CN103191731A - Au-Pd bimetallic catalyst for preparing methyl formate by selective oxidation of methanol as well as preparation method and application thereof - Google Patents
Au-Pd bimetallic catalyst for preparing methyl formate by selective oxidation of methanol as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an Au-Pd bimetallic catalyst for preparing methyl formate by selective oxidation of methanol. The Au-Pd bimetallic catalyst comprises a carrier and active components, namely Au oxide and Pd oxide, wherein the loading amount of Au is 0.25-5.0wt%, the loading amount of Pd is 0.25-5.0wt%, and the balance is the graphene carrier. The Au-Pd bimetallic catalyst disclosed by the invention has the advantages of low reaction temperature, high catalytic activity and good stability.
Description
Technical field
The invention belongs to a kind of Catalysts and its preparation method and application, be specifically related to a kind of Au-Pd bimetallic catalyst for selective oxidation of methanol methyl formate processed and its preparation method and application.
Technical background
Methyl formate (Methyl Formate is called for short MF), molecular formula is C
2H
4O
2, structural formula is HCOOCH
3, molecular weight 60.5 is a kind of colourless liquid with aromatic odor.Its fusing point-99.38 ℃, 32 ℃ of boiling points, relative density 0.98, combustion heat 978.7kJ/mol, 214 ℃ of critical-temperatures, flash-point-32 ℃, 449 ℃ of ignition temperatures, be dissolved in water, ethanol, methyl alcohol, ether, be described as omnipotent chemical intermediate, can synthesize many chemical products.Can prepare formic acid as the MF hydrolysis; It is synthetic that MF can be used for the amide-type product; It is synthetic that MF also can be used for Ester; MF can also be for the synthesis of materials such as ethylene glycol, ethanedioic acid acid anhydride, fluorescent whitening agent, hydrogen cyanide.
Traditional synthetic methyl formate method mainly contains following three kinds:
Methanol carbonylation, methyl alcohol obtain MF with CO at the autoclave internal reaction under the sodium methoxide effect:
CH
3OH+CO → HCOOCH
3(formula 1-1)
These catalytic reaction characteristics are 70～80 ℃ of reaction temperatures, and reaction pressure is 35～4.0MPa, and methanol conversion～30%, MF selectively are that Lee 100%[is along sweet smell, gas chemical industry; 05 phase in 2000].But this technology is to H among methanol feedstock and the CO
2O, CO
2And O
2Impurity requires very strict, because hydrolysis can take place its sodium methoxide catalyst that adopts, is very easy to inactivation; In addition, hydrolysis produces, and to receive the solubility of formates in reaction medium big inadequately, can produce deposition in consersion unit and pipeline, reactor can be contaminated and pipeline may be blocked; And sodium methoxide has strong corrosion, has the serious environmental pollution problem, and is unfavorable to person health.
Methanol dehydrogenation method, methanol vapor phase dehydriding are that methyl alcohol dehydrogenation on copper-based catalysts generates MF:
2CH
3OH → HCOOCH
3+ 2H
2(formula 1-2)
It is single that this reaction has a raw material, the advantage that the no three wastes are produced, but this reacts and is the endothermic reaction, needs outside heat supply, 260～300 ℃ of reaction temperatures, and methanol conversion 33～40%, MF selective 85～93%.This reaction is subjected to the thermodynamics of reactions equilibrium-limited, and the reaction temperature height consumes big.And copper-based catalysts all in this reaction can be assembled, and produce phase transformation and inactivation [Wang Lefu, Chemical Reaction Engineering and technology, 1994,10 volumes 403～407].
In addition, also have directly methyl formate method processed of synthesis gas, though it has characteristics such as Atom economy, because its production capacity is low, severe reaction conditions etc., the industrialization of still being unrealized.
Consider from overall power consumption and process efficiency, more than several technologies certain limitation is all arranged, therefore researching and developing a kind of simple, efficient production methyl formate catalyst system and catalyzing becomes the future studies direction.Wherein selective oxidation of methanol methyl formate processed is subjected to extensive concern:
2CH
3OH+O
2→ CH
3OOCH+2H
2O (formula 1-3)
This is reflected on the thermodynamics is feasible, and conversion of methanol and the thermodynamic limitation that is not subjected to such as selective.Its key problem is to seek appropriate catalyst reaction can be carried out under the condition that is oxidant with oxygen or air, and catalyst should have high methanol conversion and MF selective [ZL 200410011181.4] simultaneously.
