CN110201690A - A kind of preparation method and purposes of photocatalysis-biodegrade compound - Google Patents
A kind of preparation method and purposes of photocatalysis-biodegrade compound Download PDFInfo
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- CN110201690A CN110201690A CN201910485107.2A CN201910485107A CN110201690A CN 110201690 A CN110201690 A CN 110201690A CN 201910485107 A CN201910485107 A CN 201910485107A CN 110201690 A CN110201690 A CN 110201690A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 244000005700 microbiome Species 0.000 claims abstract description 20
- 239000003094 microcapsule Substances 0.000 claims abstract description 16
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 14
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 claims abstract description 11
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001963 growth medium Substances 0.000 claims description 10
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 10
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002775 capsule Substances 0.000 claims description 9
- 239000002609 medium Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 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 description 8
- 235000010413 sodium alginate Nutrition 0.000 claims description 8
- 239000000661 sodium alginate Substances 0.000 claims description 8
- 229940005550 sodium alginate Drugs 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 6
- 238000009630 liquid culture Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000011081 inoculation Methods 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000006166 lysate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002255 vaccination Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 235000015097 nutrients Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 230000002906 microbiologic effect Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 20
- 238000006731 degradation reaction Methods 0.000 abstract description 20
- 230000000813 microbial effect Effects 0.000 abstract description 8
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000008439 repair process Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000002689 soil Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 241000193764 Brevibacillus brevis Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241001478240 Coccus Species 0.000 description 1
- 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 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/36—Adaptation or attenuation of cells
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- Bioinformatics & Cheminformatics (AREA)
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- Biomedical Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
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Abstract
The invention discloses a kind of photocatalysis-biodegrade compound preparation methods and purposes；The present invention prepares microcapsules-microorganism consortium-photocatalysis compound for degrading polycyclic aromatic hydrocarbons, and efficient degradation microorganism consortium is suspended in microcapsules inner space, and by nanometer visible-light photocatalyst Ag3PO4@Fe3O4It is anchored on microcapsule membrane.In this system, nanometer Ag3PO4@Fe3O4It integrates with the acclimated microorganism consortium in microcapsules without reducing its degradation efficiency.Microorganism and photocatalyst separation are released their degradation potentiality and prevent adverse effect caused by photochemical catalyst by fixed microcapsules.Using microcapsules-microorganism consortium-photocatalysis chemical combination objects system, the limitation of other technologies is not only breached, but also provides new method for the integrated application of photochemistry and microbial technique in actual repair application.
Description
Technical field:
The invention belongs to environmental areas, and in particular to a kind of preparation method and purposes of photocatalysis-biodegrade compound.
Background technique:
With the development of industry, polycyclic aromatic hydrocarbon becomes pollutant generally existing in environment, polycyclic aromatic hydrocarbon
(Polycyclic aromatic hydrocarbons, abbreviation PAHs) be it is a kind of have environmental persistence, bioaccumulation and
Highly toxic organic pollutant is widely present in the surrounding mediums such as big gas and water and soil.PAHs has teratogenesis, carcinogenicity
With the toxicity such as mutagenicity, there is potential hazard to human health and ecological environment.PAHs can be made by atmospheric sedimentation and precipitation
With entering in soil, inhibit soil normal function.
Photochemical catalyst, the bioremediation technology based on microorganism conversion and degradation are used to degrading polycyclic aromatic hydrocarbons, some
Conventional catalyst such as TiO2And ZrO2It is used successfully to degradation organic contamination under ultraviolet light, but mass energy can be consumed, while can be right
Microorganism in soil adversely affects.
Summary of the invention:
The invention discloses a kind of photocatalysis-biodegrade compound preparation methods and purposes；The present invention prepares micro- glue
Capsule-microorganism consortium-photochemical catalyst compound is used for degrading polycyclic aromatic hydrocarbons, efficient degradation microorganism consortium is suspended in micro-
In capsule space, and by nanometer visible-light photocatalyst Ag3PO4@Fe3O4It is anchored on microcapsule membrane.In this system
In, nanometer Ag3PO4@Fe3O4It integrates with the acclimated microorganism consortium in microcapsules without reducing its degradation efficiency.Pass through fixation
Microorganism and photocatalyst separation are released their degradation potentiality and prevent unfavorable shadow caused by photochemical catalyst by microcapsules
It rings.Using microcapsules-microorganism consortium-photochemical catalyst chemical combination objects system, the limitation of other technologies, Er Qiewei are not only breached
The integrated application of photochemistry and microbial technique in actual repair application provides new method.
