CN109046363A - A kind of method that supported bimetal catalyst efficiently synthesizes DBE - Google Patents
A kind of method that supported bimetal catalyst efficiently synthesizes DBE Download PDFInfo
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- CN109046363A CN109046363A CN201811120927.3A CN201811120927A CN109046363A CN 109046363 A CN109046363 A CN 109046363A CN 201811120927 A CN201811120927 A CN 201811120927A CN 109046363 A CN109046363 A CN 109046363A
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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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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- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
Abstract
The present invention discloses a kind of method that supported bimetal catalyst efficiently synthesizes DBE, comprising the following steps: in a kettle, DBE is prepared through liquid phase catalytic hydrogenation reaction under the action of activated carbon supported bimetallic catalyst in N, N- dibenzylidene ethylenediamine.The present invention can further promote the activity of catalyst, have the advantages that reaction speed is fast, target product selectivity is high under the premise of guaranteeing that target product is highly selective.
Description
Technical field
The present invention relates to a kind of methods that supported bimetal catalyst efficiently synthesizes DBE.
Background technique
DBE is a kind of medicine intermediate, mainly for the production of benzathine penicillin G, long-acting mould V, long-acting ampicillin and
Long-acting cephalosporins medicine and other medicines.Industrial mainly by N at present, N- dibenzylidene ethylenediamine is prepared through catalytic hydrogenation
DBE.Wherein hydrogenation catalyst is the key technology of the technique.
It is mainly Pd/C and Pt/C that industrial N, N- dibenzylidene ethylenediamine, which add hydrogen to prepare catalyst used in DBE,.But
The problem of common Pd/C or Pt/C catalyst is all taken into account there is activity and selectivity difficulty.If this be primarily due to Pd/C or
Pt/C catalyst activity is too low, then is easy to happen polymerization reaction, generates the by-products such as more benzyl ethylenediamines；If Pd/C or Pt/C
Catalyst activity is excessively high, then leads to more serious C-N hydrogenolysis, generates the by-products such as monobenzyl ethylenediamine.Therefore, design is lived
Property hydrogenation catalyst appropriate, be the effective way for obtaining the DBE of high yield.And adding auxiliary agent to modified catalyst performance is
A kind of common method.Such as Chinese patent CN201810287219.2 discloses a kind of double gold of the support type for efficiently synthesizing DBE
Metal catalyst and preparation method thereof, the catalyst activity component are precious metals pd or Pt, auxiliary agent Sn, when it is urged applied to liquid phase
When changing hydrogenation synthesis DBE, there is preferable target product selectivity, and yield can be made to reach 96wt% or more.Commonsense method system
Although standby additive modification catalyst can promote the selectivity of target product, the activity for reducing catalyst will also tend to.
Under the premise of guaranteeing that target product is highly selective, the activity of catalyst is further promoted, is very significant
, it may have very big challenge.Therefore, one kind method that is highly selective, efficiently synthesizing DBE is sought to industrial production with great
Application value.
Summary of the invention
The technical problem to be solved in the present invention is that providing one kind for N, N- dibenzylidene ethylenediamine adds through liquid-phase catalysis
Hydrogen prepares catalyst and its application of DBE, and this method has the advantages that reaction speed is fast, target product selectivity is high.
In order to solve the above technical problems, the present invention adopts the following technical scheme: a kind of supported bimetal catalyst efficiently closes
At the method for DBE, comprising the following steps: in a kettle, N, N- dibenzylidene ethylenediamine is in activated carbon supported bimetallic catalytic
DBE is prepared through liquid phase catalytic hydrogenation reaction under the action of agent.
Further, the preparation method of the activated carbon supported bimetallic catalyst, comprising the following steps:
1) active carbon for being used to prepare catalyst is weighed, using equi-volume impregnating carried noble metal and Zn.According to activity
The hole of charcoal holds and content of metal, and configuration and active carbon hole hold the mixed containing precious metal chemical complex and the compound containing Zn of same volume
Solution is closed, wherein tenor is consistent with catalyst loadings；
5) solution of metal-containing compound is added drop-wise to dropwise in active carbon, and stirred evenly；
6) catalyst after dipping is dried in vacuo to 4~20h at 20~30 DEG C；
7) catalyst after drying 3~10h of reduction is carried out to bear to get active carbon at 50~100 DEG C under H2 atmosphere
Carry bimetallic catalyst.
Further, the noble metal is the one or several kinds of Pd, Pt, and the precious metal chemical complex is
The one or several kinds of H2PdCl4, Pd (NO3) 2, H2PtCl6 or Pt (NO3) 2, the compound containing Zn are ZnCl2, Zn
(NO3) 2 one or several kinds.
Further, the granularity of activated carbon is 100~1000 mesh, preferably 150~800 mesh；Specific surface area is 600
~2000m2/g, preferably 1000~1800m2/g；0.3~0.8ml/g of Kong Rongwei, preferably 0.4~0.7ml/g.
