CN102179166A - Method for increasing synchronous flue gas desulfuration and denitrification efficiency of bio-membrane packed tower by using external carbon source - Google Patents
Method for increasing synchronous flue gas desulfuration and denitrification efficiency of bio-membrane packed tower by using external carbon source Download PDFInfo
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Abstract
本发明公开一种通过外加碳源以提高生物膜填料塔烟气同时脱硫脱氮效率的技术方法。属于生物法工业废气净化技术领域。本发明依据微生物学原理，应用生物膜填料塔烟气同时脱硫脱氮系统(单塔系统)，通过在循环液中分别外加低分子有机碳源的方法，实验筛选出添加乙酸钠作为外加碳源，对提高生物膜填料塔烟气同时脱硫脱氮效率的效果最优。当在循环液中按最佳浓度50mmol/L(毫摩尔/升)添加乙酸钠时，生物膜填料塔对烟气中SO2和NOx的脱除效率可达到最高值100％和81.94％。与原有技术[发明专利ZL200610011013.4]相比，应用本发明技术方法能够使用于烟气同时脱硫脱氮的生物膜填料塔脱除SO2和NOx的效率分别提高2.75％～3.12％和19.00％～19.14％，在生物法烟气同时脱硫脱氮技术应用效果上有了明显的提高(以对NOx脱除效率的提高最为显著)。
The invention discloses a technical method for improving the simultaneous desulfurization and denitrification efficiency of flue gas in a biofilm packing tower by adding an external carbon source. The invention belongs to the technical field of biological method industrial waste gas purification. Based on the principles of microbiology, the present invention uses a biofilm packing tower flue gas simultaneous desulfurization and denitrification system (single tower system), through the method of separately adding low-molecular organic carbon sources in the circulating liquid, and experimentally screens out the addition of sodium acetate as an additional carbon source , which has the best effect on improving the efficiency of simultaneous desulfurization and denitrification of flue gas in the biofilm packed tower. When sodium acetate is added to the circulating fluid at an optimum concentration of 50mmol/L (mmol/liter), the removal efficiency of SO2 and NOx in the flue gas can reach the highest value of 100% and 81.94%. Compared with the original technology [invention patent ZL200610011013.4], the application of the technical method of the present invention can increase the efficiency of removing SO2 and NOx by 2.75% to 3.12% and 19.00% respectively in the biofilm packed tower used for simultaneous desulfurization and denitrification of flue gas % to 19.14%, and the application effect of simultaneous desulfurization and denitrification technology of biological flue gas has been significantly improved (the improvement of NOx removal efficiency is the most significant).
Description
技术领域technical field
本发明公开一种通过外加碳源以提高生物膜填料塔烟气同时脱硫脱氮效率的技术方法。属于生物法工业废气净化技术领域。The invention discloses a technical method for improving the simultaneous desulfurization and denitrification efficiency of flue gas in a biofilm packing tower by adding an external carbon source. The invention belongs to the technical field of biological method industrial waste gas purification.
背景技术Background technique
工业过程排放的SO2、NOx的危害作为环境污染的一大问题早已引起世界各国政府及环保部门的高度重视。随着对烟气中SO2、NOx协同造成酸雨及其二次污染--光化学烟雾的进一步认识，人们急迫希望研究出新的工艺技术，使SO2和NOx一次性同步去除。这类综合处理性工艺技术无论是对现有脱硫系统的改造，还是对新建烟气净化系统投资及运行成本的降低和净化效率的提高，都具有重要意义。As a major problem of environmental pollution, the harm of SO 2 and NOx emitted by industrial processes has already attracted great attention from governments and environmental protection departments all over the world. With the further understanding of SO 2 and NOx synergistically causing acid rain and its secondary pollution - photochemical smog, people urgently hope to develop a new process technology to simultaneously remove SO 2 and NOx at one time. This kind of comprehensive treatment process technology is of great significance not only for the transformation of the existing desulfurization system, but also for the reduction of investment and operating costs and the improvement of purification efficiency of the new flue gas purification system.
