CN1740317A - A kind of method for preparing immobilized particles that is used for the surface water reparation - Google Patents
A kind of method for preparing immobilized particles that is used for the surface water reparation Download PDFInfo
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Abstract
The present invention relates to the cell fixation microbial preparation, the specifically a kind of method for preparing immobilized particles that surface water is repaired, 1 of being used for) in the PVA-NaAlg coagulant liquid that is pre-mixed, add gac, zeolite powder or diatomite, and add yeast extract paste; 2) add the thalline seed liquor in coagulant liquid, granulate, gel particles splashes into the linking agent chemically crosslinked, and after reinforcing in fixing agent then, with sterilized water water logging bubble, flushing makes immobilization particle.Advantage of the present invention is: even by optimizing the fill a prescription immobilization particle microtexture of each components contents preparation of PIV-NaAlg coagulant liquid, porosity is greater than 92%, and the diffusion mass transfer excellent performance is for microorganism provides good living environment; Immobilization particle physical strength height, life-time service is not broken, and outside atmosphere is had significant patience, to being that the polluted surface water of leading indicator has clear and definite repairing effect with COD.
Description
Technical field
The present invention relates to the cell fixation biotechnological formulation, specifically a kind of PVA-NaAlg embedded immobilization microbial technology.
Background technology
The surface water pollution problem is the product of modern industrial or agricultural high speed development, at the intensive industrial town of heavy chemical industry, this phenomenon is particularly outstanding, because polluting the water quality type lack of water phenomenon that causes aggravates gradually, at present, China is polluted the section more than 1/3, urban waters more than 90% is seriously polluted, the annual direct economic loss that causes because of surface water pollution is above 4,500 hundred million yuans, the regional water environment damage causes environmental capacity to continue to descend, not only seriously restricted Economic development, also caused the unstable incident of the normal property sent out society because of water pollutes dispute, surface water is administered and is repaired and become a reality and urgent environmental protection problem.
Features such as polluted surface water has the approach of getting dirty and the distribution region is wide, flowability is big, seasonality is strong, Pollutant levels are low, complicated polluting property has increased the difficulty of conventional repair techniques enforcement.The reparation of tradition microorganism is to utilize the Degradation of free bacterium to subdue the technology of pollutent, recovery clean environment, more complicated along with pollutent trend composition, easily accumulate characteristics such as difficult degradation and toxic effect be more long-term, the defective of tradition microorganism recovery technique manifests gradually, as effectively degradation bacteria concentration is low in: the unit volume, reactor start-up is slow, thalline easily runs off, be in weak tendency, toxin immunity infringement ability, the hydraulics of fierceness is changed sensitivity etc. with indigenous bacterium competition, therefore, need exploitation badly and be more suitable for the novel practical biotechnology that surface water is repaired.
Microbial immobilized being meant carried out the special biotechnology of fixed to intact cell, can avoid the stability of artificial destruction biological enzyme activity and biochemical reaction, the relative flow rate of cell is fast, be higher than in thinning ratio under the situation of microorganism growth rate, effectively contaminated solution environment remediation problem; It is active that microorganism can keep after immobilization for a long time, and can reuse; Certain physics or the chemistry set up between carrier and cell are got in touch; strengthened the stability of cell; the immobilization microenvironment of building shields to microorganism cells; help shielding the infringement of indigenous bacterium, phage and toxicant pair cell;, hydraulics lower for the organic contamination substrate concentration changes inapparent (unhurried current or static) polluted surface water; can reconcile physicalies such as immobilization particle pore size, physical dimension, mechanical property, proportion, reinforcing mass transfer characteristic easily according to polluting feature.Therefore, immobilized microorganism has bright application prospect undoubtedly in reparation surface water field.
The key of microbial immobilized technology is suitable solid support material of screening and the immobilization technology condition of determining optimization.
