CN110302797A - A kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation and its application - Google Patents
A kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation and its application Download PDFInfo
- Publication number
- CN110302797A CN110302797A CN201910616352.2A CN201910616352A CN110302797A CN 110302797 A CN110302797 A CN 110302797A CN 201910616352 A CN201910616352 A CN 201910616352A CN 110302797 A CN110302797 A CN 110302797A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hypergravity
- dipping
- carrier
- waste water
- 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.)
- Pending
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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to loaded catalyst preparation and technical field of waste water processing, the problems such as loaded catalyst active component dispersion degree is not high, load is uneven, load capacity is low, the production cycle is long is prepared for current infusion process, bi-component manganese base supported catalyst and its application of a kind of preparation of hypergravity spray-stain method are provided, cross flow type is rotary packed bed to make hypergravity equipment, γ-Al2O3As filler, metal mixed salt solution makees maceration extract, so that maceration extract is sprayed the liquid after carrier surface, dipping under hypergravity effect and returns to reservoir circulation dipping, hot-air stripping filler removes presoma surface moisture；300 ~ 700 DEG C of high-temperature roastings are to get bi-component manganese base supported catalyst.Catalyst obtained makees filler, using aerator as contact reactor, above-mentioned catalyst is added, make nitrobenzene waste water and the ozone gas haptoreaction under catalyst, the catalyst prepared has that active component is uniformly dispersed, large specific surface area, catalytic activity are high, advantage with short production cycle.
Description
Technical field
The invention belongs to loaded catalyst preparation and technical field of waste water processing, and in particular to a kind of hypergravity spray-stain method
The bi-component manganese base supported catalyst of preparation and its application, the catalyst are useless for heterogeneous catalysis ozone oxidation nitrobenzene
Water.
Background technique
Heterogeneous catalysis ozone Oxidation Treatment organic wastewater using the absorption of catalyst, is urged by introducing solid catalyst
Change characteristic, catalysis ozone, which decomposes, generates more OH free radicals, and causes a series of radical chain reaction, to thoroughly drop
Solve the persistent organic pollutants in waste water.Heterogeneous catalysis has high catalytic activity, mineralization of organic material rate height, without secondary dirt
It contaminates, be easily recycled the advantages of processing, thus receive significant attention.It focuses primarily upon metal composite oxide at present and support type is urged
The development of the solid catalysts such as agent, modified mineral.
Loaded catalyst includes the (CN 102091619 such as aluminium oxide, molecular sieve, ceramics, active carbon with porous material
B, 2012.10.24；CN 101811049 B, 2013.03.27；CN 106311270 B, 2018.09.11；CN 103586026
A ,2014.02.19；CN 105289585 B, 2018.04.03) it is carrier, by Determination of multiple metal elements or metal oxide supported
Thereon, in conjunction with the interaction of carrier and active component, the dissolution of metal ion is avoided, enhances its catalytic activity, and have both
The good advantage of carrier large specific surface area itself, high mechanical strength and thermal stability.Metal member currently used for heterogeneous catalysis
Element mainly has noble metal, transition metal and rare-earth metal series.Wherein transition metal price is relatively cheap, raw material is easy to get, is catalyzed
Activity is high and is concerned.And its catalytic activity of manganese catalyst series is the most prominent, is most widely used, but its anti-SO2With it is anti-
H2The ability of O is poor, needs to adulterate other components to improve its catalytic activity.Common carrying method have infusion process, the precipitation method,
Mixing method, ion-exchange etc., wherein infusion process principle is when active component solution is contacted with porous carrier in capillary pressure
It is penetrated into inside support voids under effect, the process with absorption is diffused in inner surface of the carrier.This method is simple, raw material is sharp
It is low with rate height, economic cost, it is easy to industrial application.The patent of invention of 106311270 B of Publication No. CN with grain active carbon or
Y type molecular sieve prepares ozone oxidation catalyst as active component as carrier, using the oxide of iron, molybdenum, tantalum, potassium, manganese, is used for
Catalytic ozonation degradation coking wastewater and agricultural chemicals waste water, TOC removal rate reach 90% or more.105289585 B of publication number CN
Patent of invention using active carbon as carrier, iron and manganese oxides are as active component, and sodium hydroxide is as precipitating reagent, using leaching
The stain precipitation method prepare loaded catalyst, handle dyeing waste water for O3 catalytic oxidation, can reach Treatment of Industrial Water discharge
Standard.
