CN111068660A - Catalyst for purifying indoor formaldehyde and application thereof - Google Patents

Catalyst for purifying indoor formaldehyde and application thereof Download PDF

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Publication number
CN111068660A
CN111068660A CN201811214025.6A CN201811214025A CN111068660A CN 111068660 A CN111068660 A CN 111068660A CN 201811214025 A CN201811214025 A CN 201811214025A CN 111068660 A CN111068660 A CN 111068660A
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catalyst
parts
weight
formaldehyde
carrier
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郑育元
陈航宁
杜辰昊
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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
    • B01J23/38—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
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • 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
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The invention relates to a catalyst for purifying indoor formaldehyde and application thereof, and mainly solves the problem of low indoor formaldehyde removal rate in the prior art. The catalyst for purifying indoor formaldehyde comprises the following components in parts by weight: a) 92.0-99.0 parts of a carrier; and supported thereon; b) 1.0-8.0 parts of active component; the active component comprises at least one of noble metal elements and rare earth elements, the noble metal comprises at least one of the substances consisting of Ru, Pd, Pt and Rh, and the rare earth elements are at least one of the substances consisting of La, Ce and Y.

Description

Catalyst for purifying indoor formaldehyde and application thereof
Technical Field
The invention relates to a catalyst for purifying indoor formaldehyde and application thereof.
Background
The formaldehyde is the most harmful pollutant in the air pollution of the current home decoration, and the release time of the formaldehyde can reach 10 to 15 years. The world health organization international agency for research on cancer rose formaldehyde to a category 1 carcinogen in 6 months of 2004. The stimulation, sensitization and gene mutation of formaldehyde to human body seriously affect the health and working efficiency of people. Because people live, work, study and rest in the room for 80% of the time, the establishment of a healthy indoor environment is the work key point of environmental protection science and technology workers.
The titanium oxide photocatalytic oxidation technology is an advanced technology for indoor air purification in the 21 st century. The technology has the advantages of mild reaction conditions, wide application range, strong oxidation capability, simple operation, energy saving, no pollution and the like. However, the technology has the disadvantage of incomplete degradation of high-concentration pollutants.
CN101274281B discloses an oxidation of formaldehyde to H at below room temperature2O and CO2The high-efficiency oxidation catalyst is characterized in that the catalyst takes cordierite honeycomb ceramic coated with Co-Ce-Sn porous composite oxide as a carrier, 0-10% of Pt active component and MoO3、CuOx、MnOx、TiO2And the like as an auxiliary agent. The method is characterized in that light, heat, electricity and other energy sources and chemical reagents are not needed to be added, the formaldehyde removal efficiency under the conditions of large air volume, high humidity and the like is far higher than that of a photocatalysis technology and a plasma technology, no by-product is generated, and the method is suitable for efficiently removing formaldehyde pollution in closed and semi-closed spaces of artificial board production workshops, rooms, building material furniture markets and the like. However, the active ingredients and auxiliaries used in this process are expensive.
CN104368325B discloses a preparation method of photodegradation formaldehyde honeycomb activated carbon, which is characterized in that: adding powdered activated carbon into a self-made cellophane mould, adding black material, stirring for a period of time, quickly adding white material, high-speed stirring, making it freely foam, curing at room temperature, forming, placing in muffle furnace, high-temp. heat-treating to obtain cellular activated carbon, adding P-25 type TiO, adding powdered activated carbon, stirring, adding black material, stirring, adding white material, stirring, high-speed stirring, making it freely foam, curing at room temp. and forming, placing in2Dispersing the nano particles into suspension by ultrasonic wave, completely soaking the prepared honeycomb activated carbon, and performing heat treatment to obtain the P-25/activated carbon composite material which has better indoor formaldehyde effect under ultraviolet lightPhotocatalytic degradation performance. But the method has incomplete capability of degrading formaldehyde.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low removal rate of formaldehyde degraded by photocatalytic reaction in the prior art, and provides a novel catalyst for purifying indoor formaldehyde. The catalyst is used for purifying formaldehyde through photocatalytic reaction and has the advantage of high formaldehyde removal rate.
The second technical problem to be solved by the present invention is to provide a method for preparing the catalyst corresponding to the first technical problem.
The invention also provides a method for purifying indoor formaldehyde by using the catalyst.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the catalyst for purifying indoor formaldehyde comprises the following components in parts by weight:
a) 92.0-99.0 parts of a carrier; and supported thereon;
b) 1.0-8.0 parts of active component;
the active component includes at least one selected from the group consisting of noble metal elements including at least one selected from the group consisting of Ru, Pd, Pt and Rh and rare earth elements selected from at least one selected from the group consisting of La, Ce and Y.
