CN106345474A - Solid-phase compound type ozone oxidation catalyst and preparation method thereof - Google Patents

Solid-phase compound type ozone oxidation catalyst and preparation method thereof Download PDF

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Publication number
CN106345474A
CN106345474A CN201610735345.0A CN201610735345A CN106345474A CN 106345474 A CN106345474 A CN 106345474A CN 201610735345 A CN201610735345 A CN 201610735345A CN 106345474 A CN106345474 A CN 106345474A
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preparation
ozone oxidation
oxidation catalyst
catalyst
solid phase
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凌明
叶国祥
李婷
郭慧
朱宏博
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Zhejiang Juneng Co Ltd
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Zhejiang Juneng Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds

Abstract

The invention belongs to the technical field of catalysts and particularly relates to an ozone catalyst with an aim to provide a solid-phase compound type ozone oxidation catalyst low in preparation cost, easy to produce and good in catalytic performance and stability. The solid-phase compound type ozone oxidation catalyst is characterized in that Ti/gamma-Al2O3 and iron hydroxide are taken as catalyst components, and the Ti/gamma-Al2O3 and iron hydroxide are subjected to adhesion through an adhesion agent and pelletizing prior to drying, calcinating and cooling to obtain the ozone oxidation catalyst; the catalyst components respectively include, by weight, 50%-80% of Ti/gamma-Al2O3 and 20%-50% of ion hydroxide; Ti/gamma-Al2O3 takes powdered gamma-aluminum oxide as a carrier and TiO2 of different crystal forms as a load type catalytic material; ion hydroxide is the catalyst material is obtained by dissolving ferrite and ferric salt in water for reaction under the alkaline condition after adding of alcohols prior to drying and grinding.

Description

Compound ozone oxidation catalyst of a kind of solid phase and preparation method thereof
Technical field
The invention belongs to catalyst technical field, particularly to a kind of ozone oxidation catalyst.
Background technology
Ozonation technology is widely applied in water treatment field, such as the sterilizing of city water, industrial wastewater Advanced treating etc..This technology is subject to get more and more in organic wastewater particularly difficult for biological degradation method for processing organic wastewater at present Attention.But due to its oxidation selectivity, ozone utilization rate is low, operating cost is high the problems such as, the popularization of ozonation technology should With severely limited.As background, improve ozone oxidation efficiency, strengthen ozone oxidation ability, reduction using catalyst The technology of operating cost receives much concern.
Solid phase ozone oxidation catalyst compares homogeneous catalyst higher using value, thus is the heat of current research Point.In solid-phase catalyst, transition metal series catalyst has higher catalysis activity, is often used as active component.Mesh Before, prepare high catalytic activity and the transition-metal catalyst of stability becomes study hotspot
Cn104646020a Chinese patent application discloses a kind of preparation method of catalyst, its preparation process: (1) With activated carbon as carrier, sequentially pass through alkali cleaning, pickling, after deionized water rinsing, dry for standby；(2) under the conditions of 50～80 DEG C Impregnate 3～5h in ferric nitrate, manganese nitrate solution, dry 2～3h at 100～120 DEG C；(3) roasting 2 at 300～500 DEG C ～3h, prepared ozone oxidation catalyst.
Cn104289250a Chinese patent application discloses a kind of preparation method of catalyst, by transition metal nitrate Solution is dissolved in cetyl trimethylammonium bromide solution, adds ammonia to form sol solution, molecular sieve is mixed in colloidal sol Stir, obtain metal oxide modified molecular sieve, modified molecular screen and adsorbent, additive through filtration washing drying and roasting Uniform mixing soluble in water, cellular activated carbon be impregnated in 20～60 minutes in this solution, dries, in 500～600 DEG C of nitrogen Roasting obtains support type ozone oxidation catalyst in 2～6 hours.
