CN1853784A - Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst - Google Patents
Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst Download PDFInfo
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- CN1853784A CN1853784A CNA200510064496XA CN200510064496A CN1853784A CN 1853784 A CN1853784 A CN 1853784A CN A200510064496X A CNA200510064496X A CN A200510064496XA CN 200510064496 A CN200510064496 A CN 200510064496A CN 1853784 A CN1853784 A CN 1853784A
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Abstract
A photolytic process for degradating organic pollutants by use of a solid photocatalyst which contains laminous clay as carrier and metal-organic match carried by said carrier includes such steps as adding oxidant and said solid photocatalyst to the solution of organic pollutants, and light irradiation while selective photocatalytic oxidizing to degradate the organic pollutants.
Description
Technical field
The present invention relates to the organic contamination substance treating method, particularly relate to a kind of method and special-purpose solid-phase photocatalyst thereof of photocatalysis degradation organic contaminant.
Background technology
The Fenton oxidizing process is (by Fe
2+And H
2O
2Hybrid reaction) be a kind of senior chemical oxidization method, be usually used in the advanced treating of waste water, to remove chemical oxygen consumption (COC) (COD), colourity and organic pollution, its mechanism of action is to utilize ferrous ion to produce hydroxyl radical free radical (HO as the catalyst of hydrogen peroxide
●), hydroxyl radical free radical has very high oxidizing potential (E=+2.8V (Vs NHE)), and electrophilic addition reaction, substitution reaction and electron transfer reaction can take place with most organic matter and make the oxidation operation degraded in it.Though the Fenton oxidizing process is a kind of very effective method of wastewater treatment, because the existence of a large amount of iron ions in the system makes that the system after handling has color.In addition, reaction generally need be carried out in less than 3 acid medium and the extensive use of problem limited this method such as the utilization rate of hydrogen peroxide is not high in course of reaction, mineralization degree is low at pH.Therefore, some Fenton method for oxidation that improved arise at the historic moment.
Recently, people are aided with ultraviolet or visible radiation with Fenton reagent, have developed light to help-the Fenton technology, have greatly improved the oxidation efficiency of Fenton reagent.This type of document has " Journal of Molecular Catalysis magazine " to roll up the 77th page article " light of radiation of visible light-Fenton degradation of dye " (Wu, K. in 1999 144; Xie, Y.; Zhao, J.; Hidaka, H.Photo-Fenton degradation of a dye under visible light irradiation, J.Mol.Catal.) and article " light degradation chlorophenoxy herbicide in the presence of iron ion and the hydrogen peroxide " (Pignatello of the 944th page of " environmental science and the technology " of American Chemical Society 1992 26 volume, J.J.Dark andphotoassisted iron (3+)-catalyzed degradation of chlorophenoxy herbicides byhydrogen peroxide, Environ.Sci.Technol.).Wherein, adopt ferrous sulfate or iron ammonium sulfate usually as light-catalysed molysite, but will accumulate a large amount of iron ions in the reaction system after handling like this, the removal of iron ion or recovery need to consume a large amount of reagent and corresponding handling process and equipment.In order to solve this critical problem, there is research to report and substitutes the homogeneous phase molysite, to realize the reusable purpose of non-discharging of catalyst with the heterophase Fenton catalyst.This type of document has article " in improving the Fenton reaction reducing agent to the desorption that improves chloride fatty compound and in transforming role " (Watts, the R.J. of the 3432nd page of American Chemical Society's " environmental science and technology " 1999 33 volume; Bottenberg, B.C.; Hess, T.F.; Jensen, M.D.; Teel, A.L.Role of reductants in the enhanced desorption and transformation ofChloroliphatic compounds by modified Fenton ' s reactions, Environ.Sci.Technol.) and people such as Swissification scholar the Kiwi article " degraded, light degradation and the biodegradation of the amino-phenol that iron oxide participates in " (Pulgarin, the C. that on " Langmiur " nineteen ninety-fives 11 the 519th page of volume, deliver; Kiwi, J.Iron oxide-mediated degradation, photodegradation, and biodegradation ofaminophenols, Langmuir, 1995,11,519).Although iron oxide has been attempted using in batch (-type) and fixed bed continuous system as the catalyst of organic pollution oxidation, and the accelerated decomposition of hydrogen peroxide and the minimizing of pollutant have been observed, but this light helps reaction only can carry out under UV-irradiation, use ultraviolet light to have some limitations, big as power consumption, cost an arm and a leg, and only contain in the sunshine and be lower than 5% ultraviolet light, therefore, attempt handling waste water to environmental protection with energy-conservationly all be extremely important with low price, visible light with low cost or sunshine.