PVA and NaAlg are two kinds of good solid support materials that are immobilized in, and a lot of microorganisms are all had embedding effect preferably, have obtained widespread use in fields such as food, pharmacy, environmental protection, new energy development and chemosynthesis; However, but traditional PVA and NaAlg embedding fixing means still exist more defective and deficiency,, NaAlg inhomogeneous as: particulate diffusion mass transfer poor performance, hole from dissolving, physical strength is low, controllable density is poor, resisting temperature changes and the potential of hydrogen changing capability is weak etc., in case dropping into the surface water reparation uses, immobilization particle is very easily broken, the thalline physiologically active is low, hydraulics and extraneous factor change by force to particulate impact fracture power, causes repairing failure.In addition, traditional a certain PVA, the usually corresponding single culture of NaAlg process for fixation lack wide spectrum adaptability, fixing unfavorable to mixed bacterium.
Summary of the invention
In order to address the above problem, the present invention is by the orthogonal test of system, PVA and two kinds of solid support materials of NaAlg are combined formation mixed gel liquid, and multiple promotor, modifying agent, the reinforcer of interpolation different concns, traditional PVA and NaAlg embedding technique for fixing have been improved, fixing condition is simplified and gentleness more, improved the multiple technologies index (performance is better) of immobilization particle, and can unite fixing altogether mixed bacterium.The immobilization particle that makes is applied to the surface water reparation, the COD value of 144 hours continuous monitoring water bodys changes, the result shows: the immobilization biological product that makes according to this prescription has the excellent repairing effect to the polluted surface water based on COD, is a kind of reliable novel environmentally-friendly biological preparation.
The technical solution used in the present invention (method for preparing immobilized particles) is: add quantitative gac to PVA-NaAlg coagulant liquid (soaking into 12-20h with the tap water) lining that is pre-mixed, zeolite powder and yeast extract paste, ratio according to 20% will be cultivated 16-20 hour mixed bacterium seed liquid and coagulant liquid mixing, under 40 ℃ and pH natural condition, by diameter is the pellet fabrication device of 3mm, produce immobilization particle according to the drip speed that per minute 20-30 drips, particle was through chemically crosslinked in 24-29 hour, in fixing agent, reinforced 20-24 hour then, soak 24h with sterilized water at last, after washing clean residual liquor, multiplication culture, standby.The concrete operations step is as follows:
(1) yeast culture base
[basic medium]: 0.3% extractum carnis, 1.0% peptone, 0.5%NaCl, 1.5-2.0%
Agar, pH=7.0-7.2;
[seed culture medium]: 1.25% glucose, 0.25% yeast extract paste, 0.1%NH
4NO
3,
0.02％MgSO
4·7H
2O，0.02％KCl，pH＝7.0-7.2；
[proliferated culture medium]: 3.0% glucose, 0.4% yeast extract paste, 0.1% extractum carnis,
0.1％NH
4NO
3，0.02％MgSO
4·7H
2O，0.02％KCl，pH＝7.0-7.2。
(2) coagulant liquid prescription (mass percent, zeolite powder can substitute with diatomite)
[feasible prescription]: polyvinyl alcohol (PVA): 9.2%-12%, sodium alginate (NaAlg): 0.3%-0.6%, activity charcoal powder: 3%-5%, zeolite powder (0.074mm content is greater than 70%): 2%-5%, yeast extract paste: 0.05%-0.14%.Soaked into 12-20 hour with 20% tap water.In 111 ℃ of following moist heat sterilization 30min, be cooled to 35 ℃-45 ℃ before using, standby.
[prescription preferably]: polyvinyl alcohol (PVA): 9.8%-11%, sodium alginate (NaAlg): 0.45%-0.55%, activity charcoal powder: 3.5%-4.5%, zeolite powder (0.074mm content is greater than 70%): 3%-4.5%, yeast extract paste: 0.08%-0.12%.Soaked into 12-20 hour with 20% tap water.In 111 ℃ of following moist heat sterilization 30min, be cooled under the aseptic condition about 38 ℃-42 ℃ before using, standby.
[better prescription]: polyvinyl alcohol (PVA): 10.3%-10.8%, sodium alginate (NaAlg): 0.48%-0.52%, activity charcoal powder: 3.8%-4.2%, zeolite powder (0.074mm content is greater than 70%): 3.4%-4.0%, yeast extract paste: 0.09%-0.11%.Soaked into 12-20 hour with 20% tap water.In 111 ℃ of following moist heat sterilization 30min, be cooled under the aseptic condition about 39 ℃-41 ℃ before using, standby.
