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鑒于全球化石燃料所面臨的枯竭危機(jī),對生物質(zhì)燃料的開發(fā)和應(yīng)用已經(jīng)成為各國關(guān)注的重點(diǎn)。其中,沼氣和生物天然氣作為可再生能源,具有利用成本低、對環(huán)境無污染的特點(diǎn),是替代常規(guī)化石能源的優(yōu)質(zhì)環(huán)保燃料。隨著大型沼氣、生物天然氣工程的快速發(fā)展,沼氣脫硫提純?yōu)楦吒郊又瞪锶細(xì)獾男枨笕找嫫惹?,沼氣凈化提純技術(shù)得到了不同程度的應(yīng)用和發(fā)展。
Given the global crisis of fossil fuel depletion, the development and application of biomass fuels have become a focus of attention for countries around the world. Among them, biogas and biogas, as renewable energy sources, have the characteristics of low utilization cost and no pollution to the environment, and are high-quality and environmentally friendly fuels that can replace conventional fossil fuels. With the rapid development of large-scale biogas and biogas engineering, the demand for desulfurization and purification of biogas into high value-added biogas is becoming increasingly urgent, and biogas purification technology has been applied and developed to varying degrees.
通過去除沼氣中的雜質(zhì),來對沼氣進(jìn)行凈化提純,提純后的甲烷氣體濃度和燃燒熱值,即可替代天然氣用作城市管道燃?xì)饣蛘哂米鬈囉萌細(xì)?,能夠?jié)約和替代大量化石能源,減少污染物和溫室氣體排放,大大提高了沼氣工程的經(jīng)濟(jì)效益和沼氣的深度利用。
By removing impurities from biogas, it is purified and purified. The concentration and combustion heat value of the purified methane gas can replace natural gas as urban pipeline gas or vehicle gas, saving and replacing a large amount of fossil energy, reducing pollutants and greenhouse gas emissions, greatly improving the economic benefits of biogas engineering and the deep utilization of biogas.
一
one
沼氣凈化提純技術(shù)利用現(xiàn)狀
Current Status of Utilization of Biogas Purification and Purification Technology
沼氣中含有硫化氫,分子式為H2S,硫化氫為易燃?;罚c空氣混合能形成爆炸性混合物,遇明火、高熱能引起燃燒爆炸,加上硫化氫遇水后會(huì)對鋼材產(chǎn)生較強(qiáng)的腐蝕特性,因此沼氣提純精制生物天然氣的預(yù)處理工序的核心即是脫除硫化氫。
Biogas contains hydrogen sulfide, with a molecular formula of H2S. Hydrogen sulfide is a flammable and hazardous chemical that can form explosive mixtures when mixed with air. It can cause combustion and explosion when exposed to open flames or high heat energy. In addition, hydrogen sulfide has strong corrosive properties on steel when it comes into contact with water. Therefore, the core of the pre-treatment process for purifying and refining natural gas from biogas is to remove hydrogen sulfide.
不同的有機(jī)廢棄物在厭氧狀態(tài)下產(chǎn)生的沼氣中的硫化氫濃度有高有低,差異比較大。造紙工業(yè)、發(fā)酵工業(yè)等由于在生產(chǎn)過程中有含硫的介質(zhì)加入,生產(chǎn)廢水產(chǎn)生的沼氣含硫化氫的濃度便比較高。如造紙行業(yè)的沼氣可高達(dá)10000-35000ppm,淀粉工業(yè)沼氣一般在10000ppm左右,生活垃圾填埋沼氣則由于產(chǎn)生過程中相對較少有硫介質(zhì)參與,因此硫化氫含量較低,一般在1000ppm以內(nèi)。
The concentration of hydrogen sulfide in biogas produced by different organic wastes under anaerobic conditions varies greatly. Due to the addition of sulfur-containing media during the production process in industries such as papermaking and fermentation, the concentration of hydrogen sulfide in the biogas produced from production wastewater is relatively high. The biogas produced in the paper industry can reach 10000-35000 ppm, while the biogas produced in the starch industry is generally around 10000 ppm. The biogas produced in the landfill of household waste has a relatively low content of hydrogen sulfide due to the relatively low involvement of sulfur media in the production process, generally within 1000 ppm.
在我國,目前沼氣的生產(chǎn)加工技術(shù)和商業(yè)化運(yùn)行系統(tǒng)也已經(jīng)逐漸成熟,通過自主創(chuàng)新、引進(jìn)并消化吸收了國外成熟先進(jìn)的高含固量的有機(jī)廢棄物厭氧消化技術(shù),其中以谷物秸稈、畜禽糞便、城市有機(jī)垃圾為處理對象的大型沼氣工程也取得了突破性進(jìn)展,因此,相應(yīng)的沼氣凈化提純工藝技術(shù)也得到發(fā)展,形成了一系列相對比較成熟的技術(shù)。
In China, the production and processing technology and commercial operation system of biogas have gradually matured. Through independent innovation, introduction, digestion and absorption of mature and advanced high solid organic waste anaerobic digestion technology from abroad, large-scale biogas projects targeting grain straw, livestock manure, and urban organic waste have also made breakthrough progress. Therefore, corresponding biogas purification and purification technology has also been developed, forming a series of relatively mature technologies.
二
two
沼氣提純精制生物天然氣脫硫技術(shù)
Biogas purification and refining technology for desulfurization of bio natural gas
國內(nèi)外用于沼氣脫硫的常見工藝有干法脫硫、PSA脫硫、化學(xué)法脫硫、生物脫硫、膜分離法脫硫等。而在沼氣提純精制生物天然氣領(lǐng)域,主要有活性碳系或氧化鐵系干法脫硫、堿洗脫硫、生物脫硫。其中,生物脫硫因?yàn)橄蛟蠚庵幸肓搜醯入s質(zhì)氣體,因此只能用于沼氣發(fā)電而不能用于沼氣精制,以下就對沼氣提純中的脫硫技術(shù)及其特點(diǎn)進(jìn)行說明:
The common processes used for biogas desulfurization both domestically and internationally include dry desulfurization, PSA desulfurization, chemical desulfurization, biological desulfurization, membrane separation desulfurization, etc. In the field of biogas purification and refining of natural gas, there are mainly activated carbon or iron oxide based dry desulfurization, alkali washing desulfurization, and biological desulfurization. Among them, biological desulfurization can only be used for biogas power generation and cannot be used for biogas refining because it introduces impurity gases such as oxygen and nitrogen into the raw gas. The following will explain the desulfurization technology and its characteristics in biogas purification:
1
one
干法脫硫
Dry desulfurization
干法脫硫是通過固體脫硫劑將氣態(tài)硫化物轉(zhuǎn)化為固體硫化物,該法特點(diǎn)是設(shè)備制造簡單、操作簡便,凈化度較高,脫硫劑可再生。但缺點(diǎn)是價(jià)值很低,達(dá)到飽和硫容后就須更換。通常用于氣量小、硫化氫含量低,需要深度脫硫的氣體脫硫,且對氣溫和水份有一定的要求。脫硫劑通常分為活性碳系、氧化鐵系、鋅錳系幾類。脫硫塔多為固定床層,多塔串聯(lián)使用,用過的脫硫劑可通過摻煤燃燒或廠家回收處理再利用。
Dry desulfurization is the process of converting gaseous sulfides into solid sulfides using solid desulfurizers. This method is characterized by simple equipment manufacturing, easy operation, high purification efficiency, and renewable desulfurizers. But the disadvantage is that the value is very low, and it needs to be replaced after reaching the saturation sulfur capacity. Usually used for gas desulfurization with small gas volume, low hydrogen sulfide content, requiring deep desulfurization, and having certain requirements for temperature and moisture. Desulfurizers are usually divided into several categories: activated carbon based, iron oxide based, and zinc manganese based. Most desulfurization towers have a fixed bed and are used in series. The used desulfurizer can be burned with coal or recycled by the manufacturer for reuse.
2
two
PSA和膜分離法脫硫
PSA and membrane separation desulfurization
變壓吸附(PSA)的原理是以吸附劑對不同的氣體在不同的壓力下,氣體吸附速率和量的不同而實(shí)現(xiàn)氣體的分離。膜分離法則是利用氣體分子大小不同能選擇性透過膜和不同氣體穿透速率不同而實(shí)現(xiàn)氣體的分離。這兩種方法分離出的硫化氫都需要再處理,同時(shí)對甲烷氣帶來較大的損失。
The principle of pressure swing adsorption (PSA) is to achieve gas separation by using adsorbents to adsorb different gases at different pressures, with varying rates and amounts of gas adsorption. The membrane separation method is to achieve gas separation by utilizing the different sizes of gas molecules that can selectively pass through the membrane and the different penetration rates of gases. The hydrogen sulfide separated by these two methods needs to be reprocessed, while also causing significant losses to methane gas.
另外,膜分離法中使用的膜要經(jīng)常更換,運(yùn)行成本較高,而變壓吸附劑和化學(xué)吸收劑可循環(huán)使用,因此,變壓吸附法相對于膜分離技術(shù)的實(shí)際應(yīng)用更廣。
In addition, the membrane used in membrane separation method needs to be replaced frequently, resulting in high operating costs. However, pressure swing adsorbents and chemical absorbents can be recycled, so pressure swing adsorption method has a wider practical application compared to membrane separation technology.
3
three
堿洗脫硫
Alkali washing desulfurization
堿洗脫硫是指采用堿液循環(huán)使用進(jìn)行脫硫,根據(jù)再生方法不同可分為:化學(xué)法和生物法。兩種方式在脫硫、硫磺處理、配堿等工序上均相同,其中采用催化劑再生的工藝叫化學(xué)再生脫硫,采用生物菌再生的工藝叫生物再生脫硫。
Alkali washing desulfurization refers to the use of alkaline solution for cyclic desulfurization, which can be divided into chemical and biological methods according to different regeneration methods. The two methods are the same in processes such as desulfurization, sulfur treatment, and alkali mixing. The process using catalyst regeneration is called chemical regeneration desulfurization, and the process using biological bacteria regeneration is called biological regeneration desulfurization.
除了再生方式不同之外,這兩種方法主要的應(yīng)用領(lǐng)域也各自不同,其中生物再生式堿洗脫硫工藝在沼氣發(fā)電氣體預(yù)處理工序中有一定的應(yīng)用,在沼氣精制天然氣的氣體脫除硫化氫實(shí)際項(xiàng)目中則尚未應(yīng)用,化學(xué)再生法相對而言應(yīng)用則更廣一些。
In addition to the different regeneration methods, the main application areas of these two methods are also different. Among them, the biological regeneration alkaline washing desulfurization process has been applied to a certain extent in the gas pretreatment process of biogas power generation, but has not been applied in the actual project of gas removal of hydrogen sulfide in biogas refined natural gas. The chemical regeneration method is relatively more widely used.
4生物脫硫
4. Biological desulfurization
生物脫硫工藝是一種新型的脫硫工藝,越來越受到企業(yè)的歡迎。生物脫硫的基本原理是利用硫桿菌屬和絲硫茵屬類微生物代謝的作用,將硫化氫與氧氣合成為硫酸鹽進(jìn)而除去沼氣中的硫氫,脫硫產(chǎn)物為硫酸鹽。
Biological desulfurization process is a new type of desulfurization process that is increasingly popular among enterprises. The basic principle of biological desulfurization is to utilize the metabolism of sulfur bacteria and silk sulfur bacteria to synthesize hydrogen sulfide and oxygen into sulfate, thereby removing sulfur and hydrogen from biogas. The desulfurization product is sulfate.
雖然其使用較為便捷,運(yùn)行成本較低,但由于脫硫過程中同時(shí)引入了雜質(zhì)氣體,在后續(xù)工序中無法去除,同時(shí)生物脫硫剛剛起步,技術(shù)還不成熟,大多使用進(jìn)口技術(shù)和設(shè)備,因此投資成本相對較高,大約為常規(guī)干法脫硫的3~5倍。
Although it is relatively convenient to use and has low operating costs, impurities are introduced during the desulfurization process, which cannot be removed in subsequent processes. At the same time, biological desulfurization is just starting and the technology is not yet mature, mostly using imported technology and equipment. Therefore, the investment cost is relatively high, about 3-5 times that of conventional dry desulfurization.
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