CN103923903B - The preparation method of a kind of immobilized microorganism oil spilling renovation agent - Google Patents
The preparation method of a kind of immobilized microorganism oil spilling renovation agent Download PDFInfo
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- CN103923903B CN103923903B CN201310016703.9A CN201310016703A CN103923903B CN 103923903 B CN103923903 B CN 103923903B CN 201310016703 A CN201310016703 A CN 201310016703A CN 103923903 B CN103923903 B CN 103923903B
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- arachidis hypogaeae
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- 244000005700 microbiome Species 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000009418 renovation Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 86
- 241000894006 Bacteria Species 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 9
- 239000000661 sodium alginate Substances 0.000 claims abstract description 9
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 9
- 239000001110 calcium chloride Substances 0.000 claims abstract description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000011010 flushing procedure Methods 0.000 claims abstract description 6
- 239000004005 microsphere Substances 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 230000001954 sterilising effect Effects 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 230000004913 activation Effects 0.000 claims description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 19
- 238000006731 degradation reaction Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
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- 235000017060 Arachis glabrata Nutrition 0.000 abstract description 6
- 241001553178 Arachis glabrata Species 0.000 abstract description 6
- 235000010777 Arachis hypogaea Nutrition 0.000 abstract description 6
- 235000018262 Arachis monticola Nutrition 0.000 abstract description 6
- 235000020232 peanut Nutrition 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 23
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- 239000011159 matrix material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005067 remediation Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
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- 239000003305 oil spill Substances 0.000 description 5
- 241000193764 Brevibacillus brevis Species 0.000 description 4
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- 230000007613 environmental effect Effects 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The preparation method of a kind of immobilized microorganism oil spilling renovation agent, it is characterised in that step is: prepare Pericarppium arachidis hypogaeae based activated carbon; Pericarppium arachidis hypogaeae based activated carbon is mixed with seed bacterium liquid and carries out adsorbing until adsorb saturated, form bacteria suspension; In above-mentioned bacteria suspension, add the sodium alginate soln of the sterilizing of 30��40 DEG C, after mixed even, it is injected into certain density CaCl with syringe2Solution Dispersion balling-up, and crosslinked 12h��24h, being fixed microbe microsphere; Finally by the immobilized microorganism microballoon normal saline flushing that obtains 2��4 times, it is finished product. Bio-based activated carbon-modified peanut is added in sodium alginate-calcium chloride entrapped immobilized carrier by the present invention first, it is to increase the physical strength of preparation and mass transfer performances, it is to increase microbic activity and degradation efficiency; Cost is low simultaneously, technique is simple to operation, and reaction conditions is gentle, and obtained renovation agent microorganism is not easily leaked, and stability and reusing are good, and have higher microorganism active and cell-volume, and the degradation rate of petroleum hydrocarbon can be reached 75-92%.
Description
Technical field
The invention belongs to oil and the technical field of biological remediation of petroleum products pollution, relate to the preparation method of a kind of immobilized microorganism oil spilling renovation agent, a specifically preparation method for immobilized microorganism oil spilling renovation agent by embedded immobilization material of sodium alginate-calcium chloride-Pericarppium arachidis hypogaeae matrix activated carbon, for the microorganism remediation of oil and petroleum products Marine Pollution.
Background technology
Along with the development of offshore oil development and sea transport industry, due to blowout, ships that transport Oil spills, knock ship to sinking and oil spill accident that the leakage etc. of oil pipeline causes takes place frequently. after oil spill accident occurs, though through physical method (such as fence recovery etc.), chemical process (sprays oil spill dispersant etc.) can remove part surface oil spilling, but remaining petroleum hydrocarbon prolonged stay is in ocean environment, Marine ecosystems and HUMAN HEALTH can be caused huge persistence infringement (PelletierE, DelilleD, DelilleB.Crudeoilbioremediationinsub-Antarcticintertidal sediments:chemistryandtoxicityofoiledresidues [J] .Mar.Environ.Res., 2004, 57 (4): 311-327.).
