Background technology
Biological denitrificaion completes mainly by nitrobacteria and denitrifying bacteria. Nitrobacteria belongs to chemotrophy type microorganism. Biological cell is only with the energy preserved with forms such as ATP, it is impossible to directly utilize the free energy that chemical reaction discharges. In good oxygen metabolism, ATP synthesizes mainly through the oxidative phosphorylation of respiratory chain. Ammoxidation phosphorylation efficiency is very low, and the ATP that can be generated by is very limited, and these energy are mainly used in electron transition to higher energy level, and this makes nitrobacteria growth very slow, and the phase is 8 ~ 36h from generation to generation. In the cell wall of nitrobacteria, peptidoglycan content is low, protein and fat content are high, therefore environmental change is more sensitive, nitrobacteria adaptability natural in nature and toleration are poor, cannot get the mastery in growth competition with heterotroph microorganism under a lot of conditions. In sewage disposal system, when in activated sludge, nitrobacteria content is relatively low, rely on regulate the environmental condition such as dissolved oxygen and pH cannot within a short period of time fast-growth breeding, the sewage disposal system removal of ammonia and nitrogen ultimately resulting in existing operation is limited in one's ability.
Nitrobacteria is divided into again ammonia oxidizing bacteria (nitrite bacteria) and nitrite-oxidizing bacteria (Nitrate bacteria), novel biological dinitrification the technology such as short-cut nitrification-denitrification and short distance nitration-anaerobic ammoxidation of development in recent years are required for nitration reaction being proceeded to the nitrous acid stage and terminating, it is desirable to ammonia nitrogen does not continue to oxidized after being converted into nitrite nitrogen by ammonia oxidizing bacteria and is made directly denitrification denitrogenation. Therefore the enrichment culture of ammonia oxidizing bacteria is very crucial. From biochemistry level, nitration reaction relates to the metabolic pathway of ammona monooxygenase, azanol oxygen also enzyme and nitrite oxidase co-catalysis, and converts along with complicated matter and energy. Adopt Biostimulation agent improve ammona monooxygenase in nitrobacteria, azanol oxygen also enzyme activity, suppress the activity of nitrite oxidase, it is possible to control nitration reaction process, be solve nitration reaction to proceed to the nitrous acid stage and one of effective way of terminating.
A lot of about the research of Biostimulation agent at present, CN200510111874.5, CN200510111876.4, CN200510111877.9 and CN200510111875.X propose the nitrobacteria growth promoter utilizing different metal salt combination respectively, and main component includes molasses, slaine (ferrous salt, manganese salt, calcium salt and magnesium salt) and adsorbent. After using this accelerator, ammonia nitrogen removal frank can improve more than 20%. But be mainly the materials such as zeolite powder, kieselguhr, Powdered Activated Carbon or flyash due to adsorbent, adding of these adsorbents will certainly increase sludge yield. CN201110315549.6 discloses the cultural method of a kind of short-cut nitrification and denitrification granular sludge, it is characterized in that regularly adding 5 ~ 15mg/L azanol; CN201010168453.7 discloses a kind of method of quickly starting oxygen-poor ammonia oxidizing biofilter, it is characterized in that step (2) adds azanol, challenge inoculation mud changes to oxygen-poor ammonia oxidizing biomembrane, more than invent mainly by the azanol inhibitory action to NOB, promote short distance nitration effect, but poky ammonia oxidizing bacteria own growth is not had facilitation. CN201410141638.7 discloses the culture fluid of a kind of nitrite bacteria and preparation and cultural method, its culture fluid formula is more complicated, the element of Growth of Cells is provided except relating to ferrum, calcium, potassium, magnesium etc., further relates to cobalt, molybdenum, manganese, zinc etc. and promote the element of enzymatic synthesis.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of cultivation ammonia oxidizing bacteria growth promoter and preparation method. This accelerator formula is simple, and preparation is easily, it is possible to in the incubation of ammonia oxidizing bacteria, it is also possible to be directly added in sewage disposal system, accelerates the startup of short-cut nitrification-denitrification and short distance nitration-anaerobic ammoxidation technique and can realize stable operation.
The present invention cultivates the accelerator of ammonia oxidizing bacteria, including slaine, polyamines, mineral acid azanol and Na2SO3, with parts by weight, slaine is 40 ~ 100 weight portions, it is preferred to 50 ~ 80 weight portions, and polyamines is 5 ~ 30 weight portions, it is preferred to 10 ~ 20 weight portions; Mineral acid azanol is 0.05 ~ 1.5 weight portion, it is preferred to 0.1 ~ 1.0 weight portion, Na2SO3It is 10 ~ 40 weight portions, it is preferred to 20 ~ 30 weight portions; Described slaine is calcium salt, magnesium salt and mantoquita, Ca2+��Mg2+And Cu2+Mol ratio be (5 ~ 15): (5 ~ 25): (0.5 ~ 5), it is preferred to (8 ~ 12): (10 ~ 20): (1 ~ 4).
Calcium salt of the present invention is CaSO4Or, it is preferable that CaCl2; Magnesium salt is MgSO4Or MgCl2, it is preferable that MgCl2; Mantoquita is CuSO4Or CuCl2, it is preferable that CuCl2��
Polyamines of the present invention is spermine, spermidine or both mixture.