The catalyst that is used for selective oxidation of methanol methyl formate processed at present mainly is divided three classes: oxide, heteropoly acid and noble metal catalyst.
In recent years, the research at metal oxide catalyst mainly contains: Mamoru etc. nineteen eighty-two first with SnO
2～MoO
3Composite metal oxide is used for selective oxidation of methanol methyl formate research processed, experiment is found can to realize 72% methanol conversion and 90% selective [the Journal of Catalysis of MF at the catalyst of Sn/Mo ratio during at 7:3 down at 160 ℃, 1982,77:279～288].V
2O
5/ TiO
2Catalyst also is the effective catalyst of selective oxidation of methanol methyl formate processed, and such catalyst can be realized selective [the Industrial ﹠amp of the MF of 90% methanol conversion and 80% in the time of 170 ℃; Engineering Chemistry Research, 1987,26:1269-1275].Wang etc. have prepared Fe
2O
3/ SiO
2Catalyst is used for selective oxidation of methanol MF processed, can realize 25～57% methanol conversion and the maximum selectivity of MF 60% in 250～275 ℃ of scopes, this catalyst reaction temperatures is higher as can be seen, simultaneously selective lower [Journal of Catalysis, 2001,202:211-219].
Heteropolyacid catalyst is a kind of difunctional green catalyst that has acid and oxidisability simultaneously, and therefore its acidity and oxidisability can be more satisfactory selective oxidation of methanol catalyst by changing the adjusting that molecular composition realize acid strength and oxidisability.The superfine H that will have the Keggin structure of bang
5PV
2Mo
10O
40Heteropolyacid catalyst is carried on ZrO
2Go up to be used for the selective oxidation of methanol reaction, experiment finds that it in the time of 220 ℃, can realize 30～40% methanol conversion, selectively can maximum reaches 52.4%[Journal of Catalysis, 2004,223:161-169].
The research of selective oxidation of methanol catalyst on noble metal mainly concentrates on ruthenium, palladium, silver, gold and auri bimetallic catalyst.The superfine report ruthenium catalyst of bang selectively can be realized the conversion ratio of methyl alcohol 20% and selective [J.Phys.Chem.B, 2005, the 109:2155-2163] of MF 60～80% at 120 ℃; Discovery Pd such as Lichtenberger have 90% MF high selectivity [Phys.Chem.Chem.Phys., 2007,9:4902-4906] simultaneously at the 40 ℃ of catalytic oxidations that just can realize methyl alcohol.Yang etc. are used for selective oxidation of methanol discovery catalyst at the conversion ratio of 300 ℃ of realizations 23% and 90% selective [Catal.Lett. with the Ag catalyst of sodium borohydride reduction, 2005,100:205-211], but the problem of this type of catalyst existence is that reaction temperature is higher and conversion ratio is on the low side.2010, people such as Wittstock utilize chemical corrosion method to prepare the Au-Ag bimetallic catalyst, this catalyst is selective at 20 ℃ of MF that just can realize 10% methanol conversion and 100%, when reaction temperature is increased to 80 ℃, methanol conversion is increased to 60%, selectively only reduce to 97%[Science2010,327:319-322].But the catalyst of this method preparation be this build catalyst, has only lip-deep Au, Ag atom to be utilized, and body mutually interior metallic atom can't be utilized, thereby cause the low problem of noble metal catalyst atom utilization.If this class bimetallic catalyst can be loaded on the carrier, its catalytic activity and gold atom utilization rate also may significantly improve.
In fact, many Au-M(Pd, Pt, Cu) etc. bimetallic catalyst successfully loaded on the conventional carriers such as metal oxide, molecular sieve and in multiple reaction, shown excellent catalytic activity.And the Au-Pd catalyst is put up the best performance in numerous Au-M bimetallic catalysts, be widely used in CO oxidation [J.Am.Chem.Soc., 2010,132:10398-10406], methane oxidation [Angew.Chem.Int.Ed., 2012,51:1-6] and oxidation of ethanol reactions such as [Science, 2006,311:362-365].There are close ties in people by the character of discovering Au-Pd catalyst activity and carrier, and this impels people to seek the more excellent new support of performance, improve activity of such catalysts, and enlarge the scope of application.
Graphene is with SP by carbon atom
2The two-dimensional nano material with hexagon honeycomb lattice structure that hybridized orbit is formed, advantage such as have that specific area is big, intensity is high and conductive capability is strong is a kind of potential excellent carriers, has broad application prospects at catalytic field.Yet at present that Graphene is also less relatively as the research report of catalyst carrier, the carrier loaded Au-Pd bimetallic catalyst of Graphene is used for the selective oxidation of methanol reaction does not have pertinent literature and patent report especially.
Summary of the invention
It is low to the purpose of this invention is to provide a kind of reaction temperature, catalytic activity height, Au-Pd bimetallic catalyst that is used for selective oxidation of methanol methyl formate processed of good stability and its preparation method and application.
The present invention is used for graphene-supported Au-Pd bimetallic catalyst selective oxidation of methanol methyl formate reaction processed first, it is good that experiment shows that this catalyst has catalytic activity, characteristics such as the selective high and life-span is long, can be under 50～120 ℃ temperate condition in 30～90% methanol conversion and 100% the methyl formate of realization methyl alcohol methyl formate processed selective.
Catalyst of the present invention is made up of the oxide of carrier and active component A u-Pd, and the load capacity of Au is 0.25～5.0wt% in the active component, and the load capacity of Pd is 0.25～5.0wt%, and surplus is the Graphene carrier.
Preparation method of the present invention evenly spreads to Au-Pd on the Graphene carrier with deposition-precipitation method.
Concrete preparation process is as follows:
(1) the Graphene carrier is added to the water, stirs, to wherein adding precipitating reagent, make the pH value of solution control in 12～14 scopes, be heated to 30～70 ℃, stir 0.5～2h, obtain the suspension of graphitiferous alkene;
(2) be that 0.5～1.0wt ‰ prepares the Au aqueous solution and the Pd aqueous solution respectively by Au, Pd content in Au solution and the Pd solution, the Au aqueous solution and the Pd aqueous solution are pressed the mixing of catalyst composition, stir, obtain the Au-Pd mixed solution;
(3) press catalyst and form, the Au-Pd mixed solution is dropwise joined in the suspension of graphitiferous alkene under constantly stirring, continue to stir 1～2h;
(4) with the precipitate with deionized water pumping rate of step (3), washing to there not being Cl
-, 100～120 ℃ of drying 12～20h, 100～300 ℃ of roasting 4～6h make catalyst in the nitrogen atmosphere.
Aforesaid Graphene carrier specific area should be greater than 100m
2/ g, the C/O mol ratio is between 6～12, and electrical conductivity is between 10～500S/cm.
Aforesaid precipitating reagent is one or more of ammoniacal liquor, NaOH, potassium hydroxide, sodium carbonate, potash, ammonium carbonate;
Aforesaid Au solution is chlorauric acid solution; Pd solution is one or more of palladium nitrate, palladium bichloride, palladium solution;
It is as follows for selective oxidation of methanol Application of Methyl Formate method processed that the present invention makes catalyst:
After catalyst activated 0.5～2h through 150～200 ℃ of air atmospheres, in atmospheric fixed bed, reaction temperature was 50～120 ℃, CH
3OH and O
2Molar ratio is 1:1～10, and reaction velocity is 3000～20000mlg
-1H
-1React under the condition, obtain methyl formate.
Compared with the prior art the present invention has following substantive distinguishing features:
1) with graphene-supported Au-Pd bimetallic catalyst for being applied to methanol oxidation methyl formate processed, still belong to the first time.
2) this catalyst has very high activity and selective, can realize that the methyl formate of methyl alcohol 30-90% conversion ratio under 50～120 ℃ of conditions and 100% is selective, and correlated results is better than the other types catalyst.
3) this catalyst has overcome the weakness of the easy inactivation of Au catalyst, has stability preferably.
Description of drawings
Fig. 1 is the projection Electronic Speculum picture of graphene-supported Au-Pd bimetallic catalyst of the present invention.
The specific embodiment:
The present invention is further elaborated below in conjunction with some specific embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, each components contents is weight percentage in the embodiments of the invention.
Embodiment 1
(1) with Graphene carrier (the specific area 120m of 1g
2/ g, C/O mol ratio 6, conductance 15S/cm) join in the 20ml water, be heated to 60oC and stir.To wherein adding 2g NaOH, pH must control 14, continue to stir 0.5h.
(2) will contain the 5ml HAuCl of Au0.0025g
4Solution and the 20ml PdCl that contains Pd0.01g
2Solution mixes, and stirs.
(3) solution for preparing in (2) is dropwise joined in (1) under constantly stirring, dropwise the back and continue to stir 2h.
(4) with the precipitate with deionized water pumping rate of (3), washing to there not being Cl
-, 110 ℃ of dry 15h, 200 ℃ of roasting 5h make catalyst A u in the nitrogen atmosphere
0.25Pd
1.0/ Graphene.
