WO2015143906A1 - A method for improving the methane production rate through acidification pretreatment of hydrogen production of kitchen waste and sludge - Google Patents
A method for improving the methane production rate through acidification pretreatment of hydrogen production of kitchen waste and sludge Download PDFInfo
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- the invention relates to a biomass energy utilization technology, in particular to a method for improving the biomethane production rate by deep acid acidification pretreatment of a kitchen waste and sludge mixed fermentation.
- Biomass energy is the most common renewable energy on the planet, and its total consumption ranks first among renewable energy.
- Urban and rural organic waste is a renewable biomass resource with a large number and serious pollution. How to realize the reduction and harmless treatment of urban and rural waste and the utilization of energy resources is a hot and difficult problem in economic and social development.
- KIM S H and others used a canteen kitchen waste to conduct fermentation and methanogenesis, and obtained fermentation data of 122.9 mL/g carbohydrate.
- Jae Kyoung et al. conducted a research on the methanation potential (BMP) of kitchen waste. The results showed that kitchen waste had higher anaerobic methanation potential, and the methanation potential of meat, cellulose, rice, cabbage and mixed waste was 482, respectively.
- the anaerobic biodegradability of 356, 294, 277, 472mL CH4/gVS was 0.82, 0.92, 0.72, 0.73, and 0.86, respectively.
- the long-term stability test was not effective, and the gas production rate was far below the UBMP study results. Yu.Sheng Wan et al.
- the main object of the present invention is to overcome the deficiencies in the prior art and to provide a method for improving the production rate of biomethane by deep acid acidification pretreatment of kitchen waste and sludge mixed fermentation.
- the solution of the present invention is:
- a method for improving the rate of methane production by preheating pretreatment of kitchen waste and sludge comprising the following steps:
- (2) 200-500 ml of fermentation raw material is added to a fermentation flask having a volume of 600 ml, and the pH is adjusted to 6.4-6.6 with a NaOH having a mass concentration of 6 mol/L; 0.2-0.5 g of yeast powder is added to inoculate a dark fermentation hydrogen-producing bacterium 20 ⁇ 50ml, pass high-purity nitrogen for 20min to create an anaerobic fermentation environment, and then perform a deep acidification pretreatment of dark fermentation hydrogen production at a constant temperature of 37 °C to obtain a deep acidification pretreatment liquid for hydrogen production;
- the kitchen waste in the step (1) is derived from a household living or catering industry; the sludge is derived from a municipal sewage treatment plant or a food processing factory.
- the dominant strain of the dark fermentation hydrogen producing bacteria is Clostridium butyricum, which is obtained by separating the anaerobic digestion sludge: the anaerobic digestion sludge is subjected to heat treatment. The methanogens are killed and the spores of the dark fermentative hydrogen producing bacteria are retained, and the culture is enriched three times, once every 72 hours.
- the dominant species of the methanogens are Methanosarcina and Methanothrix, which are anaerobic activated sludge of the biogas digester without heat treatment. It is obtained by multiple enrichment and culture in the incubator.
- the invention significantly increases the production rate of biomethane by deep acidification pretreatment of dark fermentation hydrogen production.
- the gas and methane components in the fermentation gas can be tested using a gas chromatograph equipped with a thermal conductivity detector; the gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 °C.
- the oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes.
- the flow rate of the carrier gas argon gas was 27 ml/min.
- Figure 1 is a process flow diagram of the present invention.
- the method for improving the methane production rate by the pretreatment of the kitchen waste and the sludge hydro-acidification comprises the following steps:
- the mixture is mixed at a mass ratio of 1:1 to obtain a pretreated raw material. Then, with a mass concentration of 1% H 2 SO 4 solution, a mixed liquid with a pretreatment raw material concentration of 20-30 g/L is prepared, and the mixed solution is hydrolyzed at a high temperature of 135 ° C for 15 minutes to obtain a fermentation raw material; the kitchen waste can be a resident.
- the kitchen waste produced in daily life or the kitchen waste produced by the catering industry may be sludge from municipal sewage treatment plants or sludge from food factories;
- yeast powder refers to concentrated yeast leaching powder, purchased from Fuyang City, Zhejiang Province, Hangzhou Fu Biological Products Factory;
- the dark fermentation hydrogen-producing bacteria are collected from anaerobic digestion sludge, and the sludge is heated to kill the methanogen to retain the spores of the dark fermentation hydrogen-producing bacteria, and the culture is enriched three times (every 72 hours) to obtain the dominant species. Clostridium butyricum.
- the pH is adjusted to 7.9-8.1 with NaOH with a mass concentration of 6 mol/L, 20-50 ml of methanogens are added, and the anaerobic environment at 37 °C is maintained for fermentation to produce methane.
- the methanogens are obtained by enriching the biogas digesters without heat treatment in the anaerobic incubator, and the dominant species are Methanosarcina and Methanothrix.
- the present invention can test hydrogen and methane components in a fermentation gas using a gas chromatograph equipped with a thermal conductivity detector.
- the gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 ° C.
- the oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes.
- the flow rate of the carrier gas argon gas was 27 ml/min.
