CN115739113A - Catalyst for catalyzing formaldehyde at room temperature and preparation method thereof - Google Patents
Catalyst for catalyzing formaldehyde at room temperature and preparation method thereof Download PDFInfo
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- CN115739113A CN115739113A CN202211476034.9A CN202211476034A CN115739113A CN 115739113 A CN115739113 A CN 115739113A CN 202211476034 A CN202211476034 A CN 202211476034A CN 115739113 A CN115739113 A CN 115739113A
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- boehmite
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 10
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 39
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- 230000032683 aging Effects 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005086 pumping Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 51
- 239000002105 nanoparticle Substances 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 13
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 13
- 229960001545 hydrotalcite Drugs 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000006378 damage Effects 0.000 abstract description 7
- 231100000956 nontoxicity Toxicity 0.000 abstract description 5
- 229910000943 NiAl Inorganic materials 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000007787 solid Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229910021642 ultra pure water Inorganic materials 0.000 description 21
- 239000012498 ultrapure water Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 238000003760 magnetic stirring Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 239000000725 suspension Substances 0.000 description 15
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 229910020068 MgAl Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- SBHHFAIXPSFQLT-UHFFFAOYSA-N methylidene(oxido)oxidanium Chemical compound [O-][O+]=C SBHHFAIXPSFQLT-UHFFFAOYSA-N 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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Abstract
The invention provides a catalyst for catalyzing formaldehyde at room temperature and a preparation method thereof. The method comprises the following steps: dissolving nickel nitrate hexahydrate and aluminum nitrate nonahydrate in a mixed solution of polyethylene glycol and cyclohexane; step two, dropwise adding ammonia water into the solution obtained in the step one, then aging, centrifuging, washing and drying to obtain a nickel-aluminum composite oxide carrier; preparing boehmite by using aluminum nitrate nonahydrate, cutting into pieces, and introducing a nickel-aluminum composite oxide carrier into the boehmite to obtain a catalyst precursor; soaking the catalyst precursor in chloroplatinic acid solution, and pumping to dry; and step five, reducing the product obtained in the step four by using a sodium borohydride reducing agent, and then stirring, centrifuging, washing and drying to obtain the catalyst. High catalytic efficiency, low cost, no toxicity and no harm.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a catalyst for catalyzing formaldehyde at room temperature and a preparation method thereof.
Background
Formaldehyde is the most common hydrocarbon in indoor polluted air recognized globally, and is the second ranked among the list of toxic and harmful air pollutants released by the chinese government. The source of the material is mainly various building materials and interior decoration materials (furniture, paint, leather) and the like. Long-term exposure to formaldehyde can cause diseases such as nasal tumors, skin cancer, respiratory system injury and the like, and cause serious harm to human health. Therefore, there is a strong need to effectively reduce the formaldehyde level in the air to improve the air quality. For example, chinese patent CN101497042A discloses a high-efficiency catalytic high-concentration formaldehyde oxidation catalyst, which uses hydrotalcite as a carrier and Pt monoatomic atoms as an active center, and can eliminate industrial high-concentration formaldehyde tail gas at normal temperature. However, the required Pt loading is high and the cost is high.
Disclosure of Invention
The invention solves one of the problems in the prior related technology to a certain extent, and therefore, the invention aims to provide the catalyst for catalyzing formaldehyde at room temperature, which has the advantages of high catalysis efficiency, low cost, no toxicity and no harm.
The above purpose is realized by the following technical scheme:
the catalyst for catalyzing formaldehyde at room temperature comprises an active component and a carrier, wherein the active component comprises platinum nanoparticles, and the carrier is a mixture of nickel-aluminum composite hydrotalcite and boehmite.
As a further improvement of the present invention, the loading amount of the platinum nanoparticles on the support is more than 0wt% and less than 1wt%.
As a further improvement of the present invention, the loading amount of the platinum nanoparticles on the support is 0.2wt%.
