CN113797926B - Formaldehyde catalytic oxidation catalyst and preparation method and application thereof - Google Patents
Formaldehyde catalytic oxidation catalyst and preparation method and application thereof Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 306
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 84
- 230000003647 oxidation Effects 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000002253 acid Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 38
- 229910001868 water Inorganic materials 0.000 claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 239000005543 nano-size silicon particle Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- 238000002390 rotary evaporation Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001569 carbon dioxide Substances 0.000 abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 9
- 238000011068 loading method Methods 0.000 abstract description 5
- 229910008051 Si-OH Inorganic materials 0.000 abstract description 4
- 229910006358 Si—OH Inorganic materials 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000007789 gas Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 208000014181 Bronchial disease Diseases 0.000 description 1
- 206010012434 Dermatitis allergic Diseases 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 208000025966 Neurological disease Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 201000008937 atopic dermatitis Diseases 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- 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
- B01J23/38—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
- 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
- B01J23/52—Gold
-
- B01J35/40—
Abstract
The invention provides a formaldehyde catalytic oxidation catalyst, which comprises a noble metal active component and an acid modified silica carrier. According to the invention, the acid modified silicon dioxide is used as the carrier of the noble metal active component, the specific surface area of the acid modified silicon dioxide carrier is increased, the Si-OH on the surface of the silicon dioxide is increased, and the catalytic effect of the formaldehyde catalytic oxidation catalyst is improved; the formaldehyde catalytic oxidation catalyst provided by the invention can completely degrade formaldehyde into water and carbon dioxide at room temperature, and has the advantages of simple preparation process, low noble metal loading, low cost and long service life.
Description
Technical Field
The invention belongs to the field of catalysts, relates to a formaldehyde catalytic oxidation catalyst, and in particular relates to a formaldehyde catalytic oxidation catalyst, a preparation method and application thereof.
Background
Formaldehyde is an indoor contaminant that is released from building, furniture materials and consumer goods. Formaldehyde is a potential carcinogen, and is a common human exposure to formaldehyde, which causes bronchial diseases, allergic dermatitis, chronic poisoning, and neurological disorders. Therefore, the effective elimination of formaldehyde in the room is vital to the physical health and environment of people. The method for eliminating formaldehyde disclosed at present mainly comprises the following steps: adsorption, plasma technology, chemical reaction, photocatalytic oxidation, thermal catalytic oxidation, and the like. The adsorption method has the defects of low adsorption capacity, difficult recycling and the like; the disadvantages of the chemical reaction method are mainly the unsafe chemical reagents and high cost.
Catalytic oxidation of formaldehyde to carbon dioxide and water at room temperature is one of the most interesting processes for eliminating formaldehyde at present. Noble metal (Pt, pd or Au) supported catalysts exhibit excellent room temperature catalytic oxidation of formaldehyde, enabling the catalytic oxidation of formaldehyde to carbon dioxide and water at room temperature. In recent years, nanosilica has been widely used as a carrier for supported catalysts due to its unique characteristics such as nanosize effect and high specific surface area. In the disclosed silica supported catalytic oxidation catalyst, however, the catalytic performance thereof is still to be further improved.
CN 107096527a discloses a high-efficiency catalyst for purifying indoor formaldehyde at normal temperature, which comprises a carrier, a noble metal active component and an auxiliary agent. The carrier of the catalyst is mesoporous oxide, and comprises at least one of aluminum oxide, titanium dioxide, silicon dioxide, cerium oxide, cobalt oxide or manganese oxide; the active component is at least one of a small amount of noble metals Pd, pt, au or Ag; the auxiliary agent is at least one of Na, K, fe, co, ce or Ni. The disclosed catalyst needs to convert formaldehyde into carbon dioxide and water under the condition of relative humidity of 50-90%, and the catalytic performance of the catalyst needs to be further improved.
