CN104624198A - Preparation method of catalyst for ozone oxidization - Google Patents
Preparation method of catalyst for ozone oxidization Download PDFInfo
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- CN104624198A CN104624198A CN201510042024.8A CN201510042024A CN104624198A CN 104624198 A CN104624198 A CN 104624198A CN 201510042024 A CN201510042024 A CN 201510042024A CN 104624198 A CN104624198 A CN 104624198A
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Abstract
The embodiment of the invention discloses a preparation method of a catalyst for ozone oxidization. The method comprises the steps of feeding a preliminarily prepared mixed aqueous solution and a preliminarily prepared hydroxide solution of iron salt and manganese salt into a vessel filled with an activated catalyst carrier, carrying out co-precipitation, enabling the concentration of generated precipitates to be gradually increased, so that the generated precipitates can be uniformly distributed in inner pores and on the outer surface of the catalyst carrier, and then roasting the catalyst carrier to obtain the catalyst. Active components of the prepared catalyst are large in specific surface area, and the catalytic effect is good. Moreover, the active components in the inner pores can be prevented from dropping and loss due to the friction of the catalyst carriers; on the other hand, the precipitate consists of iron or manganese hydroxide, so that no pollutant is generated in the roasting process.
Description
Technical field
The present invention relates to field of catalyst preparation, particularly a kind of preparation method of the catalyst for ozone oxidation.
Background technology
In recent years, New Coal Chemical technology is applied gradually, and coal chemical industry enterprises, while utilizing these New Coal Chemical technology creation benefits, also can produce a large amount of sewage.Due to the organic matter containing a large amount of difficult degradation in these sewage, as phenols, polycyclic aromatic hydrocarbon, heterocyclic compound etc., make its COD (ChemicalOxygen Demand, COD) and colourity all higher.
Now, the general sewage adopting ozonation technology to carry out these difficult degradations of advanced treating.Ozonation technology utilizes ozone under the effect of catalyst, decomposes and produce free radical isoreactivity intermediate, and utilize the organic matter in the reactive intermediate degradation of sewage produced, thus reduce the COD of sewage, reduce the colourity of sewage.In the art, catalyst plays a very important role, and therefore, how preparing efficient catalyst is key point.
At present, the preparation for the catalyst of ozone oxidation generally adopts impregnated with nitrate method, and by dipping, roasting makes active component, such as iron, manganese on a catalyst support oxide carried.The weak point of this method is: on the one hand, and due in dipping process, most active component can be deposited on the outer surface of catalyst carrier, when carrying out sewage disposal, easily coming off because of the friction between catalyst carrier, running off.On the other hand, in catalyst roasting process, nitrate can produce the polluters such as a large amount of nitrogen oxide.
Summary of the invention
For solving the problem, the embodiment of the invention discloses a kind of preparation method of the catalyst for ozone oxidation.Technical scheme is as follows:
For a preparation method for the catalyst of ozone oxidation, comprise the following steps:
Catalyst carrier after activation is placed in container, under stirring, by the molysite prepared in advance, manganese salt mixed aqueous solution and hydroxide aqueous solution and stream join in described container and carry out co-precipitation, the speed that adds of hydroxide aqueous solution is regulated to ensure that the liquid in container is alkalescence, until molysite, manganese salt mixed aqueous solution add complete, obtain depositing iron, manganese precipitated catalyst carrier and mixed liquor;
Iron will be deposited, manganese precipitated catalyst carrier will soak 6 ~ 15 hours in mixed liquor, and then filter, wash, dry and roasting, obtain the catalyst for ozone oxidation.
Wherein, the activation method of described catalyst carrier is: non-activated catalyst carrier is placed in acid solution, refluxes 2 ~ 4 hours under the condition of 60 ~ 80 DEG C, and then washing is to neutral, drying for standby.
Wherein, described acid is the one in nitric acid, hydrochloric acid and sulfuric acid.
Wherein, described catalyst carrier is the one in active carbon, molecular sieve, aluminium oxide.