But in above-mentioned preparation process, solute is limited by diffusion absorption and is easy in catalyst drying process migration,
Lead to the problem of active component poor dispersion, load are uneven, active site is reduced.For equi-volume impregnating, activity
Component dispersion degree is very poor, and granular size is different；Excessive infusion process, immersion period is long, the bad control of load capacity；And dipper precipitation
Method, sedimentation cycle is long, easily formation egg-shell catalyst.Therefore it provides a kind of active component dispersion degree height, Load Balanced, comparing table
Area is big, activity is high, loaded catalyst preparation method with short production cycle, is of great significance.
High-gravity technology (High Gravity Technology, Higee) is strengthened as a kind of novel chemical process
Technology generates super gravity field by the high speed rotation of packed bed, make air-liquid under Elevated Gravity porous media or duct in
Liquid shear is very thin liquid film and small liquid mist, drop by flowing, huge shearing force, increases phase boundary specific surface area,
Phase interface renewal rate is accelerated, to greatly improve mass transfer rate, the microcosmic mixing alternate for two has traditional reactor
Incomparable advantage can be widely applied to the chemical processes such as absorption, rectifying, extraction, absorption.
Summary of the invention
Prepare that the generally existing active component dispersion degree of loaded catalyst is not high, load is uneven for current infusion process
Even, the problems such as load capacity is low, the production cycle is long, the present invention is intended to provide a kind of preparation bi-component manganese base load of hypergravity spray-stain method
Type catalyst and the method and device for being used for O3 catalytic oxidation nitrobenzene waste water, in conjunction with the hypergravity that can strengthen gas-liquid-solid mass transfer
Equipment, loaded catalyst active component dispersion degree height, Load Balanced, the activity height, with short production cycle, catalytic activity of preparation
It is high.
Hypergravity equipment of the present invention is the cross_flow rotating packed bed (CN having disclosed
201510093434.5), packing layer is the mixing filled layer of wire packing and carrier.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of bi-component manganese of hypergravity spray-stain method preparation
Base supported catalyst, it is rotary packed bed as hypergravity equipment using cross flow type, with carrier γ-Al2O3As filler, metal salt
Mixed solution makes maceration extract aerosol dispersion under hypergravity effect, sprays the liquid after carrier surface, dipping as maceration extract
It returns to reservoir and just recycles dipping, hot-air stripping filler removes presoma surface moisture；Then through 300 ~ 700 DEG C of high temperature
Roasting is to get bi-component manganese base supported catalyst.
In the metal mixed salt solution concentration of metal ions proportion be M: Mn=1:1,1:2,1:4, M Cu or
Fe, in terms of total concentration of metal ions, concentration of salt solution is 0.1 ~ 0.3 mol/L.
γ-the Al2O3Diameter of carrier is 1-2 mm, and loading is 50 g/L.
The method for preparing the catalyst, the specific steps are as follows:
(1) impregnation: γ-Al2O3Filling even enters cross_flow rotating packed bed after Vehicle element；Metal salt is mixed with dipping
Liquid is placed in reservoir, is pumped into cross_flow rotating packed bed inner cavity through circulation, maceration extract is uniformly sprayed at via liquid distribution trough
Carrier bed inner edge radially comes into full contact with dipping under the effect of high speed centrifugation power with Sprayable and carrier, the liquid after dipping
Body returns to reservoir and carries out circulation dipping；
(2) high-temperature roasting: after the completion of dipping, being passed through 120 DEG C of hot-airs and carry out stripping to bed, remove presoma surface moisture,
Fixed active component, through 300-700 DEG C of high-temperature roasting.
