CN108996709B - A kind of round-the-clock composite photocatalyst collaboration system and preparation method thereof - Google Patents
A kind of round-the-clock composite photocatalyst collaboration system and preparation method thereof Download PDFInfo
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- CN108996709B CN108996709B CN201810985203.9A CN201810985203A CN108996709B CN 108996709 B CN108996709 B CN 108996709B CN 201810985203 A CN201810985203 A CN 201810985203A CN 108996709 B CN108996709 B CN 108996709B
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- phenol
- sodium alginate
- degrading bacteria
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 15
- 241000894006 Bacteria Species 0.000 claims abstract description 86
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 230000000593 degrading effect Effects 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 241000222173 Candida parapsilosis Species 0.000 claims abstract description 23
- 229940055022 candida parapsilosis Drugs 0.000 claims abstract description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 88
- 239000000377 silicon dioxide Substances 0.000 claims description 44
- 239000000661 sodium alginate Substances 0.000 claims description 44
- 235000010413 sodium alginate Nutrition 0.000 claims description 44
- 229940005550 sodium alginate Drugs 0.000 claims description 44
- 230000015556 catabolic process Effects 0.000 claims description 36
- 238000006731 degradation reaction Methods 0.000 claims description 36
- 239000000725 suspension Substances 0.000 claims description 29
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- 239000001110 calcium chloride Substances 0.000 claims description 23
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 23
- 239000002077 nanosphere Substances 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229960001126 alginic acid Drugs 0.000 claims description 4
- 235000010443 alginic acid Nutrition 0.000 claims description 4
- 239000000783 alginic acid Substances 0.000 claims description 4
- 229920000615 alginic acid Polymers 0.000 claims description 4
- 150000004781 alginic acids Chemical class 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000002068 microbial inoculum Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 61
- 239000004408 titanium dioxide Substances 0.000 abstract description 29
- 239000002351 wastewater Substances 0.000 abstract description 25
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 12
- 239000010865 sewage Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 229960000935 dehydrated alcohol Drugs 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- -1 weaving Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- 239000011806 microball Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- NRWCNEBHECBWRJ-UHFFFAOYSA-M trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)C NRWCNEBHECBWRJ-UHFFFAOYSA-M 0.000 description 3
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 description 3
- 241001474374 Blennius Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 241000589516 Pseudomonas Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000588986 Alcaligenes Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000726108 Blastocystis Species 0.000 description 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 101100242191 Tetraodon nigroviridis rho gene Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 230000034303 cell budding Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052564 epsomite Inorganic materials 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 230000005405 multipole Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- QBNKFXYJSJOGEL-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ti+4] QBNKFXYJSJOGEL-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011218 seed culture Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-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
- 238000009941 weaving Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
A kind of round-the-clock composite photocatalyst collaboration system, the Candida parapsilosis bacteria agent that it is embedded by optically catalytic TiO 2 microballoon with sodium alginate form.When handling relatively deep depth, phenol sewage of translucency difference, phenol that the system still is able in effectively degrading waste water meets industrial requirement, inventor has found in R&D process simultaneously, and such combination is so that titanium dioxide is normally playing the bioactivity for nor affecting on Phenol-degrading Bacteria Strains when photocatalysis.
Description
Technical field
It degrades field the present invention relates to sewage, and in particular to a kind of microorganism/photocatalysis composite degradation system and its preparation
Method.