Mineral acid azanol of the present invention is one or more in oxammonium hydrochloride., oxammonium sulfate. or phosphatic hydroxylamine, it is preferred to oxammonium hydrochloride..
The preparation method cultivating ammonia oxidizing bacteria accelerator of the present invention, including following content: (1) prepares metal salt solution according to consisting of and weight portion: slaine is 40 ~ 100 weight portions, being preferably 50 ~ 80 weight portions, described slaine is calcium salt, magnesium salt and mantoquita, Ca in slaine2+��Mg2+And Cu2+Mol ratio be (5 ~ 15): (5 ~ 25): (0.5 ~ 5), it is preferred to (8 ~ 12): (10 ~ 20): (1 ~ 4); (2) by 10 ~ 40 weight portions, it is preferred to 20 ~ 30 weight portion Na2SO3Join in metal salt solution; (3) by 5 ~ 30 weight portions before using, it is preferred to the polyamines of 10 ~ 20 weight portions and 0.05 ~ 1.5 weight portion, it is preferred to the mineral acid azanol of 0.1 ~ 1.0 weight portion joins in metal salt solution.
Calcium salt described in step of the present invention (1) is CaSO4Or CaCl2, it is preferable that CaCl2; Magnesium salt is MgSO4Or MgCl2, it is preferable that MgCl2; Mantoquita is CuSO4Or CuCl2, it is preferable that CuCl2��
Polyamines described in step of the present invention (3) is spermine, spermidine or both mixture. Described mineral acid azanol is one or more in oxammonium hydrochloride., oxammonium sulfate. or phosphatic hydroxylamine, it is preferred to oxammonium hydrochloride..
Cultivation ammonia oxidizing bacteria accelerator of the present invention may be used for the incubation of ammonia oxidizing bacteria, may be used for improving the ammonia nitrogen removal effect of sewage disposal system, it is also possible to quickly starting and the fast quick-recovery of the system that is hit for short-cut nitrification and denitrification and short distance nitration-anaerobic ammoxidation system. Concrete needs determines dosage according to sewage character, treating capacity and treatment effect. In use, first accelerator is dissolved, then according to promoter concentration 0.5 ~ 50mg/L adds in sewage.
Compared with prior art, the method have the advantages that
1, utilize the metal ion that slaine provides to grow required element as ammonia oxidizing bacteria, simultaneously as the activity of the component raising enzyme of enzyme, it is possible to fast degradation substrate, accelerate enzymatic reaction process. Polyamines and metal ion combined effect, it is possible to accelerate cell proliferation, and settleability and the stability of gather in the crops thalline can be improved, prolongation thalline service life.
2, mineral acid azanol and Na2SO3Cooperation add, contribute to the dissolved oxygen of control system, be possible not only to make azanol directly to participate in the metabolic process of ammonia oxidizing bacteria as substrate, shorten enzymatic reaction process, and can as the activator accelerated cell growth of azanol oxygen also enzyme. Additionally, due to azanol can suppress the activity of nitrite oxidase under anaerobism or anoxia condition, therefore the cooperation of the two is added with and helps suppress nitrite nitrogen to be further converted into nitrate nitrogen.
3, the present invention is by selecting composition and the proportioning of ammonia oxidizing bacteria growth promoter, at slaine, polyamines, mineral acid azanol and Na2SO3Combined effect under, it is achieved the purpose of fast culture ammonia oxidizing bacteria. The invention solves the problem that ammonia oxidizing bacteria growth is slow, nitration reaction process can also be controlled simultaneously, improve water treatment effect. After using accelerator, ammonia oxidizing bacteria growth rate can increase by 10 ~ 100 times, and in nitrifying process, nitrosoation rate reaches more than 70%.
The accelerator formula cultivating ammonia oxidizing bacteria of embodiment 1 ~ 4 and comparative example 1-6 is in Table 1.
The formula of table 1 accelerator and ratio
In waste water produced by certain enterprise, ammonia nitrogen concentration is 150mg/L, adopts SBR technique to process, and adds accelerator of the present invention startup stage that device going into operation. The accelerator that in utilization, table proportioning configures, configuration concentration is 0.5g/L, every day is that 15mg/L adds according to promoter concentration in sewage, after adding 15 days, aeration phase nitrosoation rate brings up to more than 60% stopping and adding, system continues to run with 10 days, and water sampling analyzes water outlet ammonia nitrogen, nitrate nitrogen and nitrite nitrogen concentration. Concrete outcome is shown in Table 2.
Table 2 adopts the treatment effect of different formulations accelerator
Water analysis data from each embodiment of table 2, when adding accelerator, water outlet ammonia nitrogen concentration is 60mg/L, nitrosoation rate only has 32%, after adding accelerator, water outlet ammonia nitrogen concentration is below 30mg/L, nitrosoation rate is all higher than 70%, and during when accelerator containing only three kinds had in formula or two kinds, water outlet ammonia nitrogen removal frank and nitrosoation rate are below 70%. As can be seen here, the growth promoter of the present invention can significantly improve the clearance of ammonia nitrogen in sewage, and after adding accelerator, nitrosoation rate is up to more than 70%.