抗生素菌渣水熱催化產油及其特性

鄭子軒; 洪晨; 李再興; 邢奕; 李益飛; 楊健; 秦巖; 趙秀梅

doi:10.13374/j.issn2095-9389.2020.09.17.003

抗生素菌渣水熱催化產油及其特性

doi: 10.13374/j.issn2095-9389.2020.09.17.003

鄭子軒¹,
洪晨^1, ,,
李再興²,
邢奕^1, ,,
李益飛¹,
楊健¹,
秦巖³,
趙秀梅⁴

1.
北京科技大學能源與環境工程學院，北京100083
2.
河北科技大學環境科學與工程學院，石家莊 050018
3.
山西大學環境與資源學院，太原 030006
4.
華北制藥集團有限責任公司，石家莊 050015

基金項目: 中央高校基本科研業務費資助項目（FRF-TP-20-010A2）

詳細信息

通訊作者:
洪晨，E-mail: hongchen000@126.com

邢奕，E-mail: xingyi@ustb.edu.cn

中圖分類號: X799.5
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- 文章訪問數: 498
- HTML全文瀏覽量: 341
- PDF下載量: 32
- 被引次數: 0
出版歷程
- 收稿日期: 2020-09-17
- 網絡出版日期: 2021-01-28
- 刊出日期: 2022-01-01

Preparation and properties of bio-oil from the antibiotic residue by hydrothermal liquefaction

1.
School of Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.
School of Environmental Science and Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China
3.
College of Environment and Resources, Shanxi University, Taiyuan 030006, China
4.
North China Pharmaceutical Co., Ltd., Shijiazhuang 050015, China

More Information

Corresponding author: HONG Chen, E-mail: hongchen000@126.com; XING Yi, E-mail: xingyi@ustb.edu.cn

摘要

摘要: 探究了菌渣的水熱液化轉換成生物油燃料的過程。結果表明，抗生素菌渣在260 ℃、保留時間是135 min時，獲得最大的生物油產率（28.01%）。通過6種不同的催化劑進行催化，加入催化劑后，生物油產率最大的是Na₂CO₃（36.06%）和NaOH（36.31%）。堿催化的生物油的含氮化合物的質量分數在41.16%～49.74%之間，而酸催化產生的生物油含氮化合物的量在57.62%～59.32%之間。通過調節催化劑Na₂CO₃、NaOH的添加量發現，在投加量為8%時，生物油含氮量均最低，Na₂CO₃和NaOH催化產生的生物油組分的含氮化合物質量分數分別為29.12%和35.67%。在催化劑投加量為10%時，對氧的脫除效果都最好，分別為32.12%和29.02%，此時產生的生物油的熱值達到最大（達到33.3220和34.7320 MJ?kg^?1）。
- 抗生素菌渣 /
- 再生能源 /
- 燃料 /
- 催化劑 /
- 水熱液化
Abstract: Antibiotic residue, a kind of biomass, is classified as hazardous waste. However, it is considered a good biomass resource because it contains rich organic matter and bacterial protein with a calorific value equivalent to that of low-rank coal. The hydrothermal method uses high-temperature liquid water as the reaction medium and reactant, which has the characteristics of high energy, fast reaction speed, large material flux, convenient feeding, and high product separation efficiency, especially avoiding the evaporation of high water content of aquatic substances. Although bio-oil obtained from the noncatalytic hydrothermal process has a high calorific value, it exhibits negative characteristics, such as high oxygen and nitrogen and high viscosity, which makes it unsuitable for use as a fuel. Therefore, catalysts are needed to improve the quality of bio-oil. This paper investigates the hydrothermal liquefaction of bacterial residues into bio-oil under a retention time of 30–240 min at 220–300 °C. Results show that the maximum yield of bio-oil is 28.01% at 260 °C for 135 min. Catalyzed by six kinds of catalysts (HCOOH, CH₃COOH, K₂CO₃, Na₂CO₃, NaOH, and KOH), the highest yield of bio-oil is achieved with Na₂CO₃ (36.06%) and NaOH (36.31%). The content of hydrocarbons and their derivatives in the produced bio-oil is found to be relatively low at varying amounts of Na₂CO₃ and NaOH catalysts. The mass fraction of nitrogen-containing compounds in the alkali-catalyzed and acid-catalyzed bio-oil is 41.16%–49.74% and 57.62%–59.32%, respectively, with the best nitrogen removal obtained at a mass dosage of 8%. In particular, the contents of nitrogen compounds in the bio-oil catalyzed by Na₂CO₃ and NaOH are 29.12% and 35.67%, respectively. The best removal effect of oxygen is achieved at a dosage of 10%. Specifically, bio-oil components produced by Na₂CO₃ and NaOH contains 32.12% and 29.02% oxygen-containing compounds, respectively. Moreover, the higher heating value (HHV) of bio-oil produced with these catalysts is the largest, with an HHV of 33.3220 and 34.7320 MJ?kg^?1 for Na₂CO₃ and NaOH, respectively.
- antibiotic residue /
- renewable energy /
- fuel /
- catalyst /
- hydrothermal liquefaction

HTML全文

圖 1 水熱反應產物收集路線圖

Figure 1. Collection route of hydrothermal reaction products

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圖 2 不同產物產率隨反應溫度的變化。（a）生物油產率；（b）固體殘渣產率；（c）水相產物產率；（d）生物氣產率

Figure 2. Yield change of different products with temperature: (a) yield of bio-oil ; (b) yield of solid residue; (c) yield of aqueous products; (d) yield of biogas

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圖 3 產物產率隨停留時間的變化。（a）生物油產率；（b）固體殘渣產率；（c）水相產物產率；（d）生物氣產率

Figure 3. Change of product yield with residence time: (a) yield of bio-oil; (b) yield of solid residue; (c) yield of aqueous products; (d) yield of biogas

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表 1 抗生素菌渣元素、工業分析（質量分數）

Table 1. Elemental and industrial analysis of antibiotic residue %

Industrial analysis				Elemental analysis
Volatile matter	Fixed carbon	Ash	Water	C	H	N	S	O^*
75.26	8.51	7.32	8.91	47.38	6.62	6.26	0.81	36.02
Note: * is obtained by difference calculation method.

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表 2 不同均相催化劑生物油產率對比

Table 2. Comparison of the bio-oil yield of different homogeneous catalysts %

Catalyst	Bio-oil production rate	Solid production rate	Liquid production rate	Gas production rate
None	28.01	26.38	18.83	27.08
HCOOH	24.31	27.86	18.93	26.90
CH₃COOH	23.31	28.04	21.22	27.43
Na₂CO₃	36.06	21.52	22.19	20.23
NaOH	36.31	25.48	22.45	23.16
K₂CO₃	29.05	24.89	22.32	24.14
KOH	29.01	24.91	22.12	23.96

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表 3 不同催化劑催化生物油氣相色譜?質譜分析

Table 3. GC/MS analysis of bio-oil catalyzed by different catalysts

No.	Retention time/min	Composition	Peak area/%
No.	Retention time/min	Composition	None	HCOOH	CH₃COOH	Na₂CO₃	K₂CO₃	NaOH	KOH
1	2.513	2-methoxy-1-3-phenylmethoxy-benzene	1.27	2.80	3.21	—	—	—	—
2	2.748	glycine	1.12	12.18	12.79	—	—	—	—
3	3.52	2,2-dimethoxybutane	1.19	2.39	5.19	—	—	—	—
4	4.236	2,4-azacyclobutanedione	2.97	9.35	6.71	—	26.79	1.82	14.36
5	5.213	Trione trioxide	7.72	6.32	3.12	5.61	—	0.59	—
6	9.242	Carbamate	—	5.67	4.16	3.05	2.73	1.66	2.56
7	15.707	Tri butyl acrylonitrile	7.12	3.18	2.19	4.07	—	1.73	—
8	17.166	Dihydromannitol	9.12	—	—	3.17	—	2.46	—
9	18.301	4-ethyl-phenol	2.19	—	—	—	—	1.50	—
10	20.072	1-isocyano-2-methyl-benzene	1.21	3.37	—	4.55	2.15	2.28	1.65
11	23.096	5-methyl-indole	6.19	3.37	5.72	9.76	5.02	2.35	1.53
12	24.21	1,2,3-triazole-4-amino-formamide	2.12	3.04	6.12	—	—	—	—
13	25.599	1,4-anhydrous-mannitol	—	—	—	—	—	3.84%	—
14	26.078	2-acrylic acid-3-methylamino-methyl ester	2.19	—	—	—	2.06	—	2.22
15	28.349	Syringol	1.86	—	—	—	—	4.38	—
16	30.191	l-tryptophan-dinitrophenyl	4.31	—	—	—	—	2.96	—
17	35.851	2,5-dione-3,6-diisopropylpiperazin	2.12	3.54	6.01	—	4.44	1.72	—
18	38.203	1,4-dione hexahydro-3-pyrrolo	3.32	—	—	—	—	2.87	—
19	39.106	1-methyl-pyrido	19.32	5.11	3.79	16.20	6.65	9.21	5.23
20	40.718	2,5-piperazinodione 3,6-bismethylpropyl	9.32	1.21	2.10	9.27	5.37	3.46	6.31
21	42.291	6-methyl-octadecane	—	—	—	—	8.75	11.49	—
22	42.966	9,12-hexadecaneate ethyl	2.12	—	12.01	—	9.48	—	20.98
23	44.006	9,12-octadecadiene ester	1.27	9.32	7.31	3.69	9.36	2.32	1.39
24	44.094	Actinomycin	0.79	0.97	0.76	0.91	0.36	0.29	0.67
25	44.239	1-heptyne-1-alcohol	1.36	—	—	—	—	12.56	—
26	44.762	Cyclopentanone	21.19	19.04	19.56	11.88	15.87	16.54	11.78
27	45.797	9,12-octadecadienoic acid	1.21	5.60	7.21	—	—	—	11.51
28	46.322	Ethyl linoleate	2.12	—	1.27	—	—	—	8.95
29	46.871	Lauramide	—	—	7.88	—	—	—	—
30	48.412	l-phenyl-cyclo	0.01	4.97	1.29	—	—	—	—
31	48.763	Methyl-1-octadecylamine	0.19	—	5.07	—	—	—	—
32	49.486	l-phenylalanyl-cyclo	—	0.64	5.32	—	—	—	—
33	50.573	6,9-pentadecadiene-alcohol	—	9.98	9.29	11.78	16.06	3.51	9.23