The preparation of above-mentioned ozone oxidation catalyst is in supported on carriers active component, and catalyst activity is higher, side Method is infusion process.But there is impregnation liquid in preparation process to waste, produce nitrogen oxides during nitrate calcination for activation and make The problems such as during becoming pollution, cost of manufacture higher and using, loss of active component leads to catalysis activity to decline.
In sum, the preparation method of existing ozone oxidation catalyst is improved, prepare a kind of catalysis activity high, steady Qualitative good, preparation cost is low and ozone oxidation catalyst of non-secondary pollution necessitates.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, providing that a kind of cost of manufacture is relatively low, being easy to produce, catalysis Excellent performance, stability are good, and the compound ozone oxidation catalyst of solid phase that in preparation process, unharmful substance produces.
In order to achieve the above object, the compound ozone oxidation catalyst of a kind of solid phase of the present invention, is with ti/ γ-al2o3 It is catalyst component with FeOOH, both drying and roastings after adhesive bonding pelletize are cooled down the ozone oxidation obtaining and urges Agent；The weight/mass percentage composition of its catalyst component is respectively as follows: ti/ γ-al2o350%-80%, FeOOH 20%-50%； Described ti/ γ-al2o3Be with powder gama-alumina as carrier, different crystal forms tio2Supported catalyst material for active component Material；Described FeOOH is will be soluble in water to ferrous salt and iron salt, reacts in the basic conditions after adding alcohols material, And the catalysis material obtaining after drying and grinding.
It is a further object of the present invention to provide a kind of preparation method of the compound ozone oxidation catalyst of solid phase, including as follows Step:
a.ti/γ-al2o3The preparation of catalysis material
Including the pretreatment of carrier, gel solution prepares, impregnates, calcines and repeats to process five processes:
The pretreatment of first step carrier: first, by powder γ-al2o3It is placed in ultrasonic shake in ethanol and acetone mixture Swing, the volume ratio of wherein ethanol and acetone is: 1:10-10:1, the concussion time is 2min-240min, to remove the organic of surface Thing；Subsequently, the γ-al after concussion being processed2o3Put into the hno of 0.1-4mol/l3In boil process 10-300min, to remove table The oxide layer in face；By the γ-al after peracid treatment2o3Take out and be washed to neutrality with ultrapure, dry at 90-150 DEG C；
Prepared by second step gel solution: ti-based compound is added and after hydrochloric acid and the mixed solution of ethanol, adds stabilizer, It is slowly added dropwise ultra-pure water under agitation, after stirring, obtain the gel of transparent and stable；
3rd step dipping: the powder γ-al that the first step was processed2o3Put into the gel solution that second step prepares In, carry out concussion dipping 1-12h, after filtering off impregnation liquid, the dusty material obtaining is dried 12-24h at 85-100 DEG C；
4th step calcining: the dusty material that the 3rd step is prepared is placed in Muffle furnace, with constant heating rate liter To 400-990 DEG C, calcining at constant temperature can get with powder gama-alumina as carrier temperature, different crystal forms tio2For active component Single treatment ti/ γ-al2o3Catalysis material；Different, the tio in active component according to calcining heat2Crystal formation can be anatase Type and rutile-type；
5th step repeats to process: by the ti/ γ-al of single treatment2o3After catalysis material repetition the 3rd step, the 4th step number time Obtain required ti/ γ-al2o3Catalysis material.
B. the preparation of FeOOH catalysis material:
First step solution is prepared: the ferrous salt of certain proportioning and iron salt is uniformly added in ultra-pure water under agitation, extremely complete CL, prepares and obtains saline solution；
Second step reacts: alcohols material is slowly added under certain mixing speed gradient the saline solution of first step preparation In, start to react 6-12h at a temperature of the alkalescence condition for 8.5-12.5 for the ph value and 80 DEG C -145 DEG C；
3rd step is dried: product is positioned in baking oven is dried after completion of the reaction, baking temperature is 81 DEG C -101 DEG C, be dried Time is 12-48h；Required FeOOH catalysis material is obtained after grinding.
