CN1994546A - Three-phase circulating fluidized bed photochemical reactor with a plurality of light sources and Fe/inorganic carrier catalyst preparation and method for processing waste water thereby - Google Patents
Three-phase circulating fluidized bed photochemical reactor with a plurality of light sources and Fe/inorganic carrier catalyst preparation and method for processing waste water thereby Download PDFInfo
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Abstract
The invention relates to a method for preparing Fe/inorganic carrier catalyst and multi-light-source three-phase circulate fluid bed chemical reactor, wherein it can improve organic mineral degree, reduce ferric waste soil and avoid second pollution; the upper sealing head and cylinder are connected by upper sealing head flange; the cylinder has horizontal several quartz muffles whose ends are connected to the cylinder; the quartz muffles have ultraviolet lamp. The invention ultraviolet radiation, solid catalyst, and oxidant, to generate hydroxyl free group, to decompose and mineralize the organic to treat waste water. The invention has high organic pollutant remove rate, high mineralize degree and simple operation.
Description
Technical field
The present invention relates to a kind of method of handling photochemical reactor and the Preparation of catalysts and the processing waste water thereof of waste water, be specifically related to the preparation of multiple light courcess three-phase circulating fluidized bed photochemical reactor and Fe/ inorganic carrier catalyst and the method for waste water of processing persistent organic pollutants thereof.
Background technology
In the last few years, many scholars helped homogeneous phase Fenton system degraded persistent organic pollutants to do many research for light.But the shortcoming of this system maximum is, the existence of the iron ion in homogeneous system makes solution have color, raises along with reaction finishes pH value, can produce a large amount of iron content mud that gives up in the course of reaction, and the cost of disposal of iron mud is higher, and easily causes secondary pollution.Simultaneously, homogeneous phase Fenton system only could be carried out under lower pH effectively.And light helps heterogeneous Fenton system can overcome above-mentioned shortcoming, its major advantage is to realize the recycling of ferro element, do not produce iron mud, mineralization of organic material degree height, the key of heterogeneous Fenton system is efficiently, the research and development and the design efficient, that be fit to the photochemical reactor of commercial Application of heterogeneous catalysis cheaply but light helps.Over nearly 10 years, people's fixedly iron ion of the solid matter that adopts iron content or carrier that begins one's study constitutes heterogeneous Fenton system oxidative degradation organic pollution.
People (Phys.Chem.B107 (2003) 7026-7035) research and utilization ion exchange resin such as people such as Kiwi.J (Langmuir 18 (2002) 9054-9066) and Parra.S by ion-exchange with the ion immobilization, but this resin must be avoided being corroded by the free radical of strong oxidizing property, so what use is Nafion ion exchange resin, this catalyst treatment effect is relatively good, but organic salinity is not high, and because costing an arm and a leg of Nafion is unsuitable for industrial applications.Also have research to use fixedly iron ion of inorganic carrier, this class carrier has carbon fiber, molecular sieve, active A l
2O
3Deng.People such as gold research makes Fe
2O
3/ Al
2O
3Catalyst (patent of invention publication number CN1562798A), its Pyrogentisinic Acid's treatment effect is good, the catalytic activity height, but because its particle diameter is bigger, unsuitable fluidisation is not suitable for three-phase circulating fluidized bed reaction system.People such as the JiyunFeng of Hong Kong University have delivered several pieces of articles (Water Research 40 (2006) 641-646, ChemicalEngineering Science 58 (2003) 679-685) and Fe is loaded on have been prepared into catalyst on the clay and are used to handle Orange II dyestuff.Its result shows that in 90min the percent of decolourization of dyestuff is 100%, and the total organic carbon removing rate is 70%, and the Fe stripping is very little, can ignore, and the result is satisfied.But because this catalyst particle size is tiny, be nanoscale, should not separate and insufficient strength, be not suitable for three-phase circulating fluidized bed reaction system.
