CN113000052A - 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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- CN113000052A CN113000052A CN202110190985.9A CN202110190985A CN113000052A CN 113000052 A CN113000052 A CN 113000052A CN 202110190985 A CN202110190985 A CN 202110190985A CN 113000052 A CN113000052 A CN 113000052A
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/007—Mixed salts
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- 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
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- 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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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- 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
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/20—Total organic carbon [TOC]
Abstract
The invention provides a wet oxidation catalyst, a preparation method and application thereof, and belongs to the technical field of catalysts. The wet oxidation catalyst takes nickel-iron hydrotalcite as a carrier and precious metal Pt as an active component; the noble metal Pt is in an electron-rich state; the mass of the active component is 0.001-1% of the mass of the carrier. The Pt in the catalyst provided by the invention is in an electron-rich state, and is beneficial to activation and transfer of oxygen, so that the Pt can promote the oxidation of formaldehyde under the condition of extremely low dosage, thereby improving the catalytic activity of the catalyst, reducing the working temperature of the catalyst, not only reducing the production cost of the catalyst, but also reducing the cost of removing formaldehyde due to low working temperature. The results of the examples show that the removal rate of formaldehyde of the wet oxidation catalyst can reach 100% at the highest under the room temperature condition, and the removal rate of TOC is more than 93%.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a wet oxidation catalyst and a preparation method and application thereof.
Background
Formaldehyde is a chemical raw material with wide application, but a large amount of wastewater containing formaldehyde is generated in the production and utilization processes of the formaldehyde, and the existence of the formaldehyde not only destroys the ecological environment of a water body, but also harms human health.
The prior art for treating the formaldehyde wastewater mainly comprises the following steps: 1. physical methods such as a high-temperature combustion method, an adsorption method, a lime method, an ion exchange method, and the like; 2. biological methods such as anaerobic and aerobic methods; 3. chemical methods such as fenton's reagent oxidation, photocatalytic method, and catalytic wet oxidation. In general, physical methods have disadvantages such as low removal rate, high running cost, and secondary pollution. Biological methods are less suitable for high concentration wastewater because high concentration wastewater can reduce the activity of microorganisms, thereby reducing the treatment effect and increasing the treatment cost. The chemical method not only has wide application range, but also can treat the wastewater with different concentrations, thereby being widely researched and applied.
The catalytic wet-type oxidant technology can more effectively remove formaldehyde in wastewater, but the existing effective catalyst has high content of noble metal, and the removal rate of formaldehyde still needs to be further improved.
Disclosure of Invention
The invention aims to provide a wet oxidation catalyst, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a wet oxidation catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier comprises nickel iron hydrotalcite, and the active component comprises a noble metal Pt; the noble metal Pt is in an electron-rich state; the mass of the active component is 0.001-1% of the mass of the carrier.
Preferably, the mass of the active component is 0.0015-0.8% of the mass of the carrier.
The invention provides a preparation method of the wet oxidation catalyst, which comprises the following steps:
mixing a divalent nickel salt, a trivalent iron salt, a precipitating agent and water to obtain a mixed solution;
adjusting the pH value of the mixed solution to 8-10, carrying out hydrothermal reaction on the mixed solution after the pH value is adjusted, and drying and calcining solid products obtained by the hydrothermal reaction in sequence to obtain a nickel-iron hydrotalcite carrier;
mixing the nickel-iron hydrotalcite carrier, the Pt precursor and water to obtain mixed feed liquid; the mass of Pt in the Pt precursor is 0.001-1% of that of the ferronickel hydrotalcite carrier;
and mixing the mixed feed liquid with a reducing agent aqueous solution, carrying out reduction reaction, carrying out solid-liquid separation on a product of the reduction reaction, drying a solid product, and roasting the obtained dried product in a hydrogen atmosphere to obtain the wet oxidation catalyst.
Preferably, the divalent nickel salt is nickel nitrate or nickel chloride; the ferric iron salt is ferric nitrate or ferric chloride; the precipitator is urea or ammonium chloride, and the molar ratio of the divalent nickel salt, the ferric salt and the precipitator is (1-5): (0.5-2): 4-10).
