CN1043699A - The production method of cyclohexylamines - Google Patents
The production method of cyclohexylamines Download PDFInfo
- Publication number
- CN1043699A CN1043699A CN88108764A CN88108764A CN1043699A CN 1043699 A CN1043699 A CN 1043699A CN 88108764 A CN88108764 A CN 88108764A CN 88108764 A CN88108764 A CN 88108764A CN 1043699 A CN1043699 A CN 1043699A
- Authority
- CN
- China
- Prior art keywords
- aniline
- product
- compounds
- hydrogen
- amino benzenes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates in the presence of the nickel catalyzator by being selected from aniline, N-(low alkyl group) aniline and the N that low alkyl group on aniline, the ring replaces, the method of the liquid phase hydrogenation reaction continuous production cyclohexylamines that N-two (low alkyl group) aniline and hydrogen carry out, this method comprises with amino benzenes compounds charging continuously, at about 2-10kg/cm
2Under the temperature of reaction pressure and about 210-240 ℃, in the presence of the aminated compounds and under condition of no solvent with the amino benzenes compounds continuous hydrogenation, the product gas that will contain product cyclohexylamines, unreacted amino benzenes compounds, by product, hydrogen and aminated compounds is discharged separation of hydrogen and aminated compounds from product gas continuously from reaction system.
Description
The present invention relates to produce the method for hexahydroaniline.More particularly, the present invention relates to produce from amino benzenes compounds the method for cyclohexylamines, this method is included in ammonia or the amine existence encircles hydrogenation with nickel catalyzator to amino benzenes compounds down.
Hexahydroaniline is the useful intermediates of production vulcanization of rubber additive, anticolodal, dyestuff, agrochemical, medicine etc.The method of known production hexahydroaniline is included in ammonia and hydrogen and has down method (day disclosure special permission communique 60-239444 and 55-51042, Japan special permission communique 45-19898,51-41627 and 45-19897 etc.) from pimelinketone, hexalin or phenol production hexahydroaniline.
Another kind of known method is to carry out hydrogenation on the aniline ring.Usually, the reaction by aniline hydrogenation production hexahydroaniline comprises following side reaction or secondary reaction.
1) generates the reaction of dicyclohexylamine owing to the deaminizating dimerisation of hexahydroaniline;
2) generate the reaction of N-cyclohexyl aniline owing to the deaminizating dimerisation of hexahydroaniline and aniline;
3) reaction that generates hexalin owing to the hydrolysis or the cyclohexene hydration effect of hexahydroaniline;
4) generate the reaction of tetrahydrobenzene owing to the deaminizating of hexahydroaniline and generate the reaction of its hydrogenated products hexanaphthene;
5) reaction of formation trimer or polymer (hereinafter being referred to as polymkeric substance) between hexahydroaniline, dicyclohexylamine and the aniline.
Therefore, suppress or eliminate these side reactions or secondary reaction and be that separating by-products is necessary the hexahydroaniline from required product effectively.
In the routine operation condition (for example, at 100kg/cm
2Under the hydrogen pressure, use nickel catalyzator, temperature of reaction is 150-200 ℃) under, the method for producing hexahydroaniline by hydrogenation on the ring of aniline has caused the early stopping of crossing that hydrogen absorbs, and contains the unreacted aniline above 50% in the hexahydroaniline that obtains.For fear of this problem, people have advised using following various technology, such as the nickel catalyzator that uses improvement or use palladium or other catalyzer.
(1) Japan's special permission communique 43-3180 discloses a kind of method of producing hexahydroaniline by the liquid phase hydrogenation of aniline.Raney cobalt catalyzer and promotor calcium oxide and yellow soda ash in this method, have been used.
This production method can obtain the unreacted aniline of 96.2% hexahydroaniline, 2.1% dicyclohexylamine, 0.5% hexanaphthene and 1.2%.Yet the shortcoming of this method is: need 30-100kg/cm
2, be preferably 50-70kg/cm
2High-response pressure, both made and add calcium oxide and can not control the additional step that side reaction and Preparation of Catalyst relate to mixed oxidization calcium and yellow soda ash fully.
