CN108218718A - A kind of catalytic hydrogenation efficiently prepares N, N- dibenzyl-ethylenediamins（DBE）Method - Google Patents
A kind of catalytic hydrogenation efficiently prepares N, N- dibenzyl-ethylenediamins（DBE）Method Download PDFInfo
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- CN108218718A CN108218718A CN201810287219.2A CN201810287219A CN108218718A CN 108218718 A CN108218718 A CN 108218718A CN 201810287219 A CN201810287219 A CN 201810287219A CN 108218718 A CN108218718 A CN 108218718A
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- Prior art keywords
- catalytic hydrogenation
- dbe
- nitrogen
- mesoporous carbon
- ethylenediamins
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 68
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 113
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 66
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000005864 Sulphur Substances 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 21
- 239000007791 liquid phase Substances 0.000 claims abstract description 18
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000012065 filter cake Substances 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- -1 nitrogenous compound Chemical class 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 238000005915 ammonolysis reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- ACYBVNYNIZTUIL-UHFFFAOYSA-N n'-benzylethane-1,2-diamine Chemical compound NCCNCC1=CC=CC=C1 ACYBVNYNIZTUIL-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 2
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- QBAKBJNOARBSGP-UHFFFAOYSA-N n-[2-(benzylideneamino)ethyl]-1-phenylmethanimine Chemical compound C=1C=CC=CC=1C=NCCN=CC1=CC=CC=C1 QBAKBJNOARBSGP-UHFFFAOYSA-N 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 34
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000003643 water by type Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- VLQJLZBKIZVWSA-UHFFFAOYSA-N 2-(benzylideneamino)ethanamine Chemical compound NCCN=CC1=CC=CC=C1 VLQJLZBKIZVWSA-UHFFFAOYSA-N 0.000 description 1
- 229930186147 Cephalosporin Natural products 0.000 description 1
- 229960000723 ampicillin Drugs 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- BVGLIYRKPOITBQ-ANPZCEIESA-N benzylpenicillin benzathine Chemical compound C=1C=CC=CC=1C[NH2+]CC[NH2+]CC1=CC=CC=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C([O-])=O)(C)C)C(=O)CC1=CC=CC=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C([O-])=O)(C)C)C(=O)CC1=CC=CC=C1 BVGLIYRKPOITBQ-ANPZCEIESA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940124587 cephalosporin Drugs 0.000 description 1
- 150000001780 cephalosporins Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000019371 penicillin G benzathine Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of catalytic hydrogenation and efficiently prepares N, and the method for N dibenzyl-ethylenediamins (DBE) includes the following steps：In a kettle, DBE is prepared through liquid phase catalytic hydrogenation reaction under the action of nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst in N, N dibenzylidene ethylenediamine；The present invention provides a kind of N, and the catalytic hydrogenation that N dibenzylidenes ethylenediamine prepares DBE through liquid phase catalytic hydrogenation efficiently prepares N, the method for N dibenzyl-ethylenediamins (DBE), and this method has the advantages that target product selectivity is high.
Description
Technical field
The present invention relates to a kind of catalytic hydrogenations efficiently to prepare N, the method for N- dibenzyl-ethylenediamins (DBE).
Background technology
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 ethylenediamines are prepared through catalytic hydrogenation
DBE.Wherein hydrogenation catalyst is the key technology of the technique.
Industrial N, N- dibenzylidene ethylenediamine Hydrogenation are mainly Pd/C and Pt/C for the 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 activities are too low, then polymerisation easily occurs, generates the by-products such as more benzyl ethylenediamines；If Pd/C or Pt/C
Catalyst activity is excessively high, then leads to the by-products such as more serious C-N hydrogenolysis, generation monobenzyl ethylenediamine.Therefore, it is necessary to it sets
The appropriate hydrogenation catalyst of meter activity, could obtain DBE in high yield.
Pd/C and Pt/C catalyst commercial at present generally using activated carbon as carrier, although activated carbon have it is cheap,
The advantages that large specific surface area, but the pore passage structure of activated carbon is based on micropore, and surface present it is neutral.Using activated carbon as carrier
Pd/C or Pt/C catalyst be applied to N, N- dibenzylidene ethylenediamines it is hydrogenated prepare DBE when, raw material and product are in activated carbon
Micropore in all there are serious diffusional resistances, this has not only slowed down reaction speed, and be easy to cause C-N hydrogenolysis and polymerization etc.
