CN109718749A - The method and application of step gradient heating calcination method preparation ozone catalyst - Google Patents
The method and application of step gradient heating calcination method preparation ozone catalyst Download PDFInfo
- Publication number
- CN109718749A CN109718749A CN201910026459.1A CN201910026459A CN109718749A CN 109718749 A CN109718749 A CN 109718749A CN 201910026459 A CN201910026459 A CN 201910026459A CN 109718749 A CN109718749 A CN 109718749A
- Authority
- CN
- China
- Prior art keywords
- ozone catalyst
- step gradient
- catalyst
- temperature
- stage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/72—Copper
-
- 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
- B01J23/75—Cobalt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
-
- 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
Abstract
The invention discloses the methods and application of a kind of step gradient heating calcination method preparation ozone catalyst, belong to environment-friendly materials field.It includes adding water and stirring aluminium base precursor material uniformly, obtains reactive precursor material；Reactive precursor material is dried, active material is obtained；Active material is roasted to obtain ozone catalyst, the method for roasting is program step gradient heating calcination method.The method of the present invention can effectively improve the efficiency of ozone catalyst removal TOC in waste water, prepare catalyst using the method for the present invention, and step is simple, easily controllable, more conducively the volume production of efficient ozone catalyst.
Description
Technical field
The invention belongs to environment-friendly materials fields, prepare more specifically to a kind of step gradient heating calcination method smelly
The method and application of VPO catalysts.
Background technique
With the development of reform and opening-up, chemical industry is emerged in large numbers like the mushrooms after rain, and a series of environment of bring is dirty therewith
Dye problem is got worse.Pesticide industry is one of Typical Representative of Fine Chemical, and pesticide waste water is because having COD total amount
Greatly, the problems such as levels of toxic substances is high, biodegradability is poor and become chemical company's problem urgently to be resolved.Ozone has extremely strong
Mineralization of organic material can be directly the lesser substance of molecular weight by oxidability.But ozone has stronger oxidation selectivity,
Cause organic pollutant that cannot be mineralized completely as CO2And H2O in turn results in ozone utilization rate and declines, while organic pollutant
Removal efficiency also reduces.In order to improve this phenomenon, by way of adding catalyst into ozone oxidation system, because of catalyst
Ozone can be decomposed into the OH with stronger catalytic capability to which the organic pollutant in catalysis oxidation water quality is to reach
The purpose of mineralising organic matter.
Heterogeneous ozone catalyst because convenient for liquid phase separation, not will cause the pollution of the active metallic ion additionally put into
Etc. advantages it is commonly used in ozone catalyst.But generally existing catalyst activity is lower, the halfway phenomenon of organic matter degradation,
Constrain the development for pesticide waste water by ozone catalyst.
Publication No. CN105366846A prior art discloses the processing method of the hundred clever agricultural chemicals waste waters of grass of one kind, use
The process of light electrolysis+ozone high grade oxidation+charcoal absorption, handles agricultural chemicals waste water, simple ozone dosage compared with
Greatly, and ozone oxidation it is highly selective so that organic matter can not be by permineralization in agricultural chemicals waste water.
Publication No. CN108097231A prior art discloses a kind of ozone catalytic oxidation catalyst and its preparation sides
Method and apply .8, mixed using by ρ type aluminium oxide, zinc oxide active component with water, prepare partial size for 1-9mm spherical pellet；
By pellet, constant temperature handles 10-24h at 60-90 DEG C again, and then calcining and activating handles 2-5h at 450-550 DEG C, obtains ozone
Oxidation catalyst.The organic matter phenolic waste water and sodium oxalate waste water being related in its case study on implementation belong to relatively degradable waste water,
Higher organic matter removal efficiency also may be implemented in ozone decomposition, it is difficult to the catalytic degradation ability of the catalyst is fully demonstrated,
It is difficult to absolutely prove that method that load active component prepares catalyst can be suitable for the waste water of other chemical companies.
