CN104004745A - Immobilized microorganism oil-spilling repairing agent and preparation method - Google Patents
Immobilized microorganism oil-spilling repairing agent and preparation method Download PDFInfo
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- CN104004745A CN104004745A CN201410190244.0A CN201410190244A CN104004745A CN 104004745 A CN104004745 A CN 104004745A CN 201410190244 A CN201410190244 A CN 201410190244A CN 104004745 A CN104004745 A CN 104004745A
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Abstract
The invention discloses an immobilized microorganism oil-spilling repairing agent. The immobilized microorganism oil-spilling repairing agent has an embedded microorganism concentration of 5*10<7> to 2*10<8> cell/g, and has carrier ingredients of mussel shell, sodium alginate and CaCl2. The immobilized microorganism oil-spilling repairing agent has a petroleum hydrocarbon degradation rate of 82-94% under the conditions of salinity of 5-55 parts per thousand, a temperature of 10-30 DEG C and a pH value of 6.5-9.0. Compared with free microorganisms, the immobilized microorganism oil-spilling repairing agent has a degradation rate improved by 39-47% and has improved environmental tolerance.
Description
Technical field
The present invention relates to the bioremediation technology that a kind of petroleum products pollutes.
Background technology
Along with the development of offshore oil development and sea transport industry, the oil spill accident causing due to the Oil spills of blowout, ships that transport, leakage of knocking ship and oil pipeline to sinking etc. takes place frequently.After oil spill accident occurs, though through physical method (as fence recovery etc.), chemical process (spraying oil spill dispersant etc.) can be removed part surface oil spilling, but remaining petroleum hydrocarbon prolonged stay is in ocean environment, can cause huge persistence infringement (Pelletier E to Marine ecosystems and HUMAN HEALTH, Delille D, Delille B.Crude oil bioremediation in sub-Antarctic intertidal sediments:chemistry and toxicity of oiled residues[J] .Mar.Environ.Res., 2004, 57 (4): 311-327.).
The bioremediation technology of at present petroleum pollution mainly taking microorganism reparation as main (Zhang Ying, etc. the Pollution control technology [J] of marine oil overflow for Xia Wenxiang, vast stretch of wooded country great waves. Qingdao College of Architectural Engineering journal, 2004,25 (1): 54-57.).Investigator finds that growth has more than 200 kind of hydro carbons degrading microorganism in seawater and fresh water both at home and abroad, comprise bacterium, fungi and algae, closely related (Fingas M.The Basic of Oil Spill Clean up (2nd edition) [M] the .USA:Lewis Publishers of oil pollution degree in its density and reproduction speed and waters, 2001,39-50.).Microbial treatment technology is the efficient remedying oil-polluted new technology of generally acknowledging in the world, can adapt to the ecotope of various complexity based on microorganism, its breeding metabolic capacity is extremely strong, various toxic substances in energy fast degradation oil, and there is many advantages (the Harayama S such as cheap, environmental friendliness, Kasai Y, Hara A.Microbial communities in oil-contaminated seawater[J] .Curr.Opin.Biotechnol., 2004,15 (3): 205-214.).The oil spilling that adopts this technical finesse physics and chemistry method to remove is the optimal path of Revegetation of Eco-environment, and to protection China marine eco-environment, the sustainable development that maintains oceanic resources has great scientific meaning and using value.
From the seventies in last century, add suitable microbial treatment petroleum pollution be just considered to a strong strategy (Atlas R M.Petroleum biodegradation and oil spill bioremediation[J] .Mar.Pollut.Bull., 1995, 31 (4-12): 178-182.), in the wild in test successfully example as: nineteen ninety utilizes Alpha BioSea to process the crude oil leakage of Texas seashore, within 2000, utilize Terra-zyme (TM) to process Japanese Nakhodka harbour crude oil leakage (Maki H, Hirayama N, Hiwatari T, et al.Crude oil bioremediation field experiment in the sea of Japan[J] .Mar.Pollut.Bull., 2003, 47 (1-6): 74-77.), summer to 1991 in 1989 year application add nutrition agent and efficient alkane degradation bacterium to Exxon prince Valdez bay, Alaska because oil tanker is revealed processing that the pollution that causes carries out etc., obtain very significantly effect (Atlad R M.Bioremediation of Petroleum Pollutants [J] .Int.Biodeter.Biodegrad., 1995, 35 (3): 317-327.).
