CN100443590C - Biocompatibility immobilized carrier, its preparation method and application in immobilized microorganism - Google Patents
Biocompatibility immobilized carrier, its preparation method and application in immobilized microorganism Download PDFInfo
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- 244000005700 microbiome Species 0.000 title abstract description 35
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
- 230000005855 radiation Effects 0.000 claims abstract description 39
- 239000012153 distilled water Substances 0.000 claims abstract description 28
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 14
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- 239000000969 carrier Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 108010093096 Immobilized Enzymes Proteins 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
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- 239000011028 pyrite Substances 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The present invention provides a preparation method of a biocompatible immobilized carrier, which belongs to the technical field of microorganism immobilization. The method comprises the following steps: (1) hydroxyethyl beta-methacrylate or hydroxyethyl acrylate, n-ethanediol dimethylacrylate and distilled water are uniformly mixed according to the volume ratio of (10 to 30): (4 to 20): (50 to 86); (2) nitrogen is led into the mixture in the step (1), and the mixture is radiated and polymerized by adopting high-energy rays with the radiation dosage of 1*10<3> to 1*10<6>Gy at the temperature of-63 to-95DEG C to form the biocompatible immobilized carrier. The biocompatible immobilized carrier prepared by the preparation method can be applied to immobilized microorganisms. The immobilized carrier prepared by the present invention has the advantages of favorable mass transfer property, high mechanical strength, long service life, etc. In addition, the immobilized carrier has micro ecological property and biocompatibility. The immobilized microorganism of the present invention has obvious effects on treatment of nitrogen polluted type sewage water and ecological remediation of water.
Description
One, technical field
The invention belongs to the immobilized microorganism technique field, relate to fixation of microbe carrier and preparation thereof, and the application of fixed microorganism carrier in microbial immobilization, in particular, be a kind of biocompatibility, little ecological property fixation support, its preparation method and the application in immobilized microorganism.
Two, background technology
Lake, the pollution of water bodys such as river and eutrophication are that human health is jeopardized in China and even many in the world areas, the severe ecological environment problem of restriction social economy Sustainable development.The water pollution situation and the body eutrophication phenomenon of China are very serious, according to investigation, cause in all kinds of nutritive substances of water pollution, mainly based on nitrogen, phosphorus.For the improvement of the polluted by nitrogen of sanitary sewage, industrial sewage, the main at present denitrification process that adopts the municipal sewage plant, technologies such as microbial film; And, mainly at present adopt nutritive salt control for the improvement of the polluted by nitrogen of natural water bodies such as lake, reservoir, desilting is dredged, methods such as chemistry, machinery are directly removed algae, biological regulation and control, and aquatic higher plant is repaired, the physics ecological engineering technology, immobilized microorganism technique etc.
Immobilized microorganism technique is an emerging technology in the bioengineering field.Begin to use this new technology with distinct advantages both at home and abroad and handle trade effluent the early 1980s, dephosphorization denitrogenation, and the organic pollutant of decomposition difficult for biological degradation has been obtained the achievement that attracts people's attention.It is compared with traditional suspended biological facture, has the processing efficiency height, and stability is strong, energy purifying and maintenance high-efficiency strain, and the biological concentration height, it is few to produce sludge quantity, advantages such as good effect of separating solid from liquid.
The key of immobilization technology should be emphasized two aspects, high performance carrier and microbial strains efficiently.The ideal fixed microorganism carrier should have following feature: to the microorganism nontoxicity, mass-transfer performance is good, and stable in properties is difficult for by microbiological degradation physical strength height, long service life etc.In existing research report, the embedded material of utilization mainly is divided into natural polymer gel-like and organic synthesis macromolecular compound two big classes.
(number of patent application 02117766.X-utilizes calcium-alginate-immobilized Pseudomonas delafieldii R-8 to carry out the method for desulfurizing oil for natural polymer gel carrier such as agar, this is had description), carrageenin etc., generally to biological nontoxic, mass-transfer performance is good, but shortcoming is: intensity is low, under anaerobic, in practice, often need to add certain additive and strengthen intensity easily by microbiological degradation.
Organic synthesis macromolecular compound gel such as polyacrylamide, polyvinyl alcohol etc., common intensity is higher, chemical stability is good, but also have the following disadvantages: mass-transfer performance is poor slightly, pair cell is active influential when carrying out embedding, often need in embedding, add the micropore canals that sorbent material strengthens immobilized spherule in actual applications, improve its mass-transfer performance.Disclose the employing polyoxyethylene glycol in addition in the number of patent application 200410020228.3 (polyethyleneglycol modified biologic silica gel containing dehydrogenase) and prepared carrier and desaturase has been carried out the modification immobilization carrier have characteristics such as mean pore size is big, but still do not broken away from the influence problem of using embedding immobilization method biologically active substance." immobilization that purifies the water body in lake polluted by nitrogen nitrated-denitrifying bacteria research " (lake science, 2000,12 (2): adopt the low-temp radiating technology to prepare that polymer support poly (HEA-14G) immobilization is nitrated, denitrifying bacterium has carried out immobilization research 119～123), obtain effect preferably.But find in actual applications because in poly (HEA-14G) polymer support, the ratio range of original concentration is narrower, the therefore difficult control of the hydrauture of the copolymerization carrier of preparing, preparation process is complicated.The preparation of fixation support needs to improve.
Three, summary of the invention
1, the technical problem that will solve
Existing fixation support technology of preparing process complexity, the fixation support of preparing can't satisfy the requirement of immobilized microorganism fully.The present invention proposes the method that a kind of application of radiation technology prepares carrier, can prepare a kind of biocompatibility fixation support, can make the fixation support physical strength increase, increase the service life, and better microorganism is carried out immobilization.
2, technical scheme
The preparation method of biocompatibility fixation support, it mainly may further comprise the steps:
(1) with methacrylic acid β hydroxyl ethyl ester or Hydroxyethyl acrylate (hydrophilic vitreous state monomer), n ethylene glycol dimethacrylate (weak hydrophobicity) and distilled water with volume ratio 10～30: 4～20: 50～86 mix;
(2) charge into nitrogen in the mixture of (1), in-63～-95 ℃ of temperature, adopting radiation dose is 1 * 10
3～1 * 10
6The high-energy ray irradiation polymerization of Gy forms the biocompatibility fixation support.
Described n ethylene glycol dimethacrylate monomer is a kind of of 2G, 4G, 9G, 14G.Energetic ray is
60The Co-gamma-rays,
137Cs-gamma-rays, electron beam.Methacrylic acid β hydroxyl ethyl ester or Hydroxyethyl acrylate, n ethylene glycol dimethacrylate and distilled water volume ratio are 20～30: 4～15: 65～75.
The biocompatibility fixation support is prepared from by above-described preparation method.
The application of biocompatibility fixation support in immobilized microorganism, it mainly may further comprise the steps:
A) the biocompatibility fixation support is cut into small pieces, makes it the back sterilization of fully expanding with distilled water immersion;
B) soak fixation support with the synthetic wastewater that contains carbon source, make the fixation support inside after synthetic wastewater fully enters expansion;
C) in fixation support, add after vibration, to leave standstill and make it to be adsorbed in the fixation support surface and enter the inner immobilization that realizes of the porous support that is full of synthetic wastewater by propagation through centrifugal gained microorganism.
Microorganism described in the step (c) is a nitrogen-cycle bacteria.Synthetic wastewater composed as follows: carbon source is in carbon 3.6～5.6g, NH in every 25L solution
4 +Ion 1.0～2.0g, NO
3 -Ion 6.1～9.2g, Mg
2+0.06～0.12g, Fe element 0.07～0.24g, and the adding buffer reagent makes that the pH value is 7.0～7.5.
Better effects if when the adding component of synthetic wastewater is following: carbon source is in carbon 3.6～5.6g, NH in every 25L solution
4 +Ion 1.0～2.0g, NO
3 -Ion 6.1～9.2g, NO
2 -Ion 3～4g, buffer reagent 7.3～10.6g, Mg
2+0.06～0.12g, Fe element 0.07～0.24g, Co
2+0.01～0.04g.
The amount of the nitrogen-cycle bacteria that adds in the fixation support among the step C can be adjusted according to the purpose that will reach.The amount that adds is many more, and effect is good more, but needed cost is also high simultaneously.
Principle of the present invention is as follows: hydrophilic monomer methacrylic acid β hydroxyl ethyl ester or Hydroxyethyl acrylate and weak hydrophobicity n ethylene glycol dimethacrylate (nG) series monomers are carried out radiation copolymerization and are formed copolymer, owing to have ethylene glycol [(OCH in n ethylene glycol dimethacrylate (nG) the series monomers molecular chain
2CH
2)
n-] group, its number is respectively 2,4,9,14, i.e. n=2,4,9,14.Along with ethylene glycol [(OCH in the n ethylene glycol dimethacrylate series monomers
2CH
2)
n-] increase of group number, the chain length of monomer molecule increases, the also corresponding increase of distance between the corsslinking molecular chain in the carrier structure behind the radiation formation multipolymer, and then causing the aperture of multipolymer microvoid structure can adjust relatively, the shape according to different microorganisms that can be artificial, size design preparation are suitable for micropore size and little environmental carrier of microorganism existence, growth, propagation.