C. the preparation of the compound ozone oxidation catalyst of solid phase
Ti/ γ-the al that step a is prepared2o3The FeOOH catalysis material that catalysis material and step b prepare with Mass percent 50%-80%:20%-50% ratio mixes, and prepares catalyst mother using entering pelletizer after adhesive bonding Grain, is a kind of compound ozone oxidation catalyst of solid phase after the cooling of master batch drying and roasting.
Preferably, in the first step of step a, described powder γ-al2o3Particle diameter be 80-90 mesh.
Preferably, in the second step of step a, described hydrochloric acid is the concentrated hydrochloric acid of 12mol/l, its usage amount is ethanol volume 1 ‰ -10 ‰；Described ti-based compound is butyl titanate, and its active component ti content is 0.3-0.8mg/l；Described Stabilizer is to analyze pure glacial acetic acid, and its usage amount is the 0.1 ‰ -0.5 ‰ of dehydrated alcohol volume, and described ultra-pure water usage amount is The 0.5%-15% of dehydrated alcohol volume.
Preferably, powder γ-al in the 3rd step of step a2o3The amount being placed in gel solution is 20-30g/l, described Concussion be immersed in and carry out at 10 DEG C -50 DEG C.
Preferably, in the 4th step of step a, described Muffle furnace heating rate is 5 DEG C/min；Described calcining at constant temperature Time is 1-8h.
Preferably, in the 5th step of step a, repeating the 3rd step, the number of times of the 4th step is 1-20 time.
Preferably, in the first step of step b, the described ferrous salt of certain proportioning and the ratio of iron salt are mol ratios fe2+: fe3+=1:10-10:1, described ferrous salt be ferrous sulfate, ferrous chloride one or more, described iron salt is nitric acid Ferrum, iron chloride one or more；Stirring adopts mechanical agitation mode, and mixing speed is 80-200rpm.
Preferably, in the second step of step b, described mixing speed gradient g value is 500-1000s-1, described alcohols thing Matter is one or more of ethylene glycol, glycerol, polyglycerol, Polyethylene Glycol；Alcohol is 1:50-1 with the volume ratio of saline solution: 5.
Preferably, the binding agent described in step c be methylcellulose, sodium carboxymethyl cellulose, polyvinyl alcohol, poly- third One or more of enol；The catalyst mother bulb particle diameter of described pelletizer preparation is 2-8mm；Described drying meanss are 60 2-8 hour is dried under the conditions of DEG C -80 DEG C；Described method of roasting is in 150 DEG C -650 DEG C roasting temperature 2-6 in Muffle furnace Hour.
Ti/ γ-al in the compound ozone oxidation catalyst of solid phase of the present invention2o3Catalysis material will have catalysiss tio2Active component is carried on powder γ-al2o3In surface or internal gutter, it is to avoid tio2The loss of active component, is a kind of steady Fixed ozone catalysing material；FeOOH catalysis material has the effect that ozone catalytic produces hydroxyl radical free radical, is a kind of Efficient catalytic ozonation material；
The main component of the compound ozone oxidation catalyst of solid phase of the present invention is γ-al2o3, anatase tio2, rutile-type tio2, FeOOH etc., these materials are uniformly distributed in inside and outside catalyst in the form of nano sized particles, and density of catalyst is 0.85-1.2t/m3, specific surface area is 3200-4500m2/m3, porosity is up to 50-70%, and physical strength is more than or equal to 800kg/ cm3, therefore this catalyst has certain capillary attraction, can be by the work in the Organic substance in waste water, ozone molecule and catalyst Property component be fully contacted, catalyst channel surfaces occur catalysis ozone reaction, greatly improve reaction rate；
The major catalytic component of the compound ozone oxidation catalyst of solid phase of the present invention is anatase tio2, rutile-type tio2、 FeOOH, the tio of two kinds of crystal formations2Water-soluble state ozone can be catalyzed, improve the oxidation of ozone direct oxidation reaction Efficiency, and FeOOH has abundant surface hydroxyl groups and very strong surface hydroxylation degree, can be divided with catalysis ozone Son generates the hydroxyl radical free radical with strong oxidizing property, improves the oxidation efficiency of ozone indirect oxidation reaction；tio2And hydroxyl oxygen Change both ferrum not only two oxidative pathways of ozone to be catalyzed, there is certain synergism, available ozone oxidation simultaneously The various organic pollution of efficient degradation, has certain broad spectrum activity.
