CN106423165B - A kind of preparation method of the palladium for being carried on aluminium surface, copper composite catalyst - Google Patents
A kind of preparation method of the palladium for being carried on aluminium surface, copper composite catalyst Download PDFInfo
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- CN106423165B CN106423165B CN201610902131.8A CN201610902131A CN106423165B CN 106423165 B CN106423165 B CN 106423165B CN 201610902131 A CN201610902131 A CN 201610902131A CN 106423165 B CN106423165 B CN 106423165B
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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Abstract
The preparation method of a kind of palladium being carried on aluminium surface, copper composite catalyst, is related to the preparing technical field of catalyst.It is 60~120 DEG C, by palladium bichloride, copper chloride, ammonium citrate and N that aluminium foil, which is soaked in temperature, it is reacted 2~5 hours in the mixed solution of the dimethylbenzene composition of N ' diisopropyl propane diamine, aluminium foil is then taken out, is washed with deionized water, sheet is obtained and is carried on the palladium of aluminium surface, copper composite catalyst.Catalyst made of the present invention is sheet, and when use is convenient as " tea-bag " and facilitates recycling, can catalyzed alkene and halogenated hydrocarbons Heck coupling reactions.
Description
Technical field
The present invention relates to the preparing technical fields of catalyst.
Background technology
Catalysis is one of production process important in chemical industry.The design of catalyst is important research class with preparation
Topic.Conventional homogeneous catalyst is difficult to recycle, and solid waste can be caused to pollute, and improves reaction cost.Although and homogeneous catalyst can return
It receives, but preparation process is more complex, and recycles link inconvenience, be easy insoluble by-product interference in being reacted.
Invention content
The purpose of the present invention is to propose to the preparation methods of a kind of palladium being carried on aluminium surface, copper composite catalyst, with convenient
It should be in large-scale production.
The technical scheme is that：It is 60~120 DEG C, by palladium bichloride, copper chloride, ammonium citrate that aluminium foil, which is soaked in temperature,
And N, N '-diisopropyl propane diamine dimethylbenzene composition mixed solution in react 2~5 hours, then take out aluminium foil, spend from
Son washing, obtains palladium, the copper composite catalyst for being carried on aluminium surface.
Catalyst made of the present invention is sheet, is a kind of " tea-bag " catalyst, i.e. catalyst can be prepared rapidly fast
Speed recycling, it is convenient as " tea-bag ", can catalyzed alkene and halogenated hydrocarbons Heck coupling reactions.This catalyst has wide
Prospects for commercial application, still, up to now, it is anti-that the catalyst of this new concept is only applicable to more incident Suzuki couplings
It answers.
The study found that in auxiliary agent ammonium citrate and N, the mixed metal prepared in the presence of N '-diisopropyl propane diamine is catalyzed
Agent has good catalytic activity, can be catalyzed Heck coupling reactions.
Further, the present invention is in the mixed solution, and a concentration of the 1.0 × 10 of the palladium bichloride-3~3.0 × 10- 3A concentration of the 1.0 × 10 of mol/L, the copper chloride-3~3.0 × 10-3A concentration of the 2.4 × 10 of mol/L, the ammonium citrate-4~3.6 × 10-4Mol/L, the N, a concentration of the 3.8 × 10 of N '-diisopropyl propane diamine-4~4.2 × 10-4mol/L.
Under conditions above, auxiliary agent citric acid and N, N '-diisopropyl propane diamine advantageously form high-ratio surface so that catalyst metals point
It dissipates uniformly, the catalyst activity prepared is higher.
In order to obtain most highly active catalyst live, the present invention in the mixed solution, the palladium bichloride it is a concentration of
1.6 ×10-3A concentration of the 1.6 × 10 of mol/L, the copper chloride-3A concentration of the 3.0 × 10 of mol/L, the ammonium citrate-4
Mol/L, the N, a concentration of the 4.0 × 10 of N '-diisopropyl propane diamine-4 mol/L。
The temperature of the mixed solution is 100 DEG C when reaction, and the reaction time is 3 hours.Groped by repeated tests
It proves, catalyst specific surface is maximum under the conditions of this temperature and time, the catalyst activity highest prepared.And such as prepare when
Between it is long can lead to catalyst metals aggregation inactivation, it is too short surface area to be caused to decline, therefore the present invention best reaction time
It is 3 hours.
Specific implementation mode
The following examples illustrate the present invention in more detail, rather than limitation of the invention further.Implement
Example 1：
1, palladium, the copper composite catalyst for being carried on aluminium surface are prepared：
The xylene solution of palladium bichloride, copper chloride, ammonium citrate and N, N '-diisopropyl propane diamine are mixed, and
Control a concentration of 1.6 × 10 of palladium bichloride in mixed liquor-3Mol/L, copper chloride in mixed liquor a concentration of 1.6 × 10- 3Mol/L, ammonium citrate in mixed liquor a concentration of 3.0 × 10-4Mol/L, N, N '-diisopropyl propane diamine is in mixed liquor
A concentration of 4.0 × 10-4mol/L。
The above mixed liquor is warming up to 100 DEG C, and again impregnates aluminium foil wherein after keeping the temperature, is taken after reaction in 3 hours
Go out aluminium foil, be washed with deionized water, obtains sheet and be carried on the palladium of aluminium surface, copper composite catalyst.
2, the activity of the catalyst obtained with the Heck coupling reactions of iodobenzene and styrene, detection preparation：
By DMF and ethyl alcohol with volume ratio for 1.4:1 ratio mixing, forms the mixed solution of DMF and ethyl alcohol.
The mixed solution of DMF and ethyl alcohol are warming up to 80 DEG C, and kept the temperature.
