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沼氣作為可再生能源的重要分支,其核心成分甲烷的清潔利用對碳中和目標(biāo)具有戰(zhàn)略意義。沼氣脫硫技術(shù)通過選擇性去除硫化氫(H?S)等含硫雜質(zhì),可顯著提升沼氣品質(zhì),延長設(shè)備使用壽命,是沼氣工程中不可或缺的凈化環(huán)節(jié)。
As an important branch of renewable energy, the clean utilization of methane, the core component of biogas, has strategic significance for achieving carbon neutrality goals. Biogas desulfurization technology can significantly improve the quality of biogas and extend the service life of equipment by selectively removing sulfur-containing impurities such as hydrogen sulfide (H ? S), making it an indispensable purification process in biogas engineering.
一、硫化氫的危害與脫硫必要性
1、 The hazards of hydrogen sulfide and the necessity of desulfurization
沼氣中硫化氫濃度通常在1000-10000ppm之間,其危害體現(xiàn)在三個方面:
The concentration of hydrogen sulfide in biogas is usually between 1000-10000ppm, and its hazards are reflected in three aspects:
設(shè)備腐蝕:H?S與水汽結(jié)合形成氫硫酸,使管道、儲氣柜腐蝕速率提升,某沼氣發(fā)電廠數(shù)據(jù)顯示,未經(jīng)脫硫的沼氣使發(fā)動機(jī)壽命縮短。
Equipment corrosion: H ? S combines with water vapor to form hydrogen sulfate, which increases the corrosion rate of pipelines and gas storage tanks. Data from a certain biogas power plant shows that desulfurized biogas shortens the engine life.
環(huán)境污染:燃燒后生成的二氧化硫(SO?)是PM2.5前體物,某生活垃圾填埋場沼氣發(fā)電項目測算,每立方米沼氣含硫量超2000ppm時,尾氣SO?濃度將超標(biāo)。
Environmental pollution: The sulfur dioxide (SO ?) generated after combustion is a precursor to PM2.5. According to calculations from a biogas power generation project at a domestic waste landfill, when the sulfur content of each cubic meter of biogas exceeds 2000ppm, the concentration of SO ?in the exhaust gas will exceed the standard.
健康風(fēng)險:H?S劇毒特性要求作業(yè)場所濃度低于10ppm,而原始沼氣中H?S濃度超標(biāo)。
Health risk: The highly toxic nature of H ? S requires a workplace concentration of less than 10ppm, while the concentration of H ? S in the original biogas exceeds the standard.
二、主流脫硫技術(shù)原理與適配場景
2、 Principles and adaptation scenarios of mainstream desulfurization technology
干法脫硫技術(shù)
Dry desulfurization technology
氧化鐵法:采用海綿鐵或陶粒負(fù)載氧化鐵,通過化學(xué)吸附將H?S轉(zhuǎn)化為硫化亞鐵(FeS)。某養(yǎng)殖場實(shí)踐表明,當(dāng)空速(GHSV)控制在100h?1時,穿透硫容可達(dá)25%(質(zhì)量分?jǐn)?shù)),吸附劑再生周期延長。
Iron oxide method: Sponge iron or ceramic particles are used to load iron oxide, and H ? S is converted into ferrous sulfide (FeS) through chemical adsorption. The practice of a certain breeding farm has shown that when the airspeed (GHSV) is controlled at 100h ?1, the breakthrough sulfur capacity can reach 25% (mass fraction), and the regeneration cycle of the adsorbent is prolonged.
活性炭法:利用活性炭表面含氧官能團(tuán)催化氧化H?S,某食品廢水處理項目采用載銅活性炭,在常溫下可將出口H?S濃度控制在5ppm以下,但需每3個月更換吸附劑。
Activated carbon method: Utilizing the oxygen-containing functional groups on the surface of activated carbon to catalyze the oxidation of H ? S. A certain food wastewater treatment project uses copper loaded activated carbon, which can control the outlet H ? S concentration below 5ppm at room temperature, but the adsorbent needs to be replaced every 3 months.
濕法脫硫技術(shù)
Wet desulfurization technology
堿液吸收法:采用氫氧化鈉或碳酸鈉溶液洗滌沼氣,反應(yīng)式為。某污水處理廠實(shí)踐顯示,當(dāng)液氣比控制在2L/m3時,脫硫效率超95%,但需定期處理含硫廢液。
Alkali absorption method: using sodium hydroxide or sodium carbonate solution to wash biogas, the reaction equation is. The practice of a certain sewage treatment plant shows that when the liquid to gas ratio is controlled at 2L/m 3, the desulfurization efficiency exceeds 95%, but sulfur-containing waste liquid needs to be treated regularly.
