CN115537412A - Oil-resistant immobilized carrier and synthesis method and application thereof - Google Patents
Oil-resistant immobilized carrier and synthesis method and application thereof Download PDFInfo
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- CN115537412A CN115537412A CN202110727785.2A CN202110727785A CN115537412A CN 115537412 A CN115537412 A CN 115537412A CN 202110727785 A CN202110727785 A CN 202110727785A CN 115537412 A CN115537412 A CN 115537412A
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- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 239000004964 aerogel Substances 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 244000005700 microbiome Species 0.000 claims abstract description 24
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004021 humic acid Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 36
- 239000003921 oil Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000011282 treatment Methods 0.000 claims description 22
- 238000000855 fermentation Methods 0.000 claims description 21
- 230000004151 fermentation Effects 0.000 claims description 21
- 239000010865 sewage Substances 0.000 claims description 20
- 239000004966 Carbon aerogel Substances 0.000 claims description 17
- 241000589517 Pseudomonas aeruginosa Species 0.000 claims description 15
- -1 rhamnose ester Chemical class 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 241000894006 Bacteria Species 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 claims description 8
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 claims description 8
- HVCOBJNICQPDBP-UHFFFAOYSA-N 3-[3-[3,5-dihydroxy-6-methyl-4-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid;hydrate Chemical compound O.OC1C(OC(CC(=O)OC(CCCCCCC)CC(O)=O)CCCCCCC)OC(C)C(O)C1OC1C(O)C(O)C(O)C(C)O1 HVCOBJNICQPDBP-UHFFFAOYSA-N 0.000 claims description 6
- 229930186217 Glycolipid Natural products 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- ZTOKUMPYMPKCFX-CZNUEWPDSA-N (E)-17-[(2R,3R,4S,5S,6R)-6-(acetyloxymethyl)-3-[(2S,3R,4S,5S,6R)-6-(acetyloxymethyl)-3,4,5-trihydroxyoxan-2-yl]oxy-4,5-dihydroxyoxan-2-yl]oxyoctadec-9-enoic acid Chemical compound OC(=O)CCCCCCC/C=C/CCCCCCC(C)O[C@@H]1O[C@H](COC(C)=O)[C@@H](O)[C@H](O)[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](COC(C)=O)O1 ZTOKUMPYMPKCFX-CZNUEWPDSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 230000002045 lasting effect Effects 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000012258 culturing Methods 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 241001052560 Thallis Species 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000011866 long-term treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 239000003876 biosurfactant Substances 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 230000002068 genetic effect Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000108664 Nitrobacteria Species 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- AHEWZZJEDQVLOP-UHFFFAOYSA-N monobromobimane Chemical compound BrCC1=C(C)C(=O)N2N1C(C)=C(C)C2=O AHEWZZJEDQVLOP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003625 trehaloses Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
- C12N11/12—Cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention relates to an oil-resistant immobilized carrier and a synthesis method and application thereof, which comprises the steps of (1) placing aerogel into acetic acid solution for reaction, taking out and washing to be neutral; (2) Dissolving humic acid in Fe (OH) 3 Adding aerogel into the solution, reacting at 50-70 ℃, and washing to be alkalescent; obtaining modified aerogel; (3) loading active metal on the modified aerogel; (4) Adsorbing the microorganism producing sugar ester on the carrier loaded with metal, and drying to obtain the immobilized carrier. The immobilized carrier provided by the invention has lasting oil resistance, can enhance the bonding force between metal and aerogel in the carrier, and improves the adsorbability and the long-acting property of the carrier.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to an oil-resistant immobilized carrier, and a synthetic method and application thereof.
Background
During the processes of oil exploitation, refining, processing and the like, a large amount of oily sewage is generated, and oil in the sewage exists in the states of floating oil, dispersed oil, emulsified oil and dissolved oil. The sewage is generally treated by adopting a combined process due to the characteristics of large discharge amount, complex components, large water quality fluctuation and the like. The floating oil and the dispersed oil can be removed by an oil separation flotation mode, and the dissolved oil and part of emulsified oil which is not easy to remove often enter a terminal biochemical unit along with the wastewater. In order to meet stricter emission standards, a three-stage biochemical treatment unit mainly comprising a biofilm reactor such as MBBR, BAF, FCBR and the like is additionally arranged. However, for oily sewage, the treatment by using the biofilm reactor cannot achieve ideal treatment effect after long-period operation.
