Background technology
In biological denitrification method, it is no matter traditional nitrification-denitrification, or novel short-cut nitrification-denitrification and short distance nitration-anaerobic ammoxidation all need the Nitrification removal of ammonia and nitrogen through nitrobacteria. 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, industrially generally can adopt and directly throw in cultured high concentration nitrobacteria in sewage disposal system to solve this problem. No matter it is in sewage disposal system, directly cultivate nitrobacteria or outside sewage disposal system, cultivate nitrobacteria, is required for adding the material promoting growth, the growth rate of nitrobacteria could be accelerated.
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 to improve the activity of these enzymes in nitrobacteria, be then solve one of slow effective way of nitrobacteria growth, nitration reaction process can be accelerated simultaneously. 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. 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 nitrobacteria growth promoter and preparation method thereof. This accelerator formula is simple, preparation is easily, it is possible to in the incubation of nitrobacteria, it is also possible to be directly added in sewage disposal system, making nitrobacteria to breed by fast-growth at short notice, the nitrobacteria activity cultivated is high, tolerance impact capacity is strong.
Nitrobacteria growth promoter of the present invention, including slaine and polyamines, 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; Described slaine is calcium salt, ferrous salt and mantoquita, Ca2+��Fe2+And Cu2+Mol ratio be (5 ~ 15): (1 ~ 8): (0.5 ~ 5), it is preferred to (8 ~ 12): (2 ~ 6): (1 ~ 4).
Calcium salt of the present invention is CaSO4Or CaCl2, it is preferable that CaSO4; Ferrous salt is FeSO4Or FeCl2, it is preferable that FeSO4; Mantoquita is CuSO4Or CuCl2, it is preferable that CuSO4��
Polyamines of the present invention is spermine, spermidine or both mixture.
Growth promoter of the present invention also includes mineral acid azanol, and content is 0.5 ~ 15 weight portion, it is preferred to 2 ~ 10 weight portions. Described mineral acid azanol is one or more in oxammonium hydrochloride., oxammonium sulfate. or phosphatic hydroxylamine, it is preferred to oxammonium sulfate..
The preparation method of nitrobacteria growth promoter 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, ferrous salt and mantoquita, Ca in slaine2+��Fe2+And Cu2+Mole allocation ratio be (5 ~ 15): (1 ~ 8): (0.5 ~ 5), it is preferred to (8 ~ 12): (2 ~ 6): (1 ~ 4); (2) by 5 ~ 30 weight portions before using, it is preferred to the polyamines of 10 ~ 20 weight portions joins in metal salt solution.
Calcium salt described in step of the present invention (1) is CaSO4Or CaCl2, it is preferable that CaSO4; Ferrous salt is FeSO4Or FeCl2, it is preferable that FeSO4; Mantoquita is CuSO4Or CuCl2, it is preferable that CuSO4��
Polyamines described in step of the present invention (2) is spermine, spermidine or both mixture.
Further, being additionally added content before using in step of the present invention (2) is 0.5 ~ 15 weight portion, being preferably the mineral acid hydroxylamines of 2 ~ 10 weight portions, described mineral acid hydroxylamines is one or more in oxammonium hydrochloride., oxammonium sulfate. or phosphatic hydroxylamine, it is preferred to oxammonium sulfate..
Nitrobacteria growth promoter of the present invention may be used for the incubation of nitrobacteria, it is possible to for improving the ammonia nitrogen removal effect of sewage disposal system, it is also possible to for quickly starting and the fast quick-recovery of the system that is hit containing ammonia 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 10 ~ 100mg/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 nitrobacteria, 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, can directly participating in the metabolic process of nitrobacteria as the substrate of azanol oxygen also enzyme, shorten enzymatic reaction process appropriate addition of mineral acid azanol, the activator simultaneously as cell can accelerated cell growth.
3, the present invention is by selecting component and the proportioning of nitrobacteria growth promoter, under the combined effect of slaine, polyamines and mineral acid azanol, it is achieved the purpose of fast culture nitrobacteria. The invention solves the problem that nitrobacteria growth is slow, may also speed up nitration reaction process simultaneously, improve the treatment effect of waste water. After using accelerator, the growth rate of nitrobacteria can increase by 10 ~ 100 times, and the ammonia nitrogen removal frank of ammonia-containing water can improve more than 30%, moreover it is possible to solves the fast recovery problem of the nitrated ammonia nitrogen removal ability of sewage disposal system being hit well.
The formula of the nitrobacteria growth promoter of embodiment 1 ~ 10 and comparative example 1-4 is in Table 1.
The formula of table 1 accelerator and ratio
The major pollutants COD concentration contained in the waste water of certain plant emissions is about 400mg/L, ammonia nitrogen concentration is about 300mg/L, this factory adopts batch activated sludge process (SBR technique) to process, but in water outlet after treatment, COD concentration is still up to more than 100mg/L less than 60mg/L ammonia nitrogen concentration. The accelerator that in utilization, table proportioning configures, configuration concentration is 0.5g/L, every day is that 40mg/L adds according to promoter concentration in sewage, after adding 15 days, ammonia nitrogen removal frank improves more than 10% stopping and adding, system continues to run with 20 days, and water sampling is analyzed water outlet ammonia nitrogen concentration and calculates ammonia nitrogen removal frank. After adding, concrete result is in Table 2, effluent quality from each embodiment of table 2, when adding accelerator, water outlet ammonia nitrogen concentration is 150mg/L, ammonia nitrogen removal frank only has 50%, and after adding accelerator, water outlet ammonia nitrogen concentration is below 50mg/L, and ammonia nitrogen removal frank is all higher than 85%, during when accelerator containing only the slaine having in formula or polyamines, water outlet ammonia nitrogen concentration still between 50 ~ 100mg/L, ammonia nitrogen removal frank is lower than 80%. As seen from the data in Table 2, the growth promoter of the present invention can significantly improve the clearance of ammonia nitrogen in sewage.
Table 2 adopts the treatment effect of different formulations accelerator
Aeration tank active sludge intermixture is carried out sludge settling ratio SV simultaneously30Detection, result is as shown in table 2, illustrates that growth promoter of the present invention contributes to mud and better settles.