This catalyst passes through 150 ℃ of online activation 1h of air atmosphere in fixed bed after, CH under the condition of normal pressure
3OH/O
2Mol ratio 1:5, reaction velocity 3000mlg
-1H
-1, 50 ℃ of reactions.Conversion of methanol 30%, selective 100% of methyl formate.
Embodiment 2
(1) with Graphene carrier (the specific area 100m of 1g
2/ g, C/O mol ratio 8, conductance 30S/cm) join in the 20ml water, be heated to 70 ℃ and stir.To wherein adding 1g KOH, pH must control 13, continue to stir 1h.
(2) will contain the 15ml HAuCl of Au0.01g
4Solution and the 20ml PdCl that contains Pd0.01g
2Solution mixes, and stirs.
(3) solution for preparing in (2) is dropwise joined in (1) under constantly stirring, dropwise the back and continue to stir 1h.
(4) with the precipitate with deionized water pumping rate of (3), washing to there not being Cl
-, 110 ℃ of dry 13h, 200 ℃ of roasting 4h make catalyst A u in the nitrogen atmosphere
1.0Pd
1.0/ Graphene.
This catalyst passes through 160 ℃ of online activation 1.5h of air atmosphere in fixed bed after, CH under the condition of normal pressure
3OH/O
2Mol ratio 1:3, reaction velocity 10000mlg
-1H
-1, 90 ℃ of reactions.Conversion of methanol 55%, selective 100% of methyl formate.
Embodiment 3
(1) with Graphene carrier (the specific area 150m of 1g
2/ g, C/O mol ratio 8, conductance 10S/cm) join in the 20ml water, be heated to 60 ℃ and stir.To wherein adding 2g KOH, pH must control 13, continue to stir 2h.
(2) will contain the 15ml HAuCl of Au0.01g
4Solution and the 40ml Pd (NO that contains Pd0.02g
3)
2Solution mixes, and stirs.
(3) solution for preparing in (2) is dropwise joined in (1) under constantly stirring, dropwising back pH value needs control 12, continues to stir 1h.
(4) with the precipitate with deionized water pumping rate of (3), washing to there not being Cl
-, 110 ℃ of dry 20h, 250 ℃ of roasting 4h in the nitrogen atmosphere.Make catalyst A u
1.0Pd
2.0/ Graphene.
This catalyst passes through 180 ℃ of online activation 1.0h of air atmosphere in fixed bed after, CH under the condition of normal pressure
3OH/O
2Mol ratio 1:5, reaction velocity 15000mlg
-1H
-1, 70 ℃ of reactions.Conversion of methanol 35%, selective 100% of methyl formate.
Embodiment 4
(1) with Graphene carrier (the specific area 300m of 1g
2/ g, C/O mol ratio 12, conductance 500S/cm) join in the 20ml water, be heated to 50 ℃ and stir.To wherein adding 3g Na
2CO
3, pH must control 14, continues to stir 1.5h.
(2) will contain the 40ml HAuCl of Au0.03g
4Solution and the 15ml PdCl that contains Pd0.01g
2Solution mixes, and stirs.
(3) solution for preparing in (2) is dropwise joined in (1) under constantly stirring, dropwise and continue to stir 1.5h.
(4) with the precipitate with deionized water pumping rate of (3), washing to there not being Cl
-, 100 ℃ of dry 12h, 300 ℃ of roasting 5h make catalyst A u in the nitrogen atmosphere
3.0Pd
1.0/ Graphene.
This catalyst passes through 200 ℃ of online activation 0.5h of air atmosphere in fixed bed after, CH under the condition of normal pressure
3OH/O
2Mol ratio 1:10, reaction velocity 20000mlg
-1H
-1, 100 ℃ of reactions.Conversion of methanol 90%, selective 100% of methyl formate.
Embodiment 5
(1) with Graphene carrier (the specific area 500m of 1g
2/ g, C/O mol ratio 10, conductance 100S/cm) join in the 20ml water, be heated to 30 ℃ and stir.To wherein adding 2g ammonium carbonate and 0.5g sodium carbonate, pH must control 12, continue to stir 0.5h.
(2) will contain the 20ml HAuCl of Au0.02g
4Solution and the 20ml Pd (AC) that contains Pd0.01g
2Solution mixes, and stirs.
(3) solution for preparing in (2) is dropwise joined in (1) under constantly stirring, dropwise the back and continue to stir 1.5h.