Wherein, described active carbon is specific area is 800 ~ 1200m
2the bar-shaped active carbon of/g.
Wherein, in described molysite, manganese salt mixed aqueous solution, the gross mass of molysite and manganese salt account for molysite, manganese salt mixed aqueous solution gross mass 10% ~ 35%, and the mol ratio of iron and manganese is (5:1) ~ (1:5).
Wherein, the anion of molysite and manganese salt is one in sulfate radical, nitrate anion and chlorion or its combination.
Wherein, described hydroxide aqueous solution can be sodium hydrate aqueous solution, potassium hydroxide aqueous solution or ammoniacal liquor, is preferably ammoniacal liquor.
Wherein, the speed that adds of molysite, manganese salt mixed aqueous solution is 3 ~ 30 ml/min, is preferably 3 ~ 20 ml/min, is more preferably 3 ~ 10 ml/min, most preferably is 3 ~ 6 ml/min.
Wherein, described roasting is specially: roasting 3 ~ 5 hours under the condition of 400 DEG C ~ 600 DEG C.
The present invention by by the molysite prepared in advance, manganese salt mixed aqueous solution and hydroxide aqueous solution and stream join in the container of the catalyst carrier after activation is housed and carry out co-precipitation, the concentration of the precipitation generated is increased gradually, be conducive to internal gutter and outer surface thereof that generated precipitation is evenly distributed in catalyst carrier like this, after roasting, the active component specific area of the catalyst obtained is large, be evenly distributed, excellent catalytic effect, and, can not come off because of the friction between catalyst carrier in the active component of internal gutter, run off.On the other hand, due to the hydroxide consisting of iron or manganese of precipitation, it is in roasting process, can not produce pollutant.
Detailed description of the invention
Inventor is when the catalyst for the preparation of ozone oxidation, unexpected discovery, molysite, manganese salt mixed aqueous solution and precipitating reagent hydroxide aqueous solution are deposited to the catalyst carrier after activation in the mode of co-precipitation, after aging, roasting, the catalytic efficiency of prepared catalyst significantly adds increasing.Reason is the mode owing to adopting co-precipitation, the concentration of the precipitation generated can be made to increase gradually, be conducive to like this making generated precipitation be evenly distributed in internal gutter and the outer surface thereof of catalyst carrier, after roasting, the active component specific area of the catalyst obtained is large, therefore, catalytic ozonation is effective.Co-precipitation mentioned here refers to when adding molysite, manganese salt mixed aqueous solution with certain speed in the container that catalyst carrier is housed, simultaneously, also in the container that catalyst carrier is housed, precipitating reagent hydroxide aqueous solution is added with certain speed, like this, produce precipitation after molysite, manganese salt and hydroxide react in a reservoir, and be uniformly dispersed by stirring.
Adopt technical scheme of the present invention for the preparation of the catalyst of ozone oxidation, catalyst carrier used needs to carry out activation process.Such one side can expand the aperture of catalyst carrier internal gutter, and also can improve the functional group of catalyst support surface not on the one hand, the precipitation be so more conducive to molysite, manganese salt generate deposits in catalyst carrier.
In actual applications, the activation method of catalyst carrier can be: non-activated catalyst carrier is placed in acid solution, refluxes 2 ~ 4 hours under the condition of 60 ~ 80 DEG C, and then washing is to neutral, drying for standby.Acid mentioned here can be the inorganic acid that this area is commonly used, such as nitric acid, hydrochloric acid or sulfuric acid etc.Preferred mass mark is 10% ~ 50% is nitric acid, and active rate is faster.
In the inventive solutions, the catalyst carrier that catalyst carrier can select this area conventional, such as active carbon, molecular sieve, aluminium oxide etc., the present invention of its concrete form does not need to limit.But because active carbon is for other catalyst carrier, its cost is much lower, therefore, the preferred active carbon of technical scheme of the present invention is catalyst carrier.In numerous active carbon kinds, inventor finds unexpectedly, wood activated charcoal is as coconut husk charcoal, mineral matter active carbon is as ature of coal charcoal, be more suitable for as catalyst carrier, when utilizing these two kinds of active carbons as catalyst carrier, at identical conditions, the catalytic oxidation efficiency of obtained catalyst is higher.
