CN101411980A - Method for preparing silicasol-supported amorphous alloy catalyst - Google Patents
Method for preparing silicasol-supported amorphous alloy catalyst Download PDFInfo
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- CN101411980A CN101411980A CNA2008101524920A CN200810152492A CN101411980A CN 101411980 A CN101411980 A CN 101411980A CN A2008101524920 A CNA2008101524920 A CN A2008101524920A CN 200810152492 A CN200810152492 A CN 200810152492A CN 101411980 A CN101411980 A CN 101411980A
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Abstract
The invention relates to a method for preparing an amorphous metal-boron (M-B, M=Fe, Co, Ni) catalyst which has ultra-small nanometer dimension and high dispersion of active compositions and is prepared through adopting silica sol as a soft load material by a simple chemical reduction method. Compared with the corresponding non-load type M-B catalyst, the M-B catalyst loaded with the silica sol shows more excellent catalytic performance in various liquid-phase reactions.
Description
Technical field
The present invention relates to a kind of new method for preparing carried non-crystal alloy catalyst.With the Ludox is support materials, adopts the chemical reduction method preparation to tap a blast furnace-boron, cobalt-boron and nickel-boron amorphous alloy catalyst.This type of catalyst shows remarkable catalytic activity in multiple liquid phase reactor.
Background technology
Making it become nano particle by the size that reduces the catalyst activity component particles is one of focus of all the time paying close attention to of numerous catalyticing research workers to improve its catalytic performance.This is that the ratio of surface atom will increase sharply because work as particle diameter below 10nm.In case particle diameter drops to 1nm, the surface atom ratio of counting will reach more than 90%, and this will mean that the particle with very small dimensions is exposed in the reactant surface substantially, thus accelerated reaction process greatly.Some noble metals, as Pt, Pd and Au is present the most common catalyst, but, they belong to rare metal and price is high, therefore, many researchs make it become nano particle improving its catalytic performance by the size that reduces other base metal, and wish that they become a kind of economical and effective catalyst and substitute noble metal.But, when preparation has the unsupported catalyst of extra small size, being agglomerated between small-particle in order to hinder the serious problems of their practical applications.
It with the amorphous alloy high degree of dispersion one of important method of improving the amorphous alloy catalyst performance.Loadization can increase the number in activated centre in the catalyst, improves catalytic activity, thereby reduces the consumption and the Preparation of catalysts cost of active metal component.Studies show that in recent years, except that conventional oxide carrier, materials such as some mesopore molecular sieves, CNT, organic-inorganic composite, macromolecule become the excellent carrier of preparation new catalyst.Yet, be carrier loaded amorphous metal-B catalyst with traditional pressed powder, the particle diameter of its active component is difficult to be controlled at below the 10nm, and this just means that catalytic efficiency is restricted to a great extent.
Through 20 years of development, amorphous alloy catalyst has been obtained bigger progress in a lot of fields.For example, CN1792439, CN1792440, CN101028599 etc. have reported microwave, the ultrasonic many new methods such as synthesizing and add macromolecule medium of assisting of adopting, can be in the degree of scatter that improves amorphous alloy in varying degrees, reduce the cluster size, improve the number of surface active composition etc., and aspect hydrogenation activity, obtained good effect.CN1179358, CN1298760, CN1375357, CN1793139 and CN101007280 etc. have reported the preparation method of amorphous alloy catalyst.Described catalyst has represented excellent catalytic performance in the hydrogenation reaction of unsaturated compounds such as aromatic hydrocarbons, alkynes, alkene, nitro compound, carbonyls, nitrile.
Different with conventional pressed powder carrier, Ludox (mSiO
2NH
2O) be a kind of safe, free of contamination environmental protection inorganic colloid, itself has some valuable characteristics, and is fine as colloidal particle, has sizable specific area (generally at 250～300m
2/ g), decentralization height, silanol grappling active component firmly etc.Therefore, the present invention as a kind of soft support materials, has prepared a kind of NiB amorphous alloy catalyst with extra small nanoscale and high degree of dispersion by simple chemical reduction method with Ludox.Compare with corresponding unsupported catalyst, silicasol-supported M-B catalyst shows more excellent catalytic performance in multiple liquid phase reactor, thereby has important application prospects.
