CN108579743A - A kind of preparation method of the low temperature high activity catalyst of catalysis benzene complete oxidation - Google Patents
A kind of preparation method of the low temperature high activity catalyst of catalysis benzene complete oxidation Download PDFInfo
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- CN108579743A CN108579743A CN201810250404.4A CN201810250404A CN108579743A CN 108579743 A CN108579743 A CN 108579743A CN 201810250404 A CN201810250404 A CN 201810250404A CN 108579743 A CN108579743 A CN 108579743A
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 230000003647 oxidation Effects 0.000 title claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 33
- 230000000694 effects Effects 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 229910004625 Ce—Zr Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003381 stabilizer Substances 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 60
- 229910052697 platinum Inorganic materials 0.000 description 19
- 229910052593 corundum Inorganic materials 0.000 description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229910018879 Pt—Pd Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- SBMYBOVJMOVVQW-UHFFFAOYSA-N 2-[3-[[4-(2,2-difluoroethyl)piperazin-1-yl]methyl]-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCN(CC1)CC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SBMYBOVJMOVVQW-UHFFFAOYSA-N 0.000 description 1
- 229910003609 H2PtCl4 Inorganic materials 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 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
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000005406 washing 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of the low temperature high activity catalyst of catalysis benzene complete oxidation, carrier is first added in the solution, fully heating reduction is carried out again after absorption chloroplatinic acid, specific method includes quantitatively weighing carrier, it immerses in ethylene glycol, then chloroplatinic acid aqueous solution is added, add NaOH aqueous solutions adjustment solution pH, stir under room temperature, allow in the solution chloroplatinic acid reach on carrier saturation absorption and etc.;Additional inorganic reducing agent need not be added in process of the present invention need not also add macromolecule stabilizer, and the content of precious metals pt is low in catalyst, catalyst preparation process is simple, and catalyst is easy to carry out and implement without high-temperature roasting and hydrogen reducing;Catalyst activity is high, stability is good.
Description
Technical field
A kind of preparation method of the low temperature high activity catalyst of catalysis benzene complete oxidation of the disclosure of the invention, belongs to low
Concentration volatile organism benzene is catalyzed completely burned processing technology field.
Background technology
Benzene is a kind of typical VOCs (volatile organism), and the chemical constitution of benzene is sufficiently stable, in natural environmental condition
Under it is not degradable, to soil, water body and air can result in persistently and seriously pollute, the harm of animals and plants and the mankind are not allowed
Ignore.If humans and animals Long Term Contact benzene can cause great damage to blood, causes slow poisoning, even result in death.
The discharge of wastewater containing benzene or exhaust gas is frequently encountered in industrial production and daily life, in order to avoid these harmful substances are largely arranged
Environment be rivals in a contest with ecological destruction, National Environmental Protection Agency has formulated relevant discharge standard (GB16297-1996《Atmosphere pollution
Comprehensive discharge standard》).
Processing for waste gas containing benzene, there are many methods at present, such as condensation method, absorption method, biotransformation method, heating power combustion
Burning method and Production by Catalytic Combustion Process etc., wherein catalytic oxidation are acknowledged as one of most effective means, and ([1] Li Weibin, Gong Hao, is urged
Change the latest developments [J] of burning removal VOCs pollutants, Acta PhySico-Chimica Sinica, 2010,26 (4):885-894.).Catalysis burning
Method is lower than heating power combustion method reaction temperature, usually within 400 DEG C, therefore the secondary pollution that not will produce nitrogen oxides etc..
Crucial technology is the preparation method of high activity and high stability catalyst in Production by Catalytic Combustion Process application process.Usually
It uses Pt as active component, but is differed greatly with the catalyst performance obtained by different carriers or different preparation methods.
For example, using tin oxide as carrier loaded Pt, for Pt/SnO2, to the catalytic activity of benzene oxidatoin, when benzene conversion ratio is up to 90%
Temperature is 320 DEG C, adds suitable CeO2This temperature value is reduced to 256 DEG C afterwards.(such as [2] kingly way, stannic oxide are carrier
Rare earth oxide is to the catalytic activity rare earths of benzene complete oxidation, and 1989, (04):32-35)Pt/Al2O3It is that preferable benzene purification is urged
Agent, when Pt contents are 0.01%, range of reaction temperature is 360-400 DEG C of ([3] Jin Yun etc., in Pt/Al2O3Benzene on catalyst
Dynamic (dynamical) influence [J] the Chemical Journal of Chinese Universities of minus 0.9 grade of interior diffusion couple, 1991 (01):84-88.)
([4] Kim H S, Kim T W, Koh H L, Lee S H, Min B R, the Complete benzene such as Kim
oxidation over Pt-Pd bimetal catalyst supported onγ-alumina:influence of Pt-
Pd ratio on the catalytic activity[J],Applied Catalysis A:General,2005,280:
Pt-Pd two-component metals 125-131.) are supported on γ-Al2O3On, it is anti-with the catalyst of 0.3wt.%Pt 2wt.%Pd contents
It answers active highest, reaction temperature that can keep benzene complete oxidation, catalyst stability test 32 hours when being 250 DEG C, transports
Row about reduced by 10% to 50 hours catalyst activities, catalytic activity and stability the urging compared with single-activity component of bimetallic component
Agent is good.
([5] Yang P, Li J, Cheng Z, Zuo S, Promoting effects of Ce the and Pt such as Yang Peng
addition on the destructive performances of V2O5/gamma-Al2O3for catalytic
combustion of benzene[J],Applied Catalysis a-General,2017,542:38-46.) report recently
The best catalyst 0.3%Pt/10%Ce-10%V/ γ-Al of performance that they are developed2O3It is 1000ppm in benzene concentration,
Air speed is 20000h-1Under the conditions of, for the T of the treating technology reaction of benzene90%Temperature is 235 DEG C.Catalyst preparation process
Middle carrier is mainly using γ-Al2O3, recycle hydrazine hydrate reduction method to obtain reduction-state by three dipping process respectively
Active component platinum.The shortcomings that its catalyst preparation process is:Step is more, will produce containing nitrogen compound in waste water after reduction.
Current already clear restoring method being affected for Pt particle surface properties, Liu Zhimin et al. ([6] Liu Zhi
It is quick, Li Xiaohong, Chen Zhijian, Ying Pinliang, Feng Zhaochi, Li Can, Pt/Al2O3Shadow of the catalyst reduction method to Pt particle surface properties
Ring [J] chemistry of fuel journals, 2009 (02):205-211.) compare in detail with hydrogen reduction method and sodium formate solution reduction method
The obtained difference on catalyst structure and performance.
Therefore a key technology of the excellent supported Pt catalysts of processability is exactly the restoring method of catalyst.With
The ethylene glycol with stabilization, easily removed is that the reduction method of solvent is to have developed a kind of method in recent years, easily controllable metal
Grain size and dispersion.The NaBH stablized such as Wu Feng et al. spent glycols4Reduction method for preparing nanometer Pt/C catalyst ([7] Wu Feng etc., work(
Energy material, 2009,40 (8) 1381), Sun Xibo et al. is used to prepare Pt/CeO2Catalyst ([8] Sun Xibo, Peng Ruosi, Li Shu
Monarch, beam Xiao Ming, Chen Limin pay fame and gain, and Wu Junliang, Ye Daiqi, Pt particle sizes are to Pt/CeO2Catalysis oxidation toluene performance influences
[J], ACTA Scientiae Circumstantiae, 2016:1-13).The former reduction process also needs that NaBH is added4As reducing agent, Pt that the latter obtains
Particle colloidal sols need to be used as stabilizer, catalyst application with PVP (polyvinylpyrrolidone, Polyvinyl Pyrrolidone)
It also needs to be removed remaining stabilizer with roasting method in the process, then be obtained again with hydrogen reducing.
Invention content
The present invention proposes a kind of Pt/Al for preparing and having high reaction activity and stability to the complete oxidation of benzene2O3And Pt/
CeZrOx catalyst methods.It is first adsorbed onto on carrier by the presoma chloroplatinic acid of Pt, then heating is gone back in ethylene glycol solution
Original adjusts catalyst surface performance by adjusting the pH of solution, and then regulates and controls catalyst reaction activity.
The purpose of the present invention is:Using new preparation method, precious metals pt loaded catalyst is prepared, can be realized in height
Waste gas containing benzene is decomposed in temperature less than the complete catalysts oxidation under 200 degrees celsius under space velocities.
The present invention adopts the following technical scheme that realize
A kind of preparation method of the low temperature high activity catalyst of catalysis benzene complete oxidation, is first added and carries in the solution
Body carries out heating reduction again after fully adsorbing chloroplatinic acid, and specific method is:
1) carrier, is quantitatively weighed, immerses in ethylene glycol, chloroplatinic acid aqueous solution is then added, adds NaOH aqueous solution tune
The pH of whole solution, it stirs under room temperature, chloroplatinic acid is allowed to reach saturation absorption on carrier in the solution;
2), above-mentioned solution under nitrogen protection and isothermal condition is heated to reduction, be cooled to room temperature after reduction,
To be separated by solid-liquid separation with the method for centrifugation, and be washed with deionized, obtained powder is vacuum dried, is pressed on tablet press machine
Piece, the particle of screening collection 40-120 mesh, evaluates it in benzene complete oxidation on atmospheric fixed bed catalyst reaction device after grinding
Activity in reaction.
As a further improvement, the weight content 0.1~1% of Pt of the present invention, the carrier is aluminium oxide
Or Ce-Zr solid solution.
As a further improvement, mass ratio ZrO of the present invention2/CeO2=2.
As a further improvement, it is neutral or alkalinity that alumina support of the present invention, which is surface,.
As a further improvement, pH=7~12 of the present invention.
As a further improvement, reaction temperature when benzene conversion ratio of the present invention reaches 99% is 145~195 degrees Celsius,
Catalytic reaction condition is:Catalyst particle size is 40-120 mesh, and a concentration of 1200-7800ppm of benzene, air is oxidant,
Reaction velocity is 6000-42000h-1。
It is characteristic of the invention that:The present invention proposes that a kind of prepare has high reaction activity and stability to the complete oxidation of benzene
Pt/Al2O3With Pt/CeZrOx catalyst methods, need not add additional inorganic reducing agent in the process need not also add height
Stabilizer molecule, the content of precious metals pt is low in catalyst, catalyst preparation process is simple, and catalyst is without high-temperature roasting and hydrogen
Gas restores, and is easy to carry out and implement;Catalyst activity is high, stability is good.Prepared Pt/Al2O3With Pt/CeZrOx catalyst energy
Realize that complete catalysts oxidation under the conditions of high-speed for waste gas containing benzene under 145~195 degrees celsius of temperature decomposes.
Description of the drawings
Fig. 1 is 0.5%Pt/Al2O3(N) catalyst is for benzene complete oxidation long-play result schematic diagram;
Fig. 2 .0.5%Pt/Al2O3(B11) catalyst is for benzene complete oxidation long-play result schematic diagram.
Specific implementation mode
Technical scheme of the present invention is further described below by specific embodiment:
Embodiment 1
Weigh the ground Al of 2.0g2O3Surface is in alkalinity (pH=8.6, La2O3(4.1%)), it is added to 50mL ethylene glycol
In solution, magnetic agitation pipettes 2mL H2PtCl4(1gPt/100mL), theoretical negative carrying capacity are 1.0wt%.3h is stirred at room temperature.Body
Be pH value be 7.It is heated to 160 DEG C of reflux 8h in the case of nitrogen protection, is cooled to room temperature.Reaction was completed that bottom portion has is yellowish-brown for reaction
Color precipitates, and reaction solution is yellowish-brown suspension.Water washing is added to centrifuge four times, no Cl-In the solution, ethyl alcohol washs 1 time, is put into
100 DEG C of oven drying 8h, obtain grey powder.Again by powder tabletting, crushing, screening, certain granules degree (such as 40-60 is collected
Mesh, 60-80 mesh or 80-120 mesh) Sample storage is spare.Catalyst is denoted as Pt/Al2O3(B7)。
Embodiment 2~4
Other conditions are with embodiment 1, except that H is added2PtCl4NaOH solution is added after solution, when being stirred at room temperature will
The pH value of solution adjusts separately to the catalyst obtained by 9,11,12 and is denoted as Pt/Al respectively2O3(B9)、Pt/Al2O3(B11)、
Pt/Al2O3(B12)。
Embodiment 5~7
Other conditions are with embodiment 3, except that the content of Pt is respectively 0.1%, 0.3% and 0.5%, it is obtained
Catalyst is denoted as 0.1%Pt/Al respectively2O3(B11), 0.3%Pt/Al2O3(B11), 0.5%Pt/Al2O3(B11)。
Embodiment 8
Other conditions are with embodiment 3, except that using CeO2-ZrO2 solid solution CeZrOx (ZrO2/CeO2=2 (matter
Measure ratio)) it is used as carrier, obtained catalyst to be denoted as 1%Pt/CeZrOx.