Preferably, the temperature of the hydrothermal reaction is 50-150 ℃ and the time is 15-24 h.
Preferably, the calcining temperature is 200-600 ℃, and the time is 2-10 h.
Preferably, the Pt precursor is chloroplatinic acid; the reducing agent in the reducing agent aqueous solution is sodium borohydride or hydrazine hydrate; the concentration of the reducing agent aqueous solution is 0.001-0.1 mol/L; the molar ratio of the reducing agent to the Pt precursor in the reducing agent aqueous solution is (1.1-2.0): 1.
preferably, the roasting temperature is 100-200 ℃, and the roasting time is 2-10 h.
The invention provides an application of the wet oxidation catalyst or the wet oxidation catalyst prepared by the preparation method in the scheme in the treatment of formaldehyde-containing wastewater.
Preferably, the method of application comprises the steps of: mixing the wet oxidation catalyst with the formaldehyde-containing wastewater, and introducing oxygen into the obtained mixed system to perform oxidation reaction; the temperature of the oxidation reaction is normal temperature.
The invention provides a wet oxidation catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier comprises nickel iron hydrotalcite, and the active component comprises a noble metal Pt; the noble metal Pt is in an electron-rich state; the mass of the active component is 0.001-1% of the mass of the carrier.
The Pt in the catalyst provided by the invention is in an electron-rich state, and is beneficial to activation and transfer of oxygen, so that the Pt can promote the oxidation of formaldehyde under the condition of extremely low dosage, thereby improving the catalytic activity of the catalyst, improving the formaldehyde removal effect, reducing the working temperature of the catalyst, not only reducing the production cost of the catalyst, but also reducing the cost for removing formaldehyde due to low working temperature. The results of the examples show that the removal rate of formaldehyde and the removal rate of TOC of the wet oxidation catalyst can reach 100% under the room temperature condition, and are more than 93%.
In addition, the catalyst prepared by the invention contains iron and nickel, so that the catalyst has stronger magnetism, is convenient to recover after formaldehyde wastewater is treated, and can greatly reduce the production cost.
The catalyst prepared by the invention also has excellent cycle performance, the activity of the catalyst is kept stable after 5 times of cycle in the process of treating the formaldehyde wastewater, the removal rate of formaldehyde is basically unchanged, and the catalyst is suitable for industrial process.
Drawings
FIG. 1 is a 4f orbital XPS characterization of Pt in the 0.0025Pt/LDHs (pre) catalyst prepared in example 1;
FIG. 2 is a 4f orbital XPS characterization of Pt in the 0.0025Pt/LDHs (pre) catalyst prepared in example 4.
Detailed Description
The invention provides a wet oxidation catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier comprises nickel iron hydrotalcite, and the active component comprises a noble metal Pt; the noble metal Pt is in an electron-rich state; the mass of the active component is 0.001-1% of the mass of the carrier.
In the invention, the mass of the active component is preferably 0.0015-0.8%, more preferably 0.002-0.75%, and even more preferably 0.0025-0.7% of the mass of the carrier. In the present invention, the active ingredient is located on the surface of the carrier; the active component is present in the form of elemental, electron-rich Pt. In the present invention, the noble metal Pt is at 4f7/2The binding energy of the orbitals is less than 71.2eV, specifically 70.4eV or 70.0eV in embodiments of the present invention.
In the invention, the molar ratio of nickel to iron in the nickel-iron hydrotalcite is preferably (1-5): (0.5 to 2), and more preferably 3: 1.
The Pt in the catalyst provided by the invention is in an electron-rich state, and is beneficial to activation and transfer of oxygen, so that the Pt can promote the oxidation of formaldehyde under the condition of extremely low consumption, thereby improving the catalytic activity of the catalyst, reducing the working temperature of the catalyst and catalyzing the efficient oxidation of formaldehyde at room temperature.
The invention provides a preparation method of the wet oxidation catalyst, which comprises the following steps: mixing a divalent nickel salt, a trivalent iron salt, a precipitating agent and water to obtain a mixed solution;
adjusting the pH value of the mixed solution to 8-10, carrying out hydrothermal reaction on the mixed solution after the pH value is adjusted, and drying and calcining solid products obtained by the hydrothermal reaction in sequence to obtain a nickel-iron hydrotalcite carrier;
mixing the nickel-iron hydrotalcite carrier, the Pt precursor and water to obtain mixed feed liquid; the mass of Pt in the Pt precursor is 0.001-1% of that of the ferronickel hydrotalcite carrier;
and mixing the mixed material liquid with a reducing agent aqueous solution, carrying out reduction reaction, carrying out solid-liquid separation on a product of the reduction reaction, drying a solid product, and roasting the obtained dried product in a hydrogen atmosphere to obtain the wet oxidation catalyst.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
According to the invention, a divalent nickel salt, a trivalent iron salt, a precipitator and water are mixed to obtain a mixed solution.
In the present invention, the divalent nickel salt is preferably nickel nitrate or nickel chloride; the ferric salt is preferably ferric nitrate or ferric chloride; the precipitating agent is preferably urea or ammonium chloride. In the present invention, when the corresponding substance of the divalent nickel salt or the trivalent iron salt also exists as a hydrate, the divalent nickel salt or the trivalent iron salt also includes a hydrate corresponding thereto. In the invention, the molar ratio of the divalent nickel salt, the trivalent iron salt and the precipitating agent is preferably (1-5): (0.5-2): (4-10), more preferably 3:1: 7.5. The invention has no special requirement on the dosage of the water, and can completely dissolve the divalent nickel salt, the trivalent ferric salt and the precipitator.
In the present invention, the process of mixing the divalent nickel salt, the trivalent iron salt, the precipitant, and water is preferably: dissolving a divalent nickel salt and a trivalent ferric salt in water to obtain a first solution; dissolving a precipitant in water to obtain a second solution; and mixing the first solution and the second solution to obtain a mixed solution.
After the mixed solution is obtained, the pH value of the mixed solution is adjusted to 8-10, and the mixed solution after the pH value is adjusted is subjected to hydrothermal reaction.
The pH value of the mixed solution is preferably adjusted to 8-10 by adopting a sodium hydroxide solution or a potassium hydroxide solution. The pH value of the mixed solution is adjusted to 8-10, so that the growth of the nickel-iron hydrotalcite carrier in the subsequent hydrothermal reaction process is facilitated.
In the invention, the temperature of the hydrothermal reaction is preferably 50-150 ℃, more preferably 60-120 ℃, and further preferably 70-100 ℃; the time is preferably 15 to 24 hours, more preferably 17 to 22 hours, and further preferably 18 to 20 hours. In the present invention, the hydrothermal reaction is preferably carried out under stirring. The invention has no special requirements on the specific stirring conditions, and can uniformly mix all the materials. In the hydrothermal reaction process, the divalent nickel salt, the trivalent ferric salt and the precipitator react to generate the ferronickel hydrotalcite.
After the hydrothermal reaction is finished, the product system of the hydrothermal reaction is preferably subjected to suction filtration and washing to obtain a solid product of the hydrothermal reaction.
After a solid product of the hydrothermal reaction is obtained, the solid product of the hydrothermal reaction is sequentially dried and calcined to obtain the nickel-iron hydrotalcite carrier.
The drying conditions of the present invention are not particularly limited, and those well known in the art may be used.
In the invention, the calcination temperature is preferably 200-600 ℃, more preferably 300-500 ℃, and most preferably 400 ℃; the calcination time is preferably 2-10 h, and more preferably 4-8 h. In the present invention, the calcination is preferably performed in an air atmosphere. In the calcining process, the nickel-iron hydrotalcite carrier forms a porous structure.
After the nickel-iron hydrotalcite carrier is obtained, mixing the nickel-iron hydrotalcite carrier, a Pt precursor and water to obtain mixed feed liquid; the mass of Pt in the Pt precursor is 0.001-1% of the mass of the ferronickel hydrotalcite carrier.
