CN1398675A - Prepn of zeolite carried polymer metal cluster - Google Patents

Prepn of zeolite carried polymer metal cluster Download PDF

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CN1398675A
CN1398675A CN 02135408 CN02135408A CN1398675A CN 1398675 A CN1398675 A CN 1398675A CN 02135408 CN02135408 CN 02135408 CN 02135408 A CN02135408 A CN 02135408A CN 1398675 A CN1398675 A CN 1398675A
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molecular sieve
metal
alcohol
metal cluster
polymer
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CN1140351C (en
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马静红
李瑞丰
任淑华
潘大海
谢克昌
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Taiyuan University of Technology
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Taiyuan University of Technology
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Abstract

A preparation of zeolite-carried high-molecular metal cluster features that an alcohol-water solution containing Pt family metal inorganic compound and an alcohol-water solution of polymer are made to contact with superfine Beta zeolite molecular sieve fully and the Pt family metal is reduced through heating reflux. Then, powdered superfine Beta zeolite molecular sieve carrying high-molecular Pt family metal cluster is produced by drying in rotary decompress evaporation mode. The said process can disperse the metal cluster homogeneously on the surface of molecular sieve, and the metal particles have small and narrowly distributed size and are stable in the air. The metal cluster may be used in catalyst for the low temperature conversion of methane and has relatively high selectivity to high-carbon hydrocarbon.

