CN109433192A - A kind of noble metal single atomic dispersion type cleaning catalyst and preparation method thereof - Google Patents
A kind of noble metal single atomic dispersion type cleaning catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109433192A CN109433192A CN201811493884.3A CN201811493884A CN109433192A CN 109433192 A CN109433192 A CN 109433192A CN 201811493884 A CN201811493884 A CN 201811493884A CN 109433192 A CN109433192 A CN 109433192A
- Authority
- CN
- China
- Prior art keywords
- noble metal
- single atomic
- dispersion type
- metal
- atomic dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000006185 dispersion Substances 0.000 title claims abstract description 75
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 75
- 238000004140 cleaning Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 239000010970 precious metal Substances 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 82
- 239000000243 solution Substances 0.000 claims description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 8
- 230000002779 inactivation Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
- 239000013068 control sample Substances 0.000 description 19
- 238000006356 dehydrogenation reaction Methods 0.000 description 19
- 239000002105 nanoparticle Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910052697 platinum Inorganic materials 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- 238000001016 Ostwald ripening Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000005686 dimethyl carbonates Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/42—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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of noble metal single atomic dispersion type cleaning catalyst of the invention and preparation method thereof.Catalyst includes component and mass percentage are as follows: 97~99.99% nano-metal-oxide carriers and 0.01~3% noble metal.Method process are as follows: take nano-metal-oxide carrier, be scattered in precious metal salt solution, form mixed solution, take ammonium salt solution, using coprecipitation, generate noble-metal-supported in the presoma of carrier surface；By quality proportioning, presoma: metal powder=1: the two is mixed, and is calcined by (1~100), generates presoma after heat treatment, and after washed drying, noble metal single atomic dispersion type cleaning catalyst is made.Noble metal is single atomic dispersion type in the catalyst of the method for the present invention preparation, and method processing cost is low, preparation process is simple, H2Removal efficiency is high, has superregulated property, can keep continuous use 60h non-inactivation, and the consume of CO is smaller.
Description
Technical field:
The invention belongs to catalyst preparation technical fields, and in particular to the present invention relates to one kind can stablize for high concentration CO
H is removed in gas2Catalyst material more particularly to a kind of active material be high load amount single atomic dispersion Pt, Pd etc.
Noble metal, carrier TiO2、Al2O3The preparation method of equal catalyst of transition metal oxide material.
Background technique:
Ethylene glycol mainly for the production of polyethylene terephthalate (PET), antifreezing agent, unsaturated polyester resin (UPR),
Lubricant, plasticizer, nonionic surfactant, explosive etc., purposes is very extensive, while the ring that terylene industrial chain is important.
Production technology there are many ethylene glycol of the whole world at present can be divided into two kinds, i.e. ethylene system and the synthesis of coal base by the difference of raw materials for production
Gas oxalate system, the former can be divided into naphtha pyrolysis ethylene, ethane cracking ethylene (stone according to the different of ethylene source again
Oily associated gas, shale gas) and ammonia from coal ethylene, and the latter's coal base oxalate system is then chiefly used in China at present.In China, second
Glycol import volume is big, and external dependence degree is high.To 2016, China possessed about 8,240,000 tons of ethylene glycol production capacity altogether, produces second altogether for cut-off
5,280,000 tons of glycol, wherein about 950,000 tons of coal-ethylene glycol, while import volume is 7,570,000 tons, import dependency degree is up to 59%.It is comprehensive
It closes many factors such as China's national situation, world energy sources demand, production cost, environmental protection to consider, coal base oxalate preparing ethylene glycol has
Good development prospect.
The main process of coal base oxalate preparing ethylene glycol is after obtaining synthesis gas as raw material using coal, then separating-purifying obtains CO
And H2, wherein CO is by catalytic coupling synthesis of oxalate, then with H2It carries out hydrogenation reaction and ethylene glycol is made, while the method can be with
Obtain the by-products such as other oxalic acid, oxamides, dimethyl carbonates with economic value.The process flow is short, intermediate link is few,
It is at low cost, it is the highest coal-ethylene glycol technology of domestic attention rate.CO using extreme high purity is to prepare oxalate in the technology
One of key of step, advantageously reduces the side reaction occurred in carbonylation, increase dimethyl oxalate, ethylene glycol it is pure
Degree and reduction important intermediate-methyl nitrite loss, therefore the production unit consumption of ethylene glycol can be reduced.But industry at present
The method of middle separating-purifying synthesis gas mainly has deep cooling evaporation and pressure-variable adsorption (PSA).CO purity is compared with deep cooling made from PSA method
Evaporation is high, and purity reaches as high as 99.5%.In the CO gas that either method of deep cooling evaporation or pressure-variable adsorption obtains,
Contain a certain amount of H2, content is according to different separating technologies up to 102~104ppm.These micro H2It can be with methyl nitrite
Reaction forms by-product, significantly affects the production cost of ethylene glycol.Currently, the dehydrogenation for PSA-CO separation gas rear end
Mainly Pd/Pt-MOx/ Si (i.e. precious metal palladium/Pt nanoparticle is carried on transition metal oxide/silicon particle) support type is urged
Agent.Since CO is adsorbable in Pd, Pt particle surface, catalyst CO intoxicating phenomenon is formed, therefore, general dehydrogenation is at this
The disadvantage that dehydrogenation activity is lower, stability is poor is all had under a reaction background.It needs frequently to replace in industrial processes and urge
Agent or in-situ regeneration, higher cost.For another angle, these dehydrogenations can also be catalyzed CO to a certain degree
Oxidation, causes the loss of CO unstripped gas, further increases production cost.
