CN1378879A - Solid photocatalyst and its preparing process - Google Patents
Solid photocatalyst and its preparing process Download PDFInfo
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- CN1378879A CN1378879A CN01110292A CN01110292A CN1378879A CN 1378879 A CN1378879 A CN 1378879A CN 01110292 A CN01110292 A CN 01110292A CN 01110292 A CN01110292 A CN 01110292A CN 1378879 A CN1378879 A CN 1378879A
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Abstract
A solid-phase photocatalyst for treating water or photocatalytic reactions is composed of carrier and metallic ions with photocatalytic activity. The said carrier is high-polymer one, and it may be sulfonated coal, the granular cationic exchange resin of polystyrene/bivinylbenzene, or polymethyacrylic acid or methyl polymethylacrylate/bivinylbenzene, or the chelated resin of polystyrene/bivinylbenzene.
Description
The invention relates to a solid-phase photocatalyst, in particular to a solid-phase photo-Fenton catalyst consisting of a carrier and metal ions with photocatalytic activity. The invention also relates to a preparation method of the solid-phase photocatalyst.
In the last decade, hydroxyl radicals (·OH) chemistry presents the characteristic that other treatment modes can not be replaced in the aspect of treating increasingly worsened industrial and domestic water body pollution, and becomes a chemical treatment method which is very popular in the present application. Compared with the traditional chemical flocculation and biological aerobic/anaerobic degradation, the method has the advantages of wide application range (almost no selectivity) for treating the polluted water body, high Chemical Oxygen Demand (COD) removal rate and mineralization rate (almost 100%), short operation process flow, simple equipment, easy operation condition and no secondary pollution generally. Wherein, Fenton reagent (iron ion or copper ion + hydrogen peroxide, Fe)2++H2O2) Is most commonly used to generate hydroxyl radicals (·OH), i.e. in a slightly acidic (pH is approximately equal to 3.0) aqueous solution, the following formula (1) reacts to generate hydroxyl radicals (OH)·OH)，And hydroxyl radical (C)·OH) is a reactive oxygen radical with strong oxidizing properties that reacts with almost any organic contaminant to degrade and mineralize it into carbon dioxide, water and inorganic salts. Generally, ferrous ions catalyze H2O2Decomposition into hydroxyl radicals (·OH) is produced by reaction3+Whether the iron ions can be rapidly reduced into ferrous ions or not. But Fe3+Returning to the catalytic Fe according to equation (2)2+This step is relatively slow and decomposes a portion of the hydrogen peroxide into less reactive superoxide radical anions and nearly inactive oxygen, affecting the yield of hydroxyl radicals and the rate of the overall degradation reaction.
Recent studies have found that UV and visible light(UV/Vis) can cause Fenton to react with the above reaction The oxidation rate of the system is improved by nearly one hundred times, and the mechanism is that ultraviolet light (UV) can improve Fe with higher quantum yield3+Reduction to Fe2+And hydroxy radical (C·OH) (according to equation 4) or a dye contaminant that absorbs visible light will be Fe3+Reduction to Fe2+Not only accelerates the circulation reaction of the catalyst, but also is extremely largeThe utilization rate of hydrogen peroxide (the main cost component of the method) is improved and the operation flow is shortened. This discovery turns future applications and research focus to the light assisted Fenton system. Such documents are "visible light irradiated photo-Fenton precipitation" from journal of molecular catalysis "1999, 144, 77-84Dyes "(wu.k, xie.y., zhao.j., Hidaka, h., Photo-fenton degradation of a dye under visible light irradiation, j.mol.c.). The ferric salt used as the photocatalyst is water-soluble ferrous sulfate or ferrous ammonium sulfate, the general light reaction dosage is 20-50 mg/L (counted by Fe), and the dark reaction dosage is larger. The removal or recovery of iron salt in the treated water body usually adopts the steps of adding alkali to neutralize the pH value of the water body to be neutral, so that the iron is flocculated and settled into iron mud in the form of hydroxide, and the iron mud is filtered and removed to meet the requirement of the discharge standard. Here, even without considering the cost of iron salts and the consumption of alkaline chemicals required to neutralize the Fenton's mildly acidic media to the near neutral pH required to settle the iron, the increased process flow and equipment operation due to this step alone is sufficient to affect the efficient operation of the overall Fenton process. In order to solve the key problem, research reports that the homogeneous Fenton catalyst is changed into a solid state form so as to achieve the aim of non-emission and repeated use of the catalyst. There is a "selective oxidation of catalysts by molecular sieve supported manganese complexes" in Nature, 1994, 369, 543-546 (Zeolite-encapsulated Mn (II) complexes for selective oxidation, Nature). But due to the molecular sieve pair Fe3+/Fe2+The bonding force is weak, the bonding force is easy to be replaced by other ions in the water body to be treated and lost, and the regeneration period is very short. In addition, there is a method of sieving molecular sieve with Fe3+/Fe2+Is treated at high temperature to form an oxide form, preventing Fe3+/Fe2+But the catalytic activity is significantly reduced. In addition, from the process implementation perspective, the molecular sieves with high stacking density are uniformly dispersed, so that the power is consumed greatly, and the light efficiency is influenced due to shading. Mixing Fe3+/Fe2+Loaded on a polyfluoro polymer (Nafion) basement membrane, the separation and dispersion effects are good, and the documents are provided with 'Langmuir' journal 1999, 15, 185-charge 192 'cation permeable membrane adjusted non-free iron system light Fenton degradation biological degradation difficultly degradable azo dye second orange' (J.Fernandez, J.Bandara, A.Lopez, Ph.Buffat, J.Kiwi, Photoassisted Fenton degradation of nanobioddable azo dye (orange II) in Fe-free solutions mediated by transfer membranes, Langmuir). However, the Nafion-based film can only convert Fe3+The ionic form can be dispersed to the membrane phase without being displaced and lost by the treated water by alkali treatment into hydroxide form, and a large amount of research proves thatThe photocatalytic activity of any crystal form of ferric oxide or colloidal ferric hydroxide in a Fenton system is far lower than that of iron in an ionic form. In addition, the polymer is complex in manufacturing process and much more expensive than common polymer materials.
In order to overcome the defects of the solid Fenton catalyst, the invention aims to provide the solid photocatalyst which is easy to realize the treatment of polluted water body in a linear flowing bed type photocatalytic reaction and can maintain the high dispersibility, high catalytic activity and high stability of the catalyst in a working medium.
The invention also aims to provide a preparation method of the solid-phase photocatalyst, and the preparation of the non-separated and high-efficiency solid-phase Fenton catalyst is a key technology for large-scale industrial application of a Fenton system.
The invention relates to a solid-phase photocatalyst, which consists of a carrier and metal ions which are bonded with the carrier and have photocatalytic activity, and is characterized in that: the carrier is a high polymer carrier, the metal ions are loaded on the high polymer carrier in a bonding mode, and the molar/mass ratio of the metal ions to the high polymer carrier is 10-6～10-2Mole/gram.
The high polymer carrier is an inorganic polymer and an organic polymer which have strong bonding capability to metal ions with photocatalytic activity, the inorganic polymer is sulfonated coal, the organic polymer is a granular cation exchange resin material of polystyrene/divinylbenzene or a granular cation exchange resin material of polymethacrylic acid, polymethyl methacrylate/divinylbenzene or a chelating resin material of polystyrene/divinylbenzene, the laboratory preparation method can be described in Japanese patent laid-open publication Sho 40-3699(1965), or a strongly acidic cation exchange resin having a sulfonic acid groupwhich is a copolymer of styrene/divinylbenzene produced by commercially available products such as Dowex brand of the American national institute (DOW), Diaion brand of Mitsubishi chemical corporation, Lewatit brand of Farbonfabriken Bayer, domestic Shanghai resin works, and southern Kao university chemical works; methacrylic acid and methyl methacrylate/divinylbenzene are copolymer weak acid cation exchange resin with carboxylic acid group or phosphate group; styrene/divinylbenzene is an iminodiacetic acid chelate resin contained in the copolymer.
The metal ions with photocatalytic activity are divalent or trivalent iron ions, divalent manganese ions and divalent copper ions.
The polymer carrier preferably has a particle size of 1 μm to 5mm, and the polymer may be sieved using a standard sieve, and may be further ground if the particle size of the commercially available product is larger than the preferred particle size.
The preparation method of the solid-phase photocatalyst comprises the following steps:
(1) pretreatment of high polymer
The high polymer carrier is washed with acid and alkali by a conventional method, rinsed to neutrality with water (distilled water, the same applies hereinafter), and soaked in water for later use.
The specific operation method for the pretreatment of the high polymer comprises the following steps: soaking the high polymer with 10% hydrochloric acid for at least 24 hours to remove impurities possibly remaining on exchange points, rinsing with water for several times, removing hydrochloric acid, treating with 8% sodium hydroxide solution to dissolve residual organic and inorganic amine/ammonium salt, rinsing with water for several times, removing sodium hydroxide, soaking with 1-2 mol/L diluted hydrochloric acid for treatment, repeatedly rinsingwith water until the clear water is neutral, and continuously soaking in water for later use.
If the column loading operation method is adopted, the treated high polymer carrier is soaked in water for column loading. The specific operation is as follows: according to the preparation quantity, a column made of glass or plastic with a rotary piston at the lower end and a height-diameter ratio of more than 25 is used, wet glass wool is plugged at the bottom to prevent high polymer from flowing out during preparation, then the treated high polymer is added into the column under the condition that the preparation column is filled with water, and the whole operation process including the subsequent bonding operation is to prevent the phenomenon of bubble inclusion in a high polymer layer, the high polymer is always kept below the liquid level of the column, otherwise, bubbles are mixed due to the dryness of the high polymer layer. If this occurs, the polymer should be poured out and the column refilled.
(2) Preparation of Metal ion solution
Firstly, preparing 0.1-0.5 mol/L dilute hydrochloric acid, nitric acid or sulfuric acid solution, then adding corresponding metal salt according to the solid-to-liquid ratio of 10-50 g/L, and stirring for dissolving. Such solutions are preferably ready-to-use and may undergo hydrolysis when left in air for extended periods of time. The metal salt is water-soluble bivalent and trivalent iron salt, water-soluble bivalent manganese salt and water-soluble bivalent copper salt.
(3) Bonding of metal ions to high polymers
Pouring metal ion solution from the upper opening of the column in batches, adjusting the flow rate by using a piston to ensure that the flow rate is not more than the flow rate of the starting leakage point calculated according to the theory to carry out exchange loading, and adjusting the molar mass ofthe added metal ions to obtain the catalyst with different loading ratios. The preparation of the loaded catalyst is carried out until the metal ion concentration of the effluent reaches more than 95% of the initial concentration of the feed. After loading, rinsing with water was continued until the effluent was free of metal ions.
Or, it can also adopt non-column operation method, in a glass or plastic container equipped with stirring device, adding water, adding treated high polymer, uniformly stirring and dispersing in water body, another dropping funnel is taken, slowly dropping prepared metal ion solution through controlling funnel valve, fully stirring, adding metal ion solution, and regulating the molar mass of added metal ion to obtain the catalyst with different load ratios. And after the metal ions are added, stirring is continuously carried out for at least 10 hours, and the loading is finished. Rinsing with water until the water rinse is free of metal ions.
The invention discovers a brand-new solid-phase Fenton photocatalyst which has high photocatalytic activity and high stability and is free of separation. The key technical point is that a functional polymer containing functional groups for adsorbing organic pollutants is screened, strong bonding force is provided between the polymer and metal ions with photocatalytic activity, and metal salt is immobilized on bonding points of the polymer in an ionic form to prepare the solid photocatalyst which is far higher than free metal ions in catalytic performance. The system for treating pollutants by Fenton photocatalysis becomes a high-efficiency, simple and convenient flowing treatment system which is carried out in a solid/liquid two-phase manner without pre-adjusting the pH value of water to be treated and realizing zero emission of iron ions. Due to the bonding characteristic of the selected high polymer, the wide pH value (2-10) and the adsorption and enrichment characteristics of pollutants, the photocatalytic activity and the tolerance capability of large pollutant concentration range fluctuation and large pH value fluctuation in practical application are improved.
The high-efficiency, high-adsorption-capacity and separation-free photo-Fenton catalyst can be used for the photocatalytic treatment of organic pollutants in industrial wastewater, urban domestic sewage, surface water and drinking water, and can also be used for photocatalytic reactions such as selective photocatalytic synthesis and the like.
The present invention will be described in further detail with reference to the following drawings and examples.
FIG. 1, acid pink dye 1X 10-5Photocatalytic degradation reaction result of M under ultraviolet irradiation
Curve 1: no photocatalyst and hydrogen peroxide.
Curve 2: 0.4 g (wet basis)/L of control sample 1 (prepared from control example 1)
Curve 3: 0.4 g (wet basis)/L of control sample 2 (prepared from control example 2)
Curve 4: 0.4 g (wet basis)/l of sample 1 was prepared as in example 1
The illumination experiment conditions are as follows: the irradiation intensity of the ultraviolet high-pressure mercury lamp is 75 milliwatt/square centimeter, the pH value of the reaction solution is 5.5, and the concentration of the hydrogen peroxide is 5 multiplied by 10-4M. the following experimental conditions were the same.
FIG. 2, 4-dichlorophenol 1X 10-5The result of photocatalytic degradation reaction of M under ultraviolet irradiation
Curve 1: no photocatalyst and hydrogen peroxide.
Curve 2: 0.4 grams (wet basis)/liter of control sample 1 (prepared from control example 1).
Curve 3: 0.4 grams (wet basis) per liter of control sample 2 (prepared from control example 2).
Curve 4: 0.4 grams (wet basis)/liter of sample 1 (prepared from example 1).
FIG. 3 shows that the catalyst degrades acid pink dye for 10 continuous cycles (each time is 1X 10 times)-5M) results of photocatalytic activity
Curve 1: 0.4 grams (wet basis) per liter of control sample 2 (prepared from control example 2).
Curve 2: 0.4 grams (wet basis)/liter of sample 1 (prepared from example 1).
FIG. 4 shows that the catalyst degrades acidic 2, 4-dichlorophenol (1X 10 dichlorophenol each time) continuously for 10 cycles-5M) results of photocatalytic activity
Curve 1: 0.4 grams (wet basis)/liter of control sample 2 (prepared from control example 1).
Curve 2: 0.4 grams (wet basis)/liter of sample 1 (prepared from example 1).
In fig. 3, curve 1 and curve 2 are the results of the removal rate of acid pink from the catalyst of sample 1 and the catalyst of control sample 2 after 10 cycles of degradation. After 10 times of circulation, the catalytic performance of the catalyst of the sample 1 is not substantially reduced, and the degradation rate is still maintained at 100% in a period of 120 minutes. While the catalytic performance of the catalyst of control sample 2 decreased gradually over 10 cycles, from 80% degradation rate in the first cycle to 32% in the tenth cycle. After 5 minutes of stopping stirring after the end of each cycle, catalyst sample 1 was allowed to settle completely to the bottom of the vessel and was easily separated from the solution.
In FIG. 4, curves 1 and 2 are the results of the removal of 2, 4-dichlorophen from the catalyst of sample 1 and the catalyst of control sample 2 after 10 cycles of degradation, respectively. After 10 times of circulation, the catalytic performance of the catalyst of the sample 1 is not substantially reduced, and the degradation rate is still maintained at 100% within a period of 100 minutes. While the catalytic performance of the catalyst of control sample 2 decreased gradually over 10 cycles, from a 72% degradation rate in the first cycle to a 14% degradation rate in the tenth cycle. After 5 minutes of stopping stirring after the end of each cycle, catalyst sample 1 was allowed to settle completely to the bottom of the vessel and was easily separated from the solution.
Example 1
20 g of styrene-divinylbenzene sulfonic acid group-containing high polymer (a product produced by Shanghai resin factory Lvbao brand) with the particle size of 0.3-0.5 mm is taken, pretreated and added into an exchange column, and the mixture is fully leached by water until the pH value of effluent is between 5 and 7. Adding ferric trichloride (FeCl)3) Is made into 10-2M aqueous HCl solution containing 0.3M4.0L of solution is loaded on the column for bonding loading until the concentration of the metal ions in the effluent reaches 0.0098M, and the loading is stopped. And continuously leaching with water to wash the metal ions adsorbed on the surface, and recycling. The effluent is rinsed with water until the effluent is free of metal ions. The bound catalyst was poured out of the column and immersed in water for use.
Example 2
20 g of selected sulfonated coal (Yingguang brand product from Zhejiang Yuyao dazzling chemical plant) with the particle size of 1.0-1.2mm is added into an exchange column after pretreatment, and is fully leached by water until the pH value of effluent is between 5 and 7. Mixing copper sulfate (CuSO)45H2O) to 10-2M contains 0.03M of H2SO43.5 liters of aqueous solution, loading on the column for bonding loading until the concentration of the metal ions in the effluent reaches 0.0095M, and stopping loading. And (4) continuously leaching with water, washing the metal ions adsorbed on the surface, and recycling for use. The effluent is rinsed with water until the effluent is free of metal ions. The bound catalyst was poured out of the column and immersed in water for use.
Example 3
Manganese sulfate is prepared into 10-3M contained 1 liter of a 0.05M aqueous sulfuric acid solution, and was charged into a dropping funnel for use. 20 g of methacrylic acid-divinylbenzene copolymerized carboxyl-containing IRC-84 cation exchange resin with the particle size of 0.33-0.50mm (a product produced by Amberlite of Rohm and Hass company in America) is pretreated and then added into a container, a sulfuric acid aqueous solution of metal ions is slowly added under stirring for bonding load, and stirring is stopped after the metal ions are added for 10 hours. Rinsing with water is continued until the water rinse is free of metal ions. The product can be used after being continuously immersed in water.
Example 4
Ammonium ferrous sulfate (FeSO)4(NH4)2SO46H2O) to 10-2M aqueous sulfuric acid solution containing 0.3M0.5 l of the solution was put into a dropping funnel for further use. Selecting methacrylic acid-divinylbenzene copolymerized phosphoric acid group-containing ES-63 type cation exchange tree with the particle size of 0.29-0.55mmFat 20 g (Duolite brand product of Duolite corporation, France), was pretreated and added to a vessel, and Fe was slowly added with stirring2+And carrying out bonding loading on theionic sulfuric acid aqueous solution until the metal ions are added, and stopping stirring after continuing stirring for 13 hours. Rinsing with water until the water washing solution contains no Fe2+Ions are removed. The product can be used after being continuously immersed in water.
Example 5
Mixing ferric nitrate (Fe (NO)3)39H2O) to 10-4M aqueous nitric acid solution containing 0.05M was charged into a dropping funnel in 4 liters and kept for future use. 20 g of PK-228 cation exchange resin (Diaion brand of Mitsubishi chemical corporation) containing sulfonic acid groups, which is selected from styrene-divinylbenzene and has the grain diameter of 0.5mm, is pretreated and then added into a container, and a nitric acid aqueous solution of metal ions is slowly added under stirring for bonding load, and stirring is continued for 15 hours until the metal ion solution is added, and then the stirring is stopped. Rinsing with water is continued until the water wash is free of metal ions. The product can be used after being continuously immersed in water.
Example 6
Mixing iron dichloride (FeCl)24H2O) to 10-2M contained 4 liters of a 0.3M hydrochloric acid aqueous solution, and charged into a dropping funnel for use. Selecting 20 g of styrene-divinylbenzene copolymerized A-1 type chelating resin (Dowex brand product of Dow company in America) with particle size of 0.5-0.85mm, adding the selected resin into a container after pretreatment, slowly adding HCl aqueous solution of divalent iron ions under stirring, carrying out bonding load, continuing stirring for 12 hours after the metal ion solution is added, and stopping stirring. Rinsing with water is continued until the water wash is free of metal ions. The product can be used after being continuously immersed in water.
Example 7
Adding cupric chloride (CuCl)22H2O) to 10-2M contained 4 liters of 0.3M aqueous HCl and was charged to a dropping funnel for future use. Selecting methacrylate-divinylbenzene copolymerized CNP-80 macroporous weak acid cation with particle size of 0.5-0.85mm20 g of the ion exchange resin (product of Lewatit brand of Farbonfabriken Bayer company, Germany) is pretreated and then added into a container, HCl aqueous solution of divalent copper ions is slowly added under stirring for bonding load, and after the metal ions are added according to the required proportion, stirring is continued for 13 hours, and the stirring is stopped. Rinsing with water is continued until the water rinse is free of metal ions. Continuing to immerse in water to makeThe application is as follows.
Comparative example 1
Aluminium sulfate is prepared into 10-2M contained 1.2 liters of a 0.3M aqueous sulfuric acid solution, and charged into a dropping funnel for standby. Selecting styrene-divinylbenzene sulfonic acid group-containing cation exchange resin (product produced by Shanghai resin factory Lvbao brand) with the particle size of 0.5-0.85mm, pretreating, adding into a container, slowly adding a sulfuric acid aqueous solution of metal ions under stirring, carrying out adsorption loading, continuing to stir for 12 hours after the metal ions are added according to the required proportion, and stopping stirring. The rinsing is continued with water until the water rinse is free of manganese ions. The product can be used after being continuously immersed in water.
Comparative example 2
And (3) taking 20 g of 5A molecular sieve with the particle size of 1-2mm, pretreating, adding into an exchange column, and sufficiently leaching with water until the pH value of effluent is 5-7. Mixing ferric nitrate (Fe (NO)3)39H2O) to 10-2M content of 0.3M HNO31.2 liters of the aqueous solution is loaded on a column for bonding loading until the concentration of the metal ions in the effluent solution is stabilized at 10-2At the value of M, the load is stopped. And (4) continuously leaching with water, washing the metal ions adsorbed on the surface, and recycling for use. The effluent is rinsed with water until the effluent is free of metal ions. The bonded catalyst is poured out of the column, dried, treated at a high temperature of 500 ℃ and then immersed in water for use.
Claims (6)
1. A solid-phase photocatalyst is composed of a carrier and metal ions which are bonded with the carrier and have photocatalytic activity, and is characterized in that: the carrier is a high polymer carrier, and the gold isThe metal ions are divalent or trivalent iron ions, divalent manganese ions and divalent copper ions; the metal ions are loaded on the high polymer carrier in a bonding mode, and the mole/mass ratio of the metal ions to the high polymer carrier is 10-6～10-2Mole/gram; the high polymer carrier is an inorganic or organic polymer, the inorganic polymer is sulfonated coal, and the organic polymer is a granular cation exchange resin material of polystyrene/divinylbenzene or a granular cation exchange resin material of polymethacrylic acid, polymethyl methacrylate/divinylbenzene or a chelating resin material of polystyrene/divinylbenzene.
2. A solid-phase photocatalyst in accordance with claim 1, characterized in that: the organic polymer is strong acid cation exchange resin with sulfonic group, which takes styrene-divinylbenzene as copolymer, or weak acid cation exchange resin with carboxylic group or phosphoric group, which takes methacrylic acid and methyl methacrylate-divinylbenzene as copolymer, or imine diacetic acid chelating resin, which takes styrene-divinylbenzene as copolymer.
3. A solid-phase photocatalyst in accordance with claim 1, characterized in that: the particle size of the high polymer carrier is 1 micron-5 mm.
4. The preparation method of the solid-phase photocatalyst comprises the following steps:
(1) pretreatment of high polymer
Washing the high polymer carrier with acid and alkali by a conventional method, rinsing the high polymer carrier to be neutral with water, and soaking the high polymer carrier in the water for column packing for later use; the high polymer carrier is an inorganic or organic polymer, the inorganic polymer is sulfonated coal, and the organic polymer is a granular cation exchange resin material of polystyrene/divinylbenzene or a granular cation exchange resin material of polymethacrylic acid, polymethyl methacrylate/divinylbenzene or a chelating resin material of polystyrene/divinylbenzene;
(2) preparation of Metal ion solution
Firstly, preparing 0.1-0.5 mol/L dilute hydrochloric acid, nitric acid or sulfuric acid solution, then adding corresponding metal salt according to the solid-to-liquid ratio of 10-50 g/L, and stirring for dissolving; the metal salt is water-soluble bivalent and trivalent ferric salt, water-soluble bivalent manganese salt and water-soluble bivalent copper salt;
(3) bonding of metal ions to high polymers
Pouring metal ion solution from the upper opening of the column in batches, adjusting the flow rate by using a piston, and ensuring that the flow rate is not more than the flow rate of an initial leakage point calculated according to a theory to carry out exchange loading until the metal ion concentration of effluent liquid is more than 95% of the initial concentration of the effluent liquid, and finishing the loading; rinsing with water is continued until the effluent is free of metal ions.
5. The preparation method of the solid-phase photocatalyst comprises the following steps:
(1) pretreatment of high polymer
Washing the high polymer carrier with acid and alkali by a conventional method, rinsing the high polymer carrier to be neutral by water (distilled water, the same as the following), soaking the high polymer carrier in the water, and packing the high polymer carrier for later use; the high polymer carrier is an inorganic or organic polymer, the inorganic polymer is sulfonated coal, and the organic polymer is a granular cation exchange resin material of polystyrene/divinylbenzene or a granular cation exchange resin material of polymethacrylic acid, polymethyl methacrylate/divinylbenzene or a chelating resin material of polystyrene/divinylbenzene;
(2) preparation of Metal ion solution
Firstly, preparing 0.1-0.5 mol/L dilute hydrochloric acid, nitric acid or sulfuric acid solution, then adding corresponding metal salt according to the solid-to-liquid ratio of 10-50 g/L, and stirring for dissolving; the metal salt is water-soluble bivalent and trivalent ferric salt, water-soluble bivalent manganese salt and water-soluble bivalent copper salt;
(3) bonding of metal ions to high polymers
Adding water into a glass or plastic container provided with a stirring device, adding the treated high polymer, uniformly stirring and dispersing in a water body, taking another dropping funnel, slowly dropping the prepared metal ion solution for standby through a control funnel valve, fully stirring, adding the metal ion solution, after the metal ion solution is added, continuously stirring for at least 10 hours, and finishing loading; rinsing with water until the water rinse is free of metal ions.
6. A method for preparing a solid-phase photocatalyst according to claim 4 or 5, characterized in that: the organic polymer is strong acid cation exchange resin with sulfonic group, which takes styrene-divinylbenzene as copolymer, or weak acid cation exchange resin with carboxylic group or phosphoric group, which takes methacrylic acid and methyl methacrylate-divinylbenzene as copolymer, or imine diacetic acid chelating resin, which takes styrene-divinylbenzene as copolymer.
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| 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 |
| CN103483487A (en) * | 2013-08-01 | 2014-01-01 | 于杰 | Novel structure product, preparation method and use of styrenic resin |
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| CN104941607A (en) * | 2013-08-12 | 2015-09-30 | 天津市阳权医疗器械有限公司 | Styrene new structure adsorption resin for clearing excess B2 microglobulin in blood |
| 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 |
| CN115159588A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for catalytically recovering elemental sulfur and ammonium ferrous sulfate from sulfur dioxide flue gas |
| 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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