γ-Al2O3Vehicle element method are as follows: deionized water is cleaned to neutrality, dry 4 h at 105 DEG C, is roasted at 300 DEG C
4 h。
Rotary packed bed revolving speed described in step (1) is 600-1200rpm, fluid flow 40-100L/h, circulation dipping
Time is 30-60min.
The hot-air stripping time is 60min, calcining time 3-6h.
Application of the catalyst in heterogeneous catalysis ozone oxidation nitrobenzene waste water, concrete application method are as follows: will be upper
It states catalyst to be placed in above contact reactor microporosity separator, reactor is provided with 1 L nitrobenzene waste water (100 mg/L), and ozone is certainly
Ozone generator generates after gas flowmeter measures that (gas phase ozone is dense by the dispersion of the porous aeration head of contact reactor bottom
Degree is 50 mg/L), it is reacted with catalyst and nitrobenzene waste water rapidly, the time is from sample tap sampling analysis at certain intervals,
The catalytic activity of the catalyst is evaluated according to the degradation rate of nitrobenzene waste water and TOC removal rate.
The present invention utilizes high-gravity technology, rotary packed bed as hypergravity equipment, catalyst carrier conduct using cross flow type
Filler makes maceration extract aerosol dispersion under super gravity field, is sprayed with liquid mist, drop state in high-speed rotating carrier surface, high
The fine drop of dispersion and the phase interface of continuous renewal are spent, scattering and permeating speed of the solute in carrier hole can be effectively improved
Rate improves the load capacity of active component, promotes active component in the uniform adsorption of carrier surface, greatly shortens dip time.Together
When, further is shortened by the production cycle, is finally fired using the quick stripping of hot-air for the drying process of shaping carrier, is made
Standby active component dispersion degree height out, even particle size, activity height, loaded catalyst with short production cycle.
Later using aerator as contact reactor, above-mentioned catalyst is added, nitrobenzene waste water and ozone gas is made to exist
Haptoreaction under catalyst, treated, and nitrobenzene waste water is analyzed from sample tap direct sample, according to nitrobenzene waste water
Degradation rate and TOC removal rate evaluate the catalytic activity of the catalyst.
The present invention utilizes high-gravity technology, with carrier γ-Al2O3As filler, make maceration extract aerosol dispersion, with liquid mist, liquid
Drop-wise state is sprayed in high-speed rotating carrier surface, the fine drop of high degree of dispersion and the phase interface of continuous renewal, can be effective
Scattering and permeating rate of the solute in carrier hole is improved, the load capacity of active component is improved, promotes active component in carrier table
The uniform adsorption in face, greatly shortening dip time, (the conventional excess impregnation time is 12 ~ 24 h, and hypergravity spray-stain method
Dip time is 30-60 min, and load capacity is about 2 ~ 4 times of conventional impregnation method).
For the drying process of shaping carrier in super gravity field, using quick 60 min of stripping of 120 DEG C of hot-airs, further
Shorten the production cycle, while with mm grades of spherical gamma-Al2O3As carrier, the forming process in catalyst later period is eliminated, is prepared
Catalyst have that active component is uniformly dispersed, large specific surface area, catalytic activity are high, advantage with short production cycle.
Detailed description of the invention
Fig. 1 is the process flow chart that hypergravity spray-stain method of the present invention prepares bi-component manganese base supported catalyst；Figure
In: 1.1- reservoir；1.2- cross_flow rotating packed bed；1.3- motor；1.4- carrier；1.5- flowmeter；1.6- valve；1.7-
Pump；1.8- blower；1.9- preheater；
Fig. 2 is the Experimental equipment of catalyst ozone oxidation degrading nitrobenzene waste water prepared by the present invention；In figure: 2.1-
Ozone generator；2.2- valve；2.3- aeration head；2.4- flowmeter；2.5- catalyst；2.6- contact reactor；2.7- micropore
Partition；2.8- tail gas absorption bottle；
Fig. 3 is the XRD diagram of catalyst prepared by embodiment 2.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawings and detailed description.But the content of present invention not by
Following embodiments are limited to.
