CN107774244A - ZrO2Base catalyst and preparation method thereof and the application in thermal degradation formaldehyde - Google Patents

ZrO2Base catalyst and preparation method thereof and the application in thermal degradation formaldehyde Download PDF

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CN107774244A
CN107774244A CN201610769737.9A CN201610769737A CN107774244A CN 107774244 A CN107774244 A CN 107774244A CN 201610769737 A CN201610769737 A CN 201610769737A CN 107774244 A CN107774244 A CN 107774244A
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zro
base catalyst
formaldehyde
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catalyst
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吕跃凯
曹翰
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Tianjin University
Tianjin Normal University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
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    • B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings

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Abstract

The invention discloses a kind of ZrO2Base catalyst and preparation method thereof and the application in thermal degradation formaldehyde, preparation method, are carried out as steps described below：Step 1, in room temperature, matched according to chemical formula, by ZrOCl2·8H2O and metal chlorination salt are put into high purity water, stir at least 30min；Wherein M=Mn, Ni or Pd；Step 2, excess of ammonia water, H are added dropwise in solution made from step 13BO3Or thiocarbamide, to generate sediment；The sediment is stood at least 0.5 hour, the foreign ion in solution is removed after standing；Step 3, step 2 gained sediment is heated into 12~14h at 100~120 DEG C, grinds at least 5min, calcined 2.5~3h at 600~700 DEG C, naturally cool to room temperature, ZrO of the invention2Thermocatalytic degraded of the base catalyst for formaldehyde organic pollution has higher efficiency, and the method for thermocatalytic degradation of formaldehyde is simple, implementation condition requirement is low, easily operated；And thermocatalytic effect is preferable.

Description

ZrO2Base catalyst and preparation method thereof and the application in thermal degradation formaldehyde
Technical field
The invention belongs to science and technology field of curbing environmental pollution, and relates in particular to a kind of ZrO2Base catalyst and its system Preparation Method and the application in thermal degradation formaldehyde.
Background technology
Formaldehyde (HCHO) is widely used in construction material and ornament materials as a kind of important chemical raw material.Study table Bright, the mankind are in content of formaldehyde >=30mg/m for a long time3Interior, various diseases can be triggered, such as skin disease and cancer, formaldehyde is Through being defined as carcinogenic and teratogenesis material by the World Health Organization.Therefore, formaldehyde pollution turns into big problem urgently to be resolved hurrily.Mesh Before, the method for the most frequently used improvement formaldehyde pollution is physical adsorption techniques, plant purification method, plasma technology and catalytic oxidation Deng, wherein, the halfway problem of removal all be present in physical adsorption techniques and plant purification method；Plasma technology power consumption is big and easy Produce secondary pollution；Catalytic oxidation, which mainly includes photocatalytic oxidation and heat catalytic oxidation method, photocatalytic oxidation, needs profit By the use of ultraviolet light as light source, cost height and short life, it is not very convenient to be applied in real life, and heat catalytic oxidation method is Under gauge without light source lower temperature, formaldehyde is changed into free of contamination carbon dioxide and water using the oxygen in air as oxide, Because its cost is low, efficiency high, removes thorough, has become and remove a kind of most promising processing side of Formaldehyde Pollution of Indoor Air at present Method, it is increasingly becoming the study hotspot of catalytic field.But most thermocatalyst is all to do carrier with oxide at present, is adopted Prepared with precious metal doping or compound method, cost is higher.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of ZrO2Base catalyst and preparation method thereof and Application in thermal degradation formaldehyde.
The present invention is achieved by following technical proposals.
A kind of ZrO2The preparation method of base catalyst, carry out as steps described below：
Step 1, in 20~25 DEG C of room temperature, according to chemical formula ZrO2- M x%, the proportioning of 0≤x≤30, by ZrOCl2· 8H2O and metal chlorination salt are put into high purity water, stir at least 30min；Wherein, described M=Mn, Ni or Pd, the x are metal The amount of the amount of ion M material and metal ions M and Zr ionic species and ratio；
Step 2, excess of ammonia water, H are added dropwise in solution made from step 13BO3Or thiocarbamide, to generate sediment；By institute State sediment and stand at least 0.5 hour, the foreign ion in solution is removed after standing；
Step 3, step 2 gained sediment is heated into 12~14h at 100~120 DEG C, grinds at least 5min, 600~ 700 DEG C of 2.5~3h of calcining, naturally cool to 20~25 degrees Celsius of room temperature, that is, obtain ZrO2Base catalyst fines.