Summary of the invention
The objective of the invention is to adopt Ludox is soft support materials, prepares amorphous metal-boron (M-B, M=Fe, Co, Ni) catalyst with extra small nanoscale and active component high degree of dispersion by simple chemical reduction method.Because in this type of catalysis material, skin effect can find full expression, thereby reaches the purpose that significantly improves catalytic activity.
The silicasol-supported amorphous state M-B of preparation provided by the invention (Ni) method of catalyst is for M=Fe, Co:
Concrete steps are as follows:
(1) silicasol-supported Fe-B Preparation of catalysts: prepare certain density KBH4 solution, concentration is 0.1～2.0mol/L, mixes with a certain amount of Ludox.Prepare certain density iron salt solutions again, concentration is 0.02～2.26mol/L, molysite and KBH
4Mol ratio be 1:2.Under certain protection gas, (1～12mL/min) drops in the above-mentioned mixed solution, and reaction is not till have gas and produce with certain speed with iron salt solutions.Fully wash with distilled water, absolute ethyl alcohol successively after products therefrom can separate by high speed centrifugation and be stored in the water or in the ethanol.
(2) silicasol-supported Co-B Preparation of catalysts: prepare certain density KBH
4Solution, concentration are 0.1～2.0mol/L, mix with a certain amount of Ludox.Prepare certain density cobalt salt solution again, concentration is 0.02～2.40mol/L, cobalt salt and KBH
4Mol ratio be 1:2.Under certain protection gas, (1～12mL/min) drops in the above-mentioned mixed solution, and reaction is not till have gas and produce with certain speed with cobalt salt solution.Below handle described in the same step (1).
(3) silicasol-supported Ni-B Preparation of catalysts: prepare certain density KBH
4Solution, concentration are 0.1～2.0mol/L, mix with a certain amount of Ludox.Prepare certain density nickel salt solution again, concentration is 0.02～2.83mol/L, nickel salt and KBH
4Mol ratio be 1:2.Under certain protection gas, (1～12mL/min) drops in the above-mentioned mixed solution, and reaction is not till have gas and produce with certain speed with nickel salt solution.Below handle described in the same step (1).
Utilize characterizing methods such as XRD, HRTEM that silicasol-supported M-B catalyst has been carried out comparatively detail analysis.Accompanying drawing 1 is silicasol-supported Fe-B, the Co-B and the XRD figure of Ni-B catalyst, and the result has shown the amorphous structure feature of catalyst.Accompanying drawing 2 is HRTEM figure of silicasol-supported Fe-B, Co-B and Ni-B catalyst, shows to prepare by the method to have 1～2nm size and monodispersed support type M-B catalyst.Silicasol-supported Fe-B, Co-B and the Ni-B catalyst of the present invention's preparation are compared with corresponding non-load type M-B catalyst, all show remarkable more catalytic activity respectively in chlorobenzene dechlorination, hydrogenation on cinnamic aldehyde and hydrogenating cyclobufene sultone.
Description of drawings
Fig. 1 is silicasol-supported M-B (M=Fe, Co, Ni) XRD figure of catalyst.(a)FeB@silica?sol，(b)Co-B@silicasol，(c)Ni-B@silica?sol
Fig. 2 is silicasol-supported M-B (M=Fe, Co, Ni) HRTEM of catalyst figure.(a)FeB@silica?sol，(b)Co-B@silicasol，(c)Ni-B@silica?sol
The specific embodiment
The present invention can describe in detail by embodiment, but they do not impose any restrictions the present invention.In these embodiments, adopt XRD determining structures of samples form, instrument is Japanese RigakuD/Max-2500 type X-ray diffractometer, and the CuK alpha ray (λ=0.115405nm).The pattern of sample and particle size adopt Japanese JEOL JEM-2010FEF type field emitted energy to filter transmission electron microscope and measure.
Comparative Examples 1
This Comparative Examples explanation Preparation of catalysts process.