CN 107398272a discloses a formaldehyde room temperature catalytic composite carrier catalyst, which comprises a honeycomb carrier and a coating layer dip-coated on the honeycomb carrier, wherein the coating layer consists of nano-scale inorganic oxide and metal active components. The preparation method of the composite carrier catalyst comprises the following steps: uniformly mixing nanoscale inorganic oxide, a metal active component precursor, sol, an auxiliary agent and deionized water, regulating pH value to obtain a mixed solution, dip-coating the mixed solution on a honeycomb carrier by adopting a dip-coating method, and sequentially drying, roasting and reducing after the dip-coating is finished to obtain the composite carrier catalyst. The disclosed catalyst has complex preparation process and is not easy for mass production.
Based on the above research, how to provide a formaldehyde catalytic oxidation catalyst, which can completely degrade formaldehyde into water and carbon dioxide at room temperature, has simple preparation process, low noble metal loading, low cost and long service life, and becomes the problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a formaldehyde catalytic oxidation catalyst which comprises a noble metal active component and an acid modified silica carrier and can completely degrade formaldehyde into water and carbon dioxide at room temperature.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a formaldehyde catalytic oxidation catalyst comprising a noble metal active component and an acid-modified silica support.
According to the invention, the acid-modified silicon dioxide is used as the carrier of the noble metal active component, so that the specific surface area of the acid-modified silicon dioxide carrier is increased, the Si-OH on the surface is increased, and the catalytic effect of the formaldehyde catalytic oxidation catalyst is improved.
Preferably, the noble metal active component in the formaldehyde catalytic oxidation catalyst accounts for 0.2 to 2.0wt%, such as 0.2wt%, 0.4wt%, 0.6wt%, 0.8wt%, 1.0wt%, 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt% or 2.0wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the noble metal active component comprises any one or a combination of at least two of Pd, pt or Au, typically but not limited to a combination of Pd and Pt, a combination of Pd and Au or a combination of Pt and Au.
Preferably, the acid-modified silica support is obtained by a process comprising the steps of:
mixing nano silicon dioxide, acid and water, carrying out solid-liquid separation after mixing, and sequentially washing and drying the obtained solid to obtain the acid modified silicon dioxide carrier.
The average particle diameter of the nanosilica is preferably 15 to 100nm, and may be, for example, 15nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the mass ratio of the nano silicon dioxide to the acid to the water is 1 (0.1-2): (15-20), for example, 1:1:15, 1:1:20, 1:1.5:15, 1:2:15, 1:0.1:20 or 1:2:20, but not limited to the listed values, and other non-listed values in the numerical range are equally applicable.
Preferably, the acid comprises any one or a combination of at least two of hydrochloric acid, nitric acid, sulfuric acid or citric acid, typically but not limited to a combination of hydrochloric acid and nitric acid, a combination of hydrochloric acid and sulfuric acid, a combination of hydrochloric acid and citric acid, a combination of nitric acid and sulfuric acid, a combination of nitric acid and citric acid or a combination of sulfuric acid and citric acid.
Preferably, the acid concentration is 0.1 to 2M, and may be, for example, 0.1M, 0.3M, 0.5M, 0.7M, 0.9M, 1.1M, 1.3M, 1.5M, 1.7M, 1.9M, or 2M, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the mixing is stirring at 25-35 ℃ for 3-8 hours.
The stirring temperature of the mixture may be 25 to 35 ℃, for example, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃,30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, or 35 ℃, but the above-mentioned stirring temperature is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable in the same manner.
The stirring time of the mixing is 3 to 8 hours, and may be, for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the solid-liquid separation mode comprises filtration.
And washing the solid obtained after the solid-liquid separation by water, wherein the end point of the water washing is the washing liquid to be neutral.