Description

The preparation of zeolite carried polymer metal cluster
Technical field
The preparation of zeolite carried polymer metal cluster of the present invention belongs to chemistry and chemical field, particularly, is the preparation method about a kind of nanometer Beta zeolite molecular sieve carried polymer platinum metal cluster.
Background technology
Metal supported catalyst is one of industrial important catalyst.Usually, inorganic carrier for example silica gel, aluminium oxide, molecular sieve etc. is used to the preparation of metal supported catalyst, to obtain big metal surface area and to stablize its highly dispersed state.Wherein the preparation method with load zeolite molecular sieve metal cluster studies at most.
US4,882,307 disclose a kind of preparation process that contains the noble metal zeolite catalyst, this process is with water miscible precious metals complex or salt and molecular sieve exchange, or with this solution impregnation molecular sieve, after drying and the roasting, use the hydrogen reducing noble metal, thereby obtain high dispersive in the metal cluster on zeolite molecular sieve surface.
US4,199,478 disclose the preparation method of metal cluster catalyst in a kind of zeolite, and this method is to remove coordination carbonyl in the carried metal carbonyl cluster (MCC) by heating to obtain carried metal bunch.
But in the above-mentioned two kinds heat treatment processes that prepare carried metal bunch, all can cause the gathering and the sintering of metallic.
US5,008,234 and US4,552,855 disclose a kind of process for preparing zeolite-metal catalyst respectively, and process is under low-temp low-pressure, the metallic atom of vaporization is dissolved in formation zero-valent metal complex in organic liquid solvent or the gas, with its dipping zeolite molecular sieve carrier, add the thermally decomposable metal complex then, metal is present in the hole of zeolite with the form of the little metal cluster of zeroth order.But the process complexity of this method, preparation is difficult, and has the agglomeration problem of metallic in the heating process equally.
High molecular polymer also can be used as the stabilizing agent of metal cluster as a kind of organic macromolecule carrier.J.Macromol.Sci.-Chem. in 1978; A12; 1117-1141; J.Macromol.Sci.-Chem. in 1979, A13 (6), 727-750 and J.Phys.Chem. in 1991; 95; 7448-7453 has reported that existence at high molecular polymer (for example polyvinyl alcohol, PVP) down with the salt of alcohol reduction noble metal, can obtain to be subjected to the list and the bimetallic colloid dispersed of high molecular polymer protection.This colloidal particle is compared with the metallic that obtains with common hydrogen reducing, has the characteristics of the little and narrowly distributing of particle diameter.While in some catalytic hydrogenation reactions, shows advantages of high catalytic activity as catalyst.But this gluey catalyst can only be used for the liquid-phase catalysis reaction.
Summary of the invention
The solid supported metallic that the objective of the invention is to overcome prior art for preparing disperses uneven shortcoming at carrier surface, provide a kind of metallic particles little, narrow distribution range, on carrier, be uniformly dispersed and the preparation method of stable zeolite molecular sieve carried polymer metal cluster.
The method of zeolite molecular sieve carried polymer metal cluster provided by the invention is, the alcohol solution of the inorganic compound of platinum group metal and the alcohol solution and the zeolite molecular sieve of high molecular polymer are mixed, under agitation add hot reflux reduction platinum group metal, place the rotary evaporator vacuum drying then.
According to preparation method provided by the present invention, zeolite molecular sieve and organic high molecular polymer the two all as the carrier and the part of metal active constituent, play a part to disperse and the stable metal particle.It is characterized in that preparation process carries out in the following order:
1, be 1 * 10 with concentration -3Mol/L-1 * 10 -2The alcohol solution of the inorganic compound of the platinum group metal of mol/L and concentration are 1 * 10 -2Mol/L-1 * 10 -1The alcohol solution of the high molecular polymer of mol/L and zeolite molecular sieve mix, and three's ratio is (5-40) * 10 -5Mol: (1-40) * 10 -4Mol: the 1g molecular sieve, stir this mixed liquor then, the time is 3-20 hour, temperature is 10-20 ℃.
2, under constantly stirring, add the hot reflux said mixture, the time is 1-5 hour.
3, in rotary evaporator, the heating reduction vaporization liquid solvent in the solidliquid mixture of back that refluxes obtains solid powdery carried metal bunch, and heating-up temperature is≤50 ℃.
Wherein said platinum group metal is meant a kind of in ruthenium, rhodium, palladium, osmium, iridium and the platinum, also can be two kinds of elements, and their compound comprises H 2PtCl 66H 2O, RuCl 33H 2O, PdCl 2, RhCl 3, H 2IrCl 66H 2O, OsO 4
Wherein said alcohol is methyl alcohol, ethanol, and the volume ratio of alcohol and water is 0.5-2 in the alcohol solution.
Described high molecular polymer is PVP and polyvinyl alcohol.
Wherein said zeolite molecular sieve is the Beta molecular sieve, and size of microcrystal is 100-200nm, and the Beta molecular sieve is before use through 30-850 ℃, and roasting is more than 10 hours, fully to remove organic amine and carbon-containing impurities in the oxygen.The preparation method of carried polymer metal cluster of the present invention has the following advantages:
1. adopt the method for pure water reduction to replace using hydrogen reducing, avoided high-temperature roasting and reduction, method is simple, processing ease.
2. owing to zeolite molecular sieve and the dual part effect of high molecular polymer, can obtain the metal cluster of polymolecularity.By tem observation as can be known, metal cluster is uniformly dispersed on the zeolite molecular sieve surface, and particle size distribution is very narrow.
