CN102151567A - Catalyst for oxidation and decomposition of organic pollutants in water with ozone and method thereof for catalyzing sewage treatment with ozone - Google Patents
Catalyst for oxidation and decomposition of organic pollutants in water with ozone and method thereof for catalyzing sewage treatment with ozone Download PDFInfo
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- CN102151567A CN102151567A CN 201110046323 CN201110046323A CN102151567A CN 102151567 A CN102151567 A CN 102151567A CN 201110046323 CN201110046323 CN 201110046323 CN 201110046323 A CN201110046323 A CN 201110046323A CN 102151567 A CN102151567 A CN 102151567A
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Abstract
The invention discloses a catalyst for oxidation and decomposition of organic pollutants in water with ozone and a method thereof for catalyzing sewage treatment with ozone, and relates to a catalyst for decomposing the organic pollutants in water and the method thereof for sewage treatment. By adopting the catalyst, the problems that the traditional solid catalyst for catalyzing the decomposition of organic pollutants in the water with ozone is easy to be oxidized and decomposed by ozone, easy to break, can dissolve out impurities, has low strength and low catalytic efficiency and is difficult to recover can be solved. The catalyst for oxidation and decomposition of the organic pollutants in the water with ozone refers to spinel ferrite or a composite of spinel ferrite; and the method of the catalyst for catalyzing the sewage treatment with ozone comprises the following steps of: adjusting pH and temperature of sewage, then introducing ozone, further adding the catalyst and treating for 1 minute-120 minutes, then using a magnetic field to recover the catalyst, and finally absorbing tail gas of the ozone. The catalyst can improve the removal rate of organic matters to 90%-100%, and can be used for sewage treatment or deep treatment of drinking water.
Description
Technical field
The present invention relates to the catalyst of organic pollution in the decomposition water and the method for disposing of sewage thereof.
Background technology
Along with developing rapidly of global economy, the problem of water resource anxiety becomes increasingly conspicuous, and many rivers, reservoir, immediate offshore area, underground water etc. all have been subjected to pollution in various degree, have reduced the function and the effect of drinking water source.Serious organic pollutants in water body particularly difficult degradation pollutant such as environmental estrogens has been proved to be there has been serious harm in health and ecological environment.The organic pollution of these difficult degradations, distributed pole is wide in water body, along with people's living standard and to the raising of water quality standard for drinking water, traditional to water technology to the deep treatment method of drinking water such as absorption method, embrane method, ozone absorbent charcoal method, can not effectively satisfy and remove organic pollution requirement in the water.
Ozone is as a kind of strong oxidizer, oxidation-reduction potential under standard state is+2.07V, can degrade and contain two isostructural easy oxidation of organic compounds of key, and can remove algae, decolouring, remove and smell flavor, intensified coagulation, raising hardly degraded organic substance and natural macromolecular biodegradability of organic matter etc., be used for the history that water treatment research has had a century.Though ozone has very strong oxidation and sterilizing ability, and be not easy to produce secondary pollution, but significant disadvantages is arranged also: the oxidability of ozone has selectivity, is difficult to remove TOC and COD in the water in the ozonisation process, is difficult to remove the problems such as pollutant of persistence difficult degradation in the water.In order to strengthen the efficient of ozonation technology, the normal method that adds catalyst that adopts promotes that ozone decomposed is hydroxyl radical free radical, accelerates organic oxidation and mineralising.
The catalytic ozonation technology is the method that under a kind of novel normal temperature and pressure those is difficult to the oxidation operation of independent oxidation of ozone or degraded.The catalytic ozonation technology utilizes a large amount of strong oxidizing property hydroxyl radical free radicals that produce in the course of reaction to come organic matter in the decomposition water, thereby reaches the purpose of purification of water quality.Existing solid ozonisation decomposition catalyst mainly contains elemental metals (Mn, Zn, Fe, Cu, Ni etc.), the compound (MnO of metal oxide or metal oxide and other material
2, FeOOH, ZnOOH, TiO
2, Al
2O
3, ZnO, Al
2O
3/ TiO
2, C/TiO
2Deng) and active carbon (mesopore activated carbon, CNT, the carbon adsorbent of various patterns) etc.The elemental metals solid catalyst is easily decomposed by ozone oxidation, low, the easy fragmentation of the composite strength of metal oxide or metal oxide and other material, cause the catalyst life cycle short, and the strong suction-operated in target contaminant and metal oxide catalyst surface causes catalytic activity significantly to reduce in the water body, and scrubbing efficient only is 70%～80%; With the activated carbon is the catalytic ozonation technology of catalyst, though can improve catalytic effect, but need to increase reprocessing facility to remove the fine particle that produces after the active carbon fragmentation, the sulphur that contains in the active carbon and other inorganic impurity possibility stripping in the ozonisation process in addition influences effluent quality; Metal oxide and activated-carbon catalyst finish the very difficult recovery in back in ozonisation technology in addition.
Summary of the invention
The present invention be to solve the catalyst of organic contamination in the existing solid ozonisation decomposition water easily by ozone oxidation decomposition, low, the easy fragmentation of intensity, have that impurity stripping, catalytic efficiency are low reclaims difficult technical problem, and provide the catalyst of organic pollution in the ozone oxidation decomposition water and the method that catalysis ozone is disposed of sewage thereof.
The catalyst that ozone oxidation of the present invention is decomposed organic pollutants is ferrospinel NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4And CaFe
2O
4In a kind of or wherein two kinds combination.
