含油污泥在ZSM-5沸石上催化热解产物特性

doi:10.11949/j.issn.0438-1157.20171398

摘要/Abstract

摘要：

采用U型固定床管式炉研究了含油污泥在ZSM-5分子筛催化剂上的热解产物特性。发现在450℃下未使用催化剂热解时，GC-MS和GC测得的油泥热解油产物中的主要成分为烷烃和烯烃，芳烃含量较低；气体产物中主要为短链烃类，氢气产量较少。而在ZSM-5分子筛的催化作用下，热解油中芳香烃产量达到88.4%，气体产物中的氢气产量和短链烃类产量均明显增加。研究了400～550℃之间分子筛对含油污泥的催化效果，发现ZSM-5在500℃时催化效果最佳，油相产率达到65.6%，油相中的沥青质和胶质含量较低，芳香烃产量达到90.9%。通过热重和XPS分析发现分子筛上的积炭主要以多环芳烃焦炭的形式存在。

关键词: 含油污泥, 分子筛, 催化热解, 芳香烃, 积炭

Abstract:

Catalytic pyrolysis of oily sludge over ZSM-5 zeolite was carried out in a U type fixed-bed tubular reactor. Gas chromatography-mass spectrometry and gas chromatography were employed to investigate the properties of the pyrolysis oil and gas product, respectively. When pyrolysis was conducted without ZSM-5, the main components in the oil product were alkanes and alkenes, and the gas product was composed of short-chain hydrocarbons with little H₂. The addition of ZSM-5 significantly increased the aromatics yield (88.4%) in the oil product. Meanwhile, the content of H₂ and short-chain hydrocarbons increased as well. The effects of temperature on the catalytic effects of ZSM-5 were studied under 400-550℃. The results showed that 65.6% of oil can be recovered at 500℃ and the aromatics yield reached up to 90.9%. Moreover, the contents of resins and asphaltenes in the oil products were relatively low at this temperature. It can be deduced that the optimum catalytic temperature with ZSM-5 in this study was 500℃. The coke deposited on the catalyst was detected by thermogravimetric and X-ray photoelectron spectroscopy analysis. It was found that the main type of coke was polyaromatics coke due to the polycondensation reaction over ZSM-5.

Key words: oily sludge, zeolite, catalytic pyrolysis, aromatic hydrocarbons, coke deposition

中图分类号:

TE992.3

林炳丞, 王君, 黄群星, 池涌. 含油污泥在ZSM-5沸石上催化热解产物特性[J]. 化工学报, 2018, 69(6): 2681-2687.

LIN Bingcheng, WANG Jun, HUANG Qunxing, CHI Yong. Products obtained from catalytic pyrolysis of oily sludge over ZSM-5 zeolite[J]. CIESC Journal, 2018, 69(6): 2681-2687.