(2) Japan's special permission communique 45-28368 discloses a kind of method from gas phase Aniline Production hexahydroaniline, it is characterized in that the alkali metal compound of alkalescence is added nickel catalyzator.The shortcoming of this technology is: because it relates to gas-phase reaction, so the molecular density of per unit volume is low, so the output of time per unit is also low and both made and added alkaline alkali metal and can not control by product fully and generate.In addition, Preparation of catalysts needs strict control to guarantee constant alkali metal content in the catalyzer.
(3) day disclosure special permission communique 59-196843 discloses a kind of production method of hexahydroaniline, and this method is with palladium catalyst aniline or nuclear substituted aniline to be carried out hydrogenation under the temperature of room temperature to 160 ℃.The shortcoming of this method is to use expensive palladium catalyst, and because the reaction times reaches 12 hours, the productive rate of this method can not be said so high.
(4) United States Patent (USP) 3,565,921 disclose a kind of use is dispersed in nickel catalyzator in inert solvent such as the 2-ethylhexyl-2-Ethylhexyl Alcohol ester, under about 180 ℃ and barometric point, continuously aniline is encircled hydrogenation and produce the method for hexahydroaniline, the transformation efficiency of aniline is 86.5% in this method, and the transformation efficiency of aniline is 50% in the method that the liquid phase of routine is carried out in batches.From the viewpoint of productive rate, be fabulous according to the successive liquid phase reaction of above-mentioned United States Patent (USP).Yet the shortcoming of this method is that the desamination reaction of aniline or hexahydroaniline can not be eliminated fully, and uses above-mentioned inert solvent can cause that inevitably production cost increases.In addition, the boiling point of inert solvent must exceed ring at least and go up about 50 ℃ of hydrogenation temperature, and in order to increase speed of response temperature of reaction is raise, and choice of Solvent will be strict.
Can find out significantly that from top cutline the ordinary method of producing hexahydroaniline by hydrogenation on the ring of aniline is not entirely satisfactory, and every kind of method all has many room for improvement to prior art.
One of purpose of the present invention provides the method that a kind of high productivity prepares the hexahydroaniline compound, and the catalyzer that uses in this method not only cheaply but also operation easily.
Another object of the present invention provides and a kind ofly forms by product and high productivity is produced the method for cyclohexylamines under lower pressure condition minimumly.
Like this, the invention provides a kind of method of continuous production cyclohexylamines, this method be exactly in the presence of the nickel catalyzator with hydrogen to being selected from aniline, the N-(low alkyl group that low alkyl group on aniline, the ring replaces) aniline and N, the amino benzenes compounds of N-two (low alkyl group) aniline carries out liquid phase hydrogenation, and it comprises the amino benzenes compounds continuously feeding.At about 2-10kg/cm
2Reaction pressure and about 210-240 ℃ temperature under, in the presence of the ammonia and do not have under the solvent situation hydrogenation of benzene aminated compounds continuously, from reaction system, discharge continuously and contain the product cyclohexylamines, the unreacted benzene aminated compounds, by product, the product gas of hydrogen and aminated compounds, separation of hydrogen and aminated compounds from product gas, cyclohexylamines is continuously recycled in the reaction system with starting raw material benzene feed aminated compounds with unreacted amino benzenes compounds and separation of by-products and with unreacted amino benzenes compounds and by product, wherein when amino benzenes compounds was the aniline of the last low alkyl group replacement of aniline or ring, aminated compounds then was an ammonia; When amino benzenes compounds is the N-(low alkyl group) during aniline, aminated compounds is single (low alkyl group) amine; And work as amino benzenes compounds is N, and during N-two (low alkyl group) aniline, aminated compounds is two (low alkyl group) amine.
The inventor has investigated on the aniline ring of routine and has formed relevant many factors with the recovery and the dicyclohexylamine of unreacted aniline with other by product in the hydrogenant method.The result, we find that the product hexahydroaniline has higher alkalescence than aniline, have caused the strong adsorption of hexahydroaniline on nickel catalyzator, have blocked the absorption of aniline on catalyzer thus, therefore be interrupted reaction, and the prolongation delay of hexahydroaniline on catalyzer various secondary reactions have been caused.
This means that the product hexahydroaniline once formation, preferably should remove from reaction system.Yet, need about 150-200 ℃ temperature of reaction usually and be not less than 50kg/cm owing to use nickel catalyzator to carry out conventional liquid phase hydrogenation reaction
2Hydrogen pressure, but find a series of like this conditions the product hexahydroaniline can be steamed from reaction system and unreacted aniline to be retained in fully in the reaction system basically be difficult.
