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沼氣作為一種新興能源其應(yīng)用越來(lái)越廣泛,在我國(guó)環(huán)保標(biāo)準(zhǔn)中嚴(yán)格規(guī)定,利用沼氣能源時(shí),沼氣氣體中H2S 含量不得超過(guò)20mg/m??。無(wú)論在工業(yè)或民用氣體中, 都必須盡可能的除去H2S。沼氣從厭氧發(fā)酵裝置產(chǎn)出時(shí),特別是在中溫或高溫發(fā)酵時(shí),攜帶有大量的H2S。由于沼氣中還有大量的水蒸汽存在,水與沼氣中的H2S共同作用,加速了金屬管道、閥門和流量計(jì)的腐蝕和堵塞。另外,H2S燃燒后生成的SO2,與燃燒產(chǎn)物中的水蒸氣結(jié)合成亞硫酸,使設(shè)備的金屬表面產(chǎn)生腐蝕,并且還會(huì)造成對(duì)大氣環(huán)境的污染,影響人體健康。因此,在使用沼氣之前,必須脫除其中的H2S。業(yè)內(nèi)常用的沼氣脫硫方法有:干法脫硫、濕法脫硫、生物法脫硫等幾種脫硫方法。
Biogas, as an emerging energy source, is becoming increasingly widely used. In China's environmental standards, it is strictly stipulated that when using biogas energy, the H2S content in biogas gas should not exceed 20mg/m??. H2S must be removed as much as possible in both industrial and civilian gases. When biogas is produced from anaerobic fermentation equipment, especially during medium or high temperature fermentation, it carries a large amount of H2S. Due to the presence of a large amount of water vapor in biogas, the combined action of water and H2S in biogas accelerates the corrosion and blockage of metal pipelines, valves, and flow meters. In addition, the SO2 generated after the combustion of H2S combines with the water vapor in the combustion products to form sulfurous acid, which corrodes the metal surface of the equipment and also causes pollution to the atmospheric environment, affecting human health. Therefore, before using biogas, H2S must be removed from it. The commonly used biogas desulfurization methods in the industry include dry desulfurization, wet desulfurization, biological desulfurization, and several other desulfurization methods.
一、干法脫硫干法脫硫是一種簡(jiǎn)易、高效、相對(duì)低成本的脫硫方式,適合用于沼氣量小,硫化氫濃度低的沼氣脫硫。一般采用常壓氧化鐵法脫硫,即在一個(gè)容器內(nèi)放入填料,填料層有活性炭、氧化鐵等,厚度0.3~0.8m,氣體以0.4~0.6m/min從一端經(jīng)過(guò)容器內(nèi)填料層,接觸時(shí)間在2~3min,硫化氫氧化成硫或者硫氧化物,余留在填料層中,凈化后的氣體從容器另一端排出。再生時(shí),將含硫化鐵的脫硫劑取出,撒上水,接觸空氣使其氧化,即可再生利用。
1、 Dry desulfurization is a simple, efficient, and relatively low-cost desulfurization method, suitable for desulfurization of biogas with low methane volume and low hydrogen sulfide concentration. Generally, atmospheric pressure iron oxide method is used for desulfurization, which involves placing fillers in a container with a layer of activated carbon, iron oxide, etc., with a thickness of 0.3-0.8m. The gas passes through the filler layer from one end of the container at a rate of 0.4-0.6m/min, with a contact time of 2-3 minutes. Hydrogen sulfide is oxidized into sulfur or sulfur oxides, which remain in the filler layer. The purified gas is discharged from the other end of the container. When regenerating, remove the desulfurizer containing iron sulfide, sprinkle it with water, and expose it to air to oxidize it, which can be regenerated and utilized.
二、濕法脫硫濕法脫硫系統(tǒng)主要包含吸收塔與再生塔這兩個(gè)部分。濃度在2%至3%之間的碳酸鈉溶液從吸收塔頂部向下噴淋,與此同時(shí),沼氣自下而上與溶液形成逆流接觸,在這個(gè)過(guò)程中硫化氫被有效去除。當(dāng)碳酸鈉溶液吸收硫化氫之后,會(huì)被輸送至再生塔,在催化劑的作用下,溶液中的硫磺得以分解,從而使碳酸鈉溶液能夠再生并被循環(huán)利用。另外,還可以采用處理廠的出水來(lái)對(duì)沼氣進(jìn)行噴淋,以去除其中的硫化氫。在溫度處于 20℃且壓力為標(biāo)準(zhǔn)大氣壓的條件下,每1m?水能夠溶解2.3m?的硫化氫。
2、 The wet desulfurization system mainly consists of two parts: the absorption tower and the regeneration tower. A sodium carbonate solution with a concentration between 2% and 3% is sprayed downwards from the top of the absorption tower. At the same time, biogas forms a counter current contact with the solution from bottom to top, effectively removing hydrogen sulfide during this process. After the sodium carbonate solution absorbs hydrogen sulfide, it will be transported to the regeneration tower. Under the action of the catalyst, the sulfur in the solution is decomposed, allowing the sodium carbonate solution to be regenerated and recycled. In addition, the effluent from the treatment plant can be used to spray biogas to remove hydrogen sulfide. At a temperature of 20 ℃ and a pressure of standard atmospheric pressure, 2.3m ? of hydrogen sulfide can be dissolved in every 1m ? of water.
