CN107159261A - A kind of method of utilization Integral electric pyrogenicity wire mesh catalyst catalytic oxidation NO - Google Patents
A kind of method of utilization Integral electric pyrogenicity wire mesh catalyst catalytic oxidation NO Download PDFInfo
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- CN107159261A CN107159261A CN201710384866.0A CN201710384866A CN107159261A CN 107159261 A CN107159261 A CN 107159261A CN 201710384866 A CN201710384866 A CN 201710384866A CN 107159261 A CN107159261 A CN 107159261A
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- distilled water
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 230000003647 oxidation Effects 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002510 pyrogen Substances 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000012153 distilled water Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000011010 flushing procedure Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 27
- 238000002604 ultrasonography Methods 0.000 claims abstract description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 16
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 2
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910001120 nichrome Inorganic materials 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- -1 Iron-chromium-aluminum Chemical compound 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000012298 atmosphere Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000010970 precious metal Substances 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 241000264877 Hippospongia communis Species 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UMWYYMCOBYVEPY-UHFFFAOYSA-N azanide;platinum(2+) Chemical compound [NH2-].[NH2-].[Pt+2] UMWYYMCOBYVEPY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002912 waste gas 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method of utilization Integral electric pyrogenicity wire mesh catalyst catalytic oxidation NO, the catalyst is made by the steps：(1) wire mesh material is placed in acetone ultrasonic oil removing, it is clean with distilled water flushing；Woven wire is placed in ultrasound in NaOH solution again, it is clean with distilled water flushing；Woven wire is finally placed in HNO3In solution ultrasound remove surface oxide, with distilled water flushing it is clean after, dry；(2) pretreated woven wire is placed in pure oxygen and calcined；(3) Pt nanoparticle sols dispersion liquid is sprayed on woven wire after firing, then dried, then be calcined the Integral electric pyrogenicity wire mesh catalyst for obtaining supporting Pt or Pd nano-particles.Active component high degree of dispersion is difficult to reunite and strong with carrier binding ability in the catalyst that the present invention is used, with noble metal dosage it is few, it is active it is high, be powered can spontaneous heating the characteristics of so that the method for the catalytic oxidation NO have energy-conservation, efficiently, the characteristic of fast reaction.
Description
Technical field
The present invention relates to a kind of method of utilization Integral electric pyrogenicity wire mesh catalyst catalytic oxidation NO.
Background technology
It is well known that coal-burning power plant, the burning of fossil fuel and ship can all give off substantial amounts of atmosphere pollution, bag
Include NO, NO2、N2O、N2O3、N2O5Etc. a variety of nitrogen oxides (NOX)。NOXIt is the main original for causing acid rain, haze, photochemical fog
Cause, therefore turn into the focus of social concerns about the technical research for reducing discharged nitrous oxides.
NOXThe main component of waste gas is NO, and NO more inertia, purification condition is more harsh.But if first NO is oxidized to
NO2, then NO can be greatly improvedXGovernance efficiency.Such as in SCR reactions, NO2Can be fast with reducing agent very at low temperature again
Speed is reacted, in addition NO2Also it is very easy to by alkali liquor absorption, passes through simple low temperature liquid phase absorption techniques, you can reach denitration
Purpose.And the core of these technologies is NO catalysis oxidation.At present, NO oxidations catalyst used mainly has granular pattern and entirety
Formula catalyst.For granular pattern catalyst, such as Chinese patent (CN102274733.A) is using manganese oxide and cupric oxide as activearm
Divide, using titanium dioxide as carrier, activity of the catalyst in low temperature is significantly improved, while also overcoming catalyst because of activearm
It is point single and easy by vapor and SO2The problem of influence.But beaded catalyst can be produced in strong exothermal reaction " focus " and
Localized hyperthermia, catalyst is easily sintered and inactivated, and beds pressure drop is high, is not suitable for the NO gases of processing high-speed.
