CN115970680A - Wet oxidation catalyst and preparation method and application thereof - Google Patents
Wet oxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN115970680A CN115970680A CN202211690839.3A CN202211690839A CN115970680A CN 115970680 A CN115970680 A CN 115970680A CN 202211690839 A CN202211690839 A CN 202211690839A CN 115970680 A CN115970680 A CN 115970680A
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Abstract
The invention belongs to the technical field of catalytic synthesis, and particularly relates to a wet oxidation catalyst, and a preparation method and application thereof. The wet oxidation catalyst provided by the invention comprises TiO 2 Carrier and carrier supported on said TiO 2 Noble metal M on a support 1 And a noble metal M 2 (ii) a The noble metal M 1 Ru, pt, pd or Rh; the noble metal M 2 Ru, pt, pd or Rh; the noble metal M 1 And noble metal M 2 Is made of TiO 2 The carrier is partially coated. The wet oxidation catalyst provided by the invention mainly comprises TiO 2 Support and in TiO 2 Active component M carried on a carrier 1 And M 2 Has high activity and good anti-loss performance. When the wet oxidation catalyst provided by the invention is used for organic amine wastewater treatment, the catalytic activity is high, the active components are not easy to run off, and the cost of organic amine wastewater treatment is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of catalytic synthesis, and particularly relates to a wet oxidation catalyst, and a preparation method and application thereof.
Background
The organic amine wastewater mainly comes from leather, tire, textile and other industries, mainly contains methylamine, triethylamine, ammonia and other trace byproducts, and belongs to high-nitrogen low-carbon wastewater with high concentration, strong toxicity and difficult biodegradation. The direct discharge of untreated organic amine wastewater can cause great harm to human bodies and the surrounding environment. The toxicity of the organic amine wastewater makes the biological treatment technology difficult to treat the organic amine wastewater.
At present, scholars at home and abroad mainly degrade organic amine wastewater by chemical methods and physical methods, wherein catalytic oxidation becomes a research hotspot due to the characteristics of large treatment capacity, excellent degradation effect, short treatment time and the like. The catalytic wet-type oxidant can efficiently treat organic amine wastewater, but the existing catalyst has poor stability and active components are easy to lose.
ZSM-5 molecular sieve (high-silicon zeolite) as a representative of solid acid catalyst can be applied to various catalytic reactions, but the pore diameter is too small, and the size of micropores can limit the catalytic degradation performance of organic amine wastewater. Researches of Wuzhen, zhang Pan Yue and the like find that the pore diameter can be enlarged by adopting the strong base modified ZSM-5 molecular sieve, the problem of limitation of micropore size on catalytic degradation can be solved, but the pore-forming rate and depth are not easy to control, and most of micropores on the outer surface of the ZSM-5 molecular sieve are damaged, so that the stability of the ZSM-5 molecular sieve is greatly reduced, and active components are easy to lose.
In summary, it is a difficult problem for those skilled in the art to obtain a catalyst with a low loss of active components on the basis of ensuring catalytic activity.
Disclosure of Invention
The invention aims to provide a wet oxidation catalyst, a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a wet oxidation catalyst comprising TiO 2 Carrier and carrier supported on said TiO 2 Noble metal M on a support 1 And noble metal M 2 (ii) a The noble metal M 1 Ru, pt, pd or Rh; the noble metal M 2 Ru, pt, pd or Rh; the noble metal M 1 And a noble metal M 2 Is coated with TiO 2 The carrier is partially coated.
Preferably, the noble metal M in the wet oxidation catalyst 1 0.001-1 wt% of noble metal M 2 The content of (B) is 0.005-5 wt%, tiO 2 The balance of carrier.
The invention also provides a preparation method of the wet oxidation catalyst, which comprises the following steps:
adding TiO into the mixture 2 NaOH, water and noble metal M 1 Mixing the precursor salts, and then sequentially carrying out hydrothermal treatment and first thermal reduction to obtain the noble metal M 1 Of TiO (2) 2 (M 1 /TiO 2 )；
Loading the noble metal M 1 Of TiO 2 2 With noble metal M 2 And mixing the precursor salt and the ethylene glycol, and then sequentially carrying out alcohol thermal reduction reaction and second thermal reduction to obtain the wet oxidation catalyst.
