CN102351309B - Azotification method by use of organic wastewater - Google Patents
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
本发明属于废水回收利用技术领域,涉及一种利用有机废水进行固氮的方法,该方法包括以下步骤:(1)有机废水灭菌后加入反应器中;(2)向反应器中接入光合细菌;(3)反应器的下部通入氮气使反应器内的气压达0.1Mpa;(4)对有机废水进行光照培养不少于96h;(5)培养结束后反应器内的液体经离心分离、脱水干燥得到固态有机氮产物。本发明利用光合细菌将有机废水中的营养物质在厌氧光照条件下利用自身固氮酶的固氮作用将空气中的氮转化为菌体蛋白和菌体色素,从而将空气中的单质氮以有机态形式转化固定,提供合适氮源形式。The invention belongs to the technical field of waste water recovery and utilization, and relates to a method for using organic waste water to fix nitrogen. The method includes the following steps: (1) adding the organic waste water into the reactor after being sterilized; (2) inserting photosynthetic bacteria into the reactor (3) Nitrogen gas is injected into the lower part of the reactor to make the air pressure in the reactor reach 0.1Mpa; (4) The organic wastewater is cultivated under light for not less than 96 hours; (5) After the cultivation, the liquid in the reactor is centrifuged, Dehydration and drying give solid organic nitrogen products. The present invention uses photosynthetic bacteria to convert the nutrients in the organic wastewater into nitrogen in the air by the nitrogen fixation of its own nitrogenase under anaerobic light conditions, thereby transforming the elemental nitrogen in the air into an organic state Form conversion fixes, providing the appropriate nitrogen source form.
Description
技术领域 technical field
本发明属于废水回收利用技术领域,涉及一种利用有机废水进行固氮的方法。 The invention belongs to the technical field of waste water recycling and relates to a method for fixing nitrogen by using organic waste water.
背景技术 Background technique
氮是多数动植物及微生物生长不可或缺的基本元素,且多数情况下生物体更易于利用有机态氮作为自身新陈代谢的氮源形式。虽然空气中约78%的成分为氮气,除少数具有自身固氮作用的微生物和植物体外,多数生物体都无法直接利用氮气。目前对空气氮源的利用还主要以化学方法进行固定转化(合成氨工艺),将空气中的氮气转化为氨的形式再进一步利用。 Nitrogen is an indispensable basic element for the growth of most animals, plants and microorganisms, and in most cases organisms are more likely to use organic nitrogen as a nitrogen source for their own metabolism. Although about 78% of the air is nitrogen, except for a few microorganisms and plants that have their own nitrogen fixation, most organisms cannot directly use nitrogen. At present, the utilization of air nitrogen source is mainly fixed conversion by chemical method (synthetic ammonia process), and the nitrogen in the air is converted into the form of ammonia for further utilization.
光合细菌是一类具有特殊生长代谢体系的古细菌,其能在不同环境条件下进行生长代谢活动,其中在厌氧光照和营养条件缺氮下的情况其可将单质氮转化自身生长代谢所需氮源,这种代谢形式是地球大气圈演变的重要组成部分。固氮作用是光合细菌固氮酶的一种自身代谢途径,该固氮过程必须在光照条件下进行,由于光合细菌的固氮酶对氧敏感,氧的存在将导致固氮酶的失活从而失去固氮活性,因此要想利用光合细菌对空气中的氮进行固定转化,必须消除空气中氧的抑制作用。 Photosynthetic bacteria are a type of archaea with a special growth and metabolism system, which can carry out growth and metabolism activities under different environmental conditions. Among them, under the conditions of anaerobic light and nitrogen deficiency under nutrient conditions, they can convert elemental nitrogen into what they need for their own growth and metabolism. Nitrogen source, this form of metabolism is an important part of the evolution of the Earth's atmosphere. Nitrogen fixation is a metabolic pathway of nitrogenase in photosynthetic bacteria. The nitrogen fixation process must be carried out under light conditions. Since the nitrogenase of photosynthetic bacteria is sensitive to oxygen, the presence of oxygen will lead to the inactivation of nitrogenase and the loss of nitrogen fixation activity. In order to use photosynthetic bacteria to fix and transform nitrogen in the air, the inhibitory effect of oxygen in the air must be eliminated.
