CN101584990A - Ru-P nano hollow ball catalyst in amorphous state as well as preparation and application thereof - Google Patents
Ru-P nano hollow ball catalyst in amorphous state as well as preparation and application thereof Download PDFInfo
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- CN101584990A CN101584990A CNA2009100534718A CN200910053471A CN101584990A CN 101584990 A CN101584990 A CN 101584990A CN A2009100534718 A CNA2009100534718 A CN A2009100534718A CN 200910053471 A CN200910053471 A CN 200910053471A CN 101584990 A CN101584990 A CN 101584990A
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Abstract
The invention belongs to the catalyst technique, and relates to Ru-P nano hollow ball catalyst in amorphous state as well as preparation and application thereof. The method for preparing hollow metal ball catalyst according to prior art is tedious; the method takes a long time; the quality is bad. The chemical composition of Ru-P nano hollow ball catalyst in amorphous state provided by the invention is Ru<x>P<y>; the hollow ball diameter is 20-100 nm, the wall thickness of the ball is 5-10 nm, and the specific surface area 50-68 m2/g. The preparation method comprises the following steps: dissolving cationic surfactant in deionized water; adding inorganic salt aqueous solution of ruthenium and hypophosphite as well as cyclohexane, stirring, raising temperature up to 50-60 DEG C., reacting for 20-40 minutes; extracting, washing, ultrasonic cleaning at 30-60 w; washing the product with deionized water and absolute alcohol. The invention has the advantages that the specific surface area of the catalyst is large; the catalysis effect is good; the catalyst can be used repeatedly with long service life; the processing technique is simple and the cost of the catalyst is low.
Description
Technical field
The invention belongs to the chemical catalyst technology, specifically a kind of Ru-P nano hollow ball catalyst in amorphous state and preparation and application.
Background technology
Amorphous alloy is the unordered and new material of shortrange order of a class long-range, its particular structure feature makes it have higher mechanical strength and decay resistance and unique electromagnetism and catalytic performance, also having eco-friendly characteristics simultaneously, is 21 century the most promising high-efficiency cleaning type new material.In order to improve catalytic effect, the key request that is used for catalyst is to have bigger specific area.Prior art adopts chemical reduction method to prepare amorphous alloy catalyst.Chinese patent ZL200610147680.5 discloses a kind of amorphous ruthenium phosphorus alloy catalyst, and it is directly to reduce the solid particle catalyst that the inorganic salts of ruthenium make with hypophosphite in the aqueous solution, and specific area is little, and reunites easily.
Nano hollow sphere material is owing to have characteristics such as cavity structure, high-specific surface area, low-density, economical with materials, cost are low, and catalytic reaction is effective, causes people's extensive concern.Hollow ball material is because unique cavity structure helps the absorption of more reactants; Owing to design feature have bigger specific area; Low-density can make material be evenly dispersed in the liquid-phase reaction system, and increase contacts with reactant, uses it for catalytic reaction and then shows the catalytic performance more superior than solid material.The method of prior art for preparing hollow metal ball material is that metal is wrapped on the material such as silicon oxide ball or Metal Ball for preparing in advance, and the method with soda acid etching or displacement reaction makes then.But this method has following shortcoming: 1, preparation process is loaded down with trivial details; 2, preparation process length consuming time; 3, the hollow ball that makes can't obtain the nano hollow ball catalyst that catalytic reaction needs because the vigorous reaction of removing in the template procedure causes the hollow ball material breakage.
Prior art shows, invents Ru-P nano hollow ball catalyst in amorphous state of a kind of excellent catalytic effect and preparation method thereof, and it is applied in the catalytic reaction is very significant.
Domestic and international by retrieval patent documentation and public publication, there is no and chemical composition of the present invention and the identical Ru-P nano hollow ball catalyst in amorphous state of hollow ball structure, also not seeing has and the identical preparation Ru-P nano hollow ball catalyst in amorphous state of the inventive method technology, hollow ball catalyst of the present invention excellent catalytic effect in industrial hydrogenation reaction simultaneously is so the present invention is creative, novelty and practicality.