参考文献 37

[1]	YAN P, LU M, YANG Q, et al. Oil recovery from refinery oily sludge using a rhamnolipid biosurfactant-producing pseudomonas[J]. Bioresource Technology, 2012, 116:24-28.
[2]	崔鹏, 郭铁. 含油污泥药剂处理方法研究进展[J]. 当代化工, 2013, 42(7):999-1002. CUI P, GUO T. Research progress in chemical treatment methods of oily sludge[J]. Contemporary Chemical Industry, 2013, 42(7):999-1002.
[3]	HU G, LI J, ZENG G. Recent development in the treatment of oily sludge from petroleum industry:a review[J]. Journal of Hazardous Materials, 2013, 261:470-490.
[4]	ESSAM A H Z, DANA M A. Fuel recovery from waste oily sludge using solvent extraction[J]. Process Safety and Environmental Protection, 2010, 88(5):318-326.
[5]	TAN W, YANG X G, TAN X F. Study on demulsification of crude oil emulsions by microwave chemical method[J]. Separation Science and Technology, 2007, 42(6):1367-1377.
[6]	XU N, WANG W, HAN P, et al. Effects of ultrasound on oily sludge deoiling[J]. Journal of Hazardous Materials, 2009, 171(1/2/3):914-917.
[7]	陈继华, 马增益, 马攀. 油泥热解机理研究[J]. 能源工程, 2012, (2):56-61. CHEN J H, MA Z Y, MA P. Mechanism of oil sludge pyrolysis[J]. Energy Engineering, 2012, (2):56-61.
[8]	全翠, 李爱民, 高宁博, 等. 采用热解方法回收油泥中原油[J].石油学报(石油加工), 2010, 26(5):742-746. QUAN C, LI A M, GAO N B, et al. Oil recovery from oily-sludge by pyrolysis method[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2010,26(5):742-746.
[9]	陈超, 李水清, 岳长涛, 等. 含油污泥回转式连续热解——质能平衡及产物分析[J]. 化工学报, 2006, 57(3):650-657. CHEN C, LI S Q, YUE C T, et al. Lab scale pyrolysis of oily sludge in continuous rotating reactor:mass/energy balance and product analysis[J]. Journal of Chemical Industry and Engineering(China), 2006, 57(3):650-657.
[10]	SHIE J L, CHANG C Y, LIN J P, et al. Use of inexpensive additives in pyrolysis of oil sludge[J]. Energy & Fuels, 2002, 16(1):102-108.
[11]	SHIE J L, LIN J P, CHANG C Y, et al. Pyrolysis of oil sludge with additives of sodium and potassium compounds[J]. Resources, Conservation and Recycling, 2003, 39(1):51-64.
[12]	SHIE J L, LIN J P, CHANG C Y, et al. Pyrolysis of oil sludge with additives of catalytic solid wastes[J]. Journal of Analytical and Applied Pyrolysis, 2004, 71(2):695-707.
[13]	WANG H, JIA H, WANG L, et al. The catalytic effect of modified bentonite on the pyrolysis of oily sludge[J]. Petroleum Science and Technology, 2015, 33(13/14):1388-1394.
[14]	刘鲁珍, 李金灵, 屈撑囤. TiO2/MCM-41的制备及对含油污泥热解过程的影响[J]. 环境工程学报, 2016, 10(12):7294-7298. LIU L Z, LI J L, QU C T. Preparation and influence of TiO2/MCM-41 on pyrolysis process of oily sludge[J]. Chinese Journal of Environmental Engineering, 2016, 10(12):7294-7298.
[15]	CHENG S, LI A M, YOSHIKAWA K. High quality oil recovery from oil sludge employing a pyrolysis process with oil sludge ash catalyst[J]. International Journal of Waste Resources, 2015, 5(2):656-660.
[16]	PÁNEK P, KOSTURA B, ?EPELÁKOVÁ I, et al. Pyrolysis of oil sludge with calcium-containing additive[J]. Journal of Analytical and Applied Pyrolysis, 2014, 108:274-283.
[17]	SUN Y, JIN B S, WU W, et al. Effects of temperature and composite alumina on pyrolysis of sewage sludge[J]. Journal of Environmental Sciences, 2015, 30:1-8.
[18]	RONALD W T, SAI P R K, NARENDRA N B. The production of gasoline range hydrocarbons from Alcell® lignin using HZSM-5 catalyst[J]. Fuel Processing Technology, 2000, 62 (1):17-30.
[19]	PAVLOVICH O N, BELOUSOVA O A, LYAPKIN A A, et al. Derivation of 2-methylnaphthalene from press residues of pressed-naphthalene production[J]. Coke and Chemistry, 2008, 51(5):184-187.
