沼氣中含有硫化氫，分子式為H2S，硫化氫為易燃危化品，與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對鋼材產生較強的腐蝕特性，因此沼氣提純精制生物天然氣的預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. When exposed to open flames and high heat, it can cause combustion and explosion. In addition, hydrogen sulfide has strong corrosion characteristics on steel when it comes into contact with water. Therefore, the core of the pre-treatment process for purifying and refining biogas is the removal of hydrogen sulfide.

不同的有機廢棄物在厭氧狀態下產生的沼氣中的硫化氫濃度有高有低，差異比較大。造紙工業、發酵工業等由于在生產過程中有含硫的介質加入，生產廢水產生的沼氣含硫化氫的濃度便比較高。如造紙行業的沼氣可高達10000-35000ppm，淀粉工業沼氣一般在10000ppm左右，生活垃圾填埋沼氣則由于產生過程中相對較少有硫介質參與，因此硫化氫含量較低，一般在1000ppm以內。

The concentration of hydrogen sulfide in biogas produced by different organic wastes under anaerobic conditions varies greatly, with varying levels. Due to the addition of sulfur-containing media in the production process, the concentration of hydrogen sulfide in the biogas produced from production wastewater is relatively high in industries such as papermaking and fermentation. For example, the biogas in the papermaking industry can reach up to 10000-35000ppm, while the biogas in the starch industry is generally around 10000ppm. For landfill biogas in household waste, the hydrogen sulfide content is relatively low, usually within 1000ppm, due to the relatively low involvement of sulfur media in the production process.

在我國，沼氣的生產加工技術和商業化運行系統也已經逐漸成熟，通過自主創新、引進并消化吸收了國外成熟先進的高含固量的有機廢棄物厭氧消化技術，其中以谷物秸稈、畜禽糞便、城市有機垃圾為處理對象的大型沼氣工程也取得了突破性進展，因此，相應的沼氣凈化工藝技術也得到發展，形成了一系列相對比較成熟的技術。

In China, the production and processing technology and commercial operation system of biogas have gradually matured. Through independent innovation, introduction, and digestion, advanced anaerobic digestion technology for high solid organic waste from abroad has been absorbed. Among them, large-scale biogas projects that treat grain straw, animal manure, and urban organic waste have also made breakthrough progress. Therefore, corresponding biogas purification process technologies have also been developed, A series of relatively mature technologies have been formed.

行業內常用的沼氣脫硫方法有：干法脫硫、濕法脫硫、絡合鐵脫硫、生物法脫硫等幾種脫硫方法。

The commonly used biogas desulfurization methods in the industry include dry desulfurization, wet desulfurization, complex iron desulfurization, and biological desulfurization.

脫硫原理

Desulfurization principle

干法脫硫

Dry desulfurization

唐山綠干法脫硫是一種簡易、高效、相對低成本的脫硫方式，一般適合用于沼氣量小，硫化氫濃度低的沼氣脫硫。干法脫除沼氣氣體中硫化氫（H2S）的設備基本原理是以O2使H2S 氧化成硫或硫氧化物的一種方法，也可稱為干式氧化法。干法設備的構成是，在一個容器內放入填料，填料層有活性炭、氧化鐵等。氣體以低流速從一端經過容器內填料層，硫化氫（H2S）氧化成硫或硫氧化物后，余留在填料層中，凈化后氣體從容器另一端排出。

Tangshan Green Dry Desulfurization is a simple, efficient, and relatively low-cost desulfurization method, generally suitable for biogas desulfurization with small biogas volume and low hydrogen sulfide concentration. The basic principle of the equipment for dry removal of hydrogen sulfide (H2S) from biogas gas is a method of using O2 to oxidize H2S into sulfur or sulfur oxides, also known as dry oxidation method. The composition of dry process equipment is to place fillers in a container, and the filler layer includes activated carbon, iron oxide, etc. The gas passes through the packing layer inside the container at a low flow rate, and hydrogen sulfide (H2S) is oxidized to sulfur or sulfur oxides, remaining in the packing layer. After purification, the gas is discharged from the other end of the container.