And conventional integral catalyzer is using cordierite honeycomb ceramic as carrier, such as Chinese patent (CN105126822.A) is with cordierite
Ceramic honey comb is carrier, and boehmite is binding agent, and manganese oxide catalyst is coated on cordierite carrier, the monoblock type oxygen
Change Mn catalyst preparation method is easier, and cost is relatively low, the catalysis oxidation available for low concentration of NO.But ceramic honey comb matrix is deposited
The shortcomings of mass transfer and heat transfer efficiency be not high, mechanical strength is not high, structure modulability is poor.In addition, for high temperature NO catalysis
Oxidation, often needs the mode of external heat source, such as：Fuel combustion is heated, resistance stove heat etc..This mode of heating energy consumption is very
Greatly, and capacity usage ratio is low.And the catalyst using metallic substrates as carrier then has low pressure drop, high mechanical strength, electric conductivity excellent
The features such as good, high heat conductance and structure controllability, therefore be considered as convenient combustion catalysis agent carrier.
The content of the invention
It is an object of the invention to provide a kind of side of utilization Integral electric pyrogenicity wire mesh catalyst catalytic oxidation NO
Method, the method for preparing catalyst that this method is used is simple, in catalyst active component effective to the material of any metal structure
High degree of dispersion is difficult to reunite and strong with carrier binding ability, with noble metal dosage it is few, it is active it is high, be powered can spontaneous heating spy
Point so that the method for the catalytic oxidation NO has energy-conservation, the efficient, characteristic of fast reaction.
For achieving the above object, the technical solution adopted by the present invention is as follows：
A kind of method of utilization Integral electric pyrogenicity wire mesh catalyst catalytic oxidation NO, described Integral electric pyrogenicity
Wire mesh catalyst is made by the steps：
(1) surface preparation of metallic substrates：Wire mesh material is placed in ultrasound 5-30min oil removings in acetone, with steaming
Distilled water is rinsed well；Woven wire is placed in ultrasound 5-30min in 5-10wt% NaOH solution again, it is dry with distilled water flushing
Only；Woven wire is finally placed in 5-10wt% HNO3Ultrasound 5-30min removes the oxide on surface in solution, uses distilled water
After rinsing well, 0.5-5h is dried at a temperature of 60-150 DEG C；
(2) preparation of wire surface coating：Pretreated woven wire is placed in pure oxygen and forged in 800-1200 DEG C
Burn 0.5-12h；
(3) Pt nanoparticle sols dispersion liquid is sprayed on woven wire after firing, then in dry at 50-150 DEG C
Dry 0.5-5h, then in 400-800 DEG C of roasting temperature 3-8h, so as to obtain supporting Pt or the Integral electric pyrogenicity of Pd nano-particles
The load capacity of wire mesh catalyst, wherein Pt or Pd is 0.01-1.0wt%.
In the present invention, the material of woven wire can be Stainless steel 316, Stainless steel 316 L, stainless steel 314, stainless steel
314L, nichrome, Aludirome, chromium aluminium molybdenum alloys etc., preferably Aludirome.
In the step (1), ultrasonic time is preferably 15-30min.Drying temperature is preferably 100-120 DEG C, drying time
Preferably 1-2h.
In the step (2), calcining heat is preferably 800-1200 DEG C, and calcination time is preferably 0.5-10h.
In the step (3), Pt nanoparticle sols dispersion liquid can be prepared via a method which：Take a certain amount of two nitrous
Base diamino platinum, adds a certain amount of oleyl amine and oleic acid, in a nitrogen atmosphere, and in reacting 1-6h at 100-300 DEG C, products therefrom is passed through
After ethanol centrifugation, precipitation, it is scattered in n-hexane, obtains Pt nanoparticle sol dispersion liquids.
