餐厨垃圾淀粉类代表组分生熟大米中温厌氧发酵产氢性能

杨煜琦; 卓桂华; 王瑛琦; 白雨欣; 陈细妹; 黄雅欣; 刘常青; 甄广印

doi:10.7524/j.issn.0254-6108.2024010304

餐厨垃圾淀粉类代表组分生熟大米中温厌氧发酵产氢性能

1.
福建师范大学，环境与资源学院、碳中和现代产业学院，福建省污染控制与资源循环利用重点实验室，福州，350007
2.
福建省环境科学研究院，福州，350013
3.
福州中城科再生资源利用有限公司，福州，350011
4.
福建师范大学，地理科学学院、碳中和未来技术学院，福州，350007
5.
城市废物资源化技术与管理福建省高校工程研究中心，福州，350007
6.
华东师范大学生态与环境科学学院，上海，200241

通讯作者: E-mail： gyzhen@des.ecnu.edu.cn

基金项目:
福建省科技厅对外合作项目（2021I0010），福建省科技计划项目（2023Y0013）和福建省科技厅计划项目（2020N5015）资助.
中图分类号: X-1; O6

Mesophilic anaerobic fermentative hydrogen production from raw and cooked rice represented starch components of food waste

1.
College of Environmental and Resource Sciences and College of Carbon Neutral Modern Industry, Fujian Key Laboratory of Pollution Control and Resource Reuse, Fujian Normal University, Fuzhou, 350007, China
2.
Fujian Academy of Environmental Sciences, Fuzhou, 350013, China
3.
Fuzhou ZCK Utilization Of Renewable Company Limited, Fuzhou, 350011, China
4.
School of Geographical Sciences and School of Carbon Neutrality Future Technology, Fujian Normal University, Fuzhou, 350007, China
5.
Fujian College and University Engineering Research Center for Municipal Solid Waste Resourceization and Management, Fuzhou, 350007, China
6.
School of Ecological and Environmental Science, East China Normal University, Shanghai, 200241，China

Corresponding author: ZHEN Guangyin, gyzhen@des.ecnu.edu.cn

Fund Project: the Foreign Cooperation Project of Fujian Provincial Department of Science and Technology (2021I0010) ，the Planned Project of Fujian Provincial of Science and Technology (2023Y0013) and the Planned Project of Fujian Provincial Department of Science and Technology (2020N5015).

摘要: 餐厨垃圾中淀粉类组分的性质是影响产氢效率的重要因素. 为探究淀粉类代表组分——大米在生、熟性状下（RR、CR）的产氢效能，本文通过中温批式小瓶试验，研究不同接种比条件下生、熟大米的厌氧发酵混合体系（RR-F、CR-F）产氢及底物变化情况. 结果表明，无论RR-F或CR-F产氢效能均随基质与种泥比(S/I)比的增大而增大，最佳S/I比为1∶1；CR产氢效能更佳，RR-F和CR-F的最大累积产氢量分别为59.62 mL·g⁻¹VS和166.97 mL·g⁻¹VS. 发酵副产物以乙酸和正丁酸为主，属于丁酸型发酵；正丁酸/乙酸比值越大，累积产氢量越大. 发酵过程中，可溶糖、可溶蛋白浓度和pH快速降低，总挥发酸（TVFA）浓度快速增加并逐趋于稳定. Pearson相关性分析表明，累积产氢量主要受可溶糖降解量、乙酸浓度的影响. 蒸煮使CR的可溶糖析出更多，导致CR-F产氢效能明显高于RR-F.
- 餐厨垃圾 /
- 大米 /
- 生熟组分 /
- 厌氧发酵 /
- 产H₂ /
- 碳水化合物 /
- 中温
Abstract: The composition and chemical properties of starch in food waste are important factors affecting its hydrogen productivity during the anaerobic fermentation. In this study, the rice, as a representative component of starch in food waste, was used as substrate before and after being cooked (raw rice, RR vs. cooked rice, CR), and a series of mesophilic batch tests were carried out at different substrate/inoculation (S/I) ratios to investigate the effects of chemical properties of starch on hydrogen production potential. The results showed that the hydrogen production efficiency of both raw and cooked rice increased with S/I ratio, and the optimal S/I ratio was 1:1. Under the optimal condition, the cooked rice gained the highest cumulative hydrogen yield of 166.97 mL·g⁻¹ VS whereas it was only 59.62 mL·g⁻¹ VS for raw rice. The main fermentation by-products were determined to be acetic acid and n-butyric acid, indicating the occurrence of butyric acid-type fermentation; moreover, the higher n-butyrate/acetate ratios, the better hydrogen productivity was observed. Additionally, soluble sugar, soluble protein, and pH level showed a rapid drop tendency during the whole process, while TVFA were accumulated rapidly and became stabilized gradually at the end of operation. Pearson correlation analysis further showed that the cumulative hydrogen yield was mainly governed by the degradation of soluble sugar and the production of acetic acid. It could be concluded that significantly higher hydrogen production from CR than RR was due to the liberation of more soluble sugar in virtue of cooking or steaming process.
- food waste /
- rice /
- raw and cooked components /
- anaerobic fermentation /
- H₂ production /
- carbohydrates /
- mesophilic