The catalyst that ozone oxidation of the present invention is decomposed organic pollutants can also be ferrospinel M
1-xN
xFe
2O
4, 0＜x＜1 wherein, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
The catalyst that ozone oxidation of the present invention is decomposed organic pollutants can also be that ferrospinel is carried on the compound that make on the carbonaceous material surface, wherein the mass ratio of ferrospinel and carbonaceous material is 0.1～1: 1, carbonaceous material is a kind of in active carbon, CNT, Graphene and the bamboo carbon or wherein several combination, and described ferrospinel is NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4, CaFe
2O
4Or M
1-xN
xFe
2O
4, 0＜x＜1 wherein, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
The catalyst that ozone oxidation of the present invention is decomposed organic pollutants can also be the compound of making of ferrospinel and metal oxide, and wherein the mass ratio of ferrospinel and metal oxide is 0.1～1: 1, and metal oxide is TiO
2, ZnO, CuO, Al
2O
3, MnO
2, NiO, Co
3O
4And V
2O
5In a kind of or several compositions wherein; Described ferrospinel is NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4, CaFe
2O
4Or M
1-xN
xFe
2O
4, 0＜x＜1 wherein, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
The method of the catalyst ozone treatment sewage of organic pollution is carried out according to the following steps in the above-mentioned ozone oxidation decomposition water: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 3～10, temperature is controlled at 15～30 ℃; Two, in the catalytic ozonation reactor, feed ozone, make the concentration of ozone reach 0.5mg/L～50mg/L, the catalyst that adds organic pollution in the ozone oxidation decomposition water then, the mass ratio of the catalyst of organic pollution and ozone is 1～50: 1 in the ozone oxidation decomposition water, handles 1min～120min; Three, be that catalyst is fixed or reclaimed to magnet or the electromagnetic field of 0.5T～1.5T with magnetic field intensity, ozone tail gas utilizes the KI solution of 5%～8% (quality) to absorb, and finishes organic pollution catalytic ozonation decomposable process in the water.
What play catalytic action in the catalyst of ozone oxidation decomposition organic pollutants of the present invention is to have the ferrospinel of octahedral structure or the compound of ferrospinel, structure for porous, the surface is easy to form high density surface hydroxyl form in the aqueous solution, so that organic pollution is difficult to absorption on its surface, solved that complicated pollutant is conducive to improve the utilization rate of ozone in the problem that catalyst surface absorption causes its catalytic activity to descend in the water body; Simultaneously catalyst has magnetic, realizes the high efficiente callback of catalyst and recycles by adding common magnet or electromagnetic field.Ferrospinel and ferrospinel complex catalyst make that organic clearance can reach 90～100% in the water, improve 20～70% than independent ozone clearance.Ferrospinel and compound mechanical strength thereof are big, non-friable among the present invention, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.Magnetic spinel ferrite and complex catalyst thereof have high catalytic activity, itself have very strong catalysis ozone and decompose the ability that produces hydroxyl radical free radical.This catalyst structure is stable, can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The present invention can be used as sewage disposal or the drinking water deep treatment technology is applied in the actual water treatment procedure, improve comprehensively the organic pollutant removal effect is fallen in difficulty in the water, can improve simultaneously the biodegradability of difficult oxidation of organic compounds, during with other water treatment technology coupling, can improve removal to total organic carbon, reduce the toxicity of water, and can by reduce dissolved organic matter concentration in the water so that reduce follow-up cholorination handle in the generation of accessory substance, for drinking water quality safety provides powerful guarantee.The present invention adopts ferrospinel with octahedral structure or its compound as the catalyst of ozonation, has expanded O
3The range of application of catalyst in the/catalysis of solid catalyst method has improved in the catalytic ozonation process removal effect to organic pollutants, can realize utilizing simultaneously adding common magnet or electromagnetic field carries out the high efficiente callback of catalyst.
Description of drawings
Fig. 1 be the specific embodiment 20 with MnFe
2O
4The clearance of DBP and the graph of relation of time in the sewage when decomposing the catalyst of organic pollutants as ozone oxidation; Fig. 2 be the specific embodiment 21 with NiFe
2O
4The clearance of DBP and the graph of relation of time in the sewage when decomposing the catalyst of organic pollutants as ozone oxidation;
The specific embodiment
The specific embodiment one: the catalyst that the ozone oxidation of present embodiment is decomposed organic pollutants is ferrospinel NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4And CaFe
2O
4In a kind of or wherein two groups combination.
When the catalyst of ozone oxidation decomposition organic pollutants was composition in the present embodiment, each ferrospinel was pressed arbitrarily than combination.
The preparation method that the ozone oxidation of present embodiment is decomposed the catalyst of organic pollutants carries out according to the following steps: a, egg at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, by the atom number of metallic element in the ferrospinel molecular formula than the nitrate that takes by weighing metallic element, wherein the mass volume ratio of ferric nitrate and egg white solution is 0.2g: 1mL, metal nitrate is joined in the egg white solution that step a obtains, be placed on then in 80 ℃ of water-baths, stir 2h～3h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h～7h; D, the product that step c is obtained are down to room temperature with mixture of ice and water, are dry 2h～3h in 50 ℃～60 ℃ the baking oven in temperature then, obtain the catalyst that ozone oxidation is decomposed organic pollutants after grinding again; Ferrospinel molecular formula among the step b is NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4Or CaFe
2O
4
What play catalytic action in the catalyst of the ozone oxidation decomposition organic pollutants of present embodiment is the ferrospinel with octahedral structure, structure for porous, the surface is easy to form high density surface hydroxyl form in the aqueous solution, so that organic pollution is difficult to absorption on its surface, solved that complicated pollutant is conducive to improve the utilization rate of ozone in the problem that catalyst surface absorption causes its catalytic activity to descend in the water body; Simultaneously catalyst has magnetic, realizes the high efficiente callback of catalyst and recycles by adding common magnet or electromagnetic field.The spinel ferrite body catalyst makes that organic clearance can reach 90～100% in the water, improves 20～70% than independent ozone clearance.The ferrospinel mechanical strength is big, non-friable among the present invention, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.The magnetic spinel ferrite catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This spinel-type catalyst structure is stable, can not be decomposed by ozone oxidation, and catalytic process can not brought the secondary pollution of heavy metal ion, does not influence health.