3. by changing the ratio of PVP chain link molal quantity and metal molar number, can obtain varigrained metal cluster.
Since superfine nano Beta molecular sieve as carrier, for the dispersion of polymer metal cluster provides big surface.
By CO-FTIR and CH on carried polymer platinum metal bunch of the present invention 4The observation of+CO-FTIR, at room temperature, CO has very strong absworption peak on Pt-PVP/Beta, has shown the polymolecularity of Pt metallic, but at CO and CH 4During coexistence, the CO absworption peak obviously weakens, and shows CH 4Can produce chemisorbed at catalyst surface.In addition, investigated CH with two-step method 4Conversion reaction on the low temperature on catalyst Pt-PVP/Beta of the present invention (100-150 ℃).The result is, in the time of 〉=100 ℃, and CH 4The absorption of can on Pt-PVP/Beta, dissociating, and in hydrogenation process thereupon, generate high carbon alkane (C 2+)
The preparation of specific embodiment embodiment 1 Pt (0.25mM)-PVP (1.25mM)/Beta (1g)
Take by weighing the Beta molecular sieve of 1g oven dry, add 4 * 10 -3The six hydration chloroplatinic acid (H of mol/L 2PtCl6H 2O) methanol (volume ratio is 1: 1) solution 64ml and 2 * 10 -2The methanol of the PVP of mol/L (PVP) (volume ratio is 1: 1) solution 63ml under 10-20 ℃, uses magnetic stirrer 10 hours, then, under magnetic agitation, be heated to 80 ℃, reflux, after solution colour becomes black by yellow, continue to reflux 3 hours, take out, pour in the rotary evaporator, water-bath is heated to 40 ℃, vacuum drying obtains the molecular sieve carried macromolecule platinum metal bunch of Beta dark gray powder.
The tem observation result, surperficial average grain diameter 4.0nm (accompanying drawing 1).Methane conversion the results are shown in Table 1 on catalyst " example 1 "
Table 1 is by the amount and the distribution of the hydrocarbon of methane conversion generation
C 2C 3C 4C 5C 6The CH that transforms 4The amount (10 of total amount HC -9Mol) 25.3 17.4 13.5 1.45 0.01 164.2 selectivity (%) 30.9 31.7 32.9 4.42 0.07
Reaction condition: sample: 250mg Pt-PVP/Beta
The first step: place (150 ℃ of methane stream moving air flows; 200ml/min; 10min)
Second step: place (150 ℃ in flow hydrogen gas air-flow; 50ml/min; 15min) the preparation of embodiment 2 Pt (0.15mM)-PVP (1.5mM)/Beta (1g)
Take by weighing the Beta molecular sieve of 1g oven dry, add 3 * 10 -3The six hydration chloroplatinic acid (H of mol/L 2PtCl 66H 2O) methanol (volume ratio is 1: 1) solution 50ml and 1.5 * 10 -2The methanol of the PVP of mol/L (PVP) (volume ratio is 1: 1) solution 100ml under 10-20 ℃, uses magnetic stirrer 8 hours, then, under magnetic agitation, be heated to 80 ℃, reflux, after solution colour becomes black by yellow, continue to reflux 3 hours, take out, pour in the rotary evaporator, water-bath is heated to 40 ℃, vacuum drying obtains the molecular sieve carried macromolecule platinum metal bunch of Beta dark gray powder.
The tem observation result, surperficial average grain diameter 3.3nm.The preparation of embodiment 3 Pd (0.25mM)-PVP (1.25mM)/Beta (1g)
Take by weighing the Beta molecular sieve of 1g oven dry, add 4 * 10 -3Palladium bichloride (the PdCl of mol/L 2) alcohol/water (volume ratio is 1: 1) solution 62.5ml and 2 * 10 -2The methanol of the PVP of mol/L (PVP) (volume ratio is 1: 1) solution 62.5ml under 10-20 ℃, uses magnetic stirrer 8 hours, then, under magnetic agitation, be heated to 80 ℃, reflux, solution colour by yellow become brown after, continue to reflux 2 hours, take out, pour in the rotary evaporator, water-bath is heated to 40 ℃, vacuum drying obtains the molecular sieve carried macromolecule palladium metal bunch light brown powder of Beta.
The tem observation result, surperficial average grain diameter 3.0nm.
The preparation of embodiment 4, Ru (0.3mM)-PVP (1.5mM)/Beta (1g)
Take by weighing the Beta molecular sieve of 1g oven dry, add 5 * 10 -3The three hydration ruthenic chloride (RuCl of mol/L 33H 2O) ethanol/water (volume ratio is 1: 1) solution 60ml and 1 * 10 -2The ethanol/water of the PVP of mol/L (PVP) (volume ratio is 1: 1) solution 150ml under 10-20 ℃, uses magnetic stirrer 5 hours, then, under magnetic agitation, be heated to 90 ℃, reflux, solution colour by orange-yellow become dark brown, continue to reflux 3 hours, take out, pour in the rotary evaporator, water-bath is heated to 50 ℃, vacuum drying obtains the molecular sieve carried macromolecule ruthenium of Beta metal cluster brown ceramic powder.
The preparation of embodiment 5, Pd+Pt (0.15+0.15mM)-PVP (1.5mM)/Beta (1g)
Take by weighing the Beta molecular sieve of 2g oven dry, add 3 * 10 -3Palladium bichloride (the PdCl of mol/L 2) alcohol/water (volume ratio is 1: 2) solution 100ml, 6 * 10 -3The six hydration chloroplatinic acid (H of mol/L 2PtCl 66H 2O) methanol (volume ratio is 1: 1) solution 50ml and 3 * 10 -2The methanol of the PVP of mol/L (PVP) (volume ratio is 2: 1) solution 100ml under 10-20 ℃, uses magnetic stirrer 5 hours, then, under magnetic agitation, be heated to 80 ℃, reflux, after solution colour becomes grey black by yellow, continue to reflux 4 hours, take out, pour in the rotary evaporator, water-bath is heated to 40 ℃, vacuum drying obtains the molecular sieve carried macromolecule palladium of Beta platinum bimetallic bunch light grey powder.
The preparation of embodiment 6, Ru+Pt (0.2+0.2mM)-PVP (2.0mM)/Beta (g)
Take by weighing the Beta molecular sieve of 2g oven dry, add 4 * 10 -3The three hydration ruthenic chloride (RuCl of mol/L 33H 2O) ethanol/water (volume ratio is 2: 1) solution 100ml, 4 * 10 -3The six hydration chloroplatinic acid (H of mol/L 2PtCl 66H 2O) ethanol/water (volume ratio is 1: 1) solution 100ml and 5 * 10 -2The ethanol/water of the PVP of mol/L (PVP) (volume ratio is 1: 1) solution 80ml under 10-20 ℃, uses magnetic stirrer 10 hours, then, under magnetic agitation, be heated to 90 ℃, reflux, solution colour by orange-yellow become black after, continue to reflux 3 hours.Take out, pour in the rotary evaporator, water-bath is heated to 50 ℃, and vacuum drying obtains the molecular sieve carried macromolecule ruthenium of Beta platinum bimetallic bunch brown-black powder.

Claims (6)

1, a kind of preparation of zeolite carried polymer metal cluster is characterized in that described preparation method, and step is carried out in the following order:
(1) getting concentration is 1 * 10 -3-1 * 10 -2The inorganic compound of the platinum group metal of mol/L pure water-soluble
Liquid, concentration are 1 * 10 -2-1 * 10 -1The alcohol solution of the high molecular polymer of mol/L and Beta
Zeolite molecular sieve mixes.
(2) stir (1) gained mixed liquor down at 10-20 ℃, time 3-20 hour,
(3) under agitation add hot reflux (2) gained mixture to variable color, continued then backflow 1-5 hour,
(4) (3) gained is placed rotary evaporator, solvent evaporated under reduced pressure, temperature are≤50 ℃, system
Get Beta zeolite molecular sieve carried polymer platinum metal cluster pressed powder.
2,, it is characterized in that described platinum group metal inorganic compound is RuCl according to the described preparation method of claim 1 33H 2O, RhCl 3, PdCl 2, OsO 4, H 2LrCl 66H 2O and H 2PtCl 6In a kind of, also can be two kinds.
3,, it is characterized in that described high molecular polymer is polyvinylpyrrolidone and polyvinyl alcohol according to the described preparation method of claim 1.
4, according to the described preparation method of claim 1, it is characterized in that the alcohol in the described alcohol solution is methyl alcohol or ethanol, alcohol is 1 with the ratio of water: 0.5-1: 2.
5, according to the described preparation method of claim 1, it is characterized in that described Beta zeolite molecular sieve is ultra-fine Beta molecular sieve, crystal grain is 100-200nm, silica alumina ratio (Si/Al) is 10-15.
6, according to the described preparation method of claim 1, it is characterized in that described carried polymer platinum metal cluster is Pd, Pt, Ru, Rh, Ir and Os monometallic bunch, and the bimetallic formed of two kinds of elements bunch wherein, as Pd-Ru, Pd-Pt, Pt-Ru.
CNB021354081A 2002-08-05 2002-08-05 Prepn of zeolite carried polymer metal cluster Expired - Fee Related CN1140351C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100391471C (en) * 2006-08-24 2008-06-04 浙江大学 Method for preparing platinum metal bunch with biological activity, and use thereof
CN101100535B (en) * 2006-06-29 2011-11-30 科莱恩金融(Bvi)有限公司 Transparent zeolite-polymer hybrid material with tunable properties
CN103586484A (en) * 2013-11-25 2014-02-19 中国科学院福建物质结构研究所 Palladium ruthenium alloy nano-particles, preparation method thereof and application thereof
CN104493193A (en) * 2014-11-24 2015-04-08 北京大学 Hydro-thermal synthetic method and application of Pt-Ru bimetal nanoparticles
CN109395774A (en) * 2017-05-09 2019-03-01 丰田自动车株式会社 Cluster carrier catalyst and its manufacturing method
CN110387252A (en) * 2018-04-17 2019-10-29 中国科学院大连化学物理研究所 A kind of method that dimethyl ether catalysis conversion system is rich in isoparaffin gasoline

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101100535B (en) * 2006-06-29 2011-11-30 科莱恩金融(Bvi)有限公司 Transparent zeolite-polymer hybrid material with tunable properties
CN100391471C (en) * 2006-08-24 2008-06-04 浙江大学 Method for preparing platinum metal bunch with biological activity, and use thereof
CN103586484A (en) * 2013-11-25 2014-02-19 中国科学院福建物质结构研究所 Palladium ruthenium alloy nano-particles, preparation method thereof and application thereof
CN103586484B (en) * 2013-11-25 2017-10-24 中国科学院福建物质结构研究所 Pd-Ru alloy nano particle and its preparation and use
CN104493193A (en) * 2014-11-24 2015-04-08 北京大学 Hydro-thermal synthetic method and application of Pt-Ru bimetal nanoparticles
CN109395774A (en) * 2017-05-09 2019-03-01 丰田自动车株式会社 Cluster carrier catalyst and its manufacturing method
CN109395774B (en) * 2017-05-09 2021-11-05 丰田自动车株式会社 Cluster-supported catalyst and method for producing same
CN110387252A (en) * 2018-04-17 2019-10-29 中国科学院大连化学物理研究所 A kind of method that dimethyl ether catalysis conversion system is rich in isoparaffin gasoline
CN110387252B (en) * 2018-04-17 2021-06-11 中国科学院大连化学物理研究所 Method for preparing gasoline rich in isoparaffin by catalytic conversion of dimethyl ether

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