CN1123393C - Solid photocatalyst and its preparing process - Google Patents
Solid photocatalyst and its preparing process Download PDFInfo
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- CN1123393C CN1123393C CN01110292A CN01110292A CN1123393C CN 1123393 C CN1123393 C CN 1123393C CN 01110292 A CN01110292 A CN 01110292A CN 01110292 A CN01110292 A CN 01110292A CN 1123393 C CN1123393 C CN 1123393C
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Abstract
The present invention discloses a solid photocatalyst and a preparation method thereof. The catalyst is composed of a carrier and metal ions which are bonded with the carrier and have the photocatalytic activity. The carrier is a high polymer carrier. The metal ions are loaded to the high polymer carrier through a bonding method. The molar / weight ratio of the metal ions to the high polymer carrier is 10<-6> to 10<-2> mol/ gram. The high polymer carrier is sulfonated coal or polystyrene/ divinylbenzene granular cation exchange resin material or polymethacrylic acid, polymethylmethacrylate / divinylbenzene granular cation exchange resin material or polystyrene / divinylbenzene chelating resin material. The catalyst of the present invention can be used for the photocatalysis treatment on industrial wastewater, domestic wastewater of cities, surface water and organic pollutants of the drinking water, and can also be used for photocatalytic reaction of selective photocatalytic synthesis, etc.
Description
The present invention relates to a kind of solid-phase photocatalyst, particularly a kind of solid phase light-Fenton catalyst of forming by carrier and metal ion with photocatalytic activity.The invention still further relates to a kind of preparation method of solid-phase photocatalyst.
In past 10 years, hydroxyl radical free radical (
OH) chemistry becomes the very universal chemical treatment method of application now having presented the characteristics that other processing modes can not replace aspect the industry of handling deterioration day by day, the life water pollution.Compare with traditional chemical flocculation, biology aerobic/anaerobic degradation, this method to handle polluted-water wide accommodation (almost non-selectivity), chemical oxygen consumption (COC) (COD) clearance and mineralization rate height (almost 100%), the operation process flow process is short and equipment is simple, operating condition is easy, and does not generally have secondary pollution.Wherein, Fenton reagent (iron ion or copper ion+hydrogen peroxide, Fe
2++ H
2O
2) be the most generally be used for producing hydroxyl radical free radical (
OH) medicament, promptly in little acid (pH ≈ 3.0) aqueous solution, take place following formula (1) reaction generate hydroxyl radical free radical (
OH), and hydroxyl radical free radical (
OH) being the active oxygen radical with strong oxidizing property, almost can reacting with any organic pollution, is carbon dioxide, water and inorganic salts with its degraded, mineralising.Usually, ferrous ion catalysis H
2O
2Be decomposed into hydroxyl radical free radical (
OH) efficient is the Fe that is generated by reaction
3+Can be determined by ferrous ion by fast restore.But Fe
3+Turned back to the Fe of catalytic action by reaction equation (2)
2+This step is relatively slow, and the part hydrogen peroxide decomposes is become the more SA superoxide radical anion and the oxygen of non-activity almost, has influence on the productive rate of hydroxyl radical free radical and the speed of whole degradation reaction.
Nearest discovers that for above-mentioned reaction, ultraviolet and visible light (Uv/Vis) can make Fenton
The oxidation rate of system improves nearly a hundred times, and its mechanism is that ultraviolet light (UV) can be with higher quantum yield with Fe
3+Be reduced to Fe
2+And hydroxy radical (
OH) (press reactional equation 4), perhaps can absorb the dyestuff contaminant of visible light Fe
3+Be reduced to Fe
2+, not only quickened the circular response of catalyst, and greatly improved the utilization rate of hydrogen peroxide (prime cost of this method is formed) and shortened operational process.This discovery will be from now on application and the research emphasis Fenton system aspect that all turned to light to help.This type of document has " Journal of Molecular Catalysis magazine " 1999,144, " light of radiation of visible light-Fenton degradation of dye " (Wu.K of 77-84, Xie.Y., Zhao.J., Hidaka, H., Photo-Fentondegradation of a dye under visible light irradiation, J.Mol.Catal.).Wherein, what adopt at present as the molysite of photochemical catalyst is water miscible ferrous sulfate or iron ammonium sulfate, and general light reaction consumption is at 20～50mg/L (in Fe), and dark reaction then consumption is bigger.In the water body after the processing removal of molysite or reclaim adopt usually add in the alkali and the pH of water body to neutral, making the iron flocculating setting is the iron mud of hydroxide form, removes by filter, and just can reach the requirement of discharge standard.Here, even do not consider molysite cost and in and the consumption of the required alkaline chemical of the nearly pH neutral that requires to sedimentation iron of Fenton micro acid medium, only move the efficient operation that just is enough to have influence on whole Fenton method because of handling process and the equipment that this step increases.For solving this key issue, there is research to report and changes homogeneous phase Fenton catalyst into solid-state form, to reach the reusable purpose of non-discharging of catalyst.This class document has on " nature " magazine 1994,369, the article of 543-546 " molecular sieve carried manganese complex is the selection of catalysts oxidation " (P.Gerrit, D.D.Vos, F.T.Starzyk, P.A.Jacobe, Zeolite-encapsulated Mn (II) complexes as catalysts for selectivealkene oxidation, Nature).But because molecular sieve is to Fe
3+/ Fe
2+Bonding force a little less than, very easily run off by other ion exchanges in the staying water, the regeneration period is very short.In addition, have Fe on the molecular sieve
3+/ Fe
2+The ionic forms high-temperature process become oxide form, prevented Fe
3+/ Fe
2+Loss, but catalytic activity significantly reduces again.In addition, from the process implementing angle, the molecular sieve that bulk density is very big evenly disperses to get up, and the one, consume bigger power, the 2nd, because shading influences optical efficiency.With Fe
3+/ Fe
2+Load on a kind of poly-fluorine macromolecule (Nafion) basement membrane, separation and dispersion effect are all relatively good, this type of document has " langmuir " magazine 1999,15,185-192 " No. two oranges of non-free iron system light Fenton degradation biological difficult degradation azo dyes that cation permeable membrane is adjusted " (J.Fernandez, J.Bandara, A.Lopez, Ph.Buffat, J.Kiwi, Photoassisted Fenton degradation of nonbiodegradable azo dye (orange II) in Fe-free solut ions mediated by cation transfermembranes, Langmuir).But the Nafion basement membrane can only be with Fe
3+Ionic forms just can be distributed to film not processed water displacement loss mutually with alkali treatment hydrate form, and a large amount of research has proved the iron oxide of any crystal formation or the iron hydroxide of colloid, and it is at the photocatalytic activity of the Fenton system iron well below ionic species.In addition, this high polymer manufacturing process complexity, the macromolecular material that price is general is relatively wanted the many of costliness.
For overcoming the shortcoming of above-mentioned solid type Fenton catalyst, the object of the present invention is to provide a kind of linear flow bed type light-catalyzed reaction processing polluted-water that is easy to be implemented in, can keep the solid-phase photocatalyst of polymolecularity, high catalytic activity and the high stability of catalyst in working media again.
The present invention also aims to provide a kind of preparation method of solid-phase photocatalyst, prepare a kind of so non-separation, efficiently solid phase Fenton catalyst be the Fenton system can heavy industrialization the key technology of utilization.
A kind of solid-phase photocatalyst of the present invention, by carrier and with it the metal ion with photocatalytic activity of bonding form, it is characterized in that: described carrier is a polymer support, described metal ion loads on the polymer support by the bonding mode, and the mole/mass ratio of described metal ion and polymer support is 10
-6～10
-2Moles per gram.
Described polymer support is a kind of metal ion with photocatalytic activity to be had the inorganic of strong bonding ability, organic polymer, inorganic polymer such as sulfonated coal, organic polymer is the granular cationic ion-exchange resin material or the polymethylacrylic acid of polystyrene/divinylbenzene, the granular cationic ion-exchange resin material of polymethyl methacrylate/divinylbenzene or the chelate resin material of polystyrene/divinylbenzene, its laboratory preparation can be clear as " Japan's special permission communique " with reference to Japan Patent, 40-3699 (1965), or use the commercially available prod, as the Dowex board of U.S. road (DOW) company, the Diaion board that Mitsubishi changes into, the Lewatit board of the Germany Farbonfabriken Bayer of Bayer AG, homemade Shanghai Resin Factory, styrene/divinylbenzene that Chemical Plant of Nankai Univ. produces is having of EVA of a sulfonic storng-acid cation exchange resin; Methacrylic acid, methymethacrylate/divinylbenzene are the weak-acid cation-exchange resin that has carboxylic acid group or phosphate of EVA; Styrene/divinylbenzene is the contained imine oxalic acid base of an EVA chelate resin.
It is described that to have the photocatalytic activity metal ion be divalence or ferric ion, divalent manganesetion, bivalent cupric ion.
Described polymer support granularity is preferably 1 micron～5 millimeters, can be with high polymer with mark sieve screening, if the commercially available prod particle diameter can be with its further porphyrize during greater than described preferable particle size.
The preparation method of a kind of solid-phase photocatalyst of the present invention, undertaken by following step:
(1) pre-treatment of high polymer
Adopt conventional method, polymer support is carried out pickling and alkali cleaning after, water (referring to distilled water, as follows) rinsing is immersed in the water standby to neutral.
The pre-treatment concrete operation method of high polymer is: with high polymer with 10% hydrochloric acid soak at least 24 hours may remaining impurities to remove on the exchange point position, for several times with water rinse, after removing hydrochloric acid, sodium hydroxide solution with 8% is handled equally, removes residual organic and inorganic amine/ammonium salt with molten, with water rinse for several times, after removing NaOH, use the watery hydrochloric acid immersion treatment of 1～2mol/L again, water rinsing to supernatant water repeatedly is neutral getting final product, and continues to be immersed in the water standby.
As adopting upper prop load operation method, it is standby the polymer support of handling should to be immersed in the water dress post.Concrete operations are as follows: the size of looking preparation amount, with a lower end tool rotary-piston, ratio of height to diameter greater than 25 the glass or the post of plastic material, with moistening glass tampon in the bottom, high polymer flows out when preventing to prepare, then in preparative column under the water-filled situation, the high polymer of handling well is joined in the post, the whole operation process, comprise bonding operation thereafter, all to prevent the gas enclosure bubble phenomenon in the high polymer layer, should remain high polymer below the liquid level of post, otherwise sneak into bubble because of the high polymer layer is dry.If this thing happens, high polymer should be poured out, adorn post again.
(2) preparation of metal ion solution
Prepare watery hydrochloric acid, nitric acid or the sulfuric acid solution of 0.1～0.5mol/L earlier, the solid-to-liquid ratio according to 10～50 grams per liters adds corresponding metal salt then, and stirring and dissolving gets final product.The best matching while using of this class solution is placed on for a long time in the air hydrolysis may take place.Described slaine is water miscible divalence and trivalent iron salt, water miscible manganous salt, water miscible cupric salt.
(3) bonding of metal ion and high polymer
Metal ion solution is poured in batches from the suitable for reading of post, adjusted flow velocity, guarantee that the flow velocity that is not more than the beginning leak source that calculates by theory exchanges load, by adjusting the catalyst that the molal weight that adds metal ion can obtain the different loads ratio with piston.Fully loaded Preparation of catalysts is 95% the getting final product when above of initial concentration that reaches adding up to the concentration of metal ions that flows out liquid.Load finishes, and water continues drip washing in flowing out liquid not till the metal ion.
Perhaps, also can adopt non-column operation method, be equipped with in the glass or plastic containers of agitating device one, put into water, add the high polymer of handling, stir and be dispersed in the water body, other gets a dropping funel, and the metal ion solution that preparation is stand-by slowly splashes into by the control hopper valve, fully stirs, add metal ion solution, by regulating the catalyst that the molal weight that adds metal ion can obtain the different loads ratio.With metal ion add finish after, continue to stir at least 10 hours, load finishes.Use water rinse, in water wash liquid not till the metal ion.
The present invention found a kind of brand-new, have highlight catalytic active, high stability and exempt to separate solid phase type Fenton photochemical catalyst.Its key technology main points are to screen a kind of functional high polymer that contains organic pollution adsorption function group, and this high polymer and have between the metal ion of photocatalytic activity and have strong bonding force, slaine is immobilized to the bonding point position of high polymer with ionic forms, be prepared into the solid type photochemical catalyst that on catalytic performance, is higher than free metal ion far away.Make Fenton photocatalysis treatment pollutant system become efficient, the easy flowing process system that a kind of pH value, the iron ion that need not adjust pending water in advance that carries out in the solid-liquid two-phase reaches zero-emission.Because the bonding performance of selected high polymer, wide pH value (2～10) and, thereby improved photocatalytic activity and the big and pH value big tolerance that fluctuates to pollutant's concentration range fluctuation in the practice to the adsorption and enrichment characteristic of pollutant.
Efficient, high absorption capacity of the present invention, the light Fenton catalyst of exempting to separate can be used for the photocatalysis treatment of organic pollution in industrial wastewater, city domestic sewage and surface water and the drinking water, can be used for also that selective photocatalysis is synthetic to wait light-catalyzed reaction.
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Fig. 1, acid brilliant pink dyestuff 1 * 10
-5The photocatalytic degradation reaction result of M under UV-irradiation
Curve 1: no photochemical catalyst and hydrogen peroxide.
Curve 2:0.4 gram (wet basis)/rise control sample 1 (by preparation in the reference examples 1)
Curve 3:0.4 gram (wet basis)/rise control sample 2 (by preparation in the reference examples 2)
Curve 4:0.4 gram (wet basis)/rise sample 1 by preparation among the embodiment 1
Illumination experiment condition: ultraviolet high voltage mercury lamp radiation intensity 75 milliwatt/square centimeters, the pH value 5.5 of reaction solution, the concentration 5 * 10 of hydrogen peroxide
-4M. following experiment condition is identical.
Fig. 2,2,4-chlorophenesic acid 1 * 10
-5M is the photocatalytic degradation reaction result under UV-irradiation
Curve 1: no photochemical catalyst and hydrogen peroxide.
Curve 2:0.4 gram (wet basis)/rise control sample 1 (by preparation in the reference examples 1).
Curve 3:0.4 gram (wet basis)/rise control sample 2 (by preparation in the reference examples 2).
Curve 4:0.4 gram (wet basis)/rise sample 1 (by preparation among the embodiment 1).
Fig. 3, continuous 10 the circulation degraded acid brilliant pink dyestuffs (each 1 * 10 of catalyst
-5M) photocatalytic activity result
Curve 1:0.4 gram (wet basis)/rise control sample 2 (by preparation in the reference examples 2).
Curve 2:0.4 gram (wet basis)/rise sample 1 (by preparation among the embodiment 1).
Fig. 4, continuous 10 the circulation degraded acidity 2 of catalyst, 4-chlorophenesic acid (each 1 * 10
-5M) photocatalytic activity result
Curve 1:0.4 gram (wet basis)/rise control sample 2 (by preparation in the reference examples 1).
Curve 2:0.4 gram (wet basis)/rise sample 1 (by preparation among the embodiment 1).
Curve 1 is the blank assay of ultraviolet light (luminous intensity 75 milliwatt/square centimeters) irradiation degraded among Fig. 1, and the light degradation reaction did not take place in 120 minutes substantially.At 0.4 gram (wet basis)/rise in the presence of sample 1 catalyst, do not regulate pH value (5.5), adding H
2O
2Concentration be 0.5 mM/liter, UV-irradiation 80 minutes, acid brilliant pink all be degraded (Fig. 1 curve 4).And in the control experiment, 0.4 gram (wet basis)/rise control sample 2 catalyst exist down, and UV-irradiation 120 minutes, acid brilliant pink still have 20% not to be degraded (Fig. 1 curve 3), and 1 of control sample has 68% be not degraded (Fig. 1 curve 2).Stopped after the reaction stirring 5 minutes, the light Fenton catalyst sample 1 of exempting to separate can be deposited to container bottom fully, is easy to separate with solution.
Curve 1 is the blank assay of ultraviolet light (luminous intensity 75 milliwatt/square centimeters) irradiation degraded among Fig. 2, and the light degradation reaction did not take place in 100 minutes substantially.At 0.4 gram (wet basis)/rise sample 1 catalyst in the presence of, adjusting pH value is 5.5, adding H
2O
2Concentration be 0.5 mM/liter, UV-irradiation 100 minutes, 2,4-two chlorophenols are by all degradeds (Fig. 1 curves 4).And in the control experiment, 0.4 gram (wet basis)/rise control sample 2 catalyst exist down, UV-irradiation 100 minutes, and 2,4-two chlorophenols still have 28% not to be degraded (Fig. 1 curve 3), and 1 of control sample has 51% be not degraded (Fig. 1 curve 2).Stopped after the reaction stirring 5 minutes, the light Fenton catalyst sample 1 of efficiently exempting to separate can be deposited to container bottom fully, is easy to separate with solution.
After curve 1 and curve 2 were respectively 10 circulation degradeds among Fig. 3, sample 1 catalyst and control sample 2 catalyst were to the result of acid brilliant pink clearance.Circulate 10 times, the catalytic performance of sample 1 catalyst does not have to reduce substantially, and the degradation rate in 120 minute cycle still remains on 100%.And the catalytic performance of control sample 2 catalyst reduces in 10 circulations gradually, by 80% the degradation rate of circulating for the first time be reduced to the tenth time 32%.After stopping to stir 5 minutes after each circular response finishes, catalyst sample 1 can be deposited to container bottom fully, and easy and solution is separated.
After curve 1 and curve 2 were respectively 10 circulation degradeds among Fig. 4, sample 1 catalyst and control sample 2 catalyst were to 2, the result of 4-two chlorophenol clearances.Circulate 10 times, the catalytic performance of sample 1 catalyst does not have to reduce substantially, and the degradation rate in 100 minute cycle still remains on 100%.And the catalytic performance of control sample 2 catalyst reduces in 10 circulations gradually, by 72% the degradation rate of circulating for the first time be reduced to the tenth time 14%.After stopping to stir 5 minutes after each circular response finishes, catalyst sample 1 can be deposited to container bottom fully, is easy to separate with solution.
Embodiment 1
Styrene-divinylbenzene of getting selected particle diameter and being 0.3～0.5mm contains sulfonic high polymer (product that the green precious board trade mark of Shanghai Resin Factory is produced) 20 grams, joins exchange column through after giving processing, the abundant drip washing of water to water outlet pH value between 5～7.With ferric trichloride (FeCl
3) be made into 10
-24.0 liters of the HCl aqueous solution that includes 0.3M of M, upper prop carries out the bonding load, reaches 0.0098M up to the concentration of metal ions that flows out liquid, stops load.Water continues drip washing, and the metal ion that is adsorbed on the surface is washed, and reclaims and uses.Water wash is in flowing out liquid not till the metal ion.From post, pour out the good catalyst of bonding, immerse in the water and can use.
