桉木化学机械浆废水好氧生物抑制特性分析及降解规律研究

doi:10.3969/j.issn.0253-2417.2024.01.005

Abstract

Abstract:

In this paper, the composition and content of organic matter in the effluent of anaerobic treatment and aerobic treatment of eucalyptus chemical mechanical pulp wastewater were analyzed by GC-MS method. The analysis of number of carbon atoms in the wastewater before and after aerobic treatment was counted, and the main bio-refractory components and degradation rules in the wastewater were analyzed. The results showed that the main residual organic pollutants after anaerobic and aerobic treatment were linalool (C10, 21.21%), methyl p-tert-butyl phenylacetate (C13, 21.39%), dihydromyrcenol (C10, 8.90%), lilial (C14, 6.16%) and citronellol (C10, 4.76%), etc, mainly containing benzene ring organic matter and bacteriostatic components, with biological refractory degradation and bacteriostatic properties. The macroscopic performance was that the removal rate of biological treatment was low. Before and after aerobic treatment, the mass fraction of alcohols in wastewater increased from 19.32% to 51.71%, the mass fraction of aldehydes increased from 3.68% to 13.35%, the mass fraction of esters decreased from 29.75% to 28.32%, and the mass fraction of benzene-containing organics increased from 32.70% to 61.06%, indicating that other organics were degraded more greatly than benzene-containing organics. It was recommended to improve the biological treatment effect by detoxification pretreatment and bioaugmentation to improve microbial activity, reduce the difficulty of subsequent deep treatment, reduce the cost of comprehensive treatment, and achieve low-cost discharge.

Key words: eucalyptus chemi-mechanical pulp wastewater, biological treatment, biological inhibition, degradation law, detoxification

CLC Number:

TQ35

Laibao DING, Qingwen TIAN, Ran YANG, Jinwei ZHU, Qi GUO, Guigan FANG. Analysis of Aerobic Biological Inhibition Characteristics and Degradation Law of Eucalyptus Chemical Mechanical Pulp Wastewater[J]. Chemistry and Industry of Forest Products, 2024, 44(1): 33-40.

Figures/Tables 4

Table 1

Organics and their contents detected in anaerobic treatment effluents"

