CN102430431B - Supported organic rhenium catalyst and preparation method thereof - Google Patents
Supported organic rhenium catalyst and preparation method thereof Download PDFInfo
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- CN102430431B CN102430431B CN 201210008694 CN201210008694A CN102430431B CN 102430431 B CN102430431 B CN 102430431B CN 201210008694 CN201210008694 CN 201210008694 CN 201210008694 A CN201210008694 A CN 201210008694A CN 102430431 B CN102430431 B CN 102430431B
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Abstract
The invention discloses a supported organic rhenium catalyst using a high-activity zirconium phosphate stratified material as a support and a preparation method thereof, belonging to the technical field of catalyst preparation. The zirconium phosphate compound in stratified structure is used as a support, and methylrhenium trioxide with catalytic activity is anchored to the surface of the zirconium phosphate compound, thereby obtaining the supported organic rhenium catalyst. The catalyst is used for catalyzing olefins to synthesize epoxy compounds by epoxidation, and has the advantages of high reactant conversion rate and high product selectivity.
Description
Technical field
The invention belongs to catalyst field, be specifically related to a kind of highly active supported organic rhenium catalyst of low load capacity take Zirconium phosphate compound as carrier and preparation method thereof.
Background technology
The chemical general formula of Zirconium phosphate compound is Zr (O
3P-R)
2NH
2O, wherein n is in conjunction with H
2The number of O can be divided into inorganic phosphate zirconium and organic phospho acid zirconium according to the difference of R group.Basic zirconium phosphate (Zr (O
3P-OH)
2NH
2O) two kinds of different structure types are arranged: alpha zirconium phosphate and γ-basic zirconium phosphate.Wherein alpha zirconium phosphate is that mode with ABAB is deposited in together between layers, and every one deck is by the approximate up and down two-layer O that is in conplane Zr atom and the Zr atom is clipped in the middle
3P-OH consists of.In the process of preparation basic zirconium phosphate, if use benzenephosphonic acid to replace phosphoric acid, then generate the same phosphonic acids zirconium with layer structure with alpha zirconium phosphate.Zirconium phosphate compound have preparation easily, crystal formation is good, layer structure is stable, water insoluble and organic solvent, heat endurance and chemical stability high.This special nature that shows in chemical and structure all has very widely it and uses in many fields such as catalysis, ion-exchange, electricity material, optical material, molecular recognition, biotechnologys.
Epoxide is the important intermediate of organic synthesis, owing to there is very active epoxy radicals in its molecular structure, can generate with reactions such as amine, phenol, alcohol, carboxylic acids the compound of a series of high added values.Expoxy propane is important industrial chemicals, mainly for the production of polyurethane and surfactant etc.The important intermediate of Styryl oxide Chang Zuowei organic synthesis, pharmaceuticals industry.7-oxa-bicyclo[4.1.0 is widely used in producing the agricultural chemicals propargite; The unsaturated-resin of high rigidity, high temperature resistant, acid and alkali-resistance; Novel, efficient photoactive coating and photosensitive adhesive; Crown ether; Merlon; Important fine chemicals hexandial etc.In recent years, supply falls short of demand for epoxide on the domestic and international market, brought wide prospect for its application study.The method of alkene direct oxidation is generally adopted in the preparation of epoxide, and oxidant can be TBHP, CHP, H
2O
2Deng, wherein directly by H
2O
2For oxidant carries out the better method that epoxidation is the realization green catalysis with alkene.Catalyst mainly concentrates on some transition-metal catalysts at present, such as Au, Ag etc.; In addition, also have the hetero-atom molecular-sieve catalyst of some titaniferous and through the molecular sieve catalyst of finishing, such as TS-1, Ti-MCM-41, Ti-SBA and Ta-SBA etc., but these catalyst exist that cost is expensive, conversion ratio or the selective shortcoming such as low.Therefore, the catalyst of seeking a kind of low cost, high activity and high selectivity is necessary.
Herrmann groups in 1988 have found the new synthetic method of methyl rhenium trioxide (MTO), and afterwards, people have begun the broad research as catalyst for MTO.MTO can be used for the many organic synthesis of catalysis, as: the alkene reaction of the oxidation reaction of olefin metathesis reaction, epoxidation reaction of olefines, aromatic, Alcohol oxidation reaction, aldehyde etc.Wherein, of greatest concern is that homogeneous phase MTO is with H
2O
2Be the oxidizer catalytic epoxidation reaction of olefines.MTO can activate H
2O
2The efficient catalytic alkene epoxidation generates epoxides, and accessory substance is H
2O is green cleaning activity process.But homogeneous catalyst is not easy to separate and reclaim, and has limited industrialized large-scale production and application.In recent years, people have successfully loaded on MTO the heterogeneous catalyst of the organic rhenium of preparation on the multiple organic and inorganic carrier, and these carriers mainly contain: Al
2O
3, MCM-41, Nb
2O
5, HZSM-5, PVP, shitosan etc.At present, the preparation method of supported organic rhenium catalyst mainly contains: infusion process, sublimed method, chemical vapour deposition technique.Iwasawa seminar applied chemistry vapour deposition process loaded on MTO in the hole of HZSM-5 in 2006, can be used for efficient catalytic benzene one-step synthesis phenol.
Summary of the invention
The purpose of this invention is to provide a kind of highly active supported organic rhenium catalyst of low load capacity take Zirconium phosphate compound as carrier and preparation method thereof.
Active component methyl rhenium trioxide (MTO) in the prepared supported organic rhenium catalyst of the present invention is dispersed in the surface of carrier, and load capacity is 0.1-20wt%, and described carrier is Zirconium phosphate compound, and its chemical general formula is: Zr (O
3P-R)
2NH
2O, wherein, R is organic group, is specially hydroxyl, aromatic radical, alkyl, carboxyl, amino acid group, sulphophenyl or crown ether; N is the quantity of the crystallization water, 1≤n≤3.
The concrete preparation process of supported organic rhenium catalyst of the present invention is as follows:
Measure carrene 1-20mL and add in the there-necked flask of 25mL, add successively the Zirconium phosphate compound of 0.1-20g and the methyl rhenium trioxide of 0.01-0.5g, at N
2Under the atmosphere protection, adopt lucifuge to process, stirring at normal temperature 1-72h, the powder that obtains is supported organic rhenium catalyst.
Above-mentioned supported organic rhenium catalyst is applied to EPOXIDATION OF ALKENES CATALYZED BY generates epoxide.
Catalytic reaction condition is: reaction temperature is 0-60 ℃, the reaction pressure normal pressure, adopt methyl alcohol or benzene as solvent, solvent load 1-10ml/10mmol alkene, every milliliter of alkene adds the above-mentioned supported organic rhenium catalyst of 0.01-2.0g, oxidant percarbamide consumption is 0.1-4.0g/mL alkene, reaction time 1-48h.
Described Zirconium phosphate compound, its chemical general formula is: Zr (O
3P-R)
2NH
2O, wherein, R is organic group, is specially hydroxyl, aromatic radical, alkyl, carboxyl, amino acid group, sulphophenyl or crown ether; N is the quantity of the crystallization water, 1≤n≤3.
Described alkene is 1-hexene, cyclohexene, cyclo-octene, styrene; The corresponding epoxide that catalyzes and synthesizes is epoxy hexane, 7-oxa-bicyclo[4.1.0, epoxide ring octane, phenyl ethylene oxide.
Described Zirconium phosphate compound adopts the preparation of nucleation crystallization isolation method.
Described nucleation crystallization isolation method concrete operation step is: the ZrOCl that takes by weighing 3-30g
28H
2O is dissolved in the deionized water, and adding the 1-10mL mass concentration is the HF solution of 40-55%, finally is diluted to the 100mL mixed solution I; And then take by weighing the benzenephosphonic acid (PhPO of 2-20g
3), the use volume ratio is that 1-third alcohol and water of (1: 1)-(1: 5) is mixed with 100mL alcohol solution II; Squeeze into mixed solution I in the full back-mixing rotating liquid-film reactor of High Rotation Speed with identical speed with alcohol solution II with binary channels constant current peristaltic pump, rapid mixing 0.5-10min, slit width between conditioned reaction device rotor and the stator is 0.01-0.05mm, operating voltage is 100V, and rotor speed is 2500-6000rpm; The colloidal state slurries that make are poured into water heating kettle, 40-120 ℃ of reaction 10-100h; With a large amount of deionized water centrifuge washing 2-5 time, to pH be 7-8, with isopropyl alcohol wash 1-3 time, wash 1-3 time with acetone, wash 1-3 time with ether, at vacuum drying chamber drying 10-48h, namely get Zirconium phosphate compound again.
The invention has the advantages that: selecting the bedded zirconium phosphate compounds is carrier, and the methyl rhenium trioxide that will have catalytic activity is anchored on the surface of Zirconium phosphate compound, thereby has obtained supported organic rhenium catalyst.The catalyst of the present invention's preparation is used for the reaction that the catalyzed alkene oxidation prepares epoxide, and at first use Shimadzu company GC-MS to carry out qualitative analysis to product, rear utilization Shimadzu gas-chromatography is carried out quantitative analysis, bearing reaction thing conversion ratio is high, the selective height of product.Concrete reactant olefin conversion ratio is up to 92.2%, and the target product epoxide selectively is up to 100%.