As a further improvement of the present invention, the nickel-aluminum molar ratio in the nickel-aluminum composite hydrotalcite is 1:9 or 1:7 or 1:5.
another object of the present invention is to provide a method for preparing a catalyst for the catalytic oxidation of formaldehyde,
the above purpose is realized by the following technical scheme:
a method for preparing a catalyst for catalyzing formaldehyde at room temperature, which is used for preparing the catalyst for catalyzing formaldehyde at room temperature according to any one of claims 1 to 4, is characterized by comprising the following steps:
dissolving nickel nitrate hexahydrate and aluminum nitrate nonahydrate into a mixed solution of polyethylene glycol and cyclohexane;
step two, dropwise adding ammonia water into the solution obtained in the step one, and then aging, centrifuging, washing and drying to obtain a nickel-aluminum composite oxide carrier;
preparing boehmite by using aluminum nitrate nonahydrate, cutting into slices, and introducing the nickel-aluminum composite oxide carrier into the boehmite to obtain a catalyst precursor;
soaking the catalyst precursor in chloroplatinic acid solution, and pumping to dry;
and step five, reducing the product obtained in the step four by using a sodium borohydride reducing agent, and then stirring, centrifuging, washing and drying to obtain the catalyst.
As a further improvement of the invention, in the second step, the mass fraction of the ammonia water is 25-28wt%.
As a further improvement of the invention, the drying temperature in the second step is 60-90 ℃, and the drying time is 15h; the drying temperature in the fifth step is 60-90 ℃, and the drying time is 12h.
As a further improvement of the present invention, in step three, the step of cutting boehmite into pieces is specifically: the boehmite was cut into thin pieces having a size of 10mm × 10mm × 2 mm.
As a further improvement of the invention, the concentration of the sodium borohydride reducing agent is 0.572 mol.L -1 。
Compared with the prior art, the invention at least comprises the following beneficial effects:
1. the invention provides a catalyst for catalyzing formaldehyde at room temperature and a preparation method thereof, wherein a mixture consisting of nickel-aluminum composite hydrotalcite and boehmite is used as a carrier, so that abundant alkaline and redox active sites are provided for the adsorption of formaldehyde, and meanwhile, the catalyst and Pt nanoparticles have a synergistic effect, and the Pt nanoparticles are used as a catalytic center, so that the dissociation of adsorbed oxygen can be promoted, and the catalyst has the advantages of high catalytic efficiency, low cost, no toxicity and no harm.
2. Due to N iAl 9 Under the synergistic effect of LDHs, pt NPs and boehmite, the composite material has enhanced formaldehyde catalytic oxidation activity at room temperature, can efficiently and completely decompose formaldehyde into CO2 and H2O by using a small amount of Pt NPs, and has low cost, no toxicity and no harm.
3. Boehmite provides a large number of hydroxyl groups that are indicated, increasing the active area of the catalyst surface by dispersing Pt nanoparticles.
Drawings
FIG. 1 is a transmission electron micrograph of Pt0.2/N iAl9-LDHs/Al OOH catalyst in the example.
Detailed Description
The present invention is illustrated by the following examples, but the present invention is not limited to these examples. Modifications to the embodiments of the invention or equivalent substitutions of parts of technical features without departing from the spirit of the invention are intended to be covered by the scope of the claims of the invention.
The first embodiment is as follows:
referring to fig. 1, the catalyst for catalyzing formaldehyde at room temperature comprises an active component and a carrier, wherein the active component comprises platinum nanoparticles, and the carrier is a mixture of nickel-aluminum composite hydrotalcite and boehmite.
The invention provides a catalyst for catalyzing formaldehyde at room temperature, which takes a mixture consisting of nickel-aluminum composite hydrotalcite and boehmite as a carrier, provides rich alkaline and redox active sites for the adsorption of formaldehyde, and simultaneously has a synergistic effect with Pt nanoparticles, and the Pt nanoparticles are taken as a catalytic center, so that the dissociation of adsorbed oxygen can be promoted, and thus active oxygen of formaldehyde oxide can be formed.
The boehmite of the present invention provides a large number of hydroxyl radicals, increasing the active area of the catalyst surface by dispersing Pt nanoparticles.
The invention is due to NiAl 9 Under the synergistic effect of LDHs, pt NPs and boehmite, the composite material has enhanced formaldehyde catalytic oxidation activity at room temperature, can efficiently and completely decompose formaldehyde into CO2 and H2O by using a small amount of Pt NPs, and has low cost, no toxicity and no harm.