Specific embodiment
With reference to application example, technical scheme and beneficial effect are further elaborated.
Embodiment 1:
a.ti/γ-al2o3The preparation of catalysis material
(1) Vehicle element: first, the powder γ-al that particle diameter is 90 mesh2o3It is placed in volume ratio ethanol: acetone=1: Ultrasonic vibration 20min in 10 mixed liquor, removes the Organic substance on surface；Subsequently, the γ-al after concussion being processed2o3Put into The hno of 0.5mol/l3In boil process 30min, to remove the oxide layer on surface；By the γ-al after peracid treatment2o3Take out It is washed to neutrality with ultrapure, dry at 105 DEG C；
(2) gel solution preparation: the concentrated hydrochloric acid of 5ml 12mol/l is dropped in 840ml dehydrated alcohol, after stirring Deca 3ml analyzes pure glacial acetic acid, is stirring evenly and then adding into 145ml butyl titanate, is slowly added dropwise 15ml under fast stirring and surpasses Pure water, obtains the gel solution of transparent and stable；
(3) impregnate: take 20g pretreated γ-al2o3Put in the gel solution of above-mentioned preparation, carry out concussion dipping 4h, filters impregnation liquid and takes out dusty material, 6h is dried at 85 DEG C；
(4) calcine: the dusty material that the 3rd step is prepared is placed in Muffle furnace, with the intensification speed that 5 DEG C/min is constant Under the conditions of rate is warming up to 400 DEG C, calcining at constant temperature 240min, you can obtain the ti/ γ-al through single treatment2o3Catalysis material；
(5) repeat to process: by the ti/ γ-al through single treatment2o3Catalysis material repeated impregnations, calcination processing 1 time, that is, Required ti/ γ-al can be obtained2o3Catalysis material.
B. the preparation of FeOOH catalysis material:
Weigh 150g feso4·7h2O and 200g fe (no3)·9h2O is dissolved in 100ml ultra-pure water, is stirred with 150rpm rotating speed Mix to being completely dissolved；Under the conditions of low whipping speed gradient g value=700s-1, in saline solution, add 15ml ethylene glycol, adjust ph To 12,110 DEG C of oil baths are reacted 6h, after precipitate is cleaned with clear water, 12h is dried as in baking oven under the conditions of 85 DEG C, grinds After mill cross 90 mesh sieves FeOOH catalysis material.
C. the preparation of the compound ozone oxidation catalyst of solid phase
Ti/ γ-al by the preparation of step a2o3Catalysis material and step b FeOOH catalysis material are mixed with mass ratio 7:3 Close uniformly, carry out bonding pelletize for binding agent with polyvinyl alcohol, preparing particle diameter is 3-5mm mother bulb, dries 4 at 70 DEG C little When, it is placed in Muffle furnace roasting 2h at 350 DEG C, the compound ozone oxidation catalyst of prepared solid phase.
