胶黏剂生产行业VOCs组分特征及臭氧生成潜势分析

doi:10.16258/j.cnki.1674-5906.2022.04.013

生态环境学报 ›› 2022, Vol. 31 ›› Issue (4): 750-758.DOI: 10.16258/j.cnki.1674-5906.2022.04.013

胶黏剂生产行业VOCs组分特征及臭氧生成潜势分析

陈雪泉¹(), 孔彬²^,^*, 兰青¹^,^**(), 余志铨³^,^**, 谢银斯¹, 黄俊毅¹

1.广东环境保护工程职业学院,广东佛山 528216
2.广州检验检测认证集团有限公司,广东广州 511447
3.广东省佛山生态环境监测站,广东佛山 528010

收稿日期:2021-08-31 出版日期:2022-04-18 发布日期:2022-06-22
通讯作者: **兰青,E-mail: 724666796@qq.com
作者简介:陈雪泉（1990生）,男,硕士,主要从事大气污染监测与控制研究。E-mail: chenxuequan00@163.com
*陈雪泉和孔彬为共同第一作者,对本文具有相同的贡献
基金资助:
国家自然科学基金项目(41201503);广东高校省级重点平台和重大科研项目(2017GKTSCX039);广东高校省级重点平台和重大科研项目(2018GkQNCX094);广东省高职院校高水平专业群建设项目-环境监测与控制技术(GSPZYQ2020004);广东省高职教育品牌专业建设项目-环境监测与控制技术

Emission Characteristics and Ozone Formation Potential Assessment of Volatile Organic Compounds (VOCs) from Adhesive Manufacturing Industry

CHEN Xuequan¹(), KONG Bin²^,^*, LAN Qing¹^,^**(), YU Zhiquan³^,^**, XIE Yinsi¹, HUANG Junyi¹

1. Guangdong Polytechnic of Environmental Protection Engineering, Foshan 528216, P. R. China
2. Guangzhou Inspection and Testing Certification Group Company Limited, Guangzhou 511447, P. R. China
3. Foshan Ecological Environment Monitoring Station, Guangdong Province, Foshan 528010, P. R. China

Received:2021-08-31 Online:2022-04-18 Published:2022-06-22

摘要/Abstract

摘要：

近年来中国环境空气质量得到明显的改善,细颗粒物污染的治理成效显著,PM_2.5浓度有所下降,但是对于臭氧污染引起的环境空气质量问题,却越发显著。臭氧污染的防控成为当前环境空气质量的工作重点,而控制挥发性有机化合物（VOCs）臭氧前体物的排放是有效防治臭氧污染的关键。为改善区域环境空气质量,深化各行业企业VOCs排放的精细化管控,采用冷阱浓缩-气相色谱/质谱法测定了胶黏剂生产行业废气VOCs组分浓度,研究了其VOCs组成特征,分析了其臭氧生成潜势（OFP）特征。结果表明：与其他典型有机溶剂使用行业相比,胶黏剂生产行业有组织废气VOCs具有独特的排放特征,其VOCs组分以含氧挥发性有机物（OVOCs）为主,占比81.23%,其中丙酮和2-丁酮是特征的VOCs物种,质量浓度分别为26.570 mg∙m^-3和13.720 mg∙m^-3。工艺源废气OFP达到49.506 mg∙m^-3,经过活性炭吸附处理后OFP降至3.161 mg∙m^-3,下降幅度达93.6%。在活性炭脱附再生过程中,催化燃烧（RCO）后排放的废气TVOCs质量浓度达到16.069 mg∙m^-3,OFP为14.739 mg∙m^-3,催化燃烧后排放的废气引起的臭氧污染问题值得关注。相比有组织排放工艺废气,生产车间和厂界无组织排放点TVOCs质量浓度分别为0.342 mg∙m^-3和0.385 mg∙m^-3,OFP为0.313 mg∙m^-3和0.354 mg∙m^-3,VOCs质量浓度较低,VOCs污染物主要以有组织排放形式为主。由于胶黏剂生产工艺过程中大量有机溶剂的使用,导致其VOCs污染以丙酮和2-丁酮污染为主要特征,应严格控制企业大规模有机溶剂的使用,加大水性胶黏剂对溶剂型胶黏剂的替代。