The loading amount of the platinum nanoparticles on the carrier is more than 0wt% and less than 1wt%. In this example, the loading amount of the platinum nanoparticles on the carrier was 0.2wt% based on the total weight of the carrier being 100%.
The molar ratio of nickel to aluminum in the nickel-aluminum composite hydrotalcite is 1:9 or 1:7 or 1:5. in this example, the molar ratio of nickel to aluminum in the nickel-aluminum composite hydrotalcite is 1:9.
in this example, the boehmite is alumina hydrate (AlOOH).
Example two:
a method for preparing a catalyst for catalyzing formaldehyde at room temperature, which is described in the first embodiment, and comprises the following steps:
dissolving nickel nitrate hexahydrate and aluminum nitrate nonahydrate into a mixed solution of polyethylene glycol and cyclohexane;
step two, dropwise adding ammonia water into the solution obtained in the step one, and then aging, centrifuging, washing and drying to obtain a nickel-aluminum composite hydrotalcite carrier;
preparing boehmite by using aluminum nitrate nonahydrate, cutting into slices, and introducing a nickel-aluminum composite hydrotalcite carrier into the boehmite to obtain a catalyst precursor;
soaking the catalyst precursor in chloroplatinic acid solution, and pumping to dry;
and step five, reducing the product obtained in the step four by using a sodium borohydride reducing agent, and then stirring, centrifuging, washing and drying to obtain the catalyst.
In the second step, the mass fraction of the ammonia water is 25-28wt%.
In the second step, the drying temperature is 60-90 ℃, and the drying time is 15h.
In the third step, the step of cutting the boehmite into pieces is specifically as follows: the boehmite was cut into thin pieces having a size of 10mm × 10mm × 2 mm.
In the fifth step, the drying temperature is 60-90 ℃, and the drying time is 12h.
In the fifth step, the concentration of the sodium borohydride reducing agent is 0.572 mol.L -1 。
The invention provides a preparation method of a formaldehyde catalyst for room-temperature catalysis, which takes a mixture consisting of nickel-aluminum composite hydrotalcite and boehmite as a carrier, provides rich alkaline and redox active sites for the adsorption of formaldehyde, and simultaneously has a synergistic effect with Pt nanoparticles, and the Pt nanoparticles are taken as a catalytic center, so that the dissociation of adsorbed oxygen can be promoted, and thus active oxygen of formaldehyde oxide can be formed.
Example three:
step one, 20.5g polyethylene glycol (PEG 400) is weighed, 100mL cyclohexane is added, magnetic stirring is carried out for mixing, and then 20mL of 1mmol Ni (NO) is rapidly added 3 ) 2 ·6H 2 O and 9mmol Al (NO) 3 ) 2 ·9H 2 A solution of O;
step two, after 10min, 4.25ml of ammonia (28 wt%) was added dropwise to the solution obtained in step one, and the resulting mixture was oven aged at 60-90 ℃ for 2h. Centrifuging the suspension, washing the collected solid with ultrapure water and ethanol 3 times;
step three, drying the solid obtained in the step two in an oven at the temperature of 60-90 ℃ for 15 hours to obtain a carrier NiAl 9 . Then using 10mmol of Al (NO) 3 ) 2 ·9H 2 O preparation of pure Al support, the product being boehmite (AlOOH). Mixing NiAl 9 Introducing into boehmite flakes to obtain a catalyst precursor NiAl 9 -LDHs/AlOOH。
Step four, weighing 300mg of catalyst precursor in 10ml of ultrapure waterThen adding H under continuous magnetic stirring 2 PtCl 6 A solution; after 1h of impregnation, 5ml of sodium borohydride (0.572 mol. L) were added rapidly -1 ) And sodium hydroxide (0.25 mol. L) -1 ) The suspension of (2) is mixed with the aqueous solution. Continuously stirring for 1h, centrifuging, and washing the collected solid with ultrapure water and ethanol for 4 times; the resulting solid was dried in an oven at 60-90 ℃ for 12h with a Pt loading of 0.2%.