Embodiment 9~10
Other conditions are with embodiment 8, except that the content of Pt is respectively 0.5% and 0.25%, obtained catalysis
Agent is denoted as 0.5%Pt/CeZrOx and 0.25%Pt/CeZrOx respectively.
Embodiment 11
Other conditions are with embodiment 3, except that being in neutrality the chromatography Al of (pH=7.0 ± 0.5) using surface2O3,
The content of Pt is 0.5%, and obtained catalyst is denoted as 0.5%Pt/Al2O3(N)。
Embodiment 12~15
Catalyst (40-60 mesh) 0.14mL prepared by Example 1~4 respectively, is fitted into fixed bed reactors, is used for
The complete oxidation of benzene, reaction condition are:Benzene concentration is 2800ppm, air speed 22000h-1.Gas chromatographic detection analyzes tail
The content of benzene in gas determines reaction conversion ratio by the peak area of benzene before and after reaction, tests and react conversion under condition of different temperatures
Rate.Several characteristic temperatures of benzene oxidatoin are listed in Table 1 below.
Catalysis of the alumina load Pt catalyst for the complete oxidation of benzene under different conditions of 1. solution alkaline of table
Activity
Example | 12 | 13 | 14 | 15 |
Catalyst | Pt/Al2O3(B7) | Pt/Al2O3(B9) | Pt/Al2O3(B11) | Pt/Al2O3(B12) |
T99/℃ | 185 | 155 | 145 | 160 |
T50/℃ | 174 | 152 | 142 | 157 |
Embodiment 16~18
Catalyst (40-60 mesh) 0.14mL prepared by Example 5~7 respectively, is fitted into fixed bed reactors, is used for
The complete oxidation of benzene, reaction condition are listed in Table 2 below several characteristic temperatures of benzene oxidatoin with example 12.
Catalytic activity of the catalyst of 2. alumina load difference Pt contents of table for the complete oxidation of benzene
Example | 16 | 17 | 18 |
Pt contents/% | 0.1 | 0.3 | 0.5 |
T99/℃ | 195 | 170 | 160 |
T50/℃ | 192 | 165 | 157 |
T10/℃ | 190 | 161 | 155 |
Embodiment 19~21
Using 1% made, 0.5% and 0.25%Pt/CeZrOx of embodiment 8~10 (granular size 40-60 mesh)
0.2mL is fitted into as catalyst in fixed bed reactors, is used for the complete oxidation of benzene.Reaction condition is:It is a concentration of
1600ppm benzene, air mass flow 100mL/min, air speed 30000h-1.They distinguish several characteristic temperatures of benzene oxidatoin
It is listed in Table 3 below.Catalytic activity of the Pt/CeZrOx catalyst of 3 difference Pt load capacity of table for the complete oxidation of benzene
Example | 19 | 20 | 21 |
Catalyst | 1%Pt/CeZrOx | 0.5%Pt/CeZrOx | 0.25%Pt/CeZrOx |
T99/℃ | 154 | 161 | 186 |
T50/℃ | 141 | 144 | 171 |
T10/℃ | 114 | 130 | 155 |
Embodiment 22~24
Using the 0.5%Pt/Al that embodiment 11 is made2O3(N) it is catalyst, other conditions are different with embodiment 19
It is that concentration in reaction process into catalyst bed benzene adjusts separately as 1200,1500 and 7800ppm, they are for benzene oxidatoin
Several characteristic temperatures be listed in Table 4 below respectively.