The report of light reflex device also increases gradually, but on the whole, the research of photochemical reactor also is confined to laboratory research substantially.The problem of photochemical reactor design is more than traditional chemical reactor complexity, except relate to the quality transmission and mix, the problems such as installation of the type of flow, kinetics, catalyst, also must this key factor of consideration light radiation.Photoreactor must be able to provide big as far as possible and can irradiated specific surface area of catalyst and will be suitable for industrialization to be amplified.Existing photochemical reactor can be divided into two types of fixed bed and fluid beds.Catalyst granules or catalyst film remain static in reactor in the fixed bed reactors, and be gentle with light, liquid reactant contact area is little, and reaction speed and treating capacity all are very limited; Catalyst granules is suspended in the gas-liquid mixture in the fluidized-bed reactor, increased the contact area of catalyst and gas, liquid reactant, effective illuminating area is improved, wherein three-phase fluid bed reactor is because its particular structure, more be applicable to the photochemical reaction system, have a wide range of applications.But the research of fluidized bed photo catalysis reactor also is less than fixed bed far away at present, and existing fluid bed photochemical reactor mostly is pulling flow type, the reactant liquor time of staying is not enough, and chemical reaction and catalyst recovery carry out in same reaction zone, and catalyst separation reclaims insufficient.
Old love equality people has invented lamp arraying type packed bed apparatus for photoreaction (patent of invention publication number CN1528513A), it is a kind of fixed bed Photoreactor of multiple light courcess, because uviol lamp limited length, uviol lamp must be formed the uviol lamp assembly by series/parallel at axial direction and be placed in the sleeve pipe, could axially amplify, fluorescent tube is changed comparatively trouble, and this reactor is fixed bed reactors, and catalyst and light are gentle, liquid reactant contact area is little.The fluidisation photo catalysis reactor (patent of invention publication number CN1508073A) of people such as Zhou Yasong invention, this reactor body is the coaxial sleeve structure, uviol lamp places the interior pipe of reactor, because the uviol lamp light intensity attenuation is very fast, the annular space narrower in width that this reactor allows is difficult to realize the industry amplificationization.
Summary of the invention
The objective of the invention is in order to solve present homogeneous phase Fenton system and to handle waste water, the mineralization of organic material degree is low, produce the useless mud of a large amount of iron content in the course of reaction, the cost of disposal height of iron mud, and easily cause secondary pollution problem, the preparation of a kind of multiple light courcess three-phase circulating fluidized bed photochemical reactor and Fe/ inorganic carrier catalyst and the method for processing waste water thereof are provided.
The overall structure of present embodiment multiple light courcess three-phase circulating fluidized bed photochemical reactor is a cuboid, mainly is made up of cylindrical shell, upper cover, upper cover flange, low head, low head flange, the water inlet pipe that has water intaking valve, the outlet pipe that has outlet valve, the air inlet pipe that has intake valve and inflator pump, the escape pipe that has air outlet valve, porous aeration board, uviol lamp and quartz socket tube; Upper cover is connected by the upper cover flange with cylindrical shell, the air inlet of escape pipe is communicated with the top of upper cover, the water inlet of outlet pipe is communicated with the top of cylindrical shell, many quartz socket tubes laterally have been installed in the cylindrical shell, two end faces of quartz socket tube are fixedlyed connected with cylindrical shell, uviol lamp is installed in the quartz socket tube, low head is connected by the low head flange with cylindrical shell, the delivery port of water inlet pipe is communicated with the top of low head, the gas outlet of air inlet pipe is communicated with the bottom of low head, the bottom of low head is equipped with the porous aeration board, and the Fe/ inorganic carrier catalyst is housed in the cylindrical shell.
The preparation method of the Fe/ inorganic carrier catalyst of adorning in the reactor of the present invention is as follows: a, preparation mass percent concentration are the copperas solution of 1.0～5.0g/L, and feed nitrogen in copperas solution, and the time is 30min; B, with through clean, 10～100 order inorganic carriers of oven dry add by 4～10g/L in the copperas solution after a step and with the preservative film sealing, stir 24h; C, will separate with copperas solution, wash inorganic carrier, then dry 6～10h under 80～150 ℃ of conditions with distilled water through the inorganic carrier that step b obtains; E, with dried inorganic carrier catalyst at 400～600 ℃ of following roasting 2～6h, obtain the Fe/ inorganic carrier catalyst.