[20]	TOSHIAKI Y, GUIDO G, SHOICHI O, et al. Selective production of benzene and naphthalene from poly(butylene terephthalate) and poly (ethylene naphthalene-2, 6-dicarboxylate) by pyrolysis in the presence of calcium hydroxide[J]. Polymer Degradation and Stability, 2006, 91(5):1002-1009.
[21]	史晓杰, 邢侃, 樊红超, 等. ZSM-5分子筛的合成与改性研究进展[J]. 无机盐工业, 2016, 48(2):6-8. SHI X J, XING K, FAN H C, et al. Advances in synthesis and modification of ZSM-5 zeolite[J]. Inorganic Chemicals Industry, 2016, 48(2):6-8.
[22]	胡尧良, BAKHSHI N N. 在HZSM-5催化剂上重质原油的催化裂解/重整试验[J]. 石油学报(石油加工), 1989, 5(1):25-32. HU Y L, BAKHSHI N N. Catalytic cracking/reforming of heavy crude oil over HZSM-5 catalyst[J]. Acta Petrolei Sinica (Petroleum Processing Section), 1989,5(1):25-32.
[23]	American Society for Testing and Materials. Standard test method for water in petroleum products and bituminous materials by distillation:ASTM D95-13[S]. ASTM International, 2013.
[24]	HUANG Q X, HAN X, MAO F Y, et al. A model for predicting solid particle behavior in petroleum sludge during centrifugation[J]. Fuel, 2014, 117:95-102.
[25]	ZHANG Y W, ZHOU Y M, HUANG L, et al. Structure and catalytic properties of the Zn-modified ZSM-5 supported platinum catalyst for propane dehydrogenation[J]. Chemical Engineering Journal, 2015, 270:352-361.
[26]	VICTOR A, MARK W S, DUSHYANT S. Investigation of the stability of Zn-based HZSM-5 catalysts for methane dehydroaromatization[J]. Applied Catalysis A:General, 2015. 505:365-374.
[27]	TAMER K, JALE Y, MITHAT Y, et al. Characterisation of products from pyrolysis of waste sludges[J]. Fuel, 2006, 85 (10/11):1498-1508.
[28]	LI X C, LI S G, YANG Y F, et al. Studies on coke formation and coke species of nickel-based catalysts in CO2 reforming of CH4[J]. Catalysis Letter, 2007, 118(1):59-63.
[29]	陈艳艳. ZSM-5分子筛合成、改性及液化气芳构化研究[D]. 淄博:山东理工大学, 2014. CHEN Y Y. The synthesis modification of ZSM-5 zeolite and the research of LPG aromatization[D]. Zibo:Shandong University of Technology, 2014.
[30]	杨海军. 含油污泥热裂解技术研究[D]. 青岛:中国石油大学(华东), 2008. YANG H J. Study on the pyrolysis technology of oily sludge[D]. Qingdao:China University of Petroleum (East China), 2008.
[31]	ANDERSON B G, SCHUMACHER R R, VAN D R, et al. An attempt to predict the optimum zeolite-based catalyst for selective cracking of naphtha-range hydrocarbons to light olefins[J]. Journal of Molecular Catalysis. A:Chemical, 2002, 181(1):291-301.
[32]	RAMOS R, GARCIA A, BOTAS J A, et al. Enhanced production of aromatic hydrocarbons by rapeseed oil conversion over Ga and Zn modified ZSM-5 catalysts[J]. Industrial & Engineering Chemistry Research, 2016, 55(50):12723-12732.
[33]	HUANG Q X, HAN X, MAO F Y, et al. A model for predicting solid particle behavior in petroleum sludge during centrifugation[J]. Fuel, 2014, 117:95-102.
[34]	TORREN R C, JUNGHO J, YU C L, et al. Catalytic fast pyrolysis of glucose with HZSM-5:the combined homogeneous and heterogeneous reactions[J]. Journal of Catalysis, 2010, 270 (1):110-124.
[35]	汪洋, 王银斌, 郭春垒, 等. 焙烧温度对HZSM-5分子筛催化甲醇制芳烃反应性能的影响[J]. 石油学报(石油加工), 2017, 33(4):639-645. WANG Y, WANG Y B, GUO C L, et al. Effect of calcination temperature on the performance of HZSM-5 catalysts in methanol to aromatics[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2017, 33(4):639-645.
[36]	BERT M W, MICHAEL P R, JACK H L. Characterization of surface carbon formed during the conversion of methane to benzene over Mo/H-ZSM-5 catalysts[J]. Catalysis Letters, 1998, 52(1):31-36.
[37]	ZHANG D S, WANG R J, WANG L J, et al. Coking and deactivation of boron modified Al-MCM-41 for vapor-phase Beckmann rearrangement reaction[J]. Journal of Molecular Catalysis A:Chemical, 2013, 366:179-185.