Detection was carried out by using Pt obtained in example 3 0.2 NiAl 9 And (3) placing LDHs/AlOOH on a miniature tubular catalyst evaluation device to perform catalytic oxidation formaldehyde reaction, and quantitatively analyzing by adopting gas chromatography. The reaction results showed that Pt 0.2 NiAl 9 The LDHs/AlOOH can completely decompose 800ppm of formaldehyde within 5h, and the catalyst is stable and not deactivated within 24 h.
Example four:
step one, 20.5g polyethylene glycol (PEG 400) is weighed, 100mL cyclohexane is added, magnetic stirring is carried out for mixing, and then 20mL of a solution containing 1mmolNi (NO) is rapidly added 3 ) 2 ·6H 2 O and 7mmol Al (NO) 3 ) 2 ·9H 2 A solution of O;
step two, after 10min, 4.25ml of ammonia (28 wt%) was added dropwise to the above obtained solution, and the resulting mixture was oven aged at 60-90 ℃ for 2h. Centrifuging the suspension, washing the collected solid with ultrapure water and ethanol 3 times;
step three, drying the solid obtained in the step two in a C oven at the temperature of 60-90 ℃ for 15h to obtain a carrier NiAl 9 . Then using 10mmol of Al (NO) 3 ) 2 ·9H 2 O preparation of pure Al support, the product being boehmite (AlOOH). Mixing NiAl 9 Introducing into boehmite flakes to obtain a catalyst precursor NiAl 9 -LDHs/AlOOH；
Step four, weighing 300mg of catalyst precursor in 10ml of ultrapure water, and then adding H under continuous magnetic stirring 2 PtCl 6 A solution; after 1h of impregnation, 5ml of sodium borohydride (0.572 mol. L) were added rapidly -1 ) And sodium hydroxide (0.252 mol. L) -1 ) The suspension of (2) is mixed with the aqueous solution. Stirring for 1 hr, centrifuging, washing the collected extract with ultrapure water and ethanolSolid for 4 times; the resulting solid was dried in an oven at 60-90 ℃ for 12h with a pt loading of 0.2%.
Detection was carried out by using Pt obtained in the fourth example 0.2 NiAl 9 And (4) putting LDHs/AlOOH on a miniature tubular catalyst evaluation device for catalytic oxidation of formaldehyde, and quantitatively analyzing by adopting gas chromatography. The reaction results showed that Pt 0.2 NiAl 9 The LDHs/AlOOH can completely decompose 650ppm formaldehyde within 5h, and the catalyst can be kept stable and not deactivated within 24 h.
Example five:
step one, 20.5g polyethylene glycol (PEG 400) is weighed, 100mL cyclohexane is added, magnetic stirring is carried out for mixing, and then 20mL of a solution containing 1mmolNi (NO) is rapidly added 3 ) 2 ·6H 2 O and 5mmol Al (NO) 3 ) 2 ·9H 2 A solution of O;
step two, after 10min, 4.25ml of ammonia (28 wt%) was added dropwise to the above obtained solution, and the resulting mixture was oven aged at 60-90 ℃ for 2h. Centrifuging the suspension, washing the collected solid with ultrapure water and ethanol 3 times;
step three, drying the solid obtained in the step two in an oven at the temperature of 60-90 ℃ for 15 hours to obtain a carrier NiAl 9 . Then using 10mmol of Al (NO) 3 ) 2 ·9H 2 O pure Al support was prepared and the product was boehmite (AlOOH). Mixing NiAl 9 Introducing into boehmite flakes to obtain a catalyst precursor NiAl 9 -LDHs/AlOOH；
Step four, weighing 300mg of catalyst precursor NiAl 9 LDHs/AlOOH in 10ml of ultrapure water, followed by addition of H under continuous magnetic stirring 2 PtCl 6 A solution; after 1h of immersion, 5ml of sodium borohydride (0.572 mol. L) were added rapidly -1 ) And sodium hydroxide (0.252 mol. L) -1 ) The suspension of (2) is mixed with the aqueous solution. Continuously stirring for 1h, centrifuging, and washing the collected solid with ultrapure water and ethanol for 4 times; the resulting solid was dried in an oven at 60-90 ℃ for 12h with a pt loading of 0.2%.
