CN102181421A - Method for strengthening activity of anaerobic ammoxidized microorganisms through polyvinyl alcohol-sodium alginate-activated carbon embedment - Google Patents
Method for strengthening activity of anaerobic ammoxidized microorganisms through polyvinyl alcohol-sodium alginate-activated carbon embedment Download PDFInfo
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Abstract
The invention belongs to the field of water treatment, and relates to a method for strengthening the activity of anaerobic ammoxidized microorganisms through polyvinyl alcohol-sodium alginate-activated carbon embedment. The method comprises the following steps of: soaking activated carbon in anaerobic ammoxidized basic inorganic salt solution, and preparing an embedding medium by using polyvinyl alcohol, sodium alginate and the activated carbon into in a proportion; and uniformly mixing treated anaerobic ammoxidized sludge and the embedding medium in a volume ratio to obtain immobilized balls, and culturing to obtain the anaerobic ammoxidized microorganisms steadily coupled on the activated carbon. The invention aims at wastewater with low carbon-nitrogen ratio, and can provide a method for embedding the anaerobic ammoxidized sludge by using the sodium alginate and the polyvinyl alcohol as carriers and the activated carbon as a strengthening agent, and a technology for strengthening the activity of the anaerobic ammoxidized microorganisms and enabling the anaerobic ammoxidized microorganisms to resist the influence of adverse environment. By the method, sewage plants can run more steadily for a long time, and the conditions of actual operation management of the sewage plants are met.
Description
Technical field
The invention belongs to water treatment field, or environmental engineering, or environmental microorganism, be a kind of method of strengthened anaerobic ammoxidation microorganism active.
Background technology
There are a large amount of nitrogen-containing pollutants in modern industry and the sanitary sewage, a large amount of nitrogen elements can cause total nitrogen rising in the water in the water, brings out body eutrophication, and the conversion of nitrogen element needs the dissolved oxygen in the consume water, thereby cause water hypoxia, other nitrogen then can be poisoned the mankind and other biological.At present, the denitrification process of employing is the nitration denitrification technology.The tradition denitride technology need add extra organic carbon source and aeration satisfying the needs of denitrogenation, so denitrification process running cost is higher, and energy consumption is huge.
The nineties in last century, the anaerobic ammonia oxidation process of novel high-efficiency and energy-saving arose at the historic moment along with the discovery of Anammox phenomenon.Anaerobic ammonia oxidation process is the denitrification process of novel high-efficiency and energy-saving, and comparing its advantage with traditional denitrification process has: (1) anaerobic ammonia oxidation microbiological is an autotrophic microorganism, and reaction process does not need to add organism; (2) anaerobic ammonium oxidation process does not need aeration, saves power consumption greatly; (3) anaerobic ammonia oxidation process can be handled high ammonia nitrogen class waste water, and unit load is higher, can reduce the volume of reactor; (4) excess sludge that technology produced is less, can save the expense of a large amount of processing mud.According to studies show that recently: the anaerobic ammonia oxidation microbiological poor growth, difficult the cultivation, anaerobic ammonia oxidation microbiological only just has activity under the high density condition; Activity also is subjected to organic substance influence easily; Therefore, how to strengthen its active and its resistance of raising, reduce the loss of mud in service, just become the difficulty that anaerobic ammonia oxidation process practicability must overcome.
The present invention is exactly the embedded immobilization technology of developing at this problem.Present technique can be more stable enrichment Anammox mud, and provide an anoxybiotic microenvironment with the protection anaerobic ammonia oxidation microbiological, strengthen the ability of its opposing organism and other unfavorable factors; Simultaneously, make microorganism and sludge loss rate lower after fixing, make things convenient for mud to reflux, can satisfy the needs that daily sewage work moves by embedding.
