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目前,國內(nèi)外主流的沼氣脫硫工藝包括化學(xué)脫硫、生物脫硫、濕法水洗脫硫等工藝。?化學(xué)脫硫(干法脫硫)化學(xué)脫硫反應(yīng)基本原理是:H2S與脫硫劑(氧化鐵)接觸,被氧化成硫或硫氧化物的一種方法,也可稱為干式氧化法。干法脫硫設(shè)備的基本構(gòu)成是:在特制的脫硫罐中放入填料(填料為氧化鐵),氣體以低流速從一端經(jīng)過脫硫塔內(nèi)填料層,把H2S吸附或吸收反應(yīng)成硫化物或多硫化物后,余留在填料層中,凈化后氣體從脫硫塔另一端排出,實(shí)現(xiàn)脫硫處理的目的。H2S與罐內(nèi)脫硫劑發(fā)生以下化學(xué)反應(yīng):Fe2O3·H2O+3H2S→Fe2S3·H2O+3H2O罐內(nèi)脫硫劑定期晾曬再生,循環(huán)使用數(shù)次后更換。脫硫劑再生反應(yīng)如下:2Fe2S3·H2O+3O2→2Fe2O3·H2O+6S脫硫劑脫硫及再生過程中,H2S與Fe2O3反應(yīng)生成Fe2S3,F(xiàn)e2S3與空氣接觸后又生成單質(zhì)硫和Fe2O3。如此H2S被氧化成單質(zhì)硫除去,同時(shí)脫硫劑得以再生。優(yōu)勢:一次性投資低,運(yùn)行穩(wěn)定,結(jié)構(gòu)簡單,使用方便。劣勢:運(yùn)行成本較高,脫硫劑失效快,需定期更換脫硫劑。
At present, the mainstream biogas desulfurization processes at home and abroad include chemical desulfurization, biological desulfurization, wet water washing desulfurization, and other processes.? The basic principle of chemical desulfurization (dry desulfurization) is that H2S comes into contact with a desulfurizer (iron oxide) and is oxidized into sulfur or sulfur oxides, also known as dry oxidation method. The basic composition of dry desulfurization equipment is to place packing (iron oxide packing) in a specially designed desulfurization tank, and the gas passes through the packing layer in the desulfurization tower at a low flow rate from one end. H2S is adsorbed or absorbed and reacted into sulfides or polysulfides, which remain in the packing layer. After purification, the gas is discharged from the other end of the desulfurization tower to achieve the purpose of desulfurization treatment. H2S undergoes the following chemical reaction with the desulfurizer in the tank: Fe2O3 · H2O+3H2S → Fe2S3 · H2O+3H2O. The desulfurizer in the tank is periodically dried and regenerated, and is replaced after several cycles of use. The regeneration reaction of desulfurizer is as follows: 2Fe2S3 · H2O+3O2 → 2Fe2O3 · H2O+6S. During the desulfurization and regeneration process of desulfurizer, H2S reacts with Fe2O3 to generate Fe2S3, which then reacts with air to produce elemental sulfur and Fe2O3. In this way, H2S is oxidized to elemental sulfur for removal, while the desulfurizer is regenerated. Advantages: Low one-time investment, stable operation, simple structure, and easy to use. Disadvantages: High operating costs, rapid failure of desulfurizers, and the need for regular replacement of desulfurizers.
生物脫硫生物脫硫技術(shù)的原理為:通過營造脫硫菌適宜的工作環(huán)境,使沼氣中H2S在脫硫菌的生物氧化還原作用下生成單質(zhì)硫被去除。脫硫系統(tǒng)屬開放系統(tǒng),微生物種群隨環(huán)境改變而變化。在大多數(shù)生物發(fā)酵罐中,微生物種類以細(xì)菌為主、真菌為次,極少有酵母菌;常用的細(xì)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pH值為2.0~2.2。從沼氣發(fā)酵罐內(nèi)導(dǎo)出的氣體進(jìn)入生物脫硫塔,同時(shí)從發(fā)酵罐內(nèi)抽出部分發(fā)酵液,用泵將發(fā)酵液從生物脫硫塔的底部抽到頂部進(jìn)行淋灑,發(fā)酵液的作用是發(fā)酵液當(dāng)中含有很多微生物,與沼氣中的H2S作用后,能夠生成含有硫單質(zhì)的細(xì)菌,存在于生物脫硫塔內(nèi)部的填充層里,這種細(xì)菌是好氧性細(xì)菌,因此,在進(jìn)行生物脫硫前,沼氣應(yīng)預(yù)先通過鼓風(fēng)機(jī)注入微量的空氣(O2),使其處于好氧狀態(tài)。如果沒有與H2S相遇,可以消耗自身成為H2SO4,通過發(fā)酵液的循環(huán)而排放出去;發(fā)酵液經(jīng)過循環(huán)后,當(dāng)其pH值降到2時(shí),需要重新更換,原來的廢水則流到貯液池等待好氧處理。利用注入的空氣和營養(yǎng)液中的水分發(fā)生以下氧化還原反應(yīng):2H2S+O2→2H2O+2S2S+3O2+2H2O→2H2SO4H2S在脫硫菌的作用下進(jìn)行氧化還原反應(yīng)后,生成單質(zhì)硫和H2SO4,貯存于塔內(nèi)填料和營養(yǎng)液內(nèi),通過填料上生物膜的脫落和營養(yǎng)液的定期外排凈化。優(yōu)勢:運(yùn)行費(fèi)用低,無需催化劑或氧化劑,無需更換濾料,脫硫效率高。劣勢:一次性投資高,過程不易控制,沼氣中氧殘留量不易控制。
The principle of biological desulfurization technology is to create a suitable working environment for desulfurization bacteria, so that H2S in biogas can be removed by the biological oxidation-reduction of desulfurization bacteria to generate elemental sulfur. The desulfurization system is an open system, and the microbial population changes with environmental changes. In most biological fermentation tanks, bacteria are the main microbial species, followed by fungi, with very few yeast; The commonly used bacteria are Acidithiobacillus ferrooxidans, denitrifying Acidithiobacillus, and sulfur excreting Acidithiobacillus, with the most successful representative