CN102513104A - Preparation method of benzaldehydes compound and novel double-metal catalyst loaded by mesoporous carbon for preparation method - Google Patents
Preparation method of benzaldehydes compound and novel double-metal catalyst loaded by mesoporous carbon for preparation method Download PDFInfo
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Abstract
The invention relates to a preparation method of a benzaldehydes compound and a catalyst for the preparation method. The catalyst is composed of 0.01-90 wt% of metal grains and 10-99.99 wt% of mesoporous carbon carrier; the metal grains are selected from any two of Pd, Au, Ag, Pt, Ru, Rh, Ni, Cu, Fe, Co, Cr, W, Mo, Ti and Ta; the weight ratio of two types of the metal is 1: (0.01-100) and the average grain diameter of the metal grains is 1-100 nm; and the mesoporous carbon carrier is prepared from a heteroatom-doped mesoporous carbon material. The content of heteroatoms in the mesoporous carbon material is 0.01-80 wt%. The catalyst provided by the invention is stable for water, air and heat and has an excellent catalytic activity; particularly, the catalyst has a high selectivity when being used for catalyzing an alcohol oxidation reaction to prepare aldehyde or ketone. The preparation method of the benzaldehydes compound provided by the invention has the advantages of high conversion rate of raw materials and good selectivity of a target product.
Description
Technical field
The invention belongs to the organic synthesis field, be specifically related to a kind of preparation method of benzaldehyde compounds and use catalyst, relate in particular to the bimetallic catalyst that a kind of novel meso-porous carbon material supports and be used for the purposes that the catalytic alcohol oxidation reaction prepares aldehydes or ketones.
Background technology
Benzaldehyde compounds (for example benzaldehyde, tolyl aldehyde, methoxybenzaldehyde, nitrobenzaldehyde etc.) is the important raw material of industry, is mainly used in the manufacturing dyestuff, medicine, spices, condiment product, important intermediate such as agricultural chemicals.Owing to the property obtained that is prone to of Atom economy and raw material, be a kind of directly effective preparation method through selective catalytic oxidation phenmethylol compounds, the key of this method is to control the selectivity of catalytic oxidation.Document (Science, 2006,311,362-365) introduced a kind of Au, the method for Pd nanocatalyst Oxybenzene methyl alcohol.Document (J.Mol.Catal.A, 1991,67,309-315) introduced and studied mechanism with the method for metal complex catalytic phenylmethanol oxidation.Recently document (J.Catal.2011,283,34-44) introduced a kind of Pd and loaded on the MnCeOx mixed oxide solvent-free catalytic oxidation phenmethylol to method of benzaldehyde.Therefore to be oxidized to the research of benzaldehyde all be the comparison popular topic to benzyl alcohol selective all the time, has important problem meaning and application value so develop a kind of catalyst to system high activity, high selectivity
Known; Meso-porous carbon material is one type of non-silicon mesoporous material; It has big specific area and pore volume, good electrical conductivity and to superior performances such as most organic solvent inertia, and it removes through calcining easily, aspect a lot of, has complementarity with oxide material; Therefore, make meso-porous carbon material all obtain at aspects such as catalysis, absorption, separation, Chu Qing, electrochemistry using widely.The metallic catalyst that is supported by material with carbon element is the effective catalyst of reactions such as catalytic hydrogenation and oxidation.As document (J.Catal.2010,270,9-15) support the catalytic hydrogenation reaction that nanometer Pd particle is used for the catalysis substituted benzene with activated carbon or carbon nano-fiber.Document (Green Chem.2010,12,1007-1011) introduced with CNT and support nanometer Pt particle and be used for catalysis nitrobenzene reduction reaction.(Chem.Commun.2008 999-1001.) has introduced the synthetic carbon-supported nanometer Pd particle of a kind of hydro-thermal method to document, and is applied to phenol hydrogenation reduction preparation cyclohexanol.Document (Science, 2009,326,1250-1252.) introduced a kind of with combine with the Lewis acid method of catalytic reduction production of phenol cyclohexanone of Pd/C.(Chem.Commun.2003 1960-1961) has synthesized catalyst such as Ru/C, Rh/C, Pd/C, Pt/C to document, and has investigated activity and the selectivity of these catalyst in the catalysis of phenol hydrogenation reaction respectively.Although use very extensively with carbon-supported noble metal catalyst, these catalyst also have its intrinsic weakness, in air, place easy inactivation like catalyst; Not high (Chem.Commun.2003 1960-1961), often need add co-catalyst (Science as catalyst to reaction selectivity in some selective reactions; 2009; 326,1250-1252.) etc., these issues limit this type Application of Catalyst.