In order to reach the invention purpose, the invention adopts the following technical scheme:
A kind of preparation method of photocatalysis-biodegrade compound, preparation process the following steps are included:
Step 1: photochemical catalyst Ag is prepared3PO4@Fe3O4:
Step 2: microorganism consortium is prepared；
Step 3: microcapsules are prepared；
Step 4: the preparation of microcapsules-microorganism consortium-photocatalysis compound: by microcapsules and microorganism consortium
It is mixed to get mixture with the weight ratio of 1:1~1:2, is added mixture in the sodium alginate soln that concentration is 2%~4%
Mixed solution is obtained, photochemical catalyst Ag is added into mixed solution3PO4@Fe3O4；Stirring obtains microcapsules-microorganism consor
Body-photocatalysis compound；Photochemical catalyst Ag3PO4@Fe3O4Mass ratio with mixed solution is 1:3~1:15；Mixture and seaweed
The mass volume ratio of acid sodium solution is 1:1~1:2g/ml.
It is further to improve, in the step 1, photochemical catalyst Ag3PO4@Fe3O4Preparation flow it is as follows:
By Fe3O4Nanoparticle is added in distilled water together with polyvinylpyrrolidone and obtains lysate, adds into lysate
Enter AgNO3Solution, ultrasound are uniformly mixed so as to obtain suspension；Then into suspension by entering 10ml Na2HPO4Solution continues ultrasound and mixes
Afterwards, isolated sediment, sediment are dried after distilling water washing to get visible light catalyst Ag is arrived3PO4@Fe3O4；Fe3O4It receives
The mass ratio of rice corpuscles, polyvinylpyrrolidone and distilled water is 0.8:0.2:10；Distilled water and AgNO3The volume ratio of solution is
1:1；AgNO3The concentration of solution is 9mol/L； Na2HPO4Solution and AgNO3The volume ratio of solution is 1:1；Na2HPO4Solution
Concentration is 3mol/L.
Further to improve, the temperature of the drying is 60 DEG C.
It is further to improve, the microorganism consortium the preparation method is as follows:
From sewage treatment plant A2The aerobic zone of/O technique takes turbid liquid to be inoculated in LB liquid medium in culture；Again
It takes in turbid liquid inoculation MSM inorganic salt liquid culture medium and cultivates under identical condition, it is inorganic in LB liquid medium and MSM
After salt fluid nutrient medium becomes muddiness, renewed vaccination suspension and repeated inoculation are distinguished three times, after being then inoculated with and becoming cloudy
LB liquid medium and the mixing of MSM inorganic salt liquid culture medium, then centrifuge washing obtain wet microorganism consortium.
It is further to improve, the volume ratio of the LB liquid medium and MSM inorganic salt liquid culture medium and turbid liquid
It is 50:1.
Further to improve, the preparation process of the microcapsules is as follows:
By 100g/L CaCl2, 12g/L carboxymethyl cellulose, 2% sodium alginate 3:1:3 in mass ratio be sufficiently mixed
After obtain mixed liquor, with syringe needle be added dropwise mixed liquor to 0.2moL/L CaCl2Solidified in solution, is obtained with stablizing capsule surface
To microcapsules.
Microcapsules-microorganism consortium-light made from a kind of above-mentioned photocatalysis-biodegrade compound preparation method
Catalyst compounds.
Further to improve, the microcapsules-microorganism consortium-photochemical catalyst compound is used for degrading polycyclic aromatic hydrocarbons.