Chinese invention patent (a kind of bionic visible light solid-phase catalyst and preparation method thereof, ZL01118066.8) complex that metal ion and nitrogenous organic ligand are formed loads on the cationic ion-exchange resin, and issuing existing malicious organic pollution (comprising coloured dye of positive ion rhodamine B, peacock green, methylene blue and pollutants such as colourless organic matter chlorophenol, quaternary amine) at radiation of visible light can be in the scope (2～9) of wider pH with the optionally oxidized degraded of higher speed.It should be noted that because vector resin is organic aggregation, its hear resistance, resistance to acids and bases are poor, and the characteristics of instability etc. make the application of these carriers be subjected to certain restriction in organic solvent.
Summary of the invention
The purpose of this invention is to provide a kind of method and special-purpose solid-phase photocatalyst thereof that can using visible light carries out photocatalysis degradation organic contaminant.
Solid-phase photocatalyst provided by the present invention comprises carrier and the metal-organic coordination compound that loads on the carrier, and wherein, carrier is a lamellar clay.
Lamellar clay commonly used is stratiform Magnesosilicate or alumino-silicate; Such clay can also be handled through surfactant; The load capacity of metal-organic coordination compound is the 0.01-2mmol/g carrier.
Metal-organic coordination compound commonly used is a metal bipyridyl complex, metalloporphyrin complex or metal ferrosin complex etc.More specifically, bipyridyl iron is arranged, bipyridyl ruthenium, bipyridyl manganese, ferriporphyrin, manganoporphyrin, cobalt porphyrin, ferrosin iron, ferrosin manganese or ferrosin cobalt etc.
Adopt conventional method, silicon magnesium (aluminium) hydrochlorate of stratiform or silicon magnesium (aluminium) hydrochlorate and the water-soluble metal-organic coordination compound of surfactant modified mistake are exchanged load, load capacity generally is controlled at 0.01 to the 2mmol/g clay, promptly can make catalyst of the present invention after the clean dry.
The method of photocatalysis degradation organic contaminant of the present invention is to add oxidant and solid-phase photocatalyst of the present invention, catalyze and degrade organic pollutants under illumination condition in organic pollution solution.
Wherein, the optical wavelength of illumination condition is 250nm-800nm, and light reaction is carried out under visible light, ultraviolet light or sunshine; Oxidant is hydrogen peroxide or molecular oxygen.
Its mode of operation can be carried out as follows: catalyst is packed in the thermopnore, and the admission space rate is 1%-80%, penetrates down in illumination then, will contain the toxic organic pollutant water body to go into by column bottoms pump, and H
2O
2And stream enters at the bottom of tower, or feeds an amount of air.Simultaneously, in the middle of light source (halogen lamp, xenon lamp, mercury lamp etc.) insertion reactor, penetrate hybrid reaction degraded down, also can in dispersion, divide back the formula light reaction in illumination.If use the sunshine degraded, then make Photoreactor that big light-receiving area is arranged as far as possible.In addition, for the bigger polluted-water of concentration, do not reach the degraded requirement as the one-level tower, the multistage tower of can contacting is handled.
The present invention loads on compound metal bipyridyl, metalloporphyrin and metal ferrosin respectively and makes solid-phase photocatalyst on the clay, under temperate condition (normal temperature and pressure), radiation of visible light out-phase water reaction system can optionally degrade positively charged or adsorption capacity is stronger on this clay organic pollution (comprising rhodamine B, peacock green and small organic molecule nitrogen, pollutants such as nitrogen-dimethylaniline); Simultaneously, through the clay of surfactant organic decoration in load after the metal organic complex, can some uncharged micromolecular compounds of absorption degradation (2,4, the 6-trichlorophenol); Catalyst is not found significantly active the reduction through recycling.The use amount of catalyst is minimum can be arrived 2 gram/ton sewage (by pollutant levels is 2 * 10
-4The M meter), if visual intensity is 110 milliwatt/square centimeters, handles waste water per ton and (contain 2 * 10
-5～1 * 10
-3M bio-refractory dyestuff and nitrogen, organic matters such as nitrogen-dimethylaniline) need in reaction bed is flowed in the suspensions of 10 gram catalyst, light reaction 3～7 hours be that degradable finishes only, there is not light-struck contrast experiment then to react hardly.