Summary of the invention
The bimetallic catalyst that technical problem to be solved by this invention provides a kind of novel mesoporous carbon to support, it prepares aldehydes or ketones to alcohol oxidation reaction and has high catalytic activity and high reaction selectivity, and this catalyst is to air and hydrothermally stable.
The present invention also will provide a kind of phenmethylol compounds catalytic oxidation to prepare the method for benzaldehyde compounds simultaneously, and this method selectivity is high.
For solving above technical problem; A kind of technical scheme that the present invention takes is: the bimetallic catalyst that a kind of novel mesoporous carbon supports; It is made up of metallic 0.01wt%～90wt% and mesoporous carbon carrier 10wt%～99.99wt%; Wherein: metallic is any two kinds that are selected among Pd, Au, Ag, Pt, Ru, Rh, Ni, Cu, Fe, Co, Cr, W, Mo, Ti and the Ta, and the weight ratio of two kinds of metals is 1: 0.01～100, and the average grain diameter of metallic is 1～100nm; The mesoporous carbon carrier is processed by the meso-porous carbon material that hetero atom mixes; The meso-porous carbon material that this hetero atom mixes is to be monomer to contain heteroatomic ionic liquid; At room temperature mix with template, calcined 1～6 hour down at 400 ℃～1000 ℃ then, be cooled to room temperature; Remove template at last and make, heteroatomic content is 0.01wt%～80wt% in this meso-porous carbon material.
Preferably, said metallic catalyst is made up of metallic 0.1wt%～50wt% and said mesoporous carbon carrier 50wt%～99.9wt%.Heteroatomic mass fraction is preferably 0.1wt%～30wt% in the meso-porous carbon material that said hetero atom mixes.
According to the present invention, said hetero atom is meant element for example nitrogen, sulphur, phosphorus, boron, the fluorine etc. outside the de-carbon hydrogen-oxygen, is mainly derived from ionic liquid.Ionic liquid includes but not limited to imidazole type ion liquid, quaternary ammonium type ionic liquid and pyridine type ionic liquid etc.; Ionic liquid can be wherein any; It also can be the combination of the different ionic liquid of same type; Can also be the combination of dissimilar different kinds of ions liquid, not special restriction.According to a concrete aspect of the present invention, said ionic liquid is preferably the cation and the formula (b) of formula (a) expression and representes anionic combination in any:
(b)N(CN)
2 -，BF
4 -，PF
6 -，Cl
-，Br
-，F
-，PO
4 3-，SO
4 2-，NO
3 -，CF
3SO
3 -，CF
3COO
-，EtOSO
3 -，MeOSO
3 -.
In the said formula (a), n is the integer between 1～20, is preferably the integer between 1～12, more preferably the integer between 1～6.
Typical ionic liquid can be for example 1-penta cyanic acid-3-methylimidazole hexafluorophosphate, 4-methyl-N-penta cyanopyridine tetrafluoroborate, 1-butyl-3-methylimidazole villaumite, 1-butyl-3-methylimidazole ethyl-sulfate salt etc.Though the ionic liquid that these are mentioned and specifically do not mention but the ionic liquid of structure with combination of above-mentioned formula (a) and formula (b) all can prepare or be purchased acquisition by those skilled in the art through known method.
According to the present invention, in the meso-porous carbon material process that the preparation hetero atom mixes, the template of use can wherein be preferably molecular sieve SBA-15, molecular sieve MCM-41 or Ludox Ludox HS for the various template that are fit to.Template generally can be through removing with ammonium acid fluoride or naoh treatment.