Embodiment 1: using process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, repeatedly with deionized water
It cleans, dry 4 h at 105 DEG C, roasts 4 h at 300 DEG C, filling even enters rotary packed bed after cooling, and loading is 40 g/L.
Molar ratio 1:2 copper nitrate, manganese acetate metal mixed salt solution are prepared by 0.18 mol/L, adjusting pH is 5.0, is placed in reservoir.
Maceration extract is pumped into cross_flow rotating packed bed through circulation, fluid flow is 40 L/h, and revolving speed is set as 600 rpm, makes it
Dipping is come into full contact with carrier, circulation dip time is 30 min.Then lead to 60 min of hot-air to take away catalyst surface water
Point, fix active component.It takes out catalyst and roasts 4 h at 500 DEG C to get Cu-Mn/ γ-Al2O3Catalyst.
Embodiment 2: using process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, repeatedly with deionized water
It cleans, dry 4h at 105 DEG C, roasts 4h at 300 DEG C, filling even enters rotary packed bed after cooling, and loading is 80 g/L.It presses
0.3 mol/L prepares molar ratio 1:1 copper nitrate, manganese acetate metal mixed salt solution, and adjusting pH is 5.0, is placed in reservoir.It will leaching
Stain liquid is pumped into cross_flow rotating packed bed through circulation, and fluid flow is 60 L/h, and revolving speed is set as 1200 rpm, makes itself and load
Body comes into full contact with dipping, and circulation dip time is 60 min.Then lead to 60 min of hot-air to take away catalyst surface moisture, make
Active component is fixed.It takes out catalyst and roasts 3 h at 700 DEG C to get Cu-Mn/ γ-Al2O3Catalyst.
Embodiment 3: using process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, repeatedly with deionized water
It cleans, dry 4 h at 105 DEG C, roasts 4 h at 300 DEG C, filling even enters rotary packed bed after cooling, and loading is 50 g/L.
Molar ratio 1:4 copper nitrate, manganese acetate metal mixed salt solution are prepared by 0.15 mol/L, adjusting pH is 5.0, is placed in reservoir.
Maceration extract is pumped into cross_flow rotating packed bed through circulation, fluid flow is 60 L/h, and revolving speed is set as 800 rpm, makes it
Dipping is come into full contact with carrier, circulation dip time is 30 min.Then lead to 60 min of hot-air to take away catalyst surface water
Point, fix active component.It takes out catalyst and roasts 4 h at 500 DEG C to get Cu-Mn/ γ-Al2O3Catalyst.
Embodiment 4: using process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, repeatedly with deionized water
It cleans, dry 4h at 105 DEG C, roasts 4h at 300 DEG C, filling even enters rotary packed bed after cooling, and loading is 50 g/L.It presses
0.1 mol/L prepares molar ratio 1:1 ferric nitrate, manganese acetate metal mixed salt solution, and adjusting pH is 5.0, is placed in reservoir.It will leaching
Stain liquid is pumped into cross_flow rotating packed bed through circulation, and fluid flow is 60 L/h, and revolving speed is set as 1200 pm, makes itself and load
Body comes into full contact with dipping, and circulation dip time is 40 min.Then lead to 60 min of hot-air to take away catalyst surface moisture, make
Active component is fixed.It takes out catalyst and roasts 6 h at 300 DEG C to get Fe-Mn/ γ-Al2O3Catalyst.
Embodiment 5: using process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, repeatedly with deionized water
It cleans, dry 4 h at 105 DEG C, roasts 4 h at 300 DEG C, filling even enters rotary packed bed after cooling, and loading is 50 g/L.
Molar ratio 1:2 ferric nitrate, manganese acetate metal mixed salt solution are prepared by 0.15 mol/L, adjusting pH is 5.0, is placed in reservoir.