[best prescription]: polyvinyl alcohol (PVA): 10.5%, sodium alginate (NaAlg): 0.5%, activity charcoal powder: 4%, zeolite powder (0.074mm content is greater than 70%): 4.1%, yeast extract paste: 0.1%.Soaked into 12-20 hour with 20% tap water.In 111 ℃ of following moist heat sterilization 30min, be cooled under the aseptic condition about 40 ℃ before using, standby.
(3) linking agent prescription (mass percent)
[feasible prescription]: the ammonium pentaborate aqueous solution of primary cross-linking agent: 8.55%-9.85%, pH=5.5-7.0; The AlCl of secondary crosslinking agent: 1.5%-3.2%
3And 0.8%-1.8%FeCl
3Mixed aqueous solution, pH=2.0-3.0.
[prescription preferably]: the ammonium pentaborate aqueous solution of primary cross-linking agent: 8.85%-9.45%, pH=5.8-6.6; The AlCl of secondary crosslinking agent: 1.8%-3.0%
3And 1.0%-1.6%FeCl
3Mixed aqueous solution, pH=2.2-2.8.
[better prescription]: the ammonium pentaborate aqueous solution of primary cross-linking agent: 9.05%-9.25%, pH=6.0-6.4; The AlCl of secondary crosslinking agent: 2.0%-2.6%
3And 1.1%-1.3%FeCl
3Mixed aqueous solution, pH=2.4-2.6.
[best prescription]: a linking agent: 9.12% the ammonium pentaborate aqueous solution, pH=6.2; Secondary crosslinking agent: 2.1% AlCl
3And 1.2%FeCl
3Mixed aqueous solution, pH=2.5.
(4) strengthening agent prescription
[feasible prescription]: the Na of 7.5%-9.5%
2SO
4The aqueous solution, the pH nature.
[prescription preferably]: the Na of 7.9%-9.1%%
2SO
4The aqueous solution, the pH nature.
[better prescription]: the Na of 8.3%-8.8%
2SO
4The aqueous solution, the pH nature.
[best prescription]: 8.45% Na
2SO
4The aqueous solution, the pH nature.
(5) multiplication culture
Immobilization particle mass concentration according to 25% under aseptic condition of preparation is joined in the proliferated culture medium controlled temperature: 28-30 ℃, shaking speed: 145rpm-155rpm, incubation time: 24 hours, change substratum afterwards, cultivate for totally 3 times, standby.
The present invention has following advantage:
1, by optimizing PIV-NaAlg coagulant liquid each components contents of filling a prescription, and utilize technical measures such as twice crosslinked and follow-up reinforcing, and the immobilization particle microtexture of preparation is even, and porosity surpasses 92%, the diffusion mass transfer excellent performance is for microorganism provides good living environment.
2, by in coagulant liquid, adding subsidiary material such as gac, mineral dust, make the immobilization particle physical strength greatly improve, average intensity 31.5Kg/cm
2, the particle excellent spring, propagation back volume increases by 8%, and the particle profile is intact, and is not broken.
3, can be used for the fixing altogether of many bacterial classifications such as bacillus, micrococcus sp, Flavobacterium, Microbacterium, every kind of bacterial activity does not reduce.
4, immobilization particle is significantly strengthened the patience of environment: immobilization bacterium adapts to lower envrionment temperature, all can keep active preferably in 15 ℃ of-35 ℃ of scopes; Variation is inertia to immobilization bacterium to pH, and in the pH=5-8 scope, the activity of immobilization bacterium does not take place obviously to change; There is tangible tolerance in immobilization bacterium to heavy metal (Cu, P, Cr, Hg, As, concentration 0.1mmol/L) toxicity.
5, phenomenon is separated in the not autolyze of NaAlg in the immobilization particle, use 180 days proliferation regenerations continuously after, bacterial activity is recovered virgin state.
6, altogether fixation of bacteria to being that the polluted surface water of leading indicator has clear and definite repairing effect with COD, throwing grain than being under 72 hours the condition for 8%-10%, repair time, COD clearance minimum is 85.2%, is up to 94.7%, and average removal rate surpasses 90%.
Embodiment
Below by embodiment the present invention is described in further detail.