有机废水中含有大量的富碳有机质,其在代谢分解过程中将消耗大量的氧气从而引起缺氧导致水中动物死亡,是水体污染的重要原因。有机废水中含有的富碳物质是一种很好的碳源物质,可为多种微生物生长代谢提供能量来源。利用光合细菌的生长代谢特性在特定环境条件下以有机废水为碳源将空气中氮进行转化固定不仅可以使有机废水得到净化处理,光合细菌转化固定下来的氮源还是多种生物利用的氮源形式。 Organic wastewater contains a large amount of carbon-rich organic matter, which consumes a large amount of oxygen in the process of metabolic decomposition, causing hypoxia and death of aquatic animals, which is an important cause of water pollution. The carbon-rich substances contained in organic wastewater are good carbon sources, which can provide energy sources for the growth and metabolism of a variety of microorganisms. Using the growth and metabolism characteristics of photosynthetic bacteria to convert and fix nitrogen in the air with organic wastewater as a carbon source under specific environmental conditions can not only purify organic wastewater, but also the nitrogen source converted and fixed by photosynthetic bacteria is also a nitrogen source for a variety of biological utilization form.
发明内容 Contents of the invention
本发明的目的是提供一种利用有机废水进行固氮的方法,可以获得有机氮产品。 The purpose of the present invention is to provide a method for nitrogen fixation using organic waste water, which can obtain organic nitrogen products.
本发明采用以下技术方案: The present invention adopts following technical scheme:
一种利用有机废水进行固氮的方法,包括以下步骤: A kind of method utilizing organic waste water to carry out nitrogen fixation, comprises the following steps:
(1)有机废水灭菌后加入反应器中;(2)向反应器中接入光合细菌,光合细菌接种量为有机废水体积的5-10%;(3)反应器的下部通入氮气使反应器内的气压达0.1Mpa;(4)对有机废水进行光照培养不少于96h,控制光照度为2000-3000 Lx,培养温度为25-30℃;(5)培养结束后反应器内的液体经离心分离、脱水干燥得到固态有机氮产物。 (1) Add the organic wastewater to the reactor after sterilization; (2) Introduce photosynthetic bacteria into the reactor, and the inoculation amount of photosynthetic bacteria is 5-10% of the volume of the organic wastewater; (3) Inject nitrogen into the lower part of the reactor to make The air pressure in the reactor is up to 0.1Mpa; (4) The organic wastewater is cultivated under light for no less than 96 hours, the light intensity is controlled at 2000-3000 Lx, and the cultivation temperature is 25-30°C; (5) The liquid in the reactor after the cultivation is completed After centrifugation, dehydration and drying, solid organic nitrogen products are obtained.
所述氮气的制备步骤为:将COD为4000-6000mg/L的有机废水送入脱氧反应器内;向脱氧反应器内加入有机废水质量1/15-1/20的好氧活性污泥;由脱氧反应器底部通入空气,空气在脱氧反应器内自下至上流动过程中氧气参与反应被消耗,排出脱氧反应器的气体去除二氧化碳后得氮气。 The preparation steps of the nitrogen gas are as follows: sending organic waste water with a COD of 4000-6000 mg/L into the deoxygenation reactor; adding aerobic activated sludge with an organic waste water quality of 1/15-1/20 in the deoxygenation reactor; The bottom of the deoxygenation reactor is fed with air, and the air flows from bottom to top in the deoxygenation reactor. Oxygen participates in the reaction and is consumed, and the gas discharged from the deoxygenation reactor removes carbon dioxide to obtain nitrogen.