Newer Anammox embedding techniques has at present:
(1) denitrogenation method for nitrosation-anaerobic ammoxidation single stage organism-200710105719.1 is had the right
This disclosure of the Invention a kind of denitrogenation method for nitrosation-anaerobic ammoxidation single stage organism, described technology utilization add behind the powdered active carbon to strengthen what form be the nitrosification flora of core and the symbiosis composite particles mud of Anammox flora two class floras with the gac, with and the coupling of reacting two kinds of reactions of the nitrosation reaction that takes place and Anammox.
(2) during a kind of embedding immobilization method for anaerobic ammoxidation mixed culture-200710032531.9 is examined; The invention provides a kind of embedding immobilization method for anaerobic ammoxidation mixed culture, comprise the obtaining of embedding medium, embedding medium mixes with mud, immobilization Anammox bead obtain steps such as activation with immobilization Anammox bead, obtaining of embedding medium is weighing polyvinyl alcohol and sodium alginate, make solution, according to the mass percent meter, the concentration 6%～10WT% of polyvinyl alcohol, the concentration of sodium alginate is 1%～2WT%, stir, make the mixing embedding medium; This method technology is simple, easy and simple to handle, cheap, embedded immobilization ANAMMOX mixes the success of training thing, can flexible design go out to act on single-minded anaerobic ammonia oxidation reactor efficiently, biological denitrification system with preposition nitrosation reaction device composition efficient stable is suitable for suitability for industrialized production, can obtain good economy, environmental benefit.
Summary of the invention
Present technique is at above open question, provide a kind of based on sodium alginate, polyvinyl alcohol crosslinked carrier, absorbent charcoal material is the active and fixed effect embedding techniques of the reinforcement of additive, utilize the loose shape vesicular structure of solid of gac to be microenvironment enrichment anaerobic ammonia oxidation microbiological, make the microorganism high densityization of FX, reduce the loss of biomass, this method has improved the efficient of denitrification process simultaneously, increase the ability of culture opposing poor environment factor, and long-time running that can be more stable.Prospect with wide popularization and application.
Invention provides a kind of method of utilizing polyvinyl alcohol-sodium alginate-gac embedding strengthened anaerobic ammoxidation microorganism active, it is characterized in that may further comprise the steps: 1. gac is carried out immersion treatment with Anammox basis inorganic salt solution; 2. polyvinyl alcohol, sodium alginate and gac are hybridly prepared into embedding medium; 3. under anaerobic Anammox mud and embedding medium uniform mixing are made mud mixed liquid, mud mixed liquid is joined CaCl
2In the solution, make immobilized spherule; 4. in the inorganic salt solution of Anammox basis, cultivate and obtain the stable anaerobic ammonia oxidation microbiological that is coupled on the gac; Described Anammox basis inorganic salt solution is made up of following material: KHCO
30.40-0.6 gL
-1, MgSO
47H
2O 0.30-0.35 gL
-1, KH
2PO
40.02-0.03 gL
-1, CaCl
20.1-0.15 gL
-1, NaNO
20.3-0.4 gL
-1, (NH
4)
2SO
40.4-0.5 gL
-1
The 1. described gac of step is the wood powder shaped activated carbon; The 3. described immobilized spherule diameter of step is 3-6mm.
The 1. described gac of step is elder generation's process acid-alkali treatment before adopting Anammox basis inorganic salt solution to carry out immersion treatment: after gac washes away impurity and dust, with tap water rinse-active charcoal, after removing dust impurity, soaked 20-30 hour with the 9-10% hydrochloric acid soln, soaked 20-30 hour with massfraction 1-2% sodium hydroxide solution again after the water flushing, water flushing is then put into physiological saline and is soaked oven dry after 20-30 hour.
The 1. described Anammox basis inorganic salt solution immersion treatment time of step is 20-30 hour.
The 3. described immobilized spherule of step is by CaCl
2Polyvinyl alcohol, sodium alginate and the Mixture of Activated Carbon of parcel and the globular solids of Anammox mud.
The culture condition that 4. step is carried out is as follows: cultivate 1-2 week under temperature 25-30 ℃ condition.
