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生物脱硫是指在一定的反应条件下,利用特殊微生物( 菌种) 的催化作用,在人为控制合理条件下将原料中的 H2S 或有机硫化合物转化为元素硫或硫酸盐的一种工艺过程。由于全球能源供应紧张、排放标准日益严格,生物脱硫工艺的技术开发受到普遍重视。
Biological desulfurization refers to a process that utilizes the catalytic action of special microorganisms (strains) under certain reaction conditions to convert H2S or organic sulfur compounds in raw materials into elemental sulfur or sulfate under controlled and reasonable conditions. Due to the tight global energy supply and increasingly strict emission standards, the technological development of biological desulfurization processes has received widespread attention.
当前,生物脱硫工艺的应用涉及沼气、油品加工,炼厂废气处理,天然气、填埋气及煤层气等诸多化石能源与新型能源领域,并在化工、造纸和采矿等工业领域中也有应用,故生物脱硫被誉为 21 世纪最有发展前景的脱硫新工艺。1) 与微生物固定在一定区域内基体上的其它生化工艺不同,S-P 工艺生物脱硫过程中微生物是游离于溶液中,且脱硫溶液在 24 h 运转周期中需要经历 12 次常压→ 8. 2 MPa 高压→常压的反复循环。长期工业运转表明: 脱硫微生物可以经受剧烈的压力变化而不影响其脱硫性能。
Currently, the application of biological desulfurization technology involves many fossil and new energy fields such as biogas, oil processing, refinery waste gas treatment, natural gas, landfill gas, and coalbed methane. It is also applied in industrial fields such as chemical, papermaking, and mining. Therefore, biological desulfurization is known as the most promising new desulfurization technology in the 21st century. 1) Unlike other biochemical processes in which microorganisms are fixed on a substrate within a certain area, the S-P process for biological desulfurization involves microorganisms being free in the solution, and the desulfurization solution needs to undergo 12 cycles of atmospheric pressure → 8 during a 24-hour operation cycle Repetitive cycle from 2 MPa high pressure to atmospheric pressure. Long term industrial operation has shown that desulfurization microorganisms can withstand drastic pressure changes without affecting their desulfurization performance.
2) 当原料气中CO2含量φ高达4 时,由于Na2CO3-NaHCO3良好的缓冲作用,仍能保持脱硫溶液 pH 值稳定,并保证净化气H2S 含量φ降到6 mg /m3以下。当单塔处理量降至66 万m3/d,原料气H2S 含量φ降至702×10-6时,净化气平均H2s φ含量降至1. 5 mg /m3,从而表明脱硫菌种的性能相当优越。
2) When the CO2 content in the feed gas reaches 4, due to the good buffering effect of Na2CO3-NaHCO3, the pH value of the desulfurization solution can still be maintained stable, and the H2S content in the purified gas can be reduced to below 6 mg/m3. When the processing capacity of a single tower drops to 660000 m3/d and the H2S content in the feed gas decreases to 702 × 10-6, the average H2S content in the purified gas decreases to 1 5 mg/m3, indicating that the performance of desulfurization bacteria is quite superior.
3) 由于生物硫黄良好的亲水性,只要采取适当的措施,S-P 生物脱硫工艺基本上不存在络合铁法工艺常见的溶液发泡和设备堵塞问题。在运转过程中,必须经常以连续或间歇方式从脱硫溶液中除去产品硫黄,维持溶液中硫黄质量浓度为0. 6 ~0. 8 的低水平可以改善操作并降低溶液的发泡倾向。同时,在闪蒸罐、缓冲罐和生物反应器出口管汇处等容易发生硫沉积的地方,在所有工况条件下均应仔细观察管道中溶液的流速。闪蒸罐宜采用立式,缓冲罐应采用锥形底部。
3) Due to the good hydrophilicity of biological sulfur, as long as appropriate measures are taken, the S-P biological desulfurization process basically does not have the common problems of solution foaming and equipment blockage in the chelated iron process. During operation, it is necessary to regularly remove product sulfur from the desulfurization solution in a continuous or intermittent manner, maintaining a sulfur mass concentration of 0 6 ~0. A low level of 8 can improve operation and reduce the foaming tendency of the solution. At the same time, in places where sulfur deposition is prone to occur such as flash evaporation tanks, buffer tanks, and bioreactor outlet manifolds, the flow rate of the solution in the pipeline should be carefully observed under all operating conditions. Flash evaporation tanks should be vertical, while buffer tanks should have a conical bottom.
4) 设备的选型、整改与装置的稳定运行密切相关。Teague 净化厂投产初期即发现吸收塔有较强烈的发泡现象,并导致净化气不合格。扫描结果发现在高负荷操作条件下,脱硫溶液滞留的区域即成为泡沫形成并堆积的区域。因此,吸收塔顶部与中部的再分配塔盘上的滞留液体就成为泡沫起源,上升气流夹带着泡沫沿填料层向上发展,最终导致强烈雾沫夹带或冲塔( 图5) 。随后对吸收塔内构件进行整改,拆除再分配塔盘,并在此空间放置填料。经此整改后,吸收塔阻力降明显改善,H2S 净化度也迅速降至 6 mg /m3以下。
4) The selection and rectification of equipment are closely related to the stable operation of the device. At the beginning of the production of Teague purification plant, it was found that the absorption tower had a strong foaming phenomenon, which led to the unqualified purified gas. The scanning results showed that under the high load operation conditions, the area where the desulfurization solution stayed became the area where foam formed and accumulated. Therefore, the trapped liquid on the redistribution tray at the top and middle of the absorber becomes the origin of foam, and the updraft carries foam upward along the packing layer, eventually leading to strong entrainment or tower flushing (Figure 5). Subsequently, the components inside the absorption tower were rectified, the redistribution tray was removed, and packing was placed in this space. After this rectification, the resistance of the absorption tower has significantly improved, and the purification degree of H2S has rapidly decreased to below 6 mg/m3.