Embodiment 2:
a.ti/γ-al2o3The preparation of catalysis material
(1) Vehicle element: first, the powder γ-al that particle diameter is 80 mesh2o3It is placed in volume ratio ethanol: acetone=5: Ultrasonic vibration 2min in 1 mixed liquor, removes the Organic substance on surface；Subsequently, the γ-al after concussion being processed2o3Put into 0.1mol/l Hno3In boil process 300min, to remove the oxide layer on surface；By the γ-al after peracid treatment2o3Taking-up ultra-pure water It is washed till neutrality, dry at 90 DEG C；
(2) gel solution preparation: the concentrated hydrochloric acid of 5ml 12mol/l is dropped in 840ml dehydrated alcohol, after stirring Deca 3ml analyzes pure glacial acetic acid, is stirring evenly and then adding into 145ml butyl titanate, is slowly added dropwise 15ml under fast stirring and surpasses Pure water, obtains the gel solution of transparent and stable；
(3) impregnate: take 20g pretreated γ-al2o3Put in the gel solution of above-mentioned preparation, carry out concussion dipping 1h, filters impregnation liquid and takes out dusty material, 5h is dried at 90 DEG C；
(4) calcine: the dusty material that the 3rd step is prepared is placed in Muffle furnace, with the intensification speed that 5 DEG C/min is constant Under the conditions of rate is warming up to 650 DEG C, calcining at constant temperature 1h, you can obtain the ti/ γ-al through single treatment2o3Catalysis material；
(5) repeat to process: by the ti/ γ-al through single treatment2o3Catalysis material repeated impregnations, calcination processing 20 times, Required ti/ γ-al2o3Catalysis material.
B. the preparation of FeOOH catalysis material:
Weigh 150g ferrous chloride and 200g iron chloride is dissolved in 100ml ultra-pure water, stirred to completely molten with 80rpm rotating speed Solution；Under the conditions of low whipping speed gradient g value=500s-1, in saline solution, add 15ml glycerol, adjust ph to 8.5,80 React 12h at DEG C, after precipitate is cleaned with clear water, 48h is dried as in baking oven under the conditions of 81 DEG C, crossing 90 mesh sieves after grinding is FeOOH catalysis material can be obtained.
C. the preparation of the compound ozone oxidation catalyst of solid phase
Ti/ γ-al by the preparation of step a2o3Catalysis material and step b FeOOH catalysis material are mixed with mass ratio 5:5 Close uniformly, carry out bonding pelletize for binding agent with methylcellulose, preparing particle diameter is 4-6mm mother bulb, dries 8 at 60 DEG C little When, it is placed in Muffle furnace roasting 6h at 150 DEG C, the compound ozone oxidation catalyst of prepared solid phase.
Embodiment 3:
a.ti/γ-al2o3The preparation of catalysis material
(1) Vehicle element: first, the powder γ-al that particle diameter is 85 mesh2o3It is placed in volume ratio ethanol: acetone= Ultrasonic vibration 240min in 10:1 mixed liquor, removes the Organic substance on surface；Subsequently, the γ-al after concussion being processed2o3Put into The hno of 4mol/l3In boil process 10min, to remove the oxide layer on surface；By the γ-al after peracid treatment2o3Take out and use Ultrapure be washed to neutrality, at 150 DEG C dry；
(2) gel solution preparation: the concentrated hydrochloric acid of 5ml 12mol/l is dropped in 840ml dehydrated alcohol, after stirring Deca 3ml analyzes pure glacial acetic acid, is stirring evenly and then adding into 145ml butyl titanate, is slowly added dropwise 15ml under fast stirring and surpasses Pure water, obtains the gel solution of transparent and stable；
(3) impregnate: take 20g pretreated γ-al2o3Put in the gel solution of above-mentioned preparation, carry out concussion dipping 12h, filters impregnation liquid and takes out dusty material, 4h is dried at 100 DEG C；
(4) calcine: the dusty material that the 3rd step is prepared is placed in Muffle furnace, with the intensification speed that 5 DEG C/min is constant Under the conditions of rate is warming up to 990 DEG C, calcining at constant temperature 8h, you can obtain the ti/ γ-al through single treatment2o3Catalysis material；
(5) repeat to process: by the ti/ γ-al through single treatment2o3Catalysis material repeated impregnations, calcination processing 10 times, Required ti/ γ-al2o3Catalysis material.
