CA1210412A - Process for preparing alkanolamines - Google Patents

Abstract

IMPROVED PROCESS FOR PREPARING ALKANOLAMINES

ABSTRACT OF THE DISCLOSURE
A process is provided for preparing alkanolamines having a high yield of monoalkanolamine which comprises reacting an alkylene oxide having from two to four carbon atoms with ammonia in a molar ratio of ammonia to alkylene oxide within the range from about 15:1 to about 50:1 at temperatures at which the reaction proceeds and at pressures high enough to maintain the reaction mixture in a single supercritical fluid phase.

S P E C I F I C A T I O N

Description

BACKGROUWD OF THE INVE~TI~N
$his invention relates to a process ror the preparation of alkanolamines and, more particularly, to a proceRs for preparing alkanolamines with high yiel~s of monoalkanolamine that may be run continuously by the reaction of alkylene oxides with a large excess of ammonia wherein the reaction mixture is maintained in a ingle phase as a ~upercritical fluid.
' It is known that alkanolamines which are used in a variety of commercial applications such as emul~ification agents for soaps and cosmetics and as a starting material for the proauction of raw materials for detergents, we~ting agents, emulsifiers, textile auxiliarie~ and the like can be obtained by ~he reaction of alkylene oxides with ammonia or amines, the yield of alkanolamines being a mixture of mono: di-: and trialXanolamaines with, generally equal relative proportions of the three alkanolamines being frequently obtained. The relative proportions of these three alkanolamines in the product mixture, however, are known to depend on the relative quantities of alkylene oxide and ammonia-that are reacted and methods have been used or suggested for achieving higher yields of one or more of the alkanolamines in the mixture by varying the proportion of reactants, such as by increasing the amount o ammonia rela~ive to the alkylene oxide to obtain increa~ed yield~ of monoalkanolamine, as well as by other proce~s changes.

There i8 aiSclo5ea~ for example, in U.S. Patent ~o. 2,196,554 to H. M. Guinot a process for preparing ~ ' ? ` 3 :~

~Z~4~2 13047 mono-hydroxylalkylamines with yields of 90%-35~ by reacting at least 30 parts by weight of ammonia with one part of alkylene oxide. Relatively dilute aqueous ammonia solutions are emplo~ed and the patent discloses that steam generate~ during concentration of the reaction mixture is used for heating subsequent reaction mixtures of aqueous ammonia and alkylene oxide to reduce the heat energy requirements for the process. Another process for preparing alXanolamines with extremely high yields of monoalkanolamines and only small amounts of the di- and trialkanolamines by reacting alkylene oxide with large excess amounts of ammonia in a liquid phase reaction system is disclosed in U.S. Patent No.
3,697,598 to Weibull et al. The molar ratio of ammonia relative to alkylene oxide ~sed in the process is within the range of 10:1 to 80:1 and the reaction is carried out in the presence of a cation exchange resin catalyst. The process of the patent i5 described as being a continuous process which is capable of being run isothermally or, preferably, adiabatically at temperatures in the range of from 20~C~ to 250C. when pressures are employed that are hi~h enough to keep the reactants and reaction products in ~he liquid phase throughout the reaction. ~here is, however, no disclosure either in the description or in the examples of the patent which show that high yields of alkanolamines of any type are obtained when the process i~ carried out either adiabatically or isothermally without the use of cation exchange resin catalysts, and patentees state that without a cation exchan~e catalyst ~Z1~4~z 13047 it i~ not possible to realize an adiabatic reaction because it is too slow. Further, in U.S. Patent No.
3,723,530 to Goetze et al., there is also disclosed a process for preparing a mixture of alkanolamines by the liquid phase reaction of ethylene oxide and a large excess of ammonia, that is mole ratios of ammonia to ethylene oxide of from 14 to 40 to one. The patent teache that when the reaction is carried out in the pre~ence of up to l mole of diethanolamine per mole o' ethylene o~ide, the product obtained will be a mixture of only monoethanolamine and triethanolamine with littl~
or no diethanolamine being present. While the process of the invention is described as being capable of being run continuously either isothermally or adiabatically, the ammonia is usually e~ployed in the form of an aqueous solution, the reaction is carried out in the liquid phase at temperatures in the range of from 60 to 150~ and pres~ures of from 20 to 120 a~mospheres, and the monoethanola~ine contsnt of the product mixture generally does not exceed 70 percent by weight.
While the procesRe~ here~ofore disclosed 5u5ge8t that they are suitable for use in preparing monoethanolamines in high yields by reacting alkylene oxides with excess amounts of ammonia, their usefulness in either batch or continuous operations depends on the presence of catalysts or ~upplemental proces~ steps~ It would be highly desirable, however, if a process was available which coul~ be used to readily prepare monoalkanolamines at practical reaction rates that did no~ involve the potential additional problems associated ~ z~ 13047 with catalysts or costs due to complicated or supplemental process steps.

SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a process for preparing alkanolamines witn high yields of monoalkanolamine which comprises reacting an alkylene oxide having from two to four carbon atoms with ammonia in a molar ratio of ammonia to al~ylene oxide within the range from about 15:1 to about S0:1 at temperatures at Which the reaction proceeds above a~out 100C. and at pressures high enough to maintain the reaction mixture in a single supercritical fluid pnase to form a product mixture containing predominantly monoalkanolamine. Unreacted ammonia, wnicA is separated from the reaction mixture, may be recycled if desired.
The temperatures employed for carrying out tne reaction are preferably as high as possible so that the reaction will proceed at a suitable rate, and temperatures above the critical temperature of the reaction mixture may be advantageously used. Tne pr~ssure should be high enough to maintain the reaction mixture in a single nomogenous supercritical fluid phase at any point during the process. The density of the reaction mixture, which is dependent upon the pressure employed at the reaction temperature and is an important consideration as to the rate at wnich the reaction proceeds, should be maintained as high as possible and generally should be at least about 15 lbs./cu. ft. (240 kg/cu.~.). The reaction can be carried out batchwise or ~ Z ~ Z 13047 continuously under isothermal or adiabatic conditions and, while no catalyst i8 required, the presence of a 3mall amount of water in the reaction mixture has an advantageou~ catalytic effect. The term "supercritical fluid" as used herein is defined as the physical state of the reaction mixture wherein either the pressure or both the temperature and pressure conditions are above the critical values therefor.

DESCRIPTIO~ OF THE INVENTI~N
.
The process of the invention comprises reacting an alkylene oxide having from two to four carbon atoms with Ammonia in a molar ratio of ammonia to alkylene oxide within the range from about 15-1 to about 50:1 at a temperature at which the reaction proceeds above about 100C. and at pressures high enough to m~intain the reaction mixture in a sinqle supercritical fluid phase for the time necessary to form a product mixture composed predominately o monoalkanolamine (generally about 15% ) and small amounts of di-and trialkanolamine and separating unreacted ammonia therefrom. The mono-di-, and trialkanolamines can also be separated if desired.
The alkylene oxides to which the process of the present invention i applicable is any l,2-alkylene oxide having from two to four carbon atoms, including ethylene oxide, propylene oxide, 1,2-butylene oxide,

2,3-butylene oxide, and isobutylene oxide.
In accordance with the present invention, it is essential that a large excess of ammonia is used in the z reaction to obtain yields of monoalXanolamines of at least 65 weight percent. It is advantageous to use about 15 to about 50 moles, and preferably from about 20 to about 35 moles, of ammonia for each mole of alkylene oxide to obtain yields in many ca~es of from about 70 to 80 weight percent. The ammonia shoul~ be added to the reaction mixture in a liquid state, generally in a substantially anhydrous condition. The liquid ammonia and alkylene oxide may be premixed just prior to fee~ing into the reaction vessel or each may be added separately to the reactor.
In accordance with the practice of the invention, it i~ important that the reaction of alkylene oxide and ammonia be carried out with the reaction mixture in a homogenous, single supercritical fluid phase so that the reaction will proceed at a suitable rate. The reaction can be carried out under isothermal or adiabatic conditions, The temperature at which the reaction ahould be carried out is within the range from about lOO-C. to about 200~C., though the upper limit of the temperature is not critical. Pre erably, the reaction temperature is wi~hin the range from about the critical te~perature of the reaction mixture (generally 'rom about 130-C.) to about 180C. Under isothermal condi~ion~, since the reac~ion is ~trongly exothermic, it i5 necessary to withdraw heat from the reaction mixture to keep the temperature approximately constant.
In the case when the reaction is to be carried out under adiabatic or nearly a~iabatic conditions, the reactants are ~reheated ~o from about 100C. to }30C.