Yang Qiuyue (MBBR process treatment oil refining sewage operation analysis, china and foreign energy source, 2020,25 (1)) adopts a mode of properly adding nutrient salts and high-quality carbon sources at a water inlet of an MBBR pool, promotes normal growth and reproduction of microorganisms, and accordingly improves the problem of difficult biofilm formation. Sang Junjiang (research on treating high-salt-content oil refining sewage by fluidized composite carrier biomembrane process, petroleum refining and chemical industry, 2017,48 (8)) adopts a novel biomembrane biochemical treatment process (FCBR) of a patent composite carrier, wherein one carrier is attached with microorganisms for reproduction and growth to form a compact biomembrane, so that the treatment efficiency is improved, the other carrier is uniformly dispersed in water to fix pollutants, so that the impact resistance is improved, the biological treatment capacity is further enhanced by carrier fluidized operation, and the treatment efficiency is improved.
At present, researchers mostly develop a great deal of work from the aspects of selection and proportioning of carrier materials, combination of carrier modification and immobilization methods and the like.
CN201610595544.6 discloses a method for treating ammonia nitrogen wastewater by utilizing porous cellulose aerogel immobilized microorganism bacteria, which is mainly used for preparing porous cellulose aerogel, nitrifying bacteria and denitrifying bacteria are adsorbed and fixed on the porous cellulose aerogel by adopting a carrier combination method, and microorganisms are fixed on the porous cellulose aerogel to treat the ammonia nitrogen wastewater, so that the method is favorable for synchronous nitrification and denitrification reaction, the ammonia nitrogen removal capacity is good, the reaction efficiency is high, the stability is high, the obtained immobilized microorganism bacteria are added into 50-100L of 100-500mg/L ammonia nitrogen wastewater according to 20-30g/L, the hydraulic retention time is 30-40h, and the ammonia nitrogen removal rate after treatment is 68-89%. However, the method utilizes the cellulose aerogel to adsorb and fix the thalli, belongs to surface adsorption, and has the phenomenon of falling off in long-term treatment due to weak bonding force between the thalli and the cellulose aerogel. Especially when used for oily sewage treatment, the adsorption capacity is poor due to pore channel blockage and poor biological activity because of oil pollution, and the long-time stable operation effect cannot be achieved.
CN201210246151.6 discloses a coupling treatment method of oil field oily sewage, firstly, the oily sewage is subjected to two-stage biological contact oxidation treatment in a biochemical pool to obtain a water body to be filtered, and then the water body to be filtered is filtered; in each stage of biological contact oxidation treatment, aeration is adopted at the lower bottom of a biochemical pool, hydrophilic fiber filler with bacillus adsorbed is adopted above the aeration, oily sewage is introduced into the biochemical pool, and the volume ratio of aerated gas to the oily sewage, the pH value in the biochemical pool, the content ratio of C, N, P and the dissolved oxygen amount are controlled. The residual emulsified oil which is not completely removed in the front-end sewage system can be thoroughly removed, the efficiency of the biochemical treatment system is improved, and the retention time of sewage in the biochemical system is shortened to about 8 hours from the original 12 hours. However, the invention adopts the hydrophilic fibrous filler with bacillus adsorbed to remove grease, the matching of specific bacteria and materials is required, and the filler and the bacteria are only combined through adsorption, so that the binding force needs to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an oil-resistant immobilization carrier, and a synthesis method and application thereof. The immobilized carrier provided by the invention has lasting oil resistance, can enhance the bonding force between metal and aerogel in the carrier, and improves the adsorbability and the long-acting property of the carrier.
The invention provides a synthesis method of an oil-resistant immobilization carrier, which comprises the following steps:
(1) Placing the aerogel in an acetic acid solution for reaction, taking out the aerogel and washing the aerogel to be neutral;
(2) Dissolving humic acid in Fe (OH) 3 Adding aerogel into the solution at 50-70 deg.CAfter the reaction, washing the mixture to be alkalescent to obtain modified aerogel;
(3) Loading active metal on the modified aerogel to obtain a metal-loaded carrier;
(4) Adsorbing the microorganisms for producing sugar ester on the metal-loaded carrier, and drying to obtain the immobilized carrier after adsorption.