Further to improve, the polycyclic aromatic hydrocarbon includes pyrene, naphthalene, phenanthrene, anthracene, fluoranthene.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with tool of the invention
Body embodiment is used to explain the present invention together, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the microcosmic schematic diagram of substance obtained.
Fig. 2 is the degradation comparison diagram of pyrene in soil sample T1, T2, T3；
Fig. 3 is the degradation comparison diagram of naphthalene in soil sample T1, T2, T3；
Fig. 4 is the degradation comparison diagram of soil sample T1, T2, T3 China and Philippines；
Fig. 5 is the degradation comparison diagram of anthracene in soil sample T1, T2, T3；
Fig. 6 is the degradation comparison diagram of fluoranthene in soil sample T1, T2, T3.
Specific embodiment:
Specific embodiments of the present invention are described in further detail with reference to the accompanying drawing, it should be understood that described herein
Embodiment for instruction and explanation of the present invention, be not intended to limit the present invention.
Embodiment 1
(1) preparation of photochemical catalyst:
By 0.8g Fe3O4It is added together with 0.2g polyvinylpyrrolidone in 10ml distilled water, 10ml is then added
The AgNO of 9mol/L3Solution is ultrasonically treated 10 minutes together.After ultrasound, by the Na of 10ml 3mol/L2HPO4Solution drop
It is added in above-mentioned suspension, continues to be ultrasonically treated after ten minutes, separating obtained sediment, in 60 DEG C of vacuum after distillation water washing
It is dry in baking oven, obtain visible light catalyst Ag3PO4@Fe3O4。
(2) preparation of microorganism consortium:
The activated sludge of inoculation comes from certain sewage treatment plant A2The aerobic zone of/O technique, takes 1ml turbid liquid to be inoculated in
50ml LB culture medium is put into culture bottle on constant-temperature table and carries out shake culture 12 hours, and the rotation speed for adjusting shaking table is
120rpm, cultivation temperature are 28 DEG C.It takes 1ml turbid liquid to be inoculated in MSM minimal medium again to train under identical condition
It supports, domestication culture is carried out to mud bacterium using pyrene, naphthalene, phenanthrene, anthracene, fluoranthene as only carbon source and energy source.Become in culture medium
It is muddy after, renewed vaccination suspension simultaneously repeat the process three times, by centrifuge washing, obtain wet microbial composite bacteria body.
(3) preparation of microcapsules:
By 100g/L CaCl2, 12g/L carboxymethyl cellulose, 2% sodium alginate be sufficiently mixed with volume ratio 3:1:3
The mixed liquor containing microcapsules is obtained afterwards, with the CaCl of syringe needle dropwise addition mixed liquor to 0.2moL/L2Solidified in solution, is solidified
Temperature is 4 DEG C, and curing time is 10min to stablize capsule surface.
(4) microcapsules-microorganism consortium-photocatalysis compound preparation:
Microcapsules and microorganism consortium obtain mixture after mixing well with the ratio of 1:1, and mixture is added to 10ml
In the sodium alginate soln of 10g/L, the mass volume ratio of mixture and sodium alginate soln is 1:2g/ml, and in stirring
Under, weigh 5g Ag3PO4@Fe3O4(1-5g) is added in above-mentioned solution, is obtained microcapsules-microorganism consortium-light and is urged
Change compound.
The substance obtained of embodiment 1 is subjected to microexamination analysis, Fe3O4The spherical shape of rule is presented, diameter is about 20-
B figure in 40nm (a figure in Fig. 1), Fig. 1 shows Ag3PO4For irregular Globate polyhedron, diameter 100-300nm exists
Bulky grain be attributed to short grained aggregation.It can be seen that by the c figure in Fig. 1, Ag3PO4And Fe3O4There is good knot between particle
It closes.It will be seen from figure 1 that visible light catalyst-microbial degradation compound is a hollow gel ball, outer surface coating
Ag3PO4@Fe3O4, microbial composite bacteria body is suspended in inside.Pass through calcium alginate UF membrane Ag3PO4@Fe3O4And microbial composite bacteria
Body.In order to preferably observe the inside and outside structure of photochemical catalyst-microbial degradation compound, SEM scanning before by its
It is crushed in liquid nitrogen, it is seen that capsule membrane (with a thickness of 100-150 μm) is made of multilayer film, and average thickness is 2-5 μm of (the figure d in Fig. 1
And e), there are Ag between every layer of crack3PO4@Fe3O4And microorganism.In the outer surface (the f figure in Fig. 1) of capsule, can see
Ag out3PO4@Fe3O4It is fluffy to be uniformly distributed.In inner surface it can be found that many microorganisms, including corynebacteria, bacillus brevis
With some coccuses (the g figure in Fig. 1).In addition, capsule shows pleated structure, there are many large-sized protrusion and sunk areas
(the h figure in Fig. 1), this form provides fabulous load situation for microorganism and photochemical catalyst.
Below with reference to the result of study in laboratory, the present invention is further described.
Embodiment 2
It takes and is not air-dried by polycyclic aromatic hydrocarbons contaminated soil, sieved with 2mm sieve stand-by.200mg/ is added in soil-like
Pyrene, naphthalene, phenanthrene, anthracene, the fluoranthene of kg, is dissolved in acetone soln together, and after mixing, equivalent is divided into three parts of T1, T2, T3.
The concentration of polycyclic aromatic hydrocarbon is 200mg/kg, embodiment 3 in T1, T2, T3 pollution sample that following example 3~5 use
The photochemical catalyst Ag prepared using embodiment 13PO4@Fe3O4, the microbial composite bacteria body that embodiment 4 is prepared using embodiment 1,
Microcapsules-microorganism consortium-photocatalysis compound that embodiment 5 is prepared using embodiment 1.
Embodiment 3
The 20g photochemical catalyst Ag of preparation is added into pollution soil sample T13PO4@Fe3O4, under visible light, temperature is 25 DEG C
Constant incubator in tested, experimental period 30 days.
Embodiment 4
20g microbe composite bacterial liquid as preparation is added in pollution soil sample T2, under visible light, the perseverance that temperature is 25 DEG C
It is tested in warm incubator, experimental period 30 days.
Embodiment 5
20g microcapsules-microorganism consortium-photochemical catalyst compound as preparation is added in pollution soil sample T3, visible
Under light, tested in the constant incubator that temperature is 25 DEG C, experimental period 30 days.
To embodiment 3~5 processing soil sample respectively at the 5th day, the 10th day, the 15th day, the 20th day, the 25th day, the 30th day
Pass through GC-MS Gc-mss polycyclic aromatic hydrocarbon content.Testing result is as shown in Fig. 2-6.By Fig. 2-6 it is found that using the present invention
Method, than it is single using photocatalysis or microbial degradation it is high-efficient, microcapsules-microorganism consortium-photocatalysis compound
95% is reached in 30 days to the degradation of total polycyclic aromatic hydrocarbon, 100% is reached to the degradation rate of naphthalene, phenanthrene, anthracene.And use photocatalysis
Or the method for microbial degradation, degradation efficiency highest are just 80%.
The basic principles, main features and advantages of the present invention have been shown and described above.Protection of the invention
Range is not limited merely to above-described embodiment, and all technical solutions belonged under thinking of the present invention belong to protection model of the invention
It encloses.It should be pointed out that for those skilled in the art, without departing from the principles of the present invention several change
Into and retouching, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (9)
1. a kind of photocatalysis-biodegrade compound preparation method, which is characterized in that preparation process the following steps are included:
Step 1: photochemical catalyst Ag is prepared3PO4@Fe3O4:
Step 2: microorganism consortium is prepared；
Step 3: microcapsules are prepared；
Step 4: the preparation of microcapsules-microorganism consortium-photocatalysis compound: by microcapsules and microorganism consortium with 1:1
The weight ratio of~1:2 is mixed to get mixture, adds mixture in the sodium alginate soln that concentration is 2%~4% and obtains
Photochemical catalyst Ag is added into mixed solution for mixed solution3PO4@Fe3O4；Stirring obtains microcapsules-microorganism consortium-light
Catalytic cpd；Photochemical catalyst Ag3PO4@Fe3O4Mass ratio with mixed solution is 1:3~1:15；Mixture and sodium alginate
The mass volume ratio of solution is 1:1~1:2g/ml.