Catalyst of the present invention can trigger H under radiation of visible light
2O
2Organic matter in the effective oxidative degradation water body of perhaps airborne molecular oxygen has been exempted the removal operation of the complexity of iron ion in the Fenton reaction system, has reduced operating cost; Catalyst carrier is a clay, has the high advantage of heat endurance height, organic solvent-resistant and mechanical strength, can overcome to adopt the defective of resin as catalyst carrier; Utilize surfactant to be inserted in the argillic horizon, clay is organised modify the prepared catalyst in back, make that some uncharged micromolecular compounds also can effectively be adsorbed onto on the catalyst, thereby be degraded by ion-exchange.The inventive method can be used for the purified treatment of organic pollution in industrial wastewater and city domestic sewage, cell sizes water supply, swimming-pool water and the drinking water, also can control degree of oxidation and carries out the selective photocatalysis oxidation by adding the low dosage oxidant.
Description of drawings
Fig. 1 is embodiment 1 a rhodamine B concentration changes with time curve;
Fig. 2 is the catalyst result of 12 degradeds of circulation rhodamine B continuously;
Fig. 3 is embodiment 2N, accelerine concentration changes with time curve;
Fig. 4 is embodiment 3 rhodamine B concentration changes with time curves;
Fig. 5 is embodiment 62,4, and the 6-trichlorophenol is change curve in time.
The specific embodiment
For the ease of the absorption of metal-organic coordination compound on clay, clay generally also needs to carry out preliminary treatment before use: clay was stirred 12 hours in the 1M sodium chloride solution, make that the clay balance cation is a sodium ion, water (referring to ultra-pure water) drip washing places vacuum desiccator standby clay to there not being chlorion to be washed then then.
One, Preparation of catalysts
The silicon magnesium ratio of getting particle diameter and be 20～30nm is 2: 1 stratiform lithium magnesium silicate (Australian Fernz SpeciallyChemicals) 10g, joins after preliminary treatment in the reaction vessel, stirs down, slowly adds bipyridyl iron (Fe (bpy)
3 2+, 2.75mmol) aqueous solution carries out the load bonding, adds the back that finishes and continues to stir 20 hours, stops to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
Two, experiment of the catalytic activity of catalyst and stability experiment
1, the visible light catalysis activity of catalyst experiment
In 1 liter of glass reactor, add and contain rhodamine B pollutant (concentration 2 * 10
-5M) 1 liter of the aqueous solution is placed in a halogen lamp in the double glazing condensation sleeve pipe, and on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Under neutrallty condition, carry out following reaction then, measure the situation that rhodamine B changed with the reaction time:
1) only add hydrogen peroxide in reaction system, and carry out illumination (luminous intensity is 110 milliwatt/square centimeters), its concentration is 2 * 10
-3M;
2) only add the present embodiment prepared catalyst in reaction system, and carry out illumination (luminous intensity is 110 milliwatt/square centimeters), consumption is 100mg/L;
3) add hydrogen peroxide and bipyridyl iron in reaction system, and carry out illumination (luminous intensity is 110 milliwatt/square centimeters), both concentration is respectively 2 * 10
-3M and 4.4 * 10
-5M;
4) add hydrogen peroxide and present embodiment prepared catalyst in reaction system, but do not carry out illumination, both concentration is respectively 2 * 10
-3M and 100mg/L;
5) add hydrogen peroxide and present embodiment prepared catalyst in reaction system, and carry out illumination (luminous intensity is 110 milliwatt/square centimeters), both concentration is respectively 2 * 10
-3M and 100mg/L.
Experimental result as shown in Figure 1, curve 1-5 is respectively the change curve of the concentration of rhodamine B under above-mentioned 5 reaction conditions with the reaction time among the figure.As seen from the figure, curve 1 is the blank light reaction that visible light (luminous intensity is 110 milliwatt/square centimeters) irradiation has only hydrogen peroxide to exist down, and the concentration of photodissociation 120min rhodamine B almost there is not variation; Curve 2 is for having only catalyst (100mg/L), and the degraded of rhodamine B also takes place hardly under illumination; Curve 3 is a radiation of visible light bipyridyl iron (4.4 * 10
-5M) and hydrogen peroxide (2 * 10
-3M) Gong Cun homogeneous reaction solution, light reaction 120min rhodamine B has degraded about 15%; Curve 4 is in the dark reaction of no visible light, in 100mg/L catalyst and 2 * 10
-3There is reaction 120min down in the hydrogen peroxide of M, and rhodamine B concentration also changes hardly; Curve 5 is sample 1 (100mg) and hydrogen peroxide (2 * 10
-3M) in the out-phase reaction system of Cun Zaiing, radiation of visible light 120min rhodamine B has degraded about 92%, and 41% TOC clearance is arranged, show that catalyst of the present invention has the ability of very strong photocatalytic degradation rhodamine B, and reaction stops to stir back 5min, catalyst can be deposited to reactor bottom, is easy to separate recycling.
2, the catalytic stability of catalyst experiment
With the catalyst that reclaims according to the above-mentioned the 5th) individual experimental conditions carries out the experiment of photocatalytic degradation rhodamine B, reclaims the back then and reuses, and carries out continuously 12 times under neutrallty condition, rhodamine B concentration curve in time is as shown in Figure 2.As seen from the figure, first three time circulation light reaction 120min, the rhodamine B degraded can reach more than 90%, and the catalytic activity of catalyst does not have to reduce substantially; The circulation light reaction 120min of back, the rhodamine B degraded slightly reduces, and can reach more than 80%, if prolong optical response time to 140min, then the degraded of rhodamine B can reach more than 85%.The result shows that catalyst of the present invention has good stability of catalytic activity, through repeatedly recycling, does not find that tangible catalytic activity reduces phenomenon.
3, the ultraviolet catalytic activity experiment of catalyst
Get catalyst 100mg and join in 1 liter of glass reactor, add rhodamine B (2 * 10 then
-5M) aqueous solution 1L, 30%H
2O
20.2 milliliter of the aqueous solution, neutrallty condition reacts timing analysis pollutant and H under uviol lamp (100W) irradiation
2O
2The decomposition effect, the ultraviolet light mean intensity is 75mW/cm
2(centre wavelength 365 nanometers).
Its result is: ultraviolet lighting 150min rhodamine B has been degraded about 85%, and 38% TOC clearance is arranged, and illustrates that catalyst also has very high photocatalytic activity under ultraviolet light.
The silicon magnesium ratio of getting particle diameter and be 20～30nm is 2: 1 stratiform lithium magnesium silicate (Australian Fernz SpeciallyChemicals) 10g, joins after preliminary treatment in the reaction vessel, stirs down, slowly adds bipyridyl manganese (Mn (bpy)
3 2+, 2.75mmol) aqueous solution carries out the load bonding, adds the back that finishes and continues to stir 20 hours, stops to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
In 1 liter of glass reactor, add and contain N, accelerine (concentration 2 * 10
-4M) 1 liter of the aqueous solution is placed in a halogen lamp in the double glazing condensation sleeve pipe, and on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Under neutrallty condition, carry out following reaction then, measure N, the situation that accelerine concentration changed with the reaction time:
1) only add hydrogen peroxide in reaction system, and carry out illumination (luminous intensity is 110 milliwatt/square centimeters), its concentration is 1 * 10
-2M;
2) add hydrogen peroxide and present embodiment prepared catalyst in reaction system, and carry out illumination (luminous intensity is 110 milliwatt/square centimeters), both concentration is respectively 1 * 10
-2M and 100mg/L.
The result as shown in Figure 3, curve 1 has only the light reaction of hydrogen peroxide existence for visible light (luminous intensity is 110 milliwatt/square centimeters) irradiation among Fig. 3, photodissociation 450min N, the concentration of accelerine reduces about 10%; Curve 2 is radiation of visible light 100mg/L catalyst and hydrogen peroxide (1 * 10
-2M) Gong Cun out-phase reaction system, after the 450min photodissociation, it is about 69% that N, accelerine have degraded, and 43% TOC clearance is arranged.Reaction system for curve 2 is stopping to stir back 5min, and the catalysis sample can be deposited to reactor bottom fully, is easy to separate recycling.
Embodiment 3,
The silicon magnesium ratio of getting particle diameter and be 20～30nm is 2: 1 stratiform lithium magnesium silicate (Australian Femz SpeciallyChemicals) 10g, joins after preliminary treatment in the reaction vessel, stirs down, slowly adds bipyridyl ruthenium (Ru (bpy)
3 2+, 2.75mmol) aqueous solution carries out the load bonding, adds the back that finishes and continues to stir 20 hours, stops to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
In 1 liter of glass reactor, add and contain rhodamine B (concentration 2 * 10
-5M) 1 liter of the aqueous solution, regulating the pH value is about 3, reactor is uncovered with the molecular oxygen in the ingress of air.One halogen lamp is placed in the double glazing condensation sleeve pipe, and on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Then, carry out following reaction, measure the situation that rhodamine B concentration changed with the reaction time:
1) in reaction system, adds bipyridyl ruthenium (4.4 * 10
-5And carry out illumination (luminous intensity is 110 milliwatt/square centimeters) M);
2) in reaction system, add present embodiment prepared catalyst (100mg/L), but do not carry out illumination;
3) in reaction system, add present embodiment prepared catalyst (100mg/L), and carry out illumination (luminous intensity is 110 milliwatt/square centimeters).
The result as shown in Figure 4, curve among Fig. 41 is visible light (luminous intensity is 110 milliwatt/square centimeters) irradiation time bipyridyl ruthenium (4.4 * 10
-5M) and the reaction solution of molecular oxygen coexistence, rhodamine B concentration changes hardly; Curve 2 is in the dark reaction of no visible light, and there are reaction 300min down in 100mg/L catalyst and molecular oxygen, and rhodamine B concentration changes hardly; The out-phase reaction system of curve 3 radiation of visible light 100mg/L catalyst and molecular oxygen coexistence, after the 300min photodissociation, it is about 75% that rhodamine B has been degraded, and 36% TOC clearance is arranged.Reaction stops to stir back 5min, and catalyst can be deposited to reactor bottom fully, is easy to separate recycling.
Embodiment 4,
The silicon magnesium ratio of getting particle diameter and be 20～30nm is 2: 1 stratiform lithium magnesium silicate (Australian Fernz SpeciallyChemicals) 10g, after preliminary treatment, join in the reaction vessel, stir down, slowly add ferriporphyrin (FePP, 2.75mmol) aqueous solution carries out the load bonding, add the back that finishes and continue to stir 20 hours, stop to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
In 1 liter of glass reactor, add and contain rhodamine B pollutant (concentration 2 * 10
-5M) 1 liter of the aqueous solution is placed in a halogen lamp in the double glazing condensation sleeve pipe, and on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Add this catalyst of 100mg and 30%H then
2O
20.2 milliliter of the aqueous solution stirs under neutrallty condition, observes rhodamine B contaminant degradation and H in the dark reaction
2O
2Decomposition.Turn on light then and carry out light reaction, timing analysis pollutant and H
2O
2The decomposition effect.Its result is: rhodamine B does not react under the dark reaction condition, and under radiation of visible light, degrade 94% in 150 minutes, and 45% TOC clearance is arranged, show that this catalyst has the ability of very strong photocatalytic degradation rhodamine B, and reaction stops to stir back 5min, catalyst can be deposited to reactor bottom, is easy to separate recycling.
Embodiment 5,
The silicon magnesium ratio of getting particle diameter and be 20～30nm is 2: 1 stratiform lithium magnesium silicate (Australian Fernz SpeciallyChemicals) 10g, with 1, the 10-ferrosin iron complex aqueous solution carries out load exchange (by load factor 0.275 mM/g clay), add the back that finishes and continue to stir 20 hours, stop to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
In 1 liter of glass reactor, add and contain rhodamine B pollutant (concentration 2 * 10
-5M) 1 liter of the aqueous solution is placed in a halogen lamp in the double glazing condensation sleeve pipe, and on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Add this catalyst of 100mg and 30%H then
2O
20.2 milliliter of the aqueous solution stirs under neutrallty condition, observes rhodamine B contaminant degradation and H in the dark reaction
2O
2Decomposition.Turn on light then and carry out light reaction, timing analysis pollutant and H
2O
2The decomposition effect.Its result is: rhodamine B is not degraded under the dark reaction condition, and under radiation of visible light, degrade 82% in 150 minutes, and 34% TOC clearance is arranged, show that this catalyst has the ability of very strong photocatalytic degradation rhodamine B, and reaction stops to stir back 5min, catalyst can be deposited to reactor bottom, is easy to separate recycling.
Embodiment 6,
The silicon magnesium ratio of getting particle diameter and be 20～30nm is 2: 1 stratiform lithium magnesium silicate (Australian Fernz SpeciallyChemicals) 10g, after preliminary treatment, join in the reaction vessel, under 80 ℃ of stirrings, slowly add cetyl-trimethyl-amine bromide (CTAB, 2.75mmol) aqueous solution carries out the load bonding, add the back that finishes and continue to stir 2 hours, stop to stir.Detect less than till the bromide ion to solution with water rinse, centrifugation then was 40 ℃ of following vacuum drying 24 hours.The clay 10g that the surfactant of learning from else's experience is handled stirs down, slowly adds bipyridyl iron (Fe (bpy)
3 2+, 2.75mmol) aqueous solution carries out the load bonding, adds the back that finishes and continues to stir 20 hours, stops to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
In 1 liter of glass reactor, add and contain 2,4,6-trichlorophenol (concentration 2 * 10
-4M) 1 liter of the aqueous solution is placed in a halogen lamp in the double glazing condensation sleeve pipe, and on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Under neutrallty condition, carry out following reaction then, measure 2,4, the situation that 6-trichlorophenol concentration changed with the reaction time:
1) only add hydrogen peroxide in reaction system, and carry out illumination (luminous intensity is 110 milliwatt/square centimeters), its concentration is 1 * 10
-2M;
2) add hydrogen peroxide and present embodiment prepared catalyst in reaction system, and carry out illumination (luminous intensity is 110 milliwatt/square centimeters), both concentration is respectively 1 * 10
-2M and 100mg/L.
The result as shown in Figure 5, curve 1 has only the light reaction of hydrogen peroxide existence for visible light (luminous intensity is 110 milliwatt/square centimeters) irradiation among Fig. 5, the concentration of photodissociation 700min trichlorophenol changes hardly; Curve 2 is radiation of visible light 100mg/L catalyst and hydrogen peroxide (1 * 10
-2M) Gong Cun out-phase reaction system, after the 700min photodissociation, it is about 66% that trichlorophenol has been degraded, and 48% TOC clearance is arranged.Stop to stir back 5min, catalyst can be deposited to reactor bottom fully, is easy to separate recycling.
Embodiment 7,
The silica alumina ratio of getting particle diameter and be 1～5um is 2: 1 lamellar aluminosilicate (U.S. Aldrich reagent company) 10g, after preliminary treatment, join in the reaction vessel, stir down, slowly add cobalt porphyrin (CoPP, 5mmol) aqueous solution carries out the load bonding, add the back that finishes and continue to stir 20 hours, stop to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
In 1 liter of glass reactor, add and contain rhodamine B pollutant (concentration 2 * 10
-5M) 1 liter of the aqueous solution is placed in a halogen lamp in the double glazing condensation sleeve pipe, and on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Add this catalyst of 100mg and 30%H then
2O
20.2 milliliter of the aqueous solution stirs under neutrallty condition, observes rhodamine B contaminant degradation and H in the dark reaction
2O
2Decomposition.Turn on light then and carry out light reaction, timing analysis pollutant and H
2O
2The decomposition effect.Its result is: rhodamine B is not degraded under the dark reaction condition, and 200min degraded 80% under radiation of visible light, and 34% TOC clearance is arranged, show that this catalyst has the ability of very strong photocatalytic degradation rhodamine B, and reaction stops to stir back 5min, catalyst can be deposited to reactor bottom, is easy to separate recycling.
Embodiment 8,
The silica alumina ratio of getting particle diameter and be 1～5um is 2: 1 lamellar aluminosilicate (U.S. Aldrich reagent company) 10g, with 1, the 10-ferrosin cobalt complex aqueous solution carries out load exchange (being undertaken by load factor 0.01 mM/g clay), adds the back that finishes and continues to stir 20 hours, stops to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
Getting catalyst 100mg joins in 1 liter of glass reactor, one halogen lamp is placed in the double glazing condensation sleeve pipe, on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Add rhodamine B (2 * 10 then
-5M) aqueous solution and 30%H
2O
20.5 milliliter of the aqueous solution stirs under neutrallty condition, observes rhodamine B contaminant degradation in the dark reaction.Turn on light then and carry out light reaction, the palliating degradation degree of timing analysis pollutant and the H of generation
2O
2Amount.Its result is: rhodamine B is not degraded under the dark reaction condition, and 300min degraded 80% under radiation of visible light, and 31% TOC clearance is arranged, show that this catalyst has the ability of very strong photocatalytic degradation rhodamine B, and reaction stops to stir back 5min, catalyst can be deposited to reactor bottom, is easy to separate recycling.
Embodiment 9,
The silica alumina ratio of getting particle diameter and be 1～5um is 2: 1 lamellar aluminosilicate (U.S. Aldrich reagent company) 10g, with 1, the 10-ferrosin manganese complex aqueous solution carries out load exchange (by load factor 2 mMs/g clay), adds the back that finishes and continues to stir 20 hours, stops to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
In 1 liter of glass reactor, add and contain rhodamine B pollutant (concentration 2 * 10
-5M) 1 liter of the aqueous solution is placed in a halogen lamp in the double glazing condensation sleeve pipe, and on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Add this catalyst of 100mg and 30%H then
2O
20.2 milliliter of the aqueous solution stirs under neutrallty condition, observes rhodamine B contaminant degradation and H in the dark reaction
2O
2Decomposition.Turn on light then and carry out light reaction, timing analysis pollutant and H
2O
2The decomposition effect.Its result is: rhodamine B is not decomposed under the dark reaction condition, and 250min degraded 86% under radiation of visible light, and 32% TOC clearance is arranged, show that this catalyst has the ability of very strong photocatalytic degradation rhodamine B, and reaction stops to stir back 5min, catalyst can be deposited to reactor bottom, is easy to separate recycling.
Embodiment 10,
The silica alumina ratio of getting particle diameter and be 1～5um is 2: 1 lamellar aluminosilicate (U.S. Aldrich reagent company) 10g, after preliminary treatment, join in the reaction vessel, stir down, slowly add manganoporphyrin (MnPP, 1mmol) aqueous solution carries out the load bonding, add the back that finishes and continue to stir 20 hours, stop to stir.Detect less than till the metal complex to solution with water rinse, centrifugation then 40 ℃ of following vacuum drying 24 hours, promptly obtains catalyst.
In 1 liter of glass reactor, add and contain rhodamine B pollutant (concentration 2 * 10
-5M) 1 liter of the aqueous solution is placed in a halogen lamp in the double glazing condensation sleeve pipe, and on every side around recirculated cooling water, (λ＞450nm) places the chuck outside to excise the following light of 450nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.Add this catalyst of 100mg and 30%H then
2O
20.2 milliliter of the aqueous solution stirs under neutrallty condition, observes rhodamine B contaminant degradation and H in the dark reaction
2O
2Decomposition.Turn on light then and carry out light reaction, timing analysis pollutant and H
2O
2The decomposition effect.Its result is: rhodamine B is not decomposed under the dark reaction condition, and 360min degraded 84% under radiation of visible light, and 33% TOC clearance is arranged, show that this catalyst has the ability of very strong photocatalytic degradation rhodamine B, and reaction stops to stir back 5min, catalyst can be deposited to reactor bottom, is easy to separate recycling.
Claims (9)
1, a kind of solid-phase photocatalyst comprises carrier and the metal-organic coordination compound that loads on the carrier, and it is characterized in that: described carrier is a lamellar clay.
2, solid-phase photocatalyst according to claim 1 is characterized in that: layered clay is stratiform Magnesosilicate or alumino-silicate.
3, solid-phase photocatalyst according to claim 1 is characterized in that: layered clay is also handled through surfactant.
4, according to claim 1 or 2 or 3 described solid-phase photocatalysts, it is characterized in that: the load capacity of described metal-organic coordination compound is the 0.01-2mmol/g carrier.
5, according to claim 1 or 2 or 3 described solid-phase photocatalysts, it is characterized in that: described metal-organic coordination compound is a metal bipyridyl complex, metalloporphyrin complex or metal ferrosin complex.
6, solid-phase photocatalyst according to claim 5 is characterized in that: described metal-organic coordination compound is a bipyridyl iron, bipyridyl ruthenium, bipyridyl manganese, ferriporphyrin, manganoporphyrin, cobalt porphyrin, ferrosin iron, ferrosin manganese or ferrosin cobalt.
7, a kind of method of photocatalysis degradation organic contaminant is to add oxidant and the described solid-phase photocatalyst of claim 1, catalyze and degrade organic pollutants under illumination condition in organic pollution solution.
8, method according to claim 7 is characterized in that: the optical wavelength of described illumination condition is 250nm-800nm.
9, according to claim 7 or 8 described methods, it is characterized in that: described oxidant is hydrogen peroxide or molecular oxygen.
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