关键词: 臭氧（Ozone）, 胶粘剂合成, 挥发性有机化合物（VOCs）, 臭氧生成潜势（OFP), 污染特征, 丙酮, 2-丁酮

Abstract:

In recent years, ambient air quality in China has improved significantly with a remarkable success in the reduction of fine particulate matter. With the steady decline of ambient PM_2.5 concentration, the problem of ozone pollution has been increasingly prominent and reducing ozone has gradually become the main focus of air pollution control. The key to effective prevention and control of ozone pollution is reducing the emission of volatile organic compounds (VOCs), which are the ozone precursors in the air. To improve the regional air quality and finely regulate the VOCs emission from various industries, this study measured the VOCs component characteristics of waste gas emitted from the adhesive manufacturing process by the cold trap condensation-gas chromatography-mass spectrometry, and determined the ozone formation potential (OFP) of VOCs. The results showed that the VOCs waste gas from adhesive manufacturing industry has its own composition characteristics different from other typical industries using organic solvents. The VOCs were mainly composed of the oxygenated VOCs (OVOCs) which accounted for 81.23% and characterized by the acetone (26.570 mg∙m^-3) and 2-butanone (13.720 mg∙m^-3). The OFP of the organized process waste gas reached 49.506 mg∙m^-3 and subsequently decreased to 3.161 mg∙m^-3 (93.6%) after activated carbon adsorption. The total VOCs of waste gas from catalytic combustion reached 16.069 mg·m^-3with an OFP of 14.739 mg∙m^-3. The ozone pollution caused by VOCs emitted from activated carbon desorption process should draw more attention. Compared to stack emissions, fugitive VOCs emissions inside the plant workshops and around the factory boundaries had lower concentrations of 0.342 mg∙m^-3 and 0.385 mg∙m^-3, respectively. The OFP in the plant workshop and in the factory boundary sites was 0.313 mg∙m^-3 and 0.354 mg∙m^-3, respectively. The VOCs contamination in the adhesive manufacturing process was mainly emitted from stacks. The massive application of organic solvents accounted for the VOCs composition characterized by 2-butanone and acetone. Based on these results, the massive use of organic solvents in the adhesive industry should be discouraged and the waterborne adhesives should be promoted over the solvent-based adhesives.

Key words: ozone, adhesive synthesis, volatile organic compounds (VOCs), ozone formation potential (OFP), pollution characteristics, acetone, 2-butanone

中图分类号:

陈雪泉, 孔彬, 兰青, 余志铨, 谢银斯, 黄俊毅. 胶黏剂生产行业VOCs组分特征及臭氧生成潜势分析[J]. 生态环境学报, 2022, 31(4): 750-758.

CHEN Xuequan, KONG Bin, LAN Qing, YU Zhiquan, XIE Yinsi, HUANG Junyi. Emission Characteristics and Ozone Formation Potential Assessment of Volatile Organic Compounds (VOCs) from Adhesive Manufacturing Industry[J]. Ecology and Environment, 2022, 31(4): 750-758.

图/表 8

参考文献 22

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编号 Number	采样点位置 Sampling location	污染源类型 Source type	采样时间 Sampling duration
1	活性炭吸附进口	有组织	瞬时采集
2	废气排放口	有组织	瞬时采集
3	RCO燃烧废气出口	有组织	瞬时采集
4	车间	无组织	1 h
5	企业边界	无组织	1 h

编号 Number	采样点位置 Sampling location	污染源类型 Source type	采样时间 Sampling duration
1	活性炭吸附进口	有组织	瞬时采集
2	废气排放口	有组织	瞬时采集
3	RCO燃烧废气出口	有组织	瞬时采集
4	车间	无组织	1 h
5	企业边界	无组织	1 h