所述脱氧反应器包括壳体,壳体底部设有曝气器,曝气器的进口与空气进气管连接,曝气器上方的壳体内壁竖向间隔交错设有向下倾斜和向上倾斜的折流板,折流板的远端与相对壳体内壁之间留有空隙;壳体顶部设有喷淋器,喷淋器的进口通过循环管与壳体底部连接,循环管的进口处设有循环泵,壳体顶部设有出气管,壳体上部设有进水管,壳体底部为倾斜状,壳体底面设有排污口;壳体上设有溢流管;进水管设于由上至下第二块折流板与第三块折流板之间。 The deoxygenation reactor includes a shell, an aerator is provided at the bottom of the shell, the inlet of the aerator is connected to the air intake pipe, and the inner wall of the shell above the aerator is vertically spaced and staggered with downward-sloping and upward-sloping Baffle plate, there is a gap between the far end of the baffle plate and the inner wall of the opposite shell; the top of the shell is provided with a shower, the inlet of the shower is connected to the bottom of the shell through a circulation pipe, and the entrance of the circulation pipe is set There is a circulating pump, the top of the casing is provided with an air outlet pipe, the upper part of the casing is provided with a water inlet pipe, the bottom of the casing is inclined, and the bottom surface of the casing is provided with a sewage outlet; the casing is provided with an overflow pipe; Between the second baffle plate and the third baffle plate.
本发明利用光合细菌将有机废水中的营养物质在厌氧光照条件下利用自身固氮酶的固氮作用将空气中的氮转化为菌体蛋白和菌体色素,从而将空气中的单质氮以有机态形式转化固定,提供合适氮源形式。 The present invention uses photosynthetic bacteria to convert the nutrients in the organic wastewater into nitrogen in the air by the nitrogen fixation of its own nitrogenase under anaerobic light conditions, thereby transforming the elemental nitrogen in the air into an organic state Form conversion fixes, providing the appropriate nitrogen source form.
本发明的过程中有机废水进入反应器之前要进行灭菌处理,防止杂菌污染,同时减少空气氧对光合细菌的抑制作用。本发明不能直接利用空气作为有机废水代谢反应的氮源,这是因为空气中氧对固氮酶有抑制作用,因此所采用的氮气必须是脱氧之后的空气,如果当微量氧存在时应增加培养时间,以便光合细菌首先进行好氧呼吸作用消耗存在的微量氧而后转入固氮代谢。 In the process of the present invention, the organic waste water needs to be sterilized before entering the reactor, so as to prevent the pollution of miscellaneous bacteria and reduce the inhibitory effect of air oxygen on photosynthetic bacteria. The present invention can not directly use air as the nitrogen source of organic wastewater metabolic reaction, this is because the oxygen in the air has inhibitory effect on nitrogenase, so the nitrogen used must be the air after deoxygenation, if the trace oxygen exists, the cultivation time should be increased , so that photosynthetic bacteria firstly carry out aerobic respiration to consume the trace oxygen that exists and then switch to nitrogen fixation metabolism.
本发明的固氮工艺简单,其主要成本在于光照培养的光照对电能消耗,如采用太阳光做自然光源,适当延长培养时间弥补太阳光周期性变化影响则可大大降低生产成本。采用本发明的方法固氮后使得氮主要以菌体蛋白和光合色素形式存在培养液中,其离心分离后菌体蛋白和菌体色素可作为动物饲料蛋白、鱼类饲料,也可灭活后作为生物发酵的补充氮源,如用作秸秆厌氧发酵的补充氮源。本发明利用有机废水获取氮气,其原理是空气作为有机废水有机质降解的氧源,有机质降解代谢过程对氧进行消耗从而消除空气中的氧气,最后经过脱除二氧化碳和水,从而获得氮气浓度为95%左右的氮气产品。 The nitrogen fixation process of the present invention is simple, and its main cost lies in the power consumption of light for light cultivation. If sunlight is used as a natural light source, the production cost can be greatly reduced by properly extending the cultivation time to compensate for the influence of periodic changes in sunlight. After adopting the method of the present invention to fix nitrogen, nitrogen mainly exists in the culture medium in the form of bacterial protein and photosynthetic pigment. After centrifugation, the bacterial protein and bacterial pigment can be used as animal feed protein and fish feed, and can also be used as animal feed after inactivation. A supplementary nitrogen source for biological fermentation, such as a supplementary nitrogen source for anaerobic fermentation of straw. The present invention uses organic waste water to obtain nitrogen. The principle is that air is used as an oxygen source for the degradation of organic matter in organic waste water. The process of organic matter degradation and metabolism consumes oxygen to eliminate oxygen in the air. Finally, carbon dioxide and water are removed to obtain a nitrogen concentration of 95. % of nitrogen products.