Summary of the invention
The object of the invention provides a kind of Ru-P nano hollow ball catalyst in amorphous state:
Another purpose of the present invention provides the preparation method of Ru-P nano hollow ball catalyst in amorphous state;
The 3rd purpose of the present invention provides the application of Ru-P nano hollow ball catalyst in amorphous state in industrial hydrogenation reaction.
The present invention seeks to realize like this:
A kind of Ru-P nano hollow ball catalyst in amorphous state:
(1) chemical composition is: Ru
xP
yX=85～92 wherein, y=8～15;
(2) the hollow ball diameter is 20～100nm, and the spheroid wall thickness is 5～10nm, specific area 50～68m
2/ g.
The preparation method of Ru-P nano hollow ball catalyst in amorphous state comprises the steps:
(1) gets double-stranded cationic surfactant, under 25 ℃, be dissolved in the deionized water;
(2) in above-mentioned solution, add inorganic salt solution and the hypophosphite and the cyclohexane of ruthenium successively, stirred 20～40 minutes;
(3) temperature in the above-mentioned solution is risen to 50～60 ℃, reacted 20～40 minutes;
(4) with absolute ethyl alcohol extraction surface activating agent; Respectively wash 2 times with deionized water and absolute ethyl alcohol then;
(5) 30～60W power ultrasonics cleaned 15～25 minutes;
(6) respectively wash 1 time with deionized water and absolute ethyl alcohol, promptly make Ru-P nano hollow ball catalyst in amorphous state.
The preparation method of Ru-P nano hollow ball catalyst in amorphous state is characterised in that:
(1) double-stranded cationic surfactant is any in two ten alkyl dimethyl quaternary amines, two dodecyl dimethyl quaternary amine or the two myristyl dimethyl quaternary amine, and anion is a kind of in chlorion or the bromide ion;
(2) surfactant is 0.003～0.015g/mL in the concentration of solution, preferred 0.007g/mL;
(3) inorganic salts of ruthenium are RuCl
3Hypophosphite is NaH
2PO
2H
2O;
(4) contained P elements in contained ruthenium element and the hypophosphite in the inorganic salts by ruthenium, the molar ratio of ruthenium and phosphorus is 1: 3～1: 8, is preferably 1: 4～1: 6;
(5) inorganic salts of ruthenium concentration in solution is 0.008～0.020mol/L, is preferably 0.012mol/L;
(6) volume ratio of cyclohexane and deionized water is 1: 5～1: 20, preferred 1: 10.
Ru-P nano hollow ball catalyst in amorphous state, the application in industrial hydrogenation reaction.
For achieving the above object, the present invention realizes by following technical solution:
A kind of amorphous ruthenium P nano hollow ball material, cavity diameter is 20～100nm, and the wall thickness of spherical shell is 5～10nm, and body is made up of metal Ru and metalloid phosphorus, available Ru
xP
yExpression, x=85-92 wherein, y=8～15, x, y are that atomic ratio is a mol ratio, specific area 50～68m
2/ g.
This amorphous ruthenium P nano hollow ball preparation methods comprises the steps:
Get double-stranded cationic surfactant, under 25 ℃, be dissolved in the deionized water of certain volume, and add inorganic salt solution and the hypophosphite and the cyclohexane of ruthenium successively, continue to stir 20～40 minutes, rising temperature to 50～60 ℃ reaction 20～40 minutes, use absolute ethyl alcohol extraction surface activating agent then, and respectively wash 2 times with deionized water and absolute ethyl alcohol, ultrasonic cleaning 15～25 minutes under 30-60W power then, respectively wash 1 time with deionized water and absolute ethyl alcohol again, promptly obtain amorphous ruthenium P nano hollow ball material.The inorganic salts of surfactant and ruthenium are respectively 0.003～0.015g/mL and 0.008～0.020mol/L in the concentration of aqueous phase, preferred 0.007g/mL and 0.012mol/L; The molar ratio of ruthenium and phosphorus is 1: 3～1: 8, preferred 1: 4～1: 6, and contained P elements in contained ruthenium element and the hypophosphite in the inorganic salts by ruthenium; The volume ratio of cyclohexane and water is 1: 5～1: 20, preferred 1: 10.