When adopting active carbon as catalyst carrier, preferred specific area is 800 ~ 1200m
2/ g, granularity is the bar-shaped active carbon of 1.5 ~ 3.0mm; With the catalyst that such active carbon is prepared as carrier, in the sewage disposal process of reality, catalyst can reach better fluidized state, thus improves catalytic oxidation efficiency, and bar-shaped active carbon is more prone to be activated.
Realize technical scheme of the present invention, first molysite, manganese salt mixed aqueous solution will be prepared, its preparation method can be: be, after the molysite of (5:1) ~ (1:5) and manganese salt mix, be added to the water iron and the mol ratio of manganese and dissolve completely.Preferably, in the molysite obtained, manganese salt mixed aqueous solution, molysite and manganese salt gross mass account for molysite, manganese salt mixed aqueous solution gross mass 10% ~ 35%, adopt the molysite of this concentration range, manganese salt mixed aqueous solution is when carrying out co-precipitation, the particle of the precipitation obtained is less, and precipitation is more evenly distributed.
It should be noted that, as long as the anion of molysite, manganese salt ensures that molysite, manganese salt can be water-soluble, concrete form the present invention of its anion does not need to limit, and the anion of such as molysite and manganese salt can be one in sulfate radical, nitrate anion, oxonium ion or its combination.
It should be noted that further, for realizing technical scheme of the present invention, needing to adopt hydroxide aqueous solution as precipitating reagent.Hydroxide aqueous solution can adopt sodium hydrate aqueous solution, potassium hydroxide aqueous solution or ammoniacal liquor etc.The present invention of its concrete form does not need to limit.But preferably ammoniacal liquor, this is because ammoniacal liquor has the features such as solubility comparatively greatly, is easily washed, accessory substance is volatile; Moreover, when adopting ammoniacal liquor as precipitating reagent, because ammoniacal liquor has certain complexing, it is flocculent deposit that molysite, manganese salt and ammoniacal liquor can be made to react the precipitation generated, this precipitation pattern and structure more orderly, more can be evenly distributed in the surface of catalyst carrier, play the effect improving catalytic efficiency.Because the concentration of ammoniacal liquor does not have substantial impact to technical scheme of the present invention, therefore, the present invention does not do concrete restriction, and preferably 10% ~ 30%.Excessive concentration or too low, is unfavorable for the adjustment to acid-base value.
In actual mechanical process, the speed that adds of molysite, manganese salt mixed aqueous solution is 3 ~ 30 ml/min, is preferably 3 ~ 20 ml/min, is more preferably 3 ~ 10 ml/min, most preferably is 3 ~ 6 ml/min.
Molysite, manganese salt mixed aqueous solution to add speed slower, to generate the uniformity of precipitation better, be more conducive to the raising of catalyst efficiency, but the time is also relatively longer.Therefore, add speed to be selected according to the actual needs by those skilled in the art.It should be noted that, when molysite, manganese salt mixed aqueous solution are added to a certain degree, such as, when adding more than half, can accelerate to add speed, to improve the preparation efficiency of catalyst, and on generate precipitation uniformity impact less.
After the molysite prepared in advance, manganese salt mixed aqueous solution are added, also will by deposit iron, manganese precipitated catalyst carrier join in the molysite in container, manganese salt mixed aqueous solution and hydroxide aqueous solution soak within 6 ~ 15 hours, carry out aging, then filter, wash, dry and roasting, obtain the catalyst for ozone oxidation.