干式脫硫主要包括主體鋼結構、脫硫劑填料、觀察窗、壓力表、溫度表等組件。脫硫塔通常設計為一用一備，交替使用，即一個脫硫，一個再生。 含有硫化氫(H2S)的沼氣進入脫硫塔底部，在穿過脫硫填料層到達頂端的過程中，H2S與脫硫劑發生以下的化學反應：

Dry desulfurization mainly includes components such as main steel structure, desulfurizer filler, observation window, pressure gauge, temperature gauge, etc. Desulfurization towers are usually designed as one for use and one for backup, alternating between one for desulfurization and one for regeneration. Biogas containing hydrogen sulfide (H2S) enters the bottom of the desulfurization tower and undergoes the following chemical reactions with the desulfurizer during the process of passing through the desulfurization packing layer and reaching the top:

第一步: Fe2O3 · H2O + 3 H2S = Fe2S3 + 4 H2O （脫硫）

Step 1: Fe2O3 · H2O+3 H2S=Fe2S3+4 H2O (desulfurization)

第二步: Fe2S3 + 3/2 O2 + 3 H2O = Fe2O3 · H2O + 2 H2O + 3 S（再生）

Step 2: Fe2S3+3/2 O2+3 H2O=Fe2O3 · H2O+2 H2O+3 S (regeneration)

含有硫化氫的沼氣首先與底部入口處荷載相對高的脫硫劑反應，反應器上部是負載低的脫硫劑層，通過設計良好的沼氣空速和線速，干式脫硫能到達良好的精脫硫效果。

Biogas containing hydrogen sulfide first reacts with a desulfurizer with a relatively high load at the bottom inlet. The upper part of the reactor is a desulfurizer layer with a low load. By designing good biogas airspeed and line speed, dry desulfurization can achieve good precision desulfurization effect.

在沼氣進入干式脫硫塔之前，應設置有冷凝水罐或沼氣顆粒過濾器。該裝置可以消除沼氣中夾雜的顆粒雜質，并使得沼氣在進入脫硫前含有一定濕度。

Before biogas enters the dry desulfurization tower, a condensate tank or biogas particle filter should be installed. This device can eliminate particle impurities in biogas and make biogas contain a certain humidity before entering desulfurization.

當觀察到脫硫劑變色，或系統壓力損失過大時，應交替使用另一個脫硫塔。當前的脫硫塔在沼氣放空后，進行自然通風，對脫硫劑進行再生。當再生效果不佳時，應從塔體底部將廢棄的脫硫劑排除，在底部排放廢棄填料的同時，相同體積的新鮮脫硫填料加入反應器中。

When discoloration of the desulfurizer or excessive pressure loss in the system is observed, another desulfurization tower should be used alternately. The current desulfurization tower undergoes natural ventilation after releasing biogas to regenerate the desulfurizer. When the regeneration effect is poor, the waste desulfurizer should be discharged from the bottom of the tower. At the same time as the waste packing is discharged at the bottom, fresh desulfurized packing of the same volume should be added to the reactor.

切記更換脫硫劑時不可時間過短，否則很容易引起放熱導致硫磺自燃。

Remember not to replace the desulfurizer for too short a time, otherwise it is easy to cause heat release and sulfur self ignition.

濕法脫硫

Wet desulfurization

濕法脫硫可以歸納分為物理吸收法、化學吸收法和氧化法三種。物理和化學方法存在硫化氫再處理問題，氧化法是以堿性溶液為吸收劑，并加入載氧體為催化劑，吸收H2S，并將其氧化成單質硫，濕法氧化法是把脫硫劑溶解在水中，液體進入設備，與沼氣混合，沼氣中的硫化氫（H2S）與液體產生氧化反應，生成單質硫吸收硫化氫的液體有氫氧化鈉、氫氧化鈣、碳酸鈉、硫酸亞鐵等。成熟的氧化脫硫法，脫硫效率可達99.5%以上。

Wet desulfurization can be classified into three types: physical absorption method, chemical absorption method, and oxidation method. There is a problem of hydrogen sulfide reprocessing in physical and chemical methods. The oxidation method uses alkaline solution as an absorbent and oxygen carrier as a catalyst to absorb H2S and oxidize it into elemental sulfur. The wet oxidation method dissolves the desulfurizer in water, and the liquid enters the equipment and mixes with biogas. Hydrogen sulfide (H2S) in biogas reacts with the liquid to generate elemental sulfur. The liquids that absorb hydrogen sulfide include sodium hydroxide, calcium hydroxide, sodium carbonate, etc Ferrous sulfate, etc. The mature oxidation desulfurization method can achieve a desulfurization efficiency of over 99.5%.