The shape according to different microorganisms that can be artificial, size design preparation are suitable for micropore size and little environmental carrier of microorganism existence, growth, propagation.The fixation support that preparation forms has good microvoid structure, constituted a kind of " little ecology " environment that is suitable for microorganism existence, growth, propagation, when external environment changed, the micro-ecological environment that microorganism can rely on carrier to provide progressively adapted to the acute variation of ambient conditions.Because fixation support has special microvoid structure, constituted the inside and outside nitrated-denitrification microenvironment of differentiation mutually of carrier, a kind of made oxidation-reduction interface that is present on the centimeter scale so just is provided.The existence of this artificial microenvironment in natural water is similar to nitrated-denitrification function that water in the natural water-the settling interface has, a kind of microenvironment be can artificially build, will water-settling interface in the natural water and oxidation-reduction microenvironment be existed only in from the planar extension to the solid with good aqueous vapor passage and nitrated-denitrification micropore three-dimensional arrangement interface.The existence of this artificial microenvironment in natural water of carrier remedied the deficiency that the water body homogeneity increases, heterogencity (heterogeneity) minimizing is cancerated the oxidation-reduction environment and water body self-purification ability descends that causes because of a large amount of aquatic higher plant declines in the present nutrition-enriched water of lake.Adopt this kind fixation support to be deployed to natural water and can play a kind of violent oxidation-reduction environment of in being similar to the homogeneity natural water of desertification, introducing a kind of made heterogencity, increase the nitrated-denitrifying capacity of water body greatly, increase the changing effect of water body nitrogen, significantly improve the effect of Ecological Recovery of Water.In addition, adopt the fixation support of this kind method preparation can use the first-generation immobilized enzyme that continues, the third generation fixed hyperplasia cell technology that grows up after the s-generation resting cell technology is carried out immobilization to microorganism, significantly improve fixed effect and the growth of microorganism, multiplication capacity, microorganism can utilize excellent biological compatibility that copolymerization carrier possesses and the affinity of microorganism is adsorbed replicating microorganism rapidly, and to external world's release and diffusion, increase the microbe population (as immobilization nitrogen-cycle bacteria quantity) of polluted-water, along with the Ammonifying bacteria in the water body, nitrite bacteria, nitrobacteria, denitrifying bacterium quantity increases greatly, and the organonitrogen in the water body is converted into ammonia nitrogen and gasiform NH through the Ammonifying bacteria ammonification
3Ammonia nitrogen is oxidized to nitric nitrogen at the carrier surface oxygen-rich area, nitric nitrogen is reduced to gaseous nitrogen in the inner oxygen-starved area of fixation support by denitrifying bacterium and enters atmosphere, the nitrate pollution thing of different shape in this affine, the absorption to microorganism of carrier, propagation, diffusion process, is strengthened being removed gradually under nitrated-denitrifying effect just in the water body.
Because the simple function group of possess hydrophilic property (OH) in methacrylic acid β hydroxyl ethyl ester and the Hydroxyethyl acrylate molecular chain, with the polymkeric substance that forms behind the n ethylene glycol dimethacrylate series monomers radio polymerization, life active compound (comprising various cells, microorganism) had certain affinity interaction-be biocompatibility.
3, beneficial effect
Fixation support by present method preparation has good, the advantages such as physical strength is high, long service life of mass transfer performances, and has little ecological property, biocompatibility.The shape according to different microorganisms that can be artificial, size design preparation are suitable for micropore size and little environmental carrier of microorganism existence, growth, propagation.Adopt the fixation support of the present invention's preparation can use the third generation fixed hyperplasia cell technology that after first-generation immobilized enzyme, s-generation resting cell technology, grows up that microorganism is carried out immobilization.Significantly improve the fixed effect of microorganism and growth, multiplication capacity, have the cell density height, speed of response is fast, product separates easily, reaction process is easy to characteristics such as control.The immobilized microorganism of adopting the preparation of this fixation support is to the sewage disposal of polluted by nitrogen type, and Ecological Recovery of Water has a significant effect.
Four, description of drawings
Fig. 1 is the microvoid structure electron micrograph of the copolymerization carrier of monomer (HEA-9G) 20/10 preparation
The microvoid structure electron micrograph of the copolymerization carrier of Fig. 2 monomer (HEA-9G) 25/5 preparation
Five, embodiment
Further specify the present invention by the following examples
Embodiment 1
As component A, weak hydrophobic 14 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 14G] are as B component with hydrophilic vitreous state monomer methacrylic acid β hydroxyl ethyl ester (2-Hydroxyethyl methylacrylate (HEMA)); Distilled water is that 25/4/70 (v/v/v) uses vibrator to mix with 1000r/min vibration 5min as component C by A: B: C;
2. behind the inflated with nitrogen, under-78 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 1cm * cm * cm fritter and is placed in the triangular flask and makes it abundant expansion, 1.03 * 10 with distilled water immersion 7d
530min sterilizes in the Pa pressure kettle.