Embodiment 1
(1) mixed bacterium slant culture
At four beef peptone basic medium (0.3% extractum carniss, 1.0% peptone, 0.5%NaCl, 1.5-2.0% agar, pH=7.0-7.2) insert genus bacillus, micrococci, Flavobacterium and microbacterium in the test tube respectively, put in 28 ℃ of-30 ℃ of incubators and cultivated 2 days.
(2) mixed bacterium seed liquid preparation
On slant medium, access 2 ring lawns with transfering loop respectively, be linked into liquid seed culture medium (1.25% glucose, 0.25% yeast extract paste, 0.1%NH
4NO
3, 0.02%MgSO
47H
2O, 0.02%KCl, pH=7.0-7.2) in, under shaking speed 130rpm-140rpm, 28 ℃ of-30 ℃ of conditions, cultivated 16-20 hour; Nutrient solution is mixed, make mixed bacterium seed liquid.
(3) coagulant liquid configuration
According to total mass 200g, take by weighing 9.8%PVA powder, 0.45%NaAlg, 3.5% activity charcoal powder, 3.0% zeolite powder (0.074mm content is greater than 70%), 0.08% yeast extract paste, soaked into 18 hours with the 40g tap water.In 111 ℃ of following moist heat sterilization 30min, be cooled to 39 ℃.
(4) linking agent configuration
According to total mass 600g, take by weighing 8.85% ammonium pentaborate, be dissolved in 91.15% distilled water, regulate pH=5.8, make primary cross-linking agent.
According to total mass 600g, take by weighing 1.8%AlCl
3And 1.0%FeCl
3, be dissolved in 97.2% distilled water, regulate pH=2.2, make the secondary crosslinking agent.
(5) strengthening agent preparation
According to total mass 600g, take by weighing 7.9%Na
2SO
4The aqueous solution, the pH nature makes strengthening agent.
(6) immobilization particle preparation
Mass percent according to 20%, measure 40ml mixed bacterium seed liquid, mixed with the 200g coagulant liquid, stirred 5 minutes rapidly, the exit diameter of packing into is the glass pellet fabrication device of 3mm, by vacuum take-off control outlet drip speed is 24 droplets/minute, and gel particles splashes into primary cross-linking agent, after the end of granulating, continued crosslinked 14 hours, with particle transfer to the secondary crosslinking agent, crosslinked once more 11 hours, then with particle transfer to strengthening agent, reinforce reaction 20 hours, use aseptic water washing at last, soaked 24 hours, make immobilization particle.
The immobilization particle physical strength that makes through above-mentioned steps reaches 26.5Kg/cm
2
(7) multiplication culture
Immobilization particle is inserted proliferated culture medium (3.0% glucose, 0.4% yeast extract paste, 0.1% extractum carnis, 0.1%NH
4NO
3, 0.02%MgSO
47H
2O, 0.02%KCl, pH=7.0-7.2) in, under shaking speed 147rpm, 29.5 ℃ of conditions, cultivated 24 hours; Change proliferated culture medium then 2 times, repeat the multiplication culture step at every turn.
(8) surface water repairing effect
Immobilization particle is thrown grain than 9%, and natural flow condition was repaired 72 hours, and the COD clearance reaches 78.5%.
Embodiment 2
Difference from Example 1 is:
Join coagulant liquid when putting,, take by weighing 10.8%PVA powder, 0.52%NaAlg, 4.2% activity charcoal powder, 4.0% zeolite powder (0.074mm content is greater than 70%), 0.11% yeast extract paste, soaked into 20 hours with the 40g tap water according to total mass 200g.In 111 ℃ of following moist heat sterilization 25min, be cooled to 38 ℃.During the configuration linking agent,, take by weighing 9.25% ammonium pentaborate, be dissolved in 90.75% distilled water, regulate pH=6.4, make primary cross-linking agent according to total mass 600g.According to total mass 600g, take by weighing 2.6%AlCl
3And 1.3%FeCl
3, be dissolved in 96.1% distilled water, regulate pH=2.6, make the secondary crosslinking agent.During the preparation strengthening agent,, take by weighing 9.1%Na according to total mass 600g
2SO
4, make strengthening agent.During the preparation immobilization particle, be 26 droplets/minute by vacuum take-off control outlet drip speed, once crosslinked 12 hours, secondary crosslinking 17 hours was reinforced reaction 23 hours, and sterilized water soaked 23 hours, made immobilization particle.