- the mixture After pre-treating the kitchen waste and the sludge, the mixture is mixed at a mass ratio of 1:1 to obtain a pretreated raw material. Then, with a mass concentration of 1% H 2 SO 4 solution, a mixture of pretreatment raw material concentration of 20g / L is prepared, and the mixture is hydrolyzed at a high temperature of 135 ° C for 15 minutes to obtain a fermentation raw material; 200 ml of the fermentation raw material is added to a volume of 600 ml. The fermentation flask was adjusted to a pH of 6.4 with a mass concentration of 6 mol/L NaOH.
- the hydrogenation deep acidification pretreatment liquid was adjusted to pH 7.9 with a concentration of 6 mol/L NaOH, 20 ml of methanogen was added, and the anaerobic environment was maintained at 37 ° C for fermentation to produce methane, and the biomethane was pretreated by deep acidification of hydrogen production. Production rates have increased by 51%.
- the methanogens were obtained from the biogas digesters without heat treatment, and were enriched and cultured in an anaerobic incubator, mainly M. mazei and M. thermomycetes.
- the hydrogen and methane components in the fermentation gas were tested using a gas chromatograph equipped with a thermal conductivity detector (purchased in Agilent 7820A, USA).
- the gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 ° C.
- the oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes.
- the flow rate of the carrier gas argon gas was 27 ml/min.
- the mixture After pre-treating the kitchen waste and the sludge, the mixture is mixed at a mass ratio of 1:1 to obtain a pretreated raw material. Then, with a mass concentration of 1% H 2 SO 4 solution to prepare a mixture of pretreatment raw material concentration of 25g / L, the mixture is hydrolyzed at a high temperature of 135 ° C for 15min to obtain a fermentation raw material; 300ml of high temperature treated mixture A ferment bottle having a volume of 600 ml was added, and the pH of the mixture was adjusted to 6.5 with a NaOH having a mass concentration of 6 mol/L.
- the hydrogenation deep acidification pretreatment liquid was adjusted to pH 8.0 with a concentration of 6 mol/L NaOH, 30 ml of methanogen was added, and the anaerobic environment was maintained at 37 ° C for fermentation to produce methane, and the deep acidification pretreatment of dark hydrogen by dark fermentation made the organism
- the production rate of methane has increased by 55%.
- the methanogens were obtained from the biogas digesters without heat treatment, and were enriched and cultured in an anaerobic incubator, mainly M. mazei and M. thermomycetes.
- the hydrogen and methane components in the fermentation gas were tested using a gas chromatograph equipped with a thermal conductivity detector (purchased in Agilent 7820A, USA).
- the gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 ° C.
- the oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes.
- the flow rate of the carrier gas argon gas was 27 ml/min.
- the mixture After pre-treating the kitchen waste and the sludge, the mixture is mixed at a mass ratio of 1:1 to obtain a pretreated raw material. Then, with a mass concentration of 1% H 2 SO 4 solution, a mixture of pretreatment raw material concentration of 30 g / L is prepared, and the mixture is hydrolyzed at a high temperature of 135 ° C for 15 min to obtain a fermentation raw material; 500 ml of the high temperature treated mixture is obtained. A ferment bottle having a volume of 600 ml was added, and the pH of the mixture was adjusted to 6.6 with a NaOH having a mass concentration of 6 mol/L.
- the hydrogenation deep acidification pretreatment liquid was adjusted to pH 8.1 with a concentration of 6 mol/L NaOH, 50 ml of methanogen was added, and the anaerobic environment was maintained at 37 ° C for fermentation to produce methane, and the deep acidification pretreatment of dark hydrogen by dark fermentation made the organism
- the production rate of methane has increased by 48%.
- the methanogens were obtained from the biogas digesters without heat treatment, and were enriched and cultured in an anaerobic incubator, mainly M. mazei and M. thermomycetes.
- the hydrogen and methane components in the fermentation gas were tested using a gas chromatograph equipped with a thermal conductivity detector (purchased in Agilent 7820A, USA).
- the gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 ° C.
- the oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes.
- the flow rate of the carrier gas argon gas was 27 ml/min.
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Abstract
Provided is a method for improving the methane production rate through acidification pretreatment of hydrogen production of kitchen waste and sludge. The method comprises: mixing the kitchen waste after crushing pretreatment with sludge, hydrolyzing the mixed solution formulated with sulfuric acid at 135℃ to obtain the fermentation materials, adding yeast powder to the fermentation materials, inoculating the dark fermentation hydrogen producing bacteria, creating the anaerobic fermenting environment by introducing the high purity nitrogen, processing dark deep acidification pretreatment of hydrogen production fermentation at the constant temperature 37℃, adding methanogenic bacteria and maintaining anaerobic environment at 37℃ to ferment and to produce methane.
Description
本发明是关于生物质能利用技术,特别涉及一种餐厨垃圾和污泥混合发酵通过产氢深度酸化预处理提高生物甲烷生产速率的方法。The invention relates to a biomass energy utilization technology, in particular to a method for improving the biomethane production rate by deep acid acidification pretreatment of a kitchen waste and sludge mixed fermentation.