Maceration extract is pumped into cross_flow rotating packed bed through circulation, fluid flow is 100 L/h, and revolving speed is set as 600 pm, makes it
Dipping is come into full contact with carrier, circulation dip time is 40 min.Then lead to 60 min of hot-air to take away catalyst surface water
Point, fix active component.It takes out catalyst and roasts 4 h at 500 DEG C to get Fe-Mn/ γ-Al2O3Catalyst.
Embodiment 6: using process flow shown in Fig. 1, with 1-2 mm spherical gamma-Al2O3For carrier, repeatedly with deionized water
It cleans, dry 4 h at 105 DEG C, roasts 4 h at 300 DEG C, filling even enters rotary packed bed after cooling, and loading is 50 g/L.
Molar ratio 1:4 ferric nitrate, manganese acetate metal mixed salt solution are prepared by 0.2 mol/L, adjusting pH is 5.0, is placed in reservoir.It will
Maceration extract is pumped into cross_flow rotating packed bed through circulation, and fluid flow is 60 L/h, and revolving speed is set as 800 pm, makes itself and load
Body comes into full contact with dipping, and circulation dip time is 30 min.Then lead to 60 min of hot-air to take away catalyst surface moisture, make
Active component is fixed.It takes out catalyst and roasts 2 h at 700 DEG C to get Fe-Mn/ γ-Al2O3Catalyst.
Embodiment 7: using catalyst made from embodiment 1, O3 catalytic oxidation treatment of Nitrobenzene waste water.Utilize Fig. 2 institute
Show experimental provision, above-mentioned catalyst is placed in above contact reactor microporosity separator, ozone is generated from ozone generator through gas
Dispersed after flowmeter metering by the porous aeration head of contact reactor bottom, is carried out with catalyst and nitrobenzene waste water rapidly anti-
It answers.
Treated, and nitrobenzene waste water is analyzed from sample tap direct sample, and the degradation rate of nitrobenzene is gone up to 100%, TOC
Except rate is up to 82%, compared with independent ozone oxidation system, TOC removal rate about improves 60%.
By Cu-Mn/ γ-Al prepared by example 22O3Catalyst carries out carry out X-ray diffraction, and diffracting spectrum is shown in Fig. 3, by
Fig. 3 shows that Cu active component is carried on carrier surface it can be seen that there are the characteristic peak of CuO, and Mn is without obvious characteristic peak, main
It will be since using manganese acetate as presoma, the Mn oxide of formation be existed with amorphous forms or is dispersed in lesser particle form
Carrier surface further proves the catalyst activity component good dispersion of hypergravity spray-stain method preparation.
Table 1 is the bi-component manganese-based catalyst catalytic ozonation results of property table under different preparation conditions.It can be seen by table 1
Bicomponent catalyst activity component load quantity out using the preparation of hypergravity spray-stain method is high, and the degradation rate of nitrobenzene can reach
100%；Compared with independent ozone oxidation system, TOC removal rate about improves 60%.Show the catalyst effect of this method preparation
Fruit is significant.
Catalyst under the different preparation conditions of table 1 ozonizes results of property
| Content of metal/wt% | Nitrobenzene degradation rate/% | TOC removal rate/% | |
| Embodiment 1 | 9.6 | 100 | 82.0 |
| Embodiment 2 | 13.8 | 95.5 | 67.8 |
| Embodiment 3 | 8.7 | 99.3 | 74.6 |
| Embodiment 4 | 6.2 | 96.1 | 61.7 |
| Embodiment 5 | 9.2 | 100 | 78.2 |
| Embodiment 6 | 10.9 | 99.4 | 75.3 |
Claims (8)
1. a kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation, it is characterised in that: with cross flow type rotary filling
Bed is expected as hypergravity equipment, with carrier γ-Al2O3As filler, metal mixed salt solution is as maceration extract, in overweight masterpiece
Make maceration extract aerosol dispersion under, sprays the return reservoir of the liquid after carrier surface, dipping and just recycle dipping, hot-air
Stripping carrier removes catalyst surface moisture；300 ~ 700 DEG C of high-temperature roastings of catalyst are then taken out to get catalyst.