The immobilization particle physical strength that makes through above-mentioned steps reaches 31.9Kg/cm
2
Immobilization particle is multiplication culture 24 hours (repeating 2 times) under shaking speed 149rpm, 28.5 ℃ of conditions, is used for the surface water reparation, and immobilization particle is thrown grain than 11%, and natural flow condition was repaired 72 hours, and the COD clearance reaches 86.5%.
Embodiment 3
Difference from Example 1 is:
Join coagulant liquid when putting,, take by weighing 10.3%PVA powder, 0.48%Na.Alg, 3.8% activity charcoal powder, 3.4% zeolite powder (0.074mm content is greater than 70%), 0.10% yeast extract paste, soaked into 22 hours with the 40g tap water according to total mass 200g.In 111 ℃ of following moist heat sterilization 28min, be cooled to 41 ℃.During the configuration linking agent,, take by weighing 9.05% ammonium pentaborate, be dissolved in 90.95% distilled water, regulate pH=6.0, make primary cross-linking agent according to total mass 600g.According to total mass 600g, take by weighing 2.0%AlCl
3And 1.1%FeCl
3, be dissolved in 96.9% distilled water, regulate pH=2.4, make the secondary crosslinking agent.During the preparation strengthening agent,, take by weighing 8.3%Na according to total mass 600g
2SO
4, make strengthening agent.During the preparation immobilization particle, be 29 droplets/minute by vacuum take-off control outlet drip speed, once crosslinked 15 hours, secondary crosslinking 13 hours was reinforced reaction 22 hours, and sterilized water soaked 22 hours, made immobilization particle.
The immobilization particle physical strength that makes through above-mentioned steps reaches 33.2Kg/cm
2
Immobilization particle is multiplication culture 24 hours (repeating 2 times) under shaking speed 150rpm, 30 ℃ of conditions, is used for the surface water reparation, and immobilization particle is thrown grain than 10%, and natural flow condition was repaired 72 hours, and the COD clearance reaches 87.1%.
Embodiment 4
Difference from Example 1 is:
Replace zeolite powder with 3.1% diatomite, make immobilization particle.
The immobilization particle physical strength that makes through above-mentioned steps reaches 32.6Kg/cm
2
Immobilization particle is multiplication culture 24 hours (repeating 2 times) under shaking speed 145rpm, 28 ℃ of conditions, is used for the surface water reparation, repairs 72 hours, and the COD clearance reaches 92.6%.
Embodiment 5
Difference from Example 1 is:
Replace yeast extract paste with 1.2% tween 80, make immobilization particle.
The immobilization particle physical strength that makes through above-mentioned steps reaches 27.2Kg/cm
2
Be used for the surface water reparation, the COD clearance reaches 82.6%.
Embodiment 6
Difference from Example 1 is:
Join coagulant liquid when putting,, take by weighing 10.5%PVA powder, 0.5%NaAlg, 4% activity charcoal powder, 4.1% zeolite powder (0.074mm content is greater than 70%), soaked into 22 hours with the 40g tap water according to total mass 200g.During the configuration linking agent,, take by weighing 9.12% ammonium pentaborate, be dissolved in 90.88% distilled water, regulate pH=6.2, make primary cross-linking agent according to total mass 600g.According to total mass 600g, take by weighing 2.1%AlCl
3And 1.2%FeCl
3, be dissolved in 96.7% distilled water, regulate pH=2.5, make the secondary crosslinking agent.During the preparation strengthening agent,, take by weighing 8.45%Na according to total mass 600g
2SO
4, make strengthening agent.During the preparation immobilization particle, be 22 droplets/minute by vacuum take-off control outlet drip speed, once crosslinked 16 hours, secondary crosslinking 10 hours was reinforced reaction 24 hours, makes immobilization particle.
The immobilization particle physical strength that makes through above-mentioned steps reaches 36.1Kg/cm
2
Immobilization particle is multiplication culture 24 hours (repeating 2 times) under shaking speed 152rpm, 28.2 ℃ of conditions, is used for the surface water reparation, and the COD clearance reaches 92.3%.
