CN107913707A - Double bond isomerization reaction sub-nanometer palladium alumina preparation method - Google Patents
Double bond isomerization reaction sub-nanometer palladium alumina preparation method Download PDFInfo
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- CN107913707A CN107913707A CN201711311471.4A CN201711311471A CN107913707A CN 107913707 A CN107913707 A CN 107913707A CN 201711311471 A CN201711311471 A CN 201711311471A CN 107913707 A CN107913707 A CN 107913707A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
Abstract
A kind of double bond isomerization reaction sub-nanometer palladium alumina preparation method, this method comprise the following steps：First, it is raw material to take chlorine Asia palladium acid, and palladium nano-solution is synthesized using solution methods；2nd, it is 1 3h of Amine Solutions hybrid reaction of 0.01 10mol/L by the palladium nano-solution in above-mentioned steps one and molar concentration, the wherein molar ratio of palladium and organic amine is 0.05 10；3rd, after treating above-mentioned steps two, solution is centrifuged, obtains sub-nanometer palladium cluster molecule solution；4th, the aluminium oxide powder of certain mass is weighed, the sub-nanometer palladium cluster molecule solution that the load for being 0.5% by mass fraction is measured in above-mentioned steps three carries out 2 12h of excessive dipping, filtering, and sub-nanometer Pd/Al can be made in washing drying2O3Catalyst；Have the characteristics that the advantages that catalytic activity is high, target product selectivity is good, can repeatedly use, catalytic activity are high and recycled stability is good.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to what a kind of double bond isomerization reaction sub-nanometer was disperseed
Pd/Al2O3Preparation method.
Background technology
Many alpha, beta-unsaturated carbonyl derivatives are useful product in itself or prepare having for other important raw and processed materials
With intermediate, their many compounds are especially widely used in perfume industry, and particularly 2,3- dimethyl but-2-enes
Aldehyde, 2- methylpentadienes aldehyde or 2-Et-6,6- diformazan hexamethylene -2- ketenes etc. largely use.The above-mentioned chemical combination reported in the literature
Thing prepares extremely complex and not necessarily has very much a productivity (being difficult to industrialize).For example, reported in US2008/0009486
The preparations of 2,3- dimethyl butyrate -2- olefine aldehydrs, its by by 2,3- dimethyl butyrate -2- enoate reductases for 2,3- dimethyl butyrates -
2- enols and the latter is oxidized to by the aldehyde by DMSO, such a approach is very long, time-consuming and productivity is low.It is presently described with
3- methyl -2- methylene butyraldehyde prepares model reaction of the preparation of 2,3- dimethyl butyrate -2- olefine aldehydrs as double bond isomerization reaction
To represent.As raw material can be by α from, the aldol reaction of-unbranched aldehyde/ketone is readily available for such a isomerization reaction.
It presently, there are difficult point to be, a kind of effective catalyst system needed in isomerization reaction, the catalyst system and catalyzing is capable of providing
The Pd//Al of high productivity and selectivity, at present routine2O3There are conversion ratio (＜ 50%) with select it is not high (<80%).
In load type metal catalyst, the metallic particles of catalyst surface is typically uneven distribution, includes a system
Row from secondary nano-scale to nanoscale even the other metal cluster of Subnano-class.This non-uniform phenomenon not only reduces metallic atom
Catalytic efficiency, and cause the generation of side reaction, while difficulty is brought to defining and studying catalytic active site.Smallest dimension
Load type metal catalyst is single atomic dispersion catalyst.The load of this catalyst surface is your mutually independent gold one by one
Belong to monatomic.On single atomic dispersion catalyst scale is several or more than ten of atom formed cluster sub-nanometer catalyst or
Claim atomic scale dispersed catalyst, the load of this catalyst surface is the small cluster (particle diameter of mutually independent noble metal one by one
Less than 2nm), this kind of cluster cannot form stable vertex, rib knead dough structure, thus in catalytic activity with large-sized metal
There is obvious difference to be.In recent years, the noble metal catalyst (abbreviation sub-nanometer catalyst) that support type sub-nanometer is disperseed due to
The advantages of active high, activated centre is single, high selectivity, become the hot topic in terms of catalyst research.With traditional catalysis
Agent is compared, and the bullion content that sub-nanometer catalyst preparation process uses is very low (＜ 1.0%).Sub-nanometer catalyst can be applied
Precondition be that suitable method can be used to prepare metal cluster on suitable carrier to be less than 2 nanometers of catalyst, but
To prepare this catalyst to be not easy to because the metal cluster that sub-nanometer is disperseed always have in carrier surface it is close to each other,
The trend mutually reunited.The present invention provides a kind of simple and practicable efficient sub-nanometer catalyst preparation process, it is intended to solves double bond
The problem of selectivity and conversion ratio be not high in isomerization.