Description of drawings
Fig. 1 is the XRD spectra of the prepared catalyst of embodiment 1;
Fig. 2 is the FTIR image of the prepared catalyst of embodiment 1;
Fig. 3 is the SEM image of the prepared catalyst of embodiment 1.
The specific embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
A: the ZrOCl that takes by weighing 14.50125g
28H
2O is dissolved in the deionized water, and adding 6mL mass concentration is 40% HF solution, finally is diluted to the 100mL mixed solution I; And then take by weighing the PhPO of 14.2281g
3, the use volume ratio is that 1-the third alcohol and water of 1: 1 is mixed with 100mL alcohol solution II; Squeeze into mixed solution I in the full back-mixing rotating liquid-film reactor of High Rotation Speed with identical speed with alcohol solution II with binary channels constant current peristaltic pump, rapid mixing 1min, slit width between conditioned reaction device rotor and the stator is 0.04mm, operating voltage is 100V, and rotor speed is 4000rpm; The colloidal state slurries that make are poured into water heating kettle, 100 ℃ of reaction 96h; With a large amount of deionized water centrifuge washing 3 times, to pH be 7, with isopropyl alcohol wash 1 time, wash 1 time with acetone, wash 1 time with ether, at the dry 24h of vacuum drying chamber, namely get Zirconium phosphate compound again; Its chemical general formula is: Zr (O
3P-R)
2NH
2O, wherein, R is phenyl; N is the quantity of the crystallization water, n=2;
B: measure the 10mL carrene and add in the there-necked flask of 25mL, add successively the Zirconium phosphate compound of steps A preparation of 1.0g and the MTO of 0.2g, at N
2Under the atmosphere protection, adopt lucifuge to process, stirring at normal temperature 24 hours, the powder that obtains is supported organic rhenium catalyst; Active component methyl rhenium trioxide in this catalyst is dispersed in the surface of carrier Zirconium phosphate compound;
C: the catalyst epoxidation of cyclohexene with step B preparation generates 7-oxa-bicyclo[4.1.0, reaction condition is: 25 ℃ of reaction temperatures, the reaction pressure normal pressure adopts methyl alcohol as solvent, solvent load 10ml/10mmol cyclohexene, every milliliter of cyclohexene adds the catalyst that 0.1g step B obtains, the percarbamide consumption is the 1.806g/mL cyclohexene, reaction time 6h, reactant cyclohexene conversion rate 92.2%, the target product 7-oxa-bicyclo[4.1.0 is selective 100%, and the TOF value of catalyst is 34.7h
-1
A: with embodiment 1;
B: measure the 10mL carrene and add in the there-necked flask of 25mL, add successively the Zirconium phosphate compound of 1.0g steps A preparation and the MTO of 0.15g, at N
2Under the atmosphere protection, adopt lucifuge to process, stirring at normal temperature 24 hours, the powder that obtains is supported organic rhenium catalyst; Active component methyl rhenium trioxide in this catalyst is dispersed in the surface of carrier Zirconium phosphate compound;
C: with the reaction condition of embodiment 1 catalyst of step B preparation is carried out the catalytic performance test, reactant cyclohexene conversion rate 41.9%, the target product 7-oxa-bicyclo[4.1.0 is selective 100%, and the TOF value of catalyst is 40.9h
-1
Embodiment 3
A: with embodiment 1;
B: with embodiment 1;
C: the catalyst cyclo-octene epoxidation with step B preparation generates the epoxide ring octane, reaction condition is: 25 ℃ of reaction temperatures, the reaction pressure normal pressure adopts methyl alcohol as solvent, solvent load 10ml/10mmol cyclo-octene, every milliliter of cyclo-octene adds the catalyst that 0.1g step B obtains, the percarbamide consumption is the 1.806g/mL cyclo-octene, reaction time 6h, reactant cyclo-octene conversion ratio 88%, target product epoxide ring octane is selective 100%, and the TOF value of catalyst is 29.7h
-1
Embodiment 4
A: with embodiment 1;
B: with embodiment 1;
C: the catalyst with step B preparation generates 7-oxa-bicyclo[4.1.0 to the cyclohexene catalytic oxidation, reaction condition is: 40 ℃ of reaction temperatures, the reaction pressure normal pressure adopts methyl alcohol as solvent, solvent load 10ml/10mmol cyclohexene, every milliliter of cyclohexene adds the catalyst that 0.1g step B obtains, the percarbamide consumption is the 1.806g/mL cyclohexene, reaction time 6h, reactant cyclohexene conversion rate 43.1%, the target product 7-oxa-bicyclo[4.1.0 is selective 100%, and the TOF value of catalyst is 16.3h