To carry out the United States Patent (USP) 3 that hydrogenation is a feature under the barometric point, 565, in 921 the method, reaction is to carry out under the temperature that is higher than aniline and hexahydroaniline boiling point, and these conditions make it must use can dissolve the inert solvent such as the 2-ethylhexyl-2-Ethylhexyl Alcohol ester of aniline and hexahydroaniline.
In these cases, the present inventor is to the vapour pressure of cyclohexylamines, amino benzenes compounds and by product, can keep the temperature condition of nickel catalyst activity aptly and cause dicyclohexylamine and the reason and the condition of other by product have been carried out detail analysis.The present invention makes on above-mentioned results of analysis.
The objective of the invention is by hydrogenation realizes helping to quicken to carry out under evaporation of product hexahydroaniline or the distillatory low pressure and under than the high temperature of common hydrogenation temperature.
The present invention has following significant advantage:
What 1) use is the nickel catalyzator of the cheapness of operation easily or preparation.
2) higher temperature of reaction has caused higher speed of response, and lower reaction pressure does not need to use high voltage bearing reactor.
3) turned back to continuously in the reaction system owing to from cyclohexylamines, separating the unreacted amino benzenes compounds and the by product (for example by distillation) that obtain, so can obtain the product cyclohexylamines (amino benzenes compounds with charging calculates, and its output is approximately greater than 99%) of unusual high yield.
4) existence of the aminated compounds in the reaction system has suppressed secondary reaction.Therefore, when aminated compounds was present in the reaction system, the desamination reaction of amino benzenes compounds and cyclohexylamines just was eliminated and by product dicyclohexylamine and other by product has been changed into cyclohexylamines.Do not find in the prior art to have in the presence of described aminated compounds with nickel catalyzator and carry out hydrogenation on the liquid phase ring.
5) because the charging of starting raw material amino benzenes compounds, hydrogen, aminated compounds, unreacted amino benzenes compounds and by product is carried out continuously, be significantly increased so produce productive rate.
Production method of the present invention describes with reference to the accompanying drawings in following.
Fig. 1 is the concrete schema of implementing of explanation production method of the present invention.
Initiation material of the present invention is amino benzenes compounds. Amino benzenes compounds not only comprises aniline but also comprises aniline, the N-(low alkyl group that anil replaces such as the upper low alkyl group of ring) aniline, N, N-two (low alkyl group) aniline etc., and these compound high productivities can be changed into its corresponding cyclohexylamines, namely change into respectively cyclohexylamine, N-(low alkyl group that low alkyl group on cyclohexylamine, the ring replaces) cyclohexylamine, N, N-two (low alkyl group) cyclohexylamine. The example of the low alkyl group of mentioning as being used as substituting group here, they can be low alkyl group such as methyl and the ethyl that contains 1-2 carbon atom. Low alkyl group on the ring The aniline that replaces comprises the aniline of monomethyl or dimethyl replacement and the aniline that single ethyl replaces. The typical example that is used for so such aniline of the present invention comprises aniline, methylphenylamine, N-ethylaniline, N, accelerine, N, the aniline that the upper dimethyl of the aniline that single ethyl replaces on the aniline that monomethyl replaces on N-diethylaniline, the ring, the ring and ring replaces.
When amino benzenes compounds was the aniline of the upper low alkyl group replacement of aniline or ring, the aminated compounds that is used for the inhibition side reaction should be ammonia. When amino benzenes compounds is the N-(low alkyl group) during aniline, aminated compounds should be corresponding list (low alkyl group) amine. And when amino benzenes compounds be N, during N-two (low alkyl group) aniline, aminated compounds should be corresponding two (low alkyl group) amine. For example, when amino benzenes compounds was methylphenylamine, aminated compounds should be methylamine, was N and work as amino benzenes compounds, and during the N-diethylaniline, aminated compounds should be diethylamine.
Mainly only relate to aniline and ammonia although the following describes, production method of the present invention also can be used for above-mentioned anil and single or two (low alkyl group) amine.