Publication No. CN106345450A prior art discloses a kind of ozone oxidation catalyst for waste water treatment,
It is the SnO using gama-alumina as carrier2And TiO2For the support type ozone oxidation catalyst of active component, its preparation method packet
Five carrier particle pretreatment, gel solution preparation, dipping, calcining and reprocessing processes are included, first step carrier particle is located in advance
Reason: firstly, aluminium oxide particles are placed in ultrasonic vibration in ethyl alcohol and acetone mixture, to remove the organic matter on surface；Then, will
Treated that aluminium oxide particles are put into HNO for concussion3In boil processing, to remove the oxide layer on surface；It will treated through peracid
Aluminium oxide particles, which take out, is washed to neutrality with ultrapure, dries at 90-150 DEG C；The preparation of second step gel solution: pink salt is dissolved
Stabilizer is added after in the mixed liquor of hydrochloric acid and dehydrated alcohol, ti-based compound is added in above-mentioned mixed solution, is being stirred
Under the conditions of ultrapure water is slowly added dropwise, obtain the gel solution of transparent and stable after mixing evenly；Third step dipping: at will be through the first step
The aluminium oxide particles managed be put into second step preparation gel solution in, carry out concussion dipping 1-12h, filter off maceration extract after will
The particulate material arrived dry 4-6h at 85-100 DEG C；The calcining of 4th step: the particulate material that third step is prepared is placed in horse
Not in furnace, heating rate is 5 DEG C/min；The calcining at constant temperature time is 1-8h, is warming up to 400- with constant heating rate
It 990 DEG C, can be obtained using gama-alumina as carrier, tin, titanium bimetallic oxide SnO2And TiO2For the primary place of active component
The support type ozone oxidation catalysis material of reason；5th step reprocessing: by the support type ozone oxidation catalysis material of single treatment
It repeats to obtain support type ozone oxidation catalyst after third step, the 4th step number are secondary.Wherein use support type ozone oxygen of the invention
Changing catalyst can be to chloromycetin wastewater, penicillin wastewater, erythromycin wastewater, streptomycin wastewater, vancomycin waste water and pipemidic acid
The antibiotic waste waters such as waste water carry out catalytic ozonation processing, have removal efficiency high, and ozone utilization rate is high, is not necessarily to outer adding medicine
The advantages that.
Summary of the invention
1. to solve the problems, such as
For the problem for how further increasing ozone catalyst activity, the present invention provides a kind of gradient increased temperature calcining legal system
The method and application of standby ozone catalyst.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of method of step gradient heating calcination method preparation ozone catalyst, comprising the following steps:
1) aluminium base precursor material is added water and stirred uniformly, obtains reactive precursor material；
2) reactive precursor material is dried, obtains active material；
3) active material is roasted to obtain ozone catalyst, the method for roasting is the heating calcining of program step gradient
Method.
Preferably, the heating of program step gradient described in step 3) calcination method are as follows:
Stage I: room temperature to discharge cold air forms the calcined precursors atmosphere stage；
Stage II: aluminium oxide active crystal phase structure temperature stage is generated；
Stage III: active component roasting molding temperature stage；
Stage IV: temperature-fall period.
Preferably, the stage I is that 90~110 DEG C are warming up to 5~10 DEG C/min, keeps the temperature 1h；Stage II be with 3~5 DEG C/
Min is warming up to 200~300 DEG C, keeps the temperature 2~4h；Stage III is that 500~600 DEG C are warming up to 3 DEG C/min, keeps the temperature 4~8h.
Preferably, the stage IV is to be cooled to 200~300 DEG C with 1~2 DEG C/min, then be down to room temperature.
Preferably, the step 2) drying temperature is 105~120 DEG C.
It preferably, further include DEXTROSE ANHYDROUS or Dextrose Monohydrate in the aluminium base precursor material.
Preferably, the preparation method of the aluminium base precursor material includes: by the aluminium containing salt and nothing in aluminium base precursor material
Water glucose or Dextrose Monohydrate are with the ratio between amount of substance for (1.5~50): 1 ratio mixes, and stirs at 25~35 DEG C equal
After even, it is placed in baking oven and is dried at 105~120 DEG C.
Preferably, the reactive precursor material further includes active component, the active component include containing Mn, Cu, Fe, Co,
The mixing of one or more of the nitrate of Zn component, sulfate, hydrochloride, acetate, oxalates, persulfate.
Preferably, the reactive precursor material obtained after aluminium base precursor material and active component being added water and stirred uniformly is dried,
The drying temperature is 60~120 DEG C, obtains active material.It dries at this temperature, it is ensured that the work in reactive precursor material
Property component, that is, metal salt is supported on aluminium base precursor material.
Preferably, the aluminium base precursor material includes aluminium isopropoxide, aluminum nitrate, sodium metaaluminate, ANN aluminium nitrate nonahydrate, oxygen
Change aluminium ball shape granular materials.
Preferably, the active constituent of the spherical granular materials of the aluminium oxide is gama-alumina, having a size of 2~4mm, grinding
It is machined to 10~400 mesh.
Preferably, material clean 3~5 times ozone catalyst deionized water that step 3) obtains will prepared.With
Remove catalyst particle surface extra metal ion and its oxide.
Preferably, the material after washing is placed in 105~110 DEG C of baking ovens and is dried, is placed in spare in drying box.
Preferably, active material described in step 3) is obtained twice according to the heating calcination method roasting of program step gradient
Ozone catalyst.