In the present invention, the Pt precursor is preferably chloroplatinic acid; the chloroplatinic acid may be, but is not limited to, chloroplatinic acid hexahydrate.
In the invention, the mass of Pt in the Pt precursor is preferably 0.0015-0.8% of the mass of the ferronickel hydrotalcite carrier, more preferably 0.002-0.75%, and even more preferably 0.0025-0.7%.
The method has no special requirement on the using amount of the water, and can completely immerse the nickel-iron hydrotalcite carrier. In the embodiment of the invention, the dosage ratio of the nickel iron hydrotalcite carrier to the water is 1g:75 mL.
In the present invention, the process of mixing the nickel iron hydrotalcite support, Pt precursor and water is preferably: dispersing the nickel-iron hydrotalcite carrier in water, adding the Pt precursor under the stirring condition, and soaking for more than 30 min.
In the present invention, the Pt precursor is preferably used as an aqueous Pt precursor solution. In the invention, the concentration of the Pt precursor water solution is preferably 5-15 mg/mL, and more preferably 10 mg/mL.
After the mixed material liquid is obtained, the mixed material liquid is mixed with a reducing agent aqueous solution to carry out reduction reaction, a product of the reduction reaction is subjected to solid-liquid separation and solid product drying, and the obtained dried product is roasted in a hydrogen atmosphere to obtain the wet oxidation catalyst.
In the present invention, the reducing agent in the reducing agent aqueous solution is preferably sodium borohydride or hydrazine hydrate; the concentration of the reducing agent aqueous solution is preferably 0.001-0.1 mol/L, more preferably 0.01-0.08 mol/L, and further preferably 0.03-0.05 mol/L. In the present invention, the molar ratio of the reducing agent to the Pt precursor in the reducing agent aqueous solution is preferably (1.1 to 2.0): 1, more preferably (1.3 to 1.8): 1, more preferably (1.4 to 1.6): 1.
according to the invention, the reducing agent aqueous solution is preferably added into the mixed feed liquid to realize the mixing of the reducing agent aqueous solution and the mixed feed liquid. In the invention, the addition mode of the aqueous solution of the reducing agent is preferably dropwise, and the invention has no special requirement on the dropwise addition rate and can be dropwise added. The invention has better reduction effect by adopting a dripping mode. The aqueous solution of the reducing agent is preferably added under stirring in the present invention. The present invention does not require any particular speed of agitation, and can employ agitation speeds well known in the art.
In the process of dropwise adding a reducing agent aqueous solution, the Pt precursor is reduced into a Pt simple substance and loaded on the surface of the ferronickel hydrotalcite carrier.
The invention has no special requirement on the time of the reduction reaction, and the precipitation is not increased any more.
The method has no special requirement on the solid-liquid separation mode, and the solid-liquid separation mode well known in the field can be adopted, and the solid-liquid separation mode can be suction filtration.
After the solid-liquid separation, the present invention preferably further comprises washing the solid product. The washing mode of the invention has no special requirement, and the washing mode which is well known in the field can be adopted.
The present invention has no special requirement on the drying mode of the solid product, and the drying mode well known in the field can be adopted.
In the invention, the roasting temperature is preferably 100-200 ℃, more preferably 120-180 ℃, and further preferably 140-160 ℃; the time is preferably 3-4 h, and more preferably 3.5 h. The method is characterized in that the ferronickel hydrotalcite carrier is partially reduced by roasting in a hydrogen atmosphere, and electrons are transferred to Pt by the reduced carrier, so that the elemental Pt is in an electron-rich state.
The invention provides an application of the wet oxidation catalyst or the wet oxidation catalyst prepared by the preparation method in the scheme in the treatment of formaldehyde-containing wastewater.
In the present invention, the method of application comprises the steps of: and mixing the wet oxidation catalyst with the formaldehyde-containing wastewater, and introducing oxygen into the obtained mixed system to perform oxidation reaction.