4. with synthetic wastewater (C
6H
12O
614g, NH
4Cl 6g, KNO
312g, NaHCO
39g, KH
2PO
40.5g, MgSO
40.5g, NaCl 0.5g, FeCl
30.5g, CoCl
20.05g) soaking fixation support, 28 ℃ of 200r/min vibration 24h also exchange synthetic wastewater 3 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 4000r/min, 4 ℃ of centrifugal 20min gained Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium drop into carrier, descend vibration 24h at 28 ℃, leave standstill 48h, make ammonification, nitrated, nitrosification and denitrifying bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in the fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt the immobilization nitrogen-cycle bacteria (Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium) of this fixation support preparation to carry out the industrial sewage processing of high organic load, as water inlet COD
Cr473.8mg/L, TN is that 112.0mg/L, carbon-nitrogen ratio are 4.23 o'clock, through the technical finesse of immobilization nitrogen-cycle bacteria, water outlet average COD
CrHave significantly and reduce, clearance reaches 76%, TN, NH
4 +The clearance of-N is respectively 80%, 94%, shows that the immobilization nitrogen-cycle bacteria technology that adopts the preparation of low-temp radiating fixation support has to remove industrial sewage high density organic loading more by force and impact the ability of degradation of organic substances and denitrogenation.
Embodiment 2
With hydrophilic vitreous state monomer Hydroxyethyl acrylate (2-Hydroxyethyl acrylate (HEA)) as component A, weak hydrophobic 9 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 9G] are as B component; Distilled water is 20/5/75 (v/v/v) as component C by A: B: C, uses vibrator to mix with 850r/min vibration 4min;
2. behind the inflated with nitrogen, under-63 ℃ temperature, control radiation dose scope is 5 * 10
4Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 1.5cm * 1.5cm * 1.5cm fritter and is placed in the triangular flask and makes it abundant expansion, 1.03 * 10 with distilled water immersion 9d
540min sterilizes in the Pa pressure kettle.
4. with synthetic wastewater (methyl alcohol 10g, NH
4Cl 5g, KNO
310g, NaHCO
37g, KH
2PO
40.5g, MgSO
40.3g, NaCl 0.5g, FeCl
30.21g, CoCl
20.025g) soaking fixation support, 28 ℃ of 200r/min vibration 24h also exchange synthetic wastewater 3 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 5000r/min, 3 ℃ of centrifugal 25min gained Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium drop into carrier, descend vibration 36h at 28 ℃, leave standstill 48h, make ammonification, nitrated, nitrosification and denitrifying bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in the fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt the immobilization nitrogen-cycle bacteria (Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium) of this fixation support preparation to purify Taihu Lake eutrophic water experiment, after the aftertreatment of lake water process immobilization nitrogen-cycle bacteria purifying treatment, TN, NH
4 +The clearance of-N, COD reaches 75% and 91.5% and 75% respectively, and effluent quality obviously improves.Adopt this preparing carriers technology immobilization nitrogen-cycle bacteria that the eutrophication control of natural water bodies such as lake, reservoir is had a significant effect.
Embodiment 3
1. select for use hydrophilic vitreous state monomer Hydroxyethyl acrylate (2-Hydroxyethyl acrylate (HEA)) as component A, weak hydrophobic 9 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 9G] are as B component; Adding distilled water as component C, is 21/9/70 (v/v/v) by A: B: C, uses vibrator to mix with 900r/min vibration 4min;
2. behind the inflated with nitrogen, under-95 ℃ temperature, control radiation dose scope is 1 * 10
5Gy adopts energetic ray (electron beam) radiation polymerization to form fixation support;
3. the carrier after the radiation is cut into 2cm * 2cm * 2cm fritter and is placed in the triangular flask and makes it abundant expansion, 1.03 * 10 with distilled water immersion 10d
545min sterilizes in the Pa pressure kettle.
4. with synthetic wastewater (C
6H
12O
69.0g, NH
4Cl 5.5g, KNO
314.9g, NaHCO
37.5g, KH
2PO
40.45g, MgSO
40.6g, FeCl
30.69g, CoCl
20.08g) soaking fixation support, 28 ℃ of 170r/min vibration 36h also exchange synthetic wastewater 3 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 7000r/min, 2 ℃ of centrifugal 30min gained Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium drop into carrier, descend vibration 28h at 28 ℃, leave standstill 50h, make ammonification, nitrated, nitrosification and denitrifying bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in the fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt the immobilization nitrogen-cycle bacteria (Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium) of this fixation support preparation to carry out the sanitary sewage disposal of high nitrogen load, when TN is 112mg/L, NH
4 +-N is about 60.5mg/L, through the technical finesse of immobilization nitrogen-cycle bacteria, TN, NH
4 +-N has significantly reduction, and clearance reaches 80%, 94% respectively.Show that the polluted by nitrogen that adopts this carrier immobilized nitrogen-cycle bacteria can effectively resist higher load impacts, have the ability of handling high nitrogen load sanitary sewage preferably.