近年来，随着许多发达国家以及中国对烟气排放的SO2、NOx及烟尘等污染物控制的环保立法日趋严格，探求技术上先进、经济上合理的新型烟气同时脱硫脱氮技术一直是环保领域的新技术前沿研究热点之一。虽然近年来国内外已出现了一些烟气同时脱硫脱氮技术，但目前大多仍处于实验研发及应用验证阶段。目前已在试验应用的烟气同时脱硫脱氮技术一般存在工艺流程复杂、设备投资大或运行费用高、对烟气中低浓度SO2和NOx的联合去除率低、副产品处置利用困难等技术或经济问题，大多难以在大范围内实现广泛的推广应用。因此，有必要结合中国的具体国情，研究开发新型的烟气同时脱硫脱氮新技术及系统装置。In recent years, as many developed countries and China have increasingly stringent environmental protection legislation on the control of pollutants such as SO 2 , NOx and soot emitted from flue gas, it has always been an important task to seek a new technology for simultaneous desulfurization and denitrification of flue gas that is technologically advanced and economically reasonable. It is one of the hotspots of new technology frontier research in the field of environmental protection. Although some flue gas desulfurization and denitrification technologies have appeared at home and abroad in recent years, most of them are still in the stage of experimental development and application verification. The flue gas simultaneous desulfurization and denitrification technologies that have been applied in the test generally have technical problems such as complex process flow, large equipment investment or high operating costs, low joint removal rate of low concentration SO2 and NOx in flue gas, and difficulties in disposal and utilization of by-products. Economic problems, most of them are difficult to achieve widespread promotion and application in a large scale. Therefore, it is necessary to study and develop new technologies and system devices for simultaneous desulfurization and denitrification of flue gas in combination with China's specific national conditions.
生物法废气净化技术作为一项废气处理新技术，以其经济、有效、污染物处理彻底、适合于处理低浓度工业废气等特点，越来越受到人们的广泛重视，因此近年来其已逐步发展成为世界上工业废气净化的一个前沿热点研究领域。该技术方法的研究与应用实践表明，其在解决几乎没有回收利用价值、净化处理难度大且费用高、同时对人体健康与生态环境的危害又不容忽视的低浓度工业废气的净化处理难题方面(在国内外都是环保方面的难题之一)，具有特殊的功效。Biological waste gas purification technology, as a new waste gas treatment technology, has been paid more and more attention by people because of its economical, effective, thorough pollutant treatment, and suitability for low-concentration industrial waste gas treatment. Therefore, it has gradually developed in recent years. It has become a frontier hot research field of industrial waste gas purification in the world. The research and application practice of this technical method shows that it can solve the problem of purification and treatment of low-concentration industrial waste gas that has almost no recycling value, is difficult and expensive to purify, and is harmful to human health and ecological environment. It is one of the difficult problems of environmental protection both at home and abroad), and has special effects.
本发明前期研究形成的“液相催化氧化-微生物组合法同时脱除烟气中二氧化硫和氮氧化物的方法”[发明专利ZL200610011013.4]，在净化性能、投资成本、运行费用、可操作性、副产品等方面均优于现有常规技术。The "liquid-phase catalytic oxidation-microorganism combination method for simultaneous removal of sulfur dioxide and nitrogen oxides in flue gas" [invention patent ZL200610011013.4] formed in the previous research of the present invention has advantages in purification performance, investment cost, operating cost and operability , by-products and other aspects are better than the existing conventional technology.
由于用于烟气同时脱硫脱氮的生物膜填料塔内的微生物是以脱硫、脱氮自养菌为主构成的复合菌群。这类以自养菌为主的复合菌群通常是以大气中二氧化碳为其主要生长碳源的，生长繁殖速度较慢。如果生物膜填料塔的操作条件改变引起这类以自养菌为主的微生物的生长环境条件变化，如气相二氧化碳碳源条件变化，就会对生物膜填料塔的烟气同时脱硫脱氮性能产生不利影响。Because the microorganisms in the biofilm packed tower used for simultaneous desulfurization and denitrification of flue gas are composite flora mainly composed of desulfurization and denitrification autotrophic bacteria. This type of composite flora mainly composed of autotrophic bacteria usually uses carbon dioxide in the atmosphere as its main growth carbon source, and its growth and reproduction speed is relatively slow. If the operating conditions of the biofilm packed tower change the growth environment conditions of such microorganisms mainly composed of autotrophic bacteria, such as changes in the gas phase carbon dioxide carbon source conditions, it will have a negative impact on the flue gas simultaneous desulfurization and denitrification performance of the biofilm packed tower. Negative Effects.