A kind of application of the ozone catalyst using preceding method preparation, the removal field for TOC in pesticide waste water.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) present invention is given up using the ozone catalyst of program step gradient heating calcination method preparation in degrading pesticide class
Excellent catalytic effect is shown during water, the middle step temperature-raising method used is directly in certain high temperature compared with the prior art
The catalyst of lower firing, TOC removal rate significantly improves the catalyst of the method for the present invention preparation under the same conditions；
(2) present procedure step gradient heating calcination method, setup phase II are to generate aluminium oxide active crystal phase structure
Temperature stage is warming up to 200~300 DEG C with 3~5 DEG C/min, is constantly formed in this temperature rise period alumina crystalline phase, crystal phase surface
It shrinks and duct collapses, form fine-porous skeleton structure, be conducive to active component load and improve catalyst activity, protected in this stage
2~4h of temperature has the function of maintaining active catalyst crystal phase structure, keeps active component intensity of load；Setup phase III is activity
Component roasting molding temperature stage, the active site of active catalyst component are evenly distributed on alumina carrier surface, high temperature
Under the conditions of aluminium oxide formed skeleton structure have certain space steric effect be not easy to gather so that active component is uniformly distributed
Collection sintering, improves the contact between carrier and active component, increases the shaping efficiency and stability of catalyst, keeps dispersibility；
It is heated up with the rate of 3 DEG C/min, so that active constituent slowly and is equably generated metal oxide layer in oxidation aluminium surface, and keep
Material improves active site in the dispersibility of carrier surface, in 500~600 DEG C of 4~8h of heat preservation, has and maintains high activity crystalline substance picture
Structure, the effect for keeping active site to be evenly distributed, keeps the active component site distributed architecture of high dispersive, maintains catalyst
High degrading activity；
(3) active material is roasted twice according to program step gradient heating calcination method in the present invention, obtained ozone
Catalyst is relative to primary ozone catalyst is roasted, and catalytic effect further increases under the same conditions, this is because secondary
Relative to primary calcining, the active component not activated completely is further activated, increases the dispersibility of material, mention for calcining
The high active site of material；
(4) the method for the present invention prepares catalyst, and step is simple, easily controllable, more conducively the volume production of efficient ozone catalyst.
Detailed description of the invention
Fig. 1 is the step gradient heating calcination method schematic diagram that embodiment 4 uses；
Fig. 2 is the step temperature-raising method schematic diagram that comparative example 4 uses.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
The aluminium base precursor material that the present embodiment uses are as follows: aluminium isopropoxide, DEXTROSE ANHYDROUS.
Take aluminium isopropoxide 14.4g to be dissolved in 100mL deionized water, then plus 5g DEXTROSE ANHYDROUS, under the conditions of 35 DEG C
6h is stirred with the revolving speed of 400r/min in blender, makes to stir evenly completely；The material stirred evenly is placed in 105 DEG C
Drying to constant weight in baking oven, takes out stand-by；
Material after drying is placed in Muffle furnace, under air atmosphere, first 90 DEG C is warming up to 5 DEG C/min, keeps the temperature 1h,
Further, 200 DEG C are warming up to 3 DEG C/min, keep the temperature 2h, further, be warming up to 550 DEG C with 3 DEG C/min, 4h is kept the temperature, with 2
DEG C/min is cooled to room temperature, will prepare material clean 3 times of obtained catalyst deionized water, to remove catalyst granules
The metal ion and its oxide of excess surface.Material after washing is placed in 105 DEG C of baking ovens and is dried, is placed in standby in drying box
With.It obtains ozone catalyst and is denoted as Y-Al-1.
Comparative example 1
Other conditions are same as Example 1, the difference is that: directly 550 degrees Celsius are warming up to 5 DEG C/min, mono- step
The material blank of firing compares, and obtains ozone catalyst and is denoted as Y-Al-0.
The Typical Representative substance 2,4 dichlorophenoxyacetic acid (calling 2,4-D in the following text) in pesticide waste water is chosen as tested organic
Object pollutant, under conditions of selecting catalyst dosage 2.5g/L, ozone usage 3g/h, reaction time 80min, removal efficiency data
It is as follows:
The comparison of 1 ozone catalyst TOC removal efficiency of table
Experimental data shows that the ozone catalyst that the direct heating mode of comparative example 1 is prepared, TOC removal rate is slightly below
The catalyst of this program step gradient heating calcination method preparation.When reaction time is 80min, the TOC removal rate of two methods
Respectively 79.3% and 89.1%, it can be seen that heated up using the staged of embodiment 1, the ozone catalytic agent material of preparation has
Better catalytic effect.
Embodiment 2
The aluminium base precursor material that the present embodiment uses are as follows: aluminum nitrate.
It weighs 7.5g ANN aluminium nitrate nonahydrate to be placed in 250mL beaker, 60mL deionized water dissolving, 350r/min room temperature is added
The material stirred evenly, is placed in 105 DEG C of baking ovens that drying to constant weight by lower stirring 6h, is taken out stand-by；
Material after drying is placed in Muffle furnace, is first warming up to 90 DEG C with 5 DEG C/min, 1h is kept the temperature, further, with 3
DEG C/min is warming up to 200 DEG C, 2h is kept the temperature, further, 550 DEG C is warming up to 3 DEG C/min, keeps the temperature 4h, be cooled to 2 DEG C/min
Room temperature, will prepare material clean 5 times of obtained catalyst deionized water, to remove the extra gold of catalyst particle surface
Belong to ion and its oxide.Material after washing is placed in 110 DEG C of baking ovens and is dried, is placed in spare in drying box.Obtain ozone
Catalyst is denoted as X-Al-1.