Embodiment 4
1. select for use hydrophilic vitreous state monomer Hydroxyethyl acrylate (2-Hydroxyethyl acrylate (HEA)) as component A, with weak hydrophobic 14 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 14G] as B component; Adding distilled water as component C, is 10/8/65 (v/v/v) by A: B: C, uses vibrator to mix with 1100r/min vibration 2min;
2. behind the inflated with nitrogen, temperature is-63 ℃～-78 ℃, and the control radiation dose is 2 * 10
4Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 1.4cm * 1.4cm * 1.4cm fritter and is placed in the triangular flask and makes it abundant expansion, 1.03 * 10 with distilled water immersion 6d
536min sterilizes in the Pa pressure kettle.
4. with synthetic wastewater (methyl alcohol 10g, NH
4Cl 2.9g, KNO
310g, NaHCO
310.3g, KH
2PO
40.5g, MgSO
40.5g, NaCl 0.5g, FeCl
30.5g, CoCl
20.05g) soaking fixation support, 28 ℃ of 200r/min vibration 24h also exchange synthetic wastewater 3 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 4500r/min, 1 ℃ of centrifugal 28min gained Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium drop into carrier, descend vibration 40h at 28 ℃, leave standstill 40h, make ammonification, nitrated, nitrosification and denitrifying bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in the fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt immobilization nitrogen-cycle bacteria (Ammonifying bacteria, nitrobacteria, nitrite bacteria and the denitrifying bacterium) 30kg of this fixation support preparation, carry out the field and purify Red Maple Lake eutrophic water experiment, at 5600m
2, flow is 2m
3The ecological engineering test site, Red Maple Lake of/s through 100 days continuous operation, is under 0～4 ℃ of condition at temperature, after the lake water process immobilization nitrogen-cycle bacteria purifying treatment, and TN, NH
4 +The clearance of-N, non-ionic ammonia reaches 74% and 89.5% and 76.5% respectively, and effluent quality obviously improves.Adopt this preparing carriers technology immobilization nitrogen-cycle bacteria that the eutrophication control of the higher natural water bodies such as natural storage type of flow velocity is had a significant effect.
Embodiment 5
1. select for use hydrophilic vitreous state monomer Hydroxyethyl acrylate (2-Hydroxyethyl acrylate (HEA)) as component A, weak hydrophobic 4 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 4G] are as B component; Adding distilled water as component C, is 27/7/50 (v/v/v) by A: B: C, uses vibrator to mix with 1100r/min vibration 6min;
2. behind the inflated with nitrogen, under-78 ℃～-88.5 ℃ temperature, the control radiation dose is 1 * 10
5Gy, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 1.5cm * 2cm * 2cm fritter and is placed in the triangular flask and makes it abundant expansion with distilled water immersion 12d, 42min sterilizes under 121 ℃ of temperature in pressure kettle.
4. with synthetic wastewater (methyl alcohol 7.5g, (NH
4)
2SO
43.4g, KNO
311g, NaHCO
39.5g, KH
2PO
41.1g, MgSO
40.42g, FeCl
30.41g) soaking fixation support, 28 ℃ of 210r/min vibration 40h also exchange synthetic wastewater 4 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 6500r/min, 0 ℃ of centrifugal 25min gained Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium drop into carrier, descend vibration 28h at 28.5 ℃, leave standstill 56h, make ammonification, nitrated, nitrosification and denitrifying bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in the fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt the immobilization nitrogen-cycle bacteria (Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium) of this fixation support preparation that Qinhuaihe River polluted-water Nanjing outside is carried out the nitrogen load and remove processing, when TN is 6.3mg/L, NH
4 +-N is about 3.4mg/L, through the technical finesse of immobilization nitrogen-cycle bacteria, TN, NH
4 +-N reduces significantly, and clearance reaches 75.6%, 91.3% respectively.Show the nitrate pollution thing that adopts this carrier immobilized nitrogen-cycle bacteria can effectively remove pollution of river water body, have the ability of handling current water (pollution of river polluted by nitrogen) preferably.
