CN112619665A - Wet oxidation heterogeneous catalyst and preparation method thereof - Google Patents

Wet oxidation heterogeneous catalyst and preparation method thereof Download PDF

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Publication number
CN112619665A
CN112619665A CN201910905804.9A CN201910905804A CN112619665A CN 112619665 A CN112619665 A CN 112619665A CN 201910905804 A CN201910905804 A CN 201910905804A CN 112619665 A CN112619665 A CN 112619665A
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wet oxidation
catalyst
heterogeneous catalyst
platinum group
tio
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陈航宁
郑育元
许丹丹
吴粮华
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—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
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B01J35/612—
    • B01J35/613—
    • B01J35/633—
    • B01J35/647—
    • B01J35/651—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • 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
    • C02F2101/32—Hydrocarbons, e.g. oil
    • 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

Abstract

The invention provides a wet oxidation heterogeneous catalyst comprising TiO2、Fe2O3And a platinum group metal simple substance. The invention also provides a preparation method of the wet oxidation heterogeneous catalyst, which comprises the following steps: step A: adding TiO into the mixture2、Fe2O3Mixing with a pore-forming agent, extruding and molding, and roasting to obtain a catalyst carrier; and B: loading a platinum group metal element in a combined state on the catalyst support; and C: to platinum group gold in a compound stateThe metal element is reduced into simple substance platinum group metal element. The wet oxidation heterogeneous catalyst provided by the invention can effectively remove COD in organic wastewater in the wastewater treatment of hydrogen peroxide produced by an anthraquinone process.

Description

Wet oxidation heterogeneous catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of organic wastewater treatment, in particular to a wet oxidation heterogeneous catalyst for treating wastewater generated in hydrogen peroxide production by an anthraquinone process and a preparation method thereof.
Background
The technological route for producing hydrogen peroxide by anthraquinone method includes dissolving alkyl anthraquinone in working solution of heavy aromatic hydrocarbon and trioctyl phosphate, carrying out catalytic hydrogenation reaction at certain temperature and pressure to obtain hydrogen anthraquinone, and then carrying out chemical processes of oxidation to obtain hydrogen peroxide, wherein the reaction equation is as follows:
Figure BDA0002213238930000011
in the production process, a large amount of high-concentration organic wastewater is discharged, and pollutants of the high-concentration organic wastewater mainly comprise heavy aromatic hydrocarbons, alkyl anthraquinone, trioctyl phosphate and the like. The wastewater has high biological toxicity and poor biodegradability, and COD in the wastewater must be degraded by an effective pretreatment means so as to be discharged into a biochemical tank for further treatment. The catalytic wet oxidation technology is an energy-saving and environment-friendly technology for treating high-concentration organic wastewater, and after the wastewater is mixed with an oxidant, organic pollutants are deeply oxidized into carbon dioxide and water under the action of a catalyst under the conditions of certain temperature and pressure. The core of the technology is to develop a corresponding high-efficiency wet oxidation catalyst aiming at the characteristics of the wastewater.
CN105712460 (a method for catalytic wet oxidation of phenol-containing wastewater) discloses a method for catalytic wet oxidation of phenol-containing wastewater. The method comprises the step of contacting the phenolic wastewater with a catalytic wet oxidation catalyst for reaction, wherein the catalyst comprises a core-shell structure component, the core-shell structure component takes activated carbon as a core, and alumina containing transition metal and rare earth metal as a shell. The catalyst prepared by the method has low COD removal efficiency.
CN104876363 (catalytic wet oxidation treatment method for up-to-standard discharge of landfill leachate) discloses a catalytic wet oxidation treatment method for up-to-standard discharge of landfill leachate. Adding polyaluminium chloride into original landfill leachate for pretreatment, then adding the pretreated landfill leachate into a reaction kettle, carrying out catalytic wet oxidation reaction under the action of an RFCC catalyst, and treating COD (chemical oxygen demand) of the landfill leachateCrAnd a color of not more than 500mg/L and 80 times, respectively, and a pH of 7 to 9. However, the catalyst has low catalytic activity when treating organic matters containing heavy aromatics, alkyl anthraquinone, trioctyl phosphate and the like.
CN103157501 (a preparation method of a catalyst for catalyzing organic pollutants in wet oxidation water) discloses a preparation method of a catalyst for catalyzing organic pollutants in wet oxidation water, which adopts a mesoporous SBA-15 molecular sieve as a carrier and CuO as an active component, and adopts an ultrasonic action for a period of time in the preparation process to promote the dispersion of the active component. But the catalyst has poor hydrothermal stability and is not suitable for treating the wastewater generated in the production of hydrogen peroxide by an anthraquinone process through catalytic wet oxidation.
Disclosure of Invention
Aiming at the problem that COD in organic wastewater can not be effectively removed in the prior art, the invention provides a wet oxidation heterogeneous catalyst for wastewater treatment in the production of hydrogen peroxide by an anthraquinone process, and the catalyst has the advantage of high COD removal efficiency.
In a first aspect, the present invention provides a wet oxidation heterogeneous catalyst comprising TiO2、Fe2O3And a platinum group metal simple substance.
According to some embodiments of the invention, the wet oxidation heterogeneous catalyst comprises the following components in parts by weight: 80-99 parts of TiO20.1-20 parts of Fe2O30.01-5 parts of platinum group metal simple substance.
According to the inventionIn a preferred embodiment, the wet oxidation heterogeneous catalyst comprises the following components in parts by weight: 90-99 parts of TiO20.1-10 parts of Fe2O30.01-5 parts of platinum group metal simple substance.
According to some embodiments of the invention, the platinum group metal element is selected from at least one of iridium (Ir), rhodium (Rh), palladium (Pd), and platinum (Pt).
According to a preferred embodiment of the present invention, the platinum group metal simple substance is Rh simple substance.
According to some embodiments of the invention, the TiO is2And Fe2O3As a support in the catalyst.
According to some embodiments of the invention, the TiO is2The crystal form of (A) is anatase type.
According to some embodiments of the invention, the elemental platinum group metal has an average particle size of ≦ 5 nm.
According to some embodiments of the invention, the wet oxidation heterogeneous catalyst has a specific surface area of 8 to 60m2/g。
According to some embodiments of the invention, the wet oxidation heterogeneous catalyst has a pore volume of 0.1 to 0.4cm3/g。
According to some embodiments of the invention, the wet oxidation heterogeneous catalyst has a pore size of 10 to 60 nm.
In a second aspect, the present invention provides a method for preparing a wet oxidation heterogeneous catalyst, comprising:
step A: adding TiO into the mixture2、Fe2O3Mixing with a pore-forming agent, extruding and molding, and roasting to obtain a catalyst carrier;
and B: loading a platinum group metal element in a combined state on the catalyst support;
and C: reducing the platinum group metal elements in a combined state into simple substance platinum group metal elements.
According to some embodiments of the invention, the TiO is2The crystal form of (A) is anatase type.
According to some embodiments of the invention, the combined platinum group metal elements are supported on the catalyst support by impregnation.
The specific surface area of the catalyst carrier is an important influence factor influencing the activity of the catalyst, and the larger the specific surface area of the catalyst carrier is, the more favorable the dispersion degree of the noble metal particles is, so that the utilization rate of the noble metal is improved, and the oxidation efficiency of the catalyst is improved. Therefore, in order to improve the specific surface area of the catalyst carrier, the organic pore-forming agent is added in the preparation process of the catalyst carrier.
According to some embodiments of the invention, the pore former comprises at least one selected from the group consisting of starch, polyethylene glycol (PEG), polyvinyl alcohol (PVA), Polyacrylamide (PAM), trimethylbenzene, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), polymethyl methacrylate (PMMA).
According to a preferred embodiment of the present invention, the pore former is selected from one or both of polyvinyl alcohol and polyethylene glycol.
According to a preferred embodiment of the present invention, the pore former comprises polyvinyl alcohol and polyethylene glycol.
According to some embodiments of the invention, the Fe2O3In an amount of TiO20.1-20% of the dosage.
According to a preferred embodiment of the invention, said Fe2O3In an amount of TiO21-10% of the dosage.
According to some embodiments of the invention, the pore former is present in an amount of TiO20.5-10% of the dosage.
According to a preferred embodiment of the present invention, the pore former is used in an amount of TiO25-10% of the dosage.
According to some embodiments of the invention, the elemental platinum group metal has an average particle size of ≦ 5 nm.
According to some embodiments of the present invention, the temperature of the calcination is 350-650 ℃ for 2-8 h.
According to some embodiments of the invention, the reduction is performed using hydrogen.
According to some embodiments of the present invention, the temperature of the reduction is 150 ℃ and 500 ℃ for 1-12 h.
In a third aspect, the present invention provides a wet oxidation heterogeneous catalyst according to the first aspect or a wet oxidation heterogeneous catalyst obtained by the preparation method according to the second aspect, for use in organic wastewater treatment.
In a fourth aspect, the invention provides a treatment method of wastewater from hydrogen peroxide production by anthraquinone process, comprising contacting the wastewater from hydrogen peroxide production by anthraquinone process with the wet oxidation heterogeneous catalyst according to the first aspect or the wet oxidation heterogeneous catalyst obtained by the preparation method according to the second aspect.
According to some embodiments of the invention, the contacting is at a temperature of 180-.
According to some embodiments of the invention, the pH of the wastewater is between 1 and 7.
According to some embodiments of the invention, the wastewater comprises hydrogen peroxide.
According to some embodiments of the invention, the hydrogen peroxide is present in an amount of 1 to 20 wt%.
According to a preferred embodiment of the invention, the hydrogen peroxide is present in an amount of 5-15 wt%.
According to some embodiments of the invention, the contacting is performed in a reactor.
According to some embodiments of the invention, the reactor is selected from any one of a fixed bed, a fluidized bed and a reaction kettle.
The waste water is working solution washing water discharged in the process of producing hydrogen peroxide by an anthraquinone method and steam condensate generated by regeneration of a hydrogenation tower catalyst, aftertreatment of a clay bed and blowing of a hydrogenation regeneration bed. The main pollutants in the wastewater are heavy aromatics, alkyl anthraquinone and degradation products thereof, trioctyl phosphate and the like. The wastewater is a light yellow clear solution, is weakly acidic and has a pH value of less than 7.
By adopting the technical scheme, the result shows that the COD content of the wastewater generated in the production of hydrogen peroxide by the anthraquinone method can be effectively reduced after the wastewater is treated, the COD of the wastewater before treatment is 46700mg/L, and the residual COD after treatment is less than 500mg/L, so that a better technical effect is achieved.
Drawings
FIG. 1 is a transmission electron micrograph of catalyst W-01 prepared according to example 1 of the present invention.
FIG. 2 is a transmission electron micrograph of catalyst W-02 prepared according to example 2 of the present invention.
FIG. 3 is a transmission electron micrograph of catalyst B-01 prepared according to comparative example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Example 1
1. Preparation of the catalyst
1.1 preparation method of catalyst carrier:
200g of TiO25g of Fe2O310g of PMMA and 85g of water were added to a kneader and mixed for 30 minutes, followed by extrusion molding. Drying at room temperature for 48h, and calcining at 550 ℃ for 4h to obtain the catalyst carrier.
1.2 preparation of the catalyst
0.5g of RhCl3The resulting solution was dissolved in 20g of water to prepare a solution A, and 100g of the catalyst support was immersed in the solution A at 25 ℃. Soaking for 8h, drying at 25 deg.C for 48h, and drying at 100 deg.C for 8h to obtain catalyst precursor. And reducing the catalyst precursor for 6h at 400 ℃ in a hydrogen atmosphere to obtain the catalytic wet oxidation catalyst W-01. The transmission electron micrograph of catalyst W-01 is shown in FIG. 1, and the specific surface area, pore volume and pore diameter data of catalyst W-01 are shown in Table 1.
2. Catalytic wet oxidation experiment
The waste water from the production of hydrogen peroxide by anthraquinone process (COD 46700mg/L, pH 4.65, hydrogen peroxide content 8.9 wt%) was pumped into a fixed bed reactor packed with 90g of catalyst W-01 by a high pressure pump, and catalytic wet oxidation was carried out at a reaction temperature of 250 ℃ and a pressure of 6.5MPa for a reaction time of 1h and a waste water flow rate of 1.5 mL/min. The reaction results are shown in Table 2.
Example 2
1. Preparation of the catalyst
1.1 preparation of catalyst support
200g of TiO25g of Fe2O35g of PEG, 5g of PVA and 85g of water were put into a kneader and mixed for 30 minutes, followed by extrusion molding. Drying at room temperature for 48h, and calcining at 550 ℃ for 4h to obtain the catalyst carrier.
1.2 preparation of the catalyst
0.5g RhCl3The resulting solution was dissolved in 20g of water to prepare a solution A, and 100g of the catalyst support was immersed in the solution A at 25 ℃. Soaking for 8h, drying at 25 deg.C for 48h, and drying at 100 deg.C for 8h to obtain catalyst precursor. And reducing the catalyst precursor for 6h at 400 ℃ in a hydrogen atmosphere to obtain the catalytic wet oxidation catalyst W-02. The transmission electron microscope of catalyst W-02 is shown in FIG. 2, and the specific surface area, pore volume and pore diameter data of catalyst W-02 are shown in Table 1.
2. Catalytic wet oxidation experiment
The waste water from the anthraquinone process for producing hydrogen peroxide (COD 46700mg/L, pH 4.65, hydrogen peroxide content 8.9 wt%) is pumped into a fixed bed reactor filled with 90g of catalyst by a high pressure pump, and catalytic wet oxidation is carried out at the reaction temperature of 250 ℃ and the pressure of 6.5MPa, and the reaction time is 1 h. The flow rate of the wastewater was 1.5 mL/min. The reaction results are shown in Table 2.
Example 3
The preparation method of the catalyst is the same as that of example 1, except that the pore-forming agent added in the step 1 is 10g of PVA, so as to obtain the catalytic wet oxidation catalyst W-03, and the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 4
The preparation method of the catalyst is the same as that of example 1, except that 10g of PEG is added as a pore-forming agent in the step 1, so as to obtain the catalytic wet oxidation catalyst W-04, and the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 5
The preparation method of the catalyst is the same as that of example 1, except that the pore-forming agents added in the step 1 are 2g of PEG and 8g of PVA, so as to obtain the catalytic wet oxidation catalyst W-05, and the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 6
The preparation method of the catalyst is the same as that of example 1, except that the pore-forming agent added in the step 1 is 8g of PEG and 2g of PVA, so as to obtain the catalytic wet oxidation catalyst W-06, and the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 7
The preparation method of the catalyst is the same as that of example 1, except that the pore-forming agent added in the step 1 is 20g of PMMA, so as to obtain the catalytic wet oxidation catalyst W-07, and the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 8
The preparation method of the catalyst is the same as that of the example 1, except that the pore-forming agent added in the step 1 is 5g of PMMA, so as to obtain the catalytic wet oxidation catalyst W-08, and the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 9
The preparation method of the catalyst is the same as that of example 1, except that the pore-forming agent added in the step 1 is 2g of PMMA, so as to obtain the catalytic wet oxidation catalyst W-09, and the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 10
The catalyst was prepared in the same manner as in example 1,except that TiO added in step 12With Fe2O3The mass ratio of (A) to (B) is 5: 1, obtaining the catalytic wet oxidation catalyst W-10, wherein the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 11
The catalyst was prepared in the same manner as in example 1, except that TiO was added in step 12With Fe2O3The mass ratio of (A) to (B) is 20: 1, obtaining the catalytic wet oxidation catalyst W-11, wherein the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 12
The catalyst was prepared in the same manner as in example 1, except that TiO was added in step 12With Fe2O3The mass ratio of (A) to (B) is 100: 1, obtaining the catalytic wet oxidation catalyst W-12, wherein the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Example 13
The catalyst was prepared in the same manner as in example 1, except that TiO was added in step 12With Fe2O3The mass ratio of (A) to (B) is 200: 1, obtaining the catalytic wet oxidation catalyst W-13, wherein the specific surface area, the pore volume and the pore diameter data are shown in Table 1.
The catalytic wet oxidation experiment was the same as in example 1, and the reaction results are shown in Table 2.
Comparative example 1
1. Preparation of the catalyst
1.1 preparation of catalyst support
200g of TiO2And 85g of water were added to the kneader and mixed for 30 minutes, followed by extrusion molding. Drying at room temperature for 48h, and calcining at 550 ℃ for 4h to obtain the catalyst carrier.