B. the preparation of FeOOH catalysis material:
Weigh 150g ferrous sulfate and 200g iron chloride is dissolved in 100ml ultra-pure water, stirred to completely molten with 200rpm rotating speed Solution；Under the conditions of low whipping speed gradient g value=1000s-1, in saline solution, add 15ml Polyethylene Glycol, adjust ph to 12.5, React 6h in 145 DEG C of oil baths, after precipitate is cleaned with clear water, 15h is dried as in baking oven under the conditions of 101 DEG C, after grinding Cross 90 mesh sieves FeOOH catalysis material.
C. the preparation of the compound ozone oxidation catalyst of solid phase
Ti/ γ-al by the preparation of step a2o3Catalysis material and step b FeOOH catalysis material are mixed with mass ratio 8:2 Close uniformly, carry out bonding pelletize for binding agent with POLYPROPYLENE GLYCOL, preparing particle diameter is 2-5mm mother bulb, dries 2 at 80 DEG C little When, it is placed in Muffle furnace roasting 2h at 650 DEG C, the compound ozone oxidation catalyst of prepared solid phase.
Test example 1
Fill the common oxygen with particle diameter for the equivalent respectively in three cylindrical reactors that specification is identical, effective volume is for 10l Change aluminium ball, commercial alumina carrier ozone catalyst (with manganese oxide, iron sesquioxide as catalytic active component) and the present invention real Apply the compound ozone oxidation catalyst of solid phase of example 1 preparation, biochemical to textile waste sewage plant under the conditions of same operational factor Pond water outlet (cod:150mg/l-200mg/l) carries out advanced treating, process conditions: waste water ph is 7-8, ozone dosage 60mg/ L, hrt are 30min, catalyst dosing rate 80%.
Different ozone catalyst catalytic effect contrasts are shown in Table 1.
Table 1
Wire feeding Water inlet cod (mg/l) Water outlet cod (mg/l) Cod clearance (%)
Common alumina balls 193 134 30.6
Commercially available ozone catalyst 188 102 45.7
Self-control ozone catalyst 195 85 56.4
By table 1 it is found that under identical service condition, the catalyst effect of present invention preparation is far above common oxygen Change aluminium ball, compare commercially available ozone catalyst, cod clearance lifting about 10%, the compound ozone of solid phase of present invention preparation is described Oxidation catalyst catalytic performance is splendid.
Test example 2
Fill the present invention with particle diameter for the equivalent respectively in four cylindrical reactors that specification is identical, effective volume is for 10l The compound ozone oxidation catalyst of solid phase of embodiment 1 preparation, to several industry wastewater and sewage under the conditions of same operational factor The biochemistry pool water outlet stood carries out advanced treating, process conditions: ozone dosage 60mg/l, hrt are 30min, catalyst dosing rate 80%；
Different industries wastewater biochemical pond goes out water treatment efficiency and is shown in Table 2；
Table 2
As shown in Table 2, under certain operating conditions, the compound ozone oxidation catalyst of solid phase of present invention preparation is to difference The biochemical tail water cod clearance of industry waste water all has 50-70%, and comparing direct ozone oxidation cod clearance is 28-40%, cod Clearance lifting nearly 30%, and the solid phase compound ozone oxidation catalyst catalytic performance of present invention preparation has broad spectrum activity.

Claims (10)

1. a kind of compound ozone oxidation catalyst of solid phase it is characterised in that: described catalyst is with ti/ γ-al2o3And hydroxyl Ferrum oxide is catalyst component, and by both, drying and roasting after adhesive bonding pelletize cools down the ozone oxidation catalyst obtaining； The weight/mass percentage composition of its catalyst component is respectively as follows: ti/ γ-al2o350%-80%, FeOOH 20%-50%；Described ti/γ-al2o3Be with powder gama-alumina as carrier, different crystal forms tio2Support materials for catalysts for active component；Institute The FeOOH stated is will be soluble in water to ferrous salt and iron salt, reacts in the basic conditions, and do after adding alcohols material The catalysis material obtaining after dry grinding.