In situ regeneration method after CO dehydrogenation purification Pd catalyst inactivation including the prior art, specific steps include:
It is passed through N2The adsorbate of purging removal catalyst surface；It is passed through O2The reunion Pd of catalyst surface is aoxidized；Be passed through HCl or
Person Cl2Redisperse is carried out to active component；It is passed through H2Reduction carries out dechlorination processing and completes regeneration.Regenerative process is filled in dehydrogenation reaction
Middle generation in situ is set, does not need additionally to build device.Catalyst after regeneration treatment, Pd metal dispersity and catalysis effect
Fruit significantly improves, and can selectively be restored to 80% of fresh catalyst or more, H2100ppm or less can be removed to.The regeneration
Method is mainly used in industrial CO gas dehydrogenation purification process.
Separately there is the application of CO dehydrogenation fluidized-bed reaction catalyst and preparation method thereof and the catalyst in a fluidized bed
Technique.The catalyst that the invention provides, chemical formula PdO/Al2O3, wherein PdO is active component, and Pd accounts for the quality of catalyst
Percentage composition is 0.05~3.0%, Al2O3It is the spheric granules of 0.5~2.5mm of diameter for carrier, specific surface area is 200~
400m2/ g, heap density are 0.5~0.9g/ml, compression strength >=50N/, Mass Loss≤0.4%.The catalyst is used
It, can be H a small amount of in CO unstripped gas in CO dehydrogenation fluidized-bed reaction process2It is removed to 50ppm or less.
There are also catalyst to disclose using mesoporous silicon material as carrier, and using platinum element as catalyst, IVA race metal helps for first
Agent, Al are the second auxiliary agent；It is 1~10%, Al load that wherein the load capacity of platinum element, which is 0.5~5%, IVA race content of metal,
Amount is 0.1~1%, and the percentage is weight percentage, and is in terms of 100% by the weight of mesoporous silicon material.
There are many more similar catalyst preparations or regeneration techniques, but these method and processes are more complex, and reaction condition is opposite
Harshness, production operation process is relatively cumbersome, and higher cost, is not suitable for large-scale industrial production.In particular, these your gold
Metal catalyst is all nano particle, is unfavorable for reducing noble metal dosage.Therefore, a degree of limit is received in practical applications
System.
Summary of the invention:
The purpose of the present invention is overcoming above-mentioned the shortcomings of the prior art, providing a kind of active material is high load amount
The noble metals such as Pt, Pd of single atomic dispersion, carrier TiO2、Al2O3A kind of monatomic point of noble metal of equal transition metal oxides
Dissipate type cleaning catalyst and preparation method thereof.Signified single atomic dispersion of the invention refers to the Pt/Pd precious metal atom of load
It is bonding of the carrier without similar atom around it., preparation low using this catalyst processing cost prepared by the present invention
Simple process, H2Removal efficiency is high.By experimental verification, the most prominent feature of this catalyst is that stability is high, can the company of holding
It is continuous to use 60h non-inactivation, and the consume of CO is smaller.
To achieve the above object, the invention adopts the following technical scheme:
A kind of noble metal single atomic dispersion type cleaning catalyst, including component and mass percentage are as follows: 97~99.99%
Nano-metal-oxide carrier and 0.01~3% noble metal.
The noble metal single atomic dispersion type cleaning catalyst can be used for chemical production field, specifically, pass through for coal
The industry of oxalate route preparing ethylene glycol, high-purity CO are produced in industrial middle and high concentration CO gas and are removed H2。
The nano-metal-oxide carrier is TiO2、Al2O3Or ZrO2One or more of, when for a variety of mixing
When, mixing match is any ratio.
Without second of auxiliary agent on the nano-metal-oxide carrier, the carrier is in granular form, granular size 1
~500nm.
The noble metal is nanoscale Pd and/or Pt, and when for the two mixing, mixing ratio is any ratio.
In the catalyst, single atomic dispersion state is presented in noble metal in the carrier.
The preparation method of the noble metal single atomic dispersion type cleaning catalyst, comprising the following steps:
(1) nano-metal-oxide carrier is taken, is scattered in precious metal salt solution, mixed solution is formed, it is described
Nano-metal-oxide carrier quality accounting is 1~50% in mixed solution；
(2) quality proportioning is pressed, mixed solution: ammonium salt solution is slowly added to mixed solution by ammonium salt solution=0.01~100
In, using coprecipitation, noble-metal-supported is generated in the presoma of carrier surface；
(3) quality proportioning is pressed, presoma: metal powder=1: the two is mixed, and calcined by (1~100), generates heat
Presoma after processing；
(4) presoma after heat treatment is washed, after drying, noble metal single atomic dispersion type cleaning catalyst is made.
In the step (1), nano-metal-oxide carrier includes nano-scale TiO2/Al2O3/ZrO2Equal metal oxygens
Compound carrier, preparation method is including but not limited to Hydrolyze method, pyrolysismethod, coprecipitation, hydro-thermal method or ball-milling method etc..
In the step (1), precious metal salt solution concentration is 1mM~1M, and ammonium salt solution concentration is 1mM~10M, described
Ammonium salt solution PH is adjusted to using after 7~12 using hydrochloric acid.
In the step (3), metal powder is microns or the nanometer powders such as Fe/Al/Ni/Co/Ti, the metal powder mistake
200 meshes.
In the step (3), the hybrid mode of presoma and metal powder are as follows: use shaking table, the devices such as blender carry out
Mixing.