The drying temperature is preferably 100 to 120 ℃, and may be, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, or 120 ℃, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
The drying time is 10 to 15 hours, and may be, for example, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours or 15 hours, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the average particle diameter of the acid-modified silica support is 15 to 100nm, and may be, for example, 15nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In a second aspect, the present invention provides a method for preparing the formaldehyde catalytic oxidation catalyst according to the first aspect, the method comprising the following steps:
(1) Mixing a palladium source, an acid modified silica carrier and a solvent, and performing rotary evaporation after mixing;
(2) And (3) drying and reducing the solid matters obtained after the rotary evaporation in the step (1) in sequence to obtain the formaldehyde catalytic oxidation catalyst.
Preferably, the step (1) of mixing the palladium source, the acid-modified silica support and the solvent is performed by dissolving the palladium source in the solvent and then adding the acid-modified silica support.
Preferably, the means of mixing in step (1) comprises post-ultrasonic agitation.
Preferably, the power of the ultrasound is 200-400W, for example, 200W, 220W, 240W, 260W, 280W, 300W, 320W, 340W, 360W, 380W or 400W, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The time of the ultrasonic treatment is 20 to 40min, for example, 20min, 22min, 25min, 28min, 30min, 32min, 35min, 38min or 40min, but the ultrasonic treatment is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
The stirring temperature may be 25 to 35 ℃, for example, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃,30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, or 35 ℃, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The stirring time is 3 to 5 hours, and may be, for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the mass ratio of the palladium source, nano silica and solvent in the step (1) is (0.05-0.2): (3-8): (50-100), for example, may be 0.05:5:70, 0.1:3:50, 0.15:8:100, 0.2:3:50 or 0.2:5:70, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the palladium source of step (1) comprises any one or a combination of at least two of palladium nitrate, palladium chloride or potassium chloropalladate, typically but not limited to a combination of palladium nitrate and palladium chloride, a combination of palladium nitrate and potassium chloropalladate or a combination of palladium nitrate and potassium chloropalladate.
Preferably, the solvent of step (1) comprises deionized water.
Preferably, the temperature of the drying in the step (2) is 100 to 120 ℃, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, but the drying method is not limited to the listed values, and other non-listed values in the numerical range are applicable.
The drying time in the step (2) is 10 to 15 hours, for example, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours or 15 hours, but the drying time is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the temperature of the reduction in the step (2) is 200 to 400 ℃, for example, 200 ℃, 225 ℃,250 ℃, 275 ℃,300 ℃, 325 ℃,350 ℃, 375 ℃, or 400 ℃, but the method is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
The time for the reduction in the step (2) is 0.5 to 3 hours, for example, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours, but the method is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the reduced gas in step (2) is a mixture of a reducing gas and a protective gas.
Preferably, the volume ratio of the reducing gas to the protective gas is 1 (5-20), for example, 1:5, 1:10, 1:15 or 1:20, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the reducing gas comprises hydrogen.
The protective gas includes any one or a combination of at least two of nitrogen, helium, argon, neon, or krypton, and typical but non-limiting combinations include combinations of nitrogen and helium, combinations of nitrogen and argon, combinations of nitrogen and neon, combinations of nitrogen and krypton, or combinations of helium and argon.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Dissolving a palladium source in a solvent, adding an acid modified silicon dioxide carrier to obtain a mixture, carrying out ultrasonic treatment on the mixture at 200-400W for 20-40 min, stirring at 25-35 ℃ for 3-5 h, and carrying out rotary evaporation;
the mass ratio of the palladium source to the acid modified silicon dioxide carrier to the solvent is (0.05-0.2): 3-8): 50-100;
(2) Drying the solid substance obtained after rotary evaporation in the step (1) at 100-120 ℃ for 10-15 h, and reducing for 0.5-3 h at 200-400 ℃ under the mixed gas of reducing gas and protective gas to obtain the formaldehyde catalytic oxidation catalyst;
the volume ratio of the reducing gas to the protective gas is 1 (5-20).
