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在沼氣、天然氣等能源氣體的凈化處理中,脫硫是不可或缺的關鍵環(huán)節(jié)。硫化氫(H?S)不僅具有強烈的腐蝕性和惡臭氣味,還會嚴重腐蝕管道設備、毒化下游催化劑,限制氣體的安全利用。在眾多脫硫技術中,生物脫硫憑借其綠色、、低成本的優(yōu)勢,正在成為越來越受關注的脫硫方案。
In the purification treatment of energy gases such as biogas and natural gas, desulfurization is an indispensable key link. Hydrogen sulfide (H2S) not only has strong corrosiveness and foul odor, but also seriously corrodes pipeline equipment, poisons downstream catalysts, and limits the safe utilization of gas. Among numerous desulfurization technologies, biological desulfurization is becoming an increasingly popular desulfurization solution due to its advantages of being green, efficient, and low-cost.
生物脫硫技術是利用脫硫微生物(主要是硫桿菌屬和絲硫菌屬)的新陳代謝作用,將硫化氫轉化為硫酸或單質硫的生物代謝技術。其核心原理是在控制氧氣濃度的條件下,通過氧化還原電位的調控實現硫化氫的選擇性轉化。在生物反應塔中,特制填料為脫硫細菌的生長繁殖提供了充足的空間,營養(yǎng)液的循環(huán)使填料保持潮濕狀態(tài)并補充細菌所需營養(yǎng)。沼氣中的硫化氫被填料表面的微生物吸收并催化轉化,生成元素硫或硫酸。整個過程的主要化學反應如下:H?S + 2O? → H?SO?,以及2H?S + O? → 2S + 2H?O。

Biological desulfurization technology is a biological metabolic technology that utilizes the metabolic processes of desulfurization microorganisms (mainly sulfur bacteria and filamentous sulfur bacteria) to convert hydrogen sulfide into sulfuric acid or elemental sulfur. The core principle is to achieve selective conversion of hydrogen sulfide by regulating the redox potential under controlled oxygen concentration conditions. In the biological reaction tower, specially designed packing provides sufficient space for the growth and reproduction of desulfurization bacteria, and the circulation of nutrient solution keeps the packing moist and replenishes the nutrients needed by the bacteria. Hydrogen sulfide in biogas is absorbed and catalytically converted by microorganisms on the surface of the filling material, producing elemental sulfur or sulfuric acid. The main chemical reactions of the entire process are as follows: H? S+2O? → H?SO? And 2H? S+O? → 2S + 2H? O。
從工藝類型來看,生物脫硫主要分為好氧脫硫和缺氧脫硫兩種路徑,二者的區(qū)別在于電子受體的不同。好氧脫硫以氧氣為電子受體,需在沼氣中泵入適量空氣;而缺氧脫硫則以硝態(tài)氮為電子受體,不僅能實現沼氣脫硫,還能同步解決水體氮污染問題。中科院成都生物研究所的研究人員曾創(chuàng)新性地提出了以硝化處理后的沼液提供脫硫菌株所需電子受體的思路,實現了同步沼氣脫硫與沼液脫氮。實驗結果表明,在不同運行條件下該系統(tǒng)可達到平均95%的H?S去除效率。
From the perspective of process types, biological desulfurization is mainly divided into two pathways: aerobic desulfurization and anaerobic desulfurization, with the difference between the two being the difference in electron acceptors. Aerobic desulfurization uses oxygen as an electron acceptor and requires pumping an appropriate amount of air into biogas; And anaerobic desulfurization uses nitrate nitrogen as an electron acceptor, which can not only achieve biogas desulfurization, but also simultaneously solve the problem of nitrogen pollution in water bodies. Researchers from the Chengdu Institute of Biology, Chinese Academy of Sciences, have innovatively proposed the idea of using nitration treated biogas slurry to provide the electron acceptors required by desulfurization strains, achieving synchronous biogas desulfurization and biogas slurry denitrification. The experimental results show that the system can achieve an average H-S removal efficiency of 95% under different operating conditions.
從技術發(fā)展沿革來看,生物脫硫經歷了三代演進。第一代干法脫硫采用硫酸鐵脫硫劑,需頻繁更換,成本高昂;第二代濕法脫硫通過堿液吸附結合催化劑再生,降低了勞動強度;第三代生物脫硫則分為一體式和分離式兩類——一體式工藝通過空氣混合沼氣在生物濾池中脫硫,適用于低濃度硫化氫場景;分離式工藝采用洗滌塔與生物反應器分步處理,解決了填料堵塞問題,適用于高濃度硫化氫及沼氣提純場景。
From the perspective of technological development, biological desulfurization has gone through three generations of evolution. The first generation of dry desulfurization uses iron sulfate desulfurizer, which requires frequent replacement and high cost; The second-generation wet desulfurization reduces labor intensity by adsorbing alkaline solution and regenerating catalyst; The third generation of biological desulfurization can be divided into two categories: integrated and separated. The integrated process uses air mixed biogas to desulfurize in a biological filter, which is suitable for low concentration hydrogen sulfide scenarios; The separation process adopts a washing tower and a bioreactor for step-by-step treatment, which solves the problem of packing blockage and is suitable for high concentration hydrogen sulfide and biogas purification scenarios.
在應用層面,生物脫硫技術已在多個領域實現產業(yè)化。國外已有較成熟的集成技術,主要包括荷蘭帕克公司的殼牌-帕克工藝和奧地利英環(huán)生物濾池脫硫工藝等。國內方面,山鷹紙業(yè)(廣東)有限公司的造紙污水處理項目便成功運用了沼氣生物濕法脫硫技術,對造紙廢水厭氧處理過程中產生的沼氣進行脫硫處理,有效降低了送入發(fā)電機中沼氣的硫化氫濃度。
At the application level, biological desulfurization technology has been industrialized in multiple fields. There are already mature integrated technologies abroad, mainly including the Shell Parker process of Dutch company Parker and the desulfurization process of Austrian ENN biofilter. Domestically, the paper-making wastewater treatment project of Shanying Paper Industry (Guangdong) Co., Ltd. has successfully applied biogas wet desulfurization technology to desulfurize the biogas generated during the anaerobic treatment of paper-making wastewater, effectively reducing the concentration of hydrogen sulfide in the biogas sent to the generator.
展望未來,隨著環(huán)保要求的日趨嚴格和可再生能源產業(yè)的快速發(fā)展,生物脫硫技術憑借其低運行成本(部分工藝運行成本可低至每立方米2分錢)、無二次污染、可回收單質硫等突出優(yōu)勢,必將在畜禽糞污處理、餐廚垃圾處理、污水處理等領域迎來更廣闊的應用前景。
Looking ahead to the future, with increasingly strict environmental requirements and the rapid development of the renewable energy industry, biological desulfurization technology, with its outstanding advantages such as low operating costs (some processes can have operating costs as low as 2 cents per cubic meter), no secondary pollution, and recyclable elemental sulfur, will surely usher in broader application prospects in fields such as livestock and poultry manure treatment, kitchen waste treatment, and sewage treatment.