In the step (3), calcination operation carries out in vacuum tube furnace, and calcination temperature is 200~500 DEG C, calcining
Time is 0.25~5h, and calcination atmosphere is vacuum, and atmosphere is argon gas, 10%H2/ Ar gaseous mixture or pure hydrogen atmosphere etc. be not oxygenous
Atmosphere.
In the step (4), using the presoma after chloroazotic acid or cyanide washing heat treatment, the concentration of cyanide
For 1mM~10M, washs and continuous or repeatedly washing can be used, until atom without precious metal in cleaning solution, solution can be returned after washing
It receives and utilizes.
The preparation method that above-mentioned catalyst material uses is that coprecipitation and heat treating process are combined.
Noble-metal-supported is in the loaded catalyst presoma of the carrier of metal oxide using coprecipitated in the present invention
Shallow lake method.The specific principle of coprecipitation is: when containing two or more cations in solution, they are to be homogeneously present in solution
In, precipitating reagent, which is added, can be obtained the uniform precipitating of various composition after precipitation reaction.It is prepare containing there are two types of or two kinds
The important method of the Ultrafines for complex oxide body of the above metallic element.The advantages of coprecipitation, is: one is passing through solution
In various chemical reactions directly obtain the uniform nano-powder material of chemical component, the second is be easy prepared sizes it is small and also point
The uniform nano-powder material of cloth.Noble-metal-supported can be obtained in metal oxide surface by after precipitating drying, calcining in we
Support type presoma.
The principle that the present invention is heat-treated is: when we metal powder and noble-metal-supported in metal oxide carrier surface
Presoma is uniformly mixed and is put into when calcining in inertia or reducing atmosphere, since pure metal has stronger oxygen at high temperature
Tendency, and it is not oxygen-containing in atmosphere.Therefore, metal powder tends to capture certain oxygen from oxide carrier, causes oxide
Oxygen vacancy concentration increases on carrier；At the same time, the noble metal being carried on oxide, at high temperature, due to the work of thermal diffusion
With generation Ostwald ripening phenomenon, i.e. noble metal granule is grown up.But during Ostwald ripening, the noble metal of oxide surface
To grow up and shift be that the form that is spread in oxide lattice with atom occurs.Lacking oxygen in oxide lattice has very strong
Riveting determine the ability of atom.Therefore, part precious metal atom is determined by a large amount of Lacking oxygen riveting.After the completion of heat treatment, king is used
The solution such as water/cyanide wash away nano particle state noble metal, and the noble metal of single atomic dispersion is due to thermodynamically high stabilization
Property cannot be washed off by chloroazotic acid/cyanide.It reuses methanol or water and separates metal oxide with metal powder.Invention institute can be obtained
State atom dispersion noble metal/oxide type CO dehydrogenation purifying and catalyzing agent material.
The present invention is prepared for atom dispersion noble metal/oxide type CO by coprecipitation and heat treating process combination technique and takes off
Hydrogen purification catalyst material.
Beneficial effects of the present invention:
1) CO dehydrogenation purifying and catalyzing agent material generally has that military service stability is bad in the prior art.Study carefully its root
This reason is that there are certain suction-operateds due to active catalyst sites various structures, and to CO, causes catalyst by CO poison
Change, so as to cause catalyst inactivation；The noble metal single atomic dispersion type cleaning catalyst that the present invention is prepared is due to active sites
Point is the noble metal of single atomic dispersion, and structure is single.CO adsorption strength on monatomic Pt- oxide interface is weaker, therefore, can
To greatly improve the characteristic of the resistance to CO of catalyst material, the military service stability of dehydrogenation is greatly improved.
2) the noble metal single atomic dispersion type cleaning catalyst that the present invention is prepared carries out CO dehydrogenation purification, for catalysis
The performance of Oxidation of Carbon Monoxide is poor, to reduce the unit consumption of CO in industrial processes, reduces production cost.
3) state of single atomic dispersion is presented in noble metal in the catalyst that is prepared of the present invention, and atom utilization is
100%.The waste liquid formed after washing removal Nanoparticulate noble metal, can also be concentrated using simpler method, be recycled, again
It utilizes.Therefore, noble metal single atomic dispersion type cleaning catalyst of the invention not only has good dehydrogenation, but also substantially
Degree reduces the usage amount of noble metal, reduces industrial cost.