~ 2 13047 before ~hey are introduced into the reactor. Because of the reaction heat involved, any selected initial reaction temperature i~ rapidly increased and the initial reaction temperatures shoul~ be chosen so that the maximum de~ired temperature will be obtained during the period of residence of the reaction mixture within the reactor. The preferred maximum temperature is between about 170~C. and 180~C. though the higher the reaction te~perature, the higher the pressure that is necessary to ~aintain the den-Qity of ~he reaction mixture as high as possible.
At such reaction temperatures, it is essential that the pres3ures imposed on the system are high enough to maintain ~he reaction mixture in a single 3upercritical fluid phase. In any case, the reaction pressure should be at least as high as the critical pre~sure o~ the reaction mixture at any point encountered during ~he process. Pre.erably, the pres~ures impo~ed on the syste~ are within the ran~e from about 170 to about 240 atmospheres. The latter is a practical upper limit and is not critical.
As pointed out hereinabove, it is important that the reaction mixture is maintained in a single phase as a supercritical fluid and that the density thereof is as high as po~sible so tha~ the reaction will proceed at a ~uitable rateO The densi~y of the reaction mixture should be above the critical density and, in general, at least 15 lb3/cu. ft. (240 kg/cu.m.).
Preferably, the den~ity of the reaction mixture should be maintained in the range of from a~ou~ 21 to about 28 ~Z~ 2 13047 lbs/cu. ft. or even higher if practical. The mole ratio of ammonia and alkylene oxide reactants and the reaction temperature have a significant effect on the density of the reaction mixture. It is important, therefore, that the reaction pressures are maintained as high as is practical so that the reaction mixture is not only maintained in a single supercritical fluid phase but that the density of said mixture i5 as high as possible 50 that the reaction will proceed at a practical rate.
While it is not essential that the process of the invention be carried out in the presence of any catalyst, advanta~eous embodiments o~ the process of the invention may be carried out with a small amount of water incorporated in the reaction mixture along with the alXylene oxide and ammonia reactants. It ha~ been found that the presence of ~mall amounts of water in the reaction mixture has an advantageous catalytic e~Çect on the reaction rate for forming alkanolamines though it does not appear to affect the yield of monoalkanola~ine in the product mixture. The amount of water that is pre3ent is not critical, and only small amounts of wa~er may achieve the catalytic affect that is desired~ In general, from about 0.5 percent up to about 5 percent by weight of water based on the weight of the reaction mixture need be present. Amounts of water greatly in excess of that which may be catalytically u~eful, however, should be a~oided to limit the energy require~ents needed to separate water from the product mixture.
After conclusion of the reaction, substantially 12~ 2 13047 all of the alkylene oxide has been reacted and the unreacted ammonia may be separated from the product mixture by any means known in the art, such as by reducing the pressure to below that at which tne ammonia is in a gaseous phase, so that the ammonia can be separated as a gas. Tne ammonia can then be recycled, if desired, by repressurizing to a liquid phase before mixing with alkylene oxide. Tne unreacted ammonia may also be separated from the product mixture by distilling under pressure. The al~anolamine analogues in the product mixture may also be separated by known distillation methods or the product mix~ure may be used as a starting material for the preparation of other organic amines.
As pointed out hereinabove, the process of tne invention may be rarried out batchwise or continuously, either under isothermal or adiabatic conditions. In an alternate embodiment of the process of the invention which is run continuously, tne ammonia and alk~lene oxide reactants in the molar ratios hereinabove described are continuously fed, eitner separately or, preferably, as a mixture, to a ~ubular reactor which is capable of operating as ef~iciently as possible as a plug-flow reactor having means for providing the pressures needed to maintain the reaction mixture in a single supercritical fluid phase. The reactor may be carried out isothermally in a tubular reactor having cooling means or, advantageously, under adiabatic conditions where the reactants are preneated to a temperature, for example, between about 100C. to - 10 - , ~2~ 13047 130C. Small amounts of water may also be added to the reaction mixture, if desired.
The residence time of the single phase supercritical fluid reaction mixture in said adiabatic reactor should be sufficiently high to permit the reaction to proceed to completion, generally in less than about 1/2 hour. At the completion of the reaction, that is generally when all the alkylene oxide has been reacted, the unreacted ammonia is separated from tne product mixture as nereinabove described and recycled to the reactor. The recycled ammonia is pressurized to a liquid state prior to mixing within tne alkyiene oxide and fresh make-up ammonia~ The product mixture which is obtained can be separated into alkanolamine components by distillation methods known in the art or can be used as a starting material for the production of materials such a organic polyamines.
This invention will ~ecome more clear when considered together with the following examples which are set forth as being merely iilustrative or the invention and which are not intended in any manner, to be limitative thereof. Unless otherwise in~icatea, all parts and percentages are by weight.