But in marine oil spill microorganism repair process, but existing effective strain runs off serious, remediation efficiency significantly descends degradation problem (De-Bashan L E, Bashan Y.Immobilized microalgae for removing pollutants:Review of practical aspects[J] .Bioresour.Technol., 2010,101 (6): 1611-1627.).So, repair peculiar processing environment for marine oil spill, this patent adopts microbial immobilized technology.Immobilized microorganism technique is compared with other bioremediation technology, can keep microorganism high-density, high reactivity, alleviate or eliminate the loss of microorganism, processing efficiency is high, tolerance to environment is strong, easy control of reaction system, can effectively improve remediation efficiency (the Takeno K that inland sea, target area is permeated with oil pollution microbiobacterial agent, Yamaoka Y, Sasaki K.Treatment of oil-containing sewage wastewater using immobilized photosynthetic bacteria[J] .World J.Microbiol.Biotechnol., 2005, 21 (8-9): 1385-1391.).
Embedded immobilization technology is as the one of process for fixation, compared with other immobilization technologies such as absorption method, crosslinking, covalent coupling method, because preparation method is simple to operation, reaction conditions is gentle easily to be realized, microorganism is difficult for leaking, stability and reusing are good, and there are higher microorganism active and cell-volume (Bao Mutai, Gong Yuanjiao, Li Yiming. the effect [J] of immobilized microorganism in degraded oily(waste)water. Wuhan University Journal (Edition), 2010,56 (1): 109-144.).Sodium alginate-CaCl
2embedding and polyvinyl alcohol-H
3bO
3embedding is the most frequently used embedding immobilization method (Massalha N, Basheer S, Sabbah I.Effect of adsorption and bead size of immobilized biomass on the rate of biodegradation of phenol at high concentration levels[J] .Ind.Eng.Chem.Res., 2007,46 (21): 6820-6824.).With respect to sodium alginate-CaCl2 entrapping method, polyvinyl alcohol-H
3bO
3though the immobilization preparation physical strength of preparation is higher, work-ing life is longer, but polyvinyl alcohol is because of comparatively difficulty of the strong balling-up of nodulizing, and the saturated boric acid solution for cross-linking polyvinyl alcohol is large to the murder by poisoning of microorganism, can significantly be reduced in microbic activity after immobilization.Sodium alginate-CaCl
2though entrapping method reaction conditions gentleness, embedded material is to no toxic biological, and the cell of embedding has higher activity, and pharmaceutical machine intensity is lower, mass transfer performances is poor.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing defect, provides a kind of lifeless matter to poison, solidify the rear immobilized microorganism oil spilling renovation agent that microorganism active is high, physical strength is high, mass transfer performances is good;
Another object of the present invention is to provide the preparation method of above-mentioned immobilized microorganism oil spilling renovation agent.
Object of the present invention is carried out specific implementation by the following technical programs:
A kind of immobilized microorganism oil spilling renovation agent, in described immobilized microorganism oil spilling renovation agent, the microorganism concn of embedding is 5 × 10
7～2 × 10
8cell/g, its carrier component comprises mussel shell, sodium alginate, CaCl
2.
As preferred version, above-mentioned immobilized microorganism oil spilling renovation agent, the per-cent that each carrier component accounts for immobilized microorganism oil spilling renovation agent is: mussel shell 1.2wt%, sodium alginate 6wt%, CaCl
20.3-0.8wt%, all the other are water.
The preparation method of above-mentioned immobilized microorganism oil spilling renovation agent, with sodium alginate-CaCl
2-modification mussel shell carries out embedding as carrier, and concrete steps are:
1) mussel shell modification;
2) by mussel shell after appropriate modification with plant daughter bacteria liquid by 1:(2～5) mass ratio mixes and adsorbs, until adsorb saturatedly, obtains adsorbing the modification mussel shell of bacterium;
3) to step 2) in add sodium alginate soln in the modification mussel shell of the absorption bacterium that obtains, after mixing, be injected into CaCl with balling-up equipment
2in solution, disperse balling-up, crosslinked 6～18h, being fixed microbe microsphere.