Claims (7)
1. one kind is used for the method for preparing immobilized particles that surface water is repaired, and it is characterized in that:
1) in the PVA-NaAlg coagulant liquid that is pre-mixed, adds gac, zeolite powder or diatomite, and interpolation yeast extract paste, their quality percentage composition is: polyvinyl alcohol 9.2%-12%, sodium alginate 0.3%-0.6%, activity charcoal powder 3%-5%, zeolite powder or diatomite 2%-5%, yeast extract paste 0.05%-0.14%, surplus is supplied with water;
2) add the bacterium seed liquor in coagulant liquid, mixing is granulated, and gel particles splashes in (the drip speed of dripping according to per minute 20-30) linking agent, through chemically crosslinked, then at the Na of mass concentration 7.5%-9.5%
2SO
4Reinforce in the fixing agent, with sterilized water water logging bubble, flushing makes immobilization particle;
Described chemically crosslinked is a secondary, and primary cross-linking agent is the ammonium pentaborate aqueous solution of mass concentration 8.55%-9.85%, pH=5.5-7.0; The secondary crosslinking agent is the AlCl of mass concentration 1.5%-3.2%
3And 0.8%-1.8%FeCl
3Mixed aqueous solution, pH=2.0-3.0.
2. according to the preparation method of the described immobilization particle of claim 1, it is characterized in that: the described chemically crosslinked time is 24-29 hour; In fixing agent, reinforced 20-24 hour.
3. according to the preparation method of the described immobilization particle of claim 1, it is characterized in that: immobilization particle mass concentration according to 25% under aseptic condition of preparation is joined in the proliferated culture medium, controlled temperature: 28-30 ℃, shaking speed: 145rpm-155rpm, incubation time: 24 hours, change substratum afterwards, cultivate for totally 3 times, standby.
4. according to the preparation method of the described immobilization particle of claim 3, it is characterized in that: described thalline is genus bacillus, micrococci, Flavobacterium and/or microbacterium; Proliferated culture medium is: 3.0% glucose, 0.4% yeast extract paste, 0.1% extractum carnis, 0.1%NH
4NO
3, 0.02%MgSO
47H
2O, 0.02%KCl, pH=7.0-7.2.
5. according to the preparation method of the described immobilization particle of claim 1, it is characterized in that: step 1) is added gac, zeolite powder or diatomite to being pre-mixed in the PVA-NaAlg coagulant liquid that soaks into 12-20h with tap water, yeast extract paste, the quality percentage composition of coagulant liquid is polyvinyl alcohol: 9.8%-11%, sodium alginate: 0.45%-0.55%, activity charcoal powder: 3.5%-4.5%, 0.074mm content is greater than 70% zeolite powder or diatomite: 3%-4.5%, yeast extract paste: 0.08%-0.12%, surplus is supplied with water; In 111 ℃ of following moist heat sterilization 30min, be cooled under the aseptic condition about 35 ℃-45 ℃ before using, standby;
Described chemically crosslinked is a secondary, the ammonium pentaborate aqueous solution of primary cross-linking agent: 8.85%-9.45%, pH=5.8-6.6; The AlCl of secondary crosslinking agent: 1.8%-3.0%
3And 1.0%-1.6%FeCl
3Mixed aqueous solution, pH=2.2-2.8; The fixing agent mass content is the Na of 7.9%-9.1%%
2SO
4
6. according to the preparation method of the described immobilization particle of claim 5, it is characterized in that: the quality percentage composition of coagulant liquid is polyvinyl alcohol: 10.3%-10.8%, sodium alginate: 0.48%-0.52%, activity charcoal powder: 3.8%-4.2%, 0.074mm content is greater than 70% zeolite powder: 3.4%-4.0%, yeast extract paste: 0.09%-0.11%, surplus is supplied with water:
Described chemically crosslinked is a secondary.The ammonium pentaborate aqueous solution of primary cross-linking agent: 9.05%-9.25%, pH=6.0-6.4; The AlCl of secondary crosslinking agent: 2.0%-2.6%
3And 1.1%-1.3%FeCl
3Mixed aqueous solution, pH=2.4-2.6; The fixing agent mass content is the Na of 8.3%-8.8%
2SO
4