The generation of side reaction is unfavorable for reaction and is smoothed out.In addition, imines or nitrile compounds carry out hydrogenation reaction under neutral environment
When be prone to polymerisation, but then can effectively inhibit the polymerisation under alkaline environment.
Therefore, it seeks a kind of highly selective, catalytic hydrogenation and efficiently prepares N, the method right and wrong of N- dibenzyl-ethylenediamins (DBE)
It is often significant.
Invention content
The technical problem to be solved in the present invention is to provide a kind of N, and N- dibenzylidene ethylenediamines are through liquid phase catalytic hydrogenation system
The catalytic hydrogenation of standby DBE efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), and this method has target product selectivity height
The advantages of.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：A kind of catalytic hydrogenation efficiently prepares N, N- bis-
The method of benzyl ethylenediamine (DBE), includes the following steps：In a kettle, N, N- dibenzylidene ethylenediamine are in nitrogen/sulphur codope
DBE is prepared through liquid phase catalytic hydrogenation reaction under the action of mesoporous carbon-loaded noble metal catalyst.
Further, the preparation method of the nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst, including following step
Suddenly：
1) nitrogen/sulphur codope mesoporous carbon for being used to prepare catalyst is weighed, is configured to the slurries of 20~90 DEG C of temperature,
The solution of soluble precious-metal compound is slowly added dropwise by noble-metal-supported amount, stirs；
2) after impregnating 0.5~8h, addition alkaline solution adjusts solution ph to 7.5~10.0, and cools the temperature to room temperature,
Filtering, filter cake are washed with deionized to neutrality；
3) filter cake at 20~90 DEG C is configured to slurries again, liquid phase reducing agent is added dropwise, stirred, filtering, filter cake spend from
Sub- water washing is dried in vacuo at 70~120 DEG C and is urged to get the nitrogen/sulphur codope mesoporous carbon-loaded noble metal to neutrality
Agent.
Further, the noble metal is the one or several kinds of Pd or Pt；The soluble precious-metal compound
One kind for H2PdCl4, K2PdCl4, Na2PdCl4, Pd (NO3) 2, H2PtCl6, K2PtCl6, Na2PtCl6 or Pt (NO3) 2
It is or several；The alkaline solution for the one kind of solution such as NaOH, KOH, NaHCO3, Na2CO3, KHCO3, K2CO3 or ammonium hydroxide or
Person is several；The liquid-phase reduction agent is the one or several kinds of hydrazine hydrate, formic acid, formaldehyde, potassium formate or sodium formate；It is described
The load capacity of noble metal is 2~10wt%, preferably 3~8wt% in nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst.
Further, the nitrogen/sulphur codope mesoporous carbon is prepared via a method which to obtain：Under an inert atmosphere, it first uses
Nitrogenous compound high-temperature ammonolysis handles mesoporous carbon, then carries out high temperature vulcanized processing with H2S and obtain nitrogen/sulfur doping mesoporous carbon.
Further, the inert atmosphere is the one or several kinds of nitrogen, argon gas, helium；The mesoporous carbon granules
It spends for 100~1000 mesh, preferably 150~800 mesh；Specific surface area is 600~2000m2/g, preferably 1000~1800m2/
g；Average pore size is 2~20nm, preferably 2~10nm.
Further, the nitrogenous compound is the one or several kinds of ammonia, urea；The nitrogenous compound with
The mass ratio of mesoporous carbon is 0.05~10：1, preferably 0.1~5：1；The quality of the H2S and the mass ratio of mesoporous carbon are
0.5~50：1, preferably 1~20：1；The high-temperature ammonolysis treatment temperature be 400~1500 DEG C, preferably 600~1200
℃；The nitrogen treatment time is 0.5~50h, preferably 1~20h；The high temperature vulcanized treatment temperature is 500~1200 DEG C, excellent
It is selected as 600~1000 DEG C；Curing time is 1~30h, preferably 2~20h.
Further, in the liquid phase catalytic hydrogenation reaction, the use of nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst
It measures as N, 0.5~3.0wt% of N- dibenzylidene ethylenediamine quality.
