CN105195152A - Preparation method of Ni-loaded honeycomb ceramic catalyst suitable for VPCE - Google Patents
Preparation method of Ni-loaded honeycomb ceramic catalyst suitable for VPCE Download PDFInfo
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- CN105195152A CN105195152A CN201510657451.7A CN201510657451A CN105195152A CN 105195152 A CN105195152 A CN 105195152A CN 201510657451 A CN201510657451 A CN 201510657451A CN 105195152 A CN105195152 A CN 105195152A
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Abstract
The invention discloses a preparation method of a Ni-loaded honeycomb ceramic catalyst suitable for VPCE. The preparation method comprises the following steps: (1) drying honeycomb ceramic at 150 DEG C, and taking the dried honeycomb ceramic as a carrier; (2) weighing a saturated Ni(NO3)2 water solution with the water absorbing capacity isometric to that of the carrier, then putting the carrier into the water solution, dipping for more than 12h until the saturated Ni(NO3)2 water solution is completely absorbed, and uniformly distributing Ni ions into the carrier; (3) roasting the carrier for more than 2 hours until nitro is removed under the condition that air atmosphere exists, and the temperature is at least 350 DEG C; and (4) reducing the carrier subjected to nitro removal under the hydrogen atmosphere with the concentration being 10%, thus obtaining the honeycomb ceramic catalyst. According to the preparation method, the process is simple, the period is short, the cost is low, the strength is high, the catalytic effect is obvious, and a good foundation is provided for researching VPCE and the catalyst, so that the preparation method is suitable for promotion and application.
Description
Technical field
The present invention relates to a kind of catalyst, that be specifically related to is a kind of preparation method carrying Ni ceramic honeycomb catalyst being applicable to VPCE.
Background technology
It is first dense that vapor phase catalytic exchanges that (VPCE) can be used for producing in heavy water process, and reactor heavy water detritiation, the production of heavy water during coming across U.S. Manhattan the earliest.The seventies in last century, the Lane-Langevin research institute of France adopts the technology of VPCE+ cryogenic rectification (CD) to carry out heavy water detritiation, and this utilizes VPCE to carry out heavy water detritiation industrial applications the earliest.
Can produce a large amount of HTOs in fusion reactor, these HTOs must reach and allow the standard of discharge just can be discharged.International Thermal-Nuclear Experimental Reactor (ITER) is intended using VPCE reaction unit to carry out water in the works and is fallen tritium, makes the HTO concentration of high concentration be reduced to the normal concentration that can discharge.
In order to improve the efficiency that hydrogen-water vapour vapor phase catalytic exchanges, reaction needed is reacted at 200 DEG C, and now two-phase is hydrogen and water vapour, and whole process need could complete rapidly under catalyst existent condition.Reactant is gas phase (vapour phase), therefore traditional hydrophilic catalyst.The catalyst used the earliest is Pt/C and Ni/Cr
2o
3, developed into Pt/Al gradually afterwards
2o
3catalyst.Following reaction is there is in VPCE process:
Catalysis exchange process is diffusion, chemisorbed, surface reaction, desorption and diffusion in the other direction: with above-mentioned first reaction HDO+H
2for example:
Reactant hydrogen gas and vapour molecule diffuse into the inside (interior diffusion) of catalyst granules, reactant chemisorbed, under the effect of catalyst, and H
2or hydrogen isotope gas carries out absorption and dissociates on active metal surface, for reaction provides active hydrogen atom, carry out isotope exchange on a catalyst, finally complete desorption and hydrogen atom combines.
From describing above, the development of catalyst is the key issue of VPCE process.The VPCE device of China is in laboratory development at present, not practice, and associated catalysts preparation is not also seen in report with test.Know from pertinent literature, the VPCE catalyst used on a large scale is mainly precious metals pt catalyst, because of its use amount huge (feather weight), so involve great expense.Its carrier mostly is C or Al
2o
3carrier, shape is granule ball-type, and type of feed is uncertain, and pressure drop is large.
Therefore, in order to reduce catalyst cost of manufacture, simplify preparation technology, improve catalyst service life, increase catalytic activity, seek a kind of easily filling, low pressure drop, intensity is large, high temperature resistant, specific area large, have with active metal the problems such as the catalyst carrier of stronger adhesion to be a difficult problem of being badly in need of at present capturing.
Summary of the invention
For above-mentioned technical deficiency, the invention provides a kind of preparation method carrying Ni ceramic honeycomb catalyst being applicable to VPCE, can solve that known VPCE catalyst cost is high well, complex process, pressure drop is high, intensity is low, specific area is little, with the problem such as active metal adhesion is poor.