Wherein, filtration, washing, drying and roasting are the conventional method of operating in this area, the present invention need not specifically limit at this, such as, filtration can be: Buchner funnel is warmed at baking oven, and paving two layers of filter paper, soaks with hot water, after playing pressure, the catalyst carrier after aging is poured into filter at once.Washing and drying can be: after Filter paper filtering, and by the dry 5 ~ 8h at 100 DEG C ~ 120 DEG C of the catalyst carrier after aging, clear water washes 3 ~ 5 times; Dry 5 ~ 8h is continued again at 100 DEG C ~ 120 DEG C.Roasting can be at 400 DEG C ~ 600 DEG C, by dried catalyst carrier roasting 3 ~ 5h in Muffle furnace.
By the agency of above, using active carbon as catalyst carrier, its cost is lower, is more suitable for commercial Application, during using ammoniacal liquor as precipitating reagent, the precipitation generated evenly, the catalytic efficiency of the catalyst generated after roasting is higher.Therefore, below just using active carbon as catalyst carrier, using ammoniacal liquor as precipitating reagent, technical scheme of the present invention is further described in more detail.
It should be noted that, in the examples below, if said percentage does not add specified otherwise, all refer to mass percent.
It should be noted that further, reagent used in following embodiment and equipment all commercially, there is no particular/special requirement.
Embodiment 1
With specific area for 800 ~ 1200m
2/ g, granularity be the bar-shaped active carbon of 1.5 ~ 3mm as catalyst carrier, the nitric acid with 45% activates refluxing under the condition of 60 DEG C for 2 hours, and then washing is to neutral, drying for standby.
The ferric sulfate of preparation 10% and manganese nitrate mixed aqueous solution, wherein, the mol ratio of iron and manganese is 5:1; The volume of ferric sulfate and manganese nitrate mixed aqueous solution is 1.5 times of active carbon volume.Ammoniacal liquor using 10% is as precipitating reagent.
Active carbon after activation is placed in container, under stirring, by the molysite prepared in advance, manganese salt mixed aqueous solution and ammoniacal liquor and stream join in described container and carry out co-precipitation, wherein, the speed that adds of molysite, manganese salt mixed aqueous solution is 3 ml/min, the speed that adds of ammoniacal liquor is regulated to ensure that the pH value of liquid in containers is 8 ~ 10, until molysite, manganese salt mixed aqueous solution add complete, and active carbon is continued soak 10 hours in mixed liquor in a reservoir, then filter, and will the solid dry 5h at 100 DEG C obtained being filtered, clear water washes 3 times; Granular activated carbon after cleaning, continues dry 5h at 100 DEG C; By dried active carbon roasting 3h in 600 DEG C of Muffle furnaces, namely obtain the catalyst for ozone oxidation.
Embodiment 2
With specific area for 800 ~ 1200m
2/ g, granularity be the bar-shaped active carbon of 1.5 ~ 3mm as catalyst carrier, the nitric acid with 10% activates refluxing under the condition of 80 DEG C for 4 hours, and then washing is to neutral, drying for standby.
The ferric sulfate of preparation 15% and manganese chloride mixed aqueous solution, wherein, the mol ratio of iron and manganese is 3:1; The volume of ferric sulfate and manganese chloride mixed aqueous solution is 1.5 times of active carbon volume.Ammoniacal liquor using 15% is as precipitating reagent.
Active carbon after activation is placed in container, under stirring, by the molysite prepared in advance, manganese salt mixed aqueous solution and ammoniacal liquor and stream join in described container and carry out co-precipitation, wherein, the speed that adds of molysite, manganese salt mixed aqueous solution is 6 ml/min, the speed that adds of ammoniacal liquor is regulated to ensure that the pH value of liquid in containers is 9 ~ 10, until molysite, manganese salt mixed aqueous solution add complete, and active carbon is continued soak 15 hours in mixed liquor in a reservoir, then filter, and will the solid dry 5h at 100 DEG C obtained being filtered, clear water washes 3 times; Granular activated carbon after cleaning, continues dry 5h at 100 DEG C; By dried active carbon roasting 6h in 400 DEG C of Muffle furnaces, namely obtain the catalyst for ozone oxidation.