在大型的脫硫工程中，一般采用先用濕法進行粗脫硫，之后再通過干法進行精脫硫。

In large-scale desulfurization projects, wet desulfurization is generally used first for coarse desulfurization, and then dry desulfurization is used for fine desulfurization.

濕法脫硫塔主體包括洗滌塔、硫化氫采樣與監測系統、堿液配置槽、供水軟水裝置、液位控制系統、支撐件和連接件。脫硫系統通過對出氣硫化氫濃度的監控以及PH值監控，實現全自動運行。

The main body of the wet flue gas desulfurization tower includes a washing tower, a hydrogen sulfide sampling and monitoring system, an alkali solution preparation tank, a water supply softening device, a liquid level control system, supporting components, and connecting components. The desulfurization system achieves fully automatic operation by monitoring the concentration of hydrogen sulfide in the outlet gas and pH value.

運行時，沼氣由下至上通過脫硫塔，Na2CO3溶液（或NaOH溶液）從頂部向下噴淋，使得H2S氣體與堿液發生了充分的化學反應。

During operation, biogas passes through the desulfurization tower from bottom to top, and Na2CO3 solution (or NaOH solution) is sprayed downwards from the top, causing sufficient chemical reaction between H2S gas and alkaline solution.

堿液存儲在脫硫塔的下方，通過計量泵自動添加，計量泵的添加控制通過對出氣H2S濃度的監控自動運行。

Alkali solution is stored below the desulfurization tower and automatically added through a metering pump. The addition control of the metering pump operates automatically by monitoring the H2S concentration in the outlet gas.

當采用碳酸鈉（Na2CO3）試劑脫硫時，主要發生如下反應：

When using sodium carbonate (Na2CO3) reagent for desulfurization, the following reactions mainly occur:

H2S + Na2CO3 = NaHS + NaHCO3 ( 1 )

H2S+Na2CO3=NaHS+NaHCO3 (1)

CO2 + Na2CO3 + H2O = 2 NaHCO3 ( 2 )

CO2+Na2CO3+H2O=2 NaHCO3 (2)

由于沼氣中含有的大量CO2成分，同樣會消耗堿液。 系統應能對反應條件（包括反應溫度、PH值）等進行控制，設置最優反應條件，盡可能地減少堿液的消耗量。

Due to the large amount of CO2 contained in biogas, it also consumes alkaline solution. The system should be able to control the reaction conditions (including reaction temperature, pH value), set the optimal reaction conditions, and minimize the consumption of alkaline solution as much as possible.

絡合鐵脫硫

Complex iron desulfurization

絡合鐵工藝是一種綠色的，基于Fe基催化劑的濕法氣體凈化技術，它集脫硫與硫磺回收于一體，在液相中直接將H2S轉化為單質S。

The complex iron process is a green, Fe based catalyst based wet gas purification technology that integrates desulfurization and sulfur recovery. It directly converts H2S into elemental S in the liquid phase.

硫化氫脫出率高（ 一步反應的脫出率99.99+% ）

High hydrogen sulfide extraction rate (99.99+% of one-step reaction)

工藝簡單、安全，系統不使用任何有毒的化學物質，也不會產生任何有害的廢棄物，控制簡單，系統安全系數高

The process is simple and safe, and the system does not use any toxic chemicals or produce any harmful waste. The control is simple, and the system has a high safety factor

適合于產量在200公斤-20噸/天的小型硫化氫脫除裝置

Suitable for small hydrogen sulfide removal devices with a production capacity of 200 kg -20 tons/day

適應H2S含量在0~100%

Adapt to H2S content between 0% and 100%

操作條件為常溫

Operating conditions are at room temperature

唐山綠源絡合鐵工藝反應原理：

The reaction principle of Tangshan Green Source Complex Iron Process:

吸收反應：

Absorption reaction:

H2S(氣體)+ 2Fe+++ 2H+ + S °+ 2Fe++

H2S (gas)+2Fe++2H++S °+2Fe++

再生反應：

Regenerative reaction:

1/2 O2 (氣體) + H2O + 2Fe++ 2OH- + 2Fe+++

1/2 O2 (gas)+H2O+2Fe++2OH -+2Fe+++

總反應：

Total reaction:

H2S + ? O2 H2O + S°

H2S+? O2 H2O+S °

絡合鐵脫硫優勢

Advantages of desulfurization with complex iron

（1）絡合鐵催化劑，工藝處理過程簡單，采用一步法處理工藝即可快速將硫化氫直接氧化為硫單質；對各種不同濃度的H2S，其脫硫后的H2S含量可低于10ppm，清除H2S效率高。

(1) The complex iron catalyst has a simple process, and the one-step treatment process can quickly oxidize hydrogen sulfide directly to sulfur elemental; For various concentrations of H2S, the H2S content after desulfurization can be lower than 10ppm, and the removal efficiency of H2S is high.

（2）系統的抗波動能力強。對于傳統的脫硫裝置，原料氣中硫化氫含量波動較大時，會造成出口凈化氣的硫化氫含量波動很大，甚至超標。絡合鐵高硫容特性，其脫硫裝置完全能自動處理以上波動情況，并不需要人為改變操作且不會影響脫硫率。

(2) The system has strong resistance to fluctuations. For traditional desulfurization devices, when the hydrogen sulfide content in the feed gas fluctuates greatly, it can cause significant fluctuations in the hydrogen sulfide content of the outlet purified gas, even exceeding the standard. The high sulfur capacity of complex iron allows its desulfurization device to automatically handle the above fluctuations without the need for manual changes in operation and without affecting the desulfurization rate.

（3）運行成本低。由于在脫硫過程中所使用的各種藥劑中的絡合鐵催化劑可再生循環使用且無副反應發生，只需補充少量的在脫硫過程中損失的絡合鐵催化劑，產出一噸硫磺藥劑運行成本1000-1500元。

(3) Low operating costs. Due to the renewable and recyclable use of complex iron catalysts in various reagents used in the desulfurization process without any side reactions, only a small amount of complex iron catalysts lost during the desulfurization process need to be supplemented, resulting in an operating cost of 1000-1500 yuan for producing one ton of sulfur reagents.

（4）絡合鐵催化劑選擇性高，副鹽產生量低。在絡合鐵脫硫中，絡合鐵離子氧化硫化氫為硫磺，脫硫過程副反應少，藥劑使用壽命長。

(4) Complex iron catalysts have high selectivity and low bysalt production. In complex iron desulfurization, complex iron ions oxidize hydrogen sulfide to sulfur, resulting in fewer side reactions and longer service life of the reagents.

（5）脫硫工作液硫容量高。最新開發的絡合鐵脫硫劑，脫硫劑循環液的硫容量不受二氧化碳的影響，其工作硫容量高達3.3kg硫磺/m藥劑，高于國外同類技術（工作硫容量較好的為0.37 kg硫磺/m藥劑）。故使用絡合鐵脫硫劑能顯著降低循環液量，降低設備尺寸，減少投資和操作成本。

(5) The desulfurization working fluid has a high sulfur capacity. The latest developed complex iron desulfurizer has a sulfur capacity that is not affected by carbon dioxide in the circulating solution of the desulfurizer. Its working sulfur capacity is as high as 3.3kg sulfur/m reagent, which is higher than similar foreign technologies (the one with better working sulfur capacity is 0.37 kg sulfur/m reagent). Therefore, the use of complex iron desulfurizers can significantly reduce the circulating liquid volume, reduce equipment size, and reduce investment and operating costs.

（6）能脫除有機硫COS、硫醇。

(6) Can remove organic sulfur COS and thiols.

（7）設備尺寸小，可有效實現橇裝化。由于工作硫容量高，設備小，可有效實現橇裝化，非常適合小項目的橇裝化要求。

(7) The device has a small size and can effectively achieve sled installation. Due to its high working sulfur capacity and small equipment, it can effectively achieve sled mounted requirements, making it very suitable for small projects.

（8）催化劑的安全性高，系統所采用的催化劑對環境及人體無毒無害，具有良好的環保效益。

(8) The safety of the catalyst is high, and the catalyst used in the system is non-toxic and harmless to the environment and human body, with good environmental benefits.

（9）系統無大量副鹽產生，環保經濟。

(9) The system does not produce a large amount of by-products, which is environmentally friendly and economical.

生物脫硫

Biological desulfurization

生物脫硫技術包括生物過濾法、生物吸附法和生物滴濾法，三種系統均屬開放系統，其微生物種群隨環境改變而變化。在生物脫硫過程中，氧化態的含硫污染物必須先經生物還原作用生成硫化物或H2S然后再經生物氧化過程生成單質硫，才能去除。在大多數生物反應器中，微生物種類以細菌為主，真菌為次，極少有酵母菌。常用的細菌是硫桿菌屬的氧化亞鐵硫桿菌，脫氮硫桿菌及排硫桿菌。最成功的代表是氧化亞鐵硫桿菌，其生長的最佳p

Biological desulfurization technology includes biological filtration, biological adsorption, and biological drip filtration, all of which belong to open systems, and their microbial populations change with environmental changes. In the process of biological desulfurization, oxidized sulfur-containing pollutants must first undergo biological reduction to generate sulfides or H2S, and then undergo biological oxidation to generate elemental sulfur in order to be removed. In most bioreactors, the microbial species are mainly bacteria, followed by fungi, and there are very few yeast. The commonly used bacteria are Thiobacillus ferrooxidans, Thiobacillus denitrifying, and Thiobacillus excreting. The most successful representative is Thiobacillus ferrooxidans, which has the best growth rate

H值為2.0～2.2。

The H value ranges from 2.0 to 2.2.

沼氣生物脫硫是20世紀90年代發展起來的新技術，在國外已得到了廣泛研究，在應用方面也取得了很大進展。國外已有較成熟的沼氣生物脫硫集成技術。

Biodesulfurization of biogas is a new technology developed in the 1990s, which has been widely studied abroad and has made great progress in application. There are already mature integrated technologies for biogas biological desulfurization in foreign countries.

工藝描述：

Process description:

將一定量的空氣導入含有硫化氫的沼氣中，混合氣體通過EnvironTec生物脫硫塔去除硫化氫。在反應器內部安裝有特殊的塑料填料，它們為脫硫細菌繁殖提供充分的空間。營養液的循環使填料保持潮濕狀態，并且補充脫硫細菌生長繁殖所需的營養。專屬菌種（如絲硫菌屬或者硫桿菌屬），借助營養液在填料中繁殖。在這種情況下，他們從混合沼氣中吸收硫化氫，并將他們轉化為單質硫，進而轉化為稀硫酸，

Introduce a certain amount of air into biogas containing hydrogen sulfide, and remove the hydrogen sulfide from the mixed gas through the EnvironTec biological desulfurization tower. Special plastic fillers are installed inside the reactor, providing ample space for the proliferation of desulfurization bacteria. The circulation of nutrient solution keeps the filler moist and supplements the nutrients needed for the growth and reproduction of desulfurization bacteria. Exclusive bacterial species (such as Thiobacillus or Thiobacillus) can reproduce in fillers using nutrient solution. In this case, they absorb hydrogen sulfide from the mixed biogas and convert it into elemental sulfur, which in turn converts into dilute sulfuric acid,

化學反應式如下：H2S + 2O2=H2SO42

The chemical reaction formula is as follows: H2S+2O2=H2SO42

H2S + O2 =2 S + 2H2OS + H2O + 1.5 O2=H2SO4

H2S+O2=2 S+2H2OS+H2O+1.5 O2=H2SO4

生成的稀硫酸在營養液和自來水的緩沖中和作用下，一起排出系統，

The generated dilute sulfuric acid is discharged from the system together with the buffering and neutralization effect of nutrient solution and tap water,

此過程周而復始。

This process repeats itself.

1 反應塔 5 營養液供應 9 熱交換器 13 營養液液位控制器

1 reaction tower 5 nutrient solution supply 9 heat exchanger 13 nutrient solution level controller

2 填料 6 稀釋用水 10 氣分析儀 14 空氣流量計

2 fillers 6 dilution water 10 gas analyzer 14 air flow meter

3 沼氣入口 7 循環液 11 pH 控制儀 15 營養液廢液排出口

3 biogas inlet 7 circulating liquid 11 pH controller 15 nutrient solution waste liquid discharge outlet

4 空氣供應 8營養液泵 12 溫度計 16安全流量控制開關

4 Air supply 8 Nutrient solution pump 12 Thermometer 16 Safety flow control switch

沼氣（3）進入反應器（1）底端，并從底端穿過填料層到達頂部。空氣（4）通過變頻控制精確添加。尾氣成分分析儀（10）對余氧濃度監控并與空氣風機連鎖。 循環液通過循環泵（8）循環噴淋。液位開關（13）控制整體的液位平衡。為了保證細菌的最佳活性，采用熱交換器（9）和溫度監測（12）對系統溫度調節控制。PH儀（11）用于控制營養液的質量（酸堿度），例如當PH低于設定值時，新鮮的營養液（5）和稀釋用水（6）自動加入脫硫塔中，在此同時，廢液（15）自動排出，并保持液位平衡。

Biogas (3) enters the bottom of reactor (1) and passes through the packing layer from the bottom to the top. Air (4) is precisely added through frequency conversion control. The exhaust gas composition analyzer (10) monitors the residual oxygen concentration and interlocks with the air fan. The circulating liquid is sprayed through the circulating pump (8). The liquid level switch (13) controls the overall liquid level balance. To ensure optimal bacterial activity, a heat exchanger (9) and temperature monitoring (12) are used to regulate and control the system temperature. The pH meter (11) is used to control the quality (acidity) of the nutrient solution. For example, when the pH is below the set value, fresh nutrient solution (5) and dilution water (6) are automatically added to the desulfurization tower. At the same time, the waste liquid (15) is automatically discharged and the liquid level is maintained in equilibrium.

方法比較

Method comparison

干法脫硫的特點

The characteristics of dry desulfurization

結構簡單，使用方便。

Simple structure and convenient use.

工作過程中無需人員值守，定期換料，一用一備，交替運行。

During the work process, there is no need for personnel to be on duty, and materials are changed regularly. One in use and one on standby operate alternately.

脫硫率新原料時較高，后期有所降低。

The desulfurization rate of new raw materials is relatively high, but it decreases in the later stage.

與濕式相比，需要定期換料。

Compared to wet type, regular material changes are required.

運行費用偏高。

The operating costs are relatively high.

濕法脫硫的特點

The characteristics of wet desulfurization

設備可長期不停的運行，連續進行脫硫。

The equipment can operate non-stop for a long time and continuously carry out desulfurization.

用PH值來保持脫硫效率，運行費用低。

Using a pH value to maintain desulfurization efficiency results in low operating costs.

工藝復雜需要專人值守。

The process is complex and requires dedicated personnel to be on duty.

設備需保養。

The equipment needs maintenance.

絡合鐵脫硫特點

Characteristics of desulfurization with complex iron

高效率： 硫化氫去除率高達99.9%

High efficiency: hydrogen sulfide removal rate up to 99.9%

高適應范圍： 可處理硫化氫濃度高達100%

High adaptability range: can handle up to 100% hydrogen sulfide concentration

低成本： 與其它脫硫技術相比，運行成本最低

Low cost: Compared to other desulfurization technologies, the operating cost is the lowest

高安全性: 設有多重的安全保護裝置

High security: equipped with multiple safety protection devices

無人值守： 系統通過在線監測系統全自動運行

Unattended: The system operates fully automatically through online monitoring system

維護簡單： 少量的維護工作

Easy maintenance: minimal maintenance work

生物脫硫的特點

The characteristics of biological desulfurization

高效率： 硫化氫去除率高達98.5%

High efficiency: hydrogen sulfide removal rate up to 98.5%

高適應范圍： 可處理硫化氫濃度高達0.8% （8000ppm）

High adaptability range: capable of handling hydrogen sulfide concentrations up to 0.8% (8000ppm)

低成本： 運行成本低

Low cost: Low operating cost

適應性: 較化學法抗波動能力差

Adaptability: Poor resistance to fluctuations compared to chemical methods

無人值守： 系統通過在線監測系統全自動運行

Unattended: The system operates fully automatically through online monitoring system

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