Embodiment 1
These embodiment explanations are preparing carriers amorphous state M-B (M=Fe, Co, Ni) process of catalyst with the Ludox.
Prepare certain density KBH
4Solution, concentration are 0.1～2.0mol/L, mix with a certain amount of Ludox.Prepare certain density iron salt solutions again, concentration is 0.02～2.26mol/L, molysite and KBH
4Mol ratio be 1:2.Under certain protection gas, (1～12mL/min) drops in the above-mentioned mixed solution, and reaction is not till have gas and produce with certain speed with iron salt solutions.Fully wash with distilled water, absolute ethyl alcohol successively after products therefrom can separate by high speed centrifugation and be stored in the water or in the ethanol.The gained catalyst is designated as A1.Changing metal salt solution is cobalt salt and nickel salt, can make silicasol-supported Co-B and Ni-B catalyst A 2 and A3 by identical method.
Embodiment 2
Support type M-B (M=Fe, Co, Ni) process of catalyst that these embodiment explanations prepare under different temperatures.
According to the method among the embodiment 1, prepared silicasol-supported M-B catalyst in different temperatures (15 ℃, 20 ℃ and 30 ℃).
Embodiment 3
These embodiment illustrate that the method that adopts embodiment 1 prepares M-B (M=Fe, Co, Ni) process of catalyst of different loads amount.
According to the method among the embodiment 1, under the situation that keeps Ludox consumption unanimity,, can obtain load capacity and be respectively 5%, 10%, 20%, 30% and 40% silicasol-supported M-B catalyst by changing the consumption of slaine.
Embodiment 4
It is preparing carriers M-B (M=Fe, Co, Ni) process of catalyst that these embodiment explanations are adopted alkalescence, neutrality and acidic silicasol respectively.
Utilize alkaline silica sol for the M-B catalyst of preparing carriers as described in example 1 above.With neutrality or acidic silicasol is that the process of the M-B catalyst of preparing carriers is: prepare certain density iron salt solutions, concentration is 0.02～2.26mol/L, mixes with a certain amount of Ludox.Prepare certain density KBH again
4Solution, concentration are 0.1～2.0mol/L, molysite and KBH
4Mol ratio be 1:2.Under certain protection gas, with KBH
4(1～12mL/min) drops in the above-mentioned mixed solution solution, and reaction is not till have gas and produce with certain speed.Fully wash with distilled water, absolute ethyl alcohol successively after products therefrom can separate by high speed centrifugation and be stored in the water or in the ethanol.Silicasol-supported Co-B and Ni-B Preparation of catalysts are with the Fe-B catalyst.
Embodiment 5
It is preparing carriers M-B (M=Fe, Co, Ni) process of catalyst that the alkaline silica sol of different-grain diameter is adopted in these embodiment explanations respectively.
(80nm 110nm) is carrier for 20nm, 60nm, according to the method among the embodiment 1, prepares silicasol-supported Fe-B, Co-B and Ni-B catalyst to adopt the alkaline silica sol of different-grain diameter respectively.
Comparative Examples 2
This Comparative Examples is used for illustrating that silicasol-supported Fe-B, Co-B and Ni-B catalyst are respectively at the catalytic performance of chlorobenzene dechlorination, hydrogenation on cinnamic aldehyde and hydrogenating cyclobufene sultone.
As shown in Figure 3, (Ni) catalyst is compared for M=Fe, Co, and under identical appreciation condition, silicasol-supported M-B catalyst all shows remarkable more catalytic activity and the reaction rate of Geng Gao with corresponding non-load type M-B.
Claims (6)
1, the invention provides with the Ludox is that (Ni) method of catalyst is preparing carriers amorphous state M-B for M=Fe, Co: prepare certain density KBH
4Solution, concentration are 0.1～2.0mol/L, mix with a certain amount of Ludox.Prepare certain density iron salt solutions again, concentration is 0.02～2.26mol/L, molysite and KBH
4Mol ratio be 1:2.Under certain protection gas, (1～12mL/min) drops in the above-mentioned mixed solution, and reaction is not till have gas and produce with certain speed with iron salt solutions.Fully wash with distilled water, absolute ethyl alcohol successively after products therefrom can separate by high speed centrifugation and be stored in the water or in the ethanol.Changing metal salt solution is cobalt salt and nickel salt, can make silicasol-supported Co-B and Ni-B catalyst by identical method.