The aerogel in the step (1) of the present invention is at least one of carbon aerogel, silicon aerogel, cellulose aerogel, etc., preferably carbon aerogel. Is usually obtained by a self-made or commercial purchase mode, and the specific surface area of the aerogel is 600-1100 m 2 The porosity is 80-98 percent.
The concentration of the acetic acid solution in the step (1) of the invention is 1.0-2.0 mol/L. Immersing the aerogel in an acetic acid solution for reaction at the temperature of 30-50 ℃ for 1.0-2.0 h. The reaction can be carried out by direct heating or water bath heating, preferably water bath heating to 30-50 ℃. The aerogel is removed and washed to neutral pH, typically 6.5 to 7.5.
Fe (OH) according to step (2) of the present invention 3 The concentration of the solution is 0.5-0.8 mol/L, fe (OH) 3 The mass ratio of the solution to the humic acid is 1:1-3:1.
Step (2) of the present invention immersing the aerogel in humic acid and Fe (OH) 3 In the mixed system of the solution, carrying out water bath oscillation reaction for 3-5 h at 50-70 ℃. After being taken out, the mixture is washed until the pH value is alkalescent, generally between 7.6 and 8.0.
The active metal in the step (3) of the invention is Cu 2+ 、Fe 2+ 、Mg 2+ Etc., preferably Fe 2+ . The supported active metal may be impregnated by impregnation methods conventionally used in the art, e.g., by an equal volume, excess impregnation, etc. Soluble salt solutions of the active metals are generally used, with the concentration of the metal ions being from 1 to 4mol/L. For example, the modified aerogel can be immersed in an active metal solution for 6 to 10 hours at a temperature of between 60 and 70 ℃.
Further, step (3) is to add an auxiliary agent comprising (NH) to the active metal solution 4 ) 6 Mo 7 O 2 ·4H 2 O and CoCl 2 The molar ratio of the two is 1:3-5, and the dosage is 0.5-1.0mg/L. The addition of the auxiliary agent is helpful for the adsorption growth of the sugar ester-producing microorganisms.
The step (4) of the invention is to immerse the carrier loaded with metal in the fermentation liquor of the microorganism producing sugar ester for the adsorption growth of thalli, and the volume ratio of the carrier loaded with metal to the fermentation liquor is 1:1-3. The adsorption growth conditions are as follows: the temperature is 20-38 ℃, preferably 20-30 ℃, the pH is 6.0-8.5, preferably 6.0-7.0, and the reaction time is 12-36h.
The microorganism for producing sugar ester in step (4) of the invention is a microorganism for producing at least one sugar ester of rhamnose ester, algal glycolipid, sophorolipid and sucrose ester by fermentation, such as at least one of pseudomonas aeruginosa for producing rhamnose ester, pseudomonas aeruginosa for producing algal glycolipid, and the like. The preparation method of the microbial fermentation broth for producing sugar ester is conventional in the art.
The drying in the step (4) of the invention is drying for 24-48 h at 35-50 ℃ to obtain the immobilized carrier. The synthesized immobilized carrier needs to be stored in vacuum before use, and the storage time is generally 1-3 months.
In a second aspect, the present invention provides an oil-resistant immobilized carrier prepared by the method of the present invention. In the prepared immobilized carrier, the metal content accounts for 1-20% of the mass of the modified aerogel, the humic acid accounts for 0.1-10% of the mass of the modified aerogel, and the sugar ester producing microorganisms account for 5-50% of the mass of the modified aerogel, preferably 10-30%.
The third aspect of the invention provides application of the synthesized immobilized carrier in an oily sewage treatment system. The active microorganism in the oily sewage treatment system is mainly any one of decarbonization bacteria, dephosphorization bacteria, denitrification bacteria and the like. These microorganisms generally do not have the ability to degrade oils or the system generally does not contain microorganisms having the ability to degrade oils.
Compared with the prior art, the invention has the following beneficial effects:
(1) The inventor of the application discovers in research that the active metal loss can be avoided by adding rhamnose ester on the basis of aerogel pretreatment, humic acid modification and active metal loading, but in the process of treating oily sewage, the effect is unstable after long-term treatment and is in a downward trend, and analysis mainly shows that the bonding force between the active metal and a carrier is weakened due to partial loss of rhamnolipid, so that the treatment effect is unstable. In order to solve this problem, the present inventors supported an active metal on a modified aerogel and then adsorbed a sugar ester-producing microorganism to grow a synthesized immobilized carrier. The synthesized immobilized carrier has lasting oil resistance in use, particularly can avoid the loss of active metal, and does not influence the sewage treatment effect and the long-term stability of system operation.
(2) The method adopts humic acid modified aerogel, then loads active metal on the modified aerogel to synthesize a pre-adsorption carrier, is favorable for the enhanced adsorption of glycolipid-producing microorganisms, and through the synergistic effect of the humic acid modified aerogel, the active metal and the modified aerogel, each substance is tightly combined, has strong binding force, and cannot run off after long-term use.
(3) The synthesized immobilized carrier has a pore structure suitable for the adsorption and propagation of functional microorganisms in a treatment system, can ensure the adsorption capacity of decarbonization and denitrification microorganisms, can avoid the falling of metal ions in the carrier in the long-term treatment process, and ensures the treatment effect.
(4) The immobilized carrier provided by the invention has good oil resistance, can keep the long-acting property of the carrier application when being used in the oily sewage treatment process, and avoids the blockage of oil substances and the pollution of carrier pore passages.
Detailed Description
The method and effects of the present invention will be described in further detail by examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the embodiment of the invention, the ammonia nitrogen concentration is measured by GB7478-87 method for measuring ammonium in water quality-distillation and titration; metal ions are measured by adopting an inductively coupled plasma mass spectrometry; the effluent suspended matter adopts GB11901-89 determination-gravimetric method of water suspended matter.
Example 1
(1) Mixing carbon aerogel (specific surface area is 800 m) 2 And the porosity is 80%) is immersed in 1.5mol/L acetic acid solution for water bath reaction, the reaction temperature is 40 ℃, the oscillation is carried out for 1.5h, and the carbon aerogel after being taken out is washed by deionized water until the pH value is 7.0, so as to obtain the pretreated carbon aerogel.
(2) According to Fe (OH) 3 The mass ratio of the solution to the humic acid is 2:1 the humic acid is dissolved in 0.6mol/L Fe (OH) 3 And adding the pretreated carbon aerogel into the solution, oscillating in a water bath at 60 ℃ for 4 hours, taking out, and washing with deionized water to pH8.0 to obtain the modified aerogel.
(3) Preparing a ferrous sulfate solution with the iron ion concentration of 1mol/L, adding the modified aerogel, and soaking for 8 hours at the temperature of 65 ℃ under the stirring condition to obtain the carrier loaded with the active metal.
(4) Mixing the carrier loaded with the active metal with the fermentation liquor of the pseudomonas aeruginosa for producing rhamnosyl ester, wherein the volume ratio of the carrier to the fermentation liquor is 1:1. Adsorbing and growing for 12h under the conditions of the temperature of 30 ℃ and the pH value of 6.5 to obtain the carrier for adsorbing the pseudomonas aeruginosa. And taking out the carrier adsorbing the microorganisms, and drying the carrier at 45 ℃ for 24 hours to finally obtain the immobilized carrier.
The rhamnose ester-producing Pseudomonas aeruginosa used in this example was obtained according to the method described in "screening of biosurfactant-producing bacteria" (Pan Bingfeng, microbiological report, 6 months 1996, 39 (3)). The strain which has stable genetic character and produces rhamnose ester is obtained by enrichment culture and screening by using a blood plate and shaking flask fermentation and re-screening, and the strain is identified as pseudomonas aeruginosa by 16SrRNA and the like.
The preparation method of the pseudomonas aeruginosa fermentation liquor comprises the following steps: selecting colony on the slant, inoculating to LB culture medium, culturing at 37 deg.C and 200rpm for 24 hr to obtain seed solutionThen inoculating the seed liquid to a fermentation culture medium according to the proportion of 5%, and culturing for 7 days at the pH of 6.5, the temperature of 35 ℃ and the rpm of 200 to obtain fermentation liquid. The fermentation medium comprises the following components in percentage by mass: 5.0% of glucose, 0.5% of yeast extract and KH 2 PO 4 、MgSO 4 、FeSO 4 ·7H 2 O and CaCl.2H 2 O is 0.02 percent.