类别/组分 Type/Component		工艺源废气 Source emission		排放口废气 Exhaust mission		RCO燃烧废气 RCO combustion emission
类别/组分 Type/Component		质量浓度 ρ/(μg∙m^-3)	占比% Proportion	质量浓度 ρ/(μg∙m^-3)	占比% Proportion	质量浓度 ρ/(μg∙m^-3)	占比% Proportion
脂肪烃 Aliphatic hydrocarbon	乙烷 Ethane	1.21	0.002	1.55	0.034	3.49	0.022
	丙烷 Dimethylmethane	0.86	0.002	0.79	0.017	2.27	0.014
	异丁烷 Iso-butane	2.66	0.005	1.51	0.033	66.10	0.411
	正戊烷 N-pentane	120.94	0.219	3.45	0.076	72.13	0.449
	2, 2-二甲基丁烷 2, 2-dimethylbutane	999.06	1.806	24.86	0.548	460.21	2.862
	环戊烷 Cyclopentane	550.42	0.995	61.96	1.366	407.41	2.534
	2, 3-二甲基丁烷 2, 3-Dimethylbutane	761.80	1.377	21.66	0.477	310.63	1.932
	2-甲基戊烷 2-methylpentane	1906.4	3.445	53.31	1.175	717.81	4.464
	3-甲基戊烷 3-methylpentane	935.14	1.690	17.76	0.391	344.44	2.142
	正己烷 N-hexane	90.87	0.164	7.56	0.167	175.18	1.090
	甲基环戊烷 Methylcyclopentane	89.44	0.161	4.49	0.099	119.51	0.743
	2,4-二甲基戊烷 2, 4-Dimethylpentan	105.70	0.191	2.30	0.051	72.12	0.449
	环己烷 Cyclohexane	93.84	0.170	5.00	0.110	118.28	0.736
	2-甲基己烷 2-Methylhexane	858.60	1.552	32.71	0.721	453.11	2.818
	2, 3-二甲基戊烷 2, 3-Dimethylpentan	483.76	0.874	14.34	0.316	269.62	1.677
	3-甲基己烷 3-Methylhexane	982.55	1.776	43.62	0.961	518.47	3.225
	正庚烷 N-heptane	668.50	1.208	18.37	0.405	313.70	1.951
	甲基环己烷 Methyl cyclohexane	216.08	0.391	2.18	0.048	79.59	0.495
	2-甲基庚烷 2-Methylheptane	100.62	0.182	0.45	0.010	29.26	0.182
	3-甲基庚烷 3-Methylheptane	134.97	0.244	0.12	0.003	23.47	0.146
	正辛烷 N-octane	93.39	0.169	0.10	0.002	13.10	0.081
芳香烃 Aromatic hydrocarbon	苯 Benzene	2.67	0.05	0.74	0.016	9.74	0.061
	甲苯 Methylbenzene	1090.58	1.971	121.46	2.677	337.81	2.101
	乙苯 Ethylbenzene	19.90	0.036	0.35	0.008	1.65	0.010
	苯乙烯 Cinnamene	10.99	0.020	0.30	0.007	20.19	0.126
	间(对)二甲苯 M-Xylene	55.69	0.101	0.52	0.011	7.58	0.047
	邻二甲苯 O-Xylene	15.00	0.027	0.40	0.009	1.87	0.012
OVOCs	丙酮 Acetone	26569	48.017	3902	86.010	8982	55.864
	异丙醇 Isopropanol	327.14	0.591	0.00	0.000	0.00	0.000
	2-丁酮 2-Butanone	13720	24.796	95.34	2.102	2105	13.092
	乙酸乙酯 Ethyl acetate	4324.51	7.816	97.50	2.149	42.64	0.265
	TVOCs	55328	100	4537	100	16069	100