The 3. described Anammox mud of step is earlier through following processing: with the phosphate buffer solution flushing of pH7.5-8.0 2-3 time, through precipitation or the acquisition of centrifugal back.
3. described Anammox mud of step and embedding medium be the 1:1-1:3 mixed by volume.
The present invention also provides a kind of embedding medium that is used for embedding strengthened anaerobic ammoxidation microorganism active, it is characterized in that being mixed with by polyvinyl alcohol, sodium alginate and the gac ratio according to mass percent 10:0.6:1.2.
The present invention provides a kind of in addition and has been applied to strengthen and the fixing solution of anaerobic ammonia oxidation microbiological, it is characterized in that being made up of following material: KHCO
30.40-0.6 gL
-1, MgSO
47H
2O 0.30-0.35 gL
-1, KH
2PO
40.02-0.03 gL
-1, CaCl
20.1-0.15 gL
-1, NaNO
20.3-0.4 gL
-1, (NH
4)
2SO
40.4-0.5 gL
-1
Below further explain the inventive method by preferred version, this method may further comprise the steps:
(1) immobilization material obtains: the selection of gac: can adopt the wood powder shaped activated carbon.At first carry out pre-treatment before the use: remove impurity and dust with flushing earlier, flushing is to going out clarification of water.Soaked 24 hours with 10% hydrochloric acid soln then, with using 2% soaking with sodium hydroxide 24 hours again after the tap water flushing, use tap water and distilled water flushing then, put into physiological saline and soak oven dry after 24 hours, put into Anammox basis inorganic salt solution and soaked 24 hours, stand-by.The basis inorganic salt solution is: KHCO
30.50 gL
-1, MgSO
47H
2O 0.34 gL
-1, KH
2PO
40.027gL
-1, CaCl
20.136 gL
-1, NaNO
20.365 gL
-1, (NH
4)
2SO
40.33 gL
-1
(2) processing of Anammox mud: Anammox mud is taken out, through the phosphate buffer solution flushing of pH7.5-8.0 3 times, through precipitation or centrifugal after stand-by.
(3) obtaining of embedding medium: polyvinyl alcohol (PVA)-sodium alginate (SA)-gac embedding immobilization method.The ratio of PVA 10%, SA 0.6% and gac 1.2 % is mixed with mixing solutions by mass percentage respectively, makes embedding medium.
(4) fixing mud process: under anaerobic, use 30 ml syringes (needle-less) then or mixed solution is dropwise joined 4% CaCl with peristaltic pump with mud and mixed solution 1:2 ratio uniform mixing by volume
2In the solution, crosslinked 12 hours, can being fixed bead, its diameter is 3-6mm.Put it into Anammox basis inorganic salt solution then and cultivate, stand-by.
(5) activation stage of embedding bead: the immobilization anaerobic ammonia oxidation microbiological need could use by activation.In temperature is under the 25-30 ℃ of condition, utilizes Anammox basis inorganic salt solution to cultivate for 1 week, makes microorganism fully attached to the surface and inside of gac, stablizes coupling.Can put into reactor after fixing, directly use.
Compared with prior art, the present invention has following beneficial effect:
(1) (ammonia nitrogen is higher than 50mg/L at the waste water of low ratio of carbon to ammonium in invention, and COD is lower than 80mg/L sewage), present technique can be more stable enrichment Anammox mud, and provide an anoxybiotic microenvironment with the protection anaerobic ammonia oxidation microbiological, strengthen the ability of its opposing organism and other unfavorable factors; Simultaneously, make microorganism and sludge loss rate lower after fixing, can satisfy the needs that daily sewage work moves by embedding.Gac has certain adsorb organic compound ability, can alleviate the influence to Anammox mud of organism and other poisonous substances, the carrying out of strengthened anaerobic ammoxidation reaction.