It is as follows to utilize apparatus of the present invention to handle the method for waste water: the Fe/ inorganic carrier catalyst of the 0.7～1.8g/L that, in reactor, packs into earlier, connect uviol lamp then, again with oxidant and waste water in the water inlet pipe inflow reactor; Two, control the flow of waste water by the water intaking valve on the adjusting water inlet pipe; Three, blast air through air inlet pipe to reactor with inflator pump, form equally distributed bubble through the porous aeration board, bubble and reactant liquor are carried Fe/ inorganic carrier catalyst particle come-up secretly, form gaseous state, solid-state, liquid three-phase fluidised form; Four, under the irradiation of uviol lamp, macromolecular organic matter is degraded to little molecule innocuous substance in the waste water, then is oxidized to carbon dioxide and water; Five, the waste water after step 4 is handled rises to cylindrical shell top waste water speed and weakens, and catalyst granules is because self gravitation and flow field effect all are back to reactor bottom, and rising again participates in new reaction again; Bubble overflows the water surface, and the escape pipe through being fixed on the upper cover place is discharged; Waste water part after the processing is discharged by outlet pipe, and another part flows back into the bottom of cylindrical shell and continues to participate in new reaction.
The mode that the multiple light courcess three-phase circulating fluidized bed photochemical reactor adopts horizontal multiple light courcess to be arranged in parallel, light is evenly distributed in the reactor, light utilization ratio height, bubble with rising is a major impetus, make the interior gas of reactor, solid, liquid three-phase be in flow regime, fully contact, and sufficient hydraulic detention time is arranged, and this reactor is easy to the industrialization amplification.The Fe/ inorganic carrier catalyst that the present invention prepares has advantages of high catalytic activity, and cost is lower, and stability is high, and mechanical strength is good, is suitable for three-phase fluid bed reactor.The present invention can make organic pollution reach higher removal in the short period of time, and the salinity height, does not cause secondary pollution, moves easyly, is easy to industrialization.In the reaction unit that contains ultra-violet radiation and solid catalyst, by adding oxidant (oxygen, ozone, hydrogen peroxide etc.), under gas, the three-phase circulating fluidized state of solid, liquid, acting in conjunction by ultra-violet radiation, solid catalyst and oxidant, produce hydroxyl radical free radical, realize effectively hardly degraded organic substance in the waste water particularly decomposition, the mineralising of larger molecular organics.The present invention adopts the horizontal multiple light courcess ultraviolet source that is arranged in parallel.At first with many quartz socket tubes laterally in reactor, uviol lamp places in the quartz socket tube, makes things convenient for the replacing of uviol lamp.This layout can make the interior any point of reactor obtain suitable light radiation intensity and be evenly distributed.Simultaneously, lateral arrangement can easily amplified reactor on the width He on the short transverse, has realized that application is amplified in the industrialization of photochemical reactor.
The present invention has organic pollutant removal rate height, salinity height, does not cause secondary pollution, and is simple to operate, is fit to the advantage of suitability for industrialized production
Description of drawings
Fig. 1 is the schematic diagram of the three phase inner circulation fluidized bed photochemical reactor structure of multiple light courcess, Fig. 2 is the schematic diagram of multiple light courcess three-phase external circulation fluidized bed photochemical reactor structure, Fig. 3 is that the present invention adopts the Fe/ organic catalyst to handle the curve map of polyacrylamide clearance in the waste water process, and Fig. 4 is the curve map of the present invention to rhodamine B clearance in the dyestuff simulated wastewater processing procedure; Among Fig. 3--expression adopts the curve map of polyacrylamide clearance in the Fe/ silochrom catalyst treatment waste water process, among Fig. 3-◇-expression employing Fe/ active A l
2O
3The curve map of polyacrylamide clearance in the catalyst treatment waste water process, among Fig. 3-△-expression adopts the curve map of polyacrylamide clearance in the Fe/ artificial zeolite catalyst treatment waste water process; Among Fig. 4--expression initial concentration is the curve map of 10mg/L rhodamine B clearance, among Fig. 4-△-expression initial concentration is the curve map of 50mg/L rhodamine B clearance.