Further, the liquid phase catalytic hydrogenation is reacted using ethyl acetate as reaction dissolvent, the addition of reaction dissolvent
With N, the quality of N- dibenzylidene ethylenediamines 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 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 is produced can obtain target 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 treats that temperature is down to room temperature, takes out reaction mixture, be filtered to remove
Catalyst, filtrate obtain target compound after distillation or rectifying.
Compared with prior art, the present invention it has the following advantages：
1) nitrogen in nitrogen/mesoporous carbon carrier of sulphur codope that the present invention uses can provide suitable alkalinity, N, N- bis-
The polymerisations such as benzal ethylenediamine；Element sulphur in carrier can form electronic effect between the metallic atom of load, appropriate to drop
The activity of low noble metal catalyst is conducive to inhibit C-N hydrogenolysis, is conducive to improve the selectivity of target product DBE.
2) carbon skeleton is directly doped into due to nitrogen and element sulphur or is keyed between carbon material with N-C or S-C, and then nitrogen member
Element not easily runs off in hydrogenation reaction, therefore nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst has in hydrogenation reaction
Good stability, catalyst are continuously applied mechanically 40 times, have no apparent inactivation.
3) nitrogen/mesoporous carbon carrier of sulphur codope that the present invention uses has larger aperture, is conducive to raw material and product exists
Reaction speed is not only accelerated in transmission in catalyst duct, but also is conducive to improve the selectivity of DBE.
4) the catalytic hydrogenation method that uses of the present invention prepares the selectivity of DBE and reaches more than 96.0wt%, imines conversion ratio
100wt%.
5) catalyst that the present invention uses does not increase noble metal without other metallic elements in addition to noble metal active component
The difficulty that catalyst recycles.
Specific embodiment
Technical scheme of the present invention is illustrated with specific embodiment below, but the scope of the present invention is not limited thereto：
Embodiment one
The mesoporous carbon of 10g is weighed, the granularity of mesoporous carbon is 800 mesh, specific surface area 1400m2/ g, average pore size 4nm,
Itself and 0.8g urea are mixed evenly, handle 5h in 1000 DEG C in a nitrogen atmosphere；It is passed through 1L/h's in a nitrogen atmosphere again
H2S handles 5h at 1000 DEG C to get to nitrogen/sulphur codope mesoporous carbon.Above-mentioned nitrogen/sulphur codope mesoporous carbon is gone in 100ml again
The slurries of 80 DEG C of temperature are configured in ionized water, the H of 10ml is slowly added dropwise2PdCl4Solution (Pd contents are 0.1g/ml), stirring
2.5h；Solution ph is adjusted to 8, and cool the temperature to room temperature, filter, filter cake is washed with deionized water with the NaOH solution of 10wt%
It washs to neutrality；Filter cake is configured to slurries at 80 DEG C again, 85% hydrazine hydrate solution of 10ml is added dropwise, stirs 2h, filtering, filter cake
It is washed with deionized to neutrality, vacuum drying is to get nitrogen/sulphur codope mesoporous carbon-loaded palladium catalyst at 100 DEG C.
Embodiment two
The mesoporous carbon of 10g is weighed, the granularity of mesoporous carbon is 400 mesh, specific surface area 1200m2/ g, average pore size 4nm,
Place it in NH3In, gas flow rate 2L/h handles 10h, then be passed through the H of 2L/h in a nitrogen atmosphere at 800 DEG C2S, at 1000 DEG C
5h is handled to get to nitrogen/sulphur codope mesoporous carbon.Above-mentioned nitrogen/sulphur codope mesoporous carbon is configured in 100ml deionized waters
The H of 6ml is slowly added dropwise in the slurries of temperature 60 C2PtCl6Solution (Pt contents are 0.1g/ml), stirs 2h；With the KOH of 10wt%
Solution adjusts solution ph to 8.5, and cools the temperature to room temperature, filters, and filter cake is washed with deionized to neutrality；Again by filter cake
Slurries are configured at 60 DEG C, the formaldehyde of 10ml is added dropwise, stir 2h, filtering, filter cake is washed with deionized to neutrality, in 90 DEG C
Lower vacuum drying is to get nitrogen/sulphur codope Performance of Platinum Nanoparticles Supported on Ordered Mesoporous Carbon.