According to the present invention, described bimetallic specifically can be Au-Pd, Au-Pt, Ag-Pt, Ru-Pd, Au-Ni, Au-Co etc.Bimetallic catalyst can prepare through the loading method of routine, and conventional loading method comprises ultrasonic method, deposition-precipitation method, sol-gal process and light deposition method etc., the wherein preferred ultrasonic method comparatively easily that adopts.Be specially: the meso-porous carbon material that mixes with hetero atom is a raw material with oxide, halide or the nitrate of metal, under hyperacoustic condition, mix, then with sodium borohydride solution with metallic reducing, filter, washing is dried and is promptly got.
Above-mentioned bimetallic catalyst prepares in the catalytic alcohol oxidation reaction and has showed excellent catalytic activity and selectivity in the aldehydes or ketones; And catalyst itself is to air; Hydro-thermal is all very stable; Therefore, the present invention also is particularly related to above-mentioned bimetallic catalyst and is used for the purposes that the catalytic alcohol oxidation reaction prepares aldehydes or ketones.For this reason; The present invention also provides a kind of method of using above-mentioned bimetallic catalyst catalytic phenylmethanol compounds preparing benzaldehyde by oxidizing compounds especially; Said benzaldehyde compounds comprises benzaldehyde and by one or more alkyl that are selected from; Alkoxyl, the substituted benzaldehyde of the group of cyanic acid and nitro, this method makes the phenmethylol compounds in the presence of bimetallic catalyst of the present invention; Generate described benzaldehyde compounds with the air or oxygen reaction, catalyst consumption is 0.01%～20% of a phenmethylol compounds weight.
According to the method for the invention, in the said bimetallic catalyst, bimetallic is preferably Au-Pd, Au-Pt, Ag-Pt or Ru-Pd.Solvent can not be adopted in this reaction; Perhaps, this reaction can be adopted and be selected from water, carrene, chloroform, toluene, benzene, ethyl acetate, n-hexane, dimethyl sulfoxide (DMSO), dimethyl formamide and the pyridine any as solvent; The pressure of oxygen or air is generally 0.1MPa～10MPa, is preferably 0.1MPa～3MPa, and the temperature of reaction is 0 ℃～250 ℃, is preferably 100 ℃～180 ℃.
Because the utilization of technique scheme, the present invention compared with prior art has following advantage:
1, to adopt by containing heteroatomic ionic liquid be the meso-porous carbon material that hetero atom that monomer is processed mixes to the carrier of catalyst of the present invention; Make and to obtain nano-sized metal particles in the deposition of carrier surface with dispersion through the valence state and the metal of heteroatomic doping regulation and control metal, thereby help strengthening its catalytic activity.
2, catalyst of the present invention is a bimetallic catalyst; The applicant finds unexpectedly; When this bimetallic catalyst that contains two kinds of metals is used for the catalytic alcohol oxidation reaction and prepares aldehydes or ketones; Its catalytic activity that shows not is the simple superposition that supports the catalytic activity that single metal shows, and has significant synergy.Preparing benzaldehyde with the catalytic phenylmethanol oxidation reaction is example, uses bimetallic catalyst of the present invention, can obtain the selectivity greater than 98%, and some bimetallic catalyst reaches more than 99.5% the selection performance of this reaction.
3, Preparation of catalysts of the present invention is simple, and to water, air and thermally-stabilised.As this catalyst soaked for 1 week in water, catalyst is not seen tangible foamed phenomenon, and activity does not subtract in the oxidation reaction of phenmethylol; Deposit in air that its catalytic phenylmethanol oxidation activity does not subtract after 5 months; In air, be heated to 550 degree, catalyst is not seen obvious decomposition.
4, the preparation method of benzaldehyde compounds of the present invention, its feed stock conversion is high, and good reaction selectivity, the recyclable utilization of catalyst, cost is lower.
The specific embodiment
Below in conjunction with specific embodiment the present invention is done further detailed explanation, but the present invention is not limited to following examples.