The bioremediation technology of current petroleum pollution mainly based on microorganism remediation (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.).Domestic and international investigator finds that growth has 200 hydrocarbons class degrading microorganisms in seawater and fresh water, comprise bacterium, fungi and algae, closely related (FingasM.TheBasicofOilSpillCleanup (2ndedition) [M] .USA:LewisPublishers of the oil pollution degree in its density and reproduction speed and waters, 2001,39-50.). Microbial treatment technology is the efficiently remedying oil-polluted new technology generally acknowledged in the world, the ecotope of various complexity can be adapted to based on microorganism, its breeding metabolic capacity is extremely strong, various toxic substance in the quick degraded oil of energy, and there is many advantages (HarayamaS such as cheap, environmental friendliness, KasaiY, HaraA.Microbialcommunitiesinoil-contaminatedseawater [J] .Curr.Opin.Biotechnol., 2004,15 (3): 205-214.). The oil spilling adopting 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 maintaining oceanic resources has great scientific meaning and using value.
From the seventies in last century, add suitable microbial treatment petroleum pollution and just it is considered as strong strategy (AtlasRM.Petroleumbiodegradationandoilspillbioremediation [J] .Mar.Pollut.Bull., 1995, 31 (4-12): 178-182.), in the wild in test successfully example as: nineteen ninety utilizes AlphaBioSea to process the crude oil leakage of Texas seashore, within 2000, utilize Terra-zyme (TM) process Japan Nakhodka harbour crude oil leakage (MakiH, HirayamaN, HiwatariT, etal.CrudeoilbioremediationfieldexperimentintheseaofJapa n [J] .Mar.Pollut.Bull., 2003, 47 (1-6): 74-77.), summer in 1989 adds, to application in 1991, the process etc. that the pollution that prince ExxonValdez bay, Alaska reveals to cause carries out by nutrition agent and efficient surfactant hydrocarbon degradation bacteria due to oil tanker, achieve obviously effect (AtladRM.BioremediationofPetroleumPollutants [J] .Int.Biodeter.Biodegrad., 1995, 35 (3): 317-327.).
But in marine oil spill microorganism remediation process, but there is effective strain runs off serious, remediation efficiency is the problem (De-BashanLE such as decline significantly, BashanY.Immobilizedmicroalgaeforremovingpollutants:Revie wofpracticalaspects [J] .Bioresour.Technol., 2010,101 (6): 1611-1627.). so, repair specific processing environment for marine oil spill, this patent adopts immobilized microorganism technology. immobilized microorganism technique is compared with other bioremediation technology, microorganism high-density can be kept, high reactivity, alleviate or eliminate the loss of microorganism, processing efficiency height, the tolerance of environment is strong, easy control of reaction system, can effectively improve the remediation efficiency (TakenoK that inland sea, target area is permeated with oil pollution microbiobacterial agent, YamaokaY, SasakiK.Treatmentofoil-containingsewagewastewaterusingim mobilizedphotosyntheticbacteria [J] .WorldJ.Microbiol.Biotechnol., 2005, 21 (8-9): 1385-1391.).
Embedded immobilization technology is as the one of process for fixation, with absorption method, crosslinking, other immobilization technologies such as covalent coupling method are compared, owing to preparation method is simple to operation, reaction conditions is gentle easily to be realized, microorganism is not easily leaked, 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 (version of science), 2010, 56 (1): 109-144.), immobilization efficiency can reach more than 70%, relatively extensively (the Zhang Xiuxia of application at present, Qin Lijiao, Wu Weilin, Deng. the preparation of immobilization oil degradation bacterium and performance research [J] thereof. environmental engineering journal, 2010, 4 (3): 659-664.).Sodium alginate-CaCl2Embedding and polyvinyl alcohol-H3BO3Embedding is the most frequently used embedding immobilization method (MassalhaN, BasheerS, SabbahI.Effectofadsorptionandbeadsizeofimmobilizedbiomas sontherateofbiodegradationofphenolathighconcentrationlev els [J] .Ind.Eng.Chem.Res., 2007,46 (21): 6820-6824.). Relative to sodium alginate-CaCl2Entrapping method, polyvinyl alcohol-H3BO3Though the immobilization preparation physical strength of preparation is higher, work-ing life is longer, but polyvinyl alcohol is because nodulizing is strong, and balling-up is comparatively difficult, and saturated boric acid solution for cross-linking polyvinyl alcohol is big to the murder by poisoning of microorganism, can significantly be reduced in microbic activity after immobilization. Sodium alginate-CaCl2Though entrapping method reaction conditions is gentle, embedded material is to no toxic biological, and the cell of embedding has higher activity, but pharmaceutical machine intensity is lower, mass transfer performances is poor.