Embodiment 3
With specific area for 800 ~ 1200m
2/ g, granularity be the bar-shaped active carbon of 1.5 ~ 3mm as catalyst carrier, the nitric acid with 25% activates refluxing under the condition of 70 DEG C for 3 hours, and then washing is to neutral, drying for standby.
The ferric nitrate of preparation 20% and manganese chloride mixed aqueous solution, wherein, the mol ratio of iron and manganese is 2:1; The volume of ferric nitrate and manganese chloride mixed aqueous solution is 1.5 times of active carbon volume.Ammoniacal liquor using 20% is as precipitating reagent.
Active carbon after activation is placed in container, under stirring, by the molysite prepared in advance, manganese salt mixed aqueous solution and ammoniacal liquor and stream join in described container and carry out co-precipitation, wherein, the speed that adds of molysite, manganese salt mixed aqueous solution is 10 ml/min, the speed that adds of ammoniacal liquor is regulated to ensure that the pH value of liquid in containers is 10 ~ 12, until molysite, manganese salt mixed aqueous solution add complete, and active carbon is continued soak 6 hours in mixed liquor in a reservoir, then filter, and will the solid dry 5h at 100 DEG C obtained being filtered, clear water washes 3 times; Granular activated carbon after cleaning, continues dry 5h at 100 DEG C; By dried active carbon roasting 5h in 500 DEG C of Muffle furnaces, namely obtain the catalyst for ozone oxidation.
Embodiment 4
With specific area for 800 ~ 1200m
2/ g, granularity be the bar-shaped active carbon of 1.5 ~ 3mm as catalyst carrier, the nitric acid with 40% refluxes and activates for 4 hours under the condition of 40 DEG C, and then washing is to neutral, drying for standby.
The ferric sulfate of preparation 20% and manganese chloride mixed aqueous solution, wherein, the mol ratio of iron and manganese is 1:1; The volume of iron chloride and manganese sulfate mixed aqueous solution is 1.3 times of active carbon volume.Ammoniacal liquor using 25% is as precipitating reagent.
Active carbon after activation is placed in container, under stirring, by the molysite prepared in advance, manganese salt mixed aqueous solution and ammoniacal liquor and stream join in described container and carry out co-precipitation, wherein, the speed that adds of molysite, manganese salt mixed aqueous solution is 20 ml/min, the speed that adds of ammoniacal liquor is regulated to ensure that the pH value of liquid in containers is 10 ~ 13, until molysite, manganese salt mixed aqueous solution add complete, and active carbon is continued soak 15 hours in mixed liquor in a reservoir, then filter, and will the solid dry 5h at 100 DEG C obtained being filtered, clear water washes 3 times; Granular activated carbon after cleaning, continues dry 5h at 100 DEG C; By dried active carbon roasting 5h in 400 DEG C of Muffle furnaces, namely obtain the catalyst for ozone oxidation.
Embodiment 5
With specific area for 800 ~ 1200m
2/ g, granularity be the bar-shaped active carbon of 1.5 ~ 3mm as catalyst carrier, the nitric acid with 45% activates refluxing under the condition of 60 DEG C for 4 hours, and then washing is to neutral, drying for standby.
The ferric sulfate of preparation 15% and manganese chloride mixed aqueous solution, wherein, the mol ratio of iron and manganese is 1:2; The volume of ferric sulfate and manganese chloride mixed aqueous solution is 1.5 times of active carbon volume.Ammoniacal liquor using 25% is as precipitating reagent.
Active carbon after activation is placed in container, under stirring, by the molysite prepared in advance, manganese salt mixed aqueous solution and ammoniacal liquor and stream join in described container and carry out co-precipitation, wherein, the speed that adds of molysite, manganese salt mixed aqueous solution is 24 ml/min, the speed that adds of ammoniacal liquor is regulated to ensure that the pH value of liquid in containers is 9 ~ 11, until molysite, manganese salt mixed aqueous solution add complete, and active carbon is continued soak 15 hours in mixed liquor in a reservoir, then filter, and will the solid dry 5h at 100 DEG C obtained being filtered, clear water washes 3 times; Granular activated carbon after cleaning, continues dry 5h at 100 DEG C; By dried active carbon roasting 5h in 400 DEG C of Muffle furnaces, namely obtain the catalyst for ozone oxidation.