Further, the ratio between cumulative volume of the quality of dinitroso diammonia platinum and oleyl amine and oleic acid is preferably 0.01-0.1g：1-
The volume ratio of 30mL, oleyl amine and oleic acid is preferably 1-5：0.5-2.
In the step (3), sintering temperature is preferably 450-600 DEG C, and roasting time is preferably 3-6h.
Integral electric pyrogenicity wire mesh catalyst is prepared with conventional NO catalyst for catalytic oxidation in the present invention essence
Difference, using the noble metal nano particles colloidal sol of previously prepared high activity, by atomized spray technology, catalyst nano grain
Son is sprayed directly into metal substrate surface, and by the guiding of surfactant, noble metal nano particles can in metal component surface
With self assembly, being formed after the noble metal nano monomolecular film of high degree of dispersion, low-temperature bake to combine in metallic substrates to high intensity
Surface.
Catalytic oxidation NO reaction of the present invention is carried out on gas-solid phase reaction device, is specially：By Integral electric pyrogenicity
Wire mesh catalyst connects wire connection D.C. regulated power supply, and by changing the electric current of D.C. regulated power supply, monoblock type is electroluminescent
Hot wire mesh catalyst can generate heat rapidly, so as to reach the temperature of catalysis oxidation, be passed through NO gases and reacted, course of reaction
Needed for heat from access circuit in Integral electric pyrogenicity wire mesh catalyst itself produced by heat, without outer
Heating source.Moreover, the energy consumption required for catalysis oxidation is extremely low.
The beneficial effects of the invention are as follows：(1) preparation method of catalyst of the present invention is easy, and hardware shape will not
Ask, to all kinds of metallic substrates strong applicabilities；(2) active component can be in metal substrate surface high degree of dispersion；(3) catalyst made from
Electroluminescent hot heating effect is good, capacity usage ratio is high, required energy consumption is extremely low；(4) the monoblock type wire mesh catalyst obtained by
Heat endurance is high, good mechanical property；(5) catalytic oxidation NO activity is high, and response is fast, and higher turn can be reached under relatively low power
Rate.
Embodiment
In order to further illustrate the present invention, specific examples below is enumerated, but do not limit the scope of the invention.
Embodiment 1
Iron-chromium-aluminum metal silk (wherein chromium：23-26%, aluminium：4.5-6.5%, remaining is iron) surface preparation：Take certain
The wire of length, is rolled into helical form.Wire is placed in acetone, ultrasonic 30min is clean with distilled water flushing.Again by gold
Category silk is placed in ultrasound 30min in 10wt% NaOH solution, clean with distilled water flushing.Wire is finally placed in 10wt%'s
HNO3Ultrasound 30min in solution, 110 DEG C dry 2hs clean with distilled water flushing.
The preparation of iron-chromium-aluminum metal silk table finishing coat：Woven wire is placed in pure oxygen atmosphere, in 950 DEG C, 3h is calcined.
The preparation of precious metals pt nano-particle：0.0173g dinitroso diammonia platinums are weighed, 2mL oleyl amines and 1mL oil is added
Under acid, nitrogen atmosphere, magnetic agitation, 200 DEG C of reaction 3h.It is cooled to after room temperature, is transferred in centrifuge tube.Add 3 times of volumes without
Water-ethanol, is centrifuged (6000rpm, 5min), and precipitation is repeated 2-3 times.Finally it is dispersed in 10mL n-hexanes.
1mL Pt nano-particle n-hexane dispersion liquids are taken to be sprayed on woven wire (quality is 2.0828g), 110 DEG C of dryings
2h, then at 500 DEG C of roasting 5h, obtains the monoblock type wire mesh catalyst that Pt load capacity is 0.05wt%.
The monoblock type wire mesh catalyst that the present embodiment is obtained is placed in reaction tube, and direct current is accessed in two ends after connecting wire
Voltage-stabilized power supply, by changing the electric current of D.C. regulated power supply, so as to realize electroluminescent hot mode of heating, lives for catalytic oxidation NO
Property test.