化石能源日益短缺和环境污染严重是当今世界面临的两大危机难题,温室效应对气候环境的严重影响使人们日益关注CO2减排问题,大力发展新能源是我国能源安全和可持续发展的必然要求。生物质能是地球上最普遍的一种可再生能源,其消费总量居可再生能源之首。城乡有机废弃物是一种可再生的生物质资源,数量庞大,污染严重,如何实现城乡废弃物的减量无害化处理和能源资源化利用,是目前经济社会发展的一个热点和难点问题。利用生物质废弃物制取油气新能源,通过发酵生产氢气和甲烷制备成压缩生物天然气,用作汽车发动机的清洁代油燃料,是国际能源环境领域的新兴前沿技术,符合我国鼓励的新能源和节能环保等战略性新兴产业政策。The increasing shortage of fossil energy and serious environmental pollution are the two major crisis problems facing the world today. The serious impact of the greenhouse effect on the climate environment has caused people to pay more and more attention to the issue of CO 2 emission reduction. The development of new energy is the inevitable result of China's energy security and sustainable development. Claim. Biomass energy is the most common renewable energy on the planet, and its total consumption ranks first among renewable energy. Urban and rural organic waste is a renewable biomass resource with a large number and serious pollution. How to realize the reduction and harmless treatment of urban and rural waste and the utilization of energy resources is a hot and difficult problem in economic and social development. The use of biomass waste to produce new oil and gas, the production of compressed natural gas by fermentation of hydrogen and methane, used as a clean substitute fuel for automobile engines, is an emerging frontier technology in the field of international energy and environment, in line with the new energy and energy encouraged by China. Strategic emerging industry policies such as energy conservation and environmental protection.
KIM S H等利用某食堂餐厨垃圾进行了发酵产甲烷的研究,获得了122.9mL/g碳水化合物的发酵数据。Jae Kyoung等进行了餐厨垃圾甲烷化潜力(BMP)研究,结果表明:餐厨垃圾具有较高厌氧甲烷化潜力,肉食、纤维素、米饭、卷心菜和混合废物的甲烷化潜力分别为482、356、294、277、472mLCH4/gVS,厌氧可生物降解性分别为0.82、0.92、0.72、0.73、0.86,但长期稳定试验效果不佳,产气率远达不至UBMP研究结果。Yu.Sheng Wan等进行了餐厨垃圾与污泥联合发酵试验,结果表明:在一定的比例下,餐厨垃圾发酵可以顺利进行。Kang等认为餐厨垃圾酸化液是抑制餐厨垃圾废物甲烷化进程的主要原因。Ghanem等认为挥发酸的累积会导致系统产气的停滞,可通过减少挥发酸浓度,恢复系统产气能力,继续进行甲烷化。然而城市垃圾的种类繁多,包括餐厨垃圾、废水厂和食品厂污泥等,如何改进发酵生产工艺提高产甲烷速率是一个技术难题,对于节能减排和发展新能源具有重要意义。KIM S H and others used a canteen kitchen waste to conduct fermentation and methanogenesis, and obtained fermentation data of 122.9 mL/g carbohydrate. Jae Kyoung et al. conducted a research on the methanation potential (BMP) of kitchen waste. The results showed that kitchen waste had higher anaerobic methanation potential, and the methanation potential of meat, cellulose, rice, cabbage and mixed waste was 482, respectively. The anaerobic biodegradability of 356, 294, 277, 472mL CH4/gVS was 0.82, 0.92, 0.72, 0.73, and 0.86, respectively. However, the long-term stability test was not effective, and the gas production rate was far below the UBMP study results. Yu.Sheng Wan et al. conducted a combined fermentation experiment of kitchen waste and sludge. The results showed that the fermentation of the kitchen waste can proceed smoothly under a certain ratio. Kang et al believe that kitchen waste acidification liquid is the main reason for inhibiting the methanation process of kitchen waste. Ghanem et al. believe that the accumulation of volatile acids will lead to the stagnation of the system's gas production, and the methanation can be continued by reducing the concentration of volatile acids and restoring the gas production capacity of the system. However, there are many types of municipal waste, including kitchen waste, waste water plant and food plant sludge. How to improve the fermentation production process and increase the methane production rate is a technical problem, which is of great significance for energy conservation and emission reduction and development of new energy.
发明内容Summary of the invention
本发明的主要目的在于克服现有技术中的不足,提供一种餐厨垃圾和污泥混合发酵通过产氢深度酸化预处理提高生物甲烷生产速率的方法。The main object of the present invention is to overcome the deficiencies in the prior art and to provide a method for improving the production rate of biomethane by deep acid acidification pretreatment of kitchen waste and sludge mixed fermentation.