Preferably, the temperature of the hydrothermal treatment is 50-200 ℃, and the heat preservation time is 5-50 h.
Preferably, the first thermal reduction is: heating the reaction system to 300-600 ℃ in protective gas, and switching the protective gas to H 2 Reducing at constant temperature for 0.5-5H, and then reacting H 2 Switching to protective gas and cooling to room temperature.
Preferably, the method further comprises, before the first thermal reduction: sequentially cooling, filtering, washing to neutrality and drying the product obtained by the hydrothermal treatment;
before the second thermal reduction, the method further comprises the following steps: sequentially filtering and washing the product obtained by the alcohol thermal reduction reaction until the filtrate is free of Cl - And drying.
Preferably, the alcohol thermal reduction reaction is as follows: will carry noble metal M 1 Of TiO 2 2 Noble metal M 2 Adjusting the pH value of the mixture of the precursor salt and the glycol to 6-12, heating to 50-150 ℃, keeping the temperature, reacting for 1-5 h, cooling the obtained reaction product to room temperature, adjusting the pH value to be below 3, and continuing to react for 1-15 h; the alcohol thermal reduction reaction is carried out in protective gas.
Preferably, the second thermal reduction is: carrying out reduction reaction for 2-12 h at the constant temperature of 300-600 ℃ in a hydrogen atmosphere.
Preferably, the noble metal M 1 The precursor salt is soluble salt of Ru, pt, pd or Rh; the noble metal M 2 The precursor salt is soluble salt of Ru, pt, pd or Rh.
The invention also provides application of the wet oxidation catalyst in the scheme or the wet oxidation catalyst obtained by the preparation method in the scheme in organic amine wastewater treatment.
The invention provides a wet oxidation catalyst comprising TiO 2 Carrier and carrier supported on said TiO 2 Noble metal M on a support 1 And noble metal M 2 (ii) a The noble metal M 1 Ru, pt, pd or Rh; the noble metal M 2 Ru, pt, pd or Rh; the noble metal M 1 And a noble metal M 2 Is made of TiO 2 The carrier is partially coated. The wet oxidation catalyst provided by the invention mainly comprises TiO 2 Support and in TiO 2 Active component noble metal M loaded on carrier 1 And a noble metal M 2 Active component noble metal M 1 And a noble metal M 2 Is partially coated with TiO 2 The special structure of the carrier coating and partial uncovering ensures that the wet oxidation catalyst has high activity and good fluid loss resistanceCan be used. Wherein the noble metal M 1 And noble metal M 2 Partially coated to provide the wet oxidation catalyst of the present invention with good fluid loss resistance, noble metal M 1 And a noble metal M 2 And part of the catalyst is exposed, so that the wet oxidation catalyst has good catalytic activity.
The invention also provides a preparation method of the wet oxidation catalyst. The invention ensures TiO through hydrothermal treatment 2 Carrier to convert noble metal M 1 Coating with precursor salt, and performing first thermal reduction to obtain noble metal M 1 Reduction of precursor salts to noble metals M 1 At this time, the noble metal M 1 Mostly by TiO 2 Coating the carrier, and then carrying out alcohol thermal reduction reaction to ensure that the noble metal M is used 2 In situ immobilization on noble Metal M 1 Bare site (noble metal M) 1 Capable of decomposing ethylene glycol to form active hydrogen species capable of reducing noble metal M 2 Precursor salts, thus noble metals M formed by thermal reduction of alcohols 2 Is fixed in noble metal M 1 Site(s) of a second thermal reduction to make TiO 2 Support for noble metal M 2 And (4) carrying out partial coating, and finally preparing the wet oxidation catalyst. The preparation method provided by the invention is convenient to operate, green and environment-friendly and has good safety.
The invention also provides application of the wet oxidation catalyst in the scheme or the wet oxidation catalyst prepared by the preparation method in the scheme in organic amine wastewater treatment. The wet oxidation catalyst provided by the invention has high catalytic activity when being used for treating organic amine wastewater, and active components are not easy to lose, so that the cost for treating the organic amine wastewater is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows Pt-0.5Pt%/TiO prepared in example 1 of the present invention 2 Electron micrograph of wet oxidation catalyst.
