白酒企业锅底水、窖底水厌氧消化及沼气回收的特性研究
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作者注意到，在当前整体上对中小型白酒企业高浓度有机废水的性 质、处理方法和厌氧产甲烷回收利用缺乏研究的同时，更缺乏针对不同 香型的酒厂因工艺过程的差异而引起废水性质的个性差异以及在废水处 理方面应采用的优化措施的实验研究，本文在介绍酱香型白酒和清香型 白酒的生产工艺、废水来源及其性质特点的基础上，对二者的厌氧产甲 烷特点进行了比较研究，筛选出酱香型白酒废水和清香型白酒废水厌氧 处理的最优操作条件，并对其进行了对比分析，说明造成不同处理效果 的原因，并提出优化的处理工艺，为白酒废水的处理提供实验依据。
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本学位论文作者完全了解我校有关保留、使用学位论文的规定，
即：我校有权保留并向国家有关部门或机构送交论文的复印件和电子
版，允许论文被查阅。本人授权武汉工程大学研究生处可以将本学位
论文的全部或部分内容编入有关数据库进行检索，可以采用影印、缩
印或扫描等复制手段保存和汇编本学位论文。
研究工作选用贵州省仁怀市茅台镇某小型酱香型白酒企业和大冶市 某中型清香型白酒企业的锅底水与窖底水及此两种废水的的混合液分别 进行了条件试验和对比分析，分析了酱香型白酒废水和清香型白酒废水 厌氧发酵回收沼气的差异。实验结果表明，中小型酱香型白酒企业，无 论是中温厌氧还是高温厌氧，锅底水单独处理效果均优于窖底水单独处 理；高温条件厌氧效果普遍好于中温；在单独厌氧处理的高温条件、中 温条件下，酱香型白酒锅底水处理效果优于清香型白酒，酱香型白酒窖 底水的处理效果也优于清香型白酒；酱香型白酒两种废水的混合样处理 效果优于单一废水的处理，锅底水与窖底水体积比为 5：1 时、进水 COD
I
武汉工程大学硕士学位论文
浓度调整为 24000mg/L 时，COD 去除效果最佳，厌氧产甲烷达最佳境况； 清香型白酒废水，锅底水与窖底水体积比为 5：1，进水 COD 为 22000mg/L 达最优处理效果，同样优于该香型白酒锅底水、窖底水单独处理；两种 香型白酒废水分别在最优比例混合及最优条件下进行厌氧实验，其出水 COD 大至相同，降解速率相差不大，产气量酱香型略高于清香型，COD 去除率酱香型和清香型分别为 90.22%和 88.99%。总体来看，酱香型白酒 废水厌氧处理易于清香型白酒废水；白酒废水厌氧产甲烷的重要参数是 pH 值、HRT 和 VFA 的积累量。最优 pH 值为 7.0。在 HRT16 h 之前，VFA 浓度随着 HRT 的增加而增大，有机物降解缓慢，处于水解酸化阶段，气 体量少，去除率低，水力停留时间 16 h 之后，有机物降解速度增快，产 气量迅猛增加， VFA 的浓度逐渐降低，有机物去除率迅速提高，在 HRT48 h 时出现峰值。
characteristics of anaerobic digestion and methane recovery of POTS of water and pit bottom water of
Liquor enterprise
Major : Enviromental Engineering Candidate : Xiong Cheng Supervisor : Associate Prof. Liu Xuqing
关键词： 酱香型白酒 清香型白酒 锅底水 窖底水 厌氧产甲烷
II
Abstract
Abstract
The distilled spirit wastewater is one kind of organic wastewater that are of high concentration and easy to be degraded. It is characterized as deep chromaticity, great variation of both water quality and volume, intermittent discharge and so on. It is analyzed that one ton of 65 degrees distilled spirit need 60 ton water and produce about 48 ton wastewater which is so large pollutant discharge. In our country only minority scale distilleries own wastewater control facilities running well, while there is little equipment for recycling methane from anaerobic process. And in small distilleries methane is of so low gas yield as well as difficult recycling that substandard wastewater or wastewater without treatment is discharged commonly. There is not a mandatory provision of recycling methane produced in anaerobic process for small and medium size distilleries. But it is encouraged to recycle methane for the heat source of anaerobic process or the fuel of power boiler. At the same time, along with the development of Liquor Industry the environment problems become more and more serious. Therefore the study on the recycling of wastewater in small and medium size distilleries has important significance to the work of energy saving and emission reduction. It is noticed by author that there are scarcely researches on the property and treatment methods of high concentration organic wastewater and recycling methane produced in anaerobic process in small and medium size distilleries, let alone the experiment researches about personality differences of wastewater along with different productive technology in different type of distilleries and what optimized measures should be employed in the treatment of wastewater. The article not only introduces the productive technology of both sauce sweet model liquor and fen-flavor liquor and the origin, property and characteristic of their wastewater, but also compares the two’s characteristics of anaerobic methane-production.