Preferably, described step 1) in, mussel shell modification step is as follows:
A, raw material mussel shell cleaning, sieve are chosen, be dried, are pulverized, mistake 40～80 mesh sieves, for subsequent use;
B, take the mussel shell crushing in step a, join the citric acid solution that concentration is 2～5wt%, stirring and evenly mixing, at room temperature floods approximately 1.0～2.0h by the feed liquid mixing, and wherein, the mass ratio of mussel shell and citric acid solution is 1:(1～3);
C, the feed liquid of having flooded is put into muffle furnace activate, take out cooling;
D, the sample after the activation making was pulverized to 120～150 mesh sieves, obtained modification mussel shell.
It is further preferred,
In described step b, citric acid solution concentration is 2.5wt%; The mass ratio of mussel shell and citric acid solution is 1:2;
Activation temperature in described step c is 300～600 DEG C, and the temperature rise rate that rises to required activation temperature from room temperature is 40～60 DEG C/min, insulation 15～30min.; Preferably activation condition is: activation temperature is 550 DEG C, and temperature rise rate is 50 DEG C/min, insulation 30min.
Preferably, described kind of daughter bacteria liquid is using Brevibacillus brevis D-1 as petroleum hydrocarbon degradation bacterium, and seed bacterial concentration is (5～8) × 10
9cell/g, wherein, seed bacterial concentration the best is 6 × 10
9cell/g.
Preferably, the concentration of described use sodium alginate is 4wt%～8wt%, and optimum concn is 6wt%; CaCl
2strength of solution is 2.5wt%～3.5wt%, and optimum concn is 3wt%.
Preferably, described step 3) in, modification mussel shell: the mass ratio of sodium alginate is 1.2:6.When injection, sodium alginate and mussel shell carrier are injected in calcium chloride solution with spherical, and calcium chloride slowly enters microballoon, and are fixed in microballoon after forming alginate calcium with sodium alginate.
Described step 3) in normal saline flushing 2～4 times for the immobilized microorganism microballoon that obtains, be finished product.
The microorganism concn of the immobilized microorganism oil spilling renovation agent embedding making is after tested 5 × 10
7～2 × 10
8cell/g, is 5～55 ‰ in salinity, and temperature is 10～30 DEG C, in the environment that pH is 6.5～9.0, can reach 82～94% to the degradation rate of petroleum hydrocarbon, and with free microbial ratio, its degradation rate improves 39%～47%, and the tolerance of environment is strengthened.
The immobilized microorganism microballoon below the present invention being made and other immobilized microorganism microballoon and common inorganic active carbon that does not add modification mussel shell compare, and comparative result is as shown in the table:
The Performance Ratio of the different immobilized microorganism microballoons of table 1 is (petroleum hydrocarbon concentration 3g/L)
As can be drawn from Table 1, the immobilized microorganism microballoon of interpolation modification mussel shell of the present invention improves a lot on physical strength and mass-transfer performance, and the cell of embedding has higher activity, can reach 94% to the degradation rate of 3g/L petroleum hydrocarbon.
Beneficial effect of the present invention:
Immobilized microorganism oil spilling renovation agent of the present invention is added into modification mussel shell in sodium alginate-calcium chloride entrapped immobilized carrier first, improve the physical strength of preparation, and due to the vesicular structure of modification mussel shell, can greatly improve its mass transfer performances, make nutritive substance more easily by microorganism panning, improved greatly microbic activity and degradation efficiency.Modification mussel shell is compared with general sorbent material-activated carbon, and raw material sources are more extensive, and price is more cheap, and makes the performance of immobilized microorganism more excellent, and discarded mussel shell recycling, has solved environmental problem and has also realized discarded mussel shell resource utilization.