Pericarppium arachidis hypogaeae accounts for the 30% of peanut quality, and main component is hemicellulose and crude fibre, and both account for the 75%��80% of Pericarppium arachidis hypogaeae quality, and the gac being excellent prepares presoma. Pericarppium arachidis hypogaeae based activated carbon is had vesicular structure, mass transfer performances can be improved, Pericarppium arachidis hypogaeae based activated carbon is joined sodium alginate-CaCl2In entrapping method, to improve the physical strength of preparation, at home and abroad have not been reported.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of immobilized microorganism oil spilling renovation agent taking sodium alginate-calcium chloride-Pericarppium arachidis hypogaeae matrix activated carbon as embedded immobilization material, improve physical strength and the mass transfer performances of preparation by adding Pericarppium arachidis hypogaeae based activated carbon, have the advantages that technique is simple, material cost is low.
The present invention solves the problems of the technologies described above the technical scheme adopted: the preparation method of a kind of immobilized microorganism oil spilling renovation agent, it is characterised in that with sodium alginate-CaCl2-Pericarppium arachidis hypogaeae based activated carbon embeds as carrier, and concrete steps are:
1) Pericarppium arachidis hypogaeae based activated carbon is prepared;
2) by appropriate Pericarppium arachidis hypogaeae based activated carbon and seed bacterium liquid in mass ratio 1:3��1:8 mix and adsorb, until adsorbing saturated, form bacteria suspension;
3) in above-mentioned 10mL bacteria suspension, add the 100mL sodium alginate soln (concentration is 3wt%��4wt%) of the sterilizing of 30��40 DEG C, after mixed even, draw with syringe and be injected into the certain density CaCl of 500mL2Dispersion balling-up in solution (concentration is 3wt%��4wt%), crosslinked 12h��24h, being fixed microbe microsphere;
4) finally by the immobilized microorganism microballoon normal saline flushing that obtains 2��4 times, it is finished product.
As improvement, the preparation process of described Pericarppium arachidis hypogaeae based activated carbon is:
A, raw material Pericarppium arachidis hypogaeae is cleared up, sieve picks, dry, pulverize, cross 25��35 orders sieves, for subsequent use;
B, take the above-mentioned Pericarppium arachidis hypogaeae crushed, join the zinc chloride activation agent solution (mass ratio of Pericarppium arachidis hypogaeae based activated carbon and liquor zinci chloridi is 1:2��1:5) that massfraction is 30-50%, stirring and evenly mixing, at room temperature floods about 0.5��1.5h by mixed even feed liquid;
C, the feed liquid flooded is put into muffle furnace activate;
D, the sample activated is taken out from muffle furnace, after cooling, sample is poured into hydrochloric acid soln (concentrated hydrochloric acid of 11��13mol/L and water volume ratio are 1:8��10) soaks 15-30min, then by sample with 70��80 DEG C of hot washes to pH neutrality;
E, the sample washed is put into electric heating convection oven, dry 3��5h at 100��120 DEG C, after taking-up, be placed in moisture eliminator cooling;
F, the sample comminution after obtained activation is crossed 150��250 orders sieves, obtained Pericarppium arachidis hypogaeae based activated carbon.
As preferably, in described step C, activation temperature is 500��700 DEG C, the temperature rise rate rising to required activation temperature from room temperature is 40��60 DEG C/min, insulation 30��90min.
Preferred again, described seed bacterium liquid is using Brevibacillus brevis D-1 as petroleum hydrocarbon degradation bacterium, and the concentration of seed bacterium liquid is 5��8.5 �� 109cell/g��
Finally, the concentration of described use sodium alginate is 3wt%��4wt%, CaCl2Strength of solution is 3wt%��4wt%, and the mass percent concentration of immobilization microballoon shared by Pericarppium arachidis hypogaeae based activated carbon is 0.6-1.8wt%, and in described immobilized microorganism oil spilling renovation agent, the microorganism concn of embedding is 6 �� 107-8��108cell/g��
Compared with prior art, it is an advantage of the current invention that:
1, first bio-based activated carbon modified peanut is added in sodium alginate calcium chloride entrapped immobilized carrier, improve the physical strength improving preparation, and the vesicular structure due to Pericarppium arachidis hypogaeae based activated carbon, can greatly improve its mass transfer performances, make nutritive substance more easily by microorganism panning, greatly improve microbic activity and degradation efficiency.
2, modified peanut based activated carbon is compared with general activated carbon, and raw material sources are more extensive, and price is more cheap, and the performance making immobilized microorganism is more excellent.