Be used for catalyst of the present invention and be preferably stable Raney nickel, can obtain by nickel is loaded on suitable carrier such as diatomite, aluminium, the silicon etc., and also can use Raney nickel catalyst. Stable nickel and Raney nickel catalyst can prepare with conventional method respectively. The content of metallic nickel can be about 5-70%(weight in stablizing Raney nickel). The ratio of catalyst preferably is about 5-40%(weight) (based on the gross weight of each liquid phase ingredient in the reaction system).
Implementing when of the present invention, the hydrogen of using for hydrogenation and as the aminated compounds of side reaction inhibitor preferably with the use of admixture of gas form, the mol ratio of hydrogen and aminated compounds is preferably 5: 0.5-3.
Be used for implementing reaction vessel of the present invention can use can anti-about 2-10kg/cm2Any reactor of pressure is preferably cylindrical reactor or reaction tower.
According to the present invention, during beginning, earlier catalyst and initiation material aniline are packed in the above-mentioned reactor. The concentration of catalyst is actually arbitrarily, and can be selected from wide region, and it can be about 5-30% weight (based on the aniline compound charging) usually. Behind the air in the hydrogen expulsion reactor, again with above-mentioned hydrogen-ammonia gaseous mixture in such a way namely with suitable speed according to appointment 2-20cm/sec linear space speed introduce from the bottom of reactor and make it by initiation material aniline main body. Pressure in the reactor is increased to 2-10kg/cm2, simultaneously with external heat for example Steam Heating temperature of reactor is risen to about 190 ℃. Subsequently, hydrogenation begins to carry out and the Heat of Formation that reacts can further impel the temperature of reaction system to bring up to about 210-240 ℃.
After this, by the charging rate of controlling hydrogen-ammonia gaseous mixture reaction pressure and temperature are remained on following level, and the product cyclohexylamine is being steamed continuously simultaneously, initiation material aniline is added to continuously carries out hydrogenation in the reactor.
The charging rate of hydrogen-ammonia gaseous mixture is controlled at about 2-20cm/sec, is preferably in the linear space velocity interval of 7-9cm/sec, if charging rate is lower than above-mentioned scope, will slow down distillation or the evaporation of cyclohexylamine, the result causes secondary reaction to increase and reaction speed reduces. On the contrary, if charging rate is higher than above-mentioned scope, tend to more easily unreacted aniline and accessory substance be steamed with the product cyclohexylamine, cause thus the Efficiency Decreasing of fractionation separates and produce the productive rate reduction.
Reaction pressure preferably is controlled at about 2-10kg/cm2, and more preferably be about 6.5-7.5kg/cm2 At 1kg/cm at least2Hydrogenation still can carry out under the pressure, but pressure is lower than 2kg/cm2Shi Fanying is slack-off. On the contrary, if pressure surpasses about 10kg/cm2, the molar fraction of cyclohexylamine in product gas will reduce, and a large amount of hydrogen are circulated, and causes thus the production economy loss.
Reaction temperature preferably is about 210-240 ℃. If temperature is lower than 210 ℃, It is insufficient to cause the product cyclohexylamine to steam, and can make hydrogenation slack-off. If temperature surpasses about 240 ℃ ceiling temperature, separating of unreacted aniline, dicyclohexylamine and other accessory substance and product cyclohexylamine will difficult, and side reaction is accelerated, and catalyst often also can be aging.
When the charging rate of hydrogen-ammonia gaseous mixture remained in the above-mentioned scope, reaction temperature almost can automatically be controlled in about 210-240 ℃ the said temperature scope. Like this, hydrogen-ammonia gaseous mixture is introduced reactor, along with the release reaction of reaction heat is activated. Simultaneously, along with steaming of product cyclohexylamine and other material, reaction heat is consumed as heat of evaporation. Although reaction heat is slightly larger than heat of evaporation, the two is balance basically. If reaction temperature surpasses about 240 ℃, can be by water composite cooling pipe or other conventional cooling way cooling reaction system to maintain the temperature in about 210-240 ℃ scope. Like this, an advantage of the present invention is exactly only not need complicated temperature control device just can control reaction temperature by the control gas flow.
Usually can be with initiation material aniline effectively from the continuously charging of bottom of reactor. The charging rate of aniline is preferably and keeps the needed speed of homeostatic reaction, namely can guarantee product cyclohexylamine stable distillation or evaporation and constant speed of the amount of liquid phase in reaction system from reaction system. With 10m3The reactor of size is example, under said temperature, pressure and hydrogen-ammonia gaseous mixture flows condition fresh initial raw material aniline can easily be caused homeostatic reaction with the speed charging of 500kg-2T/hr.
