CN1820850A - Non-crystalline alloy catalyst of uniform grain size and its preparing method - Google Patents
Non-crystalline alloy catalyst of uniform grain size and its preparing method Download PDFInfo
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- CN1820850A CN1820850A CN 200610024774 CN200610024774A CN1820850A CN 1820850 A CN1820850 A CN 1820850A CN 200610024774 CN200610024774 CN 200610024774 CN 200610024774 A CN200610024774 A CN 200610024774A CN 1820850 A CN1820850 A CN 1820850A
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Abstract
The present invention discloses non-crystalline alloy catalyst of uniform grain size and its preparation process. The catalyst is spherical grains of size in 10-500 nm. The preparation process includes: mixing metal salt solution and ligand solution well to form stable metal complex, adding reductant to obtain homogeneously mixed solution, ultrasonic initiation of reduction in the solution to obtain black solid, and washing separately with deionized water and absolute ethyl alcohol to obtain the non-crystalline alloy catalyst of uniform grain size. The said preparation process can maintain the high homogeneity and dispersion of the metal salt and reductant components, so as to prepare high performance non-crystalline alloy with uniform grain size. The catalyst may be used in hydrogenating various compounds with unsaturated functional radical and has hydrogenating performance superior to non-crystalline alloy prepared through conventional chemical reduction process.
Description
Technical field
The present invention relates to the uniform amorphous alloy catalyst of a kind of grain size, be specifically related to narrow distribution amorphous alloy catalyst and preparation method thereof.
Background technology
Amorphous alloy is meant that the atom or their the mixing arrangement that constitute alloy are unordered fully, spatially do not present periodicity and translation, therefore amorphous alloy is that a class structurally has the unordered and new catalytic material of shortrange order characteristics of long-range, its particular structure feature is given its excellent catalytic activity, selectivity, the anti-poisoning and decay resistance, also has eco-friendly characteristics simultaneously.
Because there is following shortcoming in the amorphous alloy catalyst of traditional quenching method preparation: have relatively high expectations to reaction unit (1), invests bigger; (2) He Cheng catalyst does not have activity, must be through activation processing before using; (3), be heated crystallization, poor heat stability can take place because amorphous structure belongs to the thermodynamics metastable state; (4) specific surface area of catalyst is less, is generally 0.1-1m
2/ g.The possibility of industrial applications is little.
At the little shortcoming of quenching method gained amorphous alloy catalyst specific area, be increasing specific surface area, general at present employing chemical reduction method prepares amorphous alloy catalyst.Adopt the amorphous alloy catalyst of chemical reduction method preparation all to have than by the much bigger specific area of quenching method gained catalyst, and need not preliminary treatment such as activation before use.In Journal ofCatalysis 150,434～438,1994, once reported for work 2.5M KBH
4The aqueous solution is at 25 ℃, be added drop-wise in the 0.1M nickel acetate ethanolic solution under stirring, use ammoniacal liquor and a large amount of distilled water washing precipitation of 6 milliliters of 8M successively, obtain a kind of amorphous state Ni-B Ultra-fine Particle Catalysts, this method has become the conventional method of preparation M-B amorphous alloy catalyst.
Adopt the ultrafine particle amorphous alloy catalyst of chemical reduction method preparation, the characteristics that surface atom is many because ultrafine particle has, surface area is big and the surface can be high, add shortrange order, the long-range disordered structure characteristics of amorphous alloy, make it have very high catalytic activity and selectivity, its catalytic activity exceeds 50-100 doubly than quenching method gained catalyst.But there is following point in this method: (1) reduction reaction is rapid, very exothermic, causes hot-spot, causes the alloying pellet of generation to reunite and/or crystallization; (2) there is the local concentration problems of too in the process of dropping reducing agent, makes this process become non-equilibrium process.Even adopt high mixing speed, the amorphous alloy catalyst particle size that makes is still very inhomogeneous, and particle size distribution range is very wide, causes that catalytic performance differs greatly, may fall increase by build-up of pressure in poor heat stability and the fixed bed reaction; (3) rapid nucleation and grow up fast and cause the particle that makes to wrap up the boron oxide compound kind of a large amount of unreduced metal oxides and decomposition, these are difficult to cause catalytic activity decline by impurity cover part active sites that physico-chemical process is removed fully.Above-mentioned factor has become the bottleneck of the industrial applications of amorphous alloy catalyst.Therefore further improve its preparation method, improve the catalysis efficiency of amorphous alloy catalyst, just have very important meaning.
The uniformity of catalyst particle size size has very important meaning to its catalytic performance.At first, the catalyst granules of uniform grading can provide the catalytic reaction activity position of homogeneous; Secondly, the amorphous alloy of uniform grading can strengthen structural stability.
