工艺参数对生物油酚醛树脂胶合板甲醛和TVOC含量的影响

doi:10.3969/j.issn.1673-5854.2021.02.006

摘要/Abstract

摘要：

为探究制胶阶段和压板阶段的6个因素（生物油替代率、醛酚比、热压温度、热压时间、热压压力、涂胶量）对胶合板中甲醛和总挥发性有机物（TVOC）含量的影响，在单因素试验基础上，设计L₂₅（5⁶）正交试验对工艺参数进行优化。采用顶空固相微萃取法（HS-SPME）和气相色谱/质谱（GC/MS）联用技术对生物油酚醛树脂胶合板（BPFP）中游离甲醛和除甲醛外的TVOC、苯酚进行检测。结果表明：当生物油替代率为60%，醛酚比值（n_F/n_P）1.6，热压温度190℃，热压时间4 min，热压压力1.2 MPa，涂胶量为200 g/cm²时，胶合板中含甲醛最低。热压温度和压力对甲醛含量有显著的影响，生物油替代率和涂胶量对胶合板中游离甲醛含量的影响较小；在生物油替代率为60%，醛酚比值2.2，热压温度190℃，热压时间5.5 min，热压压力1.4 MPa，涂胶量为210 g/cm²时，胶合板中TVOC含量最低。

关键词: 生物油酚醛树脂, 甲醛, 总挥发性有机物, 固相微萃取, 安全性

Abstract:

To explore the effects of 6 factors (bio-oil replacement ratio, molar ratio of formaldehyde and phenol (n_F/n_P), hot press temperature, pressure and time, and amount of adhesives) of the resin preparation and hot press processes on the content of formaldehyde and total volatile organic compounds (TVOC) in the bio-oil phenol formaldehyde plywood (BPFP) panels, an L₂₅ (5⁶) orthogonal experiment design was executed. Head space solid-phase micro-extractions (HS-SPME) combined with gas chromatography/mass spectrometry (GC/MS) was employed to detect the content of free formaldehyde and TVOC in the BPFP panels. The results showed that under the conditions of the bio-oil replacement ratio of 60%, n_F/n_P of 1.6, hot press temperature of 190 ℃, hot press duration of 4 min, hot press pressure of 1.2 MPa, and amount of adhesives applied of 200 g/cm², formaldehyde emissions was the lowest. Hot press temperature and pressure had a significant effect on the formaldehyde content, whereas the replacement ratio of fast pyrolysis bio-oil to phenol and the amount of wood adhesives applied had a minor effect. Under the conditions of bio-oil replacement ratio of 60%, n_F/n_P of 2.2, hot press temperature of 190 ℃, hot press duration of 5.5 min, hot press pressure of 1.4 MPa, and amount of adhesives applied of 210 g/cm², the content of TVOC in the plywood was the lowest.

Key words: bio-oil phenolic resin, formaldehyde, total volatile organic compound, solid-phase micro-extraction, safety

中图分类号:

TQ35

黄萍, 杨帆, 贾亮亮, 李健, 李冬兵. 工艺参数对生物油酚醛树脂胶合板甲醛和TVOC含量的影响[J]. 生物质化学工程, 2021, 55(2): 38-44.

Ping HUANG, Fan YANG, Liangliang JIA, Jian LI, Dongbing LI. Effect of Process Parameters on Formaldehyde and TVOC Content in Plywood Bonded with Bio-oil Phenol Formaldehyde Resins[J]. Biomass Chemical Engineering, 2021, 55(2): 38-44.

图/表 5

图1

表1

正交试验设计及结果"

试验号 trial number	A 生物油替代率/% bio-oil replacement ratio	B 醛酚比(n_F/n_P) molar ratio between formaldehyde and phenol	C 热压温度/℃ hot press temperature	D 热压时间/min hot press time	E 热压压力/ MPa hot press pressure	F 涂胶量/ (g·cm^-2) amount of adhesives	相对峰面积peak area (×10⁹)
试验号 trial number	A 生物油替代率/% bio-oil replacement ratio	B 醛酚比(n_F/n_P) molar ratio between formaldehyde and phenol	C 热压温度/℃ hot press temperature	D 热压时间/min hot press time	E 热压压力/ MPa hot press pressure	F 涂胶量/ (g·cm^-2) amount of adhesives	甲醛 formaldehyde	TVOC	苯酚 phenol
1	20	1.4	150	3.5	0.8	180	0.23	9.65	6.42
2	20	1.6	160	4.0	1.0	190	0.08	6.91	4.82
3	20	1.8	170	4.5	1.2	200	0.14	5.88	2.67
4	20	2.0	180	5.0	1.4	210	0.24	3.80	0.81
5	20	2.2	190	5.5	1.6	220	0.25	3.80	0.43
6	30	1.4	160	4.5	1.4	220	0.14	6.97	4.07
7	30	1.6	170	5.0	1.6	180	0.19	5.53	2.61
8	30	1.8	180	5.5	0.8	190	0.15	4.37	1.26
9	30	2.0	190	3.5	1.0	200	0.18	5.29	1.45
10	30	2.2	150	4.0	1.2	210	0.20	3.73	0.87
11	40	1.4	170	5.5	1.0	210	0.13	4.93	2.00
12	40	1.6	180	3.5	1.2	220	0.16	6.13	1.40
13	40	1.8	190	4.0	1.4	180	0.13	3.17	0.16
14	40	2.0	150	4.5	1.6	190	0.38	4.91	0.17
15	40	2.2	160	5.0	0.8	200	0.20	4.49	0.10
16	50	1.4	180	4.0	1.6	200	0.18	4.43	1.17
17	50	1.6	190	4.5	0.8	210	0.10	4.11	0.38
18	50	1.8	150	5.0	1.0	220	0.35	5.51	1.05
19	50	2.0	160	5.5	1.2	180	0.16	3.66	0.42
20	50	2.2	170	3.5	1.4	190	0.21	3.44	0.23
21	60	1.4	190	5.0	1.2	190	0.09	3.64	0.14
22	60	1.6	150	5.5	1.4	200	0.16	4.27	0.54
23	60	1.8	160	3.5	1.6	210	0.24	3.96	0.41
24	60	2.0	170	4.0	0.8	220	0.14	4.03	0.09
25	60	2.2	180	4.5	1.0	180	0.17	4.17	0.08
k₁	0.19	0.15	0.26	0.20	0.16	0.18
k₂	0.17	0.14	0.16	0.15	0.18	0.18
k₃	0.20	0.20	0.16	0.19	0.15	0.17
k₄	0.20	0.22	0.18	0.21	0.18	0.18
k₅	0.16	0.21	0.15	0.17	0.25	0.21
R	0.04	0.08	0.11	0.06	0.10	0.04
k′₁	6.01	5.92	5.61	5.69	5.33	5.24
k′₂	5.18	5.39	5.20	4.45	5.36	4.65
k′₃	4.73	4.58	4.76	5.21	4.61	4.87
k′₄	4.23	4.34	4.58	4.59	4.33	4.11
k′₅	4.01	3.93	4.00	4.21	4.53	5.29
R′	2.00	1.99	1.61	1.48	1.03	1.18
k″₁	3.03	2.76	1.81	1.98	1.65	1.94
k″₂	2.05	1.95	1.96	1.42	1.88	1.32
k″₃	0.77	1.11	1.52	1.47	1.10	1.19
k″₄	0.65	0.59	0.94	0.94	1.16	0.89
k″₅	0.25	0.34	0.51	0.93	0.96	1.41
R″	2.78	2.42	1.45	1.05	0.92	1.05

表1

表2

表3

表4

参考文献 17

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因素 factor	平方和(×10¹⁵) sum of square	自由度 degrees of freedom	F值 F value	F临界值 F threshold	显著性(P) saliency
生物油替代率bio-oil replacement ratio	6.51	4	1.45	6.39
n_F/n_P	25.5	4	5.70	6.39
热压温度hot press temperature	41.6	4	9.31	6.39	*
热压时间hot press time	13.7	4	3.07	6.39
热压压力hot press pressure	29.5	4	6.59	6.39	*
涂胶量amount of adhesives	4.47	4	1.00	6.39

因素 factor	平方和(×10¹⁵) sum of square	自由度 degrees of freedom	F值 F value	F临界值 F threshold	显著性(P) saliency
生物油替代率bio-oil replacement ratio	12.7	4	2.76	6.39
n_F/n_P	13.2	4	2.86	6.39
热压温度hot press temperature	7.5	4	1.64	6.39
热压时间hot press time	7.4	4	1.61	6.39
热压压力hot press pressure	4.6	4	1.00	6.39
涂胶量amount of adhesives	4.7	4	1.01	6.39

因素factor	平方和(×10¹⁵) sum of square	自由度 degrees of freedom	F值 F value	F临界值 F threshold	显著性(P) saliency
生物油替代率bio-oil replacement ratio	26.7	4	9.11	6.39	*
n_F/n_P	20.0	4	6.80	6.39	*
热压温度hot press temperature	7.4	4	2.53	6.39
热压时间hot press time	3.8	4	1.30	6.39
热压压力hot press pressure	3.1	4	1.06	6.39
涂胶量amount of adhesives	2.9	4	1.00	6.39

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