石化中间储罐挥发性有机物排放特征与反应活性

doi:10.16085/j.issn.1000-6613.2021-1842

摘要/Abstract

摘要：

中间储罐是石化企业的主要挥发性有机物（VOCs）排放源，对大气环境产生重要影响。本文对我国某石化企业炼化中间产物、污油、石化中间产物等中间储罐大呼吸过程进行了采样监测，分析了VOCs排放特征并建立了有机污染物图谱。基于OH自由基损失速率和最大增量反应活性法，分别量化了大呼吸过程大气反应活性和臭氧生成潜势（OFP）。结果表明，中间储罐大呼吸过程VOCs浓度高达数万毫克每立方米，单位体积物料周转量VOCs排放强度达到0.55~71.3g/m³。不同储罐排放特征差异大，炼化中间产物及污油储罐VOCs组成以烷烃为主，石化中间产物储罐VOCs以烯烃和芳香烃为主；C₃~C₇烷烃、C₃~C₄烯烃、苯、甲苯和丙酮等是首要污染物。中间储罐大呼吸损耗气具有较高大气光化学反应活性和臭氧生成潜势（OFP），OH自由基损失速率常数接近1.43×10⁴~2.37×10⁶s^-1，OFP达到2.84×10⁵~7.53×10⁷mg/m³，焦化污油反应活性与OFP较低，乙烯裂解重油储罐较高。大呼吸过程反应活性及臭氧生成潜势主要源于烷烃和烯烃组分，甲基戊烷、正己烷和甲基环己烷等C₆～C₇烷烃、C₃~C₅烯烃和二甲苯等是需要优先控制高活性物质。

关键词: 中间储罐, 石化企业, 挥发性有机物, 排放源, 臭氧生成潜势

Abstract:

Petrochemical intermediate storage tanks are key volatile organic compounds (VOCs) emission sources which play vital roles in regional air pollution and abatement. During the working loss process, the intermediate product tank vents of refining and petrochemical processes and waste oil tanks in a petrochemical facility were sampled and measured in this study. The emission characteristics of VOCs were analyzed and speciated source profiles for specific sources were developed. The ambient photochemical reactivity were developed based on the value of OH loss rate. By virtue of the maximum increment reactivity method, ozone formation potential of sources were determined. The results suggested that level of VOCs from working loss process reaches tens of thousands mg/m³, and the corresponding emission strength ranged from 0.55g/m³ to 71.3g/m³ per material turnover. The VOCs emission characteristics differed among specific tanks, with refining process related tank and waste oil tank dominant in alkane and petrochemical tank prevailing in alkene and aromatics. The C₃—C₇ alkane, C₃—C₄ alkene, benzene, toluene and acetone were ranked as primary pollutants with highest weight percentage. The intermediate storage tank vented VOCs features in relative high photochemical reactivity (1.43×10⁴—2.37×10⁶s^-1) and OFP (2.84×10⁵—7.53×10⁷mg/m³), with waste oil tank of delayed coking process having the lowest value and heavy oil product of ethylene cracking process the highest value. The alkane and alkene were found to contribute mostly to VOCs related photochemical reactivity and OFP during the working loss process. The C₆—C₇ alkane such as methylpentane, hexane and methylcyclohexane, C₃—C₅ alkene, and xylene were recommended to give preferred control priority.

Key words: intermediate storage tank, petrochemical facility, volatile organic compounds, emission source, ozone formation potential

中图分类号:

曹冬冬, 李兴春, 薛明. 石化中间储罐挥发性有机物排放特征与反应活性[J]. 化工进展, 2022, 41(7): 3974-3982.

CAO Dongdong, LI Xingchun, XUE Ming. Emission characteristics and photochemical reactivity of volatile organic compounds from petrochemical intermediate storage tanks[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3974-3982.