The preferred two alkyl dimethyl quaternary amines of double-stranded cationic surfactant, preferred two ten alkyl dimethyl quaternary amines or two dodecyl dimethyl quaternary amine or two myristyl dimethyl quaternary amine; Anion is chlorion or bromide ion.
The inorganic salts of ruthenium are RuCl
3
Hypophosphite is NaH
2PO
2H
2O.
The amorphous ruthenium P nano hollow ball for preparing has cavity structure, specific area is big, be uniformly dispersed, excellent catalytic effect, can be used as alkene, alkynes, aromatic hydrocarbons and contain the hydrogenation catalyst of unsaturated functional group compounds such as itrile group, nitro and carbonyl, especially the reaction that the liquid phase hydrogenation of maltose is prepared maltitol has good catalytic effect, and is better than the Raney Nickel catalyst that prior art is used greatly.
The present invention has changed the defective of traditional not high and easy reunion of phosphorus series non-crystalline state alloy catalyst specific area, further improved reaction efficiency, and preparation condition is simply gentle, with low cost, and long catalytic life, can reuse and keep catalytic performance constant substantially, be easy to get for industrial hydrogenation reaction provides efficiently, eco-friendly catalyst.
The product of the present invention's preparation carries out structural characterization by following means:
The XRD figure spectrum that employing obtains on Japan Rigaku D/Max-RB of science type X-ray diffractometer is carried out the crystalline phase analysis of product; Employing is carried out the appearance structure analysis of product at the photo that Japan's (JEOL JEM2010) type high-resolution-ration transmission electric-lens obtains; Adopt the automatic physical adsorption appearance of QuantaChrome Nova 4000e type to measure the specific area of product.
Advantage of the present invention is:
1, specific surface area of catalyst is big;
2, excellent catalytic effect;
3, catalyst can be reused, long catalytic life;
4, production technology is simple, and the catalyst cost is low.
Description of drawings
Fig. 1 is the XRD figure spectrum of the product of embodiment 2 preparations;
Fig. 2 is the TEM photo of the product of embodiment 2 preparations.
The specific embodiment
To give further in detail the present invention, illustrate clearly and completely by the following examples, but protection domain of the present invention is not limited.
The all samples that makes with method provided by the present invention is amorphous state.Agents useful for same is for analyzing pure or chemical pure among the embodiment.
Embodiment 1
The two ten alkyl dimethyl ammonium chlorides of 0.25g are dissolved in the 75mL deionized water under 25 ℃, and add the RuCl of 0.10mol/L successively
3Aqueous solution 10mL and 0.43g NaH
2PO
2H
2O and 5.0mL cyclohexane; Continue to stir 40 minutes rising temperature to 50 ℃ reaction 20 minutes; With absolute ethyl alcohol extraction surface activating agent, and respectively wash 2 times with deionized water and absolute ethyl alcohol; Ultrasonic cleaning 15 minutes under 40W power then; Respectively wash 1 time with deionized water and absolute ethyl alcohol, promptly obtain Ru-P nano hollow ball catalyst in amorphous state, represent with Ru-P-HS-1, recording the body phase composition is Ru
91.5P
8.5, specific area is 56m
2/ g.
