CN1018451B - Method of producing aziridines - Google Patents
Method of producing aziridinesInfo
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- CN1018451B CN1018451B CN88103932A CN88103932A CN1018451B CN 1018451 B CN1018451 B CN 1018451B CN 88103932 A CN88103932 A CN 88103932A CN 88103932 A CN88103932 A CN 88103932A CN 1018451 B CN1018451 B CN 1018451B
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- aziridine
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Abstract
A process for producing an aziridine compound represented by general formula (II), wherein R, X, Y are defined in the description, in the presence of a catalyst in the vapor phase conducting intramolecularly dehydrating to form a reaction product containing the aziridine compound, and recovering the aziridine compound in the presence of an amine compound.
Description
The present invention relates to a kind of method of producing aziridine cpd, this method is included in the vapour phase condition and in the presence of a kind of catalyzer the alkanolamine of following logical formula I representative is carried out intramolecular dehydration, and reclaims the aziridine of the logical formula II of gained in the presence of a kind of amine compound from the reaction product that contains this aziridine.
R represents H in above-mentioned reactions steps, and methyl or ethyl, X are OH or NH
2, and Y is NH when X is OH
2, when X is NH
2The time Y be OH.
Aziridine is a kind of 3 Yuans cyclic cpdss with very gross distortion, and it has the reactivity of ring-opening reaction and amine simultaneously, and can be used as the intermediate of all cpds.Particularly aziridine is as the raw material of agricultural chemicals and medicine, and as the amine type polymkeric substance of yarn fabric treatment agent in industrial widespread use.
A kind of method of known production aziridine cpd is the method for typically producing aziridine, and this method is included in the liquid phase and handles monoethanolamine vitriol with concentrated alkali solution, and this method is already in industrial application.Yet, a lot of shortcomings are arranged in industrial this method.For example, need to use a large amount of sulphur bronsted lowry acids and bases bronsted lowries as auxiliary material, so productivity is low.In addition, generate the low inorganic salt byproduct of utility value.
Produce the shortcoming of aziridine in order to overcome this liquid phase, reported recently various in the vapour phase condition in the presence of catalyzer, need not use auxiliary material, method by alkanolamine molecule inner dewatering reaction direct production aziridine cpd (is seen U.S. Patent number 4301036,4289656,4337175 and 4477591 and European publication 227461,228898 and 230776).Yet these existing trials mainly are at the catalyzer at the molecule inner dewatering reaction of vapour phase, but do not propose a kind of commercial run that obtains required aziridine from the gaseous reaction product mixture.
Producing the process of aziridine cpd from alkanolamine by vapour phase processes, reaction product gas contains various by products, for example has the carbonyl compound of following logical formula III
The wherein as above definition of logical formula I of R, this compound is corresponding to raw material alkanolamine and various amine.If the raw material alkanolamine is monoethanolamine, monoisopropanolamine or 2-amino-1-butanols, the carbonyl compound of logical formula III is respectively acetaldehyde, acetone or methylethylketone accordingly.For example U.S. Patent number 4337175 and 4477591 is described, and during from monoethanolamine production aziridine, acetaldehyde is main byproduct, and also generates the byproduct of mono aminoethane and pyrazine class.Europe publication 227461,228898 and 230776 has also been described carbonyl compound and the various amine that main byproduct is logical formula III.
Industrial when producing organic compound by vapour phase processes, general embodiment be from the vapour-phase reaction product, reclaim required product and with its purification so that obtain the finished product.Yet industrial have following problem by vapour phase processes from alkanolamine production aziridine cpd.At first, the aziridine cpd of logical formula II generally has lower boiling and very high vapour pressure.And their reactive behavior of tool is very strong, is easy to carry out polymerization and other reactions.In addition, as the above-mentioned by product that vapour phase processes generated in, carbonyl compound tends to and the reaction of desired aziridine, generates adducts.Thereby the productive rate of desired aziridine descends.Therefore when producing aziridines compound, these problems must be properly settled with vapour phase processes.
The method that the purpose of this invention is to provide a kind of alkanolamine vapor phase production aziridine can reclaim aziridine cpd effectively from the vapour-phase reaction product.
The inventor once made extensive studies reaching this purpose, and find in the presence of a kind of amine compound, can very carry out effectively recycling step with (or) distilation steps.
Therefore, according to the invention provides the method for a kind of production by the aziridine cpd of following general formula representative,
（Ⅱ）
Wherein R represents hydrogen, or methyl or ethyl,
This method comprises a kind of alkanolamine with following general formula representative:
Wherein R such as above-mentioned definition, X is OH or NH
2, and
Y is NH when X is OH
2, when X is NH
2The time Y be OH, carry out intramolecular dehydration in the vapour phase condition with in the presence of a kind of catalyzer with reactions steps (A), contain the reaction product of this aziridine cpd with generation, and with this reaction product through any one treatment step of following (1) to (3),
(1) reaction product is delivered to recycling step (B), and in the presence of a kind of amine compound, reclaimed aziridine cpd, or
(2) reaction product is delivered to distilation steps (C), and in the presence of a kind of amine compound, distilled aziridine cpd, or
(3) reactant is delivered to recycling step (B), and in the presence of a kind of amine compound, is reclaimed aziridine cpd, again the aziridine cpd that reclaims is delivered to distilation steps (C), and in the presence of a kind of amine compound with its distillation.
In the presence of a kind of catalyzer, the alkanolamine that will lead to formula I in the vapour phase condition carries out the reactions steps (A) of intramolecular dehydration, existing describe and these are described similar method and also can be applicable among the present invention in the above-mentioned patent document of quoting.For example, alkanolamine is passed through catalyst layer.If when needing, available a kind of rare gas element such as nitrogen are diluted to suitable concentration with alkanolamine, or in order to suppress side reaction, can be with ammonia, water vapor, hydrogen etc. are added in the unstripped gas.Another way, also available ammonia replaces all rare gas elementes.Working pressure is normal pressure or decompression or pressurized conditions.Temperature of reaction is usually 300 to 500 ℃ of scopes.The space velocity of unstripped gas depends on the type of unstripped gas and the type of concentration and catalyzer etc., generally at 50 to 5000/ hours.Catalyst system therefor can be those catalyzer that above-mentioned citing document is mentioned.And with the catalyzer of the siliceous or phosphorus in European publication numbers 227461,228898 and 230776, mentioned for preferred.
Feature of the present invention is with in the step process of the formed reaction product of reactions steps (A) by above-mentioned (1), (2) or (3), to obtain aziridine cpd.When the present invention is characterized in from the reaction product that reactions steps (A) forms, to obtain aziridine cpd, recycling step (B) and (or) distilation steps (C) is to carry out in the presence of a kind of amine compound.Amine compound can suppress aziridine recycling step (B) and (or) polyreaction of distilation steps (C), and make it can stable existence.The carbonyl compound by product that problem is in reaction product and is contained can react with aziridine cpd, and recycling step (B) and (or) form adducts in the distilation steps (C).Yet when amine compound existed, the carbonyl compound by product was and this amine compound reaction, forms a kind of stable adducts, and can not react with aziridine cpd.This amine compound has produced following effect as a result:
(1) prevents that the aziridine cpd productive rate from descending.
(2), and can prevent that the aziridine cpd quality from reducing owing to the carbonyl compound with by-product contains.
(3) prevent that aziridine cpd stability from reducing.
In the present invention, there is the various kinds of amine compound can be used as foregoing amine compound.The primary amine compounds is effective especially because they can be immediately with reaction product in the reaction of by product carbonyl compound, generate stable Schiff bases.Secondary-amine compound is also effective, because their energy and carbonyl compound reaction generate stable adducts.The object lesson of amine compound comprises the alkanol primary amine with 2 to 6 carbon atoms, as monoethanolamine and monoisopropanolamine; Aliphatic primary amine with 2 to 8 carbon atoms is as ethamine and quadrol; Has the primary aromatic amine of seldom crossing 8 carbon atoms, as aniline; And have the alkanol secondary amine that is no more than 8 carbon atoms, as diethanolamine and diisopropanolamine (DIPA).Preferably the alkanolamine of this amine compound and raw material is identical, because it can together reclaim with unreacted raw material and circulate, makes process fairly simple like this.If with other amine compound, need to reclaim and re-use amine compound, must reclaim and re-use unreacted raw material independently like this.Make process complicated like this, and this amine compound might be used as impurity and comprise in the product.
(1) set by step will deliver to recycling step (B) in the reaction product that reactions steps (A) obtains, and reclaim the aziridine cpd of general formula (II) in the presence of this amine compound.If the reaction product that obtains from reactions steps (A), the amount of unreacted alkanol amine also enough works as this amine compound, then can be on demand simply with the reaction product condensation and with it recovery, thus finish recycling step (B).On the other hand, if the quantity not sufficient of unreacted alkanolamine itself is to play the time spent of doing of this amine compound, then will deliver to retrieving arrangement, and in the presence of the amine of q.s, will lead to the aziridine cpd recovery of formula II from the reaction product that reactions steps (A) obtains.Under latter event, way is to use an absorption tower easily, and by common mode amine compound is input in the tower as absorption liquid.
When the enough but recycling step of the quantity not sufficient of unreacted alkanol amine be by water as absorption liquid and do not add other amine compound, polymerization can take place in aziridine cpd.If with aqueous sodium hydroxide solution as absorption liquid to prevent polyreaction, then the by product carbonyl compound will react with aziridine, generates adducts, makes the productive rate decline of aziridine.
The consumption of amine compound depends on various factors in recycling step, as the composition of reaction product, and the kind of amine compound, the temperature of retrieving arrangement and structure.Preferred amine consumption is at least 0.1 mole for every mole of aziridine cpd of time per unit in reaction product, and every mole of its consumption of carbonyl compound is at least 1 mole.If the amount of amine very little, the stability of aziridine cpd will be low, and perhaps carbonyl compound can not reaction becomes a kind of adducts with amine compound fully, and the productive rate of aziridine cpd will descend.Can use the aqueous solution of amine compound as absorption liquid.If the viscosity ratio of this amine compound is higher, can be by amine compound be dissolved in the water, and the low viscosity solution that uses gained improves the effect that contacts of amine compound and reaction product as absorption liquid.Can suppress to have the volatility of more lower boiling amine compound by the mode of using the aqueous solution.Yet in absorption liquid, contain the reversed reaction that too many water can cause carbonyl compound and amine compound adducts, and carbonyl compound can not successfully be removed.Therefore, when amine compound is input into the absorption tower with aqueous solution form, though the concentration of amine compound in the absorption liquid that is input into can be according to reaction product in the content of water change, preferably be adjusted at least 30% volumetric molar concentration, particularly at least 80% volumetric molar concentration.Temperature by absorption liquid bulk absorption aziridine cpd can change according to the type of absorption liquid, but is suitable with 0 ℃ to 80 ℃.Working pressure can normal pressure or employing decompression or pressurization.Generally absorbing by an absorption tower is easily.The absorption tower can be a packing type, tower tray shape, and the multitube type, spray-type or wet wall type also can be the combinations of these types.
(2) or (3) set by step are that the reaction product that obtains from reactions steps (A) is delivered to distilation steps (C), and in the presence of the amine compound of capacity aziridine cpd are distilled.
To in recycling step (B), in the presence of amine compound, deliver to distilation steps (C) by the resulting liquid that contains aziridine cpd, in the presence of this amine compound, distill out aziridine cpd [step (3)].Another way will not sent recycling step of the present invention (B) to from the reaction product liquid that contains aziridine cpd that reactions steps (A) obtains, and can [step (2)] distill effectively in the presence of this amine compound according to the present invention.If the amine compound that the liquid of nitrogenous third acridine compound contains has enough amounts to produce effect as unreacted raw material alkanolamine, just need not resupply aminated compounds.Otherwise, need to resupply amine compound to Distallation systm, then aziridine cpd is distilled.Add distillation tower preferably with the liquid mixing of this amine compound and nitrogenous third acridine compound, and with mixture.Another way is that amine compound is added distillation tower in addition.Particularly when the liquid that contains aziridine that is input into distillation tower contained water, the amine compound preferably position more than the loading tray of distillation tower was added, and can avoid required aziridine cpd and by-product carbonyl compound to generate adducts so effectively.Adducts by this carbonyl compound and amine compound generate causes reversed reaction owing to there is water to exist near the loading tray position, thereby discharges this carbonyl compound, and rises by distillation tower as a kind of low boiling component.Owing to add amine compound in the above described manner, the amine compound of q.s is arranged, and water falls by distillation tower as high-boiling-point impurity more than loading tray, the result reduces in the amount of this place's water.Even therefore have the carbonyl compound of by-product to discharge, it changes into adducts with amine compound again immediately, so can carry out distilation steps under the situation of not losing aziridine basically.
The amount of amine compound can suitably be selected according to the amount of the type that is present in the compound in the Distallation systm and ratio, carbonyl compound etc. in the distillation tower.Preferably there is at least 0.05 mole amine compound in every mole of aziridine cpd in the Distallation systm to be input into; And every mole of carbonyl compound meter exists at least 1 mole, especially best 5 moles amine compound; And there is 1 mole amine compound at least in every mole of water.If with respect to aziridine, the amount of amine compound is very little the time, and it suppresses aziridine cpd polymeric ability is inadequate.On the other hand, if with respect to carbonyl compound or water, the amount of amine compound is very little the time, and it is insufficient that carbonyl compound and amine compound are transformed into the degree of adducts.The result might make the productive rate of aziridine reduce, and carbonyl compound will be comprised in the aziridine overhead product, or the stability of gained aziridine cpd is reduced.
Carry out when the operation repeated multiple times that will distill aziridine cpd, distilation steps of the present invention (C) can be applicable to any these distillation procedures.
Distillation can any routine method carry out in batches or continuously, distillation tower can be selected for use such as packing tower or tray column.Working pressure can be a normal pressure, or decompression or pressurization.Service temperature can be come suitably selected according to stability of type, carbonyl compound and the amino-complex adducts of aziridine cpd or the like.Preferably the tower top temperature of distillation tower is between 10 to 100 ℃.If temperature is too high, aziridine cpd can change into other compound.If temperature is too low, increase at the condensation cost of heat exchanger so that industrial be disadvantageous.Above-mentioned distillation can high yield obtain highly purified aziridine cpd.
The more convenient mode of implementing the inventive method is in reactions steps (A), with the alkanolamine of logical formula I not diluted and pass through catalyst layer in fact, make alkanolamine carry out intramolecular dehydration, carry out and be preferably under the reduced pressure of 10 to 500 mmhg in vapour phase.React after alkanolamine dilutes with diluent gas such as nitrogen, and when reclaiming reaction product with recycling step, expellant gas still contains required product and unreacted material, the productive rate of required product just might reduce.Need circulate expellant gas or its processing become non-poisonous material of equipment in addition.Otherwise, as the not dilution basically before reaction of initial alkanolamine, in recycling step, then can avoid the productive rate of required aziridine cpd to descend, large-scale exhaust gas disposal apparatus can omit or simplify.Reaction product can directly be delivered to distilation steps in the case, and can omit recycling step.Owing to there is not incondensible gas, distillation procedure is very smooth.Under latter event, preferably reaction product is cooled to the operational condition that is suitable for distillation tower by a water cooler with it, is input into distillation tower then.In distillation tower, it is fractionated into mainly cut of forming by aziridine and the distillation residue of forming by unreacted alkanolamine, water and other high-boiling-point impurity.If when needing, the principal constituent that obtains from the distillation cat head is that the cut of aziridine cpd can be purified by it is imported rectifying tower again, so that obtain the higher aziridine cpd of purity.To remove from the bottom of distillation tower by the mixture that water and other high-boiling-point impurity of unreacted start-of-chain alkanolamine, generation are formed simultaneously.If when needing, alkanolamine can be reclaimed so that re-use from mixture.Certainly, in order to make initial alkanolamine evaporation or increase activity of such catalysts smoothly, can add nitrogen in a small amount, ammonia etc.Run counter to because in reactions steps, there is no like this for above-mentioned purpose of the present invention.
Fig. 1 and Fig. 2 represent the schema of optimum implementation of the present invention.Referring now to these figure the present invention is described.
Fig. 1 is the method that comprises the production aziridine of reactions steps, recycling step and distilation steps.
Send the raw material alkanolamine to vaporizer 101 by pipeline 1, and make its vaporization by heating.By pipeline 2 rare gas element such as nitrogen, helium or argon and optional and ammonia, water vapor or hydrogen are input into vaporizer 101 together suppressing side reaction, and the concentration of regulating alkanolamine.Then raw gas mixture is input into the vapour phase dehydration reactor 102 that is filled with catalyzer by pipeline 3.Reactor 102 can be general fixed bed, fluidized-bed or moving-bed.The reaction product of leaving reactor 102 comprises aziridine cpd, unreacted alkanolamine, water, carbonyl compound and amine compound except that as the rare gas element of feed diluent.Reaction product is delivered to water cooler 103 and is cooled to suitable temperature by pipeline 4.After the cooling, it is delivered to the bottom on absorption tower 104 by pipeline 5, appropriate filler is filled into the inside on absorption tower 104, and will be input into the top on absorption tower 104 by the absorption liquid that liquid amine compounds or its aqueous solution are formed from pipeline 6, and it is contacted with reaction product on filler, absorption reaction product thus.Unabsorbed gaseous mixture by pipeline 7 from the absorption tower 104 top discharge go out.The liquid that has absorbed aziridine cpd is discharged from the bottom of tower by pipeline 8, and distillation tower 105 is delivered in charging as distillatory, distills.Designing apparatus makes amine compound to be input in the raw material by the pipeline 9 that is installed in the loading tray top, and amine compound is input into distillation tower by the pipeline 10 that is installed in this tower tray top on demand.Carbonyl compound and amine compound reaction contained in the liquid that has absorbed aziridine cpd generate high boiling adducts.Obtain required aziridine cpd by pipeline 11 from distillation tower 105 cats head as overhead product.High boiling product comprises the high boiling point adducts of water, carbonyl compound and amine compound, and the amine compound of adding, and can pass through pipeline 12 with it discharge from tower bottom.Can reclaim alkanolamine or amine compound from high boiling product on demand.If when needing, the aziridine cpd that obtains from pipeline 11 can be delivered to rectifying tower, to obtain highly purified aziridine cpd.
Fig. 2 is another embodiment, and this scheme is that alkanolamine does not dilute the catalyst layer that passes through that is about to basically, and carries out intramolecular dehydration in the vapour-phase reaction step, then the gained reaction product is delivered to distilation steps.
The raw material alkanolamine is delivered to vaporizer 201 by pipeline 21, and heating vaporization under reduced pressure.The alkanolamine of vaporization is input into vapour phase dehydration reactor 202 by pipeline 22.The reaction product of leaving reactor 202 comprises aziridine cpd, unreacted alkanolamine, water, carbonyl compound and amine compound.Reaction product is delivered to water cooler 203 and is cooled to suitable temp by pipeline 23, and send it to distillation tower 204 by pipeline 24 and distill.On demand equipment design is become and amine compound can be added in the raw material by pipeline 25, or the pipeline by being installed in the loading tray top 26 is input into distillation tower with amine compound.Be contained in carbonyl compound and amine compound reaction in the reaction product, generate the high boiling point adducts.Through distillation, obtain required aziridine overhead product by pipeline 27.High boiling product comprises the high boiling point adducts of water, carbonyl compound and amine compound, unreacted alkanolamine and the amine compound that is added, by pipeline 28 from the bottom of distillation tower with it discharge, on demand, from higher-boiling compound, reclaim alkanolamine or amine compound.If when needing, can deliver to rectifying tower from the aziridine cpd that pipeline 27 obtains, and in the presence of amine compound, distill, to obtain highly purified aziridine cpd.
Be described more specifically the present invention by following example.With gas-chromatography the adducts of the amine compound in the reaction product, aziridine cpd, carbonyl compound and amine-carbonyl compound is analyzed, and water-content is analyzed with Ka Erfeixiu water-content instrument, in recycling step, the recovery percent of the aziridine that reclaims calculates with following formula:
Rate of recovery %=(aziridine cpd of recovery (mole number/hour))/(aziridine cpd of generation (mole number/hour)) * 100
Example 1
This example explanation is (1) and use the inventive method of Fig. 1 device set by step.
Preparation of catalysts
Example 13 according to European publication 227461 prepares catalyzer.
With silicon-dioxide (300 gram), 788.7 gram hydrated bartas, eight hydrates, 10.0 gram sodium hydroxide and 6.2 gram zirconium white dispersion suspensions are in 3 premium on currency.Fully stir, with the suspension heating and be concentrated into the claylike material of a kind of white.Be molded into diameter about 5 millimeters and the about 5 millimeters cylindrical particle of length.Be dried, and, obtain having the catalyzer of following composition, Si 600 ℃ of calcinings 2 hours
1.0Ba
0.5Na
0.05Zr
0.01(except the atomic ratio, oxygen).
Dehydration reaction step (A)
It is in 25 millimeters the stainless steel reaction pipe that 200 milliliters of catalyzer are filled into internal diameter, as reactor 102, and is heated to 390 ℃ with heating medium.The raw gas mixture that to be made up of monoethanolamine and nitrogen (volume ratio 10: 90) was with air speed 1500 hours
-1Lead to into reaction tubes, make the monoethanolamine reaction.Analysis demonstrates, and reaction product contains the aziridine of 4.9% volume, the acetaldehyde of 0.3% volume, the monoethanolamine of 3.6% volume, the water vapor of 5.0% volume, the nitrogen of 85.3% volume, and the monoethanolamine of a spot of ammonia and dimerization.
Recycling step (B)
To water cooler 103, be cooled to 110 ℃ and be input into the bottom that internal diameter is the stainless steel tube absorption tower 104 of 1000 millimeters of 25 millimeters, length from the reaction product that reaction tubes is discharged.It is 3 millimeters filler (Dickson filler) that 104 inside, absorption tower contain diameter, and being filled into bed stuffing height is 700 millimeters.To remain on 40 ℃ as the monoethanolamine that absorbs liquid and be input into the absorption tower by pipeline 6 from cat head, and it is contacted with reaction product with flow 980 Grams Per Hours.The absorption liquid that has absorbed aziridine is discharged from the bottom on absorption tower.Measure the rate of recovery of aziridine by analyzing expel liquid.Can determine that thus the aziridine that generates has 99.6% to be absorbed by monoethanolamine in reactions steps.In aforesaid liquid, there is not the acetaldehyde that generates as by product in the reactions steps.And record generated the amount of N-ethylidene-1-oxyethylamine (acetaldehyde and as the reaction product of the monoethanolamine of absorption agent) and the amount of the acetaldehyde of by-product corresponding.
Example 2-6
The explanation of these examples is (1) and use the method for Fig. 1 device set by step.
Repeat example 1, difference is that the type of being input into absorption liquid, temperature and amount are changed, and recovering condition and result list at table 1.
Example 7
This example explanation is (1) and use the method for Fig. 1 device set by step.
Preparation of catalysts
Example 3 preparation catalyzer according to United States Patent (USP) 4477591.
Under agitation Columbium pentoxide (20 gram) is dissolved in 200 milliliters of warm water.With ammoniacal liquor the pH value of solution is adjusted to 7.0.The sedimentation and filtration that generates is separated, washes with water, and be dissolved in 320 milliliters of 10%(weight) oxalic acid aqueous solution in.Add hydrated barta eight hydrates of 0.8 gram in addition.With particle diameter be 5 millimeters silicon carbide (240 milliliters) be impregnated in the solution and with solution evaporation to doing, calcined 3 hours in air draught at 500 ℃, obtain containing 3.7%(weight) Columbium pentoxide and 0.5%(weight) the barytic catalyzer (Nb that is stated from carrier
1.2Ba
0.1O
2.6).
Dehydration reaction step (A)
Repeat the dehydration reaction step of example 1, difference is to use above-mentioned catalyzer, and makes temperature of reaction into 420 ℃.Record reaction product and contain the 2.1%(volume) aziridine, the 0.7%(volume) acetaldehyde, the 6.5%(volume) monoethanolamine, the 2.5%(volume) water vapor, the 87.3%(volume) nitrogen and the monoethanolamine of in a small amount ammonia, ethamine and dimerization.
Recycling step (B)
Same procedure by example 1 is delivered to recycling step with reaction product.Recovering condition and result are as shown in table 1.
Example 8
Fig. 1 device and the method for (1) are set by step used in this example explanation.
Preparation of catalysts
Example 25 preparation catalyzer are disclosed No. 230776 according to European patent.
Aluminum nitrate nonahydrate (900 gram) is dissolved in 2.4 premium on currency, and the solution that under agitation 357.6 gram triammonium phosphates is dissolved in 2.4 premium on currency is added wherein.The sedimentation and filtration that generates is separated, and wash with water, add 73.6 gram barium oxide and 100 ml waters, mixture is fully mediated, the claylike material of gained is molded into external diameter is about 5 millimeters, the cylindrical particle that length is about 9 millimeters, and be dried, obtained catalyzer at 2 o'clock 1000 ℃ of calcinings then, its composition becomes Al
1P
1Ba
0.2(atom ratio that deoxygenation is outer).
Dehydrating step (A)
Repeat the dehydration reaction step of example 1, difference is to use the catalyzer of above-mentioned gained, makes temperature of reaction into 420 ℃, and raw gas mixture changes the mixture of monoisopropanolamine and nitrogen into, and its volume ratio is 20: 80.After measured, reaction product contains the 7.9%(volume) the 2-methylaziridine, the 1.2%(volume) acetone and 8.0%(volume) monoisopropanolamine, the 8.0%(volume) water vapor, the 72.6%(volume) nitrogen and the ammonia in a small amount and the monoisopropanolamine of dimerization.
Recycling step (B)
Reaction product is delivered to recycling step, and reclaim the 2-methylaziridine with example 1 identical method, difference is to use monoisopropanolamine (20 ℃) instead as absorption liquid, and input flow rate is 2200 Grams Per Hours.Recovering condition and result list at table 1.
Example 9
The device of Fig. 1 and the method for (1) are set by step used in this example explanation.
Preparation of catalysts
With cesium carbonate (114.0 gram), 92.4 gram diammonium phosphate, 17.4 gram magnesium hydroxides, 26.6 gram thallium trinitrate (TTN)s and 255.0 gram aluminum oxide are added in 2 premium on currency, and heating concentrates it and obtains white claylike material.This material is molded into about 5 millimeters of external diameter, the about 5 millimeters cylindrical pellet of length, with particle drying, calcined 2 hours in air draught at 600 ℃, obtain catalyzer, it consists of Mg
0.2Cs
0.7P
0.7Tl
0.1Al
5.0(atomic ratio except the oxygen).
Dehydrating step (A)
Repeat the dehydration reaction step identical as example 1, difference is to use above-mentioned catalyzer, changes temperature of reaction into 400 ℃, and raw gas mixture changes the mixture that contains 2-amino-1-butanols and nitrogen into, and its volume ratio is 20: 80.After measured, reaction product contains the 7.3%(volume) 2-ethyl aziridine, the 1.4%(volume) methylethylketone, the 9.1%(volume) 2-amino-1-butanols, the 7.5%(volume) water vapor, the 73.0%(volume) the 2-amino-1-butanols of nitrogen and a spot of ammonia and dimerization.
Recycling step (B)
Reaction product is sent to as the identical recycling step of example 1 to reclaim 2-ethyl aziridine.Recovering condition and result list at table 1.
Example 10
The device of Fig. 1 and the method for (3) are set by step used in this example explanation.
Preparation of catalysts
According to No. 228898 examples of European publication 7 preparation catalyzer.
Calcium nitrate tetrahydrate (590.5 gram) is dissolved in 1 premium on currency under agitation solution is heated to 80 ℃ simultaneously, and add 1 liter of aqueous solution that contains 537.0 gram Sodium phosphate dibasics (dodecahydrate).Mixture was placed 1 hour, and added ammoniacal liquor and make its pH keep alkalescence.With mixture cooling, filter precipitate and separate, and wash with water and obtain white solid.Solid is molded into about 5 millimeters of external diameter, the about 5 millimeters cylinder shape particle of length, and drying was calcined 2 hours in air draught at 500 ℃ then, obtained catalyzer, and it consists of Ca
0.9Na
0.1P
0.5(atomic ratio that deoxygenation is outer).
Dehydration reaction step (A)
Carry out the dehydrating step identical as example 1, difference is the catalyzer with 200 milliliters of gained, and temperature of reaction is changed to 400 ℃, and raw gas mixture to use instead by monoethanolamine and nitrogen volume ratio be 20: 80 mixture.Reaction product gas has determined except that aziridine is primary product have acetaldehyde to generate by gas chromatographic analysis.
Recycling step (B)
Then reaction product is delivered to as the identical recycling step of example 1 to reclaim aziridine.The liquid that analysis revealed is discharged from 104 bottoms, absorption tower does not contain the by product acetaldehyde that generates reactions steps (A), and the amount of by product acetaldehyde of the amount of N-ethylidene-1-oxyethylamine (acetaldehyde and be used as the reaction product of the monoethanolamine of absorption liquid) and generation of generating is corresponding.
Distilation steps (C)
The liquid of will be in recycling step discharging from the bottom, absorption tower is delivered on the stainless steel distillation tower packing layer 0.6 meter position, this distillation tower internal diameter is 50 millimeters, the filler floor height is 2.4 meters and fills with Dickson filler (6 millimeters), tower top pressure is 200 mmhg, carry out continuous still battery with reflux ratio=4, tower top temperature is 25 ℃.Obtain the aziridine product by pipeline 11.The liquid composition and the result that deliver to distillation tower list in table 2.
Example 11
The device of Fig. 1 and the method for (3) are set by step used in this example explanation.
Repeat example 10, difference is to replace monoethanolamine with quadrol as absorption liquid in recycling step (B), and the water distilling apparatus in distilation steps is 1/5th of the used water distilling apparatus size of example 10.The liquid composition and the result that deliver to distillation tower list at table 2.
Example 12
The explanation of this example is according to the method for step (3).
To be cooled to room temperature with cold water from the reaction product gas that example 10 reactions steps (A) are discharged, be cooled to-30 ℃ of solution that contain aziridine with condensation with cooling agent then.Monoethanolamine is added the liquid of condensation, and the solution of gained is sent to distillation by the method for example 10.Deliver to the composition of distillation tower solution and the results are shown in table 2.
Example 13
The explanation of this example is according to the method for step (3).
Monoethanolamine is added in the example 10 in the aziridine cut of distillation gained, and the solution of gained used with example 1 identical operations distill.Deliver to the solution composition of distillation tower and the results are shown in table 2.
Example 14
Fig. 1 device and the method for (3) are set by step used in this example explanation.
Preparation of catalysts
According to No. 227461 examples of European publication 14 preparation catalyzer.With silicon-dioxide (300 gram), 132.8 gram strontium hydroxides, eight hydrates, 2.4 gram lithium hydroxides and 12.8 gram aluminum oxide are made suspension in 1 premium on currency.Heating under fully stirring concentrates suspension.Enriched product is molded into about 5 millimeters of outside diameter, the about 5 millimeters cylindrical particle of length.Drying, and obtained catalyzer in 2 hours 600 ℃ of calcinings, consist of Si
1Sr
0.1Li
0.02Al
0.05(atomic ratio that deoxygenation is outer).
Dehydration reaction step (A)
Carry out the dehydration reaction step identical with example 10, difference is to use above-mentioned prepared catalyzer, device size be example 10 used 1/5th, the Heating temperature of thermal medium is 400 ℃, and replaces monoethanolamine with Yi Bingchunan.
, record except that principal reaction product 2-methylaziridine the reaction product analysis with gas-chromatography, also have acetone.
Recycling step (B)
With the same procedure of example 10, will be from the recovery such as 2-methylaziridine the reactant gases product that dehydration reaction step (A) is discharged, difference is to use the retrieving arrangement of reduced size, and replaces monoethanolamine with Yi Bingchunan.
Analysis revealed, the liquid that discharge 104 bottoms from the absorption tower does not contain the by product acetone that generates reactions steps, and generates acetone and product 1-isopropylidene amino-2-propyl alcohol as the Yi Bingchunan reaction of absorption liquid.
Distilation steps (C)
The liquid that to discharge from the bottom, absorption tower in recycling step (B) with example 11 identical methods distills, and only is to use the water distilling apparatus of reduced size, is input into the liquid composition of distillation tower and the results are shown in table 2.
Example 15
The device of Fig. 2 and the method for (2) are set by step used in this example explanation.
Dehydration reaction step (A)
1 liter of catalyzer with the preparation of example 8 methods is filled in the stainless steel reaction pipe of 25 millimeters of internal diameters,, is heated to 420 ℃ with heating medium as reactor 202.Monoethanolamine is input in the vaporizer 201, and with the monoethanolamine of vaporization with air speed 1000 hours
-1Lead to into reaction tubes, the pipe outlet is that the pressure of 400 mmhg carries out successive reaction.Record reaction product and contain the 67.6%(volume) monoethanolamine, the 12.7%(volume) aziridine, the 15.6%(volume) water, the 1.35%(volume) a spot of amine of acetaldehyde and a kind of dimerisation products.
Distilation steps (C)
The reaction product that reactions steps (A) is obtained is cooled to 100 ℃ in water cooler 203, and it is input into to distillation tower 204, this distillation tower is 50 millimeters of internal diameters, high 2000 millimeters stainless steel tube, the position that is input into is counted from the top about distillation tower greatly and always is about 1/3, and distills with reflux ratio=4.Stainless steel carry the Mcmahon filler that dense part contains 6.35 millimeters of diameters, 400 millimeters of packing heights, containing diameter in recovery part is 6.35 millimeters Mcmahon filler, 1200 millimeters of packing heights.
By pipeline 27, obtaining purity with the flow of 291 Grams Per Hours from the distillation cat head is 98.1%(weight) aziridine.Water is unique impurity.Acetaldehyde and the reaction of unreacted monoethanolamine generate a kind of adducts and discharge from tower bottom by pipeline 28.
Example 16
The device of this example explanatory view 2 and the method for (2) set by step.
Dehydration reaction step (A)
Carry out the dehydration reaction step of example 15, difference is to replace monoethanolamine with monoisopropanolamine, and the control tube top hole pressure is 60 mmhg, with air speed 200 hours
-1The monoisopropanolamine of vaporization is led in the reaction tubes.Record reaction product and contain the 9.9%(volume) monoisopropanolamine, the 36.0%(volume) the 2-methylaziridine, the 40.1%(volume) water, the 5.0%(volume) acetone and in a small amount ammonia and a kind of dimerisation products.
Distilation steps (C)
Send the reaction product that above-mentioned reactions steps (A) obtains to distillation tower with example 15 identical methods.Monoisopropanolamine is added the distillation tower with the amine opening for feed of flow on distillation column reaction thing opening for feed of 447 Grams Per Hours.With the identical method of example 15 at the pressure of 60 mmhg, reaction product is distilled with reflux ratio=8.
Is 97.8%(weight from the recovered overhead of distillation tower to purity) 2-methyl-aziridine, flow be 335 Grams Per Hours.2-methyl-aziridine of 98.1% that recyclable above-mentioned reaction generates.Water almost is unique impurity.Acetone and monoisopropanolamine reaction generate a kind of adducts, discharge at the bottom of tower through pipeline 28.
Example 17
The device of Fig. 2 is used in this example explanation, and (3) method set by step.
Dehydration reaction step (A)
Repeat the dehydration reaction step of example 15, difference is to change reaction pressure into 100 mmhg from 500 mmhg, and air speed was from 100 hours
-1Change 400 hours into
-1The analysis revealed reaction product contains the 42.4%(volume) monoethanolamine, the 24.7%(volume) aziridine, the 27.1%(volume) water, the 1.8%(volume) acetaldehyde and the ammonia in a small amount and the monoethanolamine of dimerization.
Recycling step (B)
To at first be cooled to room temperature from the reaction product that dehydration reaction step is discharged, and further be chilled to-10 ℃ of solution that obtain containing aziridine with condensation and recovery with cooling agent with cold water.Analysis revealed, this solution are not contained in the by-product acetaldehyde that generates in the reactions steps, and record the amount that generates N-ethylidene-1-aminoethyle alcohol (acetaldehyde and as the reaction product between the monoethanolamine of the raw material) amount corresponding to by product acetaldehyde.
Distilation steps (C)
To be input into distillation tower at the solution that recycling step obtains, and distill with the method identical with example 15 distilation steps.Obtaining purity from cat head with the flow of 267 Grams Per Hours is 98.3% aziridine, and its productive rate is to generate 99.0% of aziridine in reactions steps.
The composition of feedstock solution and the results are shown in table 2 in the distillation tower.
Claims (5)
1, a kind of method of producing by the aziridine cpd of logical formula II representative,
Wherein R represents hydrogen, methyl or ethyl,
This method comprises a kind of alkanolamine with logical formula I representative,
Wherein R such as above-mentioned definition, X and Y are OH or NH
2, and Y is NH when X is OH
2, when X is NH
2The time Y be OH, under the vapour phase condition, in reactions steps (A), carrying out intramolecular dehydration in the presence of a kind of catalyzer, generate the reaction product of nitrogenous third acridine compound, and reaction product reclaims aziridine cpd thus,
It is characterized in that the recovery method of described aziridine cpd is to be selected from:
(1) reaction product is delivered to recycling step (B), and in the presence of a kind of amine compound, reclaim aziridine cpd, the usage quantity of described amine compound is that time per unit every mole of this aziridine cpd in this reaction product uses at least 0.1 mole, and every mol of by-products carbonyl compound uses at least 1 mole in this reaction product; Or
(2) reaction product is delivered to distilation steps (C), and in the presence of a kind of amine compound, distill aziridine cpd, the usage quantity of described amine compound is that every mole of this aziridine cpd sending into this Distallation systm uses at least 0.05 mole, every mole of this carbonyl compound uses at least 1 mole, and every mole of water is used at least 1 mole; Or
(3) reaction product is delivered to recycling step (B), and in the presence of a kind of amine compound, reclaim aziridine cpd, the usage quantity of described amine compound is that time per unit every mole of this aziridine cpd in this reaction product uses at least 0.1 mole, and every mole of this carbonyl compound uses at least 1 mole in this reaction product; Again the aziridine cpd that reclaims is delivered to Distallation systm, and in the presence of a kind of amine compound with its distillation, the usage quantity of described amine compound is that every mole of this aziridine cpd sending into this Distallation systm uses at least 0.05 mole, every mole of this carbonyl compound uses at least 1 mole, and every mole of water is used at least 1 mole;
Described amine compound is to be selected from: primary aromatic amine, the tool that aliphatic primary amine, the tool of the alkanol primary amine of 2 to 6 carbon atoms of tool, 2 to 8 carbon atoms of tool is no more than 8 carbon atoms is no more than the alkanol secondary amine of 8 carbon atoms;
The temperature of used still-process is that distillation tower withstands on 10-100 ℃ of scope.
2, according to the process of claim 1 wherein in reactions steps (A), lead to the strand alkanolamine by logical formula I of not diluted into that a catalyst layer reacts, then reaction product is directly delivered to water distilling apparatus (C).
3, according to the process of claim 1 wherein in distilation steps (C), described amine compound is to add from the loading tray top of distillation tower.
4, according to the process of claim 1 wherein that this amine compound is to be selected from: monoethanolamine, monoisopropanolamine, ethamine, quadrol, aniline, diethanolamine, diisopropanolamine (DIPA).
5, according to the process of claim 1 wherein that this amine compound is with identical by the raw material alkanolamine of logical formula I.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP156,617/87 | 1987-06-25 | ||
| JP15661787 | 1987-06-25 | ||
| JP172,989/87 | 1987-07-13 | ||
| JP17298987 | 1987-07-13 | ||
| JP25386887 | 1987-10-09 | ||
| JP253,868/87 | 1987-10-09 | ||
| JP265,443/87 | 1987-10-22 | ||
| JP26544387 | 1987-10-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1030230A CN1030230A (en) | 1989-01-11 |
| CN1018451B true CN1018451B (en) | 1992-09-30 |
Family
ID=27473429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88103932A Expired CN1018451B (en) | 1987-06-25 | 1988-06-23 | Method of producing aziridines |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1018451B (en) |
| CA (1) | CA1287635C (en) |
| ES (1) | ES2007188A6 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643452B (en) * | 2011-02-16 | 2013-06-12 | 中国中化股份有限公司 | Method for improving aziridine cross-linking agent stability |
| CN104792725B (en) * | 2015-04-30 | 2018-01-23 | 西安近代化学研究所 | Monoethanolamine dehydration prepares the rapid analysis method of aziridine product stream |
| CN110003072A (en) * | 2019-03-15 | 2019-07-12 | 宁夏倬昱新材料科技有限公司 | A kind of preparation method of 2- methylaziridine |
-
1988
- 1988-04-11 ES ES8801098A patent/ES2007188A6/en not_active Expired
- 1988-04-18 CA CA000564395A patent/CA1287635C/en not_active Expired - Fee Related
- 1988-06-23 CN CN88103932A patent/CN1018451B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030230A (en) | 1989-01-11 |
| ES2007188A6 (en) | 1989-06-01 |
| CA1287635C (en) | 1991-08-13 |
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