CN101077795B - Composite biological adsorption and preparing method thereof - Google Patents
Composite biological adsorption and preparing method thereof Download PDFInfo
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- CN101077795B CN101077795B CN200610081112XA CN200610081112A CN101077795B CN 101077795 B CN101077795 B CN 101077795B CN 200610081112X A CN200610081112X A CN 200610081112XA CN 200610081112 A CN200610081112 A CN 200610081112A CN 101077795 B CN101077795 B CN 101077795B
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Abstract
The present invention relates to one kind of composite biological adsorbent and its preparation process. The adsorbent is chitosan or dextran cross-linked resin with supported titania photocatalyst and surface heavy metal ion blotting, and has the functions of adsorbing heavy metal ion, and degrading and eliminating organic pollutant, pathogen and microbe from water solution. The adsorbent is prepared through cross-linking and supporting titania photocatalyst onto chitosan and other saccharide biomass, coupling molecular engram with nanometer titania photocatalyst to form surface heavy metal ion blotting in the surface. The adsorbent has high adsorption capacity, high heavy metal selectivity, and high capacity of degrading and eliminating organic pollutant, pathogen and microbe.
Description
Technical field
The present invention relates to a kind of compound bio adsorbent and preparation method thereof, particularly relate to compound multi-functional absorption agent of a kind of molecular engram and photocatalysis and preparation method thereof, this adsorbent can be applicable to removal, the recovery of heavy metal ion, removal of organic pollution, pathogen and microorganism and degraded are mainly used in the improvement of industrial wastewater and the deep purifying of drinking water.This preparation method relates to molecular imprinting and nano titanium dioxide photocatalysis load technology.
Background technology
Drinking Water in China is polluted at present, is meant that mainly ammonia nitrogen, organic matter and heavy metal ion harmful substance contents exceed standard, along with water pollution is serious day by day, and the water outlet after the conventional two stage treatment of water factory, the pollution of pathogenic microorganisms and heavy metal ion is also in continuous expansion.Traditional treatment process such as " coagulation-precipitations-filtration-sterilization " can only be removed suspension in the water, colloidal solid, and obviously not enough with respect to the removal ability of the dissolved organic matter in the contaminated water source, particularly adds Cl
2Sterilization back forms three causes (cause lure, teratogenesis, carcinogenic) material and predecessor thereof, conventional treatment method is difficult to remove especially.Therefore people have carried out broad research to the drinking water deep treatment technology.To the control drinking water pollution with increase water quality, when having brought into play better effect, also there is certain limitation in the general technology such as absorption, oxidation, biodegradation and membrane filtration that adopt: be limited in scope as secondary pollution, removal etc.In addition, in industrial wastewaters such as plating, dyestuff, process hides, metallurgy, electronics, contain contents of many kinds of heavy metal ion and organic pollution, at present, the processing method commonly used to this class waste water has method of chemical treatment, ion-exchange, adsorption method of separation, membrane separation process and microbial method etc., when these methods contain high concentration heavy metal ion solution in processing, effect is better, but when containing the micro heavy ion, processing all has certain defective, as complex process, cost is high or produce secondary pollution, and to the problems such as removal ability of organic pollution.