2. a kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation according to claim 1, feature
Be: concentration of metal ions proportion is M: Mn=1:1,1:2,1:4 in the metal mixed salt solution, and M is Cu or Fe, with total
Concentration of metal ions meter, concentration of salt solution are 0.10 ~ 0.30 mol/L.
3. a kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation according to claim 1, feature
It is: the γ-Al2O3Diameter of carrier is 1-2 mm, and loading is 50 g/L.
4. the method for preparing claims 1 or 2 or 3 catalyst, it is characterised in that: specific step is as follows:
(1) impregnation: γ-Al2O3Filling even enters cross_flow rotating packed bed after Vehicle element；Metal salt is mixed with dipping
Liquid is placed in reservoir, is pumped into cross_flow rotating packed bed inner cavity through circulation, maceration extract is uniformly sprayed at via liquid distribution trough
Carrier bed inner edge radially comes into full contact with dipping under the effect of high speed centrifugation power with Sprayable and carrier, the liquid after dipping
Body returns to reservoir and carries out circulation dipping；
(2) high-temperature roasting: after the completion of dipping, being passed through 120 DEG C of hot-airs and carry out stripping to bed, remove catalyst surface moisture,
Fixed active component, takes out 300-700 DEG C of high-temperature roasting after catalyst.
5. the method according to claim 4 for preparing catalyst, it is characterised in that: γ-Al2O3Vehicle element method are as follows:
Deionized water is cleaned to neutrality, dry 4 h at 105 DEG C, roasts 4 h at 300 DEG C.
6. the method according to claim 4 for preparing catalyst, it is characterised in that: rotary packed bed described in step (1)
Revolving speed is 600-1200 rpm, and fluid flow is 40-100 L/h, and circulation dip time is 30-60 min.
7. the method according to claim 4 for preparing catalyst, it is characterised in that: the hot-air stripping time is 60
Min, calcining time are 3-6 h.
8. application of the catalyst according to claim 1 or 2 in heterogeneous catalysis ozone oxidation nitrobenzene waste water, special
Sign is: concrete application method are as follows: catalyst is placed in above contact reactor microporosity separator, and it is 100 that reactor, which is provided with concentration,
The 1 L nitrobenzene waste water of mg/L, ozone is generated from ozone generator passes through contact reactor bottom after gas flowmeter measures
Porous aeration head dispersion, gas phase ozone concentration be 50 mg/L, reacted with catalyst and nitrobenzene waste water rapidly, be spaced
Time, from sample tap sampling analysis, the catalytic activity of the catalyst was evaluated according to the degradation rate of nitrobenzene waste water and TOC removal rate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910616352.2A CN110302797A (en) | 2019-07-09 | 2019-07-09 | A kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910616352.2A CN110302797A (en) | 2019-07-09 | 2019-07-09 | A kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation and its application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110302797A true CN110302797A (en) | 2019-10-08 |
Family
ID=68080006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910616352.2A Pending CN110302797A (en) | 2019-07-09 | 2019-07-09 | A kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110302797A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111063534A (en) * | 2019-12-09 | 2020-04-24 | 江苏奥玛德新材料科技有限公司 | Manufacturing process of high-filling easy-cutting iron-based amorphous nanocrystalline alloy iron core |
| CN112331866A (en) * | 2020-11-06 | 2021-02-05 | 中北大学 | Fe/Co-N-MCF composite catalyst for fuel cell and preparation method thereof |
| CN112657517A (en) * | 2020-12-29 | 2021-04-16 | 北京化工大学 | Preparation method of molybdenum disulfide-based nano catalytic material |