The preparation method of the immobilized microorganism oil spilling renovation agent of the present invention taking sodium alginate-calcium chloride-modification mussel shell as embedded immobilization material, improve physical strength and the mass transfer performances of preparation by mussel shell after interpolation modification, have the advantages that technique is simple, material cost is low, and reaction conditions gentleness, the renovation agent microorganism making is difficult for leaking, stability and reusing are good, and have higher microorganism active and cell-volume, can reach 82～94% to the degradation rate of petroleum hydrocarbon.
Brief description of the drawings
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, for explaining the present invention, is not construed as limiting the invention together with embodiments of the present invention.In the accompanying drawings:
Fig. 1 is the outward appearance photo (diameter 3-5mm) of embedded immobilization microbial microballoon of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
Embodiment 1:
A preparation method for immobilized microorganism oil spilling renovation agent taking sodium alginate-calcium chloride-modification mussel shell as embedded immobilization material, concrete steps are:
1, the preparation of modification mussel shell
1) cleaning of raw material mussel shell, sieve are chosen, are dried, are pulverized, cross 80 mesh sieves, for subsequent use;
2) take the above-mentioned mussel shell crushing, join massfraction and be 2.5% citric acid solution, wherein, the mass ratio of mussel shell and citric acid solution is 1:2, and the feed liquid mixing is at room temperature flooded about 1.5h by stirring and evenly mixing;
3) feed liquid of having flooded is put into high temperature muffle furnace, rise to 550 DEG C of required activation temperatures from room temperature, temperature rise rate is 50 DEG C/min, insulation 30min.
4) sample having activated is taken out from muffle furnace, cooling;
5) sample after the activation making was pulverized to 140 mesh sieves, made modification mussel shell.
2, the petroleum hydrocarbon degradation bacterium adopting
The petroleum hydrocarbon degradation bacterium that embedding is used is the bacterial classification Brevibacillus brevis D-1 filtering out from certain Oceanic Samples, be 25-35 ‰ in salinity, temperature is 15-25 DEG C, in the environment that pH is 7.5-8.5, can reach 35-55% to the degradation rate of crude oil (concentration 1-5g/L).
3, embedding
1) by modification mussel shell with plant daughter bacteria liquid mass ratio 1:3 and mix and adsorb, until adsorb saturatedly, the modification mussel shell of bacterium is adsorbed in preparation;
2) add sterilized sodium alginate soln (sodium alginate concentration is 6wt%) toward the modification mussel shell of above-mentioned absorption bacterium, wherein, modification mussel shell: the mass ratio of sodium alginate is 1.2:6, after mixing, is injected into CaCl with balling-up equipment
2in solution (concentration is 3wt%), disperse balling-up, crosslinked 16h, being fixed microbe microsphere, the mass percent concentration of the shared immobilized microspheres of modification mussel shell is 1.3%;
3) by the immobilized microorganism microballoon obtaining normal saline flushing 2～4 times, be finished product, shape is shown in Fig. 1;
4) finally the immobilized microorganism oil spilling renovation agent making is saved backup under the condition of 0～4 DEG C.
The microorganism concn of the immobilized microorganism oil spilling renovation agent embedding making is after tested 2 × 10
8cell/g, is 5～55 ‰ in salinity, and temperature is 10～30 DEG C, and the degradation rate to petroleum hydrocarbon in the environment that pH is 6.5～9.0 reaches 94%.
Embodiment 2:
A preparation method for immobilized microorganism oil spilling renovation agent taking sodium alginate-calcium chloride-modification mussel shell as embedded immobilization material, concrete steps are:
1, the preparation of modification mussel shell
1) cleaning of raw material mussel shell, sieve are chosen, are dried, are pulverized, cross 40 mesh sieves, for subsequent use;
2) take the above-mentioned mussel shell crushing, join massfraction and be 5% citric acid solution, wherein, the mass ratio of mussel shell and citric acid solution is 1:1, and the feed liquid mixing is at room temperature flooded about 2.0h by stirring and evenly mixing;
3) feed liquid of having flooded is put into high temperature muffle furnace, rise to 300 DEG C of required activation temperatures from room temperature, temperature rise rate is 60 DEG C/min, insulation 30min.