In the above-mentioned technical solutions, in the step 1, stir as magnetic agitation.
In the above-mentioned technical solutions, the metal chlorination salt is MnCl2·4H2O、NiCl2·6H2O or PdCl2。
One kind ZrO made from above-mentioned preparation method2Base catalyst.
In the above-mentioned technical solutions, metal ions M enters ZrO2Lattice in substitution Zr ions and occupy the Zr ions Position.
A kind of above-mentioned ZrO2Application of the base catalyst in thermal degradation formaldehyde.
In the above-mentioned technical solutions, at 25~70 DEG C, under without special illumination condition, by the ZrO2Base catalyst is put Put in formaldehyde environment at least 25 hours.
In the above-mentioned technical solutions, at 50~65 DEG C, under without special illumination, by the ZrO2Base catalyst is placed on At least 25 hours in closed formaldehyde environment.
In the above-mentioned technical solutions, as M=Mn, 15 ＜ x≤20, preferably x=20.
In the above-mentioned technical solutions, as M=Ni, 0 ＜ x≤9, preferably x=1.
In the above-mentioned technical solutions, as M=Pd, 0 ＜ x≤25, preferably x=20.
Compared to prior art, ZrO of the invention2Thermocatalytic degraded of the base catalyst for formaldehyde organic pollution has Higher efficiency, the method for thermocatalytic degradation of formaldehyde is simple, implementation condition requires low, easily operated；And thermocatalytic effect is preferable.
Brief description of the drawings
Fig. 1 is pure ZrO2The ZrO being prepared with embodiment 22The X-ray diffraction spectrum (XRD) of-Mnx% samples；
Fig. 2 is Fig. 1 partial enlarged drawing；
Fig. 3 is pure ZrO2And ZrO2The high-resolution TEM spectrograms of-Mnx% samples, (a) pure ZrO2, (b) ZrO2- Mnx% (x= 5), (c) ZrO2- Mnx% (x=20)；
Fig. 4 is pure ZrO2And ZrO2- Mnx% samples thermocatalytic degraded HCHO products CO2Concentration~time graph；
Fig. 5 is pure ZrO2The ZrO being prepared with embodiment 32The X-ray diffraction spectrum of-Nix% samples；
Fig. 6 is Fig. 5 partial enlarged drawing；
Fig. 7 is pure ZrO2And ZrO (A)2- Ni9% (B) HR-TEM figures；
Fig. 8 is pure ZrO2And ZrO2- Nix% samples thermocatalytic degraded HCHO generations CO2Concentration~time graph；
Fig. 9 is pure ZrO2The ZrO being prepared with embodiment 42The X-ray diffraction spectrum of-Pdx% samples；
Figure 10 is pure ZrO2(A)、ZrO2- Pd5% (B) and ZrO2- Pd20% (C, D) high-resolution TEM；
Figure 11 is pure ZrO2And ZrO2- Pdx% samples thermocatalytic degraded HCHO generations CO2Concentration~time graph.
Embodiment
In the embodiment of the present invention, medicine purchase situation is as follows：
The crystal formation and crystal structure of sample are by x-ray powder diffraction instrument (model and parameter：RigakuD/max-2500, Cu Target, K α lines, Japan) measure.Transmission electron microscope model Tecnai G2F20 (Philips).Gas chromatograph model GC7890F (Shanghai Techcomp Instrument Ltd.).
According to bibliography (Zhang C, He H, Tanaka K.Catalytic performance and mechanism of a Pt/TiO2catalyst for the oxidation of formaldehyde at room temperature[J].Applied Catalysis B:Environmental,2006,65(1):37-43) understand, in formaldehyde During being degraded by thermocatalytic, formic acid is oxidized to first, and then formic acid is dehydrated, and produces intermediate product carbon monoxide, finally Intermediate product carbon monoxide is oxidized by oxygen generation carbon dioxide again, according to the conservation of carbon before and after reaction, by determining two The concentration of carbonoxide come determine by thermocatalytic degraded formaldehyde amount.
To reach convenient test ZrO2The effect of base catalyst degradation formaldehyde, establishes a simulated environment, tests prove that should Simulated environment and actual environment test ZrO2The degree of accuracy of base catalyst degradation effect of formaldehyde is almost identical.Therefore, in the present invention Embodiment in, ZrO is tested using the simulated environment2Base catalyst degradation effect of formaldehyde.Using simulated environment Test ZrO2The method of base catalyst degradation formaldehyde is as follows：
In tube type closed glass reactor (400mL), by appropriate (5~10g) catalyst ultrasonic disperse to ethanol solution In, mixed liquor is obtained, mixed liquor is coated on slide with knife coating, fixed blade coating area is 7cm × 2.1cm, afterwards by two The slide of piece attached catalyst is put into reactor, sealing, is noted using microsyringe into tube type closed glass reactor Enter 10uL formalins, tube type closed glass reactor is placed in 338K insulating box, without special illumination (i.e. dark bar Part) under, (at least 1 hour) formaldehyde volatilizees and in catalyst surface adsorption equilibrium completely after certain time, every 4h sample decimations 0.4mL reacting gas.
By the product CO after reacting gas injection gas chromatograph detection formaldehyde and Degradation Formaldehyde2, gas chromatograph use TDX-01 (1m × φ 3mm) chromatographic column, utilizes high-purity N2Make carrier gas, hydrogen flame detector (FID), detector fills with chromatogram intercolumniation There is reburner, CO can be achieved2Hydrogenation reaction (CO2+4H2→CH4+2H2O), and then formaldehyde and CO are detected2Change in concentration.
With reference to the accompanying drawings and examples to the ZrO of the present invention2Base catalyst and preparation method thereof and in thermal degradation formaldehyde In application be described in detail,
Embodiment 1
Pure ZrO2The direct hydrolysis precipitation method are taken to prepare：
Step 1, in 20~25 DEG C of room temperature, by ZrOCl2·8H2O is put into 16mL high purity waters, stirs 30min.
Step 2, the Cl ions in solution are removed to generate precipitation in solution left standstill 40min made from step 1；
Step 3, step 2 gained sediment is heated into 12h at 100 DEG C, grinds 5min, 2.5h is calcined at 600 DEG C, it is naturally cold But to 20~25 degrees Celsius of room temperature, that is, ZrO is obtained2Powder.
Following pure ZrO2It is the ZrO prepared by embodiment 12Powder.
Embodiment 2
Step 1, in 20~25 DEG C of room temperature, according to chemical formula ZrO2- Mnx%, the proportioning of 0 ＜ x≤30, by ZrOCl2· 8H2O and MnCl2·4H2O is put into 16mL high purity waters, stirs 30min；X is the amount and metal ion of metal ions M n material The ratio of the amount sum of Mn and Zr ionic species.
Step 2, excess of ammonia water is added dropwise in solution made from step 1, with give birth to brown into sediment；By the precipitation Thing stands 40min, and the Cl ions in solution are removed after standing；
Step 3, step 2 gained sediment is heated into 12h at 100 DEG C, grinds 5min, 2.5h is calcined at 600 DEG C, it is naturally cold But to 20~25 degrees Celsius of room temperature, that is, ZrO is obtained2Base catalyst fines.
Fig. 1 is the pure ZrO that embodiment 1 is prepared2The ZrO being prepared with embodiment 22The X ray of-Mnx% samples spreads out Spectrum (XRD) is penetrated, Fig. 2 is Fig. 1 partial enlarged drawing, wherein, curve 1 is pure ZrO2Catalyst, curve 2 are x=1 ZrO2- Mnx% base catalyst, curve 3 are x=5 ZrO2- Mnx% catalyst, curve 4 are x=9 ZrO2- Mnx% catalyst, curve 5 be x=15 ZrO2- Mnx% catalyst, curve 6 are x=20 ZrO2- Mnx% catalyst, curve 7 are x=30 ZrO2- Mnx% catalyst.
As seen from the figure, pure ZrO2And ZrO2- Mnx% samples 30.1 °, 34.5 °, 35.1 °, 50.1 °, 50.5 °, 59.2 °, 59.9 °, 62.6 ° there is the characteristic peak of Tetragonal, the characteristic peak of monoclinic phase occur in 28.1 ° and 31.2 ° of positions, present monocline and The mixing phase structure in four directions.Remaining ZrO2- Mnx% samples disappear at the peak of 28.1 ° and 31.4 ° positions, show single Tetragonal, and increasing with Mn ions dosages, each characteristic peak are moved to wide-angle.Can by common knowledge Know, metal ion can enter the lattice of oxide by two ways, and one kind is clearance-type doping, only when metal ion When radius is much smaller than the metal ion in oxide, Doped ions could enter in the interstitial void of oxide；Another kind is to take Adulterated for formula, when the radius of Doped ions is close to metal ion radius in oxide, tend to occur the doping of substitution formula.At this In the embodiment 2 of invention, Doped ions Mn2+Ionic radius be 66pm, ZrO2Middle Zr4+Ionic radius is 72pm, if Mn2+ ZrO is entered with clearance-type2Lattice, lattice parameter will be caused to become big, volume becomes big, it can be seen from Bragg diffraction formula, XRD Diffraction maximum the movement of small angle will occur.But in fig. 1 and 2, XRD results show that diffraction maximum is offset to wide-angle.Therefore, Mn2+ZrO can not possibly be entered in a manner of clearance-type2Lattice.If on the contrary, Mn2+Zr is instead of into lattice4+Position, due to Mn2+Less than Zr4+Radius, therefore ZrO will be caused2Cell parameter and unit cell volume reduce, X-ray diffraction peak will be to wide-angle It is mobile, it is consistent with test result, therefore Mn2+It is likely to substitute formula doping way to enter ZrO2Lattice.
Fig. 3 is ZrO2、ZrO2- Mnx% (x=5) and ZrO2The high-resolution TEM spectrograms of-Mnx% (x=20) sample, Fig. 3 (a) in, 0.297nm interplanar distance is marked to correspond to pure ZrO2(101) face of sample, in Fig. 3 (b), ZrO2- Mnx% (x=5) sample The interplanar distance in (101) face of product is 0.294nm, and this interplanar distance is in ZrO2It is 0.292nm in-Mnx% (x=20) sample (as shown in Figure 3 c), the results showed that, ZrO after doping2The interplanar distance of-Mnx% samples reduces, consistent with XRD results, therefore, Mn ions enter ZrO to substitute formula to adulterate2Lattice.
According to the method described above using simulated environment test ZrO2Base catalyst thermo-catalytic degradation of formaldehyde, according to generation CO2It is dense Degree is active to evaluate the thermocatalytic of catalyst, and test result is as shown in Figure 4.
For blank not let alone the blank assay of what catalyst, blank assay carries out 22h in thermal decomposition Formaldehyde Test in Fig. 4 Afterwards, only has trace amounts of CO in reactor2Generation, HCHO will not be decomposed substantially under the conditions of illustrating thermocatalytic.As seen from the figure, pure ZrO2 Thermocatalytic degradation of formaldehyde generation CO2Activity it is very low, reaction 22h generation CO2Concentration is only 37.6374 × 10-6mol·L-1。 For the sample of doping, ZrO2- Mn20% thermocatalytic activity highest, about pure ZrO22.8 times, reaction 22h generation CO2's Concentration is 103.8891 × 10-6mol·L-1。
Embodiment 3
Step 1, in 20~25 DEG C of room temperature, according to chemical formula ZrO2- Nix% proportioning, by ZrOCl2·8H2O and NiCl2·6H2O is put into 16mL high purity waters, stirs at least 30min；X is the amount and metal ion Ni of metal ion Ni material With the ratio of the amount sum of Zr ionic species.
Step 2, excess of ammonia water is added dropwise in solution made from step 1, to generate sediment (molten made from step 1 Ammoniacal liquor is added dropwise in liquid, after stopping generation sediment into solution, stops that ammoniacal liquor is added dropwise.)；The sediment is stood into 40min, it is quiet Postpone the Cl ions removed in solution；
Step 3, step 2 gained sediment is heated into 12h at 100 DEG C, grinds 5min, 2.5h is calcined at 600 DEG C, it is naturally cold But to 20~25 degrees Celsius of room temperature, that is, ZrO is obtained2Base catalyst fines.
The crystal structure information of sample is obtained using X-ray diffraction spectra, as a result as shown in Figure 5 and Figure 6, wherein, it is bent Line 1 is pure ZrO2, curve 2 is x=0.5 ZrO2- Nix% catalyst, curve 3 are x=1 ZrO2- Nix% catalyst, curve 4 be x=5 ZrO2- Nix% catalyst, curve 5 are x=9 ZrO2- Nix% catalyst.
As seen from the figure, pure ZrO2And ZrO2- Ni0.5% samples 30.1 °, 34.5 °, 35.1 °, 50.1 °, 50.5 °, 59.2 °, 59.9 °, 62.6 ° there is the characteristic peak of Tetragonal, the characteristic peak of monoclinic phase occur in 28.1 ° and 31.2 ° of positions, are single Oblique and tetragonal structure mixing phase structure.ZrO2- Ni1%, ZrO2- Ni5% and ZrO2- Ni9% samples show complete four directions Crystal structure.Fig. 6 is the diffraction maximum after 30.1 ° of characteristic peak amplification by Tetragonal, hence it is evident that finds out ZrO after doping2- Nix% The diffraction maximum of sample moves to wide-angle direction, and with the increase of Ni dopings, move angle increase.During doping, When the ionic radius of doped metal ion metal ion radius close in oxide lattice, doped metal ion will enter oxygen Compound lattice substituted metal ion, and its position is occupied, form the doping of substitution formula.When doped metal ion radius is much smaller than oxidation In thing lattice during the radius of metal ion, doped metal ion will enter in the structure cell of oxide, form clearance-type doping.Mix Miscellaneous Ni2+Ionic radius be 69pm, ZrO2Zr in lattice4+Ionic radius is 72pm, and both ionic radius are very close, Ni ions It cannot be introduced into ZrO2Interstitial void, and probably to substitute formula doping way to enter ZrO2Lattice and occupy Zr ions Position.If Ni ionic compartmentation Zr ion positions, because Ni ionic radius are smaller, will cause ZrO2Interplanar distance (d hkl), Cell parameter (a, b, c), unit cell volume etc. reduce, by Bragg diffraction formula dhklSin θ=k λ understand that x-ray diffraction angle will Moved to wide-angle, this is consistent with XRD test results.
Fig. 7 (A) is pure ZrO2HR-TEM figure, mark 0.297nm fringe spacing to correspond to ZrO2(101) face of crystal, figure 7 (B) are ZrO2- Ni9% HR-TEM figures, its fringe spacing be 0.294nm, and fringe spacing is corresponding to crystal in HR-TEM figures Interplanar distance, show ZrO2The interplanar distance of-Ni9% samples is less than ZrO2Interplanar distance, that is, mix Ni2+Sample after ion Interplanar distance reduces, and this and XRD result are consistent.
In summary, Ni2+Ion is to substitute formula doping way to enter ZrO2Lattice and occupy the position of Zr ions.
According to the above method using simulated environment by test ZrO2Base catalyst thermo-catalytic degradation of formaldehyde, according to generation CO2It is dense Degree is active to evaluate the thermocatalytic of catalyst, and test result is as shown in Figure 8.Fig. 8 is ZrO2And ZrO2- Nix% sample thermocatalytic bars The HCHO that degraded under part produces CO2Concentration curve, as seen from the figure, when Ni dopings be 1% when, generate CO2Amount it is most, With best thermocatalytic activity.Wherein, thermally decompose and only have trace amounts of CO in Formaldehyde Test (the blank curve for not putting catalyst)2 Generation, HCHO will not be decomposed substantially under the conditions of showing thermocatalytic.Pure ZrO2There are faint thermocatalytic activity, reaction 22h generations CO2Concentration is 37.6374 × 10-6molL-1, ZrO2- Ni0.5%, ZrO2- Ni5% and ZrO2- Ni9% thermocatalytic activity It is weaker, ZrO2- Ni1% thermocatalytic activity is apparently higher than pure ZrO2, it generates CO2Concentration is 54.9596 × 10-6molL-1, It is approximately pure ZrO21.5 times.
Embodiment 4
Step 1, in 20~25 DEG C of room temperature, according to chemical formula ZrO2- Pdx% proportioning, by ZrOCl2·8H2O and PdCl2 It is put into 16mL high purity waters, stirs 30min；X is the amount and metal ion Pd and Zr ionic species of metal ion Pd material Measure the ratio of sum.
