CN111889092A - Preparation method of catalyst for decomposing residual hydrogen peroxide in Fenton effluent, catalyst and application of catalyst - Google Patents

Preparation method of catalyst for decomposing residual hydrogen peroxide in Fenton effluent, catalyst and application of catalyst Download PDF

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CN111889092A
CN111889092A CN202010747899.9A CN202010747899A CN111889092A CN 111889092 A CN111889092 A CN 111889092A CN 202010747899 A CN202010747899 A CN 202010747899A CN 111889092 A CN111889092 A CN 111889092A
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catalyst
hydrogen peroxide
activated carbon
nitrate
alkali liquor
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CN111889092B (en
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荆开石
高学顺
姜晓锋
王诗涵
张宏科
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Wanhua Chemical Group Co Ltd
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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
    • 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)
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B01J35/615—
    • B01J35/635—
    • B01J35/638—
    • B01J35/64—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Abstract

The invention discloses a catalyst for decomposing residual hydrogen peroxide in Fenton (Fenton) effluent and a preparation method thereof, and mainly solves the problem that the residual hydrogen peroxide in Fenton effluent mostly affects the activity of a subsequent biochemical system. The carrier of the catalyst is a mixture of dried sludge and waste activated carbon, a waste polyurethane thermal insulation material is used as a pore-expanding agent, and the metal modified catalyst is synthesized by an in-situ one-step process. The preparation scheme has the advantages of simple process, low cost, developed gaps of the prepared catalyst, strong catalytic decomposition effect on hydrogen peroxide in wastewater, and realization of reduction and recycling of sludge, activated carbon and waste polyurethane thermal insulation materials.

Description

Preparation method of catalyst for decomposing residual hydrogen peroxide in Fenton effluent, catalyst and application of catalyst
Technical Field
The invention relates to the technical field of wastewater treatment in chemical engineering and environmental engineering, in particular to a preparation method of a catalyst for decomposing residual hydrogen peroxide in Fenton effluent.
Background
Increasingly serious water environment pollution gradually becomes a great obstacle for restricting the sustainable development of industry and society, the advanced oxidation technology is a main means for treating the waste water of refractory organic matters at present, and the advanced oxidation is characterized by generating hydroxyl free radicals (OH) with strong oxidation capacity, so that the macromolecular refractory organic matters are oxidized into low-toxicity or non-toxic micromolecular substances.
The Fenton oxidation method is to treat refractory organic matters by using OH free radicals generated by hydrogen peroxide catalysis, and is the most commonly used advanced oxidation process due to the advantages of simple process, wide oxidation range and the like. However, after the Fenton reaction is terminated, a large amount of hydrogen peroxide (H) still remains in the water body2O2) Molecule of formula I, due to2O2The biological activity of microorganisms in a biochemical system is seriously inhibited, so that the biochemical efficiency of the system is reduced, partial COD is contributed to cause the deficiency of the COD value of effluent, and bubbles generated by continuous decomposition of the effluent cause serious sludge suspension phenomenon to cause difficulty in sludge-water separation.
The main factors affecting the decomposition of hydrogen peroxide include: temperature, pH, light, catalysis; when the temperature is higher than 100 ℃, the decomposition speed of the hydrogen peroxide is obviously accelerated; the hydrogen peroxide is stable under an acidic condition and is decomposed under an alkaline condition, but the decomposition speed is slow; aiming at the decomposition of residual hydrogen peroxide in Fenton effluent, the optimal process scheme is catalytic decomposition.
The magnetic synthetic ferrite prepared by pottery scenic light and the like (pottery scenic light and the like, magnetic synthesis of ferrite catalyst and influence thereof on the decomposition reaction of hydrogen peroxide [ J ]. the chemical bulletin, 2003,54(7):942-945) has higher catalytic activity in catalyzing the decomposition reaction of hydrogen peroxide, but the synthesis method of the catalyst is complex and has higher cost.
The invention patent CN 201410499540.9 discloses a low-concentration hydrogen peroxide decomposition catalyst, but the active component is not uniformly impregnated, so that the hydrogen peroxide decomposition performance is unstable.
The invention patent CN 201710509154.7 discloses that a modified ZSM-5 catalyst is used for decomposing low-concentration hydrogen peroxide, but the catalyst has shorter service life due to smaller aperture and poorer mass transfer effect.
Aiming at the defects of the prior art, a catalyst which has simple preparation process, high decomposition efficiency, stable performance and no secondary pollution needs to be developed.
Disclosure of Invention
The invention aims to provide a catalyst for decomposition of hydrogen peroxide in Fenton effluent, the catalyst has the advantages of simple preparation scheme, low cost, developed prepared catalyst gaps, high decomposition efficiency, stable performance, stronger catalytic decomposition effect on the hydrogen peroxide in wastewater, and capability of realizing reduction and recycling of sludge, activated carbon and waste polyurethane.
The invention also aims to provide the catalyst for decomposing the residual hydrogen peroxide in Fenton effluent and the application of the catalyst in catalyzing the Fenton effluent hydrogen peroxide decomposition reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a catalyst for decomposing residual hydrogen peroxide in Fenton effluent is characterized in that a mixture of dried sludge and waste activated carbon is used as a carrier, waste polyurethane foam is used as a pore-expanding agent, and a metal oxide active component is loaded on the carrier by adopting an in-situ one-step process to obtain the catalyst for decomposing the residual hydrogen peroxide in the Fenton effluent.