Comparative example 2
Other conditions are same as Example 2, the difference is that: directly 550 degrees Celsius are warming up to 5 DEG C/min, mono- step
The material blank of firing compares, and obtains ozone catalyst and is denoted as X-Al-0；
The Typical Representative substance 2,4 dichlorophenoxyacetic acid (calling 2,4-D in the following text) in pesticide waste water is chosen as tested organic
Object pollutant, selecting catalyst dosage 2g/L, ozone flow 2L/min, ozone usage 3g/h, the condition of reaction time 80min
Under, removal efficiency data are as follows:
The comparison of 2 ozone catalyst TOC removal efficiency of table
It is analyzed from data as can be seen that being prepared using material prepared by step gradient heating calcination method compared with a step temperature-raising method
Material removal effect improve 8.3%, through the control group that compares, using the material of this method preparation in preceding 40min
Degradation rate faster, illustrates that the material of this method preparation has preferable catalytic effect.
Embodiment 3
The aluminium base precursor material that the present embodiment uses are as follows: alumina particle；Active component are as follows: Gerhardite.
The alumina particle catalyst for taking commercially available 2~4mm partial size, with grinder by particulate abrasive at 30~60 purposes thin
Grain weighs 30g catalyst, and 6.42g Gerhardite is added, and supported catalyst is placed in 110 DEG C after being stirred well to uniformly
It is dried in baking oven, then material taking-up is placed in ceramic crucible, is placed in Muffle furnace, is first warming up to 90 DEG C with 5 DEG C/min,
1h is kept the temperature, further, 200 DEG C is warming up to 3 DEG C/min, keeps the temperature 2h, further, 550 DEG C is warming up to 3 DEG C/min, protects
Warm 4h is cooled to room temperature with 2 DEG C/min, and will prepare material clean 4 times of obtained catalyst deionized water are urged with removal
The metal ion and its oxide of catalyst particles excess surface.Material after washing is placed in 110 DEG C of baking ovens and is dried, is placed in dry
It is spare in dry case.It is denoted as K-Al-1.
Comparative example 3
Other conditions are same as Example 2, the difference is that: 550 DEG C of firings are directly warming up to 5 DEG C/min, mono- step
Material blank control, be denoted as K-Al-10；
The Typical Representative substance 2,4 dichlorophenoxyacetic acid (calling 2,4-D in the following text) in pesticide waste water is chosen as tested organic
Object pollutant, selecting catalyst dosage 2.5g/L, ozone flow 2L/min, ozone usage 3g/h, the condition of reaction time 80min
Under, removal efficiency data are as follows:
The comparison of 3 ozone catalyst TOC removal efficiency of table
It is compared by experimental data it is known that the catalysis prepared by 3 step gradient of embodiment heating calcination method
Agent is 87.6% in the TOC removal rate of 80min, and the material removing rate than the preparation of 3 one-step method of comparative example improves 5.8%, and
The TOC degradation rate of preceding 40min relatively faster, illustrates that the catalyst that 3 method of embodiment is prepared has relatively better catalysis effect
Fruit.
Embodiment 4
The aluminium base precursor material that the present embodiment uses are as follows: aluminium isopropoxide, Dextrose Monohydrate；Active component are as follows: seven hydration nitre
Sour cobalt.
It weighs 14.4g aluminium isopropoxide to be dissolved in 100mL deionized water, 5g Dextrose Monohydrate is added, adds 4.2g's
Seven nitric hydrate cobalts, uniform stirring under the conditions of 25 DEG C are subsequently placed in 120 DEG C of baking ovens that drying to constant weight；Place the material in potteries
In porcelain crucible, in Muffle kiln roasting, the baking modes taken are program step gradient heating roasting method, and specific steps are such as
Under:
As shown in Figure 1, being first warming up to 90 DEG C with 5 DEG C/min, heat preservation 1h is further warming up to 200 DEG C with 3 DEG C/min,
2h is kept the temperature, further, 550 DEG C is warming up to 3 DEG C/min, keeps the temperature 5h, room temperature is cooled to 2 DEG C/min, obtained catalyst
Material clean 3 times will prepared with deionized water, to remove catalyst particle surface extra metal ion and its oxide.
Material after washing is placed in 105 DEG C of baking ovens and is dried, is placed in spare in drying box.It obtains ozone catalyst and is denoted as Y-Al-11.
Comparative example 4
Other conditions are same as Example 1, the difference is that: 550 DEG C of firings are directly warming up to 5 DEG C/min, mono- step
Material blank control, obtain ozone catalyst and be denoted as Y-Al-02, temperature-rise period is as shown in Figure 2.