发明内容：Invention content:
为了提高生物膜填料塔的烟气同时脱硫脱氮效率，本发明依据微生物学原理，对通过外加碳源促进具有同时脱硫脱氮性能的以自养菌为主的微生物的生长来提高生物膜填料塔烟气同时脱硫脱氮效率的技术方法进行了实验研究，并形成了通过外加碳源提高生物膜填料塔烟气同时脱硫脱氮效率的新型技术方法。In order to improve the simultaneous desulfurization and denitrification efficiency of the flue gas of the biofilm packing tower, the present invention, based on the principle of microbiology, promotes the growth of microorganisms with simultaneous desulfurization and denitrification performance, mainly autotrophic bacteria, to improve the biofilm packing. The technical method of simultaneous desulfurization and denitrification efficiency of tower flue gas has been experimentally studied, and a new technical method for improving the simultaneous desulfurization and denitrification efficiency of biofilm packing tower flue gas by adding an external carbon source has been formed.
本发明的目的在于克服前期研究形成的催化氧化-生物法同时脱除烟气中SO2、NOx技术所涉及的复合菌群是以脱硫、脱氮自养菌为主构成的，这类以自养菌为主的微生物通常是以大气中二氧化碳为其主要生长碳源的，生长繁殖速度较慢的问题，发明一种通过添加适量的低分子有机碳源，很好地改善了生物膜填料塔中具有同时脱硫脱氮性能的以自养菌为主的微生物的仅以气相中二氧化碳为其唯一生长碳源的生长环境条件，促进了以自养菌为主的脱硫、脱氮复合菌群的快速生长繁殖，解决这类脱硫、脱氮复合菌群依靠单一气相二氧化碳碳源生长且受环境条件变化影响较大的问题。The purpose of the present invention is to overcome the catalytic oxidation-biological method formed in the previous research. The complex flora involved in the technology of simultaneously removing SO 2 and NOx from flue gas is mainly composed of desulfurization and denitrification autotrophic bacteria. Bacteria-based microorganisms usually use carbon dioxide in the atmosphere as their main carbon source for growth, and the growth and reproduction speed is slow. By adding an appropriate amount of low-molecular organic carbon source, the invention of a biofilm packing tower is well improved. The growth environment conditions of microorganisms mainly composed of autotrophic bacteria that have simultaneous desulfurization and denitrification performance only use carbon dioxide in the gas phase as their only growth carbon source, which promotes the growth of the desulfurization and denitrification composite bacteria mainly composed of autotrophic bacteria. Rapid growth and reproduction can solve the problem that this kind of desulfurization and denitrification composite bacteria grows on a single gas-phase carbon dioxide carbon source and is greatly affected by changes in environmental conditions.
本发明一种外加碳源提高生物膜填料塔烟气同时脱硫脱氮效率的方法，其特征是在生物膜填料塔系统循环液储槽的循环液中，加入乙酸钠作为一种低分子有机碳源，搅拌均匀后通过循环泵使添加物随循环液体喷淋到塔内的生物膜上，供具有同时脱硫脱氮性能的以自养菌为主的微生物吸收利用，从而获得提高生物膜填料塔烟气同时脱硫脱氮效率的效果。The present invention is a method for improving the simultaneous desulfurization and denitrification efficiency of flue gas in a biofilm packing tower by adding an external carbon source. After stirring evenly, the additives are sprayed onto the biofilm in the tower with the circulating liquid through the circulating pump, and can be absorbed and utilized by microorganisms mainly composed of autotrophic bacteria with simultaneous desulfurization and denitrification performance, so as to obtain an improved biofilm packed tower The effect of simultaneous flue gas desulfurization and denitrification efficiency.
所述最适于外加的低分子有机碳源为乙酸钠。The most suitable low-molecular-weight organic carbon source is sodium acetate.
循环液中添加乙酸钠的最佳浓度为50mmol/L(毫摩尔/升)。The optimal concentration of sodium acetate added to the circulating fluid is 50mmol/L (mmol/L).