Embodiment 2
Iron-chromium-aluminum metal silk (wherein chromium：23-26%, aluminium：4.5-6.5%, remaining is iron) surface preparation：Take certain
The wire of length, is rolled into helical form.Wire is placed in acetone, ultrasonic 30min is clean with distilled water flushing.Again by gold
Category silk is placed in ultrasound 30min in 10wt% NaOH solution, clean with distilled water flushing.Wire is finally placed in 10wt%'s
HNO3Ultrasound 30min in solution, 110 DEG C dry 2hs clean with distilled water flushing.
The preparation of iron-chromium-aluminum metal silk table finishing coat：Woven wire is placed in pure oxygen atmosphere, in 950 DEG C, 3h is calcined.
The preparation of precious metals pt nano-particle：0.0346g dinitroso diammonia platinums are weighed, 4mL oleyl amines and 2mL oil is added
Under acid, nitrogen atmosphere, magnetic agitation, 200 DEG C of reaction 3h.It is cooled to after room temperature, is transferred in centrifuge tube.Add 3 times of volumes without
Water-ethanol, is centrifuged (6000rpm, 5min), and precipitation is repeated 2-3 times.Finally it is dispersed in 10mL n-hexanes.
1mL Pt nano-particle n-hexane dispersion liquids are taken to be sprayed on woven wire (quality is 2.0832g), 110 DEG C of dryings
2h, then at 500 DEG C of roasting 5h, obtains the monoblock type wire mesh catalyst that Pt load capacity is 0.1wt%.
The monoblock type wire mesh catalyst that the present embodiment is obtained is placed in reaction tube, and direct current is accessed in two ends after connecting wire
Voltage-stabilized power supply, by changing the electric current of D.C. regulated power supply, so as to realize electroluminescent hot mode of heating, lives for catalytic oxidation NO
Property test.
Embodiment 3
Iron-chromium-aluminum metal silk (wherein chromium：23-26%, aluminium：4.5-6.5%, remaining is iron) surface preparation：Take certain
The wire of length, is rolled into helical form.Wire is placed in acetone, ultrasonic 30min is clean with distilled water flushing.Again by gold
Category silk is placed in ultrasound 30min in 10wt% NaOH solution, clean with distilled water flushing.Wire is finally placed in 10wt%'s
HNO3Ultrasound 30min in solution, 110 DEG C dry 2hs clean with distilled water flushing.
The preparation of iron-chromium-aluminum metal silk table finishing coat：Woven wire is placed in pure oxygen atmosphere, in 950 DEG C, 3h is calcined.
The preparation of precious metals pt nano-particle：0.0692g dinitroso diammonia platinums are weighed, 9mL oleyl amines and 3mL oil is added
Under acid, nitrogen atmosphere, magnetic agitation, 200 DEG C of reaction 3h.It is cooled to after room temperature, is transferred in centrifuge tube.Add 3 times of volumes without
Water-ethanol, is centrifuged (6000rpm, 5min), and precipitation is repeated 2-3 times.Finally it is dispersed in 10mL n-hexanes.
1mL Pt nano-particle n-hexane dispersion liquids are taken to be sprayed on woven wire (quality is 2.0832g), 110 DEG C of dryings
2h, then at 500 DEG C of roasting 5h, obtains the monoblock type wire mesh catalyst that Pt load capacity is 0.2wt%.
The monoblock type wire mesh catalyst that the present embodiment is obtained is placed in reaction tube, and direct current is accessed in two ends after connecting wire
Voltage-stabilized power supply, by changing the electric current of D.C. regulated power supply, so as to realize electroluminescent hot mode of heating, lives for catalytic oxidation NO
Property test.
Embodiment 4
Iron-chromium-aluminum metal silk (wherein chromium：23-26%, aluminium：4.5-6.5%, remaining is iron) surface preparation：Take certain
The wire of length, is rolled into helical form.Wire is placed in acetone, ultrasonic 30min is clean with distilled water flushing.Again by gold
Category silk is placed in ultrasound 30min in 10wt% NaOH solution, clean with distilled water flushing.Wire is finally placed in 10wt%'s
HNO3Ultrasound 30min in solution, 110 DEG C dry 2hs clean with distilled water flushing.
The preparation of iron-chromium-aluminum metal silk table finishing coat：Woven wire is placed in pure oxygen atmosphere, in 850 DEG C, 3h is calcined.
The preparation of precious metals pt nano-particle：0.0692g dinitroso diammonia platinums are weighed, 9mL oleyl amines and 3mL oil is added
Under acid, nitrogen atmosphere, magnetic agitation, 200 DEG C of reaction 3h.It is cooled to after room temperature, is transferred in centrifuge tube.Add 3 times of volumes without
Water-ethanol, is centrifuged (6000rpm, 5min), and precipitation is repeated 2-3 times.Finally it is dispersed in 10mL n-hexanes.
1mL Pt nano-particle n-hexane dispersion liquids are taken to be sprayed on woven wire (quality is 2.0832g), 110 DEG C of dryings
2h, then at 500 DEG C of roasting 5h, obtains the monoblock type wire mesh catalyst that Pt load capacity is 0.2wt%.
The monoblock type wire mesh catalyst that the present embodiment is obtained is placed in reaction tube, and direct current is accessed in two ends after connecting wire
Voltage-stabilized power supply, by changing the electric current of D.C. regulated power supply, so as to realize electroluminescent hot mode of heating, lives for catalytic oxidation NO
Property test.
Embodiment 5
Iron-chromium-aluminum metal silk (wherein chromium：23-26%, aluminium：4.5-6.5%, remaining is iron) surface preparation：Take certain
The wire of length, is rolled into helical form.Wire is placed in acetone, ultrasonic 30min is clean with distilled water flushing.Again by gold
Category silk is placed in ultrasound 30min in 10wt% NaOH solution, clean with distilled water flushing.Wire is finally placed in 10wt%'s
HNO3Ultrasound 30min in solution, 110 DEG C dry 2hs clean with distilled water flushing.
The preparation of iron-chromium-aluminum metal silk table finishing coat：Woven wire is placed in pure oxygen atmosphere, in 900 DEG C, 3h is calcined.
The preparation of precious metals pt nano-particle：0.0692g dinitroso diammonia platinums are weighed, 9mL oleyl amines and 3mL oil is added
Under acid, nitrogen atmosphere, magnetic agitation, 200 DEG C of reaction 3h.It is cooled to after room temperature, is transferred in centrifuge tube.Add 3 times of volumes without
Water-ethanol, is centrifuged (6000rpm, 5min), and precipitation is repeated 2-3 times.Finally it is dispersed in 10mL n-hexanes.
1mL Pt nano-particle n-hexane dispersion liquids are taken to be sprayed on woven wire (quality is 2.0832g), 110 DEG C of dryings
2h, then at 500 DEG C of roasting 5h, obtains the monoblock type wire mesh catalyst that Pt load capacity is 0.2wt%.
The monoblock type wire mesh catalyst that the present embodiment is obtained is placed in reaction tube, and direct current is accessed in two ends after connecting wire
Voltage-stabilized power supply, by changing the electric current of D.C. regulated power supply, so as to realize electroluminescent hot mode of heating, lives for catalytic oxidation NO
Property test.
Embodiment 6
Iron-chromium-aluminum metal silk (wherein chromium：23-26%, aluminium：4.5-6.5%, remaining is iron) surface preparation：Take certain
The wire of length, is rolled into helical form.Wire is placed in acetone, ultrasonic 30min is clean with distilled water flushing.Again by gold
Category silk is placed in ultrasound 30min in 10wt% NaOH solution, clean with distilled water flushing.Wire is finally placed in 10wt%'s
HNO3Ultrasound 30min in solution, 110 DEG C dry 2hs clean with distilled water flushing.