Example 1 A 2 liter (1984 ml.) stainless steel autoclave having a high speed agitator and equipped with charginy, sampling, and temperature control means was used in carrying out the reaction runs of this example. A
series of reactions wexe run using liquid anhydrous ~21~ 13047 ammonia, water, and ethylene oxide in the proportions reported in Table I. The ammonia and water were charged to the autoclave which was evacuated to a pressure of about 1 mm Hg absolute and then witn vigorous agitation were heated to 170C. The etnylene oxide was then charged to the autoclave and, with vigorous agitation, the reaction temperature was maintained at 170C. for 30 minutes. ~ sample of tne reaction mixture was taken after the time indicated in Table I during each o the reaction runs of tnis example. After 30 minutes, the reaction mixture was cooled to below 50C. and unreacted ammonia was vented from the autoclave until tne pressure in the autoclave indicated essentially complete removal of gas. The liquid product mixture was then drained from the autoclave and the composition thereof was determined by-gas chromatographic analy~is.
The amount of ammonia and ethylene oxide reactants used were inten~ea to obtain an average ammonia to ethylene oxide mole ratio of 25:1 for each of the reaction runs of this example. The average density of the reaction mixture during each of the reaction runs of this example was 24 lbs./cu. ft.
A summary of the proportion of ingredients, reaction conditions and composition of tne product mixtures for each of the reaction runs of this example are reported in Table I.
It is apparent from results shown in Table I
that an alkanolamine mixt~re was prepared with a high yield of monoal~anolamine during each of the runs of this example.

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The proportion of ingredients, temperature and pressure condition's and analysis results (used analytical procedures described in example 1) for eacn of the reaction runs of this Example are summarized in Table II.
It is apparent from the results shown in Table II that an alliauolamine product mixture containing high yields of morroethanolamine was prepared during eacn reaction run of this example. The reaction rate for each o the runs would be suitable but the resul~s snow that the reaction rate for runs 1 to 4 which were maintained at an average density of 22 lbs/cu. ft. was somewhat slower than the reaction rate for runs 5 to 8 which were maintained at an average density of 24 lbs/cu.ft.

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~L2~4~2 Example 3 A mixture of 786.4 grams (46.2 moles) of ammonia and 15.7 grams of water was charged to tne stirred autoclave described in Example 1 whicn had previousl~ been vacuated to about one millimeter of Hg vacuum. The mixture was heated to 170C. and 3900 psig with stirring and 54.l grams (1~23 moles) of ethylene oxide were injected into the stirred mixture. The density of the reaction mixture was maintained a~ an average of 27 lbs./cu. ft.
Small samples of the reaction mixture were periodically removed from the autoclave and analyzed by mass spectrometry for residual ethylene oxide and tne sample times and conversion of ethylene oxide are shown below in Table III.
TABLE III

Time, Minutes ~ Conversion Sample Number from EO Injection Based on Residual EO

1 3 74.9 2 6 77.2 3 9 92.3 4 24 100.0 After 30 minutes from the time ethylene oxide was added, the mixture in the autoclave was cooled to below 50C. and the unreacted ammonia was se~arated from the product mixture. The liquid product mixture was discharged from the autoclave and analyzed for alkanolamine composition by gas chromatography. The product mixture was determined to contain 84.03 percent monoethanolamine, 14.36 percent diethanolamine, and 1.60 percent triethanolamine.
F~r comparison purposes, ~ne following reaction ~Z~

run was carried out in the autoclave reactor described in Example l.
In this control, a mixture of 678 grams (3~.81 moles) of ammonia and 13.57 grams of water was charged to the evacuated, stirred autoclave of Example l and heated to 120C. Nitrogen gas was added to the autoclave until a pressure of 2000 psig was o~tained.
Ethylene oxide ~72.98 grams, 1.659 moles) was injected into the stirred mixture in the autoclave and tne temperature was maintained at 120C. during the entire run. The reaction mixture in the autoclave was a single phase li~uid.
Small samples were periodically removed from the autoclave reactor and analyzed by mass spectrometry for residual ethylene oxide and the results are summarized in Table V, below.
TABLE V

~ime, Minutes ~ Conversion Sample Number from EO Injection Based on Residual E9 1 ~ 16.25 2 10 33.00 3 15 35.25 56.00 73.00 6 30 82.75 7 40 92.50 The reaction was continued at 120C. for an additional 138 minutes after which the mixture was cooled, unreacted ammonia was separated therefromr and the liquid product ~ixture was recovered and analyzed by gas chromatography.
The product mixture was determined to contain 74.44 percent of monoethanolamine, 21.17 percent ~. .

~Z1~4~Z

diethanolamine, and 4.38 percent triethanolamine. While the liquid phase reaction resulted in nigh yields of monoethanolamine, the reaction rate was determined slow to be suitable.

Claims (14)

WHAT IS CLAIMED IS:

1. A process for preparing alkanolamines having a high yield of monoalkanolamine which comprises reacting an alkylene oxide having from two to four carbon atoms with ammonia in a molar ratio of ammonia to alkylene oxide within the range from about 15:1 to about 50:1 at temperatures at which the reaction proceeds above about 100°C., and at pressures high enough to maintain the reaction mixture in a single supercritical fluid phase to form a product mixture containing predominantly monoalkanolamine.

2. The process of claim 1 wherein the density of the reaction mixture is above 15 lbs./cu. ft.

3. The process of claim 1 wherein the reaction is carried out in the presence of a small, catalytically effective amount of water.

4. The process of claim 1 wherein the reaction temperature is up to about 200°C.

5. The process of claim 1 wherein the reaction is carried out at pressures in the range from about 170 to 240 atmospheres.

6. The process of claim 5 wherein the density of the reaction mixture is in the range from about 21 to about 28 lbs./cu. ft.

7. The process of claim 1 wherein the reaction temperature is in the range from about the critical temperature of the reaction mixture to about 180°C.

8. The process of claim 6 wherein the reaction temperature is in the range from about the critical temperature of the reaction mixture to about 180°C.

9. The process of claim 8 wherein the reaction is carried out in the presence of a small, catalytically effective amount of water.

10. The process of claim 9 wherein the process is carried out adiabatically.

11. The process of claim 1 wherein unreacted ammonia is separated from the product mixture.

12. The process of claim 11 wherein a product mixture containing predominately monoalkanolamine is recovered.

13. The process of claim 3 wherein the density of the reaction mixture is in the range from about 21 to about 28 lbs./cu. ft.

14. The process of claim 13 wherein the reaction is carried out in the presence of from about 0.5 to 5 percent by weight of water based on the weight of the reaction mixture.