类别/组分 Type/Component		工艺源废气 Source emission		排放口废气 Exhaust mission		RCO燃烧废气 RCO combustion emission
类别/组分 Type/Component		质量浓度 ρ/(μg∙m^-3)	占比% Proportion	质量浓度 ρ/(μg∙m^-3)	占比% Proportion	质量浓度 ρ/(μg∙m^-3)	占比% Proportion
脂肪烃 Aliphatic hydrocarbon	乙烷 Ethane	1.21	0.002	1.55	0.034	3.49	0.022
	丙烷 Dimethylmethane	0.86	0.002	0.79	0.017	2.27	0.014
	异丁烷 Iso-butane	2.66	0.005	1.51	0.033	66.10	0.411
	正戊烷 N-pentane	120.94	0.219	3.45	0.076	72.13	0.449
	2, 2-二甲基丁烷 2, 2-dimethylbutane	999.06	1.806	24.86	0.548	460.21	2.862
	环戊烷 Cyclopentane	550.42	0.995	61.96	1.366	407.41	2.534
	2, 3-二甲基丁烷 2, 3-Dimethylbutane	761.80	1.377	21.66	0.477	310.63	1.932
	2-甲基戊烷 2-methylpentane	1906.4	3.445	53.31	1.175	717.81	4.464
	3-甲基戊烷 3-methylpentane	935.14	1.690	17.76	0.391	344.44	2.142
	正己烷 N-hexane	90.87	0.164	7.56	0.167	175.18	1.090
	甲基环戊烷 Methylcyclopentane	89.44	0.161	4.49	0.099	119.51	0.743
	2,4-二甲基戊烷 2, 4-Dimethylpentan	105.70	0.191	2.30	0.051	72.12	0.449
	环己烷 Cyclohexane	93.84	0.170	5.00	0.110	118.28	0.736
	2-甲基己烷 2-Methylhexane	858.60	1.552	32.71	0.721	453.11	2.818
	2, 3-二甲基戊烷 2, 3-Dimethylpentan	483.76	0.874	14.34	0.316	269.62	1.677
	3-甲基己烷 3-Methylhexane	982.55	1.776	43.62	0.961	518.47	3.225
	正庚烷 N-heptane	668.50	1.208	18.37	0.405	313.70	1.951
	甲基环己烷 Methyl cyclohexane	216.08	0.391	2.18	0.048	79.59	0.495
	2-甲基庚烷 2-Methylheptane	100.62	0.182	0.45	0.010	29.26	0.182
	3-甲基庚烷 3-Methylheptane	134.97	0.244	0.12	0.003	23.47	0.146
	正辛烷 N-octane	93.39	0.169	0.10	0.002	13.10	0.081
芳香烃 Aromatic hydrocarbon	苯 Benzene	2.67	0.05	0.74	0.016	9.74	0.061
	甲苯 Methylbenzene	1090.58	1.971	121.46	2.677	337.81	2.101
	乙苯 Ethylbenzene	19.90	0.036	0.35	0.008	1.65	0.010
	苯乙烯 Cinnamene	10.99	0.020	0.30	0.007	20.19	0.126
	间(对)二甲苯 M-Xylene	55.69	0.101	0.52	0.011	7.58	0.047
	邻二甲苯 O-Xylene	15.00	0.027	0.40	0.009	1.87	0.012
OVOCs	丙酮 Acetone	26569	48.017	3902	86.010	8982	55.864
	异丙醇 Isopropanol	327.14	0.591	0.00	0.000	0.00	0.000
	2-丁酮 2-Butanone	13720	24.796	95.34	2.102	2105	13.092
	乙酸乙酯 Ethyl acetate	4324.51	7.816	97.50	2.149	42.64	0.265
	TVOCs	55328	100	4537	100	16069	100