In a third aspect, the present invention provides the use of the formaldehyde catalytic oxidation catalyst of the first aspect, the use comprising purifying indoor air.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the acid modified silicon dioxide is used as a carrier of the noble metal active component, the specific surface area of the acid modified silicon dioxide carrier is increased, and the Si-OH on the surface of the silicon dioxide is increased, so that the catalytic effect of the formaldehyde catalytic oxidation catalyst is improved; the formaldehyde catalytic oxidation catalyst provided by the invention can completely degrade formaldehyde into water and carbon dioxide at room temperature, and has the advantages of simple preparation process, low noble metal loading, low cost and long service life.
Drawings
FIG. 1 is a graph of formaldehyde conversion as a function of reaction time for the formaldehyde catalytic oxidation catalyst provided in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a formaldehyde catalytic oxidation catalyst, which comprises a noble metal active component Pd and an acid modified silica carrier, wherein the content of the noble metal active component Pd in the formaldehyde catalytic oxidation catalyst is 0.5wt%.
The acid modified silicon dioxide carrier is prepared by the following preparation method:
stirring and mixing nano silicon dioxide, nitric acid and water for 6 hours at 30 ℃, filtering after mixing, washing the solid obtained by filtering with water, wherein the end point of the water washing is neutral of a washing liquid, and then drying for 12 hours at 110 ℃ to obtain the acid modified silicon dioxide carrier with the average particle size of 50nm;
the mass ratio of the nano silicon dioxide to the nitric acid to the water is 1:1.2:18, the average particle size of the nano silicon dioxide is 40nm, and the concentration of the nitric acid is 1.0M.
The preparation method of the formaldehyde catalytic oxidation catalyst comprises the following steps:
(1) Dissolving palladium nitrate in deionized water, adding an acid modified silicon dioxide carrier to obtain a mixture, carrying out ultrasonic treatment on the mixture at 300W for 30min, and then stirring at 30 ℃ for 4h, and carrying out rotary evaporation;
the mass ratio of the palladium nitrate to the acid modified silicon dioxide carrier to the deionized water is 0.06:5:80;
(2) Drying the solid substance obtained after rotary evaporation in the step (1) for 12 hours at 110 ℃, and reducing the solid substance for 1 hour at 350 ℃ under the mixed gas of hydrogen and nitrogen to obtain the formaldehyde catalytic oxidation catalyst; the volume ratio of the hydrogen to the nitrogen is 1:9.
The change chart of the formaldehyde conversion rate of the formaldehyde catalytic oxidation catalyst along with the reaction time is shown in fig. 1, and the removal rate of formaldehyde is 100% as shown in fig. 1, and the formaldehyde catalytic oxidation catalyst has a long service life, and the conversion rate of the formaldehyde catalytic oxidation catalyst is maintained unchanged within 32 h.
Example 2
The embodiment provides a formaldehyde catalytic oxidation catalyst, which comprises a noble metal active component Pt and an acid modified silica carrier, wherein the content of the noble metal active component Pt in the formaldehyde catalytic oxidation catalyst is 1wt%.
The acid modified silicon dioxide carrier is prepared by the following preparation method:
stirring and mixing nano silicon dioxide, hydrochloric acid and water for 7 hours at 25 ℃, filtering after mixing, washing the solid obtained by filtering with water, wherein the end point of the water washing is neutral of a washing liquid, and then drying for 15 hours at 100 ℃ to obtain the acid modified silicon dioxide carrier with the average particle size of 30 nm;
the mass ratio of the nano silicon dioxide to the hydrochloric acid to the water is 1:1.5:15, the average particle size of the nano silicon dioxide is 40nm, and the concentration of the hydrochloric acid is 1.5M.