本发明中利用有机废水获得氮气时,有机废水COD需要进行控制,这是因为当有机废水COD过低时则不能完全消除空气中含有的氧气,而当有机废水COD过高时则有大量的CO2、CO等新杂质气体生成,不仅增加吸收碱液的消耗量也影响获得氮气的纯度。控制COD使得有机废水的降解代谢停留在好氧和微好氧层次,避免有机质在厌氧状态下更多杂气的生成。利用有机废水获得氮气的方法简单、能耗低,在获取氮气的同时对有机废水还有一定的净化作用,利用本发明方法获取的气体中氮气浓度(体积百分比)可达到95%左右,产气中还含有少量浓度的氧气和一氧化碳气体,可作为获取高纯氮气的前驱气体。 When utilizing organic waste water to obtain nitrogen in the present invention, organic waste water COD needs to be controlled, and this is because when the organic waste water COD is too low, the oxygen contained in the air cannot be completely eliminated, and when the organic waste water COD is too high, there is a large amount of CO 2. The generation of new impurity gases such as CO not only increases the consumption of the absorbed lye but also affects the purity of the obtained nitrogen. Controlling COD keeps the degradation and metabolism of organic wastewater at the aerobic and micro-aerobic level, avoiding the generation of more miscellaneous gases in the anaerobic state of organic matter. The method of obtaining nitrogen by using organic waste water is simple and low in energy consumption. While obtaining nitrogen, it also has a certain purification effect on organic waste water. The nitrogen concentration (volume percentage) in the gas obtained by using the method of the present invention can reach about 95%. It also contains a small concentration of oxygen and carbon monoxide gas, which can be used as a precursor gas for obtaining high-purity nitrogen.
利用有机废水获得氮气所用的脱氧反应器结构设计简单,布局合理,设置折流板,能够使空气在反应器内实现充分自下至上的折流,保证空气中的氧气最大程度地被有机质降解代谢消耗掉。 The deoxygenation reactor used to obtain nitrogen from organic wastewater has a simple structure design, reasonable layout, and baffles, which can make the air fully baffle from bottom to top in the reactor, ensuring that the oxygen in the air is degraded and metabolized by organic matter to the greatest extent. Use up.
附图说明 Description of drawings
图1为本发明中所用脱氧反应器的结构示意图; Fig. 1 is the structural representation of used deoxygenation reactor among the present invention;
图2为脱氧反应器使用时系统的结构示意图。 Figure 2 is a schematic structural diagram of the system when the deoxygenation reactor is in use.
具体实施方式 Detailed ways
试验采用饴糖厂生产废水作样品,一部分经紫外灭菌后用作光合细菌营养底物,一部分用于空气脱氧介质使用。 The test uses the waste water produced by the malt sugar factory as a sample, part of which is used as a nutrient substrate for photosynthetic bacteria after being sterilized by ultraviolet light, and part of which is used as an air deoxygenation medium.