2, under different temperatures (15 ℃, 20 ℃ and 30 ℃), according to support type M-B (M=Fe, Co, Ni) catalyst of the method for claim 1 preparation.
3, prepare load capacity according to the method for claim 1 and be respectively 5%, 10%, 20%, 30% and 40% silicasol-supported M-B (M=Fe, Co, Ni) catalyst.
4, adopting alkalescence, neutrality and acidic silicasol respectively according to the method for claim 1 is preparing carriers M-B (M=Fe, Co, Ni) catalyst.Utilize alkaline silica sol for described in the M-B catalyst such as claim 1 of preparing carriers.With neutrality or acidic silicasol is that the process of the M-B catalyst of preparing carriers is: prepare certain density iron salt solutions, concentration is 0.02～2.26mol/L, mixes with a certain amount of Ludox.Prepare certain density KBH again
4Solution, concentration are 0.1～2.0mol/L, molysite and KBH
4Mol ratio be 1:2.Under certain protection gas, with KBH
4(1～12mL/min) drops in the above-mentioned mixed solution solution, and reaction is not till have gas and produce with certain speed.Fully wash with distilled water, absolute ethyl alcohol successively after products therefrom can separate by high speed centrifugation and be stored in the water or in the ethanol.Silicasol-supported Co-B and Ni-B Preparation of catalysts are with the Fe-B catalyst.
5, (80nm 110nm) is preparing carriers M-B (M=Fe, Co, Ni) catalyst for 20nm, 60nm to adopt the alkaline silica sol of different-grain diameter respectively according to the method for claim 1.
6, the method according to claim 1 prepares silicasol-supported Fe-B, Co-B and the application in chlorobenzene dechlorination, hydrogenation on cinnamic aldehyde and hydrogenating cyclobufene sultone respectively of Ni-B catalyst.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829575A (en) * | 2010-05-17 | 2010-09-15 | 天津市安凯特催化剂有限公司 | Preparation method and application of composite nano nickel catalyst |
| CN102580748A (en) * | 2011-12-20 | 2012-07-18 | 太原理工大学 | Amorphous alloy catalyst for hydrogenating dinitrotoluene and application of amorphous alloy catalyst |
| CN103952719A (en) * | 2014-03-28 | 2014-07-30 | 中国科学院物理研究所 | Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof |
| CN110921808A (en) * | 2020-01-16 | 2020-03-27 | 郑州大学 | Sewage treatment method |
| CN111359655A (en) * | 2020-04-27 | 2020-07-03 | 宁夏大学 | High-carbon olefin hydroformylation heterogeneous Co-based catalyst |
-
2008
- 2008-10-27 CN CNA2008101524920A patent/CN101411980A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829575A (en) * | 2010-05-17 | 2010-09-15 | 天津市安凯特催化剂有限公司 | Preparation method and application of composite nano nickel catalyst |
| CN102580748A (en) * | 2011-12-20 | 2012-07-18 | 太原理工大学 | Amorphous alloy catalyst for hydrogenating dinitrotoluene and application of amorphous alloy catalyst |
| CN102580748B (en) * | 2011-12-20 | 2014-05-28 | 太原理工大学 | Amorphous alloy catalyst for hydrogenating dinitrotoluene and application of amorphous alloy catalyst |
| CN103952719A (en) * | 2014-03-28 | 2014-07-30 | 中国科学院物理研究所 | Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof |
| CN110921808A (en) * | 2020-01-16 | 2020-03-27 | 郑州大学 | Sewage treatment method |
| CN110921808B (en) * | 2020-01-16 | 2021-12-10 | 郑州大学 | Sewage treatment method |
| CN111359655A (en) * | 2020-04-27 | 2020-07-03 | 宁夏大学 | High-carbon olefin hydroformylation heterogeneous Co-based catalyst |
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Open date: 20090422 |