4) sample having activated is taken out from muffle furnace, cooling;
5) sample after the activation making was pulverized to 150 mesh sieves, made modification mussel shell.
2, the petroleum hydrocarbon degradation bacterium adopting
The petroleum hydrocarbon degradation bacterium that embedding is used is the bacterial classification Brevibacillus brevis D-1 filtering out from certain Oceanic Samples, be 25-35 ‰ in salinity, temperature is 15-25 DEG C, in the environment that pH is 7.5-8.5, can reach 35-55% to the degradation rate of crude oil (concentration 1-5g/L).
3, embedding
1) by appropriate modification mussel shell with plant daughter bacteria liquid mass ratio 1:5 and mix and adsorb, until adsorb saturatedly, the modification mussel shell of bacterium is adsorbed in preparation;
2) add sterilized sodium alginate soln (sodium alginate concentration is 8wt%) toward the modification mussel shell of above-mentioned absorption bacterium, wherein, modification mussel shell: the mass ratio of sodium alginate is 1.2:6, after mixing, is injected into CaCl with balling-up equipment
2in solution (concentration is 2.5wt%), disperse balling-up, crosslinked 6h, being fixed microbe microsphere, the mass percent concentration of the shared immobilized microspheres of modification mussel shell is 0.8%;
3) by the immobilized microorganism microballoon obtaining normal saline flushing 2～4 times, be finished product;
4) finally the immobilized microorganism oil spilling renovation agent making is saved backup under the condition of 0～4 DEG C.
The microorganism concn of the immobilized microorganism oil spilling renovation agent embedding making is after tested 1 × 10
8cell/g, is 5～55 ‰ in salinity, and temperature is 10～30 DEG C, and the degradation rate to petroleum hydrocarbon in the environment that pH is 6.5～9.0 reaches 89.8%.
Embodiment 3:
A preparation method for immobilized microorganism oil spilling renovation agent taking sodium alginate-calcium chloride-modification mussel shell as embedded immobilization material, concrete steps are:
1, the preparation of modification mussel shell
1) cleaning of raw material mussel shell, sieve are chosen, are dried, are pulverized, cross 80 mesh sieves, for subsequent use;
2) take the above-mentioned mussel shell crushing, join massfraction and be 2% citric acid solution, wherein, the mass ratio of mussel shell and citric acid solution is 1:3, and the feed liquid mixing is at room temperature flooded about 1.0h by stirring and evenly mixing;
3) feed liquid of having flooded is put into high temperature muffle furnace, rise to 600 DEG C of required activation temperatures from room temperature, temperature rise rate is 50 DEG C/min, insulation 15min.
4) sample having activated is taken out from muffle furnace, cooling;
5) sample after the activation making was pulverized to 120-150 mesh sieve, made modification mussel shell.
2, the petroleum hydrocarbon degradation bacterium adopting
The petroleum hydrocarbon degradation bacterium that embedding is used is the bacterial classification Brevibacillus brevis D-1 filtering out from certain Oceanic Samples, be 25-35 ‰ in salinity, temperature is 15-25 DEG C, in the environment that pH is 7.5-8.5, can reach 35-55% to the degradation rate of crude oil (concentration 1-5g/L).
3, embedding
1) by appropriate modification mussel shell with plant daughter bacteria liquid mass ratio 1:3 and mix and adsorb, until adsorb saturatedly, the modification mussel shell of bacterium is adsorbed in preparation;
2) add sterilized sodium alginate soln (sodium alginate concentration is 4wt%) toward the modification mussel shell of above-mentioned absorption bacterium, wherein, modification mussel shell: the mass ratio of sodium alginate is 1.2:6, after mixing, is injected into CaCl with balling-up equipment
2in solution (concentration is 3wt%), disperse balling-up, crosslinked 18h, being fixed microbe microsphere, the mass percent concentration of the shared immobilized microspheres of modification mussel shell is 1.6%;
3) by the immobilized microorganism microballoon obtaining normal saline flushing 2～4 times, be finished product;
4) finally the immobilized microorganism oil spilling renovation agent making is saved backup under the condition of 0～4 DEG C.