The preparation method of the formaldehyde catalytic oxidation catalyst comprises the following steps:
(1) Dissolving palladium chloride in deionized water, adding an acid modified silicon dioxide carrier to obtain a mixture, carrying out ultrasonic treatment on the mixture at 250W for 35min, and then stirring at 25 ℃ for 5h, and carrying out rotary evaporation;
the mass ratio of the palladium chloride to the acid modified silicon dioxide carrier to the deionized water is 0.1:4:100;
(2) Drying the solid material obtained after rotary evaporation in the step (1) at 120 ℃ for 11 hours, and reducing the solid material at 300 ℃ for 1.5 hours under the mixed gas of hydrogen and nitrogen to obtain the formaldehyde catalytic oxidation catalyst; the volume ratio of the hydrogen to the nitrogen is 1:10.
Example 3
The embodiment provides a formaldehyde catalytic oxidation catalyst, which comprises a noble metal active component Au and an acid modified silica carrier, wherein the content of the noble metal active component Au in the formaldehyde catalytic oxidation catalyst is 1.5wt%.
The acid modified silicon dioxide carrier is prepared by the following preparation method:
stirring and mixing nano silicon dioxide, sulfuric acid and water for 4 hours at 35 ℃, filtering after mixing, washing the solid obtained by filtering with water, wherein the end point of the water washing is neutral of a washing liquid, and then drying for 10 hours at 120 ℃ to obtain the acid modified silicon dioxide carrier with the average particle size of 50nm;
the mass ratio of the nano silicon dioxide to the sulfuric acid to the water is 1:1:20, the average particle size of the nano silicon dioxide is 50nm, and the concentration of the sulfuric acid is 0.8M.
The preparation method of the formaldehyde catalytic oxidation catalyst comprises the following steps:
(1) Dissolving palladium chloride in deionized water, adding an acid modified silicon dioxide carrier to obtain a mixture, carrying out ultrasonic treatment on the mixture at 350W for 25min, and then stirring at 35 ℃ for 3h, and carrying out rotary evaporation;
the mass ratio of the palladium chloride to the acid modified silicon dioxide carrier to the deionized water is 0.15:6:50;
(2) Drying the solid substance obtained after rotary evaporation in the step (1) at 100 ℃ for 13 hours, and reducing the solid substance at 250 ℃ for 2.5 hours under the mixed gas of hydrogen and nitrogen to obtain the formaldehyde catalytic oxidation catalyst; the volume ratio of the hydrogen to the nitrogen is 1:15.
Example 4
The embodiment provides a formaldehyde catalytic oxidation catalyst, which comprises a noble metal active component Pd and an acid modified silica carrier, wherein the content of the noble metal active component Pd in the formaldehyde catalytic oxidation catalyst is 2wt%.
The acid modified silicon dioxide carrier is prepared by the following preparation method:
stirring and mixing nano silicon dioxide, nitric acid and water for 4 hours at 35 ℃, filtering after mixing, washing the solid obtained by filtering with water, wherein the end point of the water washing is neutral of a washing liquid, and then drying at 100 ℃ for 15 hours to obtain the acid modified silicon dioxide carrier with the average particle size of 100nm;
the mass ratio of the nano silicon dioxide to the nitric acid to the water is 1:2:20, the average particle size of the nano silicon dioxide is 100nm, and the concentration of the nitric acid is 2M.
The preparation method of the formaldehyde catalytic oxidation catalyst comprises the following steps:
(1) Dissolving palladium nitrate in deionized water, adding an acid modified silicon dioxide carrier to obtain a mixture, carrying out ultrasonic treatment on the mixture at 400W for 20min, and then stirring at 35 ℃ for 3h, and carrying out rotary evaporation;
the mass ratio of the palladium nitrate to the acid modified silicon dioxide carrier to the deionized water is 0.2:3:100;
(2) Drying the solid substance obtained after rotary evaporation in the step (1) at 100 ℃ for 15 hours, and reducing the solid substance at 200 ℃ for 0.5 hour under the mixed gas of hydrogen and nitrogen to obtain the formaldehyde catalytic oxidation catalyst; the volume ratio of the hydrogen to the nitrogen is 1:5.