1.2 preparation of the catalyst
0.5g RhCl3The resulting solution was dissolved in 20g of water to prepare a solution A, and 100g of the catalyst support was immersed in the solution A at 25 ℃. Soaking for 8h, drying at 25 deg.C for 48h, and drying at 100 deg.C for 8h to obtain catalyst precursor. The catalyst precursor is reduced for 6 hours at 400 ℃ in a hydrogen atmosphere to obtain the catalytic wet oxidation catalyst B-01. The transmission electron microscope of catalyst B-01 is shown in FIG. 3, and the specific surface area, pore volume and pore diameter data of catalyst B-01 are shown in Table 1.
2. Catalytic wet oxidation experiment
The waste water from the anthraquinone process for producing hydrogen peroxide (COD 46700mg/L, pH 4.65, hydrogen peroxide content 8.9 wt%) is pumped into a fixed bed reactor filled with 90g of catalyst by a high pressure pump, and catalytic wet oxidation is carried out at the reaction temperature of 250 ℃ and the pressure of 6.5MPa, and the reaction time is 1 h. The flow rate of the wastewater was 1.5 mL/min. The reaction results are shown in Table 2.
Comparative example 2
1. Preparation of the catalyst
1.1 preparation of catalyst support
200g of TiO25g of Fe2O3And 85g of water were added to the kneader and mixed for 30 minutes, followed by extrusion molding. Drying at room temperature for 48h, and calcining at 550 ℃ for 4h to obtain the catalyst carrier.
1.2 preparation of the catalyst
0.5g of RhCl3The resulting solution was dissolved in 20g of water to prepare a solution A, and 100g of the catalyst support was immersed in the solution A at 25 ℃. Soaking for 8h, drying at 25 deg.C for 48h, and drying at 100 deg.C for 8h to obtain catalyst precursor. The catalyst precursor is reduced for 6 hours at 400 ℃ in a hydrogen atmosphere to obtain the catalytic wet oxidation catalyst B-02. The specific surface area, pore volume and pore diameter data of catalyst B-02 are shown in Table 1.
2. Catalytic wet oxidation experiment
The waste water from the production of hydrogen peroxide by anthraquinone process (COD 46700mg/L, pH 4.65, hydrogen peroxide content 8.9 wt%) was pumped into a fixed bed reactor packed with 90g of catalyst B-02 by a high pressure pump, and catalytic wet oxidation was carried out at a reaction temperature of 250 ℃ and a pressure of 6.5MPa for 1 h. The flow rate of the wastewater was 1.5 mL/min. The reaction results are shown in Table 2.
Comparative example 3
1. Preparation of the catalyst
1.1 preparation of catalyst support
200g of TiO210g of PMMA and 85g of water were added to a kneader and mixed for 30 minutes, followed by extrusion molding. Drying at room temperature for 48h, and calcining at 550 ℃ for 4h to obtain the catalyst carrier.
1.2 preparation of the catalyst
0.5g of RhCl3The resulting solution was dissolved in 20g of water to prepare a solution A, and 100g of the catalyst support was immersed in the solution A at 25 ℃. Soaking for 8h, drying at 25 deg.C for 48h, and drying at 100 deg.C for 8h to obtain catalyst precursor. The catalyst precursor is reduced for 6 hours at 400 ℃ in a hydrogen atmosphere to obtain the catalytic wet oxidation catalyst B-03. The specific surface area, pore volume and pore size data for catalyst B-03 are shown in Table 1.
2. Catalytic wet oxidation experiment
The waste water from the production of hydrogen peroxide by anthraquinone process (COD 46700mg/L, pH 4.65, hydrogen peroxide content 8.9 wt%) was pumped into a fixed bed reactor packed with 90g of catalyst B-03 by a high pressure pump, and catalytic wet oxidation was carried out at a reaction temperature of 250 ℃ and a pressure of 6.5MPa for 1 h. The flow rate of the wastewater was 1.5 mL/min. The reaction results are shown in Table 2.