4 0.5%Pt/Al of table2O3(N) catalytic activity of the catalyst for the benzene complete oxidation of various concentration
Example | 22 | 23 | 24 |
The concentration of benzene | 1200 | 1500 | 7800 |
T/p99p/℃ | 175 | 160 | 178 |
T50/℃ | 154 | 148 | 174 |
T10/℃ | 140 | 100 | 170 |
Embodiment 25~27
Other conditions are with embodiment 23, except that entering the dense of catalyst bed gas space velocity and benzene in reaction process
The difference of degree, conversion temperature when they reach 99% for the conversion ratio of benzene oxidatoin are listed in Table 5 below respectively.
5 0.5%Pt/Al of table2O3(N) catalysis of the catalyst for benzene complete oxidation under various concentration and space velocities
Activity
Example | 25 | 26 | 27 |
Concentration/ppm of benzene | 3900 | 3100 | 2200 |
Air speed/h-1 | 6000 | 15000 | 42000 |
T99/℃ | 175 | 180 | 175 |
Embodiment 28
Other conditions are with embodiment 23, except that used catalyst granular size is 80-120 mesh, temperature of reactor
Be 170 DEG C, for benzene completely oxidizing catalyst long-play stability result as shown in Figure 1.
Embodiment 29
Other conditions urge the complete oxidation of benzene except that it is 165 DEG C that temperature of reactor is constant with embodiment 18
100 hours continuous operation results of agent are as shown in Figure 2.
The foregoing is merely better embodiments of the present invention, but scope of protection of the present invention is not limited thereto, any ripe
Know those skilled in the art in the technical scope disclosed by the present invention, the technique according to the invention design be subject to equivalent replacement or
The technical solution for changing gained, should all be covered by protection scope of the present invention.
Claims (6)
1. a kind of preparation method of the low temperature high activity catalyst of catalysis benzene complete oxidation, it is characterized in that first adding in the solution
Enter carrier, carries out heating reduction again after fully adsorbing chloroplatinic acid, specific method is:
1) carrier, is quantitatively weighed, immerses in ethylene glycol, chloroplatinic acid aqueous solution is then added, it is molten to add the adjustment of NaOH aqueous solutions
The pH of liquid, it stirs under room temperature, chloroplatinic acid is allowed to reach saturation absorption on carrier in the solution;
2), above-mentioned solution under nitrogen protection and isothermal condition is heated to reduction, be cooled to room temperature after reduction, with from
The method of the heart to be separated by solid-liquid separation, and is washed with deionized, and obtained powder is vacuum dried, the tabletting on tablet press machine,
The particle of 40-120 mesh is collected in screening after grinding, it is evaluated on atmospheric fixed bed catalyst reaction device in benzene complete oxidation
In activity.
2. the preparation method of the low temperature high activity catalyst of catalysis benzene complete oxidation according to claim 1, special
Sign is the weight content 0.1~1% of the Pt, and the carrier is aluminium oxide or Ce-Zr solid solution.
3. the preparation method of the low temperature high activity catalyst of catalysis benzene complete oxidation according to claim 2, special
Sign is mass ratio ZrO2/CeO2=2.
4. the preparation method of the low temperature high activity catalyst of catalysis benzene complete oxidation according to claim 2, special
It is surface is neutral or alkalinity that sign, which is the alumina support,.
5. the preparation method of the low temperature high activity catalyst of catalysis benzene complete oxidation according to claim 1, special
Sign is pH=7~12.
6. the system of the low temperature high activity catalyst of the catalysis benzene complete oxidation according to claims 1 or 2 or 3 or 4 or 5
Preparation Method, characterized in that reaction temperature when benzene conversion ratio reaches 99% is 145~195 degrees Celsius, and catalytic reaction condition is:
Catalyst particle size is 40-120 mesh, and a concentration of 1200-7800ppm of benzene, air is oxidant, reaction velocity 6000-
42000h-1。
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CN111545199A (en) * | 2020-05-26 | 2020-08-18 | 北京工业大学 | Supported platinum-tin bimetallic catalyst for efficient oxidation and purification of paraxylene |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111545199A (en) * | 2020-05-26 | 2020-08-18 | 北京工业大学 | Supported platinum-tin bimetallic catalyst for efficient oxidation and purification of paraxylene |
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