Embodiment 6
1. select for use hydrophilic vitreous state monomer methacrylic acid β hydroxyl ethyl ester (2-Hydroxyethyl methylacrylate (HEMA)) as component A, weak hydrophobic 2 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 2G] are as B component; Adding distilled water as component C, is 31/4/65 (v/v/v) by A: B: C, uses vibrator to mix with 750r/min vibration 10min;
2. after using nitrogen saturated, in-88.5 ℃ temperature range, control radiation dose scope is 1 * 10
5Gy～1 * 10
6Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 1.6cm * 2.0cm * 2.0cm fritter and is placed in the triangular flask and makes it abundant expansion with distilled water immersion 6d, 40min sterilizes under 121 ℃ of high temperature.
4. with synthetic wastewater (C
6H
12O
614.5g, NH
4Cl 5.5g, KNO
311.5g, NaHCO
39.5g, KH
2PO
40.5g, MgSO
40.5g, CoCl
20.05g) soaking fixation support, 28.5 ℃ of 250r/min vibration 20h also exchange synthetic wastewater 4 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 6000r/min, 0 ℃ of centrifugal 30min gained Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium drop into carrier, descend vibration 24h at 28 ℃, leave standstill 48h, make ammonification, nitrated, nitrosification and denitrifying bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in the fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt the immobilization nitrogen-cycle bacteria (Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium) of this fixation support preparation that Nanjing Black Warrior lake water is carried out the experiment of eutrophication water removal nitrate pollution thing, through the nitrogen experiment of immobilization nitrogen-cycle bacteria technical transform lake, TN, NH
4 +-N, NO
3 --N and NO
2 --N, all have significantly and to reduce, clearance is respectively 80%, 85.4%, and 79% and 77%, show that the immobilization nitrogen-cycle bacteria technology that adopts the fixation support preparation has the strong ability of removing tourism lake polluted by nitrogen.
Embodiment 7
1. select for use hydrophilic vitreous state monomer Hydroxyethyl acrylate (2-Hydroxyethyl acrylate (HEA)) as component A, with weak hydrophobic 2 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 2G] as B component; Adding distilled water as component C, is 30/20/86 by A: B: C, (v/v/v), uses vibrator to mix with 1000r/min vibration 6min;
2. after using nitrogen saturated, under-93.5 ℃ temperature, the control radiation dose is 1 * 10
4～1 * 10
5Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 2.0cm * 2.0cm * 2.0cm fritter and is placed in the triangular flask and makes it abundant expansion, 1.03 * 10 with distilled water immersion 10d
536min sterilizes in the Pa pressure kettle.
4. with synthetic wastewater (methyl alcohol 9g, NH
4Cl 5g, KNO
310g, NaHCO
37g, KH
2PO
40.5g, MgSO
40.5g) soaking fixation support, 28 ℃ of 240r/min vibration 24h also exchange synthetic wastewater 3 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 7500r/min, 0 ℃ of centrifugal 30min gained Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium drop into carrier, descend vibration 30h at 28 ℃, leave standstill 48h, make ammonification, nitrated, nitrosification and denitrifying bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in the fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt immobilization nitrogen-cycle bacteria (Ammonifying bacteria, nitrobacteria, nitrite bacteria and the denitrifying bacterium) 30kg of this fixation support preparation to add waterplant, carry out open-air purifying eutrophic water experiment in China man pond ecological engineering test district, at 5000m
2The ecological engineering test site through 150 days continuous operation, is under 10 ℃～38 ℃ conditions at temperature, after the purifying treatment of lake water through immobilization nitrogen-cycle bacteria+waterplant, and TN, NH
4 +-N, NO
3 --N, NO
2 -The clearance of-N reaches 74%～78% and 89.5%～91%, 76.5～79%, 73.%～75% respectively, and water quality is obviously improved.Adopt this preparing carriers technology immobilization nitrogen-cycle bacteria that the eutrophication control of natural water bodies such as breed type is had a significant effect.
Embodiment 8
1. select for use hydrophilic vitreous state monomer Hydroxyethyl acrylate (2-Hydroxyethyl acrylate (HEA)) as component A, with weak hydrophobic 2 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 2G] as B component; Adding distilled water as component C, is 10/4/55 by A: B: C, (v/v/v), uses vibrator to mix with 1000r/min vibration 6min;
2. after using nitrogen saturated, under-95 ℃ temperature, the control radiation dose is 1 * 10
3～1 * 10
4In the Gy scope, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 2.0cm * 2.0cm * 2.0cm fritter and is placed in the triangular flask and makes it abundant expansion, 1.03 * 10 with distilled water immersion 10d
536min sterilizes in the Pa pressure kettle.