Under these conditions, the cyclohexylamine of generation can be directly steams as product gas from reaction system or evaporates with a small amount of unreacted aniline and accessory substance and hydrogen and ammonia. Because the distillation of unreacted aniline and accessory substance or evaporation are not significantly under these conditions, so can expeditiously the product cyclohexylamine be separated with other distillate. In addition, cyclohexylamine can be fast and effeciently desorb from the catalyst, this has just suppressed the formation of the accessory substance that comprises polymer, guarantees to urge Change agent the long-term life-span is arranged.
When take aniline as initiation material, the accessory substance that steams with cyclohexylamine under these conditions has dicyclohexylamine, cyclohexene, cyclohexane, N-cyclohexyl aniline etc., product gas composition beyond dehydrogenation and the ammonia contains has an appointment 70-85%(by weight, lower with) cyclohexylamine, about 3-7% unreacted aniline, about 10-18% dicyclohexylamine, about 1-3%N-cyclo-hexylamine and the cyclohexene and the cyclohexane that are less than about 1%.
When cooling, product gas can easily be divided in fact by hydrogen and ammonia gas phase of forming and the liquid phase that comes down to be made up of product hexahydroaniline, unreacted aniline and by product.For this cooling operation, can use common condenser, and product gas is cooled to be no more than about 60 ℃ temperature.
The isolating gas phase of being made up of hydrogen and ammonia in fact can be by directly or carry out behind the purifying whereby, can effectively utilizing hydrogen-ammonia mixture as putting into the part of the hydrogen-ammonia gas mixture in the reactor and being recycled in the hydrogenation system.
On the other hand, can separate hexahydroaniline in the liquid phase by the fractionation of liquid phase.This fractionation purifying can be effectively carrying out at least about the tower that 10 tower trays are arranged at one under the barometric point or the 200-500mmHg that reduces pressure according to appointment.In this connection, preferably use two separation columns so as to make mainly by hexanaphthene and tetrahydrobenzene form low boil cut in first tower by fractionation, in second tower, carry out product hexahydroaniline and other material such as unreacted aniline again, dicyclohexyl aniline separates with N-cyclohexyl aniline.Certainly, above-mentioned fractionation process can carry out effectively by single distillation tower.In a word, for those skilled in the art, be easy with fractionating process separating ring hexylamine and unreacted aniline and by product, and, can utilize any known method in order to reach same purpose.
Unreacted aniline and by product (the particularly by product beyond low boiling substance such as tetrahydrobenzene and the hexanaphthene) can be used as an integral body and be recycled in the reaction system that transforms the generation hexahydroaniline.In addition, can increase the production productive rate by carrying out above-mentioned steps continuously.Because the output of low boil cut such as hexanaphthene and tetrahydrobenzene is little, so methods such as available burning are handled it.
Unreacted aniline and by product are being recycled in the process of reacting again in the reactor, with respect to fresh starting raw material aniline, the unreacted aniline that loads in reactor and the ratio of by product are optional from wide region, but common ratio is unreacted aniline and the by product of the fresh feed aniline of every part of weight corresponding to about 0.05～0.5 preferably about 0.2～0.4 part of weight.If ratio is lower than this scope, unreacted aniline and the by product in the container such as surge tank will increase so.If ratio surpasses above-mentioned scope, the loadings of starting raw material aniline is reduced and the product productive rate is lowered.
When unreacted aniline and by product being recycled to when reacting again in the reaction system, reaction still can be used above-mentioned hydrogen-ammonia feed speed by above-mentioned same mode, under same temperature and pressure and carry out continuously, subsequently also can with hexahydroaniline from product gas separation and the circulation of unreacted aniline and by product carry out in the same manner as described above.The charging of starting raw material aniline and round-robin unreacted aniline and by product preferably can keep the amount constant speed of liquid phase in the reactor to carry out with such speed.
By such operate continuously,, the consumption of catalyzer can be reduced to 1kg or still less for producing 1 ton of hexahydroaniline.