Embodiment 6
With specific area for 800 ~ 1200m
2/ g, granularity be the bar-shaped active carbon of 1.5 ~ 3mm as catalyst carrier, the nitric acid with 45% refluxes and activates for 4 hours under the condition of 60 DEG C, and then washing is to neutral, drying for standby.
The ferric sulfate of preparation 15% and manganese chloride mixed aqueous solution, wherein, the mol ratio of iron and manganese is 1:5; The volume of ferric sulfate and manganese chloride mixed aqueous solution is 1.5 times of active carbon volume.Ammoniacal liquor using 30% is as precipitating reagent.
Active carbon after activation is placed in container, under stirring, by the molysite prepared in advance, manganese salt mixed aqueous solution and ammoniacal liquor and stream join in described container and carry out co-precipitation, wherein, the speed that adds of molysite, manganese salt mixed aqueous solution is 30 ml/min, the speed that adds of ammoniacal liquor is regulated to ensure that the pH value of liquid in containers is 9 ~ 10, until molysite, manganese salt mixed aqueous solution add complete, and active carbon is continued soak 12 hours in mixed liquor in a reservoir, then filter, and will the solid dry 5h at 100 DEG C obtained being filtered, clear water washes 3 times; Granular activated carbon after cleaning, continues dry 5h at 100 DEG C; By dried active carbon roasting 5h in 400 DEG C of Muffle furnaces, namely obtain the catalyst for ozone oxidation.
Sewage disposal is tested
It is the catalytic ozonation tower for ozone oxidation well known in the art that the equipment adopted is tested in sewage disposal, this catalytic ozonation tower, also referred to as ozone reactor, ozone mixing column, ozone throwing device etc., is the key device realizing ozone high grade oxidation reaction.
Catalytic ozonation tower forms primarily of oxidizing tower housing, proprietary tower inner assembly and proprietary ozone catalyst filler.In oxidizing tower, ozone mixes with the efficient of sewage, and pollutant reacts with ozone generation efficient oxidation under catalyst action, and pollutant levels are reduced.Detailed process is generally as follows:
The ozone that ozone generator produces is connected on ozonation aerated device by pipeline, pass through aerator, ozone is cut into less bubble, sewage is entered by water inlet, through supporting layer and catalyst filling, carries out catalytic oxidation wherein, the organic matter of difficult degradation is by open loop, chain rupture, become the organic matter of easily degraded, after reaction, sewage is discharged through delivery port.The ozone tail gas that ozone oxidation tower produces, through overhead collection, is connected to vent ozone destructor device by pipeline and processes.
The each 6L of catalyst prepared in embodiment 1 ~ 6 is loaded in catalytic ozonation tower respectively, processes coal liquifaction sewage (1 respectively
#), textile printing and dyeing sewage (2
#), containing polymer sewage from oil extraction (3
#), wherein, process coal liquifaction sewage (1
#) time, retention time of sewage is 30 minutes, and ozone dosage is 750mg/L; Process textile printing and dyeing sewage (2
#) time, retention time of sewage is 30 minutes, and ozone dosage is 150mg/L; Process polymer sewage from oil extraction (3
#) time, retention time of sewage is 30 minutes, and ozone dosage is 300mg/L, and sewage disposal result is respectively as shown in table 1 and table 2.
As can be seen from table 1 and table 2, when adopting catalyst prepared in embodiment 1 ~ 6 to carry out ozone oxidation advanced treating to sewage, can more than 90% be reached to the clearance of coal liquifaction sewage and textile printing and dyeing COD of sewage, can more than 80% be reached to the clearance containing polymer sewage from oil extraction COD.Meanwhile, very high removal efficiency is had, more than 95% to the colourity of sewage.And when adopting the catalyst prepared by impregnated with nitrate method under equal conditions to carry out the experiment of sewage ozone Oxidation Treatment, to the clearance of COD of sewage substantially 70%, to the clearance of the colourity of sewage also about 70%.Its catalytic efficiency of the catalyst for ozone oxidation prepared by visible technical scheme of the present invention is higher, good catalytic activity.