Detection was carried out by using Pt obtained in the fifth example 0.2 NiAl 9 Placing LDHs/AlOOH on a micro-tube type catalyst evaluation deviceCarrying out catalytic oxidation reaction on formaldehyde, and carrying out quantitative analysis by adopting gas chromatography. The reaction results showed that Pt 0.2 NiAl 9 The LDHs/AlOOH can partially decompose 380ppm formaldehyde within 5 hours, the conversion rate is 70 percent, and the catalyst is kept stable and is not deactivated within 24 hours.
Example six:
step one, 20.5g polyethylene glycol (PEG 400) is weighed, 100ml cyclohexane is added, and mixed by magnetic stirring, and then 20ml 1mmol Ni (NO) is rapidly added 3 ) 2 ·6H 2 O and 9mmolAl (NO) 3 ) 2 ·9H 2 A solution of O;
step two, after 10min, 4.25ml of ammonia (28 wt%) was added dropwise to the above obtained solution, and the resulting mixture was oven aged at 60-90 ℃ for 2h. Centrifuging the suspension, washing the collected solid with ultrapure water and ethanol 3 times;
step three, drying the solid obtained in the step two in an oven at the temperature of 60-90 ℃ for 15 hours to obtain a carrier NiAl 9 . Then using 10mmol of Al (NO) 3 ) 2 ·9H 2 O preparation of pure Al support, the product being boehmite (AlOOH). Mixing NiAl 9 Introducing into boehmite flakes to obtain a catalyst precursor NiAl 9 -LDHs/AlOOH；
Step four, weighing 300mg of catalyst precursor NiAl 9 LDHs/AlOOH in 10ml of ultrapure water, followed by addition of H under continuous magnetic stirring 2 PtCl 6 A solution; after 1h of immersion, 5ml of sodium borohydride (0.572 mol. L) were added rapidly -1 ) And sodium hydroxide (0.252 mol. L) -1 ) The aqueous solution is mixed with the suspension of (1). Continuously stirring for 1h, centrifuging, and washing the collected solid with ultrapure water and ethanol for 4 times; the resulting solid was dried in an oven at 60-90 ℃ for 12h with a Pt loading of 0.1%.
Detection was carried out by using Pt obtained in the fifth example 0.1 NiAl 9 And (4) putting LDHs/AlOOH on a miniature tubular catalyst evaluation device for catalytic oxidation of formaldehyde, and quantitatively analyzing by adopting gas chromatography. The reaction results showed that Pt 0.1 NiAl 9 The LDHs/AlOOH can partially decompose 620ppm formaldehyde within 5 hours, the conversion rate is 83 percent, and the catalyst is kept stable and is not deactivated within 24 hours.
Comparative example 1:
step one, 20.5g of polyethylene glycol (PEG 400) is weighed, 100ml of cyclohexane is added, magnetic stirring is carried out for mixing, and then 20ml of polyethylene glycol (PEG 400) containing 1mmol of Mg (NO) is rapidly added 3 ) 2 ·6H 2 O and 9mmolAl (NO) 3 ) 2 ·9H 2 A solution of O;
step two, after 10min, 4.25ml of ammonia (28 wt%) was added dropwise to the above obtained solution, and the resulting mixture was oven aged at 60-90 ℃ for 2h. Centrifuging the suspension, washing the collected solid 3 times with ultrapure water and ethanol;
step three, drying the solid obtained in the step two in an oven at the temperature of 60-90 ℃ for 15 hours to obtain a carrier MgAl 9 . Then using 10mmol Al (NO) 3 ) 2 ·9H 2 O preparing pure Al carrier, and grinding boehmite (AlOOH) into powder. MgAl is added 9 Mixing with boehmite powder to obtain catalyst precursor MgAl 9 -LDHs/AlOOH；
Step four, weighing 300mg of catalyst precursor MgAl 9 10mL of (E) -LDHs/AlOOH ultrapure water, then H was added under continuous magnetic stirring 2 PtCl 6 A solution; after 1h of immersion, 5ml of sodium borohydride (0.572 mol. L) were added rapidly -1 ) And sodium hydroxide (0.252 mol. L) -1 ) The aqueous solution is mixed with the suspension of (1). Continuously stirring for 1h, centrifuging, and washing the collected solid with ultrapure water and ethanol for 4 times; 12h is dried in an oven at the temperature of 60-90 ℃, and the loading capacity of Pt is 0.2%.