序号 No.	保留时间/min retention time	化合物 compound	分子式 molecular formula	相对峰面积/% relative peak area
1	3.966	丁酸butanoic acid	C₄H₈O₂	0.51
2	4.760	1-氨基-1-环戊醇cyclopentanemethanol, 1-amino	C₆H₁₃NO	0.35
3	5.406	戊酸pentanoic acid	C₅H₁₀O₂	0.53
4	6.889	己酸hexanoic acid	C₆H₁₂O₂	0.24
5	7.122	八甲基环四硅氧烷cyclotetrasiloxane, octamethyl-	C₈H₂₄O₄Si₄	1.84
6	7.708	D-柠檬烯D-limonene	C₁₀H₁₆	8.38
7	7.938	苯甲醇benzyl alcohol	C₇H₈O	0.63
8	8.360	二氢月桂烯醇7-octen-2-ol, 2, 6-dimethyl-	C₁₀H₂₀O	2.91
9	8.474	对甲苯酚p-cresol	C₇H₈O	1.66
10	8.803	芳樟醇linalool	C₁₀H₁₈O	7.72
11	9.047	α-乙基己酸hexanoic acid, 2-ethyl-	C₈H₁₆O₂	0.16
12	9.099	葑醇fenchol	C₁₀H₁₈O	0.59
13	9.311	2, 4-二甲基-2, 4-庚二烯醛2, 4-heptadienal, 2, 4-dimethyl-	C₉H₁₄O	0.30
14	9.551	十甲基环五硅氧烷cyclopentasiloxane, decamethyl-	C₁₀H₃₀O₅Si₅	2.94
15	10.243	1-苯乙酸乙酯1-phenylethyl acetate	C₁₀H₁₂O₂	1.14
16	10.338	N-乙酰-4-甲氧基苯丙胺4-methoxyamphetamine, N-acetyl	C₁₂H₁₇NO₂	0.32
17	10.737	香茅醇citronellol	C₁₀H₂₀O	4.72
18	11.248	1-甲基-4-(1-甲基乙烯基)环己醇1-methyl-4-(1-methylethenyl)-cyclohexanol	C₁₀H₁₈O	0.17
19	11.356	甲酸松油酯terpinyl formate	C₁₁H₁₈O₂	0.25
20	11.701	顺-2-(1, 1-二甲基乙基)环己醇乙酸酯(cyclohexanol, 2-(1, 1-dimethylethyl)-, acetate, cis-)	C₁₂H₂₂O₂	7.92
21	11.860	吲哚indole	C₈H₇N	0.18
22	12.016	十二甲基环六硅氧烷cyclohexasiloxane, dodecamethyl-	C₁₂H₃₆O₆Si₆	2.63
23	12.426	3-烯丙基过氧基-对烷p-menthane, 3-allylperoxy-	C₁₃H₂₄O₂	0.33
24	12.784	α, 2, 6, 6-四甲基-1-环己烯-1-甲醇1-cyclohexene-1-methanol, α, 2, 6, 6-tetramethyl-	C₁₁H₂₀O	0.16
25	13.399	α-柏木烯α-cedrene	C₁₅H₂₄	1.31
26	13.539	2-异丙基-5-甲基-9-亚甲基-双环[4.4.0]癸-1-烯bicyclo[4.4.0]dec-1-ene, 2-isopropyl-5-methyl-9- methylene-	C₁₅H₂₄	0.38
27	13.639	罗汉柏烯cis-thujopsene	C₁₅H₂₄	2.22
28	14.249	十四甲基环七硅氧烷cycloheptasiloxane, tetradecamethyl-	C₁₄H₄₂O₇Si₇	1.23
29	14.563	N- (2-氯乙氧基)羰基-异己酯- D-正亮氨酸D-norleucine, N-(2-chloroethoxy)carbonyl-, isohexyl ester	C₁₅H₂₈ClNO₄	1.21
30	14.753	2, 5-二甲基-苯丁酸benzenebutanoic acid, 2, 5-dimethyl-	C₁₂H₁₆O₂	0.39
31	15.173	白檀醇2-buten-1-ol, 2-ethyl-4-(2, 2, 3-trimethyl-3- cyclopenten-1-yl)-	C₁₄H₂₄O	0.55
32	15.536	邻苯二甲酸二乙酯diethyl phthalate	C₁₂H₁₄O₄	1.42
33	15.627	对叔丁基苯乙酸甲酯benzeneacetic acid, 4-(1, 1-dimethylethyl)-, methyl ester	C₁₃H₁₈O₂	15.59
34	15.779	1-(3, 6, 6-三甲基-1, 6, 7, 7a-四氢环戊并[c]吡喃-1-基)乙酮1-(3, 6, 6-trimethyl-1, 6, 7, 7a-tetrahydrocyclopenta[c]pyran-1-yl)ethanone	C₁₃H₁₈O₂	1.26
35	15.981	雪松醇cedrol	C₁₅H₂₆O	1.52