7. according to the preparation method of the described immobilization particle of claim 5, it is characterized in that: the quality percentage composition of coagulant liquid is a polyvinyl alcohol: 10.5%, and sodium alginate: 0.5%, activity charcoal powder: 4%, 0.074mm content is greater than 70% zeolite powder: 4.1%, yeast extract paste: 0.1%;
Described chemically crosslinked is a secondary, a linking agent: 9.12% the ammonium pentaborate aqueous solution, pH=6.2; Secondary crosslinking agent: 2.1% AlCl
3And 1.2%FeCl
3Mixed aqueous solution, pH=2.5; The fixing agent mass content is 8.45% Na
2SO
4
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|---|---|---|---|
| CNB2004100503257A CN100451111C (en) | 2004-08-27 | 2004-08-27 | Process for producing fixed particle to repair surface water |
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|---|---|---|---|
| CNB2004100503257A CN100451111C (en) | 2004-08-27 | 2004-08-27 | Process for producing fixed particle to repair surface water |
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| CN100451111C CN100451111C (en) | 2009-01-14 |
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| WO2008040157A1 (en) * | 2006-09-28 | 2008-04-10 | Wuhan Probiotic Spring Biotechnology Co., Ltd. | One kind of artificial biomembrane and its preparation method |
| CN100443591C (en) * | 2006-07-25 | 2008-12-17 | 南开大学云南研究院 | Composite organic-inorganic material film as immobilized cell carrier |
| CN101177679B (en) * | 2006-11-08 | 2011-04-13 | 中国科学院沈阳应用生态研究所 | Preparation method of immobilization bacterium for restoring polycyclic aromatic hydrocarbons contaminated soil |
| CN101168736B (en) * | 2006-10-27 | 2011-08-03 | 中国科学院沈阳应用生态研究所 | Introduced bacterium microorganism immobilization method used for repairing soil and special-purpose device for the same |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3839136B2 (en) * | 1997-07-02 | 2006-11-01 | 独立行政法人科学技術振興機構 | Microorganism-immobilized magnetic carrier, production method thereof and wastewater treatment method |
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2004
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|---|---|---|---|---|
| CN100443591C (en) * | 2006-07-25 | 2008-12-17 | 南开大学云南研究院 | Composite organic-inorganic material film as immobilized cell carrier |
| WO2008040157A1 (en) * | 2006-09-28 | 2008-04-10 | Wuhan Probiotic Spring Biotechnology Co., Ltd. | One kind of artificial biomembrane and its preparation method |
| US8586342B2 (en) * | 2006-09-28 | 2013-11-19 | Wuhan Probiotic Spring Biotechnology Co., Ltd. | Artificial biomembrane and the method for manufacturing the same |
| CN101168736B (en) * | 2006-10-27 | 2011-08-03 | 中国科学院沈阳应用生态研究所 | Introduced bacterium microorganism immobilization method used for repairing soil and special-purpose device for the same |
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| CN106635855A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Microbacterium kitamiense and culture application thereof |
| CN107235620A (en) * | 2017-05-22 | 2017-10-10 | 安徽省通源环境节能股份有限公司 | A kind of long-acting comprehensive sediment repairing agent and preparation method thereof |
| CN111471673A (en) * | 2019-12-26 | 2020-07-31 | 沈阳药科大学 | Immobilized carrier and preparation method and application thereof |
| CN111484135A (en) * | 2020-05-06 | 2020-08-04 | 北京工业大学 | Preparation and application of efficient anaerobic ammonium oxidation composite bacteria embedded bioactive filler |
| CN111484134A (en) * | 2020-05-06 | 2020-08-04 | 北京工业大学 | Preparation and application of denitrification embedded biological annular active filler |
| CN111484134B (en) * | 2020-05-06 | 2022-03-22 | 北京工业大学 | Preparation and application of denitrification embedded biological annular active filler |
| CN111484135B (en) * | 2020-05-06 | 2022-03-22 | 北京工业大学 | Preparation and application of efficient anaerobic ammonium oxidation composite bacteria embedded bioactive filler |
| CN112725327A (en) * | 2021-02-26 | 2021-04-30 | 华东理工大学 | Preparation method and application of cell immobilization carrier |
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