Because the special cavitation of ultrasonic wave, the huge energy that produces during the collapse of ultrasonic cavitation bubble makes metal-complex key obtain activation, slow release metal ions, thereby be implemented in reduction reaction taking place at the uniform velocity under the relatively mild reaction condition, adopt the auxiliary reduction of ultrasonic wave, helps metallic and disperse, particle diameter is evenly distributed, specific area increases, and the active sites number increases, and therefore utilizing ultrasonic wave to prepare ultrafine amorphous attitude alloy catalyst is a research direction.
Summary of the invention
One of technical problem to be solved by this invention provides the uniform amorphous alloy catalyst of a kind of high-performance grain size;
Two of technical problem to be solved by this invention provides above-mentioned Preparation of catalysts method.
The technical scheme that realizes the object of the invention may further comprise the steps:
(1) slaine (being selected from nickel, cobalt, iron, ruthenium, palladium, platinum) solution is fully mixed according to 1: 0.2～12 mole proportioning with part (being selected from cyanogen, sulphur cyanogen, different sulphur cyanogen, acetate, sulfurous acid, thiosulfuric acid, ammonia, oxalic acid, nitrilotriacetic acid, ethylenediamine, diethylamine, citric acid, ethylenediamine tetra-acetic acid) solution, form stable metal complex, the preferred mole of metal salt solution and ligand solution proportioning is 1: 6～10;
(2) be that 1: 1～6 ratio adds reducing agent (being selected from sodium borohydride, potassium borohydride or its mixture) and fully mixes in the reducing agent and the mol ratio of slaine, because metal complex quite stable, the adding of reducing agent can not make metallic reducing, obtains the uniform and stable solution of concentration through fully mixing;
(3) above-mentioned solution is introduced ultrasonic wave, the huge energy that produces during the collapse of ultrasonic cavitation bubble makes metal-complex key obtain activation, slow release metal ions, thereby be implemented in reduction reaction at the uniform velocity takes place under the relatively mild reaction condition, used ultrasonic frequency is 10～90kHz, power is 20～100W, and reaction temperature is 0～100 ℃, preferred 0～50 ℃.；
(4) black solid that obtains is used deionized water and absolute ethanol washing respectively, makes the uniform amorphous alloy of grain size.
Characteristics of the present invention are: can keep high homogeneity, dispersiveness between slaine and each component of reducing agent in the entire reaction course that amorphous alloy generates, be the Perfected process of the uniform amorphous alloy of preparation high-performance grain size.
Amorphous alloy provided by the invention can be used for alkene, alkynes, aromatic hydrocarbons, nitrile, nitro compound, carbonyls etc. and contains the hydrogenation catalyst of unsaturated functional group compound, and obtains being higher than the hydrogenation activity and the selectivity of the amorphous alloy that the conventional chemical reducing process prepares.For example under identical reaction condition, the Co-B amorphous alloy that the initial hydrogen-absorption speed that the acetonitrile selective hydrogenation generates ethamine prepares with the conventional chemical reducing process is 18.7mmol/h.gCo during for catalyst, and can reach 37.4～46.3mmol/h.gCo with the uniform Co-B amorphous alloy of footpath provided by the invention size during for catalyst.
Description of drawings
Fig. 1 is the XRD spectra of the product of embodiment 1 preparation.
Fig. 2 is the TEM photo of the product of embodiment 1 preparation.
The specific embodiment
Come by the following examples the present invention is given further instruction (agents useful for same is a chemical pure among the embodiment), it should be noted that the following examples only as illustrating, content of the present invention is not limited thereto.
Embodiment 1:
Step 1: with quantitative CoCl
2Be dissolved in the distilled water, add quantitative ammonia spirit, fully mix, obtain the green solution of clear, CoCl
2With the mole proportioning of ammoniacal liquor be: 1: 1.
Step 2: in above-mentioned solution, add quantitative KBH
4, fully mix.Material molar ratio: Co
2+/ BH
4 -=1: 4.
Step 3: above solution is heated to 5 ℃, is that 20kHz, power are that the ultrasonic probe of 50W directly stretches into and carries out ultrasonic processing in the mixed liquor with frequency.Gradual slow generates black particle in the solution, and has gas to emerge.
Step 4: with the black particle that makes water and absolute ethanol washing repeatedly, obtaining grain size is the Co-B amorphous alloy of 200nm.
Embodiment 2:
Step 1: with quantitative NiCl
2Be dissolved in the distilled water, add quantitative ethylenediamine solution, fully mix, obtain the blue solution of clear, NiCl
2With the mole proportioning of ethylenediamine be: 1: 5.