Background technique
Photocatalysis technology due to its can efficiently degradation of contaminant, applied in many fields, such as environmental pollution
The fields such as improvement, health care；In many photochemical catalysts, especially nano-TiO2Having in catalytic degradation water and in air
The performance advantage that machine pollutant field shows causes the extensive concern of researcher, and it has nontoxic, and chemical property is steady
It is fixed, and it has the characteristics that contaminant degradation that selective, catalytic activity is not high, although most of titanium dioxide can only be inhaled
It is low that receipts account for the full spectral energy 5% or so of sunlight, catalytic efficiency, but because it is one after another opened up by the major research team of its significant advantage
Further research is opened, is Detitanium-ore-type and unformed two if Chinese patent CN106824152A reports a kind of titanium dioxide
Titanium oxide composition, substantially increases photocatalysis efficiency；Microstructure group of the scientific research personnel to photochemical catalysts such as titanium dioxide at present
Set out at research, exploitation has the higher photochemical catalyst of quantum efficiency, for photochemical catalyst practical commercial production with proposing
Feasible scheme.But photochemical catalyst can only play catalytic action under the excitation of light, in various photochemical catalysts, nano-titanium dioxide
Photochemical catalyst plays catalytic action under the excitation of ultraviolet light, and by some toxicity, big, bio-refractory organic pollutant thoroughly drops
Solution is nontoxic inorganic molecules.However, in organic sewage process field, the bad situation of illumination condition such as the sewage depth of water, night
When late, catalytic degradation that at this moment titanium dioxide optical catalyst hardly plays catalytic action, leverages organic sewage
Energy.
Problem of environmental pollution becomes increasingly conspicuous with the development of economy, and global water pollution is on the rise, China's water pollution
Mainly from industrial pollution discharge of wastewater, wherein phenol is important industrial chemicals, be widely used in phenolic resin, oil refining,
In coke, dyestuff, weaving, insecticide, medicine and pesticide producing, and become one of the major pollutants of these industrial wastewaters.Contain
Phenolic waste water has toxic action to organism, and is difficult to be degraded, straight without liver detoxification by the contact of skin, mucous membrane
It taps into blood circulation, cell is caused to be destroyed and lose vigor.When phenol content reaches 5-10mg/L in water, fish can be caused big
Amount is dead, with wastewater containing phenol irrigated farmland, can also make crop production reduction or withered.Therefore, the discharge of phenol wastewater is not only right
Environment causes seriously to pollute, and also endangers the growth and breeding of human health and biology.
Separated some Phenol-degrading Bacteria Strains out mainly include bacterium and fungi two major classes both at home and abroad at present.Bacterium mainly includes
Pseudomonas, bacillus, Alcaligenes and Rhod；Fungi mainly includes Blastocystis, candida and not
Lever Pseudomonas etc., and there is preferable degradation of phenol effect.
Summary of the invention
It is an object of that present invention to provide the good round-the-clock complex lights of a kind of wide adaptability, catalytic degradation phenol sewage effect to urge
Change collaboration system.
Another object of the present invention is to provide the preparation method of above-mentioned composite photocatalyst system.
The object of the invention is achieved through the following technical solutions:
A kind of round-the-clock composite photocatalyst collaboration system, it is characterised in that: it is by optically catalytic TiO 2 microballoon and seaweed
The phenol degrading microbial inoculum composition of sour sodium embedding.When handling relatively deep depth, phenol sewage of translucency difference, which still is able to
Effectively the phenol in degrading waste water, meet industrial requirement.
In order to further increase the stability of composite photocatalyst system of the present invention and the bioactivity of degradation bacteria, above-mentioned phenol
Degradation bacteria is Candida parapsilosis bacterium.
Above-mentioned Candida parapsilosis bacterium (Candida parapsilosis) is GIM 2.190.
Preferably, the phenol degrading bacteria agent mass parts of above-mentioned optically catalytic TiO 2 microballoon and the embedding of above-mentioned sodium alginate
Than for 5~9:0.5~3.
Specifically, the phenol degrading bacteria agent of above-mentioned sodium alginate embedding is will to contain sodium alginate, sodium bicarbonate bottom
The suspension of object, Candida parapsilosis bacterium thallus, hanging drop of uniform size is prepared into parallel microchannel reactor；
By hanging drop obtained in CaCl2Reaction obtains in solution；Preferably, in order to preferably keep Candida parapsilosis bacterium
Bioactivity, preferably maintain even suspension state in waste water at spherical shape simultaneously, in the suspension, sodium alginate matter
It is preferably 2.5-3.5%, the Candida parapsilosis bacterium thallus that amount concentration, which is preferably 3-4%, the sodium bicarbonate mass concentration,
Concentration is preferably 0.3-0.4mg/ml, the CaCl2CaCl in solution2Mass concentration be preferably 10-20%；The suspension with
CaCl2The volume ratio of solution is 1:100-1000.
In order to further improve the stability of composite photocatalyst system of the present invention, the phenol drop of above-mentioned sodium alginate embedding
Solution bacteria agent also uses silica nanosphere to load；The Phenol-degrading Bacteria Strains of the silica nanosphere and sodium alginate embedding
The mass ratio of microbial inoculum is 1:0.3-0.5.
It is highly preferred that the phenol degrading bacteria agent of the sodium alginate embedding of above-mentioned silica nanosphere load does positive charge
Change processing；Above-mentioned optically catalytic TiO 2 microballoon positive chargeization processing.
The technical problem that composite photocatalyst system of the present invention efficiently solves microorganism and nano-photocatalyst can not coexist,
It realizes the compound system simultaneously and is uniformly dispersed, does not reunite, stable system performance is excellent, places 1 month or more and will not occur
Sedimentation phenomenon, agglomeration and the poor environment of translucency can not effectively degradation of phenol waste water the problems such as.
A kind of preparation method of round-the-clock composite photocatalyst collaboration system, it is characterised in that:
By containing sodium alginate, sodium bicarbonate substrate, Candida parapsilosis bacterium thallus suspension, use parallel microchannel
Reactor is prepared into hanging drop of uniform size；By hanging drop obtained in CaCl2Reaction obtains alginic acid in solution
The phenol degrading bacteria agent of sodium embedding；It is mixed to prepare with titanium dioxide microballoon sphere.
Preferably, the phenol degrading bacteria agent mass parts of above-mentioned optically catalytic TiO 2 microballoon and the embedding of above-mentioned sodium alginate
Than for 5~9:0.5~3.
In above-mentioned suspension, sodium alginate mass concentration is preferably that 3-4%, the sodium bicarbonate mass concentration are preferably
2.5-3.5%, the Candida parapsilosis bacterium cell concentration are preferably 0.3-0.4mg/ml, the CaCl2CaCl in solution2's
Mass concentration is preferably 10-20%；The suspension and CaCl2The volume ratio of solution is 1:100-1000.
Above-mentioned titanium dioxide microballoon sphere particle is made as follows: hexadecylamine being dissolved into dehydrated alcohol, is then added
Isopropyl titanate is added in KCl solution, the stirring at normal temperature in stirring in water bath device, and the white titania that stirring at normal temperature obtains is suspended
Liquid is stood at normal temperature, then collects titanium dioxide microballoon sphere particle with filter, and with washes of absolute alcohol titanium dioxide microballoon sphere
Particle；In order to control the formation of microsphere particle, the range of strict temperature control is needed, temperature range is best at 15 DEG C -20 DEG C.
It is further preferred that a kind of preparation method of composite photocatalyst system, it is characterised in that:
(1), by containing sodium alginate, sodium bicarbonate substrate, Candida parapsilosis bacterium thallus suspension, 120cm/
Min flow velocity is prepared into suspension of uniform size with parallel microchannel reactor；By hanging drop obtained in CaCl2Solution
Middle reaction obtains the phenol degrading bacteria agent of sodium alginate embedding；In the suspension, sodium alginate mass concentration be 3%, it is described
Sodium bicarbonate mass concentration is 3.5%, the Candida parapsilosis bacterium cell concentration is 0.4mg/ml, the CaCl2In solution
CaCl2Mass concentration be 15%；The suspension and CaCl2The volume ratio of solution is 1:600.
(2), the preparation of the phenol degrading bacteria agent of silicon dioxide carried sodium alginate embedding:
The phenol degrading bacteria agent of the sodium alginate embedding of step (1) preparation is made into suspension bacteria liquid and nano silica
Sphere is mixed and stirred for, and adsorbs and fixes bacterium solution equably in the hole of nanosphere；The nano silica sphere partial size
For 30-50nm, specific surface area 1000-1500m2/ g, hole solvent are 0.05-1.8ml/g；
(3), the phenol degrading bacteria agent of silicon dioxide carried sodium alginate embedding obtained above and titanium dioxide is micro-
Ball is mixed to prepare composite photocatalyst system；The optically catalytic TiO 2 microballoon and the silicon dioxide carried sodium alginate embed
Phenol degrading bacteria agent mass parts ratio be 7:2.
It is further preferred that above-mentioned silica supports are first carried out positive charge processing；And first by above-mentioned dioxy
Change the processing of titanium microballoon positive chargeization.
Specifically, above-mentioned silica supports first carry out positive charge processing, it is in above-mentioned steps (2), by nanometer
Silica sphere is scattered in dry toluene, is sufficiently stirred at room temperature, and N- trimethoxy silicon substrate propyl-N, N, N- tri- is added
The methanol solution of ammonio methacrylate reacts 6-8 hours at 0.3-0.5MPa, 80-85 DEG C；Mixed solution centrifugation, after centrifugation
The solid arrived is cleaned with second alcohol and water, is dried in 60-90 DEG C of baking oven overnight up to positive charge nano silica sphere.
Specifically, by the processing of above-mentioned titanium dioxide microballoon sphere positive chargeization: titanium dioxide microballoon sphere particle is dissolved in anhydrous second
In alcohol, ATPES silane coupling agent, stirring in water bath back flow reaction is added in ultrasonic treatment；Then it is cleaned and is made with deionized water.
The Candida parapsilosis bacterium that the present invention uses is purchased from Guangdong Province's Culture Collection (GDMCC), protects
Hiding number is GIM2.190.
The present invention have it is following the utility model has the advantages that
Titanium dioxide microballoon sphere of the present invention/Phenol-degrading Bacteria Strains compound system efficiently solves living microorganism and nano-photo catalytic
The technical problem that agent can not coexist, titanium dioxide microballoon sphere, Phenol-degrading Bacteria Strains are normal simultaneously under illumination condition plays Pyrogentisinic Acid's
Degradation, the collaboration efficient degradation for realizing Pyrogentisinic Acid.No matter Phenol-degrading Bacteria Strains are illumination condition is good and illumination item in system of the present invention
In the phenolic waste water water body of part difference, all there is good biological degradation activity, whether do not played by titanium dioxide microballoon sphere completely
Photocatalysis and the influence of photocatalysis power, while titanium dioxide microballoon sphere absorption property of the present invention is excellent, it is useless to be enriched with
Phenol in water further increases degradation efficiency；Through detecting, the Phenol-degrading Bacteria Strains in present complex system are in various striation parts
Under in (illumination condition or poor condition) phenolic waste water, 70% or more is reached in 60h degradation rate to phenolic waste water containing 1000mg/L,
Degradation vigor is excellent in, and is suitble to industrialization actual production requirement.Present complex system is uniformly dispersed, does not reunite simultaneously,
It places and sedimentation phenomenon, agglomeration will not occur using 3 months or more, present complex system stability is excellent；From
And present complex system efficiently solves the titanium dioxide optical catalyst in the imperfect phenolic waste water processing of illumination condition and makes
Confinement problems, the present invention realize daytime, night round-the-clock efficient degradation phenolic waste water.
Specific embodiment
The optimal example of the present invention is specifically described below by embodiment, it is necessary to which indicated herein is following reality
It applies example and is served only for that invention is further explained, should not be understood as limiting the scope of the invention, the skill in the field
Art personnel can make some nonessential modifications and adaptations to the present invention according to aforementioned present invention content.
2.190 colonial morphology of Candida parapsilosis bacterium (Candida parapsilosis) GIM that the present invention uses:
In YM culture medium culture 72 hours, microscopic morphology was cell ellipse, and multipole budding has pseudohypha；Cream color has light
Pool, smooth wet, neat in edge.
The preparation of Candida parapsilosis bacterium bacterium solution:
The activation passage of test tube master clock bacterial strain is carried out with PDA slant medium, is switched through 1 time within bacterial strain every 4 weeks.Bacterial strain turns
26 DEG C of activation culture 48h on new PDA solid plate are connected to, then is transferred to seed culture medium and is used as fermentation seed for 24 hours.
The strain selected finally is inoculated into liquid culture medium, i.e., is packed into 50mlCza culture medium (grape in 250ml triangular flask
Sugared 30g, NaNO 33g, yeast extract 1g, K2HPO 1g, MgSO4·7H2O 0.5g, KCl 0.5g, FeSO47H2O
0.01g, water 1000mL, pH 6.0；Containing 0.5% glutamic acid), bacterial strain, 28 DEG C of shaking table cultures are accessed by 2% inoculum concentration
48h；6000r min -1 is centrifuged 10min, collects thallus, both obtains Candida parapsilosis strain daughter bacteria liquid.
Embodiment 1:
A kind of round-the-clock composite photocatalyst collaboration system, is prepared as follows:
(1), by containing 3% sodium alginate, 3.5% sodium bicarbonate substrate, 0.4mg/ml Candida parapsilosis bacterium thallus
Suspension, in terms of mass concentration, 120cm/min flow velocity is prepared into suspension of uniform size with parallel microchannel reactor
Liquid；By hanging drop obtained in CaCl2Reaction obtains the phenol degrading bacteria agent of sodium alginate embedding in solution；The CaCl2
CaCl in solution2Mass concentration be 15%；The suspension and CaCl2The volume ratio of solution is 1:600.
(2), the preparation of the phenol degrading bacteria agent of silica nanosphere load sodium alginate embedding:
By nano silica sphere, (nano silica sphere partial size is 30-50nm, specific surface area 1000-1500m2/
G, hole solvent are 0.05-1.8ml/g) positive charge processing is carried out, it disperses nano silica sphere in dry toluene, receive
Mass volume ratio (g/ml) 1:30 of rice silica sphere and dry toluene, is sufficiently stirred 55 minutes at room temperature, and N- tri- is added
Methanol solution, N- trimethoxy silicon substrate propyl-N, N, N- the trimethyl chlorine of methoxyl group silicon substrate propyl-N, N, N- trimethyl ammonium chloride
The volume ratio of the methanol solution and dry toluene of changing ammonium is 1:15, N- trimethoxy silicon substrate propyl-N, N, N- trimethyl ammonium chloride
Methanol solution in methanol quality score be 60%, reacted 8 hours at 0.4MPa, 85 DEG C；Mixed solution centrifugation, after centrifugation
The solid arrived is cleaned with second alcohol and water, is dried in 90 DEG C of baking ovens overnight up to positive charge nano silica sphere；By step
(1) the phenol degrading bacteria agent of the sodium alginate embedding prepared is made into the nano silica of suspension bacteria liquid Yu above-mentioned positive charge
Sphere is mixed and stirred for, and adsorbs and fixes bacterium solution equably in the hole of nanosphere；Nano silica sphere and alginic acid
The mass ratio of the phenol degrading bacteria agent of sodium embedding is 1:0.5；
(3), by the processing of optically catalytic TiO 2 microballoon positive chargeization: titanium dioxide microballoon sphere particle is dissolved in dehydrated alcohol
In, the quality volume (mg/ml) of titanium dioxide microballoon sphere and dehydrated alcohol than being 6:1, it is silane coupled that ATPES is added in ultrasonic treatment
Agent, ATPES and dehydrated alcohol volume ratio be 1:50,60-70 DEG C stirring in water bath back flow reaction 10-12 hours；Then deionization is used
Water cleaning is made three times；
(4), by the Phenol-degrading Bacteria Strains bacterium of positive charge silica nanosphere obtained above load sodium alginate embedding
Agent and positive charge oxide/titanium dioxide photocatalytic microball are mixed to prepare composite photocatalyst system；The optically catalytic TiO 2 microballoon with
The phenol degrading bacteria agent mass parts ratio of the silica nanosphere load sodium alginate embedding is 7:2.
No matter Phenol-degrading Bacteria Strains are light transmittance is good and the phenol of light transmittance difference in composite degradation system made from above method
In waste water water body, all there is good biological degradation activity, completely not by titanium dioxide microballoon sphere whether play photocatalysis,
And the influence of photocatalysis power；Through detecting, Phenol-degrading Bacteria Strains in compound system phenolic waste water under the conditions of various light
In, 80% is reached in 60h degradation rate to phenolic waste water containing 1000mg/L, degradation vigor is excellent in, and is suitble to industrialization practical
Degradation requires.The compound system is uniformly dispersed, does not reunite simultaneously, and stable system performance is excellent, places observation in 3 months also without going out
Existing sedimentation phenomenon, agglomeration and the poor environment of translucency can not effectively degradation of phenol waste water phenomena such as.
Embodiment 2:
A kind of composite photocatalyst system, is prepared as follows:
(1), by containing 4% sodium alginate, 2.5% sodium bicarbonate substrate, 0.3mg/ml Candida parapsilosis bacterium thallus
Suspension, in terms of mass concentration, 120cm/min flow velocity is prepared into suspension of uniform size with parallel microchannel reactor
Liquid；By hanging drop obtained in CaCl2Reaction obtains the phenol degrading bacteria agent of sodium alginate embedding in solution；The CaCl2
CaCl in solution2Mass concentration be 10%；The suspension and CaCl2The volume ratio of solution is 1:1000.
(2), the preparation of the phenol degrading bacteria agent of silica nanosphere load sodium alginate embedding:
By nano silica sphere, (nano silica sphere partial size is 30-50nm, specific surface area 1000-1500m2/
G, hole solvent are 0.05-1.8ml/g) positive charge processing is carried out, it disperses nano silica sphere in dry toluene, receive
Mass volume ratio (g/ml) 1:20 of rice silica sphere and dry toluene, is sufficiently stirred 40 minutes at room temperature, and N- tri- is added
Methanol solution, N- trimethoxy silicon substrate propyl-N, N, N- the trimethyl chlorine of methoxyl group silicon substrate propyl-N, N, N- trimethyl ammonium chloride
The volume ratio of the methanol solution and dry toluene of changing ammonium is 1:20, N- trimethoxy silicon substrate propyl-N, N, N- trimethyl ammonium chloride
Methanol solution in methanol quality score be 50%, reacted 10 hours at 0.3MPa, 80 DEG C；Mixed solution centrifugation, after centrifugation
The solid arrived is cleaned with second alcohol and water, is dried in 80 DEG C of baking ovens overnight up to positive charge nano silica sphere；By step
(1) the phenol degrading bacteria agent of the sodium alginate embedding prepared is made into the nano silica of suspension bacteria liquid Yu above-mentioned positive charge
Sphere is mixed and stirred for, and adsorbs and fixes bacterium solution equably in the hole of nanosphere；Nano silica sphere and alginic acid
The mass ratio of the phenol degrading bacteria agent of sodium embedding is 1:0.3；
(3), by the processing of optically catalytic TiO 2 microballoon positive chargeization: titanium dioxide microballoon sphere particle is dissolved in dehydrated alcohol
In, the quality volume (mg/ml) of titanium dioxide microballoon sphere and dehydrated alcohol than being 4:1, it is silane coupled that ATPES is added in ultrasonic treatment
Agent, ATPES and dehydrated alcohol volume ratio be 1:40,75 DEG C stirring in water bath back flow reaction 9 hours；Then three are cleaned with deionized water
It is secondary to be made；
(4), by the Phenol-degrading Bacteria Strains bacterium of positive charge silica nanosphere obtained above load sodium alginate embedding
Agent and positive charge oxide/titanium dioxide photocatalytic microball are mixed to prepare composite photocatalyst system；The optically catalytic TiO 2 microballoon with
The phenol degrading bacteria agent mass parts ratio of the silica nanosphere load sodium alginate embedding is 3:1.
No matter Phenol-degrading Bacteria Strains are light transmittance is good and the phenol of light transmittance difference in composite degradation system made from above method
In waste water water body, all there is good biological degradation activity, completely not by titanium dioxide microballoon sphere whether play photocatalysis,
And the influence of photocatalysis power；Through detecting, Phenol-degrading Bacteria Strains in compound system phenolic waste water under the conditions of various light
In, 70% is reached in 60h degradation rate to phenolic waste water containing 1000mg/L, degradation vigor is excellent in, and is suitble to industrialization practical
Degradation requires.The compound system is uniformly dispersed, does not reunite simultaneously, and stable system performance is excellent, places observation in 3 months also without going out
Existing sedimentation phenomenon, agglomeration and the poor environment of translucency can not effectively degradation of phenol waste water phenomena such as.
Embodiment 3:
A kind of composite photocatalyst system, is prepared as follows:
(1), by containing 3.5% sodium alginate, 3% sodium bicarbonate substrate, 0.35mg/ml Candida parapsilosis bacterium thallus
Suspension, in terms of mass concentration, 100cm/min flow velocity is prepared into suspension of uniform size with parallel microchannel reactor
Liquid；By hanging drop obtained in CaCl2Reaction obtains the phenol degrading bacteria agent of sodium alginate embedding in solution；The CaCl2
CaCl in solution2Mass concentration be 20%；The suspension and CaCl2The volume ratio of solution is 1:100.
(2), the preparation of the phenol degrading bacteria agent of silica nanosphere load sodium alginate embedding:
By nano silica sphere, (nano silica sphere partial size is 30-50nm, specific surface area 1000-1500m2/
G, hole solvent are 0.05-1.8ml/g) positive charge processing is carried out, it disperses nano silica sphere in dry toluene, receive
Mass volume ratio (g/ml) 1:25 of rice silica sphere and dry toluene, is sufficiently stirred 50 minutes at room temperature, and N- tri- is added
Methanol solution, N- trimethoxy silicon substrate propyl-N, N, N- the trimethyl chlorine of methoxyl group silicon substrate propyl-N, N, N- trimethyl ammonium chloride
The volume ratio of the methanol solution and dry toluene of changing ammonium is 1:25, N- trimethoxy silicon substrate propyl-N, N, N- trimethyl ammonium chloride
Methanol solution in methanol quality score be 55%, reacted 12 hours at 0.35MPa, 60 DEG C；Mixed solution centrifugation, after centrifugation
Obtained solid is cleaned with second alcohol and water, is dried in 70 DEG C of baking ovens overnight up to positive charge nano silica sphere；It will step
Suddenly the phenol degrading bacteria agent of the sodium alginate embedding of (1) preparation is made into the nanometer titanium dioxide of suspension bacteria liquid Yu above-mentioned positive charge
Silicon ball body is mixed and stirred for, and adsorbs and fixes bacterium solution equably in the hole of nanosphere；Nano silica sphere and seaweed
The mass ratio of the phenol degrading bacteria agent of sour sodium embedding is 1:0.4；
(3), by the processing of optically catalytic TiO 2 microballoon positive chargeization: titanium dioxide microballoon sphere particle is dissolved in dehydrated alcohol
In, the quality volume (mg/ml) of titanium dioxide microballoon sphere and dehydrated alcohol than being 6:1, it is silane coupled that ATPES is added in ultrasonic treatment
Agent, ATPES and dehydrated alcohol volume ratio be 1:60,90 DEG C stirring in water bath back flow reaction 7 hours；Then three are cleaned with deionized water
It is secondary to be made；
(4), by the Phenol-degrading Bacteria Strains bacterium of positive charge silica nanosphere obtained above load sodium alginate embedding
Agent and positive charge oxide/titanium dioxide photocatalytic microball are mixed to prepare composite photocatalyst system；The optically catalytic TiO 2 microballoon with
The phenol degrading bacteria agent mass parts ratio of the silica nanosphere load sodium alginate embedding is 8:1.
No matter Phenol-degrading Bacteria Strains are light transmittance is good and the phenol of light transmittance difference in composite degradation system made from above method
In waste water water body, all there is good biological degradation activity, completely not by titanium dioxide microballoon sphere whether play photocatalysis,
And the influence of photocatalysis power；Through detecting, Phenol-degrading Bacteria Strains in compound system phenolic waste water under the conditions of various light
In, 65% is reached in 60h degradation rate to phenolic waste water containing 1000mg/L, degradation vigor is excellent in, and is suitble to industrialization practical
Degradation requires.The compound system is uniformly dispersed, does not reunite simultaneously, and stable system performance is excellent, places observation in 2 months also without going out
Existing sedimentation phenomenon, agglomeration and the poor environment of translucency can not effectively degradation of phenol waste water phenomena such as.
Claims (6)
1. a kind of round-the-clock composite photocatalyst collaboration system, it is characterised in that: it is by optically catalytic TiO 2 microballoon and alginic acid
The phenol degrading microbial inoculum composition of sodium embedding, the Phenol-degrading Bacteria Strains are Candida parapsilosis bacterium；The optically catalytic TiO 2
Microballoon and the phenol degrading bacteria agent mass parts ratio of sodium alginate embedding are 5~9:0.5~3.
2. round-the-clock composite photocatalyst collaboration system as described in claim 1, it is characterised in that: the sodium alginate embedding
Phenol degrading bacteria agent be will containing sodium alginate, sodium bicarbonate substrate, Candida parapsilosis bacterium thallus suspension, with simultaneously
Row micro passage reaction is prepared into suspension of uniform size, by hanging drop obtained in CaCl2Reaction obtains in solution
's.
3. round-the-clock composite photocatalyst collaboration system as claimed in claim 2, it is characterised in that: the sodium alginate quality is dense
Degree is 3-4%, the sodium bicarbonate mass concentration is 2.5-3.5%, the Candida parapsilosis bacterium cell concentration is 0.3-
0.4mg/ml, the CaCl2CaCl in solution2Mass concentration be 10-20%；The suspension and CaCl2The volume ratio of solution
For 1:100-1000.
4. round-the-clock composite photocatalyst collaboration system as claimed in claim 3, it is characterised in that: the sodium alginate embedding
Phenol degrading bacteria agent also uses silica nanosphere to load；The phenol of the silica nanosphere and sodium alginate embedding
The mass ratio of degradation bacterium preparation is 1:0.3-0.5.
5. round-the-clock composite photocatalyst collaboration system as claimed in claim 4, it is characterised in that: the silica nanosphere
The phenol degrading bacteria agent of the sodium alginate embedding of load does positive chargeization processing；The optically catalytic TiO 2 microballoon positive charge
Change processing.
6. a kind of preparation method of round-the-clock composite photocatalyst collaboration system, it is characterised in that:
By containing sodium alginate, sodium bicarbonate substrate, Candida parapsilosis bacterium thallus suspension, reacted with parallel microchannel
Device is prepared into suspension of uniform size；By hanging drop obtained in CaCl2Reaction obtains sodium alginate embedding in solution
Phenol degrading bacteria agent；It is mixed to prepare with optically catalytic TiO 2 microballoon；The optically catalytic TiO 2 microballoon and above-mentioned sea
The phenol degrading bacteria agent mass parts ratio of mosanom embedding is 5~9:0.5~3.
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| CN201910334803.3A CN109879449A (en) | 2018-08-28 | 2018-08-28 | A kind of preparation method of the composite catalyzing system of efficient degradation wastewater containing phenol |
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| CN109824103B (en) | 2019-03-28 | 2021-05-28 | 中国环境科学研究院 | Medium material for removing phenol pollution of underground water, preparation method and application thereof |
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