2. a kind of preparation method of photocatalysis-biodegrade compound as described in claim 1, which is characterized in that the step
In rapid one, photochemical catalyst Ag3PO4@Fe3O4Preparation flow it is as follows:
By Fe3O4Nanoparticle is added in distilled water together with polyvinylpyrrolidone and obtains lysate, is added into lysate
AgNO3Solution, ultrasound are uniformly mixed so as to obtain suspension；Then into suspension by entering 10ml Na2HPO4Solution continues ultrasound and mixes
Afterwards, isolated sediment, sediment are dried after distilling water washing to get visible light catalyst Ag is arrived3PO4@Fe3O4；Fe3O4It receives
The mass ratio of rice corpuscles, polyvinylpyrrolidone and distilled water is 0.8:0.2:10；Distilled water and AgNO3The volume ratio of solution is
1:1；AgNO3The concentration of solution is 9mol/L；Na2HPO4Solution and AgNO3The volume ratio of solution is 1:1；Na2HPO4Solution it is dense
Degree is 3mol/L.
3. a kind of preparation method of photocatalysis-biodegrade compound as claimed in claim 2, which is characterized in that described dry
Dry temperature is 60 DEG C.
4. a kind of preparation method of photocatalysis-biodegrade compound as described in claim 1, which is characterized in that described micro-
Biological consortium the preparation method is as follows:
From sewage treatment plant A2The aerobic zone of/O technique takes turbid liquid to be inoculated in LB liquid medium in culture；Muddiness is taken again
It is cultivated under identical condition in liquid inoculation MSM inorganic salt liquid culture medium, in LB liquid medium and MSM inorganic salt liquid
After culture medium becomes muddiness, renewed vaccination suspension and repeated inoculation are distinguished three times, then by the LB liquid after being inoculated with and becoming cloudy
Body culture medium and the mixing of MSM inorganic salt liquid culture medium, then centrifuge washing, obtain wet microorganism consortium.
5. a kind of preparation method of photocatalysis-biodegrade compound as claimed in claim 4, which is characterized in that the LB
The volume ratio of fluid nutrient medium and MSM inorganic salt liquid culture medium and turbid liquid is 50:1.
6. a kind of preparation method of photocatalysis-biodegrade compound as described in claim 1, which is characterized in that described micro-
The preparation process of capsule is as follows:
By 100g/L CaCl2, 12g/L carboxymethyl cellulose, 2% sodium alginate 3:1:3 in mass ratio be sufficiently mixed after obtain
Mixed liquor, with the CaCl of syringe needle dropwise addition mixed liquor to 0.2moL/L2Solidified in solution, obtains micro- glue to stablize capsule surface
Capsule.
7. micro- glue made from a kind of a kind of any photocatalysis-biodegrade compound preparation method of claim 1-6
Capsule-microorganism consortium-photochemical catalyst compound.
8. a kind of purposes of the preparation method of photocatalysis-biodegrade compound as claimed in claim 7, which is characterized in that
Microcapsules-microorganism consortium-photochemical catalyst the compound is used for degrading polycyclic aromatic hydrocarbons.
9. microcapsules-microorganism made from a kind of preparation method of photocatalysis-biodegrade compound as claimed in claim 8
Consortium-photocatalysis compound purposes, which is characterized in that the polycyclic aromatic hydrocarbon includes pyrene, naphthalene, phenanthrene, anthracene, fluoranthene.
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| CN110743397A (en) * | 2019-11-26 | 2020-02-04 | 天津工业大学 | Preparation method of silver phosphate-containing calcium alginate antibacterial hydrogel filtering membrane |
| CN110743397B (en) * | 2019-11-26 | 2021-10-08 | 中科瑞阳膜技术（北京）有限公司 | Preparation method of silver phosphate-containing calcium alginate antibacterial hydrogel filtering membrane |
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Application publication date: 20190906 |