糖蜜发酵工业废液农用的环境安全风险

doi:10.3864/j.issn.0578-1752.2023.03.008

摘要/Abstract

摘要：

糖蜜是甘蔗或甜菜制糖工业的一种副产物。糖蜜发酵工业主要指制糖工业的下游工业中以糖蜜为发酵原料的酒精和酵母等发酵工业。在糖蜜发酵酒精和酵母过程中可产生大量废液（即糖蜜发酵工业废液）。出于对这类糖蜜发酵工业废液的资源化利用考虑，很多产糖国（如巴西、印度和中国等）都有将这类废液以直接土地处置方式用于农作物灌溉施肥或土壤改良。由于糖蜜发酵工业废液属于处理难度大的高浓度有机废水，还属于多种重金属污染废水，随着一些产糖国对糖蜜发酵工业废液的长期农田处置，所引发出土壤-作物-水系生态环境问题也日益暴露。目前，我国部分企业以这类废液为原料生产有机水溶肥料，其产品在水溶肥市场上占一定比重（约占32%），但对这类废液长期农用的环境安全风险研究及其监测数据尚不充足。本文收集了1980年以来国内外公开发表的关于糖蜜发酵工业废液水质污染特征及其农用的环境影响等相关科研文献，通过对相关研究数据调研和综述分析，评估糖蜜发酵工业废液农用的环境安全风险：（1）糖蜜发酵工业废液水质严重超标，且具有生态毒性特征。这类废液含高负荷有机污染物、强酸性、高盐度，并含多种重金属等污染物，除As、Hg、Cd、Pb和Cr等5种重金属外，还含有Mn、Cu、Zn、Ni和Se等，且污染物浓度大多超出《农田灌溉水质标准》（GB 5084—2021）。（2）糖蜜发酵工业废液农用存在农田污染风险。从该类废液农灌的土壤样品中检出Cu、Cd、Cr、Zn、Ni、Mn、Pb和Cl等污染物，其浓度是对照土壤的10—641倍。（3）糖蜜发酵工业废液农用存在农产品安全风险。用该类废液灌溉的作物，如小麦和芥菜籽粒中也检出Cu、Cd、Cr、Zn、Ni、Mn和Pb等污染物，其浓度是对照作物的3—12倍，均已超出FAO/WHO规定的允许限值，且大多超出我国《食品中污染物限量》（GB 2762—2017）标准。鉴于糖蜜发酵工业废液农用存在的环境安全风险，长期使用可能对人类健康产生危害。因此，有必要对以该类废液为原料的有机水溶肥料产品加强质量检测及风险管控，进而为糖蜜发酵工业废液农用提供安全保障。

关键词: 糖蜜, 制糖工业, 酵母工业, 酒精工业, 发酵工业, 发酵工业废液

Abstract:

Sugar molasses is a by-product from sugar industries. The sugar molasses-based fermentation industries mainly refer to the fermentation industries using molasses from sugar mills as raw materials for alcohol or yeast fermentation. A large volume of effluents can be produced in the process of sugar molasses-based alcohol or yeast fermentation. Considering the possibility of resource utilization with such effluents, many sugar-producing countries (such as Brazil, India, and China) use the effluents for crop irrigation and fertilization or soil remediation directly into the farmlands by waste disposal methods. Because the effluents from sugar molasses-based fermentation industries are both high concentration organic wastewater, and heavy metal-polluted wastewater, which are difficult to be treated. With the long-term disposal of such effluents into the farmlands in some sugar-producing countries, the problems about ecological environment pollution in soil-crop-water systems are increasingly exposed. At present, some fertilizer production enterprises in China use such effluents as raw materials to produce organic water-soluble fertilizers (accounting for 32%), but the long-term research and monitoring data about environmental safety risks for agricultural application of the effluents from sugar molasses-based fermentation industries are still lack. This paper collected the relevant scientific research literatures since 1980 on the pollution characteristics of the effluents from sugar molasses-based fermentation industries, and their environmental impacts on agricultural application. Through the investigation and review on the relevant research data, this paper evaluated the environmental safety risks for agricultural application of the effluents from sugar molasses-based fermentation industries: (1) Such effluents were at a risk of seriously exceeding the limits for water quality standards, and a risk of ecotoxicity to plants. For example, such effluents had strong acidity, and high salinity, and contained not only high load organic pollutants, but also several heavy metals including 5 heavy metals (As, Hg, Cd, Pb and Cr), as well as other pollutants (such as Mn, Cu, Zn, Ni and Se, etc.). The concentrations of these pollutants mostly exceeded the limits of the Standards for Irrigation Water Quality (GB 5084—2021). (2) Such effluents for agricultural application were at a risk of farmland pollution. The concentrations of pollutants (such as Cu, Cd, Cr, Zn, Ni, Mn, Pb and Cl) detected from the soil samples irrigated with such effluents were about 10-641 times higher than those in the control soil. (3) Such effluents for agricultural application were at a safety risk of agricultural products. The concentrations of pollutants (such as Cu, Cd, Cr, Zn, Ni, Mn and Pb) detected in the grains of crops (wheat and mustard) irrigated with such effluents were about 3-12 times higher than those in the control crops, in which all the pollutants detected in the crops irrigated with such effluents exceeded both the allowable limits specified by FAO/WHO, but also the Maximum Levels of Contaminants in Food (GB 2762—2017) specified by China. In view of the issue of environmental safety risks for agricultural application of such effluents, therefore, it is necessary to strengthen the quality detection and risk control on the organic water-soluble fertilizer products with such effluents as raw material, to enable the safety of effluent utilization in agriculture.

Key words: sugar molasses, sugar industry, molasses-based yeast industry, molasses-based alcohol industry, sugar molasses-based fermentation industry, effluents from fermentation industry

王小彬, 闫湘, 李秀英, 涂成, 孙兆凯. 糖蜜发酵工业废液农用的环境安全风险[J]. 中国农业科学, 2023, 56(3): 490-507.

WANG XiaoBin, YAN Xiang, LI XiuYing, TU Cheng, SUN ZhaoKai. Environmental Safety Risks in Agricultural Application of Effluents from Sugar Molasses-Based Fermentation Industries[J]. Scientia Agricultura Sinica, 2023, 56(3): 490-507.

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链接本文: https://www.chinaagrisci.com/CN/10.3864/j.issn.0578-1752.2023.03.008

https://www.chinaagrisci.com/CN/Y2023/V56/I3/490

图/表 5

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糖蜜发酵酒精、酵母工艺及其废液排放相关参数"

	制糖工业 Sugar industry	糖蜜发酵酒精工业 Molasses-based alcohol industry	糖蜜发酵酵母工业 Molasses-based yeast industry
主要原料Main raw materials	甘蔗/甜菜Sugarcane/beet	糖蜜Sugar molasses	糖蜜Sugar molasses
生产工艺流程 Production process	甘蔗压榨→蔗汁清洗→蒸发煮糖 →离心分蜜^[21] Sugarcane crushing→cane juice cleaning→evaporation by sugar boiling→molasses separation by centrifugation^[21]	糖蜜发酵(酒曲)→蒸馏^[65] Molasses fermentation (distiller's yeast)→ distillation^[65]	糖蜜预处理→发酵(酵母菌)→分离→浓缩→干燥^[65] Molasses pretreatment→fermentation (yeast)→separation→condensation→ drying^[65]
糖蜜产出率(糖蜜/作物产量) Molasses/crop yield (%)	甘蔗糖蜜约3%-4%^[16] Cane molasses about 3%-4%^[16] 甜菜糖蜜约5%^[17] Beet molasses about 5% ^[17]
糖蜜消耗量 (糖蜜/成品) Molasses consumption (molasses/products)		4.8 t糖蜜/1 t酒精^[6] 4.8 t molasses/1 t alcohol ^[6]	5 t糖蜜/1 t酵母^[26] 5 t molasses/1 t yeast^[26]
废液排放量 (废液/成品) Effluent discharge ( effluent / products)	1 t糖蜜/3 t蔗糖^[3] 1 t molasses/3 t cane sugar^[3]	12-16 t废液/1 t酒精^[4] 12-16 t effluent/1 t alcohol^[4]	60-150 t废液/1 t干酵母^[5] 60-150 t effluent/1 t dry yeast^[5]
废液主要污染特征 Pollution characteristics of molasses-based effluents		高浓度有机物--可生化性差；高浓度硫酸盐--pH低^[16,39] High concentrated organic matter--poor biodegradability; high concentrated sulfate-- low pH^[16,39]	高浓度有机物--可生化性差；高浓度硫酸盐--pH低^[2,64] High concentrated organic matter-- poor biodegradability; high concentrated sulfate--low pH^[2,64]
废液主要处理方法 Main methods for treatment of molasses-based effluents		生化处理/浓缩法等^[16,39] Biochemical treatment /condensation method, etc^[16,39]	生化处理/浓缩法等^[2,64] Biochemical treatment /condensation method, etc^[2,64]
废液主要利用方法 Main methods for utilization of molasses-based effluents	发酵酒精或酵母等^[2,16] Fermented alcohol or yeast, etc^[2,16]	直接农灌法/水溶肥等^[16,39] Direct crop irrigation /water soluble fertilizers, etc^[16,39]	直接农灌法/水溶肥等^[2,64] Direct crop irrigation /water soluble fertilizers, etc^[2,64]
水污染物排放标准 Related discharge standards of water pollutants	制糖工业水污染物排放标准 (GB 21909—2008)^[66] Discharge Standard of Water Pollutants for Sugar Industry (GB 21909—2008)^[66]	发酵酒精和白酒工业水污染物排放标准 (GB 27631—2011) ^[62] Discharge Standard of Water Pollutants for Fermentation Alcohol and Distilled Spirits Industry (GB 27631—2011) ^[62]	酵母工业水污染物排放标准(GB 25462—2010)^[63] Discharge Standard of Water Pollutants for Yeast Industry (GB 25462—2010)^[63]

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项目 Item	糖蜜发酵酒精工业废液 Effluents from alcohol industry		糖蜜发酵酵母工业废液 Effluents from yeast industry		GB 27631— 2011^[62]	GB 25462— 2010^[63]
项目 Item	污染特征 Values	超标倍数 Over-limit multiple	污染特征 Values	超标倍数 Over-limit multiple	GB 27631— 2011^[62]	GB 25462— 2010^[63]
pH	3.0-5.7		3.5-6.0		6-9	6-9
BOD₅(mg·L^-1) ^a)	20000-80000	667-2667	3600-13780	90-345	30	40
COD_Cr(mg·L^-1) ^b)	30000-180000	200-1200	8000-140000	53-933	150	150
SS (mg·L^-1) ^c)	925-6000	19-120	170-5000	2-71	50	70
色度(稀释倍数) Colourity (dilution ratio)	2000-5000	67-167	400-45800	7-763	30	60
氨氮NH₃-N (mg·L^-1)	40-890	4-89	100-1200	7-80	10	15
总氮Total N (mg·L^-1)	500-12800	25-640	120-3000	5-120	20	25
总磷PO₄^3- (mg·L^-1)	10-3800	13-4750	2.4-400	2-400	0.8	1.0
总钾K₂O (mg·L^-1)	1000-25000		3000-7000
硫酸盐SO₄^2- (mg·L^-1)	6400-8000		400-8800
有机物OM (%)	5.5-9.6		8.1-9.2
参考文献Ref.	[39-53]		[32,54-61]

项目 Item	糖蜜发酵酒精工业废液 Effluents from alcohol industry	糖蜜发酵酵母工业废液 Effluents from yeast industry	WHO	GB 5084—2021	GB/T 14848—2017
项目 Item	糖蜜发酵酒精工业废液 Effluents from alcohol industry	糖蜜发酵酵母工业废液 Effluents from yeast industry	WHO	GB 5084—2021	Ⅲ	Ⅳ	Ⅴ
Hg	0-1			≤0.001	≤0.001	≤0.002	>0.002
Cd	0.007-2.37		0.01	≤0.01	≤0.005	≤0.01	>0.01
As	0.0056-0.5		0.1	≤0.05-0.1	≤0.01	≤0.05	>0.05
Pb	0.0056-8.8		5.0	≤0.2	≤0.01	≤0.1	>0.1
Cr	0.01-50.6		0.1	≤0.1(VI)	≤0.05	≤0.1	>0.1
Ni	0.019-5	0.02	0.2	≤0.2	≤0.02	≤0.1	>0.1
Cu	0.05-940	3.2-7.8	0.2	≤0.5-1.0	≤1.0	≤1.5	>1.5
Zn	0.0056-20	10-340	2.0	≤2.0	≤1.0	≤5.0	>5.0
Cl	71-42096	63000-67300	140-350	≤350	≤250	≤350	>350
Na	27-28000	19300-55090	69-207		≤200	≤400	>400
Se	0.0056-0.5	0.2	0.02	≤0.02	≤0.01	≤0.1	>0.1
Mn	3.11-6410	7.97-66.7	0.2		≤0.1	≤1.5	>1.5
酚Phenol	0-10000			1	≤0.002	≤0.01	>0.01
EC(μS·cm^-1)	8294-96000	25500-27600	700-3000
参考文献Ref.	[11,13,39,44,51,70-86]	[87-89]	[90]	[91]		[92]

	Cu	Cd	Cr	Zn	Ni	Mn	Pb	Cl	EC (μS·cm^-1)
污水Distillery effluent^[13] (mg·L^-1)	3.12±0.24	2.37±0.06	3.03±0.21	14.11±1.16	2.24±0.3	5.03±0.92	1.46±0.21	1860±36.85	10760±40
污泥Distillery sluge^[99] (mg·kg^-1)	118.96±2.54	2.05±0.53	8.12±0.18	130.26±8.43	27.20±2.64	88.24±0.44	19.76±0.65	355±59.25	3700±210
水质标准Standard for water quality (mg·L^-1)
WHO^[90]	0.2	0.01	0.1	2.0	0.2	0.2	5.0	140-350	700-3000
GB 5084—2021^[91]	≤0.5-1.0	≤0.01	≤0.1	≤2.0	≤0.2		≤0.2	≤350
土壤Soil (mg·kg^-1) CK (Control)	0.98±0.02	BDL	2.34±0.16	6.72±1.42	1.24±0.03	2.11±0.04	1.08±0.03	104±7.35	2030±10
+污水 Effluent	40.83±2.24	9.90±0.76	313±10.21	143±4.16	42.24±3.31	1352±10.92	30.81±2.21	1014.0±36.65	2490±20
土壤标准Standard for soil quality (mg·kg^-1)
GB 15618—2018^[100]	≤50	≤0.3	≤150	≤200	≤60		≤70	≤200^[101]
农作物籽粒Crop seed (mg·kg^-1)
小麦籽粒Wheat^[13] CK (Control)	1.06±0.03	BDL	1.82±0.22	7.24±2.04	BDL	6.36±2.16	BDL
+污水 Effluent	5.06±0.63	1.06±0.03	8.16±2.05	28.26±3.18	4.12±1.03	18.43±2.16	8.06±1.16
芥菜籽粒Mustard^[13] CK (Control)	1.86±0.19	0.46±0.03	1.26±0.57	8.34±1.83	BDL	12.86±1.72	BDL
+污水 Effluent	5.26±1.23	1.20±0.06	6.26±1.20	28.16±3.06	4.08±0.82	157.3±2.09	7.06±1.18
绿豆Green gram^[99] CK (Control)	7.81±0.24	0.04±0.001	3.21±0.11	24.76±1.06	BDL	2.58±0.05
+20%污泥 Sluge	14.15±0.46	0.62±0.024	9.79±0.42	64.19±2.05	7.00±0.22	16.16±0.50
农产品标准Standard for food (mg·kg^-1)
FAO/WHO^[102]	3.0	0.21	0.02	27.4	1.63	2.0	0.43
GB 2762—2017^[103] 蔬菜/谷物 Vagetable/cereal	≤10^[104]	≤0.05/≤0.2	≤0.5/≤1.0	≤20^[105]	1.0		≤0.2/≤0.2