为解决上述技术问题,本发明的解决方案是:
In order to solve the above technical problems, the solution of the present invention is:
提供一种餐厨垃圾和污泥产氢酸化预处理提高甲烷生产速率的方法,具体包括下述步骤:A method for improving the rate of methane production by preheating pretreatment of kitchen waste and sludge, comprising the following steps:
(1)将粉碎预处理后的餐厨垃圾和污泥按照质量比1:1进行混合,得到预处理原料;将预处理原料与质量浓度为1%的H2SO4溶液配制成混合液,混合液中预处理原料的浓度为20~30g/L;将混合液在135℃下水解处理15min;(1) Mixing the kitchen waste and sludge after the pulverization pretreatment according to a mass ratio of 1:1 to obtain a pretreated raw material; preparing the pretreated raw material with a H 2 SO 4 solution having a mass concentration of 1% to prepare a mixed solution, The concentration of the pretreated raw material in the mixed solution is 20-30 g/L; the mixed solution is hydrolyzed at 135 ° C for 15 min;
(2)将200~500ml的发酵原料加入容积为600ml的发酵瓶,用质量浓度为6mol/L的NaOH调节pH为6.4~6.6;加入0.2~0.5g酵母粉,接种暗发酵产氢菌20~50ml,通入高纯氮气20min营造厌氧发酵环境,然后恒温37℃进行暗发酵产氢深度酸化预处理,得到产氢深度酸化预处理液体;(2) 200-500 ml of fermentation raw material is added to a fermentation flask having a volume of 600 ml, and the pH is adjusted to 6.4-6.6 with a NaOH having a mass concentration of 6 mol/L; 0.2-0.5 g of yeast powder is added to inoculate a dark fermentation hydrogen-producing bacterium 20~ 50ml, pass high-purity nitrogen for 20min to create an anaerobic fermentation environment, and then perform a deep acidification pretreatment of dark fermentation hydrogen production at a constant temperature of 37 °C to obtain a deep acidification pretreatment liquid for hydrogen production;
(3)用质量浓度为6mol/L的NaOH调节产氢深度酸化预处理液体使pH为7.9~8.1,加入20~50ml产甲烷菌,保持37℃厌氧环境进行发酵联产甲烷。(3) Adjusting the hydrogenation deep-acidification pretreatment liquid with a concentration of 6 mol/L NaOH to make the pH 7.9-8.1, adding 20-50 ml methanogens, and maintaining the 37 °C anaerobic environment for fermentation to produce methane.
本发明中,所述步骤(1)中的餐厨垃圾来源于居民家庭生活或餐饮业;所述污泥来源于城市污水处理厂或食品加工厂。In the present invention, the kitchen waste in the step (1) is derived from a household living or catering industry; the sludge is derived from a municipal sewage treatment plant or a food processing factory.
本发明中,所述步骤(2)中,所述暗发酵产氢菌的优势菌种为丁酸梭菌,是由厌氧消化污泥分离得到的:由厌氧消化污泥经过加热处理,杀死产甲烷菌并保留暗发酵产氢菌的芽孢,培养富集三次,每72小时一次。In the present invention, in the step (2), the dominant strain of the dark fermentation hydrogen producing bacteria is Clostridium butyricum, which is obtained by separating the anaerobic digestion sludge: the anaerobic digestion sludge is subjected to heat treatment. The methanogens are killed and the spores of the dark fermentative hydrogen producing bacteria are retained, and the culture is enriched three times, once every 72 hours.
本发明中,所述步骤(3)中,产甲烷菌的优势菌种为甲烷八叠球菌(Methanosarcina)和甲烷丝菌(Methanothrix),是将不经过加热处理的沼气池活性污泥在厌氧培养箱中多次富集培养得到的。In the present invention, in the step (3), the dominant species of the methanogens are Methanosarcina and Methanothrix, which are anaerobic activated sludge of the biogas digester without heat treatment. It is obtained by multiple enrichment and culture in the incubator.
本发明通过暗发酵产氢深度酸化预处理显著提高生物甲烷的生产速率。The invention significantly increases the production rate of biomethane by deep acidification pretreatment of dark fermentation hydrogen production.
可以使用装备了热导检测器的气相色谱仪测试发酵气体中的氢气和甲烷成分;气相色谱仪运行参数为:进样口温度为200℃,检测器温度为300℃,初始柱箱温度为65℃。实验中的柱箱温度采用程序升温,总时间为6分钟,初始温度为65℃,保持1分钟,随后升温速率设置为25℃/min,经过3.2分钟后直到最终温度达到145℃,随后继续保持1.8分钟。载气氩气的流速为27ml/min。The gas and methane components in the fermentation gas can be tested using a gas chromatograph equipped with a thermal conductivity detector; the gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 °C. The oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes. The flow rate of the carrier gas argon gas was 27 ml/min.
与现有技术相比,本发明的有益效果是:Compared with the prior art, the beneficial effects of the present invention are:
餐厨垃圾和污泥混合发酵通过产氢深度酸化预处理显著提高了甲烷生产速率,使生产甲烷的速率峰值时间减少约50%,因而单位容积发酵罐设备对废弃物的处理降解时间减少约50%,使单个设备在单位时间内对废弃物的处理量提高了一倍左右。Mixing of kitchen waste and sludge through the deep acidification pretreatment of hydrogen production significantly increases the methane production rate, reducing the peak time of methane production by about 50%, thus reducing the treatment degradation time of waste per unit volume of fermenter equipment by about 50. %, which allows a single device to double the amount of waste processed per unit of time.
图1为本发明的工艺流程图。
Figure 1 is a process flow diagram of the present invention.
下面结合附图与具体实施方式对本发明作进一步详细描述:The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
如图1所示,餐厨垃圾和污泥产氢酸化预处理提高甲烷生产速率的方法具体包括下述步骤:As shown in FIG. 1 , the method for improving the methane production rate by the pretreatment of the kitchen waste and the sludge hydro-acidification comprises the following steps:
(1)将餐厨垃圾和污泥粉碎预处理后,按照质量比为1:1进行混合,得到预处理原料。然后与质量浓度为1%的H2SO4溶液配制成预处理原料浓度为20~30g/L的混合液,将混合液在高温135℃水解处理15min,得到发酵原料;餐厨垃圾可以是居民日常生活产生的餐厨垃圾或者是餐饮业产生的餐厨垃圾,污泥可以是城市污水处理厂污泥或者是食品厂污泥;(1) After pre-treating the kitchen waste and sludge, the mixture is mixed at a mass ratio of 1:1 to obtain a pretreated raw material. Then, with a mass concentration of 1% H 2 SO 4 solution, a mixed liquid with a pretreatment raw material concentration of 20-30 g/L is prepared, and the mixed solution is hydrolyzed at a high temperature of 135 ° C for 15 minutes to obtain a fermentation raw material; the kitchen waste can be a resident. The kitchen waste produced in daily life or the kitchen waste produced by the catering industry may be sludge from municipal sewage treatment plants or sludge from food factories;
(2)将200~500ml经过高温处理的发酵原料加入容积为600ml的发酵瓶,用质量浓度为6mol/L的NaOH调节pH为6.4~6.6。加入0.2~0.5g酵母粉,接种暗发酵产氢菌20~50ml,通入高纯氮气20min营造厌氧发酵环境,然后恒温37℃进行暗发酵产氢深度酸化预处理,得到产氢深度酸化预处理液体;其中,酵母粉是指浓缩酵母浸出粉,购自浙江省富阳市杭富生物制品厂;(2) 200 to 500 ml of the fermented raw material subjected to high temperature treatment is added to a fermentation flask having a volume of 600 ml, and the pH is adjusted to 6.4 to 6.6 with a NaOH having a mass concentration of 6 mol/L. Add 0.2-0.5g yeast powder, inoculate 20~50ml of dark fermentation hydrogen-producing bacteria, and pass high-purity nitrogen for 20min to create an anaerobic fermentation environment, then carry out deep acidification pretreatment of dark fermentation by constant temperature at 37 °C to obtain deep acidification pretreatment of hydrogen production. Treatment liquid; wherein, yeast powder refers to concentrated yeast leaching powder, purchased from Fuyang City, Zhejiang Province, Hangzhou Fu Biological Products Factory;
暗发酵产氢菌采集自厌氧消化污泥分离得到,该污泥经过加热处理杀死产甲烷菌保留暗发酵产氢菌的芽孢,培养富集三次(每72小时一次)得到优势菌种为丁酸梭菌。The dark fermentation hydrogen-producing bacteria are collected from anaerobic digestion sludge, and the sludge is heated to kill the methanogen to retain the spores of the dark fermentation hydrogen-producing bacteria, and the culture is enriched three times (every 72 hours) to obtain the dominant species. Clostridium butyricum.
(3)对产氢深度酸化预处理液体用质量浓度为6mol/L的NaOH调节pH为7.9~8.1,加入20~50ml产甲烷菌,保持37℃厌氧环境进行发酵联产甲烷。(3) For the deep acidification pretreatment liquid, the pH is adjusted to 7.9-8.1 with NaOH with a mass concentration of 6 mol/L, 20-50 ml of methanogens are added, and the anaerobic environment at 37 °C is maintained for fermentation to produce methane.
其中,产甲烷菌采用不经过加热处理的沼气池活性污泥,在厌氧培养箱中多次富集培养得到,其优势菌种为甲烷八叠球菌(Methanosarcina)和甲烷丝菌(Methanothrix)。Among them, the methanogens are obtained by enriching the biogas digesters without heat treatment in the anaerobic incubator, and the dominant species are Methanosarcina and Methanothrix.
本发明可使用装备了热导检测器的气相色谱仪测试发酵气体中的氢气和甲烷成分。气相色谱仪运行参数为:进样口温度为200℃,检测器温度为300℃,初始柱箱温度为65℃。实验中的柱箱温度采用程序升温,总时间为6分钟,初始温度为65℃,保持1分钟,随后升温速率设置为25℃/min,经过3.2分钟后直到最终温度达到145℃,随后继续保持1.8分钟。载气氩气的流速为27ml/min。The present invention can test hydrogen and methane components in a fermentation gas using a gas chromatograph equipped with a thermal conductivity detector. The gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 ° C. The oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes. The flow rate of the carrier gas argon gas was 27 ml/min.
