CN102233272A - Catalyst for preparing ethylene diamine through amination of ethylene glycol and preparation method thereof - Google Patents
Catalyst for preparing ethylene diamine through amination of ethylene glycol and preparation method thereof Download PDFInfo
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- CN102233272A CN102233272A CN2010101522227A CN201010152222A CN102233272A CN 102233272 A CN102233272 A CN 102233272A CN 2010101522227 A CN2010101522227 A CN 2010101522227A CN 201010152222 A CN201010152222 A CN 201010152222A CN 102233272 A CN102233272 A CN 102233272A
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Abstract
The invention provides a solid catalyst for preparing ethylene diamine through catalytic amination of ethylene glycol. The catalyst takes copper and nickel as main components and zirconium as an auxiliary component; and other metal components can be one or more than one of zinc, aluminum, titanium, manganese and cerium. The invention further provides a preparation method of the solid catalyst. The preparation method is characterized in that the catalyst is prepared through the processes of roasting, reducing and re-roasting by utilizing a coprecipitation method.
Description
Technical field
The present invention relates to a kind of is the catalyst of key component with the copper and mickel, the reaction that this catalyst ethylene glycol and ammonia hydrogenating amination prepare ethylenediamine.Reaction equation is as follows:
HOCH
2CH
2OH+2NH
3--＞NH
2CH
2CH
2NH
2+2H
2O
The method for preparing catalyst that the present invention relates to is the coprecipitation of improvement, and method of the present invention is improved to roasting, reduction, roasting again with the roasting process in the coprecipitation.
Technical background
Ethylenediamine is important basic chemical industry raw material, as solvent, stabilizing agent, chelating agent, synthetic resin, medicine, inhibitor.In recent years, heighten along with being used for non-phosphate detergent TEAD (tetraacetyl ethylene diamine) demand, ethylenediamine is as the corresponding increase of raw materials requirement amount of TEAD.
The method for preparing ethylenediamine and other ethylene amines has been described in the document.
Before ethylene glycol or the monoethanolamine hydrogenating amination technology, generally adopt dichloroethanes and ammonia prepared in reaction ethylenediamine under alkali condition.
According to PEP Report No.138, " alkylamine ", SRI International, in March, 1981, especially the 7th, 8,13～16,43～107,113,117 page, dichloroethanes and ammonia generate ethylenediamine with mol ratio reaction in 1: 15, and productive rate surpasses 20%.
The shortcoming of this method is to use a large amount of bronsted lowry acids and bases bronsted lowries in the production process, and the by-product chloride damages environment.
Technology by monoethanolamine and ammonia hydrogenating amination system ethylenediamine is the main technique of producing ethylenediamine at present.
There is active not high shortcoming in the catalyst that Girbotal process uses based on hydrogen type molecular sieve.USP4918233 discloses monoethanolamine and ammonia is the catalyst of raw material synthesis of ethylenediamine.Catalyst is a hydrogen type molecular sieve, 300～340 ℃ of reaction temperatures, and monoethanolamine liquid air speed is 0.15h
-1, conversion ratio is 54%, the selectivity 56% of ethylenediamine, and the yield of ethylenediamine is up to 30%.
Patent 200610167715.1 discloses a kind of improved hydrogen type molecular sieve as catalyst, on forming, outside the hydrogen type molecular sieve, add aluminium oxide and/or metal ion Sb, Zn, Nb, Zr, Mo, the conversion ratio of monoethanolamine reaches 68%, and the yield of ethylenediamine reaches 44.1%.
Monoethanolamine is made by oxirane and ammonia react, and oxirane is made by ethene and oxygen reaction, and its primary raw material is from oil.And ethylene glycol can make oxalate by the methyl alcohol carbonylation, and repeated hydrogenation makes, and its primary raw material is from coal.
In recent years, ethylene glycol is directly made ethylenediamine becomes a kind of more excellent technology.
A kind of method of being produced ethylene amines and monoethanolamine by ethylene glycol is disclosed in the patent 2007800005568.0 of BASF European Co.,Ltd's application.Use two-stage reaction technology, first section can be used all known catalyst, and second section use is main catalyst by ruthenium and cobalt, pressure 200bar, 150～170 ℃ of temperature, the conversion ratio 46% of ethylene glycol.
Use the reaction of catalysis of solid catalyst ethylene glycol system ethylenediamine, two hydroxyls are by two amino replacements.Each hydroxyl is all experienced hydroxyl by the amino replacement and is dehydrogenated to aldehyde, and ammonium aldehyde addition dehydration is imines, and imines is hydrogenated to the amine three-step reaction.
Wherein dehydrogenation and be hydrogenated to the committed step of this reaction.
The good catalyst of alcohol dehydrogenase is a copper-based catalysts, and there are two problems in copper-based catalysts in this dehydrogenation reaction, and a problem is ammonia poisoning, and another problem is thermo-responsive, and this reaction is exothermic reaction, under the high temperature, and the easy sintering of copper-based catalysts and inactivation.And other metals can solve the problems referred to above of copper-based catalysts as auxiliary element or auxiliary agent.
The good catalyst of hydrogenation is a nickel-base catalyst.
In catalyst, add other metal components,, can make two kinds of main active component collaborative works well of copper and mickel, finish dehydrogenation, two committed steps of hydrogenation as aluminium, manganese, zinc, titanium, cerium.
This patent uses with copper and mickel and is key component, and zirconium is the catalyst of helper component, and ethylene glycol and ammonia prepare ethylenediamine through single step reaction, do not use noble metal.As auxiliary agent, increased the stability of copper catalyst with aluminium, manganese, zinc, titanium, cerium.
Prepare this catalyst with coprecipitation.Usually, the solid catalyst of coprecipitation preparation, through the reactor of packing into after precipitation, ageing, washing, drying, the roasting, use the reduction back.This patent finds, after the roasting for the first time, and experience reduction, the process of roasting again, activity of such catalysts improves more than 20%, and stability is better reacted after 1000 hours, and catalyst activity is not less than 90% of fresh catalyst.
Summary of the invention
A kind of solid catalyst of catalysis ethylene glycol ammonification system ethylenediamine, this catalyst is key component with the copper and mickel, and zirconium is a helper component, and other metal components can be in zinc, aluminium, titanium, manganese, the cerium one or more.To account for the percentage composition of all metals be 5～40% to copper in the catalyst, and nickel accounts for 5～30%, and zirconium accounts for 10～30%, and zinc accounts for 0～20%, and aluminium accounts for 0～20%, and titanium accounts for 0～20%, and manganese accounts for 0～20%, and cerium accounts for 0～20%.
Another object of the present invention is this Preparation of catalysts method, uses coprecipitation to prepare this catalyst, and its difference is, catalyst is through bakes to burn the article, reduction, the process of roasting again.
For the first time after the roasting, experience reduction, the process of roasting again, activity of such catalysts improves more than 20%, and stability is better reacted after 1000 hours, and catalyst activity is not less than 90% of fresh catalyst.
The Preparation of catalysts method is not limited to once reduce, the step of roasting again.In order to pursue better catalyst activity and stability, the roasting of catalyst experience, reduction, again after the roasting, can experience the process of reduction, roasting for the third time for the second time again, the catalyst performance that obtains can be better, but effect can along with reduction, again the roasting process number of times increase and weaken.
Description of drawings
The specific embodiment
This patent uses with copper and mickel and is key component, and zirconium is the catalyst of helper component, and ethylene glycol and ammonia prepare ethylenediamine through single step reaction, do not use noble metal.As auxiliary agent, increased the stability of copper catalyst with aluminium, manganese, zinc, titanium, cerium.
The reaction of catalyst ethylene glycol system ethylenediamine, two hydroxyls are by two amino replacements.Each hydroxyl is all experienced hydroxyl by the amino replacement and is dehydrogenated to aldehyde, and ammonium aldehyde addition dehydration is imines, and imines is hydrogenated to the amine three-step reaction, and is as follows:
R-CH
2OH--＞R-CHO+H
2
R-CHO+NH
3--＞R-CH＝NH+H
2O
R-CH＝NH+H
2--＞R-CH
2NH
2
R is HO-CH
2Or NH
2-CH
2
Wherein dehydrogenation and be hydrogenated to the committed step of this reaction.
The good catalyst of alcohol dehydrogenase is a copper-based catalysts, and there are two problems in copper-based catalysts in this dehydrogenation reaction, and a problem is ammonia poisoning, and another problem is thermo-responsive, and this reaction is exothermic reaction, under the high temperature, and the easy sintering of copper-based catalysts and inactivation.And other metals can solve the problems referred to above of copper-based catalysts as auxiliary agent.
The good catalyst of hydrogenation is a nickel-base catalyst.
In catalyst, add other components,, can make two kinds of main active component collaborative works well of copper and mickel, finish dehydrogenation, two committed steps of hydrogenation as aluminium, manganese, zinc, titanium, cerium.To account for the percentage composition of all metals be 5～40% to copper in the catalyst, and nickel accounts for 5～30%, and zirconium accounts for 10～30%, and zinc accounts for 0～20%, and aluminium accounts for 0～20%, and titanium accounts for 0～20%, and manganese accounts for 0～20%, and cerium accounts for 0～20%.
Prepare this catalyst with coprecipitation.Usually, the solid catalyst of coprecipitation preparation, through the reactor of packing into after precipitation, ageing, washing, drying, the roasting, use the reduction back.This patent finds, after the roasting for the first time, and experience reduction, the process of roasting again, activity of such catalysts improves more than 20%, and stability is better reacted after 1000 hours, and catalyst activity is not less than 90% of fresh catalyst.
The Preparation of catalysts method is not limited to once reduce, the step of roasting again.In order to pursue better catalyst activity and stability, the roasting of catalyst experience, reduction, again after the roasting, can experience the process of reduction, roasting for the third time for the second time again, the catalyst performance that obtains can be better, but effect can along with reduction, again the roasting process number of times increase and weaken.
The effect of reduction, roasting again is that each metal component in the catalyst is better disperseed, and forms specific crystal formation, and this crystal formation makes each metal component better act synergistically, to realize the better activity and the stability of catalyst.
The Preparation of catalysts method is as follows:
Dispose the salpeter solution of other metals of zirconyl chloride solution, 0.5～1 mol of the copper nitrate of 0.5～1 mol and nickel nitrate solution, 0.5～1 mol respectively, composition according to the target catalyst mixes, 80 ℃ of temperature, under the stirring of 2000 rev/mins of rotating speeds, drip the NaOH or the sodium carbonate liquor of 0.5～1 mol, generate precipitation, the PH of control terminal point is 9～11.Ageing 0.5～1 hour spends deionised water and is precipitated to electrical conductivity below 100 μ s/cm.Under 120 ℃ of conditions, toasted 5 hours, 500 ℃ of following roastings 12 hours, after the pulverizing, make the cylindrical particle catalyst of diameter 5mm, high 5mm with tablet press machine.Catalyst after the moulding is with containing H
25～15% hydrogen nitrogen mixture body reduces to catalyst, and the reduction temperature interval is 150～220 ℃, 10 hours recovery times.Catalyst air or oxygen after the reduction being lower than under 500 ℃ the temperature, carries out roasting again under 300 ℃, roasting 24 hours becomes operable catalyst after the cooling.
Again the temperature of roasting than the first time sintering temperature low, generally low 100～250 ℃, to realize the active and stable of catalyst the best.
Embodiment
Embodiment all adopts following catalyst activity evaluation method.
A long 3m, internal diameter is that the stainless steel tube of 32mm is as reactor, loading catalyst 2.8kg, one cover robot control system(RCS) realizes the control for reaction raw materials charging, charge proportion, reaction temperature, reaction pressure, raw material from enter reactor, from the reactor lower part discharging, after the reaction through-70 ℃ of coolings, collect liquid, carry out component analysis, calculate the conversion ratio of ethylene glycol and the selectivity of ethylenediamine with gas-chromatography.
Reaction condition is as follows:
240 ℃ of reaction temperatures, pressure 3.0Mpa, the material charging rate be 0.5g ethylene glycol/g catalyst per hour, the inlet amount of ammonia is 4 times of ethylene glycol molal quantity, uses the assist gas of hydrogen as reaction, keeps reaction pressure 3.0Mpa.
Embodiment 1
Metal component is a copper 40%, nickel 30%, and the catalyst of zirconium 30%, with the coprecipitation preparation, only 500 ℃ of calcinings 12 hours, the result of activity rating was ethylene glycol conversion ratio 46%, the selectivity 52% of ethylenediamine.Through hydrogeneous 10% hydrogen, the reduction of nitrogen mixture body, and roasting 24 hours again under 300 ℃, ethylene glycol conversion ratio 66%, the selectivity 73% of ethylenediamine.
Embodiment 2
Metal component is a copper 30%, nickel 20%, and zirconium 15%, cerium 20%, the catalyst of manganese 15%, with the coprecipitation preparation, only 500 ℃ of calcinings 12 hours, the result of activity rating was ethylene glycol conversion ratio 55%, the selectivity 61% of ethylenediamine.Through hydrogeneous 10% hydrogen, the reduction of nitrogen mixture body, and roasting 24 hours again under 300 ℃, ethylene glycol conversion ratio 68%, the selectivity 78% of ethylenediamine.
Embodiment 3
Metal component is a copper 40%, nickel 20%, and zirconium 10%, titanium 10%, the catalyst of manganese 20%, with the coprecipitation preparation, only 500 ℃ of calcinings 12 hours, the result of activity rating was ethylene glycol conversion ratio 58%, the selectivity 45% of ethylenediamine.Through hydrogeneous 10% hydrogen, the reduction of nitrogen mixture body, and roasting 24 hours again under 300 ℃, ethylene glycol conversion ratio 62%, the selectivity 58% of ethylenediamine.
Embodiment 4
Metal component is a copper 20%, nickel 30%, and zirconium 30%, zinc 10%, the catalyst of aluminium 10%, with the coprecipitation preparation, only 500 ℃ of calcinings 12 hours, the result of activity rating was ethylene glycol conversion ratio 38%, the selectivity 76% of ethylenediamine.Through hydrogeneous 10% hydrogen, the reduction of nitrogen mixture body, and roasting 24 hours again under 400 ℃, ethylene glycol conversion ratio 50%, the selectivity 77% of ethylenediamine.
Embodiment 5
Metal component is a copper 40%, nickel 5%, and zirconium 30%, zinc 5%, the catalyst of cerium 20%, with the coprecipitation preparation, only 500 ℃ of calcinings 12 hours, the result of activity rating was ethylene glycol conversion ratio 88%, the selectivity 23% of ethylenediamine.Through hydrogeneous 10% hydrogen, the reduction of nitrogen mixture body, and roasting 24 hours again under 350 ℃, ethylene glycol conversion ratio 90%, the selectivity 49% of ethylenediamine.
Embodiment 6
Metal component is a copper 5%, nickel 30%, and zirconium 15%, zinc 20%, the catalyst of aluminium 20%, cerium 10%, with the coprecipitation preparation, only 500 ℃ of calcinings 12 hours, the result of activity rating was ethylene glycol conversion ratio 18%, the selectivity 80% of ethylenediamine.Through hydrogeneous 10% hydrogen, the reduction of nitrogen mixture body, and roasting 24 hours again under 400 ℃, ethylene glycol conversion ratio 22%, the selectivity 81% of ethylenediamine.Reduce for the second time through hydrogeneous 10% hydrogen, nitrogen mixture body, and roasting for the third time 12 hours under 300 ℃, ethylene glycol conversion ratio 23%, the selectivity 81% of ethylenediamine.
Claims (5)
1. the solid catalyst of a catalysis ethylene glycol ammonification system ethylenediamine, this catalyst is key component with the copper and mickel, and zirconium is a helper component, and other metal components can be in zinc, aluminium, titanium, manganese, the cerium one or more.
2. according to the catalyst of claim 1, to account for the percentage composition of all metals be 5～40% to copper in the described catalyst, and nickel accounts for 5～30%, and zirconium accounts for 10～30%.
3. according to the catalyst of claim 1, zinc accounts for 0～20% in the described catalyst, and aluminium accounts for 0～20%, and titanium accounts for 0～20%, and manganese accounts for 0～20%, and cerium accounts for 0～20%.
4. a coprecipitation prepares the method for above-mentioned catalyst, it is characterized in that, experiences roasting, reduction, the process of roasting again after the catalyst drying.
5. according to the method for claim 4, it is characterized in that the temperature of roasting is lower than the temperature of roasting for the first time again.
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Application publication date: 20111109 |