The specific embodiment
The specific embodiment one: the overall structure of (referring to Fig. 1, Fig. 2) present embodiment multiple light courcess three-phase circulating fluidized bed photochemical reactor is a cuboid, mainly is made up of cylindrical shell 1, upper cover 2, upper cover flange 3, low head 4, low head flange 5, the water inlet pipe 6 that has water intaking valve 21, the outlet pipe 7 that has outlet valve 20, the air inlet pipe 8 that has intake valve 18 and inflator pump 17, the escape pipe 9 that has air outlet valve 19, porous aeration board 10, uviol lamp 11 and quartz socket tube 12; Upper cover 2 is connected by upper cover flange 3 with cylindrical shell 1, the air inlet of escape pipe 9 is communicated with the top of upper cover 2, the water inlet of outlet pipe 7 is communicated with the top of cylindrical shell 1, many quartz socket tubes 12 laterally have been installed in the cylindrical shell 1, two end faces of quartz socket tube 12 are fixedlyed connected with cylindrical shell 1, uviol lamp 11 is installed in the quartz socket tube 12, low head 4 is connected by low head flange 5 with cylindrical shell 1, the delivery port of water inlet pipe 6 is communicated with the top of low head 4, the gas outlet of air inlet pipe 8 is communicated with the bottom of low head 4, the bottom of low head 4 is equipped with porous aeration board 10, and the Fe/ inorganic carrier catalyst is housed in the cylindrical shell 1.
The specific embodiment two: increased deflector 13 in the multiple light courcess three-phase circulating fluidized bed photochemical reactor of (referring to Fig. 1) present embodiment, enlarged funnel 14 and water outlet baffle plate 15, two end faces of deflector 13 are fixedlyed connected with the inwall of cylindrical shell 1, fixedly connected with the upper end of cylindrical shell 1 in the lower end that enlarges funnel 15, upper cover 2 is connected by upper cover flange 3 with expansion funnel 14, fixedlys connected with the inwall that enlarges funnel 14 in the two ends of water outlet baffle plate 15.Other is identical with the specific embodiment one.
The structure of the reactor of present embodiment has constituted the three phase inner circulation fluidized bed photocatalytic reaction system of multiple light courcess.Form between present embodiment reactor deflector 13 and cylindrical shell 1 inwall and fall the stream district, form the up-flow district between the deflector 13, the top in the reactor has formed in solid-liquid displacement zone, the low head 4 and has formed the recirculating zone.The reactor of present embodiment has simple in structure, stable advantage.
The specific embodiment three: increased solid phase carrier pipe 16 in the multiple light courcess three-phase circulating fluidized bed photochemical reactor of (referring to Fig. 2) present embodiment, solid phase carrier pipe 16 is installed in the outside of cylindrical shell 1, fixedlying connected with the top of cylindrical shell 1 in the upper end of solid phase carrier pipe 16, fixedlys connected with the bottom of cylindrical shell in the lower end of solid phase carrier pipe 16; The import of solid phase carrier pipe 16 is communicated with the top of cylindrical shell 1, and the outlet of solid phase carrier pipe 16 is communicated with the bottom of cylindrical shell 1.Other is identical with the specific embodiment one.
The structure of the reactor of present embodiment has constituted multiple light courcess three-phase external circulation fluidized bed light-catalyzed reaction system.Form the up-flow district between present embodiment reactor shell 1 inwall, form between solid phase carrier pipe 16 inwalls and fall the stream district, the top in the reactor has formed in solid-liquid displacement zone, the low head 4 and has formed the recirculating zone.The reactor of present embodiment has can be controlled the catalyst input amount and can change easily or the advantage of regenerated catalyst.
The specific embodiment four: the preparation method of the Fe/ inorganic carrier catalyst that present embodiment is adorned in reactor is as follows: a, preparation mass percent concentration are the copperas solution of 1.0～5.0g/L, and in copperas solution, feeding nitrogen, the time is 30min; B, with through clean, 10～100 order inorganic carriers of oven dry add by 4～10g/L in the copperas solution after a step and with the preservative film sealing, stir 24h; C, will separate with copperas solution, wash inorganic carrier, then dry 6～10h under 80～150 ℃ of conditions with distilled water through the inorganic carrier that step b obtains; E, with dried inorganic carrier at 400～600 ℃ of following roasting 2～6h, obtain the Fe/ inorganic carrier catalyst.