Detailed Description
The invention provides a wet oxidation catalyst comprising TiO 2 Carrier and carrier supported on said TiO 2 Noble metal M on a support 1 And a noble metal M 2 (ii) a The noble metal M 1 Ru, pt, pd or Rh; the noble metal M 2 Ru, pt, pd or Rh; the noble metal M 1 And a noble metal M 2 Is made of TiO 2 The carrier is partially coated.
The wet oxidation catalyst provided by the invention comprises TiO 2 A carrier; tiO in the wet oxidation catalyst 2 The content of the carrier is preferably 94 to 99.994wt%, more preferably 95 to 99wt%, and further preferably 96 to 98wt%.
The wet oxidation catalyst provided by the invention comprises a carrier supported on the TiO 2 Noble metal M on a support 1 And a noble metal M 2 (ii) a The noble metal M 1 Ru, pt, pd or Rh; the noble metal M 2 Ru, pt, pd or Rh; noble metal M in the wet oxidation catalyst 1 The content of (B) is preferably 0.001 to 1wt%, more preferably 0.01 to 0.8wt%, and further preferably 0.1 to 0.5wt%; noble metal M in the wet oxidation catalyst 2 The content of (B) is preferably 0.005 to 5wt%, more preferably 0.01 to 3wt%, and further preferably 0.1 to 1wt%. In the present invention, the wet oxidation catalyst has a general formula of M 2 -M 1 /TiO 2 。
The invention also provides a preparation method of the wet oxidation catalyst, which comprises the following steps:
adding TiO into the mixture 2 NaOH, water and noble metal M 1 Mixing the precursor salts, and then sequentially carrying out hydrothermal treatment and first thermal reduction to obtain the noble metal M 1 Of TiO 2 2 (M 1 /TiO 2 )；
Loading the noble metal M 1 Of TiO 2 2 With noble metals M 2 Mixing the precursor salt and ethylene glycol, and sequentially performing alcohol thermal reduction reaction and second heatReducing to obtain the wet oxidation catalyst.
In the invention, tiO is mixed with 2 NaOH, water and noble metal M 1 Mixing the precursor salts, and then sequentially carrying out hydrothermal treatment and first thermal reduction to obtain the noble metal M 1 Of TiO 2 2 (M 1 /TiO 2 ). In the present invention, the TiO is 2 Is commercially available TiO 2 (ii) a The noble metal M 1 The precursor salt is preferably soluble salt of Ru, pt, pd or Rh; the soluble salt of Pt is preferably H 2 PtCl 6 ·6H 2 O; the soluble salt of Pd is preferably PdCl 2 (ii) a The soluble salt of Rh is preferably RhCl 3 ·3H 2 O; the TiO is 2 And NaOH are preferably 1 to 10, more preferably 2 to 9; the TiO is 2 And water in a mass ratio of preferably 1 to 10; the TiO is 2 And a noble metal M 1 The mass ratio of the precursor salt is preferably 1-10000 to 16000, more preferably 2-1000; the temperature of the hydrothermal treatment is preferably 50-200 ℃, more preferably 90-150 ℃, and further preferably 120 ℃, and the heat preservation time is preferably 5-50 h, more preferably 10-40 h, and further preferably 20-30 h; the equipment for the hydrothermal treatment is preferably a polytetrafluoroethylene lining reaction kettle; the first thermal reduction preferably further comprises: sequentially cooling, filtering, washing to neutrality and drying the product obtained by the hydrothermal treatment; the final temperature of the cooling is preferably room temperature; the filtration is preferably suction filtration; the washing reagent is preferably deionized water; the drying temperature is preferably 40 to 120 ℃, more preferably 60 to 90 ℃.
