在全球積極尋求可持續(xù)能源解決方案的大背景下，沼氣作為一種可再生的清潔能源，正逐漸走進(jìn)人們的視野。從有機(jī)廢棄物的厭氧發(fā)酵中誕生，沼氣蘊(yùn)含著巨大的能量潛力。然而，原始沼氣中常伴有硫化氫這一 “雜質(zhì)”，它不僅氣味刺鼻、具有腐蝕性，還會(huì)在燃燒時(shí)產(chǎn)生污染性更強(qiáng)的二氧化硫，嚴(yán)重阻礙沼氣的廣泛應(yīng)用。因此，沼氣脫硫技術(shù)便成為了釋放沼氣清潔能量的關(guān)鍵鑰匙。

Against the backdrop of actively seeking sustainable energy solutions globally, biogas, as a renewable and clean energy source, is gradually entering people's vision. Born from anaerobic fermentation of organic waste, biogas contains enormous energy potential. However, raw biogas often contains hydrogen sulfide as an "impurity", which not only has a pungent odor and corrosiveness, but also produces more polluting sulfur dioxide during combustion, seriously hindering the widespread application of biogas. Therefore, biogas desulfurization technology has become the key to releasing clean energy from biogas.

一、沼氣脫硫的緊迫性

1、 The urgency of biogas desulfurization

硫化氫在沼氣中雖然含量相對(duì)較少，卻有著不可忽視的危害。從對(duì)設(shè)備的影響來看，當(dāng)沼氣中的硫化氫與水接觸時(shí)，會(huì)形成具有強(qiáng)腐蝕性的氫硫酸，這對(duì)于沼氣輸送管道、儲(chǔ)存設(shè)備以及利用沼氣的各類燃燒器具來說，都是巨大的威脅，會(huì)顯著縮短設(shè)備的使用壽命，增加維護(hù)成本。從環(huán)境角度出發(fā)，未經(jīng)脫硫的沼氣在燃燒時(shí)，硫化氫會(huì)轉(zhuǎn)化為二氧化硫排放到大氣中，成為酸雨形成的重要 “元兇” 之一，對(duì)生態(tài)環(huán)境造成破壞。并且，硫化氫本身還是一種毒性氣體，高濃度的硫化氫會(huì)對(duì)人體的神經(jīng)系統(tǒng)、呼吸系統(tǒng)等造成嚴(yán)重?fù)p害，威脅到操作人員的生命健康。所以，無論是為了保障沼氣利用設(shè)備的正常運(yùn)行，還是為了減少對(duì)環(huán)境和人體的危害，沼氣脫硫都刻不容緩。

Although the content of hydrogen sulfide in biogas is relatively low, it has significant hazards that cannot be ignored. From the perspective of its impact on equipment, when hydrogen sulfide in biogas comes into contact with water, it forms highly corrosive hydrogen sulfate, which poses a huge threat to biogas transmission pipelines, storage equipment, and various combustion appliances that utilize biogas. This significantly shortens the service life of equipment and increases maintenance costs. From an environmental perspective, when desulfurized biogas is burned, hydrogen sulfide is converted into sulfur dioxide and emitted into the atmosphere, becoming one of the important "culprits" of acid rain formation and causing damage to the ecological environment. Moreover, hydrogen sulfide itself is a toxic gas, and high concentrations of hydrogen sulfide can cause serious damage to the human nervous system, respiratory system, etc., threatening the life and health of operators. Therefore, whether it is to ensure the normal operation of biogas utilization equipment or to reduce the harm to the environment and human health, biogas desulfurization is urgent.

二、各顯神通的脫硫技術(shù)

2、 Various desulfurization technologies that demonstrate their unique abilities

（一）干法脫硫

（1） Dry desulfurization

干法脫硫是一種較為傳統(tǒng)且應(yīng)用廣泛的脫硫方法，其中氧化鐵脫硫劑的使用尤為常見。氧化鐵脫硫的原理主要基于其對(duì)硫化氫的催化、氧化與吸附作用。當(dāng)含有硫化氫的沼氣通過填充有氧化鐵脫硫劑的脫硫塔時(shí)，硫化氫與氧化鐵發(fā)生化學(xué)反應(yīng)：Fe?O??H?O + 3H?S = Fe?S??H?O + 3H?O + 5.2 千卡 ，在這個(gè)過程中，硫化氫被氧化成硫離子并被氧化鐵吸附，從而達(dá)到脫硫的目的。當(dāng)脫硫劑使用一段時(shí)間后，如果檢測到脫硫塔出口的硫化氫濃度接近設(shè)計(jì)值，就表明脫硫劑已經(jīng)飽和，需要進(jìn)行再生或更換。再生過程則是在有氧條件下進(jìn)行，反應(yīng)式為：2Fe?S??H?O + 3O? = 2Fe?O??H?O + 6S + 94.2 千卡 。若氣體中氧氣含量充足（O?/H?S＞2.5 時(shí)），脫硫和再生反應(yīng)可以實(shí)現(xiàn)連續(xù)進(jìn)行 ，反應(yīng)式可合并為：2H?S + O? = 2H?O + 2S。