being Acidithiobacillus ferrooxidans, whose optimal pH value for growth is 2.0-2.2. The gas exported from the biogas fermentation tank enters the biological desulfurization tower, and at the same time, a portion of the fermentation liquid is extracted from the fermentation tank. The fermentation liquid is pumped from the bottom to the top of the biological desulfurization tower for sprinkling. The function of the fermentation liquid is that it contains many microorganisms. After reacting with H2S in the biogas, bacteria containing sulfur can be generated, which exist in the filling layer inside the biological desulfurization tower. These bacteria are aerobic bacteria. Therefore, before carrying out biological desulfurization, a small amount of air (O2) should be injected into the biogas through a blower to keep it in an aerobic state. If it does not come into contact with H2S, it can be consumed to become H2SO4 and discharged through the circulation of fermentation broth; After the fermentation broth is circulated, when its pH value drops to 2, it needs to be replaced again, and the original wastewater flows to the storage tank for aerobic treatment. The following oxidation-reduction reactions occur using the water in the injected air and nutrient solution: 2H2S+O2 → 2H2O+2S2SS+3O2+2H2O → 2H2SO4H2S undergoes oxidation-reduction reactions under the action of desulfurizing bacteria, generating elemental sulfur and H2SO4, which are stored in the tower packing and nutrient solution, and purified through the shedding of biofilm on the packing and regular discharge of nutrient solution. Advantages: Low operating costs, no need for catalysts or oxidants, no need to replace filter media, high desulfurization efficiency. Disadvantages: High one-time investment, difficult process control, and difficulty in controlling residual oxygen in biogas.
濕法脫硫濕法脫硫裝置由吸收塔與再生塔組成。用濃度為2%~3%的碳酸鈉溶液作為吸收劑,吸收沼氣中的H2S。碳酸鈉溶液從吸收塔頂部噴淋向下與沼氣進(jìn)行逆流吸收。當(dāng)硫化氫含量較高,且對凈化后氣體品質(zhì)要求非常高的時(shí)候采用濕法脫硫。濕法脫硫工藝較為復(fù)雜,成本較高,但穩(wěn)定性較好。表2.3? 幾種主要沼氣脫硫技術(shù)的比較序號(hào)對比項(xiàng)優(yōu)點(diǎn)缺點(diǎn)適用范圍1化學(xué)脫硫結(jié)構(gòu)簡單,使用方便;運(yùn)行操作簡單,無需人員值守。需要定期更換濾料;運(yùn)行費(fèi)用較高;脫硫劑失效快。適用于H2S含量低的中小項(xiàng)目或精脫硫環(huán)節(jié)。2生物脫硫運(yùn)行費(fèi)用低,能耗低;無需催化劑或氧化劑;無需更換濾料;脫硫效率高。一次性投資高;過程不易控制;沼氣中氧含量不易控制。適用于H2S含量高或大型沼氣項(xiàng)目。3濕法脫硫脫硫效果好;穩(wěn)定性好工藝復(fù)雜、成本高對氣體凈化要求非常高的情況。
The wet desulfurization device consists of an absorption tower and a regeneration tower. Use a sodium carbonate solution with a concentration of 2% to 3% as an absorbent to absorb H2S from biogas. Sodium carbonate solution is sprayed downwards from the top of the absorption tower and undergoes countercurrent absorption with biogas. When the hydrogen sulfide content is high and the quality requirements for the purified gas are very high, wet desulfurization is used. The wet desulfurization process is relatively complex and costly, but it has good stability. Table 2.3? Comparison of several main biogas desulfurization technologies, advantages and disadvantages, applicable scope: 1. Chemical desulfurization has a simple structure and is easy to use; The operation is simple and does not require personnel to be on duty. Regular replacement of filter media is required; High operating costs; The desulfurizer fails quickly. Suitable for small and medium-sized projects or precision desulfurization processes with low H2S content. 2. Low operating costs and energy consumption for biological desulfurization; No need for catalysts or oxidants; No need to replace the filter material; High desulfurization efficiency. High one-time investment; The process is not easy to control; The oxygen content in biogas is difficult to control. Suitable for high H2S content or large-scale biogas projects. 3. Wet desulfurization has good desulfurization effect; Good stability, complex process, high cost, and extremely high requirements for gas purification.
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