(4) with the precipitate with deionized water pumping rate of (3), washing to there not being Cl
-, 120 ℃ of dry 15h, 250 ℃ of roasting 6h make catalyst A u in the nitrogen atmosphere
2.0Pd
1.0/ Graphene.
This catalyst passes through 150 ℃ of online activation 1h of air atmosphere in fixed bed after, condition of normal pressure CH
3OH/O
2Mol ratio 1:8, reaction velocity 10000mlg
-1H
-1, 80 ℃ of reactions.Conversion of methanol 90%, selective 100% of methyl formate.
Embodiment 6
(1) with Graphene carrier (the specific area 200m of 1g
2/ g, C/O mol ratio 6, conductance 100S/cm) join in the 20ml water, be heated to 60 ℃ and stir.To wherein adding 4g K
2CO
3, pH must control 14, continues to stir 0.5h.
(2) will contain the 15ml HAuCl of Au0.01g
4Solution and the 50ml PdCl that contains Pd0.05g
2Solution mixes, and stirs.
(3) solution for preparing in (2) is dropwise joined in (1) under constantly stirring, dropwise the back and continue to stir 2h.
(4) with the precipitate with deionized water pumping rate of (3), washing to there not being Cl
-, 120 ℃ of dry 18h, 150 ℃ of roasting 5h make catalyst A u in the nitrogen atmosphere
1.0Pd
5.0/ Graphene.
This catalyst passes through 200 ℃ of online activation 1.5h of air atmosphere in fixed bed after, CH under the condition of normal pressure
3OH/O
2Mol ratio 1:2, reaction velocity 15000mlg
-1H
-1, 100 ℃ of reactions.Conversion of methanol 70%, selective 100% of methyl formate.
Claims (6)
1. Au-Pd bimetallic catalyst that is used for selective oxidation of methanol methyl formate processed, it is characterized in that catalyst is made up of the oxide of carrier, active component A u oxide and Pd, the load capacity of Au is 0.25～5.0wt%, and the load capacity of Pd is 0.25～5.0wt%, and surplus is the Graphene carrier.
2. the preparation method of a kind of Au-Pd bimetallic catalyst for selective oxidation of methanol methyl formate processed as claimed in claim 1 is characterized in that comprising the steps:
(1) the Graphene carrier is added to the water, stirs, to wherein adding precipitating reagent, make the pH value of solution control in 12～14 scopes, be heated to 30～70 ℃, stir 0.5～2h, obtain the suspension of graphitiferous alkene;
(2) be that 0.5～1.0wt ‰ prepares the Au aqueous solution and the Pd aqueous solution respectively by Au, Pd content in Au solution and the Pd solution, the Au aqueous solution and the Pd aqueous solution are pressed the mixing of catalyst composition, stir, obtain the Au-Pd mixed solution;
(3) press catalyst and form, the Au-Pd mixed solution is dropwise joined in the suspension of graphitiferous alkene under constantly stirring, continue to stir 1～2h;
(4) with the precipitate with deionized water pumping rate of step (3), washing to there not being Cl
-, 100～120 ℃ of drying 12～20h, 100～300 ℃ of roasting 4～6h make catalyst in the nitrogen atmosphere.
3. the preparation method of a kind of Au-Pd bimetallic catalyst for selective oxidation of methanol methyl formate processed as claimed in claim 2 is characterized in that described Graphene carrier specific area is greater than 100m
2/ g, the C/O mol ratio is between 6～12, and electrical conductivity is between 10～500S/cm.
4. the preparation method of a kind of Au-Pd bimetallic catalyst for selective oxidation of methanol methyl formate processed as claimed in claim 2 is characterized in that described precipitating reagent is one or more of ammoniacal liquor, NaOH, potassium hydroxide, sodium carbonate, potash, ammonium carbonate.
5. the preparation method of a kind of Au-Pd bimetallic catalyst for selective oxidation of methanol methyl formate processed as claimed in claim 2 is characterized in that described Au solution is chlorauric acid solution; Pd solution is one or more of palladium nitrate, palladium bichloride, palladium solution.
6. the application of a kind of Au-Pd bimetallic catalyst for selective oxidation of methanol methyl formate processed as claimed in claim 1 is characterized in that application process is as follows:
After catalyst activated 0.5～2h through 150～200 ℃ of air atmospheres, in atmospheric fixed bed, reaction temperature was 50～120 ℃, CH
3OH and O
2Molar ratio is 1:1～10, and reaction velocity is 3000～20000mlg
-1H
-1React under the condition, obtain methyl formate.
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