Get selected particle diameter and be sulfonated coal 20 grams (Yuyao, Zhejiang win honour for chemical plant win honour for board product) of 1.0-1.2mm, join exchange column through after giving processing, the abundant drip washing of water to water outlet pH value between 5～7.With copper sulphate (CuSO
45H
2O) be made into 10
-2The H that includes 0.03M of M
2SO
43.5 liters of the aqueous solution, upper prop carries out the bonding load, reaches 0.0095M up to the concentration of metal ions that flows out liquid, stops load.Water continues drip washing, and the metal ion that is adsorbed on the surface is washed, and is recovered in usefulness.Water wash is in flowing out liquid not till the metal ion.From post, pour out the good catalyst of bonding, immerse in the water and can use.
Manganese sulfate is made into 10
-31 liter of the aqueous sulfuric acid that includes 0.05M of M, in the dropping funel of packing into, standby.Getting selected particle diameter is carboxylic IRC-84 cationic ion-exchange resin 20 grams of 0.33-0.50mm methacrylic acid-divinylbenzene copolymerization, (product that the U.S. Rohm and Hass Amberlite of company trade mark is produced) joins in the container through after giving processing, stir the aqueous sulfuric acid that slowly adds metal ion down, carry out the bonding load, after the metal ion adding is finished, continuing stirring 10 hours, stopping to stir.Water continues rinsing, in water wash liquid not till the metal ion.Continue to immerse in the water, can use.
With iron ammonium sulfate (FeSO
4(NH
4)
2SO
46H
2O) be made into 10
-20.5 liter of the aqueous sulfuric acid that includes 0.3M of M, in the dropping funel of packing into, standby.Get and select ES-63 type cationic ion-exchange resin 20 grams (product of the French Duolite Duolite of company board) that particle diameter is 0.29-0.55mm methacrylic acid-phosphorous acidic group of divinylbenzene copolymerization, join in the container, stir the slow down Fe of adding through after giving processing
2+The aqueous sulfuric acid of ion carries out the bonding load, after the metal ion adding is finished, is continuing stirring 13 hours, stops to stir.Water continues rinsing, does not contain Fe in water lotion
2+Till the ion.Continue to immerse in the water, can use.
Embodiment 5
With ferric nitrate (Fe (NO
3)
39H
2O) be made into 10
-44 liters of the aqueous solution of nitric acid that includes 0.05 M of M, in the dropping funel of packing into, standby.Get and selected handle particle diameter through porphyrize and contain sulfonic PK-228 cationic ion-exchange resin (Mitsubishi changes into the Diaion board of company) 20 grams for styrene-divinylbenzene of～0.5mm, join in the container through after giving processing, stir the aqueous solution of nitric acid that slowly adds metal ion down, carry out the bonding load, after the metal ion solution adding is finished, continuing stirring 15 hours, stopping to stir.Water continues rinsing, in water lotion not till the metal ion.Continue to immerse in the water, can use.
With ferrous chloride (FeCl
24H
2O) be made into 10
-24 liters of the aqueous hydrochloric acid solutions that includes 0.3M of M, in the dropping funel of packing into, standby.Getting selected particle diameter and be A-1 type chelating resin 20 grams (product of the Dowex board of U.S. Dow company) that 0.5-0.85mm styrene-divinylbenzene copolymerization contains the imine oxalic acid base gets selected, join in the container through after giving processing, stir the HCl aqueous solution that slowly adds ferrous ion down, carry out the bonding load, after the metal ion solution adding is finished, continuing stirring 12 hours, stopping to stir.Water continues rinsing, in water lotion not till the metal ion.Continue to immerse in the water, can use.
Embodiment 7
With dichloride copper (CuCl
22H
2O) be made into 10
-24 liters of the HCl aqueous solution that includes 0.3M of M, in the dropping funel of packing into, standby.Get and select CNP-80 macroporous ion exchange resin 20 grams (the German Farbonfabriken Bayer Lewatit of company board product) that particle diameter is methacrylate-divinylbenzene copolymerization of 0.5-0.85mm, join in the container through after giving processing, stir the HCl aqueous solution that slowly adds bivalent cupric ion down, carry out the bonding load, after ratio finishes the metal ion adding on request, continuing stirring 13 hours, stopping to stir.Water continues rinsing, in water wash liquid not till the metal ion.Continue to immerse in the water, can use.
Reference examples 1
Aluminum sulfate is made into 10
-21.2 liters of the aqueous sulfuric acids that includes 0.3M of M, in the dropping funel of packing into, standby.The SDEB styrene diethylenebenzene of getting selected particle diameter and be 0.5～0.85mm contains sulfonic cationic ion-exchange resin (product that the green precious board trade mark of Shanghai Resin Factory is produced), join in the container through after giving processing, stir the aqueous sulfuric acid that slowly adds metal ion down, adsorb load, after ratio finishes the metal ion adding on request, continuing stirring 12 hours, stopping to stir.Water continues rinsing, in water wash liquid, do not contain manganese ion till.Continue to immerse in the water, can use.
Reference examples 2
Get particle diameter and be 5A molecular sieve 20 grams of 1-2mm, join exchange column through after giving processing, the abundant drip washing of water to water outlet pH value between 5～7.With ferric nitrate (Fe (NO
3)
39H
2O) be made into 10
-2The HNO that includes 0.3M of M
31.2 liters of the aqueous solution, upper prop carries out the bonding load, is stabilized in 10 up to the concentration of metal ions that flows out liquid
-2On the M value, stop load.Water continues drip washing, and the metal ion that is adsorbed on the surface is washed, and is recovered in usefulness.Water wash is in flowing out liquid not till the metal ion.Pour out the good catalyst of bonding from post, drying after 500 ℃ of high-temperature process, immerses in the water and can use.
Claims (6)
1. solid-phase photocatalyst, by carrier and with it the metal ion with photocatalytic activity of bonding form, it is characterized in that: described carrier is a polymer support, described metal ion is divalence or ferric ion, divalent manganesetion, bivalent cupric ion; Described metal ion loads on the polymer support by the bonding mode, and the mole/mass ratio of described metal ion and polymer support is 10
-6～10
-2Moles per gram; Described polymer support is a kind of inorganic or organic polymer, described inorganic polymer is a sulfonated coal, and organic polymer is granular cationic ion-exchange resin material or polymethylacrylic acid, the granular cationic ion-exchange resin material of polymethyl methacrylate/divinylbenzene or the chelate resin material of polystyrene/divinylbenzene of polystyrene/divinylbenzene.
2. according to a kind of solid-phase photocatalyst of claim 1, it is characterized in that: described organic polymer be styrene-divinylbenzene be having of EVA sulfonic storng-acid cation exchange resin or methacrylic acid, methymethacrylate-divinylbenzene be that the weak-acid cation-exchange resin that has carboxylic acid group or phosphate or the styrene-divinylbenzene of EVA is the contained imine oxalic acid base of EVA chelate resin.
3. according to a kind of solid-phase photocatalyst of claim 1, it is characterized in that: described polymer support granularity is 1 micron～5 millimeters.
4. the preparation method of a solid-phase photocatalyst, undertaken by following step:
(1) pre-treatment of high polymer
Adopt conventional method, polymer support is carried out pickling and alkali cleaning after, to neutral, it is standby to be immersed in the water dress post with water rinse; Described polymer support is a kind of inorganic or organic polymer, described inorganic polymer is a sulfonated coal, and organic polymer is granular cationic ion-exchange resin material or polymethylacrylic acid, the granular cationic ion-exchange resin material of polymethyl methacrylate/divinylbenzene or the chelate resin material of polystyrene/divinylbenzene of polystyrene/divinylbenzene;
(2) preparation of metal ion solution
Prepare watery hydrochloric acid, nitric acid or the sulfuric acid solution of 0.1～0.5mol/L earlier, the solid-to-liquid ratio according to 10～50 grams per liters adds corresponding metal salt then, and stirring and dissolving gets final product; Described slaine is water miscible divalence and trivalent iron salt, water miscible manganous salt, water miscible cupric salt;
(3) bonding of metal ion and high polymer
Metal ion solution is poured in batches from the suitable for reading of post, adjust flow velocity with piston, the flow velocity that assurance is not more than the beginning leak source that calculates by theory exchanges load, is 95% when above of the initial concentration that adds up to the concentration of metal ions that flows out liquid, and load finishes; Water continues drip washing in flowing out liquid not till the metal ion.
5. the preparation method of a solid-phase photocatalyst, undertaken by following step:
(1) pre-treatment of high polymer
Adopt conventional method, polymer support is carried out pickling and alkali cleaning after, water (referring to distilled water, as follows) rinsing is to neutral, it is standby to be immersed in the water dress post; Described polymer support is a kind of inorganic or organic polymer, described inorganic polymer is a sulfonated coal, and organic polymer is granular cationic ion-exchange resin material or polymethylacrylic acid, the granular cationic ion-exchange resin material of polymethyl methacrylate/divinylbenzene or the chelate resin material of polystyrene/divinylbenzene of polystyrene/divinylbenzene;
(2) preparation of metal ion solution
Prepare watery hydrochloric acid, nitric acid or the sulfuric acid solution of 0.1～0.5mol/L earlier, the solid-to-liquid ratio according to 10～50 grams per liters adds corresponding metal salt then, and stirring and dissolving gets final product; Described slaine is water miscible divalence and trivalent iron salt, water miscible manganous salt, water miscible cupric salt;
(3) bonding of metal ion and high polymer
Be equipped with in the glass or plastic containers of agitating device one, put into water, add the high polymer of handling, stirring is dispersed in the water body, and other gets a dropping funel, the metal ion solution that preparation is stand-by slowly splashes into by the control hopper valve, fully stir, add metal ion solution, after the metal ion adding is finished, continue to stir at least 10 hours, load finishes; Use water rinse, in water wash liquid not till the metal ion.
6. according to the preparation method of a kind of solid-phase photocatalyst of claim 4 or 5, it is characterized in that: described organic polymer be styrene-divinylbenzene be having of EVA sulfonic storng-acid cation exchange resin or methacrylic acid, methymethacrylate-divinylbenzene be that the weak-acid cation-exchange resin that has carboxylic acid group or phosphate or the styrene-divinylbenzene of EVA is the contained imine oxalic acid base of EVA chelate resin.
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|---|---|---|---|---|
| CN100388979C (en) * | 2005-04-19 | 2008-05-21 | 中国科学院化学研究所 | Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst |
| CN100531911C (en) * | 2005-10-25 | 2009-08-26 | 中国科学院化学研究所 | Solid phase catalytic auxiliary and its preparation method and use |
| CN1990600B (en) * | 2005-12-27 | 2010-09-22 | 中国石油化工股份有限公司 | Method for preparing composite material |
| CN100493713C (en) * | 2006-09-25 | 2009-06-03 | 中国科学院化学研究所 | Visible light photocatalyst for constructing non-nitrogen and iron complex with hydrogen-like quinone and uses of the same |
| CN101824117B (en) * | 2010-02-04 | 2012-02-22 | 中南大学 | Chelate resin immobilized with dendrimer and preparation method thereof |
| CN101829603B (en) * | 2010-04-20 | 2012-03-07 | 华东师范大学 | Preparation method of beta-iron oxide hydroxides loaded resin and application thereof in photocatalysis |
| CN103721746B (en) * | 2012-10-12 | 2016-04-13 | 中国石油化工股份有限公司 | Electrolytic oxidation Industrial Wastewater Treatment composite catalyst and preparation method thereof |
| CN103483487B (en) * | 2013-08-01 | 2015-06-24 | 天津市阳权医疗器械有限公司 | Novel structure product, preparation method and use of styrenic resin |
| CN104941607B (en) * | 2013-08-12 | 2017-02-01 | 天津市阳权医疗器械有限公司 | Styrene resin adsorption agent for clearing high beta2 microglobulin in blood |
| CN115159588B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Method for catalytically recycling elemental sulfur and ferrous ammonium sulfate from sulfur dioxide flue gas |
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2001
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