大庆罐底油泥热解特性及污染物释放特性

doi:10.16085/j.issn.1000-6613.2021-0365

摘要/Abstract

摘要：

大庆罐底油泥属于高含油污泥，资源回收潜力大，同时具有黏度大、黏结性强、成分复杂、自然沉降慢等特性。本文对大庆油田高含油污泥的热解特性及污染物释放特性进行研究，分别测试了不同热解终温和升温速率下气/液/渣三相产品的品质和成分。结果表明，热解气中C₂H₄的释放量明显高于其余气体。CO₂气体仅在700℃处出现一个峰值，H₂在700℃之前释放量偏低，在700~800℃之间大量释放；热解终温和升温速率的增加会导致热解油低链烃类的大量生成，中链烃类呈现先增加后降低的趋势；热解终温会对固相产物中的SiO₂和CaCO₃产生一定的影响，而升温速率对固相产物几乎无影响。采用在线烟气分析仪测试了气相产物中的N、S、Cl小分子污染物的释放特性。HCN、NH₃在600℃时向NO_x转化；600℃以下绝大部分含氯化合物会发生释放；含硫污染物成双峰释放，600℃以上的峰主要源于硫酸盐的分解。

关键词: 高含油污泥, 废物处理, 热解, 热力学, 污染物释放, 热解终温, 升温速率

Abstract:

Daqing tank bottom sludge is a kind of sludge with high oil content and great resource recovery potential. It also has the characteristics of high viscosity, strong adhesion, complex composition and slow natural settlement. In this study, the pyrolysis characteristics and pollutant release characteristics of high oil sludge in Daqing were investigated. The quality and composition of gas/liquid/slag three-phase products under different final pyrolysis temperature and heating rate were tested. The results showed that the amount of C₂H₄ released from pyrolysis gas was significantly higher than that from other gases. CO₂ gas only had a peak value at 700℃, and H₂ was released before 700℃, and a large amount of H₂ was released between 700℃ and 800℃; the increase of final pyrolysis temperature and heating rate will lead to a large number of low chain hydrocarbons, and medium chain hydrocarbons showed a trend of first increase and then decrease; final pyrolysis temperature would have a certain effect on SiO₂ and CaCO₃ in solid products, while heating rate has little effect on solid products influence. The release characteristics of N, S and Cl small molecule pollutants in gaseous products were measured by on-line flue gas analyzer. HCN and NH₃ were the precursors of NO_x and convert to NO_x at 600℃; most of the chlorinated compounds would be released below 600℃; sulfur pollutants were released in two peaks, and the peaks above 600℃ were mainly due to the decomposition of sulfate.

Key words: high oil content sludge, waste disposal, pyrolysis, thermodynamics, pollutant release, final temperature, heating rate

中图分类号:

TE992.3

郑发, 李浩文, 林法伟, 张岩, 吴越强, 陈钊, 马文臣, 陈冠益. 大庆罐底油泥热解特性及污染物释放特性[J]. 化工进展, 2022, 41(1): 476-484.

ZHENG Fa, LI Haowen, LIN Fawei, ZHANG Yan, WU Yueqiang, CHEN Zhao, MA Wenchen, CHEN Guanyi. Pyrolysis characteristics and pollutant release characteristics of Daqing oil sludge[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 476-484.

图/表 11

表1 大庆油田高含油污泥含油率和元素分析（质量分数）单位：%

编号	C	H	N	S	含油率
H-1^#	67.35	8.15	0.13	0.23	60.1
H-2^#	78.09	9.92	0.16	0.18	55.9
H-3^#	81.42	11.13	0.08	0.06	69.9
H-4^#	81.21	11.30	0.10	0.05	90.4
H-5^#	80.78	11.54	0.06	0.04	84.9

图1 热解装置图1—气瓶；2—气体流量控制器；3—立式热解炉；4—热电偶；5—吊篮；6—堵头；7—油泥样品；8—温度控制器；9—伴热带；10—乙醇；11—热解油

图2 H-3#含油污泥不同终温热解三相产率

图3 H-3#含油污泥不同终温热解油成分分析

图4 H-3#含油污泥不同终温热解气释放特性

图5 H-3#含油污泥不同终温热解渣FTIR谱图

图6 H-3#含油污泥不同终温热解渣XRD谱图

图7 大庆油田高含油污泥热解气污染物释放图

图8 H-3#含油污泥不同升温速率热解三相产率

图9 H-3#含油污泥不同升温速率热解油成分分析

图10 H-3#含油污泥不同升温速率热解渣FTIR谱图

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