CN107233883A - A kind of mesoporous Ag2O‑MnO2Catalyst and its preparation and application - Google Patents
A kind of mesoporous Ag2O‑MnO2Catalyst and its preparation and application Download PDFInfo
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- CN107233883A CN107233883A CN201710458918.4A CN201710458918A CN107233883A CN 107233883 A CN107233883 A CN 107233883A CN 201710458918 A CN201710458918 A CN 201710458918A CN 107233883 A CN107233883 A CN 107233883A
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- mesoporous
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 56
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 16
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 238000002803 maceration Methods 0.000 claims abstract description 10
- 239000002210 silicon-based material Substances 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 29
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 150000007529 inorganic bases Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 description 11
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 210000002966 serum Anatomy 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003708 ampul Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health 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
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- BYOBIQOEWYNTMM-UHFFFAOYSA-N manganese;nitric acid Chemical compound [Mn].O[N+]([O-])=O BYOBIQOEWYNTMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000462 teratogen Toxicity 0.000 description 1
- 239000003439 teratogenic agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000012855 volatile organic compound 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
- B01J23/54—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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of mesoporous Ag2O‑MnO2Catalyst and its preparation and application.Methods described includes：(1) preparation of meso-porous titanium dioxide manganese：Using mesoporous silicon material as template, by the dipping of manganese nitrate solution, remove dry, roasting after maceration extract and obtain presoma, then remove template and obtain the meso-porous titanium dioxide manganese；(2) load of silver oxide：Silver oxide is loaded to the meso-porous titanium dioxide Mn catalyst that the load silver oxide is obtained on the meso-porous titanium dioxide manganese that step (1) is obtained.It is with low cost compared with expensive Pt loaded catalysts the invention provides formaldehyde catalyst is removed.
Description
Technical field
It is to be related to a kind of mesoporous Ag specifically the present invention relates to chemical field2O-MnO2Catalyst and its preparation and should
With.
Background technology
Formaldehyde confirms as carcinogenic, teratogen by IARC and the World Health Organization, is in Toxic
The matter list umber one.News media report：" it is relevant containing formaldehyde with room air that children obtain leukaemia ".Formaldehyde or one kind
Photochemical activity very strong volatile organic matter (VOCs), is easy to and nitrogen oxides (NOx) occur photochemical reaction formed carefully
Particle (PM2.5) is very big to human body and environmental hazard.With the raising of people's quality of life and health standards, room is effectively removed
Interior formaldehyde or the outdoor formaldehyde yield of reduction, which turn into, improves air ambient urgent problem.
Removing the method for formaldehyde mainly has absorption method, photocatalytic method and catalytic oxidation.Wherein, catalytic oxidation is a kind of
The formaldehyde minimizing technology for developing and having a extensive future, it has, and removal efficiency is high, initiation temperature is low, applied widely, equipment
The advantages of simple to operate and non-secondary pollution, directly formaldehyde can be changed into CO2And H2O.The key of the technology is catalyst
Development.
Metal oxide catalyst is because cost is cheap, aboundresources and receive much concern.In all poly-metal deoxides,
MnO2The performance of formaldehyde is removed with best low temperature, the temperature of conversion formaldehyde completely is less than or equal to 150 DEG C.Nevertheless, MnO2
Formaldehyde clearance is very low at room temperature.
Noble metal catalyst has good low temperature formaldehyde removal efficiency.Usually using the noble metals such as Pt, Pd, Au, Ag as
Active sites are supported on different types of carrier and are made.Oxidation of formaldehyde activity from by force to it is weak arrangement be usually：Pt>Pd>Rh>Au
>Ag.Precious metals pt loaded catalyst, which has, can convert formaldehyde such as Pt/ completely under best formaldehyde removal efficiency, normal temperature
TiO2、Pt/MnOx-CeO2And Pt/Fe2O3Deng.Pt/TiO2Catalyst has been used in air purifier, but has the disadvantage cost
Too high, Catalyst Production and popularization are restricted.
At present, the catalyst for obtaining low cost, good active high, stability, low temperature or even normal temperature removal formaldehyde is still to grind
Study carefully focus and difficult point.Using relatively cheap precious metals ag as active component, with the mesoporous MnO that specific surface area is larger2For carrier,
The mesoporous Ag prepared2O-MnO2Catalyst cost is relatively low, low temperature or normal temperature formaldehyde clearance is higher, stability is good, with good
Industrialization prospect.
