Background technology
In biological denitrification method, no matter be 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.Biomass cells can only utilize the energy preserved with forms such as ATP, the free energy that can not directly utilize chemical reaction to discharge.In good oxygen metabolism, ATP synthesizes mainly through the oxidative phosphorylation of respiratory chain.Ammonia oxidation phosphorylation efficiency is very low, and the ATP that can produce is very limited, and these energy are mainly used in transition of electron to higher energy level, and it is very slow that this makes nitrobacteria grow, and the phase is 8 ~ 36h from generation to generation.In the cell walls of nitrobacteria, peptidoglycan content is low, protein and lipid content high, therefore more responsive to environmental change, the nitrobacteria adaptability that occurring in nature is natural and tolerance poor, cannot get the mastery in growth competition with heterotroph microorganism under a lot of condition.In Sewage treatment systems, when in active sludge, nitrobacteria content is lower, rely on regulate the envrionment conditions such as dissolved oxygen and pH cannot within a short period of time quick growth and breeding, finally cause the Sewage treatment systems removal of ammonia and nitrogen of existing operation limited in one's ability, the cultured high density nitrobacteria of direct input in Sewage treatment systems industrially usually can be adopted to solve this problem.No matter be directly in Sewage treatment systems, cultivate nitrobacteria or cultivate nitrobacteria outward in Sewage treatment systems, all need the material adding growth promoting effects, the growth velocity of nitrobacteria could be accelerated.
From biochemistry level, nitration reaction relates to the pathways metabolism of ammona monooxygenase, azanol oxygen also enzyme and nitrite oxidase co-catalysis, and transforms along with the matter and energy of complexity.Adopt Biostimulation agent to improve the activity of these enzymes in nitrobacteria, be then solve nitrobacteria to grow one of slow effective way, 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-salts to combine respectively, and main component comprises molasses, metal-salt (ferrous salt, manganese salt, calcium salt and magnesium salts) and sorbent material.After using this promotor, ammonia nitrogen removal frank can improve more than 20%.But due to the sorbent material mainly material such as zeolite powder, diatomite, Powdered Activated Carbon or flyash, adding of these sorbent materials will certainly increase sludge yield.CN201110315549.6 discloses a kind of cultural method 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 adding azanol in step (2), challenge inoculation mud changes to oxygen-poor ammonia oxidizing microbial film, more than invent the restraining effect mainly utilizing azanol to NOB, promote short distance nitration effect.CN201410141638.7 discloses a kind of nutrient solution of nitrite bacteria and preparation and cultural method, its nutrient solution formula more complicated, the element of Growth of Cells being provided except relating to iron, calcium, potassium, magnesium etc., also relating to the element that cobalt, molybdenum, manganese, zinc etc. promote enzymic synthesis.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of nitrobacteria growth stimulant and its preparation method and application.This promotor formula is simple, preparation easily, may be used in the culturing process of nitrobacteria, also can directly be added in Sewage treatment systems, make nitrobacteria can quick growth and breeding at short notice, the nitrobacteria activity of cultivating be high, withstand shock ability is strong.
Nitrobacteria growth stimulant of the present invention, comprises metal-salt and polyamines, and with parts by weight, metal-salt is 40 ~ 100 weight parts, and be preferably 50 ~ 80 weight parts, polyamines is 5 ~ 30 weight parts, is preferably 10 ~ 20 weight parts; Described metal-salt is calcium salt, magnesium salts, ferrous salt and mantoquita, Ca
2+, Mg
2+, Fe
2+and Cu
2+mol ratio be (5 ~ 15): (5 ~ 25): (1 ~ 8): (0.5 ~ 5), be preferably (8 ~ 12): (10 ~ 20): (2 ~ 6): (1 ~ 4).
Calcium salt of the present invention is CaSO
4or CaCl
2, preferred CaSO
4; Magnesium salts is MgSO
4or MgCl
2, preferred MgSO
4; Ferrous salt is FeSO
4or FeCl
2, preferred FeSO
4; Mantoquita is CuSO
4or CuCl
2, preferred CuSO
4.
Polyamines of the present invention is spermine, spermidine or both mixtures.
Promotor of the present invention can also comprise mineral acid azanol, and content is 0.5 ~ 15 weight part, is preferably 2 ~ 10 weight parts.Described mineral acid azanol is one or more in oxammonium hydrochloride, oxammonium sulfate or phosphatic hydroxylamine, is preferably oxammonium sulfate.