Dry desulfurization is a relatively traditional and widely used desulfurization method, among which the use of iron oxide desulfurizer is particularly common. The principle of iron oxide desulfurization is mainly based on its catalytic, oxidation, and adsorption effects on hydrogen sulfide. When biogas containing hydrogen sulfide passes through a desulfurization tower filled with iron oxide desulfurizer, hydrogen sulfide reacts chemically with iron oxide: Fe?O?? H?O + 3H? S = Fe? S??H? O + 3H? During the process of O+5.2 kcal, hydrogen sulfide is oxidized into sulfur ions and adsorbed by iron oxide, thereby achieving the purpose of desulfurization. After using the desulfurizer for a period of time, if the hydrogen sulfide concentration at the outlet of the desulfurization tower is detected to be close to the design value, it indicates that the desulfurizer is saturated and needs to be regenerated or replaced. The regeneration process is carried out under aerobic conditions, and the reaction equation is: 2Fe? S??H? O + 3O? =  2Fe? O??H? O+6S+94.2 kcal. If the oxygen content in the gas is sufficient (O?/H? S>2.5), the desulfurization and regeneration reactions can be carried out continuously, and the reaction equation can be combined as: 2H? S+O= 2H? O+2S.

干法脫硫具有諸多優(yōu)點(diǎn)，首先是脫硫精度高，能夠?qū)⒄託庵械牧蚧瘹浜拷档偷胶艿偷乃剑黄浯?，其設(shè)備相對(duì)簡單，占地面積小，建設(shè)周期短，一次性投資資金較少；再者，日常維護(hù)費(fèi)用低，操作簡便，故障率低。然而，它也存在一些不足，例如脫硫劑需要定期更換或再生，這增加了一定的勞動(dòng)強(qiáng)度和運(yùn)行成本；在處理高濃度硫化氫的沼氣時(shí)，脫硫劑的消耗較快，經(jīng)濟(jì)性會(huì)受到影響。

Dry desulfurization has many advantages. Firstly, it has high desulfurization accuracy and can reduce the hydrogen sulfide content in biogas to a very low level; Secondly, its equipment is relatively simple, occupies a small area, has a short construction period, and requires less one-time investment funds; Furthermore, the daily maintenance cost is low, the operation is easy, and the failure rate is low. However, it also has some shortcomings, such as the need for regular replacement or regeneration of desulfurizers, which increases certain labor intensity and operating costs; When dealing with biogas with high concentration of hydrogen sulfide, the consumption of desulfurizer is relatively fast, which will affect the economy.

（二）濕法脫硫

（2） Wet desulfurization

濕法脫硫是讓沼氣與液體脫硫劑在特定設(shè)備中充分接觸，從而脫除硫化氫的方法。以較為常用的 888 法為例，它以純堿作為吸收劑，以 888 法為載氧體。整個(gè)脫硫和再生過程是連續(xù)在線的，脫硫與再生同時(shí)進(jìn)行，無需設(shè)置備用脫硫塔。在脫硫過程中，硫化氫與純堿溶液發(fā)生反應(yīng)被吸收，而 888 催化劑則在其中起到加速反應(yīng)和載氧的作用，使吸收了硫化氫的溶液能夠在自吸空氣的條件下進(jìn)行再生，將硫化物轉(zhuǎn)化為單質(zhì)硫并分離出來 。

Wet desulfurization is a method of removing hydrogen sulfide by fully contacting biogas with liquid desulfurizer in specific equipment. Taking the commonly used 888 method as an example, it uses soda ash as the absorbent and 888 method as the oxygen carrier. The entire desulfurization and regeneration process is continuous online, and desulfurization and regeneration are carried out simultaneously without the need for a backup desulfurization tower. During the desulfurization process, hydrogen sulfide reacts with soda ash solution and is absorbed. The 888 catalyst accelerates the reaction and supports oxygen, allowing the solution that has absorbed hydrogen sulfide to regenerate under self-priming air conditions, converting sulfide into elemental sulfur and separating it.