The preparation of iron-chromium-aluminum metal silk table finishing coat：Woven wire is placed in pure oxygen atmosphere, in 1000 DEG C, 3h is calcined.
The preparation of precious metals pt nano-particle：0.0692g dinitroso diammonia platinums are weighed, 9mL oleyl amines and 3mL oil is added
Under acid, nitrogen atmosphere, magnetic agitation, 200 DEG C of reaction 3h.It is cooled to after room temperature, is transferred in centrifuge tube.Add 3 times of volumes without
Water-ethanol, is centrifuged (6000rpm, 5min), and precipitation is repeated 2-3 times.Finally it is dispersed in 10mL n-hexanes.
1mL Pt nano-particle n-hexane dispersion liquids are taken to be sprayed on woven wire (quality is 2.0832g), 110 DEG C of dryings
2h, then at 500 DEG C of roasting 5h, obtains the monoblock type wire mesh catalyst that Pt load capacity is 0.2wt%.
The monoblock type wire mesh catalyst that the present embodiment is obtained is placed in reaction tube, and direct current is accessed in two ends after connecting wire
Voltage-stabilized power supply, by changing the electric current of D.C. regulated power supply, so as to realize electroluminescent hot mode of heating, lives for catalytic oxidation NO
Property test.
Embodiment 7
Iron-chromium-aluminum metal silk (wherein chromium：23-26%, aluminium：4.5-6.5%, remaining is iron) surface preparation：Take certain
The wire of length, is rolled into helical form.Wire is placed in acetone, ultrasonic 30min is clean with distilled water flushing.Again by gold
Category silk is placed in ultrasound 30min in 10wt% NaOH solution, clean with distilled water flushing.Wire is finally placed in 10wt%'s
HNO3Ultrasound 30min in solution, 110 DEG C dry 2hs clean with distilled water flushing.
The preparation of iron-chromium-aluminum metal silk table finishing coat：Woven wire is placed in pure oxygen atmosphere, in 950 DEG C, 1h is calcined.
The preparation of precious metals pt nano-particle：0.0692g dinitroso diammonia platinums are weighed, 9mL oleyl amines and 3mL oil is added
Under acid, nitrogen atmosphere, magnetic agitation, 200 DEG C of reaction 3h.It is cooled to after room temperature, is transferred in centrifuge tube.Add 3 times of volumes without
Water-ethanol, is centrifuged (6000rpm, 5min), and precipitation is repeated 2-3 times.Finally it is dispersed in 10mL n-hexanes.
1mL Pt nano-particle n-hexane dispersion liquids are taken to be sprayed on woven wire (quality is 2.0832g), 110 DEG C of dryings
2h, then at 500 DEG C of roasting 5h, obtains the monoblock type wire mesh catalyst that Pt load capacity is 0.2wt%.
The monoblock type wire mesh catalyst that the present embodiment is obtained is placed in reaction tube, and direct current is accessed in two ends after connecting wire
Voltage-stabilized power supply, by changing the electric current of D.C. regulated power supply, so as to realize electroluminescent hot mode of heating, lives for catalytic oxidation NO
Property test.
Embodiment 8
Iron-chromium-aluminum metal silk (wherein chromium：23-26%, aluminium：4.5-6.5%, remaining is iron) surface preparation：Take certain
The wire of length, is rolled into helical form.Wire is placed in acetone, ultrasonic 30min is clean with distilled water flushing.Again by gold
Category silk is placed in ultrasound 30min in 10wt% NaOH solution, clean with distilled water flushing.Wire is finally placed in 10wt%'s
HNO3Ultrasound 30min in solution, 110 DEG C dry 2hs clean with distilled water flushing.
The preparation of iron-chromium-aluminum metal silk table finishing coat：Woven wire is placed in pure oxygen atmosphere, in 950 DEG C, 5h is calcined.
The preparation of precious metals pt nano-particle：0.0692g dinitroso diammonia platinums are weighed, 9mL oleyl amines and 3mL oil is added
Under acid, nitrogen atmosphere, magnetic agitation, 200 DEG C of reaction 3h.It is cooled to after room temperature, is transferred in centrifuge tube.Add 3 times of volumes without
Water-ethanol, is centrifuged (6000rpm, 5min), and precipitation is repeated 2-3 times.Finally it is dispersed in 10mL n-hexanes.
1mL Pt nano-particle n-hexane dispersion liquids are taken to be sprayed on woven wire (quality is 2.0832g), 110 DEG C of dryings
2h, then at 500 DEG C of roasting 5h, obtains the monoblock type wire mesh catalyst that Pt load capacity is 0.2wt%.
The monoblock type wire mesh catalyst that the present embodiment is obtained is placed in reaction tube, and direct current is accessed in two ends after connecting wire
Voltage-stabilized power supply, by changing the electric current of D.C. regulated power supply, so as to realize electroluminescent hot mode of heating, lives for catalytic oxidation NO
Property test.
Embodiment 9
Iron-chromium-aluminum metal silk (wherein chromium：23-26%, aluminium：4.5-6.5%, remaining is iron) surface preparation：Take certain
The wire of length, is rolled into helical form.Wire is placed in acetone, ultrasonic 30min is clean with distilled water flushing.Again by gold
Category silk is placed in ultrasound 30min in 10wt% NaOH solution, clean with distilled water flushing.Wire is finally placed in 10wt%'s
HNO3Ultrasound 30min in solution, 110 DEG C dry 2hs clean with distilled water flushing.
The preparation of iron-chromium-aluminum metal silk table finishing coat：Woven wire is placed in pure oxygen atmosphere, in 950 DEG C, 10h is calcined.
The preparation of precious metals pt nano-particle：0.0692g dinitroso diammonia platinums are weighed, 9mL oleyl amines and 3mL oil is added
Under acid, nitrogen atmosphere, magnetic agitation, 200 DEG C of reaction 3h.It is cooled to after room temperature, is transferred in centrifuge tube.Add 3 times of volumes without
Water-ethanol, is centrifuged (6000rpm, 5min), and precipitation is repeated 2-3 times.Finally it is dispersed in 10mL n-hexanes.
1mL Pt nano-particle n-hexane dispersion liquids are taken to be sprayed on woven wire (quality is 2.0832g), 110 DEG C of dryings
2h, then at 500 DEG C of roasting 5h, obtains the monoblock type wire mesh catalyst that Pt load capacity is 0.2wt%.
The monoblock type wire mesh catalyst that the present embodiment is obtained is placed in reaction tube, and direct current is accessed in two ends after connecting wire
Voltage-stabilized power supply, by changing the electric current of D.C. regulated power supply, so as to realize electroluminescent hot mode of heating, lives for catalytic oxidation NO
Property test.
Embodiment 10
The sample that each embodiment is obtained, for testing catalytic oxidation activity.With NO：500ppm catalysis oxidation conducts
Probe reaction, is 6 × 10 in air speed4Catalytic oxidation performance evaluation is carried out under conditions of ml/gh.Monoblock type woven wire is urged
Agent is placed in reactor, and catalyst two ends are respectively turned on wire and are connected with D.C. regulated power supply, is changed electric current, is made catalyst fast
Speed heating, so that the temperature required for reaching catalysis oxidation, is passed through NO gases and is reacted.
Required power the results are shown in Table 1 as catalytic oxidation performance evaluation criterion when reaching 60% using NO oxidizabilities.