The Typical Representative substance 2,4 dichlorophenoxyacetic acid (calling 2,4-D in the following text) in pesticide waste water is chosen as tested organic
Object pollutant, selecting catalyst dosage 2.5g/L, ozone flow 2L/min, ozone usage 3g/h, the condition of reaction time 80min
Under, removal efficiency data are as follows:
The comparison of 4 ozone catalyst TOC removal efficiency of table
Comparative test data, after load active component Co, the caltalyst for taking the method for the present invention to prepare reveals
Better catalytic performance, compared with a step temperature-raising method TOC removal rate in comparative example 4 improves 12%, and the degradation rate of preceding 40min
Relatively faster, twice or so of the further degradation rate of temperature-raising method is connect, the degradation reaction time is shortened.Illustrate the method for the present invention
The catalyst of preparation has certain superior function.
Embodiment 5
The aluminium base precursor material that the present embodiment uses are as follows: alumina particle；Active component are as follows: manganese nitrate.
It is small to be ground into 10~20 purposes with grinder by the alumina particle catalyst for taking commercially available 2~4mm partial size for catalyst
Particle.30g catalyst is weighed, 50% manganese nitrate solution of 4.53mL is added, sets supported catalyst after being stirred well to uniformly
It is dried in 110 DEG C of baking ovens, then material taking-up is placed in ceramic crucible, is placed in Muffle furnace, first with 5 DEG C/min heating
To 90 DEG C, 1h is kept the temperature, further, is warming up to 200 DEG C with 3 DEG C/min, heat preservation 2h is further warming up to 3 DEG C/min
550 DEG C, 6h is kept the temperature, room temperature is cooled to 2 DEG C/min, will prepare material clean 3 times of obtained catalyst deionized water,
To remove catalyst particle surface extra metal ion and its oxide.Material after washing is placed in 105 DEG C of baking ovens and is dried
It is dry, it is placed in spare in drying box.It obtains ozone catalyst and is denoted as K-Al-11.
Comparative example 5
Other conditions are same as Example 5, the difference is that: directly 550 degrees Celsius are warming up to 5 DEG C/min, mono- step
The material blank of firing compares, and obtains ozone catalyst and is denoted as K-Al-00.
The Typical Representative substance 2,4 dichlorophenoxyacetic acid (calling 2,4-D in the following text) in pesticide waste water is chosen as tested organic
Object pollutant, selecting catalyst dosage 2.5g/L, ozone flow 2L/min, ozone usage 3g/h, the condition of reaction time 80min
Under, removal efficiency data are as follows:
The comparison of 5 ozone catalyst TOC removal efficiency of table
It is gone using ozone catalyst prepared by the stage temperature-rising method of embodiment 5 compared to 5 one step temperature-raising method TOC of comparative example
Except rate improves 4.4%, mineralization of organic material degree is more thorough after illustrating reaction, illustrates that the catalyst is more applicable for the agriculture
The degradation of medicine waste water.
Embodiment 6
The catalyst baked in case study on implementation 3 is subjected to after baking, institute according to the method for roasting in case study on implementation 3
Obtained ozone catalyst is denoted as K-Al-2, chooses the Typical Representative substance 2 in pesticide waste water, 4- dichlorphenoxyacetic acid (under
Claim 2,4-D) it is used as tested organic pollutant, selecting catalyst dosage 2.5g/L, ozone flow 2L/min, ozone usage 3g/
Under conditions of h, reaction time 80min, removal efficiency data are as follows:
The comparison of 6 ozone catalyst TOC removal efficiency of table
It is found by data comparison, during the present embodiment, identical quadratic program step gradient liter is used to material
Warm therapy promotes the TOC removal rate for identical waste water of degrading again, illustrates the catalyst recycling performance of this method preparation
It is excellent, can be used as that the chemokine means after the reduction of rear catalyst activity are used for multiple times.
Embodiment 7
The other conditions of the present embodiment are same as Example 1, the difference is that: the additional amount of DEXTROSE ANHYDROUS is
8.5g, staged temperature-rising method are as follows: the material after drying is placed in Muffle furnace, is first warming up to 90 DEG C with 10 DEG C/min, heat preservation
1h is further warming up to 300 DEG C with 5 DEG C/min, keeps the temperature 4h, further, is warming up to 600 DEG C with 3 DEG C/min, keeps the temperature 8h,
Be cooled to room temperature with 1.6 DEG C/min, obtain ozone catalyst, in the catalyst and embodiment 1 catalyst under the same conditions, drop
The TOC removal rate effect for solving identical waste water is suitable.
Embodiment 8
The other conditions of the present embodiment are same as Example 1, the difference is that: the additional amount of DEXTROSE ANHYDROUS is
0.25g, staged temperature-rising method are as follows: the material after drying is placed in Muffle furnace, is first warming up to 90 DEG C with 8 DEG C/min, heat preservation
1h is further warming up to 250 DEG C with 4 DEG C/min, keeps the temperature 3h, further, is warming up to 500 DEG C with 3 DEG C/min, keeps the temperature 6h,
Be cooled to room temperature with 2 DEG C/min, obtain ozone catalyst, in the catalyst and embodiment 1 catalyst under the same conditions, degradation
The TOC removal rate effect of identical waste water is suitable.