图 1 实验装置图

Figure 1. Experimental setup

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图 2 不同S/I对RR-F和CR-F厌氧发酵产氢的影响

Figure 2. Effect of different S/I ratios on cumulative hydrogen yield of RR-F and CR-F

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图 3 RR-F和CR-F指标初始浓度（a）及RR的表面（b）、横截面（d）与CR的表面（c）、横截面（e）的微观结构

Figure 3. Initial concentrations of soluble sugar and soluble protein in RR-F and CR-F （a） and microstructure of surface and cross section of RR （b, and d） and CR （c, and e）

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图 4 RR-F和CR-F厌氧发酵产氢过程中底物（a）可溶糖浓度，（b）可溶蛋白浓度，（c）氨氮浓度的变化

Figure 4. Variation in the concentrations of （a） soluble sugar, （b） soluble protein, and （c） ammonia nitrogen during anaerobic fermentation of RR-F and CR-F

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图 5 厌氧发酵产氢过程中（a）RR-F1、RR-F2、CR-F1、CR-F2中的VFAs变化，（b）正丁酸/乙酸比值的变化，（c）最大累积产氢量和正丁酸/乙酸比值的关系，以及（d）pH 的变化

Figure 5. Variation of VFAs （a） RR-F1, RR-F2, CR-F1, and CR-F2 and n-butyric acid/acetic acid ratio （b） in different operational conditions, （f） the relationship between maximum cumulative hydrogen yield and n-butyric acid/acetic acid ratio, and （g） variation of pH during anaerobic fermentation

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图 6 厌氧发酵过程基础理化指标相关性热图

Figure 6. Correlation matrices of different environmental variables in anaerobic fermentation process

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表 1 大米厌氧发酵产氢的修正Gompertz模型的动力学常数

Table 1. Estimated parameters of modified Gompertz equation for RR-F and CR-F

实验组 Reactor	最大累积产氢量/ $ (\mathrm{m}\mathrm{L}\cdot {\mathrm{g}}^{-1} $ VS） Maximum cumulative hydrogen volume	最大产氢速率/（ $ \mathrm{m}\mathrm{L}\cdot {\mathrm{g}}^{-1} $ VS） Maximum Hydrogen yield	产氢延迟时间/（h） Hydrogen production delay	拟合系数（R²） Fit coefficient
RR-F1	46.540	2.470	33.540	0.979
RR-F2	59.615	2.210	24.690	0.968
CR-F1	116.610	6.890	20.840	0.985
CR-F2	166.970	3.590	24.774	0.997

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餐厨垃圾全球范围产生量已达到13亿t^[1]. 其有机物含量高（VS含量达85%—95%），含水率高（约75%—85%）^[2]. 如果不妥当处理会对环境产生负面影响，甚至直接或间接影响人类的健康. 但另一方面，餐厨垃圾由于富含有机质及营养元素，是理想的厌氧消化基质；通过厌氧消化可产生中间产物，如氢气（H₂）和挥发酸（VFAs）以及末端产物甲烷（CH₄）等，较好地实现资源化利用. 其中，H₂单位重量的热值最大，为142.35 $ \mathrm{k}\mathrm{J}\cdot {\mathrm{g}}^{-1} $，被视为最清洁和最理想的能源载体^{[3 − 4]}. 因此，餐厨垃圾厌氧发酵产氢具有良好的发展前景.