Step 2: in above-mentioned solution, add quantitative NaBH
4, fully mix.Material molar ratio: Ni
2+/ BH
4 -=1: 4.
Step 3: above solution is heated to 20 ℃, is that 10kHz, power are that the ultrasonic probe of 50W directly stretches into and carries out ultrasonic processing in the mixed liquor with frequency.Gradual slow generates black particle in the solution, and has gas to emerge.
Step 4: with the black particle that makes water and absolute ethanol washing repeatedly, obtaining grain size is the Ni-B amorphous alloy of 100nm.
Embodiment 3:
Step 1: with quantitative PdCl
2Be dissolved in the distilled water, add quantitative oxalic acid solution, fully mix, obtain the pink solution of clear, PdCl
2With the mole proportioning of oxalic acid be: 1: 0.5.
Step 2: in above-mentioned solution, add quantitative KBH
4, fully mix.Material molar ratio: Pd
2+/ BH
4 -=1: 3.
Step 3: above solution is heated to 20 ℃, is that 70kHz, power are that the ultrasonic probe of 50W directly stretches into and carries out ultrasonic processing in the mixed liquor with frequency.Gradual slow generates black particle in the solution, and has gas to emerge.
Step 4: with the black particle that makes water and absolute ethanol washing repeatedly, obtaining grain size is the Pd-B amorphous alloy of 10nm.
Embodiment 4:
Step 1: with quantitative RuCl
3Be dissolved in the distilled water, add quantitative ammonia spirit, fully mix, obtain the brown solution of clear, RuCl
3With the mole proportioning of ammoniacal liquor be: 1: 10.
Step 2: in above-mentioned solution, add quantitative KBH
4, fully mix.Material molar ratio: Ru
5+/ BH
4 -=1: 5.
Step 3: above solution is heated to 20 ℃, is that 30kHz, power are that the ultrasonic probe of 50W directly stretches into and carries out ultrasonic processing in the mixed liquor with frequency.Gradual slow generates black particle in the solution, and has gas to emerge.
Step 4: with the black particle that makes water and absolute ethanol washing repeatedly, obtaining grain size is the Ru-B amorphous alloy of 20nm.
Product with the present invention's preparation carries out structural characterization by following means: the 18 kilovolts of amorphous structures that change target x-ray diffractometer (XRD) working sample of D/max-rB type that adopt Japanese company of science to produce; The shape and size that the JEM-2010 transmission electron microscope (TEM) that utilizes Japanese JEOL company to produce is directly observed product.From Fig. 1 XRD spectra, the disperse peak shape of its about 45 ° of positions can determine that the sample that makes is an amorphous state.As seen the sample that makes from Fig. 2 photo is the sphere that particle diameter is evenly distributed, smooth surface.All alloy samples that make with method provided by the present invention are the spheric granules that particle diameter is evenly distributed.
Claims (9)
1, the uniform amorphous alloy catalyst of a kind of grain size, this amorphous alloy catalyst is a spherical particle, particle diameter is in the scope of 10～500nm.
According to the described amorphous alloy catalyst of claim 1, it is characterized in that 2, described amorphous alloy is a kind of in Co-B amorphous alloy or Ni-B amorphous alloy or Pd-B amorphous alloy or the Ru-B amorphous alloy.
3, a kind of method that is used to prepare claim 1 or the even amorphous alloy catalyst of 2 described grain sizes may further comprise the steps:
(1) metal salt solution is fully mixed with ligand solution, form stable metal complex, the mole proportioning of described metal salt solution and ligand solution is 1: 0.2～12;
(2) add reducing agent and fully mix, obtain the uniform solution of concentration, the mol ratio of described reducing agent and slaine is 1: 1～6;
(3) above-mentioned solution is caused reduction reaction with ultrasonic wave, described reduction reaction temperature is 0～100 ℃, and described ultrasonic frequency is 10～90kHz;
(4) black solid that obtains is used deionized water and absolute ethanol washing respectively, makes the uniform amorphous alloy of grain size.
4,, it is characterized in that the described slaine of step (1) is selected from a kind of in the inorganic salts of nickel, cobalt, iron, ruthenium, palladium, platinum or the organo-metallic compound according to the described preparation method of claim 3.
5, according to the preparation method of the even amorphous alloy catalyst of the described grain size of claim 3, it is characterized in that: the described part of step (1) is selected from a kind of in cyanogen, sulphur cyanogen, different sulphur cyanogen, acetate, sulfurous acid, thiosulfuric acid, ammonia, oxalic acid, nitrilotriacetic acid, ethylenediamine, diethylamine, citric acid or the ethylenediamine tetra-acetic acid.