Further, in the liquid phase catalytic hydrogenation reaction, the dosage of activated carbon supported bimetallic catalyst is N, N- bis-
0.5~3.0wt% of benzal ethylenediamine quality.
Further, the liquid phase catalytic hydrogenation is reacted using ethyl acetate as reaction dissolvent, the additional amount of reaction dissolvent
With N, the quality of N- dibenzylidene ethylenediamine is calculated as 0.5~3.0ml/g.
Further, the reaction temperature of liquid phase catalytic hydrogenation reaction is 50~120 DEG C, preferably 60~110 DEG C.
Further, in the described liquid phase catalytic hydrogenation reaction, control Hydrogen Vapor Pressure is 0.2~3.0MPa, preferably 0.3
~1.0MPa.
Liquid phase catalytic hydrogenation reaction of the present invention, produces target can be obtained by conventional post-processing after completion of the reaction
Object, such as following post-processing approach can be used: after completion of the reaction, it is down to room temperature to temperature, reaction mixture is taken out, is filtered to remove
Catalyst, filtrate obtain target compound after distillation or rectifying.
Compared with prior art, the present invention having the advantage that
1) catalyst of the present invention uses equi-volume impregnating, and precipitates direct hydrogen reducing without lye and prepare,
The metal partial size of gained catalyst is small, and catalytic activity is high.
2) it is restored using normal-temperature vacuum is dry with lower temperature in catalyst preparation process of the present invention, it can be ensured that gained is urged
The metal partial size of agent is smaller, and catalytic activity is high.
3) catalyst of the present invention is added to Zn auxiliary agent, and Zn can play synergistic effect with noble metal, will in catalytic hydrogenation reaction
On Hydrogen spillover to neighbouring Zn on noble metal, which not only provides more hydrogenation sites, while reducing noble metal
The content of upper overactivity hydrogen, to maintain high target product selectivity while improving catalytic hydrogenation reaction rate.
4) precipitate direct hydrogen also without lye when catalyst of the present invention uses equi-volume impregnating so that noble metal with
Zn combine it is closer, can more preferably play synergistic effect.
5) selectivity that the catalytic hydrogenation method that the present invention uses prepares DBE is greater than 96.5wt%, imines conversion ratio reaches
100wt%.
Specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto:
Embodiment one
10g active carbon is weighed, granularity is 800 mesh, specific surface area 1400m2/g, Kong Rongwei 0.6ml/g, and configuration 6ml contains
The mixed solution of H2PdCl4 and ZnCl2 (quality in mixed solution containing Pd is 0.2g, and the quality containing Zn is 0.3g)；It will mixing
Solution is added drop-wise in active carbon dropwise, and is stirred evenly.Catalyst after dipping is dried in vacuo 10h at 25 DEG C.It will dry
Catalyst afterwards carries out reduction 6h at 60 DEG C under H2 atmosphere to get active carbon-supported palladium-zinc catalyst.
Embodiment two
10g active carbon is weighed, granularity is 500 mesh, specific surface area 1200m2/g, Kong Rongwei 0.5ml/g, and configuration 5ml contains
The mixed solution of H2PtCl6 and ZnCl2 (quality in mixed solution containing Pt is 0.2g, and the quality containing Zn is 0.4g)；It will mixing
Solution is added drop-wise in active carbon dropwise, and is stirred evenly.Catalyst after dipping is dried in vacuo 20h at 20 DEG C.It will dry
Catalyst afterwards carries out reduction 3h at 100 DEG C under H2 atmosphere to get activated carbon supported platinum-zinc catalyst.
Embodiment three
10g active carbon is weighed, granularity is 150 mesh, specific surface area 800m2/g, Kong Rongwei 0.8ml/g, and configuration 8ml contains Pt
(NO3) mixed solution of 2 and Zn (NO3) 2 (quality in mixed solution containing Pt is 0.4g, and the quality containing Zn is 0.2g)；It will mix
It closes solution to be added drop-wise in active carbon dropwise, and stirs evenly.Catalyst after dipping is dried in vacuo 4h at 30 DEG C.It will dry
Catalyst afterwards carries out reduction 10h at 50 DEG C under H2 atmosphere to get activated carbon supported platinum-zinc catalyst.
Example IV
10g active carbon is weighed, granularity is 800 mesh, specific surface area 600m2/g, Kong Rongwei 0.4ml/g, and configuration 4ml contains Pd
(NO3) mixed solution of 2 and Zn (NO3) 2 (quality in mixed solution containing Pd is 0.2g, and the quality containing Zn is 0.2g)；It will mix
It closes solution to be added drop-wise in active carbon dropwise, and stirs evenly.Catalyst after dipping is dried in vacuo 6h at 30 DEG C.It will dry
Catalyst afterwards carries out reduction 5h at 70 DEG C under H2 atmosphere to get active carbon-supported palladium-zinc catalyst.