Wuhan Institute of Technology Wuhan, Hubei 430074, P. R. China
May, 2012
摘要
摘要
白酒废水是一种色度深、水质水量变化浮度较大、不间断排放的易 降解的高浓度有机废水。据分析，每生产 1 吨 65%vol 白酒，约耗水 60 吨，产生废水 48 吨，排污量很大。在我国，白酒废水治理设施运行较为 正常的企业是少数规模化的大型公司，建有回收利用厌氧过程所产沼气 装置并不多见，而一批小酒厂基于产气量小、回收利用困难的实际，废 水不治理或不达标直接排放的情况还大量存在。国家目前并未对中小型 酒厂做出强制性的回收利用厌氧过程所产甲烷的规定，但鼓励回收沼气 “用于厌氧换热的热源或供给动力锅炉直接燃烧”，同时，近年来随着 白酒行业的迅猛发展，其对环境的影响越来越严重。因此，探讨中小型 酒厂废水的综合利用，对推动白酒行业的节能减排工作有着重要意义。
分类号 X703 UDC
学校编号 10490 密级
武汉工程大学
硕士学位论文
题目：白酒企业锅底水、窖底水厌氧 消化及沼气回收的特性研究
学科专业：
环境工程
研究方向： 水污染控制理论与技术
研 究 生：
熊诚
指导教师：
刘煦晴（副教授）
2012 年 5 月
独创性声明
本人声明所呈交的学位论文是我个人在导师指导下进行的研究 工作及取得的研究成果。尽我所知，除文中已经标明引用的内容外， 本论文不包含任何其他个人或集体已经发表或撰写过的研究成果。对 本文的研究做出贡献的个人和集体，均已在文中以明确方式标明。本 人完全意识到本声明的法律结果由本人承担。
III
武汉工程大学硕士学位论文
The study is mainly on the comparative analysis and conditioning tests of bottom pot water, bottom cellar water and their mixed liquor separately from one sauce sweet model distillery in Maotai Town and another fen-flavor model distillery in Daye City. Further this study discusses the difference of recycling methane from anaerobic fermentation in two types of distilled spirit wastewater. The results of the testing demonstrates that the treatment effect of bottom pot water alone is better than that of bottom cellar water alone under the circumstances of either hyperthermy anaerobic or mesotherm anaerobic. And comparing with mesotherm anaerobic the treatment effect under the circumstances of hyperthermy anaerobic is generally better. When treated alone under the circumstances of both hyperthermy anaerobic and mesotherm anaerobic, the treatment effect of bottom pot water and bottom cellar water in sauce sweet model liquor is superior to that in fen-flavor liquor. The treatment effect of mixed sauce sweet model liquor is superior to bottom pot water or bottom cellar water alone. Furthermore, while the volume ratio of bottom pot water and bottom cellar water is 5:1 and the inflow COD is 24000mg/L, the COD removal and volume of methane anaerobic -production both achieve the best condition. The result is the same to fen-flavor liquor, except that the inflow COD is 22000mg/L. When mixed bottom pot water and bottom cellar water with the optimal proportion, the COD in effluent and the rates of degradation in two types of wastewater are more or less the same. Yet the quantity of methane produced in sauce sweet model liquor wastewater is slightly higher than that in fen-flavor. Moreover the best removal rates of COD are 90.22% and 88.99% respectively. In conclusion, sauce sweet model liquor wastewater is easier to be treated than fen-flavor liquor wastewater. The important parameters in anaerobic methane-production of distilled spirit wastewater are pH value, HRT and cumulant of volatile fatty acid (VFA). The best pH value is 7.0. Before hydraulic retention time (HRT) is 16h, the gas production rate of methane is not high and the COD removal rate is low