The invention has no special requirement on the concentration of formaldehyde in the formaldehyde-containing wastewater, and the concentration can be any. In the present invention, the concentration of formaldehyde in the formaldehyde-containing wastewater is 1000 ppm.
In the present invention, when the concentration of formaldehyde in the wastewater is less than 1000ppm, the amount of the wet oxidation catalyst is preferably 1 to 10g/L, more preferably 3 to 7g/L, and still more preferably 4 to 6 g/L.
In the present invention, the amount of the oxygen is preferably such that the pressure of the mixed system is 0.5 to 5MPa, more preferably 1 to 4MPa, and even more preferably 2 to 3 MPa.
In the present invention, the oxidation reaction is preferably carried out at normal temperature.
In the invention, the time of the oxidation reaction is preferably 1-12 h, and more preferably 2-8 h. In the examples of the present invention, the time of the oxidation reaction was 3 hours.
The wet oxidation catalyst provided by the present invention, the preparation method and the application thereof are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) 2.44gNi (NO)3)2·6H2O，1.13gFe(NO3)3·9H2Dissolving O in 30mL of deionized water;
(2) dissolving 1.26g of urea in 30mL of deionized water, mixing with the solution in the step (1), and uniformly stirring to obtain a mixed solution;
(3) dropwise adding a sodium hydroxide solution into the mixed solution to adjust the pH value of the solution to 8.5;
(4) placing the mixed solution with the adjusted pH value into a hydrothermal reaction kettle, wherein the reaction temperature is 50 ℃, and the reaction time is 19 hours;
(5) after hydrothermal treatment, carrying out suction filtration, washing and drying on the obtained product, and calcining the product in a muffle furnace at 400 ℃ for 6 hours to obtain a nickel-iron hydrotalcite carrier, which is recorded as LDHs (hyd);
(6) dispersing 1g of LDHs (hyd) in 75mL of water, adding 6.65 mu L of chloroplatinic acid hexahydrate under the stirring condition, and soaking for 30min, wherein the concentration of the chloroplatinic acid hexahydrate is 10 mg/mL;
(7) 1mLNaBH was added with stirring4(0.1mol/L) of aqueous solution, and carrying out reduction reaction;
(8) and (3) carrying out suction filtration, washing and drying on a product obtained by the reduction reaction, and roasting in a hydrogen atmosphere at the roasting temperature of 100 ℃ for 3h to obtain the 0.0025Pt/LDHs (hyd) wet oxidation catalyst.
XPS characterization of the 0.0025Pt/LDHs (hyd) wet oxidation catalyst prepared in example 1 is shown in FIG. 1. The dotted line in FIG. 1 is the sum of the three peaks, and from the XPS nist database, Pt is at 4f7/2The orbital binding energy was 71.2eV, whereas the binding energy of Pt in the catalyst of example 1 was shifted to a low band, the binding energy was 70.4eV, and Pt was in an electron-rich state, in a negative valence state.
Example 2
The only difference from example 1 was that the amount of chloroplatinic acid hexahydrate solution added was adjusted to 2.66. mu.L, and the resulting catalyst was reported as 0.001Pt/LDHs (hyd).
Example 3
The only difference from example 1 was that the amount of chloroplatinic acid hexahydrate solution added was adjusted to 26.60. mu.L, and the resulting catalyst was reported as 0.01Pt/LDHs (hyd).
Example 4
(1) Mixing 6.03g of NiCl2·6H2O、2.28g FeCl3·6H2Dissolving O in 500mL of deionized water to obtain a mixed solution;
(2) dissolving 9.63g of ammonium chloride in 400mL of deionized water to obtain a solution;
(3) mixing the solution in the step (2) with the solution in the step (1) to obtain a mixed solution;
(4) dropwise adding a sodium hydroxide solution into the mixed solution to adjust the pH value of the solution to 9;
(5) carrying out hydrothermal reaction on the mixed solution after the pH value is adjusted under stirring, wherein the reaction temperature is 60 ℃, and the reaction time is 22 h; carrying out suction filtration, washing and drying on the obtained product, and then calcining for 6h at 400 ℃ to obtain a nickel-iron hydrotalcite carrier, which is recorded as LDHs (pre);
(6) dispersing 1g of LDHs (pre) in 75mL of water, adding 6.65 mu L of chloroplatinic acid hexahydrate under the stirring condition, and soaking for 30min, wherein the concentration of the chloroplatinic acid hexahydrate is 10 mg/mL;
(7) 1mLNaBH was added with stirring4(0.1mol/L) of aqueous solution, and carrying out reduction reaction;
(8) and (3) carrying out suction filtration, washing and drying on a product obtained by the reduction reaction, and roasting in a hydrogen atmosphere at the roasting temperature of 100 ℃ for 3h to obtain the wet oxidation catalyst which is marked as 0.0025Pt/LDHs (pre).