Embodiment five
10g active carbon is weighed, granularity is 400 mesh, specific surface area 1800m2/g, Kong Rongwei 0.7ml/g, and configuration 7ml contains
The mixed solution of H2PdCl4 and Zn (NO3) 2 (quality in mixed solution containing Pd is 0.5g, and the quality containing Zn is 0.3g)；It will mix
It closes solution to be added drop-wise in active carbon dropwise, and stirs evenly.Catalyst after dipping is dried in vacuo 16h at 20 DEG C.It will do
Catalyst after dry carries out reduction 4h at 80 DEG C under H2 atmosphere to get active carbon-supported palladium-zinc catalyst.
Embodiment six
10g active carbon is weighed, granularity is 300 mesh, specific surface area 1000m2/g, Kong Rongwei 0.5ml/g, and configuration 5ml contains
The mixed solution of Pt (NO3) 2 and ZnCl2 (quality in mixed solution containing Pt is 0.1g, and the quality containing Zn is 0.2g)；It will mixing
Solution is added drop-wise in active carbon dropwise, and is stirred evenly.Catalyst after dipping is dried in vacuo 12h at 20 DEG C.It will dry
Catalyst afterwards carries out reduction 7h at 60 DEG C under H2 atmosphere to get activated carbon supported platinum-zinc catalyst.
Embodiment seven to 12
The different activities charcoal supported bimetal catalyst that embodiment seven to 12 has investigated the preparation of embodiment one to six is adding
Hydrogen prepares the performance in DBE reaction.
In 500ml stainless steel cauldron, the N of 100g, N- dibenzylidene ethylenediamine, 100ml ethyl acetate, 0.8g is added
Activated carbon supported bimetallic catalyst, close reaction kettle, three times with the air in nitrogen replacement reaction kettle, then with hydrogen displacement three
It is secondary；By temperature rise to 90 DEG C, hydrogen press as 0.8MPa, start to stir, stirring rate 900r/min, react 0.5h；Stop reaction, to
Temperature is cooled to room temperature, and takes out reaction solution, Filtration of catalyst, filtrate gas chromatographic analysis.Experimental result such as 1 institute of table
Show.
The catalytic hydrogenation property of 1 different activities charcoal supported bi-metallic of table
Embodiment 13 to 17
Embodiment 13 to 17, which has been investigated active carbon-supported palladium-zinc catalyst and has been catalyzed under different hydrogenation conditions, to be added
Hydrogen prepares DBE reactivity worth.In 500ml stainless steel cauldron, the N of 100g, N- dibenzylidene ethylenediamine, 150ml second is added
Active carbon-supported palladium-zinc catalyst prepared by acetoacetic ester, 1.0g embodiment one, closes reaction kettle, in nitrogen replacement reaction kettle
Air three times, then with hydrogen displacement three times；After range needed for temperature and hydrogen pressure are risen to reaction, start to stir, stirring rate
1200r/min reacts 1h；Stop reaction, be cooled to room temperature to temperature, takes out reaction solution, Filtration of catalyst, filtrate gas
Analysis of hplc.Experimental result is as shown in table 2.
Catalytic performance of 2 active carbon-supported palladiums of the table-zinc catalyst under different hydrogenation conditions
Embodiment 18
Activated carbon supported platinum-zinc catalyst that embodiment 18 has investigated the preparation of embodiment two is adding hydrogen preparation DBE reaction
In apply performance.In 500ml stainless steel cauldron, the N of 100g, N- dibenzylidene ethylenediamine, 200ml acetic acid second is added
Activated carbon supported platinum-zinc catalyst prepared by ester, 1.0g embodiment two, closes reaction kettle, with the sky in nitrogen replacement reaction kettle
Gas three times, then with hydrogen is replaced three times；By temperature rise to 80 DEG C, hydrogen press as 0.6MPa, start to stir, stirring rate 900r/
Min reacts 1h；Stop reaction, be cooled to room temperature to temperature, takes out reaction solution, Filtration of catalyst, filtrate gas-chromatography
Analysis.Catalysis after reaction continues to apply experiment, and adds fresh two catalyst of embodiment of 0.01g every time, applies reality
The condition tested is identical, and experimental result is as shown in table 3.
Activated carbon supported platinum-the zinc catalyst of table 3 applies performance
Certainly, the representative instance of above only the application, in addition to this, the application can also have other a variety of specific implementations
Mode, all technical solutions formed using equivalent substitution or equivalent transformation, is all fallen within this application claims within the scope of.
Claims (8)
1. a kind of method that supported bimetal catalyst efficiently synthesizes DBE, which comprises the following steps: in reaction kettle
In, N, N- dibenzylidene ethylenediamine is prepared under the action of activated carbon supported bimetallic catalyst through liquid phase catalytic hydrogenation reaction
To DBE.
2. a kind of method that supported bimetal catalyst efficiently synthesizes DBE as described in claim 1, which is characterized in that described
Activated carbon supported bimetallic catalyst preparation method, comprising the following steps:
1) active carbon for being used to prepare catalyst is weighed, using equi-volume impregnating carried noble metal and Zn.According to active carbon
Hole holds and content of metal, and it is molten to configure the mixing containing precious metal chemical complex and the compound containing Zn for holding same volume with active carbon hole
Liquid, wherein tenor is consistent with catalyst loadings；
2) solution of metal-containing compound is added drop-wise to dropwise in active carbon, and stirred evenly；
3) catalyst after dipping is dried in vacuo to 4~20h at 20~30 DEG C；
4) catalyst after drying is carried out to 3~10h of reduction under H2 atmosphere at 50~100 DEG C to get activated carbon supported double
Metallic catalyst.
3. a kind of method that supported bimetal catalyst efficiently synthesizes DBE as claimed in claim 2, which is characterized in that described
Noble metal be Pd, Pt one or several kinds, the precious metal chemical complex be H2PdCl4, Pd (NO3) 2, H2PtCl6 or
The one or several kinds of Pt (NO3) 2, the compound containing Zn are the one or several kinds of ZnCl2, Zn (NO3) 2.
4. a kind of method that supported bimetal catalyst efficiently synthesizes DBE as claimed in claim 2, which is characterized in that described
Granularity of activated carbon be 100~1000 mesh, specific surface area be 600~2000m2/g, 0.3~0.8ml/g of Kong Rongwei.
5. a kind of method that supported bimetal catalyst efficiently synthesizes DBE as described in claim 1, which is characterized in that described
In liquid phase catalytic hydrogenation reaction, the dosage of activated carbon supported bimetallic catalyst is N, the 0.5 of N- dibenzylidene ethylenediamine quality
~3.0wt%.
6. a kind of method that supported bimetal catalyst efficiently synthesizes DBE as described in claim 1, which is characterized in that described
Liquid phase catalytic hydrogenation react using ethyl acetate as reaction dissolvent, the additional amount of reaction dissolvent with N, N- dibenzylidene ethylenediamine
Quality is calculated as 0.5~3.0ml/g.
7. a kind of method that supported bimetal catalyst efficiently synthesizes DBE as described in claim 1, which is characterized in that described
Liquid phase catalytic hydrogenation reaction reaction temperature be 50~120 DEG C, preferably 60~110 DEG C.
8. a kind of method that supported bimetal catalyst efficiently synthesizes DBE as described in claim 1, which is characterized in that described
Liquid phase catalytic hydrogenation reaction in, control Hydrogen Vapor Pressure be 0.2~3.0MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112191243A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | High-dispersion nitrogen-sulfur co-doped catalyst, preparation thereof and application of catalyst in synthesizing N, N-dibenzylethylenediamine |
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| CN106748813A (en) * | 2016-12-31 | 2017-05-31 | 浙江工业大学 | One kind synthesis N, the method for N dibenzyl-ethylenediamins |
| CN106957231A (en) * | 2016-01-11 | 2017-07-18 | 江苏圣奥化学科技有限公司 | The preparation method of N, N '-bis- (alkyl)-p-phenylenediamine |
| CN107413335A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of mesoporous carbon microspheres carry composite catalyst and preparation method and application |
| CN108218718A (en) * | 2018-03-30 | 2018-06-29 | 浙江辰阳化工有限公司 | A kind of catalytic hydrogenation efficiently prepares N, N- dibenzyl-ethylenediamins（DBE）Method |
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- 2018-09-26 CN CN201811120927.3A patent/CN109046363A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957231A (en) * | 2016-01-11 | 2017-07-18 | 江苏圣奥化学科技有限公司 | The preparation method of N, N '-bis- (alkyl)-p-phenylenediamine |
| CN106748813A (en) * | 2016-12-31 | 2017-05-31 | 浙江工业大学 | One kind synthesis N, the method for N dibenzyl-ethylenediamins |
| CN107413335A (en) * | 2017-03-31 | 2017-12-01 | 浙江工业大学 | A kind of mesoporous carbon microspheres carry composite catalyst and preparation method and application |
| CN108218718A (en) * | 2018-03-30 | 2018-06-29 | 浙江辰阳化工有限公司 | A kind of catalytic hydrogenation efficiently prepares N, N- dibenzyl-ethylenediamins（DBE）Method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112191243A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | High-dispersion nitrogen-sulfur co-doped catalyst, preparation thereof and application of catalyst in synthesizing N, N-dibenzylethylenediamine |
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Application publication date: 20181221 |