Example 2
(1) Carbon aerogel (specific surface area 800 m) 2 And the porosity is 80%) is immersed in 1mol/L acetic acid solution for water bath reaction, the reaction temperature is 30 ℃, the oscillation is carried out for 1h, the carbon aerogel is taken out and washed by deionized water until the pH value is 6.5, and the pretreated carbon aerogel is obtained.
(2) According to Fe (OH) 3 The mass ratio of the solution to the humic acid is 1:1 humic acid is added to 0.5mol/LFe (OH) 3 And adding the pretreated carbon aerogel into the solution, oscillating the solution in a water bath at 50 ℃ for 3 hours, taking out the solution, and washing the solution with deionized water until the pH value is 7.6 to obtain the modified aerogel.
(3) Preparing a ferrous sulfate solution with the iron ion concentration of 2mol/L, adding the modified aerogel into the solution, and soaking for 6 hours at the temperature of 60 ℃ under the stirring condition to obtain the loaded metal carrier.
(4) Mixing the metal-loaded carrier with the fermentation liquor of pseudomonas aeruginosa for producing the algal glycolipid, wherein the volume ratio of the carrier to the fermentation liquor is 1:3. Adsorbing and growing for 24h at 25 ℃ and pH7.0 to obtain the carrier for adsorbing the microorganisms. Taking out the carrier adsorbing the microorganisms, and drying the carrier at 35 ℃ for 48 hours to finally obtain the immobilized carrier.
Pseudomonas aeruginosa producing trehalose esters used in this example was obtained according to the method described in "screening of biosurfactant-producing bacteria" (Pan Bingfeng, microbiological report, 6 months 1996, 39 (3)). The strain which has stable genetic character and produces trehalose ester is obtained by enrichment culture and screening by using a blood plate, and the strain is identified as pseudomonas aeruginosa by 16SrRNA and the like.
The preparation method of the pseudomonas aeruginosa fermentation liquor comprises the following steps: selecting colony on the slant, inoculating to LB culture medium, culturing at 37 deg.C and 200rpm for 24 hr to obtain seed solutionThen inoculating the seed liquid to a fermentation culture medium according to the proportion of 5%, and culturing for 7 days at the pH of 6.8, the temperature of 37 ℃ and the rpm of 200 to obtain fermentation liquid. The fermentation medium comprises the following components in percentage by mass: 2.0% of glucose, 0.5% of yeast extract, 1.0% of peptone and KH 2 PO 4 、MgSO 4 、FeSO 4 ·7H 2 O and CaCl.2H 2 O is 0.02 percent.
Example 3
(1) Mixing carbon aerogel (specific surface area is 800 m) 2 And the porosity is 80%) is immersed in 2.0mol/L acetic acid solution for water bath reaction, the reaction temperature is 50 ℃, the oscillation is carried out for 2 hours, and the carbon aerogel after pretreatment is obtained after the carbon aerogel is taken out and washed by deionized water until the pH value is 7.4.
(2) According to Fe (OH) 3 The mass ratio of the solution to the humic acid is 3:1 humic acid is added to 0.8mol/L Fe (OH) 3 And adding the pretreated aerogel into the solution, oscillating in a water bath at 70 ℃ for 5h, taking out, and washing with deionized water to pH7.8 to obtain the modified aerogel.
(3) Preparing a ferrous sulfate solution with the iron ion concentration of 2mol/L, adding the modified aerogel into the solution, and stirring and dipping for 10 hours at 70 ℃ to obtain the loaded metal carrier.
(4) The volume ratio of the carrier loaded with metal to the pseudomonas aeruginosa producing rhamnose ester is 1:2. Adsorbing and growing for 36h at the temperature of 25 ℃ and the pH value of 6.0 to obtain a carrier adsorbing microorganisms; and taking out the carrier adsorbing the microorganisms, and drying at 40 ℃ for 36h to finally obtain the immobilized carrier.
Example 4
The difference from example 1 is that: silicon aerogel is adopted to replace carbon aerogel, and the specific surface area of the silicon aerogel is 1000m 2 In terms of a/g, the porosity is 85%. Finally, the immobilized carrier is prepared.
Example 5
The same as example 1, except that: cellulose aerogel is adopted to replace carbon aerogel, and the specific surface area of the cellulose aerogel is 900m 2 In terms of a/g, the porosity is 95%. Finally, the immobilized carrier is prepared.
Example 6
In the same wayExample 1, the difference is: the metal ions adopt Cu 2+ And preparing a copper chloride solution of 3mol/L to replace a ferric sulfate solution. Finally, the immobilized carrier is prepared.
Example 7
The difference from example 1 is that: the metal ion is Mg 2+ A4 mol/L magnesium sulfate solution is prepared to replace a ferric sulfate solution. Finally, the immobilized carrier is prepared.
Example 8
The same as example 1, except that: adding (NH) to the active metal ion solution at a ratio of 0.5mg/L 4 ) 6 Mo 7 O 2 ·4H 2 O and CoCl 2 Wherein (NH) 4 ) 6 Mo 7 O 2 ·4H 2 O and CoCl 2 Is 1:4. Finally, the immobilized carrier is prepared.
Comparative example 1
The difference from example 1 is that: and (3) directly modifying the humic acid in the step (2) without carrying out the pretreatment process in the step (1) on the aerogel. Finally, the immobilized carrier is prepared.
Comparative example 2
The difference from example 1 is that: in the step (2), humic acid is not used during modification, and only Fe (OH) is used 3 And (3) solution. Finally, the immobilized carrier is prepared.
Comparative example 3
The difference from example 1 is that: in the step (2), when humic acid is modified, the humic acid is dissolved in water, namely Fe (OH) is not adopted 3 And (3) solution. Finally, the immobilized carrier is prepared.
Comparative example 4
The same as example 1, except that: adding aerogel in the step (2), and reacting at 35 ℃. Finally, the immobilized carrier is prepared.
Comparative example 5
The difference from example 1 is that: and (3) washing to be neutral, rather than weakly alkaline after the reaction in the step (2). Finally, the immobilized carrier is prepared.
Comparative example 6
The difference from example 1 is that: and (3) the modified aerogel is not loaded with metal ions. Finally, the immobilized carrier is prepared.
Comparative example 7
The difference from example 1 is that: and (4) adopting rhamnolipid to replace the pseudomonas aeruginosa fermentation liquor for producing the rhamnolipid. Finally, the immobilized carrier is prepared.
Test example
The immobilization carrier prepared in examples 1-8 and comparative examples 1-7 was mixed with the nitrifying bacteria suspension according to the solid-to-liquid ratio of 1:5 to perform immobilization, and the nitrifying bacteria were immobilized when the ammonia nitrogen concentration reached 30mg/L and the ammonia nitrogen concentration in the effluent was less than 2mg/L within 6 hours.
The immobilized nitrobacteria is used for the deep denitrification treatment of oily wastewater, the concentration of ammonia nitrogen in the wastewater is 30mg/L, the concentration of petroleum is 10.0mg/L, and other metal ions are not detected in inlet water. After the test is continuously carried out for 3 months, the treatment effect is inspected, the content of the metal element is detected, and the specific result is shown in table 1.
TABLE 1
As can be seen from Table 1, the oil-resistant immobilized carrier prepared by the method has good ammonia nitrogen removal effect in three months of operation, the concentration of suspended matters in effluent is low, and metal ions are hardly detected in the effluent. The immobilized carriers prepared in comparative examples 1 to 7, which are not synthesized according to the present invention, have the phenomenon that metal ions fall off from the immobilized material, and the situation that the carriers are contaminated, both of which result in the deterioration of ammonia nitrogen treatment effect.