The wire mesh catalyst CO catalytic oxidation performance evaluation of table 1
Claims (10)
1. a kind of method of utilization Integral electric pyrogenicity wire mesh catalyst catalytic oxidation NO, it is characterised in that：Described is whole
The electroluminescent hot wire mesh catalyst of body formula is made by the steps：
(1) surface preparation of metallic substrates：Wire mesh material is placed in ultrasound 5-30min oil removings in acetone, distilled water is used
Rinse well；Woven wire is placed in ultrasound 5-30min in 5-10wt% NaOH solution again, it is clean with distilled water flushing；Most
Woven wire is placed in 5-10wt% HNO afterwards3Ultrasound 5-30min removes the oxide on surface in solution, uses distilled water flushing
After clean, 0.5-5h is dried at a temperature of 60-150 DEG C；
(2) preparation of wire surface coating：Pretreated woven wire is placed in pure oxygen in 800-1200 DEG C of calcining
0.5-12h；
(3) Pt nanoparticle sols dispersion liquid is sprayed on woven wire after firing, then in dry at 50-150 DEG C
0.5-5h, then in 400-800 DEG C of roasting temperature 3-8h, so as to obtain the Integral electric pyrogenicity gold of supporting Pt or Pd nano-particles
Category mesh catalyst, wherein Pt or Pd load capacity are 0.01-1.0wt%.
2. the method as described in claim 1, it is characterised in that：The catalytic oxidation NO reaction is enterprising in gas-solid phase reaction device
OK, it is specially：Integral electric pyrogenicity wire mesh catalyst is connected into wire connection D.C. regulated power supply, it is steady by changing direct current
The electric current of voltage source, Integral electric pyrogenicity wire mesh catalyst can generate heat rapidly, so as to reach the temperature of catalysis oxidation, be passed through
NO gases are reacted, Integral electric pyrogenicity wire mesh catalyst of the heat needed for course of reaction in access circuit
Heat produced by itself, without external heat source.
3. method as claimed in claim 1 or 2, it is characterised in that：The material of woven wire is Stainless steel 316, stainless steel
316L, stainless steel 314, stainless steel 314L, nichrome, Aludirome or chromium aluminium molybdenum alloys.
4. method as claimed in claim 3, it is characterised in that：The material of woven wire is Aludirome.
5. method as claimed in claim 1 or 2, it is characterised in that：In the step (1), ultrasonic time is 15-30min.
6. method as claimed in claim 1 or 2, it is characterised in that：In the step (1), drying temperature is 100-120 DEG C,
Drying time is 1-2h.
7. method as claimed in claim 1 or 2, it is characterised in that：In the step (2), calcining heat is 800-1200 DEG C,
Calcination time is 0.5-10h.
8. method as claimed in claim 1 or 2, it is characterised in that：In the step (3), Pt nanoparticle sol dispersion liquids
It is prepared via a method which：A certain amount of dinitroso diammonia platinum is taken, a certain amount of oleyl amine and oleic acid are added, in nitrogen atmosphere
Under, in reacting 1-6h at 100-300 DEG C, products therefrom centrifuges through ethanol, precipitate after, be scattered in n-hexane, obtain Pt nanometers
Colloidal sol dispersion liquid.
9. method as claimed in claim 8, it is characterised in that：The quality of dinitroso diammonia platinum and the totality of oleyl amine and oleic acid
The ratio between product is 0.01-0.1g：The volume ratio of 1-30mL, oleyl amine and oleic acid is 1-5：0.5-2.
10. method as claimed in claim 1 or 2, it is characterised in that：In the step (3), sintering temperature is 450-600 DEG C,
Roasting time is 3-6h.
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| CN112206784A (en) * | 2020-08-31 | 2021-01-12 | 浙江工业大学 | Application of metal mesh supported metal particle catalyst in reaction for catalytically synthesizing pterostilbene |
| CN112206785A (en) * | 2020-08-31 | 2021-01-12 | 浙江工业大学 | Metal mesh loaded metal particle catalyst and preparation method and application thereof |
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