TABLE 1 physical Properties of the catalysts
Examples Catalyst and process for preparing same Specific surface area m2/g Pore volume cm3/g Pore size nm
Example 1 W-01 23.9 0.202 32.9
Example 2 W-02 32.5 0.239 28.8
Example 3 W-03 22.6 0.198 30.6
Example 4 W-04 30.8 0.227 29.7
Example 5 W-05 31.7 0.231 29.5
Example 6 W-06 33.8 0.242 28.3
Example 7 W-07 31.5 0.213 35.8
Example 8 W-08 18.3 0.189 34.2
Example 9 W-09 14.6 0.179 36.2
Example 10 W-10 10.2 0.125 45.8
Example 11 W-11 12.4 0.132 43.1
Practice ofExample 12 W-12 16.9 0.212 30.7
Example 13 W-13 18.5 0.23 27.4
Comparative example 1 B-01 16.2 0.204 25.7
Comparative example 2 B-02 13.7 0.173 36.5
Comparative example 3 B-03 17.5 0.192 29.3
TABLE 2 reaction results
Figure BDA0002213238930000101
Figure BDA0002213238930000111
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A wet oxidation heterogeneous catalyst comprising TiO2、Fe2O3And a platinum group metal simple substance.
2. The wet oxidation heterogeneous catalyst according to claim 1, comprising the following components in parts by weight: 80-99 parts, preferably 90-99 parts, of TiO20.1 to 20 parts, preferably 0.1 to 10 parts, of Fe2O30.01-5 parts of platinum group metal simple substance, and/or the platinum group metal simple substance is Rh simple substance.
3. Heterogeneous catalyst for wet oxidation according to claim 1 or 2, characterized in that said TiO is2The crystal form of (A) is anatase type; and/or the average particle size of the platinum group metal simple substance is less than or equal to 5 nm.
4. Wet oxidation heterogeneous catalyst according to any of claims 1-3, wherein the wet oxidation heterogeneous catalyst has a specific surface area of 8-60m2/g, and/or of the wet oxidation heterogeneous catalystThe pore volume is 0.1-0.4cm3/g, and/or the pore size of the wet oxidation heterogeneous catalyst is 10-60 nm.
5. A method of preparing a wet oxidation heterogeneous catalyst, comprising:
step A: adding TiO into the mixture2、Fe2O3Mixing with a pore-forming agent, extruding and molding, and roasting to obtain a catalyst carrier;
and B: loading a platinum group metal element in a combined state on the catalyst support;
and C: reducing the platinum group metal elements in a combined state into simple substance platinum group metal elements.
6. The method according to claim 5, wherein the TiO is2The crystal form of (A) is anatase type; and/or the pore-forming agent comprises at least one selected from starch, polyethylene glycol, polyvinyl alcohol, polyacrylamide, trimethylbenzene, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and polymethyl methacrylate; and/or the average particle size of the platinum group metal simple substance is less than or equal to 5 nm; and/or said Fe2O3In an amount of TiO20.1-20% of the dosage, preferably 1-10%; and/or the dosage of the pore-forming agent is TiO2The amount is 0.5-10%, preferably 5-10%.
7. The preparation method according to claim 5 or 6, characterized in that the roasting temperature is 350-650 ℃ and the roasting time is 2-8 h; and/or
The reduction is carried out by adopting hydrogen, preferably, the temperature of the reduction is 150-500 ℃, and the time is 1-12 h.
8. Use of a wet oxidation heterogeneous catalyst according to any one of claims 1-4 or obtained by the preparation method according to any one of claims 5-7 in the treatment of organic wastewater.
9. A treatment method of waste water from the production of hydrogen peroxide by anthraquinone process, comprising contacting the waste water from the production of hydrogen peroxide by anthraquinone process with the wet oxidation heterogeneous catalyst according to any one of claims 1 to 4 or the wet oxidation heterogeneous catalyst obtained by the preparation method according to any one of claims 5 to 7, preferably, the contacting temperature is 180-300 ℃, the pressure is 2-12MPa, and the time is 10-120 minutes.
10. A treatment method according to claim 9, wherein the pH of the wastewater is 1-7, and/or wherein the wastewater comprises hydrogen peroxide, preferably in an amount of 1-20 wt%, preferably 5-15 wt%.
CN201910905804.9A 2019-09-24 2019-09-24 Wet oxidation heterogeneous catalyst and preparation method thereof Pending CN112619665A (en)

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