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表 4 不同催化劑催化產生生物油元素分析（質量分數）

Table 4. Analysis of bio-oil elements produced by different catalysts %

Catalyst	C	H	N	S	O	High heating value/ （MJ?kg^?1）
None	65.19	8.06	9.19	1.06	12.96	30.1230
HCOOH	72.212	8.68	8.71	1.47	10.12	31.0229
CH₃COOH	72.103	8.61	8.67	1.40	10.32	31.0010
Na₂CO₃	74.16	8.77	6.88	1.18	9.01	33.3210
NaOH	73.14	8.73	6.97	1.24	9.27	34.7390
K₂CO₃	73.19	8.74	7.01	1.22	9.97	32.2920
KOH	73.12	8.76	7.06	1.36	9.91	32.1980

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表 5 Na₂CO₃不同梯度生物油成分分析（質量分數）

Table 5. Composition analysis of bio-oil with different gradients of Na₂CO₃

No.	Retention time/min	Composition	Peak area/%
No.	Retention time/min	Composition	0%	1%	3%	5%	8%	10%
1	3.517	2,2-dimethoxybutane	—	—	21.85	4.13	—	—
2	5.224	Trione trioxide	7.72	—	—	—	—	5.61
3	9.235	Methyl carbamate butyl ester	1.19	1.70	2.39	1.98	4.19	3.05
4	12.481	Methyl carbamate	1.97	—	2.41	2.04	—	—
5	15.69	Tri butyl acrylonitrile	7.12	1.87	—	5.86	—	4.07
6	17.189	Dihydromannitol	4.12	—	—	—	—	3.17
7	18.3	4-ethyl-Phenol	1.12	0.98	—	2.81	—	—
8	20.067	1-isocyano-2-methyl-Benzene	—	—	4.73	1.95	2.44	4.55
9	23.1	5-methyl-indole	1.19	2.28	—	4.59	3.71	4.73
10	25.477	alanine	7.12	—	—	3.00	—	—
11	26.081	2-acrylic acid,3dimethyl-ester	3.12	4.82	—	1.46	—	—
12	26.099	1-ethyl-indole	6.27	—	—	—	—	5.03
13	28.355	Syringol	9.20	—	—	4.90	—	—
14	35.853	2,5-dione,3,6-diisopropylpiperazin	2.12	2.79	3.16	7.32	—	—
15	39.112	1-methyl-9- pyrido-indole	19.71	8.92	5.41	12.30	7.16	16.20
16	40.704	3,6methyl propyl piperazinodione	9.32	—	4.14	—	3.04	16.66
17	42.458	Ethyl hexadecanoate	—	—	10.18	—	—	—
18	44.043	Deoxyspermidine guanidin	—	—	4.85	—	—	—
19	44.094	Actinomycin	—	—	—	—	—	0.67
20	44.753	Cyclopentanone	21.19	13.28	9.15	14.85	28.69	11.88
21	45.733	9,12-octadecadienoic acid	7.21	—	18.82	—	—	—
22	48.638	2-amino-5carboxyl-imidazole	2.12	8.29	—	7.55	—	—
23	48.726	1-methyl-octadecylamine	0.72	—	—	—	17.32	—
24	49.783	Pyrrolo pyrazine	3.27	—	—	14.10	—	—
25	50.57	6,9-pentadecadiene-1-alcohol	0.02	15.07	12.91	—	23.46	11.78

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表 6 NaOH不同梯度生物油成分分析（質量分數）

Table 6. Composition analysis of bio-oil with different gradients of NaOH

No.	Retention time /min	Composition	Peak area/%
No.	Retention time /min	Composition	0%	1%	3%	5%	8%	10%
1	3.521	2,2-dimethoxybutane	1.19	7.22	—	—	—	—
2	4.245	3-diethyl-2,4-azacyclobutanedione	—	—	—	0.37	—	1.82
3	5.229	Trione trioxide	7.72	0.55	—	—	—	0.59
4	9.238	butyl methyl phenyl ester	1.97	1.75	2.86	1.89	2.01	1.66
5	9.843	2-phenylpentan-3-isopropyl-alcohol	—	1.22	—	—	—	—
6	12.484	Methyl carbamate	1.97	2.23	—	—	—	—
7	15.693	Tri butyl acrylonitrile	7.12	2.91	5.17	2.95	2.03	1.73
8	16.689	Amino propanol	—	—	—	2.50	—	—
9	17.169	Dihydromannitol	2.12	—	—	—	1.92	2.46
10	17.665	1,6-dicarboxylic acid-pyrido imidazole	—	—	—	0.76	—	—
11	18.296	4-ethyl-Phenol	1.20	1.93	—	3.12	2.21	1.50
12	20.066	1-isocyano-2-methyl-benzene	1.12	—	6.08	—	—	2.28
13	23.105	5-methyl-indole	6.19	2.75	3.60	9.09	1.26	2.35
14	25.472	alanine	7.12	—	—	5.91	—	—
15	25.599	1,4-anhydrous-mannitol	3.12	—	—	—	—	3.84
16	26.076	2-acrylic acid,3-methylamino-ester	—	3.24	4.68	—	—	—
17	27.035	isopropyl-3-phenylpropanamide	—	1.28	—	2.28	1.29	1.32
18	28.355	Syringol	7.21	—	—	0.93	2.91	4.38
19	29.266	2,7-dimethyl-indolizine	—	—	—	2.18	—	—
20	30.191	N-dinitrophenyl-l-tryptophan	—	—	—	—	—	2.96
21	32.682	6-ethyl-2,3-dimethyl pyridine	—	—	—	3.99	—	—
22	32.69	2triazine-3-keone	—	—	—	—	2.37	—
23	38.203	1,4-dionePyrrolo pyrazine	—	—	—	—	—	2.87
24	38.29	2,5-dione,3,6-diisopropyl piperazin	2.12	5.45	3.27	5.42	3.76	1.72
25	39.089	1-methyl-indole	19.71	9.22	6.82	7.10	7.93	9.21
26	40.711	2,5-piperazinodione, 3,6-bis (2-methylpropyl-	9.32	—	9.61	4.88	3.52	3.46
27	41.719	1-methyl-indole	—	—	—	—	5.10	—
28	42.291	6-methyl-octadecane	—	—	—	—	—	11.49
29	44.006	Deoxyspermidine guanidin	—	—	10.98	4.72	—	—
30	44.239	1-heptyne-alcohol	—	—	—	—	—	12.56
31	44.791	Cyclopentanone, oxime	6.06	13.29	11.77	13.08	21.76	16.54
32	45.724	9,12-octadecadienoic acid	—	—	—	—	13.08	—
33	45.755	linoleic acid	7.21	—	—	9.40	—	—
34	45.758	1-alcohol-tetradece	0.87	—	14.18	—	—	—
35	48.679	2-amino-imidazole	2.12	5.75	—	9.46	—	—
36	48.731	1-octadecylamine	0.72	—	—	—	12.53	—
37	49.495	Cyclo-(1-leucyl-l-phenylalanyl)	—	11.21	20.98	5.01	—	—
38	50.581	1-alcohol-pentadecadiene	0.02	—	—	4.05	14.89	3.51

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表 7 兩均相催化劑不同投加量元素分析結果（質量分數）

Table 7. Element analysis results of different dosage of two homogeneous catalysts %

Catalyst	Catalyst dosage	C	H	N	S	O	High heating value/ （MJ?kg^?1）
None	0	65.19	8.06	9.19	1.06	12.96	30.1290
Na₂CO₃	1	71.48	8.68	6.29	1.25	12.30	31.9690
	3	72.28	8.66	7.07	1.29	10.71	32.3950
	5	72.39	8.57	7.15	1.21	10.68	32.3390
	8	73.64	8.38	6.83	1.23	9.93	32.6510
	10	74.16	8.77	6.88	1.18	9.01	33.3220
NaOH	1	72.46	8.65	7.01	1.36	10.52	34.4750
	3	72.22	8.72	7.19	1.31	10.57	34.4690
	5	68.12	8.60	6.45	1.03	15.80	33.5620
	8	70.75	8.86	6.11	0.89	13.39	34.4700
	10	73.14	8.73	6.97	1.24	9.27	34.7320

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