The microorganism concn of the immobilized microorganism oil spilling renovation agent embedding making is after tested 9.7 × 10
7cell/g, is 5～55 ‰ in salinity, and temperature is 10～30 DEG C, and the degradation rate to petroleum hydrocarbon in the environment that pH is 6.5～9.0 reaches 93.4%.
Embodiment 4:
A preparation method for immobilized microorganism oil spilling renovation agent taking sodium alginate-calcium chloride-modification mussel shell as embedded immobilization material, concrete steps are:
1, the preparation of modification mussel shell
1) cleaning of raw material mussel shell, sieve are chosen, are dried, are pulverized, cross 80 mesh sieves, for subsequent use;
2) take the above-mentioned mussel shell crushing, join massfraction and be 2% citric acid solution, wherein, the mass ratio of mussel shell and citric acid solution is 1:2.5, and the feed liquid mixing is at room temperature flooded about 2.0h by stirring and evenly mixing;
3) feed liquid of having flooded is put into high temperature muffle furnace, rise to 600 DEG C of required activation temperatures from room temperature, temperature rise rate is 50 DEG C/min, insulation 30min.
4) sample having activated is taken out from muffle furnace, cooling;
5) sample after the activation making was pulverized to 150 mesh sieves, made modification mussel shell.
2, the petroleum hydrocarbon degradation bacterium adopting
The petroleum hydrocarbon degradation bacterium that embedding is used is the bacterial classification Brevibacillus brevis D-1 filtering out from certain Oceanic Samples, be 25-35 ‰ in salinity, temperature is 15-25 DEG C, in the environment that pH is 7.5-8.5, can reach 35-55% to the degradation rate of crude oil (concentration 1-5g/L).
3, embedding
1) by appropriate modification mussel shell with plant daughter bacteria liquid mass ratio 1:5 and mix and adsorb, until adsorb saturatedly, the modification mussel shell of bacterium is adsorbed in preparation;
2) add sterilized sodium alginate soln (sodium alginate concentration is 5.5wt%) toward the modification mussel shell of above-mentioned absorption bacterium, wherein, modification mussel shell: the mass ratio of sodium alginate is 1.2:6, after mixing, is injected into CaCl with balling-up equipment
2in solution (concentration is 3.5wt%), disperse balling-up, crosslinked 10h, being fixed microbe microsphere, the mass percent concentration of the shared immobilized microspheres of modification mussel shell is 1.4%;
3) by the immobilized microorganism microballoon obtaining normal saline flushing 2～4 times, be finished product;
4) finally the immobilized microorganism oil spilling renovation agent making is saved backup under the condition of 0～4 DEG C.
The microorganism concn of the immobilized microorganism oil spilling renovation agent embedding making is after tested 9.2 × 10
7cell/g, is 5～55 ‰ in salinity, and temperature is 10～30 DEG C, and the degradation rate to petroleum hydrocarbon in the environment that pH is 6.5～9.0 reaches 92.8%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an immobilized microorganism oil spilling renovation agent, is characterized in that: in described immobilized microorganism oil spilling renovation agent, the microorganism concn of embedding is 5 × 10
7～2 × 10
8cell/g, its carrier component comprises mussel shell, sodium alginate, CaCl
2.
2. immobilized microorganism oil spilling renovation agent according to claim 1, is characterized in that: the per-cent that each carrier component accounts for immobilized microorganism oil spilling renovation agent is: mussel shell 1.2wt%, sodium alginate 6wt%, CaCl
20.3-0.8wt%, all the other are water.
3. a preparation method for immobilized microorganism oil spilling renovation agent, is characterized in that: with sodium alginate-CaCl
2-modification mussel shell carries out embedding as carrier, and concrete steps are:
1) mussel shell modification;
2) by mussel shell after appropriate modification with plant daughter bacteria liquid by 1:(2～5) mass ratio mixes and adsorbs, until adsorb saturatedly, obtains adsorbing the modification mussel shell of bacterium;
3) to step 2) in add sodium alginate soln in the modification mussel shell of the absorption bacterium that obtains, after mixing, be injected into CaCl with balling-up equipment
2in solution, disperse balling-up, crosslinked 6～18h, being fixed microbe microsphere.