典型行业 Typical industry	主要VOCs组分 VOCs characteristics	文献来源 Reference
胶黏剂合成 Adhesive synthesis	丙酮 (48.0%)、2-丁酮 (24.8%)、乙酸乙酯 (7.8%)、2-甲基戊烷 (3.4%)、甲苯 (1.9%)	本文
油漆制造 Paint manufacturing	2-甲基戊烷 (16.7%)、甲苯 (14.0%)、乙酸乙酯 (10.1%)、3-甲基戊烷 (8.6%)、邻二甲苯 (6.4%)、间二甲苯 (6.1%)、对二甲苯 (6.1%)、乙醇 (5.7%)。	包亦姝等, 2020
印刷 Printing	异丙醇 (42.85%)、2-甲基己烷 (7.18%)、3-甲基己烷 (6.35%)、庚烷 (6.34%)	方莉等, 2019
	正癸烷 (12.3%)、正壬烷 (8.2%)、丙酮 (8.2%)、正十一烷 (7.0%)、正丁醛 (5.2%)	莫梓伟等, 2015
	乙醇 (36.5%)、乙酸乙酯 (11.8%)、异丙醇 (11.0%)、邻二甲苯 (8.4%)、对二甲苯 (6.0%)、间二甲苯 (6.0%)、丙酮 (5.4%)	包亦姝等, 2020
家具制造 Cabinet making	乙醇 (36.71%)、乙酸乙酯 (8.22%)、丙酮 (7.77%)、二氯甲烷 (7.35%)、间/对-二甲苯 (5.51%)	方莉等, 2019
家具制造 Cabinet making	乙酸乙酯 (17.3%)、邻二甲苯 (10.0%)、乙醇 (9.5%)、间二甲苯 (9.0%)、对二甲苯 (9.0%)、甲苯 (6.8%)、异丙醇 (6.3%)、乙苯 (5.1%)	包亦姝等, 2020
人造板制造 Wood-based panel manufacturing	乙醇 (33.7%)、乙酸乙酯 (20.4%)、异丙醇 (13.4%)	包亦姝等, 2020
汽车制造 Automobile making	丙酮 (15.3%)、3-甲基己烷 (7.1%)、正庚烷 (6.0%)、2-甲基己烷 (5.0%)、间/对-二甲苯 (5.0%)	莫梓伟等, 2015

胶黏剂生产行业VOCs组分特征及臭氧生成潜势分析

Emission Characteristics and Ozone Formation Potential Assessment of Volatile Organic Compounds (VOCs) from Adhesive Manufacturing Industry

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物种 species	$K_{i}^{OH}$(×10¹²) 298 K	γ_i	工艺源废气 Source emission		吸附后排放 Exhaust mission		RCO排放 RCO emission
物种 species	$K_{i}^{OH}$(×10¹²) 298 K	γ_i	C′ (×10^-9)	$\rho _{i}^{\prime }$/(mg·m^-3)	C′ (×10^-9)	$\rho _{i}^{\prime }$/(mg∙m^-3)	C′ (×10^-9)	$\rho _{i}^{\prime }$/(mg∙m^-3)
乙烷 Ethane	0.9	0.25	0.01	0.30	0.01	0.39	0.03	0.87
丙烷 Dimethylmethane	1.15	0.48	0.02	0.41	0.02	0.38	0.06	1.09
异丁烷 Iso-butane	2.12	1.21	0.09	3.21	0.05	1.82	2.25	79.98
正戊烷 N-pentane	3.94	1.04	6.14	125.78	0.17	3.58	3.66	75.02
2, 2-二甲基丁烷 2, 2-dimethylbutane	2.32	0.82	25.00	819.23	0.62	20.38	11.52	377.37
环戊烷 Cyclopentane	5.16	2.4	37.65	1321.01	4.24	148.70	27.87	977.80
2, 3-二甲基丁烷 2, 3-Dimethylbutane	6.3	1.07	51.77	815.12	1.47	23.18	21.11	332.38
2-甲基戊烷 2-methylpentane	5.6	1.5	115.17	2859.63	3.22	79.97	43.36	1076.71
3-甲基戊烷3-methylpentane	5.7	1.5	57.50	1402.70	1.09	26.63	21.18	516.66
正己烷 N-hexane	5.61	0.98	5.50	89.06	0.46	7.41	10.60	171.67
甲基环戊烷 Methylcyclopentane	—	2.8	—	250.42	—	12.58	—	334.62
2, 4-二甲基戊烷 2, 4-Dimethylpentan	4.77	1.5	4.68	158.54	0.10	3.46	3.19	108.18
环己烷 Cyclohexane	7.49	1.28	7.76	120.12	0.41	6.40	9.79	151.40
2-甲基己烷 2-Methylhexane	—	0.96	—	824.26	—	31.41	—	434.99
2, 3-二甲基戊烷 2, 3-Dimethylpentan	—	1.31	—	633.72	—	18.78	—	353.21
3-甲基己烷 3-Methylhexane	—	1.4	—	1375.57	—	61.06	—	725.86
正庚烷 N-heptane	7.15	0.81	44.35	541.49	1.22	14.88	20.81	254.10
甲基环己烷Methyl cyclohexane	10.4	1.8	21.28	388.94	0.21	3.91	7.84	143.27
2-甲基庚烷 2-Methylheptane	—	0.96	—	96.59	—	0.43	—	18.48
3-甲基庚烷 3-Methylheptane	—	0.96	—	133.62	—	0.12	—	23.24
正辛烷 N-octane	8.68	0.6	6.60	56.03	0.01	0.06	0.93	7.86
苯 Benzene	1.23	0.42	0.04	1.12	0.01	0.31	0.14	4.09
甲苯 Methylbenzene	5.96	2.7	65.68	2944.56	7.32	327.95	20.35	912.08
乙苯 Ethylbenzene	7.1	2.7	0.93	40.23	0.02	0.95	0.10	4.5
苯乙烯 Cinnamene	—	2.2	—	24.17	—	0.66	—	44.43
间(对)二甲苯 M-Xylene	19	7.4	9.27	412.10	0.09	3.84	1.26	56.09
邻二甲苯 O-Xylene	13.7	6.5	1.78	97.52	0.05	2.59	0.22	12.7
丙酮 Acetone	0.17	0.56	72.40	14879.05	10.63	2185.27	24.48	5030.11
异丙醇 Isopropanol	5.1	0.54	25.85	176.66	0.00	0.00	0.00	0.00
2-丁酮 2-Butanone	1.22	1.18	216.14	16189.98	1.50	112.50	33.17	2484.24
乙酸乙酯 Ethyl acetate	—	0.63	—	2724.44	—	61.42	—	26.86
总和 Total			775.63	49505.58	32.93	3161.03	263.91	14739.27

