生物甲烷系统的组分分析与综合评价

doi:10.11949/0438-1157.20201928

摘要/Abstract

摘要：

明确生物甲烷过程中原料、沼液和沼渣的组成与系统的综合评价，在优化生物甲烷系统、减少污染物排放等方面都具有重要意义。研究了牛粪、猪粪、秸秆、餐厨垃圾和鸡粪等五种典型原料的生物甲烷系统，分析原料、沼气、沼液和沼渣的组成，并在此基础上构建了包含绿色度、甲烷产率、沼液沼渣的重金属污染度和潜在生态风险四个方面的生物甲烷系统综合评价体系。研究结果表明：猪粪原料的生物甲烷系统绿色度和甲烷产率最高，分别达到0.222和212 ml·g^-1，但其沼渣的重金属污染度最高；牛粪原料的生物甲烷系统绿色度较高，达到0.200，沼渣的重金属污染度最低，但甲烷产率仅有116 ml·g^-1；秸秆原料的生物甲烷系统沼渣的潜在生态风险最低，沼液的重金属污染度和潜在生态风险较低，但绿色度和甲烷产率偏低；鸡粪原料的生物甲烷系统甲烷产率较高，达到183 ml·g^-1，但沼液的重金属污染度和潜在生态风险都最高，且绿色度较低；餐厨垃圾原料的生物甲烷系统性能最差，绿色度和甲烷产率最低，并且沼渣的潜在生态风险最高。

关键词: 生物甲烷系统, 原料, 沼液和沼渣, 组分分析, 评价

Abstract:

Biomethane system can produce methane from organic wastes, which has developed rapidly in the past twenty years. However, biomethane system has some disadvantages, such as complex raw material source, low utilization rate of organic matter, high output of biogas slurry and biogas residue. Therefore, it is very important to clarify and evaluate the composition of raw materials, biogas slurry and biogas residue during the process of biomethane system, and then optimize the biomethane system and reduce pollutant emissions. In present study, the biomethane system of typical raw materials was established. The component of raw materials, biogas, biogas slurry and biogas residue were analyzed. Moreover, the comprehensive evaluation system of biomethane system with green degree, methane yield, contamination degree of heavy metals and potential ecological risk was constructed. The advantages and disadvantages of the biomethane system with five different raw materials were obtained. The green degree and methane yield were the highest in the biomethane system of swine manure with 0.222 and 212 ml·g^-1, respectively, whereas the contamination degree of heavy metals of biogas residue was the highest. The green degree was 0.200 in the biomethane system of cattle manure, and the contamination degree of heavy metals of biogas residue was the lowest, but the methane yield was only 116 ml·g^-1. The potential ecological risk and contamination degree of heavy metals of biogas slurry were the lowest in the biomethane system of straw, whereas the green degree and methane yield was low. The methane yield was 183 ml·g^-1 in the biomethane system of chicken manure, however the contamination degree of heavy metals and potential ecological risk of biogas slurry were the highest, and the green degree was low. The biomethane system of food waste raw materials has the worst performance, the lowest green degree and methane yield, and the highest potential ecological risk of biogas residue.

Key words: biomethane system, raw materials, slurry and residue, component analysis, evaluation

中图分类号:

S 216.4

柯蓝婷, 王远鹏, 郑艳梅, 李清彪. 生物甲烷系统的组分分析与综合评价[J]. 化工学报, 2021, 72(7): 3801-3813.

KE Lanting, WANG Yuanpeng, ZHENG Yanmei, LI Qingbiao. Component analysis and comprehensive evaluation of biomethane systems[J]. CIESC Journal, 2021, 72(7): 3801-3813.

图/表 12

图1 实验装置示意图

Fig.1 Diagrammatic drawing of experimental equipment

表1 重金属生物毒性系数Tri和背景参考值CRi

Table 1 Toxic response factors and background reference level of heavy metals

重金属	$T r i$	$C R i$ /（沼液）(μg·L^-1)	$C R i$ /（沼渣^[35]）(mg·kg^-1)
As	10	10	15
Cd	30	5	1.0
Cr	2	50	90
Cu	5	1000	50
Hg	40	1	0.25
Pb	5	10	70
Zn	1	1000	175

表1 重金属生物毒性系数Tri和背景参考值CRi

Table 1 Toxic response factors and background reference level of heavy metals

重金属	$T r i$	$C R i$ /（沼液）(μg·L^-1)	$C R i$ /（沼渣^[35]）(mg·kg^-1)
As	10	10	15
Cd	30	5	1.0
Cr	2	50	90
Cu	5	1000	50
Hg	40	1	0.25
Pb	5	10	70
Zn	1	1000	175

表2 生物甲烷系统中各组分的背景参考值ciR

Table 2 Background reference level of component in biomethane system

组分	$c i R$ （沼液）/(mg·L^-1)	$c i R$ （沼渣）/(mg·kg^-1)
As	0.5	40
Cd	0.1	1.0
Cr	1.5	300
Cu	2	400
Hg	0.05	1.5
Pb	1	500
Zn	5	500
COD	500	—
NH₄⁺-N	25	—
PO₄^3-	1	—

表2 生物甲烷系统中各组分的背景参考值ciR

Table 2 Background reference level of component in biomethane system

组分	$c i R$ （沼液）/(mg·L^-1)	$c i R$ （沼渣）/(mg·kg^-1)
As	0.5	40
Cd	0.1	1.0
Cr	1.5	300
Cu	2	400
Hg	0.05	1.5
Pb	1	500
Zn	5	500
COD	500	—
NH₄⁺-N	25	—
PO₄^3-	1	—

表3 五种原料生物甲烷系统的基本运行情况

Table 3 Basic parameters of biomethane systems from five substrates

运行参数	牛粪	猪粪	秸秆	餐厨垃圾	鸡粪
原料质量/g	22.30	24.81	5.20	22.19	23.32
TS含量/%	28.14	25.01	92.03	20.67	25.16
VS含量/%	17.94	16.12	76.85	18.03	17.15
初始TS质量/g	6.28	6.20	4.79	4.59	5.87
初始VS质量/g	4.00	4.00	4.00	4.00	4.00
反应后TS质量/g	3.51	3.03	2.82	2.69	3.05
TS移除率/%	44.11	51.13	41.13	41.39	48.04
反应体积/L	0.20	0.20	0.20	0.20	0.20

图2 五种原料生物甲烷系统的沼气和甲烷产率

Fig.2 Biogas and methane yield of biomethane systems from five substrates

图3 五种典型生物质原料生物甲烷系统沼液的COD（a）、多糖（b）、氨氮（c）和磷酸根浓度（d）

Fig.3 COD (a), polysaccharide (b), NH4+-N (c) and PO43- (d) concentration of slurry from biomethane systems of five substrates

图4 五种原料生物甲烷系统的原料及沼渣中可溶性组分、半纤维素、纤维素、木质素和灰分含量

Fig.4 Solute, hemicellulose, cellulose, lignin and ash content of raw material and residue from biomethane systems of five substrates

图5 五种原料生物甲烷系统原料和沼渣中碳含量（a）、氮含量（b）、硫含量（c）、氢含量（d）、碳氮比（e）和碳氢比（f）

Fig.5 C content (a), N content (b), S content (c), H content (d), C∶N (e) and C∶H (f) of raw material and residue from biomethane systems of five substrates

表4 五种原料生物甲烷系统的重金属含量

Table 4 Heavy metals content of biomethane systems from five substrates

重金属种类	浓度分布	牛粪	猪粪	秸秆	餐厨垃圾	鸡粪
As	原料浓度/(mg·kg^-1)	0.516±0.061	0.773±0.088	0.412±0.056	0.498±0.084	0.731±0.013
	沼液浓度/(μg·L^-1)	3.460±0.358	9.739±0.401	3.904±0.258	3.848±0.100	16.336±0.996
	沼渣浓度/(mg·kg^-1)	0.617±0.056	0.713±0.077	0.541±0.023	1.003±0.091	0.263±0.027
Cd	原料浓度/(mg·kg^-1)	0.135±0.004	0.287±0.066	0.239±0..018	0.094±0.008	0.201±0.009
	沼液浓度/(μg·L^-1)	0.590±0.029	0.332±0.050	0.162±0.017	0.559±0.057	1.106±0.098
	沼渣浓度/(mg·kg^-1)	0.421±0.050	0.278±0.008	0.376±0.051	0.288±0.062	0.478±0.010
Cr	原料浓度/(mg·kg^-1)	5.240±0.098	10.329±0.935	3.049±0.122	2.926±0.435	1.020±0.313
	沼液浓度/(μg·L^-1)	26.466±4.773	15.157±0.589	17.052±0.846	27.126±0.939	54.288±5.010
	沼渣浓度/(mg·kg^-1)	3.528±0.077	6.546±0.883	6.927±0.601	2.104±0.624	3.550±0.269
Cu	原料浓度/(mg·kg^-1)	25.427±0.925	65.325±6.034	36.164±2.090	15.185±0.751	52.814±5.689
	沼液浓度/(μg·L^-1)	102.554±8.971	59.666±6.817	28.726±2.851	45.549±2.013	178.156±8.678
	沼渣浓度/(mg·kg^-1)	64.140±6.192	110.277±8.713	71.441±6.191	24.857±0.844	78.480±4.647
Hg	原料浓度/(mg·kg^-1)	0.124±0.019	0.059±0.002	0.048±0.003	0.327±0.057	0.028±0.002
	沼液浓度/(μg·L^-1)	0.236±0.008	0.004±0.000	0.193±0.015	0.117±0.007	0.506±0.041
	沼渣浓度/(mg·kg^-1)	0.179±0.009	0.146±0.014	0.030±0.002	0.835±0.053	0.228±0.015
Pb	原料浓度/(mg·kg^-1)	0.519±0.061	0.647±0.084	0.419±0.041	0.248±0.012	0.211±0.040
	沼液浓度/(μg·L^-1)	3.420±0.074	1.090±0.082	1.736±0.093	1.311±0.082	1.999±0.080
	沼渣浓度/(mg·kg^-1)	1.094±0.053	0.987±0.069	0.734±0.031	0.411±0.034	0.500±0.039
Zn	原料浓度/(mg·kg^-1)	173.933±9.156	284.267±18.677	238.230±19.560	54.942±4.733	212.408±11.427
	沼液浓度/(μg·L^-1)	410.492±30.889	172.310±5.965	154.432±9.269	246.271±8.343	497.088±28.334
	沼渣浓度/(mg·kg^-1)	246.751±14.917	500.338±47.739	463.365±13.419	118.443±7.612	357.921±20.907

表4 五种原料生物甲烷系统的重金属含量

Table 4 Heavy metals content of biomethane systems from five substrates

重金属种类	浓度分布	牛粪	猪粪	秸秆	餐厨垃圾	鸡粪
As	原料浓度/(mg·kg^-1)	0.516±0.061	0.773±0.088	0.412±0.056	0.498±0.084	0.731±0.013
	沼液浓度/(μg·L^-1)	3.460±0.358	9.739±0.401	3.904±0.258	3.848±0.100	16.336±0.996
	沼渣浓度/(mg·kg^-1)	0.617±0.056	0.713±0.077	0.541±0.023	1.003±0.091	0.263±0.027
Cd	原料浓度/(mg·kg^-1)	0.135±0.004	0.287±0.066	0.239±0..018	0.094±0.008	0.201±0.009
	沼液浓度/(μg·L^-1)	0.590±0.029	0.332±0.050	0.162±0.017	0.559±0.057	1.106±0.098
	沼渣浓度/(mg·kg^-1)	0.421±0.050	0.278±0.008	0.376±0.051	0.288±0.062	0.478±0.010
Cr	原料浓度/(mg·kg^-1)	5.240±0.098	10.329±0.935	3.049±0.122	2.926±0.435	1.020±0.313
	沼液浓度/(μg·L^-1)	26.466±4.773	15.157±0.589	17.052±0.846	27.126±0.939	54.288±5.010
	沼渣浓度/(mg·kg^-1)	3.528±0.077	6.546±0.883	6.927±0.601	2.104±0.624	3.550±0.269
Cu	原料浓度/(mg·kg^-1)	25.427±0.925	65.325±6.034	36.164±2.090	15.185±0.751	52.814±5.689
	沼液浓度/(μg·L^-1)	102.554±8.971	59.666±6.817	28.726±2.851	45.549±2.013	178.156±8.678
	沼渣浓度/(mg·kg^-1)	64.140±6.192	110.277±8.713	71.441±6.191	24.857±0.844	78.480±4.647
Hg	原料浓度/(mg·kg^-1)	0.124±0.019	0.059±0.002	0.048±0.003	0.327±0.057	0.028±0.002
	沼液浓度/(μg·L^-1)	0.236±0.008	0.004±0.000	0.193±0.015	0.117±0.007	0.506±0.041
	沼渣浓度/(mg·kg^-1)	0.179±0.009	0.146±0.014	0.030±0.002	0.835±0.053	0.228±0.015
Pb	原料浓度/(mg·kg^-1)	0.519±0.061	0.647±0.084	0.419±0.041	0.248±0.012	0.211±0.040
	沼液浓度/(μg·L^-1)	3.420±0.074	1.090±0.082	1.736±0.093	1.311±0.082	1.999±0.080
	沼渣浓度/(mg·kg^-1)	1.094±0.053	0.987±0.069	0.734±0.031	0.411±0.034	0.500±0.039
Zn	原料浓度/(mg·kg^-1)	173.933±9.156	284.267±18.677	238.230±19.560	54.942±4.733	212.408±11.427
	沼液浓度/(μg·L^-1)	410.492±30.889	172.310±5.965	154.432±9.269	246.271±8.343	497.088±28.334
	沼渣浓度/(mg·kg^-1)	246.751±14.917	500.338±47.739	463.365±13.419	118.443±7.612	357.921±20.907

图6 五种原料生物甲烷系统碳（a）、氮（b）、磷（c）的物料平衡

Fig.6 C (a), N (b) and P (c) mass balance of biomethane systems from five substrates

图7 五种原料生物甲烷系统绿色度（a）、甲烷产率（b）、沼液沼渣重金属污染度（c）和沼液沼渣潜在生态风险情况（d）

Fig.7 Green degree (a), methane yield (b), contamination degree (c) and risk indices (d) of biomethane systems from five substrates

表5 五种原料生物甲烷系统绿色度情况

Table 5 Green degree of biomethane systems from five substrates

Raw materials	$G D k 1 s, i n$		$G D k 2 e$	$G D k 3 s, o u t$					$Δ G D u$
	EUP	ECP		GWP	EUP		ECP
	EUP	ECP		GWP	Slurry	Residue	Slurry	Residue
CAM	-0.24382	-0.16872	-0.00741	-0.00287	-0.04395	-0.05687	-0.00036	-0.10063	0.20044
SM	-0.20177	-0.28099	-0.00603	-0.00436	-0.07127	-0.05886	-0.00021	-0.12024	0.22180
St	-0.11954	-0.16757	-0.00713	-0.00359	-0.05011	-0.05375	-0.00015	-0.10172	0.07066
KW	-0.15366	-0.09018	-0.00805	-0.00256	-0.16480	-0.04585	-0.00023	-0.07413	-0.05178
CHM	-0.24622	-0.19075	-0.00644	-0.00404	-0.15710	-0.05133	-0.00059	-0.11157	0.10590

表5 五种原料生物甲烷系统绿色度情况

Table 5 Green degree of biomethane systems from five substrates

Raw materials	$G D k 1 s, i n$		$G D k 2 e$	$G D k 3 s, o u t$					$Δ G D u$
	EUP	ECP		GWP	EUP		ECP
	EUP	ECP		GWP	Slurry	Residue	Slurry	Residue
CAM	-0.24382	-0.16872	-0.00741	-0.00287	-0.04395	-0.05687	-0.00036	-0.10063	0.20044
SM	-0.20177	-0.28099	-0.00603	-0.00436	-0.07127	-0.05886	-0.00021	-0.12024	0.22180
St	-0.11954	-0.16757	-0.00713	-0.00359	-0.05011	-0.05375	-0.00015	-0.10172	0.07066
KW	-0.15366	-0.09018	-0.00805	-0.00256	-0.16480	-0.04585	-0.00023	-0.07413	-0.05178
CHM	-0.24622	-0.19075	-0.00644	-0.00404	-0.15710	-0.05133	-0.00059	-0.11157	0.10590

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