Detailed description of the invention:
Fig. 1 be embodiment 2 prepare presoma (2% nano particle Pt is carried on TiO2Surface) STEM photo；
Fig. 2 be embodiment 2 prepare presoma (2% nano particle Pt is carried on TiO2Surface) it is calcined through mixed metal powder
Afterwards, the particle diameter distribution rule and FE-STEM photo of Pt particle before being washed using chloroazotic acid；
Fig. 3 is noble metal single atomic dispersion type Pt/TiO prepared by embodiment 22The AC-STEM-HAADF of cleaning catalyst
Photo, wherein that indicate in the circle and box is monatomic Pt；
Fig. 4 is the noble metal single atomic dispersion type Pt/TiO of Examples 1 to 2 preparation2Cleaning catalyst and pure TiO2Essence
Thin XRD spectrum；
Fig. 5 is the noble metal single atomic dispersion type Pt/TiO of Examples 1 to 2 preparation2Cleaning catalyst and control sample 2
SXAS map, in conjunction with XRD spectrum and AC-STEM photo, it can be appreciated that single atomic dispersion is presented in Pt on catalyst；
Fig. 6 is the noble metal single atomic dispersion type Pt/TiO of Examples 1 to 2 preparation2Cleaning catalyst, control sample 2 and
Pure TiO2XPS map；
Fig. 7 is the noble metal single atomic dispersion type Pt/TiO of Examples 1 to 2 preparation2Cleaning catalyst is calcined in air
Temperature-conversion ratio the curve of front and back and control sample 1 and control sample 2 in CO catalytic oxidation, in specially pure CO environment；
Fig. 8 is noble metal single atomic dispersion type Pt/TiO prepared by embodiment 22Cleaning catalyst and control sample 2 are in CO gas
Temperature-conversion ratio curve in stream in hydrogen catalytic combustion reaction, mixed with 1%H in specially CO2Environment in；
Fig. 9 is noble metal single atomic dispersion type Pt/TiO prepared by embodiment 22Cleaning catalyst and control sample 2 are in CO gas
Hydrogen catalytic combustion stable reaction linearity curve in stream, in which:
Noble metal single atomic dispersion type Pt/TiO prepared by embodiment 12Cleaning catalyst Pt load capacity is 0.1%, is
0.1%SACs；
Noble metal single atomic dispersion type Pt/TiO prepared by embodiment 22Cleaning catalyst Pt load capacity is 0.5%, is
0.5%SACs；
Control sample 1 is the Pt/TiO that Pt nano particle load capacity is 0.1%2Forerunner's body catalyst, i.e., 0.1%
clusters；
Control sample 2 is the Pt/TiO that Pt nano particle load capacity is 0.5%2Forerunner's body catalyst, i.e., 0.5%
clusters；
Specific embodiment:
Below with reference to embodiment, the present invention is described in further detail.
The present invention will be further explained below with reference to the attached drawings.
Nano-metal-oxide carrier is using the homemade TiO of the prior art in embodiment2Carrier or market are commercially available
P25 carrier, chloroazotic acid, the aqueous solution etc. of Cymag be all from market purchase；
The present invention will be further described with reference to the examples below, but the present invention is including but not limited to following implementations
Example.
Embodiment 1
A kind of noble metal single atomic dispersion type cleaning catalyst, including component and mass percentage are as follows: 99.9%TiO2
Carrier and 0.1%Pt, for removing H in high concentration CO gas2, wherein TiO2Carrier granular size is 20~30nm, the catalysis
In agent, Pt is in TiO2Single atomic dispersion state is presented in carrier.
The preparation method of the noble metal single atomic dispersion type cleaning catalyst, comprising the following steps:
In vacuum glove box, 136.12g butyl titanate is weighed, and be diluted to 200mL using dehydrated alcohol.It weighs
Chloroplatinic acid (the molecular formula H of 0.2g2PtCl6·6H2O), magnetic agitation be dissolved in the ethanol solution (referred to hereinafter as the solution be A0
Solution).Another configuration 200mL 0.1M sal volatile, and PH is adjusted to 8 using micro hydrochloric acid and (it is molten that the solution is hereafter known as B0
Liquid).A0 solution is placed in 60 DEG C of water-baths and stirs and keeps the temperature.Then B0 solution is slowly added in A0 solution, in solution
Precipitating no longer generate, continue stir 1h after raise the temperature to 80 DEG C.It is evaporated, powder can be collected to A0 solution
And dry, Pt, which is obtained, with form of nanoparticles is supported on TiO2The precursor powder of carrier surface, finally by precursor powder with
The ratio uniform of titanium valve in mass ratio 1: 5 mixes, and is placed in the vacuum tube furnace of Ar atmosphere after 400 DEG C of calcining 5h, and calcining is produced
Object passes through chloroazotic acid every time for 24 hours, after pickling three times, that is, dries after collecting, noble metal single atomic dispersion type Pt/TiO is made2Purification
Catalyst, the load capacity of platinum is 0.1% in catalyst.
Embodiment 2
A kind of noble metal single atomic dispersion type cleaning catalyst, including component and mass percentage are as follows: 99.5%TiO2
Carrier and 0.5%Pt, for removing H in high concentration CO gas2, wherein TiO2Carrier granular size is 20~30nm, the catalysis
In agent, Pt is in TiO2Single atomic dispersion state is presented in carrier.
The preparation method of the noble metal single atomic dispersion type cleaning catalyst, comprising the following steps:
In vacuum glove box, 136.12g butyl titanate is weighed, and be diluted to 200mL using dehydrated alcohol.Weigh 1g
Chloroplatinic acid (molecular formula H2PtCl6·6H2O), magnetic agitation is dissolved in the ethanol solution (referred to hereinafter as the solution is solution A).
Another configuration 200mL 0.1M sal volatile, and PH was adjusted to for 8 (solution is hereafter known as B solution) using micro hydrochloric acid.By A
Solution is placed in 60 DEG C of water-baths and stirs and keep the temperature.Then B solution is slowly added in solution A, no longer to the precipitating in solution
It generates, continues to raise the temperature to 80 DEG C after stirring 1h.It is evaporated to solution A, can powder be collected and be dried, obtained
Pt is supported on TiO with form of nanoparticles2The precursor powder of carrier surface, in precursor powder, Pt load capacity is 2%, should
Presoma STEM photo is placed in as shown in Figure 1, finally mix precursor powder with the ratio uniform of titanium valve in mass ratio 1: 5
In the vacuum tube furnace of Ar atmosphere after 400 DEG C of calcining 5h, the particle diameter distribution of Pt particle rule and FE-STEM photo as shown in Fig. 2,
Calcined product is passed through into chloroazotic acid every time for 24 hours later, after pickling three times, that is, is dried after collecting, noble metal single atomic dispersion is made
Type Pt/TiO2Cleaning catalyst, the load capacity of platinum is 0.5%, AC-STEM-HAADF photo as shown in figure 3, figure in catalyst
That indicate in middle circle and box is monatomic Pt, it can be found that single atomic dispersion is presented in Pt atom, Pt element presents single former
Son is dispersed in Detitanium-ore-type TiO2Surface；
Control sample 1 and 2 is separately taken respectively, in which:
Control sample 1 be the Pt nano particle load capacity that uses mode of the embodiment of the present invention to prepare for 0.1% Pt/TiO2Before
Drive body catalyst, i.e. 0.1%clusters；
Control sample 2 be the Pt nano particle load capacity that uses mode of the embodiment of the present invention to prepare for 0.5% Pt/TiO2Before
Drive body catalyst, i.e. 0.5%clusters.
