CN102179245B - Application of palladium/active carbon catalyst in synthesizing N,N'-dibenzylethylenediamine - Google Patents
Application of palladium/active carbon catalyst in synthesizing N,N'-dibenzylethylenediamine Download PDFInfo
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- CN102179245B CN102179245B CN 201110057500 CN201110057500A CN102179245B CN 102179245 B CN102179245 B CN 102179245B CN 201110057500 CN201110057500 CN 201110057500 CN 201110057500 A CN201110057500 A CN 201110057500A CN 102179245 B CN102179245 B CN 102179245B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 132
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- JUHORIMYRDESRB-UHFFFAOYSA-N benzathine Chemical compound C=1C=CC=CC=1CNCCNCC1=CC=CC=C1 JUHORIMYRDESRB-UHFFFAOYSA-N 0.000 title abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- 239000000243 solution Substances 0.000 claims abstract description 52
- 238000005406 washing Methods 0.000 claims abstract description 22
- 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 claims abstract description 18
- -1 sodium halide Chemical class 0.000 claims abstract description 17
- 230000007935 neutral effect Effects 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 10
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 54
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 14
- 238000001914 filtration Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 5
- 229910003603 H2PdCl4 Inorganic materials 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 238000003756 stirring Methods 0.000 description 37
- 229910052757 nitrogen Inorganic materials 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 12
- 235000002639 sodium chloride Nutrition 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000000376 reactant Substances 0.000 description 11
- 230000004044 response Effects 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- 241000370738 Chlorion Species 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 229960002668 sodium chloride Drugs 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930186147 Cephalosporin Natural products 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- MTRNNCLQPVCDLF-UHFFFAOYSA-N benzyl-[2-(benzylazaniumyl)ethyl]azanium;diacetate Chemical compound CC(O)=O.CC(O)=O.C=1C=CC=CC=1CNCCNCC1=CC=CC=C1 MTRNNCLQPVCDLF-UHFFFAOYSA-N 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
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940124587 cephalosporin Drugs 0.000 description 1
- 150000001780 cephalosporins Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ACYBVNYNIZTUIL-UHFFFAOYSA-N n'-benzylethane-1,2-diamine Chemical compound NCCNCC1=CC=CC=C1 ACYBVNYNIZTUIL-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 235000019371 penicillin G benzathine Nutrition 0.000 description 1
- BBTOYUUSUQNIIY-ANPZCEIESA-N phenoxymethylpenicillin 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)COC1=CC=CC=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C([O-])=O)(C)C)C(=O)COC1=CC=CC=C1 BBTOYUUSUQNIIY-ANPZCEIESA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Chemical group 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a palladium/active carbon catalyst and application thereof in synthesizing N,N'-dibenzylethylenediamine. The palladium/active carbon catalyst is prepared by the following steps of: impregnating active carbon by using aqueous solution of sodium halide, filtering, and washing a filter cake until halogen ions are absent; impregnating the treated active carbon by using aqueous solution of H2PdCl4; and regulating the pH value of the solution until the solution is alkaline, filtering, washing a filter cake until the filter cake is neutral, and reducing the filter cake by using a reducing agent, and drying the obtained neutral product to obtain the palladium/active carbon catalyst. The palladium/active carbon catalyst has controllable size, most palladium particles in the catalyst have the particle size of 2 to 5nm, the catalyst is used for synthesizing the N,N'-dibenzylethylenediamine by N,N'-dibenzylidene ethylenediamine through catalytic hydrogenation reduction, and has high activity, selectivity and stability; moreover, the catalyst is easy to prepare, environment-friendly and suitable for industrial application, and precious metal palladium is easy to recover.
Description
(1) technical field
The present invention relates to a kind of palladium activated-carbon catalyst and at N, N '-dibenzylidene ethylenediamine catalytic hydrogenation prepares N, the application in N '-dibenzyl-ethylenediamin.
(2) background technology
N, N '-dibenzyl-ethylenediamin diacetate salt (being called for short DBED), be widely used in producing benzathine penicillin G, benzathine penicillin V, long-acting ampicillin and long-acting cephalosporins medicine and other medicine, a kind of medicine intermediate of important high added value, hundreds of millions of especially with its synthetic antibiotic medicine output value.
At present, the DBED synthetic method is domestic basic or adopt organic synthesis method take benzyl chloride and ethylenediamine as raw material.This route has the advantages such as technique is simple, flow process is shorter, investment is little, be at present comparatively ripe, use more a kind of synthesis technique.But this synthesis technique product yield low (being only 30% left and right), poor product quality, environmental pollution large (1 ton of DBED of every production will produce 8 tons of organic sewages) has seriously restricted the sustainable development of DBED compound probability.Catalytic reduction method because of have operating environment gentleness, good product quality, the advantage such as reaction selectivity is high, pollution-free and post processing is easy, be widely used in chemical industry, be a kind of synthetic technology of cleaning of maturation.Adopt the catalytic reduction technology by N, N '-dibenzylidene ethylenediamine synthesizes N, N '-dibenzyl-ethylenediamin, more further salify is green, the high efficient technology of synthetic DBED.
Catalyst be catalytic reduction technique core, United States Patent (USP) [US 2773098] report Pd/C, Pt/C and Pt/Al
2O
3Catalyst is N, and N '-dibenzylidene ethylenediamine catalytic hydrogenating reduction synthesizes N, the effective catalyst of N '-dibenzyl-ethylenediamin.But this reaction requires catalyst must possess high activity and stable, could reduce the generation of the accessory substances such as monobenzyl ethylenediamine, avoids reaction selectivity to descend and catalysqt deactivation, reduces production costs thereby improve reaction yield.The load type metal catalyst that adopts the conventional method preparation effectively the regulation and control metallic particles in the form of carrier surface, be that metal active constituent usually is dispersed in carrier surface with the form of inhomogeneous wide distribution, the quantity of carrier surface metal effective active position does not increase by on a year-on-year basis along with the raising of content of metal, accumulation occurs and does not bring into play its due catalytic performance in the metallic particles of considerable part, make using rate of metal low, restricting the activity, selective and stable of load type metal catalyst.
(3) summary of the invention
First technical problem that the present invention will solve is to provide a kind of palladium activated-carbon catalyst of controlled dimensions, in this catalyst, most palladium grain diameter is 2～5nm, use it for N, N '-dibenzylidene ethylenediamine catalytic hydrogenating reduction synthesizes N, N '-dibenzyl-ethylenediamin, catalyst activity, selective and stability is all higher; And this catalyst preparation is simple, environmental friendliness, and precious metal palladium easily reclaims, and is applicable to commercial Application.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of palladium activated-carbon catalyst, preparation by the following method: first active carbon is used sodium halide aqueous solution impregnation process, then filtration, Washing of Filter Cake are to halogen ion-free, the active carbon dipping H2PdCl4 aqueous solution that to process again, then regulator solution pH value to alkalescence, is filtered, and filter cake is washed to neutrality, filter cake is reduced with reducing agent, namely get described palladium activated-carbon catalyst after the neutral products drying that obtains.
Further, the specific area of described carrier active carbon is preferably 1300～1700m
2/ g.
Further, described sodium halide solution is preferably sodium chloride solution, and concentration is preferably 0.125～2.5mol/l.The volume that adds of described sodium halide solution is counted 2～20ml/g with quality of activated carbon, preferred 8～12ml/g.Described " active carbon with sodium halide aqueous solution impregnation process " can at room temperature carry out preferred 1～5 hour of dip time.
Further, be preferably that 2～6wt% adds H by palladium loading (being the mass percent of palladium/active carbon in the palladium activated-carbon catalyst)
2PdCl
4The aqueous solution.Described " the active carbon dipping H that will process
2PdCl
4The aqueous solution ", preferred 60～90 ℃ of dipping temperature, specifically can carry out in accordance with the following steps: the active carbon that first will process is made into the slurries of 60～90 ℃ of temperature, is that 2～6wt% slowly drips H by the palladium loading
2PdCl
4Solution dropwises rear stirring 2～10 hours.
The active carbon dipping H that further, will process
2PdCl
4After the aqueous solution, preferred regulator solution pH value to 7.1～9.
Further, described reducing agent is preferably hydrazine hydrate solution, and described reduction is specially: filter cake is made into slurries, drips hydrazine hydrate solution, stirring reaction filters and obtains neutral products.The mass ratio that feeds intake of described hydrazine hydrate and palladium is 0.15～6: 1.Preferred 10～50 ℃ of reduction reaction temperature, more preferably 25～35 ℃; Reaction time is preferably 1～5 hour, more preferably 2～3 hours.
Under gained neutral products room temperature of the present invention in air preliminarily dried, get wet sample and be described palladium activated-carbon catalyst.The most palladium grain diameter of the palladium activated-carbon catalyst that the present invention makes is at 2～5nm, and preferred palladium grain diameter more than 75% is 2～5nm.
Second technical problem that the present invention will solve is to provide described palladium activated-carbon catalyst at synthetic N, application in N '-dibenzyl-ethylenediamin, described application is specially: with N, N '-dibenzylidene ethylenediamine is raw material, under palladium activated-carbon catalyst and hydrogen effect, make described N by catalytic hydrogenation, N '-dibenzyl-ethylenediamin.
Further, described synthetic N, the reaction of N '-dibenzyl-ethylenediamin is carried out in the aliphatic alcohols organic solvent, described aliphatic alcohols organic solvent particular methanol or ethanol.The addition of common described aliphatic alcohols organic solvent is with N, and the quality of N '-dibenzylidene ethylenediamine is counted 1～4ml/g
Further, at N, in N '-dibenzyl-ethylenediamin synthetic, described catalytic hydrogenation is carried out under the reaction temperature of 50～110 ℃, 0.3～1.0MPa reaction pressure condition.Preferable reaction temperature is 60～90 ℃, and preferred reaction pressure is 0.5～0.7MPa.Usually after extremely no longer inhaling hydrogen, reaction stops reaction.
Further, at N, in N '-dibenzyl-ethylenediamin synthetic, the consumption of described palladium activated-carbon catalyst is N, 0.25～2%, preferred 0.5～1.0% of N '-dibenzylidene ethylenediamine quality.
the described N of the concrete recommendation of the present invention, N '-dibenzylidene ethylenediamine catalytic hydrogenating reduction synthesizes N, the method of N '-dibenzyl-ethylenediamin is carried out in accordance with the following steps: add in autoclave through the present invention and process the palladium activated-carbon catalyst that makes, it adds quality is N, 0.25～2% of N '-dibenzylidene ethylenediamine quality, with raw material N, the mixing material of N '-dibenzylidene ethylenediamine and aliphatic alcohols organic solvent joins in autoclave, close autoclave, go out air in reactor with nitrogen replacement, then with hydrogen exchange nitrogen and to adjust reaction temperature be 60～90 ℃, reaction pressure is 0.5～0.7MPa, begin to stir, isothermal reaction is not until till inhaling hydrogen, stop reaction, take out the product liquid that described reaction obtains, filter out catalyst and remove excessive organic solvent and namely obtain N, N '-dibenzyl-ethylenediamin.
The present invention compared with prior art, beneficial effect of the present invention is:
(1) the present invention uses the sodium halide aqueous solution, and particularly sodium chloride is processed active carbon, and sodium-chloride water solution can recycle, and has overcome the shortcoming that common employing nitric acid pretreatment absorbent charcoal carrier produces a large amount of spent acid.Simultaneously, process active carbon with sodium-chloride water solution also very little on physical arrangement impacts such as the specific surface of active carbon and pore structures.Use sodium-chloride water solution to process active carbon, introduce anionic part or the group of inorganic agent self at activated carbon surface, therefore the kind of group is single, and can control exactly the quantity of the group of introducing on activated carbon surface by the concentration that changes sodium chloride solution.And use nitric acid pretreatment active carbon, to introduce polytype oxy radical at activated carbon surface, interact to regulate by oxy radical and palladium compound presoma the size of controlling the Metal Palladium particle size, use very difficult kind and the quantity that control exactly the activated carbon surface oxy radical of oxidisability wet treatment method such as nitric acid.Therefore, the present invention can introduce at activated carbon surface functional ion or the group that needs exactly, structure meets N, N '-dibenzylidene ethylenediamine catalytic hydrogenating reduction synthesizes N, the Metal Palladium decentralized environment that N '-dibenzyl-ethylenediamin catalystic converter system requires, the controlled activated carbon supported palladium catalyst of preparation active component particle size satisfies the requirement of this catalystic converter system.The palladium activated-carbon catalyst major part of the present invention even palladium grain diameter more than 75% is 2～5nm, the Metal Palladium active component is dispersed in carrier surface with uniform granule form, using rate of metal improves greatly, shows the activity that is better than other activated carbon supported palladium catalyst, selective and stable.
(2) the prepared palladium activated-carbon catalyst of the present invention is at N, and N '-dibenzylidene ethylenediamine catalytic hydrogenating reduction synthesizes N, and in the reaction of N '-dibenzyl-ethylenediamin, product selectivity is good, substantially more than 90%, has even obtained the product selectivity higher than 97%.
(3) the prepared palladium activated-carbon catalyst of the present invention is reusable more than 50 times, greatly reduces the catalyst use cost, has reduced pollution and energy consumption in catalyst recovery, regenerative process, has important economic worth and Significance for Environment.
(4) description of drawings
Figure 1A is the high power transmission electron microscope picture of the palladium activated-carbon catalyst that makes of embodiment 5;
Figure 1B is the particle diameter distribution map of the palladium activated-carbon catalyst that makes of embodiment 5.
(5) specific embodiment:
Below with specific embodiment, technical scheme of the present invention is described, but protection scope of the present invention is not limited to this:
Embodiment one
Take the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the NaCl solution that 120 ml concns are 0.5mol/l 2 hours, filter, with the deionized water washing to detecting without chlorion.Then the active carbon of processing is mixed with the 100ml slurries of temperature 60 C, slowly drip the H2PdCl4 solution (Pd content is 0.02g/ml) of 10 milliliters, stir 4h, again with 10% NaOH solution regulator solution pH value to alkalescent (pH=7.1), and cool the temperature to room temperature, filter, the deionized water washing is to neutral.Unreduced catalyst is configured to the slurries of 150ml under 30 ℃, then slowly drips 55% hydrazine hydrate solution of 2 milliliters, continue to stir 2 hours.Catalyst after reduction after filtration, deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 3.5nm.
Embodiment two
Take the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the NaCl solution that 120 ml concns are 1.0mol/l 2 hours, filter, with the deionized water washing to detecting without chlorion.Then the active carbon of processing is mixed with the 100ml slurries of temperature 70 C, slowly drips the H of 20 milliliters
2PdCl
4Solution (Pd content is 0.02g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cools the temperature to room temperature, filters, and the deionized water washing is to neutrality.Unreduced catalyst is configured to the slurries of 150ml under 30 ℃, then slowly drips 55% hydrazine hydrate solution of 2ml, continue to stir 2 hours.Catalyst after reduction after filtration, deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 3.0nm.
Embodiment three
Take the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the NaCl solution that 120 ml concns are 1.5mol/l 2 hours, filter, with the deionized water washing to detecting without chlorion.Then the active carbon of processing is mixed with the 100ml slurries of 80 ℃ of temperature, slowly drips the H of 20 milliliters
2PdCl
4Solution (Pd content is 0.02g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cools the temperature to room temperature, filters, and the deionized water washing is to neutrality.Unreduced catalyst is configured to the slurries of 150ml under 30 ℃, then slowly drips 55% hydrazine hydrate solution of 2ml, continue to stir 2 hours.Catalyst after reduction after filtration, deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 2.0nm.
Embodiment four
Take the 10g active carbon, the specific area of active carbon is 1400m
2/ g, active carbon are immersed in the NaCl solution that 120 ml concns are 2.0mol/l 2 hours, filter, with the deionized water washing to detecting without chlorion.Then the active carbon of processing is mixed with the 100ml slurries of 90 ℃ of temperature, slowly drips the H of 20 milliliters
2PdCl
4Solution (Pd content is 0.02g/ml) stirs 8h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cools the temperature to room temperature, filters, and the deionized water washing is to neutrality.Unreduced catalyst is configured to the slurries of 150ml under 30 ℃, then slowly drips 55% hydrazine hydrate solution of 2ml, continue to stir 2 hours, catalyst after reduction after filtration, deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 4.3nm.