The specific embodiment five: the carrier of the Fe/ inorganic carrier catalyst of present embodiment is silochrom, active A l
2O
3Or artificial zeolite.Other is identical with the specific embodiment four.
The specific embodiment six: the method that present embodiment is handled waste water is as follows: the Fe/ inorganic carrier catalyst of the 0.7～1.8g/L that, in reactor, packs into earlier, connect uviol lamp 11 then, again with oxidant and waste water in water inlet pipe 6 inflow reactors; Two, control the flow of waste water by the water intaking valve 21 on the adjusting water inlet pipe 6; Three, blast air through air inlet pipe 6 to reactor with inflator pump 17, form equally distributed bubble through porous aeration board 10, bubble and reactant liquor are carried Fe/ inorganic carrier catalyst particle come-up secretly, form gaseous state, solid-state, liquid three-phase fluidised form; Four, under the irradiation of uviol lamp 11, macromolecular organic matter is degraded to little molecule innocuous substance in the waste water, then is oxidized to carbon dioxide and water; Five, the waste water after step 4 is handled rises to cylindrical shell 1 top waste water speed and weakens, and catalyst granules is because self gravitation and flow field effect all are back to reactor bottom, and rising again participates in new reaction again; Bubble overflows the water surface, and the escape pipe 11 through being fixed on upper cover 2 places is discharged; Waste water part after the processing is discharged by outlet pipe 9, and another part flows back into the bottom of cylindrical shell 1 and continues to participate in new reaction.
The specific embodiment seven: the oxidant of present embodiment is oxygen, ozone or hydrogen peroxide.Other is identical with the specific embodiment six.
The specific embodiment eight: the oxidant of present embodiment is that mass percent concentration is 30% hydrogen peroxide, and 30% hydrogen peroxide consumption is 20～1000mg/L.Other is identical with the specific embodiment six.
The specific embodiment nine: (referring to Fig. 1) present embodiment is handled the oxidant that uses in the step 1 of method for waste water and is hydrogen peroxide, and the waste water in step 5 after step 4 is handled rises to expansion funnel 14 waste water speed to be weakened.Other is identical with the specific embodiment six.
The specific embodiment ten: (referring to Fig. 2) present embodiment is handled the oxidant that uses in the step 1 of method for waste water and is hydrogen peroxide, and catalyst granules in step 5 is because self gravitation and flow field effect all are back to reactor bottom along solid phase carrier pipe 16.Other is identical with the specific embodiment six.
The specific embodiment 11: the power of present embodiment uviol lamp is 8～20W.Other is identical with the specific embodiment six.
The specific embodiment 12: the Preparation of catalysts method in the present embodiment is as follows: a, preparation mass percent concentration are the copperas solution of 3.0g/L, and feed nitrogen in copperas solution, and the time is 30min; B, will through clean, 40～60 order inorganic carriers of oven dry press that 4g/L adds in the copperas solution after a step and with preservative film sealing, stirring 24h; C, will separate with copperas solution, wash inorganic carrier with distilled water, then dry 6h under 105 ℃ of conditions through the inorganic carrier that step b obtains; E, with dried inorganic carrier at 550 ℃ of following roasting 5h, obtain the Fe/ inorganic carrier catalyst.
In order to detect the treatment effect of the inventive method, adopt Fe/ silochrom catalyst, Fe/ artificial zeolite catalyst, Fe/ active A l respectively to waste water
2O
3Catalyst uses reactor shown in Figure 1 to carry out the Processing Test of organic wastewater with difficult degradation thereby macromolecule polyalcohol polyacrylamide.Preparation of catalysts adopts the method for the specific embodiment 12, and carrier has adopted silochrom, artificial zeolite and active A l respectively in the specific embodiment nine methods
2O
3Respectively with Fe/ silochrom catalyst, Fe/ artificial zeolite catalyst, Fe/ active A l
2O
3Catalyst places the present invention's reactor shown in Figure 1, and adopting the low pressure mercury lamp of 22 8W is light source, and waste water is the polyacrylamide solution about 100mg/L, and the dosage of catalyst is 0.7g/L, and 30% hydrogen peroxide consumption is 250mg/L.Adopt the method for the specific embodiment ten to handle waste water, the wherein content of polyacrylamide is measured in certain hour sampling in every interval.Which kind of catalyst no matter experimental result as can be seen from the figure, adopt as shown in Figure 3, and it all is very high for the clearance of polyacrylamide that this light helps the heterogeneous catalytic oxidation system, and the reaction time surpasses 2h, and the clearance of polyacrylamide all reaches more than 90%.