And,, so just increased productive rate widely owing to hydrogenation on the ring of aniline under condition of the present invention is so rapidly so that the residence time in the reactor only is about 5-120 minute.
In addition, can not comprise that content is no more than about 0.5% tetrahydrobenzene and hexanaphthene and proportion and is no more than about 0.1% polymkeric substance by all by products that above-mentioned reaction again changes into hexahydroaniline.Therefore, the hexahydroaniline productive rate based on the purifying of aniline charging is no less than about 99.4%.
Like this, production method of the present invention can guarantee that high yield and high purity ground effectively produce cyclohexylamines, therefore have very high industrial value.
Following embodiment further specifies of the present invention, and never should think limitation of the scope of the invention.
Embodiment 1
It is that 1m, volume are 10m that 150kg is stablized nickel catalyzator (SN-110, Sakai chemical company limited is loaded on the diatomite) and the 2 tons of aniline internal diameter of packing into
3Reaction tower in, and make internal atmosphere become hydrogen atmosphere.Then, hydrogen-ammonia gas mixture (mol ratio is 5: 1) is blasted from the reaction tower bottom continuously, the maintenance internal pressure is 7kg/cm
2, linear space speed is 7cm/sec, and internal temperature is risen to 190 ℃.
Then, by the hydrogenation heat release, temperature can raise automatically.Be controlled at 7-9cm/sec(linear space speed in input speed with hydrogen-ammonia mixture) in, the temperature of reaction system is remained on 225 ℃.Simultaneously, with aniline continuously from the bottom feed of reaction tower so that the tower fluid level remain on the constant level, thereby the reaction stable state is carried out.
The product gas that will obtain from reaction tower is cooled to 60 ℃ with condenser under above-mentioned pressure, product gas is divided in fact gas phase of being made up of hydrogen and ammonia and the liquid phase of being made up of product hexahydroaniline, unreacted aniline and by product in fact.
With above-mentioned gas phase again as the part of the hydrogen-ammonia gas mixture of the reaction tower of packing into.After reaction reaches stable state, find that liquid phase contains hydro carbons such as the tetrahydrobenzene and the hexanaphthene of 75% hexahydroaniline, 15% dicyclohexylamine, 9% unreacted aniline and N-cyclohexyl aniline and no more than 1%.
Above-mentioned liquid phase is imported first under barometric point have in the separation column of 40 bubble decies, from the low cut (hexanaphthene, tetrahydrobenzene and other hydro carbons) that boils of recovered overhead, and thing importing in bottom is had in second separation column of 45 bubble decies.Obtained required hexahydroaniline from second separation column top, by product (dicyclohexylamine, N-cyclohexyl aniline etc.) is recovered from the bottom as distillation leftover and unreacted aniline and height boil.
Unreacted aniline and the height by product that boils is recycled in the reaction system.So the amount of round-robin aniline and the high byproduct mixture of boiling is that the charging of every part of weight aniline is corresponding to 0.25-0.3 part weight.The pressure and temperature of maintenance reaction system and the input speed of hydrogen-ammonia mixture are with last identical, and fresh starting raw material aniline, unreacted aniline and the height by product that boils introduced from reaction tower bottom continuously, to keep the constant fluid level in the reactor, keep homeostatic reaction thus.
Then,, gas phase is recycled in the reaction system,, isolates hexahydroaniline, and unreacted aniline and the height by product that boils is turned back in the reaction system the liquid phase fractionation with above-mentioned same mode cooled product gas.In this way, proceed reaction process.
As a result, can produce 49.6 tons of product hexahydroaniline from 50 tons of aniline chargings.The hexahydroaniline purity of Sheng Chaning is 99.9% thus.
Embodiment 2
Use N, accelerine replaces aniline, replaces ammonia with dimethylamine, carries out hydrogenation under the identical condition of other condition and embodiment 1.
As a result, with based on starting raw material N, it is 99.9% N that 99.5% productive rate of accelerine has obtained purity, the N-dimethylcyclohexylam,ne.
Embodiment 3
Replace stablizing nickel catalyzator with Raney nickel catalyst, carry out hydrogenation under the identical condition of other condition and embodiment 1, the result obtains the hexahydroaniline of purity 99.9% with 99.4% productive rate based on the aniline charging.
Embodiment 4
With monomethylaniline is replaced aniline and uses ammonia, under other condition and embodiment 1 the same terms, carry out hydrogenation.