Embodiment five
Take the 10g active carbon, the specific area of active carbon is 1500m
2/ g, active carbon are immersed in the NaCl solution that 120 ml concns are 2.5mol/l 2 hours, filter, and to detecting without chlorion, then the active carbon of processing are mixed with the 100ml slurries of 80 ℃ of temperature with the deionized water washing, slowly drip the H of 30 milliliters
2PdCl
4Solution (Pd content is 0.02g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cool the temperature to room temperature, filter, the deionized water washing is configured to unreduced catalyst the slurries of 150ml to neutral under 30 ℃, then slowly drip 55% hydrazine hydrate solution of 2ml, continue to stir 2 hours, the catalyst after reduction after filtration, the deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 5.0nm.
Embodiment six
Take the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the NaCl solution that 120 ml concns are 1.5mol/l 2 hours, filter, and to detecting without chlorion, then the active carbon of processing are mixed with the 100ml slurries of 80 ℃ of temperature with the deionized water washing, slowly drip the H of 20 milliliters
2PdCl
4Solution (Pd content is 0.02g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=9), and cool the temperature to room temperature, filter, the deionized water washing is configured to unreduced catalyst the slurries of 150ml to neutral under 30 ℃, then slowly drip 55% hydrazine hydrate solution of 2ml, continue to stir 2 hours, the catalyst after reduction after filtration, the deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 3.8nm.
Embodiment seven to embodiment 17 is used for N with the Pd/C catalyst that above-mentioned method for making makes, and N '-dibenzylidene ethylenediamine catalytic hydrogenating reduction synthesizes N, the example of N '-dibenzyl-ethylenediamin:
Embodiment seven
in the stainless steel autoclave, the Pd/C catalyst 0.125g that adds embodiment one preparation, N, N '-dibenzylidene ethylenediamine 50g, ethanol 50ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 50 ℃, reaction pressure is 0.3MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 91.2%.
Embodiment eight
in the stainless steel autoclave, the Pd/C catalyst 0.25g that adds embodiment two preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 100ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 60 ℃, reaction pressure is 0.4MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 94.0%.
Embodiment nine
in the stainless steel autoclave, the Pd/C catalyst 0.5g that adds embodiment three preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 150ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 70 ℃, reaction pressure is 0.6MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 97.0%.
Embodiment ten
in the stainless steel autoclave, the Pd/C catalyst 0.5g that adds embodiment four preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 200ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 90 ℃, reaction pressure is 0.8MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 91.5%.
Embodiment 11
in the stainless steel autoclave, the Pd/C catalyst 0.25g that adds embodiment five preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 100ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 70 ℃, reaction pressure is 0.6MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 94.7%.
Embodiment 12
in the stainless steel autoclave, the Pd/C catalyst 0.2g that adds embodiment six preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 100ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 70 ℃, reaction pressure is 0.6MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 95.3%.
Embodiment 13
in the stainless steel autoclave, the Pd/C catalyst 1g that adds embodiment three preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 100ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 70 ℃, reaction pressure is 0.6MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 95.6%.
Embodiment 14
in the stainless steel autoclave, the Pd/C catalyst 0.5g that adds embodiment three preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 100ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 110 ℃, reaction pressure is 0.6MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 89.8%.
Embodiment 15
in the stainless steel autoclave, the Pd/C catalyst 0.5g that adds embodiment three preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 100ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 70 ℃, reaction pressure is 1.0MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 96.1%.
Embodiment 16
in the stainless steel autoclave, the Pd/C catalyst 0.5g that adds embodiment three preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 100ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 70 ℃, reaction pressure is 0.6MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, N, the content of N '-dibenzyl-ethylenediamin is 94.4%.
Embodiment 17
In the stainless steel autoclave, the Pd/C catalyst 0.5g that adds embodiment three preparations, N, N '-dibenzylidene ethylenediamine 50g, ethanol 150ml, the off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in reactor, be warming up to 70 ℃, reaction pressure is 0.6MPa, begins to stir 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min, stop reaction, take out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and the content of each component is shown in Table 1.The amount of adding catalyst according to table 1 is subsequently applied mechanically experiment.
Table 1Pd/C catalyst is applied mechanically the experiment catalyst Catalytic Hydrogenation Properties
Claims (9)
1. the palladium activated-carbon catalyst is at synthetic N, and the application in N '-dibenzyl-ethylenediamin is characterized in that described being applied as: with N, N '-dibenzylidene ethylenediamine is raw material, under palladium activated-carbon catalyst and hydrogen effect, make described N by catalytic hydrogenation, N '-dibenzyl-ethylenediamin; Described palladium activated-carbon catalyst prepares by the following method: first with active carbon with sodium halide aqueous solution impregnation process, then filter, Washing of Filter Cake is to halogen ion-free, then the active carbon that will process floods H
2PdCl
4The aqueous solution, then regulator solution pH value to alkalescence, is filtered, and filter cake is washed to neutrality, and filter cake is reduced with reducing agent, namely gets the palladium activated-carbon catalyst after the neutral products drying that obtains; Described sodium halide solution is sodium chloride solution.
2. application as claimed in claim 1 is characterized in that described synthetic N, and the reaction of N '-dibenzyl-ethylenediamin is carried out in the aliphatic alcohols organic solvent.
3. application as claimed in claim 2 is characterized in that described catalytic hydrogenation carries out under the reaction temperature of 50～110 ℃, 0.3～1.0MPa reaction pressure condition.
4. application as described in one of claim 1 ~ 3, the consumption that it is characterized in that described palladium activated-carbon catalyst is N, 0.25 ~ 2% of N '-dibenzylidene ethylenediamine quality.
5. application as claimed in claim 1, the specific area that it is characterized in that described active carbon is 1300 ~ 1700m
2/ g.
6. application as described in claim 1 or 5, is characterized in that described H
2PdCl
4The addition of the aqueous solution is: be that 2 ~ 6wt% adds H by the palladium loading
2PdCl
4The aqueous solution.
7. application as claimed in claim 1, the concentration that it is characterized in that described sodium halide solution is 0.125-2.5mol/L; The volume that adds of described sodium halide solution is counted 2～20mL/g with quality of activated carbon.
8. application as claimed in claim 1 is characterized in that described regulator solution pH value to alkalescence is: regulator solution pH value to 7.1 ~ 9.
9. application as claimed in claim 1 is characterized in that described reducing agent is hydrazine hydrate solution.
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| CN104607182A (en) * | 2015-01-15 | 2015-05-13 | 安徽华业香料股份有限公司 | Preparation of nano-palladium catalyst as well as application of nano-palladium catalyst to synthesis of vanillin compounds |
| CN106466602B (en) * | 2015-08-17 | 2019-03-29 | 中国科学院金属研究所 | A kind of carbon-carried palladium catalyst and its preparation method and application |
| CN106732555B (en) * | 2016-11-25 | 2018-06-05 | 江西省汉氏贵金属有限公司 | The alpha-alkylization of ketone and alcohol reaction palladium carbon catalyst and preparation method thereof |
| CN106748813B (en) * | 2016-12-31 | 2019-05-28 | 浙江工业大学 | A kind of synthesis N, the method for N '-dibenzyl-ethylenediamin |
| CN108218718B (en) * | 2018-03-30 | 2020-12-29 | 浙江辰阳化工有限公司 | Method for efficiently preparing N, N-dibenzyl ethylenediamine through catalytic hydrogenation |
| CN109012716A (en) * | 2018-06-25 | 2018-12-18 | 浙江工业大学 | A kind of sulphur carbon ball supported precious metal catalyst and its preparation and the application in synthesis N, N '-dibenzyl-ethylenediamin |
| 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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| CN1817455A (en) * | 2006-03-21 | 2006-08-16 | 浙江工业大学 | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation |
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