三、生物脫硫生物脫硫工藝由洗滌塔、生物反應(yīng)器以及沉淀脫水三個(gè)部分構(gòu)建而成。其中最為核心的環(huán)節(jié)在于噬硫細(xì)菌的馴化培育過(guò)程。生物脫硫的原理是借助無(wú)色細(xì)菌把硫化物氧化轉(zhuǎn)化為單質(zhì)硫,其化學(xué)反應(yīng)式如下所示:通過(guò)該反應(yīng)生成的單質(zhì)硫會(huì)含有少量雜質(zhì),這些含雜質(zhì)的硫可應(yīng)用于硫酸工業(yè)領(lǐng)域。在硫燃燒制備硫酸期間,其中少量殘留的生物質(zhì)會(huì)自動(dòng)被清除。生物脫硫還有一個(gè)優(yōu)勢(shì)是針對(duì)沼氣可以運(yùn)用處理廠的出水來(lái)吸收硫化氫,并且吸收液能夠與含有高濃度COD的有機(jī)廢水共同進(jìn)行治理,如此一來(lái)便節(jié)省了處理COD所需投入的費(fèi)用。不過(guò)就當(dāng)前而言,生物脫硫技術(shù)在我國(guó)的實(shí)際應(yīng)用還比較有限。
3、 The biological desulfurization process consists of three parts: a washing tower, a bioreactor, and precipitation dehydration. The most crucial step is the domestication and cultivation process of sulfur eating bacteria. The principle of biological desulfurization is to use colorless bacteria to oxidize sulfides into elemental sulfur, and its chemical reaction formula is as follows: the elemental sulfur generated through this reaction will contain a small amount of impurities, which can be used in the sulfuric acid industry. During the preparation of sulfuric acid by sulfur combustion, a small amount of residual biomass will be automatically removed. Another advantage of biological desulfurization is that it can use the effluent from the treatment plant to absorb hydrogen sulfide for biogas, and the absorption liquid can be treated together with organic wastewater containing high concentration COD, thus saving the cost of COD treatment. However, currently, the practical application of biological desulfurization technology in China is still relatively limited.
四、總結(jié)
4、 Summary
在沼氣處理中,若沼氣里硫化氫含量偏高且氣量較大,濕法脫硫法較為適用,此方法不僅能脫除硫化氫,還可去除部分二氧化碳,進(jìn)而提升沼氣中甲烷的比例。倘若場(chǎng)地面積有限,可選擇干法脫硫,不過(guò)其脫硫劑通常每三個(gè)月就需要更換一次。當(dāng)沼氣被用作燃?xì)鈾C(jī)等的燃料時(shí),為防止沼氣噴嘴或燃?xì)鈾C(jī)運(yùn)行出現(xiàn)問(wèn)題,沼氣還需進(jìn)行深度凈化與過(guò)濾,以便清除氣體中的固體顆粒。過(guò)濾裝置包含沙礫過(guò)濾器、氣體過(guò)濾器等。生物脫硫在國(guó)內(nèi)現(xiàn)階段的應(yīng)用尚不廣泛,主要是因?yàn)槠渫顿Y成本相對(duì)較高。
In biogas treatment, if the hydrogen sulfide content in biogas is high and the gas volume is large, wet desulfurization method is more suitable. This method can not only remove hydrogen sulfide, but also remove some carbon dioxide, thereby increasing the proportion of methane in biogas. If the site area is limited, dry desulfurization can be chosen, but the desulfurizer usually needs to be replaced every three months. When biogas is used as fuel for gas engines, etc., in order to prevent problems with the biogas nozzle or gas engine operation, biogas also needs to be deeply purified and filtered to remove solid particles from the gas. The filtering device includes gravel filters, gas filters, etc. The application of biological desulfurization is not yet widely used in China at present, mainly due to its relatively high investment cost.
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