Due to the active components, the catalyst has the effect of removing formaldehyde through ultraviolet light catalytic oxidation.
The technical key of the invention is the choice of the active ingredient, as far as the carrier is concerned, it is reasonable and without inventive effort for the person skilled in the art to choose. For example, but not limited to, the carrier includes one selected from the group consisting of titanium oxide, zirconium oxide, and aluminum oxide.
In the above-mentioned embodiment, the carrier is preferably titanium oxide (hereinafter, referred to as TiO)2)。
In the above technical solution, preferably, the noble metal includes at least two of Ru, Pd, and Pt at the same time, and the combination of the two noble metals in the active component has a synergistic effect in improving the formaldehyde removal efficiency. At this time, the ratio between the two noble metal elements is not particularly limited as long as a comparable synergistic effect can be obtained by simultaneously including the noble metal active element. By way of non-limiting example, the mass ratio of the ratio between the two noble metal elements may be 0.5 to 5, and within this mass ratio range, non-limiting specific point values may be 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, and the like.
In the above technical scheme, the active component preferably includes both a noble metal element and a rare earth element, and the rare earth element is preferably Ce and/or La. The combination of the noble metal elements and the rare earth elements has a synergistic effect in improving the formaldehyde removal efficiency. At this time, the ratio between the noble metal element and the rare earth element is not particularly limited, and as long as the noble metal element and the rare earth element are included at the same time, a comparable synergistic effect can be obtained. By way of non-limiting example, the mass ratio of the noble metal element to the rare earth element may be 0.5 to 5, and within this mass ratio, non-limiting specific point values may be 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, and the like.
In the above technical solution, it is preferable that the rare earth element includes Ce and La at the same time. Ce and La have a synergistic effect in improving the formaldehyde removal efficiency. At this time, the ratio between Ce and La is not particularly limited as long as the rare earth element simultaneously includes the rare earth metal active element to achieve a comparable synergistic effect. By way of non-limiting example, the mass ratio between Ce and La may be 0.5 to 5, and within this mass ratio range, by way of non-limiting specific point values, may be 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, and so forth.
To solve the second technical problem, the technical solution of the present invention is as follows:
the method for preparing the catalyst according to any of the preceding technical problems, comprising:
mixing a carrier and the solution of the noble metal element, drying and reducing;
or mixing a catalyst precursor containing a carrier and a rare earth element with the solution of the noble metal element, drying and reducing.
When the catalyst comprises both a noble metal and a rare earth metal, the preparation method preferably comprises:
1) mixing the carrier powder, the rare earth active component solution and a binder, molding, drying and roasting to obtain a molded active carrier;
2) and mixing the formed active carrier with the solution of the active element, drying, and reducing the compound noble metal to obtain the catalyst.
In the technical scheme, the roasting temperature in the step 1) is preferably 550-750 ℃; the roasting time is preferably 2.0-4.0 h.
In the above technical solution, the reduction is preferably gas phase reduction.
In the above technical solution, the reducing agent used for the reduction is preferably a gas containing hydrogen.
In the technical scheme, the reduction temperature in the step 2) is 350-500 ℃, and the reduction time is preferably 3.0-4.5 h.
In the above technical scheme, the particle size of the carrier powder in step 1) is not particularly limited, and it can be understood that the finer the powder, the more uniform the subsequent mixing. Such as but not limited to TiO2The average particle size of the powder is 2-10 nm, and the preparation method of the catalyst carrier of the invention is not particularly limited, such as but not limited to: tablet forming, rolling ball forming, extrusion molding and the like, and the binder used may be an organic binder (e.g., CMC, methylcellulose, dry starch and the like) or an inorganic binder (e.g., titanium sol, aluminum sol, silica sol and the like).
In the technical scheme, the roasting temperature in the step 1) is further preferably 600-700 ℃, and the roasting time is preferably 2.2-3.5 h.
In the above technical scheme, the solution of the active ingredient in the steps 1) and 2) is preferably a solution prepared from the active ingredient and water.
In the technical scheme, the reduction temperature in the step 2) is preferably 400-450 ℃, and the reduction time is preferably 3.5-4.0 h.
To solve the third technical problem, the technical scheme of the invention is as follows:
a method for purifying formaldehyde in a room, comprising contacting air containing formaldehyde with the catalyst of claim 1 or 2 in the presence of ultraviolet light to react the formaldehyde with oxygen in the air to remove the formaldehyde.
In the technical scheme, the reaction temperature is preferably 20-30 ℃, and more preferably 22-28 ℃.
In the above technical scheme, the reaction pressure is preferably normal pressure.
In the technical scheme, the relative humidity of the environment is preferably 40-60%, and further preferably 45-55%.
In the technical scheme, the wavelength of the ultraviolet lamp is preferably 10-400 nm, and further preferably 200-300 nm.
The evaluation method of the catalyst of the present invention is as follows: the reaction closed space is 1m3An ultraviolet lamp is used as a light source, and the initial concentration of formaldehyde in the space is 20mg/m3. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST. The formaldehyde removal rate was calculated as an index of the catalyst activity at the evaluation time of 4 hours.
By adopting the technical scheme of the invention, an ultraviolet lamp is used as a light source, formaldehyde is contacted with a catalyst in a closed space, and the catalyst comprises 6 parts of active component and 94 parts of TiO in parts by weight2Under the conditions that the reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50 percent, and the wavelength lambda of an ultraviolet lamp is 254nm, the highest formaldehyde removal rate can reach 99.6 percent, and a better technical effect is obtained.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Detailed Description
[ example 1 ]
1. Preparation of the support
90 parts by weight of nano TiO2Mixing the powder (average particle diameter of 5nm) in a kneader, adding 8 weight parts of titanium sol (50 wt%) and 80 weight parts of water, kneading, extruding, rolling, drying at 100 deg.C for 16 hr, and drying in muffle furnace 60Roasting at 0 ℃ for 3.0h to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
Mixing 94 parts by weight of spherical carrier and 130 parts by weight of H2PtCl6The aqueous solution (containing 6 parts by weight of Pt) was mixed, allowed to stand at room temperature for 4 hours, then dried in an oven at 110 ℃ for 16 hours, and then dried at 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 2 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size 5nm) was mixed in a kneader, 8 parts by weight of titanium sol (50% by weight) and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball, dried at 100 ℃ for 16 hours, and then calcined at 600 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
Mixing 94 weight portions of spherical carrier and 130 weight portions of RuCl3The mixed aqueous solution (containing 6 parts by weight of Ru) was mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, and then at 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 3 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size 5nm) was mixed in a kneader, 8 parts by weight of titanium sol (50% by weight) and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball, dried at 100 ℃ for 16 hours, and then calcined at 600 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
Mixing 94 parts by weight of spherical carrier and 130 parts by weight of PdCl2Aqueous solutions (containing 6 parts by weight of Pd) were mixed, left to stand at room temperature for 4H, then dried in an oven at 110 ℃ for 16H, and then at 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 4 ]
1. Catalyst preparation
90 parts by weight of nano TiO2The powder (average particle diameter 5nm) was mixed in a kneader, and an aqueous solution containing 10 parts by weight of cerium nitrate (containing 6 parts by weight of Ce), 8 parts by weight of titanium sol (50% by weight) and 70 parts by weight of water were poured, kneaded, extruded, rolled into a ball, dried at 100 ℃ for 16 hours, and then calcined at 600 ℃ in a muffle furnace for 3.0 hours to obtain a spherical catalyst having a diameter of 3 mm.
2. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 5 ]
1. Catalyst preparation
90 parts by weight ofNano TiO 22The powder (average particle size 5nm) was mixed in a kneader, and an aqueous solution containing 10 parts by weight of lanthanum nitrate (containing 6 parts by weight of La), 8 parts by weight of titanium sol (50% by weight) and 70 parts by weight of water were poured, kneaded, extruded, rolled into a ball, dried at 100 ℃ for 16 hours, and then calcined at 600 ℃ in a muffle furnace for 3.0 hours to obtain a spherical catalyst having a diameter of 3 mm.
2. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 6 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size 5nm) was mixed in a kneader, 8 parts by weight of titanium sol (50% by weight) and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball, dried at 100 ℃ for 16 hours, and then calcined at 600 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
Mixing 94 parts by weight of spherical carrier and 130 parts by weight of H2PtCl6-RuCl3The mixed aqueous solution (containing 3 parts by weight of Pt and 3 parts by weight of Ru) was mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by drying at 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 7 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size 5nm) was mixed in a kneader, 8 parts by weight of titanium sol (50% by weight) and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball, dried at 100 ℃ for 16 hours, and then calcined at 600 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
Mixing 94 parts by weight of spherical carrier and 130 parts by weight of H2PtCl6-PdCl2The mixed aqueous solution (containing 3 parts by weight of Pt and 3 parts by weight of Pd) was mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by H at 400 ℃2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 8 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size 5nm) was mixed in a kneader, 8 parts by weight of titanium sol (50% by weight) and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball, dried at 100 ℃ for 16 hours, and then calcined at 600 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
Mixing 94 weight portions of spherical carrier and 130 weight portions of RuCl3-PdCl2The mixed aqueous solution (containing 3 parts by weight of Ru and 3 parts by weight of Pd) was mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by drying at 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 9 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size 5nm) was mixed in a kneader, and an aqueous solution containing 10 parts by weight of cerium nitrate (containing 2 parts by weight of Ce), 8 parts by weight of titanium sol (50% by weight) and 70 parts by weight of water were poured, kneaded, extruded, rolled into balls, dried at 100 ℃ for 16 hours, and then calcined at 600 ℃ in a muffle furnace for 3.0 hours to obtain spherical active carriers having a diameter of 3 mm.
2. Catalyst preparation
Mixing 96 parts by weight of spherical active carrier and 130 parts by weight of H2PtCl6-RuCl3The mixed aqueous solution (containing 2 parts by weight of Pt and 2 parts by weight of Ru) was mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by drying at 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 10 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size 5nm) is put into a kneader to be mixed, and then aqueous solution containing 10 parts by weight of lanthanum nitrate (containing 2 parts by weight of La), 8 parts by weight of titanium sol (50% by weight) and 70 parts by weight of water are poured into the kneader to be kneaded, extruded into strips, rolled ball shaped, dried at 100 ℃ for 16h and then roasted at 600 ℃ in a muffle furnace for 3.0h to obtain the spherical active carrier with the diameter of 3 mm.
2. Catalyst preparation
Mixing 96 parts by weight of spherical active carrier and 130 parts by weight of H2PtCl6-RuCl3The mixed aqueous solution (containing 2 parts by weight of Pt and 2 parts by weight of Ru) was mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by drying at 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 11 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size of 5nm) is put into a kneader to be mixed, 10 parts by weight of mixed aqueous solution of cerium nitrate and lanthanum nitrate (containing 1 part by weight of Ce and 1 part by weight of La), 8 parts by weight of titanium sol (50 percent by weight) and 70 parts by weight of water are poured, kneading, strip extrusion and ball rolling are carried out, drying is carried out for 16h at 100 ℃, and then, the spherical active carrier with the diameter of 3mm is obtained after roasting is carried out for 3.0h at 600 ℃ in a muffle furnace.
2. Catalyst preparation
Mixing 96 parts by weight of spherical active carrier and 130 parts by weight of H2PtCl6-RuCl3The mixed aqueous solution (containing 2 parts by weight of Pt and 2 parts by weight of Ru) was mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by drying at 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 12 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size of 5nm) is put into a kneader to be mixed, 10 parts by weight of mixed aqueous solution of cerium nitrate and lanthanum nitrate (containing 1.5 parts by weight of Ce and 0.5 part by weight of La), 8 parts by weight of titanium sol (50% wt) and 70 parts by weight of water are poured, kneading, bar extrusion and ball rolling are carried out, drying is carried out for 16h at 100 ℃, and then roasting is carried out for 3.0h at 600 ℃ in a muffle furnace to obtain the spherical active carrier with the diameter of 3 mm.
2. Catalyst preparation
Mixing 96 parts by weight of spherical active carrier and 130 parts by weight of H2PtCl6-RuCl3The mixed aqueous solution (containing 2 parts by weight of Pt and 2 parts by weight of Ru) was mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by drying at 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
[ example 13 ]
1. Preparation of the support
90 parts by weight of nano TiO2The powder (average particle size of 5nm) is put into a kneader to be mixed, 10 parts by weight of mixed aqueous solution of cerium nitrate and lanthanum nitrate (containing 0.5 part by weight of Ce and 1.5 parts by weight of La), 8 parts by weight of titanium sol (50% wt) and 70 parts by weight of water are poured, kneading, bar extrusion and ball rolling are carried out, drying is carried out for 16h at 100 ℃, and then roasting is carried out for 3.0h at 600 ℃ in a muffle furnace to obtain the spherical active carrier with the diameter of 3 mm.
2. Catalyst preparation
Mixing 96 parts by weight of spherical active carrier and 130 parts by weight of H2PtCl6-RuCl3The mixed aqueous solution (containing 2 parts by weight of Pt and 2 parts by weight of Ru) was mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by drying at 400 ℃ in H2-N2Reduction in an atmosphere4H to obtain a catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was taken and charged into a closed space to carry out a reaction. The reaction temperature is 25 ℃, the pressure is normal pressure, the environmental humidity is 50%, and the wavelength lambda of an ultraviolet lamp is 254 nm. Formaldehyde was measured using a British PPM Formaldehyde detector PPM-400 ST.
The catalyst composition and the evaluation results are shown in Table 1.
TABLE 1
(parts by weight)
Figure BDA0001833104700000111

Claims (10)

1. The catalyst for purifying indoor formaldehyde comprises the following components in parts by weight:
a) 92.0-99.0 parts of a carrier; and supported thereon;
b) 1.0-8.0 parts of active component;
the active component includes at least one selected from the group consisting of noble metal elements including at least one selected from the group consisting of Ru, Pd, Pt and Rh and rare earth elements selected from at least one selected from the group consisting of La, Ce and Y.
2. The catalyst according to claim 1, wherein the carrier comprises at least one selected from the group consisting of titania, zirconia, and alumina.
3. A method of preparing the catalyst of claim 1, comprising:
mixing a carrier and the solution of the noble metal element, drying and reducing;
or mixing a catalyst precursor containing a carrier and a rare earth element with the solution of the noble metal element, drying and reducing.
4. The method according to claim 3, wherein the reduction is a gas phase reduction.
5. The method according to claim 3, wherein the reduction temperature is 350 to 500 ℃.
6. A method for purifying formaldehyde in a room, comprising contacting air containing formaldehyde with the catalyst of claim 1 or 2 in the presence of ultraviolet light to react the formaldehyde with oxygen in the air to remove the formaldehyde.
7. The process according to claim 6, wherein the reaction temperature is 20 to 30 ℃.
8. The process according to claim 6, wherein the reaction pressure is atmospheric pressure.
9. The process according to claim 6, characterized in that the ambient relative humidity is 40-60%.
10. The process according to claim 6, wherein the UV lamp has a wavelength of 10 to 400 nm.
CN201811214025.6A 2018-10-18 2018-10-18 Catalyst for purifying indoor formaldehyde and application thereof Pending CN111068660A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101559377A (en) * 2009-05-21 2009-10-21 浙江师范大学 Supported catalyst for eliminating formaldehyde, preparation method and application thereof
CN102941111A (en) * 2012-11-20 2013-02-27 中国科学院生态环境研究中心 Metal carrier loaded catalyst for purifying formaldehyde at room temperature
CN103736484A (en) * 2014-01-13 2014-04-23 中山大学 Supported integrated catalyst for formaldehyde purification and preparation method thereof
CN104162425A (en) * 2014-07-21 2014-11-26 贝谷科技股份有限公司 Catalyst for complete catalytic oxidation of indoor low concentration formaldehyde at room temperature
CN105080540A (en) * 2014-05-14 2015-11-25 中国石油化工股份有限公司 Wet oxidation catalyst and preparation method thereof
CN107096527A (en) * 2017-05-22 2017-08-29 西安石油大学 A kind of normal-temperature efficient catalysis oxidation formaldehyde catalyst, preparation method and application
CN107282042A (en) * 2016-04-13 2017-10-24 中国石油化工股份有限公司 The catalyst of waste water is handled for wet oxidation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101559377A (en) * 2009-05-21 2009-10-21 浙江师范大学 Supported catalyst for eliminating formaldehyde, preparation method and application thereof
CN102941111A (en) * 2012-11-20 2013-02-27 中国科学院生态环境研究中心 Metal carrier loaded catalyst for purifying formaldehyde at room temperature
CN103736484A (en) * 2014-01-13 2014-04-23 中山大学 Supported integrated catalyst for formaldehyde purification and preparation method thereof
CN105080540A (en) * 2014-05-14 2015-11-25 中国石油化工股份有限公司 Wet oxidation catalyst and preparation method thereof
CN104162425A (en) * 2014-07-21 2014-11-26 贝谷科技股份有限公司 Catalyst for complete catalytic oxidation of indoor low concentration formaldehyde at room temperature
CN107282042A (en) * 2016-04-13 2017-10-24 中国石油化工股份有限公司 The catalyst of waste water is handled for wet oxidation
CN107096527A (en) * 2017-05-22 2017-08-29 西安石油大学 A kind of normal-temperature efficient catalysis oxidation formaldehyde catalyst, preparation method and application

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