Embodiment three
The mesoporous carbon of 10g is weighed, the granularity of mesoporous carbon is 150 mesh, specific surface area 1000m2/ g, average pore size 10nm,
Itself and 4g urea are mixed evenly, handle 3h in 1200 DEG C under helium atmosphere, then be passed through the H of 3L/h in a nitrogen atmosphere2S,
5h are handled at 600 DEG C to get to nitrogen/sulphur codope mesoporous carbon.By above-mentioned nitrogen/sulphur codope mesoporous carbon in 100ml deionized waters
In be configured to the slurries of 40 DEG C of temperature, the Pd (NO of 10ml are slowly added dropwise3)2Solution (Pd contents are 0.005g/ml), stirs 4h；With
Ammonium hydroxide adjusts solution ph to 9, and cools the temperature to room temperature, filters, and filter cake is washed with deionized to neutrality；Again by filter cake in
Slurries are configured at 40 DEG C, 30ml formic acid is added dropwise, stir 4h, filtering, filter cake is washed with deionized to neutrality, true at 80 DEG C
Sky is dry to get nitrogen/sulphur codope mesoporous carbon-loaded palladium catalyst.
Example IV
The mesoporous carbon of 10g is weighed, the granularity of mesoporous carbon is 200 mesh, specific surface area 1000m2/ g, average pore size 20nm,
Itself and 8g urea are mixed evenly, handle 13h in 500 DEG C in a nitrogen atmosphere, then be passed through the H of 1L/h in a nitrogen atmosphere2S,
15h are handled at 900 DEG C to get to nitrogen/sulphur codope mesoporous carbon.By above-mentioned nitrogen/sulphur codope mesoporous carbon in 100ml deionized waters
In be configured to the slurries of 90 DEG C of temperature, the K of 10ml is slowly added dropwise2PtCl6Solution (Pt contents are 0.03g/ml), stirs 1h；With
The KOH solution of 10wt% adjusts solution ph to 9.5, and cools the temperature to room temperature, filters, and filter cake is washed with deionized into
Property；Filter cake at 30 DEG C is configured to slurries again, 15ml formic acid is added dropwise, stirs 4h, filtering, filter cake is washed with deionized into
Property, vacuum drying is to get nitrogen/sulphur codope Performance of Platinum Nanoparticles Supported on Ordered Mesoporous Carbon at 100 DEG C.
Embodiment five
The mesoporous carbon of 10g is weighed, the granularity of mesoporous carbon is 600 mesh, specific surface area 1100m2/ g, average pore size 15nm,
Itself and 10g urea are mixed evenly, handle 10h in 600 DEG C in a nitrogen atmosphere, then be passed through the H of 5L/h in a nitrogen atmosphere2S,
2h are handled at 1000 DEG C to get to nitrogen/sulphur codope mesoporous carbon.By above-mentioned nitrogen/sulphur codope mesoporous carbon in 100ml deionized waters
In be configured to the slurries of temperature 70 C, the Na of 10ml is slowly added dropwise2PdCl4Solution (Pd contents are 0.02g/ml), stirs 2h；With
The NaOH solution of 10wt% adjusts solution ph to 8.5, and cools the temperature to room temperature, filters, filter cake be washed with deionized to
It is neutral；Filter cake is configured to slurries at 30 DEG C again, the hydrazine hydrate of the 85wt% of 3ml is added dropwise, stirs 4h, filtering, filter cake is spent
Ion water washing is to neutrality, and vacuum drying is to get nitrogen/sulphur codope mesoporous carbon-loaded palladium catalyst at 110 DEG C.
