CN105623766A - 一种可燃气体脱氧、脱氮的生物处理方法 - Google Patents
一种可燃气体脱氧、脱氮的生物处理方法 Download PDFInfo
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Abstract
本发明涉及一种可燃气体脱氧、脱氮的生物处理方法，包括以下步骤：(1)将有机废水、含氧/氮可燃气体、好氧活性污泥通入密闭式脱氧生物反应器进行好氧生物反应脱氧；(2)将无氮培养基、脱氧后的含氮可燃气体、自生厌氧化能异养固氮菌通入密闭式脱氮生物反应器进行厌氧生物反应脱氮。与现有的高温高压化学催化脱氧和超低温深冷脱氧脱氮相比，本发明利用微生物的相关代谢功能实现可燃气体脱氧、脱氮在常温常压条件下运行，对设备和控制要求较低，运行稳定性较高，整体过程安全性较高；脱氧过程无需消耗甲烷、一氧化碳、氢气、焦炭、甲醇等能源物质；脱氮过程在常压下进行，无需多级压缩制冷，能耗较低。
Description
技术领域
本发明属于气体脱氧、脱氮技术领域，具体涉及一种可燃气体脱氧、脱氮的生物处理方法。
背景技术
煤层气、页岩气、焦炉煤气、生物质燃气、填埋气等可燃的非常规天然气或废气的开发利用日益受到国际社会的关注。以上可燃气体中通常混有不同量的氧气、氮气。氧气的存在会给可燃气体在运输、分离和利用过程中造成较大的安全隐患；而氮气的存在会降低可燃气体的热值，影响终端利用的经济效益。为了安全、高值利用以上可燃气体，脱氧、脱氮是必要环节，尤其是脱氧步骤。
目前，可燃气体脱氧主要采用化学催化反应来消耗气体中的氧，例如甲烷催化燃烧除氧(公开专利CN101664679B)、焦炭催化燃烧除氧(授权专利ZL02113627.0)、一氧化碳催化燃烧除氧(公开专利CN100579653C)、氢气催化燃烧除氧(公开专利CN100579653C)、甲醇催化燃烧除氧(公开专利CN103599775A)。以上化学催化脱氧工艺，一方面需要消耗可燃气中的甲烷、一氧化碳、氢气，或者消耗***外界供给的氢气、焦炭、甲醇等，造成能源的浪费；另一方面，由于化学催化脱氧是一个放热反应，必然在高温高压条件下运行，对设备要求以及运行安全都是极大的挑战。
目前，可燃气体脱氮由于难度较大，很少有脱氮应用。专利“含氧煤层气的脱氧、脱氮***”(公开专利CN103484184A)公开了一种采用深冷分离进行脱氧脱氮的方法，但该方法能耗较高。
综述以上，有必要开发一种更为安全、低耗、高效的可燃气体脱氧、脱氮工艺。
发明内容
本发明的目的在于克服现有技术中的不足，提供可燃气体脱氧、脱氮的生物处理方法，实现可燃气体安全、低耗、高效的脱氧、脱氮。
本发明中可燃气体脱氧、脱氮的生物处理方法，包括以下步骤：
(1)将有机废水、含氧/氮可燃气体、好氧活性污泥通入密闭式脱氧生物反应器，控制密闭式生物反应器内温度20～35℃、pH值6.5～8.5，好氧活性污泥利用有机废水中的有机质和含氧/氮可燃气体中的氧气进行好氧呼吸代谢，消耗含氧/氮可燃气体中的氧气；
有机质+O2→CO2+H2O
(2)将无氮培养基、脱氧后的含氮可燃气体、自生厌氧化能异养固氮菌通入密闭式脱氮生物反应器，控制密闭式生物反应器内温度25～68℃、pH值6.5～8.5，自生厌氧化能异养固氮菌利用无氮培养基中的非氮营养物质和含氮可燃气体中的氮气进行自生厌氧化能固氮代谢，消耗含氮可燃气体中的氮气。
非氮营养物质+N2→细胞蛋白质+NH4 +
所述的有机废水包括但不局限于生活污水和工业有机废水；
所述的含氧/氮可燃气体包括但不局限于煤层气、页岩气、焦炉煤气、生物质燃气、填埋气；
所述的好氧活性污泥来源于污水处理厂；
所述无氮培养基配方为每升水中含葡萄糖5～20g，KH2PO40.2～3g，MgSO4·7H2O0.2～0.5g，NaCl0.2～1g，FeSO40.05～0.1g，CaCl2·2H2O0.2～0.5g，NaMoO40.01～0.03g，CaCO33～5g，L-抗坏血酸0.2～0.4g；
所述自生厌氧化能异养固氮菌包括但不局限于丙酮丁醇梭菌(Clostridiumacetobutylicum)、拜氏梭菌(Clostridiumbeijerinckii)、丁酸梭菌(Clostridiumbutyricum)、克氏梭菌(Clostridiumkluyverii)、巴斯德梭菌(Clostridiumpasteurianum)、亨氏梭菌(Clostridiumhungatei)、Clostridiumformicoaceticum、Clostridiumakagii、Clostridiumacidisoli、Thermoanaerobacteriumthermosaccharolyticum；应用时添加它们的一种菌或多种菌组合；
所述的密闭式脱氧生物反应器和密闭式脱氮生物反应器类型包括搅拌式反应器、鼓泡塔反应器、微泡反应器、膜反应器，优选为膜反应器，根据可燃气体中氧、氮含量的高低可串联设置多级脱氧/氮生物反应器保证处理后气体中的氧、氮含量达到要求；
所述的密闭式脱氧生物反应器和密闭式脱氮生物反应器设置气体自循环回路，延长反应器内气液接触时间，提高反应器的氧、氮脱除效率。
与现有的高温高压化学催化脱氧和超低温深冷脱氧脱氮相比，本发明的创新之处在于，利用微生物的相关代谢功能实现可燃气体脱氧、脱氮在常温常压条件下运行。采用该发明方法具有三个优势：1)脱氧、脱氮在常温常压条件下运行，对设备和控制要求较低，运行稳定性较高，整体过程安全性较高；2)脱氧过程消耗的是有机废水中的有机质，无需消耗甲烷、一氧化碳、氢气、焦炭、甲醇等能源物质，处理过程的能源效率较高，而且脱氧过程本身具有污水处理作用；3)脱氮过程在常压下进行，无需多级压缩制冷，能耗较低。
附图说明
图1是本发明方法的工艺流程示意图
具体实施方式
以下结合附图和具体实施方式对本发明进行详细说明。
实施例1：
对某垃圾填埋场的填埋气进行脱氧、脱氮处理，填埋气收集量为10000m3/d，填埋气主要成分为CH450％、CO240％、O22％、N26％。收集填埋气和附近生活污水，将它们和污水处理厂的好氧活性污泥通入密闭式脱氧膜生物反应器，控制反应器内温度20℃、pH值6.5进行好氧呼吸代谢，好氧活性污泥中的好氧化能异养菌通过反应式(有机质+O2→CO2+H2O)消耗O2；配制无氮培养基，配方为每升水中含葡萄糖5g，KH2PO40.2g，MgSO4·7H2O0.2g，NaCl0.2g，FeSO40.05g，CaCl2·2H2O0.2g，NaMoO40.01g，CaCO33g，L-抗坏血酸0.2g，将无氮培养基、脱氧后的填埋气、丙酮丁醇梭菌(Clostridiumacetobutylicum)通入两级密闭式脱氮微泡生物反应器，控制反应器内温度25℃、pH值6.5进行厌氧固氮代谢，丙酮丁醇梭菌利用无氮培养基中的非氮营养物质和填埋气中的氮气进行自生厌氧固氮代谢，按照反应式(非氮营养物质+N2→细胞蛋白质+NH4 +)消耗填埋气中的氮气，最后获得成分为CH453％、CO245％、O20.1％、N20.3％的填埋气。
实施例2：
对某小型煤矿煤层气进行脱氧、脱氮处理，煤层气收集量为20000m3/d，煤层气中O25％、N215％，其余主要为CH4。收集煤层气和附近淀粉生产废水，将它们和污水处理厂的好氧活性污泥通入两级密闭式脱氧鼓泡生物反应器，控制反应器内温度28℃、pH值7.5进行好氧呼吸代谢，好氧活性污泥中的好氧化能异养菌通过反应式(有机质+O2→CO2+H2O)消耗O2；配制无氮培养基，配方为每升水中含葡萄糖13g，KH2PO41.5g，MgSO4·7H2O0.35g，NaCl0.6g，FeSO40.07g，CaCl2·2H2O0.35g，NaMoO40.02g，CaCO34g，L-抗坏血酸0.3g，将无氮培养基、脱氧后的煤层气、Clostridiumformicoaceticum、Clostridiumakagii、Clostridiumacidisoli通入三级密闭式脱氮膜生物反应器，控制反应器内温度45℃、pH值7.5进行厌氧固氮代谢，Clostridiumformicoaceticum、Clostridiumakagii、Clostridiumacidisoli利用无氮培养基中的非氮营养物质和煤层气中的氮气进行自生厌氧固氮代谢，按照反应式(非氮营养物质+N2→细胞蛋白质+NH4 +)消耗煤层气中的氮气，最后获得O20.3％、N20.7％的煤层气。