In a specific embodiment, the preparation method comprises the following steps:
1) ultrasonically cleaning the sludge under the stirring state, removing impurities, performing suction filtration on the sludge, drying and crushing;
2) soaking waste activated carbon by using a solvent, cleaning the activated carbon by using deionized water, drying and crushing the activated carbon;
3) washing waste polyurethane foam with deionized water, drying and crushing;
4) preparing an alkali liquor, sequentially adding the dried sludge, the activated carbon powder and the waste polyurethane foam into the alkali liquor in a stirring state, stirring for 12-24 h, and then transferring the alkali liquor to an infrared atmosphere to irradiate for 10-50 h to obtain a suspension A.
5) Preparing a nitrate solution, adding the nitrate solution into the suspension A under the stirring state, adding a certain amount of linoleic acid, stirring for 12-24 h, and then transferring to the temperature of 20-50 ℃ for ultrasonic dissolution to prepare a sol solution B;
6) standing and aging the sol solution B at room temperature for 20-30 h, drying at 100-130 ℃ for 12-24 h after aging, roasting at 250-400 ℃ for 2-10 h in an oxygen-enriched atmosphere, and removing the waste polyurethane thermal insulation material of the pore expanding agent; and finally, roasting at 500-680 ℃ for 2-8 h to obtain the catalyst, and crushing for later use.
In the step 1), the dried sludge is subjected to ultrasonic treatment for 2-5 hours, dried at 100-130 ℃ for 5-10 hours, and crushed and sieved by 100 meshes.
In the step 2), ethanol is used for soaking the waste activated carbon for 20-40 hours, the waste activated carbon is dried for 5-10 hours at the temperature of 100-130 ℃, and the waste activated carbon is crushed and sieved by a sieve of 100 meshes.
In the step 3), the waste polyurethane foam is dried for 5-10 hours at the temperature of 100-130 ℃, and then is crushed and sieved for 500 meshes.
In the step 4), alkali treatment is carried out on the catalyst carrier and the pore-enlarging agent by using alkali liquor, wherein the alkali liquor is sodium hydroxide or potassium hydroxide, and the mass concentration of the alkali liquor is 0.5-4%; preferably, the mass ratio of the dried sludge to the activated carbon to the waste polyurethane foam is 1: 2-5: 0.05-0.1, and the mass ratio of the alkali liquor to the dried sludge is 20-50: 1; more preferably, the irradiation temperature of the alkali liquor for infrared treatment is 60-120 ℃.
Wherein the nitrate in the step 5) is any one of manganese nitrate, zinc nitrate, aluminum nitrate, silver nitrate or palladium nitrate; preferably, the concentration of the nitrate aqueous solution is 10-30%; more preferably, linoleic acid is added as a dispersing agent, and the mass ratio of the linoleic acid to the nitrate is 1: 5-10.
In another aspect of the invention, the catalyst for decomposing the residual hydrogen peroxide in Fenton effluent is prepared by the catalyst preparation method.
Wherein the catalyst comprises the following components in percentage by mass: active components: 1-10% and the balance of catalyst carrier.
On the other hand, the catalyst prepared by the method is used for catalyzing decomposition reaction of hydrogen peroxide in Fenton effluent, and is suitable for the condition that the content of residual hydrogen peroxide in wastewater is 100-10000 ppm; preferably, when the catalyst is used, the catalyst is extruded into strips and is filled in a reaction tube, Fenton effluent enters the reaction tube, and the volume airspeed of wastewater is 0.1-10 h-1The reaction temperature is 10-50 ℃; more preferably, the volume space velocity is 0.5-5 h-1The reaction temperature is 15-45 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the catalyst carrier is a mixture of dried sludge and waste activated carbon, a waste polyurethane thermal insulation material is used as a pore-expanding agent, oleic acid is used as a dispersing agent, and activated components such as manganese, zinc, aluminum, silver, palladium and the like are loaded on the catalyst by an in-situ one-step process.
(2) According to the catalyst, waste polyurethane is added as a pore-expanding agent on the basis of a catalyst carrier, and the prepared final catalyst carrier has the microporous pore volume, the mesoporous pore volume and the macroporous pore volume which are respectively 1: 98.5: 0.5, 1-10: 40-60: 20-30, the volume ratio of the macropores is greatly increased, and the catalytic effect of the catalyst is obviously improved.
(3) The catalyst for decomposing the residual hydrogen peroxide in the Fenton effluent is suitable for decomposing the residual hydrogen peroxide in the wastewater by 100-10000 ppm, has a wide application range, can solve the problem that the residual hydrogen peroxide in the Fenton effluent affects the activity of a subsequent biochemical system, and can reduce and recycle sludge, activated carbon and waste polyurethane.
Drawings
FIG. 1 is a graph showing the pore size distribution of three catalysts, example 1 and comparative examples 2 and 3.
FIG. 2 shows N for three catalysts of example 1 and comparative examples 2 and 32Adsorption-desorption isotherms.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
A catalyst for catalyzing hydrogen peroxide to decompose in Fenton effluent is characterized in that a catalyst carrier is a mixture of dried sludge and waste activated carbon, a waste polyurethane thermal insulation material is used as a pore-expanding agent, and metal oxides such as active components of manganese, zinc, aluminum, silver, palladium and the like are loaded on the catalyst carrier by adopting an in-situ one-step process. Compared with the two-step method, the one-step method is characterized in that the salt of the active component of the catalyst is fully mixed with the catalyst carrier and the pore-expanding agent, and the catalyst can be prepared by aging and roasting without the carrier treatment and the active component loading step which are independently carried out, so that the preparation process is simpler.
The preparation method comprises the following specific steps:
1) under magnetic stirring, ultrasonically cleaning the sludge for 2-5 h, removing impurities, carrying out suction filtration, drying at 100-130 ℃ for 5-10 h, and crushing and screening for 100 meshes.
2) Soaking the waste activated carbon in ethanol for 20-40 h, cleaning the activated carbon for 3 times by using deionized water, drying the waste activated carbon at 100-130 ℃ for 5-10 h, and crushing and screening by 100 meshes.
3) And (2) cleaning the waste polyurethane heat-insulating material for 3 times by using deionized water, drying the waste polyurethane foam for 5-10 hours at the temperature of 100-130 ℃, and crushing and screening the waste polyurethane foam for 500 meshes.
4) Preparing an alkali liquor, sequentially adding the dried sludge, the activated carbon powder and the waste polyurethane foam into the alkali liquor under magnetic stirring, stirring for 12-24 h, and then transferring the alkali liquor to an infrared atmosphere to irradiate for 10-50 h to obtain a suspension A.
In the step, alkali liquor is used for carrying out alkali treatment on the catalyst carrier, so that the carrier has an alkaline group, and the alkaline group and the active component have a synergistic enhanced decomposition effect and can accelerate the decomposition of hydrogen peroxide. The alkali liquor is sodium hydroxide or potassium hydroxide, the mass concentration of the alkali liquor is 0.5-4%, and the mass ratio of the alkali liquor to the dried sludge is 20-50: 1. in the catalyst carrier, the mass ratio of the dried sludge to the activated carbon to the polyurethane foam is 1: 2-5: 0.05-0.1.
In the step, the suspension is subjected to infrared treatment, so that the particle size uniformity can be improved, and pore channels and pore volume structures of the catalyst are regulated; the infrared irradiation temperature is 60-120 ℃, and the irradiation time is 10-50 h.
5) And (3) adding the nitrate solution into the suspension A under the stirring state, adding a certain amount of linoleic acid, stirring for 12-24 h, and then transferring to the temperature of 20-50 ℃ for ultrasonic dissolution to prepare a sol solution B, wherein the concentration of the prepared nitrate aqueous solution is 10-30%.
In this step, the nitrate is manganese nitrate, zinc nitrate, aluminum nitrate, silver nitrate, or palladium nitrate. The nitrates are finally converted into active metal oxide components, and the active metal oxide components are uniformly loaded on the catalyst carrier through an in-situ one-step method. In order to achieve better dispersion, linoleic acid is added as a dispersing agent, so that the nitrate can be uniformly distributed in the pore channels of the catalyst carrier, and the mass ratio of the linoleic acid to the nitrate is 1: 5-10.
6) And standing and aging the sol solution B at room temperature for 20-30 h, drying at 100-130 ℃ for 12-24 h after aging, roasting at 250-400 ℃ for 2-10 h in an oxygen-enriched atmosphere, removing the polyurethane thermal insulation material serving as the pore expanding agent, and roasting at 500-680 ℃ for 2-8 h to obtain the catalyst.
In the step, the catalyst carrier is roasted for 2-10 hours at 250-400 ℃ in an oxygen-enriched atmosphere, so that the polyurethane heat-insulating material is thoroughly decomposed into carbon dioxide and water, a pore structure with developed pores is formed on the catalyst carrier, the loading of active components on catalyst pores is facilitated, and the inactivation time of the catalyst is slowed down.
Finally, the prepared catalyst only contains active components and catalyst carriers, and does not contain a waste polyurethane pore-expanding agent. The catalyst comprises the following components in percentage by mass: active components: 1-10% and the balance of catalyst carrier.
The dried sludge, the waste activated carbon and the waste polyurethane thermal insulation material are main wastes generated in a chemical industry park, the resource and reduction research of the dried sludge, the waste activated carbon and the waste polyurethane thermal insulation material becomes a main social concern, and the waste activated carbon or the sludge has an application prospect in adsorbing materials. In the invention, sludge and waste activated carbon are used as carriers of the catalyst.
When the catalyst is used, the catalyst needs to be extruded into strips for forming, the particle size of the catalyst is 4mm, the catalyst is cylindrical, and the specific surface area of the catalyst is 200-500 m2The pore volume is 0.9-1.2 mL/g, and the micropore volume: mesoporous pore volume: and (3) the large pore volume is 1-10: 40-60: 20 to 30.
The catalyst is used for catalyzing decomposition of hydrogen peroxide in Fenton effluent, and the content of residual hydrogen peroxide in Fenton effluent is applicable within the range of 50-10000 ppm, preferably 100-5000 ppm.
The method comprises the steps of filling a catalyst into a reaction tube, directly feeding Fenton effluent into the reaction tube for catalytic decomposition, wherein the filling amount of the catalyst is 100ml, and the volume airspeed of wastewater is 0.1-10 h-1The reaction temperature is 10-50 ℃; the preferable volume space velocity is 0.5-5 h-1The reaction temperature is 15-45 ℃.
The present invention is further illustrated by the following more specific examples, which are not intended to limit the scope of the invention in any way.
The embodiment of the invention adopts the following raw materials:
sludge, waste activated carbon and waste polyurethane thermal insulation materials are all produced in the Wanhua chemical park.
Manganese nitrate, zinc nitrate, aluminum nitrate, silver nitrate, palladium nitrate, linoleic acid, ethanol are all AR, national drug group chemical reagents, Inc.
Fenton waste water is collected from the Wanhua chemical wastewater treatment system.
An infrared irradiation instrument: the WS70-1 far infrared dryer is used, and the wavelength of the far infrared dryer is 100-1000 mu m.
Electric heating constant temperature air blast drying cabinet: DHG-9070A-N electric heating constant temperature forced air drying oven, jyoizhou zhibori instruments ltd.
Electronic analytical balance: using a CH1403142 electronic analytical balance, mettler-toledo international trade ltd.
An ultrasonic cleaner: the KQ-500DE ultrasonic cleaner, ultrasonic instruments Inc. of Kunshan was used.
Program-controlled box-type electric furnace: the SGM. T80/10A programmable box furnace, Sigma furnace, Inc. of Luoyang was used.
Example 1:
ultrasonically cleaning the sludge for 2 hours under magnetic stirring, drying for 7 hours at 110 ℃ after suction filtration, crushing and screening to 100 meshes; soaking the waste activated carbon for 20h by using ethanol, washing for 3 times by using deionized water, drying for 6h at 110 ℃, crushing and screening for 100 meshes; and (3) washing the waste polyurethane heat-insulating material for 3 times by using deionized water, drying for 8 hours at 100 ℃, and crushing and screening for 500 meshes. Preparing 200g of 1% (mass fraction) sodium hydroxide alkali liquor, adding the dried sludge, the activated carbon powder and the waste polyurethane foam into the alkali liquor according to the mass ratio of 1:2:0.05 (the dried sludge is calculated according to 10 g) under magnetic stirring, stirring for 12h, transferring the alkali liquor to an infrared atmosphere, and irradiating for 30h at the infrared irradiation temperature of 90 ℃ to obtain suspension A. Taking 4.5g of Mn (NO)3)2·4H2And preparing manganese nitrate solution with the concentration of 30% by using O, adding the nitrate solution into the suspension A under the stirring state, adding 0.5g of linoleic acid, stirring for 12h, transferring to the suspension A to be ultrasonically dissolved at 50 ℃ to prepare a sol solution B, standing and aging the sol solution B at room temperature for 20h, drying at 105 ℃ for 12h after aging, roasting at 280 ℃ for 8h under the oxygen-enriched atmosphere, roasting at 560 ℃ for 6h to obtain the 3 Mn/sludge-carbon-based catalyst, and extruding the catalyst into strips (4mm) for later use. The specific surface area of the catalyst was tested to be 400m2The pore volume is 1.2mL/g, the micropore volume: mesoporous pore volume: large pore volume 1: 45: 30.
catalyst for catalytic decomposition of Fenton effluent hydrogen peroxideThe residual hydrogen peroxide content in the Fenton wastewater is 8600 ppm. The loading of the catalyst is 100ml, and the space velocity of the volume of the waste water is 1h-1The reaction temperature is 20 ℃, the content of hydrogen peroxide in the catalyzed wastewater is 30ppm, and the stable operation is carried out for 1000 hours.
Example 2:
ultrasonically cleaning the sludge for 4 hours under magnetic stirring, drying for 5 hours at 130 ℃ after suction filtration, crushing and screening to 100 meshes; soaking the waste activated carbon for 30h by using ethanol, washing for 3 times by using deionized water, drying for 7h at 120 ℃, crushing and screening for 100 meshes; and (3) washing the waste polyurethane heat-insulating material for 3 times by using deionized water, drying for 6 hours at 110 ℃, and crushing and screening by using a 500-mesh sieve. Preparing 300g of 0.5% potassium hydroxide alkali liquor, adding the dried sludge, the activated carbon powder and the waste polyurethane foam into the alkali liquor in a mass ratio of 1:3:0.06 (the dried sludge is calculated by 10 g) under magnetic stirring, stirring for 18h, transferring the alkali liquor to an infrared atmosphere, and irradiating for 20h at the infrared irradiation temperature of 70 ℃ to obtain suspension A. 17g of Zn (NO) are taken3)2·6H2And adding a nitrate solution prepared from O into the suspension A with the concentration of 25% under the stirring state, adding 3g of linoleic acid, stirring for 24 hours, transferring to the suspension A to be ultrasonically dissolved at 20 ℃ to prepare a sol solution B, standing and aging the sol solution B at room temperature for 26 hours, drying at 115 ℃ for 15 hours after aging, roasting at 250 ℃ for 6 hours under the oxygen-enriched atmosphere, roasting at 600 ℃ for 7 hours to obtain a 10 Zn/sludge-carbon-based catalyst, and extruding the catalyst into strips (4mm) for later use. The specific surface area of the catalyst is 500m2The pore volume is 1.0mL/g, the micropore volume: mesoporous pore volume: large pore volume 1: 60: 25.
the catalyst is used for catalytic decomposition of hydrogen peroxide in Fenton effluent, and the content of residual hydrogen peroxide in Fenton wastewater is 5000 ppm. The loading of the catalyst is 100ml, and the space velocity of the volume of the wastewater is 0.5h-1The reaction temperature is 30 ℃, the content of hydrogen peroxide in the catalyzed wastewater is 30ppm, and the stable operation is carried out for 900 hours.
Example 3:
ultrasonically cleaning the sludge for 5 hours under magnetic stirring, drying for 10 hours at 100 ℃ after suction filtration, crushing and screening to 100 meshes; soaking waste activated carbon in ethanol for 40 hr, washing with deionized water for 3 times, and drying at 100 deg.CDrying for 10h, crushing and screening by 100 meshes; and (3) washing the waste polyurethane heat-insulating material for 3 times by using deionized water, drying for 5 hours at 130 ℃, and crushing and screening by using a 500-mesh sieve. Preparing 500g of 0.2% potassium hydroxide alkali liquor, adding the dried sludge, the activated carbon powder and the waste polyurethane foam into the alkali liquor in a mass ratio of 1:5:0.1 (the dried sludge is calculated by 10 g) under magnetic stirring, stirring for 24 hours, transferring the alkali liquor to an infrared atmosphere, and irradiating for 10 hours at the infrared irradiation temperature of 120 ℃ to obtain suspension A. Taking 34g of Al (NO)3)3·9H2Preparing an aluminum nitrate solution with the concentration of 20% by using O, adding the nitrate solution into the suspension A under the stirring state, adding 4g of linoleic acid, stirring for 12h, transferring to 30 ℃ for ultrasonic dissolution to prepare a sol solution B, standing and aging the sol solution B at room temperature for 30h, drying at 130 ℃ for 13h after aging, roasting at 400 ℃ for 2h under the oxygen-enriched atmosphere, roasting at 680 ℃ for 2h to obtain a 7 Al/sludge-carbon-based catalyst, and extruding the catalyst into strips (4mm) for later use. The specific surface area of the catalyst is 410m2The pore volume is 1.0mL/g, the micropore volume: mesoporous pore volume: large pore volume 1: 45: 25.
the catalyst is used for catalytic decomposition of hydrogen peroxide in Fenton effluent, and the content of residual hydrogen peroxide in Fenton wastewater is 10000 ppm. The loading of the catalyst is 100ml, and the space velocity of the volume of the wastewater is 0.1h-1The reaction temperature is 60 ℃, the content of hydrogen peroxide in the catalyzed wastewater is 40ppm, and the stable operation lasts 910 h.
Example 4:
ultrasonically cleaning the sludge for 3 hours under magnetic stirring, drying for 8 hours at 120 ℃ after suction filtration, crushing and screening to 100 meshes; soaking waste activated carbon for 35h by using ethanol, washing for 3 times by using deionized water, drying for 5h at 130 ℃, and crushing and screening for 100 meshes; and (3) washing the waste polyurethane heat-insulating material for 3 times by using deionized water, drying for 10 hours at 120 ℃, and crushing and screening for 500 meshes. Preparing 400g of 4% sodium hydroxide alkali liquor, adding the dried sludge, the activated carbon powder and the waste polyurethane foam into the alkali liquor according to the mass ratio of 1:3.5:0.07 (the dried sludge is calculated according to 10 g) under magnetic stirring, stirring for 21h, transferring the alkali liquor to an infrared atmosphere, and irradiating for 50h at the infrared irradiation temperature of 60 ℃ to obtain suspension A. 2.8g of AgNO was taken3Preparing silver nitrate solution with the concentration of 15 percent and stirringAdding a nitrate solution into the suspension A under a stirring state, adding 0.5g of linoleic acid, stirring for 20h, transferring to 40 ℃ for ultrasonic dissolution to prepare a sol solution B, standing and aging the sol solution B at room temperature for 28h, drying at 100 ℃ for 24h after aging, roasting at 350 ℃ for 10h in an oxygen-enriched atmosphere, finally roasting at 650 ℃ for 8h to obtain a 3 Ag/sludge-carbon-based catalyst, and extruding the catalyst into strips (4mm) for later use. The specific surface area of the catalyst is 450m2The pore volume is 1.1mL/g, the micropore volume: mesoporous pore volume: large pore volume 1: 50: 30.
the catalyst is used for catalytic decomposition of hydrogen peroxide in Fenton effluent, and the content of residual hydrogen peroxide in Fenton wastewater is 600 ppm. The loading of the catalyst is 100ml, and the space velocity of the volume of the waste water is 10h-1The reaction temperature is 10 ℃, the content of hydrogen peroxide in the catalyzed wastewater is 20ppm, and the operation is stable for 990 h.
Example 5:
ultrasonically cleaning the sludge for 2 hours under magnetic stirring, drying for 6 hours at 140 ℃ after suction filtration, crushing and screening to 100 meshes; soaking the waste activated carbon for 25h by using ethanol, washing for 3 times by using deionized water, drying for 9h at 110 ℃, crushing and screening for 100 meshes; and (3) washing the waste polyurethane heat-insulating material for 3 times by using deionized water, drying for 7 hours at 120 ℃, and crushing and screening for 500 meshes. Preparing 300g of 3% sodium hydroxide alkali liquor, adding the dried sludge, the activated carbon powder and the waste polyurethane foam into the alkali liquor according to the mass ratio of 1:4.5:0.09 (the dried sludge is calculated by 10 g) under magnetic stirring, stirring for 15h, transferring the alkali liquor to an infrared atmosphere, and irradiating for 40h at the infrared irradiation temperature of 110 ℃ to obtain suspension A. 1.3g of Pd (NO)3)2·2H2Preparing a palladium nitrate solution with the concentration of 10% by using O, adding the nitrate solution into the suspension A under the stirring state, adding 0.2g of linoleic acid, stirring for 22h, transferring to the suspension B to be ultrasonically dissolved at 30 ℃ to prepare a sol solution B, standing and aging the sol solution B at room temperature for 23h, drying at 120 ℃ after aging for 19h, roasting at 375 ℃ for 5h under an oxygen-enriched atmosphere, roasting at 640 ℃ for 4h to obtain a 1 Pd/sludge-carbon-based catalyst, and extruding the catalyst into strips (4mm) for later use. The specific surface area of the catalyst is 500m2The pore volume is 1.1mL/g, the micropore volume: mesoporous pore volume: big (a)Pore volume 1: 55: 25.
the catalyst is used for catalytic decomposition of hydrogen peroxide in Fenton effluent, and the content of residual hydrogen peroxide in Fenton wastewater is 300 ppm. The loading of the catalyst is 100ml, and the space velocity of the volume of the wastewater is 7h-1The reaction temperature is 40 ℃, the content of hydrogen peroxide in the catalyzed wastewater is 15ppm, and the stable operation lasts 1200 h.
Example 6:
ultrasonically cleaning the sludge for 5 hours under magnetic stirring, drying for 8 hours at 110 ℃ after suction filtration, crushing and screening to 100 meshes; soaking the waste activated carbon for 30h by using ethanol, washing for 3 times by using deionized water, drying for 6h at 115 ℃, crushing and screening for 100 meshes; and (3) washing the waste polyurethane heat-insulating material for 3 times by using deionized water, drying for 9 hours at 125 ℃, and crushing and screening for 500 meshes. Preparing 300g of 2% potassium hydroxide alkali liquor, adding the dried sludge, the activated carbon powder and the waste polyurethane foam into the alkali liquor according to the mass ratio of 1:3.5:0.1 (the dried sludge is calculated according to 10 g) under magnetic stirring, stirring for 20h, transferring the alkali liquor to an infrared atmosphere, and irradiating for 30h at the infrared irradiation temperature of 100 ℃ to obtain suspension A. Taking 9.1g of Mn (NO)3)2.4H2Preparing a manganese nitrate solution with the concentration of 20% by using O, adding the nitrate solution into the suspension A under the stirring state, adding 1.5g of linoleic acid, stirring for 18h, transferring to 35 ℃ for ultrasonic dissolution to prepare a sol solution B, standing and aging the sol solution B at room temperature for 25h, drying at 110 ℃ for 20h after aging, roasting at 400 ℃ for 3h under an oxygen-enriched atmosphere, roasting at 680 ℃ for 6h to obtain a 5 Mn/sludge-carbon-based catalyst, and extruding the catalyst into strips (4mm) for later use. The specific surface area of the catalyst is 450m2The pore volume is 1.2mL/g, the micropore volume: mesoporous pore volume: large pore volume 1: 60: 25.
the catalyst is used for catalytic decomposition of hydrogen peroxide in Fenton effluent, and the content of residual hydrogen peroxide in Fenton wastewater is 8600 ppm. The loading of the catalyst is 100ml, and the space velocity of the volume of the waste water is 2h-1The reaction temperature is 40 ℃, the content of hydrogen peroxide in the catalyzed wastewater is 40ppm, and the stable operation lasts 950 hours.
Comparative example 1:
adjusting pH of Fenton effluent to 10 using sodium hydroxide solution for Fenton effluent bisAnd (3) decomposing the blank by using oxygen water, wherein the content of residual hydrogen peroxide in the Fenton wastewater is 8600 ppm. No catalyst loading, waste water volume space velocity of 2h-1The reaction temperature is 40 ℃, and the content of hydrogen peroxide in the catalyzed wastewater is 2900 ppm.
Comparative example 2:
taking 4.5g of Mn (NO)3)2.4H2And (2) preparing a manganese nitrate solution from O, wherein the concentration of the manganese nitrate solution is 30%, adding 32.4g of alumina carrier to disperse in a nitrate aqueous solution under the stirring state, carrying out isovolumetric impregnation for 20h, then drying at 125 ℃, finally roasting at 680 ℃ for 6h to obtain a 5 Mn/alumina catalyst, and extruding the catalyst into strips (4mm) for later use. The specific surface area of the catalyst was 460m2The pore volume is 0.4mL/g, the micropore volume: mesoporous pore volume: large pore volume 1: 98.5: 0.5.
the catalyst is used for catalytic decomposition of hydrogen peroxide in Fenton effluent, and the content of residual hydrogen peroxide in Fenton wastewater is 8600 ppm. The loading of the catalyst is 100ml, and the space velocity of the volume of the waste water is 2h-1The reaction temperature is 40 ℃, the content of hydrogen peroxide in the catalyzed wastewater is 150ppm, and the stable operation is carried out for 260 hours.
Comparative example 3:
ultrasonically cleaning the sludge for 2 hours under magnetic stirring, drying for 7 hours at 110 ℃ after suction filtration, crushing and screening to 100 meshes; soaking the waste activated carbon in ethanol for 20h, washing with deionized water for 3 times, drying at 110 deg.C for 6h, pulverizing, and sieving with 100 mesh sieve. Preparing 200g of 1% (wt) sodium hydroxide alkali liquor, adding the dried sludge and the activated carbon powder into the alkali liquor according to the mass ratio of 1:2 (the dried sludge is calculated according to 10 g) under magnetic stirring, stirring for 12h, transferring the alkali liquor to an infrared atmosphere, and irradiating for 30h at the infrared irradiation temperature of 90 ℃ to obtain suspension A. Taking 4.5g of Mn (NO)3)2.4H2And O, preparing a manganese nitrate solution with the concentration of 30%, adding the nitrate solution into the suspension A under the stirring state, stirring for 12h, transferring to 50 ℃ for ultrasonic dissolution to prepare a sol solution B, standing and aging the sol solution B at room temperature for 20h, drying at 105 ℃ for 12h after aging, roasting at 560 ℃ for 6h to obtain a 4 Mn/sludge-carbon-based catalyst, and extruding the catalyst into strips (4mm) for later use. The specific surface area of the catalyst was tested to be 430m2The pore volume is 0.7mL/g, the micropore volume: mesoporous pore volume: large pore volume 1: 96: 3.
the catalyst is used for catalytic decomposition of hydrogen peroxide in Fenton effluent, and the content of residual hydrogen peroxide in Fenton wastewater is 8600 ppm. The loading of the catalyst is 100ml, and the space velocity of the volume of the waste water is 1h-1The reaction temperature is 20 ℃, the content of hydrogen peroxide in the catalyzed wastewater is 100ppm, and the stable operation is carried out for 430 hours.
Table 1 data table of the embodiment of the present invention
Examples 1 Examples 2 Examples 3 Fruit of Chinese wolfberry Applying (a) to Example 4 Examples 5 Examples 6 To pair Ratio of Example 1 Comparative example 2 Comparative example 3
Alkali solution g 200 300 500 400 300 300 200
Concentration of alkali liquor 1％ 0.5％ 0.2％ 4％ 3％ 2％ 1％
Dried sludge g 10 10 10 10 10 10 10
Activated carbon powder g 20 30 50 35 45 35 20
Waste polyurethane Foam g 0.5 0.6 1 0.7 0.9 1 0
Species of nitrate Mn (NO3)2 ·4H2O Zn (NO3)2 ·6H2O Al (NO3)3 ·9H2O AgN O3 Pd (NO3)2 ·2H2O Mn (NO3)2 ·4H2O Mn (NO3)2 ·4H2O Mn (NO3)2 ·4H2O
Nitrate g 4.5 17 34 2.8 1.3 9.1 4.5 4.5
Linoleic acid g 0.5 3 4 0.5 0.2 1.5 0 0
Loaded metal Ratio of 4％ 10％ 7％ 3％ 1％ 5％ 4％ 4％
Specific surface area m2/ g 400 500 410 450 500 450 460 430
Pore volume mL/g 1.2 1 1 1.1 1.1 1.2 0.6 0.7
Pore volume ratio (micro) Hole: mesopore: big (a) Hole) 1：45： 30 1：60： 25 1：45： 25 1： 50： 30 1：55： 25 1：60： 25 1： 98.5： 0.5 1：96：3
Residual double of waste water Oxygen water content 8600 5000 10000 600 300 8600 860 0 8600 8600
Content after catalysis ppm 30 30 40 20 15 40 290 0 150 100
Stable operation Time h 1000 900 910 990 1200 950 260 430
Wherein, the pore diameter distribution diagram, N, of the three catalysts of example 1, comparative example 2 and comparative example 3 of the present invention2The adsorption-desorption isotherms are shown in fig. 1 and 2. As can be seen from the figure, the proportion of the large pore area of the catalyst prepared in the example 1 of the invention is far higher than that of the catalyst prepared in the comparative examples 2 and 3, which shows that the large pore volume is remarkably improved by using the waste polyurethane as the pore-expanding agent.
From the experimental results of catalytic reaction, the catalyst prepared by the invention can catalytically decompose the residual hydrogen peroxide content in the wastewater from 300-10000ppm to 15-40ppm, and meets the acceptable range (less than 50ppm) of hydrogen peroxide entering a biochemical system. The comparative example 1 is a blank experiment, the content of residual hydrogen peroxide in the wastewater is treated from 8600ppm to 2900ppm, and the residual hydrogen peroxide is far out of the acceptable range of a biochemical system; similarly, the comparative example 2 adopts a conventional alumina-supported metal oxide catalyst, and the content of residual hydrogen peroxide in the wastewater is treated from 8600ppm to 150 ppm; comparative example 3 the residual hydrogen peroxide content in the wastewater is treated from 8600ppm to 100ppm by using the catalyst with the same carrier but not including the pore-expanding agent; the residual hydrogen peroxide content of the wastewater treated by the three comparative examples can not meet the acceptable range of a biochemical system. In addition, the catalyst prepared by the invention has long reaction stable operation time, the stable time of the alumina carrier catalyst in the comparative example 2 is 260h, the stable time of the catalyst which does not use polyurethane pore-expanding in the comparative example 3 is only 430h, and the catalyst prepared by the invention can stably operate for over 900h, and has remarkable catalytic decomposition effect and wide application range.
The embodiment of the invention provides a catalyst for decomposing residual hydrogen peroxide in Fenton effluent and a preparation method thereof. After pore expansion of polyurethane, the macroporous volume of the catalyst is obviously increased, the pores are more developed (the microporous volume: the mesoporous volume: the macroporous volume is 1-10: 40-60: 20-30), the mass transfer capacity of the catalyst is enhanced, uniform loading of metal oxides is facilitated, the catalyst has a strong catalytic decomposition effect on hydrogen peroxide in wastewater, the reaction stabilization time is prolonged, and reduction and recycling of sludge, activated carbon and waste polyurethane are realized.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.

Claims (10)

1. A preparation method of a catalyst for decomposing residual hydrogen peroxide in Fenton effluent is characterized in that a mixture of dried sludge and waste activated carbon is used as a carrier, waste polyurethane foam is used as a pore-expanding agent, and a metal oxide active component is loaded on the carrier by adopting an in-situ one-step process to obtain the catalyst for decomposing the residual hydrogen peroxide in the Fenton effluent.
2. The method for preparing a catalyst according to claim 1, comprising the following preparation steps:
1) ultrasonically cleaning the sludge under the stirring state, removing impurities, performing suction filtration on the sludge, drying and crushing;
2) soaking waste activated carbon by using a solvent, cleaning the activated carbon by using deionized water, drying and crushing the activated carbon;
3) washing waste polyurethane foam with deionized water, drying and crushing;
4) preparing an alkali liquor, sequentially adding the dried sludge, the activated carbon powder and the waste polyurethane foam into the alkali liquor in a stirring state, stirring for 12-24 h, and then transferring the alkali liquor to an infrared atmosphere to irradiate for 10-50 h to obtain a suspension A.
5) Preparing a nitrate solution, adding the nitrate solution into the suspension A under the stirring state, adding a certain amount of linoleic acid, stirring for 12-24 h, and then transferring to the temperature of 20-50 ℃ for ultrasonic dissolution to prepare a sol solution B;
6) standing and aging the sol solution B at room temperature for 20-30 h, drying at 100-130 ℃ for 12-24 h after aging, roasting at 250-400 ℃ for 2-10 h in an oxygen-enriched atmosphere, and removing the waste polyurethane thermal insulation material of the pore expanding agent; and finally, roasting at 500-680 ℃ for 2-8 h to obtain the catalyst, and crushing for later use.
3. The preparation method of the catalyst according to claim 2, wherein in the step 1), the dried sludge is subjected to ultrasonic treatment for 2-5 hours, dried at 100-130 ℃ for 5-10 hours, and crushed and sieved by a 100-mesh sieve.
4. The method for preparing the catalyst according to claim 2, wherein in the step 2), the waste activated carbon is soaked in ethanol for 20-40 hours, dried at 100-130 ℃ for 5-10 hours, and crushed and sieved for 100 meshes.
5. The preparation method of the catalyst according to claim 2, wherein in the step 3), the waste polyurethane foam is dried at 100-130 ℃ for 5-10 h, and then is crushed and sieved by 500 meshes.
6. The preparation method of the catalyst according to claim 2, wherein in the step 4), alkali treatment is performed on the catalyst carrier and the pore-expanding agent by using alkali liquor, wherein the alkali liquor is sodium hydroxide or potassium hydroxide, and the mass concentration of the alkali liquor is 0.5-4%; preferably, the mass ratio of the dried sludge to the activated carbon to the waste polyurethane foam is 1: 2-5: 0.05-0.1, and the mass ratio of the alkali liquor to the dried sludge is 20-50: 1; more preferably, the irradiation temperature of the alkali liquor for infrared treatment is 60-120 ℃.
7. The method for preparing a catalyst according to claim 2, wherein the nitrate in the step 5) is any one of manganese nitrate, zinc nitrate, aluminum nitrate, silver nitrate or palladium nitrate; preferably, the concentration of the nitrate aqueous solution is 10-30%; more preferably, linoleic acid is added as a dispersing agent, and the mass ratio of the linoleic acid to the nitrate is 1: 5-10.
8. A catalyst for decomposition of residual hydrogen peroxide from Fenton effluent prepared by the catalyst preparation method according to any one of claims 1 to 7.
9. The catalyst according to claim 8, wherein the catalyst comprises the following components in percentage by mass: active components: 1-10% and the balance of catalyst carrier.
10. The catalyst prepared by the method of any one of claims 1 to 7 is used for catalyzing the decomposition reaction of the hydrogen peroxide of Fenton effluent, and is preferably suitable for wastewater with the residual hydrogen peroxide content of 100-10000 ppm; more preferably, when the catalyst is used, the catalyst is extruded into strips and is filled in a reaction tube, Fenton effluent enters the reaction tube, and the volume space velocity of wastewater is 0.1-10 h-1The reaction temperature is 10-50 ℃; more preferably, the volume space velocity is 0.5-5 h-1The reaction temperature is 15-45 ℃.
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CN106076256A (en) * 2016-07-06 2016-11-09 中山大学 A kind of preparation method and applications of nanometer Fe (0) porous mud material with carbon element
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