The content of the invention
It is an object of the present invention to provide a kind of mesoporous Ag2O-MnO2The preparation method of catalyst；
Another object of the present invention is to provide the mesoporous Ag that the preparation method is prepared2O-MnO2Catalyst；
A further object of the present invention is to provide the mesoporous Ag2O-MnO2The application of catalyst.
For up to above-mentioned purpose, on the one hand, the invention provides a kind of mesoporous Ag2O-MnO2The preparation method of catalyst, its
In, methods described includes：
(1) preparation of meso-porous titanium dioxide manganese：Using mesoporous silicon material as template, by the dipping of manganese nitrate solution, remove
Dried after maceration extract, roasting obtains presoma, then remove template and obtain the meso-porous titanium dioxide manganese；
(2) load of silver oxide：Silver oxide is loaded on the meso-porous titanium dioxide manganese that step (1) is obtained and obtains the load
The meso-porous titanium dioxide Mn catalyst of silver oxide.
According to some of the invention specific embodiments, wherein, it using silver nitrate is presoma to meso-porous titanium dioxide that step (2), which is,
Manganese is loaded.
According to some of the invention specific embodiments, wherein, step (2) includes silver nitrate being dissolved in ammoniacal liquor that to form silver-colored ammonia molten
Liquid, the meso-porous titanium dioxide manganese that addition step (1) is obtained is well mixed, and is then added hydrogen peroxide and is reacted, after reaction terminates, mistake
Filter, dry and roasting obtain the meso-porous titanium dioxide Mn catalyst of the load silver oxide.
According to some specific embodiments of the invention, wherein, step (2) is reacted after 2-5h, is filtered, is dried and be calcined
To the meso-porous titanium dioxide Mn catalyst of the load silver oxide.
According to some specific embodiments of the invention, wherein, step (2) is reacted after 3h, and filtering, dry and roasting are obtained
The meso-porous titanium dioxide Mn catalyst of the load silver oxide.
According to some specific embodiments of the invention, wherein, the ammoniacal liquor quality consumption of step (2) is silver nitrate quality
30-300 times.
According to some specific embodiments of the invention, wherein, the dioxygen water quality of step (2) is the 50- of silver nitrate quality
400 times.
According to some specific embodiments of the invention, wherein, the silver ammino solution quality of step (2) is meso-porous titanium dioxide manganese matter
5-20 times of amount.
According to some specific embodiments of the invention, wherein, the mass concentration of the hydrogen peroxide of step (2) is 20%-
30%.
According to some specific embodiments of the invention, wherein, the mass concentration of the ammoniacal liquor of step (2) is 15%-25%.
According to some specific embodiments of the invention, wherein, the sintering temperature of step (2) is 350-420 DEG C.
According to some specific embodiments of the invention, wherein, the time of the roasting of step (2) is 4-8h.
According to some specific embodiments of the invention, wherein, the temperature of the drying of step (2) is 60-100 DEG C.
According to some specific embodiments of the invention, wherein, step (2) adds stirring 30-180min after hydrogen peroxide and carried out
Reaction, is then filtered, dry and roasting obtains the mesoporous Ag2O-MnO2Catalyst.
According to some specific embodiments of the invention, wherein, step (2) is filtering 1-3 times, then dries and roasting is obtained
The mesoporous Ag2O-MnO2Catalyst.
According to some specific embodiments of the invention, wherein, step (1) is after presoma is obtained, by obtained presoma
Impregnated again with manganese nitrate solution, dry, be calcined after removing maceration extract, the step of impregnating, dry, being calcined repeats 0-5 times.
Wherein it is understood that it is of the present invention repeat 0-5 time in refer to the step for 0 time and without repeatedly,
That is after presoma is obtained, " obtained presoma is impregnated with manganese nitrate solution again, is removed and is dried, roasts after maceration extract
Burn " in process in quotation marks and be not present, i.e. methods described is obtained after presoma, and presoma is directly removed to template and done again
It is dry to obtain the meso-porous titanium dioxide manganese；
And according to some specific embodiments of the invention, wherein after presoma is obtained, obtained presoma is used into nitre again
Sour manganese solution is impregnated, and dries, is calcined after evaporation removing maceration extract, and the step (the step of impregnating, dry, being calcined) is repeated 1-3 times.