Claims (20)
1. A synthetic method of an oil-resistant immobilization carrier is characterized by comprising the following steps:
(1) Placing the aerogel in an acetic acid solution for reaction, taking out the aerogel and washing the aerogel to be neutral;
(2) Dissolving humic acid in Fe (OH) 3 Adding aerogel into the solution, reacting at 50-70 ℃, and washing to be alkalescent to obtain modified aerogel;
(3) Loading active metal on the modified aerogel to obtain a metal-loaded carrier;
(4) Adsorbing the microorganisms for producing sugar ester on the metal-loaded carrier, and drying to obtain the immobilized carrier after adsorption.
2. The method of claim 1, wherein: the aerogel in the step (1) is at least one of carbon aerogel, silicon aerogel and cellulose aerogel, and preferably the carbon aerogel.
3. The method according to claim 1 or 2, characterized in that: the specific surface area of the aerogel in the step (1) is 600-1100 m 2 The porosity is 80-98 percent.
4. The method of claim 1, wherein: the concentration of the acetic acid solution in the step (1) is 1.0-2.0 mol/L.
5. The method according to claim 1 or 4, characterized in that: immersing the aerogel in an acetic acid solution for reaction at the temperature of 30-50 ℃ for 1.0-2.0 h.
6. The method of claim 5, wherein: directly heating or heating in water bath in the step (1), preferably heating in water bath to 30-50 ℃ for reaction.
7. The method of claim 1, wherein: and (2) taking out the aerogel in the step (1), and washing until the pH value is neutral, wherein the pH value is generally 6.5-7.5.
8. The method of claim 1, wherein: step (2) said Fe (OH) 3 The concentration of the solution is 0.5-0.8 mol/L, fe (OH) 3 The mass ratio of the solution to the humic acid is 1:1-3:1.
9. The method according to claim 1 or 8, characterized in that: step (2) immersing aerogel in humusAcids and Fe (OH) 3 In the mixed system of the solution, carrying out water bath oscillation reaction for 3-5 h at 50-70 ℃.
10. The method of claim 9, wherein: and (3) taking out the product from the step (2), and washing the product until the pH value is alkalescent, preferably 7.6-8.0.
11. The method of claim 1, wherein: the active metal in the step (3) is Cu 2+ 、Fe 2+ 、Mg 2+ Preferably Fe 2+ 。
12. The method according to claim 1 or 11, characterized in that: and (3) soaking the substrate for 6-10 hours at 60-70 ℃ by using a soluble salt solution of active metal, wherein the concentration of metal ions is 1-4 mol/L.
13. The method according to claim 1 or 11, characterized in that: adding an auxiliary agent (comprising (NH) into the solution of the active metal in the step (3) 4 ) 6 Mo 7 O 2 ·4H 2 O and CoCl 2 The molar ratio of the two is 1:3-5, and the dosage is 0.5-1.0mg/L.
14. The method of claim 1, wherein: and (4) soaking the metal-loaded carrier in fermentation liquor of the microorganism producing the sugar ester for adsorbing and growing thallus, wherein the volume ratio of the metal-loaded carrier to the fermentation liquor is 1:1-3.
15. The method according to claim 1 or 14, characterized in that: the adsorption growth conditions in the step (4) are as follows: the temperature is 20-38 deg.C, preferably 20-30 deg.C, pH is 6.0-8.5, preferably 6.0-7.0, and reaction time is 12-36h.
16. The method of claim 1, wherein: the microorganism producing the sugar ester in the step (4) is a microorganism producing at least one sugar ester of rhamnose ester, algal glycolipid, sophorolipid and sucrose ester by fermentation, preferably at least one of pseudomonas aeruginosa producing the rhamnose ester and pseudomonas aeruginosa producing the algal glycolipid.
17. The method of claim 1, wherein: the drying in the step (4) is drying for 24-48 h at 35-50 ℃ to obtain the immobilized carrier.
18. The method of claim 1, wherein: the immobilized carrier synthesized in the step (4) needs to be stored in vacuum before use, and the storage time is 1-3 months.
19. An oil-resistant immobilization carrier synthesized by the method according to any one of claims 1 to 18.
20. The use of the immobilized carrier of claim 19, which is characterized in that the immobilized carrier is used in an oily sewage treatment system, and is directly added into the oily sewage treatment system, or is loaded when a newly-built oily sewage treatment system is started, and the active microorganism in the oily sewage treatment system is mainly any one of denitrifying bacteria, dephosphorizing bacteria and denitrifying bacteria.
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