Embodiment 2
Under 25 ℃, be dissolved in the two lauryl dimethyl amine bromides of 0.50g in the 75mL deionized water; And add the RuCl of 0.10mol/L successively
3Aqueous solution 10mL and 0.53g NaH
2PO
2H
2O and 8.5mL cyclohexane; Continue to stir 30 minutes rising temperature to 55 ℃ reaction 30 minutes; With absolute ethyl alcohol extraction surface activating agent; Respectively wash 2 times with deionized water and absolute ethyl alcohol; Ultrasonic cleaning 20 minutes under 50W power then; Respectively wash 1 time with deionized water and absolute ethyl alcohol, promptly get Ru-P nano hollow ball catalyst in amorphous state, represent with Ru-P-HS-2, recording the body phase composition is Ru
85.6P
14.4, specific area is 68m
2/ g.
Fig. 1 is the XRD figure spectrum of the prepared sample of present embodiment, can determine that from figure the sample that makes is an amorphous structure; Fig. 2 is the TEM photo of the prepared sample of present embodiment, is nano-hollow ball from the visible gained sample of photo, and cavity diameter is 20-100nm, and the spherical shell wall thickness is 8nm.
Embodiment 3
Under 25 ℃, be dissolved in the two myristyl dimethyl chlorination amine of 1.0g in the 75mL deionized water; And add the RuCl of 0.10mol/L successively
3Aqueous solution 15mL and 0.80g NaH
2PO
2H
2O and 15mL cyclohexane; Continue to stir 20 minutes rising temperature to 60 ℃ reaction 40 minutes; With absolute ethyl alcohol extraction surface activating agent; And respectively wash 2 times with deionized water and absolute ethyl alcohol; Ultrasonic cleaning 25 minutes under 60W power is then respectively washed 1 time with deionized water and absolute ethyl alcohol again, promptly obtains Ru-P nano hollow ball catalyst in amorphous state, represents that with Ru-P-HS-3 recording the body phase composition is Ru
89.8P
10.2, specific area is 52m
2/ g.
Embodiment 4
Gained Ru-P nano hollow ball catalyst in amorphous state among the embodiment 1,2,3 is used for the reaction of high pressure liquid phase hydrogenation of maltose malt sugar alcohol.
Concrete steps are: add the 0.08g catalyst in the 500ml autoclave successively, 10% maltose solution of 50ml mass ratio charges into 3.0MPa hydrogen after airtight, and heated constant temperature is in 100 ℃ of needed reaction temperatures.Pressure in the heating process mesohigh still rises gradually, opens magnetic stirring apparatus after reaching balance, and hydrogenation reaction begins.For eliminating the influence of diffusion effect to kinetics, the control mixing speed is 1200rpm.React after 2 hours the product liquid chromatographic detection of being furnished with CARBOsep COREGEL 87C chromatographic column and differential refraction detector.Column temperature: 80 ℃; Phase flows: deionized water; Flow velocity: 0.6ml/min.Analysis result shows that catalyst is 100% to the selectivity of maltitol, and maltitol is unique product in detectability, and the mensuration of maltose conversion ratio obtains from the liquid chromatogram data.The catalytic performance data are shown in Table 1.
Embodiment 5
The embodiment 2 prepared Ru-P nano hollow ball catalyst in amorphous state that are used for high pressure liquid phase hydrogenation of maltose malt sugar alcohol reaction system among the embodiment 4 are carried out centrifugation, be applied in the reaction described in the embodiment 4 for the second time by liquid phase hydrogenation of maltose malt sugar alcohol with ethanol washing back.
Present embodiment has been measured Ru-P nano hollow ball catalyst in amorphous state and has been carried out the catalytic performance that secondary uses, and concrete data are shown in Table 1.
Embodiment 6
The Ru-P nano hollow ball catalyst in amorphous state that is used for high pressure liquid phase hydrogenation of maltose malt sugar alcohol reaction system among the embodiment 5 is carried out centrifugation, with being applied to for the third time in the reaction described in the embodiment 4 after the ethanol washing by liquid phase hydrogenation of maltose malt sugar alcohol.
Present embodiment has been measured the catalytic performance that Ru-P nano hollow ball catalyst in amorphous state carries out three uses, and concrete data are shown in Table 1.