Example 5
The embodiment provides a formaldehyde catalytic oxidation catalyst, which comprises a noble metal active component Pd and an acid modified silica carrier, wherein the content of the noble metal active component Pd in the formaldehyde catalytic oxidation catalyst is 0.2wt%.
The acid modified silicon dioxide carrier is prepared by the following preparation method:
stirring and mixing nano silicon dioxide, nitric acid and water for 8 hours at 25 ℃, filtering after mixing, washing the solid obtained by filtering with water, wherein the end point of the water washing is neutral of a washing liquid, and then drying for 10 hours at 120 ℃ to obtain the acid modified silicon dioxide carrier with the average particle size of 15 nm;
the mass ratio of the nano silicon dioxide to the nitric acid to the water is 1:0.1:15, the average particle size of the nano silicon dioxide is 15nm, and the concentration of the nitric acid is 0.1M.
The preparation method of the formaldehyde catalytic oxidation catalyst comprises the following steps:
(1) Dissolving palladium nitrate in deionized water, adding an acid modified silicon dioxide carrier to obtain a mixture, carrying out ultrasonic treatment on the mixture at 200W for 40min, and then stirring at 25 ℃ for 5h, and carrying out rotary evaporation;
the mass ratio of the palladium nitrate to the acid modified silicon dioxide carrier to the deionized water is 0.05:8:50;
(2) Drying the solid material obtained after rotary evaporation in the step (1) for 10 hours at 120 ℃, and reducing the solid material for 3 hours at 400 ℃ under the mixed gas of hydrogen and nitrogen to obtain the formaldehyde catalytic oxidation catalyst; the volume ratio of the hydrogen to the nitrogen is 1:20.
Example 6
The present example provides a formaldehyde catalytic oxidation catalyst, which is the same as example 1 except that the mass ratio of palladium nitrate, acid-modified silica carrier and deionized water is 0.01:5:80 when preparing the formaldehyde catalytic oxidation catalyst, so that the content of Pd as the noble metal active component in the formaldehyde catalytic oxidation catalyst is 0.1 wt%.
Example 7
The present example provides a formaldehyde catalytic oxidation catalyst, which is the same as example 1 except that the mass ratio of palladium nitrate, acid-modified silica carrier and deionized water is 0.01:7:100 when preparing the formaldehyde catalytic oxidation catalyst, so that the content of Pd as the noble metal active component in the formaldehyde catalytic oxidation catalyst is 0.05 wt%.
Example 8
This example provides a formaldehyde catalytic oxidation catalyst which differs from example 1 only in that the acid-modified silica has an average particle diameter of 500nm, the remainder being the same as example 1;
the preparation method of the formaldehyde catalytic oxidation catalyst is the same as that of the example 1.
Example 9
This example provides a formaldehyde catalytic oxidation catalyst which differs from example 1 only in that the acid-modified silica has an average particle diameter of 1000nm, the remainder being the same as example 1;
the preparation method of the formaldehyde catalytic oxidation catalyst is the same as that of the example 1.
Example 10
The present example provides a formaldehyde catalytic oxidation catalyst comprising a noble metal active component Pd and an acid-modified silica carrier, wherein the noble metal active component Pd in the formaldehyde catalytic oxidation catalyst accounts for 0.5wt%, and the preparation method of the acid-modified silica carrier is the same as that of example 1;
the preparation method of the formaldehyde catalytic oxidation catalyst is different from that of the example 1 in that the reduction temperature is 100 ℃, the reduction time is 0.5h, and the rest is the same as the example 1.
Comparative example 1
The comparative example provides a formaldehyde catalytic oxidation catalyst, which comprises a noble metal active component Pd and a nano silicon dioxide carrier, wherein the content of the noble metal active component Pd in the formaldehyde catalytic oxidation catalyst is 0.5wt%, and the average particle diameter of the nano silicon dioxide is 50nm;
the preparation method of the formaldehyde catalytic oxidation catalyst is different from that of the example 1 in that the acid-modified silica carrier is replaced by the nano silica carrier in an equivalent amount, and the rest is the same as the example 1.
