CN105233690A - Preparation method for palladium-loaded diatomite composite material - Google Patents
Preparation method for palladium-loaded diatomite composite material Download PDFInfo
- Publication number
- CN105233690A CN105233690A CN201410332119.9A CN201410332119A CN105233690A CN 105233690 A CN105233690 A CN 105233690A CN 201410332119 A CN201410332119 A CN 201410332119A CN 105233690 A CN105233690 A CN 105233690A
- Authority
- CN
- China
- Prior art keywords
- diatomite
- palladium
- composite material
- preparation
- acac
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method for a palladium-loaded diatomite composite material. The method comprises the following steps: (1) dissolving a certain amount of PdCl2 in concentrated hydrochloric acid, and fully stirring and heating the solution to enable PdCl2 to be completely dissolved; (2) adding diatomite particles into the solution and carrying out uniform stirring to allow full impregnation; (3) adding an excess amount of acetylacetone and carrying out full stirring, adjusting the pH value of the obtained solution to be 7 to 9 by using NaOH or KOH such that a yellow precipitate Pd(acac)2 is generated at the surface and the interior of the diatomite, and subjecting the diatomite impregnated with the Pd(acac)2 to filtering and drying; and (4) finally, subjecting the obtained intermediate, i.e. the diatomite supporting Pd(acac)2, to medium-temperature heating and calcining so as to obtain the palladium-loaded diatomite composite material. The preparation method for the palladium-loaded diatomite composite material provided by the invention one-time completes two process steps of synthesis of Pd(acac)2 and impregnation of the diatomite in a traditional method, has the advantages of simple method, mild reaction, easy control and reliable technology, can be used for preparation of the high-performance palladium-loaded diatomite composite material, and can be applied in the fields of separation and extraction of hydrogen isotopes.
Description
Technical field
The present invention relates to the preparation method of a kind of year palladium diatomite composite material, the synthesized palladium diatomite composite material that carries can be used as high-performance hydrogen isotope separation material, is applied to Purification for hydrogen isotopes, separation and extraction technical 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 effect.Wherein, hydrogen isotope separation is one of core technology utilizing deuterium tritium fusion energy, and the performance of parting material is then the key factor determining separative efficiency.In numerous hydrogen isotope separation materials, carry palladium diatomite (Pd/K) composite and there is the advantage that specific area is large and palladium load capacity is high, can cushion to inhale and put internal stress in hydrogen cyclic process, the contact interface that increases hydrogen and palladium, improve and inhale/hydrogen discharge reaction and isotope exchange rate [I.A.Fisher, WestinghouseSavannahRiverCompany-RP-93-401 (1993)]; The volume of splitter can also be reduced and improve separating property people such as [, J.AlloysComp., 62 (1999) 293] K.L.Shanahan of system.Therefore, Pd/K composite stores as hydrogen isotope, separation and extraction material obtains and studies concern greatly, is widely used in recent years in fusion fuel circulation and tritium treatment process.
In palladium salting liquid wet impregnation-decomposition method that the preparation method that present stage Pd/K composite is main is the proposition of U.S. Sa Fanna river National Laboratory, this laboratory utilizes the presomas such as palladium nitrate, palladium bichloride, palladium nitrate ammonium, by its solution nature impregnating kieselguhr carrier, ageing, the air-dry rear Pd/K composite [people such as K.L.Shanahan preparing different palladium content, J.AlloysComp., 62 (1999) 293; W.C.Mosley, WestinghouseSavannahRiverCompany-TR-90-24 (1990)].Although the method is the main method of testing at present and adopting in certain applications, but its presoma is inorganic palladium salt, violent because flooding the too high reaction of rear heat resolve temperature, very easily destroy structure of diatomite, and Pd/K composite separating property after diatomite efflorescence, can be caused to reduce and block piece-rate system.
Inventor place seminar reports and adopts palladium acetylacetonate (Pd (acac) in open source literature rare metal 2011 (35) 2:238-243
2) be presoma, be that solvent floods the method preparing Pd/K composite naturally with chloroform, reduce heat decomposition temperature, but Pd (acac)
2water insoluble, need the organic solvents such as chloroform be introduced; And processing cost is higher than PdCl
2, be unfavorable for industrialization promotion; Key is Pd (acac)
2the diffusivity of molecule is less than PdCl
2the pd existed in the form of an ion in solution
2+diffusivity, be unfavorable for immersing diatomite pore interior, cause the palladium salt distribution of adsorbing uneven, repeatedly to inhale/put after hydrogen circulation easily powder of detached.