| CN112675808A (en) * | 2020-11-19 | 2021-04-20 | 中北大学 | Hypergravity preparation method and application of nano ferrous sulfide composite material |
| CN114289027A (en) * | 2021-11-24 | 2022-04-08 | 山东华特环保科技有限公司 | Efficient composite ozone catalyst and preparation method and application thereof |
| CN114632524A (en) * | 2022-05-18 | 2022-06-17 | 中国环境科学研究院 | Copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment and preparation method thereof |
| CN114768826A (en) * | 2022-04-28 | 2022-07-22 | 北京清新环境技术股份有限公司 | Catalyst, rotary steaming, dipping and drying method thereof and application |
| CN115624970A (en) * | 2022-08-18 | 2023-01-20 | 扬州博克莱生物医药科技有限公司 | Catalyst for reducing nitro compound by continuous liquid phase hydrogenation of micro-fixed bed, and preparation method and application thereof |
| CN115845872A (en) * | 2022-12-14 | 2023-03-28 | 北京化工大学 | Method for preparing monolithic catalyst by using supergravity reactor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040982A (en) * | 1976-01-12 | 1977-08-09 | Nalco Chemical Company | Ozonization catalyst |
| US20120228237A1 (en) * | 2009-11-30 | 2012-09-13 | Harbin Institute Of Technology | Advanced Treatment Method of Feed Water by Combination of Metal Zinc and Ozone |
| CN105013504A (en) * | 2015-07-20 | 2015-11-04 | 华南理工大学 | Loaded binary composite metal oxide catalytic ozonation catalyst and preparation method thereof |
| CN108854931A (en) * | 2018-07-06 | 2018-11-23 | 中北大学 | A kind of device and method preparing metallic catalyst |
| CN108855199A (en) * | 2017-05-08 | 2018-11-23 | 天津工业大学 | A kind of composite catalyst and preparation method thereof for catalytic ozonation processing industrial wastewater |
-
2019
- 2019-07-09 CN CN201910616352.2A patent/CN110302797A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040982A (en) * | 1976-01-12 | 1977-08-09 | Nalco Chemical Company | Ozonization catalyst |
| US20120228237A1 (en) * | 2009-11-30 | 2012-09-13 | Harbin Institute Of Technology | Advanced Treatment Method of Feed Water by Combination of Metal Zinc and Ozone |
| CN105013504A (en) * | 2015-07-20 | 2015-11-04 | 华南理工大学 | Loaded binary composite metal oxide catalytic ozonation catalyst and preparation method thereof |
| CN108855199A (en) * | 2017-05-08 | 2018-11-23 | 天津工业大学 | A kind of composite catalyst and preparation method thereof for catalytic ozonation processing industrial wastewater |
| CN108854931A (en) * | 2018-07-06 | 2018-11-23 | 中北大学 | A kind of device and method preparing metallic catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 张光明 等编著: "《水处理高级氧化技术》", 31 October 2007, 哈尔滨：哈尔滨工业大学出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111063534A (en) * | 2019-12-09 | 2020-04-24 | 江苏奥玛德新材料科技有限公司 | Manufacturing process of high-filling easy-cutting iron-based amorphous nanocrystalline alloy iron core |
| CN112331866A (en) * | 2020-11-06 | 2021-02-05 | 中北大学 | Fe/Co-N-MCF composite catalyst for fuel cell and preparation method thereof |
| CN112675808A (en) * | 2020-11-19 | 2021-04-20 | 中北大学 | Hypergravity preparation method and application of nano ferrous sulfide composite material |
| CN112657517A (en) * | 2020-12-29 | 2021-04-16 | 北京化工大学 | Preparation method of molybdenum disulfide-based nano catalytic material |
| CN112657517B (en) * | 2020-12-29 | 2023-07-25 | 北京化工大学 | Preparation method of molybdenum disulfide-based nano catalytic material |
| CN114289027A (en) * | 2021-11-24 | 2022-04-08 | 山东华特环保科技有限公司 | Efficient composite ozone catalyst and preparation method and application thereof |
| CN114768826A (en) * | 2022-04-28 | 2022-07-22 | 北京清新环境技术股份有限公司 | Catalyst, rotary steaming, dipping and drying method thereof and application |
| CN114768826B (en) * | 2022-04-28 | 2024-06-14 | 北京清新环境技术股份有限公司 | Catalyst, rotary steaming impregnation drying method and application thereof |
| CN114632524A (en) * | 2022-05-18 | 2022-06-17 | 中国环境科学研究院 | Copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment and preparation method thereof |
| CN115624970A (en) * | 2022-08-18 | 2023-01-20 | 扬州博克莱生物医药科技有限公司 | Catalyst for reducing nitro compound by continuous liquid phase hydrogenation of micro-fixed bed, and preparation method and application thereof |
| CN115624970B (en) * | 2022-08-18 | 2024-05-07 | 扬州博克莱生物医药科技有限公司 | Catalyst for continuous liquid-phase hydrogenation reduction of nitro compounds in micro-fixed bed, and preparation method and application thereof |
| CN115845872A (en) * | 2022-12-14 | 2023-03-28 | 北京化工大学 | Method for preparing monolithic catalyst by using supergravity reactor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110302797A (en) | A kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation and its application | |
| CN110302796A (en) | A kind of Mn-Fe-Cu/ γ-Al of hypergravity fluidisation spray-stain method preparation2O3Catalyst and its application | |
| CN105457643B (en) | A kind of preparation method of activated carbon supported type catalyst for Electrocatalysis Degradation organic wastewater | |
| CN105502447B (en) | A kind of method that hot forming oil column prepares alumina globule | |
| CN102502944B (en) | Zone heterogeneous catalytic oxidation technology for removing pollutants by red-mud catalyst | |
| CN108380214B (en) | A kind of preparation of modified meerschaum and method applied to wastewater treatment | |
| CN108623457A (en) | The catalytic decomposition process of formic acid | |
| CN110152682A (en) | A kind of organic wastewater ozone oxidation catalyst and its preparation method and application | |
| CN106944027A (en) | A kind of millimetre-sized mesoporous ozone oxidation catalyst and its methods for making and using same | |
| CN109731575A (en) | The Fenton sludge catalyst of catalytic ozonation nbsCOD and its preparation, application method | |
| CN110102312A (en) | A kind of one-dimensional cuprous oxide/silver/zinc oxide nanometer rods optic catalytic composite material and the preparation method and application thereof | |
| CN100548434C (en) | Be used for removing the filter medium and preparation method thereof of water ammonia nitrogen and the filter core of making by this filter medium | |
| CN109012671A (en) | A kind of preparation method of activated carbon supported ferric oxide solid Fenton reagent | |
| CN106512988B (en) | A kind of molecular sieve carried type MnO2- ZnO ozone catalyst and preparation method thereof | |
| CN113548698B (en) | Ternary hydrotalcite-like metal oxide, preparation method thereof and application of activated peroxymonosulfate in degrading organic pollutants | |
| CN108970608A (en) | Loaded noble metal catalyst with clad structure and preparation method thereof and the application in Cu (II) liquid phase catalytic reduction | |
| CN108620060A (en) | A kind of bismuth molybdate graphene aerogel compound and preparation method thereof | |
| CN109621941A (en) | A kind of spent bleaching clay prepares catalytic ozonation catalyst and its preparation and application | |
| CN106345450A (en) | Loaded ozonation catalyst and preparation method and application thereof | |
| CN105983433B (en) | Method for preparing aromatic hydrocarbon by methanol catalysis, catalyst for preparing aromatic hydrocarbon by methanol and preparation method thereof | |
| CN102008965A (en) | Method for preparing ozone catalytic oxidation catalyst for treating cyanide waste water | |
| CN109364926A (en) | The preparation method of catalyst for desulfurization wastewater class Fenton's reaction removal ammonia nitrogen | |
| CN108993531A (en) | A kind of method of spent FCC catalyst resource utilization | |
| CN107497478A (en) | A kind of ultraviolet catalytic removes VOCs catalyst and preparation method thereof | |
| CN105817236B (en) | A kind of toluene low-temperature combustion catalyst and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191008 |
|
| RJ01 | Rejection of invention patent application after publication |