XPS characterization of the 0.0025Pt/LDHs (pre) wet oxidation catalyst prepared in example 4 is shown in FIG. 2. The dashed line in FIG. 2 is the sum of the three peaks, and from the XPS nist database, Pt is at 4f7/2The orbital binding energy was 71.2eV, whereas the binding energy of Pt in the catalyst of example 4 was shifted to a low band, the binding energy was 70.0eV, and Pt was in an electron-rich state, with a negative valence.
Example 5
The other steps were the same as in example 3 except that the amount of chloroplatinic acid hexahydrate solution added in example 3 was adjusted to 2.66. mu.L, and the catalyst thus obtained was designated as 0.001Pt/LDHs (pre).
Example 6
The other steps were the same as in example 3 except that the amount of chloroplatinic acid hexahydrate in example 3 was adjusted to 26.6. mu.L, and the catalyst thus obtained was designated as 0.01Pt/LDHs (pre).
Comparative example 1
Catalyst preparation referring to example 1, except that chloroplatinic acid hexahydrate was not added, ldhs (pre) catalysts were prepared.
Comparative example 2
Catalyst preparation referring to example 4, except that chloroplatinic acid hexahydrate was not added, ldhs (pre) catalysts were prepared.
Comparative example 3
Preparing Pt/LDHs (hyd-im) catalyst by an impregnation method.
LDHs (hyd) carrier preparation same as comparative example 1;
1g of LDHs (hyd) carrier was added with 2.26. mu.L of chloroplatinic acid hexahydrate solution (10mg/mL), evaporated to dryness using a rotary evaporator, and then H2Roasting the mixture for 3 hours at 100 ℃ in the atmosphere to obtain the catalyst which is marked as 0.0025Pt/LDHs (hyd-im).
Comparative example 4
The Pt/LDHs (pre-im) catalyst is prepared by an impregnation method.
LDHs (pre) vectors were prepared as in example 4;
1g of LDHs (pre) carrier was added with 2.26. mu.L of chloroplatinic acid hexahydrate solution (10mg/mL), evaporated to dryness using a rotary evaporator, and then H2Roasting for 3h at 100 ℃ in the atmosphere to obtain the catalyst 0.0025Pt/LDHs (pre-im).
Application examples 1 to 6
The catalyst of the embodiment 1-6 is added into the inner liner of the reaction kettle, the adding amount of the catalyst is 5g/L, and then the prepared formaldehyde simulation reaction solution (prepared by formaldehyde solution and water, wherein the concentration of formaldehyde is 1000ppm) is added. After the reaction kettle is sealed, 2MPa of oxygen is filled into the reaction kettle, the reaction temperature is room temperature, and the reaction time is 3 hours. After the reaction, the reaction liquid was centrifuged and filtered, and then analyzed for TOC removal rate and formaldehyde removal rate, and the results are shown in table 1.
TABLE 1 catalytic Effect of catalysts obtained in examples 1 to 6
As can be seen from the data in Table 1, the wet oxidation catalyst prepared by the invention has excellent catalytic activity at room temperature, Pt/LDHs with different noble metal loading amounts all show excellent catalytic performance, the formaldehyde removal rate reaches 100%, and the TOC removal rate can reach more than 93%.
Comparative application examples 1 to 4
The application conditions were as in application example 1 except that the catalyst was changed to those of comparative examples 1 to 4. The results are shown in Table 2.
TABLE 2 catalytic effect of comparative examples 1 to 4 catalysts
From the results in table 2, it can be seen that when the noble metal Pt is not supported or the catalyst is prepared by the impregnation method, the catalytic activity of the catalyst is very low, the TOC removal rate is less than 30%, and the formaldehyde removal rate is up to 40.7%, which indicates that the catalyst prepared by the present invention has excellent ability to treat formaldehyde in wastewater at low temperature.
And (3) testing the stability of the catalyst:
after the performance test reaction of the application example 1 and the application example 4, the catalyst and the solution after the reaction are separated by magnetism to obtain the catalyst after the reaction, the catalyst is placed in an oven to be dried for reuse, the subsequent performance test operation is carried out in the same way as the application example 1, and the catalyst is recycled for five times in the process. The data after five cycles are shown in table 3.
Table 3 catalytic effect of five cycles of using the catalysts of example 1 and example 4
From the results in table 3, it can be seen that the catalyst prepared by the present invention has good low temperature catalytic activity after being recycled for many times.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A wet oxidation catalyst comprising a carrier and an active component supported on the carrier, characterized in that the carrier comprises a nickel iron hydrotalcite and the active component comprises a noble metal Pt; the noble metal Pt is in an electron-rich state; the mass of the active component is 0.001-1% of the mass of the carrier.
2. The wet oxidation catalyst according to claim 1, wherein the mass of the active component is 0.0015 to 0.8% of the mass of the carrier.
3. A method for preparing a wet oxidation catalyst according to claim 1 or 2, comprising the steps of:
mixing a divalent nickel salt, a trivalent iron salt, a precipitating agent and water to obtain a mixed solution;
adjusting the pH value of the mixed solution to 8-10, carrying out hydrothermal reaction on the mixed solution after the pH value is adjusted, and drying and calcining solid products obtained by the hydrothermal reaction in sequence to obtain a nickel-iron hydrotalcite carrier;
mixing the nickel-iron hydrotalcite carrier, the Pt precursor and water to obtain mixed feed liquid; the mass of Pt in the Pt precursor is 0.001-1% of that of the ferronickel hydrotalcite carrier;
and mixing the mixed feed liquid with a reducing agent aqueous solution, carrying out reduction reaction, carrying out solid-liquid separation on a product of the reduction reaction, drying a solid product, and roasting the obtained dried product in a hydrogen atmosphere to obtain the wet oxidation catalyst.
4. The production method according to claim 3, wherein the divalent nickel salt is nickel nitrate or nickel chloride; the ferric iron salt is ferric nitrate or ferric chloride; the precipitator is urea or ammonium chloride, and the molar ratio of the divalent nickel salt, the ferric salt and the precipitator is (1-5): (0.5-2): 4-10).
5. The preparation method according to claim 3, wherein the hydrothermal reaction is carried out at a temperature of 50 to 150 ℃ for 15 to 24 hours.
6. The preparation method according to claim 3, wherein the calcining temperature is 200-600 ℃ and the calcining time is 2-10 h.
7. The production method according to claim 3, wherein the Pt precursor is chloroplatinic acid; the reducing agent in the reducing agent aqueous solution is sodium borohydride or hydrazine hydrate; the concentration of the reducing agent aqueous solution is 0.001-0.1 mol/L; the molar ratio of the reducing agent to the Pt precursor in the reducing agent aqueous solution is (1.1-2.0): 1.
8. the preparation method according to claim 3, wherein the roasting temperature is 100-200 ℃ and the roasting time is 2-10 h.
9. Use of the wet oxidation catalyst according to claim 1 or 2 or the wet oxidation catalyst prepared by the preparation method according to any one of claims 3 to 8 for treating formaldehyde-containing wastewater.
10. The application according to claim 9, characterized in that the method of application comprises the steps of: mixing the wet oxidation catalyst with the formaldehyde-containing wastewater, and introducing oxygen into the obtained mixed system to perform oxidation reaction; the temperature of the oxidation reaction is normal temperature.
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