Wherein it is understood that repetition of the present invention, is that after presoma is obtained, " presoma will be used into nitre again
The step of dry, roasting after sour manganese solution dipping, removing maceration extract ", is repeatedly；For example when being repeated 3 times, it is：Before obtaining
Drive after body, presoma is impregnated with manganese nitrate solution again, remove and dried after maceration extract, roasting, then by the presoma after roasting
Impregnated again with manganese nitrate solution, remove and dried after maceration extract, then roasting is impregnated with manganese nitrate solution again, is removed after maceration extract
Dry, then roasting removes template and obtain the meso-porous titanium dioxide manganese.
The manganese nitrate of the present invention includes non-hydrate and its various hydrate forms, for example four water manganese nitrates, six water nitric acid
Manganese etc..
According to some specific embodiments of the invention, wherein, methods described step (1) is included using mesoporous silicon material as template
Agent, by the dipping of manganese nitrate solution, then dry roasting removes template, described mesoporous by filtering and being dried to obtain
Manganese dioxide, pore volume is 0.1~0.3cm3/ g, specific surface area is 40~100m2/ g, pore-size distribution is in 1.9~12nm.
According to some of the invention specific embodiments, wherein, step (1) be washed with water after filtration filter cake to pH be 7-9.
According to some specific embodiments of the invention, wherein, step (1) described mesoporous silicon material is selected from KIT-6, SBA-
15th, one or more mixing in SBA-16, MCM-41 and MCM-48, can be commercially available acquisition or conventional with prior art
Method is obtained.
According to some specific embodiments of the invention, wherein, step (1) manganese nitrate solution concentration is 0.25~1.0mol/
L, quality consumption is 0.45~1.8 times of template quality.
According to some of the invention specific embodiments, wherein, step (1) be with the aqueous solution soaking presoma of inorganic base with
Remove template.
According to some specific embodiments of the invention, wherein, step (1) is that presoma is placed in after the aqueous solution of inorganic base
30-120min is stirred to remove template.
According to some specific embodiments of the invention, wherein, step (1) described inorganic base is selected from sodium hydroxide or hydroxide
Potassium.
According to some specific embodiments of the invention, wherein, step (1) is obtained after presoma, with the aqueous solution of inorganic base
Presoma is soaked, is filtered after stirring, is filtered after filter cake to be used to the aqueous solution soaking of inorganic base, stirring 30-120min again, and will filter
The step of being filtered after the aqueous solution soaking stirring of cake inorganic base repeats 0-5 times.
Wherein it is understood that it is of the present invention repeat 0-5 times in refer to the step and be not present for 0 time, also
It is to say the process of " by being filtered after the aqueous solution soaking stirring of filter cake inorganic base " and be not present, i.e. methods described obtains forerunner
After body, with the aqueous solution soaking presoma of inorganic base, stir filtering convection drying after 30-120min and obtain the meso-porous titanium dioxide
Manganese.
But according to some of the invention specific embodiments, wherein, step (1) is by the aqueous solution soaking of filter cake inorganic base
The step of being filtered after stirring repeats 1-3 times.
According to some specific embodiments of the invention, wherein, the roasting is to be calcined 4-8h at 200-400 DEG C.
According to some specific embodiments of the invention, wherein, step (1) roasting is roasting 6h.
According to some specific embodiments of the invention, wherein, step (1) methods described is included using mesoporous silicon material as template
Agent, by the dipping of manganese nitrate solution, dries at 60-100 DEG C, is then calcined, then removes template, by filtering and drying
Obtain the meso-porous titanium dioxide manganese.