3, preparation method is simple to operation, and reaction conditions is gentle, and obtained renovation agent microorganism is not easily leaked, and stability and reusing are good, and have higher microorganism active and cell-volume, and the degradation rate of petroleum hydrocarbon can be reached 75-92%.
Accompanying drawing explanation
Fig. 1 be the immobilized microorganism oil spilling renovation agent of the present invention manufacture craft schema;
Fig. 2 is the stereoscan photograph of the present invention, wherein a is Pericarppium arachidis hypogaeae based activated carbon stereoscan photograph, b is the blank microballoon stereoscan photograph of embedded immobilization, and c is embedded immobilization microbial microballoon stereoscan photograph, and d is the outward appearance photo (diameter 4-5mm) of embedded immobilization microbial microballoon.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Examples of implementation 1
A preparation method for immobilized microorganism oil spilling renovation agent by embedded immobilization material of sodium alginate-calcium chloride-Pericarppium arachidis hypogaeae matrix activated carbon, concrete steps are:
1, the preparation of Pericarppium arachidis hypogaeae matrix activated carbon
1) cleared up by raw material Pericarppium arachidis hypogaeae, sieve picks, dry, pulverizing, crosses 30 order sieves, for subsequent use.
2) take the above-mentioned Pericarppium arachidis hypogaeae crushed, join the zinc chloride activation agent solution (mass ratio of Pericarppium arachidis hypogaeae and liquor zinci chloridi is 1:3) that massfraction is 40%, stirring and evenly mixing, mixed even feed liquid is at room temperature flooded about 1h;
3) feed liquid flooded being put into high temperature muffle furnace, rise to required activation temperature 600 DEG C from room temperature, temperature rise rate is 50 DEG C/min, insulation 45min.
4) sample activated is taken out from high temperature muffle furnace, after cooling, sample is poured into hydrochloric acid soln (concentrated hydrochloric acid of 12mol/L and water volume ratio are 1:9) soaks 20min, then by sample with 75 DEG C of hot washes to pH weakly acidic pH.
5) sample washed being put into electric heating convection oven, 110 DEG C are dried 4h, cool in moisture eliminator.
6) sample comminution after obtained activation is crossed 200 order sieves, and obtained Pericarppium arachidis hypogaeae based activated carbon, the stereoscan photograph of Pericarppium arachidis hypogaeae based activated carbon is shown in Fig. 2 (a).
2. the petroleum hydrocarbon degradation bacterium adopted
The petroleum hydrocarbon degradation bacterium of embedding is the bacterial classification Brevibacillus brevis D-1 filtered out from certain ocean sample, is 25-35 �� in salinity, and temperature is 15-25 DEG C, pH be 7.5-8.5 environment in the degradation rate of crude oil (concentration 1-5g/L) can be reached 35-55%.
3, (Fig. 1 is shown in technical process) is embedded
1) obtained appropriate Pericarppium arachidis hypogaeae based activated carbon and seed bacterium liquid are mixed according to mass ratio 1:4 carry out adsorbing until adsorb saturated, form bacteria suspension;
2) in above-mentioned 10mL bacteria suspension, add the 100mL sodium alginate soln (concentration is 3wt%��4wt%) of the sterilizing of 30��40 DEG C, after mixed even, draw with syringe and be injected into the certain density CaCl of 500mL2Dispersion balling-up in solution (concentration is 3wt%��4wt%), crosslinked 12h��24h, being fixed microbe microsphere.
3) finally by the immobilized microorganism microballoon normal saline flushing that obtains 3 times, it is finished product.
Examples of implementation 2
A preparation method for immobilized microorganism oil spilling renovation agent by embedded immobilization material of sodium alginate-calcium chloride-Pericarppium arachidis hypogaeae matrix activated carbon, concrete steps are:
1, the preparation of Pericarppium arachidis hypogaeae matrix activated carbon
1) cleared up by raw material Pericarppium arachidis hypogaeae, sieve picks, dry, pulverizing, crosses 30 order sieves, for subsequent use.
2) take the above-mentioned Pericarppium arachidis hypogaeae crushed, join the zinc chloride activation agent solution (mass ratio of Pericarppium arachidis hypogaeae and liquor zinci chloridi is 1:2) that massfraction is 50%, stirring and evenly mixing, mixed even feed liquid is at room temperature flooded about 0.5h;
3) feed liquid flooded being put into high temperature muffle furnace, rise to required activation temperature 700 DEG C from room temperature, temperature rise rate is 50 DEG C/min, insulation 30min.
4) sample activated is taken out from high temperature muffle furnace, after cooling, sample is poured into hydrochloric acid soln (concentrated hydrochloric acid of 13mol/L and water volume ratio are 1:10) soaks 15min, then by sample with 80 DEG C of hot washes to pH weakly acidic pH.
5) sample washed being put into electric heating convection oven, 110 DEG C are dried 4h, cool in moisture eliminator.
6) sample comminution after obtained activation is crossed 200 order sieves, and obtained Pericarppium arachidis hypogaeae based activated carbon, the stereoscan photograph of Pericarppium arachidis hypogaeae based activated carbon is shown in Fig. 2 (a).
2. the petroleum hydrocarbon degradation bacterium adopted
The petroleum hydrocarbon degradation bacterium of embedding is the bacterial classification Brevibacillus brevis D-1 filtered out from certain ocean sample, is 25-35 �� in salinity, and temperature is 15-25 DEG C, pH be 7.5-8.5 environment in the degradation rate of crude oil (concentration 1-5g/L) can be reached 35-55%.
3, (Fig. 1 is shown in technical process) is embedded
1) obtained appropriate Pericarppium arachidis hypogaeae based activated carbon and seed bacterium liquid are mixed according to mass ratio 1:8 carry out adsorbing until adsorb saturated, form bacteria suspension;
2) in above-mentioned 10mL bacteria suspension, add the 100mL sodium alginate soln (concentration is 3wt%��4wt%) of the sterilizing of 30��40 DEG C, after mixed even, draw with syringe and be injected into the certain density CaCl of 500mL2Dispersion balling-up in solution (concentration is 3wt%��4wt%), crosslinked 12h, being fixed microbe microsphere.
3) finally by the immobilized microorganism microballoon normal saline flushing that obtains 4 times, it is finished product.
Examples of implementation 3
A preparation method for immobilized microorganism oil spilling renovation agent by embedded immobilization material of sodium alginate-calcium chloride-Pericarppium arachidis hypogaeae matrix activated carbon, concrete steps are:
1, the preparation of Pericarppium arachidis hypogaeae matrix activated carbon
1) cleared up by raw material Pericarppium arachidis hypogaeae, sieve picks, dry, pulverizing, crosses 30 order sieves, for subsequent use.
2) take the above-mentioned Pericarppium arachidis hypogaeae crushed, join the zinc chloride activation agent solution (mass ratio of Pericarppium arachidis hypogaeae and liquor zinci chloridi is 1:2) that massfraction is 30%, stirring and evenly mixing, mixed even feed liquid is at room temperature flooded about 1.5h;
3) feed liquid flooded being put into high temperature muffle furnace, rise to required activation temperature 500 DEG C from room temperature, temperature rise rate is 50 DEG C/min, insulation 60min.
4) sample activated is taken out from high temperature muffle furnace, after cooling, sample is poured into hydrochloric acid soln (concentrated hydrochloric acid of 11mol/L and water volume ratio are 1:8) soaks 30min, then by sample with 70-80 DEG C of hot wash to pH weakly acidic pH.
5) sample washed being put into electric heating convection oven, 110 DEG C are dried 4h, cool in moisture eliminator.
6) sample comminution after obtained activation is crossed 200 order sieves, and obtained Pericarppium arachidis hypogaeae based activated carbon, the stereoscan photograph of Pericarppium arachidis hypogaeae based activated carbon is shown in Fig. 2 (a).
2. the petroleum hydrocarbon degradation bacterium adopted
The petroleum hydrocarbon degradation bacterium of embedding is the bacterial classification Brevibacillus brevis D-1 filtered out from certain ocean sample, is 25-35 �� in salinity, and temperature is 15-25 DEG C, pH be 7.5-8.5 environment in the degradation rate of crude oil (concentration 1-5g/L) can be reached 35-55%.
3, (Fig. 1 is shown in technical process) is embedded
1) obtained appropriate Pericarppium arachidis hypogaeae based activated carbon and seed bacterium liquid are mixed according to mass ratio 1:3 carry out adsorbing until adsorb saturated, form bacteria suspension;
2) in above-mentioned 10mL bacteria suspension, add the 100mL sodium alginate soln (concentration is 3wt%��4wt%) of the sterilizing of 30��40 DEG C, after mixed even, draw with syringe and be injected into the certain density CaCl of 500mL2Dispersion balling-up in solution (concentration is 3wt%��4wt%), crosslinked 24h, being fixed microbe microsphere.