6, according to the described preparation method of claim 3, the mole proportioning that it is characterized in that described metal salt solution of step (1) and ligand solution is 1: 6～10;
7,, it is characterized in that the described reducing agent of step (2) is selected from a kind of or the two mixture in sodium borohydride, the potassium borohydride according to the described preparation method of claim 3.
8, according to the described preparation method of claim 3, the mol ratio that it is characterized in that reducing agent and slaine is 1: 4.
9,, it is characterized in that described reduction reaction temperature is 0～50 ℃ according to the described preparation method of claim 3.
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| CN102614880A (en) * | 2012-01-12 | 2012-08-01 | 西北师范大学 | Preparation and application of carbon-supported amorphous metallic nickel |
| US9045381B2 (en) | 2010-10-19 | 2015-06-02 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| CN105148918A (en) * | 2015-07-05 | 2015-12-16 | 桂林电子科技大学 | Preparation method and application of Co-B/Ni-B amorphous nanosphere composite alloy catalyst |
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| CN105798323A (en) * | 2016-03-18 | 2016-07-27 | 西北师范大学 | Method for preparing transition metal-boron alloy material with large specific surface area on ball milling-assisted interface |
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| CN109999801A (en) * | 2019-04-28 | 2019-07-12 | 中国烟草总公司郑州烟草研究院 | M-B@Pd-B@Al2O3Catalyst and preparation method thereof, application |
| CN110013848A (en) * | 2019-04-28 | 2019-07-16 | 中国烟草总公司郑州烟草研究院 | A kind of catalyst and preparation method thereof adding hydrogen gamma-valerolactone for levulic acid |
| US10533028B2 (en) | 2014-09-04 | 2020-01-14 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses as catalysts in processes for formation and/or hydrogenation of esters, amides and related reactions |
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| US9045381B2 (en) | 2010-10-19 | 2015-06-02 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| CN102614880A (en) * | 2012-01-12 | 2012-08-01 | 西北师范大学 | Preparation and application of carbon-supported amorphous metallic nickel |
| US10533028B2 (en) | 2014-09-04 | 2020-01-14 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses as catalysts in processes for formation and/or hydrogenation of esters, amides and related reactions |
| US10562767B2 (en) | 2014-09-04 | 2020-02-18 | Yeda Research And Development Co. Ltd. | Liquid-organic hydrogen carrier systems based on catalytic peptide formation and hydrogenation |
| CN105148918A (en) * | 2015-07-05 | 2015-12-16 | 桂林电子科技大学 | Preparation method and application of Co-B/Ni-B amorphous nanosphere composite alloy catalyst |
| CN105148918B (en) * | 2015-07-05 | 2020-05-05 | 桂林电子科技大学 | Preparation method and application of Co-B/Ni-B amorphous nanosphere composite alloy catalyst |
| CN105702971A (en) * | 2016-01-27 | 2016-06-22 | 西安科技大学 | Core-shell gold@ cobalt-boron catalyst for fuel cell |
| CN105702971B (en) * | 2016-01-27 | 2018-01-12 | 西安科技大学 | A kind of hud typed golden@cobalts B catalyst of fuel cell |
| CN105798323A (en) * | 2016-03-18 | 2016-07-27 | 西北师范大学 | Method for preparing transition metal-boron alloy material with large specific surface area on ball milling-assisted interface |
| CN105798323B (en) * | 2016-03-18 | 2018-04-06 | 西北师范大学 | The method that ball milling assistant interface prepares bigger serface transition metal boron alloy material |
| CN107243646A (en) * | 2017-06-08 | 2017-10-13 | 桂林电子科技大学 | A kind of high-ratio surface Co B alloy nano pieces and preparation method and application |
| CN108823602A (en) * | 2018-07-12 | 2018-11-16 | 北京化工大学 | A kind of vulcanization ruthenium particulate composite, preparation method and the usage |
| CN109985623A (en) * | 2019-04-28 | 2019-07-09 | 中国烟草总公司郑州烟草研究院 | A kind of catalyst and preparation method thereof adding hydrogen gamma-valerolactone for levulic acid |
| CN109999801A (en) * | 2019-04-28 | 2019-07-12 | 中国烟草总公司郑州烟草研究院 | M-B@Pd-B@Al2O3Catalyst and preparation method thereof, application |
| CN110013848A (en) * | 2019-04-28 | 2019-07-16 | 中国烟草总公司郑州烟草研究院 | A kind of catalyst and preparation method thereof adding hydrogen gamma-valerolactone for levulic acid |
| CN109999801B (en) * | 2019-04-28 | 2022-02-11 | 中国烟草总公司郑州烟草研究院 | M-B@Pd-B@Al2O3Catalyst and preparation method and application thereof |
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