Noble metal single atomic dispersion type Pt/TiO prepared by Example 1 and 2 respectively2Cleaning catalyst and above-mentioned control
Sample carries out relevant comparative's experiment, and it is as follows to draw a conclusion:
(2% nano particle Pt is carried on TiO to presoma prepared by embodiment 22Surface) STEM photo is as shown in Fig. 1,
Since Pt differs larger with Ti atomic number, different brightness is presented under STEM dark field mode, wherein white spot zone generation
Table Pt, gray area represent TiO2, black region is background；By Fig. 1 it is readily apparent that in presoma, Pt metal is to receive
The form of rice grain is carried on TiO2Carrier surface, Pt nanoparticle size are mainly distributed on 2~3nm (as shown in Fig. 2),
TiO2Particle diameter about 15~20nm.Attached drawing 4 shows this TiO2Crystal form be Detitanium-ore-type.
The noble metal single atomic dispersion type Pt/TiO prepared as shown in Fig. 3 for embodiment 22The AC- of cleaning catalyst
STEM-HAADF photo uses chloroazotic acid multiple later when calcining 5h in an ar atmosphere after evenly mixing using titanium valve and presoma
Washing catalyst presoma simultaneously separates removal titanium valve, in the observation of common Flied emission transmission electron microscope, TiO2The Pt of carrier surface
Particle is invisible；When going to observe these samples using spherical aberration correction transmission electron microscope, Pt element is inlayed in the form of single atomic dispersion
Embedded in TiO2In lattice；Attached drawing 2 shows that after incorporation titanium valve Ar atmosphere calcining, ruler has occurred in part Pt particle in presoma
Modest ability is big；In conjunction with attached drawing 1 and attached drawing 2, by the quantity and size statistic of the Pt particle to same area region, we can estimate
Calculate TiO2It is monatomic to there is the Pt that the common Flied emission transmission electron microscope in part does not observe in carrier surface.
Attached drawing 4 is the noble metal single atomic dispersion type Pt/TiO of Examples 1 to 2 preparation2Cleaning catalyst and pure TiO2's
Fine XRD spectrum；Since the constituent content of Pt is lower, so XRD can't detect platinum or the peak of its compound.But we can
To compare the lattice internal stress situation of carrier, part TiO is learnt2Displacement doping has occurred in lattice, and crystal face constant has slight receipts
Contracting.
Attached drawing 5 is the noble metal single atomic dispersion type Pt/TiO of Examples 1 to 2 preparation2Cleaning catalyst and control sample 2
SXAS map characterized in catalyst macroscopical using the synchrotron radiation X-ray of high brightness, high-energy and high monochromaticity
The distribution situation of upper Pt element is further demonstrated in conjunction with XRD spectrum and AC-STEM photo, the present embodiment through mix titanium valve,
And pass through 400 DEG C of calcining 5h of Ar atmosphere, the noble metal single atomic dispersion type Pt/TiO prepared after chloroazotic acid pickling2Cleaning catalyst sample
Pt element in product is in single atomic dispersion.
Attached drawing 6 is the noble metal single atomic dispersion type Pt/TiO of Examples 1 to 2 preparation2Cleaning catalyst, control sample 2 with
And pure TiO2XPS map, show certain positive charge on the monatomic sample P t element band of Examples 1 to 2 preparation, in conjunction with figure
2~5, it has further proved Pt and single atomic dispersion is presented；
Fig. 7 is the noble metal single atomic dispersion type Pt/TiO of Examples 1 to 2 preparation2Cleaning catalyst is calcined in air
Temperature-conversion ratio the curve of front and back and control sample 1 and control sample 2 in CO catalytic oxidation.It shows that embodiment 2 is made
Standby load capacity can hardly be catalyzed CO oxidation in the sample of monatomic distribution for 0.5%, Pt.In lower temperature (60~100
DEG C) conversion ratio be lower than 5%.The application that this characteristic is conducive in CO dehydrogenation purification will not remove that is, while dehydrogenation
CO causes the loss of CO.
Attached drawing 8 is noble metal single atomic dispersion type Pt/TiO prepared by embodiment 22Cleaning catalyst and control sample 2 are in CO
Temperature-conversion ratio curve in air-flow in hydrogen catalytic combustion reaction.It sufficiently shows single atomic dispersion prepared by embodiment 2
Pt/TiO2Catalyst has the performance of good hydrogen catalyzed burning.All hydrogen catalytics can be aoxidized at about 100 DEG C, and
The conversion ratio of CO only 1~2% at this time.
Fig. 9 is noble metal single atomic dispersion type Pt/TiO prepared by embodiment 22Cleaning catalyst and control sample 2 are in CO gas
Hydrogen catalytic combustion stable reaction linearity curve in stream.By the continuous catalysis oxidation experiment of the 60h in high concentration CO air-flow, Dan Yuan
Muonic catalysis agent shows excellent CO air-flow Dehydrogenation Stability, and by the reaction of 60h, catalyst activity is almost without any damage
It loses.As a comparison, 2 nano particle of control sample is carried on TiO2On catalyst also have certain CO dehydrogenation detergent power, but
CO unit consumption is larger and stability is poor, rapid deactivation.It is almost inactivated after 60h.The above experimental data sufficiently demonstrates the list
The superiority of catalyst aims catalytic property of dehydrogenation purification process in CO air-flow of atom dispersion.
Embodiment 3
A kind of noble metal single atomic dispersion type cleaning catalyst, including component and mass percentage are as follows: 98.2%TiO2
Carrier and 1.8%Pd, for removing H in high concentration CO gas2, wherein TiO2Carrier granular size is 20~30nm, the catalysis
In agent, Pd is in TiO2Single atomic dispersion state is presented in carrier.
The preparation method of the noble metal single atomic dispersion type cleaning catalyst, comprising the following steps:
In vacuum glove box, 85.08g butyl titanate is weighed, and be diluted to 200mL using dehydrated alcohol, weigh 1g
Palladium tetrachloride (molecular formula PdCl4), magnetic agitation is dissolved in the ethanol solution (referred to hereinafter as the solution is A2 solution).
Another configuration 200mL 0.1M sal volatile, and PH is adjusted to 8 using micro hydrochloric acid and (solution is hereafter known as B2
Solution).A2 solution is placed in 60 DEG C of water-baths and stirs and keeps the temperature.Then B2 solution is slowly added in solution A, in solution
Precipitating no longer generate, continue stir 1h after raise the temperature to 80 DEG C.It is evaporated, powder can be collected to solution A
And dry, Pd, which is obtained, with form of nanoparticles is supported on TiO2The precursor powder of carrier surface, finally by precursor powder with
The ratio uniform of titanium valve in mass ratio 1: 10 mixes, and is placed in 400 DEG C of calcining 5h in the vacuum tube furnace of Ar atmosphere.It is every by chloroazotic acid
It is secondary after pickling three times, that is, to be dried after collecting for 24 hours, obtained noble metal single atomic dispersion type Pd/TiO2Cleaning catalyst, this reality
The load capacity for applying palladium in example is 1.8%, and palladium is presented monatomic state and is scattered in carrier surface.
Embodiment 4
A kind of noble metal single atomic dispersion type cleaning catalyst, including component and mass percentage are as follows: 99.1%TiO2
Carrier and 0.9%Pt, for removing H in high concentration CO gas2, wherein TiO2Carrier granular size is 20~30nm, the catalysis
In agent, Pt is in TiO2Single atomic dispersion state is presented in carrier.
The preparation method of the noble metal single atomic dispersion type cleaning catalyst, comprising the following steps:
80g P25 powder is weighed, and is diluted to 200mL using dehydrated alcohol.Weighing the chloroplatinic acid of 1g, (molecular formula is
H2PtCl6·6H2O), magnetic agitation is dissolved in the ethanol solution (referred to hereinafter as the solution is A3 solution).Another configuration 200mL 1M carbon
Sour hydrogen ammonium salt solution, and PH was adjusted to for 10 (solution is hereafter known as B3 solution) using micro hydrochloric acid and 1M sal volatile.It will
A3 solution is placed in 60 DEG C of water-baths and stirs and keep the temperature.Then B3 solution is slowly added in A3 solution, to the precipitating in solution
It no longer generates, continues to raise the temperature to 80 DEG C after stirring 1h.It is evaporated to A3 solution, can powder be collected and be dried
It is dry, Pt, which is obtained, with form of nanoparticles is supported on TiO2Powder and titanium valve are finally pressed quality by the precursor powder of carrier surface
Ratio uniform mixing than 1: 5, is placed in 500 DEG C of calcining 5h in the vacuum tube furnace of hydrogen-argon-mixed atmosphere.By the water of Cymag
Solution washing after washing three times, that is, dries after collecting every time for 24 hours, noble metal single atomic dispersion type Pt/TiO is made2Purification
Catalyst, the load capacity of platinum is 0.9% in this embodiment, and platinum is in single atomic dispersion in carrier surface.
Embodiment of the present invention is only the description carried out to the preferred embodiment of the present invention, not to the present invention
Conception and scope be defined, under the premise of not departing from design philosophy of the present invention, in this field engineers and technicians to this
The all variations and modifications that the technical solution of invention is made, should all fall into protection scope of the present invention, and the present invention is claimed
Technology contents are all described in the claims.
Claims (10)
1. a kind of noble metal single atomic dispersion type cleaning catalyst, which is characterized in that including component and mass percentage are as follows: 97
~99.99% nano-metal-oxide carrier and 0.01~3% noble metal.
2. noble metal single atomic dispersion type cleaning catalyst according to claim 1, which is characterized in that the noble metal
Single atomic dispersion type cleaning catalyst produces industrial middle and high concentration through the industry of oxalate route preparing ethylene glycol or high-purity CO for coal
H in CO gas2Removal.
3. noble metal single atomic dispersion type cleaning catalyst according to claim 1, which is characterized in that the nanogold
Category oxide carrier is TiO2、Al2O3Or ZrO2One or more of, when for a variety of mixing, mixing match is any ratio.
4. noble metal single atomic dispersion type cleaning catalyst according to claim 1, which is characterized in that the carrier is in
Graininess, grain diameter are 1~500nm.
5. noble metal single atomic dispersion type cleaning catalyst according to claim 1, which is characterized in that the noble metal
For nanoscale Pd and/or Pt, when for the two mixing, mixing ratio is any ratio.
6. the preparation method of noble metal single atomic dispersion type cleaning catalyst described in claim 1, which is characterized in that including with
Lower step:
(1) nano-metal-oxide carrier is taken, is scattered in precious metal salt solution, mixed solution, the mixing are formed
Nano-metal-oxide carrier quality accounting is 1~50% in solution；
(2) quality proportioning is pressed, mixed solution: ammonium salt solution is slowly added in mixed solution by ammonium salt solution=0.01~100,
Using coprecipitation, noble-metal-supported is generated in the presoma of carrier surface；
(3) quality proportioning is pressed, presoma: metal powder=1: the two is mixed, and calcined by (1~100), generates heat treatment
Presoma afterwards；
(4) presoma after heat treatment is washed, after drying, noble metal single atomic dispersion type cleaning catalyst is made.
7. the preparation method of noble metal single atomic dispersion type cleaning catalyst according to claim 6, which is characterized in that institute
In the step of stating (1), nano-metal-oxide carrier is nano-scale TiO2/Al2O3/ZrO2Metal oxide carrier, it is described
Precious metal salt solution concentration is 1mM~1M, and ammonium salt solution concentration is 1mM~10M, and the ammonium salt solution uses hydrochloric acid by PH tune
Section is to using after 7~12.
8. the preparation method of noble metal single atomic dispersion type cleaning catalyst according to claim 6, which is characterized in that institute
In the step of stating (3), metal powder Fe, Al, Ni, Co or Ti powder, the metal powder crosses 200 meshes.
9. the preparation method of noble metal single atomic dispersion type cleaning catalyst according to claim 6, which is characterized in that institute
In the step of stating (3), calcination operation carries out in vacuum tube furnace, and calcination temperature is 200~500 DEG C, calcination time 0.25
~5h, atmosphere are argon gas, 10%H2/ Ar gaseous mixture or pure hydrogen atmosphere.
10. the preparation method of noble metal single atomic dispersion type cleaning catalyst according to claim 6, which is characterized in that
In the step (4), using chloroazotic acid or cyanide washing heat treatment after presoma, the concentration of cyanide be 1mM~
10M, washing atom without precious metal into cleaning solution, solution recycles after washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811493884.3A CN109433192B (en) | 2018-12-07 | 2018-12-07 | Noble metal monoatomic dispersion type purification catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811493884.3A CN109433192B (en) | 2018-12-07 | 2018-12-07 | Noble metal monoatomic dispersion type purification catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109433192A true CN109433192A (en) | 2019-03-08 |
| CN109433192B CN109433192B (en) | 2021-06-01 |
Family
ID=65556866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811493884.3A Active CN109433192B (en) | 2018-12-07 | 2018-12-07 | Noble metal monoatomic dispersion type purification catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109433192B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110124664A (en) * | 2019-06-18 | 2019-08-16 | 中国科学院长春应用化学研究所 | Metal platinum black nanocluster catalyst and preparation method thereof |
| CN110292924A (en) * | 2019-04-16 | 2019-10-01 | 北京氦舶科技有限责任公司 | A kind of methanol low-temperature decomposing catalyst and preparation method thereof |
| CN111517278A (en) * | 2020-03-24 | 2020-08-11 | 中南大学 | Ti3C2TxApplication of MXenes non-noble metal heterogeneous catalyst in formic acid dehydrogenation |
| CN111790377A (en) * | 2019-12-26 | 2020-10-20 | 东北石油大学 | Monoatomic catalyst, preparation method and application thereof |
| CN112044434A (en) * | 2020-10-20 | 2020-12-08 | 北京单原子催化科技有限公司 | Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof |
| CN113070058A (en) * | 2021-03-04 | 2021-07-06 | 青岛创启新能催化科技有限公司 | Composite carrier monoatomic catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof |
| CN114471543A (en) * | 2022-02-23 | 2022-05-13 | 北京工业大学 | Method for preparing platinum-based noble metal catalyst by wet process |
| CN116116405A (en) * | 2022-11-04 | 2023-05-16 | 佛山东佛表面科技有限公司 | Single-atom cluster type noble metal integral type silk screen catalyst for CO reduction of NO |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219214A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for hydrogen removal of CO mixed gas by selective oxidation |
| CN102284286A (en) * | 2011-06-30 | 2011-12-21 | 中国科学院福建物质结构研究所 | Preparation method of sol-gel catalyst for deeply removing a little hydrogen in industrial CO gas |
| CN102583374A (en) * | 2012-02-09 | 2012-07-18 | 中国科学院福建物质结构研究所 | Purification process of industrial CO gas for preparing oxalate or carbonic ester |
| CN102649554A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for CO gas oxidative dehydrogenation |
| CN106622225A (en) * | 2016-12-29 | 2017-05-10 | 天津大学 | Photochemical preparation method of single atom Au for catalytic degradation of VOCs |
| CN106914237A (en) * | 2017-02-28 | 2017-07-04 | 清华大学 | A kind of monoatomic preparation method of metal |
| CN107570149A (en) * | 2017-09-19 | 2018-01-12 | 青岛科技大学 | A kind of monatomic method for preparing catalyst using mesoporous TiO 2 as carrier |
| CN107649124A (en) * | 2016-07-25 | 2018-02-02 | 中国科学院大连化学物理研究所 | A kind of single atomic dispersion noble metal catalyst and its application |
-
2018