3) finally by the immobilized microorganism microballoon normal saline flushing that obtains 2 times, it is finished product.
In above 3 examples of implementation, embedded immobilization microbial microballoon stereoscan photograph is shown in Fig. 2 (c), and Fig. 2 (d) is shown in by outward appearance photo. The microorganism concn of immobilized microorganism preparation embedding obtained after tested is 5 �� 107-7��108Cell/g is 5-55 �� in salinity, and temperature is 10-30 DEG C, pH be 6.5-9.0 environment in the degradation rate of petroleum hydrocarbon can be reached 75-92%, compared with free microorganism, its degradation rate improves 37%-46%, and the tolerance of environment is strengthened.
The immobilized microorganism microballoon below the present invention obtained and other do not add the immobilized microorganism microballoon of modified peanut based activated carbon and common inorganic activated carbon compares, comparative result is as shown in the table:
The Performance comparision of the different immobilized microorganism microballoon of table 1
As can be drawn from Table 1, the immobilized microorganism microballoon of the interpolation modified peanut based activated carbon of the present invention improves a lot in physical strength and mass-transfer performance, and the cell of embedding has higher activity, and the degradation rate of petroleum hydrocarbon can be reached 75-92%.
Claims (3)
1. the preparation method of an immobilized microorganism oil spilling renovation agent, it is characterised in that with sodium alginate-CaCl2-Pericarppium arachidis hypogaeae based activated carbon embeds as carrier, and concrete steps are:
1) Pericarppium arachidis hypogaeae based activated carbon is prepared;
2) appropriate Pericarppium arachidis hypogaeae based activated carbon and seed bacterium liquid are mixed according to mass ratio 1:3��1:8 carry out adsorbing until adsorb saturated, form bacteria suspension;
3) 100mL, the concentration that add the sterilizing of 30��40 DEG C in the above-mentioned bacteria suspension of 10mL are the sodium alginate soln of 3wt%��4wt%, mixed even after, draw with syringe and be injected into 500mL, concentration is the CaCl of 3wt%��4wt%2Solution disperses balling-up, crosslinked 12h��24h, being fixed microbe microsphere;
4) finally by the immobilized microorganism microballoon normal saline flushing that obtains 2��4 times, it is finished product;
The preparation process of above-mentioned Pericarppium arachidis hypogaeae based activated carbon is:
A, raw material Pericarppium arachidis hypogaeae is cleared up, sieve picks, dry, pulverize, cross 25��35 orders sieves, for subsequent use;
B, taking the above-mentioned Pericarppium arachidis hypogaeae crushed, join the zinc chloride activation agent solution that massfraction is 30-50%, the mass ratio of Pericarppium arachidis hypogaeae and liquor zinci chloridi is 1:2��1:5, stirring and evenly mixing, and mixed even feed liquid is at room temperature flooded about 0.5��1.5h;
C, the feed liquid flooded is put into muffle furnace activate;
D, the sample activated is taken out from muffle furnace, after cooling, sample is poured into the concentrated hydrochloric acid of 11��13mol/L and water volume ratio be 1:8��10 aqueous hydrochloric acid in soak 15-30min, again that sample is neutral to pH with 70��80 DEG C of hot washes after taking-up;
E, the sample washed is put into electric heating convection oven, dry 3��5h at 100��120 DEG C, after taking-up, be placed in moisture eliminator cooling;
F, the sample comminution after obtained activation is crossed 150��250 orders sieves, obtained Pericarppium arachidis hypogaeae based activated carbon.
2. preparation method according to claim 1, it is characterised in that the activation temperature in described step C is 500��700 DEG C, the temperature rise rate rising to required activation temperature from room temperature is 40��60 DEG C/min, insulation 30-90min.
3. preparation method according to claim 1, it is characterised in that the concentration of described sodium alginate is 3wt%��4wt%, CaCl2Strength of solution is 3wt%��4wt%, and the mass percent concentration of immobilization microballoon shared by Pericarppium arachidis hypogaeae based activated carbon is 0.6-1.8%, and in described immobilized microorganism oil spilling renovation agent, the microorganism concn of embedding is 6 �� 107-8��108cell/g��
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