Embodiment 9
The other conditions of the present embodiment are same as Example 3, the difference is that: Gerhardite is added and stirs evenly
Supported catalyst is placed in 60 DEG C of baking ovens afterwards and is dried, then obtains ozone catalyst through staged temperature-rising method, the catalyst with
In embodiment 1 catalyst under the same conditions, the TOC removal rate effect of the identical waste water of degradation it is suitable.
It discusses in process of the present invention in detail above, the catalyst of either different raw material preparations still loads difference
The catalyst of active component can be realized the promotion of catalyst catalytic performance, mine using staged Elevated Temperature Conditions of the invention
It is more thorough to change organic matter, improves the halfway Catalysis Today of ozone catalyst catalytic performance, the popularization to ozone catalyst
There is certain impetus.
It should be noted that those skilled in the art are it should be appreciated that in above-mentioned specific embodiment
Described operating procedure, it is only for illustrate the case study on implementation in process of the present invention, it is not limited to present invention itself, only
If all falling in claim model of the invention to variation, the modification of above-mentioned case study on implementation within the scope of true spirit
In enclosing.
Claims (10)
1. a kind of method of step gradient heating calcination method preparation ozone catalyst, which comprises the following steps:
1) aluminium base precursor material is added water and stirred uniformly, obtains reactive precursor material；
2) reactive precursor material is dried, obtains active material；
3) active material is roasted to obtain ozone catalyst, the method for roasting is program step gradient heating calcination method.
2. the method for step gradient heating calcination method preparation ozone catalyst according to claim 1, which is characterized in that
The heating calcination method of program step gradient described in step 3) are as follows:
Stage I: room temperature to discharge cold air forms the calcined precursors atmosphere stage；
Stage II: aluminium oxide active crystal phase structure temperature stage is generated；
Stage III: active component roasting molding temperature stage；
Stage IV: temperature-fall period.
3. the method for step gradient heating calcination method preparation ozone catalyst according to claim 2, which is characterized in that
Stage I is that 90~110 DEG C are warming up to 5~10 DEG C/min, keeps the temperature 1h；Stage II is to be warming up to 200~300 with 3~5 DEG C/min
DEG C, keep the temperature 2~4h；Stage III is that 500~600 DEG C are warming up to 3 DEG C/min, keeps the temperature 4~8h.
4. the method for gradient increased temperature calcination method preparation ozone catalyst according to claim 3, which is characterized in that the stage IV
To be cooled to 200~300 DEG C with 1~2 DEG C/min, then it is down to room temperature.
5. the method for step gradient heating calcination method preparation ozone catalyst according to claim 2, which is characterized in that
It further include DEXTROSE ANHYDROUS or Dextrose Monohydrate in the aluminium base precursor material.
6. the method for step gradient heating calcination method preparation ozone catalyst according to claim 5, which is characterized in that
The preparation method of the aluminium base precursor material include: by aluminium base precursor material aluminium containing salt and DEXTROSE ANHYDROUS or a water Portugal
Grape sugar is with the ratio between amount of substance for (1.5~50): 1 ratio mixing at 25~35 DEG C after mixing evenly, is placed in baking oven
105~120 DEG C of drying.
7. the method for step gradient heating calcination method preparation ozone catalyst according to claim 2 or 5, feature exist
In the reactive precursor material further includes active component, and the active component includes the nitric acid containing Mn, Cu, Fe, Co, Zn component
The mixing of one or more of salt, sulfate, hydrochloride, acetate, oxalates, persulfate.
8. the method for step gradient heating calcination method preparation ozone catalyst according to claim 7, which is characterized in that
The reactive precursor material obtained after aluminium base precursor material and active component are added water and stirred uniformly is dried, and the drying temperature is
60~120 DEG C, obtain active material.
The calcination method preparation ozone catalyst 9. step gradient described in any one of according to claim 1~6 or 8 heats up
Method, which is characterized in that obtain active material described in step 3) twice according to the heating calcination method roasting of program step gradient
To ozone catalyst.