实施例1Example 1
将餐厨垃圾和污泥粉碎预处理后,按照质量比为1:1进行混合,得到预处理原料。然后与质量浓度为1%的H2SO4溶液配制成预处理原料浓度为20g/L的混合液,将混合液在高温135℃水解处理15min,得到发酵原料;将200ml发酵原料加入容积为600ml的发酵瓶,用质量浓度为6mol/L的NaOH调节混合液的pH为6.4。加入0.2g酵母粉,接种暗发酵产氢菌20ml,通入高纯氮气20min营造厌氧发酵环境,然后恒温37℃进行暗发酵产氢深度酸化预处理;暗发酵产氢菌采集自厌氧消化污泥分离得到,该污泥经过
加热处理杀死产甲烷菌保留暗发酵产氢菌的芽孢,培养富集三次(每72小时一次)得到优势菌种为丁酸梭菌。对产氢深度酸化预处理液体用质量浓度为6mol/L的NaOH调节pH为7.9,加入20ml甲烷菌,保持37℃厌氧环境进行发酵联产甲烷,通过产氢深度酸化预处理使生物甲烷的生产速率提高了51%。产甲烷菌采用不经过加热处理的沼气池活性污泥,在厌氧培养箱中多次富集培养得到,主要为甲烷八叠球菌和甲烷丝菌。After pre-treating the kitchen waste and the sludge, the mixture is mixed at a mass ratio of 1:1 to obtain a pretreated raw material. Then, with a mass concentration of 1% H 2 SO 4 solution, a mixture of pretreatment raw material concentration of 20g / L is prepared, and the mixture is hydrolyzed at a high temperature of 135 ° C for 15 minutes to obtain a fermentation raw material; 200 ml of the fermentation raw material is added to a volume of 600 ml. The fermentation flask was adjusted to a pH of 6.4 with a mass concentration of 6 mol/L NaOH. Add 0.2g of yeast powder, inoculate 20ml of dark fermentation hydrogen-producing bacteria, and pass high-purity nitrogen for 20min to create an anaerobic fermentation environment, then carry out dark fermentation acidification deep-acidification pretreatment at 37 °C; dark fermentation hydrogen production bacteria collected from anaerobic digestion The sludge is separated, and the sludge is heated to kill the methanogen to retain the spores of the dark fermentation hydrogen-producing bacteria, and the culture is enriched three times (every 72 hours) to obtain the dominant species is Clostridium butyricum. The hydrogenation deep acidification pretreatment liquid was adjusted to pH 7.9 with a concentration of 6 mol/L NaOH, 20 ml of methanogen was added, and the anaerobic environment was maintained at 37 ° C for fermentation to produce methane, and the biomethane was pretreated by deep acidification of hydrogen production. Production rates have increased by 51%. The methanogens were obtained from the biogas digesters without heat treatment, and were enriched and cultured in an anaerobic incubator, mainly M. mazei and M. thermomycetes.
使用装备了热导检测器的气相色谱仪(购置于Agilent 7820A,美国)测试发酵气体中的氢气和甲烷成分。气相色谱仪运行参数为:进样口温度为200℃,检测器温度为300℃,初始柱箱温度为65℃。实验中的柱箱温度采用程序升温,总时间为6分钟,初始温度为65℃,保持1分钟,随后升温速率设置为25℃/min,经过3.2分钟后直到最终温度达到145℃,随后继续保持1.8分钟。载气氩气的流速为27ml/min。The hydrogen and methane components in the fermentation gas were tested using a gas chromatograph equipped with a thermal conductivity detector (purchased in Agilent 7820A, USA). The gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 ° C. The oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes. The flow rate of the carrier gas argon gas was 27 ml/min.
实施例2Example 2
将餐厨垃圾和污泥粉碎预处理后,按照质量比为1:1进行混合,得到预处理原料。然后与质量浓度为1%的H2SO4溶液配制成预处理原料浓度为25g/L的混合液,将混合液在高温135℃水解处理15min,得到发酵原料;将300ml经过高温处理的混合液加入容积为600ml的发酵瓶,用质量浓度为6mol/L的NaOH调节混合液的pH为6.5。加入0.3g酵母粉,接种暗发酵产氢菌30ml,通入高纯氮气20min营造厌氧发酵环境,然后恒温37℃进行暗发酵产氢深度酸化预处;暗发酵产氢菌采集自厌氧消化污泥分离得到,该污泥经过加热处理杀死产甲烷菌保留暗发酵产氢菌的芽孢,培养富集三次(每72小时一次)得到优势菌种为丁酸梭菌。对产氢深度酸化预处理液体用质量浓度为6mol/L的NaOH调节pH为8.0,加入30ml甲烷菌,保持37℃厌氧环境进行发酵联产甲烷,通过暗发酵产氢深度酸化预处理使生物甲烷的生产速率提高了55%。产甲烷菌采用不经过加热处理的沼气池活性污泥,在厌氧培养箱中多次富集培养得到,主要为甲烷八叠球菌和甲烷丝菌。After pre-treating the kitchen waste and the sludge, the mixture is mixed at a mass ratio of 1:1 to obtain a pretreated raw material. Then, with a mass concentration of 1% H 2 SO 4 solution to prepare a mixture of pretreatment raw material concentration of 25g / L, the mixture is hydrolyzed at a high temperature of 135 ° C for 15min to obtain a fermentation raw material; 300ml of high temperature treated mixture A ferment bottle having a volume of 600 ml was added, and the pH of the mixture was adjusted to 6.5 with a NaOH having a mass concentration of 6 mol/L. Add 0.3g of yeast powder, inoculate 30ml of dark fermentation hydrogen-producing bacteria, and pass high-purity nitrogen for 20min to create an anaerobic fermentation environment, then conduct a dark fermentation at pH 37 °C for deep acidification. The dark fermentation hydrogen-producing bacteria are collected from anaerobic digestion. The sludge is separated, and the sludge is heated to kill the methanogen to retain the spores of the dark fermentation hydrogen-producing bacteria, and the culture is enriched three times (every 72 hours) to obtain the dominant species is Clostridium butyricum. The hydrogenation deep acidification pretreatment liquid was adjusted to pH 8.0 with a concentration of 6 mol/L NaOH, 30 ml of methanogen was added, and the anaerobic environment was maintained at 37 ° C for fermentation to produce methane, and the deep acidification pretreatment of dark hydrogen by dark fermentation made the organism The production rate of methane has increased by 55%. The methanogens were obtained from the biogas digesters without heat treatment, and were enriched and cultured in an anaerobic incubator, mainly M. mazei and M. thermomycetes.