图/表 9

参考文献 35

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序号	中间储罐	所属单元区	采样位置及排放环节
1	催化蜡油	炼油厂油品车间	呼吸阀，大呼吸过程
2	催化油浆	炼油厂油品车间	呼吸阀，大呼吸过程
3	管线吹扫污油	炼炼油厂油品车间	呼吸阀，大呼吸过程
4	炼油污油	炼油厂常减压车间	呼吸阀，大呼吸过程
5	焦化原料	炼油厂焦化车间	呼吸阀，大呼吸过程
6	焦化污油	炼油厂焦化车间	呼吸阀，大呼吸过程
7	乙烯裂解重油	乙烯厂	呼吸阀，大呼吸过程
8	乙烯裂解调和油	乙烯厂	呼吸阀，大呼吸过程
9	炼油污水污油	炼油污水厂	呼吸阀，大呼吸过程

序号	中间储罐	所属单元区	采样位置及排放环节
1	催化蜡油	炼油厂油品车间	呼吸阀，大呼吸过程
2	催化油浆	炼油厂油品车间	呼吸阀，大呼吸过程
3	管线吹扫污油	炼炼油厂油品车间	呼吸阀，大呼吸过程
4	炼油污油	炼油厂常减压车间	呼吸阀，大呼吸过程
5	焦化原料	炼油厂焦化车间	呼吸阀，大呼吸过程
6	焦化污油	炼油厂焦化车间	呼吸阀，大呼吸过程
7	乙烯裂解重油	乙烯厂	呼吸阀，大呼吸过程
8	乙烯裂解调和油	乙烯厂	呼吸阀，大呼吸过程
9	炼油污水污油	炼油污水厂	呼吸阀，大呼吸过程

烷烃		烯烃	芳香烃	含氧物质
乙烷	2，3-二甲基丁烷	乙烯	苯	丙烯醛
丙烷	2-甲基戊烷	丙烯	甲苯	丙酮
异丁烷	3-甲基戊烷	反-2-丁烯	乙苯	MTBE
正丁烷	2，4-二甲基戊烷	1-丁烯	间/对-二甲苯	乙酸乙酯
异戊烷	甲基环戊烷	顺-2-丁烯	邻-二甲苯	乙酸乙烯酯
正戊烷	2-甲基己烷	1，3-丁二烯	苯乙烯	异丙醇
正己烷	2，3-二甲基戊烷	1-戊烯	异丙苯	THF
正庚烷	3-甲基己烷	反-2-戊烯	正丙苯	己酮
正辛烷	2，2，4-三甲基戊烷	异戊二烯	1，3，5-三甲基苯
正壬烷	甲基环己烷	顺-2-戊烯	1，2，4-三甲基苯
正葵烷	2，3，4-三甲基戊烷	1-己烯	1，2，3-三甲基苯
十一烷	2-甲基庚烷		1，4-二乙基苯
环戊烷	3-甲基庚烷		2-乙基甲苯
环己烷	十二烷		3-乙基甲苯
2，2-二甲基丁烷			4-乙基甲苯

烷烃		烯烃	芳香烃	含氧物质
乙烷	2，3-二甲基丁烷	乙烯	苯	丙烯醛
丙烷	2-甲基戊烷	丙烯	甲苯	丙酮
异丁烷	3-甲基戊烷	反-2-丁烯	乙苯	MTBE
正丁烷	2，4-二甲基戊烷	1-丁烯	间/对-二甲苯	乙酸乙酯
异戊烷	甲基环戊烷	顺-2-丁烯	邻-二甲苯	乙酸乙烯酯
正戊烷	2-甲基己烷	1，3-丁二烯	苯乙烯	异丙醇
正己烷	2，3-二甲基戊烷	1-戊烯	异丙苯	THF
正庚烷	3-甲基己烷	反-2-戊烯	正丙苯	己酮
正辛烷	2，2，4-三甲基戊烷	异戊二烯	1，3，5-三甲基苯
正壬烷	甲基环己烷	顺-2-戊烯	1，2，4-三甲基苯
正葵烷	2，3，4-三甲基戊烷	1-己烯	1，2，3-三甲基苯
十一烷	2-甲基庚烷		1，4-二乙基苯
环戊烷	3-甲基庚烷		2-乙基甲苯
环己烷	十二烷		3-乙基甲苯
2，2-二甲基丁烷			4-乙基甲苯

采样点	浓度/mg·m^-3		相对质量分数/%
采样点	CH₄	VOCs	CH₄	VOCs
催化蜡油罐	85.6	890.4	8.8	91.2
催化油浆罐	19.3	499.7	3.7	96.3
炼油厂污油罐	1020	2190	31.8	68.2
焦化原料罐	10800	33100	24.6	75.4
焦化污油罐	507	64793	0.8	99.2
裂解重油罐	49.9	11050.1	0.4	99.6
裂解调和罐	3.9	1486.1	0.3	99.7
炼油污水污油罐	20900	48000	30.3	69.7