Embodiment 1
The Au-Pd catalyst that the mesoporous carbon that present embodiment provides a kind of nitrogen to mix supports, it prepares through following steps:
(1), 1g 1-ethyl-3-methylimidazole dicyan amine salt and 1.5g template SBA-15 are at room temperature mixed; Be warmed up to 900 ℃ of calcinings 3 hours then; Take off SBA-15 with the ammonium acid fluoride branch behind the cool to room temperature; Obtain the meso-porous carbon material 0.7g that nitrogen mixes, elementary analysis shows that nitrogen content is 11.8%, and its specific area is at 150～1200m
2/ g.
(2), getting the meso-porous carbon material that 0.1g nitrogen mixes joins in the 50ml ethanol; Ultrasonic 10 minutes; Adding 1ml concentration respectively is the gold chloride of 1mg/ml and the ethanolic solution of palladium bichloride; Continue after ultrasonic 10 minutes to add the 10mg sodium borohydride reduction, suction filtration wash repeatedly, obtains the Au-Pd catalyst that the mesoporous carbon of nitrogen doping supports after the drying.
Embodiment 2
The Au-Pd catalyst that present embodiment provides the mesoporous carbon of a kind of nitrogen and phosphor codoping to support, it prepares through following steps:
(1), 1g 1-penta cyanic acid-3-methylimidazole hexafluorophosphate and 1.5g template Ludox HS40 are at room temperature mixed; Be warmed up to 900 ℃ of calcinings 2 hours then; Take off Ludox HS 40 with the ammonium acid fluoride branch behind the cool to room temperature, obtain the meso-porous carbon material 0.6g of nitrogen and phosphor codoping, elementary analysis shows that nitrogen content is 11.3%; Phosphorus content is 0.1%, and its specific area is at 150～1200m
2/ g.
(2), the meso-porous carbon material of getting above-mentioned nitrogen of 0.1g and phosphor codoping joins in the 50ml ethanol; Ultrasonic 10 minutes; Add the gold chloride that concentration is 1mg/ml and the ethanolic solution 1ml of palladium bichloride respectively; Continue after ultrasonic 10 minutes to add the 10mg sodium borohydride reduction, suction filtration is washed repeatedly, obtains the Au-Pd catalyst that the mesoporous carbon of nitrogen and phosphor codoping supports after the drying.
Embodiment 3
The Au-Pd catalyst that present embodiment provides the mesoporous carbon of a kind of nitrogen and sulphur codope to support, it prepares through following steps:
(1), 1g 1-butyl-3-methylimidazole dicyan amine salt, 0.5g 1-butyl-3-methylimidazole ethyl-sulfate salt and 2.5g template Ludox HS 40 are at room temperature mixed; Be warmed up to 900 ℃ of calcinings 2 hours then; Take off Ludox HS 40 with the ammonium acid fluoride branch behind the cool to room temperature, obtain the meso-porous carbon material 0.7g of nitrogen and sulphur codope, elementary analysis shows that nitrogen content is 11.6%; The content of sulphur is 0.3%, and its specific area is at 150～1200m2/g.
(2), the meso-porous carbon material of getting above-mentioned nitrogen of 0.1g and sulphur codope joins in the 50ml deionized water; Ultrasonic 10 minutes; Add the gold chloride that concentration is 1mg/ml and the aqueous solution 1ml of palladium bichloride respectively; Continue after ultrasonic 10 minutes to add the 10mg sodium borohydride reduction, suction filtration is washed repeatedly, obtains the Au-Pd catalyst that the mesoporous carbon of nitrogen and sulphur codope supports after the drying.
Embodiment 4
The Au-Pt catalyst that the mesoporous carbon that present embodiment provides a kind of nitrogen to mix supports; It prepares through following steps: get the meso-porous carbon material of the nitrogen doping of 0.1g embodiment 1 preparation, join in the 50ml deionized water ultrasonic 10 minutes; Add the gold chloride that concentration is 1mg/ml and the aqueous solution 1ml of chloroplatinic acid respectively; Continue after ultrasonic 10 minutes to add the 10mg sodium borohydride reduction, suction filtration wash repeatedly, obtains the Au-Pt catalyst that the mesoporous carbon of nitrogen doping supports after the drying.
Embodiment 5
The Ag-Pd catalyst that the mesoporous carbon that present embodiment provides a kind of nitrogen to mix supports; It prepares through following steps: get the meso-porous carbon material of the nitrogen doping of 0.1g embodiment 1 preparation, join in the 50ml deionized water ultrasonic 10 minutes; Add the silver nitrate that concentration is 1mg/ml and the aqueous solution 1.5ml of palladium chloride respectively; Continue after ultrasonic 10 minutes to add the 11mg sodium borohydride reduction, suction filtration wash repeatedly, obtains the Ag-Pd catalyst that the mesoporous carbon of nitrogen doping supports after the drying.
Embodiment 6
The Rh-Pd catalyst that the mesoporous carbon that present embodiment provides a kind of nitrogen to mix supports; It prepares through following steps: get the meso-porous carbon material of the nitrogen doping of 0.1g embodiment 1 preparation, join in the 50ml deionized water ultrasonic 10 minutes; Add the rhodium chloride that concentration is 1mg/ml and the aqueous solution 1ml of palladium chloride respectively; Continue after ultrasonic 10 minutes to add the 12mg sodium borohydride reduction, suction filtration wash repeatedly, obtains the Rh-Pd catalyst that the mesoporous carbon of nitrogen doping supports after the drying.
Embodiment 7
The Rh-Au catalyst that the mesoporous carbon that present embodiment provides a kind of nitrogen to mix supports; It prepares through following steps: the meso-porous carbon material of getting the nitrogen doping of 0.1g embodiment 1 preparation joins in the 50ml deionized water; Ultrasonic 10 minutes, add the rhodium chloride that concentration is 1mg/ml and the aqueous solution 1ml of gold chloride respectively, continue to add after ultrasonic 10 minutes the 9mg sodium borohydride reduction; Suction filtration washing repeatedly obtains the Rh-Au catalyst that mesoporous carbon that nitrogen mixes supports after the drying.
Embodiment 8
Present embodiment provides the catalyst benzyl alcohol oxidation prepared in reaction method of benzaldehyde of a kind of embodiment of use 1; Practical implementation is following: with the 40g phenmethylol; The catalyst of 20mg embodiment 1 joins in the 100mL there-necked flask; In 100 ℃ of oil bath heating, mechanical agitation, logical oxygen (or air) reaction 12 hours.Adopt the method for filtering that catalyst is separated with reactant liquor, reactant liquor is used gas chromatographic detection, mark in doing with toluene, and detecting the conversion ratio that obtains phenmethylol is 100%, the selectivity of benzaldehyde is greater than 95%.Under identical reaction condition, with the metal A u-Pd catalyst of common activated carbon loaded, the conversion ratio of phenmethylol is 70%, and the selectivity of benzaldehyde is merely 45%.
Embodiment 9
Present embodiment provides the catalyst cyclohexanol oxidation reaction of a kind of embodiment of use 2 to prepare the method for cyclohexanone; Specific as follows: with the 40g cyclohexanol; The catalyst of 15mg embodiment 2 joins in the 100mL there-necked flask; In 80 ℃ of oil bath heating, mechanical agitation, logical oxygen (or air) reaction 12 hours.Adopt the method for filtering that catalyst is separated with reactant liquor, reactant liquor is used gas chromatographic detection, mark in doing with toluene, and detecting the conversion ratio that obtains cyclohexanol is 100%, the selectivity of cyclohexanone is greater than 98%.
Embodiment 10
Present embodiment provides the catalyst benzyl carbinol oxidation reaction of a kind of embodiment of use 3 to prepare the method for phenylacetaldehyde; Specific as follows: with the 40g benzyl carbinol; The catalyst of 15mg embodiment 3 joins in the 100mL there-necked flask; In 80 ℃ of oil bath heating, mechanical agitation, logical oxygen (or air) reaction 12 hours.Adopt the method for filtering that catalyst is separated with reactant liquor, reactant liquor is used gas chromatographic detection, mark in doing with toluene, and detecting the conversion ratio that obtains benzyl carbinol is 100%, the selectivity of phenylacetaldehyde is greater than 97%.