For achieving the above object, the present invention's technical scheme of dealing with problems is as follows:
Be applicable to the preparation method carrying Ni ceramic honeycomb catalyst of VPCE, described catalyst is by the ceramic honey comb as carrier, and load is formed on carrier and as the elemental nickel of catalytic active component; Described preparation method then comprises the following steps:
(1) ceramic honey comb is dried at 150 DEG C, and it can be used as carrier;
(2) the saturated Ni (NO with carrier equal-volume water absorption is measured
3)
2the aqueous solution, then puts into this aqueous solution dipping more than 12 hours, until carrier is by saturated Ni (NO by carrier
3)
2the aqueous solution all absorbs, and the distribution of Ni uniform ion in the carrier;
(3) atmosphere be air, under temperature is at least the condition of 350 DEG C, by carrier calcination more than 2 hours, until it removes nitro;
(4) reducing removing the carrier after nitro under the hydrogen atmosphere of 10% concentration, obtaining ceramic honeycomb catalyst.
Further, described step (1) ~ (4) circulation twice.
In order to improve the combination property of catalyst further, described ceramic honey comb is cordierite honeycomb ceramic.
Compared with prior art, the present invention has following beneficial effect:
(1) present invention process is simple, manufacturing cycle is short, preparation cost is cheap, catalytic effect is obvious, for the follow-up study of VPCE and catalyst thereof provides very valuable reference.
(2) the present invention is using ceramic honey comb as carrier, the saturated Ni (NO of equal-volume water absorption
3)
2the aqueous solution is as maceration extract, after via roasting (air atmosphere, 350 DEG C of conditions) denitration base and reduction (hydrogen atmosphere), the load of Ni on ceramic honey comb can be realized, wherein not only raw material sources are extensive, with low cost for this, and it is substantially free from foreign meter, and the combination between Ni and carrier is tight, Ni particle difficult drop-off; Meanwhile, according to SEM shape appearance figure, catalyst prepared by the present invention, its surface is the Ni cluster of homodisperse about 300nm, and Ni particle is about 10nm, and load capacity is large, contributes to increasing specific area.Therefore, the present invention both ensure that the purity of catalyst, substantially increased again the catalytic effect of catalyst.
(3) the present invention selects cordierite honeycomb ceramic as carrier, is not only beneficial to filling, reduces pressure drop, and can ensure that catalyst stably catalytic reaction can occur in course of reaction further, can also keep catalytic effect for a long time simultaneously.
(4) cost performance of the present invention is high, practical, can be used for the production in enormous quantities of VPCE catalyst, and therefore, the present invention has very large market development potential, and it has outstanding substantive distinguishing features and significant progress compared to existing technology.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
Fig. 2 is the SEM shape appearance figure carrying the ceramic honeycomb catalyst of Ni prepared by the present invention
Fig. 3 is the EDS result schematic diagram of carrying the ceramic honeycomb catalyst of Ni prepared by the present invention.
Fig. 4 is the change curve schematic diagram that the static catalysis of the present invention exchanges deuterium content in hydrogen.
The change curve schematic diagram of tail gas deuterium content when Fig. 5 is VPCE of the present invention.
Detailed description of the invention
Illustrate that the invention will be further described with embodiment below in conjunction with accompanying drawing, mode of the present invention includes but are not limited to following examples.
As shown in Figure 1, the invention provides the ceramic honeycomb catalyst of a kind of load Ni, it is applicable to hydrogen-water vapour phase catalysis and exchanges (VPCE) aspect.The present invention is using ceramic honey comb as carrier, elemental nickel (Ni) is as catalytic active component material, and adopt the techniques such as oven dry, equal-volume-liquid impregnation, roasting and hydrogen reducing to process ceramic honey comb, thus obtained catalyst, its preparation process comprises as follows:
(1) ceramic honey comb is dried at 150 DEG C, and it can be used as carrier;
(2) the saturated Ni (NO with carrier equal-volume water absorption is measured
3)
2the aqueous solution, then puts into this aqueous solution dipping more than 12 hours, until carrier is by saturated Ni (NO by carrier
3)
2the aqueous solution all absorbs, and the distribution of Ni uniform ion in the carrier;
(3) atmosphere be air, under temperature is at least the condition of 350 DEG C, by carrier calcination more than 2 hours, until it removes nitro;
(4) reducing removing the carrier after nitro under the hydrogen atmosphere of 10% concentration, obtaining ceramic honeycomb catalyst.
In order to improve the load capacity of ceramic honey comb further, said process can repetitive cycling twice.
In addition, the catalyst due to VPCE needs to carry out catalyst operation in the adverse circumstances such as high temperature (200 DEG C), gas shock, high humility, and therefore, in order to improve the combination property of catalyst, the present invention has selected cordierite honeycomb ceramic as carrier.Because cordierite honeycomb ceramic has high temperature resistant, that specific area is large, structural strength is high advantage, catalyst thus can be made in course of reaction stably catalytic reaction can to occur, and catalytic effect can be kept for a long time.
Fig. 2 is the SEM pattern (1um) of the catalyst utilizing the present invention to prepare, as seen from Figure 2, and catalyst prepared by the present invention, Ni is wherein uniformly dispersed, and Ni cluster is about 300nm, Ni particle is about 10nm, load capacity is large, is conducive to the catalytic effect strengthening catalyst; Meanwhile, combine closely between Ni and substrate (cordierite), Ni particle difficult drop-off.