(2) the immobilization material application cost is cheap, is immobilization material at polyvinyl alcohol (the PVA)-sodium alginate (SA) that is easy to obtain, and being aided with Powdered Activated Carbon is enhancer additives.Anaerobic ammonia oxidation microbiological is grown in solid netted loose type porous material easily, and can stablize attached to the inboard, duct, in hole and the duct.Polyvinyl alcohol (PVA)-sodium alginate (SA) is extremely low to bio-toxicity with gac, be widely used in water treatment and the biological absorbing process, have good and economic and practicality, long-term operation does not have and swells, disintegrate, cause secondary pollution problems, have impact resistance preferably, physical stability and physical strength.
(3) it is simple that the operation journey is crossed in invention immobilization, but flexible Application is in specificity Anammox packed column reactor and mini-reactor, can be in large-scale application, gac can be effectively by the microorganic adhesion of anaerobic growth, and has certain absorption degradation performance.
(4) behind the adding gac, allow the embedding bead have certain adsorb organic compound ability, can alleviate the influence of organism and other poisonous substances, the carrying out of strengthened anaerobic ammoxidation reaction Anammox mud.Simultaneously, gac can increase the amount of embedding bead absorption anaerobic ammonia oxidation microbiological, increases specific surface area, the strengthened anaerobic ammoxidation activity.
Description of drawings
Fig. 1 is certain hour internal reference group, sodium alginate (SA), polyvinyl alcohol (PVA), polyvinyl alcohol-sodium alginate (PVA-SA) and polyvinyl alcohol (PVA)-sodium alginate (SA)-gac NH
4 +-N removal amount relation table.
Fig. 2 is certain hour internal reference group, sodium alginate (SA), polyvinyl alcohol (PVA), polyvinyl alcohol-sodium alginate (PVA-SA) and polyvinyl alcohol (PVA)-sodium alginate (SA)-gac NO
3 --N removal amount relation table.
Embodiment
Embodiment 1
Utilize the wood powder shaped activated carbon to be reinforcer strengthened anaerobic ammoxidation microorganism active.The wood powder shaped activated carbon is that feed purification forms with shell and wood chip, and outward appearance is a black fine-powder shape, and is nontoxic, tasteless, have big a, high adsorption capacity of specific surface area.Be applicable to the purification industry of water quality such as sugaring, pharmacy, beverage, drinks, food, printing and dyeing, papermaking, chemical industry, trade effluent, the decolouring of organism solvent, deodorizing, refining, purification and sewage disposal aspect also are extensive use of.Wood powder shaped activated carbon physics, chemical property analysis, analytical results is as shown in table 1:
Table 1 gac physical and chemical performance analytical results
| Analysis project | Test data | Analysis project | Test data |
| Iodine number | ＞900mg/g | Methylene blue adsorption value | ≥8ml |
| Specific surface area | ＞1000m 2/g | Moisture content | ≤8% |
| PH value | Neutral |
(1) immobilization material obtains: the wood powder shaped activated carbon is carried out pre-treatment: remove impurity and dust with the tap water flushing earlier, wash to clarification of water outlet.Soaked 24 hours with the 8%-10% hydrochloric acid soln then, with using the 2-4% soaking with sodium hydroxide again 24 hours after the tap water flushing, use tap water and distilled water flushing then, put into physiological saline and soak oven dry after 24 hours, put into Anammox basis inorganic salt solution and soaked 24 hours, stand-by.
The basis inorganic salt solution is: KHCO
30.50 gL
-1, MgSO
47H
2O 0.34 gL
-1, KH
2PO
40.027gL
-1, CaCl
20.136 gL
-1, NaNO
20.365 gL
-1, (NH
4)
2SO
40.33 gL
-1
(2) Anammox mud is taken out, through the phosphate buffer solution flushing of pH7.5-8.0 3 times, through precipitation or centrifugal after stand-by.
(3) with polyvinyl alcohol (PVA)-sodium alginate (SA)-gac respectively by mass percentage the ratio of PVA 10%, SA 0.6% and gac 1.2 % be mixed with mixing solutions, make embedding medium.
(4) fixing mud process: under anaerobic, use 30 ml syringes (needle-less) that mixed solution is dropwise joined 4% CaCl then with mud and mixed solution 1:2 ratio uniform mixing by volume
2In the solution, crosslinked 12 hours, being fixed bead, diameter were 3-6mm.Put it into Anammox basis inorganic salt solution then and cultivate, stand-by.With basic inorganic salt solution flushing three times, soaked then 24 hours, be collected at last in 1 liter of vial, add 0.5 liter of basic inorganic salt solution, whole process is all under anaerobic carried out.
(5) activation stage of embedding bead: in temperature is under the 25-30 ℃ of condition, utilizes Anammox basis inorganic salt solution to cultivate 7 days, can put into reactor after fixing, and directly uses.
Under anaerobic, will add target sewage through the activatory bead, the sequence batch (reaction, wherein COD of sewage is less than 50mg/L, and ammonia nitrogen loading is 0.07kg/m
3, the nitrite load is 0.09kg/m
3, the reaction times is 15 days, heavy shallow lake 6 hours, water outlet detects COD clearance 90%(and is mainly charcoal absorption), ammonia nitrogen removal frank 100%, nitrite clearance are 100%.Calculate and respectively handle NO
2 --N removal amount/NH
4 +-N removal amount ratio in 1.24～1.40 scopes, average 1.28, NO
3 --N growing amount/NH
4 +-N removal amount ratio is in 0.17～0.24 scope, and average is 0.22.Nitrogen removal rate is more than 90%.Immobilization material is through 6 order batch reaction processes, and ammonia nitrogen and nitrite clearance are constant substantially, and nitrogen removal rate is kept more than 85%, and is respond well.In this external simultaneous test, getting the suspended sludge of equivalent and sodium alginate (SA), polyvinyl alcohol (PVA), polyvinyl alcohol-sodium alginate (PVA-SA) etc. carries out embedding, polyvinyl alcohol (PVA)-sodium alginate (SA)-gac embedding group is contrasted, result such as Fig. 1, Fig. 2 show that polyvinyl alcohol (PVA)-sodium alginate (SA)-gac embedding group effect is best.
Embodiment 2
(1) immobilization material obtains: the wood powder shaped activated carbon is carried out pre-treatment: remove impurity and dust with the tap water flushing earlier, wash to clarification of water outlet.Soaked 24 hours with 8% hydrochloric acid soln then, with using 2% soaking with sodium hydroxide 24 hours again after the tap water flushing, use tap water and distilled water flushing then, put into physiological saline and soak oven dry after 24 hours, put into Anammox basis inorganic salt solution and soaked 24 hours, stand-by.
The basis inorganic salt solution is: KHCO
30.50 gL
-1, MgSO
47H
2O 0.30 gL
-1, KH
2PO
40.027gL
-1, CaCl
20.136 gL
-1, NaNO
20.4 gL
-1, (NH
4)
2SO
40.35 gL
-1
(2) Anammox mud is taken out, through the phosphate buffer solution flushing of pH7.5-8.0 3 times, through precipitation or centrifugal after stand-by.
(3) with polyvinyl alcohol (PVA)-sodium alginate (SA)-gac respectively by mass percentage the ratio of PVA 10%, SA 0.6% and gac 1.2 % be mixed with mixing solutions, make embedding medium.
(4) fixing mud process: under anaerobic, use 30 ml syringes (needle-less) that mixed solution is dropwise joined 4% CaCl then with mud and mixed solution 1:3 ratio uniform mixing by volume
2In the solution, crosslinked 10 hours, being fixed bead, diameter were 4-6mm.Put it into Anammox basis inorganic salt solution then and cultivate, stand-by.With basic inorganic salt solution flushing three times, soaked then 24 hours, be collected at last in 2.5 liters of vials, add 1.2 liters of basic inorganic salt solutions, whole process is all under anaerobic carried out.
(5) activation stage of embedding bead: in temperature is under 25 ℃ of conditions, utilizes Anammox basis inorganic salt solution to cultivate 6 days, can put into reactor after fixing, and directly uses.
To add target sewage through the activatory bead, the sequence batch (reaction, wherein COD of sewage is less than 45mg/L, and ammonia nitrogen loading is 0.09kg/m
3, the nitrite load is 0.12kg/m
3, the reaction times is 15 days, heavy shallow lake 6 hours, water outlet detects COD clearance 95%(and is mainly charcoal absorption), ammonia nitrogen removal frank 99%, nitrite clearance are 100%.Nitrogen removal rate is more than 92%.Immobilization material is through 6 order batch reaction processes, and ammonia nitrogen removal frank is 95%-99%, and the nitrite clearance is 98%-100%, nitrogen removal rate 80%-89%, and bead does not have fragmentation, and treatment effect is good.
Claims (10)
1. a method of utilizing polyvinyl alcohol-sodium alginate-gac embedding strengthened anaerobic ammoxidation microorganism active is characterized in that may further comprise the steps: 1. gac is carried out immersion treatment with Anammox basis inorganic salt solution; 2. polyvinyl alcohol, sodium alginate and gac are hybridly prepared into embedding medium; 3. under anaerobic Anammox mud and embedding medium uniform mixing are made mud mixed liquid, mud mixed liquid is joined CaCl
2In the solution, make immobilized spherule; 4. in the inorganic salt solution of Anammox basis, cultivate and obtain the stable anaerobic ammonia oxidation microbiological that is coupled on the gac; Described Anammox basis inorganic salt solution is made up of following material: KHCO
30.40-0.6 gL
-1, MgSO
47H
2O 0.30-0.35 gL
-1, KH
2PO
40.02-0.03 gL
-1, CaCl
20.1-0.15 gL
-1, NaNO
20.3-0.4 gL
-1, (NH
4)
2SO
40.4-0.5 gL
-1
2. the method for claim 1 is characterized in that the 1. described gac of step is the wood powder shaped activated carbon; The 3. described immobilized spherule diameter of step is 3-6mm.
3. the method for claim 1, it is characterized in that the 1. described gac of step elder generation's process acid-alkali treatment before adopting Anammox basis inorganic salt solution to carry out immersion treatment: after gac washes away impurity and dust, with tap water rinse-active charcoal, after removing dust impurity, soaked 20-30 hour with the 9-10% hydrochloric acid soln, soaked 20-30 hour with massfraction 1-2% sodium hydroxide solution after the water flushing, water flushing is then put into physiological saline and is soaked oven dry after 20-30 hour again.
4. the method for claim 1 is characterized in that the 1. described Anammox basis inorganic salt solution immersion treatment time of step is 20-30 hour.
5. the method for claim 1 is characterized in that the 4. described cultivation of step is: cultivate 1-2 week under temperature 25-30 ℃ condition.
6. the method for claim 1 is characterized in that the 3. described Anammox mud of step is earlier through following processing: with the phosphate buffer solution flushing of pH7.5-8.0 2-3 time, through precipitation or the acquisition of centrifugal back.
7. the method for claim 1 is characterized in that 3. described Anammox mud of step and embedding medium 1:1～1:3 mixed by volume.
8. the method for claim 1, it is characterized in that step 3. in the syringe of 30 ml needle-less or with peristaltic pump mixed solution dropwise to be joined massfraction be 4%CaCl
2In the solution, crosslinked 10-14 hour.
9. an embedding medium that is used for embedding strengthened anaerobic ammoxidation microorganism active according to claim 1 is characterized in that being mixed with by polyvinyl alcohol, sodium alginate and the gac ratio according to mass percent 10:0.6:1.2.
10. one kind is applied to strengthen and the fixing solution of anaerobic ammonia oxidation microbiological, it is characterized in that being made up of following material: KHCO
30.40-0.6 gL
-1, MgSO
47H
2O 0.30-0.35 gL
-1, KH
2PO
40.02-0.03 gL
-1, CaCl
20.1-0.15 gL
-1, NaNO
20.3-0.4 gL
-1, (NH
4)
2SO
40.4-0.5 gL
-1
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