4. the preparation method of immobilized microorganism oil spilling renovation agent according to claim 3, is characterized in that: described step 1) in, mussel shell modification step is as follows:
A, raw material mussel shell cleaning, sieve are chosen, be dried, are pulverized, mistake 40～80 mesh sieves, for subsequent use;
B, take the mussel shell crushing in step a, join the citric acid solution that concentration is 2～5wt%, stirring and evenly mixing, at room temperature floods approximately 1.0～2.0h by the feed liquid mixing, and wherein, the mass ratio of mussel shell and citric acid solution is 1:(1～3);
C, the feed liquid of having flooded is put into muffle furnace activate, take out cooling;
D, the sample after the activation making was pulverized to 120～150 mesh sieves, obtained modification mussel shell.
5. the preparation method of immobilized microorganism oil spilling renovation agent according to claim 4, is characterized in that: in described step b, citric acid solution concentration is 2.5wt%; The mass ratio of mussel shell and citric acid solution is 1:2.
6. the preparation method of immobilized microorganism oil spilling renovation agent according to claim 4, it is characterized in that: the activation temperature in described step c is 300～600 DEG C, the temperature rise rate that rises to required activation temperature from room temperature is 40～60 DEG C/min, insulation 15～30min; Preferably activation condition is: activation temperature is 550 DEG C, and temperature rise rate is 50 DEG C/min, insulation 30min.
7. the preparation method of immobilized microorganism oil spilling renovation agent according to claim 3, is characterized in that: described kind of daughter bacteria liquid is using Brevibacillus brevis D-1 as petroleum hydrocarbon degradation bacterium, and seed bacterial concentration is (5～8) × 10
9cell/g, wherein, seed bacterial concentration is preferably 6 × 10
9cell/g.
8. the preparation method of immobilized microorganism oil spilling renovation agent according to claim 3, is characterized in that: the concentration of described use sodium alginate is 4wt%～8wt%, and preferred concentration is 6wt%; CaCl
2strength of solution is 2.5wt%～3.5wt%, and preferred concentration is 3wt%.
9. the preparation method of immobilized microorganism oil spilling renovation agent according to claim 3, is characterized in that: described step 3) in, modification mussel shell: the mass ratio of sodium alginate is 1.2:6.
10. the preparation method of immobilized microorganism oil spilling renovation agent according to claim 3, is characterized in that: described step 3) in normal saline flushing 2～4 times for the immobilized microorganism microballoon that obtains, be finished product.
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| CN104841388A (en) * | 2015-04-13 | 2015-08-19 | 浙江海洋学院 | Preparation method for resin adsorbent compounded with mussel shell powder |
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| CN106520750A (en) * | 2016-12-08 | 2017-03-22 | 浙江海洋大学 | Immobilized microbial repairing agent for spilled oil and preparation method thereof |
| CN107583618A (en) * | 2017-09-27 | 2018-01-16 | 浙江海洋大学 | A kind of sodium alginate/mussel shell powder microballoon and application thereof |
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| CN110484528A (en) * | 2019-08-27 | 2019-11-22 | 浙江海洋大学 | Utilize the method for Immobilized hyphae combined treatment oily wastewater |
| CN110484528B (en) * | 2019-08-27 | 2021-03-30 | 浙江海洋大学 | Method for treating oily sewage by utilizing immobilized bacteria and algae combination |
| EP3789351A1 (en) * | 2019-09-04 | 2021-03-10 | Wen-Lung Chin | Water deodorizer and method for making it |
| CN110656103A (en) * | 2019-09-17 | 2020-01-07 | 中国石油天然气股份有限公司 | Composite immobilization carrier for improving microorganism immobilization efficiency and preparation method and application thereof |
| CN110980960A (en) * | 2019-11-26 | 2020-04-10 | 浙江永续环境工程有限公司 | Oil-removing microbial inoculum and sludge treatment technology using same |
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