物种 Species	车间 Workshop		厂界 Factory boundary
物种 Species	质量浓度 (ρ_i) Mass concentration	臭氧生成潜势) Ozone formation potential	质量浓度 (ρ_i) Mass concentration	臭氧生成潜势) Ozone formation potential
乙烯 Ethylene	—	—	2.71	20.02
乙烷 Ethane	—	—	0.57	0.14
丙烷 Dimethylmethane	—	—	0.12	0.06
异丁烷 Iso-butane	—	—	0.23	0.28
正戊烷 Npentane	—	—	0.29	0.30
2, 3-二甲基丁烷 2, 3-Dimethylbutane	—	—	3.00	3.21
2-甲基戊烷 2-methylpentane	17.94	26.92	3.27	4.91
3- 甲基戊烷 3-methylpentane	—	—	0.26	0.39
正己烷 N-hexane	—	—	0.35	0.34
苯 Benzene	—	—	1.46	0.61
环己烷 Cyclohexane	—	—	0.11	0.14
2-甲基己烷 2-methylhexane	1.38	1.32	0.24	0.23
2, 3-二甲基戊烷 2, 3-Dimethylpentane	0.66	0.86	0.11	0.14
2, 2, 4-三甲基戊烷 2, 2, 4-trimethylpentane	1.02	0.95	—	—
3-甲基己烷 3-methylhexane	1.91	2.67	0.31	0.44
正庚烷 N-heptane	—	—	0.17	0.14
甲苯 Methylbenzene	20.00	53.99	35.5	95.87
乙苯 Ethylbenzene	—	—	0.40	1.09
间(对)二甲苯 M-Xylene	—	—	1.07	7.90
丙酮 Acetone	176.96	99.10	—	—
苯乙烯 Cinnamene	—	—	2.18	4.80
邻二甲苯 O-xylene	—	—	0.49	3.20
2-丁酮 2-Butanone	91.11	107.51	—	—
乙酸乙酯 Ethyl acetate	31.40	19.78	332.63	209.55
总计 Total	342.38	313.10	385.47	353.78

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