CN105233690B - A kind of preparation method for carrying palladium diatomite composite material - Google Patents
A kind of preparation method for carrying palladium diatomite composite material Download PDFInfo
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- CN105233690B CN105233690B CN201410332119.9A CN201410332119A CN105233690B CN 105233690 B CN105233690 B CN 105233690B CN 201410332119 A CN201410332119 A CN 201410332119A CN 105233690 B CN105233690 B CN 105233690B
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Abstract
The invention discloses a kind of preparation method for carrying palladium diatomite composite material, comprise the following steps：(1) by a certain amount of PdCl2It is dissolved in concentrated hydrochloric acid, is sufficiently stirred for and heats, is completely dissolved it；(2) to adding diatomite particle in solution and stirring, it is sufficiently impregnated；(3) add excessive acetylacetone,2,4-pentanedione and be sufficiently stirred for, solution ph to 7~9 is adjusted with NaOH or KOH, in diatomite surface and internal generation yellow mercury oxide Pd (acac)2, will be impregnated of Pd (acac)2Diatomite filtering, dry；(4) finally by the intermediate of gained --- load Pd (acac)2The middle temperature heating and calcining of diatomite obtain carry palladium diatomite composite material.Pd (acac) in disposable completion conventional method of the invention2Synthesis impregnates two process procedures with diatomite, and method is simple, reaction is gentle, be easily controlled, technically reliable, can be used to preparing high-performance and carries palladium diatomite composite material, and is applied to hydrogen isotope separation, extraction field.
Description
Technical field
The present invention relates to a kind of preparation method for carrying palladium diatomite composite material, synthesized load palladium diatomite composite material
Can be used as high-performance hydrogen isotope separation material, be applied to Purification for hydrogen isotopes, separate and extractive technique field.
Background technology
Due to fossil energy growing tension in current world wide, therefore fusion energy is just giving play to more and more important work
With.Wherein, hydrogen isotope separation is that, using one of core technology of deuterium tritium fusion energy, and the performance of separation material is then to determine point
From the key factor of efficiency.In numerous hydrogen isotope separation materials, carrying palladium diatomite (Pd/K) composite has than table
Area is big and palladium load capacity advantage high, can buffer contact circle for inhaling the internal stress, increase hydrogen and palladium put in hydrogen cyclic process
Face, raising suction/hydrogen discharge reaction and isotope exchange rate [I.A.Fisher, Westinghouse Savannah River
Company-RP-93-401(1993)]；The volume that splitter can also be reduced and the separating property for improving system
[K.L.Shanahan et al., J.AlloysComp., 62 (1999) 293].Therefore, Pd/K composites are stored up as hydrogen isotope
Deposit, separate and extract material and obtained great research concern, fusion fuel circulation and tritium treatment are widely used in recent years
In technique.
It is the palladium salt that U.S. Sa Fanna rivers National Laboratory proposes in the main preparation method of Pd/K composites at this stage
Its solution is soaked naturally using presomas such as palladium nitrate, palladium bichloride, palladium nitrate ammoniums in solution wet impregnation-decomposition method, the laboratory
Stain diatomite support, ageing, air-dry after be prepared for different palladium contents Pd/K composites [K.L.Shanahan et al.,
J.Alloys Comp., 62 (1999) 293；W.C.Mosley, Westinghouse Savannah River Company-TR-
90-24(1990)].Although the method is the main method tested at present with used in certain applications, its presoma is nothing
Machine palladium salt, because the too high reaction of heat resolve temperature is violent after dipping, is highly vulnerable to breakage structure of diatomite, and can be made after diatomite efflorescence
Reduced into Pd/K composite separating properties and block piece-rate system.
Seminar is in open source literature rare metal 2011 (35) 2 where inventor：Reported in 238-243 and use levulinic
Ketone palladium (Pd (acac)2) it is presoma, the method for preparing Pd/K composites is impregnated naturally by solvent of chloroform, reduce heat point
Solution temperature, but Pd (acac)2It is water insoluble, the organic solvents such as chloroform need to be introduced；And processing cost is higher than PdCl2, it is unfavorable for industry
Change and promote；Key is Pd (acac)2The diffusivity of molecule is less than PdCl2The pd existed in the form of an ion in solution2+Diffusion
Ability, is unfavorable for immersing diatomite pore interior, causes the palladium salt skewness of absorption, repeatedly inhales/put easily efflorescence after hydrogen circulation
Come off.
The content of the invention
For the defect existing for the preparation technology of load palladium diatomite composite material in the prior art, the purpose of the present invention exists
In a kind of preparation method of new load palladium diatomite composite material is provided, the preparation method process is simple, reaction is gentle, easily control
System, technically reliable, Load Balanced.
To achieve the above object, the present invention uses following technical scheme：
The present invention carries palladium diatomite composite material using one-step synthesis method, by PdCl2Directly exist with acetylacetone,2,4-pentanedione reaction
Pd (acac) is generated on diatomite support2, the intermediate is that can obtain Pd/K composites by calcining, specially：
A kind of preparation method for carrying palladium diatomite composite material, comprises the following steps：
(1) by a certain amount of PdCl2It is dissolved in concentrated hydrochloric acid, is sufficiently stirred for and heats, is completely dissolved it；
(2) to adding diatomite particle in solution and stirring, it is sufficiently impregnated；
(3) add excessive acetylacetone,2,4-pentanedione and be sufficiently stirred for, solution ph is adjusted to 7~9 with NaOH or KOH, in diatomite
Surface and internal generation yellow mercury oxide Pd (acac)2, will be impregnated of Pd (acac)2Diatomite filtering, dry；
(4) finally by the intermediate of gained --- load Pd (acac)2The middle temperature heating and calcining of diatomite obtain carry palladium
Diatomite composite material.
The concentration of concentrated hydrochloric acid is 30~38% in the step (1), and heating-up temperature is 30~90 DEG C, and mixing time is more than
5min。
Can be in PdCl2During dissolving, to adding appropriate amount of deionized water to be diluted in solution, silicon is then added thereto to again
Diatomaceous earth particle.
The granularity of diatomite particle is 0~100 mesh, preferably 20~80 mesh, porosity of=in the step (2)
80%.
The diatomite apparent volume added in the step (2) is the 50%~200% of liquor capacity, when stirring, dipping
Between be more than 10min.
Step (3) need not be washed after the sediment filtering for obtaining different from conventional precipitation method technique by a large amount of water
Except chloride, the removal in step (4) after chlorion is to be dried.
Middle temperature heating and calcining in the step (4) is that 270~600 DEG C of thermal decompositions, insulation are heated in hydrogen atmosphere
20~120min；Then raise temperature to 600~1300 DEG C of sintering more than 60min.
Because palladium does not react with acetylacetone,2,4-pentanedione, hydrochloric acid, NaOH or KOH under the cited reaction conditions, the Pd/K that will can be obtained
Composite again with PdCl2Hydrochloric acid solution mixing, dipping, repeat step (2)~(4), can gradually improve Pd/K be combined
The palladium load capacity of material.
The present invention both make use of PdCl2Pd in solution2+Diffusivity it is strong, be easy to inside immersion diatomite, cost is relative
More low advantage；Pd (acac) is make use of again2Decomposition temperature it is low, ensure that structure of diatomite is complete, in neutral, follow-up load
The advantages of there is no secondary dissolving in palladium；It is disposable to complete Pd (acac) in conventional method2Synthesis impregnates two techniques with diatomite
Link.The Pd/K composites obtained by the method for the present invention have good uniformity, can be directly used for the same position of filling hydrogen
Plain splitter, carries out hydrogen isotope separation.
Compared with existing load palladium diatomite composite material technology of preparing, the invention has the advantages that：
(1) equipment is simple, technological process is short needed for the present invention, simple operation, with low cost, it is only necessary to which a step precipitation reaction is
Pd (acac) can formed2While it is uniformly distributed in diatomaceous surface and hole.
(2) Pd/K composite woods are prepared with the inorganic palladium salt dipping-decomposition method such as traditional palladium nitrate, palladium bichloride, palladium nitrate ammonium
Material is compared, Pd (acac)2Decomposition temperature it is low, reaction is gentle, survivable structure of diatomite.
(3) with the Pd (acac) of report in this seminar open source literature2Dipping-decomposition method prepares Pd/K composite phases
Than by Pd (acac)2Synthesis united two into one with the process of impregnating kieselguhr, decomposition obtain Metal Palladium granular size, distribution
More uniform, load capacity is higher, while avoiding introducing chloroform etc. for dissolving Pd (acac)2Organic solvent, also further drop
Low cost, is easy to promote and realize commercial applications.
Brief description of the drawings
Fig. 1 is Pd/K composite microscopic appearance electron scanning micrographs prepared by the embodiment of the present invention 1.
Fig. 2 is the X-ray energy spectrum analysis of spectra of Pd/K composites prepared by the embodiment of the present invention 1.
Specific embodiment
The invention will be further described by the following examples, but the present invention is not limited to following examples.
Embodiment 1
By 8.33g (0.047mol) PdCl2It is dissolved in the concentrated hydrochloric acid that 10mL concentration is 38%, liquid is heated to 40 DEG C
Stirring 10min, adds the dilution of 100mL deionized waters after lowering the temperature.5g granularities are subsequently added for 20~80 mesh, porosity be not low
In 90% diatomite particle, (apparent volume is 14cm3), stirring 60min allows it to be sufficiently impregnated in the solution.Add 9.41g
Acetylacetone,2,4-pentanedione, and add NaOH to adjust solution ph to 7, it is now all inside and outside diatomite particle to be soaked with PdCl2It is equal at solution
Yellow mercury oxide is produced, obtaining surface and pore interior after filtering, drying has loaded Pd (acac)2Diatomite particle
19.01g.The intermediate is heated to 600 DEG C of thermal decompositions in hydrogen atmosphere, the flow of hydrogen is 20sccm, is incubated 60min,
1300 DEG C of sintering 60min are then raised temperature to, final Pd/K composite 9.83g are obtained, palladium load capacity is 49.14%.The material
Material hydrogen-sucking amount is 0.62wt%, can inhale and put hydrogen recycling more than 3200 times.This sample is observed using SEM
Its microscopic appearance, photo is shown in Fig. 1, it can be found that the crystalline particle of Metal Palladium is uniformly distributed in the surface and hole of diatomite support
Inside gap；Energy spectrum analysis is carried out to it, spectrogram is shown in Fig. 2, confirm as palladium with diatomaceous composite.
Embodiment 2
By 8.33g (0.047mol) PdCl2It is dissolved in the concentrated hydrochloric acid that 19mL concentration is 37%, liquid is heated to 50 DEG C
Stirring 20min, adds the dilution of 80mL deionized waters after lowering the temperature.4g granularities are subsequently added for 20~60 mesh, porosity be not low
In 90% diatomite particle, (apparent volume is 12cm3), stirring 90min allows it to be sufficiently impregnated in the solution.Add 9.41g
Acetylacetone,2,4-pentanedione, and add KOH to adjust solution ph to 7.5, it is now all inside and outside diatomite particle to be soaked with PdCl2It is equal at solution
Yellow mercury oxide is produced, obtaining surface and pore interior after filtering, drying has loaded Pd (acac)2Diatomite particle
18.06g.The intermediate is heated to 500 DEG C of thermal decompositions in hydrogen atmosphere, the flow of hydrogen is 50sccm, is incubated 40min,
1100 DEG C of sintering 90min are then raised temperature to, final Pd/K composite 8.79g are obtained, palladium load capacity is 54.49%.The material
Material hydrogen-sucking amount is 0.69wt%, can inhale and put hydrogen recycling more than 2800 times.