10. a kind of method preparation using step gradient as claimed in claim 9 heating calcination method preparation ozone catalyst
The application of ozone catalyst, the removal field for TOC in pesticide waste water.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910026459.1A CN109718749B (en) | 2019-01-11 | 2019-01-11 | method for preparing ozone catalyst by stepped gradient temperature rise calcining method and application |
| AU2019101810A AU2019101810A4 (en) | 2019-01-11 | 2019-12-25 | Method for preparing ozone catalyst by means of stepped gradient temperature elevation calcination method and use thereof |
| AU2019421318A AU2019421318A1 (en) | 2019-01-11 | 2019-12-25 | Method for preparing ozone catalyst by means of stepped gradient temperature elevation calcination method and use thereof |
| PCT/CN2019/128257 WO2020143450A1 (en) | 2019-01-11 | 2019-12-25 | Method for preparing ozone catalyst by means of stepped gradient temperature elevation calcination method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910026459.1A CN109718749B (en) | 2019-01-11 | 2019-01-11 | method for preparing ozone catalyst by stepped gradient temperature rise calcining method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109718749A true CN109718749A (en) | 2019-05-07 |
| CN109718749B CN109718749B (en) | 2019-12-13 |
Family
ID=66299005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910026459.1A Active CN109718749B (en) | 2019-01-11 | 2019-01-11 | method for preparing ozone catalyst by stepped gradient temperature rise calcining method and application |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN109718749B (en) |
| AU (2) | AU2019421318A1 (en) |
| WO (1) | WO2020143450A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020143450A1 (en) * | 2019-01-11 | 2020-07-16 | 南京大学盐城环保技术与工程研究院 | Method for preparing ozone catalyst by means of stepped gradient temperature elevation calcination method and use thereof |
| CN111437818A (en) * | 2020-04-28 | 2020-07-24 | 盐城师范学院 | Novel heterogeneous ozone catalyst for treating wastewater and preparation method thereof |
| CN112452338A (en) * | 2020-12-24 | 2021-03-09 | 江苏治水有数环保科技有限公司 | Ozone catalytic oxidation catalyst for advanced treatment of badan pesticide wastewater and preparation method thereof |
| CN112827497A (en) * | 2020-12-31 | 2021-05-25 | 福建省农业科学院农业工程技术研究所 | Preparation method of ozone catalytic material |
| CN113171783A (en) * | 2021-04-21 | 2021-07-27 | 中化环境科技工程有限公司 | Microporous honeycomb ozone catalyst and preparation method and application thereof |
| CN114433071A (en) * | 2021-12-29 | 2022-05-06 | 江苏世清环保科技有限公司 | Denitration catalyst prepared by taking attapulgite as carrier and preparation method thereof |
| CN115959711A (en) * | 2022-12-21 | 2023-04-14 | 江苏宇星科技有限公司 | Preparation process of high-dispersity iron oxide |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111992204B (en) * | 2020-09-17 | 2022-07-19 | 福建省晋蓝环保科技有限公司 | Ozone oxidation catalyst, preparation method and ozone catalytic oxidation device |
| CN113198462B (en) * | 2021-03-29 | 2022-07-19 | 中山大学 | Ozone catalytic oxidation catalyst and preparation method and application thereof |
| CN114111228A (en) * | 2021-06-16 | 2022-03-01 | 合肥国轩高科动力能源有限公司 | Lithium battery rapid drying method |
| CN113941316A (en) * | 2021-11-30 | 2022-01-18 | 武夷学院 | Method for preparing biochar by modifying excess sludge of urban sewage plant |
| CN114433055B (en) * | 2022-03-10 | 2022-12-23 | 苏州大学 | Carbon catalyst with highly-open hierarchical pore structure and preparation method and application thereof |
| CN114904506A (en) * | 2022-04-28 | 2022-08-16 | 济南市环境研究院(济南市黄河流域生态保护促进中心) | Ozone catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005005799A1 (en) * | 2003-07-09 | 2005-01-20 | Robert Bosch Gmbh | Cooled device for metering reducing agent to the exhaust gas of a combustion engine |
| CN108097231A (en) * | 2017-12-27 | 2018-06-01 | 苏州大学 | A kind of ozone oxidation catalyst and its preparation method and application |
| CN108246299A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | The deep treatment method of ozone oxidation catalyst, preparation method and sewage |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4895388A (en) * | 1972-03-21 | 1973-12-07 | ||
| CN108435180A (en) * | 2018-02-05 | 2018-08-24 | 北京铭泽源环境工程有限公司 | A kind of support type ozone high grade oxidation catalyst and preparation method thereof |
| CN108452799B (en) * | 2018-05-10 | 2021-06-22 | 北京化工大学 | Preparation method of supported silver catalyst and application of supported silver catalyst in preparation of benzaldehyde by catalyzing anaerobic dehydrogenation of benzyl alcohol |
| CN108970620A (en) * | 2018-07-26 | 2018-12-11 | 大连海川博创环保科技有限公司 | A kind of preparation method removing Organic substance in water and total nitrogen ozone oxidation catalyst |
| CN109718749B (en) * | 2019-01-11 | 2019-12-13 | 南京大学盐城环保技术与工程研究院 | method for preparing ozone catalyst by stepped gradient temperature rise calcining method and application |
-
2019
- 2019-01-11 CN CN201910026459.1A patent/CN109718749B/en active Active
- 2019-12-25 AU AU2019421318A patent/AU2019421318A1/en active Pending
- 2019-12-25 WO PCT/CN2019/128257 patent/WO2020143450A1/en active Application Filing