Chitin, shitosan and derivative thereof have nontoxic and good absorption property, as water treatment agent, can effectively handle heavy metal ion-containing waste water, have the adsorption capacity height, the selectivity height, and adsorption capacity is generally at 40～100mg/g.But directly make water treatment agent with shitosan, cost is too high, and is easy to run off in acid solution, is difficult to reclaim.Many at present employing chitosan derivatives or cross-linked chitosan are cooked water treatment agent.Chitosan derivatives, as grafting carboxymethyl chitosan glycopolymers, it is to Pd
2+And Cd
2+Has bigger adsorption capacity; Cross-linked chitosan phendioxin 5-hat-5 ethers and cross-linked chitosan phendioxin 8-hat-6 ethers are to Ag
+, Pb
2+, Cd
2+Deng higher absorption property and selectivity are arranged.The adsorption capacity of the chitosan resin after crosslinked has certain decline, but swelling not do not run off, and mechanical strength is good, and is reusable.It is also effective especially that crosslinked N-CMC is removed metal ion, as Pb harmful in the carrier-free radioactive element Co-60 in the nuke rubbish, the drinking water
2+And Cd
2+And the Mn of big concentration
2+The spent glycol bisglycidyl ether carries out crosslinked to shitosan, the crosslinked resin of gained is to Cu
2+Ion has the good adsorption effect, but compares with uncrosslinked shitosan, and sequestering power descends.At " high Chemical Engineering journal " the 15th volume the 1st phase " spherical Ni
2+The research of template chitosan resin absorption property transitivity " in people such as () He Xiaojin, reported the adsorptivity and the selectivity that improve chitosan crosslinked resin with the trace method, this method Ni
2+Trace solion, epoxychloropropane and ethylene glycol bis shrink glycidyl ethers are that crosslinking agent prepares the spherical shell polysaccharide resins, that is: shitosan is dissolved in containing NiSO
4.6H
2In the acetic acid solution of O, through granulation formation in curing agent alkali lye, through washing, add that crosslinking agent is crosslinked, washing, the desorb of strippant hydrochloric acid, washing, obtain the crosslinked chitosan resin handled through trace with regenerative agent sig water and washing again.This resin is to Ni
2+, Cu
2+, Zn
2+Have selectivity, compare with the crosslinked chitosan resin of handling without trace, its adsorbance improves 2 times.It is still higher to recycle 10 adsorption capacities.In " modern chemical industry " 2003 the 23rd the 3rd phases of volume, " novel mycelium coats preparation of adsorbent and reaches Ni
2+The research of ionic adsorption performance " in (people such as Su Haijia), reported that surperficial coating adsorbent can reduce the use cost of adsorbent.At " Joumal of Chemical Technology and Biotechnology " 2005 the 80th volumes the 4th phase " Preparation of a surface molecular imprinted adsorbent for Ni
2+Based on Penicillium chrysogenum " in people such as () Su Haijia, reported and adopted mycelium surface molecular engram method can improve adsorptive selectivity the metal target ion.
Above-mentioned various chitosan resins mainly are applicable to absorption removal heavy metal ion.Not obvious to removal effects such as organic pollution in the sewage and other microorganisms.
Nano-TiO
2Be a kind of n type semi-conducting material,, show the not available quantum size effect of traditional titanium dioxide, skin effect, small-size effect and macro quanta tunnel effect because red shift and blue shift take place the infrared vibration absworption peak of nanometer powder crystal simultaneously.Utilize TiO
2Living radical with strong oxidizing property (mainly being hydroxyl radical free radical) or hydrogen peroxide free radical that light-catalyzed reaction produces can be with the micro quantity organic pollutant in the water (as halogenated aliphatic hydrocarbon, nitro-aromatic, phenols etc.) oxidation Decomposition, and finally are oxidized to H
2O and CO
2Deng inorganic molecules; Simultaneously can kill a large amount of microorganisms such as Escherichia coli, bacteriophage, algae, bacterium and fungi.But TiO
2The nanometer powder catalyst is easily inactivation, reunion in use, reclaims difficulty, and people are with TiO for this reason
2Load on the various carriers, improve its catalytic activity, application carrier mainly contains in the research both at home and abroad: carriers such as active carbon, glass, silica gel, extra large sand, pottery, quartz.Result of study shows, adopts various carriers, and the efficiency of light energy utilization and catalytic efficiency are all had in various degree raising.But titanium dichloride load is bright in reporting to the research of bio-carriers such as shitosan.
Summary of the invention
The purpose of this invention is to provide a kind of both can Adsorption of Heavy Metal Ions, can degrade and remove the multifunctional composite biological adsorbent of organic pollution, pathogen and microorganism in the aqueous solution again; Another object of the present invention is the preparation method who proposes this compound adsorbent, and this method crosslinked loaded titanium dioxide photocatalyst on saccharide biomass such as shitosan obtains adsorbent of the present invention; Optimum purpose of the present invention is the preparation method who proposes the multi-functional compound adsorbent of molecular engram and the coupling of nano titanium dioxide photocatalysis load technology, this method is crosslinked immobilized titanium dioxide on Biomedias such as shitosan not only, make the surface have higher heavy metal ion blotting simultaneously, thereby improve the adsorption capacity, heavy metal selectivity of adsorbent and the ability of organic pollution, pathogen and microbial degradation and removal.
Compound adsorbent of the present invention is shitosan or the glucan crosslinked resin that a kind of load has titanium dioxide optical catalyst, and wherein the amount ratio of shitosan or glucan and TiO2 (by mass ratio) is: 100: 0.1-1: 10g/g.
The preferred scheme of the present invention is: it is nucleocapsid structure that above-mentioned load has the shitosan of titanium dioxide optical catalyst or glucan crosslinked resin, the nuclear core material is mycelium, agricultural wastes or inorganic material, clad is shitosan or the glucan that load has titanium dioxide optical catalyst, wherein by quality ratio, coating layer material is 1 with the amount ratio of nuclear core material: 50-20: 1g/g.
The more excellent scheme of the present invention is: above-mentioned load has the shitosan of titanium dioxide optical catalyst or glucan crosslinked resin surface that the heavy metal ion blotting that stays by the trace method is arranged, to improve the adsorptive selectivity of adsorbent.
The discarded mycelium of above-mentioned nuclear core material fermentation industry is: mould mycelia, saccharomycete, lemon mycelia; Agricultural wastes are: skin of beancurd, stalk, corncob; Inorganic medium is: active carbon, glass, silica gel, extra large sand, pottery, active carbon, quartz, zeolite.
Above-mentioned shitosan comprises the derivative of shitosan: CMC, N-CMC, grafting CMC, shitosan phendioxin 5-hat-5 ethers or shitosan phendioxin 8-hat-6 ethers.
Above-mentioned TiO2 is nm-class rutile-type or Detitanium-ore-type; The nano-TiO of metal-doped or nonmetal doping
2
Shitosan of the present invention or glucan crosslinked resin are spherical resin, and spherolite directly is 0.1-50mm.
Compound bio preparation of adsorbent method of the present invention: shitosan or glucan are dissolved in the acid solution, add nano titanium oxide mixing, spread loads, the consumption of shitosan and nano titanium oxide by quality ratio, the amount ratio of shitosan or glucan and TiO2 is: 100: 0.1-1: 10g/g.Add crosslinking agent then, the consumption of crosslinking agent is the every gram adsorbent of 0.01～10ml/, mixed crosslinked 0.5～24 hour down at 10～80 ℃, the crosslinked mixed solution that finishes is added drop-wise in the curing solution, consolidation liquid concentration is 0.5%～20%wt, the consumption of curing agent is the every gram adsorbent of 5～200ml/, solidified 0.5-24 hour, and obtained shitosan or glucan crosslinked resin that load has titanium dioxide optical catalyst, that is: the compound bio adsorbent.
The preferred nucleocapsid structure compound bio of the present invention preparation of adsorbent method: in the acid solution of above-mentioned shitosan or glucan dissolving, adding mycelium, agricultural wastes or inorganic material nuclear core material earlier mixes, coats, add nano titanium oxide mixing, spread loads again, it is crosslinked to add crosslinking agent then, obtains examining core and coats load outward the shitosan of titanium dioxide optical catalyst or the nucleocapsid structure crosslinked resin of glucan are arranged.Wherein by quality ratio, coating layer material is 1 with the amount ratio of nuclear core material: 50-20: 1g/g.
The compound bio preparation of adsorbent method of the molecular engram of optimum of the present invention and optically catalytic TiO 2 coupling: in the shitosan mixed solution that adds titanium dioxide, add the trace solion and carry out the trace processing, trace solion concentration is 20～10000mg/L, trace solion and sorbent material amount ratio are 5～50ml/g, the trace processing time is in 6 hours, add crosslinking agent again, the consumption of crosslinking agent is the every gram adsorbent of 0.01～10ml/, mixed crosslinked 0.5～24 hour down at 10～80 ℃, the crosslinked mixed solution that finishes is added drop-wise in the curing solution, consolidation liquid concentration is 0.5%～20%wt, the consumption of curing agent is the every gram adsorbent of 5～200ml/, solidified 0.5-24 hour, wash then, desorb and regeneration post processing obtain the shitosan of molecular engram and optically catalytic TiO 2 coupling or the crosslinked resin compound bio adsorbent of glucan.
After above-mentioned trace is handled, the regeneration last handling process is: use the deionized water rinsing microballoon, to neutral, microballoon is carried out desorb to stripping workshop, stripping liquid concentration is 0.01-20%wt, the consumption of strippant is the every gram shitosan of 5～50ml/, stirs desorb 0.5-10 hour, microballoon is moved in the actified solution regenerate again, regenerative agent concentration is 0.05～2mol/L in the regenerated liquid, the consumption of regenerative agent is the every gram adsorbent of 10～50ml/, and is after the regeneration, that the microballoon flushing is extremely neutral.
Above-mentioned trace solion is nickel, chromium, copper, silver, lead, manganese, aluminium, mercury, zinc or cadmium salt soln.Strippant is hydrochloric acid, nitric acid, sulfuric acid, acetate, oxalic acid or chelating agent, and chelating agent is iminodiacetic acid, ether azoles or disodium edta.
The crosslinking agent that the present invention uses is the selected crosslinking agent of common chitosan crosslinked resin: ethylene glycol bis shrink glycidyl ethers, glutaraldehyde, formaldehyde, epoxychloropropane, vulcabond or ethylene glycol bis glycidol ether.
The present invention adopts that fluid bed, agitator or revolving bed mix, coating, spread loads, wherein, feeds nitrogen or air, operating gas velocity 0.1～20m/s, load time 0.5h～12h during the fluid bed load; Rotating speed is 20～200 rev/mins when stirring load, 10～80 ℃ of temperature; During the revolving bed load 20～200 rev/mins, 10～80 ℃ of temperature.
Compound adsorbent of the present invention both can Adsorption of Heavy Metal Ions, can degrade and remove again organic pollution, pathogen and microorganism in the aqueous solution realization multi-functional compound; Adopt the prepared water treatment agent of the present invention, be applicable to the content 1～2000ppm of heavy metal ion, pH is 2～11 scopes, and organic pollution COD concentration is 50-2000ppm, and bacterial content is: 0-10
5The drinking water deep of cfu/ml is administered or Industrial Wastewater Treatment, as: the improvement of dyestuff, plating, metallurgy, process hides, electronics and phenol wastewater etc.Adsorbent repeatedly uses and reaches that adsorption capacity and organic removal rate and sterilizing rate obviously do not go down more than 20 times yet.
The preparation method of the compound adsorbent that the present invention proposes, adopt crosslinked immobilized nano TiO 2s such as shitosan or glucan, not only can Adsorption of Heavy Metal Ions, also fully can bring into play the photocatalysis of titanium dioxide, obviously improve compound adsorbent organic matter, pathogen and microbial degradation and removal ability.Compound adsorbent particularly of the present invention is all higher through trace processing adsorption capacity and selectivity.Preferred in addition nucleocapsid structure adsorbent can be saved cost.
The specific embodiment
Below by embodiment method provided by the invention is further specified, but not thereby limiting the invention, also should comprise: do not departing under the scope of the invention condition, disclosed scheme is carried out the apparent various changes of those skilled in the art.
The measuring method of the heavy metal ion adsorbed capacity of the present invention is as follows: the aqueous solution that 0.15g adsorbent and 50ml is contained heavy metal ion joins in the conical flask of 150ml, at room temperature, rotating speed 150dyn/m vibrates after 24 hours (adsorption equilibrium), survey GOLD FROM PLATING SOLUTION and belong to ion concentration, calculate adsorption capacity according to following formula.Q=(Co-Ce) V/W (mg/g) is wherein: Q-adsorption capacity (mg/g); Concentration of heavy metal ion (mg/L) before the Co-absorption; The concentration (mg/L) of Ce-absorption back heavy metal ion; W-adsorbent dry weight (g); V-liquor capacity (L).
The measuring method of organic pollution of the present invention or removal of microorganisms rate is as follows: the aqueous solution that 0.15g adsorbent and 50ml is contained organic pollution or microorganism joins in the conical flask of 150ml, at room temperature, rotating speed 150dyn/m vibrates after 6-24 hour (degraded balance), survey residue organic pollution or microorganism concn in the solution, calculate adsorption capacity according to following formula.R=(Po-Pe)/Po (mg/g) is wherein: R-clearance (mg/g); The concentration (mg/L) of organic pollution or microorganism before the Po-degraded; The concentration (mg/L) of Pe-degraded back organic pollution or microorganism.
Embodiment 1: get in the aqueous hydrochloric acid solution that glucan 10g is dissolved in 10ml, 0.01M, with the immobilized average grain diameter of fluid bed be 50nm mix Fe anatase type nano TiO
20.01g, operating gas velocity 20m/s, immobilized time 12h.Add the 0.1ml glutaraldehyde and make crosslinking agent, 80 ℃ of crosslinking temperatures, crosslinking time 0.5 hour.Filtration spends deionised water after neutrality, and adding 200ml, 0.5% sodium phosphate trimer are made curing agent, behind the curing 1h, filters and spends deionised water to neutral, and drying obtains the biological adsorption agent that dried resin is the area load nano TiO 2.Get 0.15g dried resin and 50ml Ag
2NO
3The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion A g
+Adsorption capacity be 36mg/g.Show that by experimental result this adsorbent can use in the scope of pH=2～11 broads; At Ag
2+Concentration is under the situation of 200mg/l, reuses 20 times, and adsorption capacity does not still have obvious reduction.Get the aqueous solution that 0.15g dried resin and 50ml contain methyl orange, join in the conical flask of 150ml, under the ultraviolet light, rotating speed 150dyn/m vibration is after 12 hours, and the clearance of surveying methyl orange in the solution is 55%.Show and in the scope of pH=2～11 broads, to use by experimental result; Under the situation that methyl orange exists, can use 20 times, degradation effect of organic compound does not still have obvious reduction.
The method of operating of embodiment 2, embodiment 3 is with embodiment 1, and operating parameter sees Table 1.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Coating layer material | Glucan 10g | CMC 10g | Shitosan 0.1g |
| Acid, consumption and concentration | Hydrochloric acid 10mi, 0.01M | Acetate 150ml, 0.05M | Citric acid 200ml, 0.5M |
| TiO2, consumption and particle diameter | Detitanium-ore-type, 0.01g ,≤50nm | Sharp too ore deposit type, 0.05g ,≤30nm | Nitrating TiO2,1g ,≤80nm |
| Crosslinking agent, consumption temperature and time | Glutaraldehyde 0.1ml, 80 ℃, 0.5hr | Two different hydrogen acid ether (hydrogen acid ester) 1.0ml, 40 ℃, 10hr | Epoxychloropropane 10ml, 10 ℃, 24hr |
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Curing agent, consumption concentration and time | Sodium phosphate trimer, 0.5%, 200ml, 1h | NaOH，10％，50ml，6h | Ammoniacal liquor, 20%, 200ml, 12h |
| Regeneration times | 20 | / | / |
| Species of metal ion, adsorption capacity Q | Ag+，36mg/g | Ni2+，45mg/g | Cu2+12mg/g |
| Organism kinds, light source, degradation rate % | Methyl orange, ultraviolet light, 55% | Methylene blue, visible light,＜30% | Visible light＜60% |
Embodiment 4: get in the aqueous hydrochloric acid solution that glucan 2g is dissolved in 10ml, 0.001M, add the silica gel 10g of particle diameter≤0.5mm, coat with revolving bed, operating gas velocity 20m/s coats time 8h.With the immobilized Fe nano-TiO of mixing of revolving bed
20.1g, operating gas velocity 200m/s, immobilized time 2h.Add 20ml ethylene glycol bis glycidol ether and make crosslinking agent, 80 ℃ of crosslinking temperatures, crosslinking time 1 hour.Filtration spends deionised water after neutrality, adds 50ml, 10%NaHCO
3Make curing agent, behind the curing 1h, filter and spend deionised water to neutral, drying obtains dried resin and is surperficial clad nano TiO2 biological adsorption agent.Get 0.15g dried resin and 50ml PbNO
3The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Pb
2+Adsorption capacity be 45mg/g.Show that by experimental result this adsorbent can use in the scope of pH=2～11 broads; At Ag
2+Concentration is under the situation of 200mg/l, reuses 20 times, and adsorption capacity does not still have obvious reduction.Get the aqueous solution that 0.15g dried resin and 50ml contain methyl orange, join in the conical flask of 150ml, under the visible light, rotating speed 150dyn/m vibration is after 12 hours, and the clearance of surveying methyl orange in the solution is 60%.Show and in the scope of pH=2～11 broads, to use by experimental result; Under the situation that methyl orange exists, can use 20 times, degradation effect of organic compound does not still have obvious reduction.
The method of operating of embodiment 5, embodiment 6 is with embodiment 4, and operating parameter sees Table 2.
| Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Coating layer material | Glucan 2g | N-CMC 1g | Shitosan phendioxin 8-is preced with-6 ether 0.1g |
| Acid, consumption and concentration | Hydrochloric acid 10ml, 0.001M | Acetate 200ml, 0.5M | Phosphatase 11 50ml, 0.05M |
| TiO2, consumption and particle diameter | The nitrating Detitanium-ore-type, 0.1g ,≤20nm | Detitanium-ore-type, 0.1g ,≤30nm | Nitrating TiO2,0.1g ,≤80nm |
| Core material, consumption and particle diameter | Silica gel 10g ,≤0.5mm | Zeolite 10g ,≤0.05mm | Penicillium notatum 10g ,≤0.5mm |
| Crosslinking agent, consumption temperature and time | Ethylene glycol bis glycidol ether 20ml, 80 ℃, lhr | Epoxychloropropane 3ml, 40 ℃, 10hr | Glutaraldehyde 0.5ml, 10 ℃, 24hr |
| Curing agent, consumption concentration and time | NaHCO3，10％，50ml，1h | Ammoniacal liquor, 10%, 300ml, 6h | Sodium phosphate trimer, 20%, 200ml, 12h |
| Regeneration times | / | / | 20 |
| Species of metal ion, adsorption capacity Q | Pb2+，45mg/g | Cr3+，32mg/g | Cd2+28mg/g |
| Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Organism kinds, light source, degradation rate % | P-nitrophenol, ultraviolet light, 65% | Methylene blue, visible light,＜60% | Methyl orange, visible light＜30% |
Embodiment 7: get grafting CMC 5g, be dissolved in the aqueous solution of nitric acid of 30ml, 0.01M, treat grafting CMC dissolving after, add 5ml, the CuSO of 2000mg/l
4The aqueous solution, trace 2 hours is with the immobilized nanometer 0.1g TiO2 of fluid bed, operating gas velocity 0.5m/s, immobilized time 12h; Drip the 10ml glutaraldehyde, 10 ℃ of crosslinking temperatures, crosslinking time 10 hours.Filtration spends deionised water to neutral, add the 200ml sodium phosphate trimer and make curing agent, solidify concentration 5% (w/w), solidify after 6 hours, filtration spends deionised water to neutral, the nitric acid that adds 25ml0.01M is cooked strippant, desorption time 24 hours, filtration spend deionised water to neutral, the sodium acid carbonate that adds 1M 50ml is cooked regenerative agent, regenerated 10 minutes, filtration spends deionised water to neutral, oven dry, and the dried resin that obtains is surface molecule print and nano TiO 2 coupled biological adsorbent.Get the Cu of 0.15g dried resin and 50ml200mg/l
2SO
4The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Cu
2+Adsorption capacity be 78mg/g.Show and in the scope of pH=2～11 broads, to use by experimental result; At Cu
2+Concentration is under the situation of 200mg/l, can use 20 times, and adsorption capacity does not still have obvious reduction.Get the aqueous solution that 0.15g dried resin and 50ml contain the 20mg/l p-nitrophenol, join in the conical flask of 150ml, under the ultraviolet light, rotating speed 50dyn/m vibration is after 4 hours, and the clearance of surveying p-nitrophenol in the solution is 92%.Get 0.15g dried resin and 50ml and contain Escherichia coli 10
4The aqueous solution of CFU/ml joins in the conical flask of 150ml, and under the ultraviolet light, rotating speed 50dyn/m vibration is after 24 hours, and colibacillary clearance is 90% in the survey solution.Show and in the scope of pH=2～11 broads, to use by experimental result; Can use 20 times, degradation effect of organic compound does not still have obvious reduction.
The method of operating of embodiment 7, embodiment 8, embodiment 9 is with embodiment 7, and operating parameter sees Table 3.
Embodiment 10: get shitosan 1g, be dissolved in 20ml, in the aqueous citric acid solution of 0.05M, treat shitosan dissolving after, add the NiSO of 5ml, 1000mg/L
4The aqueous solution, trace 0.5 hour adds the anatase type nano TiO of particle diameter less than 30nm
20.01g, with stirring load, 100 rev/mins of rotating speeds, 40 ℃ of temperature; The active carbon 1g that adds particle diameter≤0.25mm coats 150 rev/mins of rotating speeds, 20 ℃ of temperature with stirring; Drip the 2ml epoxychloropropane, 60 ℃ of crosslinking temperatures, crosslinking time 2 hours.Solidify with 200ml NaHCO curing agent, solidify concentration 5% (w/w), solidify after 6 hours, 100ml, the sulfuric acid of 0.05M is cooked strippant, desorption time 12 hours, filtration spend deionised water to neutral, the NaOH that adds 0.05M 100ml cooks regenerative agent, regenerates 10 minutes, filters to spend deionised water to neutral, oven dry, the dried resin that obtains is molecular engram and nano TiO 2 coupled biological adsorbent.Get 0.15g dried resin and 50ml, 200mg/l Ni
2SO
4The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Ni
2+Adsorption capacity be 48mg/g.Show and in the scope of pH=2～11 broads, to use by experimental result; At Ni
2+Concentration is under the situation of 400mg/l, can use 20 times, and adsorption capacity does not still have obvious reduction.Get the aqueous solution that 0.15g dried resin and 50ml contain the 20mg/l p-nitrophenol, join in the conical flask of 150ml, under the ultraviolet light, rotating speed 50dyn/m vibration is after 4 hours, and the clearance of surveying p-nitrophenol in the solution is 70%., get 0.15g dried resin and 50ml and contain Candida albicans 10
4The aqueous solution of CFU/ml joins in the conical flask of 150ml, and under the ultraviolet light, rotating speed 100dyn/m vibration is after 24 hours, and the clearance of surveying Candida albicans in the solution is 70%.Show and in the scope of pH=2～11 broads, to use by experimental result; Under the situation that Escherichia coli exist, can use 20 times, sterilizing rate does not still have obvious reduction.
The method of operating of embodiment 10, embodiment 11, embodiment 12 is with embodiment 10, and operating parameter sees Table 3.
Comparative Examples 1: get dried mould mycelia of 0.15g and 50ml NiSO
4The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Ni
2+Adsorption capacity be 20.1mg/g.Access times 3 times obviously reduce to the adsorption capacity of Ni2+ with to the degradation rate of methyl orange.Get dried mould mycelia of 0.15g and 50ml methyl orange aqueous solution, join in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), the clearance of surveying methyl orange in the solution is 10%.Access times 2 times are almost 0 to the degradation rate of methyl orange.Comparative Examples 2: get 0.15g pure chitosan and 50ml CuSO
4The aqueous solution joins in the conical flask of 150ml, and at room temperature, rotating speed 100dyn/m vibration 24 hours is surveyed GOLD FROM PLATING SOLUTION and belonged to ion Cu
2+Adsorption capacity be 55mg/g.PH can not be lower than 4.0 during use.Get the 0.15g pure chitosan and the 50ml Escherichia coli aqueous solution, join in the conical flask of 150ml, at room temperature, after vibrate under the rotating speed 100dyn/m, visible light 24 hours (adsorption equilibrium), colibacillary degradation rate is 10% in the survey solution.PH can not be lower than 4.0 during use.Comparative Examples 3: get 0.15g and mix the Fe nano-TiO
2With 50ml CuSO
4The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 100dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Cu
2+Adsorption capacity be 5mg/g.Mix the Fe nano-TiO
2Need centrifugal recovery, lose bigger.Get and mix the Fe nano-TiO
2With the 50ml Escherichia coli aqueous solution, join in the conical flask of 150ml, at room temperature, after vibrate under the rotating speed 100dyn/m, visible light 24 hours (adsorption equilibrium), colibacillary degradation rate is 95% in the survey solution.Mix the Fe nano-TiO
2Need centrifugal recovery, lose bigger.
Claims (5)
1. compound bio preparation of adsorbent method, it is characterized in that, shitosan or glucan are dissolved in the acid solution, the concentration of acid is 0.001-0.5M, acid is 1～200ml/g with the amount ratio of shitosan or glucan, adding the nuclear core material earlier mixes, coat, coating layer material is 1 with the amount ratio of nuclear core material: 50-20: 1g/g, adding nano titanium oxide again mixes, spread loads, add the trace solion then and carry out the trace processing, trace solion concentration is 20～10000mg/L, trace solion consumption is the every gram adsorbent of 1～50ml/, the trace processing time is in 6 hours, it is crosslinked to add crosslinking agent again, the amount ratio of shitosan and nano titanium oxide is 100: 0.1-1: 10g/g, mixed crosslinked 0.5～24 hour down at 10～80 ℃, the crosslinked mixed solution that finishes is added drop-wise in the curing solution solidifies, curing solution concentration is 0.5%～20%wt, the consumption of curing agent is the every gram adsorbent of 5～200ml/, solidified 0.5-24 hour, and washed then, desorb and regeneration post processing obtain the compound bio adsorbent.
2. preparation method according to claim 1 is characterized in that, the trace solion is nickel, chromium, copper, silver, lead, manganese, aluminium, mercury, zinc or cadmium salt soln; Strippant is hydrochloric acid, nitric acid, sulfuric acid, acetate, oxalic acid or chelating agent, and chelating agent is iminodiacetic acid, ether azoles or disodium edta.
3. preparation method according to claim 1 is characterized in that, crosslinking agent is ethylene glycol bis shrink glycidyl ethers, glutaraldehyde, formaldehyde, epoxychloropropane, vulcabond or ethylene glycol bis glycidol ether.
4. preparation method according to claim 1 is characterized in that, adopts fluid bed, agitator or revolving bed to carry out the titanium dioxide spread loads or/and coat mixing, wherein, feed nitrogen or air, operating gas velocity 0.1～20m/s, load time 0.5h～12h during the fluid bed load; Rotating speed is 20～200 rev/mins when stirring load, 10～80 ℃ of temperature; During the revolving bed load 20～200 rev/mins, 10～80 ℃ of temperature.
5. according to the preparation method of claim 1, it is characterized in that described nuclear core material is mycelium, agricultural wastes or inorganic material.
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