Mesoporous Ag of the present invention2O-MnO2The method of catalyst can be specifically included：
1. pure mesoporous silicon material is added and be dissolved in the manganese nitrate solution of water or other solvents (preferred alcohol), by excess
Dipping, after ultrasonic vibration, then evaporation superfluous water or other solvents are dried at 60~100 DEG C, are calcined at 200~400 DEG C
(preferably 200 DEG C), obtain mesoporous Mn oxide presoma；Manganese nitrate is dissolved in water or other solvents (preferred alcohol), added
Mesoporous Mn oxide presoma, after excessive dipping, ultrasonic vibration, evaporation superfluous water or other solvents, then 60~100
Dried at DEG C, be calcined (preferably 380 DEG C) at 200~400 DEG C, obtain the mesoporous Mn oxide presoma with high compactedness.With
Upper step is repeated 0~3 time.Mesoporous Mn oxide presoma is soaked with sodium hydroxide solution, 30~120min of magnetic agitation is (excellent
Select 60min), filtering obtains filter cake.Filter cake is soaked once with same sodium hydroxide solution again, 30~120min of magnetic agitation
(preferably 60min), is refiltered, and the filter cake is washed with deionized more than 4 times, is dried at 60~100 DEG C, is produced mesoporous MnO2
Powder.
2. 0.08-0.48g (preferably 0.315g) silver nitrate is dissolved in the silver-colored ammonia of formation in 10-20ml (preferably 15ml) ammoniacal liquor molten
Liquid, adds 1-3g (preferably 1g) meso-porous titanium dioxide manganese powder end, and quick stirring forms mixed serum.Then 10 are slowly added into again
~30ml hydrogen peroxide (preferably 15ml), makes it be reacted with mixed serum and discharges gas, stirring 30-180min is (preferably
120min) by drying, 350-420 DEG C of roasting process at filtering 1-3 times, 60~100 DEG C, mesoporous Ag is obtained2O-MnO2Catalysis
Agent.
On the other hand, present invention also offers the mesoporous Ag that the preparation method is prepared2O-MnO2Catalyst.
Another aspect, present invention also offers described mesoporous Ag2O-MnO2Application of the catalyst in formaldehyde is removed.
According to some specific embodiments of the invention, wherein, described mesoporous Ag2O-MnO2Catalyst is in formaldehyde is removed
Application temperature range for normal temperature to 100 DEG C.
According to some specific embodiments of the invention, wherein, the described meso-porous titanium dioxide Mn catalyst for loading silver oxide
The pressure of application in formaldehyde is removed is 1 atmospheric pressure.
According to some specific embodiments of the invention, wherein, described mesoporous Ag2O-MnO2Catalyst is removing formaldehyde
Reactor is fixed bed reactors.
According to some specific embodiments of the invention, wherein, described mesoporous Ag2O-MnO2Catalyst removes the mistake of formaldehyde
Journey includes：Formaldehyde gas and air are passed through and are loaded with the mesoporous Ag2O-MnO2The reactor of catalyst, can directly turn formaldehyde
It is melted into CO2And H2O。
In summary, the invention provides a kind of mesoporous Ag2O-MnO2Catalyst and its preparation and application.The present invention's urges
Agent has the following advantages that：
It is with low cost compared with expensive Pt loaded catalysts the invention provides formaldehyde catalyst is removed.
Moreover, stability is good, low temperature removes formaldehyde efficiency high, 50% is up in 35 DEG C of formaldehyde clearances, 50 DEG C can remove formaldehyde completely,
The product of catalytic reaction is CO2And H2O.The present invention has Industry Promotion value.
Brief description of the drawings
Fig. 1 is the mesoporous Ag of embodiment 12O-MnO2The XRD of catalyst；
Fig. 2 is the mesoporous Ag of embodiment 12O-MnO2The SEM figures of catalyst；
Fig. 3 is the mesoporous Ag of embodiment 22O-MnO2The XRD of catalyst；
Fig. 4 is the mesoporous Ag of embodiment 22O-MnO2The SEM figures of catalyst；
Fig. 5 is the mesoporous Ag of embodiment 32O-MnO2The XRD of catalyst.
The mesoporous Ag of Fig. 62O-MnO2Catalyst removes the stability test figure of formaldehyde.
Embodiment
The beneficial effect for describing the implementation process of the present invention in detail below by way of specific embodiment and producing, it is intended to which help is read
Reader more fully understand the present invention essence and feature, not as to this case can practical range restriction.
Embodiment 1
Present embodiments provide mesoporous Ag2O-MnO2Catalyst, it is prepared according to following steps：
Step one：8.0g KIT-6 mesoporous silicons are added to 80ml, 0.91mol/L Mn (NO3)2·4H2O ethanol solutions
In, after excessive dipping, ultrasonic vibration, 50 DEG C of evaporation excess ethyl alcohols, in 100 DEG C of dryings, 200 DEG C of roastings, obtain mesoporous manganese
Oxide precursor；The mesoporous Mn oxide presoma of gained is added to 80ml, 0.91mol/L Mn (NO3)2·4H2O ethanol
In solution, after excessive dipping, ultrasonic vibration, then 50 DEG C of evaporation unnecessary alcohols are calcined at 100 DEG C of dryings, 380 DEG C,
Obtain the mesoporous Mn oxide presoma with high compactedness.By mesoporous Mn oxide presoma 2.0mol/L NaOH solution
Immersion, magnetic agitation 60min, filtering obtains filter cake.Filter cake is soaked once with same NaOH solution again, magnetic agitation
60min, is refiltered, and the filter cake is washed with deionized more than 4 times, is dried at 90 DEG C, is produced mesoporous MnO2Powder.
Step 2：By the mesoporous MnO of 1g2Powder is added in silver ammino solution (silver nitrate 0.316g, the ammoniacal liquor of mass fraction 28%
15ml), quick stirring forms mixed serum.Then 15ml hydrogen peroxide (mass concentration 30%) is slowly added into again, makes it with mixing
Close slurries to react and discharge after gas, stirring 120min through drying, 400 DEG C of roasting process at filter 23,90 DEG C, obtain
Mesoporous Ag2O-MnO2Catalyst.
Using X-ray powder diffraction (XRD) to above-mentioned mesoporous Ag2O-MnO2Powder is detected, is characterized with the presence or absence of oxidation
Silver-colored crystalline phase.Mesoporous Ag can be observed beneficial to SEM (SEM)2O-MnO2Surface texture featur.
Fig. 1 and Fig. 2 is mesoporous Ag2O-MnO2XRD spectra and the SEM figure of catalyst.XRD spectra shows that the catalyst is present
Ag2O crystalline phases.SEM figures show that Ag addition does not change clearly ordered mesopore structure, simply become the hole wall of catalyst
It is thick.Do not find that Ag nano-particles are dispersed in mesoporous Ag2O-MnO2On catalyst.
Embodiment 2
Step one：The mesoporous MnO of the present embodiment2The preparation method and technological parameter of powder are same as Example 1.
Step 2：By the mesoporous MnO of 1g2Powder is added in silver ammino solution (silver nitrate 0.016g, the ammoniacal liquor of mass fraction 28%
15ml), quick stirring forms mixed serum.Then 15ml hydrogen peroxide (mass concentration 30%) is slowly added into again, makes it with mixing
Close slurries to react and discharge after gas, stirring 120min through drying, 400 DEG C of roasting process at filter 23,90 DEG C, obtain
Mesoporous Ag2O-MnO2Catalyst.
Using XRD to above-mentioned mesoporous Ag2O-MnO2Powder is detected, is characterized and be whether there is silver oxide crystalline phase.It is beneficial to
SEM can observe mesoporous Ag2O-MnO2Surface texture featur.
Fig. 3 and Fig. 4 is mesoporous Ag2O-MnO2XRD spectra and the SEM figure of catalyst.XRD spectra shows that the catalyst is not deposited
In silver oxide crystalline phase, show Ag2O is uniformly dispersed.SEM figures show Ag addition without the meso-hole structure for changing catalyst,
There is no Ag nano-particles to be dispersed in catalyst surface.
Embodiment 3
Step one：The mesoporous MnO of the present embodiment2The preparation method and technological parameter of powder are same as Example 1.
Step 2：By the mesoporous MnO of 1g2Powder is added in silver ammino solution (silver nitrate 0.008g, the ammoniacal liquor of mass fraction 28%
15ml), quick stirring forms mixed serum.Then 15ml hydrogen peroxide (mass concentration 30%) is slowly added into again, makes it with mixing
Close slurries to react and discharge after gas, stirring 120min through drying, 400 DEG C of roasting process at filter 23,90 DEG C, obtain
Mesoporous Ag2O-MnO2Catalyst.
Using XRD to above-mentioned mesoporous Ag2O-MnO2Powder is detected, is characterized and be whether there is silver oxide crystalline phase.Fig. 5 is
Mesoporous Ag2O-MnO2The XRD spectra of catalyst.Spectrogram shows that silver oxide crystalline phase is not present in the catalyst, shows Ag2O is scattered equal
It is even.
Embodiment 4
Mesoporous Ag2O-MnO2Catalyst removes the estimation of stability experiment of formaldehyde
The mesoporous Ag prepared to above-described embodiment 1-32O-MnO2The formaldehyde of catalyst removes reactivity and tested.Instead
Answer condition：In internal diameter to be loaded in 8mm quartz ampoule fixed bed reactors under 0.2g catalyst, normal pressure, concentration of formaldehyde 100ppm,
50 DEG C of reaction temperature, air speed 30000h-1, reaction raw materials and the analysis of product utilization on-line chromatograph, reaction result is shown in Fig. 6.It is mesoporous
Ag2O-MnO2Catalyst stability is good.
Embodiment 5
Mesoporous Ag2O-MnO2Catalyst removes the active appraisal experiment of formaldehyde
The mesoporous Ag prepared to above-described embodiment 1-32O-MnO2The formaldehyde of catalyst removes reactivity and tested.Instead
Answer condition：In internal diameter to be loaded in 8mm quartz ampoule fixed bed reactors under 0.2g catalyst, normal pressure, concentration of formaldehyde 100ppm,
Air speed 30000h-1.After stable reaction, reaction raw materials and the analysis of product utilization on-line chromatograph, reaction result are shown in Table 1.
The catalyst of the present invention of table 1 removes the activity data of formaldehyde
| Catalyst | T20/ % | T50/ % | T90/ % |
| Embodiment 1 | Room temperature | 35℃ | 45℃ |
| Embodiment 2 | Room temperature | 40℃ | 55℃ |
| Embodiment 3 | 30℃ | 50℃ | 70℃ |
Embodiment 6
Initial concentration is to mesoporous Ag2O-MnO2The evaluation of catalyst formaldehyde catalytic activity influence.
The mesoporous Ag prepared to above-described embodiment 12O-MnO2The formaldehyde of catalyst removes reactivity and tested.Reaction
Condition：Reacted in the case where internal diameter is filling 0.2g catalyst (40~60 mesh) in 8mm quartz ampoule fixed bed reactors, normal pressure, first
Aldehyde initial concentration 100-1500ppm, air speed 30000h-1.After stable reaction, reaction raw materials and the analysis of product utilization on-line chromatograph,
Reaction result is shown in Table 2.The product of catalytic reaction is CO2And H2O。
The catalyst of the present invention of table 2 removes the activity data of various concentrations formaldehyde
| Initial concentration of formaldehyde | T20/ % | T50/ % | T90/ % |
| 100ppm | Room temperature | 35℃ | 45℃ |
| 600ppm | Room temperature | 50℃ | 80℃ |
| 1500ppm | 70℃ | 80℃ | 100℃ |
The method of the present invention is the more excellent result of current removal formaldehyde, with good industrialization prospect.It is high with price
Expensive Pt loaded catalysts are compared, with low cost.Moreover, stability is good, low temperature (- 50 DEG C of normal temperature) removes formaldehyde efficiency high,
50% is up in 35 DEG C of formaldehyde clearances, 50 DEG C can remove formaldehyde completely.
Claims (10)
1. a kind of mesoporous Ag2O-MnO2The preparation method of catalyst, wherein, methods described includes：
(1) preparation of meso-porous titanium dioxide manganese：Using mesoporous silicon material as template, by the dipping of manganese nitrate solution, dipping is removed
Dried after liquid, roasting obtains presoma, then remove template and obtain the meso-porous titanium dioxide manganese；
(2) load of silver oxide：Silver oxide is loaded to the load oxidation is obtained on the meso-porous titanium dioxide manganese that step (1) is obtained
The meso-porous titanium dioxide Mn catalyst of silver.
2. preparation method according to claim 1, wherein, step (2) is that meso-porous titanium dioxide manganese is entered by presoma of silver nitrate
Row load；Preferred steps (2) include silver nitrate being dissolved in ammoniacal liquor formation silver ammino solution, add the mesoporous dioxy that step (1) is obtained
Change manganese to be well mixed, then add hydrogen peroxide and reacted, reaction (preferably reacts 2-5h after terminating；More preferably react 3h) mistake
Filter, dry and roasting obtain the mesoporous Ag2O-MnO2Catalyst.