The preparation method of nitrobacteria growth stimulant of the present invention, comprise following content: (1) prepares metal salt solution according to following composition and weight part: metal-salt is 40 ~ 100 weight parts, be preferably 50 ~ 80 weight parts, described metal-salt is calcium salt, ferrous salt and mantoquita, Ca in metal-salt
2+, Mg
2+, Fe
2+and Cu
2+mol ratio be (5 ~ 15): (5 ~ 25): (1 ~ 8): (1 ~ 4), be preferably (8 ~ 12): (10 ~ 20): (2 ~ 6): (1 ~ 4); (2) by 5 ~ 30 weight parts before using, the polyamines being preferably 10 ~ 20 weight parts joins in metal salt solution.
Calcium salt described in step of the present invention (1) is CaSO
4or CaCl
2, preferred CaSO
4; Magnesium salts is MgSO
4or MgCl
2, preferred MgSO
4; Ferrous salt is FeSO
4or FeCl
2, preferred FeSO
4; Mantoquita is CuSO
4or CuCl
2, preferred CuSO
4.
Polyamines described in step of the present invention (2) is spermine, spermidine or both mixtures.
Further, also adding content before using in step of the present invention (2) is 0.5 ~ 15 weight part, be preferably the mineral acid azanol of 2 ~ 10 weight parts, described mineral acid azanol is one or more in oxammonium hydrochloride, oxammonium sulfate or phosphatic hydroxylamine, is preferably oxammonium sulfate.
Nitrobacteria growth stimulant of the present invention may be used for the culturing process of nitrobacteria, may be used for the ammonia nitrogen removal effect improving Sewage treatment systems, can also be used for containing the quick startup of ammonia system and the fast quick-recovery of the system that is hit.Concrete needs are according to sewage character, treatment capacity and treatment effect determination dosage.In use, first promotor is dissolved, then add according to promoter concentration 10 ~ 100mg/L in sewage.
Compared with prior art, the present invention has following beneficial effect:
1, the metal ion utilizing metal-salt to provide, as the element required for nitrobacteria growth, improves the activity of enzyme simultaneously as the component of enzyme, can fast degradation substrate, accelerates enzymatic reaction process.Polyamines and metal ion acting in conjunction, can accelerate cell proliferation, and can improve settleability and the stability of gathered in the crops thalline, extends thalline work-ing life.
2, mineral acid azanol add in right amount can as the matrix of azanol oxygen also enzyme participate in directly nitrobacteria metabolic process, shorten enzymatic reaction process, simultaneously can accelerated cell growth as the activator of cell.
3, the present invention is by selecting component and the proportioning of nitrobacteria growth stimulant, under the acting in conjunction of metal-salt, polyamines and mineral acid azanol, realizes the object of fast culture nitrobacteria.The invention solves nitrobacteria and grow slow problem, nitration reaction process can also be accelerated simultaneously, improve the treatment effect of waste water.After using promotor, the growth velocity of nitrobacteria can increase by 10 ~ 100 times, and the ammonia nitrogen removal frank of ammonia-containing water can improve more than 30%, can also solve the fast recovery problem of the nitrated ammonia nitrogen removal ability of the Sewage treatment systems be hit well.
The formula of the nitrobacteria growth stimulant of embodiment 1-8 and comparative example 1-4 is in table 1.
The formula of table 1 promotor and ratio
The principal pollutant COD concentration contained in the waste water of certain enterprise discharge is about 800mg/L, ammonia nitrogen concentration is about 200mg/L, this factory adopts batch activated sludge process (SBR technique) to process, but in water outlet after treatment, COD concentration is for being less than 60mg/L ammonia nitrogen concentration still up to more than 60mg/L.Utilization is shown the promotor that proportioning configures, configuration concentration is 0.5g/L, every day is that 20mg/L adds according to promoter concentration in sewage, after adding 15 days, ammonia nitrogen removal frank improves more than 10% to be stopped adding, system continues operation 10 days, and water sampling analyzes water suspension concentration and water outlet ammonia nitrogen concentration and calculates ammonia nitrogen removal frank.Add rear concrete result in table 2.
Table 2 adopts the treatment effect of different ingredients promotor
From the effluent quality of each embodiment of table 2, when adding promotor, water outlet concentration of suspension is 150mg/L, water outlet ammonia nitrogen concentration is 80mg/L, ammonia nitrogen removal frank only has 60%, after adding promotor, water outlet concentration of suspension is all lower than 100mg/L, water outlet ammonia nitrogen concentration is all lower than 15mg/L, ammonia nitrogen removal frank is all greater than 90%, when promotor is only containing the metal-salt in formula or polyamines, water outlet concentration of suspension between 120 ~ 140mg/L, water outlet ammonia nitrogen concentration still between 50 ~ 70mg/L, ammonia nitrogen removal frank is lower than 80%.As can be seen here, growth stimulant of the present invention is used can to significantly improve the clearance of ammonia nitrogen in dirt.In addition, the flocculating property of mud can also be improved, reduce water outlet concentration of suspension.