CN101642719B - Anchor ligand modified metal supported catalyst and preparation method and application thereof - Google Patents
Anchor ligand modified metal supported catalyst and preparation method and application thereof Download PDFInfo
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- CN101642719B CN101642719B CN2008101178985A CN200810117898A CN101642719B CN 101642719 B CN101642719 B CN 101642719B CN 2008101178985 A CN2008101178985 A CN 2008101178985A CN 200810117898 A CN200810117898 A CN 200810117898A CN 101642719 B CN101642719 B CN 101642719B
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Abstract
The invention discloses an anchor ligand modified metal supported catalyst and a preparation method and application thereof. The catalyst consists of a carrier, a metal component and an organic ligand, wherein the carrier is silicon dioxide, MCM-41 or SBA-15; the metal component is noble metal rhodium; the organic ligand is an organic phosphine ligand containing alkoxy silane group; and the metal component accounts for 0.1 to 5.0 percent of the total weight of the catalyst, and the organic ligand accounts for 5.0 to 25.0 percent of the total weight of the catalyst. In the catalyst, the organic ligand and the metal component are all directly fixed on the carrier; and simultaneously the coordination function exists between the organic ligand and the metal, and an active species is generated in situ. The catalyst can be used for hydroformylation of olefins to prepare multiple kinds of organic aldehyde, has high catalytic activity and excellent stability, and is easily separated.
Description
Technical field
The present invention relates to a kind of anchor ligand modified metal supported catalyst.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to the application of above-mentioned catalyst in hydroformylation of olefin.
Background technology
The homogeneous catalysis system reaction condition is gentle, and catalytic efficiency is high.But in practical application, usually be subject to the separating step of complicacy and expensive catalysts and reaction raw materials and product.Heterogeneous catalysis is owing to catalyst and separating easily of reaction raw materials and product are widely used in large-scale commercial production, but the catalytic activity of heterogeneous catalyst and selectivity of product are relatively poor relatively.A large amount of scientific research personnel are devoted to develop a kind of metal complex catalyst of novel heterogeneousization in decades in the past, and this catalyst can separate easily with reaction raw materials and product as heterogeneous catalyst, has the high catalytic performance of homogeneous catalyst again.
Li etc. (Journal of Physical Chemistry B, 2006,110:22942-22946) prepared and a kind of Ru complex compound anchor is incorporated into the new catalyst on the mesopore material and is applied to the isomerization reaction of 1-phenyl-1-hydroxyl-3-butylene.This Preparation of catalysts method comprised for two steps: at first the positive silane of tetraethyl, 2-(diphenylphosphine) ethyl triethoxysilane (DPPTS) are gone out the SBA-15 that anchor closes DPPTS with prepared in reaction such as hydrochloric acid, and then with RuCl
2(PPh
3)
3The SBA-15 prepared in reaction of closing DPPTS with anchor goes out the SBA-15 catalyst that anchor closes the Ru complex compound.
(Journal of Molecular Catalysis A:Chemical such as Michalska; 2004; 208:187-194) use the organosilan monomer of vinyl functionalization to close the polymer carrier of vinyl-functional, then with transition metal complex Pt (PPh through polymerisation generation anchor
3)
4Or [Rh (CO)
2Cl]
2Carrier Deng with vinyl-functional reacts, and makes Pt or Rh indirect securement to carrier, obtains the heterogeneous catalyst of anchor metal complex compound, and is applied in the hydrosilylation of 1-hexene.
Jones etc. (Topics in Catalysis, 2005,34:67-76) prepared the silica-gel catalyst that anchor closes the CuBr complex compound through four kinds of diverse ways:
Method one is at first on silica gel, to close through Si-O-Si key anchor to contain-NH
2The organic matter of functional group, then through in the 2-formoxyl pyridine-C=O and carrier on anchor close-NH
2Between dehydration pyridine radicals group is fixed on the carrier, introduce CuBr at last, prepare the silica-gel catalyst that anchor closes the CuBr complex compound through the coordination of N in Cu and the pyridine;
Method two is earlier 2-formoxyl pyridine and the reaction of 1-(amino) propyl trimethoxy silane to be generated the pyridine compounds that contains trimethoxy silane; Effect through trimethoxy silane and silica gel surface silanol group is incorporated into pyridine group anchor on the carrier again; Introduce CuBr at last, prepare the silica-gel catalyst that anchor closes the CuBr complex compound through the coordination of N in Cu and the pyridine;
Method three is that the pyridine compounds that contains trimethoxy silane, CuBr and silica gel are prepared the silica-gel catalyst that anchor closes the CuBr complex compound through the one pot reaction method;
Method four is the CuBr complex compounds that contain trimethoxy silane on the first pyridine synthesis part, and the effect through trimethoxy silane and silica gel surface silanol group is incorporated into CuBr complex compound anchor on the silica-gel carrier then.
Jones etc. have further compared the catalytic performance that anchor that this four kinds of methods prepare closes the silica-gel catalyst of CuBr complex compound: wherein the catalyst catalytic performance prepared of method four is best.
United States Patent (USP) U.S.P.5,789,333 have reported a kind of multiple catalyst for reaction systems such as hydroformylation, olefin oxidation, isomerisation of olefin that can be used for.In this catalyst system; Transition metal Rh etc. links through coordinate bond and organic ligand; Organic ligand is through firm being fixed on the carrier of Si-O-Si key, on carrier, supports another kind of metal promoter simultaneously the catalytic performance of this catalyst is played facilitation.
United States Patent (USP) U.S.P.6,331,601 reported a kind of load single active sites catalyst and be applied in the polymerisation of alkene.Transition metal is fixed on the carrier through the organic ligand of a bridge-type bidentate on this catalyst, connects through covalent bond between organic ligand and carrier.Preparation of catalysts comprised for two steps: at first organic ligand is fixed on the carrier of ammonia functionalization, and then transistion metal compound and the organic ligand that is fixed on the carrier are reacted the heterogeneous catalyst that obtains anchor metal complex compound.
United States Patent (USP) U.S.P.7,288,672 have reported that the anchor that hydroformylation is used closes catalyst.The organic ligand of functionalization is combined in the carrier inner surface through the Si-O-Si key anchor that generates with the carrier surface hydroxyl reaction on this catalyst, and the coordination indirect securement of transition metal through the organic ligand that closes with anchor is to carrier; Perhaps inorganic heteropoly acid is supported on the carrier, it is fixed on the carrier indirectly through the effect of transition metal complex and heteropoly acid.
Above-mentioned catalyst all is that organic ligand is incorporated on the carrier through the direct anchor of covalent bond, transition metal through with the coordination indirect securement of part to carrier, as shown in Figure 1.Though these anchors close catalyst the transition metal complex anchor have been incorporated on the carrier and since the coordinate bond between metal and part relatively a little less than, usually causing the loss of metal after the reaction for a long time, and then reducing the catalytic performance of catalyst because of the coordinate bond fracture.
Chinese patent CN 1422695 A have reported a kind of new catalyst that is used for hydroformylation of olefin, and this catalyst is made up of main active component, auxiliary agent, carrier and organic homogeneous catalyst part.The Preparation of catalysts method is following: earlier main active component is loaded on the carrier through infusion process; And then the solution of this metal supported catalyst with organic homogeneous catalyst part fully contacted, last room temperature vacuum extracts solvent and obtains the metal supported catalyst that organic ligand is modified.The adding of auxiliary element can improve the reaction and the stability of catalyst effectively in the catalyst.The hydroformylation of olefin that this catalyst applications is carried out in paste state bed reactor; With the similar mild reaction conditions of corresponding homogeneous catalysis under; Its catalytic performance and homogeneous catalyst are basic identical, and can accomplish the separation of catalyst through simple filtering.
Yan etc. ((Journal of Molecular Catalysis A:Chemical, 2005,234:1-7) a kind of novel ligand modified heterogeneous catalyst is applied to the hydroformylation reaction of propylene in the fixed bed reactors.The Preparation of catalysts method is following: earlier with carrier S iO
2Be impregnated into RhCl
3In the solution, obtain heterogeneous catalyst Rh/SiO through drying, roasting, reduction then
2Again with Rh/SiO
2Be incorporated into part triphenylphosphine (PPh
3) solution in, stir after half an hour the room temperature vacuum and extract solvent and obtain ligand modified heterogeneous catalyst PPh
3-Rh/SiO
2This catalyst has and the similar catalytic performance of homogeneous catalyst, and separates easily with reaction raw materials and product, in long course of reaction, has avoided the loss of metal.
Above-mentioned two kinds of catalyst all are that metal is directly loaded on the carrier, introduce organic ligand then, and original position generates active specy through the coordination of part and metal, and is as shown in Figure 2.Though this type catalyst has been fixed to metal component on the carrier firmly; But since organic ligand just through and metal between more weak coordination and indirect securement to carrier, so in course of reaction for a long time, usually reduce the catalytic performance of catalyst because of the loss of organic ligand.
Metal complex catalyst mainly is made up of metal and part two parts; As stated; Method with heterogeneousization of metal complex catalyst all is a kind of key components in the direct fixing metal complex compound on carrier at present, and another component is passed through the coordinate bond indirect securement to carrier then.This usually can cause the loss of active component in the course of reaction for a long time, and then reduces the catalytic performance of catalyst.
Summary of the invention
In order to address the above problem, the object of the present invention is to provide a kind of anchor ligand modified metal supported catalyst.
The present invention also aims to provide above-mentioned Preparation of catalysts method.
The present invention has carried out research repeatedly to the method for heterogeneousization of metal complex catalyst, has proposed to modify metal supported catalyst with anchor ligand.On this catalyst, part and metal component all directly are fixed on the carrier, have coordination and original position generation active specy between part and the metal simultaneously.
Specifically, catalyst provided by the invention is made up of carrier, metal component and organic ligand.Carrier is selected silica, MCM-41, SBA-15 etc., the most suitable silica of selecting for use for use; Metal component is selected VIII family metal for use, because of the activity of rhodium in the VIII family metal is the highest, so preferred rhodium; Organic ligand select for use can with the organic matter that contains N or P of silicon hydroxyl effect, mainly be the organophosphorus ligand that contains alkoxysilane groups, wherein best with 2-(diphenylphosphine) ethyl triethoxysilane activity.In addition, metal component accounts for 0.01-10.0% in total catalyst weight, and organic ligand accounts for 0.1-40.0% in total catalyst weight.Further optimize, metal component accounts for 0.1-5.0% in total catalyst weight, and organic ligand accounts for 5.0-25.0% in total catalyst weight.
In addition, in above-mentioned catalyst, the specific area of carrier is 100-1000m
2/ g, pore volume are 0.5-2.0cm
3/ g, pore-size distribution is at 1.0-100.0nm.
Method for preparing catalyst provided by the invention the steps include:
1) with the solubility salt of metal component, for example solution is processed in nitrate, chloride or the dissolving of carbonate water, and in this solution, dry then, roasting is also reduced with carrier impregnation.Baking temperature is 293-473K, and sintering temperature is 373-873K, and reduction temperature is 373-873K.
2) organic ligand is dissolved in the organic solvent, organic solvent adopts benzene, toluene, oxolane, chloroform, methyl alcohol etc., when organic part is 2-(diphenylphosphine) ethyl triethoxysilane, preferably uses benzene, toluene or oxolane.
3) solid with step 1 gained joins in the solution of step 2 gained, heats up then and stirs a period of time, and temperature is 293-473K, and mixing time is 0.5-100h.After the stirring it is chilled to room temperature, filters then, fully wash resulting solid with organic solvent, at last with resulting solid at ambient temperature vacuum extract solvent, promptly obtain anchor ligand modified metal supported catalyst.
Catalyst of the present invention can be used in the hydroformylation reaction of catalyzed alkene, can in fixed-bed process, carry out.Its typical operating condition is: reaction temperature 353-453K, reaction pressure 0.5-10.0MPa, gas space velocity 500-10000h
-1The reaction evaluating of catalyst in fixed bed shows: it is easy with excellent stability and catalyst separation that anchor ligand modified metal supported catalyst of the present invention has advantages of high catalytic activity.
Description of drawings
Fig. 1 is the structural representation that known anchor closes catalyst.
Fig. 2 is the structural representation of the heterogeneous catalyst of well known ligands modification.
Fig. 3 is that anchor of the present invention closes the Rh/SiO that 2-(diphenylphosphine) ethyl triethoxysilane is modified
2The structural representation of catalyst.
Fig. 4 is that anchor of the present invention closes the Rh/SiO that 2-(diphenylphosphine) ethyl triethoxysilane is modified
2The catalytic performance of catalyst in the ethene hydroformylation reaction.
Fig. 5 is the Rh/SiO that ethyl diphenylphosphine of the present invention is modified
2The catalytic performance of catalyst in the ethene hydroformylation reaction.
The specific embodiment
For better explanation Preparation of catalysts method and the application in hydroformylation of olefin thereof, enumerate the preparation and the application implementation example of some catalyst samples below, but the invention is not restricted to cited instance.
Get 5.0g silica gel, boiling 10 hours, 393K is dry, and is subsequent use.Preparation contains the RhCl of 0.05 gram Rh
3Aqueous solution 10.0ml floods above-mentioned silica gel with this aqueous solution, after the air dry in baking oven in 393K baking 12 hours, then in Muffle furnace in 573K roasting 4 hours, under the 393K condition, use H at last
2Reduced 4 hours, and promptly obtained the Rh load capacity and be 1% Rh/SiO
2Catalyst.
Embodiment 2
Get 0.22g 2-(diphenylphosphine) ethyl triethoxysilane and be dissolved in the 3.0ml toluene, add the Rh/SiO of 0.30g embodiment 1 preparation
2Catalyst stirred this mixture 15 hours then at ambient temperature, afterwards with it under 383K oil bath condition, refluxing and stirring 6 hours.Filter after mixture after refluxing is chilled to room temperature naturally; With the abundant wash solids of toluene until can't be in filtrating with liquid chromatographic detection to the phosphine part; At last with resulting solid at ambient temperature vacuum extract solvent, the anchor that promptly obtains black closes the Rh/SiO that 2-(diphenylphosphine) ethyl triethoxysilane is modified
2Catalyst, Fig. 3 be the structural representation of catalyst for this reason.
Embodiment 3
Get 0.062g ethyl diphenylphosphine and be dissolved in the 3.0ml toluene, add the Rh/SiO of 0.30g embodiment 1 preparation
2Catalyst stirred this mixture 15 hours then at ambient temperature, afterwards with it under 383K oil bath condition, refluxing and stirring 6 hours.Mixture after refluxing is chilled to the room temperature final vacuum naturally extracts the Rh/SiO that solvent promptly obtains the ethyl diphenylphosphine modification of black
2Catalyst.
Embodiment 4
The anchor of embodiment 2 preparations is closed the Rh/SiO that 2-(diphenylphosphine) ethyl triethoxysilane is modified
2Catalyst joins in the fixed bed reactors, earlier at 393K, normal pressure, H
2Air speed 2000h
-1Reduction is 12 hours under the condition, then with H
2Switch to synthesis gas (H
2: CO=1: 1), at 393K, 1.0MPa, synthesis gas air speed 2000h
-1Begin reaction under the condition.Reactant is collected with the collecting tank that the deionized water of 100ml cooling is housed with, and the product propionic aldehyde all is dissolved in the water of collecting tank.Product liquid uses the HP-6890N gas chromatographic analysis of being furnished with FFAP capillary column and fid detector, adopts ethanol to make interior mark.Reaction end gas uses the HP-6890N gas-chromatography of being furnished with Porapak-QS post and TCD detector to carry out on-line analysis.Reaction result is seen Fig. 4.Rh content before and after the reaction on the catalyst adopts ICP-AES to measure, and phosphine part content adopts elemental analyser to measure.After reaction was carried out 1000 hours, Rh on the catalyst and phosphine part did not all run off.
Embodiment 5
Ethene hydroformylation reaction in the fixed bed just is changed to catalyst the Rh/SiO of the ethyl diphenylphosphine modification of embodiment 3 preparations with embodiment 4
2Catalyst.Reaction result is seen Fig. 5.After reaction was carried out 110 hours, the phosphine part on the catalyst had run off 48%.
Embodiment 6
Ethene hydroformylation reaction in the fixed bed just is changed to catalyst the Rh/SiO of 0.3g embodiment 1 preparation with embodiment 4
2Catalyst.The TOF value of catalyst is 2.7h
-1
Can know by above-mentioned result, anchor ligand modified metal supported catalyst of the present invention, for example anchor closes the Rh/SiO that 2-(diphenylphosphine) ethyl triethoxysilane is modified
2The ethene hydroformylation reaction of catalyst applications in fixed bed reactors, it is easy with excellent stability and catalyst separation to have advantages of high catalytic activity, in long course of reaction, has avoided the loss of metal component and organic ligand.
Claims (4)
1. an anchor ligand modified metal supported catalyst is made up of carrier, metal component and organic ligand; Wherein:
Carrier is silica, MCM-41 or SBA-15;
Metal component is a rhodium, accounts for the 0.01-10.0% of total catalyst weight;
Organic ligand is 2-(diphenylphosphine) ethyl triethoxysilane, accounts for the 0.1-40.0% of total catalyst weight;
Prepare through following method:
A) with carrier impregnation in the aqueous solution of the solubility salt of metal component, dry then, roasting and reduction, baking temperature is 293-473K, sintering temperature is 373-873K, reduction temperature is 373-873K;
B) organic ligand is dissolved in the organic solvent, organic solvent adopts benzene, toluene or oxolane;
C) product that step a is obtained joins in the solution of organic ligand of step b, under the 293-473K condition, stirs 0.5-100 hour then; After the stirring it is chilled to room temperature, filters then, fully wash resulting solid with organic solvent, resulting solid vacuum at ambient temperature extracts solvent, promptly obtains anchor ligand modified metal supported catalyst;
The solubility salt of metal component is nitrate, chloride or carbonate.
2. according to the described catalyst of claim 1, it is characterized in that: the specific area of carrier is 100-1000m
2/ g, pore volume are 0.5-2.0cm
3/ g, pore-size distribution is at 1.0-100.0nm.
3. according to the described catalyst of claim 1, it is characterized in that: metal component accounts for the 0.1-5.0% of total catalyst weight; Organic ligand accounts for the 5.0-25.0% of total catalyst weight.
4. the application of the described catalyst of claim 1 in hydroformylation of olefin, reaction temperature 353-453K, reaction pressure 0.5-10.0MPa, gas space velocity 500-10000h
-1
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012004352A2 (en) | 2010-07-08 | 2012-01-12 | Stichting Voor De Technische Wetenschappen | Mesoporous diphosphine-transition metal complex catalyst for hydroformylation |
| CN103521268B (en) * | 2012-07-03 | 2016-01-20 | 中国科学院大连化学物理研究所 | A kind of heterogeneous catalyst being applied to hydroformylation of olefin and preparation method thereof |
| CN105363445B (en) * | 2014-08-25 | 2018-04-06 | 中国科学院大连化学物理研究所 | A kind of method for preparing Rh base catalyst and Rh bases catalyst and application |
| CN106140302B (en) * | 2015-04-03 | 2018-11-27 | 中国科学院大连化学物理研究所 | One kind containing the organic mixed polymers-metal heterogeneous catalyst of phosphine and its methods and applications |
| CN106824295A (en) * | 2015-12-03 | 2017-06-13 | 中国科学院大连化学物理研究所 | A kind of Vehicle element method of rhodium base catalyst and its application and rhodium base catalyst |
| PL422782A1 (en) * | 2017-09-07 | 2019-03-11 | Politechnika Lubelska | Mesoporous silica, modified with metal compounds and method for modification of mesoporous silica with metal compounds |
| CN112387280B (en) * | 2020-11-26 | 2022-10-21 | 山东新和成药业有限公司 | Method for preparing isopentenal by oxidizing enol |
| CN113522366B (en) * | 2021-07-27 | 2022-08-02 | 中国科学院兰州化学物理研究所 | Monophosphine-containing porous organic polymer in-situ packaging rhodium catalytic material, and preparation method and application thereof |
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| CN1422695A (en) * | 2001-12-06 | 2003-06-11 | 中国科学院大连化学物理研究所 | Catalyst for preparing various of organic aldehyde by alefin hydro-formylation and preparation method thereof |
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| US7288672B2 (en) * | 2004-03-29 | 2007-10-30 | Council Of Scientific & Industriual Research | Process for preparation of esters of hydroxy tiglic Aldehydes |
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Patent Citations (3)
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| CN1422695A (en) * | 2001-12-06 | 2003-06-11 | 中国科学院大连化学物理研究所 | Catalyst for preparing various of organic aldehyde by alefin hydro-formylation and preparation method thereof |
| US7288672B2 (en) * | 2004-03-29 | 2007-10-30 | Council Of Scientific & Industriual Research | Process for preparation of esters of hydroxy tiglic Aldehydes |
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Non-Patent Citations (1)
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| Li Yan，et al..Ligand modified real heterogeneous catalysts for fixed-bed hydroformylation of propylene.《Journal of Molecular Catalysis A: Chemical》.2005,第234卷1-7. * |
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