In the present invention, the first thermal reduction is preferably: heating the reaction system to 300-600 ℃ in protective gas, and switching the protective gas to H 2 Reducing at constant temperature for 0.5-5H, and then reacting H 2 Switching to protective gas and cooling to room temperature; the first thermal reduction apparatus is preferably an atmospheric furnace; the shielding gas is preferably nitrogen or argon. In the present invention, the TiO is 2 NaOH, water and noble metal M 1 The precursor salt mixture is preferably: adding TiO into the mixture 2 Mixing with NaOH aqueous solution uniformlyAnd (4) homogenizing, and mixing the obtained mixed solution with the precursor salt of the noble metal M1.
Obtaining the noble metal M 1 Of TiO 2 2 (M 1 /TiO 2 ) Then, the invention combines M 1 /TiO 2 Noble metal M 2 And mixing the precursor salt and the ethylene glycol, and then sequentially carrying out alcohol thermal reduction reaction and second thermal reduction to obtain the wet oxidation catalyst. In the present invention, the noble metal M 2 Preferably Ru, pt, pd or Rh; said M 1 /TiO 2 And ethylene glycol preferably in a mass ratio of 1 to 10, more preferably 2 to 9; the M is 1 /TiO 2 Noble metal M 2 The precursor salt and the ethylene glycol are preferably mixed: mixing ethylene glycol with M 1 /TiO 2 After ultrasonic mixing, inert gas is introduced and stirred at room temperature (first stirring), and noble metal M is added 2 Stirring the glycol solution of the precursor salt at room temperature (denoted as second stirring); said M 1 /TiO 2 Noble metal M 2 The equipment for mixing the precursor salt and the ethylene glycol is preferably a three-neck round-bottom flask; the ultrasonic equipment is preferably an ultrasonic instrument; the time of the ultrasonic treatment is preferably 0.5 to 5 hours, and more preferably 2 to 4 hours; the oil bath heating equipment is preferably an oil bath pan; the first stirring time is preferably 10 to 60min, and more preferably 30 to 50min; the second stirring time is preferably 10 to 60min, and more preferably 40 to 50min.
In the present invention, the thermal reduction reaction of alcohol is preferably: will carry noble metal M 1 Of TiO (2) 2 Noble metal M 2 Adjusting the pH value of the mixture of the precursor salt and the glycol to 6-12 (marked as a first pH value), heating to 50-150 ℃ (marked as a first temperature), keeping the temperature for reaction for 1-5 h (marked as a first reaction time), then cooling the obtained reaction product to room temperature, adjusting the pH value to be below 3 (marked as a second pH value), and continuing the reaction for 1-15 h (marked as a second reaction time); the first pH value is preferably 7 to 11, more preferably 8 to 10; adjusting the noble metal M 1 Of TiO 2 2 Noble metal M 2 The reagent used for the pH value of the mixture of the precursor salt and the glycol is preferably NaOH glycol solution; adjusting the noble metal M 1 Of TiO 2 2 Noble and honourMetal M 2 Preferably, the pH of the mixture of the precursor salt and ethylene glycol is followed by stirring of the resulting product (denoted as third stirring); the third stirring time is preferably 10 to 60min, and more preferably 20 to 50min; the first temperature is preferably 60 to 130 ℃, and more preferably 80 to 110 ℃; the first reaction time is preferably 2 to 5 hours, and more preferably 3 to 4 hours; the second pH value is preferably 1 to 3, more preferably 1 to 2; the reagent used for adjusting the pH value after cooling the obtained reaction product to room temperature is preferably hydrochloric acid; the second reaction time is preferably 6 to 12 hours, and more preferably 8 to 10 hours; the alcohol thermal reduction reaction is preferably carried out in a protective gas; the shielding gas is preferably nitrogen or argon.
In the present invention, the second thermal reduction is preferably: carrying out constant-temperature reduction reaction for 2-12 h at 300-600 ℃ in hydrogen atmosphere; the temperature of the second thermal reduction is preferably 350 to 550 ℃, more preferably 400 to 500 ℃, and the time of the second thermal reduction is preferably 3 to 10 hours, more preferably 5 to 8 hours. In the present invention, it is preferable that before the second thermal reduction, the method further comprises: sequentially filtering and washing the product obtained by the alcohol thermal reduction reaction until the filtrate is free of Cl - And drying; the filtration is preferably vacuum filtration; the washing reagent is preferably deionized water; the drying device is preferably a vacuum drying oven, the drying temperature is preferably 40-120 ℃, more preferably 60-100 ℃, further preferably 80 ℃, and the heat preservation time is preferably 2-48 h, more preferably 10-30 h.
The invention also provides application of the wet oxidation catalyst in the scheme or the wet oxidation catalyst obtained by the preparation method in the scheme in organic amine wastewater treatment.
In the present invention, the application of the wet oxidation catalyst in the organic amine wastewater treatment preferably comprises the following steps: mixing the wet oxidation catalyst and the organic amine wastewater to perform catalytic oxidation reaction. In the present invention, the mass ratio of the wet oxidation catalyst to the organic amine waste water is preferably 1 to 10.
In order to further illustrate the present invention, the following examples are given as illustrative embodiments of the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of a wet oxidation catalyst comprises the following steps:
(1) Adding TiO into the mixture 2 After being mixed with NaOH aqueous solution evenly, 0.0665g of noble metal precursor salt H is added 2 PtCl 6 ·6H 2 O, obtaining a mixed solution;
(2) Transferring the mixed solution into a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 140 ℃ for 20h, cooling to room temperature, then carrying out suction filtration and washing by using deionized water until the pH value of the filtrate is neutral, drying the solid powder obtained by suction filtration at 100 ℃ to obtain noble metal modified TiO 2 ；
(3) Modifying the obtained noble metal into TiO 2 Putting the solid powder into an atmosphere furnace, heating to 500 ℃ in nitrogen, and switching the inert gas to H 2 Reducing for 2H at constant temperature, and after reduction, adding H 2 Switching to inert gas and cooling to room temperature to obtain Pt/TiO 2 ；
(4) Adding ethylene glycol and Pt/TiO into a three-neck round-bottom flask 2 And placing the mixture in an ultrasonic instrument for ultrasonic treatment for 2 hours;
(5) Transferring the three-neck round-bottom flask into an oil bath pot, introducing inert gas to exhaust the air in the flask, stirring at room temperature for 40min, measuring 6.65mL of 10g/LH 2 PtCl 6 Adding a glycol solution noble metal precursor salt into the three-neck flask, and stirring at room temperature for 40min;
(6) Adding NaOH glycol solution into the obtained solution, adjusting the pH value to 8, continuously stirring for 40min, raising the temperature to 120 ℃, reacting for 3h, and continuously introducing nitrogen for protection in the whole process;
(7) Stopping heating after the reaction is finished, cooling to room temperature, adjusting the pH value to 2 with hydrochloric acid solution, continuously stirring for 8h, carrying out vacuum filtration on the obtained solid-liquid mixture, and washing with deionized water until the filtrate is free of Cl - Then, the obtained material is placed in a vacuum drying oven, dried for 24h at 100 ℃, and then thermally treated for 4h at 400 ℃ in a hydrogen atmosphere to obtain 0.5% of Pt-0.5% of Pt/TiO 2 Catalyst, appearance as shown in FIG. 1Shown in the figure.
FIG. 1 shows Pt-0.5Pt%/TiO prepared in this example 2 Electron micrograph of catalyst, it can be seen from FIG. 1 that Pt active component (black particles) is partially coated with TiO 2 Carrier coating (contrast around Pt nanoparticles is lighter in color and shines).
Example 2
This example differs from example 1 in that 0.069g of Na was added in step (1) 2 PdCl 4 The solid was otherwise the same as in example 1, to give 0.5% Pt-0.5Pd%/TiO 2 A catalyst.
Example 3
This example differs from example 1 in that 6.9mL of 10g/L Na was added in step (5) 2 PdCl 4 Ethylene glycol solution, otherwise the same as in example 1, 0.5% Pd-0.5Pt%/TiO 2 A catalyst.
Example 4
This example differs from example 1 in that 0.064g of RhCl was added in step (1) 3 ·3H 2 O solid, otherwise the same as in example 1, 0.5% Pt-0.5 Rh%/TiO% was obtained 2 A catalyst.