Comparative example 2
The comparative example provides a formaldehyde catalytic oxidation catalyst comprising precious metal active components Pd and gamma-Al 2 O 3 The carrier, the Pd content of the noble metal active component in the formaldehyde catalytic oxidation catalyst is 0.5wt%, and the gamma-Al 2 O 3 The average particle diameter of the carrier is 50nm;
the preparation method of the formaldehyde catalytic oxidation catalyst is different from example 1 in that the acid-modified silica carrier is replaced by gamma-Al in equal amount 2 O 3 The carrier was the same as in example 1.
The test methods and results of the formaldehyde catalytic oxidation catalysts provided in the above examples and comparative examples are as follows:
the test method of formaldehyde catalytic oxidation reaction activity comprises the following steps: 60mg of the formaldehyde catalytic oxidation catalyst provided in the examples and comparative examples above was loaded on a fixed bed reactor, and gas was introduced at a temperature of 25℃and a relative humidity of 35% at a reaction space velocity of 100000mL/g/h at a total flow rate of 100mL/min, with He as an equilibrium gas containing 20vol% oxygen and 150ppm formaldehyde.
The test results are shown in table 1:
TABLE 1
From table 1, the following points can be seen:
(1) The invention provides a formaldehyde catalytic oxidation catalyst which can completely degrade formaldehyde into water and carbon dioxide at room temperature, and has the advantages of simple preparation process, low noble metal loading, low cost and long service life.
(2) As is clear from examples 1 and examples 6 to 7, the noble metal active component Pd contents of examples 6 to 7 are respectively 0.1wt% and 0.05wt%, and the formaldehyde conversion after 32 hours is slightly reduced as compared with example 1; it is thus known that when the content of the noble metal active component is too low, the catalytic performance of the formaldehyde catalytic oxidation catalyst is lowered for a long period of time.
(3) As is clear from examples 1 and examples 8 to 9, the average particle diameters of the acid-modified silica supports of examples 8 to 9 were 500nm and 1000nm, respectively, and the formaldehyde conversion after 32 hours was slightly decreased as compared with example 1; from this, it is found that when the particle diameter of the carrier is too large, the catalytic performance of the formaldehyde catalytic oxidation catalyst is lowered for a long period of time.
(4) As is clear from examples 1 and 10, the reduction temperature of example 10 was 100deg.C, and the formaldehyde conversion after 32 hours was slightly decreased as compared with example 1; it is thus found that when the reduction temperature of the catalyst for catalytic oxidation of formaldehyde is low, the catalytic performance of the resulting catalyst for catalytic oxidation of formaldehyde is lowered over a long period of time.
(5) As is clear from examples 1 and comparative examples 1 to 2, comparative examples 1 to 2 respectively employ nanosilica and gamma-Al 2 O 3 As a carrier, the formaldehyde conversion after 32h was reduced compared to example 1; according to the invention, the acid modified silicon dioxide is used as the carrier of the noble metal active component, the specific surface area of the acid modified silicon dioxide carrier is increased, the Si-OH on the surface is increased, and the catalytic effect of the formaldehyde catalytic oxidation catalyst is improved.
In summary, the invention provides a formaldehyde catalytic oxidation catalyst, which adopts acid modified silicon dioxide as a carrier of noble metal active components, so that the catalytic effect of the formaldehyde catalytic oxidation catalyst is improved; the formaldehyde catalytic oxidation catalyst provided by the invention can completely degrade formaldehyde into water and carbon dioxide at room temperature, and has the advantages of simple preparation process, low noble metal loading, low cost and long service life.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (18)
1. A method for preparing a formaldehyde catalytic oxidation catalyst, which is characterized by comprising the following steps:
(1) Mixing a palladium source, an acid modified silica carrier and a solvent, and performing rotary evaporation after mixing;
(2) The solid matters obtained after the rotary evaporation in the step (1) are dried and reduced in sequence to obtain the formaldehyde catalytic oxidation catalyst;
wherein, the average grain diameter of the acid modified silicon dioxide carrier in the step (1) is 15-100 nm; the concentration of the acid used for modifying the silicon dioxide is 0.9-1.5M; the mass ratio of the palladium source to the acid modified silicon dioxide carrier to the solvent is (0.05-0.2): 3-8): 50-100;
the reduced gas in the step (2) is a mixed gas of a reducing gas and a protective gas; the volume ratio of the reducing gas to the protective gas is 1 (5-15).
2. The preparation method according to claim 1, wherein the noble metal active component in the formaldehyde catalytic oxidation catalyst accounts for 0.2-2.0 wt%.
3. The process of claim 1, wherein the acid-modified silica support is obtained by a process comprising the steps of:
mixing nano silicon dioxide, acid and water, carrying out solid-liquid separation after mixing, and sequentially washing and drying the obtained solid to obtain the acid modified silicon dioxide carrier.
4. The method according to claim 3, wherein the nanosilica has an average particle diameter of 15 to 100nm.
5. The preparation method according to claim 3, wherein the mass ratio of the nano silicon dioxide to the acid to the water is 1 (0.1-2): 15-20.
6. A method of manufacture according to claim 3, wherein the acid comprises any one or a combination of at least two of hydrochloric acid, nitric acid, sulfuric acid or citric acid.
7. The preparation method according to claim 3, wherein the mixed nano silica, acid and water are stirred at 25 to 35 ℃ for 3 to 8 hours.
8. A method of preparing according to claim 3, wherein the means for solid-liquid separation comprises filtration.
9. The method according to claim 3, wherein the solid obtained by solid-liquid separation after mixing is dried at a temperature of 100 to 120 ℃ for a time of 10 to 15 hours.
10. The method of claim 1, wherein the step (1) of mixing the palladium source, the acid-modified silica support and the solvent is performed by dissolving the palladium source in the solvent and then adding the acid-modified silica support.
11. The method of claim 1, wherein the means of mixing in step (1) comprises post-ultrasonic agitation.
12. The method according to claim 11, wherein the power of the ultrasound is 200 to 400W for 20 to 40min.
13. The method according to claim 11, wherein the stirring is carried out at a temperature of 25 to 35 ℃ for a time of 3 to 5 hours.
14. The method of claim 1, wherein the palladium source in step (1) comprises any one or a combination of at least two of palladium nitrate, palladium chloride, or potassium palladium chloride.
15. The method according to claim 1, wherein the drying in step (2) is carried out at a temperature of 100 to 120 ℃ for a time of 10 to 15 hours.
16. The method according to claim 1, wherein the temperature of the reduction in the step (2) is 200 to 400 ℃ for 0.5 to 3 hours.
17. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Dissolving a palladium source in a solvent, adding an acid modified silicon dioxide carrier to obtain a mixture, carrying out ultrasonic treatment on the mixture at 200-400W for 20-40 min, stirring at 25-35 ℃ for 3-5 h, and carrying out rotary evaporation;
the mass ratio of the palladium source to the acid modified silicon dioxide carrier to the solvent is (0.05-0.2): 3-8): 50-100;
(2) Drying the solid substance obtained after rotary evaporation in the step (1) at 100-120 ℃ for 10-15 h, and reducing for 0.5-3 h at 200-400 ℃ under the mixed gas of reducing gas and protective gas to obtain the formaldehyde catalytic oxidation catalyst;
the volume ratio of the reducing gas to the protective gas is 1 (5-15).
18. Use of a formaldehyde catalytic oxidation catalyst obtainable by a process according to any one of claims 1 to 17, wherein said use comprises purifying indoor air.
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