本发明技术区别于原有技术[发明专利ZL200610011013.4]的主要不同点在于：为了使生物膜填料塔能够保持较高的烟气同时脱硫脱氮效率，原有技术的措施是定期向循环液储槽中添加补充水、氮磷营养成分、专用金属离子组合催化剂等，而没有考虑到以自养菌为主的脱硫、脱氮复合菌群在其生长繁殖中碳源也是一个重要因素。本发明通过添加适量的低分子有机碳源乙酸钠，很好地改善了生物膜填料塔中具有同时脱硫脱氮性能的以自养菌为主的微生物的仅以气相中二氧化碳为其唯一生长碳源的生长环境条件，促进了以自养菌为主的脱硫、脱氮复合菌群的快速生长繁殖，其作用的宏观结果就是使生物膜填料塔的烟气同时脱硫脱氮效率有了较大的提高(具体详见实施例)。The main difference between the technology of the present invention and the original technology [invention patent ZL200610011013.4] is that in order to enable the biofilm packed tower to maintain a high flue gas desulfurization and denitrification efficiency at the same time, the measure of the original technology is to periodically inject Supplementary water, nitrogen and phosphorus nutrients, special metal ion combination catalysts, etc. are added to the storage tank, without considering that the carbon source is also an important factor in the growth and reproduction of the desulfurization and denitrification complex bacterial flora dominated by autotrophic bacteria. In the present invention, by adding an appropriate amount of low-molecular organic carbon source sodium acetate, the biofilm packing tower with simultaneous desulfurization and denitrification performance is well improved. The microorganisms mainly composed of autotrophic bacteria only use carbon dioxide in the gas phase as their only growth carbon. The growth and environmental conditions of the source promote the rapid growth and reproduction of the desulfurization and denitrification compound flora mainly composed of autotrophic bacteria. The improvement (see the embodiment for details).
当在循环液中按最佳浓度50mmol/L(毫摩尔/升)添加乙酸钠时，生物膜填料塔对烟气中SO2和NOx的脱除效率可达到最高值100％和81.94％。与原有技术[发明专利ZL200610011013.4]相比，应用本发明技术方法能够使用于烟气同时脱硫脱氮的生物膜填料塔脱除SO2和NOx的效率分别提高2.75％～3.12％和19.00％～19.14％，在生物法烟气同时脱硫脱氮技术应用效果上有了明显的提高(以对NOx脱除效率的提高最为显著)。When sodium acetate is added to the circulating fluid at an optimal concentration of 50mmol/L, the removal efficiency of SO2 and NOx in the flue gas can reach the highest values of 100% and 81.94%. Compared with the original technology [invention patent ZL200610011013.4], the application of the technical method of the present invention can increase the efficiency of removing SO2 and NOx by 2.75% to 3.12% and 19.00% respectively in the biofilm packed tower used for simultaneous desulfurization and denitrification of flue gas % to 19.14%, and the application effect of simultaneous desulfurization and denitrification technology of biological flue gas has been significantly improved (the improvement of NOx removal efficiency is the most significant).
本发明由实验得出的在循环液中添加乙酸钠的最佳浓度为50mmol/L(毫摩尔/升)。按此最佳浓度添加乙酸钠操作时，生物膜填料塔对烟气中SO2和NOx的脱除效率可达到最高值，分别100％和81.94％。The optimum concentration of adding sodium acetate in the circulation fluid obtained by the present invention is 50mmol/L (mmol/liter) obtained through experiments. When adding sodium acetate at this optimal concentration, the removal efficiency of SO2 and NOx in the flue gas of the biofilm packed tower can reach the highest value, 100% and 81.94%, respectively.
本发明的生物法烟气同时脱硫脱氮技术原理、技术方案、专用金属离子组合催化剂配制及使用方法、生物膜填料塔实验系统装置及其操作运行方法等，均与前期研究形成的“液相催化氧化-微生物组合法同时脱除烟气中二氧化硫和氮氧化物的方法”[发明专利ZL200610011013.4]的相同，再此不再重述。The technical principle, technical scheme, preparation and use method of the special metal ion combination catalyst, the device of the biofilm packing tower experimental system and its operation method, etc. of the present invention are all in line with the "liquid phase" formed in the previous research. Catalytic oxidation-microbial combination method simultaneously removes sulfur dioxide and nitrogen oxides from flue gas" [invention patent ZL200610011013.4] is the same, and will not be repeated here.
与原有技术[发明专利ZL200610011013.4]相比，应用本发明技术方法能够使用于烟气同时脱硫脱氮的生物膜填料塔的脱除SO2效率提高2.75％～3.12％、脱除NOx效率提高19.00％～19.14％，在生物法烟气同时脱硫脱氮技术应用效果上有了明显的提高(以对NOx脱除效率的提高最为显著)。Compared with the original technology [invention patent ZL200610011013.4], the application of the technical method of the present invention can increase the efficiency of SO2 removal by 2.75% to 3.12%, and the efficiency of NOx removal by the biofilm packed tower used for simultaneous desulfurization and denitrification of flue gas. The increase is 19.00%-19.14%, and the application effect of simultaneous desulfurization and denitrification technology of biological flue gas has been significantly improved (the improvement of NOx removal efficiency is the most significant).
本发明技术将在工业低浓度SO2和NOx废气污染控制方面具有广阔的应用前景。The technology of the invention will have broad application prospects in the control of industrial low-concentration SO2 and NOx waste gas pollution.
附图说明Description of drawings
图1本发明技术方法使用的生物膜填料塔烟气同时脱硫脱氮系统的工艺流程示意图。Fig. 1 is a schematic diagram of the technological process of the flue gas simultaneous desulfurization and denitrification system of the biofilm packing tower used in the technical method of the present invention.
图中：1-预处理器(必要时使用)；2-引风机；3-生物膜填料塔；4-循环液储槽及泵。In the figure: 1-preprocessor (used when necessary); 2-induced fan; 3-biofilm packing tower; 4-circulating liquid storage tank and pump.
具体实施方式：Detailed ways:
本发明具体实施方法是将乙酸钠化学试剂按最佳浓度配比剂量加入到生物膜填料塔系统循环液储槽的循环液体中，并搅拌均匀，之后通过循环泵使其随循环液体喷淋到塔内的生物膜上供具有同时脱硫脱氮性能的以自养菌为主的微生物吸收利用。随着循环液在生物膜填料塔内的循环喷淋流动，润湿的生物膜中的以自养菌为主的脱硫、脱氮微生物即可将液相中的乙酸钠作为生长基质碳源充分吸收利用。操作中，可通过定时测定循环液中乙酸钠的浓度和生物膜填料塔的烟气同时脱硫脱氮效率，适时按最佳浓度数值补加适量的乙酸钠试剂，以使生物膜填料塔能够保持较高的烟气同时脱硫脱氮效率。The specific implementation method of the present invention is to add the sodium acetate chemical reagent into the circulating liquid in the circulating liquid storage tank of the biofilm packed tower system according to the optimal concentration ratio, and stir evenly, and then spray it with the circulating liquid through the circulating pump. The biofilm in the tower is used for the absorption and utilization of microorganisms mainly autotrophic bacteria with simultaneous desulfurization and denitrification performance. With the circulating liquid spraying and flowing in the biofilm packed tower, the desulfurization and denitrification microorganisms in the wetted biofilm can fully use sodium acetate in the liquid phase as a growth matrix carbon source. Absorb and utilize. During operation, the concentration of sodium acetate in the circulating fluid and the simultaneous desulfurization and denitrification efficiency of the flue gas in the biofilm packed tower can be measured regularly, and an appropriate amount of sodium acetate reagent can be added according to the optimal concentration value at the right time, so that the biofilm packed tower can maintain High flue gas simultaneous desulfurization and denitrification efficiency.
实施例1～3：
在采用液相催化氧化-微生物法操作的生物膜填料塔系统上进行外加碳源的同时脱除烟气中SO2和NOx的处理实验。生物膜填料塔系统由预处理器、引风机、一个生物膜填料塔、循环液储槽及循环泵组成，其流程和连接方式见如图1所示。The treatment experiment of removing SO 2 and NOx from the flue gas while adding an external carbon source was carried out on the biofilm packed tower system operated by liquid-phase catalytic oxidation-microbial method. The biofilm packed tower system consists of a preprocessor, an induced draft fan, a biofilm packed tower, a circulating liquid storage tank and a circulating pump. The flow and connection methods are shown in Figure 1.