As a result, be 99.8% 4-methyl cyclohexylamine 99.3% productive rate of monomethylaniline is obtained purity based on starting raw material.
Comparing embodiment 1
35g aniline and 2g are stablized nickel catalyzator pack in the 200ml autoclave, at 70kg/cm
2Hydrogen pressure and 200 ℃ temperature under carry out hydrogenation up to no longer absorbing hydrogen.Reaction times is 30 minutes.This reaction obtains the 34.5g hydrogenated products.Product consists of 24% hexahydroaniline, 63% aniline, 11% dicyclohexylamine, 0.3% tetrahydrobenzene and hexanaphthene (respectively) and 1% polymkeric substance.
Claims (10)
1, a kind of method of continuous production cyclohexylamines, it be by in the presence of the nickel catalyzator with hydrogen to being selected from aniline, N-(low alkyl group) aniline and the N that low alkyl group on aniline, the ring replaces, the amino benzenes compounds of N-two (low alkyl group) aniline carries out liquid phase hydrogenation to be realized, this method comprises the amino benzenes compounds continuously feeding, at about 2-10kg/cm
2Reaction pressure and about 210-240 ℃ temperature under, when aminated compounds exists and under solvent-free condition with amino benzenes compounds hydrogenation continuously, from reaction system, discharge continuously and contain the product cyclohexylamines, unreacted amino benzenes compounds, by product, the product gas of hydrogen and aminated compounds, separation of hydrogen and aminated compounds from product gas, separating unreacted amino benzenes compounds and by product is continuously recycled in the reaction system with starting raw material benzene feed aminated compounds with cyclohexylamines and with unreacted amino benzenes compounds and by product, wherein, when amino benzenes compounds was the aniline of the last low alkyl group replacement of aniline or ring, aminated compounds was an ammonia; When amino benzenes compounds was N-(low alkyl group) aniline, aminated compounds was single (low alkyl group) amine; When amino benzenes compounds is N, during N-two (low alkyl group) aniline, aminated compounds is two (low alkyl group) amine.
2, according to the process of claim 1 wherein that described amino benzenes compounds is that aniline, the ring that monomethyl replaces aniline, ring on gone up the aniline of single ethyl replacement or encircled the upward aniline of dimethyl replacement, and described aminated compounds is an ammonia.
3, according to the process of claim 1 wherein that described amino benzenes compounds is selected from N-C
1-C
2Alkyl) aniline and N, N-two (C
1-C
2Alkyl) aniline, and described aminated compounds is selected from list (C respectively
1-C
2Alkyl) amine and two (C
1-C
2Alkyl) amine.
4, according to the process of claim 1 wherein that hydrogen and aminated compounds are used as mol ratio and are about 5: the gaseous mixture form of the hydrogen of 0.5-3 and aminated compounds is with the linear space speed charging of about 2-20cm/sec.
5, according to the method for claim 4, wherein said linear space speed is about 7-9cm/sec.
6, according to the process of claim 1 wherein that reaction pressure is about 6.5-7.5kg/cm
2
7, according to the process of claim 1 wherein that hydrogen and aminated compounds in the product gas are recycled in the reaction system.
8, be recycled according to unreacted amino benzenes compounds and by product the ratio that the process of claim 1 wherein with 0.05-0.5 part weight of every part of weight benzene feed aminated compounds.
9, according to the process of claim 1 wherein, so that the maintenance of the fluid level in the reaction system is constant with benzene feed aminated compounds and round-robin unreacted benzene aminated compounds and by product charging continuously.
10, reacted the method for continuous production hexahydroaniline in the presence of nickel catalyzator by the liquid phase hydrogenation of aniline and hydrogen, this method comprises the aniline continuously feeding, at about 2-10kg/cm
2Under reaction pressure and the about 210-240 ℃ temperature, in the presence of ammonia and during solvent-free the existence with the aniline continuous hydrogenation, the product gas that will contain product hexahydroaniline, unreacted aniline, by product, hydrogen and ammonia is discharged from reaction system continuously, separation of hydrogen and ammonia from product gas, unreacted aniline is separated with hexahydroaniline with by product, and unreacted aniline and by product are continuously recycled in the reaction system with initial charge raw material aniline.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15725687 | 1987-06-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1043699A true CN1043699A (en) | 1990-07-11 |
| CN1021322C CN1021322C (en) | 1993-06-23 |
Family
ID=15645674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88108764 Expired - Fee Related CN1021322C (en) | 1987-06-24 | 1988-12-23 | Method for production of cyclohexylamines |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1021322C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690204A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing cyclohexanediamine |
| WO2015032189A1 (en) * | 2013-09-03 | 2015-03-12 | 万华化学集团股份有限公司 | Catalyst used for resource utilization of a fixed bed aniline distillation residue and method for preparing said catalyst |
| CN109651164A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of aniline hydrogenation synthesis cyclohexylamine |
| CN111848475A (en) * | 2020-07-08 | 2020-10-30 | 西安近代化学研究所 | Preparation method of cyclohexyltriamine and preparation method of cyclohexyl triisocyanate (thiocyanate) |
| CN113149846A (en) * | 2021-05-31 | 2021-07-23 | 金城化学(江苏)有限公司 | Secondary hydrogenation process and device for byproducts in cyclohexylamine production process |
-
1988
- 1988-12-23 CN CN 88108764 patent/CN1021322C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690204A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing cyclohexanediamine |
| WO2015032189A1 (en) * | 2013-09-03 | 2015-03-12 | 万华化学集团股份有限公司 | Catalyst used for resource utilization of a fixed bed aniline distillation residue and method for preparing said catalyst |
| CN109651164A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of aniline hydrogenation synthesis cyclohexylamine |
| CN109651164B (en) * | 2017-10-10 | 2021-11-30 | 中国石油化工股份有限公司 | Method for synthesizing cyclohexylamine by aniline hydrogenation |
| CN111848475A (en) * | 2020-07-08 | 2020-10-30 | 西安近代化学研究所 | Preparation method of cyclohexyltriamine and preparation method of cyclohexyl triisocyanate (thiocyanate) |
| CN113149846A (en) * | 2021-05-31 | 2021-07-23 | 金城化学(江苏)有限公司 | Secondary hydrogenation process and device for byproducts in cyclohexylamine production process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1021322C (en) | 1993-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1089741C (en) | Recovery of a secondary ethylene stream from an ethylene purification process | |
| CN1060150C (en) | Process | |
| CN1086384C (en) | Separation method of product gas mixture for catalytic synthesis of methyl mercaptan | |
| CN1035379C (en) | Process for preparing 6-caprolactone | |
| US20170204049A1 (en) | Method for producing bis (aminomethyl) cyclohexane | |
| CN1034531A (en) | Dehydrogenation method of cyclohexenone | |
| CN1045578A (en) | The preparation method of eylylene diisocyanate | |
| CN1228305C (en) | Preparation processo f methyl methacrylate | |
| CN1021322C (en) | Method for production of cyclohexylamines | |
| CN1158841A (en) | Esterification of (meth) acrylic acid with alkanol | |
| US4914239A (en) | Method for production of cyclohexylamines | |
| CN103420776A (en) | Preparation method for methyl cyclopentene | |
| CN1117062C (en) | Process for generating vinyl carboxylate esters | |
| CN87105587A (en) | The production method of Tetra hydro Phthalic anhydride | |
| CN1060153C (en) | A process for the production of cyclohexanedimethanol | |
| CN1158840A (en) | Esterification of (meth) acrylic acid with alkanol | |
| CN1675166A (en) | Method for the production of isophorondiamine (IDPA, 3-aminomethyl-3,5,5-trimethylcyclohexylamine) having a high cis/trans-isomer ratio | |
| CN1616387A (en) | Method for preparing bisphenol A | |
| CN1176058C (en) | Method for producing phthallic anhydride according to specifications | |
| CN1116617A (en) | Process for producing acetic anhydride and acetic acid | |
| CN1680276A (en) | Purification of 1,3-bis(aminomethyl)cyclohexane by distillation | |
| CN107428674A (en) | The isomerization method of 1,3,3 trimethyl 1 (aminomethyl) aminocyclohexanes | |
| JP2003342236A (en) | Method for producing dimethyl carbonate | |
| US3657345A (en) | Isomer enrichment of 1 4-cyclohexanediamine | |
| CN113754539A (en) | Purification and decoloration method of dimethyl oxalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |