脫硫工藝
Desulfurization process
沼氣脫硫是為了避免硫化氫腐蝕設(shè)備、硫化氫中毒，以及防止沼氣燃燒時(shí)，硫化氫被氧化成二氧化硫或三氧化硫造成更大的危害。其脫除方法如下：
The purpose of biogas desulfurization is to avoid hydrogen sulfide corrosion of equipment, hydrogen sulfide poisoning, and to prevent hydrogen sulfide from being oxidized into sulfur dioxide or sulfur trioxides when biogas is burned. The removal method is as follows:
生物降解工藝
Biodegradation process
沼氣中的硫可以通過(guò)微生物被去除。大部分的硫氧化細(xì)菌都屬于硫桿菌屬，且大多都是自養(yǎng)的，即他們可以利用沼氣中的二氧化碳來(lái)滿足其C營(yíng)養(yǎng)的需要，主要生成物是單質(zhì)硫，也有部分硫酸根，在溶液中形成硫酸會(huì)造成腐蝕。根據(jù)沼氣中不同不同的硫化氫含量，可以往沼氣中通入2%-6%的空氣，以滿足生物氧化硫化物的需要。
Sulfur in biogas can be removed by microorganisms. Most of the sulfur oxidizing bacteria belong to the genus Thiobacillus, and most of them are autotrophic, that is, they can use carbon dioxide in biogas to meet their c nutrition needs, the main product is elemental sulfur, but also part of sulfate, which will cause corrosion when sulfuric acid is formed in the solution. According to different content of hydrogen sulfide in biogas, 2% - 6% air can be introduced into biogas to meet the needs of biooxidation of sulfide.
更直接和簡(jiǎn)單的方法是直接往厭氧消化罐或儲(chǔ)氣罐中通入一定量的氧或空氣并保持一定時(shí)間，因?yàn)榱驐U菌隨處可見(jiàn)，所以并不需要接種。消化物的表面可以提供給他們一個(gè)微觀好氧環(huán)境和必須的營(yíng)養(yǎng)以供它們生長(zhǎng)，并會(huì)形成菌落上面附著一層黃色的硫。適當(dāng)?shù)臏囟?、反?yīng)時(shí)間和空氣量可以使硫化氫減少至50ppm。
The most direct and simple method is to directly inject a certain amount of oxygen or air into the anaerobic digestion tank or air storage tank and keep it for a certain period of time. Because Thiobacillus can be seen everywhere, it does not need to be inoculated. The surface of digestive products can provide them with a micro aerobic environment and necessary nutrients for their growth, and will form a layer of yellow sulfur on the colony. Appropriate temperature, reaction time and air quantity can reduce hydrogen sulfide to 50ppm.
對(duì)于不同的甲烷含量，沼氣在空氣中的爆炸范圍為6%-12%，所以必須采取一定的安全措施以避免給沼氣中通入過(guò)量的空氣。
For different methane content, the explosion range of biogas in the air is 6% - 12%. Therefore, certain safety measures must be taken to avoid excessive air in the biogas.
生物濾床工藝
Biofilter Process
在大型厭氧消化罐生產(chǎn)沼氣中，水洗和生物脫硫常常被聯(lián)合起來(lái)用以去除硫化氫。可以使用廢水或者消化罐中的上清液從濾床頂部通入，沼氣從底部通入，進(jìn)入濾床前的沼氣中通入4%-6%的空氣，濾床為水吸收硫化氫和脫硫微生物的生長(zhǎng)都提供了一個(gè)充足的接觸面。在丹麥，有幾家工業(yè)污水處理廠和很多農(nóng)場(chǎng)發(fā)酵產(chǎn)沼都在使用此種工藝凈化沼氣。
In the production of biogas in large-scale anaerobic digesters, water washing and biological desulfurization are often combined to remove hydrogen sulfide. Waste water or supernatant in digestion tank can be used to enter from the top of the filter bed, biogas from the bottom, and 4% - 6% air can be introduced into the biogas before entering the filter bed. The filter bed provides a sufficient contact surface for the water to absorb hydrogen sulfide and the growth of desulfurization microorganisms. In Denmark, several industrial wastewater treatment plants and many farms are using this process to purify biogas.
消化污泥中加氯化鐵工藝
Process of adding ferric chloride to digested sludge
直接往消化污泥中加入氯化鐵，氯化鐵會(huì)和硫化氫反應(yīng)而形成硫化鐵鹽顆粒。這種方法可以使硫化氫的產(chǎn)生量大為減少，但不能減少到天然氣或汽車(chē)燃料所要求的水平，需要再進(jìn)一步處理。這種去除工藝的投資成本較少，只需要一個(gè)盛氯化鐵溶液的罐子和一個(gè)定量泵，主要成本是氯化鐵產(chǎn)生的。
Adding ferric chloride directly into the digestion sludge, ferric chloride will react with hydrogen sulfide to form iron sulfide particles. This method can greatly reduce the production of hydrogen sulfide, but it can not be reduced to the level required by natural gas or automobile fuel, and further treatment is needed. The investment cost of this removal process is less. Only a tank and a quantitative pump are needed. The main cost is produced by ferric chloride.
沼氣脫硫
Biogas desulfurization
氧化鐵吸收工藝
Iron oxide absorption process
硫化氫易于氫氧化鐵、氧化鐵反應(yīng)成硫化鐵，此反應(yīng)是略微的吸熱反應(yīng)，溫度要求12℃，反應(yīng)溫度需要一定量的水，所以沼氣不能太干，但是應(yīng)該避免生成冷凝水使球狀氯化鐵粘在一起，減少了反應(yīng)表面。
Hydrogen sulfide is easy to react with iron hydroxide and iron oxide to form iron sulfide, which is a slight endothermic reaction. The minimum temperature is required to be 12 ℃, and the optimum reaction temperature requires a certain amount of water, so biogas cannot be too dry, but condensate should be avoided to make the spherical iron chloride stick together and reduce the reaction surface.
產(chǎn)生的硫化鐵可以被空氣氧化再生，生成氧化鐵或者氫氧化鐵和硫單質(zhì)，再生過(guò)程中會(huì)放出大量的熱，因此常常會(huì)發(fā)生自燃。由于在氧化鐵的表面上會(huì)覆蓋一層硫單質(zhì)，所以在經(jīng)過(guò)很多次重復(fù)使用后，就需要更換氧化鐵和氫氧化鐵。通常，一個(gè)裝置中配有兩個(gè)反應(yīng)床，當(dāng)一個(gè)在進(jìn)行脫硫的過(guò)程中，另一個(gè)可以進(jìn)行再生。
The iron sulfide produced can be oxidized and regenerated by air to form iron oxide or iron hydroxide and sulfur. During the regeneration process, a lot of heat will be released, so spontaneous combustion often occurs. Since the surface of iron oxide will be covered with a layer of sulfur, it is necessary to replace iron oxide and iron hydroxide after repeated use for many times. Generally, one unit is equipped with two reaction beds. When one is in the process of desulfurization, the other can be regenerated.
氧化鐵木片吸收工藝
Absorption process of iron oxide wood chips
在木片上覆蓋一層氧化鐵相對(duì)于相同量的氧化鐵有更大的比表面積和較低的密度，大約100g的氧化鐵木片可以吸收20g的硫化氫。這種方法在美國(guó)很流行，價(jià)格相對(duì)較低，但是必須注意再生氧化鐵過(guò)濾器的時(shí)候溫度不能太高。
Covering a layer of iron oxide on the wood chip has a larger specific surface area and a lower density than the same amount of iron oxide. About 100g of iron oxide wood chip can absorb 20g of hydrogen sulfide. This method is very popular in the United States, the price is relatively low, but it must be noted that the temperature of regeneration iron oxide filter cannot be too high.
赤泥顆粒吸收工藝
Red mud particle absorption process
氧化鋁生產(chǎn)中產(chǎn)生的廢物赤泥可以被做成顆粒狀用來(lái)吸收硫化氫，它有著更大的比表面積，不足之處就是密度比氧化鐵木片大得多。在德國(guó)和瑞士大部分的污水處理廠都使用這種方法。
Red mud, a waste produced in alumina production, can be made into granules to absorb hydrogen sulfide. It has a larger specific surface area, but its density is much larger than that of iron oxide wood chips. This method is used in most sewage treatment plants in Germany and Switzerland.
活性炭吸附工藝
Activated carbon adsorption process
在變壓吸附系統(tǒng)中硫化氫可以通過(guò)用碘化鉀浸泡過(guò)的活性炭去除，硫化氫被轉(zhuǎn)化為單質(zhì)硫和水，硫被活性炭吸收，此反應(yīng)條件為：壓力7-8×105Pa，溫度50℃到70℃，在壓縮氣體的過(guò)程中很容易使溫度到達(dá)50℃以上。通常氣體停留時(shí)間為4-8小時(shí)。在連續(xù)運(yùn)行的情況下，系統(tǒng)要包含兩個(gè)吸附裝置，如果硫化氫的濃度在3ppm以上，需要進(jìn)行再生。
In PSA system, hydrogen sulfide can be removed by activated carbon soaked in potassium iodide. Hydrogen sulfide is converted into elemental sulfur and water, and sulfur is absorbed by activated carbon. The optimum conditions for this reaction are: pressure 7-8 × 105Pa, temperature 50 ℃ - 70 ℃. In the process of compressed gas, it is easy to make the temperature above 50 ℃. Generally, the gas residence time is 4-8 hours. Under the condition of continuous operation, the system shall include two adsorption devices. If the concentration of hydrogen sulfide is above 3ppm, regeneration is required.
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2020-06-10