4. with synthetic wastewater (methyl alcohol 9g, NH
4Cl 5g, KNO
310g, NaHCO
37g, KH
2PO
40.5g, MgSO
40.5g) soaking fixation support, 28 ℃ of 240r/min vibration 24h also exchange synthetic wastewater 3 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 7500r/min, 0 ℃ of centrifugal 30min gained Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium drop into carrier, descend vibration 30h at 28 ℃, leave standstill 48h, make ammonification, nitrated, nitrosification and denitrifying bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in the fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt immobilization nitrogen-cycle bacteria (Ammonifying bacteria, nitrobacteria, nitrite bacteria and the denitrifying bacterium) 30kg of this fixation support preparation to add waterplant, carry out open-air purifying eutrophic water experiment in China man pond ecological engineering test district, at 5000m
2The ecological engineering test site through 150 days continuous operation, is under 10 ℃～38 ℃ conditions at temperature, after the purifying treatment of lake water through immobilization nitrogen-cycle bacteria+waterplant, and TN, NH
4 +-N, NO
3 --N, NO
2 -The clearance of-N reaches 74%～78% and 89.5%～91%, 76.5～79%, 73.%～75% respectively, and water quality is obviously improved.Adopt this preparing carriers technology immobilization nitrogen-cycle bacteria that the eutrophication control of natural water bodies such as breed type is had a significant effect.
Embodiment 9
1. select for use hydrophilic vitreous state monomer Hydroxyethyl acrylate (2-Hydroxyethyl acrylate (HEA)) as component A, with weak hydrophobic 2 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 2G] as B component; Adding distilled water as component C, is 20/10/76 by A: B: C, (v/v/v), uses vibrator to mix with 1000r/min vibration 6min;
2. after using nitrogen saturated, under-93.5 ℃～-95 ℃ temperature, the control radiation dose is 1 * 10
3～1 * 10
4In the Gy scope, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 2.0cm * 2.0cm * 2.0cm fritter and is placed in the triangular flask and makes it abundant expansion, 1.03 * 10 with distilled water immersion 10d
536min sterilizes in the Pa pressure kettle.
4. with synthetic wastewater (methyl alcohol 9g, NH
4Cl 5g, KNO
310g, NaHCO
37g, KH
2PO
40.5g, MgSO
40.5g) soaking fixation support, 28 ℃ of 240r/min vibration 24h also exchange synthetic wastewater 3 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 7500r/min, 0 ℃ of centrifugal 30min gained Ammonifying bacteria, nitrobacteria, nitrite bacteria and denitrifying bacterium drop into carrier, descend vibration 30h at 28 ℃, leave standstill 48h, make ammonification, nitrated, nitrosification and denitrifying bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in the fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt immobilization nitrogen-cycle bacteria (Ammonifying bacteria, nitrobacteria, nitrite bacteria and the denitrifying bacterium) 30kg of this fixation support preparation to add waterplant, carry out open-air purifying eutrophic water experiment in China man pond ecological engineering test district, at 5000m
2The ecological engineering test site through 150 days continuous operation, is under 10 ℃～38 ℃ conditions at temperature, after the purifying treatment of lake water through immobilization nitrogen-cycle bacteria+waterplant, and TN, NH
4 +-N, NO
3 --N, NO
2 -The clearance of-N reaches 74%～78% and 89.5%～91%, 76.5～79%, 73.%～75% respectively, and water quality is obviously improved.Adopt this preparing carriers technology immobilization nitrogen-cycle bacteria that the eutrophication control of natural water bodies such as breed type is had a significant effect.
Embodiment 10
1. select for use hydrophilic vitreous state monomer Hydroxyethyl acrylate (2-Hydroxyethyl acrylate (HEA)) as component A, with weak hydrophobic 14 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 2G] as B component; Adding distilled water as component C, is 19/6/70 by A: B: C, (v/v/v), uses vibrator to mix with 1000r/min vibration 6min;
2. after using nitrogen saturated, under-88.5 ℃ temperature, the control radiation dose is 1 * 10
3～1 * 10
4In the Gy scope, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 1.4cm * 1.4cm * 1.4cm fritter and is placed in the triangular flask and makes it abundant expansion, 1.03 * 10 with distilled water immersion 10d
536min sterilizes in the Pa pressure kettle.
4. with synthetic wastewater (C
6H
12O
6250g, (NH
4)
2SO
412.5g, MgSO
47.5g, NaCl7.5g, FeSO
40.9g, MnSO
40.75g, Ca
3(PO
4)
250g, 25L pH7.2) soaks fixation support, and 28 ℃ of 240r/min vibration 24h also exchange synthetic wastewater 3 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 7500r/min, 0 ℃ of centrifugal 30min gained phosphorus fungus, fermentation and acid bacterium drop into carrier, descend vibration 30h at 28 ℃, leave standstill 48h, make phosphorus fungus, fermentation and acid bacterium alternately under aerobic conditions and anaerobic condition, be adsorbed in fixation support surface and enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt the immobilization bacterium (phosphorus fungus, fermentation and acid bacterium) of this fixation support preparation to carry out phosphorous industrial sewage processing, operation process is the SBR method, water inlet 0.5h, and anoxia stirring 3 hours, aeration 7 hours, sedimentation and drawing 3 hours is as water inlet COD
Cr513.5mg/L, when TP is 103.0mg/L, through the immobilization bacterium technical finesse, water outlet average T P and COD
CrHave significantly and to reduce, clearance is respectively 80%, 83%, shows that immobilization bacterium (phosphorus fungus, the fermentation and acid bacterium) technology that adopts the fixation support preparation has to remove industrial sewage high density organic loading more by force and impact the ability of degradation of organic substances and dephosphorization.