The content of the invention
The present invention provides a kind of double bond isomerization reaction sub-nanometer palladium alumina preparation method, its technology mainly solved
Problem is：Pd/Al at present2O3For catalyst during double bond isomerization reaction, side reaction is higher, and reaction speed is relatively slow, conversion
Rate is low and is difficult to apply mechanically.
In order to solve the above technical problems, the present invention provides a kind of double bond isomerization reaction sub-nanometer palladium aluminium oxide preparation side
Method, this method comprise the following steps：
First, it is raw material to take chlorine Asia palladium acid, and palladium nano-solution is synthesized using solution methods；
2nd, the palladium nano-solution in above-mentioned steps one is mixed with the Amine Solutions that molar concentration is 0.01-10mol/L
1-3h is reacted, the wherein molar ratio of palladium and organic amine is 0.05-10；
3rd, after treating above-mentioned steps two, solution is centrifuged, obtains sub-nanometer palladium cluster molecule solution；
4th, the aluminium oxide powder of certain mass is weighed, the load for being 0.5% by mass fraction is measured in above-mentioned steps three
Sub-nanometer palladium cluster molecule solution carries out excessive dipping 2-12h, filtering, and sub-nanometer Pd/Al can be made in washing drying2O3Catalysis
Agent；
Organic amine molecule in the step poly- two is histidine, one kind in mercaptoethylmaine, hexa, preferably mercapto
Base ethamine.
Compared with prior art, the present invention has the following advantages：
1st, sub-nanometer Pd/Al obtained by hybrid mode of the present invention2O3Catalyst solves double-bond isomerization and crosses conversion ratio in kind
The shortcomings that low, selective not high.
2nd, the sub-nanometer Pd/Al that the present invention is prepared2O3Catalyst to face in hydrogen reaction process, has catalytic activity
High, the characteristics of target product selectivity is good, the advantages that can repeatedly using, catalytic activity are high and recycled stability is good；
3rd, sub-nanometer Pd/Al obtained by sub-nanometer palladium Supported alumina of the present invention2O3Catalyst can have in double-bond isomerism reaction
Preferable activity, the sub-nanometer palladium load reduction active decrease speed of catalyst, shorten the reaction time, further increases
Economic benefit.
Embodiment
Below in conjunction with preferred embodiment a kind of double bond isomerization reaction sub-nanometer Pd/Al is provided to the present invention2O3Preparation side
Method is further described.
Embodiment 1, a kind of double bond isomerization reaction sub-nanometer Pd/Al2O3Preparation method, its step are specific as follows.
Step 1：The chlorine Asia palladium aqueous acid of the 0.01mol/L of certain volume is added in flask, in N2Under protection, heating
To 100 DEG C, the sodium citrate aqueous solution of 0.1mol/L is rapidly joined by the amount that palladium and sodium citrate molar ratio are 1, continues to heat
1h is stirred, is cooled to room temperature, obtains the palladium Nano sol solution of particle shape；
Step 2：By the palladium Nano sol in above-mentioned steps 1 and histidine in molar ratio 1, a certain amount of 0.01mol/ is added
L-His mixes, under ultrasound on normal-temperature reaction 1h；
Step 3：After reaction, suspended matter and sediment are centrifuged off, solution is collected, up to sub-nanometer palladium cluster molecule；
Step 4：The aluminium oxide powder of certain mass is weighed, is measured by the load that mass fraction is 0.5% in above-mentioned steps 3
Sub-nanometer palladium cluster molecule solution carry out excessive dipping 8h, filtering, sub-nanometer Pd/Al can be made in washing drying2O3Catalysis
Agent.
Embodiment 2, a kind of double bond isomerization reaction sub-nanometer Pd/Al2O3Preparation method, its step are specific as follows.