Summary of the invention
For in prior art carry palladium diatomite composite material preparation technology existing for defect, the object of the present invention is to provide a kind of newly carry the preparation method of palladium diatomite composite material, this preparation method's process is simple, reaction temperature and, easily control, technically reliable, Load Balanced.
For achieving the above object, the present invention is by the following technical solutions:
The present invention adopts one-step synthesis method to carry palladium diatomite composite material, passes through PdCl
2react with acetylacetone,2,4-pentanedione and directly on diatomite support, generate Pd (acac)
2, this intermediate can obtain Pd/K composite through calcining, is specially:
A preparation method for year palladium diatomite composite material, comprises the steps:
(1) by a certain amount of PdCl
2be dissolved in concentrated hydrochloric acid, fully stir and heat, making it dissolve completely;
(2) in solution, add diatomite particle and stir, fully flooding;
(3) add excessive acetylacetone,2,4-pentanedione and fully stir, regulating solution ph to 7 ~ 9 with NaOH or KOH, all generating yellow mercury oxide Pd (acac) on diatomite surface and inside
2, Pd (acac) will be impregnated of
2diatomite filtration, drying;
(4) finally by the intermediate of gained---load Pd (acac)
2diatomite in warm heating and calcining obtain carry a palladium diatomite composite material.
In described step (1), the concentration of concentrated hydrochloric acid is 30 ~ 38%, and heating-up temperature is 30 ~ 90 DEG C, and mixing time is greater than 5min.
Can at PdCl
2during dissolving, in solution, add appropriate amount of deionized water dilute, and then add diatomite particle wherein.
In described step (2), the granularity of diatomite particle is 0 ~ 100 order, is preferably 20 ~ 80 orders, porosity of=80%.
The diatomite apparent volume added in described step (2) is 50% ~ 200% of liquor capacity, and stirring, dip time are greater than 10min.
Step (3) is different from conventional precipitation method technique, removing chloride, removing after chlorion is to be dried in step (4) after the sediment obtained filters without the need to being rinsed by large water gaging.
Middle temperature heating and calcining in described step (4), for be heated to 270 ~ 600 DEG C of thermal decompositions in hydrogen atmosphere, is incubated 20 ~ 120min; Be warming up to 600 ~ 1300 DEG C of sintering more than 60min subsequently.
Because palladium does not react with acetylacetone,2,4-pentanedione, hydrochloric acid, NaOH or KOH under the cited reaction conditions, can by the Pd/K composite that obtains again with PdCl
2hydrochloric acid solution mixing, dipping, repeat step (2) ~ (4), successively can improve the palladium load capacity of Pd/K composite.
The present invention both make use of PdCl
2pd in solution
2+diffusivity strong, to be easy to immerse diatomite inner, the advantages such as cost is relatively lower; Make use of again Pd (acac)
2decomposition temperature low, ensure that structure of diatomite is complete, there is not the advantages such as secondary dissolving in palladium that is neutral, follow-up load; Disposablely complete Pd in conventional method (acac)
2synthesis and diatomite flood two process procedures.The Pd/K composite obtained by method of the present invention has good uniformity, can be directly used in filling hydrogen isotope separation post, carry out hydrogen isotope separation.
Compared with existing year palladium diatomite composite material technology of preparing, tool of the present invention has the following advantages:
(1) equipment required for the present invention is simple, technological process is short, simple operation, with low cost, only need a step precipitation reaction can in formation Pd (acac)
2while make it be uniformly distributed in diatomaceous surface and hole.
(2) flood with inorganic palladium salt such as traditional palladium nitrate, palladium bichloride, palladium nitrate ammoniums-decomposition method is prepared compared with Pd/K composite, Pd (acac)
2decomposition temperature low, reaction temperature and, survivable structure of diatomite.
(3) with the Pd (acac) that reports in this seminar open source literature
2dipping-decomposition method is prepared Pd/K composite and is compared, by Pd (acac)
2synthesis and the process of impregnating kieselguhr unite two into one, it is more even to decompose the Metal Palladium granular size, the distribution that obtain, and load capacity is higher, avoids introducing chloroform etc. for dissolving Pd (acac) simultaneously
2organic solvent, further reduces cost, be convenient to promote and realize commercial applications.
