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沼气监测系统在沼气提纯生物天然气技术中的应用

一、 沼气提纯

1、 Biogas purification

沼气的成分主要为甲烷(50%~60%)和二氧化碳(40%~50%),沼气提纯技术通过去除沼气中杂质成分,可以提高沼气中甲烷含量和能量密度,进而制得高品质生物天然气。精制后的生物天然气通过加压调制后可以用作汽车和火车燃料。在德国和瑞典,新建沼气工程多配有相应沼气精制设备,沼气提纯技术已成为目前沼气能源应用方面的研究热点。

The main components of biogas are methane (50%~60%) and carbon dioxide (40%~50%). Biogas purification technology can improve the methane content and energy density in biogas by removing impurities, thereby producing high-quality biogas. The refined bio natural gas can be used as fuel for cars and trains after being pressurized and modulated. In Germany and Sweden, new biogas projects are often equipped with corresponding biogas refining equipment, and biogas purification technology has become a research hotspot in the application of biogas energy.

目前工业应用的沼气脱碳制备生物天然气的工艺主要有高压水洗、物理吸收、化学吸收、变压吸附、膜分离等。这些方法的本质是将二氧化碳从沼气中分离出并排放到大气中,是一种抛弃式脱碳,这不仅造成温室气体排放,而且极大地浪费了二氧化碳资源。

At present, the industrial application of biogas decarbonization to produce biogas mainly includes high-pressure water washing, physical absorption, chemical absorption, pressure swing adsorption, membrane separation, etc. The essence of these methods is to separate carbon dioxide from biogas and emit it into the atmosphere, which is a form of abandoned decarbonization. This not only causes greenhouse gas emissions, but also greatly wastes carbon dioxide resources.

如果进行二氧化碳加氢甲烷化脱碳,则可以利用二氧化碳资源提高生物天然气产量,是一种利用式脱碳。

If carbon dioxide hydrogenation methane decarbonization is carried out, carbon dioxide resources can be utilized to increase the production of biogas, which is a utilization type decarbonization.

二、 加氢提纯技术分类

2、 Classification of hydrogenation purification technology

根据加氢方式的不同,沼气提纯方式可分为原位加氢提纯和异位加氢提纯。所谓原位加氢提纯方式,是将外源氢气直接通入真是的沼气发酵体系中,在原位把沼气中的CO2转化成CH4,达到纯化升级沼气的目的,国外学者针对加氢提纯技术做了一系列探索性研究:

According to different hydrogenation methods, biogas purification methods can be divided into in-situ hydrogenation purification and ex situ hydrogenation purification. The so-called in-situ hydrogenation purification method is to directly introduce external hydrogen gas into the real biogas fermentation system, convert CO2 in biogas into CH4 in situ, and achieve the purpose of purifying and upgrading biogas. Foreign scholars have conducted a series of exploratory studies on hydrogenation purification technology:

1、 原位加氢提纯

1. In situ hydrogenation purification

以畜禽粪便和絮状污泥等固体废物的发酵体系为研究对象,实验证明通入外源氢气确实可以有效地提高沼气的生成速率和甲烷浓度,而沼气中的二氧化碳含量由对比实验中的38%降12%,初步取得了沼气提纯效果。

Taking the fermentation system of solid waste such as animal manure and flocculent sludge as the research object, experiments have shown that the introduction of exogenous hydrogen gas can effectively improve the generation rate and methane concentration of biogas. The carbon dioxide content in biogas has been reduced from 38% in the comparative experiment to 12%, and the preliminary purification effect of biogas has been achieved.

此外为了解决原位沼气提纯中pH值升高的问题,他们开展了与酸性废物共发酵实验研究,把发酵体系的pH值有效地控制在8.0以下;针对气液传质速率低这一难点,采用中空纤维膜(HFM)组件曝气来代替传统微孔曝气方式,提高了H2在发酵液界面处的气液传质。

In addition, in order to solve the problem of pH increase in in-situ biogas purification, they conducted co fermentation experiments with acidic waste, effectively controlling the pH value of the fermentation system below 8.0; In response to the difficulty of low gas-liquid mass transfer rate, hollow fiber membrane (HFM) module aeration was adopted instead of traditional microporous aeration to improve the gas-liquid mass transfer of H2 at the fermentation liquid interface.

结果表明,在55℃发酵温度和150r/min搅拌强度下,当以1440mL/(L?d)的速率持续通气时,H2会被消耗完全,CH4的浓度达到90.2%,而在不通氢的发酵体系中,产生的沼气只含有55.4%的CH4,CO2的比重占44.6%。

The results showed that under a fermentation temperature of 55 ℃ and a stirring intensity of 150r/min, when continuously aerated at a rate of 1440mL/(L? D), H2 was completely consumed, and the concentration of CH4 reached 90.2%. However, in a fermentation system without hydrogen, the produced biogas only contained 55.4% CH4, and the proportion of CO2 accounted for 44.6%.

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2、 异位加氢提纯

2. Ectopic hydrogenation purification

异位沼气提纯实验中,富集有嗜氢甲烷菌的厌氧反应器被作为单独的沼气提纯单元,经提纯处理后,沼气中CH4达到95%左右,成功实现沼气提纯。

In the experiment of heterotopic biogas purification, an anaerobic reactor enriched with hydrogen loving methane bacteria was used as a separate biogas purification unit. After purification treatment, the CH4 in biogas reached about 95%, successfully achieving biogas purification.

在氢气来源方面,除了利用可再生电能电解水制氢外,还可用焦炉气代替纯氢气,同步实现沼气提纯和焦炉气资源化双重目的。

In terms of hydrogen sources, in addition to using renewable electricity to electrolyze water for hydrogen production, coke oven gas can also be used instead of pure hydrogen to achieve the dual goals of biogas purification and coke oven gas resource utilization simultaneously.

三、 国内加氢提纯技术发展现状

3、 Development status of domestic hydrogenation purification technology

近期,科学院成都生物研究所开展了高温原位加氢甲烷化制备生物天然气的研究,直接将氢气通入猪粪厌氧消化反应器内,平均甲烷产率从未加氢阶段的222L/kgVS提高292L/kgVS,平均相对甲烷含量从66%提高83%。

Recently, the Chinese Academy of Sciences Chengdu Institute of Biology has carried out the research on the preparation of biological natural gas by high-temperature in-situ hydro methanation. Hydrogen is directly introduced into the pig manure anaerobic digestion reactor, and the average methane yield has increased from 222L/kgVS in the hydrogenation stage to 292L/kgVS, and the average relative methane content has increased from 66% to 83%.

通过微生物多样性分析表明,严格氢营养型产甲烷菌Methanoculleus、Methanobrevibacter、Methanobacterium是高温原位加氢甲烷化系统的主要产甲烷菌,且外源氢气的加入会弱化同型产乙酸菌与氢营养型产甲烷菌之间的互营协作关系,而作为种间电子传递载体的甲酸钠的加入有助丙酸降解产乙酸,从而保证系统的稳定。

Through microbial diversity analysis, it was shown that strictly hydrogenotrophic methanogens Methanoculleus, Methanobrevibacter, and Methanobacterium are the main methanogens in high-temperature in-situ hydrogenation methanation systems. The addition of exogenous hydrogen weakens the cooperative relationship between homotrophic methanogens and hydrogenotrophic methanogens, while the addition of sodium formate as an interspecies electron transfer carrier helps to degrade propionic acid and produce acetic acid, thereby ensuring system stability.

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