其中的生物膜填料塔是塔径为100mm的小型玻璃生物膜填料塔，填料塔内分两段装填直径为2.5cm的类球形陶粒，填料体积3.18L×2。实验操作均在常温常压条件下进行，气体流量为0.10～0.15m3/h，烟气中SO2和NOX浓度分别为3000～3500mg/m3、500～1000mg/m3，循环液流量为12～15L/h，循环液pH 1.0～1.5。生物膜填料塔进、出口SO2和NOX气体浓度采用英国产烟气分析仪KM900进行测定，液相中SO2和NOX的量采用常规化学法测定。The biofilm packing tower is a small glass biofilm packing tower with a tower diameter of 100mm. The packing tower is filled with spherical ceramsite with a diameter of 2.5cm in two sections, and the packing volume is 3.18L×2. The experimental operations are all carried out under normal temperature and pressure conditions, the gas flow rate is 0.10-0.15m 3 /h, the SO 2 and NO X concentrations in the flue gas are 3000-3500mg/m 3 , 500-1000mg/m 3 , the circulating liquid flow rate 12~15L/h, circulating fluid pH 1.0~1.5. The gas concentration of SO 2 and NO X at the inlet and outlet of the biofilm packed tower is measured by a British flue gas analyzer KM900, and the amount of SO 2 and NO X in the liquid phase is measured by conventional chemical methods.
本发明依据微生物学原理，应用上述生物膜填料塔烟气同时脱硫脱氮系统(单塔系统)，通过在循环液中分别外加乙酸钠、酒石酸钾钠、葡萄糖、甲醇等4种低分子有机碳，并逐一实验考察它们对提高生物膜填料塔烟气同时脱硫脱氮效率的效果。在循环液中添加4种低分子有机碳的浓度范围分别是：乙酸钠45～55mmol/L(毫摩尔/升)，酒石酸钾钠45～55mmol/L，甲醇45～55mmol/L，葡萄糖3.8～4.5mmol/L。 实验结果如表1所示。Based on the principle of microbiology, the present invention applies the above-mentioned biofilm packing tower flue gas simultaneous desulfurization and denitrification system (single tower system), by adding four kinds of low-molecular organic carbons such as sodium acetate, potassium sodium tartrate, glucose and methanol to the circulating liquid respectively. , and one by one to investigate their effects on improving the efficiency of simultaneous desulfurization and denitrification of flue gas in biofilm packed towers. The concentration ranges of adding four kinds of low-molecular organic carbon in the circulating fluid are: sodium acetate 45-55mmol/L (mmol/L), potassium sodium tartrate 45-55mmol/L, methanol 45-55mmol/L, glucose 3.8- 4.5mmol/L. The experimental results are shown in Table 1.
经对表1中的实验结果进行对比分析，发现在循环液中按50mmol/L的浓度添加乙酸钠作为外加碳源，对提高生物膜填料塔烟气同时脱硫脱氮效率的效果最优，其脱除SO2和NOx的效率比不外加碳源时的分别提高了2.75～3.12％和19.00～19.14％，对SO2和NOx的最高脱除效率分别达到了100％和81.94％，使生物法烟气同时脱硫脱氮技术的应用效果有了明显的提高(以脱除NOx效率的提高最为显著)。After comparative analysis of the experimental results in Table 1, it was found that adding sodium acetate as an external carbon source at a concentration of 50mmol/L in the circulating fluid had the best effect on improving the efficiency of simultaneous desulfurization and nitrogen removal of flue gas in the biofilm packed tower. The removal efficiency of SO 2 and NOx increased by 2.75-3.12% and 19.00-19.14%, respectively, compared with that without adding carbon source, and the highest removal efficiency of SO 2 and NOx reached 100% and 81.94%, making the biological method The application effect of simultaneous flue gas desulfurization and denitrification technology has been significantly improved (the most significant improvement is the efficiency of NOx removal).
表1同时脱除烟气中SO2和NOx的实验结果Table 1 Experimental results of simultaneous removal of SO2 and NOx from flue gas
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