Embodiment 3
By 17.74g (0.1mol) PdCl2It is dissolved in the concentrated hydrochloric acid that 30mL concentration is 36%, liquid is heated to 60 DEG C
Stirring 15min, adds the dilution of 180mL deionized waters after lowering the temperature.Be subsequently added 10g granularities for 20~40 mesh, porosity not
(apparent volume is 30cm to diatomite particle less than 90%3), stirring 120min allows it to be sufficiently impregnated in the solution.Add
20.04g acetylacetone,2,4-pentanediones, and add NaOH to adjust solution ph to 8, it is now all inside and outside diatomite particle to be soaked with PdCl2It is molten
Yellow mercury oxide is produced at liquid, obtaining surface and pore interior after filtering, drying has loaded Pd (acac)2Diatomite particle
40.08g.The intermediate is heated to 350 DEG C of thermal decompositions in hydrogen atmosphere, the flow of hydrogen is 100sccm, is incubated 30min,
1200 DEG C of sintering 120min are then raised temperature to, final Pd/K composite 20.44g are obtained, palladium load capacity is 51.08%.Should
Material hydrogen-sucking amount is 0.65wt%, can inhale and put hydrogen recycling more than 3000 times.
Claims (8)
1. it is a kind of carry palladium diatomite composite material preparation method, it is characterised in that use one-step synthesis method, specifically include as follows
Step：
(1) by a certain amount of PdCl2It is dissolved in concentrated hydrochloric acid, is sufficiently stirred for and heats, is completely dissolved it；
(2) to adding diatomite particle in solution and stirring, it is sufficiently impregnated；
(3) add excessive acetylacetone,2,4-pentanedione and be sufficiently stirred for, solution ph is adjusted to 7~9 with NaOH or KOH, on diatomite surface
With internal generation yellow mercury oxide Pd (acac)2, will be impregnated of Pd (acac)2Diatomite filtering, dry；
(4) finally by the intermediate of gained --- load Pd (acac)2The middle temperature heating and calcining of diatomite obtain carry palladium diatomite
Composite.
2. it is according to claim 1 carry palladium diatomite composite material preparation method, it is characterised in that：The step (1)
The concentration of middle concentrated hydrochloric acid is 30~38%, and heating-up temperature is 30~90 DEG C, and mixing time is more than 5min.
3. it is according to claim 1 carry palladium diatomite composite material preparation method, it is characterised in that：Step (1) is obtained
To solution be diluted with deionized water, then carry out step (2).
4. it is according to claim 1 carry palladium diatomite composite material preparation method, it is characterised in that：The step (2)
The granularity of middle diatomite particle is 0~100 mesh, porosity of=80%.
5. it is according to claim 4 carry palladium diatomite composite material preparation method, it is characterised in that：Described diatomite
The granularity of particle is 20~80 mesh.
6. it is according to claim 1 carry palladium diatomite composite material preparation method, it is characterised in that：The step (2)
The diatomite apparent volume of middle addition is the 50%~200% of liquor capacity, and stirring, dip time are more than 10min.
7. it is according to claim 1 carry palladium diatomite composite material preparation method, it is characterised in that：The step (4)
In middle temperature heating and calcining be heated in hydrogen atmosphere 270~600 DEG C thermal decomposition, be incubated 20~120min；Then heat up
To 600~1300 DEG C of sintering more than 60min.
8. it is according to claim 1 carry palladium diatomite composite material preparation method, it is characterised in that：The load palladium that will be obtained
Diatomite composite material again with PdCl2Hydrochloric acid solution mixing, dipping, repeat step (2)~(4), with improve carry palladium diatom
The palladium load capacity of soil composite material.
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Effective date of registration: 20190624 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: No. 2, Xinjie street, Xicheng District, Beijing, Beijing Patentee before: General Research Institute for Nonferrous Metals |