Embodiment 11～26
Embodiment 11～26 is for using the embodiment of catalyst benzyl alcohol oxidation prepared in reaction benzaldehyde of the present invention, and the operating procedure of embodiment 11～26 is with embodiment 8.Reaction condition and corresponding reaction conversion ratio and the benzaldehyde selectivity of each embodiment have been provided in the table 1.
The reaction condition of table 1 embodiment 11～26 and result
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to let the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. bimetallic catalyst that novel mesoporous carbon supports, it is made up of metallic 0.01wt%～90wt% and mesoporous carbon carrier 10wt%～99.99wt%, it is characterized in that:
Said metallic is any two kinds that are selected among Pd, Au, Ag, Pt, Ru, Rh, Ni, Cu, Fe, Co, Cr, W, Mo, Ti and the Ta, and the weight ratio of two kinds of metals is 1: 0.01～100, and the average grain diameter of said metallic is 1～100nm;
Said mesoporous carbon carrier is processed by the meso-porous carbon material that hetero atom mixes; The meso-porous carbon material that said hetero atom mixes is to be monomer to contain heteroatomic ionic liquid; At room temperature mix with template, calcined 1～6 hour down at 400 ℃～1000 ℃ then, be cooled to room temperature; Remove template at last and make, heteroatomic content is 0.01wt%～80wt% in the said meso-porous carbon material.
2. the bimetallic catalyst that novel mesoporous carbon according to claim 1 supports is characterized in that: said bimetallic catalyst is made up of metallic 0.1wt%～50wt% and said mesoporous carbon carrier 50wt%～99.9wt%.
3. the bimetallic catalyst that novel mesoporous carbon according to claim 1 supports is characterized in that: heteroatomic content is 0.1wt%～30wt% in the meso-porous carbon material that said hetero atom mixes.
4. the bimetallic catalyst that novel mesoporous carbon according to claim 1 and 2 supports is characterized in that: described ionic liquid is one or more the combination that is selected from imidazole type ion liquid, quaternary ammonium type ionic liquid and the pyridine type ionic liquid.
5. the bimetallic catalyst that novel mesoporous carbon according to claim 4 supports is characterized in that: said ionic liquid is that the cation and the formula (b) of formula (a) expression represented anionic combination in any:
(b)N(CN)
2 -，BF
4 -，PF
6 -，Cl
-，Br
-，F
-，PO
4 3-，SO
4 2-，NO
3 -，CF
3SO
3 -，CF
3COO
-，EtOSO
3 -，MeOSO
3 -.
In the said formula (a), n is the integer between 1～20.
6. the bimetallic catalyst that novel mesoporous carbon according to claim 1 and 2 supports; It is characterized in that: described template is molecular sieve SBA-15, molecular sieve MCM-41 or Ludox LudoxHS, and at last through removing with ammonium acid fluoride or naoh treatment.
7. the bimetallic catalyst that supports of the described novel mesoporous carbon of claim 1 is used for the purposes that the catalytic alcohol oxidation reaction prepares aldehydes or ketones.
8. a phenmethylol compounds catalytic oxidation prepares the method for benzaldehyde compounds; Said benzaldehyde compounds comprises benzaldehyde and by one or more alkyl that are selected from; Alkoxyl; The substituted benzaldehyde of the group of cyanic acid and nitro, said method make said phenmethylol compounds in the presence of catalyst, generate described benzaldehyde compounds with the air or oxygen reaction; It is characterized in that: said catalyst is the bimetallic catalyst that the described novel mesoporous carbon of each claim supports in the claim 1 to 6, and said catalyst consumption is 0.01%～20% of a said phenmethylol compounds weight.
9. method according to claim 8 is characterized in that: in the said bimetallic catalyst, bimetallic is Au-Pd, Au-Pt, Ag-Pt or Ru-Pd.
10. method according to claim 8 is characterized in that: solvent is not adopted in said reaction; Perhaps, said reaction is adopted and is selected from water, carrene, chloroform, toluene, benzene, ethyl acetate, n-hexane, dimethyl sulfoxide (DMSO), dimethyl formamide and the pyridine any as solvent; The pressure of said oxygen or air is 0.1MPa～10Mpa, and the temperature of said reaction is 0 ℃～250 ℃.
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