Ind Eng Chem Res, 2008, 47(15):5298-5303. doi: 10.1021/ie070647t
[7]	ZARETSKIJ M I, YAKOVLEV I P, TYRLOV A A, CHARTOV E M. Extractive separation of isomers of cresol in fluid-fluid system[J]. Koks Khim, 2002, (3):30-33.
[8]	SHIAU L D, HUANG C H, LIU K F. Separation of the cresol isomers by stripping crystallization[J]. Asia-Pac J Chem Eng, 2012, 7(S1):S26-S31. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=10.1002/apj.629
[9]	TOMITA T, SUZUKI K, SATOMI Y, HIRAMINE T. Method for separation p-cresol: JP, 2007137787[P]. 2007-03-14.
[10]	NAMBA S, KANAI Y, SHOJI H, YASHIMA T. Separation of p-isomers from disubstituted benzenes by means of shape-selective adsorption on mordenite and ZSM-5 zeolites[J]. Zeolites, 1984, 4(1):77-80. doi: 10.1016/0144-2449(84)90078-2
[11]	乐英红, 唐颐, 高滋.化学液相沉积法精细调变沸石孔径[J].石油学报(石油加工), 1997, 13(1):30-35. http://www.cnki.com.cn/Article/CJFDTotal-SXJG701.005.htm LE Ying-hong, TANG Yi, GAO Zi. Fine modulated zeolite pore size by chemical liquid phase deposition[J]. Acta Pet Sin (Pet Process Sect), 1997, 13(1):30-35. http://www.cnki.com.cn/Article/CJFDTotal-SXJG701.005.htm
[12]	NEUZIL R W, ROSBACK D H. Process for the separation of cresol isomers: US, 3969422[J]. 1976-07-13.
[13]	VIJAYAKUMAR J, CHIKKALA S K, MANDAL S, MAYADEVI S. Adsorption of cresols on zinc-aluminium hydroxides-A comparison with zeolite-X[J]. Sep Sci Technol, 2011, 46(3):483-488. doi: 10.1080/01496395.2010.510494
[14]	YUE Y H, TANG Y, LIU Y, GAO Z. Chemical liquid deposition zeolites with controlled pore-opening size and shape-selective separation of isomers[J]. Ind Eng Chem Res, 1996, 35(2):430-433. http://cn.bing.com/academic/profile?id=ea5340a029b3bc5eedd91f279f7d8de8&encoded=0&v=paper_preview&mkt=zh-cn
[15]	乐英红, 唐颐, 阚勇志, 高滋.化学液相沉积法调变沸石孔径及异构体择形分离[J].化学学报, 1996, 54(6):591-597. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=hxxb199606012 LE Ying-hong, TANG Yi, KAN Yong-zhi, GAO Zi. Pore size control of NaY zeolite by chemical liquid deposition and shape-selective separation[J]. Acta Chim Sin, 1996, 54(6):591-597. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=hxxb199606012
[16]	LEE K R, TAN C S. Separation of m-and p-cresols in compressed propane using modified HZSM-5 pellets[J]. Ind Eng Chem Res, 2000, 39(4):1035-1038. doi: 10.1021/ie990613o
[17]	高振楠, 杜淑凤, 李文博, 李克健.煤炭直接液化产品油碱洗提酚过程研究[J].煤炭学报, 2009, 34(10):1383-1387. doi: 10.3321/j.issn:0253-9993.2009.10.017 GAO Zhen-nan, DU Shu-feng, LI Wen-bo, LI Ke-jian. Study on caustic washing process for extracting phenolics direct coal liquefaction product distillate[J]. J China Coal Soc, 2009, 34(10):1383-1387. doi: 10.3321/j.issn:0253-9993.2009.10.017
[18]	EMEIS C A. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J]. J Catal, 1993, 141(2):347-354. doi: 10.1006-jcat.1993.1145/
[19]	MITSUYOSHI D, KUROIWA K, KATAOKA Y, NAKAGAWA T, KOSAKA M, NAKAMURA K, SUGANUMA S, ARAKI Y, KATADA N. Shape selectivity in toluene disproportionation into para-xylene generated by chemical vapor deposition of tetramethoxysilane on MFI zeolite catalyst[J]. Microporous Mesoporous Mater, 2017, 242:118-126. doi: 10.1016/j.micromeso.2017.01.022
[20]	江露. CaO-SiO₂-P₂O₅-FeO熔渣结构与粘度的基础研究[D].重庆: 重庆大学, 2015. JIANG Lu. Fundamental research on the structure and viscosity of molten CaO-SiO₂-P₂O₅-FeO Slag[D]. Chongqing: Chongqing University, 2015.
[21]	IVANDA M, CLASEN R, HORNFECK M, KIEFER W. Raman spectroscopy on SiO₂ glasses sintered from nanosized particles[J]. J Non-Crys Solids, 2003, 322:46-52. doi: 10.1016/S0022-3093(03)00172-8
[22]	郝天亮, 陈钢进. SiO₂薄膜的微观结构与驻极体特性的相关性研究[J].功能材料, 2014, 45(22):22091-22095. doi: 10.3969/j.issn.1001-9731.2014.22.019 HAO Tian-liang, CHEN Gang-jin. Study on relations between microstructures and electret properties of SiO₂ film[J]. J Funct Mater, 2014, 45(22):22091-22095. doi: 10.3969/j.issn.1001-9731.2014.22.019