2. a kind of compound ozone oxidation catalyst of solid phase preparation method it is characterised in that: comprise the steps:
a.ti/γ-al2o3The preparation of catalysis material: include the pretreatment of carrier, gel solution preparation, dipping, calcining and repetition Five processes of process:
The pretreatment of first step carrier: first, by powder γ-al2o3It is placed in ultrasonic vibration in ethanol and acetone mixture, its The volume ratio of middle ethanol and acetone is: 1:10-10:1, and the concussion time is 2min-240min, to remove the Organic substance on surface；With Afterwards, the γ-al after concussion being processed2o3Put into the hno of 0.1-4mol/l3In boil process 10-300min, to remove surface Oxide layer；By the γ-al after peracid treatment2o3Take out and be washed to neutrality with ultrapure, dry at 90-150 DEG C；
Prepared by second step gel solution: ti-based compound is added and adds stabilizer after hydrochloric acid and the mixed solution of ethanol, stirring It is slowly added dropwise ultra-pure water under the conditions of mixing, after stirring, obtain the gel of transparent and stable；
3rd step dipping: the powder γ-al that the first step was processed2o3Put in the gel solution that second step prepares, enter The dusty material obtaining is dried 12-24h after filtering off impregnation liquid at 85-100 DEG C by row concussion dipping 1-12h；
4th step calcining: the dusty material that the 3rd step is prepared is placed in Muffle furnace, is warming up to constant heating rate 400-990 DEG C, calcining at constant temperature can get with powder gama-alumina as carrier, different crystal forms tio2For active component one Ti/ γ-the al of secondary process2o3Catalysis material；
5th step repeats to process: by the ti/ γ-al of single treatment2o3Obtain after catalysis material repetition the 3rd step, the 4th step number time Required ti/ γ-al2o3Catalysis material.
B. the preparation of FeOOH catalysis material:
First step solution is prepared: the ferrous salt of certain proportioning and iron salt is uniformly added in ultra-pure water under agitation, to completely molten Solution, prepares and obtains saline solution；
Second step reacts: under certain mixing speed gradient, alcohols material is slowly added in the saline solution of first step preparation, Start to react 6-12h at a temperature of the alkalescence condition for 8.5-12.5 for the ph value and 80 DEG C -145 DEG C；
3rd step is dried: product is positioned in baking oven is dried after completion of the reaction, baking temperature is 81 DEG C -101 DEG C, drying time For 12-48h；Required FeOOH catalysis material is obtained after grinding.
C. the preparation of the compound ozone oxidation catalyst of solid phase
Ti/ γ-the al that step a is prepared2o3The FeOOH catalysis material that catalysis material and step b prepare is with quality Percentage ratio 50%-80%:20%-50% ratio mixes, and prepares catalyst master batch using entering pelletizer after adhesive bonding, female It is a kind of compound ozone oxidation catalyst of solid phase after grain drying and roasting cooling.
3. a kind of compound ozone oxidation catalyst of solid phase according to claim 2 preparation method it is characterised in that: step In the first step of rapid a, described powder γ-al2o3Particle diameter be 80-90 mesh.
4. a kind of compound ozone oxidation catalyst of solid phase according to claim 2 preparation method it is characterised in that: step In the second step of rapid a, described hydrochloric acid is the concentrated hydrochloric acid of 12mol/l, and its usage amount is the 1 ‰ -10 ‰ of ethanol volume；Described titanium Based compound is butyl titanate, and its active component ti content is 0.3-0.8mg/l；Described stabilizer is to analyze pure ice vinegar Acid, its usage amount is the 0.1 ‰ -0.5 ‰ of dehydrated alcohol volume, and described ultra-pure water usage amount is dehydrated alcohol volume 0.5%-15%.
