CN108671940A - The preparation method and application of AlNi-PILC material load PdOx nanocrystalline catalysts - Google Patents
The preparation method and application of AlNi-PILC material load PdOx nanocrystalline catalysts Download PDFInfo
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- CN108671940A CN108671940A CN201810485353.3A CN201810485353A CN108671940A CN 108671940 A CN108671940 A CN 108671940A CN 201810485353 A CN201810485353 A CN 201810485353A CN 108671940 A CN108671940 A CN 108671940A
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- nanocrystalline
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910002673 PdOx Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910001151 AlNi Inorganic materials 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 9
- 239000004927 clay Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 5
- 241000894007 species Species 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 239000000523 sample Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000001239 high-resolution electron microscopy Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000976924 Inca Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GKPXMGUNTQSFGA-UHFFFAOYSA-N but-2-ynyl 1-methyl-3,6-dihydro-2h-pyridine-5-carboxylate;4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CC#CCOC(=O)C1=CCCN(C)C1 GKPXMGUNTQSFGA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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- 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
- B01J23/892—Nickel and noble metals
-
- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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
- B01J37/16—Reducing
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- 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
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Abstract
The invention discloses a kind of AlNi column clays (AlNi PILC) and its load PdOxThe preparation method and application of nanocrystalline catalyst；AlNi pillaring agents are synthesized by high temperature and pressure one step hydro thermal method in above-mentioned preparation method, and then synthesize AlNi PILC；Using AlNi PILC as carrier, the PdO of high temperature solution phase reduction method one-step synthesis method high dispersive is utilizedxNanocrystalline catalyst, the application of the catalysis burning for Low Concentration of Benzene.The present invention solves the technical issues of " promotion improves specific surface area, pore volume and the stability of traditional column clay, promotes stability, high dispersion and the dimensional homogeneity of active specy in supported PdO catalyst ".It is simple, repeated high that the present invention has preparation method；The AlNi PILC materials of synthesis have the good characteristics such as bigger serface, large aperture；Active specy PdO has high dispersion and dimensional homogeneity in catalyst, is used for the catalytic degradation of Low Concentration of Benzene, and catalytic activity is excellent.
Description
Technical field
The present invention relates to chemical catalyst fabricating technology field, especially a kind of AlNi-PILC loads PdOx nanometers
The preparation method and application of brilliant catalyst.
Background technology
To obtain high activity, the catalysis material of high stability it is necessary to forming a large amount of catalytic active site and be conducive to
The adsorption activation of VOCs molecules.Theoretically, to realize that this target can be from the aspect of two, first is using big
Specific surface, nanoporous carrier material catalytic active component is disperseed well, and be conducive to reactant molecule
Adsorption desorption；Second is to improve its dispersibility, stability etc., and then generation is good so that the structure of active phase is optimized
Catalytic performance.
Most of loaded catalyst is prepared at present uses traditional preparation method (such as infusion process, coprecipitation), it is difficult to
Control the dispersion degree of active component, the particle diameter distribution of load, it is inhomogenous, performance is unstable so as to cause active sites the defects of.
Invention content
The purpose of the present invention is to solve above-mentioned the deficiencies in the prior art to be provided a kind of logical by simplifying synthesis step
It crosses high temperature and pressure one step hydro thermal method and obtains the compound pillaring agents of AlNi, and then the method for preparing AlNi-PILC.It is with AlNi-PILC
Carrier, using high temperature solution phase reduction method one-step method, provide a kind of PdOx for benzene catalysis burning with high degree of dispersion it is nanocrystalline/
The preparation method of AlNi-PILC catalyst.
To achieve the goals above, a kind of PdOx designed by the present invention is nanocrystalline/preparation method of AlNi-PILC,
Include the following steps：
1) preparation of AlNi-PILC
First, Locron L (aluminium chloride, Al are taken2(OH)5Cl·2-3H2A concentration of 1.5mol/L of O, Al ion)
It is added in autoclave with nickel nitrate solution (1.0mol/L), the molar ratio of Al/Ni is adjusted to 5/1；Secondly, autoclave is put
Enter drying in baking oven, it is 100 DEG C to adjust oven temperature, is waited after placing 16h, takes out autoclave and naturally cools to 30 DEG C；Finally, will
Solution in autoclave takes out, and adds the concentration of deionized water dilution Al ions to 0.1mol/L, obtains AlNi combined columns
Agent, for use；
It first, will be above-mentioned at 60 DEG C using the inorganic grade montmorillonites (MMT) of the KSF of Aladdin companies as starting material
The compound pillaring agents of AlNi in step are slowly dropped in 2wt%MMT, and in terms of 1g MMT, the dosage of Al is 20mmol；Secondly,
After stirring turbid solution 3h, centrifugation to no Cl-；Finally, turbid solution in an oven 110 DEG C drying after, roasted at 500 DEG C of Muffle furnace
2h obtains AlNi-PILC.The specific surface area and pore volume of MMT and AlNi-PILC, such as the following table 1：
The specific surface area and pore volume of table 1MMT and AlNi-PILC
ABET specific surface areas；Pore specific surface area in b；
C is in P/P0The total pore volume of=0.99 time calculating material；D is calculated according to t-plot methods.
2) AlNi-PILC loads PdOxThe preparation method of nanocrystalline catalyst comprising following step：
First, using 1) the middle AlNi-PILC prepared as carrier, three mouthfuls of burnings are added in AlNi-PILC and excessive ethylene glycol
In bottle, after stirring 0.5h, a certain amount of H is added2PdCl4Solution continues to stir 12h under high pure nitrogen protection；Again, it uses
NaOH solution adjusts pH of mixed to 3h after 11, is stirred at 165 DEG C, takes out three-necked flask, is cooled to room temperature, centrifugation to no Cl-；
Finally, 110 DEG C of drying in an oven roast 2h at 400 DEG C of Muffle furnace, and wherein Pd load capacity is 0.2wt%, obtains PdOx and receives
Meter Jing/AlNi-PILC catalyst.
A kind of AlNi-PILC loads PdOx nanocrystalline catalysts, are a kind of completely new nano particles provided in the present invention
PdO catalyst, can be used for Low Concentration of Benzene catalysis burning.
The present invention compared with prior art, has following advantage：
1. preparing AlNi-PILC pillaring agents using high temperature and pressure one-step method, method is simple, repeatability is high；
2. the AlNi-PILC materials of synthesis have the good characteristics such as bigger serface, large aperture；
3. using high temperature solution phase reduction method one-step synthesis method PdOx it is nanocrystalline/AlNi-PILC catalyst, active specy PdOx tools
There are good stability, high dispersion and dimensional homogeneity (1-2nm), is used for the catalytic degradation of Low Concentration of Benzene, catalytic effect
Well.
Description of the drawings
Fig. 1 is that prepared by the AlNi-PILC of the present invention and its loading type Pd Ox nanocrystalline catalysts are catalyzed burner for benzene
Skill flow chart；
Fig. 2 is the XRD spectra of MMT, AlNi-PILC；
Fig. 3 a are the high resolution electron microscopy figure one of AlNi-PILC；
Fig. 3 b are the high resolution electron microscopy figure two that AlNi-PILC loads PdOx nanocrystalline catalysts；
Fig. 3 c are the energy spectrum diagram of Pd/AlNi-PILC；
Pd/MMT, Pd/ that Fig. 4 is Pd/AlNi-PILC-IM prepared by infusion process and prepared by liquid phase high temperature reduction method
The catalytic activity figure of AlNi-PILC catalysts degradation Low Concentration of Benzene.
The durability of Fig. 5 Pd/AlNi-PILC, chlorine-resistant, water vapor resistance lab diagram
Specific implementation mode
Present invention will be further explained below with reference to the attached drawings and examples.
A kind of preparation method of new A lNi-PILC is provided in the present embodiment comprising following step：
1) preparation of AlNi-PILC
The 1.0mol/L nickel nitrate solutions of the Locron L and certain volume that measure 10mL, 6.0mol/L are added to autoclave
In, the molar ratio of Al/Ni is adjusted to 5/1, then add deionized water dilute solution to make a concentration of the 1.5 of Al ions into autoclave
mol/L；Sealing autoclave is simultaneously dried in an oven, and oven temperature is 100 DEG C, drying time 16h, and it is naturally cold to take out reaction kettle
But to 30 DEG C, the solution inside autoclave is taken out and deionized water is added to be diluted to 600mL, i.e., Al ions is a concentration of
0.1mol/L obtains the compound pillaring agents of AlNi, for use.
Using the inorganic grade montmorillonites (MMT) of the KSF of Aladdin companies as starting material；The AlNi combined columns at 60 DEG C
Agent is slowly dropped to in the prepared 2wt%MMT of deionized water, and in terms of 1g MMT, the dosage of Al is 20 mmol；It utilizes
Mechanical agitation turbid solution；It is taken out after dripping off, centrifugation to no Cl-(being examined with silver nitrate solution)；In an oven after 110 DEG C of drying,
2h is roasted under 500 DEG C of Muffle furnace (10 DEG C/min), obtains AlNi-PILC.
As shown in Figure 1, additionally providing a kind of preparation side of AlNi-PILC loads PdOx nanocrystalline catalysts in the present embodiment
Method comprising following step：Using the AlNi-PILC prepared among the above as carrier, 40-60 mesh single-sizes are worn into, for use；Profit
With liquid phase high temperature reduction one-step method, three-necked flask is added in AlNi-PILC and excessive ethylene glycol (as solvent and reducing agent)
In, after stirring 0.5h, a certain amount of H is added2PdCl4Solution continues to be stirred overnight under high pure nitrogen protection and (stir full
12h)；After NaOH solution adjusting pH of mixed to 11,3h is stirred at 165 DEG C, is taken out three-necked flask, is cooled to room temperature,
It centrifuges to no Cl-(being examined with silver nitrate solution)；It dries for 110 DEG C, is roasted under 400 DEG C of Muffle furnace (10 DEG C/min) in an oven
2h, wherein Pd load capacity be 0.2wt%, obtain PdOx it is nanocrystalline/AlNi-PILC catalyst.
A kind of application of AlNi-PILC loads PdOx nanocrystalline catalysts, is that above-mentioned AlNi-PILC loads PdOx nanometers
Brilliant catalyst can be used for the catalysis burning of Low Concentration of Benzene.
To obtained by above-mentioned implementation AlNi-PILC and PdOx nanocrystalline catalysts carry out X-ray diffraction, specific surface area and
The experiments such as pore volume, high resolution electron microscopy measurement, determination of activity and durability, as described below：
1, specific surface area and pore volume measurement result：
Testing conditions：Clay material specific surface area and pore volume are in II 3020apparatus of Tristar
(Micromeritics Company, USA) liquid nitrogen temperature (77K).Sample vacuumizes pretreatment 4h at 200 DEG C.Using
Barrett- Joyner-Halenda (BJH) method measures pore volume.It the results are shown in Table 1..
As can be seen from Table 1, the S of AlNi-PILCBETAnd VpRespectively in 375m2/ g and 0.21cm3/ g, much larger than MMT's.
Also greater than conventional method synthesis column clay specific surface area (generally in 200-300m2/g).This method provide a kind of step
The method of rapid simple synthesis column clay, and its structure is much better than common column clay.
2, X-ray diffraction measure result：
Testing conditions：Clay material phase structure is measured using X-ray diffraction (XRD) method, and experiment exists
It is carried out on PANalytical type X-ray powder diffraction instrument, Cu K alpha rays, tube voltage 40kV, tube current 40mA, scans 2 θ models
It is trapped among 1-10 °, 0.02 °/s of sweep speed.Interlamellar spacing is calculated by Bragg equation：2d001Sin θ=n λ, λ=
0.154nm.See Fig. 2.
Fig. 2 is the XRD spectra of MMT and AlNi-PILC, it can be seen from the figure that 2 θ values of clay are toward small angle after pillared
Degree offset, is calculated using Bragg equation, learns that its interlamellar spacing becomes larger.Wherein, the AlNi-PILC after 500 DEG C roast 2h
D001Value reaches 2.11nm, the numerical value (1.26nm) of MMT is much larger than, this is because into the AlNi polymerizing cationicallies in underground layer
Size be more than MMT in cation size, illustrate synthesis AlNi-PILC be successful.
3, high resolution electron microscopy figure result：
High resolution electron microscopy analyzes (HRTEM), and the pattern of material, work are obtained using JEM-21000F (HR) type transmission electron microscope
Voltage is 200kV.It is sliced, then is measured after sample epoxy resin embedding.Sample powder is scattered in absolute ethyl alcohol, is set super
5min is vibrated under sound wave, suspended sample is fished for the copper mesh for being coated with carbon film, is packed into Electronic Speculum pretreatment chamber after to be dried, turns after evacuation
Enter measuring chamber, observe pattern, absorbs photo.Energy dispersive X-ray spectroscopy (EDS) experiments are profits
With OXFORD INCA come the chemical composition of determination sample.See Fig. 3.
Fig. 3 is the high resolution electron microscopy figure of PdOx/AlNi-PILC nanocrystalline catalysts, and preparation is can be seen that from Fig. 3 a
AlNi-PILC still has uniform layer structure after high-temperature roasting, is a kind of micropore-mesopore of typical two-dimensional layered structure
Composite material.It can be seen that, PdOx is nanocrystalline to have preferable interaction with AlNi-PILC carriers so that PdOx in Fig. 3 b
Nanocrystalline size is within the scope of 1-2nm, and uniform monodisperse is in carrier surface.Fig. 3 c are carried out to Pd/AlNi-PILC catalyst
Energy spectrum analysis, it can be found that the Elemental Diffractions peak such as Pd, Al, Ni, illustrates that the preparation of catalyst is successful from figure.
4, catalytic degradation low concentration is carried out to the AlNi-PILC load PdOx nanocrystalline catalysts obtained by above-described embodiment
The application test of benzene：
Activity rating (is first weighed, Tianjin) in WFS-3010 and is carried out on device, and experiment condition is as follows：Catalyst 200mg, benzene are dense
Degree is 1000ppm, air speed 20000h-1, gas flow rate 120mL/min.Using gas-chromatography (FID) (Shimazu, GC-
14C, Japan) on-line checking, data are recorded and analyzed by N2000 Data Processing in Chromatography Workstation, see Fig. 5.
Fig. 5 is Pd/MMT, the activity figure of Pd/AlNi-PILC-IM (infusion process) and Pd/AlNi-PILC catalyst, by scheming
It can be seen that the result of different catalysis benzene burnings all shows typical " S " type curve, i.e., there is certain urge to catalysis burning
Change effect, but different carriers and method for preparing catalyst are to catalytic effect or differentiated.Active sequence is as follows:Pd/
AlNi-PILC>Pd/AlNi-PILC-IM>Pd/MMT.The temperature of the degradable benzene of Pd/AlNi-PILC-IM and Pd/MMT is distinguished
In 300 DEG C and 350 DEG C.Pd/AlNi-PILC catalyst has best catalytic performance, can degradable low concentration at 250 DEG C
Benzene, it is 50 DEG C lower than Pd/AlNi-PILC.Show that Pd/AlNi-PILC is excellent according to characterization result and activity data to urge
Change PdO of the performance with it in highly dispersed statexNano-particle.Using liquid phase high temperature reduction method, using AlNi-PILC as carrier, prepare
PdOxParticle size only has 1-2nm, and it is more uniform be dispersed in carrier surface, which greatly enhances the utilizations of active component
Rate, therefore with the activity of higher catalysis burning benzene
In order to further probe into the melange effect of sample introduction gas, the chlorobenzene of 10,000ppm vapor and 100ppm are also drawn
Enter in test experiments.In addition, catalyst also uses above-mentioned same device and item to the research of the catalysis combustion stability of benzene
Part.
In the stability test that 240 DEG C carry out Pd/AlNi-PILC catalyst, under lasting 1000h reactions, activity
94% or so is maintained, the activity of stable catalytic degradation benzene is shown.In addition in the 100h most started, 100ppm is added
Chlorobenzene, due to compete active site absorption and oxidation so that catalytic activity slightly reduces.When continuously adding 10,000ppm
When water, due to the Effect of Competitive Adsorption, catalytic activity further decreases.But when water and chlorobenzene are removed simultaneously, catalysis is lived
Property is restored to initial high activity again.As a result illustrate, Pd/AlNi-PILC not only to the benzene compounds without chlorine and containing chlorine all
With high catalytic performance, still there is good repellence to wet condition, show stable catalytic property.
Claims (2)
1. a kind of preparation method of AlNi-PILC material loads PdOx nanocrystalline catalysts, which is characterized in that including step below
Suddenly：
First, the compound pillaring agents of AlNi are synthesized using high temperature and pressure one step hydro thermal method, and then synthesized with bigger serface, macropore
The AlNi-PILC of diameter, for use；Secondly, AlNi-PILC and excessive ethylene glycol are added in three-necked flask, after stirring 0.5h, are added
Enter a certain amount of H2PdCl4Solution, in high-purity N2Continue to stir 12h under protection；Again, pH of mixed is adjusted using NaOH solution
To after 11,3h is stirred at 165 DEG C, takes out three-necked flask, is cooled to 25 DEG C, centrifugation to no Cl-；Finally, 110 DEG C of bakings in an oven
It is dry, 2h is roasted at 400 DEG C of Muffle furnace, and programmed rate is 10 DEG C/min, wherein Pd load capacity is 0.2wt%, is obtained
PdOx is nanocrystalline/AlNi-PILC catalyst.
2. a kind of application of AlNi-PILC material loads PdOx nanocrystalline catalysts, it is characterized in that the AlNi-PILC is loaded
PdOx nanocrystalline catalysts can be used for the catalysis burning of Low Concentration of Benzene.
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