The specific embodiment two: the catalyst that the ozone oxidation of present embodiment is decomposed organic pollutants is ferrospinel M
1-xN
xFe
2O
4, 0＜x＜1 wherein, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
The method for preparing catalyst of organic pollution carries out according to the following steps in the ozone oxidation decomposition water of present embodiment: a, egg clearly at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, by the atom number of metallic element in the ferrospinel molecular formula than the nitrate that takes by weighing metallic element, wherein the mass volume ratio of ferric nitrate and egg white solution is 0.2g: 1mL, metal nitrate is joined in the egg white solution that step a obtains, be placed on then in 80 ℃ of water-baths, stir 2h～3h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h～7h; D, the product that step c is obtained are reduced to room temperature with mixture of ice and water, are placed on temperature then and are dry 2h～3h in 50 ℃～60 ℃ the baking oven, obtain the catalyst of organic pollution in the ozone oxidation decomposition water after grinding again; Ferrospinel M among the step b
1-xN
xFe
2O
4, 0＜x in the formula＜1, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
What play catalytic action in the catalyst of the ozone oxidation decomposition organic pollutants of present embodiment is the ferrospinel with octahedral structure, structure for porous, the surface is easy to form high density surface hydroxyl form in the aqueous solution, so that organic pollution is difficult to absorption on its surface, solved that complicated pollutant is conducive to improve the utilization rate of ozone in the problem that catalyst surface absorption causes its catalytic activity to descend in the water body; Simultaneously catalyst has magnetic, realizes the high efficiente callback of catalyst and recycles by adding common magnet or electromagnetic field.The spinel ferrite body catalyst makes that organic clearance can reach 90～100% in the water, improves 20～70% than independent ozone clearance.The ferrospinel mechanical strength is big, non-friable among the present invention, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.The magnetic spinel ferrite catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This spinel-type catalyst structure is stable, can not be decomposed by ozone oxidation, and catalytic process can not brought the secondary pollution of heavy metal ion, does not influence health.
The specific embodiment three: what present embodiment and the specific embodiment two were different is: ferrospinel M
1-xN
xFe
2O
40.1＜x in the formula＜0.9.Other is identical with the specific embodiment two.
The specific embodiment four: what present embodiment and the specific embodiment two were different is: ferrospinel M
1-xN
xFe
2O
4X=0.3 in the formula.Other is identical with the specific embodiment two.
The specific embodiment five: the ozone oxidation of present embodiment is decomposed the catalyst of organic pollutants for ferrospinel is carried on the compound that make on the carbonaceous material surface, wherein the mass ratio of ferrospinel and carbonaceous material is 0.1～1: 1, carbonaceous material is a kind of in active carbon, CNT, Graphene and the bamboo carbon or wherein several combination, and described ferrospinel is NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4, CaFe
2O
4Or M
1-xN
xFe
2O
4, M
1-xN
xFe
2O
40＜x in the formula＜1, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
When the catalyst of organic pollution in the ozone oxidation decomposition water was composition, each ferrospinel was pressed arbitrarily than combination in the present embodiment.
When carbonaceous material was composition in the present embodiment, each carbonaceous material was pressed arbitrarily than combination.
The preparation method that the ozone oxidation of present embodiment is decomposed the catalyst of organic pollutants carries out according to the following steps: a, egg at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, by the atom number of metallic element in the ferrospinel molecular formula than the nitrate that takes by weighing metallic element, wherein the mass volume ratio of ferric nitrate and egg white solution is 0.2g: 1mL, mass ratio by ferric nitrate and carbonaceous material is 0.2～1 again: 1 takes by weighing carbonaceous material, metal nitrate and carbonaceous material are joined in the egg white solution that step a obtains, be placed on then in 80 ℃ of water-baths, stir 2h～3h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h～7h; D, the product that step c is obtained are down to room temperature with mixture of ice and water, are placed on then temperature and are dry 2h～3h in 50 ℃～60 ℃ the baking oven, obtain the catalyst that ozone oxidation is decomposed organic pollutants after grinding again; Ferrospinel described in the step b is NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4, CaFe
2O
4Or M
1-xN
xFe
2O
4, M
1-xN
xFe
2O
40＜x in the formula＜1, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N; Carbonaceous material described in the step b is a kind of in active carbon, CNT, Graphene and the bamboo carbon or wherein several combination.
What play catalytic action in the catalyst of the ozone oxidation decomposition organic pollutants of present embodiment is that the ferrospinel that will have octahedral structure loads on the carbonaceous material, structure for porous, increased the specific area of catalyst, also increased the catalytic activity point position of catalyst surface, the surface is easy to form high density surface hydroxyl form in the aqueous solution, the adsorption ability reduces, so that organic pollution is difficult to absorption on its surface, solved the problem that complicated pollutant causes its catalytic activity to descend in catalyst surface absorption in the water body, be conducive to improve the utilization rate of ozone, the quantity that also makes catalysis ozone produce hydroxyl radical free radical increases, so that the organic matter degradation successful improves.This spinel ferrite body catalyst makes that the organic matter removal rate can reach 90～100% in the water, under identical static catalysis ozone experiment condition, can improve 40～70% to organic degradation effect in the water than independent ozone clearance, catalyst has magnetic in addition, realizes the high efficiente callback of catalyst and recycles by adding common magnet or electromagnetic field.Composite catalyst body mechanical strength is big, non-friable among the present invention, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.The magnetic composite catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This catalyst structure is stable, can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The specific embodiment six: what present embodiment and the specific embodiment five were different is: the mass ratio of ferrospinel and carbonaceous material is 0.1～0.9: 1.Other is identical with the specific embodiment five.
The specific embodiment seven: what present embodiment and the specific embodiment five were different is: the mass ratio of ferrospinel and carbonaceous material is 0.6: 1.Other is identical with the specific embodiment five.
The specific embodiment eight: what present embodiment was different from one of specific embodiment five to seven is: ferrospinel M
1-xN
xFe
2O
40.1＜x in the formula＜0.9.Other is identical with one of specific embodiment five to seven.
The specific embodiment nine: what present embodiment was different from one of specific embodiment five to seven is: ferrospinel M
1-xN
xFe
2O
4X=0.6 in the formula.Other is identical with one of specific embodiment five to seven.
The specific embodiment ten: the catalyst that the ozone oxidation of present embodiment is decomposed organic pollutants is the compound of making of ferrospinel and metal oxide, wherein the mass ratio of ferrospinel and metal oxide is 0.1～1: 1, and metal oxide is TiO
2, ZnO, CuO, Al
2O
3, MnO
2, NiO, Co
3O
4And V
2O
5In a kind of or several compositions wherein; Described ferrospinel is NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4, CaFe
2O
4Or M
1-xN
xFe
2O
4, 0＜x＜1 wherein, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
When the metal oxide in the present embodiment was composition, each metal oxide was pressed arbitrarily than combination.