Handle the effect of waste water in order to detect the inventive method, use the Processing Test of the present invention's reactor shown in Figure 1 the waste water from dyestuff rhodamine B.This experiment adopts the Fe/ silochrom as catalyst, and Fe/ silochrom Preparation of catalysts adopts the method for the specific embodiment 12.Fe/ silochrom catalyst is placed reactor shown in Figure 1, adopting the low pressure mercury lamp of 22 8W is light source, waste water is the rhodamine B solution about 10mg/L or 50mg/L, the dosage of catalyst is 0.7g/L, 30% hydrogen peroxide consumption is 22.5mg/L in the processing 10mg/L rhodamine B solution reactor, and 30% hydrogen peroxide consumption is 90mg/L in the processing 50mg/L rhodamine B solution reactor.Adopt the method for the specific embodiment nine to handle waste water, the wherein content of rhodamine B is measured in certain hour sampling in every interval.Experimental result as shown in Figure 4, as can be seen from the figure, initial concentration is the rhodamine B solution of 10mg/L, behind the 15min, the clearance of rhodamine B has reached more than 90%, behind the 45min, clearance nearly 99%; For initial concentration is the rhodamine B solution of 50mg/L, and behind the 45min, the clearance of rhodamine B has reached more than 90%, behind the 2h, and clearance nearly 99%.This system can reach higher removal in the short period of time to the waste water from dyestuff rhodamine B.
Claims (10)
1, a kind of multiple light courcess three-phase circulating fluidized bed photochemical reactor, the overall structure that it is characterized in that it is a cuboid, mainly is made up of cylindrical shell (1), upper cover (2), upper cover flange (3), low head (4), low head flange (5), the water inlet pipe (6) that has water intaking valve (21), the outlet pipe (7) that has outlet valve (20), the air inlet pipe (8) that has intake valve (18) and inflator pump (17), the escape pipe (9) that has air outlet valve (19), porous aeration board (10), uviol lamp (11) and quartz socket tube (12); Upper cover (2) is connected by upper cover flange (3) with cylindrical shell (1), the air inlet of escape pipe (9) is communicated with the top of upper cover (2), the water inlet of outlet pipe (7) is communicated with the top of cylindrical shell (1), many quartz socket tubes (12) laterally have been installed in the cylindrical shell (1), two end faces of quartz socket tube (12) are fixedlyed connected with cylindrical shell (1), uviol lamp (11) is installed in the quartz socket tube (12), low head (4) is connected by low head flange (5) with cylindrical shell (1), the delivery port of water inlet pipe (6) is communicated with the top of low head (4), the gas outlet of air inlet pipe (8) is communicated with the bottom of low head (4), the bottom of low head 4 is equipped with porous aeration board (10), and cylindrical shell is equipped with the Fe/ inorganic carrier catalyst in (1).
2, multiple light courcess three-phase circulating fluidized bed photochemical reactor according to claim 1, it is characterized in that having increased in the multiple light courcess three-phase circulating fluidized bed photochemical reactor deflector (13), enlarge funnel (14) and water outlet baffle plate (15), two end faces of deflector (13) are fixedlyed connected with the inwall of cylindrical shell (1), fixedly connected with the upper end of cylindrical shell (1) in the lower end that enlarges funnel (15), upper cover (2) is connected by upper cover flange (3) with expansion funnel (14), fixedlys connected with the inwall that enlarges funnel (14) in the two ends of water outlet baffle plate (15).