- 2019-12-25 AU AU2019101810A patent/AU2019101810A4/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005005799A1 (en) * | 2003-07-09 | 2005-01-20 | Robert Bosch Gmbh | Cooled device for metering reducing agent to the exhaust gas of a combustion engine |
| CN108246299A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | The deep treatment method of ozone oxidation catalyst, preparation method and sewage |
| CN108097231A (en) * | 2017-12-27 | 2018-06-01 | 苏州大学 | A kind of ozone oxidation catalyst and its preparation method and application |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020143450A1 (en) * | 2019-01-11 | 2020-07-16 | 南京大学盐城环保技术与工程研究院 | Method for preparing ozone catalyst by means of stepped gradient temperature elevation calcination method and use thereof |
| CN111437818A (en) * | 2020-04-28 | 2020-07-24 | 盐城师范学院 | Novel heterogeneous ozone catalyst for treating wastewater and preparation method thereof |
| CN112452338A (en) * | 2020-12-24 | 2021-03-09 | 江苏治水有数环保科技有限公司 | Ozone catalytic oxidation catalyst for advanced treatment of badan pesticide wastewater and preparation method thereof |
| CN112827497A (en) * | 2020-12-31 | 2021-05-25 | 福建省农业科学院农业工程技术研究所 | Preparation method of ozone catalytic material |
| CN113171783A (en) * | 2021-04-21 | 2021-07-27 | 中化环境科技工程有限公司 | Microporous honeycomb ozone catalyst and preparation method and application thereof |
| CN113171783B (en) * | 2021-04-21 | 2023-03-21 | 中化环境科技工程有限公司 | Microporous honeycomb ozone catalyst and preparation method and application thereof |
| CN114433071A (en) * | 2021-12-29 | 2022-05-06 | 江苏世清环保科技有限公司 | Denitration catalyst prepared by taking attapulgite as carrier and preparation method thereof |
| CN115959711A (en) * | 2022-12-21 | 2023-04-14 | 江苏宇星科技有限公司 | Preparation process of high-dispersity iron oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109718749B (en) | 2019-12-13 |
| AU2019421318A1 (en) | 2021-06-24 |
| WO2020143450A1 (en) | 2020-07-16 |
| AU2019101810A4 (en) | 2021-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109718749A (en) | The method and application of step gradient heating calcination method preparation ozone catalyst | |
| CN109647431A (en) | A kind of catalyst, preparation method and the usage for catalytic ozonation processing used water difficult to degradate | |
| CN109174141A (en) | A kind of preparation method of composite Nano catalysis material | |
| CN104289250A (en) | Loaded type ozone catalyst and preparation method and application thereof | |
| CN106268908A (en) | A kind of graphite-phase C removing removal organic polluter3n4doping TiO2float type ecological restoration material of load expanded perlite and preparation method thereof | |
| CN109731574A (en) | A kind of preparation method of catalyst complex carrier, the catalyst based on the carrier and catalyst | |
| CN105727927B (en) | A kind of netted high efficiency photocatalyst BiVO4Preparation method | |
| CN105013500B (en) | Heterogeneous fenton catalyst of degrading azoic dye waste water and its production and use | |
| CN102500356A (en) | Preparation method for carbon nanotube-nano-bismuth vanadate composite photocatalyst | |
| CN106745170A (en) | A kind of cobalt doped cerium oxide nano materials of laminated structure and its preparation and application | |
| CN102489290A (en) | Preparation method of nano bismuth vanadate photocatalyst loaded on active carbon fiber | |
| CN105727921B (en) | A kind of nano-TiO2Diatomite composite photocatalytic agent and preparation method thereof | |
| CN108479772B (en) | Gold-doped nano zinc oxide composite material, preparation method thereof and application thereof in photocatalytic degradation of tetracycline | |
| CN114392762A (en) | Two-dimensional MXene nano-structure based composite material and preparation method thereof | |
| CN108855084A (en) | A method of high porosity ozone oxidation nbsCOD catalyst is prepared using Fenton iron cement | |
| US20210170385A1 (en) | Fabrication process for efficient visible light photocatalysts | |
| CN105289577A (en) | Vanadium tantalum/niobate photocatalyst and preparation method and application of vanadium tantalum/niobate photocatalyst | |
| WO2020093517A1 (en) | Photocatalytic material for efficient and selective reduction and removal of nitrate nitrogen in water, and preparation method thereof | |
| CN106925253A (en) | A kind of preparation method of nanoscale ozone oxidation catalyst and application | |
| CN106345474A (en) | Solid-phase compound type ozone oxidation catalyst and preparation method thereof | |
| CN109317146A (en) | A kind of magnetic oxygenated graphene composite catalyst of titanium dioxide-and preparation method thereof | |
| CN111450854B (en) | Efficient nano photo-Fenton catalyst and preparation method thereof | |
| CN109621975B (en) | Supported ozone catalytic oxidation catalyst and preparation method and application thereof | |
| CN115090319B (en) | Ozone catalyst and preparation method and application thereof | |
| CN109529815A (en) | A kind of preparation method of the modified manganese oxide molecular sieve catalyzer of base metal of catalysis burning toluene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |