CN1136991C - Preparation of metal compounding material molecular sieve composite material - Google Patents

Abstract

The present invention relates to a method for preparing metal compounding material molecular sieve composite materials, which belongs to the physicochemical field, and is characterized in that ML/MCM-41 is used as a raw material, and metal compounding materials are fixed on a molecular sieve substrate by a recrystallization method. The method is simple and practical. The metal compounding materials with different surface properties can be effectively fixed on the molecular sieve substrate. The method of the present invention is an effective and common application method for preparing metal compounding material/molecular sieve composite materials. In addition, molecular sieve composite materials with high carrying capacity for the metal compounding materials can be prepared by the method.

Description

The preparation of metal compounding material molecular sieve composite material

Technical field

The preparation method of metal compounding material molecular sieve composite material of the present invention belongs to the physical chemistry field, specifically is exactly a kind of new preparation method who metal complex fixed sealing of different nature is loaded in the molecular sieve matrix.

Technical background

In the disclosed at present report, about the preparation method who metal complex is fixed in the molecular sieve matrix has three kinds usually: free ligand method, template agent synthetic method and zeolite synthetic method [(1) K.J.Baulkus Jr., A.K.Khanmamedova, K.M.Dixon and F.Bedioui, Appl.Catal.143 (1996) 159, (2) P.P.Knops-Gerrits, D.D.Vos, F.Thibault-Starzys and P.A.Jacobs, Nature, 369 (1994) 5431; (3) C.R.Jacob, S.P.Varky, andP.Ratnasamy, Microporous and Mesoporous Materials, 22 (1998) 465; (4) B.Z.Zhan and X.Y.Li, Chem.Commun., 349 (1998)], these methods all are by different modes, the three-dimensional restriction of the special space that utilizes host molecule sieve aperture road structure to be had realizes fixing the object metal complex.Common selected material of main part is X, y-type zeolite, owing to be subjected to the restriction of less port size of selected material of main part and vestibule volume, adopts the metal complex that said method can not be bigger with molecular dimension to be fixed in the vestibule of molecular sieve effectively; Simultaneously small apertures size and vestibule volume also are unfavorable for effective diffusion of reactant and product in the macromolecular reaction.In order to overcome above-mentioned deficiency, have the novel M41S series mesopore material that the aperture is big, pore size distribution evenly reaches Large ratio surface and be used as material of main part.Though M41S series mesopore material has bigger port size and vestibule volume, but its special pore passage structure and surface nature, make metal complex fixedly being different from general micro porous molecular sieve thereon, if metal complex will be anchored on securely on the M41S series mesopore material, need functionalized processing is carried out on its surface, just can make and produce certain bonding action [(5) C.J.Liu between its surface and some metal complex, S.G.Li, W.Q.Pang and C.M.Che, Chem.Commun. (1997) 65; (6) P.Sutra, D.Bruner, Chem.Commun., (1996) 2485; A.Bleloch, B.F.G.Johnson, S.V.Ley, A.J.Price, D.S.Shephard and A.W.Thomas, Chem.Commun., (1999) 1907], not only made the unusual very complicated of preparation process like this, and the character of complex proposed certain requirement that incompatibility has thereon fixing of various metal complexs of different nature; The pore passage structure of M41S is difficult to metal complex is applied space steric effect simultaneously.

Summary of the invention

The objective of the invention is to propose a kind of metal complex can be fixed in preparation method in the molecular sieve matrix effectively, it can be effectively applied in the heterogeneous catalytic reaction.

The preparation of metal compounding material molecular sieve composite material of the present invention is characterized in that it being a kind of preparation method that metal complex can be fixed on effectively in the molecular sieve matrix.This method is MCM-41, the MCM-41S (ML/MCM-41 that metal complex is arranged with load, M is a transition metal, and L is an organic ligand) be predecessor, utilize crystallization technology again, make it change ML/ (MCM-41)/Y under certain condition into, metal complex is fixed in the molecular sieve matrix.Preparation process was sealed in the reactor for after in proportion ML/MCM-41, sodium metaaluminate, directed agents and sodium hydrate aqueous solution fully being mixed, in room temperature to 90 ℃ following crystallization 1-10 days.MCM-41 series mesopore material silica alumina ratio (mole) is more than or equal to 30, is fixed in metal complex size in the molecular sieve matrix greater than the duct size of micro porous molecular sieve.

Infrared spectrum (FTIR) figure Fig. 3 that X-ray diffraction (XRD) figure Fig. 2 that description of drawings Fig. 1 is fixed with the molecular sieves compound material of Fephen is fixed with the molecular sieves compound material of Fephen (a), FeQx (b) and FeSA (c) is fixed with diffuse reflection spectrum (DRS) figure of the molecular sieves compound material of Fephen (1), FeQx (2) and FeSA (3)

The specific embodiment

The preparation method of the predecessor of ML/MCM-41 of the present invention is as follows: example 1: the ML/MCM-41 with the preparation of direct crystallization method is a predecessor

Concrete preparation method is as follows: with ML (M=Fe, Co, Cr, Cu, Mn; L=o-phenanthroline (phenanthroline, be abbreviated as: phen), 8-hydroxy-quinoline (8-quinolinol, be abbreviated as Qx), salicylic acid (Salicylic acid, be abbreviated as: SA), bigeminy pyrrole fixed (2,2 '-bipyridyl is abbreviated as: the bipy) special alkali (Schift-bases of Schiff, be abbreviated as: salen), phthalocyanine (phthalocyanine, be abbreviated as: Pc), porphyrin (porphyrin) mixes according to a certain percentage with the reactant mixture of MCM-41, be sealed in the stainless steel cauldron that is lined with the polytetrafluoroethylene (PTFE) pad, 120 ℃ of following crystallization, after treating that crystallization is finished, the gained solid is fully washed with deionized water, to remove surfactant as much as possible, sample after will washing then obtains ML/MCM-41 in 90 ℃ of following freeze-day with constant temperature.

Example 1.1 is as follows: earlier with 6.08g CTAB and 85ml water glass solution ([SiO ₂]=1.30M, [OH ^-]=0.75M) mixes, subsequently with the sodium aluminate solution ([Al of 11.8ml ₂O ₃]=0.047M, [OH ^-]=0.17M) slowly adds, and uses the H of 8.7ml again ₂SO ₄(3.77M) solution is regulated the pH value of above-mentioned prepared gel, at last again with Fe (phen) ₃Cl ₂Complex compound adds, after itself and reactant mixture fully mixed, be sealed in the stainless steel cauldron that is lined with the polytetrafluoroethylene (PTFE) pad, 120 ℃ of following crystallization, after treating that crystallization is finished, the gained solid is fully washed with deionized water, and the sample after will washing then obtains the Fephen/MCM-41 predecessor in 90 ℃ of following freeze-day with constant temperature.

Example 1.2 is as follows: earlier with 6.08g CTAB and 85ml water glass solution ([SiO ₂]=1.30M, [OH ^-]=0.75M) mixes, subsequently with the sodium aluminate solution ([Al of 11.8ml ₂O ₃]=0.047M, [OH ^-]=0.17M) slowly adds, and uses the H of 8.7ml again ₂SO ₄(3.77M) solution is regulated the pH value of above-mentioned prepared gel, again the sulfonated phthalocyanine cobalt complex is added at last, after itself and reactant mixture fully mixed, be sealed in the stainless steel cauldron that is lined with the polytetrafluoroethylene (PTFE) pad, 120 ℃ of following crystallization, treat that crystallization is finished after, the gained solid is fully washed with deionized water, sample after will washing then obtains sulfonated phthalocyanine cobalt network/MCM-41 predecessor in 90 ℃ of following freeze-day with constant temperature.Example 2: the ML/MCM-41 with immersion process for preparing is a predecessor

Concrete preparation method is as follows: will mix with certain density metal ethanolic solution by a certain percentage through 550 ℃ of baked MCM-41 mesopore materials, and under stirring condition, be evaporated to dried in 50 ℃ of left and right sides scopes.Example is as follows: 2g is placed 1.2g Fe (phen) through 550 ℃ of baked MCM-41 ₃Cl ₂The 20ml ethanolic solution in, under stirring condition, in 50 ℃ of left and right sides scopes, be evaporated to dried, the Fephen/MCM-41 predecessor.Example 3: the ML/MCM-41 with the hetero-atom molecular-sieve preparation is a predecessor

Concrete preparation method is as follows: M-MCM-41 (the described method of preparation process reference literature) and the organic ligand of certain M/Si are carried out getting the ML/MCM-41 predecessor after the complexing.Example is as follows: 1.2g is crossed Fe-MCM-41 (Si/Fe=100) through 550 ℃ of roastings, place 10ml to contain the ethanolic solution of the adjacent luxuriant and rich with fragrance network quinoline of 1.0g, complexing is 24 hours under room temperature, after filtration, dried Fephen/MCM-41 predecessor.

Be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in adopting the resulting ML/MCM-41 predecessor of distinct methods and waterglass, sodium metaaluminate and directed agents fully to mix to be enclosed within, under specified criteria, synthesize ratio range: (5-10) SiO ₂: Al ₂O ₃: (1.5-3.0) Na ₂O: (0-0.4) ML: (350-920) H ₂O.Main feature of the present invention is simple, can be fixed in effectively in the molecular sieve matrix having positive electricity, negative electricity and neutral metal complex, having widened the range of choice to metal complex greatly, is a kind of preparation method with broad applicability of preparation metal compounding material molecular sieve composite material.Can prepare the composite that is fixed with the high content gold metal complex by the content of modulation metal complex in the MCM mesopore material, this is that the at present existing preparation method of employing institute is inaccessiable.By M-MCM-41 being carried out crystallization and crystal formation conversion processing, can obviously improve M-MCM-41 metal component leakage in catalytic reaction.In addition, this method is not subjected to the restriction of metal complex molecular dimension yet.Realize that preferred example of the present invention is as follows:

1. at first with 1.78ml water glass solution ([SiO ₂]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO ₂: Al ₂O ₃: 16Na ₂O: 320H ₂O) mix, then with 0.89ml sodium aluminate solution ([Al ₂O ₃]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, adopt the prepared FephenL/MCM-41 predecessor 1.0g of infusion process last the adding again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 2 days under 363K, the Fephen sample that products therefrom is fixed after washing, ethanol extracting, crystalline phase is Y type (seeing accompanying drawing 1).The FTIR figure of sample and the spectrogram that diffuses are seen accompanying drawing 2 and accompanying drawing 3 respectively.

2. at first with 1.78ml water glass solution ([SiO ₂]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO ₂: Al ₂O ₃: 16Na ₂O: 320H ₂O) mix, then with 0.89ml sodium aluminate solution ([Al ₂O ₃]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, adopt the prepared sulfonated phthalocyanine cobalt/MCM-41 predecessor 1.0g of direct crystallization method last the adding again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 5 days under 333K, products therefrom is fixed the sample of sulfonated phthalocyanine cobalt after washing, ethanol extracting, crystalline phase is the Y type.

3. at first with 1.78ml water glass solution ([SiO ₂]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO ₂: Al ₂O ₃: 16Na ₂O: 320H ₂O) mix, then with 0.89ml sodium aluminate solution ([Al ₂O ₃]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, adopt the prepared FeSA/MCM-41 predecessor 1.0g of infusion process last the adding again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 2 days under 363K, the FeSA sample that products therefrom is fixed after washing, ethanol extracting, crystalline phase is the Y type.The FTIR figure of sample and the spectrogram that diffuses are seen accompanying drawing 2 and accompanying drawing 3 respectively.

4. at first with 1.78ml water glass solution ([SiO ₂]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO ₂: Al ₂O ₃: 16Na ₂O: 320H ₂O) mix, then with 0.89ml sodium aluminate solution ([Al ₂O ₃]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, add at last prepared FeQx/MCM-41 predecessor 1.0g again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 5 days under 333K, the FeQx sample that products therefrom is fixed after washing, ethanol extracting, crystalline phase is the Y type.The FTIR figure of sample and the spectrogram that diffuses are seen accompanying drawing 2 and accompanying drawing 3 respectively.

5. at first with 1.78ml water glass solution ([SiO ₂]=7.0M, [OH]=4.07M), 94ml water, 1.2g NaOH, 3ml structure directing agent (15SiO ₂: Al ₂O ₃: 16Na ₂O: 320H ₂O) mix, then with 0.89ml sodium aluminate solution ([Al ₂O ₃]=2.72M, [OH]=9.7M) dropwise adds under stirring condition, generate silica-alumina gel, adopt the prepared CrQx/MCM-41 predecessor 1.0g of hetero-atom molecular-sieve complexometry last the adding again, be lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE) pad in being enclosed within after fully mixing with silica-alumina gel, under self-generated pressure and static conditions, thermostatic crystallization is 5 days under 333K, the CrQx sample that products therefrom is fixed after washing, ethanol extracting, crystalline phase is the Y type.

Metal compounding material molecular sieve composite material by this method preparation not only has very high thermo qualitative and chemical stability and shape selective catalysis performance etc., but also can replace to come the surface property of modulation zeolite by the isomorphous of ion-exchange or backbone element, making it be applicable to different reaction requirements, is a kind of novel heterogeneousization of homogeneous reaction catalyst.This method is not limited by assembled metal complex size and the existence form in synthetic system, has extensive applicability.

Claims (4)

1. the preparation method of metal compounding material molecular sieve composite material, it is characterized in that with ML/MCM-41, ML/MCM-41S be predecessor, adopt crystallization method again, change ML/MCM-41 into ML/ (MCM-41)/Y, metal complex is fixed in the molecular sieve matrix, its preparation process is for after fully mixing ML/MCM-41, sodium metaaluminate, directed agents and sodium hydrate aqueous solution in proportion, be sealed in the reactor, in room temperature to 90 ℃ following crystallization 1-10 days, products therefrom after filtration, washing, organic solvent extracting and dry back be standby.

2. according to the described preparation method of claim 1, it is characterized in that with ML/MCM-41 being predecessor, the ML/MCM-41 predecessor is synthetic by original position, the method for dipping and the complexing of metallic MCM-41S series mesopore material obtains, the predecessor that is adopted is the mesopore series material that load has metal complex, its silica alumina ratio (mole) is more than or equal to 30, MCM-41S comprises the M-MCM-41 series material that hetero atom replaces, and M is a transition metal.

3. according to the described preparation method of claim 1, the metal complex that will have different electrical properties is fixed in the molecular sieve matrix.

4. according to the described preparation method of claim 1, be fixed in metal complex size in the molecular sieve matrix greater than the duct size of micro porous molecular sieve.

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