The Pt obtained in comparative example 1 was examined 0.2 MgAl 9 And (3) putting LDHs/AlOOH in a miniature tubular catalyst evaluation device to perform catalytic oxidation formaldehyde reaction, and quantitatively analyzing by adopting gas chromatography. The reaction results showed that Pt 0.2 MgAl 9 The LDHs/AlOOH can only completely decompose 360ppm of formaldehyde within 6 hours, and the catalyst is stable and not inactivated within 24 hours.
Comparative example 2:
step one, 20.5g polyethylene glycol (PEG 400) is weighed, 100ml cyclohexane is added, magnetic stirring is carried out for mixing, and then 20ml of 1mmol Ca (NO) is rapidly added 3 ) 2 ·6H 2 O and 9mmolAl (NO) 3 ) 2 ·9H 2 A solution of O;
step two, after 10min, 4.25mL of ammonia (28 wt%) was added dropwise to the solution obtained above, and the resulting mixture was oven aged at 60-90 ℃ for 2h. Centrifuging the suspension, washing the collected solid 3 times with ultrapure water and ethanol;
step three, drying the solid obtained in the step two in an oven at the temperature of 60-90 ℃ for 15 hours to obtain a carrier CaAl 9 . Then using 10mmol Al (NO) 3 ) 2 ·9H 2 O preparing pure Al carrier, and grinding boehmite (AlOOH) into powder. Adding CaAl 9 Mixing with boehmite powder to obtain catalyst precursor CaAl 9 -LDHs/AlOOH；
Step four, weighing 300mg of catalyst precursor CaAl 9 LDHs/AlOOH in 10mL of ultrapure water, followed by addition of H under continuous magnetic stirring 2 PtCl 6 A solution; after 1h of immersion, 5mL of sodium borohydride (0.572 mol. L) was added rapidly -1 ) And sodium hydroxide (0.252 mol. L) -1 ) The suspension of (2) is mixed with the aqueous solution. Continuously stirring for 1h, centrifuging, and washing the collected solid with ultrapure water and ethanol for 4 times; drying in an oven at 60-90 ℃ for 12h, wherein the loading capacity of Pt is 0.2%;
detection was carried out by adding Pt obtained in the above comparative example 2 0.2 CaAl 9 And (4) putting the LDHs/AlOOH in a miniature tubular catalyst evaluation device for catalytic oxidation of formaldehyde, and quantitatively analyzing by adopting gas chromatography. The reaction results showed that Pt 0.2 CaAl 9 The LDHs/AlOOH only completely decomposes 420ppm of formaldehyde within 8h, and the catalyst is stable and not deactivated within 24 h.
COMPARATIVE EXAMPLE 3 (No Pt NPs)
Step one, 20.5g polyethylene glycol (PEG 400) is weighed, 100ml cyclohexane is added, magnetic stirring is carried out for mixing, and then 20ml of 1mmol Ni (NO) is rapidly added 3 ) 2 ·6H 2 O and 9mmolAl (NO) 3 ) 2 ·9H 2 A solution of O;
step two, after 10min, 4.25mL of ammonia (28 wt%) was added dropwise to the above solution, and the resulting mixture was oven aged at 60-90 ℃ for 2h. Centrifuging the suspension, washing the collected solid with ultrapure water and ethanol 3 times;
step three, drying the solid obtained in the step two in an oven at the temperature of 60-90 ℃ for 15 hours to obtain a carrier NiAl 9 . Then using 10mmol of Al (NO) 3 ) 2 ·9H 2 O preparation of pure Al support, the product being boehmite (AlOOH). Mixing NiAl 9 Into boehmite flakes to obtain NiAl 9 -LDHs/AlOOH；
Step four, mixing the NiAl 9 And (3) placing LDHs/AlOOH on a miniature tubular catalyst evaluation device to perform catalytic oxidation formaldehyde reaction, and quantitatively analyzing by adopting gas chromatography. The reaction result shows that NiAl 9 The LDHs/AlOOH can partially decompose 450ppm formaldehyde within 5h, the conversion rate is 76%, and the catalyst is kept stable and is not deactivated within 24 h.