Embodiment six
The mesoporous carbon of 10g is weighed, the granularity of mesoporous carbon is 400 mesh, specific surface area 1300m2/ g, average pore size 8nm, will
It is mixed evenly with 10g urea, handles 6h in 650 DEG C in a nitrogen atmosphere, then be passed through the H of 1L/h in a nitrogen atmosphere2S,
1000 DEG C of processing 20h are to get to nitrogen/sulphur codope mesoporous carbon.By above-mentioned nitrogen/sulphur codope mesoporous carbon in 100ml deionized waters
In be configured to the slurries of temperature 70 C, the H of 10ml is slowly added dropwise2PtCl6Solution (Pt contents are 0.015g/ml), stirs 2h；With
The NaOH solution of 10wt% adjusts solution ph to 8.5, and cools the temperature to room temperature, filters, filter cake be washed with deionized to
It is neutral；Filter cake is configured to slurries at 30 DEG C again, the hydrazine hydrate of the 85wt% of 3ml is added dropwise, stirs 4h, filtering, filter cake is spent
Ion water washing is to neutrality, and vacuum drying is to get nitrogen/sulphur codope Performance of Platinum Nanoparticles Supported on Ordered Mesoporous Carbon at 110 DEG C.
Embodiment seven to 12
Embodiment seven to 12 has investigated different nitrogen/sulphur codope mesoporous carbon-loaded noble metal of the preparation of embodiment one to six
Performance of the catalyst in Hydrogenation reacts for DBE.
In 500ml stainless steel cauldrons, the N of 100g, N- dibenzylidenes ethylenediamine, 100ml ethyl acetate, 0.8g are added in
Nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst closes reaction kettle, with the air in nitrogen replacement reaction kettle three times, then
With hydrogen displacement three times；By temperature rise to 90 DEG C, hydrogen pressure for 0.8MPa, start to stir, stir speed (S.S.) 900r/min, react 1h；
Stop reaction, treat that temperature is cooled to room temperature, take out reaction solution, Filtration of catalyst, filtrate gas chromatographic analysis.Experiment knot
Fruit is as shown in table 1.
The Catalytic Hydrogenation Properties of the different nitrogen/sulphur codope mesoporous carbon-loaded noble metals of table 1
Embodiment 13 to 17
Embodiment 13 to 17 has investigated nitrogen/sulphur codope mesoporous carbon-loaded palladium catalyst in different hydrogenation conditions
Lower catalytic hydrogenation prepares DBE reactivity worth.In 500ml stainless steel cauldrons, the N of 100g is added in, N- dibenzylidenes ethylenediamine,
Nitrogen/sulphur codope mesoporous carbon-loaded palladium catalyst prepared by 150ml ethyl acetate, 1.0g embodiments one, closes reaction kettle, uses nitrogen
Air in gas replacement reaction kettle three times, then with hydrogen is replaced three times；After temperature and hydrogen pressure are risen to range needed for reaction, start
Stirring, stir speed (S.S.) 1200r/min react 2h；Stop reaction, treat that temperature is cooled to room temperature, take out reaction solution, be filtered to remove and urge
Agent, filtrate gas chromatographic analysis.Experimental result is as shown in table 2.
2 nitrogen of table/catalytic performance of the sulphur codope mesoporous carbon-loaded palladium catalyst under different hydrogenation conditions
Embodiment 18
Nitrogen/sulphur codope Performance of Platinum Nanoparticles Supported on Ordered Mesoporous Carbon that embodiment 18 has investigated the preparation of embodiment two is standby in Hydrogenation
Performance is applied mechanically in DBE reactions.In 500ml stainless steel cauldrons, the N of 100g, N- dibenzylidenes ethylenediamine, 200ml are added in
Nitrogen/sulphur codope mesoporous carbon-loaded palladium catalyst prepared by ethyl acetate, 1.0g embodiments one, closes reaction kettle, is put with nitrogen
The air changed in reaction kettle three times, then with hydrogen is replaced three times；By temperature rise to 80 DEG C, hydrogen pressure for 0.6MPa, start to stir,
Stir speed (S.S.) 900r/min reacts 2h；Stop reaction, treat that temperature is cooled to room temperature, taking-up reaction solution, Filtration of catalyst,
Filtrate gas chromatographic analysis.Catalysis after reaction continues to apply mechanically experiment, and adds the fresh embodiments one of 0.01g every time
Catalyst, the condition for applying mechanically experiment is identical, and experimental result is as shown in table 3.
3 nitrogen of table/sulphur codope mesoporous carbon-loaded palladium catalyst applies mechanically performance
Certainly, it is the representative instance of the application more than, 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 (10)
1. a kind of catalytic hydrogenation efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), which is characterized in that including following step
Suddenly：In a kettle, N, N- dibenzylidene ethylenediamine pass through under the action of nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst
DBE is prepared in liquid phase catalytic hydrogenation reaction.