Embodiment 11
1. select for use hydrophilic vitreous state monomer methacrylic acid β hydroxyl ethyl ester (2-Hydroxyethyl methylacrylate (HEMA)) as component A, weak hydrophobic 9 ethylene glycol dimethacrylates [Polyethylene glycoldimethacrylate 9G] are as B component; Adding distilled water as component C, is 28/10/62 (v/v/v) by A: B: C, uses vibrator to mix with 750r/min vibration 10min;
2. after using nitrogen saturated, in-63 ℃～95 ℃ temperature range, control radiation dose scope is 1 * 10
5Gy～1 * 10
6Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms fixation support;
3. the carrier after the radiation is cut into 1.6cm * 2.0cm * 2.0cm fritter and is placed in the triangular flask and makes it abundant expansion with distilled water immersion 6d, 40min sterilizes under 121 ℃ of high temperature.
4. with synthetic wastewater (Na
2S
2O
3250g, K
2HPO
4100g, KH
2PO
4100g, NH
4Cl 10g, MgSO
420g, FeSO
40.05g, MnSO
4, 0.05g, 25L, pH7.0～7.8) and soak fixation support, 28.5 ℃ of 250r/min vibration 20h also exchange synthetic wastewater 4 times, make the fixation support inside after synthetic wastewater fully enters expansion;
5. will be in right amount behind 6000r/min, 0 ℃ of centrifugal 30min the gained thiobacillus drop into carrier, descend vibration 24h at 28 ℃, leave standstill 48h, make thiobacillus enter the copolymerization carrier inside that is full of the good micropore growing environment of having of synthetic wastewater, make it to be immobilized by propagation.
6. adopt the immobilization thiobacillus coal slurry of this fixation support preparation to carry out desulfurization, the result shows, adopt the carrier immobilized thiobacillus of low-temp radiating technology preparation, through the immobilization thiobacillus about 3 hours coal slurry is carried out pre-treatment, clearance to the sulphur in the pyrite is about 65%, shows that the immobilization thiobacillus has removal effect preferably to the sulphur in the pyrite.
Claims (4)
1. the preparation method of a biocompatibility fixation support, it mainly may further comprise the steps:
(1) with methacrylic acid β hydroxyl ethyl ester or Hydroxyethyl acrylate, n ethylene glycol dimethacrylate and distilled water with volume ratio 10～30: mix at 4～20: 50～86, and n wherein is 2,4,9 or 14;
(2) charge into nitrogen in (1) mixture, in-63～-95 ℃ of temperature, adopting radiation dose is 1 * 10
3～1 * 10
6The high-energy ray irradiation polymerization of Gy forms the biocompatibility fixation support.
2. the preparation method of biocompatibility fixation support according to claim 1 is characterized in that described energetic ray is
60The Co-gamma-rays,
137Cs-gamma-rays or electron beam.
3. the preparation method of biocompatibility fixation support according to claim 2 is characterized in that described methacrylic acid β hydroxyl ethyl ester or Hydroxyethyl acrylate, n ethylene glycol dimethacrylate and distilled water volume ratio are 20～30: 4～15: 65～75.
4. a biocompatibility fixation support is characterized in that being prepared from by claim 1 or 2 or 3 described preparation methods.
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| CN111186909B (en) * | 2020-01-24 | 2022-01-04 | 辽宁中舟得水环保科技有限公司 | Method for treating epoxypropane wastewater by efficient anaerobic process |
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| Title |
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| 净化湖泊水体氮污染的固定化硝化-反硝化菌研究. 李正魁等.湖泊科学，第12卷第2期. 2000 |
| 净化湖泊水体氮污染的固定化硝化-反硝化菌研究. 李正魁等.湖泊科学，第12卷第2期. 2000 * |
| 固定化增殖氮循环细菌群SBR法净化富营养化湖水. 李正魁等.核技术，第24卷第8期. 2001 |
| 固定化增殖氮循环细菌群SBR法净化富营养化湖水. 李正魁等.核技术，第24卷第8期. 2001 * |
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