Comparative example 4 (No Pt NPs, no AlOOH)
Step one, 20.5g polyethylene glycol (PEG 400) is weighed, 100ml cyclohexane is added, magnetic stirring is carried out for mixing, and then 20ml of 1mmol Ni (NO) is rapidly added 3 ) 2 ·6H 2 O and 9mmolAl (NO) 3 ) 2 ·9H 2 A solution of O;
step two, after 10min, 4.25ml of ammonia (28 wt%) was added dropwise to the above obtained solution, and the resulting mixture was oven aged at 60-90 ℃ for 2h. Centrifuging the suspension, washing the collected solid with ultrapure water and ethanol 3 times;
step three, drying the solid obtained in the step two in an oven at the temperature of 60-90 ℃ for 15 hours to obtain a carrier NiAl 9 ；
The NiAl obtained in comparative example 4 was examined 9 And (4) putting the LDHs on a miniature tubular catalyst evaluation device for catalytic oxidation of formaldehyde, and quantitatively analyzing by using gas chromatography. The reaction result shows that NiAl 9 LDHs can only partially decompose 170ppm of formaldehyde, the conversion rate is 50%, and the catalyst is stable and not inactivated within 24 h.
Comparative example 5: (with Al) 2 O 3 As a carrier)
Step one, 50ml of 0.5mol/L aluminum nitrate solution is measured, 12g of urea is added into the solution to ensure that the urea and Al < 3+ > are mixedAnd (2) transferring the solution into a 100ml reaction kettle according to a molar ratio of 8 2 O 3 A carrier;
step two, weighing 300mg of the carrier obtained in step (1) in 10mL of ultrapure water, and then adding H under continuous magnetic stirring 2 PtCl 6 A solution; after 1h of immersion, 5ml of sodium borohydride (0.572 mol. L) were added rapidly -1 ) And sodium hydroxide (0.252 mol. L) -1 ) The aqueous solution is mixed with the suspension of (1). Continuously stirring for 1h, centrifuging, and washing the collected solid with ultrapure water and ethanol for 4 times; drying the obtained solid in an oven at 60 ℃ for 12h, wherein the loading capacity of Pt is 0.2%;
the Pt obtained in comparative example 5 was examined 0.2 Al 2 O 3 The material is placed on a miniature tubular catalyst evaluation device for catalytic oxidation of formaldehyde, and gas chromatography quantitative analysis is adopted. The reaction results showed that Pt 0.2 Al 2 O 3 Can partially decompose 500ppm formaldehyde, the conversion rate is 80 percent, and the catalyst can be kept stable and not deactivated within 24 hours.
The above-described preferred embodiments should be considered as examples of the embodiments of the present application, and any technical deductions, substitutions, improvements and the like, which are similar, approximate or based on the present application, should be considered as the protection scope of the present patent.
Claims (9)
1. The catalyst for catalyzing formaldehyde at room temperature is characterized by comprising an active component and a carrier, wherein the active component comprises platinum nanoparticles, and the carrier is a mixture consisting of nickel-aluminum composite hydrotalcite and boehmite.
2. The catalyst for catalyzing formaldehyde at room temperature according to claim 1, wherein the loading amount of the platinum nanoparticles on the carrier is greater than 0wt% and less than 1wt%.
3. The catalyst for catalyzing formaldehyde at room temperature according to claim 1 or 2, wherein the loading amount of the platinum nanoparticles on the carrier is 0.2wt%.
4. The catalyst for catalyzing formaldehyde at room temperature according to claim 1, wherein the molar ratio of nickel to aluminum in the nickel-aluminum composite hydrotalcite is 1:9 or 1:7 or 1:5.
5. a method for preparing a room-temperature formaldehyde catalyst, which is used for preparing the room-temperature formaldehyde catalyst as claimed in any one of claims 1 to 4, and is characterized by comprising the following steps:
dissolving nickel nitrate hexahydrate and aluminum nitrate nonahydrate in a mixed solution of polyethylene glycol and cyclohexane;
step two, dropwise adding ammonia water into the solution obtained in the step one, then aging, centrifuging, washing and drying to obtain a nickel-aluminum composite oxide carrier;
preparing boehmite by using aluminum nitrate nonahydrate, cutting into slices, and introducing the nickel-aluminum composite oxide carrier into the boehmite to obtain a catalyst precursor;
soaking the catalyst precursor in chloroplatinic acid solution, and pumping to dry;
and step five, reducing the product obtained in the step four by using a sodium borohydride reducing agent, and then stirring, centrifuging, washing and drying to obtain the catalyst.
6. The method for preparing the room-temperature catalytic formaldehyde catalyst according to claim 5, wherein in the second step, the mass fraction of the ammonia water is 25-28wt%.
7. The method of claim 5, wherein the formaldehyde catalyst is prepared by the following steps: the drying temperature in the second step is 60-90 ℃, and the drying time is 15h; and the drying temperature in the fifth step is 60-90 ℃, and the drying time is 12h.
8. The method for preparing the room-temperature catalytic formaldehyde catalyst according to claim 5, wherein the method comprises the following steps: in the third step, the step of cutting the boehmite into pieces specifically comprises the following steps: the boehmite was cut into thin pieces having a size of 10mm × 10mm × 2 mm.
9. The method for preparing the room-temperature catalytic formaldehyde catalyst according to claim 5, wherein the method comprises the following steps: in the fifth step, the concentration of the sodium borohydride reducing agent is 0.572 mol.L -1 。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040230A (en) * | 2016-06-02 | 2016-10-26 | 华东理工大学 | Method for preparing integrated catalyst for low-temperature catalytic oxidation of formaldehyde |
| CN106964348A (en) * | 2017-04-14 | 2017-07-21 | 南京工业大学 | Formaldehyde pollutant room-temperature catalytic oxidation catalyst and preparation method and application thereof |
| CN109939692A (en) * | 2019-02-14 | 2019-06-28 | 北京氦舶科技有限责任公司 | A kind of manganese oxide catalyst and its preparation method and application |
| CN111097422A (en) * | 2019-12-09 | 2020-05-05 | 广东省石油与精细化工研究院 | Catalyst for removing formaldehyde and preparation method and application thereof |
| CN113019393A (en) * | 2021-03-19 | 2021-06-25 | 郑州轻工业大学 | Platinum nano catalyst, preparation method thereof and method for synthesizing aromatic amine by selective hydrogenation of aromatic nitro compound |
| CN113908852A (en) * | 2021-10-08 | 2022-01-11 | 北京化工大学 | High-efficiency high-concentration formaldehyde catalysis oxidation catalyst and preparation method thereof |
-
2022
- 2022-11-23 CN CN202211476034.9A patent/CN115739113A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040230A (en) * | 2016-06-02 | 2016-10-26 | 华东理工大学 | Method for preparing integrated catalyst for low-temperature catalytic oxidation of formaldehyde |
| CN106964348A (en) * | 2017-04-14 | 2017-07-21 | 南京工业大学 | Formaldehyde pollutant room-temperature catalytic oxidation catalyst and preparation method and application thereof |
| CN109939692A (en) * | 2019-02-14 | 2019-06-28 | 北京氦舶科技有限责任公司 | A kind of manganese oxide catalyst and its preparation method and application |
| CN111097422A (en) * | 2019-12-09 | 2020-05-05 | 广东省石油与精细化工研究院 | Catalyst for removing formaldehyde and preparation method and application thereof |
| CN113019393A (en) * | 2021-03-19 | 2021-06-25 | 郑州轻工业大学 | Platinum nano catalyst, preparation method thereof and method for synthesizing aromatic amine by selective hydrogenation of aromatic nitro compound |
| CN113908852A (en) * | 2021-10-08 | 2022-01-11 | 北京化工大学 | High-efficiency high-concentration formaldehyde catalysis oxidation catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LIFAN QIN ET AL: "Efficient Decomposition of Formaldehyde on Ni-Al Hydrotalcite/AlOOH Nanocomposites Decorated with Pt Nanoparticles at Ambient Temperature", 《CHEMNANOMAT》, vol. 7, pages 1 - 2 * |
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