Fig. 3 is the EDS test result of the catalyst utilizing the present invention to prepare, as seen from Figure 3, and catalyst prepared by the present invention, catalyst only contains the Ni of cordierite and load, there are not other impurity, element composition is simple, and therefore obtained catalyst purity is quite high.
Be described with the effect of an example to catalyst prepared by the present invention below.
As shown in Figure 4, carry in filling 168g () in the batch reactor of Ni ceramic honeycomb catalyst, hydrogen is 1.6mol, deuterium-oxide is 2.92ml, be swift in response and occur and finally stablize, illustrate that catalyst catalytic performance is superior, the deuterium-oxide of 5% can be reduced to about 3.6% concentration.
And as shown in Figure 5, carrying in the small-sized VPCE dynamic response of Ni ceramic honeycomb catalyst in filling 168g (), hydrogen flowing quantity is 1L/min, and deuterium-oxide flow is 32ml/h, tail gas deuterium about concentration 3000ppm during molecular balance.
Above-mentioned two situations, time static, the deuterium-oxide of 5% drops to 3.6%, illustrates that the catalytic effect of catalyst own is superior; And final result during VPCE is 4.7%, although compared to slightly poor during static state, this is that therefore this is not the problem of catalyst catalytic performance because the technological parameter of VPCE device design itself is also in the design phase.
The present invention, by a kind of novel catalyst of design, solves the various problems that existing VPCE catalyst is existing at present well.Further, adopt the preparation method of the present invention's design, after replacing carrier and catalytic active component, can be applied in equally in the preparation of other loaded catalysts.Therefore, compared to existing technology, technological progress is fairly obvious in the present invention, and it breaches the constraint of prior art well, and the follow-up study for VPCE provides strong place mat.
Above-described embodiment is only one of the preferred embodiment of the present invention; should not be used for limiting the scope of the invention; in every case in body design thought of the present invention and the change having no essential meaning made mentally or polishing; its technical problem solved is still consistent with the present invention, all should be included within protection scope of the present invention.
Claims (3)
1. be applicable to the preparation method carrying Ni ceramic honeycomb catalyst of VPCE, it is characterized in that, described catalyst is by the ceramic honey comb as carrier, and load is formed on carrier and as the elemental nickel of catalytic active component; Described preparation method then comprises the following steps:
(1) ceramic honey comb is dried at 150 DEG C, and it can be used as carrier;
(2) the saturated Ni(NO with carrier equal-volume water absorption is measured
3)
2the aqueous solution, then puts into this aqueous solution dipping more than 12 hours, until carrier is by saturated Ni(NO by carrier
3)
2the aqueous solution all absorbs, and the distribution of Ni uniform ion in the carrier;
(3) atmosphere be air, under temperature is at least the condition of 350 DEG C, by carrier calcination more than 2 hours, until it removes nitro;
(4) reducing removing the carrier after nitro under the hydrogen atmosphere of 10% concentration, obtaining ceramic honeycomb catalyst.
2. the preparation method carrying Ni ceramic honeycomb catalyst being applicable to VPCE according to claim 1, is characterized in that, described step (1) ~ (4) circulation twice.
3. the preparation method carrying Ni ceramic honeycomb catalyst being applicable to VPCE according to claim 1 and 2, it is characterized in that, described ceramic honey comb is cordierite honeycomb ceramic.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116328848A (en) * | 2023-04-06 | 2023-06-27 | 安徽中核桐源科技有限公司 | Aluminum-based catalyst for improving isotope abundance as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011011877A1 (en) * | 2009-07-29 | 2011-02-03 | Stuart Andrew T B | Chlorate and chlorine dioxide systems adapted for the production of deuterium enriched water |
| CN104174420A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院大连化学物理研究所 | Silicon carbide based monolithic catalyst for synthetic gas methanation and preparation method |
-
2015
- 2015-10-12 CN CN201510657451.7A patent/CN105195152A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011011877A1 (en) * | 2009-07-29 | 2011-02-03 | Stuart Andrew T B | Chlorate and chlorine dioxide systems adapted for the production of deuterium enriched water |
| CN104174420A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院大连化学物理研究所 | Silicon carbide based monolithic catalyst for synthetic gas methanation and preparation method |
Non-Patent Citations (3)
| Title |
|---|
| V.ALMÃŞAN等: "A dynamic method for the study of H/D exchange on Ni catalysts", 《APPLIED SURFACE SCIENCE》 * |
| 中国核学会核材料专业委员会编: "《"98核材料会议文集》", 30 November 1999, 北京：原子能出版社 * |
| 朱洪法编著: "《催化剂载体制备及应用技术》", 31 October 2014, 北京：石油工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116328848A (en) * | 2023-04-06 | 2023-06-27 | 安徽中核桐源科技有限公司 | Aluminum-based catalyst for improving isotope abundance as well as preparation method and application thereof |
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Address after: 610000 Sichuan Province, Chengdu Shuangliu the Milky Way Road No. 596 Applicant after: Inst. of Materials, Chinese Academy of Engineering Physics Address before: 621700 Jiangyou, Sichuan Huafeng village, No. 9, No. Applicant before: Inst. of Materials, Chinese Academy of Engineering Physics |
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Application publication date: 20151230 |