The preparation method that the ozone oxidation of present embodiment is decomposed the catalyst of organic pollutants carries out according to the following steps: a, egg at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, by the atom number of metallic element in the ferrospinel molecular formula than the nitrate that takes by weighing metallic element, wherein the mass volume ratio of ferric nitrate and egg is 0.2g: 1mL, mass ratio by ferric nitrate and metal oxide is 0.2～1 again: 1 takes by weighing metal oxide, metal nitrate and metal oxide are joined in the egg white solution that step a obtains, be placed on then in 80 ℃ of water-baths, stir 2h～3h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h～7h; D, the product that step c is obtained are down to room temperature with mixture of ice and water, are placed on then temperature and are dry 2h～3h in 50 ℃～60 ℃ the baking oven, obtain the catalyst that ozone oxidation is decomposed organic pollutants after grinding again; Ferrospinel described in the step b is NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4, CaFe
2O
4Or M
1-xN
xFe
2O
4, M1-xNxFe
2O
40＜x in the formula＜1, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N; Metal oxide described in the step b is TiO
2, ZnO, CuO, Al
2O
3, MnO
2, NiO, Co
3O
4And V
2O
5In a kind of or several compositions wherein.
What play catalytic action in the catalyst of the ozone oxidation decomposition organic pollutants of present embodiment is that the ferrospinel that will have octahedral structure loads on metal oxide surface, structure for porous, increased the specific area of catalyst, also increased the catalytic activity point position of catalyst surface, the surface is easy to form high density surface hydroxyl form in the aqueous solution, the adsorption ability reduces, so that organic pollution is difficult to absorption on its surface, solved the problem that complicated pollutant causes its catalytic activity to descend in catalyst surface absorption in the water body, be conducive to improve the utilization rate of ozone, the quantity that also makes catalysis ozone produce hydroxyl radical free radical increases, so that the organic matter degradation successful improves.This ferrospinel composite catalyst makes that the organic matter removal rate can reach 90～100% in the water, under identical static catalysis ozone experiment condition, can improve 40～70% to organic degradation effect in the water than independent ozone clearance, catalyst has magnetic in addition, realizes the high efficiente callback of catalyst and recycles by adding common magnet or electromagnetic field.The composite catalyst mechanical strength is big, non-friable among the present invention, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.The magnetic composite catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This catalyst structure is stable, can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The specific embodiment 11: what present embodiment and the specific embodiment ten were different is: the mass ratio of ferrospinel and metal oxide is 0.2～0.8: 1.Other is identical with the specific embodiment ten.
The specific embodiment 12: what present embodiment and the specific embodiment ten were different is: the mass ratio of ferrospinel and metal oxide is 0.5: 1.Other is identical with the specific embodiment ten.
The specific embodiment 13: the method for the catalyst ozone treatment sewage of organic pollution is carried out according to the following steps in the ozone oxidation decomposition water of present embodiment: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 3～10, temperature is controlled at 15～30 ℃; Two, in the catalytic ozonation reactor, feed ozone, make the concentration of ozone reach 0.5mg/L～50mg/L, the catalyst that adds organic pollution in the ozone oxidation decomposition water then, the mass ratio of the catalyst of organic pollution and ozone is 1～50: 1 in the ozone oxidation decomposition water, handles 1min～120min; Three, be that catalyst is fixed or reclaimed to magnet or the electromagnetic field of 0.5T～1.5T with magnetic field intensity, ozone tail gas utilizes the KI solution of 5%～8% (quality) to absorb, and finishes organic pollution catalytic ozonation decomposable process in the water.
In the present embodiment in the ozone oxidation decomposition water catalyst of organic pollution make that organic clearance can reach 90～100% in the water, improve 20～70% than independent ozone clearance.Ferrospinel and compound mechanical strength thereof are big, non-friable, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.Magnetic catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This catalyst structure is stable, can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The specific embodiment 14: what present embodiment and the specific embodiment 13 were different is: in the step 1 pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 4～9, temperature is controlled at 18～25 ℃.Other is identical with the specific embodiment 13.
The specific embodiment 15: what present embodiment and the specific embodiment 13 were different is: in the step 1 pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 6, temperature is controlled at 20 ℃.Other is identical with the specific embodiment 13.
The specific embodiment 16: what present embodiment was different with one of specific embodiment 13 to 15 is: the concentration of ozone reaches 3mg/L～40mg/L in the step 2, the mass ratio of the catalyst of organic pollution and ozone is 5～40: 1 in the ozone oxidation decomposition water, and the processing time is 5min～100min.Other is identical with one of specific embodiment 13 to 15.
The specific embodiment 17: what present embodiment was different with one of specific embodiment 13 to 15 is: the concentration of ozone reaches 20mg/L in the step 2, the mass ratio of the catalyst of organic pollution and ozone is 20: 1 in the ozone oxidation decomposition water, and the processing time is 60min.Other is identical with one of specific embodiment 13 to 15.
The specific embodiment 18: what present embodiment was different with one of specific embodiment 13 to 17 is: the magnetic field intensity in the step 3 is 0.5T～1.5T, and the concentration that absorbs the KI solution of ozone tail gas is 5.5%～7.5% (quality).Other is identical with one of specific embodiment 13 to 17.
The specific embodiment 19: what present embodiment was different with one of specific embodiment 13 to 17 is: the magnetic field intensity in the step 3 is 1.0T, and the concentration that absorbs the KI solution of ozone tail gas is 6.5% (quality).Other is identical with one of specific embodiment 13 to 17.
The specific embodiment 20: the ozone oxidation of present embodiment is decomposed the method for the catalyst ozonisation decomposition organic pollutants of organic pollutants and carried out according to the following steps: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 5.6, temperature is controlled at 15 ℃; Two, in the catalytic ozonation reactor, pass into ozone, make the concentration of ozone reach 7mg/L, add then MnFe
2O
4, MnFe
2O
4With the mass ratio of ozone be 20: 1, the processing time is 60min; Three, with magnetic field intensity be the magnetic field recovery MnFe of 0.1T
2O
4, ozone tail gas utilizes 5% KI solution absorption, finishes organic pollutants catalytic ozonation decomposable process.