Accompanying drawing explanation
Fig. 1 is Pd/K composite microscopic appearance electron scanning micrograph prepared by the embodiment of the present invention 1.
Fig. 2 is the X-ray energy spectrum analysis of spectra of Pd/K composite prepared by the embodiment of the present invention 1.
Detailed description of the invention
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) PdCl
2being dissolved in 10mL concentration is in the concentrated hydrochloric acid of 38%, and heating liquid to 40 DEG C is stirred 10min, adds the dilution of 100mL deionized water after lowering the temperature.Add that 5g granularity is 20 ~ 80 orders subsequently, porosity be not less than 90% diatomite particle (apparent volume is 14cm
3), stirring 60min is allowed to condition in solution and fully floods.Add 9.41g acetylacetone,2,4-pentanedione again, and add NaOH and regulate solution ph to 7, now allly inside and outside diatomite particle be soaked with PdCl
2solution place all produces yellow mercury oxide, obtains surface and pore interior equal load Pd (acac) after filtration, drying
2diatomite particle 19.01g.This intermediate is heated in hydrogen atmosphere 600 DEG C of thermal decompositions, the flow of hydrogen is 20sccm, insulation 60min, and be warming up to 1300 DEG C of sintering 60min subsequently, obtain final Pd/K composite 9.83g, palladium load capacity is 49.14%.This material hydrogen-sucking amount is 0.62wt%, can inhale to put hydrogen and recycle more than 3200 times.Adopt its microscopic appearance of sem observation to this sample, Fig. 1 is shown in by photo, can find that the crystalline particle of Metal Palladium is distributed in surface and the pore interior of diatomite support uniformly; Carry out energy spectrum analysis to it, spectrogram is shown in Fig. 2, confirms as palladium and diatomaceous composite.
Embodiment 2
By 8.33g (0.047mol) PdCl
2being dissolved in 19mL concentration is in the concentrated hydrochloric acid of 37%, and heating liquid to 50 DEG C is stirred 20min, adds the dilution of 80mL deionized water after lowering the temperature.Add that 4g granularity is 20 ~ 60 orders subsequently, porosity be not less than 90% diatomite particle (apparent volume is 12cm
3), stirring 90min is allowed to condition in solution and fully floods.Add 9.41g acetylacetone,2,4-pentanedione again, and add KOH and regulate solution ph to 7.5, now allly inside and outside diatomite particle be soaked with PdCl
2solution place all produces yellow mercury oxide, obtains surface and pore interior equal load Pd (acac) after filtration, drying
2diatomite particle 18.06g.This intermediate is heated in hydrogen atmosphere 500 DEG C of thermal decompositions, the flow of hydrogen is 50sccm, insulation 40min, and be warming up to 1100 DEG C of sintering 90min subsequently, obtain final Pd/K composite 8.79g, palladium load capacity is 54.49%.This material hydrogen-sucking amount is 0.69wt%, can inhale to put hydrogen and recycle more than 2800 times.
Embodiment 3
By 17.74g (0.1mol) PdCl
2being dissolved in 30mL concentration is in the concentrated hydrochloric acid of 36%, and heating liquid to 60 DEG C is stirred 15min, adds the dilution of 180mL deionized water after lowering the temperature.Add that 10g granularity is 20 ~ 40 orders subsequently, porosity be not less than 90% diatomite particle (apparent volume is 30cm
3), stirring 120min is allowed to condition in solution and fully floods.Add 20.04g acetylacetone,2,4-pentanedione again, and add NaOH and regulate solution ph to 8, now allly inside and outside diatomite particle be soaked with PdCl
2solution place all produces yellow mercury oxide, obtains surface and pore interior equal load Pd (acac) after filtration, drying
2diatomite particle 40.08g.This intermediate is heated in hydrogen atmosphere 350 DEG C of thermal decompositions, the flow of hydrogen is 100sccm, insulation 30min, and be warming up to 1200 DEG C of sintering 120min subsequently, obtain final Pd/K composite 20.44g, palladium load capacity is 51.08%.This material hydrogen-sucking amount is 0.65wt%, can inhale to put hydrogen and recycle more than 3000 times.
Claims (8)
1. carry a preparation method for palladium diatomite composite material, it is characterized in that, adopt one-step synthesis method, specifically comprise the steps:
(1) by a certain amount of PdCl
2be dissolved in concentrated hydrochloric acid, fully stir and heat, making it dissolve completely;
(2) in solution, add diatomite particle and stir, fully flooding;
(3) add excessive acetylacetone,2,4-pentanedione and fully stir, regulating solution ph to 7 ~ 9 with NaOH or KOH, all generating yellow mercury oxide Pd (acac) on diatomite surface and inside
2, Pd (acac) will be impregnated of
2diatomite filtration, drying;
(4) finally by the intermediate of gained---load Pd (acac)
2diatomite in warm heating and calcining obtain carry a palladium diatomite composite material.
2. the preparation method of according to claim 1 year palladium diatomite composite material, is characterized in that: in described step (1), the concentration of concentrated hydrochloric acid is 30 ~ 38%, and heating-up temperature is 30 ~ 90 DEG C, and mixing time is greater than 5min.
3. the preparation method of according to claim 1 year palladium diatomite composite material, is characterized in that: the solution deionized water that step (1) obtains diluted, then carries out step (2).
4. the preparation method of according to claim 1 year palladium diatomite composite material, is characterized in that: in described step (2), the granularity of diatomite particle is 0 ~ 100 order, porosity of=80%.
5. the preparation method of according to claim 4 year palladium diatomite composite material, is characterized in that: the granularity of described diatomite particle is 20 ~ 80 orders.
6. the preparation method of according to claim 1 year palladium diatomite composite material, is characterized in that: the diatomite apparent volume added in described step (2) is 50% ~ 200% of liquor capacity, and stirring, dip time are greater than 10min.
7. the preparation method of according to claim 1 year palladium diatomite composite material, is characterized in that: the middle temperature heating and calcining in described step (4), for be heated to 270 ~ 600 DEG C of thermal decompositions in hydrogen atmosphere, is incubated 20 ~ 120min; Be warming up to 600 ~ 1300 DEG C of sintering more than 60min subsequently.
8. the preparation method of according to claim 1 year palladium diatomite composite material, is characterized in that: by obtain carry palladium diatomite composite material again with PdCl
2hydrochloric acid solution mixing, dipping, repeat step (2) ~ (4), carry the palladium load capacity of palladium diatomite composite material to improve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410332119.9A CN105233690B (en) | 2014-07-11 | 2014-07-11 | A kind of preparation method for carrying palladium diatomite composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410332119.9A CN105233690B (en) | 2014-07-11 | 2014-07-11 | A kind of preparation method for carrying palladium diatomite composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105233690A true CN105233690A (en) | 2016-01-13 |
| CN105233690B CN105233690B (en) | 2017-06-20 |
Family
ID=55031662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410332119.9A Active CN105233690B (en) | 2014-07-11 | 2014-07-11 | A kind of preparation method for carrying palladium diatomite composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105233690B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903349A (en) * | 2016-06-07 | 2016-08-31 | 中国工程物理研究院核物理与化学研究所 | Large-area palladium membrane device for hydrogen isotope separation |
| CN112851954A (en) * | 2019-11-27 | 2021-05-28 | 吉林大学 | Covalent organic framework, composite material thereof, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1010464A2 (en) * | 1998-12-17 | 2000-06-21 | Agency Of Industrial Science And Technology | Palladium ceria supported catalyst and process for the synthesis of methanol |
| CN1531996A (en) * | 2003-03-21 | 2004-09-29 | 金坛市凌云化工厂 | Preparation of modified hydrogen at-ing catalyst and use |
| WO2008101602A2 (en) * | 2007-02-19 | 2008-08-28 | Dsm Ip Assets B.V. | Catalysts containing platinum group metal nanoparticles and process for production of dispersions of nanoparticles of platinum group metal |
| CN101485354A (en) * | 2009-02-27 | 2009-07-22 | 浙江大学 | Modified Pd-containing ethylene-absorbing agent and preparation method thereof |
-
2014
- 2014-07-11 CN CN201410332119.9A patent/CN105233690B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1010464A2 (en) * | 1998-12-17 | 2000-06-21 | Agency Of Industrial Science And Technology | Palladium ceria supported catalyst and process for the synthesis of methanol |