Embodiment 7
RuCl with 8.0mL
3The aqueous solution (0.10mol/L) and 0.43g NaH
2PO
2H
2O and 0.33gCH
3COONa is dissolved in the 7.0mL deionized water, and to regulate pH value with the NaOH solution of 2.0mol/L be 11, reacted 30 minutes down at 50 ℃, and the black particle of generation washs respectively 3 times with deionized water and absolute ethyl alcohol, promptly obtain solid amorphous ruthenium phosphorus catalyst, represent with Ru-P-RE.
This control experiment gained catalyst is used for embodiment 4 described reactions by liquid phase hydrogenation of maltose malt sugar alcohol, and its catalytic performance data are shown in Table 1.
Embodiment 8
NiCl with 0.33g
26H
2O and 0.74g NaH
2PO
2H
2O and 0.57g CH
3COONa is dissolved in the 15mL deionized water, and to regulate pH value with the NaOH solution of 2.0mol/L be 11, reacted 30 minutes down at 90 ℃, and the black particle of generation washs respectively 3 times with deionized water and absolute ethyl alcohol, promptly obtain solid amorphous nickel phosphorus catalyst, represent with Ni-P-RE.
This control experiment gained catalyst is used for embodiment 4 described reactions by liquid phase hydrogenation of maltose malt sugar alcohol, and its catalytic performance data are shown in Table 1.
Embodiment 9
CoCl with 0.33g
26H
2O and 0.74g NaH
2PO
2H
2O and 0.57g CH
3COONa is dissolved in the 15mL deionized water, and to regulate pH value with the NaOH solution of 2.0mol/L be 11, reacted 30 minutes down at 90 ℃, and the black particle of generation washs respectively 3 times with deionized water and absolute ethyl alcohol, promptly obtain solid amorphous cobalt phosphorus catalyst, represent with Co-P-RE.
This control experiment gained catalyst is used for embodiment 4 described reactions by liquid phase hydrogenation of maltose malt sugar alcohol, and its catalytic performance data are shown in Table 1.
Embodiment 10
Industrial Raney Nickel catalyst 0.08g is used for embodiment 4 described reactions by liquid phase hydrogenation of maltose malt sugar alcohol, and its catalytic performance data are shown in Table 1.
The catalytic performance of catalyst among table 1 embodiment
| Catalyst | Reaction times | Specific area (m 2/g) | Conversion ratio (%) | Selectivity (%) |
| Ru-P-HS-1 | 1 | 56 | 92 | 100 |
| Ru-P-HS-2 | 1 | 68 | 99 | 100 |
| Ru-P-HS-3 | 1 | 52 | 87 | 100 |
| Ru-P-HS-2 | 2 | 68 | 98 | 100 |
| Ru-P-HS-2 | 3 | 68 | 98 | 100 |
| Ru-P-RE | 1 | Do not survey | 69 | 100 |
| Ni-P-RE | 1 | Do not survey | 23 | 100 |
| Co-P-RE | 1 | Do not survey | 18 | 100 |
| Raney Nickel | 1 | Do not survey | 10 | 75 |
Annotate: the reaction time is 2 hours
As seen from Table 1, the amorphous ruthenium P nano hollow ball material of the present invention's preparation is used for liquid phase hydrogenation of maltose malt sugar alcohol, show excellent catalytic performance, hydrogenation performance apparently higher than phosphorus series non-crystalline state alloys such as traditional ruthenium phosphorus, farther hydrogenation performance far above Raney Nickel catalyst, and long catalytic life can reuse and keep catalytic performance constant.
Claims (4)
1, a kind of Ru-P nano hollow ball catalyst in amorphous state:
(1) chemical composition is: Ru
xP
yX=85～92 wherein, y=8～15;
(2) the hollow ball diameter is 20～100nm, and the spheroid wall thickness is 5～10nm, specific area 50～68m
2/ g.
2, the preparation method of Ru-P nano hollow ball catalyst in amorphous state comprises the steps:
(1) gets double-stranded cationic surfactant, under 25 ℃, be dissolved in the deionized water;
(2) in above-mentioned solution, add inorganic salt solution and the hypophosphite and the cyclohexane of ruthenium successively, stirred 20～40 minutes;
(3) temperature in the above-mentioned solution is risen to 50～60 ℃, reacted 20～40 minutes;
(4) with absolute ethyl alcohol extraction surface activating agent; Respectively wash 2 times with deionized water and absolute ethyl alcohol then;
(5) 30～60W power ultrasonics cleaned 15～25 minutes;
(6) respectively wash 1 time with deionized water and absolute ethyl alcohol, promptly make Ru-P nano hollow ball catalyst in amorphous state.
3, the preparation method of Ru-P nano hollow ball catalyst in amorphous state according to claim 2 is characterized in that:
(1) double-stranded cationic surfactant is any in two ten alkyl dimethyl quaternary amines, two dodecyl dimethyl quaternary amine or the two myristyl dimethyl quaternary amine, and anion is a kind of in chlorion or the bromide ion;
(2) surfactant is 0.003～0.015g/mL in the concentration of solution, preferred 0.007g/mL;
(3) inorganic salts of ruthenium are RuCl
3Hypophosphite is NaH
2PO
2H
2O;
(4) contained P elements in contained ruthenium element and the hypophosphite in the inorganic salts by ruthenium, the molar ratio of ruthenium and phosphorus is 1: 3～1: 8, is preferably 1: 4～1: 6;
(5) inorganic salts of ruthenium concentration in solution is 0.008～0.020mol/L, is preferably 0.012mol/L;
(6) volume ratio of cyclohexane and deionized water is 1: 5～1: 20, preferred 1: 10.
4, a kind of Ru-P nano hollow ball catalyst in amorphous state, the application in industrial hydrogenation reaction.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862673A (en) * | 2010-06-28 | 2010-10-20 | 南开大学 | New method for preparing loaded Ru2P under mild condition |
| CN102179248A (en) * | 2011-03-22 | 2011-09-14 | 上海师范大学 | Double-layer hollow amorphous alloy nanometer ball as well as preparation method and application thereof |
| CN108658880A (en) * | 2018-06-26 | 2018-10-16 | 广东工业大学 | A kind of preparation method of ultra-violet absorber |
| CN108736029A (en) * | 2018-06-01 | 2018-11-02 | 东莞理工学院 | Hollow ball chain structure silver-platinum ruthenium composite material and preparation method and its application in electrocatalytic oxidation ethyl alcohol |
| CN110317180A (en) * | 2019-07-26 | 2019-10-11 | 广东工业大学 | A kind of preparation method of ultraviolet absorber |
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2009
- 2009-06-19 CN CN2009100534718A patent/CN101584990B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862673A (en) * | 2010-06-28 | 2010-10-20 | 南开大学 | New method for preparing loaded Ru2P under mild condition |
| CN102179248A (en) * | 2011-03-22 | 2011-09-14 | 上海师范大学 | Double-layer hollow amorphous alloy nanometer ball as well as preparation method and application thereof |
| CN108736029A (en) * | 2018-06-01 | 2018-11-02 | 东莞理工学院 | Hollow ball chain structure silver-platinum ruthenium composite material and preparation method and its application in electrocatalytic oxidation ethyl alcohol |
| CN108736029B (en) * | 2018-06-01 | 2021-10-01 | 东莞理工学院 | Hollow sphere chain structure silver-platinum ruthenium composite material and application thereof in electrocatalytic oxidation of ethanol |
| CN108658880A (en) * | 2018-06-26 | 2018-10-16 | 广东工业大学 | A kind of preparation method of ultra-violet absorber |
| CN108658880B (en) * | 2018-06-26 | 2021-09-03 | 广东工业大学 | Preparation method of ultraviolet absorbent |
| CN110317180A (en) * | 2019-07-26 | 2019-10-11 | 广东工业大学 | A kind of preparation method of ultraviolet absorber |
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