3. preparation method according to claim 2, wherein, the ammoniacal liquor quality consumption of step (2) is the 30- of silver nitrate quality
300 times；Dioxygen water quality is 50-400 times of silver nitrate quality；Silver ammino solution quality is the 5-20 of meso-porous titanium dioxide manganese quality
Times；It is preferred that the mass concentration of the hydrogen peroxide is 20%-30%；It is preferred that the mass concentration of the ammoniacal liquor is 15%-28%.
4. preparation method according to claim 2, wherein, the temperature of the roasting of step (2) is 350-420 DEG C；It is preferred that roasting
The time of burning is 4-8h.
5. preparation method according to claim 2, wherein, the drying temperature of step (2) is 60-100 DEG C.
6. preparation method according to claim 1, wherein, step (1) is after presoma is obtained, by obtained presoma again
Impregnated with manganese nitrate solution, dry, be calcined after removing maceration extract, the step of impregnating, dry, being calcined repeats 0-5 times, preferably repeats
1-3；It is preferred that methods described is included using mesoporous silicon material as template, and by the dipping of manganese nitrate solution, dry roasting, then
Template is removed, by filtering and being dried to obtain the meso-porous titanium dioxide manganese；It is preferred that filter cake is washed with water after filtration, Ran Hougan
It is dry to obtain the meso-porous titanium dioxide manganese；Further preferably be washed with water after filtration filter cake to pH be 7-9；It is preferred that the mesoporous silicon material
One or more mixing in KIT-6, SBA-15, SBA-16, MCM-41 and MCM-48；It is preferred that manganese nitrate solution concentration
For 0.25~1.0mol/L, quality consumption is 0.45~1.8 times of template quality；It is preferred that the dipping is under ultrasound condition
Impregnated；It is preferred that methods described is included using mesoporous silicon material as template, by the dipping of manganese nitrate solution, at 60-100 DEG C
Lower drying, is then calcined, then removes template, by filtering and being dried to obtain the meso-porous titanium dioxide manganese.
7. preparation method according to claim 1, wherein, step (1) be with the aqueous solution soaking presoma of inorganic base with
Remove template；Preferably presoma is placed in after the aqueous solution of inorganic base and stirs 30-120min to remove template；It is preferred that institute
State inorganic base and be selected from sodium hydroxide or potassium hydroxide；It is also preferred that the molar concentration of inorganic base is 1~3mol/L；It is preferred that obtaining
After presoma, with the aqueous solution soaking presoma of inorganic base, filtered after stirring, filter cake used to the aqueous solution soaking of inorganic base again,
Stir and filtered after 30-120min, and will be repeated 0-5 times the step of filtering after the aqueous solution soaking stirring of filter cake inorganic base；It is excellent
Choosing is repeated 1-3 times.
8. preparation method according to claim 1, wherein, step (1) roasting is calcined at 200-400 DEG C；It is excellent
It is 4-8h to select roasting time.
9. the mesoporous Ag that the preparation method described in claim 1~8 any one is prepared2O-MnO2Catalyst.
10. the mesoporous Ag described in claim 92O-MnO2Application of the catalyst in formaldehyde is removed；The temperature wherein preferably applied
Between normal temperature~100 DEG C, the temperature range more preferably applied is -50 DEG C of normal temperature；It is preferred that reaction pressure is 1 atmospheric pressure.
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| CN112512682A (en) * | 2018-11-30 | 2021-03-16 | 住友化学株式会社 | Catalyst for aldehyde decomposition |
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| CN108579746A (en) * | 2018-04-19 | 2018-09-28 | 福建农林大学 | A kind of preparation method and applications of zinc oxide/silver oxide composite photo-catalyst |
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| CN112221496A (en) * | 2020-10-13 | 2021-01-15 | 天津大学 | Catalyst for multi-metal oxide-based diesel oxidation catalyst and preparation method thereof |
| CN116037110A (en) * | 2023-02-13 | 2023-05-02 | 珠海格力电器股份有限公司 | Preparation method of manganese oxide loaded platinum catalyst and catalyst |
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