Step 1：The chlorine Asia palladium aqueous acid of the 0.01mol/L of certain volume is added in flask, in N2Under protection, heating
To 100 DEG C, the sodium citrate aqueous solution of 0.1mol/L is rapidly joined by the amount that palladium and sodium citrate molar ratio are 0.5, continue plus
Thermal agitation 1h, is cooled to room temperature, and obtains the palladium Nano sol solution of particle shape；
Step 2：By the palladium Nano sol in above-mentioned steps 1 and histidine in molar ratio 1, a certain amount of 0.01mol/ is added
L-His mixes, under ultrasound on normal-temperature reaction 1h；
Step 3：After reaction, suspended matter and sediment are centrifuged off, solution is collected, up to sub-nanometer palladium cluster molecule；
Step 4：The aluminium oxide powder of certain mass is weighed, is measured by the load that mass fraction is 0.5% in above-mentioned steps 3
Sub-nanometer palladium cluster molecule solution carry out excessive dipping 8h, filtering, sub-nanometer Pd/Al can be made in washing drying2O3Catalysis
Agent.
Embodiment 3, a kind of double bond isomerization reaction sub-nanometer Pd/Al2O3Preparation method, its step are specific as follows.
Step 1：The chlorine Asia palladium aqueous acid of the 0.01mol/L of certain volume is added in flask, in N2Under protection, heating
To 100 DEG C, the sodium citrate aqueous solution of 0.1mol/L is rapidly joined by the amount that palladium and sodium citrate molar ratio are 0.5, continue plus
Thermal agitation 1h, is cooled to room temperature, and obtains the palladium Nano sol solution of particle shape；
Step 2：By the palladium Nano sol in above-mentioned steps 1 and mercaptoethylmaine in molar ratio 1, add a certain amount of
0.01mol/L histidines mix, under ultrasound on normal-temperature reaction 1h；
Step 3：After reaction, suspended matter and sediment are centrifuged off, solution is collected, up to sub-nanometer palladium cluster molecule；
Step 4：The aluminium oxide powder of certain mass is weighed, is measured by the load that mass fraction is 0.5% in above-mentioned steps 3
Sub-nanometer palladium cluster molecule solution carry out excessive dipping 8h, filtering, sub-nanometer Pd/Al can be made in washing drying2O3Catalysis
Agent.
Embodiment 4, a kind of double bond isomerization reaction sub-nanometer Pd/Al2O3Preparation method, its step are specific as follows.
Step 1：The chlorine Asia palladium aqueous acid of the 0.01mol/L of certain volume is added in flask, by palladium and four n-octyl bromides
The molar ratio for changing amine is that 0.5 amount rapidly joins the four octyl group bromination carbaryl solution of 0.1mol/L, stirs 30min, Ran Houjia
Enter the toluene solution of the lauryl mercaptan of a timing, in N2Under protective condition, a certain amount of sodium borohydride is added, finally continues to stir
3h, after reaction layering, goes water removal phase, vacuum distillation concentration organic phase, adds ethanol and centrifuged, obtain the palladium nanometer of particle shape
Sol solution；
Step 2：By the palladium Nano sol in above-mentioned steps 1 and mercaptoethylmaine in molar ratio 1, add a certain amount of
0.01mol/L histidines mix, under ultrasound on normal-temperature reaction 1h；
Step 3：After reaction, suspended matter and sediment are centrifuged off, solution is collected, up to sub-nanometer palladium cluster molecule；
Step 4：The aluminium oxide powder of certain mass is weighed, is measured by the load that mass fraction is 0.5% in above-mentioned steps 3
Sub-nanometer palladium cluster molecule solution carry out excessive dipping 8h, filtering, sub-nanometer Pd/Al can be made in washing drying2O3Catalysis
Agent.
Embodiment 5, a kind of double bond isomerization reaction sub-nanometer Pd/Al2O3Preparation method, its step are specific as follows.
Step 1：The chlorine Asia palladium aqueous acid of the 0.01mol/L of certain volume is added in flask, by palladium and sodium citrate
The amount that molar ratio is 1 rapidly joins the sodium citrate aqueous solution of 0.1mol/L, then quick a certain amount of toward adding in above-mentioned solution
Sodium borohydride solution, it is cooled to room temperature, obtains the palladium Nano sol solution of particle shape；；
Step 2：By the palladium Nano sol in above-mentioned steps 1 and hexa in molar ratio 1, add a certain amount of
0.01mol/L hexas mix, under ultrasound on normal-temperature reaction 1h；
Step 3：After reaction, suspended matter and sediment are centrifuged off, solution is collected, up to sub-nanometer palladium cluster molecule；
Step 4：The aluminium oxide powder of certain mass is weighed, is measured by the load that mass fraction is 0.5% in above-mentioned steps 3
Sub-nanometer palladium cluster molecule solution carry out excessive dipping 8h, filtering, sub-nanometer Pd/Al can be made in washing drying2O3Catalysis
Agent.
