CN102179245A - Palladium/active carbon catalyst and application thereof in synthesizing N,N'-dibenzylethylenediamine - Google Patents
Palladium/active carbon catalyst and application thereof in synthesizing N,N'-dibenzylethylenediamine Download PDFInfo
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- CN102179245A CN102179245A CN 201110057500 CN201110057500A CN102179245A CN 102179245 A CN102179245 A CN 102179245A CN 201110057500 CN201110057500 CN 201110057500 CN 201110057500 A CN201110057500 A CN 201110057500A CN 102179245 A CN102179245 A CN 102179245A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 144
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 56
- 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 51
- 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 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 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 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 52
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- 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
- 230000008569 process Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 150000002500 ions Chemical class 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
- 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
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 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 36
- 229910052757 nitrogen Inorganic materials 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 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
- 238000005516 engineering process Methods 0.000 description 7
- 241000370738 Chlorion Species 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 229960002668 sodium chloride Drugs 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 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
- 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
- 238000007598 dipping method 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
- 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
Images
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, be a kind of medicine intermediate of important high added value, hundreds of millions of especially with its synthetic antibiotic medicine output value.
At present, domestic basic still the employing with benzyl chloride and ethylenediamine of DBED synthetic method is the organic synthesis method of raw material.This route has advantages such as technology is simple, flow process is short, investment is little, is comparatively ripe at present, more a kind of synthesis technique of application.But this synthesis technique product yield low (only being about 30%), poor product quality, environmental pollution big (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 has obtained using widely in chemical industry because of having advantages such as operating environment gentleness, good product quality, reaction selectivity height, pollution-free and post processing are easy, is a kind of synthetic technology of cleaning of maturation.Adopt the catalytic reduction technology by N, N '-dibenzylidene ethylenediamine synthesizes N, N '-dibenzyl-ethylenediamin, and further salify is green, the high efficient technology of synthetic DBED again.
Catalyst be catalytic reduction technology 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 accessory substances such as monobenzyl ethylenediamine, avoids reaction selectivity to descend and catalysqt deactivation, reduces production costs thereby improve reaction yield.Adopt the load type metal catalyst of conventional method preparation can't regulate and control the form of metallic particles effectively at 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 takes place and does not bring into play its due catalytic performance in the metallic particles of considerable part, make using rate of metal low, restricting activity, selectivity and the stability of load type metal catalyst.
(3) summary of the invention
First technical problem that the present invention will solve provides a kind of palladium activated-carbon catalyst of controlled dimensions, most palladium grain diameter is 2～5nm in this catalyst, use it for N, N '-dibenzylidene ethylenediamine catalytic hydrogenating reduction synthesizes N, N '-dibenzyl-ethylenediamin, catalyst activity, selectivity and stability are all higher; And this Preparation of Catalyst is simple, environmental friendliness, and precious metal palladium reclaims easily, 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: earlier active carbon is used sodium halide aqueous solution impregnation process, filtration then, filter cake washing are to halogen-free ion, again processed active carbon is flooded the H2PdCl4 aqueous solution, regulator solution pH value is filtered to alkalescence then, and filter cake is washed to neutrality, filter cake is reduced with reducing agent, promptly 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 adding volume 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 that 2～6wt% adds H preferably by palladium loading (being the mass percent of palladium/active carbon in the palladium activated-carbon catalyst)
2PdCl
4The aqueous solution.Describedly " processed active carbon is flooded H
2PdCl
4The aqueous solution ", preferred 60～90 ℃ of dipping temperature, specifically can carry out according to following steps: earlier processed active carbon being made into the slurries of 60～90 ℃ of temperature, is that 2～6wt% slowly drips H by the palladium loading
2PdCl
4Solution dropwises the back and stirred 2～10 hours.
Further, processed active carbon is being flooded H
2PdCl
4Behind 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 the 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 a raw material, under palladium activated-carbon catalyst and hydrogen effect, make described N by catalytic hydrogenation, N '-dibenzyl-ethylenediamin.
Further, described synthetic N, being reflected in the aliphatic alcohols organic solvent of N '-dibenzyl-ethylenediamin carried out, 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 50～110 ℃ reaction temperature, 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 according to following steps: add through the present invention in autoclave and handle 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 the autoclave, close autoclave, go out air in the 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 stops reaction till not inhaling hydrogen, take out the product liquid that described reaction obtains, filter out catalyst and remove excessive organic solvent and promptly 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 handled 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, it is also very little to physical arrangement influences such as the specific surface of active carbon and pore structures to handle active carbon with sodium-chloride water solution.Use sodium-chloride water solution to handle active carbon, introduce the anionic part or the group of inorganic agent self at activated carbon surface, therefore the kind of group is single, and can control the quantity of the group of introducing on the activated carbon surface exactly by the concentration that changes sodium chloride solution.And use nitric acid pretreatment active carbon, be to introduce polytype oxy radical at activated carbon surface, interact by oxy radical and palladium compound presoma and to regulate the size of control Metal Palladium particle size, use oxidisability wet treatment method such as nitric acid to be difficult to control exactly the kind and the quantity of activated carbon surface oxy radical.Therefore, the present invention can introduce functional ion or the group that needs at activated carbon surface 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.Palladium activated-carbon catalyst major part of the present invention even 75% above palladium grain diameter are 2～5nm, the Metal Palladium active component is dispersed in carrier surface with uniform granule form, using rate of metal improves greatly, shows to be better than other active carbon-supported palladium activity of such catalysts, selectivity and stability.
(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%, even has obtained to be higher than 97% product selectivity.
(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, the regenerative process, has important economic value and Significance for Environment.
(4) description of drawings
The high power transmission electron microscope picture of the palladium activated-carbon catalyst that Figure 1A makes for embodiment 5;
The particle diameter distribution map of the palladium activated-carbon catalyst that Figure 1B makes for 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 thereto:
Embodiment one
Take by weighing 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, and spend deionised water and do not detect to there being chlorion.Then the active carbon of handling is mixed with the 100ml slurries of 60 ℃ of temperature, slowly drip 10 milliliters H2PdCl4 solution (Pd content is 0.02g/ml), 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 ℃, slowly drips 2 milliliters 55% hydrazine hydrate solution then, continue to stir 2 hours.Catalyst after the 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 by weighing 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, and spend deionised water and do not detect to there being chlorion.Then the active carbon of handling is mixed with the 100ml slurries of 70 ℃ of temperature, slowly drips 20 milliliters H
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 ℃, slowly drips 55% hydrazine hydrate solution of 2ml then, continue to stir 2 hours.Catalyst after the 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 by weighing 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 spend deionised water and do not detect to there being chlorion.Then the active carbon of handling is mixed with the 100ml slurries of 80 ℃ of temperature, slowly drips 20 milliliters H
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 ℃, slowly drips 55% hydrazine hydrate solution of 2ml then, continue to stir 2 hours.Catalyst after the 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 by weighing 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, and spend deionised water and do not detect to there being chlorion.Then the active carbon of handling is mixed with the 100ml slurries of 90 ℃ of temperature, slowly drips 20 milliliters H
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 ℃, slowly drips 55% hydrazine hydrate solution of 2ml then, continue to stir 2 hours, catalyst after the 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 by weighing 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 spend deionised water and do not detect to there being chlorion, then the active carbon of handling are mixed with the 100ml slurries of 80 ℃ of temperature, slowly drip 30 milliliters H
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 ℃, slowly drip 55% hydrazine hydrate solution of 2ml then, continue to stir 2 hours, the catalyst after the 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 by weighing 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 spend deionised water and do not detect to there being chlorion, then the active carbon of handling are mixed with the 100ml slurries of 80 ℃ of temperature, slowly drip 20 milliliters H
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 ℃, slowly drip 55% hydrazine hydrate solution of 2ml then, continue to stir 2 hours, the catalyst after the 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, 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 the reactor, be warming up to 50 ℃, reaction pressure is 0.3MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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, 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 the reactor, be warming up to 60 ℃, reaction pressure is 0.4MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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, 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 the 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 stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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, 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 the reactor, be warming up to 90 ℃, reaction pressure is 0.8MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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, 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 the 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 stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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, 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 the 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 stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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, 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 the 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 stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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, 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 the reactor, be warming up to 110 ℃, reaction pressure is 0.6MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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, 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 the reactor, be warming up to 70 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 90min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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, 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 the 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 stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas chromatographic analysis, and N, the content of N '-dibenzyl-ethylenediamin are 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 the 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 each components contents is shown in Table 1.The amount of adding catalyst according to table 1 is applied mechanically experiment subsequently.
Table 1Pd/C catalyst is applied mechanically the experiment catalyst Catalytic Hydrogenation Properties
Claims (10)
1. palladium activated-carbon catalyst is characterized in that described palladium activated-carbon catalyst prepares by the following method: earlier with active carbon with sodium halide aqueous solution impregnation process, filter then, the filter cake washing is to halogen-free ion, again processed active carbon flooded H
2PdCl
4The aqueous solution, regulator solution pH value is filtered to alkalescence then, and filter cake is washed to neutrality, and filter cake is reduced with reducing agent, promptly gets the palladium activated-carbon catalyst after the neutral products drying that obtains.
2. palladium activated-carbon catalyst as claimed in claim 1, the specific area that it is characterized in that described active carbon is 1300～1700m
2/ g.
3. palladium activated-carbon catalyst as claimed in claim 1 or 2 is characterized in that described H
2PdCl
4The addition of the aqueous solution is: by the palladium loading is that 2～6wt% adds H
2PdCl
4The aqueous solution.
4. palladium activated-carbon catalyst as claimed in claim 1 is characterized in that described sodium halide solution is sodium chloride solution, and concentration is 0.125-2.5mol/l; The adding volume of described sodium halide solution is counted 2～20ml/g with quality of activated carbon.
5. palladium activated-carbon catalyst 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.
6. palladium activated-carbon catalyst as claimed in claim 1 is characterized in that described reducing agent is a hydrazine hydrate solution.
7. palladium activated-carbon catalyst as claimed in claim 1 is at synthetic N, application in N '-dibenzyl-ethylenediamin, it is characterized in that described being applied as: with N, N '-dibenzylidene ethylenediamine is a raw material, under palladium activated-carbon catalyst and hydrogen effect, make described N by catalytic hydrogenation, N '-dibenzyl-ethylenediamin.
8. application as claimed in claim 7 is characterized in that described synthetic N, and being reflected in the aliphatic alcohols organic solvent of N '-dibenzyl-ethylenediamin carried out.
9. application as claimed in claim 8 is characterized in that described catalytic hydrogenation carries out under 50～110 ℃ reaction temperature, 0.3～1.0MPa reaction pressure condition.
10. as the described application of one of claim 7～9, the consumption that it is characterized in that described palladium activated-carbon catalyst is N, 0.25～2% of N '-dibenzylidene ethylenediamine quality.
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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 |
| CN106466602A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院金属研究所 | A kind of carbon-carried palladium catalyst and its preparation method and application |
| CN106732555A (en) * | 2016-11-25 | 2017-05-31 | 江西省汉氏贵金属有限公司 | α alkylated reaction palladium carbon catalysts of ketone and alcohol and preparation method thereof |
| CN106748813A (en) * | 2016-12-31 | 2017-05-31 | 浙江工业大学 | One kind synthesis N, the method for N dibenzyl-ethylenediamins |
| 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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| CN106466602A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院金属研究所 | A kind of carbon-carried palladium catalyst and its preparation method and application |
| 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 |
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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 |
| 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 |
| 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 |
| 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 |
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