Step 2, in solution made from step 1 be added dropwise excess of ammonia water, using generate sediment (addition ammoniacal liquor concentration as 10%)；The sediment is stood into 40min, the Cl ions in solution are removed after standing：Solution is filtered, used after filtering Deionized water is washed to sediment, to remove Cl ions；
Step 3, step 2 gained sediment is heated into 12h at 100 DEG C, grinds 5min, 2.5h is calcined at 600 DEG C, it is naturally cold But to 20~25 degrees Celsius of room temperature, that is, ZrO is obtained2Base catalyst fines.
Fig. 9 is ZrO2And ZrO2The XRD spectra of-Pdx% series of samples, curve 1 are pure ZrO made from embodiment 12, it is bent Line 2 is x=1 ZrO2- Pdx% catalyst, curve 3 are x=5 ZrO2- Pdx% catalyst, curve 4 are x=9 ZrO2- Pdx% catalyst, curve 5 are x=15 ZrO2- Pdx% catalyst, curve 6 are x=20 ZrO2- Pdx% catalyst, curve 7 be x=25 ZrO2- Pdx% catalyst.
As shown in Figure 9, pure ZrO2In 30.1 °, 34.5 °, 35.1 °, 50.1 °, 50.5 °, 59.2 °, 59.9 °, 62.6 ° of appearance The diffraction maximum of Tetragonal, there is the characteristic peak of monoclinic phase, therefore pure ZrO in 28.1 ° and 31.2 ° of positions2It is that monocline and four directions are tied The mixed phase of structure, ZrO2- Pd1% and ZrO2- Pd5% diffraction maximum and pure ZrO2It is similar, and monocline and the mixed phase in four directions, The ZrO of higher concentration2- Pdx% samples disappear in 28.1 ° and 31.2 ° of diffraction maximum, and complete tetragonal structure is presented, and In ZrO2- Pd15%, ZrO2- Pd20% and ZrO2PdO diffraction maximum is detected in-Pd25% samples.
With pure ZrO2Compare, Pd doping ZrO2In low concentration doping, it is inclined that small angle occurs the diffraction maximum of sample to the left for peak position Move, moved as Pd concentration increases to 9% beginning toward wide-angle direction.
The mode that metal ion enters in oxide crystal generally has two kinds, and clearance-type doping and substitution formula are adulterated.Gap Formula doping is that Doped ions are by between the lattice of crystal when the radius of metal ion is much smaller than the metal ion in oxide In gap；And when the radius of metal ion and the close metal ion radius of oxide species, tend to occur the doping of substitution formula.Pd2+From Sub- radius is 84pm, slightly larger than Zr4+Ionic radius (72pm), therefore when doping concentration is relatively low, Pd2+Can not possibly be with clearance-type Into ZrO2Lattice, can only be to substitute Zr4+Form enter ZrO2Lattice, due to Pd2+Ionic radius is larger, into ZrO2 Cell parameter is caused to become big with unit cell volume after lattice, so as to which diffraction maximum is offset to low-angle.When concentration increases to 9%, by Gradually there is PdO precipitation, and diffraction maximum is gradually offset to wide-angle, because valence state turn occurs for Pd ions in sintering process Become, become the Pd that ionic radius is 62pm4+, Pd4+Ionic radius is less than Zr4+, substitute ZrO2Middle Zr4+Position will cause sample Cell parameter and volume accordingly diminish, and the skew of diffraction maximum wide-angle, are coincide with result.
Figure 10 is pure ZrO2(A)、ZrO2- Pd5% (B) and ZrO2- Pd20% (C, D) high-resolution TEM.It is pure ZrO to scheme A2 HR-TEM figure, mark 0.297nm fringe spacing to correspond to ZrO2(101) face of crystal, figure B is ZrO2- Pd5% HR-TEM Figure, its fringe spacing is 0.299nm, and figure C and D is ZrO2- Pd20% HR-TEM figures, corresponding fringe spacing is 0.292nm, and Pure ZrO2Compare, ZrO2- Pd5% sample fringe spacings are slightly increased, and this is due to the larger Pd of ionic radius2+Substitute Zr4+Enter Enter ZrO2Lattice, cause its cell parameter increase, interplanar distance increase.And ZrO2The fringe spacing of-Pd20% samples reduces, then It is because of Pd in sintering process2+It is transformed to the larger Pd of ionic radius4+, this result and XRD analysis are consistent.In addition, In ZrO20.263nm fringe spacing is found that in-Pd20% samples, through analysis, this corresponds to PdO (101) crystal face, shown Occur PdO in enriched sample, it is consistent with XRD results.