1 mmol iodobenzenes, 1 mmol styrene, 1 mmol N, N '-diisopropyl propane diamine and 1 is taken to be carried on aluminium surface
Palladium, copper composite catalyst put into 1.5 mL, 80 DEG C of DMF and ethyl alcohol mixed solution in, heat preservation react within 72 hours,
After reaction through thin-layer chromatography, separation obtains coupled product --- 1,2- talan, yield 81%.And catalyst can be as
" tea-bag " is equally rapid after the reaction to be taken out, and recycling uses.
Embodiment 2：Other conditions examine the catalyst activity prepared by different palladium bichloride concentration with embodiment 1, experiment
It the results are shown in Table 1.
The different palladium bichloride concentration of table 1 prepare the inspection of catalyst activity
From the above results, when palladium bichloride a concentration of 1.6 × 10-3The catalyst activity highest prepared when mol/L（It is real
Apply example 1）.
Embodiment 3：Other conditions examine the catalyst activity prepared by different copper chloride concentrations with embodiment 1, experiment
It the results are shown in Table 2.
The different copper chloride concentrations of table 2 prepare the inspection of catalyst activity
From the above results, when copper chloride concentration is 1.6 × 10-3The catalyst activity highest prepared when mol/L（It is real
Apply example 1）.
Embodiment 4：Other conditions examine the catalyst activity prepared by different ammonium citrate concentration with embodiment 1, real
It tests and the results are shown in Table 3.
The different ammonium citrate concentration of table 3 prepare the inspection of catalyst activity
From the above results, when ammonium citrate a concentration of 3.0 × 10-4The catalyst activity highest prepared when mol/L
（Embodiment 1）.
Embodiment 5：Other conditions examine different N, urging prepared by N '-diisopropyl propane diamine concentration with embodiment 1
Agent activity, experimental result are shown in Table 4.
4 difference N, N '-diisopropyl propane diamine concentration of table prepares the inspection of catalyst activity
From the above results, work as N, N '-diisopropyl propane diamine a concentration of 4.0 × 10-4The catalysis prepared when mol/L
Agent activity highest（Embodiment 1）.
Embodiment 6：Other conditions examine the catalyst activity prepared by different temperatures with embodiment 1, experimental result is shown in
Table 5.
5 different temperatures of table prepares the inspection of catalyst activity
From the above results, the catalyst activity highest prepared when temperature is 100 DEG C（Embodiment 1）.
Embodiment 7：Other conditions examine the catalyst activity prepared by different temperatures with embodiment 1, experimental result is shown in
Table 6.
The different soaking times of table 6 prepare the inspection of catalyst activity
From the above results, the catalyst activity highest prepared when soaking time is 3 h（Embodiment 1）.
Claims (3)
1. the preparation method of a kind of palladium being carried on aluminium surface, copper composite catalyst, it is characterised in that：Aluminium foil is soaked in temperature
For 60~120 DEG C, by palladium bichloride, copper chloride, ammonium citrate and N, the mixing of the dimethylbenzene composition of N '-diisopropyl propane diamine is molten
It is reacted 2~5 hours in liquid, then takes out aluminium foil, be washed with deionized water, obtain palladium, the copper composite catalyst for being carried on aluminium surface；
In the mixed solution, a concentration of the 1.0 × 10 of the palladium bichloride-3~3.0 × 10-3The concentration of mol/L, the copper chloride
It is 1.0 × 10-3~3.0 × 10-3A concentration of the 2.4 × 10 of mol/L, the ammonium citrate-4~3.6 × 10-4It is mol/L, described
A concentration of the 3.8 × 10 of N, N '-diisopropyl propane diamine-4~4.2 × 10-4 mol/L。
2. preparation method according to claim 1, it is characterised in that：In the mixed solution, the palladium bichloride it is dense
Degree is 1.6 × 10-3A concentration of the 1.6 × 10 of mol/L, the copper chloride-3Mol/L, the ammonium citrate a concentration of 3.0 ×
10-4Mol/L, the N, a concentration of the 4.0 × 10 of N '-diisopropyl propane diamine-4 mol/L。
3. preparation method according to claim 1 or 2, it is characterised in that：The temperature of the mixed solution is 100 when reaction
DEG C, the reaction time is 3 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709572A (en) * | 2005-04-29 | 2005-12-21 | 四川大学 | Aryl halide to olefin arylation carrying bimetallic catalyst, and its preparing method |
| CN103041826A (en) * | 2013-01-14 | 2013-04-17 | 中国科学院福建物质结构研究所 | Bimetal nanometer catalyst as well as preparation and application method thereof |
| JP5437742B2 (en) * | 2009-08-26 | 2014-03-12 | 北興化学工業株式会社 | Compound synthesis method and synthesis reaction catalyst |
| CN104353460A (en) * | 2014-11-14 | 2015-02-18 | 扬州大学 | Preparation method of copper and ferrum composite catalyst loaded on aluminum surface |
-
2016
- 2016-10-17 CN CN201610902131.8A patent/CN106423165B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709572A (en) * | 2005-04-29 | 2005-12-21 | 四川大学 | Aryl halide to olefin arylation carrying bimetallic catalyst, and its preparing method |
| JP5437742B2 (en) * | 2009-08-26 | 2014-03-12 | 北興化学工業株式会社 | Compound synthesis method and synthesis reaction catalyst |
| CN103041826A (en) * | 2013-01-14 | 2013-04-17 | 中国科学院福建物质结构研究所 | Bimetal nanometer catalyst as well as preparation and application method thereof |
| CN104353460A (en) * | 2014-11-14 | 2015-02-18 | 扬州大学 | Preparation method of copper and ferrum composite catalyst loaded on aluminum surface |
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