使用装备了热导检测器的气相色谱仪(购置于Agilent 7820A,美国)测试发酵气体中的氢气和甲烷成分。气相色谱仪运行参数为:进样口温度为200℃,检测器温度为300℃,初始柱箱温度为65℃。实验中的柱箱温度采用程序升温,总时间为6分钟,初始温度为65℃,保持1分钟,随后升温速率设置为25℃/min,经过3.2分钟后直到最终温度达到145℃,随后继续保持1.8分钟。载气氩气的流速为27ml/min。The hydrogen and methane components in the fermentation gas were tested using a gas chromatograph equipped with a thermal conductivity detector (purchased in Agilent 7820A, USA). The gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 ° C. The oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes. The flow rate of the carrier gas argon gas was 27 ml/min.
实施例3Example 3
将餐厨垃圾和污泥粉碎预处理后,按照质量比为1:1进行混合,得到预处理原料。然后与质量浓度为1%的H2SO4溶液配制成预处理原料浓度为30g/L的混合液,将混合液在高温135℃水解处理15min,得到发酵原料;将500ml经过高温处理的混合液加入容积为600ml的发酵瓶,用质量浓度为6mol/L的NaOH调节混合液的pH为6.6。加入
0.5g酵母粉,接种暗发酵产氢菌50ml,通入高纯氮气20min营造厌氧发酵环境,然后恒温37℃进行暗发酵产氢深度酸化预处;暗发酵产氢菌采集自厌氧消化污泥分离得到,该污泥经过加热处理杀死产甲烷菌保留暗发酵产氢菌的芽孢,培养富集三次(每72小时一次)得到优势菌种为丁酸梭菌。对产氢深度酸化预处理液体用质量浓度为6mol/L的NaOH调节pH为8.1,加入50ml甲烷菌,保持37℃厌氧环境进行发酵联产甲烷,通过暗发酵产氢深度酸化预处理使生物甲烷的生产速率提高了48%。产甲烷菌采用不经过加热处理的沼气池活性污泥,在厌氧培养箱中多次富集培养得到,主要为甲烷八叠球菌和甲烷丝菌。After pre-treating the kitchen waste and the sludge, the mixture is mixed at a mass ratio of 1:1 to obtain a pretreated raw material. Then, with a mass concentration of 1% H 2 SO 4 solution, a mixture of pretreatment raw material concentration of 30 g / L is prepared, and the mixture is hydrolyzed at a high temperature of 135 ° C for 15 min to obtain a fermentation raw material; 500 ml of the high temperature treated mixture is obtained. A ferment bottle having a volume of 600 ml was added, and the pH of the mixture was adjusted to 6.6 with a NaOH having a mass concentration of 6 mol/L. Add 0.5g of yeast powder, inoculate 50ml of dark fermentation hydrogen-producing bacteria, and pass high-purity nitrogen for 20min to create an anaerobic fermentation environment, then carry out dark fermentation to deep acidification pre-treatment at 37 °C; dark fermentation hydrogen-producing bacteria collected from anaerobic digestion The sludge is separated, and the sludge is heated to kill the methanogen to retain the spores of the dark fermentation hydrogen-producing bacteria, and the culture is enriched three times (every 72 hours) to obtain the dominant species is Clostridium butyricum. The hydrogenation deep acidification pretreatment liquid was adjusted to pH 8.1 with a concentration of 6 mol/L NaOH, 50 ml of methanogen was added, and the anaerobic environment was maintained at 37 ° C for fermentation to produce methane, and the deep acidification pretreatment of dark hydrogen by dark fermentation made the organism The production rate of methane has increased by 48%. The methanogens were obtained from the biogas digesters without heat treatment, and were enriched and cultured in an anaerobic incubator, mainly M. mazei and M. thermomycetes.
使用装备了热导检测器的气相色谱仪(购置于Agilent 7820A,美国)测试发酵气体中的氢气和甲烷成分。气相色谱仪运行参数为:进样口温度为200℃,检测器温度为300℃,初始柱箱温度为65℃。实验中的柱箱温度采用程序升温,总时间为6分钟,初始温度为65℃,保持1分钟,随后升温速率设置为25℃/min,经过3.2分钟后直到最终温度达到145℃,随后继续保持1.8分钟。载气氩气的流速为27ml/min。The hydrogen and methane components in the fermentation gas were tested using a gas chromatograph equipped with a thermal conductivity detector (purchased in Agilent 7820A, USA). The gas chromatograph operating parameters are: inlet temperature 200 ° C, detector temperature 300 ° C, initial oven temperature 65 ° C. The oven temperature in the experiment was programmed for a total time of 6 minutes, the initial temperature was 65 ° C, held for 1 minute, then the heating rate was set to 25 ° C / min, after 3.2 minutes until the final temperature reached 145 ° C, and then continue to maintain 1.8 minutes. The flow rate of the carrier gas argon gas was 27 ml/min.
最后,需要注意的是,以上列举的仅是本发明的具体实施例。显然,本发明不限于以上实施例,还可以有很多变形。本领域的普通技术人员能从本发明公开的内容中直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Finally, it should be noted that the above enumerated are only specific embodiments of the invention. It is apparent that the present invention is not limited to the above embodiment, and many variations are possible. All modifications that can be directly derived or referenced by those skilled in the art from this disclosure are considered to be the scope of the invention.
Claims (4)
- 餐厨垃圾和污泥产氢酸化预处理提高甲烷生产速率的方法,其特征在于,具体包括下述步骤:The method for improving the methane production rate by the pretreatment of the kitchen waste and the sludge by hydrogenation is characterized in that the following steps are specifically included:(1)将粉碎预处理后的餐厨垃圾和污泥按照质量比1:1进行混合,得到预处理原料;将预处理原料与质量浓度为1%的H2SO4溶液配制成混合液,混合液中预处理原料的浓度为20~30g/L;将混合液在135℃下水解处理15min,得到发酵原料;(1) Mixing the kitchen waste and sludge after the pulverization pretreatment according to a mass ratio of 1:1 to obtain a pretreated raw material; preparing the pretreated raw material with a H 2 SO 4 solution having a mass concentration of 1% to prepare a mixed solution, The concentration of the pretreated raw material in the mixed solution is 20-30 g/L; the mixed solution is hydrolyzed at 135 ° C for 15 min to obtain a fermentation raw material;(2)将200~500ml的发酵原料加入容积为600ml的发酵瓶,用质量浓度为6mol/L的NaOH调节pH为6.4~6.6;加入0.2~0.5g酵母粉,接种暗发酵产氢菌20~50ml,通入高纯氮气20min营造厌氧发酵环境,然后恒温37℃进行暗发酵产氢深度酸化预处理,得到产氢深度酸化预处理液体;(2) 200-500 ml of fermentation raw material is added to a fermentation flask having a volume of 600 ml, and the pH is adjusted to 6.4-6.6 with a NaOH having a mass concentration of 6 mol/L; 0.2-0.5 g of yeast powder is added to inoculate a dark fermentation hydrogen-producing bacterium 20~ 50ml, pass high-purity nitrogen for 20min to create an anaerobic fermentation environment, and then perform a deep acidification pretreatment of dark fermentation hydrogen production at a constant temperature of 37 °C to obtain a deep acidification pretreatment liquid for hydrogen production;(3)用质量浓度为6mol/L的NaOH调节产氢深度酸化预处理液体使pH为7.9~8.1,加入20~50ml产甲烷菌,保持37℃厌氧环境进行发酵联产甲烷。(3) Adjusting the hydrogenation deep-acidification pretreatment liquid with a concentration of 6 mol/L NaOH to make the pH 7.9-8.1, adding 20-50 ml methanogens, and maintaining the 37 °C anaerobic environment for fermentation to produce methane.
- 根据权利要求1所述的方法,其特征在于,所述步骤(1)中的餐厨垃圾来源于居民家庭生活或餐饮业;所述污泥来源于城市污水处理厂或食品加工厂。The method according to claim 1, wherein the kitchen waste in the step (1) is derived from a resident family life or a catering industry; and the sludge is derived from a municipal sewage treatment plant or a food processing factory.
- 根据权利要求1所述的方法,其特征在于,所述步骤(2)中,所述暗发酵产氢菌的优势菌种为丁酸梭菌,是由厌氧消化污泥分离得到的:由厌氧消化污泥经过加热处理,杀死产甲烷菌并保留暗发酵产氢菌的芽孢,培养富集三次,每72小时一次。The method according to claim 1, wherein in the step (2), the dominant species of the dark fermentation hydrogen producing bacteria is Clostridium butyricum, which is obtained by separating anaerobic digestion sludge: The anaerobic digestion sludge is heat treated to kill the methanogens and retain the spores of the dark fermentation hydrogen producing bacteria, and the culture is enriched three times, once every 72 hours.
- 根据权利要求1所述的方法,其特征在于,所述步骤(3)中,所述产甲烷菌的优势菌种为甲烷八叠球菌和甲烷丝菌,是将不经过加热处理的沼气池活性污泥在厌氧培养箱中多次富集培养得到的。 The method according to claim 1, wherein in the step (3), the dominant species of the methanogens are M. mazei and M. sphaeroides, which are biogas digester activities which are not subjected to heat treatment. The sludge is enriched and cultured several times in an anaerobic incubator.
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