| CN1531996A (en) * | 2003-03-21 | 2004-09-29 | 金坛市凌云化工厂 | Preparation of modified hydrogen at-ing catalyst and use |
| WO2008101602A2 (en) * | 2007-02-19 | 2008-08-28 | Dsm Ip Assets B.V. | Catalysts containing platinum group metal nanoparticles and process for production of dispersions of nanoparticles of platinum group metal |
| CN101485354A (en) * | 2009-02-27 | 2009-07-22 | 浙江大学 | Modified Pd-containing ethylene-absorbing agent and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| NAGENDRANATH MAHATA1 ET AL.: "Influence of Palladium Precursors on Structural Properties and Phenol Hydrogenation Characteristics of Supported Palladium Catalysts", 《JOURNAL OF CATALYSIS》 * |
| 吉亚莉 等: "载钯硅藻土复合材料吸/放氢循环性能和抗粉化性能研究", 《稀有金属》 * |
| 陈伟 等: "载钯硅藻土的制备及其吸放氢性能研究", 《原子能科学技术》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903349A (en) * | 2016-06-07 | 2016-08-31 | 中国工程物理研究院核物理与化学研究所 | Large-area palladium membrane device for hydrogen isotope separation |
| CN105903349B (en) * | 2016-06-07 | 2017-06-27 | 中国工程物理研究院核物理与化学研究所 | A kind of large area palladium film device for hydrogen isotope separation |
| CN112851954A (en) * | 2019-11-27 | 2021-05-28 | 吉林大学 | Covalent organic framework, composite material thereof, preparation method and application |
| CN112851954B (en) * | 2019-11-27 | 2022-11-08 | 吉林大学 | Covalent organic framework, composite material thereof, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105233690B (en) | 2017-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110743624B (en) | Acetylene hydrochlorination copper-based catalyst and preparation method and application thereof | |
| CN107342110B (en) | A kind of UO2The preparation process of graphene hybrid fuel pressed powder | |
| CN103721645B (en) | A kind of carbon aerogels for electric adsorption electrode and preparation method thereof | |
| CN105478120A (en) | Preparation method for red mud-based iron-series catalyst and application of red mud-based iron-series catalyst in hydrogen production through cracking of methane | |
| CN110252410B (en) | Ternary composite photocatalyst, preparation method and application thereof | |
| CN108499537A (en) | A kind of foam metal/preparation of metal organic framework composite material and the application of ammonia gas absorption | |
| CN103008684A (en) | Method for preparing metal nanoparticles by means of atmospheric pressure cold plasmas | |
| CN104773730A (en) | Method for preparing graphene | |
| CN105977502A (en) | Three-dimensional graphene/silver nanoparticle composite material employing nickel foam as matrix and preparation method of three-dimensional graphene/silver nanoparticle composite material | |
| CN111151299B (en) | Copper alkoxide complex catalyst, preparation method thereof and application thereof in acetylene hydrochlorination | |
| CN101899487A (en) | Method for in-situ enzymolysis and recovery of cellulose system | |
| CN104911639A (en) | Supported silver nanonet, and preparation method and application thereof | |
| CN109433195A (en) | A kind of method that solvent-thermal method prepares charcoal supported noble metal catalyst | |
| Bonggotgetsakul et al. | A method for coating a polymer inclusion membrane with palladium nanoparticles | |
| CN104986791A (en) | Preparation method for nanopore structure copper/cuprous oxide/copper oxide composite material | |
| CN110734049A (en) | method for preparing nitrogen-doped carbon material with high specific surface area by using potassium phthalimide | |
| CN109112568A (en) | It is a kind of based on boron, the catalyst of nitrogen co-doped mesoporous carbon and its preparation method and application | |
| CN105233690A (en) | Preparation method for palladium-loaded diatomite composite material | |
| CN105126738A (en) | Preparation method of porous composite material for removal of fluorine ions from water | |
| CN113680326A (en) | Sulfonic acid COFs membrane and preparation method and application thereof | |
| CN103894158A (en) | Preparation method and application of palladium adsorption material | |
| CN110655138A (en) | Preparation method and application of MOFs composite material | |
| CN105043839A (en) | Method for separating and enriching fulvic acid in soil through activated carbon | |
| CN104307523A (en) | One-step method for preparation of iron loaded activated carbon catalyst from rice husk pyrolytic carbon | |
| CN107176649B (en) | Method for separating 2-naphthalenesulfonic acid in wastewater by using iron-loaded copper macroporous resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
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 |