餐厨垃圾组分复杂，主要由淀粉、蛋白质、油脂和纤维素组成^[5]. 不同组分的理化性质不同，产氢性能也不同. 关于餐厨垃圾不同组分厌氧发酵产氢已进行较多研究，淀粉类，如米饭^{[6 − 7]}、土豆^{[6 − 7]}、谷类食品^[8]以及意大利面、面条和面包^[9]等；纤维素类如胡萝卜、卷心菜^[10]、莴苣^[6]、水果果皮^[11]等；蛋白质类如鸡蛋^[8,10,12]、瘦肉^[6]、牛奶^[13]等；油脂类如食用油、肥肉^[6]、鸡皮^[10]等. 餐厨垃圾的组分含量变化是影响产氢效率的重要因素^{[14 − 15]}. 研究发现，餐厨垃圾挥发性固体中碳水化合物含量达到35.5%、脂质24.1%、蛋白质14.4%^[16]，因此餐厨垃圾中主要成分为碳水化合物，对餐厨垃圾产氢起到重要影响作用. 同时，许多研究表明，H₂的产量在很大程度上取决于碳水化合物含量^[17]. Alibardi等^[18]研究了有机物中碳水化合物、蛋白质、脂质对H₂产量、VFAs产量和碳转移途径影响，结果表明，H₂产量与碳水化合物含量呈线性相关，而蛋白及脂质对其影响较小. 餐厨垃圾中，米饭等淀粉类以及果蔬等纤维素类是构成碳水化合物的主要组分. 其中大米是五大主食之一，且是中国南方地区主要主食，因此大米为南方餐厨垃圾中主要淀粉类物质. Kobayashi等^[8]研究发现产氢量与淀粉类浓度呈显著正相关，与纤维素浓度呈负相关. 许多研究表明，对比其他组分（葱^[19]、苹果^[19]、猪肉^[19]、白菜^[20]、鸡蛋^[20]和肥肉^[20]），发现以米饭为基质产氢效果最好^{[6,10,19 − 22]}.

虽然以米饭为基质进行厌氧发酵产氢已进行一定研究，却主要以已加工煮熟的米饭为主. 而在餐厨垃圾组分中，除了熟米饭（CR）外，其实还有因发霉、受潮等原因而丢弃的生米（RR）. 关于以RR为基质进行发酵产氢目前较少见到相关报道，而对比RR、CR产氢效能则更少见到相关报道. 本文以大米作为餐厨垃圾中淀粉类组分的代表，研究了淀粉类代表性组分生、熟性质的产氢潜能和发酵过程中副产物的释放规律. 主要研究内容如下：（1）探究了代表组分的厌氧发酵产氢潜能，对比了大米在生、熟条件下的产氢情况，并确定最佳接种量；（2）对代表组分厌氧发酵产氢过程进行追踪，分析副产物的释放规律和底物的变化情况，确定主要代谢途径和发酵产氢类型.

餐厨垃圾淀粉类代表组分生熟大米中温厌氧发酵产氢性能

通讯作者: E-mail： gyzhen@des.ecnu.edu.cn

Mesophilic anaerobic fermentative hydrogen production from raw and cooked rice represented starch components of food waste

Corresponding author: ZHEN Guangyin, gyzhen@des.ecnu.edu.cn

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餐厨垃圾淀粉类代表组分生熟大米中温厌氧发酵产氢性能

通讯作者: E-mail： gyzhen@des.ecnu.edu.cn

English Abstract

Mesophilic anaerobic fermentative hydrogen production from raw and cooked rice represented starch components of food waste

Corresponding author: ZHEN Guangyin, gyzhen@des.ecnu.edu.cn

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1.1. 实验原料

1.2. 实验方法

1.3. 分析项目与分析方法

2.1. 厌氧发酵产氢效能分析

2.2. 厌氧发酵混合体系主要初始指标分析

2.3. 厌氧发酵过程中底物指标的变化情况

2.3.1. 可溶糖浓度的变化

2.3.2. 可溶蛋白及氨氮浓度的变化

2.3.3. TVFA及VFAs的变化

2.3.4. pH的变化

2.3.5. 相关性分析

目录

餐厨垃圾淀粉类代表组分生熟大米中温厌氧发酵产氢性能

通讯作者: E-mail： gyzhen@des.ecnu.edu.cn

Mesophilic anaerobic fermentative hydrogen production from raw and cooked rice represented starch components of food waste

Corresponding author: ZHEN Guangyin, gyzhen@des.ecnu.edu.cn

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餐厨垃圾淀粉类代表组分生熟大米中温厌氧发酵产氢性能

通讯作者: E-mail： gyzhen@des.ecnu.edu.cn

English Abstract

Mesophilic anaerobic fermentative hydrogen production from raw and cooked rice represented starch components of food waste

Corresponding author: ZHEN Guangyin, gyzhen@des.ecnu.edu.cn

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1.1. 实验原料

1.2. 实验方法

1.3. 分析项目与分析方法

2.1. 厌氧发酵产氢效能分析

2.2. 厌氧发酵混合体系主要初始指标分析

2.3. 厌氧发酵过程中底物指标的变化情况

2.3.1. 可溶糖浓度的变化

2.3.2. 可溶蛋白及氨氮浓度的变化

2.3.3. TVFA及VFAs的变化

2.3.4. pH的变化

2.3.5. 相关性分析

目录