According to the method described above using simulated environment test ZrO2Base catalyst thermo-catalytic degradation of formaldehyde, according to generation CO2It is dense Degree is active to evaluate the thermocatalytic of catalyst, and test result is as shown in figure 11.
Figure 11 shows in ZrO2After introducing Pd ions in system, corresponding thermocatalytic activity increases, wherein thermocatalytic Activity most strong is ZrO2- Pd20% samples, generate CO2Concentration is 301.8378 × 10-6mol·L-1, it is approximately pure ZrO28.0 Times.ZrO2The catalytic activity of-Pdx% samples increases and improved with doping, and when doping reaches to a certain degree, catalytic activity is not Raise, or even begin to decline again, show that Pd ion dopings show a kind of optimization relation to the activity influence of catalyst, it is optimal to mix Miscellaneous amount is 20%, i.e. ZrO2- Pd20% catalytic activity highest.
The content recorded according to present invention part carries out the thermocatalytic drop that PARA FORMALDEHYDE PRILLS(91,95) can be achieved in technical arrangement plan Solution, shows the property basically identical with above-described embodiment after tested.
Exemplary description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal Fall into protection scope of the present invention.

Claims (10)

  1. A kind of 1. ZrO2The preparation method of base catalyst, it is characterised in that carry out as steps described below：
    Step 1, in 20~25 DEG C of room temperature, according to chemical formula ZrO2- Mx%, the proportioning of 0≤x≤30, by ZrOCl2·8H2O and gold Category chlorate is put into high purity water, stirs at least 30min；Wherein, described M=Mn, Ni or Pd, the x are the thing of metal ions M The amount of the amount of matter and metal ions M and Zr ionic species and ratio；
    Step 2, excess of ammonia water, H are added dropwise in solution made from step 13BO3Or thiocarbamide, to generate sediment；Will be described heavy Starch stands at least 0.5 hour, and the foreign ion in solution is removed after standing；
    Step 3, step 2 gained sediment is heated into 12~14h at 100~120 DEG C, at least 5min is ground, at 600~700 DEG C 2.5~3h is calcined, 20~25 degrees Celsius of room temperature is naturally cooled to, that is, obtains ZrO2Base catalyst fines.
  2. 2. ZrO according to claim 12The preparation method of base catalyst, it is characterised in that in the step 1, stirring For magnetic agitation.
  3. 3. ZrO according to claim 22The preparation method of base catalyst, it is characterised in that the metal chlorination salt is MnCl2·4H2O、NiCl2·6H2O or PdCl2。
  4. A kind of 4. ZrO made from preparation method with described in claims 1 to 3 any one2Base catalyst.
  5. 5. ZrO according to claim 42Base catalyst, it is characterised in that metal ions M enters ZrO2Lattice in substitute Zr ions and the position for occupying the Zr ions.
  6. A kind of 6. ZrO made from preparation method with described in claims 1 to 3 any one2Base catalyst is in thermal degradation formaldehyde Application.
  7. 7. application according to claim 6, it is characterised in that at 25~70 DEG C, under without special illumination condition, by institute State ZrO2Base catalyst is placed in formaldehyde environment at least 25 hours, preferably 50~65 DEG C.
  8. 8. application according to claim 7, it is characterised in that as M=Mn, 15 ＜ x≤20, preferably x=20.
  9. 9. application according to claim 7, it is characterised in that as M=Ni, 0 ＜ x≤9, preferably x=1.
  10. 10. application according to claim 7, it is characterised in that as M=Pd, 0 ＜ x≤25, preferably x=20.
CN201610769737.9A 2016-08-30 2016-08-30 ZrO2Base catalyst and preparation method thereof and the application in thermal degradation formaldehyde Pending CN107774244A (en)

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