By conventional method prepare palladium/aluminium oxide catalyst with implement 1-5 prepare sub-nanometer palladium/aluminium oxide catalyst into
Row double bond isomerization reaction, is isomerized to represent, reaction condition is with 3- methyl -2- methylene butyraldehyde：By a certain amount of catalyst
It is encased in tubular reactor, leads to N2Heating, at the same add a certain amount of 3- methyl -2- methylene butyraldehyde and hydrogen source (formic acid or
Limonene), in N2Under the conditions of collect product and pass through GC internal standard methods measure yield.The result is shown in table 1 below.
Result of 1 different catalysts of table in 3- methyl -2- methylene butyraldehyde isomerization reactions
As it can be seen from table 1 the activity of sub-nanometer palladium/aluminium oxide catalyst has been carried than conventional palladium/aluminium oxide active
Height, is obviously improved in terms of isomerisation selectivity, further to implement 4 in catalyst use, discovery can repeatedly into
Row is applied mechanically.
The above, is only presently preferred embodiments of the present invention, and any restrictions are not done to the present invention, every according to invention skill
Any simple modification, change and the equivalent structure change that art substantially makees above example, still fall within the technology of the present invention
In the protection domain of scheme.
Claims (6)
1. a kind of double bond isomerization reaction sub-nanometer palladium alumina preparation method, it is characterised in that this method comprises the concrete steps that：
A) using chlorine Asia palladium acid as raw material, palladium nano-cluster solution is synthesized using solution methods；
B) it is the Amine Solutions hybrid reaction 1-3h of 0.01-10mol/L by palladium nano-solution and molar concentration, wherein palladium is with having
The molar ratio of machine amine is 0.05-10；
C) after above-mentioned steps b) ties speed, solution is centrifuged, obtains sub-nanometer palladium cluster molecule solution；
D) the aluminium oxide powder of certain mass is weighed, the Ya Na obtained by the load measurement above-mentioned steps c) that mass fraction is 1%
Rice palladium cluster molecule solution carries out excessive dipping 2-12h, and filtering, washing drying can sub-nanometer Pd/Al2O3Catalyst.
2. double bond isomerization reaction according to claim 1 sub-nanometer palladium alumina preparation method, it is characterised in that：On
State in step a), be to add sodium citrate aqueous solution, stirring condition in the chlorine Asia palladium acid solution under 95-100 DEG C of temperature conditionss
Lower reaction 1-3h, chlorine Asia palladium acid and the molar ratio of sodium citrate are 0.2-1.
A kind of 3. double bond isomerization reaction sub-nanometer palladium alumina preparation method described in claim 1, it is characterised in that on
State in step a), chlorine Asia palladium acid solution is mixed with the toluene solution containing lauryl mercaptan, it is under agitation that the chlorine is sub-
Palladium acid is mutually transferred to organic phase from water, then adds sodium borohydride reduction and obtains the toluene solution of palladium nanometer, wherein chlorine Asia palladium acid
Molar ratio with lauryl mercaptan is 0.2-0.5, and chlorine Asia palladium acid and the molar ratio of sodium borohydride are 0.1-0.5.
4. the double bond isomerization reaction sub-nanometer palladium alumina preparation method according to Claims 2 or 3, its feature exist
In：In above-mentioned steps b), the hybrid reaction of the palladium nano-solution and Amine Solutions is that agitated under sonication carries out.
5. double bond isomerization reaction according to claim 4 sub-nanometer palladium alumina preparation method, it is characterised in that：On
State in step b), organic amine molecule is histidine, one kind in mercaptoethylmaine, hexa.
6. double bond isomerization reaction according to claim 5 sub-nanometer palladium alumina preparation method, it is characterised in that：On
State in step d), the specific surface area of the aluminium oxide powder is in 150-300m2/g。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112893859A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | AuPd alloy nano-cluster and synthesis method thereof |
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