纤维板中气味物质的化学组成、气味特征和风险值分析

doi:10.16085/j.issn.1000-6613.2024-0794

摘要/Abstract

摘要：

在系统分析纤维板中气味物质化学组成的基础上，通过测定和收集这些气味物质的嗅阈值（odor threshold, OT）和最低关注浓度值（lowest concentration of interest，LCI）数据，计算和评估各个气味物质的气味活度值和风险值，以此为高风险和刺激性气味物质的治理明确治理对象，提供治理依据。研究结果表明，纤维板中释放较多的气味物质是苯系物、萜烯类化合物、乙酸、己醛等小分子物质。虽然乙酸（强烈、刺鼻、类似醋的气味），丙酸（辛辣醋味），苯乙烯（刺鼻的类似橡胶味），对、间二甲苯（刺激性芳香味），1-丁醇（酒精辛辣味），邻二甲苯（刺激性芳香味），苯甲醛（苦杏仁味），糠醛（似苯甲醛的特殊气味）等组分具有刺激性的气味，但是气味活度值大于1的主要是己醛、壬醛、辛醛、庚醛等醛类化合物和长叶烯、α-蒎烯等萜烯类物质。对醛类、萜烯类这些物质的减控治理是降低纤维板气味的主要途径。气味物质的风险值既与其释放量大小有关，也与其LCI值有关。虽然纤维板气味物质中含有2-甲基萘、二甲苯等中低毒性物质，但是这些物质的风险值都远小于1。

关键词: 纤维板, 气味物质, 化学组成, 气味活度值, 风险值

Abstract:

In order to clarify the treatment target for high-risk and pungent odor substances, the odor threshold (OT) and the lowest concentration of interest (LCI) data were measured and collected, and the odor activity value (OAV) and risk value (R) were calculated and evaluated, based on the systematic analysis of odor substances in fiberboards. The results showed that benzene series, terpenes, acetic acid, hexaldehydes and other small molecules were the most odor substances released in fiberboards. Although acetic acid (strong, pungent, similar smell to vinegar ), propionic acid ( spicy vinegar odor), styrene (pungent, similar smell to rubber), p-, m-xylene ( irritating aromatic odor ), 1-butanol ( alcohol spicy odor ), o-xylene ( irritating aromatic odor ), benzaldehyde ( bitter almond odor ), and furfural (similar smell to benzaldehyde ) had irritating odor, the main odor substances (OAV>1) werealdehydes such as hexanal, nonanal, pentanal, and heptanal, and terpenes such as longifolene and $α$ $- p i n e n e$ . The reduction of aldehydes and terpenes was the main way to reduce the pungent odor of fiberboards. The risk value of odor substances was related to both the amount of release and the LCI value. Although fiberboards contained low and medium toxic substances such as 2-methylnaphthalene and xylene, the risk values of these substances were far less than 1.

Key words: fiberboard, odor compound, chemical composition, odor activity value, risk value

中图分类号:

TQ351

杨芳, 邹献武, 朱黎明. 纤维板中气味物质的化学组成、气味特征和风险值分析[J]. 化工进展, 2024, 43(S1): 615-626.

YANG Fang, ZOU Xianwu, ZHU Liming. Chemical composition, odor characterization and risk value analysis of odor compounds from fiberboards[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 615-626.

图/表 7

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样品代号	板材厚度/ mm	板材密度/g·m^-3	板材含水率/%	甲醛释放量/mg·m^-3	TVOC释放量/mg·m^-3	气味等级
H-FB	18	0.79	7.0	0.072	0.4626	3
M-FB	18	0.76	5.9	0.065	0.2319	2
L-FB	18	0.80	5.3	0.006	0.0943	2

样品代号	板材厚度/ mm	板材密度/g·m^-3	板材含水率/%	甲醛释放量/mg·m^-3	TVOC释放量/mg·m^-3	气味等级
H-FB	18	0.79	7.0	0.072	0.4626	3
M-FB	18	0.76	5.9	0.065	0.2319	2
L-FB	18	0.80	5.3	0.006	0.0943	2

序号	CAS#	化合物英文名称	化合物中文名称	释放量/mg∙m^-3
序号	CAS#	化合物英文名称	化合物中文名称	H-FB	M-FB	L-FB
1	64-19-7	acetic acid	乙酸	0.0056	—	—
2	71-36-3	1-butanol	1-丁醇	0.0051	0.0017	—
3	1979-09-4	propanoic acid	丙酸	—	—	0.0041
4	71-41-0	1-pentanol	1-戊醇	—	—	0.0018
5	108-88-3	toluene	甲苯	0.0108	0.0044	0.0013
6	66-25-1	hexanal	己醛	0.0037	0.0024	0.0160
7	35796	furfural	糠醛	—	—	0.0015
8	100-41-4	ethylbenzene	乙苯	0.0568	0.0277	0.0008
9	106-42-3、108-38-3	m，p-xylene	对、间二甲苯	0.2071	0.1048	0.0021
10	111-71-7	heptanal	庚醛	—	—	0.0026
11	108-94-1	cyclohexanone	环己酮	0.0023	0.0007	—
12	100-42-5	styrene	苯乙烯	0.0043	0.0018	—
13	95-47-6	o-xylene	邻二甲苯	0.0594	0.0292	—
14	100-52-7	benzaldehyde	苯甲醛	0.0025	0.0017	—
15	80-56-8	α-pinene	α-蒎烯	0.0503	0.0324	—
16	111-70-6	1-heptanol	庚醇	—	—	0.0008
17	110-93-0	6-methyl-5-hepten-2-one	甲基庚烯酮	—	—	0.0012
18	79-92-5	camphene	莰烯	0.0023	—	—
19	124-13-0	octanal	辛醛	—	—	0.0048
20	18172-67-3	laevo-β-pinene	左旋-β-蒎烯	0.0019	0.0013	—
21	541-73-1	1,3-dichloro-benzene	间二氯苯	—	0.0008	—
22	104-76-7	2-ethyl-1-hexanol	2-乙基己醇	0.0096	0.0027	0.0174
23	5989-27-5	d-limonene	d-柠檬烯	0.0084	0.0042	—
24	111-87-5	1-octanol	辛醇	—	—	0.0012
25	98-86-2	acetophenone	苯乙酮	0.0020	—	0.0010
26	124-19-6	nonanal	壬醛	0.0034	0.0010	0.0064
27	103-09-3	acetic acid, 2-ethylhexyl ester	乙酸辛酯	—	—	0.0048
28	507-70-0	endo-borneol	龙脑	—	—	0.0019
29	535-77-3	m-cymene	间伞花烃	—	0.0012	—
30	112-31-2	decanal	癸醛	—	—	0.0015
31	275-51-4	azulene	甘菊环烃	0.0020	—	—
32	103-11-7	2-ethylhexyl acrylate	丙烯酸辛酯	—	—	0.0019
33	6165-40-8	7-methyl-pentadecane	7-甲基十五烷	—	0.0021	—
34	91-57-6	2-methyl-naphthalene	2-甲基萘	0.0023	—	—
35	5461-02-9	undecyl butyrate	丁酸十一酯	0.0031	—	—
36	77-68-9	propanoic acid, 2-methyl-, 3-hydroxy-2,2,4-trimethylpentyl ester	醇脂-12	—	0.0012	0.0008
37	1137-12-8	longicyclen (+)-	长叶环烯	—	—	0.0015
38	3650-28-0	sativene	苜蓿烯	—	—	0.0010
39	629-59-4	tetradecane	十四烷	0.0031	0.0015	—
40	131-11-3	dimethyl phthalate	邻苯二甲酸二甲酯	0.0023	—	—
41	475-20-7	longifolene	长叶烯	0.0061	0.0034	0.0159
42	469-61-4	α-cedrene	α-柏木烯	0.0026	0.0021	0.0013
43	629-62-9	pentadecane	十五烷	—	0.0012	—
44	629-92-5	nonadecane	十九烷	0.0027	—	—
45	629-94-7	heneicosane	二十一烷	0.0029	0.0008	—
46	77-53-2	cedrol	雪松醇	—	—	0.0011

序号	CAS#	化合物英文名称	化合物中文名称	释放量/mg∙m^-3
序号	CAS#	化合物英文名称	化合物中文名称	H-FB	M-FB	L-FB
1	64-19-7	acetic acid	乙酸	0.0056	—	—
2	71-36-3	1-butanol	1-丁醇	0.0051	0.0017	—
3	1979-09-4	propanoic acid	丙酸	—	—	0.0041
4	71-41-0	1-pentanol	1-戊醇	—	—	0.0018
5	108-88-3	toluene	甲苯	0.0108	0.0044	0.0013
6	66-25-1	hexanal	己醛	0.0037	0.0024	0.0160
7	35796	furfural	糠醛	—	—	0.0015
8	100-41-4	ethylbenzene	乙苯	0.0568	0.0277	0.0008
9	106-42-3、108-38-3	m，p-xylene	对、间二甲苯	0.2071	0.1048	0.0021
10	111-71-7	heptanal	庚醛	—	—	0.0026
11	108-94-1	cyclohexanone	环己酮	0.0023	0.0007	—
12	100-42-5	styrene	苯乙烯	0.0043	0.0018	—
13	95-47-6	o-xylene	邻二甲苯	0.0594	0.0292	—
14	100-52-7	benzaldehyde	苯甲醛	0.0025	0.0017	—
15	80-56-8	α-pinene	α-蒎烯	0.0503	0.0324	—
16	111-70-6	1-heptanol	庚醇	—	—	0.0008
17	110-93-0	6-methyl-5-hepten-2-one	甲基庚烯酮	—	—	0.0012
18	79-92-5	camphene	莰烯	0.0023	—	—
19	124-13-0	octanal	辛醛	—	—	0.0048
20	18172-67-3	laevo-β-pinene	左旋-β-蒎烯	0.0019	0.0013	—
21	541-73-1	1,3-dichloro-benzene	间二氯苯	—	0.0008	—
22	104-76-7	2-ethyl-1-hexanol	2-乙基己醇	0.0096	0.0027	0.0174
23	5989-27-5	d-limonene	d-柠檬烯	0.0084	0.0042	—
24	111-87-5	1-octanol	辛醇	—	—	0.0012
25	98-86-2	acetophenone	苯乙酮	0.0020	—	0.0010
26	124-19-6	nonanal	壬醛	0.0034	0.0010	0.0064
27	103-09-3	acetic acid, 2-ethylhexyl ester	乙酸辛酯	—	—	0.0048
28	507-70-0	endo-borneol	龙脑	—	—	0.0019
29	535-77-3	m-cymene	间伞花烃	—	0.0012	—
30	112-31-2	decanal	癸醛	—	—	0.0015
31	275-51-4	azulene	甘菊环烃	0.0020	—	—
32	103-11-7	2-ethylhexyl acrylate	丙烯酸辛酯	—	—	0.0019
33	6165-40-8	7-methyl-pentadecane	7-甲基十五烷	—	0.0021	—
34	91-57-6	2-methyl-naphthalene	2-甲基萘	0.0023	—	—
35	5461-02-9	undecyl butyrate	丁酸十一酯	0.0031	—	—
36	77-68-9	propanoic acid, 2-methyl-, 3-hydroxy-2,2,4-trimethylpentyl ester	醇脂-12	—	0.0012	0.0008
37	1137-12-8	longicyclen (+)-	长叶环烯	—	—	0.0015
38	3650-28-0	sativene	苜蓿烯	—	—	0.0010
39	629-59-4	tetradecane	十四烷	0.0031	0.0015	—
40	131-11-3	dimethyl phthalate	邻苯二甲酸二甲酯	0.0023	—	—
41	475-20-7	longifolene	长叶烯	0.0061	0.0034	0.0159
42	469-61-4	α-cedrene	α-柏木烯	0.0026	0.0021	0.0013
43	629-62-9	pentadecane	十五烷	—	0.0012	—
44	629-92-5	nonadecane	十九烷	0.0027	—	—
45	629-94-7	heneicosane	二十一烷	0.0029	0.0008	—
46	77-53-2	cedrol	雪松醇	—	—	0.0011

序号	CAS#	化合物英文名称	化合物中文名称	测量值	文献值^[13]/mg·m^-3
序号	CAS#	化合物英文名称	化合物中文名称	测量值	识别阈值r	觉察阈值d	未知d还是r
1	13466-78-9	3-carene	3-蒈烯	1.0982	8.6~9.1	9.3	—
2	127-91-3	β-pinene	β-蒎烯	17.6571	35~38	0.18~65	—
3	99-83-2	α-phellandrene	α-水芹烯	0.0016	2.9~3.9	—	—
4	99-85-4	γ-terpinene	γ-松油烯	0.0020	1.4~1.6	2.5-55	—
5	586-62-9	terpinolene	萜品油烯	0.0086	—	—	—
6	1632-73-1	fenchol	葑醇	0.0299	—	—	0.14
7	507-70-0	endo-borneol	龙脑	0.0114	—	0.052	—
8	98-55-5	α-terpineol	α-松油醇	0.3855	0.0125~110	0.01~0.86	0.0208
9	19894-97-4	(-)-myrtenol	桃金娘烯醇	0.0401	—	—	—
10	80-57-9	verbenone	马苄烯酮	0.0080	—	—	—
11	123-35-3	β-myrcene	β-月桂烯	0.3754	0.13~0.15	—	0.041~0.1125
12	99-86-5	α-terpinen	α-松油烯	0.0022	2.35~2.45	7.9	—
13	3779-61-1	trans-β-ocimene	反-β-罗勒烯	0.0064	—	—	0.0187
14	4501-58-0	α-campholenal	α-龙脑烯醛	0.0072	—	—	—
15	471-16-9	rans-sabinol	反式-桧醇	0.5419	—	—	—
16	562-74-3	terpinen-4-ol	4-松油醇T	0.0040	11.7~12.2	—	0.59
17	140-67-0	estragole	草蒿脑	0.2363	—	0.00013	—
18	6485-40-1	(-)-carvone	左旋香芹酮	0.0070	0.10~0.12	0.034~0.15	0.0166~0.025
19	87-44-5	caryophyllene	石竹烯	0.0043	11-13	—	1.5
20	6753-98-6	humulene	蛇麻烯	0.0016	—	—	—
21	1686-56-2	pimaradiene	海松二烯	0.0034	—	—	—
22	80-56-8	α-pinene	α-蒎烯	0.0300	25~29	0.1~105	0.00036~0.016
23	5989-27-5	d-limonene	d-柠檬烯	0.0436	2.2~2.3	0.045~55	0.0059~4.70
24	17699-16-0	trans-sabinene hydrate	反式桧烯水合物	0.0078	9.2~10	—	—
25	142878-08-8	isodaucene	异胡萝卜烯	0.0010	—	—	—
26	3856-25-5	copaene	古巴烯	0.0020	—	—	—
27	489-29-2	β-maaliene	β-马榄烯	0.0019	—	—	—
28	475-20-7	longifolene	长叶烯	0.0024	—	—	—
29	11028-42-5	cedrene	雪松烯	0.0013	—	—	—
30	73209-42-4	trans-calamenene	反式菖蒲烯	0.0006	—	—	—
31	483-76-1	δ-cadinene	δ-杜松烯	0.0016	—	—	—
32	2867-05-2	α-thujene	α-侧柏酮	0.1714	—	—	—
33	527-84-4	o-cymene	邻伞花烃	0.2569	0.004~0.005	—	—
34	470-82-6	eucalyptol	桉叶油醇	9.9854	0.00062~0.05	0.003~2	0.000069~7
35	10482-56-1	L-α-terpineol	L-α-松油醇	0.2775	—	—	—
36	106-22-9	citronellol	香茅醇	0.0118	0.8~1.0	0.28~2.8	0.00012~0.0465
37	94-59-7	safrole	黄樟素	0.0784	0.01~4.8	0.00035~30	0.00007
38	97-53-0	eugenol	丁香酚	0.0139	0.007~3.8	0.005~0.23	0.000008~0.11
39	17699-14-8	α-cubebene	α-荜澄茄烯	0.1706	—	—	—
40	93-15-2	methyleugenol	甲基丁香酚	0.0074	—	—	—
41	14912-44-8	ylangene	依兰烯	0.0175	—	—	—
42	30021-74-0	γ-muurolene	γ-依兰油烯	0.1410	—	—	—
43	18252-46-5	cis-α-bergamotene	顺式-α-香柠檬烯	0.0162	—	—	—
44	512-61-8	α-santalene	α-檀香烯	6.1513	—	—	—
45	13474-59-4	trans-α-bergamotene	反式-α-香柠檬烯	0.5091	—	—	—
46	28973-97-9	cis-β-farnesene	顺式-β-金合欢烯	0.0355	—	—	—
47	25532-78-9	epi-β-santalene	表-β-檀香烯	0.1537	—	—	—
48	511-59-1	β-santalene	β-檀香烯	1.8708	—	—	—
49	39029-41-9	γ-cadinene	γ-杜松烯	0.0233	—	—	—
50	20307-83-9	β-sesquiphellandrene	β-倍半水芹烯	0.0598	—	—	—
51	18252-44-3	β-copaene	β-古巴烯	0.1652	—	—	—
52	17066-67-0	β-eudesmene	β-桉叶烯	0.0196	—	—	—
53	515-17-3	γ-selinene	γ-蛇床烯	0.0395	—	—	—
54	3691-11-0	δ-guaiene	δ-愈创木烯	0.0185	—	—	—
55	10208-80-7	α-muurolene	α-依兰油烯	0.0306	—	—	—
56	1139-17-9	isolongifolol	异长叶醇	0.0432	—	—	—
57	464-49-3	(+)-camphor	(+)-樟脑	0.0009	—	—	—
58	469-61-4	α-cedrene	α-柏木烯	0.0113	—	—	—
59	470-40-6	cis-thujopsene	顺式罗汉柏烯	0.0630	—	—	—
60	29873-99-2	γ-elemene	γ-榄香烯	0.0008	—	—	—
61	1461-03-6	β-himachalene	β-喜玛拉雅烯	0.0068	—	—	—
62	77-53-2	cedrol	雪松醇	0.5126	—	—	—
63	28400-11-5	β-acorenol	β-菖蒲醇	0.0144	—	—	—
64	515-69-5	α-bisabolol	α-甜没药醇	0.0013	—	—	—