5. a kind of compound ozone oxidation catalyst of solid phase according to claim 2 preparation method it is characterised in that: step Powder γ-al in 3rd step of rapid a2o3The amount being placed in gel solution is 20-30g/l, and described concussion is immersed in 10 DEG C -50 Carry out at DEG C.
6. a kind of compound ozone oxidation catalyst of solid phase according to claim 2 preparation method it is characterised in that: step In 4th step of rapid a, described Muffle furnace heating rate is 5 DEG C/min；The described calcining at constant temperature time is 1-8h.
7. a kind of compound ozone oxidation catalyst of solid phase according to claim 2 preparation method it is characterised in that: step In 5th step of rapid a, repeat the 3rd step, the number of times of the 4th step is 1-20 time.
8. a kind of compound ozone oxidation catalyst of solid phase according to claim 2 preparation method it is characterised in that: step In the first step of rapid b, the described ferrous salt of certain proportioning and the ratio of iron salt are mol ratios fe2+: fe3+=1:10-10:1, institute The ferrous salt stated be ferrous sulfate, ferrous chloride one or more, described iron salt is ferric nitrate, one kind of iron chloride or several Kind；Stirring adopts mechanical agitation mode, and mixing speed is 80-200rpm.
9. a kind of compound ozone oxidation catalyst of solid phase according to claim 2 preparation method it is characterised in that: step In the second step of rapid b, described mixing speed gradient g value is 500-1000s-1, and described alcohols material is ethylene glycol, glycerol, poly- One or more of glycerol, Polyethylene Glycol；Alcohol is 1:50-1:5 with the volume ratio of saline solution.
10. a kind of compound ozone oxidation catalyst of solid phase according to claim 2 preparation method it is characterised in that: Binding agent described in step c is one of methylcellulose, sodium carboxymethyl cellulose, polyvinyl alcohol, POLYPROPYLENE GLYCOL or several Kind；The catalyst mother bulb particle diameter of described pelletizer preparation is 2-8mm；Described drying meanss are to dry under the conditions of 60 DEG C -80 DEG C Dry 2-8 hour；Described method of roasting is in 150 DEG C -650 DEG C roasting temperature 2-6 hours in Muffle furnace.
CN201610735345.0A 2016-08-26 2016-08-26 Solid-phase compound type ozone oxidation catalyst and preparation method thereof Pending CN106345474A (en)

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CN109225242A (en) * 2018-10-16 2019-01-18 南京工业大学 A kind of composite nano attapulgite haydite ozone catalyst and its preparation method and application
CN109731574A (en) * 2018-06-29 2019-05-10 光大水务（深圳）有限公司 A kind of preparation method of catalyst complex carrier, the catalyst based on the carrier and catalyst
CN112973662A (en) * 2021-02-25 2021-06-18 中节能环保投资发展(江西)有限公司 Method for preparing ozone catalyst by doping rare earth enrichment with excess sludge and application
CN113042052A (en) * 2021-03-30 2021-06-29 中建三局绿色产业投资有限公司 TiO2Al/Si-C-based porous core-shell separation spherical catalyst and preparation method and application thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109731574A (en) * 2018-06-29 2019-05-10 光大水务（深圳）有限公司 A kind of preparation method of catalyst complex carrier, the catalyst based on the carrier and catalyst
CN109225242A (en) * 2018-10-16 2019-01-18 南京工业大学 A kind of composite nano attapulgite haydite ozone catalyst and its preparation method and application
CN112973662A (en) * 2021-02-25 2021-06-18 中节能环保投资发展(江西)有限公司 Method for preparing ozone catalyst by doping rare earth enrichment with excess sludge and application
CN113042052A (en) * 2021-03-30 2021-06-29 中建三局绿色产业投资有限公司 TiO2Al/Si-C-based porous core-shell separation spherical catalyst and preparation method and application thereof
CN113042052B (en) * 2021-03-30 2022-04-29 中建三局绿色产业投资有限公司 TiO2Al/Si-C-based porous core-shell separation spherical catalyst and preparation method and application thereof

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