实施例3：
对某炼焦厂的焦炉煤气进行脱氧、脱氮处理，焦炉煤气收集量为20000m3/d，气体组成H255％、CH420％、CO9％、CO25％、N25％、O20.8％。收集焦炉煤气和附近酒精生产废水，将它们和污水处理厂的好氧活性污泥通入密闭式脱氧搅拌生物反应器，控制反应器内温度35℃、pH值8.5进行好氧呼吸代谢，好氧活性污泥中的好氧化能异养菌通过反应式(有机质+O2→CO2+H2O)消耗O2；配制无氮培养基，配方为每升水中含葡萄糖20g，KH2PO43g，MgSO4·7H2O0.5g，NaCl1g，FeSO40.1g，CaCl2·2H2O0.5g，NaMoO40.03g，CaCO35g，L-抗坏血酸0.4g，将无氮培养基、脱氧后的焦炉煤气、Thermoanaerobacteriumthermosaccharolyticum通入两级密闭式脱氮微泡生物反应器，控制反应器内温度68℃、pH值8.5进行厌氧固氮代谢，Thermoanaerobacteriumthermosaccharolyticum利用无氮培养基中的非氮营养物质和焦炉煤气中的氮气进行自生厌氧固氮代谢，按照反应式(非氮营养物质+N2→细胞蛋白质+NH4 +)消耗焦炉煤气中的氮气，最后获得O20.05％、N20.5％的焦炉煤气。
最后，还需要注意的是，以上列举的仅是本发明的具体实施例。显然，本发明不限于以上实施例，还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。
Claims (8)
1.一种可燃气体脱氧、脱氮的生物处理方法，其特征在于，该方法包括以下步骤：
(1)将有机废水、含氧/氮可燃气体、好氧活性污泥通入密闭式脱氧生物反应器，控制密闭式生物反应器内温度20～35℃、pH值6.5～8.5，好氧活性污泥利用有机废水中的有机质和含氧/氮可燃气体中的氧气进行好氧呼吸代谢，消耗含氧/氮可燃气体中的氧气，
有机质+O2→CO2+H2O；
(2)将无氮培养基、脱氧后的含氮可燃气体、自生厌氧化能异养固氮菌通入密闭式脱氮生物反应器，控制密闭式生物反应器内温度25～68℃、pH值6.5～8.5，自生厌氧化能异养固氮菌利用无氮培养基中的非氮营养物质和含氮可燃气体中的氮气进行自生厌氧化能固氮代谢，消耗含氮可燃气体中的氮气，
非氮营养物质+N2→细胞蛋白质+NH4 +。
2.根据权利要求1所述的一种可燃气体脱氧、脱氮的生物处理方法，其特征在于，步骤(2)中的自生厌氧化能异养固氮菌包括但不局限于丙酮丁醇梭菌、拜氏梭菌、丁酸梭菌、克氏梭菌、巴斯德梭菌、亨氏梭菌；应用时添加它们的一种菌或多种菌组合。
3.根据权利要求1所述的一种可燃气体脱氧、脱氮的生物处理方法，其特征在于，步骤(2)中的无氮培养基配方为每升水中含葡萄糖5～20g，KH2PO40.2～3g，MgSO4·7H2O0.2～0.5g，NaCl0.2～1g，FeSO40.05～0.1g，CaCl2·2H2O0.2～0.5g，NaMoO40.01～0.03g，CaCO33～5g，L-抗坏血酸0.2～0.4g。
4.根据权利要求1所述的一种可燃气体脱氧、脱氮的生物处理方法，其特征在于，步骤(1)中的密闭式脱氧生物反应器和步骤(2)中的密闭式脱氮生物反应器类型包括搅拌式反应器、鼓泡塔反应器、微泡反应器或膜反应器。
5.根据权利要求1所述的一种可燃气体脱氧、脱氮的生物处理方法，其特征在于，步骤(1)中的密闭式脱氧生物反应器和步骤(2)中的密闭式脱氮生物反应器可设置一级或串联设置多级。
6.根据权利要求1所述的一种可燃气体脱氧、脱氮的生物处理方法，其特征在于，步骤(1)中的密闭式脱氧生物反应器和步骤(2)中的密闭式脱氮生物反应器设置气体自循环回路。
7.根据权利要求1所述的一种可燃气体脱氧、脱氮的生物处理方法，其特征在于，步骤(1)中的有机废水包括但不局限于生活污水和工业有机废水，步骤(1)中的好氧活性污泥来源于污水处理厂。
8.根据权利要求1所述的一种可燃气体脱氧、脱氮的生物处理方法，其特征在于，含氧/氮可燃气体包括但不局限于煤层气、页岩气、焦炉煤气、生物质燃气或填埋气。
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