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A Thesis Submitted in Fulfillment of the Requirements for the Degree of Master of Engineering
武汉工程大学硕士学位论文vi11课题背景12白酒的分类13白酒生产工艺及其废水的来源性质和特点131酱香型白酒132清香型白酒14白酒废水主要处理方法13141预处理方法13142二级处理方法15143后处理方法2115本课题的研究意义2216论文创新点2521厌氧生物处理三阶段理论25211水解发酵阶段25212产氢产乙酸阶段26213产甲烷阶段2622厌氧微生物群说理论2931试验废水2932试验污泥2933试验装置29武汉工程大学硕士学位论文viii34试验方法及步骤30341酱香型白酒废水30342清香型白酒废水3541酱香型白酒35411中温厌氧锅底水窖底水对比35412高温厌氧锅底水窖底水对比36413中温和高温条件下锅底水实验对比37414中温和高温条件下窖底水实验对比38415混合废水实验探讨3842清香型白酒46421中温厌氧锅底水窖底水对比46422高温厌氧锅底水窖底水对比47423中温和高温条件下锅底水实验对比48424中温和高温条件下窖底水实验对比49425混合废水实验4943酱香型和清香型白酒废水对比分析53431中温厌氧锅底水对比53432中温厌氧窖底水对比54433高温厌氧锅底水对比55434高温厌氧窖底水对比55435高温厌氧最优比例混合废水实验对比分析5645酱香型和清香型白酒废水厌氧处理差异分析5951结论59511酱香型白酒废水59512清香型白酒废水59513两种香型白酒废水对比ix52建议60参考文献65攻读硕士期间已发表的论文73武汉工程大学硕士学位论文绪论11课题背景酒精类废水是我国排放有机污染物第二大的轻工业废水中国白酒行业实行生产许可制度到现在已有一万八千家白酒企业其中到2009年底有8824家企业拥有白酒生产许可证相对1999减少了12万余家白酒企业
学位论文作者签名： 年月日
学位论文版权使用授权书
本学位论文作者完全了解我校有关保留、使用学位论文的规定，
即：我校有权保留并向国家有关部门或机构送交论文的复印件和电子
版，允许论文被查阅。本人授权武汉工程大学研究生处可以将本学位
论文的全部或部分内容编入有关数据库进行检索，可以采用影印、缩
印或扫描等复制手段保存和汇编本学位论文。
研究工作选用贵州省仁怀市茅台镇某小型酱香型白酒企业和大冶市 某中型清香型白酒企业的锅底水与窖底水及此两种废水的的混合液分别 进行了条件试验和对比分析，分析了酱香型白酒废水和清香型白酒废水 厌氧发酵回收沼气的差异。实验结果表明，中小型酱香型白酒企业，无 论是中温厌氧还是高温厌氧，锅底水单独处理效果均优于窖底水单独处 理；高温条件厌氧效果普遍好于中温；在单独厌氧处理的高温条件、中 温条件下，酱香型白酒锅底水处理效果优于清香型白酒，酱香型白酒窖 底水的处理效果也优于清香型白酒；酱香型白酒两种废水的混合样处理 效果优于单一废水的处理，锅底水与窖底水体积比为 5：1 时、进水 COD
I
武汉工程大学硕士学位论文
浓度调整为 24000mg/L 时，COD 去除效果最佳，厌氧产甲烷达最佳境况； 清香型白酒废水，锅底水与窖底水体积比为 5：1，进水 COD 为 22000mg/L 达最优处理效果，同样优于该香型白酒锅底水、窖底水单独处理；两种 香型白酒废水分别在最优比例混合及最优条件下进行厌氧实验，其出水 COD 大至相同，降解速率相差不大，产气量酱香型略高于清香型，COD 去除率酱香型和清香型分别为 90.22%和 88.99%。总体来看，酱香型白酒 废水厌氧处理易于清香型白酒废水；白酒废水厌氧产甲烷的重要参数是 pH 值、HRT 和 VFA 的积累量。最优 pH 值为 7.0。在 HRT16 h 之前，VFA 浓度随着 HRT 的增加而增大，有机物降解缓慢，处于水解酸化阶段，气 体量少，去除率低，水力停留时间 16 h 之后，有机物降解速度增快，产 气量迅猛增加， VFA 的浓度逐渐降低，有机物去除率迅速提高，在 HRT48 h 时出现峰值。
characteristics of anaerobic digestion and methane recovery of POTS of water and pit bottom water of
Liquor enterprise
Major : Enviromental Engineering Candidate : Xiong Cheng Supervisor : Associate Prof. Liu Xuqing
关键词： 酱香型白酒 清香型白酒 锅底水 窖底水 厌氧产甲烷
II
Abstract
Abstract
The distilled spirit wastewater is one kind of organic wastewater that are of high concentration and easy to be degraded. It is characterized as deep chromaticity, great variation of both water quality and volume, intermittent discharge and so on. It is analyzed that one ton of 65 degrees distilled spirit need 60 ton water and produce about 48 ton wastewater which is so large pollutant discharge. In our country only minority scale distilleries own wastewater control facilities running well, while there is little equipment for recycling methane from anaerobic process. And in small distilleries methane is of so low gas yield as well as difficult recycling that substandard wastewater or wastewater without treatment is discharged commonly. There is not a mandatory provision of recycling methane produced in anaerobic process for small and medium size distilleries. But it is encouraged to recycle methane for the heat source of anaerobic process or the fuel of power boiler. At the same time, along with the development of Liquor Industry the environment problems become more and more serious. Therefore the study on the recycling of wastewater in small and medium size distilleries has important significance to the work of energy saving and emission reduction. It is noticed by author that there are scarcely researches on the property and treatment methods of high concentration organic wastewater and recycling methane produced in anaerobic process in small and medium size distilleries, let alone the experiment researches about personality differences of wastewater along with different productive technology in different type of distilleries and what optimized measures should be employed in the treatment of wastewater. The article not only introduces the productive technology of both sauce sweet model liquor and fen-flavor liquor and the origin, property and characteristic of their wastewater, but also compares the two’s characteristics of anaerobic methane-production.
Wuhan Institute of Technology Wuhan, Hubei 430074, P. R. China
May, 2012
摘要
摘要
白酒废水是一种色度深、水质水量变化浮度较大、不间断排放的易 降解的高浓度有机废水。据分析，每生产 1 吨 65%vol 白酒，约耗水 60 吨，产生废水 48 吨，排污量很大。在我国，白酒废水治理设施运行较为 正常的企业是少数规模化的大型公司，建有回收利用厌氧过程所产沼气 装置并不多见，而一批小酒厂基于产气量小、回收利用困难的实际，废 水不治理或不达标直接排放的情况还大量存在。国家目前并未对中小型 酒厂做出强制性的回收利用厌氧过程所产甲烷的规定，但鼓励回收沼气 “用于厌氧换热的热源或供给动力锅炉直接燃烧”，同时，近年来随着 白酒行业的迅猛发展，其对环境的影响越来越严重。因此，探讨中小型 酒厂废水的综合利用，对推动白酒行业的节能减排工作有着重要意义。
分类号 X703 UDC
学校编号 10490 密级
武汉工程大学
硕士学位论文
题目：白酒企业锅底水、窖底水厌氧 消化及沼气回收的特性研究
学科专业：
环境工程
研究方向： 水污染控制理论与技术
研 究 生：
熊诚
指导教师：
刘煦晴（副教授）
2012 年 5 月
独创性声明
本人声明所呈交的学位论文是我个人在导师指导下进行的研究 工作及取得的研究成果。尽我所知，除文中已经标明引用的内容外， 本论文不包含任何其他个人或集体已经发表或撰写过的研究成果。对 本文的研究做出贡献的个人和集体，均已在文中以明确方式标明。本 人完全意识到本声明的法律结果由本人承担。
III
武汉工程大学硕士学位论文
The study is mainly on the comparative analysis and conditioning tests of bottom pot water, bottom cellar water and their mixed liquor separately from one sauce sweet model distillery in Maotai Town and another fen-flavor model distillery in Daye City. Further this study discusses the difference of recycling methane from anaerobic fermentation in two types of distilled spirit wastewater. The results of the testing demonstrates that the treatment effect of bottom pot water alone is better than that of bottom cellar water alone under the circumstances of either hyperthermy anaerobic or mesotherm anaerobic. And comparing with mesotherm anaerobic the treatment effect under the circumstances of hyperthermy anaerobic is generally better. When treated alone under the circumstances of both hyperthermy anaerobic and mesotherm anaerobic, the treatment effect of bottom pot water and bottom cellar water in sauce sweet model liquor is superior to that in fen-flavor liquor. The treatment effect of mixed sauce sweet model liquor is superior to bottom pot water or bottom cellar water alone. Furthermore, while the volume ratio of bottom pot water and bottom cellar water is 5:1 and the inflow COD is 24000mg/L, the COD removal and volume of methane anaerobic -production both achieve the best condition. The result is the same to fen-flavor liquor, except that the inflow COD is 22000mg/L. When mixed bottom pot water and bottom cellar water with the optimal proportion, the COD in effluent and the rates of degradation in two types of wastewater are more or less the same. Yet the quantity of methane produced in sauce sweet model liquor wastewater is slightly higher than that in fen-flavor. Moreover the best removal rates of COD are 90.22% and 88.99% respectively. In conclusion, sauce sweet model liquor wastewater is easier to be treated than fen-flavor liquor wastewater. The important parameters in anaerobic methane-production of distilled spirit wastewater are pH value, HRT and cumulant of volatile fatty acid (VFA). The best pH value is 7.0. Before hydraulic retention time (HRT) is 16h, the gas production rate of methane is not high and the COD removal rate is low
保 密 Ο ， 在 年解密后适用本授权书。
本论文属于
不保密 Ο。
（请在以上方框内打“√”）
学位论文作者签名：
指导教师签名：
年月日
年月日
A Thesis Submitted in Fulfillment of the Requirements for the Degree of Master of Engineering
武汉工程大学硕士学位论文vi11课题背景12白酒的分类13白酒生产工艺及其废水的来源性质和特点131酱香型白酒132清香型白酒14白酒废水主要处理方法13141预处理方法13142二级处理方法15143后处理方法2115本课题的研究意义2216论文创新点2521厌氧生物处理三阶段理论25211水解发酵阶段25212产氢产乙酸阶段26213产甲烷阶段2622厌氧微生物群说理论2931试验废水2932试验污泥2933试验装置29武汉工程大学硕士学位论文viii34试验方法及步骤30341酱香型白酒废水30342清香型白酒废水3541酱香型白酒35411中温厌氧锅底水窖底水对比35412高温厌氧锅底水窖底水对比36413中温和高温条件下锅底水实验对比37414中温和高温条件下窖底水实验对比38415混合废水实验探讨3842清香型白酒46421中温厌氧锅底水窖底水对比46422高温厌氧锅底水窖底水对比47423中温和高温条件下锅底水实验对比48424中温和高温条件下窖底水实验对比49425混合废水实验4943酱香型和清香型白酒废水对比分析53431中温厌氧锅底水对比53432中温厌氧窖底水对比54433高温厌氧锅底水对比55434高温厌氧窖底水对比55435高温厌氧最优比例混合废水实验对比分析5645酱香型和清香型白酒废水厌氧处理差异分析5951结论59511酱香型白酒废水59512清香型白酒废水59513两种香型白酒废水对比ix52建议60参考文献65攻读硕士期间已发表的论文73武汉工程大学硕士学位论文绪论11课题背景酒精类废水是我国排放有机污染物第二大的轻工业废水中国白酒行业实行生产许可制度到现在已有一万八千家白酒企业其中到2009年底有8824家企业拥有白酒生产许可证相对1999减少了12万余家白酒企业