2. a kind of catalytic hydrogenation as described in claim 1 efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), feature
It is, the preparation method of the nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst includes the following steps：
1) nitrogen/sulphur codope mesoporous carbon for being used to prepare catalyst is weighed, the slurries of 20~90 DEG C of temperature are configured to, by expensive
The solution of soluble precious-metal compound is slowly added dropwise in content of metal, stirs；
2) after impregnating 0.5~8h, addition alkaline solution adjusts solution ph to 7.5~10.0, and cools the temperature to room temperature, mistake
Filter, filter cake are washed with deionized to neutrality；
3) filter cake at 20~90 DEG C is configured to slurries again, liquid phase reducing agent is added dropwise, stirred, filtering, filter cake deionized water
Washing is to neutrality, and vacuum drying is to get the nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst at 70~120 DEG C.
3. a kind of catalytic hydrogenation as claimed in claim 2 efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), feature
Be, the noble metal be Pd or Pt one or several kinds, the soluble precious-metal compound for H2PdCl4,
The one or several kinds of K2PdCl4, Na2PdCl4, Pd (NO3) 2, H2PtCl6, K2PtCl6, Na2PtCl6 or Pt (NO3) 2, institute
One or several kinds of the alkaline solution for solution such as NaOH, KOH, NaHCO3, Na2CO3, KHCO3, K2CO3 or ammonium hydroxide are stated, it is described
Liquid-phase reduction agent be hydrazine hydrate, formic acid, formaldehyde, potassium formate or sodium formate one or several kinds, the nitrogen/sulphur codope is situated between
The load capacity of noble metal is 2~10wt% in the carbon supported precious metal catalyst of hole.
4. a kind of catalytic hydrogenation as claimed in claim 2 efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), feature
It is, the preparation method of the nitrogen/sulphur codope mesoporous carbon includes the following steps：Under an inert atmosphere, nitrogenous compound is first used
High-temperature ammonolysis handles mesoporous carbon, then carries out high temperature vulcanized processing with H2S and obtain nitrogen/sulfur doping mesoporous carbon.
5. a kind of catalytic hydrogenation as claimed in claim 4 efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), feature
It is, the inert atmosphere is nitrogen, the one or several kinds of argon gas, helium, and the mesoporous carbon granularity is 100~1000
Mesh, specific surface area are 600~2000m2/g, and average pore size is 2~20nm.
6. a kind of catalytic hydrogenation as claimed in claim 4 efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), feature
It is, the nitrogenous compound is ammonia, the one or several kinds of urea, the quality of the nitrogenous compound and mesoporous carbon
Than being 0.05~10：1, the quality of the H2S and the mass ratio of mesoporous carbon are 0.5~50：1, high-temperature ammonolysis processing
Temperature is 400~1500 DEG C, and the nitrogen treatment time is 0.5~50h, and the high temperature vulcanized treatment temperature is 500~1200 DEG C,
Curing time is 1~30h.
7. a kind of catalytic hydrogenation as described in claim 1 efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), feature
It is, in the liquid phase catalytic hydrogenation reaction, the dosage of nitrogen/sulphur codope mesoporous carbon-loaded noble metal catalyst is N, and N- bis- is sub-
0.5~3.0wt% of benzyl ethylenediamine quality.
8. a kind of catalytic hydrogenation as described in claim 1 efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), feature
It is, the liquid phase catalytic hydrogenation is reacted using ethyl acetate as reaction dissolvent, and the addition of reaction dissolvent is with N, bis- benzal of N-
The quality of base ethylenediamine is calculated as 0.5~3.0ml/g.
9. a kind of catalytic hydrogenation as described in claim 1 efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE), feature
It is, the reaction temperature of liquid phase catalytic hydrogenation reaction is 50~120 DEG C.
10. a kind of catalytic hydrogenation as described in claim 1 efficiently prepares N, the method for N- dibenzyl-ethylenediamins (DBE) is special
Sign is, in liquid phase catalytic hydrogenation reaction, control Hydrogen Vapor Pressure is 0.2~3.0MPa.
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