Example 5
This example differs from example 1 in that 6.4mL of 10g/L RhCl was added in step (5) 3 Ethylene glycol solution, otherwise the same as in example 1, 0.5% Rh-0.5Pt%/TiO 2 A catalyst.
Comparative example 1
This comparative example differs from example 1 in that 0.133g of H was added in step (1) 2 PtCl 6 ·6H 2 O noble metal precursor salt, and the preparation of the catalyst is finished in the step (3), and the catalyst is recorded as 1Pt%/TiO 2 。
Comparative example 2
This comparative example differs from example 1 in that the catalyst preparation starts from step (4) and ethylene glycol and TiO are added 2 13.3mL of 10g/L H was measured in step (5) 2 PtCl 6 Ethylene glycol solution noble metal, catalyst 1Pt% -TiO 2 。
The wet oxidation catalysts prepared in examples 1 to 5 of the present invention were subjected to catalytic oxidation performance tests under the following conditions: 0.1g of 0.5% Pt-Pt/TiO 2 Mixing a catalyst and 10mL of wastewater with a pH value of 10 (the content of dimethylformamide is 1000ppm, the content of COD is 1300 mg/L), placing the mixture into a high-pressure reaction kettle, and carrying out catalytic reaction for 2 hours under the conditions that the temperature is 180 ℃ and the pressure is 2 MPa; the ammonia nitrogen content was detected by the na's reagent method, the active component loss was detected by ICP, and the metal loss rate of the catalyst, the ammonia nitrogen conversion rate in the wastewater and the removal rate of COD after the catalytic reaction were calculated, the results are shown in table 1.
TABLE 1 catalytic Oxidation Performance of Wet Oxidation catalysts prepared in examples 1 to 5
| Examples | COD conversion (%) | Ammonia nitrogen conversion (%) | Metal loss (%) |
| 1 | 98.3 | 97.5 | No loss was detected |
| 2 | 96.6 | 95.2 | No loss was detected |
| 3 | 97.2 | 96.8 | No loss was detected |
| 4 | 99.1 | 98.3 | No loss was detected |
| 5 | 98.5 | 97.1 | No bleed was detected |
The catalysts prepared in comparative examples 1 to 2 of the present invention were subjected to catalytic oxidation performance tests under the same conditions as above, and the results are shown in table 2.
TABLE 2 catalytic Oxidation Performance of catalysts prepared in comparative examples 1-2
| Comparative example | COD conversion (%) | Ammonia-nitrogen conversion (%) | Metal loss (%) |
| 1 | 58.7 | 47.8 | No loss was detected |
| 2 | 91.9 | 90.2 | 26.1 |
As is clear from tables 1 and 2, comparative example 1, in which a double amount of noble metal precursor salt was added, produced a single metal catalyst 1Pt%/TiO 2 Comparative example 2A single metal catalyst 1Pt%/TiO was prepared by adding double the amount of a noble metal precursor salt 2 The invention adds noble metal precursor salt twice to prepare the wet oxidation catalyst. Compared with the single metal catalysts prepared in the comparative examples 1 and 2, the wet oxidation catalyst prepared by the invention has high catalytic efficiency which can reach 99.1%, the ammonia nitrogen conversion rate can reach 98.3%, and no metal loss occurs, so that the wet oxidation catalyst provided by the invention has high catalytic activity when being used for organic amine wastewater treatment, active components are not easy to lose, and the cost of organic amine wastewater treatment is reduced. In addition, comparative example 1, in which only hydrothermal treatment and the first thermal reduction were performed, the noble metal of the prepared catalyst was mostly coated and the active sites were insufficient, resulting in poor catalytic performance of the catalyst.
The above examples show that the wet oxidation catalyst provided by the invention is used for organic amine wastewater treatment, and has high catalytic activity and active components are not easy to run off.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A wet oxidation catalyst comprising TiO 2 Carrier and carrier supported on said TiO 2 Noble metal M on a support 1 And a noble metal M 2 (ii) a The noble metal M 1 Ru, pt, pd or Rh; the noble metal M 2 Ru, pt, pd or Rh; the noble metal M 1 And a noble metal M 2 Is coated with TiO 2 The carrier is partially coated.
2. The wet oxidation catalyst of claim 1 wherein the noble metal M of the wet oxidation catalyst is noble metal M 1 0.001-1 wt% of a noble metal M 2 The content of (B) is 0.005-5 wt%, tiO 2 The balance of carrier.
3. A method for preparing a wet oxidation catalyst according to any one of claims 1 to 2, comprising the steps of:
adding TiO into the mixture 2 NaOH, water and noble metal M 1 Mixing the precursor salts, and then sequentially carrying out hydrothermal treatment and first thermal reduction to obtain the noble metal M 1 Of TiO 2 2 ；
Loading the noble metal M 1 Of TiO 2 2 With noble metal M 2 And mixing the precursor salt and the ethylene glycol, and then sequentially carrying out alcohol thermal reduction reaction and second thermal reduction to obtain the wet oxidation catalyst.
4. The preparation method according to claim 3, wherein the hydrothermal treatment temperature is 50-200 ℃ and the holding time is 5-50 h.
5. The method of claim 3, wherein the first thermal reduction is: heating the reaction system to 300-600 ℃ in protective gas, and switching the protective gas to H 2 Reducing at constant temperature for 0.5-5H, and then reacting H 2 Switching to protective gas and cooling to room temperature.
6. The method of claim 3 or 5, further comprising, prior to the first thermal reduction: sequentially cooling, filtering, washing to neutrality and drying the product obtained by the hydrothermal treatment;
before the second thermal reduction, the method further comprises the following steps: sequentially filtering and washing the product obtained by the alcohol thermal reduction reaction until the filtrate is free of Cl - And drying.
7. The method according to claim 3, wherein the alcohol thermal reduction reaction is: will carry noble metal M 1 Of TiO 2 2 Noble metal M 2 Adjusting the pH value of a mixture of the precursor salt and the glycol to 6-12, heating to 50-150 ℃, keeping the temperature, reacting for 1-5 h, cooling the obtained reaction product to room temperature, adjusting the pH value to be below 3, and continuing to react for 1-15 h; the alcohol thermal reduction reaction is carried out in protective gas.
8. The method of claim 3, wherein the second thermal reduction is: carrying out reduction reaction for 2-12 h at the constant temperature of 300-600 ℃ in the hydrogen atmosphere.
9. The method according to claim 3, wherein the noble metal M is 1 The precursor salt is soluble salt of Ru, pt, pd or Rh; the noble metal M 2 The precursor salt is soluble salt of Ru, pt, pd or Rh.
10. Use of the wet oxidation catalyst according to any one of claims 1 to 2 or the wet oxidation catalyst obtained by the production method according to any one of claims 3 to 9 in organic amine wastewater treatment.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854900A (en) * | 2016-04-27 | 2016-08-17 | 厦门大学 | Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof |
| WO2016173285A1 (en) * | 2015-04-28 | 2016-11-03 | 华南理工大学 | Supported catalyst having core-shell structure, preparation method therefor, and application thereof |
| CN109465008A (en) * | 2018-11-19 | 2019-03-15 | 厦门大学 | A kind of catalytic wet oxidation catalyst and its preparation method and application |
| CN111135823A (en) * | 2020-01-14 | 2020-05-12 | 厦门大学 | Wet oxidation catalyst and preparation method and application thereof |
| CN113000052A (en) * | 2021-02-19 | 2021-06-22 | 厦门大学 | Wet oxidation catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016173285A1 (en) * | 2015-04-28 | 2016-11-03 | 华南理工大学 | Supported catalyst having core-shell structure, preparation method therefor, and application thereof |
| CN105854900A (en) * | 2016-04-27 | 2016-08-17 | 厦门大学 | Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof |
| CN109465008A (en) * | 2018-11-19 | 2019-03-15 | 厦门大学 | A kind of catalytic wet oxidation catalyst and its preparation method and application |
| CN111135823A (en) * | 2020-01-14 | 2020-05-12 | 厦门大学 | Wet oxidation catalyst and preparation method and application thereof |
| CN113000052A (en) * | 2021-02-19 | 2021-06-22 | 厦门大学 | Wet oxidation catalyst and preparation method and application thereof |
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