36	16.205	二氢茉莉酮酸甲酯methyl 2-(3-oxo-2-pentylcyclopentyl)acetate	C₁₃H₂₂O₃	1.19
37	16.241	十六甲基环八硅氧烷cyclooctasiloxane, hexadecamethyl-	C₁₆H₄₈O₈Si₈	0.83
38	16.509	水杨酸己酯n-hexyl salicylate	C₁₃H₁₈O₃	0.61
39	17.279	α-己基肉桂醛octanal, 2-(phenylmethylene)-	C₁₅H₂₀O	2.27
40	17.862	6-(1, 1-二甲基硫脲)-苯并噻唑-2(3H)-硫酮benzothiazole-2(3H)-thione, 6-(1, 1-dimethylthioureido)-	C₁₀H₁₁N₃S₃	0.53
41	17.980	十八甲基环壬硅氧烷cyclononasiloxane, octadecamethyl-	C₁₈H₅₄O₉Si₉	0.31
42	18.444	1, 3, 4, 6, 7, 8-六氢-4, 6, 6, 7, 8, 8-六甲基-环戊并[g]-2-苯并吡喃cyclopenta[g]-2-benzopyran, 1, 3, 4, 6, 7, 8-hexahydro- 4, 6, 6, 7, 8, 8-hexamethyl-	C₁₈H₂₆O	1.86
43	19.521	十六甲基八硅氧烷octasiloxane, hexadecamethyl-	C₁₆H₅₀O₇Si₈	0.18
44	19.715	富马酸, 2-辛基十三酸-2-炔-1-酯fumaric acid, 2-octyl tridec-2-yn-1-yl ester	C₂₅H₄₂O₄	0.16
45	20.439	1, 1-二氯-1-硅-2, 3-苯并-4, 5-噻吩并环戊二烯1, 1-dichloro-1-sila-2, 3-benzo-4, 5-thiophenocyclopentadiene	C₁₀H₆Cl₂SSi	12.90
46	20.654	甲基4-羟基硬脂酸酯octadecanoic acid, 4-hydroxy-, methyl ester	C₁₉H₃₈O₃	0.27
47	20.946	十六甲基七硅氧烷heptasiloxane, hexadecamethyl-	C₁₆H₄₈O₆Si₇	0.16
48	21.549	3-乙基-5-(2-乙基丁基)十八烷octadecane, 3-ethyl-5-(2-ethylbutyl)-	C₂₆H₅₄	0.40
49	21.962	(2, 2-二甲基-3-[3, 7, 12-三甲基-14-(1, 4, 4-三甲基环己-2-烯基)十四烷-3, 7, 11-三烯基]环氧乙烷(2, 2-dimethyl-3-[3, 7, 12-trimethyl-14-(1, 4, 4-trimethylcyclohex-2-enyl)tetradeca-3, 7, 11-trienyl]oxirane	C₃₀H₅₀O	0.30
50	22.411	溴代三十烷triacontane, 1-bromo-	C₃₀H₆₁Br	0.50
51	22.658	17α, 21β-28, 30-双降藿烷17α, 21β-28, 30-bisnorhopane	C₂₈H₄₈	0.18
52	22.926	2, 6-二羟基苯乙酮2, 6-dihydroxyacetophenone	C₁₄H₂₄O₃Si₂	0.28
53	23.239	1, 1, 3, 6-四甲基-2-(3, 6, 10, 13, 14-五甲基-3-乙基十五烷基)环己烷1, 1, 3, 6-tetramethyl-2-(3, 6, 10, 13, 14- pentamethyl-3-ethylpentadecyl)cyclohexane	C₃₂H₆₄	0.48
54	24.028	5β-胆甾烷- 3-酮-环1，2-乙二醛cholestan-3-one, cyclic 1, 2-ethanediyl aetal, (5β)-	C₂₉H₅₀O₂	0.50
55	24.798	1, 54-二溴-五十四烷tetrapentacontane, 1, 54-dibromo-	C₅₄H₁₀₈Br₂	0.46
56	25.566	5β-胆甾烷-3-酮乙缩醛5β-cholestan-3-one ethylene acetal	C₂₉H₅₀O₂	0.61
57	26.433	dasycarpidan-1-methanol, acetate	C₂₀H₂₆N₂O₂	0.62
58	27.451	4-乙酰氧亚氨基-6, 6-二甲基-3-甲基磺酰基-4，5，6，7-四氢苯并[c]噻吩-1-羧酸甲酯4-acetyloxyimino-6, 6-dimethyl-3-methylsulfanyl-4, 5, 6, 7-tetrahydro-benzo[c]thiophene-1-carboxylic acid methyl ester	C₁₅H₁₉NO₄S₂	0.58
59	28.623	2-(十六烷氧基)乙酯十八烷酸octadecanoic acid, 2-(hexadecyloxy)ethyl ester	C₃₆H₇₂O₃	0.16