濕法脫硫的優(yōu)勢明顯，它的工作硫容高，對(duì)不同含量的硫化氫氣體適應(yīng)性好，無論是低濃度還是高濃度的硫化氫沼氣，都能取得理想的脫硫效果；脫硫效率高，凈化后氣體中硫化氫含量穩(wěn)定；還具有消除和抑制硫泡沫堵塔的功能，再生效率高，溶液清亮，自清洗能力強(qiáng)，甚至還有洗塔作用，能夠降低脫硫塔的阻力。此外，溶液組份簡單，生產(chǎn)操作方便，催化劑活性好，消耗低。不過，濕法脫硫也有其局限性，設(shè)備投資相對(duì)較大，運(yùn)行過程中需要消耗一定量的化學(xué)藥劑，可能會(huì)產(chǎn)生一些含硫廢水，如果處理不當(dāng)，會(huì)造成二次污染。

The advantages of wet desulfurization are obvious. It has a high working sulfur capacity and good adaptability to different concentrations of hydrogen sulfide gas. Whether it is low or high concentration hydrogen sulfide biogas, it can achieve ideal desulfurization effect; High desulfurization efficiency and stable hydrogen sulfide content in the purified gas; It also has the function of eliminating and inhibiting sulfur foam blocking the tower, with high regeneration efficiency, clear solution, strong self-cleaning ability, and even the role of tower washing, which can reduce the resistance of the desulfurization tower. In addition, the solution composition is simple, the production operation is convenient, the catalyst activity is good, and the consumption is low. However, wet desulfurization also has its limitations. The equipment investment is relatively large, and a certain amount of chemical agents need to be consumed during operation, which may produce some sulfur-containing wastewater. If not treated properly, it can cause secondary pollution.

（三）生物脫硫

（3） Biological desulfurization

生物脫硫是利用微生物的新陳代謝活動(dòng)來實(shí)現(xiàn)脫硫的新型技術(shù)。其基本原理是基于雙膜理論，硫化氫氣體首先在氣液界面上由氣相轉(zhuǎn)移到液相（遵循亨利定律：HS? + OH? = H?O + HS? ），然后水溶液中的硫氫根離子被脫硫微生物吸附，從水中轉(zhuǎn)移至微生物體內(nèi)（HS? →(細(xì)胞膜 + HS?) ），* 后在微生物體內(nèi)，硫氫根被轉(zhuǎn)化成單質(zhì)硫或硫酸根 ，作為吸收劑的堿液被再生，重新吸收硫化氫（(細(xì)胞膜 + HS?)→S + H?O 或 (細(xì)胞膜 + HS?)→SO??? + H?O ）。

Biological desulfurization is a new technology that utilizes the metabolic activity of microorganisms to achieve desulfurization. The basic principle is based on the double membrane theory, where hydrogen sulfide gas first transfers from the gas phase to the liquid phase at the gas-liquid interface (following Henry's law: HS? + OH? =  H?O + HS? ）， Then, the hydrogen sulfide ions in the aqueous solution are adsorbed by desulfurization microorganisms and transferred from the water to the microbial body (HS? → (cell membrane+HS?)). After that, in the microbial body, the hydrogen sulfide ions are converted into elemental sulfur or sulfate ions, and the alkaline solution used as an absorbent is regenerated to reabsorb hydrogen sulfide ((cell membrane+HS?) → S+H?)? O or (cell membrane+HS?) → SO+ H?O ）。

目前應(yīng)用在沼氣中的生物脫硫主要分為一體式生物脫硫和分離式生物脫硫。一體式生物脫硫是將一定量的空氣導(dǎo)入含有硫化氫的沼氣中，混合氣體通過生物濾池、生物滴濾池以去除硫化氫，脫硫副產(chǎn)物一般為硫酸或者硫酸鹽 。這種方式脫硫效率高，可達(dá) 95% - 99%，運(yùn)行成本低，自動(dòng)化程度高，操作簡便，造價(jià)較低 。但缺點(diǎn)是填料易堵，影響處理效果和增加勞動(dòng)強(qiáng)度，且空氣直接與沼氣混合，存在安全風(fēng)險(xiǎn)，運(yùn)行控制精度要求高，產(chǎn)生的低濃度硫酸較難處理，也不能處理硫化氫濃度高于 15000ppm 的沼氣 。分離式生物脫硫工藝則是含硫化氫的沼氣氣體首先進(jìn)入生物洗滌塔，在塔內(nèi)與混合液中堿反應(yīng)從沼氣中脫除硫化氫，然后生物洗滌液進(jìn)入生物反應(yīng)器，在反應(yīng)器底部有空氣分布系統(tǒng)給微生物提供氧氣，將反應(yīng)器中的硫化物轉(zhuǎn)化為單質(zhì)硫，同時(shí)堿液得到再生，可重復(fù)使用 。它的脫硫效率高（可達(dá) 99% 以上），年運(yùn)行成本低，自動(dòng)化程度高操作簡便，沼氣不與空氣直接混合運(yùn)行安全，能處理高濃度的硫化氫沼氣 ，不過運(yùn)行成本略高于一體式生物脫硫 。

At present, biological desulfurization applied in biogas is mainly divided into integrated biological desulfurization and separated biological desulfurization. Integrated biological desulfurization is the process of introducing a certain amount of air into biogas containing hydrogen sulfide, and then passing the mixed gas through a biological filter or a biological drip filter to remove hydrogen sulfide. The by-products of desulfurization are usually sulfuric acid or sulfate. This method has high desulfurization efficiency, reaching 95% -99%, low operating costs, high degree of automation, easy operation, and low cost. However, the disadvantage is that the filling material is prone to clogging, which affects the treatment effect and increases labor intensity. In addition, air is directly mixed with biogas, which poses safety risks. The operation control accuracy requirements are high, and the low concentration sulfuric acid produced is difficult to treat. It also cannot treat biogas with hydrogen sulfide concentration higher than 15000ppm. The separated biological desulfurization process is that the biogas gas containing hydrogen sulfide first enters the biological washing tower, where it reacts with alkali in the mixed solution to remove hydrogen sulfide from the biogas. Then, the biological washing solution enters the bioreactor, where an air distribution system at the bottom of the reactor provides oxygen to microorganisms, converting sulfides in the reactor into elemental sulfur. At the same time, the alkali solution is regenerated and can be reused. It has high desulfurization efficiency (up to 99% or more), low annual operating cost, high degree of automation, easy operation, safe operation without direct mixing of biogas with air, and can handle high concentration hydrogen sulfide biogas, but the operating cost is slightly higher than that of integrated biological desulfurization.

三、選擇合適的脫硫方案

3、 Choose a suitable desulfurization solution

在實(shí)際應(yīng)用中，選擇何種沼氣脫硫技術(shù)需要綜合多方面因素考量。如果沼氣中硫化氫濃度較低，且處理規(guī)模較小，干法脫硫因其設(shè)備簡單、成本低等優(yōu)勢可能是較好的選擇；對(duì)于中等規(guī)模且硫化氫濃度適中的沼氣處理項(xiàng)目，濕法脫硫的高效性和對(duì)不同濃度的適應(yīng)性使其具有競爭力；而當(dāng)面對(duì)大規(guī)模、高濃度硫化氫的沼氣，或者對(duì)環(huán)保要求極高、追求低運(yùn)行成本的情況時(shí)，生物脫硫技術(shù)，尤其是分離式生物脫硫工藝，就展現(xiàn)出獨(dú)特的優(yōu)勢。同時(shí)，還需要考慮項(xiàng)目所在地的資源條件、技術(shù)水平、投資預(yù)算以及后期的運(yùn)行維護(hù)等因素，通過全面的技術(shù)經(jīng)濟(jì)分析，制定出 * 適合的沼氣脫硫方案。

In practical applications, the choice of biogas desulfurization technology requires comprehensive consideration of multiple factors. If the concentration of hydrogen sulfide in biogas is low and the treatment scale is small, dry desulfurization may be a better choice due to its advantages of simple equipment and low cost; For medium-sized biogas treatment projects with moderate hydrogen sulfide concentration, the high efficiency of wet flue gas desulfurization and its adaptability to different concentrations make it competitive; When facing large-scale, high concentration hydrogen sulfide biogas, or situations with extremely high environmental requirements and pursuit of low operating costs, biological desulfurization technology, especially the separated biological desulfurization process, exhibits unique advantages. At the same time, it is necessary to consider factors such as the resource conditions, technological level, investment budget, and later operation and maintenance of the project location, and develop a suitable biogas desulfurization plan through comprehensive technical and economic analysis.

沼氣脫硫技術(shù)作為沼氣高效清潔利用的關(guān)鍵環(huán)節(jié)，在未來的能源領(lǐng)域中有著廣闊的發(fā)展前景。隨著科技的不斷進(jìn)步，無論是傳統(tǒng)脫硫技術(shù)的優(yōu)化升級(jí)，還是新型生物脫硫技術(shù)的深入研究與應(yīng)用，都將助力沼氣在能源舞臺(tái)上綻放更加耀眼的光芒，為實(shí)現(xiàn)可持續(xù)能源發(fā)展目標(biāo)貢獻(xiàn)重要力量。

As a key link in the efficient and clean utilization of biogas, biogas desulfurization technology has broad development prospects in the future energy field. With the continuous advancement of technology, whether it is the optimization and upgrading of traditional desulfurization technology or the in-depth research and application of new biological desulfurization technology, it will help biogas shine brighter on the energy stage and contribute important forces to achieving sustainable energy development goals.

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