The ozone oxidation of present embodiment is decomposed the catalyst MnFe of organic pollutants
2O
4The preparation method carry out according to the following steps: a, egg at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, press ferrospinel molecular formula MnFe
2O
4The atom number ratio of middle metallic element takes by weighing manganese nitrate and ferric nitrate, wherein the mass volume ratio of the egg white solution that obtains of ferric nitrate and step a is 0.2g: 1mL, and manganese nitrate and ferric nitrate are joined in the egg white solution that step a obtains, and is placed on then in 80 ℃ of water-baths, stir 2h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h; D, the product that step c is obtained are down to room temperature with mixture of ice and water, are dry 2h in 60 ℃ the baking oven in temperature then, obtain the catalyst that ozone oxidation is decomposed organic pollutants after grinding again.
MnFe in the present embodiment
2O
4Micron powder for porous, the initial concentration of dibutyl phthalate in the sewage (DBP) is 0.5mg/L, in the experimentation respectively 0,3,5,10,20,30,40,50, the 60min sampling, the clearance of DBP in the test sewage, in the sewage that obtains the relation curve of the clearance of DBP and time as shown in Figure 1, a is MnFe among the figure
2O
4The relation curve of the clearance of DBP and time in the sewage under the catalytic ozonation condition, b are the clearance of adjacent DBP in the sewage under the independent ozonisation condition and the relation curve of time, as can be seen from Figure 1, and cellular MnFe
2O
4Process 60min catalytic ozonation reaches 90% to the removal efficient of DBP.
Through the catalytic ozonation reaction of 60min, Mn in the solution when having measured the reaction end
4+Concentration be 0.003mg/L, Fe
2+Concentration be 0.005mg/L, two heavy metal species ion stripping concentrations meet the requirement of drinking water sanitary standard (GB5749-2006) fully.
The catalyst MnFe of present embodiment
2O
4Mechanical strength is big, non-friable, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.The magnetic spinel ferrite catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This spinel-type catalyst MnFe
2O
4Stability Analysis of Structures can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The specific embodiment 21: the ferrospinel catalyst ozonisation of present embodiment is decomposed the method for organic pollutants and carried out according to the following steps: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 5.6, temperature is controlled at 15 ℃; Two, in the catalytic ozonation reactor, pass into ozone, make the concentration of ozone reach 9mg/L, add then NiFe
2O
4, NiFe
2O
4With the mass ratio of ozone be 15: 1, the processing time is 60min; Three, with magnetic field intensity be the magnetic field recovery NiFe of 0.1T
2O
4, ozone tail gas utilizes 5% KI solution absorption, finishes organic pollutants catalytic ozonation decomposable process.
The ozone oxidation of present embodiment is decomposed the catalyst n iFe of organic pollutants
2O
4The preparation method carry out according to the following steps: a, egg at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, press ferrospinel molecular formula NiFe
2O
4The atom number ratio of middle metallic element takes by weighing nickel nitrate and ferric nitrate, wherein the mass volume ratio of ferric nitrate and egg white solution is 0.2g: 1mL, and nickel nitrate and ferric nitrate are joined in the egg white solution that step a obtains, and is placed on then in 80 ℃ of water-baths, stir 2h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h; D, the product that step c is obtained are down to room temperature with mixture of ice and water, are dry 2h in 60 ℃ the baking oven in temperature then, obtain the catalyst that ozone oxidation is decomposed organic pollutants after grinding again.
NiFe in the present embodiment
2O
4Micron powder for porous, the initial concentration of dibutyl phthalate in the sewage (DBP) is 0.5mg/L, in the experimentation respectively 0,3,5,10,20,30,40,50, the 60min sampling, the clearance of DBP in the test sewage, in the sewage that obtains the relation curve of the clearance of DBP and time as shown in Figure 2, a is NiFe among the figure
2O
4The relation curve of the clearance of DBP and time in the sewage under the catalytic ozonation condition, b are the clearance of DBP in the sewage under the independent ozonisation condition and the relation curve of time, as can be seen from Figure 2, and cellular NiFe
2O
4Process 60min catalytic ozonation reaches 100% to the removal efficient of DBP.
Through the catalytic ozonation reaction of 60min, the concentration of heavy metal ion of stripping in the solution when having measured the reaction end, Ni
2+Stripping concentration be 0.001mg/L, Fe
2+Stripping concentration be 0.003mg/L, two heavy metal species ion stripping concentrations meet the requirement of drinking water sanitary standard (GB 5749-2006) fully.
The catalyst n iFe of present embodiment
2O
4Mechanical strength is big, non-friable, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.The magnetic spinel ferrite catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This spinel-type catalyst n iFe
2O
4Stability Analysis of Structures can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The specific embodiment 22: the ferrospinel catalyst ozonisation of present embodiment is decomposed the method for organic pollutants and carried out according to the following steps: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 5.6, temperature is controlled at 15 ℃; Two, in the catalytic ozonation reactor, pass into ozone, make the concentration of ozone reach 9mg/L, add then ferrospinel catalyst n iFe
2O
4, NiFe
2O
4With the mass ratio of ozone be 15: 1, the processing time is 60min; Three, with magnetic field intensity be the magnetic field recovery NiFe of 0.1T
2O
4, ozone tail gas utilizes 5% KI solution absorption, finishes organic pollutants catalytic ozonation decomposable process.
The ozone oxidation of present embodiment is decomposed the catalyst n iFe of organic pollutants
2O
4The preparation method carry out according to the following steps: a, egg at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, press ferrospinel molecular formula NiFe
2O
4The atom number ratio of middle metallic element takes by weighing nickel nitrate and ferric nitrate, wherein the mass volume ratio of the egg white solution that obtains of ferric nitrate and step a is 0.2g: 1mL, and nickel nitrate and ferric nitrate are joined in the egg white solution that step a obtains, and is placed on then in 80 ℃ of water-baths, stir 2h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h; D, the product that step c is obtained are down to room temperature with mixture of ice and water, are dry 2h in 60 ℃ the baking oven in temperature then, obtain the catalyst that ozone oxidation is decomposed organic pollutants after grinding again.
NiFe in the present embodiment
2O
4Micron powder for porous, the initial concentration of dibutyl phthalate in the sewage (DMP) is 0.5mg/L, in the experimentation respectively 0,3,5,10,20,30,40,50, the 60min sampling, the clearance of DMP in the test sewage, cellular ferrospinel NiFe
2O
4Process 30min catalytic ozonation reaches 100% to the removal efficient of DMP, can improve 65% than the clearance (28%) to DMP in the independent ozonisation same time.
Through the catalytic ozonation reaction of 60min, the concentration of heavy metal ion of stripping in the solution when having measured the reaction end, Ni
2+Stripping concentration be 0.001mg/L, Fe
2+Stripping concentration be 0.003mg/L, two heavy metal species ion stripping concentrations meet the requirement of drinking water sanitary standard (GB 5749-2006) fully.
The catalyst n iFe of present embodiment
2O
4Mechanical strength is big, non-friable, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.The magnetic spinel ferrite catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This spinel-type catalyst n iFe
2O
4Stability Analysis of Structures can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The specific embodiment 23: the ferrospinel catalyst ozonisation of present embodiment is decomposed the method for organic pollutants and carried out according to the following steps: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 5.6, temperature is controlled at 15 ℃; Two, in the catalytic ozonation reactor, pass into ozone, make the concentration of ozone reach 7mg/L, add then spinel ferrite body catalyst MnFe
2O
4, MnFe
2O
4With the mass ratio of ozone be 20: 1, the processing time is 60min; Three, with magnetic field intensity be the magnetic field recovery NiFe of 0.1T
2O
4, ozone tail gas utilizes 5% KI solution absorption, finishes organic pollutants catalytic ozonation decomposable process.
The ozone oxidation of present embodiment is decomposed the catalyst MnFe of organic pollutants
2O
4The preparation method carry out according to the following steps: a, egg at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, press ferrospinel molecular formula MnFe
2O
4The atom number ratio of middle metallic element takes by weighing manganese nitrate and ferric nitrate, wherein the mass volume ratio of the egg white solution that obtains of ferric nitrate and step a is 0.2g: 1mL, and manganese nitrate and ferric nitrate are joined in the egg white solution that step a obtains, and is placed on then in 80 ℃ of water-baths, stir 2h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h; D, the product that step c is obtained are down to room temperature with mixture of ice and water, are dry 2h in 60 ℃ the baking oven in temperature then, obtain the catalyst that ozone oxidation is decomposed organic pollutants after grinding again.
MnFe in the present embodiment
2O
4Micron powder for porous, the initial concentration of dibutyl phthalate in the sewage (DMP) is 0.5mg/L, in the experimentation respectively 0,3,5,10,20,30,40,50, the 60min sampling, the clearance of DMP in the test sewage, cellular ferrospinel MnFe
2O
4Process 30min catalytic ozonation reaches 100% to the removal efficient of DMP, can improve 65% than the clearance (28%) to DMP in the independent ozonisation same time.
Through the catalytic ozonation reaction of 60min, the concentration of heavy metal ion of stripping in the solution when having measured the reaction end, Mn
4+Stripping concentration be 0.003mg/L, Fe
2+Stripping concentration be 0.003mg/L, two heavy metal species ion stripping concentrations meet the requirement of drinking water sanitary standard (GB 5749-2006) fully.
The catalyst MnFe of present embodiment
2O
4Mechanical strength is big, non-friable, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.The magnetic spinel ferrite catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This spinel-type catalyst MnFe
2O
4Stability Analysis of Structures can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The specific embodiment 24: the method for organic pollution is carried out according to the following steps in the ferrospinel catalyst ozonisation decomposition water of present embodiment: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 5.6, temperature is controlled at 15 ℃; Two, in the catalytic ozonation reactor, feed ozone, make the concentration of ozone reach 6.8mg/L, add spinel ferrite body catalyst Mn then
0.6Zn
0.4Fe
2O
4, Mn
0.6Zn
0.4Fe
2O
4With the mass ratio of ozone be 20: 1, the processing time is 60min; Three, with magnetic field intensity be the magnetic field recovery Mn of 0.1T
0.6Zn
0.4Fe
2O
4, ozone tail gas utilizes 5% KI solution absorption, finishes organic pollution catalytic ozonation decomposable process in the water.
The catalyst Mn of organic pollution in the ozone oxidation decomposition water of present embodiment
0.6Zn
0.4Fe
2O
4The preparation method carry out according to the following steps: a, egg clearly at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, press ferrospinel molecular formula Mn
0.6Zn
0.4Fe
2O
4The atom number ratio of middle metallic element takes by weighing manganese nitrate, zinc nitrate and ferric nitrate, wherein the mass volume ratio of the egg white solution that obtains of ferric nitrate and step a is 0.2g: 1mL, manganese nitrate, zinc nitrate and ferric nitrate are joined in the egg white solution that step a obtains, be placed on then in 80 ℃ of water-baths, stir 2h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h; D, the product that step c is obtained are reduced to room temperature with mixture of ice and water, are dry 2h in 60 ℃ the baking oven in temperature then, obtain the catalyst of organic pollution in the ozone oxidation decomposition water after grinding again.
Mn in the present embodiment
0.6Zn
0.4Fe
2O
4Be the micron powder of porous, the initial concentration of dibutyl phthalate in the sewage (DMP) is 0.5mg/L, in the experimentation respectively 0,3,5,10,20,30,40,50, the 60min sampling, the clearance of DMP in the test sewage, ferrospinel Mn
0.6Zn
0.4Fe
2O
4Catalysis ozone degraded DMP clearance just reaches 100% in 25min, can improve 50% than the clearance (28%) to DMP in the identical time of independent ozonisation.
Through the catalytic ozonation reaction of 60min, the concentration of heavy metal ion of stripping in the solution when having measured the reaction end, Ni
2+Stripping concentration be 0.0009mg/L, Fe
2+Stripping concentration be 0.003mg/L, two heavy metal species ion stripping concentrations meet the requirement of drinking water sanitary standard (GB 5749-2006) fully.
The catalyst Mn of present embodiment
0.6Zn
0.4Fe
2O
4Mechanical strength is big, non-friable, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle was 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.The magnetic spinel ferrite catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This spinel-type catalyst Mn
0.6Zn
0.4Fe
2O
4Stability Analysis of Structures can not be decomposed by ozone oxidation, and catalytic process can not brought the secondary pollution of heavy metal ion, does not influence health.
The specific embodiment 25: the ferrospinel catalyst ozonisation of present embodiment is decomposed the method for organic pollutants and carried out according to the following steps: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 5.6, temperature is controlled at 15 ℃; Two, in the catalytic ozonation reactor, pass into ozone, make the concentration of ozone reach 8mg/L, add then NiFe
2O
4/ Graphene, NiFe
2O
4The mass ratio of/Graphene and ozone is 10: 1, and the processing time is 60min; Three, with magnetic field intensity be the magnetic field recovery NiFe of 0.1T
2O
4/ Graphene, ozone tail gas utilize 5% KI solution absorption, finish organic pollutants catalytic ozonation decomposable process.