Table 1

Table 2

Types and contents of organics in aerobic treatment effluents"

序号 No.	保留时间/min retention time	化合物 compound	分子式 molecular formula	相对峰面积/% relative peak area
1	7.125	八甲基环四硅氧烷cyclotetrasiloxane, octamethyl-	C₈H₂₄O₄Si₄	0.48
2	7.705	D-柠檬烯D-limonene	C₁₀H₁₆	1.83
3	7.830	苯甲醇benzyl alcohol	C₇H₈O	4.39
4	8.250	α-甲基-苯甲醇benzenemethanol, alpha-methyl-	C₈H₁₀O	1.19
5	8.383	二氢月桂烯醇7-octen-2-ol, 2, 6-dimethyl-	C₁₀H₂₀O	8.90
6	8.863	芳樟醇linalool	C₁₀H₁₈O	21.21
7	9.315	二氢芳樟醇1, 2-dihydrolinalool	C₁₀H₂₀O	0.52
8	9.554	十甲基环五硅氧烷cyclopentasiloxane, decamethyl-	C₁₀H₃₀O₅Si₅	1.01
9	9.618	香茅醛citronellal	C₁₀H₁₈O	2.31
10	9.961	2-叔丁基环己醇cyclohexanol, 2-(1, 1-dimethylethyl)-	C₁₀H₂₀O	4.70
11	10.045	2-叔丁基环己醇cyclohexanol, 2-(1, 1-dimethylethyl)-	C₁₀H₂₀O	1.08
12	10.240	α-松油醇alpha-terpineol	C₁₀H₁₈O	0.52
13	10.337	4-烯丙基苯甲醚estragole	C₁₀H₁₂O	0.33
14	10.724	香茅醇citronellol	C₁₀H₂₀O	4.76
15	10.936	马鞭草烯醇trans-verbenol	C₁₀H₁₆O	2.13
16	11.096	橙花醇cis-3, 7-dimethyl-2, 6-octadien-1-ol	C₁₀H₁₈O	0.39
17	11.345	柠檬醛citral	C₁₀H₁₆O	2.29
18	11.704	顺-2-(1, 1-二甲基乙基)环己醇乙酸酯cyclohexanol, 2-(1, 1-dimethylethyl)-, acetate, cis-	C₁₂H₂₂O₂	3.06
19	12.014	十二甲基环六硅氧烷cyclohexasiloxane, dodecamethyl-	C₁₂H₃₆O₆Si₆	0.77
20	13.406	α-柏木烯(-)-alpha-Cedrene	C₁₅H₂₄	0.23
21	13.639	罗汉柏烯cis-Thujopsene	C₁₅H₂₄	0.32
22	14.250	十四甲基环七硅氧烷cycloheptasiloxane, etradecamethyl-	C₁₄H₄₂O₇Si₇	0.29
23	14.492	2, 2, 2-三氯-1-苯基乙醇2, 2, 2-trichloro-1-phenylethanol	C₈H₇Cl₃O	1.34
24	14.756	铃兰醛lilial	C₁₄H₂₀O	6.16
25	15.231	5, 9-二甲基三环[6.3.0.0(1, 5)]十一烷-4-酮tricyclo[6.3.0.0(1, 5)]undecan-4-one, 5, 9-dimethyl-	C₁₃H₂₀O	0.31
26	15.601	对叔丁基苯乙酸甲酯4-tert phenylacetate	C₁₃H₁₈O₂	21.39
27	15.782	柏木脑cedrol	C₁₅H₂₆O	0.58
28	16.211	二氢茉莉酮酸甲酯cyclopentaneacetic acid, 3-oxo-2-pentyl-, methyl ester	C₁₃H₂₂O₃	3.21
29	16.505	水杨酸正己酯n-hexyl salicylate	C₁₃H₁₈O₃	0.66
30	16.563	2-甲基-3-[4-叔丁基]苯基丙酸propanoic acid, 2-methyl-3-[4-t-butyl]phenyl-	C₁₄H₂₀O₂	0.46
31	17.280	α-己基肉桂醛octanal, 2-(phenylmethylene)-	C₁₅H₂₀O	2.59
32	18.444	1, 3, 4, 6, 7, 8-六氢-4, 6, 6, 7, 8, 8-六甲基-环戊并[g]-2-苯并吡喃cyclopenta[g]-2-benzopyran, 1, 3, 4, 6, 7, 8-hexahydro- 4, 6, 6, 7, 8, 8-hexamethyl-	C₁₈H₂₆O	0.59

Table 2

Fig.1

Fig.2

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Analysis of Aerobic Biological Inhibition Characteristics and Degradation Law of Eucalyptus Chemical Mechanical Pulp Wastewater

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