氧化法:通過次氯酸鈉(NaClO)或雙氧水(H?O?)將H?S氧化為單質(zhì)硫,某垃圾填埋場采用此工藝,使出口H?S濃度低于1ppm,但運(yùn)行成本較高。
Oxidation method: Sodium hypochlorite (NaClO) or hydrogen peroxide (H ? O ?) is used to oxidize H ? S into elemental sulfur. This process is adopted by a certain landfill site to achieve an outlet H? S concentration of less than 1ppm, but the operating cost is relatively high.
生物脫硫技術(shù)
Biological desulfurization technology
直接氧化法:利用硫氧化細(xì)菌(如Thiobacillus)將H?S直接氧化為硫酸,某酒廠沼氣工程應(yīng)用此技術(shù),在pH 1-2條件下實(shí)現(xiàn)98%脫硫效率,但需控制硫酸根濃度防止菌體失活。
Direct oxidation method: using sulfur oxidizing bacteria (such as Thiobacillus) to directly oxidize H ? S into sulfuric acid. This technology is applied in a biogas project of a certain distillery to achieve 98% desulfurization efficiency under pH 1-2 conditions, but the concentration of sulfate ions needs to be controlled to prevent bacterial inactivation.
間接氧化法:通過化學(xué)吸收+生物再生組合工藝,某農(nóng)業(yè)廢棄物處理項目采用此工藝,使脫硫劑再生效率提升,運(yùn)行成本降低。
Indirect oxidation method: Through a combination of chemical absorption and biological regeneration process, a certain agricultural waste treatment project adopts this process to improve the regeneration efficiency of desulfurizer and reduce operating costs.
三、技術(shù)選型的核心考量因素
3、 Core considerations for technology selection
沼氣規(guī)模:小型養(yǎng)殖場(<100m3/h)宜選干法脫硫,大型沼氣工程(>500m3/h)適合濕法或生物脫硫。
Biogas scale: Small scale farms (<100m 3/h) should choose dry desulfurization, while large-scale biogas projects (>500m3/h) are suitable for wet or biological desulfurization.
硫化氫濃度:低濃度(<5000ppm)沼氣可采用生物法,高濃度(>10000ppm)需前置干法預(yù)處理。
Hydrogen sulfide concentration: Low concentration (<5000ppm) biogas can be treated by biological methods, while high concentration (>10000ppm) requires pre dry pretreatment.
資源化需求:需回收硫磺的項目宜選氧化法,需副產(chǎn)硫酸的項目可選生物直接氧化法。
Resource utilization requirements: Projects that require sulfur recovery should choose oxidation method, while projects that require by-product sulfuric acid can choose biological direct oxidation method.
四、典型應(yīng)用場景與效益分析
4、 Typical application scenarios and benefit analysis
養(yǎng)殖場沼氣工程:采用干法+生物法組合工藝,使沼氣熱值提升,發(fā)動機(jī)維護(hù)周期延長。
Farm biogas project: adopting a combination of dry and biological processes to increase the calorific value of biogas and extend the maintenance cycle of the engine.
垃圾填埋氣發(fā)電:通過濕法脫硫+膜分離,使甲烷純度達(dá),發(fā)電效率提升。
Landfill gas power generation: By wet desulfurization and membrane separation, methane purity is achieved and power generation efficiency is improved.
工業(yè)廢水處理:應(yīng)用生物脫硫技術(shù),使沼氣中H?S濃度達(dá)標(biāo),滿足鍋爐燃燒要求。
Industrial wastewater treatment: Applying biological desulfurization technology to meet the H ? S concentration standard in biogas and meet the requirements of boiler combustion.
五、技術(shù)發(fā)展趨勢與挑戰(zhàn)
5、 Technological development trends and challenges
生物脫硫工業(yè)化:通過基因編輯技術(shù)培育耐酸菌株,使生物脫硫反應(yīng)器體積減少。
Industrialization of biological desulfurization: Cultivate acid resistant strains through gene editing technology to reduce the volume of biological desulfurization reactors.
資源化利用:從脫硫廢液中回收單質(zhì)硫或硫酸,某示范工程實(shí)現(xiàn)硫資源回收率超。
Resource utilization: Recovering elemental sulfur or sulfuric acid from desulfurization waste liquid, a demonstration project achieved a sulfur resource recovery rate exceeding.
隨著碳交易市場完善,沼氣脫硫技術(shù)的經(jīng)濟(jì)性將顯著提升。通過技術(shù)創(chuàng)新與工藝優(yōu)化,沼氣脫硫正從末端治理向資源化利用轉(zhuǎn)型,為農(nóng)業(yè)廢棄物、工業(yè)廢水等領(lǐng)域提供清潔能源解決方案,助力碳中和目標(biāo)實(shí)現(xiàn)。
With the improvement of the carbon trading market, the economic viability of biogas desulfurization technology will be significantly enhanced. Through technological innovation and process optimization, biogas desulfurization is transitioning from end of pipe treatment to resource utilization, providing clean energy solutions for agricultural waste, industrial wastewater and other fields, and helping to achieve carbon neutrality goals.
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