CN104289229A - Preparation method for load transition metal catalyst for ozone oxidation as well as load transition metal catalyst and application thereof - Google Patents
Preparation method for load transition metal catalyst for ozone oxidation as well as load transition metal catalyst and application thereof Download PDFInfo
- Publication number
- CN104289229A CN104289229A CN201410583425.XA CN201410583425A CN104289229A CN 104289229 A CN104289229 A CN 104289229A CN 201410583425 A CN201410583425 A CN 201410583425A CN 104289229 A CN104289229 A CN 104289229A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- transition metal
- hour
- metal catalyst
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a preparation method for a load transition metal catalyst for ozone oxidation. The preparation method comprises the following steps: placing a catalyst carrier raw material in a NaOH aqueous solution, soaking, drying, preparing activated aluminum oxide sol, soaking catalyst particles in the activated aluminum oxide sol, drying and roasting, so as to obtain a coating, repeating the steps until a catalyst carrier coated for multiple times is obtained, enabling the content of the activated aluminum oxide coating to be 5-15% of the catalyst carrier in weight, soaking the catalyst carrier in an aqueous solution containing active constituents of transition metal, dying and roasting, so as to obtain the load transition metal catalyst. The load transition metal catalyst is high in ozone catalytic activity, the COD concentration of organic wastewater can be reduced to 50 mg/L below from 100 mg/L by the load transition metal catalyst, the load transition metal catalyst has a stable catalytic effect during the process of treating organic wastewater through catalytic ozonation, and the catalytic activity is not changed basically after the load transition metal catalyst continuously runs for multiple days in a fixed bed reactor.
Description
[technical field]
The present invention relates to loading transition metallic catalyst, particularly a kind of loading transition metallic catalyst for ozone oxidation, its preparation method and application.
[background technology]
In recent years, drinking water pollution problem has caused the extensive attention of people, particularly in drinking water, some hardly degraded organic substances are the major pollutants matter causing drinking water quality to worsen, thus the new wastewater treatment method be applied in extensive water treatment is researched and developed, hardly degraded organic substance in effective removal water, becomes the task of top priority.Ozone is strong due to its strong oxidizing property, is widely used in recent years in water treatment field.
But the solubility of ozone in water is lower and easily decompose, utilization ratio is lower, operating cost is high and have selective, this limits its development to a certain extent.Although many hardly degraded organic substances, are not easily thoroughly decomposed into CO by organic matter in ozone oxidize water
2and H
2o, its product is usually for being difficult to small carboxylic acid molecules's type organic of mineralising, and the toxicity of intermediate product is likely stronger.Therefore, need to adopt the method for catalysis to strengthen the oxidability of ozone oxidation unit.
Therefore, people by adding metal ion or solid metallic, metal oxide as the heterogeneous catalytic ozonation technology of catalyst on carrier.At present, catalyst used in multi-phase catalytic ozonation technique mainly loading transition metallic catalyst, metal or the metal oxide of load have FeOOH, Al
2o
3, TiO
2, MnO
x, Fe
2o
3, Ni
2o
3deng, its catalytic activity main manifestations is to the catalytic decomposition of ozone and the generation promoting OH.The efficiency of catalytic ozonation process depends primarily on the pH value of catalyst and surface nature thereof, solution, and these factors can affect ozonolysis reactions in the character of catalyst surface active position and solution.Catalyst carrier carrier is one of key factor affecting catalyst efficiency, its Main Function is to provide effective ratio area and suitable pore structure, and the mechanical strength that catalyst is obtained and heat endurance, play a part activated centre and save active component consumption.Be generally used for treatment catalyst carrier and have Al
2o
3, TiO
2, active carbon and pottery etc.
Compared with homogeneous catalysis ozonation technology, heterogeneous catalytic ozonation has that catalyst can reuse, high oxidation activity, easily recycling and the low advantage of cost of water treatment, show wide application prospect in water treatment field, and be expected to become a kind of water technology having very much industrial application value.
[summary of the invention]
The object of the invention is to overcome prior art defect, obtain at a kind of novel loading transition metallic catalyst, realize ozone/loading transition metallic catalyst catalytic oxidation system to remove the organic matter of difficult degradation in water.
To achieve these goals, the invention provides a kind of preparation method of the loading transition metallic catalyst for ozone oxidation, said method comprising the steps of:
A, NaOH aqueous solution catalyst support material being placed in 3-5% by weight soak 1-4 hour, dry at normal temperatures after rinsing, then at 90-105 DEG C dry 2-4 hour;
B, take Al (NO
3)
39H
2o is dissolved in deionized water, is configured to the Al (NO of 0.5-1.5mol/L
3)
3solution, slowly adds aluminium powder at 85-95 DEG C, until Al (NO
3)
3the pH value of solution is 3-4, then adds dispersant hydroxylamine hydrochloride, stirs, and obtains active oxidation Alumina gel;
C, the catalyst granules after processing of step A is soaked 2-4 hour in the active oxidation Alumina gel of step B, under normal temperature after drying at 90-105 DEG C dry 2-6 hour, then roasting 4-6 hour at 400-550 DEG C, obtains the catalyst carrier of primary coating;
D, repetition steps A-C 2-4 time, obtain repeatedly the catalyst carrier of coating, make activated alumina coating levels be with the 5-15% of catalyst carrier weighing scale;
E, prepare with the active component of metallic element weighing scale 6-15% and co-catalyst mixed aqueous solution, the catalyst carrier of the repeatedly coating of step D is immersed in 4-8 hour in described mixed aqueous solution, after air drying, again at 80-120 DEG C of dry 2-6 hour, then at 600-850 DEG C of roasting 4-6 hour, loading transition metallic catalyst is obtained.
In the present invention, preferably described catalyst support material is selected from active carbon, aluminium oxide, haydite, zeolite.
More preferably, described catalyst support material is spherical, graininess, bulk or column.
According to one preferred embodiment, in step B, the weight ratio of dispersant hydroxylamine hydrochloride in active oxidation Alumina gel is 1-5%.
In the present invention, the active component of step e can be selected from Mn (NO
3)
2, Cu (NO
3)
2or Fe (NO
3)
3in one or more, or MnSO
4, CuSO
4or Fe
2(SO
4)
3in one or more, or MnCl
2, CuCl
3or FeCl
3in one or more active components.
In addition, the co-catalyst of step e is selected from KNO
3or NaNO
3in one or more, or K
2sO
4or Na
2sO
4in one or more, or one or more co-catalysts in KCl or NaCl.
According to one preferred embodiment, the air drying of step e dries or dries up with nitrogen.
The invention still further relates to the application of loading transition metallic catalyst in water treatment that above-mentioned preparation method obtains.
Below will explain technical scheme of the present invention further.
The invention provides a kind of preparation method of the loading transition metallic catalyst for ozone oxidation, the method comprises the following steps:
A, get porous material active carbon, aluminium oxide, haydite or zeolite, spherical, graininess, bulk or column, in order to increase the Hole Wall Roughness of catalyst support material, make the degree of adhesion of support material and aluminum oxide coating layer better, catalyst support material is immersed in 1-4 hour in the NaOH aqueous solution with gauge 3-5%, natural drying at normal temperatures or air-dry after rinsing, then at 90-105 DEG C dry 2-4 hour;
B, take aluminum nitrate Al (NO
3)
39H
2o is dissolved in deionized water, is configured to the Al (NO of 0.5-1.5mol/L
3)
3solution, slowly adds aluminium powder at 85-95 DEG C, be creamy white or canescence translucent, until Al (NO
3)
3the pH value of solution is 3-4, and now solution becomes colorless transparent clarification shape, then adds dispersant hydroxylamine hydrochloride, stirs, and obtains active oxidation Alumina gel;
C, the catalyst support material particle after processing of step A is soaked 2-4 hour in the active oxidation Alumina gel of step B, first dry at normal temperatures after taking out support material particle, and then after at 90-105 DEG C dry 2-6 hour, then roasting 4-6 hour at 400-550 DEG C, obtains the catalyst carrier through primary coating.Described coating is aluminium oxide, observes in hole shape under an electron microscope.Because active oxidation Alumina gel is solution, be molecular level, therefore load gained coating is nanoscale load;
D, in order to improve activated alumina coating levels, repeating steps A-C 2-4 time, obtaining repeatedly the catalyst carrier of coating, make final activated alumina coating levels be with the 5-15% of catalyst carrier total weight;
E, to prepare with the active component of metallic element weighing scale 6-15% and co-catalyst (with total restatement 1-5%) mixed aqueous solution.Wherein, active component is the salt of Mn, Cu or Fe, such as, be selected from Mn (NO
3)
2, Cu (NO
3)
2or Fe (NO
3)
3in one or more mixture, or MnSO
4, CuSO
4or Fe
2(SO
4)
3in one or more mixture, or MnCl
2, CuCl
2or FeCl
3in one or more mixture.Correspondingly, co-catalyst can be the salt of K or Na, such as KNO
3or NaNO
3in one or more, or K
2sO
4or Na
2sO
4in one or more, or one or more co-catalysts in KCl or NaCl.
The catalyst carrier of the repeatedly coating of step D is immersed in 4-8 hour in the aqueous solution containing active component and co-catalyst, air drying (such as dry or dry up with nitrogen) after taking out, again at 80-120 DEG C of dry 2-6 hour, then at 600-850 DEG C of roasting 4-6 hour, loading transition metallic catalyst is obtained.
Loading transition metallic catalyst of the present invention being applied in water treatment field, can processing the organic wastewater containing being difficult to degradation of organic substances, reaction condition is gentle, can effectively remove in waste water the organic matter being difficult to biochemical degradation at normal temperature and pressure.
Compared with prior art, the present invention has following feature:
(1) compared with independent ozone oxidation, this catalyst shows very high ozone catalytic activity, and when the reaction time is 0-180min, the organic wastewater COD that COD concentration can be about 100mg/L is reduced to below 50mg/L.
(2) catalyst of the present invention has stable catalytic effect in the process of catalytic ozonation process organic wastewater, run 15 days continuously in fixed bed reactors after, and catalytic activity substantially constant (see accompanying drawing 2);
(3) carrier that this catalyst is used and active component and co-catalyst and production equipment cheap and easy to get, production cost is lower, can not cause secondary pollution, is applicable to suitability for industrialized production and uses.
[accompanying drawing explanation]
Fig. 1: load Mn-Cu-Na/ activated alumina catalyst prepared by the present invention is catalytic ozonation degradation organic pollution COD curve map over time under condition of different pH;
Fig. 2: load Mn-Cu-Na/ activated alumina catalyst prepared by the present invention when catalytic ozonation is continuously long-running to water outlet COD degradation design sketch.
[detailed description of the invention]
Following examples are used for explaining technical scheme of the present invention without limitation.Those skilled in the art can use for reference content of the present invention, the links such as suitable change material, parameter, technique realize other object corresponding, its relevant change does not all depart from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and all should be deemed to be included within scope of the present invention.
In the present invention, if no special instructions, " part " is weight portion, and " % " is all weight percentage, and " ratio " is weight ratio.
Embodiment 1 prepares load Mn-Cu-Na/ activated alumina catalyst
A, active aluminum oxide carrier to be soaked 2 hours in 3wt%NaOH solution, after then using tap water 3 times, leave standstill under normal temperature and dry, then 105 DEG C of dryings 2 hours, for subsequent use.
B, take 450g Al (NO
3)
39H
2o, is dissolved in 1000ml water, is heated to 90 DEG C of isothermal reactions, and substep adds aluminium powder, amounts to 30g, till solution ph is increased between 3-4 gradually.Become colorless by cloudy grey after solution adds aluminium powder transparent.After making water white active oxidation Alumina gel, the hydroxylamine hydrochloride adding 20g, as dispersant, stirs, for subsequent use.
C, get the catalyst particle carriers prepared in steps A, be immersed in step B in water white active oxidation Alumina gel, total immersion was taken out after 2 hours.Then leave standstill 12h at normal temperatures to dry, then 90 DEG C of dryings 6 hours, and roasting 4 hours at 450 DEG C, obtain the catalyst carrier of primary coating.Repeat above-mentioned steps 2 times, obtain the catalyst carrier through 3 coatings.
D, remove ionized water 1L, add 325g Mn (NO
3)
2, 294g Cu (NO
3)
2with 369g NaNO
3, obtain the Mn (NO with metallic element weighing scale 10%
3)
2, Cu (NO
3)
2, NaNO
3mixed aqueous solution, for subsequent use.
E, be soaked in the mixed aqueous solution of step D by the catalyst carrier through 3 coatings, take out after 4 hours, nitrogen dries up, and 105 DEG C of dryings 3 hours, last 700 DEG C of roastings 5 hours, make load Mn-Cu-Na/ activated alumina catalyst.
Test the Catalytic Ozonation Activity of above-mentioned load Mn-Cu-Na/ activated alumina catalyst:
In 1L cylindrical drum bubble semi batch reacor, carry out the Catalytic Ozonation Activity of the catalyst of Evaluation operation example 1 with Hebei steel plant reverse osmosis concentrated water COD (COD concentration is for 100.5mg/L).
Reaction temperature is 25 DEG C, pH=5.00-10.00, and the gas flow of ozonized oxygen gas mist is 0.1L/min, and adopt pure oxygen source ozone generator to provide ozone, ozone concentration is 80mg/L.The ozone oxidation time is 10-180min, independent ozone oxidation and load Mn-Cu-Na/ activated alumina catalyst under condition of different pH catalytic ozonation degradation organic pollution COD data are as shown in table 1 over time.
Table 1: ozone oxidation and load Mn-Cu-Na/ activated alumina catalyst catalytic ozonation degradation organic pollution COD data over time under condition of different pH separately
Fig. 1 gives load Mn-Cu-Na/ activated alumina catalyst catalytic ozonation degradation organic pollution COD curve map over time under condition of different pH.From in figure, when pH is 8.25, independent ozone oxidation is to the removal effect of reverse osmosis concentrated water COD and not obvious (in 60min, COD only degrades to 77.45mg/L, clearance only has 22%), after adding catalyst, under reacting the condition of more than 1 hour, COD degradable is to below 50mg/L, clearance reaches about 55%, compares improve 33% with independent ozone.Under different pH condition, after adding load Mn-Cu-Na/ activated alumina catalyst, reverse osmosis concentrated water COD removes speed and all obviously accelerates, and just can reach the clearance of 45-55% in 60min.Result shows, the catalyst activity of embodiment 1 is fine, affect very little, and preparation cost is lower, is easy to Separation of Solid and Liquid and recycling, can be applied to the process of actual water body by pH value.
Fig. 2 gives load Mn-Cu-Na/ activated alumina catalyst when catalytic ozonation is continuously long-running to water outlet COD degradation design sketch.From in figure, when pH=8.25, run 15 days continuously in fixed bed reactors after, catalytic activity is substantially constant.
Embodiment 2 prepares load Mn-Cu-Fe-K/ activated alumina catalyst
A, activated carbon granule to be soaked 1 hour in 5wt%NaOH solution, leave standstill under normal temperature after rinsing and dry, then 90 DEG C of dryings 4 hours, for subsequent use.
B, take 375g Al (NO
3)
39H
2o, is dissolved in 1000ml water, is heated to 85 DEG C, and substep adds aluminium powder 28g, till solution ph is increased between 3-4 gradually.Become colorless by cloudy grey after solution adds aluminium powder transparent.After making water white active oxidation Alumina gel, the hydroxylamine hydrochloride adding 15g, as dispersant, stirs, for subsequent use.
C, get the catalyst particle carriers prepared in steps A, be immersed in step B in water white active oxidation Alumina gel, total immersion was taken out after 3 hours.Then leave standstill 12h at normal temperatures to dry, then 105 DEG C of dryings 2 hours, and roasting 4 hours at 550 DEG C, obtain the catalyst carrier of primary coating.Repeat above-mentioned steps 3 times, obtain the catalyst carrier through 4 coatings.
D, remove ionized water 1000mL, add 461g MnSO
4h
2o, 586g CuSO
45H
2o, 536g Fe
2(SO
4)
3with 288g KCl, obtain with the MnSO of metallic element weighing scale 15%
4, CuSO
4, Fe
2(SO
4)
3with KCl mixed aqueous solution, for subsequent use.
E, be soaked in the mixed aqueous solution of step D by the catalyst carrier through 4 coatings, take out after 6 hours, air-dry, 80 DEG C of dryings 6 hours, last 850 DEG C of roastings 4 hours, make load Mn-Cu-Fe-K/ activated alumina catalyst.
Test the Catalytic Ozonation Activity of above-mentioned load Mn-Cu-Fe-K/ activated alumina catalyst in the same manner as example 1, as shown in table 2.
Table 2: ozone oxidation and load Mn-Cu-Fe-K/ activated alumina catalyst catalytic ozonation degradation organic pollution COD data over time under condition of different pH separately
Result shows, the catalyst activity of embodiment 3 shows similar to embodiment 1, affects little by pH value, high to COD clearance.In addition, when pH=8.25, run 15 days continuously in fixed bed reactors after, catalytic activity is substantially constant.
Embodiment 3 prepares load Mn-Cu-Fe-Na/ activated alumina catalyst
A, activated carbon granule to be soaked 4 hours in 4wt%NaOH solution, leave standstill under normal temperature after rinsing and dry, then 95 DEG C of dryings 3 hours, for subsequent use.
B, take 430g Al (NO
3)
39H
2o, is dissolved in 1000ml water, is heated to 95 DEG C, and substep adds aluminium powder 30g, till solution ph is increased between 3-4 gradually.Become colorless by cloudy grey after solution adds aluminium powder transparent.After making water white active oxidation Alumina gel, the hydroxylamine hydrochloride adding 10g, as dispersant, stirs, for subsequent use.
C, get the catalyst particle carriers prepared in steps A, be immersed in step B in water white active oxidation Alumina gel, total immersion was taken out after 4 hours.Then leave standstill at normal temperatures and dry, then 100 DEG C of dryings 4 hours, and roasting 6 hours at 400 DEG C, obtain the catalyst carrier of primary coating.Repeat above-mentioned steps 2 times, obtain the catalyst carrier through 3 coatings.
D, remove ionized water 1000mL, add 115g MnCl
2, 133g CuCl
22H
2o, 241gFeCl
36H
2o and 126g NaCl, obtains with the MnCl of metallic element weighing scale 5%
2, CuCl
2, FeCl
3with NaCl mixed aqueous solution, for subsequent use.
E, be soaked in the mixed aqueous solution of step D by the catalyst carrier through 3 coatings, take out after 8 hours, air-dry, 120 DEG C of dryings 2 hours, last 600 DEG C of roastings 6 hours, make load Mn-Cu-Fe-Na/ activated alumina catalyst.
Test the Catalytic Ozonation Activity of above-mentioned load Mn-Cu-Fe-K/ activated alumina catalyst in the same manner as example 1, as shown in table 2.
Table 3: ozone oxidation and load Mn-Cu-Fe-Na/ activated alumina catalyst catalytic ozonation degradation organic pollution COD data over time under condition of different pH separately
Result shows, the catalyst activity of embodiment 3 shows similar to embodiment 1, affects little by pH value, high to COD clearance.
The Catalytic Ozonation Activity degradable organic pollutant COD Data Comparison over time of embodiment 4 haydite and different modes load Mn-Cu-Na/ ceramsite catalyst.
1# catalyst preparing:
Ceramsite carrier is soaked 2 hours in 3wt%NaOH solution, after then using tap water 3 times, leaves standstill under normal temperature and dry, then 105 DEG C of dryings 2 hours, for subsequent use.
2# catalyst preparing:
A, ceramsite carrier to be soaked 2 hours in 3wt%NaOH solution, after then using tap water 3 times, leave standstill under normal temperature and dry, then 105 DEG C of dryings 2 hours, for subsequent use.
Mn (the NO of B, compound concentration 10% (with metallic element weighing scale)
3)
2, Cu (NO
3)
2, NaNO
3mixed aqueous solution 1L (about dissolves 325g Mn (NO in 1L water
3)
2, dissolve 294g Cu (NO
3)
2, dissolve 369g NaNO
3)), for subsequent use.
C, ceramsite carrier steps A prepared are soaked in step B mixed aqueous solution and take out after 4 hours, dry or dry up with nitrogen, and 105 DEG C of dryings 3 hours, last 700 DEG C of roastings 5 hours, make load Mn-Cu-Na/ ceramsite catalyst.
3# catalyst preparing:
A, ceramsite carrier to be soaked 2 hours in 3wt%NaOH solution, after then using tap water 3 times, leave standstill under normal temperature and dry, then 105 DEG C of dryings 2 hours, for subsequent use.
B, take 450g Al (NO
3)
39H
2o, is dissolved in 1000ml water, is heated to 90 DEG C of isothermal reactions, and substep adds aluminium powder, amounts to 30g, till solution ph is increased between 3-4 gradually.Cloudy grey after solution adds aluminium powder becomes colorless transparent, and after making water white active oxidation Alumina gel, the hydroxylamine hydrochloride adding 20g, as dispersant, stirs, for subsequent use.
C, get the ceramsite carrier prepared in steps A, be immersed in step B in water white active oxidation Alumina gel, total immersion was taken out after 2 hours.Then leave standstill at normal temperatures and dry, then 100 DEG C of dryings 4 hours, and roasting 4 hours at 450 DEG C, obtain the catalyst carrier of primary coating.
Mn (the NO of D, compound concentration 10% (with metallic element weighing scale)
3)
2, Cu (NO
3)
2, NaNO
3mixed aqueous solution 1L (about dissolves 325g Mn (NO in 1L water
3)
2, dissolve 294g Cu (NO
3)
2, dissolve 369g NaNO
3)), for subsequent use.
E, the ceramsite carrier after step C coating is soaked in step D mixed aqueous solution takes out after 4 hours, dry or dry up with nitrogen, 105 DEG C of dryings 3 hours, last 700 DEG C of roastings 5 hours, make load Mn-Cu-Na/ primary coating activated alumina ceramsite catalyst.
4# catalyst preparing:
A, ceramsite carrier to be soaked 2 hours in 3wt%NaOH solution, after then using tap water 3 times, leave standstill under normal temperature and dry, then 105 DEG C of dryings 2 hours, for subsequent use.
B, take 450g Al (NO
3)
39H
2o, is dissolved in 1000ml water, is heated to 90 DEG C of isothermal reactions, and substep adds aluminium powder, amounts to 30g, till solution ph is increased between 3-4 gradually.Cloudy grey after solution adds aluminium powder becomes colorless transparent, and after making water white active oxidation Alumina gel, the hydroxylamine hydrochloride adding 20g, as dispersant, stirs, for subsequent use.
C, get the ceramsite carrier prepared in a certain amount of steps A, be immersed in step B in water white active oxidation Alumina gel, total immersion was taken out after 2 hours.Then leave standstill at normal temperatures and dry, then 100 DEG C of dryings 4 hours, and roasting 4 hours at 450 DEG C, obtain the catalyst carrier of primary coating.Repeat above-mentioned steps 2 times, by the time through the carrier of three coatings.
Mn (the NO of D, compound concentration 10% (with metallic element weighing scale)
3)
2, Cu (NO
3)
2, NaNO
3mixed aqueous solution 1L (about dissolves 325g Mn (NO in 1L water
3)
2, dissolve 294g Cu (NO
3)
2, dissolve 369g NaNO
3)), for subsequent use.
E, the ceramsite carrier after 1L step C coating is soaked in 1L step D mixed aqueous solution takes out after 4 hours, dry or dry up with nitrogen, 105 DEG C of dryings 3 hours, last 700 DEG C of roastings 5 hours, make load Mn-Cu-Na/ many coating activated alumina ceramsite catalysts.
In 1L column Continuous Flow fixed bed reactors, evaluate the Catalytic Ozonation Activity of above-mentioned four kinds of catalyst with Heilungkiang refinery company reverse osmosis concentrated water COD (COD concentration is for 112.3mg/L).
Reaction temperature is 25 DEG C, wastewater pH=7.33, and the gas flow of ozonized oxygen gas mist is 0.1L/min, and adopt pure oxygen source ozone generator to provide ozone, ozone concentration is 80mg/L.Waste water time of staying in ozone oxidation tower is 2h, after running 72h continuously, measures water outlet COD.Data are as shown in table 4 over time for the catalytic ozonation degradation organic pollution COD of haydite and different modes load Mn-Cu-Na/ ceramsite catalyst.
Table 4: the Catalytic Ozonation Activity degradable organic pollutant COD Data Comparison over time of haydite and different modes load Mn-Cu-Na/ ceramsite catalyst
Table 4 gives the Catalytic Ozonation Activity degradable organic pollutant COD curve map over time of haydite and different modes load Mn-Cu-Na/ catalyst.From in table, add load Mn-Cu-Na/ many coating activated alumina ceramsite catalysts, reverse osmosis concentrated water COD clearance is high, reaches the clearance of 53.0%, compares other catalyst prods (without coating or only through primary coating) and has significant superiority.
Claims (8)
1., for a preparation method for the loading transition metallic catalyst of ozone oxidation, it is characterized in that said method comprising the steps of:
A, NaOH aqueous solution catalyst support material being placed in 3-5% by weight soak 1-4 hour, dry at normal temperatures after rinsing, then at 90-105 DEG C dry 2-4 hour;
B, take Al (NO
3)
39H
2o is dissolved in deionized water, is configured to the Al (NO of 0.5-1.5mol/L
3)
3solution, slowly adds aluminium powder at 85-95 DEG C, until Al (NO
3)
3the pH value of solution is 3-4, then adds dispersant hydroxylamine hydrochloride, stirs, and obtains active oxidation Alumina gel;
C, the catalyst granules after processing of step A is soaked 2-4 hour in the active oxidation Alumina gel of step B, under normal temperature after drying at 90-105 DEG C dry 2-6 hour, then roasting 4-6 hour at 400-550 DEG C, obtains the catalyst carrier of primary coating;
D, repetition steps A-C 2-4 time, obtain repeatedly the catalyst carrier of coating, make activated alumina coating levels be with the 5-15% of catalyst carrier weighing scale;
E, prepare with the active component of metallic element weighing scale 6-15% and co-catalyst mixed aqueous solution, the catalyst carrier of the repeatedly coating of step D is immersed in 4-8 hour in described mixed aqueous solution, after air drying, again at 80-120 DEG C of dry 2-6 hour, then at 600-850 DEG C of roasting 4-6 hour, loading transition metallic catalyst is obtained.
2. preparation method according to claim 1, is characterized in that described catalyst support material is selected from active carbon, aluminium oxide, haydite, zeolite.
3. preparation method according to claim 1 and 2, is characterized in that described catalyst support material is spherical, graininess, bulk or column.
4. preparation method according to claim 1, is characterized in that in step B, the weight ratio of dispersant hydroxylamine hydrochloride in active oxidation Alumina gel is 1-5%.
5. preparation method according to claim 1, is characterized in that the active component of step e is selected from Mn (NO
3)
2, Cu (NO
3)
2or Fe (NO
3)
3in one or more, or MnSO
4, CuSO
4or Fe
2(SO
4)
3in one or more, or MnCl
2, CuCl
2or FeCl
3in one or more active components.
6. preparation method according to claim 2, is characterized in that the co-catalyst of step e is selected from KNO
3or NaNO
3in one or more, or K
2sO
4or Na
2sO
4in one or more, or one or more co-catalysts in KCl or NaCl.
7. preparation method according to claim 2, is characterized in that the air drying of step e dries or dries up with nitrogen.
8. the application of loading transition metallic catalyst in water treatment that obtain of preparation method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410583425.XA CN104289229A (en) | 2014-10-27 | 2014-10-27 | Preparation method for load transition metal catalyst for ozone oxidation as well as load transition metal catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410583425.XA CN104289229A (en) | 2014-10-27 | 2014-10-27 | Preparation method for load transition metal catalyst for ozone oxidation as well as load transition metal catalyst and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104289229A true CN104289229A (en) | 2015-01-21 |
Family
ID=52309316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410583425.XA Pending CN104289229A (en) | 2014-10-27 | 2014-10-27 | Preparation method for load transition metal catalyst for ozone oxidation as well as load transition metal catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104289229A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105080565A (en) * | 2015-06-03 | 2015-11-25 | 博天环境集团股份有限公司 | Method for preparing supported ozone oxidation catalyst |
| CN105618080A (en) * | 2016-01-30 | 2016-06-01 | 凯姆德（北京）能源环境科技有限公司 | Ozone catalytic oxidation catalyst for treating reverse osmosis concentrated water and preparation method of catalyst |
| CN106466643A (en) * | 2016-08-31 | 2017-03-01 | 江苏兴海环保科技有限公司 | A kind of preparation method of the catalyst for wastewater treatment |
| CN106475120A (en) * | 2016-08-31 | 2017-03-08 | 江苏兴海环保科技有限公司 | A kind of preparation method of ozone oxidation catalyst |
| CN106552644A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Difficult biochemical waste water ozone catalyst and preparation method thereof |
| CN106824253A (en) * | 2017-01-13 | 2017-06-13 | 上海纳旭实业有限公司 | A kind of support type ozone catalyst and preparation and application for dyeing waste water biochemistry pre-treatment |
| CN106964349A (en) * | 2017-02-24 | 2017-07-21 | 河北科技大学 | Ozone catalytic oxidation catalyst, its preparation method and application |
| CN108057455A (en) * | 2017-12-28 | 2018-05-22 | 天津碧水源膜材料有限公司 | Ozone catalytic oxidation catalyst and its preparation method and application |
| CN108126739A (en) * | 2017-12-19 | 2018-06-08 | 济南大学 | Catalyst of COD and preparation method thereof in a kind of ozone heterocatalysis oxidized waste water |
| CN108745361A (en) * | 2018-05-28 | 2018-11-06 | 上海安居乐环保科技股份有限公司 | A kind of VOCs room-temperature catalytic oxidations material and its preparation method and application |
| CN109647431A (en) * | 2019-02-21 | 2019-04-19 | 渤海水业股份有限公司 | A kind of catalyst, preparation method and the usage for catalytic ozonation processing used water difficult to degradate |
| CN111250087A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Preparation method and application of catalyst for catalyzing ozone oxidation |
| CN111468106A (en) * | 2020-04-28 | 2020-07-31 | 光大水务科技发展（南京）有限公司 | Ceramsite catalyst for sewage treatment and preparation and application methods thereof |
| CN114849719A (en) * | 2022-06-08 | 2022-08-05 | 北京碧水源膜科技有限公司 | Composite catalyst, preparation method thereof and wastewater treatment method |
| WO2023223058A1 (en) | 2022-05-20 | 2023-11-23 | Aristotle University Of Thessaloniki-E.L.K.E. | Method for the removal of micropollutants by the application of heterogeneous catalytic ozonation from water |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385239A (en) * | 2001-05-14 | 2002-12-18 | 中国科学院山西煤炭化学研究所 | Catalyst for catalytic purifying car tail gas and preparation process thereof |
| CN101185884A (en) * | 2007-12-27 | 2008-05-28 | 哈尔滨工业大学 | Catalyst for catalyzing ozone oxidation and preparation method thereof |
| CN101811049A (en) * | 2009-02-19 | 2010-08-25 | 中国科学院生态环境研究中心 | Method for preparing honeycomb ceramic catalyst for catalytically ozonizing organic matters in water |
| CN102029165A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Method for preparing ozone catalytic oxidation catalyst for treating coking wastewater |
| CN103084184A (en) * | 2011-10-27 | 2013-05-08 | 常州牛翼环保科技有限公司 | Manganese-iron composite oxide supported catalyst for removing ozone in indoor air |
| CN103112878A (en) * | 2012-12-28 | 2013-05-22 | 中国神华能源股份有限公司 | Method for preparing aluminum oxide with large specific surface area |
| CN103586026A (en) * | 2013-11-26 | 2014-02-19 | 北京碧水源科技股份有限公司 | Carbon supported catalyst for ozone oxidation, and preparation method and use thereof |
-
2014
- 2014-10-27 CN CN201410583425.XA patent/CN104289229A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385239A (en) * | 2001-05-14 | 2002-12-18 | 中国科学院山西煤炭化学研究所 | Catalyst for catalytic purifying car tail gas and preparation process thereof |
| CN101185884A (en) * | 2007-12-27 | 2008-05-28 | 哈尔滨工业大学 | Catalyst for catalyzing ozone oxidation and preparation method thereof |
| CN101811049A (en) * | 2009-02-19 | 2010-08-25 | 中国科学院生态环境研究中心 | Method for preparing honeycomb ceramic catalyst for catalytically ozonizing organic matters in water |
| CN102029165A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Method for preparing ozone catalytic oxidation catalyst for treating coking wastewater |
| CN103084184A (en) * | 2011-10-27 | 2013-05-08 | 常州牛翼环保科技有限公司 | Manganese-iron composite oxide supported catalyst for removing ozone in indoor air |
| CN103112878A (en) * | 2012-12-28 | 2013-05-22 | 中国神华能源股份有限公司 | Method for preparing aluminum oxide with large specific surface area |
| CN103586026A (en) * | 2013-11-26 | 2014-02-19 | 北京碧水源科技股份有限公司 | Carbon supported catalyst for ozone oxidation, and preparation method and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 叶青，王道等: "氧化铝溶胶及涂层研究", 《北京工业大学学报》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080565A (en) * | 2015-06-03 | 2015-11-25 | 博天环境集团股份有限公司 | Method for preparing supported ozone oxidation catalyst |
| 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 |
| CN106552644B (en) * | 2015-09-30 | 2020-07-10 | 中国石油化工股份有限公司 | Ozone catalyst for difficult biochemical wastewater and preparation method thereof |
| CN106552644A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Difficult biochemical waste water ozone catalyst and preparation method thereof |
| CN105618080A (en) * | 2016-01-30 | 2016-06-01 | 凯姆德（北京）能源环境科技有限公司 | Ozone catalytic oxidation catalyst for treating reverse osmosis concentrated water and preparation method of catalyst |
| CN106466643A (en) * | 2016-08-31 | 2017-03-01 | 江苏兴海环保科技有限公司 | A kind of preparation method of the catalyst for wastewater treatment |
| CN106475120A (en) * | 2016-08-31 | 2017-03-08 | 江苏兴海环保科技有限公司 | A kind of preparation method of ozone oxidation catalyst |
| CN106824253A (en) * | 2017-01-13 | 2017-06-13 | 上海纳旭实业有限公司 | A kind of support type ozone catalyst and preparation and application for dyeing waste water biochemistry pre-treatment |
| CN106964349A (en) * | 2017-02-24 | 2017-07-21 | 河北科技大学 | Ozone catalytic oxidation catalyst, its preparation method and application |
| CN108126739A (en) * | 2017-12-19 | 2018-06-08 | 济南大学 | Catalyst of COD and preparation method thereof in a kind of ozone heterocatalysis oxidized waste water |
| CN108057455A (en) * | 2017-12-28 | 2018-05-22 | 天津碧水源膜材料有限公司 | Ozone catalytic oxidation catalyst and its preparation method and application |
| CN108745361A (en) * | 2018-05-28 | 2018-11-06 | 上海安居乐环保科技股份有限公司 | A kind of VOCs room-temperature catalytic oxidations material and its preparation method and application |
| CN111250087A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Preparation method and application of catalyst for catalyzing ozone oxidation |
| CN111250087B (en) * | 2018-11-30 | 2021-04-23 | 中国科学院大连化学物理研究所 | Preparation method and application of catalyst for catalyzing ozone oxidation |
| CN109647431A (en) * | 2019-02-21 | 2019-04-19 | 渤海水业股份有限公司 | A kind of catalyst, preparation method and the usage for catalytic ozonation processing used water difficult to degradate |
| CN109647431B (en) * | 2019-02-21 | 2022-04-22 | 渤海水业股份有限公司 | Catalyst for catalytic oxidation treatment of refractory wastewater by ozone, preparation method and application thereof |
| CN111468106A (en) * | 2020-04-28 | 2020-07-31 | 光大水务科技发展（南京）有限公司 | Ceramsite catalyst for sewage treatment and preparation and application methods thereof |
| WO2023223058A1 (en) | 2022-05-20 | 2023-11-23 | Aristotle University Of Thessaloniki-E.L.K.E. | Method for the removal of micropollutants by the application of heterogeneous catalytic ozonation from water |
| CN114849719A (en) * | 2022-06-08 | 2022-08-05 | 北京碧水源膜科技有限公司 | Composite catalyst, preparation method thereof and wastewater treatment method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104289229A (en) | Preparation method for load transition metal catalyst for ozone oxidation as well as load transition metal catalyst and application thereof | |
| US11059033B2 (en) | Catalyst for catalytic oxidation treatment of organic wastewater, preparation method thereof, and application thereof | |
| Forouzesh et al. | Transformation of persulfate to free sulfate radical over granular activated carbon: effect of acidic oxygen functional groups | |
| WO2021196522A1 (en) | Supported two-component metal oxide catalyst for advanced treatment of petrochemical wastewater and preparation method therefor | |
| CN105013504A (en) | Loaded binary composite metal oxide catalytic ozonation catalyst and preparation method thereof | |
| CN105233838B (en) | A kind of O using activated bentonite as carrier3/H2O2Preparation method, catalyst and its application of catalyst | |
| Li et al. | Preparation of the Mn-Fe-Ce/γ-Al2O3 ternary catalyst and its catalytic performance in ozone treatment of dairy farming wastewater | |
| CN107051468A (en) | Load the preparation method and application of poly-metal deoxide ozone catalytic oxidation catalyst | |
| CN106540686A (en) | For the activated carbon supported manganese dioxide titanium dioxide ozone catalyst and preparation method of advanced treating | |
| CN105854900A (en) | Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof | |
| CN110540285A (en) | Heterogeneous ozone catalysis and micro-nano bubble combined sewage treatment method | |
| CN107252686A (en) | A kind of processing method of phenol wastewater | |
| CN115279489A (en) | Metal oxide nanoparticles supported on glass foams and/or glass ceramic foams and use thereof for heterogeneous catalysis in the gas and/or liquid phase | |
| CN106552644B (en) | Ozone catalyst for difficult biochemical wastewater and preparation method thereof | |
| KR100738676B1 (en) | Transition metal catalysts based on ceria-zirconia for wet air oxidation of refractory wastewater | |
| CN106955686B (en) | Preparation method and application of ozone oxidation catalyst of diatomite-loaded multi-metal oxide | |
| CN101264996B (en) | Method for treating aniline waste water by absorption-low temperature dry method | |
| Sun et al. | Ozone catalytic oxidation capacity of Ti‐Co@ Al2O3 for the treatment of biochemical tailwater from the coal chemical industry | |
| CN115999547B (en) | Preparation method and application of supported bi-component metal oxide catalytic ozonation catalyst | |
| CN114804323B (en) | Wastewater oxidation treatment method based on ozone | |
| CN107585852B (en) | Method and device for carrying out heterogeneous catalytic oxidation on COD (chemical oxygen demand) in wastewater by using ozone | |
| TW201625356A (en) | Preparation of ceramic supported catalyst and the applications for catalytic ozonation to degrade organic wastewater | |
| Li et al. | Effect of the oxidation of activated carbon by hydrogen peroxide on its catalytic activity in the regeneration of Co (II) TETA | |
| CN114225928A (en) | High-strength carbon-based heterogeneous catalyst and preparation method thereof | |
| CN114524503A (en) | Method for treating printing and dyeing wastewater through ozone catalytic oxidation by using iron-manganese/biochar |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150121 |
|
| RJ01 | Rejection of invention patent application after publication |