3, multiple light courcess three-phase circulating fluidized bed photochemical reactor according to claim 1, it is characterized in that having increased in the multiple light courcess three-phase circulating fluidized bed photochemical reactor solid phase carrier pipe, solid phase carrier pipe (16) is installed in the outside of cylindrical shell (1), fixedlying connected with the top of cylindrical shell (1) in the upper end of solid phase carrier pipe (16), fixedlys connected with the bottom of cylindrical shell in the lower end of solid phase carrier pipe (16); The import of solid phase carrier pipe (16) is communicated with the top of cylindrical shell (1), and the outlet of solid phase carrier pipe (16) is communicated with the bottom of cylindrical shell (1).
4, multiple light courcess three-phase circulating fluidized bed photochemical reactor according to claim 1 is characterized in that it is the Fe/ inorganic carrier catalyst of carrier that catalyst adopts inorganic porous material.
5, the preparation method of the Fe/ inorganic carrier catalyst of dress in the described multiple light courcess three-phase circulating fluidized bed photochemical reactor of claim 4, it is characterized in that it is finished by following steps: a, preparation mass percent concentration are the copperas solution of 1.0～5.0g/L, and in copperas solution, feeding nitrogen, the time is 30min; B, with through clean, 10～100 order inorganic carriers of oven dry add by 4～10g/L in the copperas solution after a step and with the preservative film sealing, stir 24h; C, will separate with copperas solution, wash inorganic carrier, then dry 6～10h under 80～150 ℃ of conditions with distilled water through the inorganic carrier that step b obtains; D, with dried inorganic carrier at 400～600 ℃ of following roasting 2～6h, obtain the Fe/ inorganic carrier catalyst.
6, the preparation method of the Fe/ inorganic carrier catalyst of dress in the multiple light courcess three-phase circulating fluidized bed photochemical reactor according to claim 4, the carrier that it is characterized in that the Fe/ inorganic carrier catalyst is silochrom, active A l
2O
3Or artificial zeolite.
7, utilize the described multiple light courcess three-phase circulating fluidized bed photochemical reactor of claim 1 to handle the method for waste water, the method that it is characterized in that handling waste water is as follows: the Fe/ inorganic carrier catalyst of the 0.7～1.8g/L that, packs in reactor earlier, connect uviol lamp (11) then, again with oxidant and waste water in water inlet pipe (6) inflow reactor; Two, control the flow of waste water by the water intaking valve (21) on the adjusting water inlet pipe (6); Three, blast air through air inlet pipe (6) to reactor with inflator pump (17), form equally distributed bubble through porous aeration board (10), bubble and reactant liquor are carried Fe/ inorganic carrier catalyst particle come-up secretly, form gaseous state, solid-state, liquid three-phase fluidization attitude; Four, under the irradiation of uviol lamp (11), macromolecular organic matter is degraded to little molecule innocuous substance in the waste water, then is oxidized to carbon dioxide and water; Five, the waste water after step 4 is handled rises to cylindrical shell (1) top waste water speed and weakens, and catalyst granules is because self gravitation and flow field effect all are back to reactor bottom, and rising again participates in new reaction again; Bubble overflows the water surface, through being fixed on escape pipe (11) discharge that upper cover (2) is located; Waste water part after the processing is discharged by outlet pipe (9), and another part flows back into the bottom of cylindrical shell (1) and continues to participate in new reaction.
8, according to the described method of utilizing the multiple light courcess three-phase circulating fluidized bed photochemical reactor to handle waste water of claim 7, it is characterized in that oxidant is oxygen, ozone or hydrogen peroxide.
9, according to the described method of utilizing the multiple light courcess three-phase circulating fluidized bed photochemical reactor to handle waste water of claim 7, it is characterized in that the oxidant that uses in the step 1 of its processing method for waste water is hydrogen peroxide, the waste water in step 5 after step 4 is handled rises to expansion funnel (14) waste water speed to be weakened.
10, according to the described method of utilizing the multiple light courcess three-phase circulating fluidized bed photochemical reactor to handle waste water of claim 7, it is characterized in that the oxidant that uses in the step 1 of its processing method for waste water is hydrogen peroxide, catalyst granules in step 5 is because self gravitation and flow field effect all are back to reactor bottom along solid phase carrier pipe (16).
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| CN102951724A (en) * | 2011-08-24 | 2013-03-06 | 轻工业环境保护研究所 | Three-phase reactor used for Fenton reaction |
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