The ozone oxidation of present embodiment is decomposed the catalyst n iFe of organic pollutants
2O
4The preparation method of/Graphene carries out according to the following steps: a, egg at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, take by weighing the 4.104g nickel nitrate, the 8.013g ferric nitrate, 20g Graphene and 40mL join nickel nitrate, ferric nitrate and Graphene in the egg white solution through the egg white solution of step a preparation, are placed on then in 80 ℃ of water-baths, stir 2h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h; D, the product that step c is obtained are down to room temperature with mixture of ice and water, are dry 2h in 60 ℃ the baking oven in temperature then, obtain the catalyst that ozone oxidation is decomposed organic pollutants after grinding again.
NiFe in the present embodiment
2O
4/ Graphene is the micron powder of porous, and the initial concentration of dibutyl phthalate in the sewage (DMP) is 0.5mg/L, in the experimentation respectively 0,3,5,10,20,30,40,50, the 60min sampling, the clearance of DMP in the test sewage, NiFe
2O
4/ Graphene catalysis ozone degraded DMP clearance just reaches 100% in 20min, can improve 70% than the clearance (33%) to DMP in the independent ozonisation same time.
Through the catalytic ozonation reaction of 60min, the concentration of heavy metal ion of stripping in the solution when having measured the reaction end, Ni
2+Concentration be 0.0008mg/L, Fe
2+Stripping concentration be 0.003mg/L, two heavy metal species ion stripping concentrations meet the requirement of drinking water sanitary standard (GB 5749-2006) fully.
The catalyst n iFe of present embodiment
2O
4/ Graphene mechanical strength is big, non-friable, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.Magnetic catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This catalyst n iFe
2O
4/ graphene-structured is stable, can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The specific embodiment 26: the ferrospinel catalyst ozonisation of present embodiment is decomposed the method for organic pollutants and carried out according to the following steps: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 5.6, temperature is controlled at 15 ℃; Two, in the catalytic ozonation reactor, pass into ozone, make the concentration of ozone reach 8mg/L, add then ferrospinel catalyst n iFe
2O
4/ TiO
2, NiFe
2O
4/ TiO
2With the mass ratio of ozone be 10: 1, the processing time is 60min; Three, with magnetic field intensity be the magnetic field recovery NiFe of 0.1T
2O
4/ TiO
2, ozone tail gas utilizes 5% KI solution absorption, finishes organic pollutants catalytic ozonation decomposable process.
The catalyst n iFe of organic pollution in the ozone oxidation decomposition water of present embodiment
2O
4/ TiO
2The preparation method carry out according to the following steps: a, egg clearly at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, take by weighing the 4.104g nickel nitrate, 8.013g ferric nitrate, 20g TiO
2With the egg white solution of 40mL, with nickel nitrate, ferric nitrate and TiO through step a preparation
2Join in the egg white solution that step a obtains, be placed on then in 80 ℃ of water-baths, stir 2h, obtain mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h; D, the product that step c is obtained are reduced to room temperature with mixture of ice and water, are dry 2h in 60 ℃ the baking oven in temperature then, obtain the catalyst of organic pollution in the ozone oxidation decomposition water after grinding again.
NiFe in the present embodiment
2O
4/ TiO
2Be the micron powder of porous, the initial concentration of dibutyl phthalate in the sewage (DMP) is 0.5mg/L, in the experimentation respectively 0,3,5,10,20,30,40,50, the 60min sampling, the clearance of DMP in the test sewage, NiFe
2O
4/ TiO
2Catalysis ozone degraded DMP clearance just reaches 100% in 25min, can improve 65% than the clearance (33%) to DMP in the independent ozonisation same time.
Through the catalytic ozonation reaction of 60min, the concentration of heavy metal ion of stripping in the solution when having measured the reaction end, Ni
2+Stripping concentration be 0.0008mg/L, Fe
2+Stripping concentration be 0.003mg/L, Ti
2+Stripping concentration be 0.006mg/L, three heavy metal species ion stripping concentrations meet the requirement of drinking water sanitary standard (GB 5749-2006) fully.
The catalyst n iFe of present embodiment
2O
4/ TiO
2Mechanical strength is big, non-friable, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.Magnetic catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This catalyst n iFe
2O
4/ TiO
2Stability Analysis of Structures can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
The specific embodiment 27: the ferrospinel catalyst ozonisation of present embodiment is decomposed the method for organic pollutants and carried out according to the following steps: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 5.6, temperature is controlled at 15 ℃; Two, in the catalytic ozonation reactor, pass into ozone, make the concentration of ozone reach 6mg/L, add then spinel ferrite body catalyst MnFe
2O
4/ ZnO, MnFe
2O
4The mass ratio of/ZnO and ozone is 10: 1, and the processing time is 60min; Three, with magnetic field intensity be the magnetic field recovery MnFe of 0.1T
2O
4/ ZnO, ozone tail gas utilize 5% KI solution absorption, finish organic pollutants catalytic ozonation decomposable process.
The catalyst MnFe of organic pollution in the ozone oxidation decomposition water of present embodiment
2O
4The preparation method of/ZnO carries out according to the following steps: a, egg clearly at room temperature stirred 30min after, obtain the egg white solution of homogeneous; B, take by weighing the 3.542g manganese nitrate, 8.013g ferric nitrate, 20g ZnO and 40mL be through the egg white solution of step 1 preparation, and nickel nitrate, ferric nitrate and ZnO are joined in the egg white solution that step a obtains, and is placed on then in 80 ℃ of water-baths, stirs 2h, obtains mixture; C, mixture that step b is obtained obtain product at 500 ℃ of roasting 5h; D, the product that step c is obtained are reduced to room temperature with mixture of ice and water, are dry 2h in 60 ℃ the baking oven in temperature then, obtain the catalyst of organic pollution in the ozone oxidation decomposition water after grinding again.
MnFe in the present embodiment
2O
4/ ZnO is the micron powder of porous, and the initial concentration of dibutyl phthalate in the sewage (DMP) is 0.5mg/L, in the experimentation respectively 0,3,5,10,20,30,40,50, the 60min sampling, the clearance of DMP in the test sewage, MnFe
2O
4/ ZnO catalysis ozone degraded DMP clearance just reaches 100% in 25min, can improve 70% than the clearance (33%) to DMP in the independent ozonisation same time.
Through the catalytic ozonation reaction of 60min, the concentration of heavy metal ion of stripping in the solution when having measured the reaction end, Mn
4+Stripping concentration be 0.003mg/L, Fe
2+Stripping concentration be 0.003mg/L, Zn
2+Stripping concentration be 0.001mg/L, three heavy metal species ion stripping concentrations meet the requirement of drinking water sanitary standard (GB 5749-2006) fully.
The catalyst MnFe of present embodiment
2O
4/ ZnO mechanical strength is big, non-friable, and consumption is few, remove the efficient height, catalysis is thorough, and life cycle is 3 months, and need not increases or transform existing water treatment facilities, the convenient application in actual water factory.Magnetic catalyst has high catalytic activity, itself has very strong catalysis ozone and decomposes the ability that produces hydroxyl radical free radical.This catalyst MnFe
2O
4/ ZnO Stability Analysis of Structures can not be decomposed by ozone oxygen, and catalytic process can not brought the secondary pollution of heavy metal ion, does not affect health.
Claims (10)
1. ozone oxidation is decomposed the catalyst of organic pollutants, it is characterized in that it is ferrospinel NiFe that ozone oxidation is decomposed the catalyst of organic pollutants
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4And CaFe
2O
4In a kind of or wherein two kinds combination.
2. ozone oxidation is decomposed the catalyst of organic pollutants, it is characterized in that it is ferrospinel M that ozone oxidation is decomposed the catalyst of organic pollutants
1-xN
xFe
2O
4, 0＜x＜1 wherein, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
3. ozone oxidation is decomposed the catalyst of organic pollutants, it is characterized in that the catalyst of ozone oxidation decomposition organic pollutants is for to be carried on the compound that make on the carbonaceous material surface with ferrospinel, wherein the mass ratio of ferrospinel and carbonaceous material is 0.1～1: 1, carbonaceous material is a kind of in active carbon, CNT, Graphene and the bamboo carbon or wherein several combination, and described ferrospinel is NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4, CaFe
2O
4Or M
1-xN
xFe
2O
4, M
1-xN
xFe
2O
40＜x in the formula＜1, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
4. ozone oxidation is decomposed the catalyst of organic pollutants, it is characterized in that it is the compound of making of ferrospinel and metal oxide that ozone oxidation is decomposed the catalyst of organic pollutants, wherein the mass ratio of ferrospinel and metal oxide is 0.1～1: 1, and metal oxide is TiO
2, ZnO, CuO, Al
2O
3, MnO
2, NiO, Co
3O
4And V
2O
5In a kind of or several compositions wherein; Described ferrospinel is NiFe
2O
4, MnFe
2O
4, CoFe
2O
4, ZnFe
2O
4, MgFe
2O
4, CuFe
2O
4, CrFe
2O
4, PbFe
2O
4, SrFe
2O
4, BaFe
2O
4, CaFe
2O
4Or M
1-xN
xFe
2O
4, M
1-xN
xFe
2O
4In 0＜x＜1, M and N are the arbitrary elements among metallic element Ni, Mn, Co, Zn, Mg, Cu, Cr, Pb, Sr, Ba and the Ca, and M is different elements with N.
5. as the method for the catalyst ozone treatment sewage of organic pollution in the described ozone oxidation decomposition water of each claim in the claim 1～4, the method that it is characterized in that the catalyst ozone treatment sewage of organic pollution in the ozone oxidation decomposition water is carried out according to the following steps: one, the pH value that contains the sewage of organic pollution in the catalytic ozonation reactor is adjusted into 3～10, temperature is controlled at 15～30 ℃; Two, in the catalytic ozonation reactor, feed ozone, make the concentration of ozone reach 0.5mg/L～50mg/L, the catalyst that adds organic pollution in the ozone oxidation decomposition water then, the mass ratio of the catalyst of organic pollution and ozone is 1～50: 1 in the ozone oxidation decomposition water, handles 1min～120min; Three, be that catalyst is fixed or reclaimed to magnet or the electromagnetic field of 0.5T～1.5T with magnetic field intensity, ozone tail gas utilizes the KI solution of 5%～8% (quality) to absorb, and finishes organic pollution catalytic ozonation decomposable process in the water.
6. the method for the catalyst ozone treatment sewage of organic pollution in the ozone oxidation decomposition water according to claim 5, it is characterized in that in the step 1 pH value that contains the sewage of organic pollution in the catalytic ozonation reactor being adjusted into 4～9, temperature is controlled at 18～25 ℃.
7. according to the method for the catalyst ozone treatment sewage of organic pollution in claim 5 or the 6 described ozone oxidation decomposition waters, it is characterized in that the concentration of ozone reaches 3mg/L～40mg/L in the step 2, the mass ratio of the catalyst of organic pollution and ozone is 5～40: 1 in the ozone oxidation decomposition water, and the processing time is 5min～100min.
8. according to the method for the catalyst ozone treatment sewage of organic pollution in claim 5 or the 6 described ozone oxidation decomposition waters, it is characterized in that the concentration of ozone reaches 20mg/L in the step 2, the mass ratio of the catalyst of organic pollution and ozone is 20: 1 in the ozone oxidation decomposition water, and the processing time is 60min.
9. according to the method for the catalyst ozone treatment sewage of organic pollution in claim 5 or the 6 described ozone oxidation decomposition waters, it is characterized in that the magnetic field intensity in the step 3 is 0.5T～1.5T, the concentration that absorbs the KI solution of ozone tail gas is 5.5%～7.5% (quality).
10. according to the method for the catalyst ozone treatment sewage of organic pollution in claim 5 or the 6 described ozone oxidation decomposition waters, it is characterized in that the magnetic field intensity in the step 3 is 1.0T, the concentration that absorbs the KI solution of ozone tail gas is 6.5% (quality).
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| CN201110046323A CN102151567B (en) | 2011-02-25 | 2011-02-25 | Catalyst for oxidation and decomposition of organic pollutants in water with ozone and method thereof for catalyzing sewage treatment with ozone |
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