It should be noted that, although embodiment 1 ~ 6 is for active carbon and ammoniacal liquor, technical scheme of the present invention is described, but those skilled in the art can adopt the technical scheme recorded in the embodiment of the present invention completely, with other catalyst carrier, such as molecular sieve, aluminium oxide etc., realize technical scheme of the present invention with other precipitating reagent such as NaOH, potassium hydroxide etc.Due to the restriction of length, the present invention is described the citing that differs of above-mentioned catalyst carrier and precipitating reagent.
The foregoing is only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention.All any amendments done within the spirit and principles in the present invention, equivalent replacement, improvement etc., be all included in protection scope of the present invention.
Table 1 is for carrying out COD clearance during ozone oxidation with catalyst prepared in embodiment 1 ~ 6
Note: COD
crthe COD value of the sewage before ozone oxidation is carried out in front expression, COD
crrear expression carry out the sewage after ozone oxidation COD value, wherein, COD
crfor adopting potassium bichromate (K
2cr
2o
7) chemical oxygen consumption (COC) that determines as oxidant.
Table 2 is for carrying out chroma removal rate during ozone oxidation with catalyst prepared in embodiment 1 ~ 6
Note: colourity (front) represents the colourity of the sewage before carrying out ozone oxidation, colourity (afterwards) represents the colourity of the sewage after carrying out ozone oxidation.
Claims (10)
1. for a preparation method for the catalyst of ozone oxidation, it is characterized in that, comprise the following steps:
Catalyst carrier after activation is placed in container, under stirring, by the molysite prepared in advance, manganese salt mixed aqueous solution and hydroxide aqueous solution and stream join in described container and carry out co-precipitation, the speed that adds of hydroxide aqueous solution is regulated to ensure that the liquid in container is alkalescence, until molysite, manganese salt mixed aqueous solution add complete, obtain depositing iron, manganese precipitated catalyst carrier and mixed liquor;
Iron will be deposited, manganese precipitated catalyst carrier will soak 6 ~ 15 hours in mixed liquor, and then filter, wash, dry and roasting, obtain the catalyst for ozone oxidation.
2. the method for claim 1, is characterized in that, the activation method of described catalyst carrier is: non-activated catalyst carrier is placed in acid, refluxes 2 ~ 4 hours under the condition of 60 ~ 80 DEG C, and then washing is to neutral, drying for standby.
3. method as claimed in claim 2, it is characterized in that, described acid is the one in nitric acid, hydrochloric acid and sulfuric acid.
4. the method for claim 1, is characterized in that, described catalyst carrier is the one in active carbon, molecular sieve, aluminium oxide.
5. method as claimed in claim 4, it is characterized in that, described active carbon is specific area is 800 ~ 1200m
2the bar-shaped active carbon of/g.
6. the method for claim 1, it is characterized in that, in described molysite, manganese salt mixed aqueous solution, the gross mass of molysite and manganese salt account for molysite, manganese salt mixed aqueous solution gross mass 10% ~ 35%, and the mol ratio of iron and manganese is (5:1) ~ (1:5).
7. the method for claim 1, is characterized in that, the anion of molysite and manganese salt is one in sulfate radical, nitrate anion and chlorion or its combination.
8. the method for claim 1, is characterized in that, described hydroxide aqueous solution is ammoniacal liquor.
9. the method for claim 1, is characterized in that, the speed that adds of molysite, manganese salt mixed aqueous solution is 3 ~ 30 ml/min, is preferably 3 ~ 20 ml/min, is more preferably 3 ~ 10 ml/min, most preferably is 3 ~ 6 ml/min.
10. the method for claim 1, is characterized in that, described roasting is specially: roasting 3 ~ 5 hours under the condition of 400 DEG C ~ 600 DEG C.
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