脱氧反应器,如图1所示,包括壳体1,壳体1底部设有曝气器2,曝气器2的进口与空气进气管3连接,曝气器2上方的壳体1内壁竖向间隔交错设有向下倾斜和向上倾斜的折流板4,折流板4的远端与相对壳体1内壁之间留有空隙;壳体1顶部设有喷淋器5,喷淋器5的进口通过循环管6与壳体1底部连接,循环管6的进口处设有循环泵7,运行过程中,循环泵7将底部的有机废水循环至喷淋器5,使得壳体1内的有机废水不断循环,多余的废水通过溢流管11排出;壳体1顶部设有出气管8,壳体1上部由上至下第二块折流板4与第三块折流板4之间设有进水管9,经进水管9不断补充有机废水,壳体1上设有溢流管11,壳体1底部为倾斜状,壳体1底面设有排污口10。
The deoxygenation reactor, as shown in Figure 1, includes a shell 1, the bottom of the shell 1 is provided with an
脱氧反应器使用时,如图2所示,脱氧反应器的空气进气管3与储气罐20连接,储气罐20与空气压缩机23连接,脱氧反应器的出气管8与碱性吸收箱21连接,碱性吸收箱21的气体出口与脱水箱22连接。
When the deoxygenation reactor is in use, as shown in Figure 2, the air inlet pipe 3 of the deoxygenation reactor is connected with the
用于空气脱氧介质部分的有机废水经调整后(COD为5550mg/L),经进水管9进入脱氧反应器的壳体1内;使水位达到壳体1内深度的2/3左右,向脱氧反应器内加入有机废水质量1/20的好氧活性污泥;利用空气压缩机23将空气压入储气罐20,空气经进气管3、曝气器2分散于脱氧反应器的底部,并在折流板4相对较高的一端汇集,随着通气量的增加,汇集的空气向折流板4较低的一端扩散进而不断向上扩散,空气在折流板4的作用下逐级向脱氧反应器的顶部运动,空气在折流的过程中,所含的O2参与有机质的降解反应而达到消除的作用,最终气体由壳体1顶部的出气管8排出。出气管8排出的空气中大部分为氮气,还含有空气中本身含有的和有机质降解产生的二氧化碳,继续通入碱性吸收箱21被碱液吸收去除二氧化碳,最后经脱水箱22脱水后得到氮气。测得氮气中的成分为:N2: 97.2%、O2: 0.8%、CO2:0%、CO:0.4%,测得溢流管11流出的有机废水中的COD为4100mg/L。运行过程中,循环泵7将底部的有机废水经循环管6循环至喷淋器5,使得壳体1内的有机废水不断循环,由进水管9不断补充有机废水,多余的废水通过溢流管11排出;运行一段时间后,关闭空气、循环泵7,打开排污口10进行排污,去除反应器内的污泥颗粒,清理后开始下一工序的运行。
The organic wastewater used in the air deoxidation medium part is adjusted (COD is 5550mg/L), enters the shell 1 of the deoxidation reactor through the water inlet pipe 9; Add the aerobic activated sludge of organic wastewater quality 1/20 in the reactor; Utilize the
经紫外灭菌后用作光合细菌营养底物的有机废水加入固氮反应器中;(2)向固氮反应器中接入接种量为有机废水体积5%的光合细菌,光合细菌是球形红假单胞菌和深红红螺菌的混合菌;(3)反应器的下部通入脱氧反应器脱水箱22排出的氮气使固氮反应器内的气压达0.1Mpa;(4)采用白炽灯对有机废水进行光照培养不少于96h,调整白炽灯与反应器距离控制光照度为2000 Lx,培养温度为25℃;(5)培养结束后反应器内的液体经离心分离、脱水干燥得到固态有机氮产物。
After ultraviolet sterilization, the organic wastewater used as the nutrient substrate of photosynthetic bacteria is added to the nitrogen fixation reactor; (2) the photosynthetic bacteria with an inoculation amount of 5% of the organic wastewater volume are inserted into the nitrogen fixation reactor, and the photosynthetic bacteria are spherical red pseudomonas Bacteria and Rhodospirillum rubrum; (3) The lower part of the reactor passes through the nitrogen gas discharged from the
试验前测试光合细菌接种液中含氮量为325mg/L,废水含氮量为97mg/L,连续培养4天后测定有机废水中含氮量为780 mg/L,由此推算连续培养后光合细菌共计固定氮为5.851g,即单位有效容积定氮量680.35 mg/L。 Before the test, the nitrogen content in the photosynthetic bacteria inoculum was tested to be 325 mg/L, and the nitrogen content in the wastewater was 97 mg/L. After 4 days of continuous culture, the nitrogen content in the organic wastewater was determined to be 780 mg/L. From this, the photosynthetic bacteria after continuous culture were calculated. The total fixed nitrogen is 5.851g, that is, the fixed nitrogen amount per unit effective volume is 680.35 mg/L.
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