CN104004736A - Heterogeneous biocatalysis accelerant and preparation method and application thereof - Google Patents
Heterogeneous biocatalysis accelerant and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heterogeneous biocatalysis accelerant; the heterogeneous biocatalysis accelerant comprises the following components in parts by weight: 34-62 parts of derivable metabolic enzyme, 1-6.5 parts of organic cofactor, 0.1-1.2 parts of inorganic cofactor, 29-45 parts of vector and 0.8-7 parts of zeolite powder. The invention further discloses a preparation method of the heterogeneous biocatalysis accelerant, comprising the following steps: immobilizing both the derivable metabolic enzyme and the organic cofactor on the vector to form enzyme-coenzyme co-immobilized compound, and combining the compound with the inorganic cofactor and the zeolite powder in proportion. The heterogeneous biocatalysis accelerant is capable of increasing the sludge activity and effective biomass in the waste water treatment system, especially capable of promoting the rapid propagation of nitrifier, improving the nitrogen removing efficiency, and promoting the sludge endogenesis nitration so as to reduce the sludge. The heterogeneous biocatalysis accelerant not only is suitable for treating various nitrogen-containing chemical wastewaters, but also can be used for treating the domestic sewage and municipal sewage.
Description
Technical field
The invention belongs to wastewater biochemical process field, be specifically related to a kind of heterogeneous biocatalysis promotor for wastewater treatment, and the preparation method of this biocatalysis promotor and purposes.
Background technology
Along with industrial development, quantity of wastewater effluent is more and more, waste water type is more complicated, a lot of contained pollutents of wastewater from chemical industry have bio-refractory characteristic, while is along with the increasingly stringent of global environmental regulation, the control index request of sewage qualified discharge is more and more higher, finds reasonable, economic, effective waste water treatment means very necessary.
Because physical chemistry improvement method cost is high, easily secondary pollution, and traditional biological process is to there being the organic pollutant treatment effect of bio-toxicity undesirable, therefore at original biological wastewater, administer technical, biological enzyme technology is high with catalysis efficiency, reaction conditions is gentle, to wastewater quality and equipment situation, require lower, speed of response is fast, temperature, concentration and toxic substance wide accommodation are become to a kind of method that solves the waste water handling problem in environmental pollution, aspect pollutant control, be used more widely gradually.A kind of biological catalyst that biological enzyme produces as viable cell in organism, great majority are comprised of protein, and under can condition very gentle in body, the various biochemical reactions of efficient catalytic, promote the metabolism of organism and do not change self catalytic performance, therefore, it can impel the quantity of microorganism to be exponential growth on the one hand, improve the organic speed of response of biological degradation simultaneously, on the other hand, biological enzyme can substitute microorganism catalysis degradation of contaminant as a kind of biochemical composition material.Use enzyme to replace microorganism as strengthening means, do not need microbial growth condition, resistance to malicious ability also improves greatly.
China's patent document (CN101538097) has proposed a kind of method of enzymatically treating of organic wastewater with difficult degradation thereby, by the coupling of enzyme-reduced form promotor, catalytic oxygen produces superoxide radical and the extremely strong hydroxyl radical free radical of oxidation capacity, thereby organism is removed from water body, enzyme used is horseradish peroxidase or hemoglobinase, and reduced form promotor is coenzyme or vitamins C.China's patent document (CN 102020347) discloses a kind of method that phenol in wastewater is removed in enzyme catalysis, mainly utilizes bio-surfactant two rhamnolipids to promote Laccase Catalyzed, and Pyrogentisinic Acid's removal effect is good, and efficiency is high, simple to operate.China's patent document (CN 102115264) has proposed a kind of processing method of biological enzyme Papermaking Wastewater Advanced Treatment, first use after Immobilization in Sodium Alginate laccase, process the second pond water outlet of papermaking enterprise sewage work, the discharged wastewater met the national standard after processing or reuse.On the whole, biological enzyme technology is improved all the time, but for wastewater from chemical industry, it is less that the biological enzyme of especially nitrogenous wastewater from chemical industry is processed research.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, the heterogeneous biocatalysis promotor of provide a kind of new lifting organic matter degradation ability, improving ammonia nitrogen processing efficiency, sludge reduction.
Another technical problem to be solved by this invention has been to provide preparation method and the purposes of above-mentioned heterogeneous biocatalysis promotor.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of heterogeneous biocatalysis promotor, is characterized in: the weight proportion of this heterogeneous biocatalysis promotor consists of:
Derivable catabolic enzymes 34～62; Organic cofactor 1～6.5;
Inorganic cofactor 0.1～1.2; Carrier 29～45;
Zeolite powder 0.8～7;
Described can be selected from one or more in urine enzyme, aliphatic amide enzyme, proteolytic enzyme, nitrate reductase, rnase, urase, amino acid acylase by induced decomposition metabolic enzyme;
Described inorganic cofactor is selected from Cu
2+, and Mn
2+, Zn
2+, Fe
2+in one or more;
Described organic cofactor is selected from one or more in vitamin H, FMN, NADH, NADPH;
Described carrier is a kind of in agarose, DEAE-dextran, sephadex.
If no special instructions, in the present invention, related raw material all can adopt commercially available prod or disclosed product otherwise.In the present invention, Cu
2+, Mn
2+, Zn
2+, Fe
2+can be from its esters, preferably from its vitriol or chlorate.
Heterogeneous biocatalysis promotor of the present invention, its preferred weight proportion consists of:
Derivable catabolic enzymes 40～50; Organic cofactor 2～5;
Inorganic cofactor 0.4～0.8; Carrier 35～40;
Zeolite powder 2～5.
The preparation method who the invention also discloses the heterogeneous biocatalysis promotor as described in above technical scheme, is characterized in: its step is as follows:
(1) described derivable catabolic enzymes and organic cofactor are fixed on same carrier altogether, form enzyme-coenzyme fixed complex altogether;
(2) by enzyme-coenzyme altogether fixed complex after mixing with inorganic cofactor, zeolite powder after dry, obtain heterogeneous biocatalysis promotor.
Preparation method of the present invention, further preferred technical scheme is:
1. in step (1), carrier is processed with phosphate buffered saline buffer in advance, and fixing means selects a kind of in absorption method, entrapping method or crosslinking, altogether fixed temperature: 30～35 ℃, and the set time: 5～10h.Described phosphate buffering liquid concentration can need to select routinely, and best≤0.5mol/L, most preferably is 0.1mol/L.
2. in step (2): described drying means can be dry for spray dried, lyophilize or oven dry.
The heterogeneous biocatalysis promotor that heterogeneous biocatalysis promotor of the present invention or preparation method of the present invention make can be processed for nitrogen work waste water, sanitary sewage, municipal wastewater.
Compared with prior art, beneficial effect of the present invention is as follows:
1. in heterogeneous biocatalysis promotor of the present invention, after enzyme-coenzyme is fixed altogether, enzyme and coenzyme are difficult for running off.Coenzyme helps the effect of catalysis and promotion organic matter degradation simultaneously, can improve the catalytic activity of enzyme, improves toxic organic compound degradation capability; Inorganic cofactor and zeolite powder, when improving enzymic activity, promote effective biomass growth, particularly nitrobacteria fast breeding, improve ammonia nitrogen removal frank, sophisticated systems biologic chain, and reformative sludge settling property, reduces sludge discharge, realizes sludge reduction.
2. high, with short production cycle, the simple process of heterogeneous biocatalysis promotor enzymic activity of the present invention, enzyme and coenzyme are all renewable, reduce processing cost.
3. heterogeneous biocatalysis promotor of the present invention is not only applicable to various nitrogenous chemical wastewater treatment, can also be applied to the processing of sanitary sewage, municipal wastewater and for processing such as polluted-water reparation such as sewage work's sewage disposal upgrading, capability improving, mud decrement, river courses.
Embodiment
Below in conjunction with specific examples, the present invention will be described, and following embodiment is only for the present invention is described, and be not used in restriction the present invention scope required for protection.
Embodiment 1, a kind of heterogeneous biocatalysis promotor, and the weight proportion of this heterogeneous biocatalysis promotor consists of:
Derivable catabolic enzymes 34; Organic cofactor 1;
Inorganic cofactor 0.1; Carrier 29;
Zeolite powder 0.8;
Described can be selected from one or more in urine enzyme, aliphatic amide enzyme, proteolytic enzyme, nitrate reductase, rnase, urase, amino acid acylase by induced decomposition metabolic enzyme;
Described inorganic cofactor is selected from Cu
2+, and Mn
2+, Zn
2+, Fe
2+in one or more;
Described organic cofactor is selected from one or more in vitamin H, FMN, NADH, NADPH;
Described carrier is a kind of in agarose, DEAE-dextran, sephadex;
Described heterogeneous biocatalysis promotor can be applied to municipal wastewater, municipal sewage plant and process nitrogenous wastewater from chemical industry.
Embodiment 2, a kind of heterogeneous biocatalysis promotor, and the weight proportion of this heterogeneous biocatalysis promotor consists of:
Derivable catabolic enzymes 62; Organic cofactor 6.5;
Inorganic cofactor 1.2; Carrier 45;
Zeolite powder 7;
Described can be selected from one or more in urine enzyme, aliphatic amide enzyme, proteolytic enzyme, nitrate reductase, rnase, urase, amino acid acylase by induced decomposition metabolic enzyme;
Described inorganic cofactor is selected from Cu
2+, and Mn
2+, Zn
2+, Fe
2+in one or more;
Described organic cofactor is selected from one or more in vitamin H, FMN, NADH, NADPH;
Described carrier is a kind of in agarose, DEAE-dextran, sephadex.
Embodiment 3, a kind of heterogeneous biocatalysis promotor, and the weight proportion of this heterogeneous biocatalysis promotor consists of:
Derivable catabolic enzymes 40; Organic cofactor 2;
Inorganic cofactor 0.4; Carrier 35;
Zeolite powder 2.All the other are all identical with embodiment 1.
Embodiment 4, a kind of heterogeneous biocatalysis promotor, and the weight proportion of this heterogeneous biocatalysis promotor consists of:
Derivable catabolic enzymes 50; Organic cofactor 5;
Inorganic cofactor 0.8; Carrier 40;
Zeolite powder 5.All the other are all identical with embodiment 1.
Embodiment 6, a kind of heterogeneous biocatalysis promotor, and the weight proportion of this heterogeneous biocatalysis promotor consists of:
Derivable catabolic enzymes 45; Organic cofactor 3;
Inorganic cofactor 0.6; Carrier 38;
Zeolite powder 3.All the other are all identical with embodiment 1.
Embodiment 7, the preparation method of the heterogeneous biocatalysis promotor of embodiment 1-6 described in any one, and its step is as follows:
(1) described derivable catabolic enzymes and organic cofactor are fixed on same carrier altogether, form enzyme-coenzyme fixed complex altogether;
(2) by enzyme-coenzyme altogether fixed complex after mixing with inorganic cofactor, zeolite powder after dry, obtain heterogeneous biocatalysis promotor.
Embodiment 8, and in the step (1) of the preparation method described in embodiment 7, carrier is processed with phosphate buffered saline buffer in advance, and fixing means selects a kind of in absorption method, entrapping method or crosslinking, altogether fixed temperature: 30～35 ℃, and the set time: 5～10h.
Embodiment 9, and in the step (1) of the preparation method described in embodiment 8, phosphate buffering liquid concentration is 0.1mol/L.
Embodiment 10, in the step (2) of the preparation method described in embodiment 8 or 9, described drying means for spraying is dry, lyophilize or oven dry.
Embodiment 11, a kind of preparation method's experiment of heterogeneous biocatalysis promotor, and its step is as follows:
(1) can be dissolved in the aqueous solution together with organic cofactor (coenzyme) 3g by induced decomposition metabolic enzyme 100g; 100ml carrier DEAE-dextran is used in advance to the phosphoric acid buffer clean of 0.1mol/L; At 35 ℃, carrier and enzyme-coenzyme aqueous solution are stirred to 10h, after filtration, DEAE-dextran-enzyme-coenzyme composition washes with water, obtains enzyme-coenzyme fixed complex altogether;
(2) enzyme-coenzyme is total to the dry rear and 0.4gCuSO of fixed complex
4, 0.1gMnSO
4and 2g zeolite powder obtains heterogeneous biocatalysis promotor after being mixed in proportion.
Embodiment 12, heterogeneous biocatalysis promotor and the comparative experiments of active sludge treatment waste water effect.
One, process waste water and take from certain chemical company, former water COD mass concentration: 2000～2200mg/L, ammonia nitrogen mass concentration: 127～150mg/L, pH6.0～7.5.
Two, test is carried out in 2 A/O ponds, A pond useful volume 15L, O pond useful volume 45L, first 2 A/O add same concentrations sludge sewage, wherein 1 A/O adds the heterogeneous biocatalysis promotor that embodiment 2 makes, and add-on is 50mg/L, and another A/O pond is not added.25～28 ℃ of test temperatures, pH 8.0, O pond dissolved oxygen 2.0～3.0mg/L, total hrt 48h.The initial sludge concentration 3000mg/L of 2 A/O left and right, fore flow adds the wastewater from chemical industry of same concentrations, volume, working time 20d.Result shows, the bio-aeration pool that does not add heterogeneous biocatalysis promotor reaches water inlet at full capacity while moving to 13d, but microscopy finds that there is many thread funguss, sludge character variation, sludge index SVI is between 140～190, there is slight sludge bulking, more than sludge concentration is increased to 4000mg/L after water inlet at full capacity; After adding the bio-aeration pool operation 7d of heterogeneous biocatalysis promotor, arrive water inlet at full capacity, water outlet COD < 100mg/L in whole service process, ammonia nitrogen < 5mg/L, sludge character is good, and better active, protozoa species is more, microscopy is not found thread fungus, sludge concentration MLSS does not raise always, is stabilized in 2000～2500mg/L, sludge index SVI < 100mL/g.
From the above results, can find out, add heterogeneous biocatalysis promotor and can effectively promote processing efficiency, shorten the treatment time, can have in the shorter time higher processing efficiency, simultaneously to suppressing thread fungus growth and promoting that sludge reduction also has certain effect.
Embodiment 13, the application test that heterogeneous biocatalysis promotor of the present invention is processed at municipal wastewater:
Heterogeneous biocatalysis promotor used comprises 20 parts of nitrate reductases by weight, 5 parts, proteolytic enzyme, 25 parts of aliphatic amide enzymes, 1 part of NADH, FMN1 part; Cu
2+0.2 part, Mn
2+0.1 part, Zn
2+0.1 part, Fe
2+0.1 part; Cu
2+from CuSO
45H
2o, Mn
2+from MnSO
4, Zn
2+from ZnSO
47H
2o, Fe
2+from FeSO
47H
2o; DEAE-Gentran 40 part; 3 parts of zeolite powders.Dosage 50～100mg/L.
Jiangsu sewage work, processes 50,000 tons/d of the water yield, and operation process adopts A-A-O technique, and Inlet and outlet water water quality is as shown in the table:
In actual moving process, because variation water quality is larger, water-inlet carbon source is not enough, therefore, this sludge of sewage treatment plant poor activity, active sludge easily disintegrates, and COD value and BOD value be fluctuation with the fluctuation of influent quality, running status is unstable, mud MLVSS/MLSS < 0.55 simultaneously, and mineral substance mud is high, flco poor activity, biomass is not enough, and situation not up to standard appears in water outlet total nitrogen, total phosphorus.
By Xiang Gai sewage work biochemistry, constructed in pond and added heterogeneous biocatalysis promotor, through bimestrial debugging, the impact resistance of system improves, and biochemical effect is remarkable, can tackle the impact of underload COD and high loading, and stable effluent quality is up to standard.The nitrated level of Sewage treatment systems is high simultaneously, and ammonia nitrogen steadily, below water outlet 1mg/L, is not entered the impact of water total nitrogen and ammonia nitrogen fluctuation, and biochemical section water outlet total phosphorus is reduced to below 1.0mg/L by original 2.5mg/L.Sludge Property improves, and MLVSS/MLSS brings up to more than 0.8, and effectively biomass increases, and sludge settling is good simultaneously, and surplus sludge volume reduces, and system sludge volume reduces by 1 times before.
From the above results, heterogeneous biocatalysis promotor of the present invention can be improved sludge system impact resistance, improves Sludge Property, increase effective microbe quantity, improve the clearance of organism, ammonia nitrogen, total phosphorus, and do not need to increase other treatment facilities, reduce cost.Visible heterogeneous biocatalysis promotor, as the auxiliary process of sewage work's treatment system, is a kind of economically viable means.
Claims (8)
1. a heterogeneous biocatalysis promotor, is characterized in that: the weight proportion of this heterogeneous biocatalysis promotor consists of:
Derivable catabolic enzymes 34～62; Organic cofactor 1～6.5;
Inorganic cofactor 0.1～1.2; Carrier 29～45;
Zeolite powder 0.8～7;
Described can be selected from one or more in urine enzyme, aliphatic amide enzyme, proteolytic enzyme, nitrate reductase, rnase, urase, amino acid acylase by induced decomposition metabolic enzyme;
Described inorganic cofactor is selected from Cu
2+, and Mn
2+, Zn
2+, Fe
2+in one or more;
Described organic cofactor is selected from one or more in vitamin H, FMN, NADH, NADPH;
Described carrier is a kind of in agarose, DEAE-dextran, sephadex.
2. heterogeneous biocatalysis promotor according to claim 1, is characterized in that: the weight proportion of this heterogeneous biocatalysis promotor consists of:
Derivable catabolic enzymes 40～50; Organic cofactor 2～5;
Inorganic cofactor 0.4～0.8; Carrier 35～40;
Zeolite powder 2～5.
3. a preparation method for heterogeneous biocatalysis promotor as claimed in claim 1 or 2, is characterized in that: its step is as follows:
(1) described derivable catabolic enzymes and organic cofactor are fixed on same carrier altogether, form enzyme-coenzyme fixed complex altogether;
(2) by enzyme-coenzyme altogether fixed complex after mixing with inorganic cofactor, zeolite powder after dry, obtain heterogeneous biocatalysis promotor.
4. preparation method according to claim 3, it is characterized in that: in step (1), carrier is processed with phosphate buffered saline buffer in advance, fixing means selects a kind of in absorption method, entrapping method or crosslinking, be total to fixed temperature: 30～35 ℃, the set time: 5～10h.
5. preparation method according to claim 4, is characterized in that: phosphate buffering liquid concentration≤0.5mol/L in step (1).
6. preparation method according to claim 4, is characterized in that: in step (1), phosphate buffering liquid concentration is 0.1mol/L.
7. preparation method according to claim 3, is characterized in that, in step (2): described drying means for spraying is dry, lyophilize or oven dry.
8. the purposes of the heterogeneous biocatalysis promotor that in heterogeneous biocatalysis promotor claimed in claim 1 or claim 2-7, the preparation method described in any one makes in nitrogenous wastewater from chemical industry, sanitary sewage, municipal wastewater are processed.
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| CN108558001A (en) * | 2017-12-28 | 2018-09-21 | 上海交通大学 | For in-situ immobilization polluted-water and the biological exciting agent and its application method of bed mud |
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