-1
Embodiment 5
A: with embodiment 1;
B: with embodiment 2;
C: the catalyst with step B preparation generates phenyl ethylene oxide to catalytic oxidation of phenylethene, reaction condition is: 82 ℃ of reaction temperatures, the reaction pressure normal pressure, adopt benzene as solvent, solvent load 10ml/10mmol styrene, every milliliter of styrene adds the catalyst that 0.2g step B obtains, the percarbamide consumption is 1.806g/mL styrene, reaction time 8h, reactant styrene conversion rate 48.6%, the target product phenyl ethylene oxide is selective 76.1%, accessory substance benzaldehyde and phenylacetaldehyde selectively be respectively 23.1% and 0.8%, the TOF value of catalyst is 34.1h
-1
Claims (7)
1. a supported organic rhenium catalyst is characterized in that, the active component methyl rhenium trioxide of described catalyst is dispersed in the surface of carrier, and load capacity is 0.1-20wt%, and described carrier is Zirconium phosphate compound, and its chemical general formula is: Zr (O
3P-R)
2NH
2O, wherein, R is hydroxyl, aromatic radical, alkyl, carboxyl, amino acid group, sulphophenyl or crown ether; N is the quantity of the crystallization water, 1≤n≤3.
2. the preparation method of a kind of supported organic rhenium catalyst according to claim 1 is characterized in that, its concrete preparation process is as follows:
Measure carrene 1-20mL and add in the there-necked flask of 25mL, add successively the Zirconium phosphate compound of 0.1-20g and the methyl rhenium trioxide of 0.01-0.5g, at N
2Under the atmosphere protection, adopt lucifuge to process, stirring at normal temperature 1-72h, the powder that obtains is supported organic rhenium catalyst.
3. preparation method according to claim 2 is characterized in that, described Zirconium phosphate compound adopts the preparation of nucleation crystallization isolation method.
4. preparation method according to claim 3 is characterized in that, described nucleation crystallization isolation method concrete operation step is: the ZrOCl that takes by weighing 3-30g
28H
2O is dissolved in the deionized water, and adding the 1-10mL mass concentration is the HF solution of 40-55%, finally is diluted to 100mL mixed solution I; And then take by weighing the benzenephosphonic acid of 2-20g, use volume ratio to be mixed with 100mL alcohol solution II for 1-third alcohol and water of (1:1)-(1:5); Squeeze into the mixed solution I in the full back-mixing rotating liquid-film reactor of High Rotation Speed with identical speed with the alcohol solution II with binary channels constant current peristaltic pump, rapid mixing 0.5-10min, slit width between conditioned reaction device rotor and the stator is 0.01-0.05mm, operating voltage is 100V, and rotor speed is 2500-6000rpm; The colloidal state slurries that make are poured into water heating kettle, 40-120 ℃ of reaction 10-100h; With a large amount of deionized water centrifuge washing 2-5 time, to pH be 7-8, with isopropyl alcohol wash 1-3 time, wash 1-3 time with acetone, wash 1-3 time with ether, at vacuum drying chamber drying 10-48h, namely get Zirconium phosphate compound again.
5. the application of a kind of supported organic rhenium catalyst according to claim 1 is characterized in that, it is applied to the catalyzing expoxidation of olefines synthesizing epoxy compound.
6. the application of a kind of supported organic rhenium catalyst according to claim 5, it is characterized in that, the reaction condition of described catalyzing expoxidation of olefines synthesizing epoxy compound is: reaction temperature is 0-60 ℃, the reaction pressure normal pressure, adopt methyl alcohol or benzene as solvent, solvent load 1-10ml/10mmol alkene, the catalyst that the method for every milliliter of alkene adding 0.01-2.0g claim 2 obtains, oxidant percarbamide consumption is 0.1-4.0g/mL alkene, reaction time 1-48h.
7. the application of a kind of supported organic rhenium catalyst according to claim 6 is characterized in that, described alkene is 1-hexene, cyclohexene, cyclo-octene or styrene; The corresponding epoxide that catalyzes and synthesizes is epoxy hexane, 7-oxa-bicyclo[4.1.0, epoxide ring octane or phenyl ethylene oxide.
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