- 2018-12-07 CN CN201811493884.3A patent/CN109433192B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219214A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for hydrogen removal of CO mixed gas by selective oxidation |
| CN102649554A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for CO gas oxidative dehydrogenation |
| CN102284286A (en) * | 2011-06-30 | 2011-12-21 | 中国科学院福建物质结构研究所 | Preparation method of sol-gel catalyst for deeply removing a little hydrogen in industrial CO gas |
| CN102583374A (en) * | 2012-02-09 | 2012-07-18 | 中国科学院福建物质结构研究所 | Purification process of industrial CO gas for preparing oxalate or carbonic ester |
| CN107649124A (en) * | 2016-07-25 | 2018-02-02 | 中国科学院大连化学物理研究所 | A kind of single atomic dispersion noble metal catalyst and its application |
| CN106622225A (en) * | 2016-12-29 | 2017-05-10 | 天津大学 | Photochemical preparation method of single atom Au for catalytic degradation of VOCs |
| CN106914237A (en) * | 2017-02-28 | 2017-07-04 | 清华大学 | A kind of monoatomic preparation method of metal |
| CN107570149A (en) * | 2017-09-19 | 2018-01-12 | 青岛科技大学 | A kind of monatomic method for preparing catalyst using mesoporous TiO 2 as carrier |
Non-Patent Citations (1)
| Title |
|---|
| 韩冰等: ""单原子催化的最新进展"", 《催化学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110292924A (en) * | 2019-04-16 | 2019-10-01 | 北京氦舶科技有限责任公司 | A kind of methanol low-temperature decomposing catalyst and preparation method thereof |
| CN110124664A (en) * | 2019-06-18 | 2019-08-16 | 中国科学院长春应用化学研究所 | Metal platinum black nanocluster catalyst and preparation method thereof |
| CN111790377A (en) * | 2019-12-26 | 2020-10-20 | 东北石油大学 | Monoatomic catalyst, preparation method and application thereof |
| CN111517278A (en) * | 2020-03-24 | 2020-08-11 | 中南大学 | Ti3C2TxApplication of MXenes non-noble metal heterogeneous catalyst in formic acid dehydrogenation |
| CN112044434A (en) * | 2020-10-20 | 2020-12-08 | 北京单原子催化科技有限公司 | Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof |
| CN112044434B (en) * | 2020-10-20 | 2023-03-28 | 北京单原子催化科技有限公司 | Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof |
| CN113070058A (en) * | 2021-03-04 | 2021-07-06 | 青岛创启新能催化科技有限公司 | Composite carrier monoatomic catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof |
| CN113070058B (en) * | 2021-03-04 | 2023-02-28 | 青岛创启新能催化科技有限公司 | Composite carrier single-atom catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof |
| CN114471543A (en) * | 2022-02-23 | 2022-05-13 | 北京工业大学 | Method for preparing platinum-based noble metal catalyst by wet process |
| CN116116405A (en) * | 2022-11-04 | 2023-05-16 | 佛山东佛表面科技有限公司 | Single-atom cluster type noble metal integral type silk screen catalyst for CO reduction of NO |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109433192B (en) | 2021-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109433192A (en) | A kind of noble metal single atomic dispersion type cleaning catalyst and preparation method thereof | |
| US9469535B2 (en) | Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO2 reforming of methane | |
| Ouyang et al. | Large-scale synthesis of sub-micro sized halloysite-composed CZA with enhanced catalysis performances | |
| CN105562113B (en) | The method of catalyst carrier and loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas | |
| CN108295848A (en) | A kind of preparation method of high-dispersion nano catalyst | |
| CN104399491B (en) | A kind of high temperature resistant methanation catalyst and preparation method thereof | |
| JP2022114919A (en) | Ammonia decomposition catalyst and ammonia decomposition method using the same | |
| CN109126808A (en) | A kind of additive modification copper-based catalysts and preparation method and applications | |
| CN107597119B (en) | Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof | |
| CN103172030A (en) | Oxide powder and preparation method thereof as well as catalyst and carrier thereof | |
| CN108525669A (en) | A kind of high degree of dispersion Silica Nanotube supported nickel catalyst and preparation method thereof | |
| CN108927156A (en) | A kind of alkynes selective hydrogenation support type alloy catalyst and preparation method thereof | |
| CN107321351A (en) | A kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction | |
| CN111229235A (en) | NiO/MgAl2O4Catalyst, preparation method and application thereof | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN107970907A (en) | A kind of nano composite oxide catalyst and its preparation method and application | |
| CN108144610A (en) | The copper-based hydrogenation catalyst of flame injection cracking process preparation and its preparation and application | |
| CN108906044A (en) | A kind of manganese cerium ruthenium composite oxide catalysts and its preparation method and application | |
| JP5660006B2 (en) | Method for producing Co3O4 / CeO2 composite catalyst for exhaust gas purification and catalyst obtained thereby | |
| WO2023035532A1 (en) | Preparation method for la1-xmn1+xo3 | |
| CN108499568B (en) | Nickel-based catalyst for reforming methane by pressurizing carbon dioxide | |
| CN102294249A (en) | Hydrotalcite type catalyst used for carrying out reforming reaction on natural gas and low carbon hydrocarbon (C1-C4) and preparation method thereof | |
| CN109261222A (en) | A kind of preparation method of the high stability bimetallic hollow core core/shell-type catalyst for the reaction of toluene steam reforming | |
| CN106984318B (en) | Bimetal cobalt-based catalyst, preparation method and application | |
| CN110893346A (en) | Bimetallic low-temperature methanation catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |