United States Patent 19 11) 4,400,539

Gibson et al. 45) Aug. 23, 1983

54 PROCESS FOR THE MANUFACTURE OF 57 ABSTRACT
ETHYLENEDAMINE There is described a continuous process for the manu
75) Inventors: Charles A. Gibson; John R. Winters, facture of ethylenediamine from the products of the
both of South Charleston, W. Va. reaction of ethylene oxide and ammonia, provision of a
continuous recycle stream of monoethanolamine to the
73 Assignee: Union Carbide Corporation, products of the reaction of ethylene oxide and ammo
Danbury, Conn. nia, the amination of such products of the reaction of
(21) Appl. No.: 307,215 ethylene oxide and ammonia combined with the mono
ethanolamine recycle in which the feed stream to the
22 Filed: Sep. 30, 1981 amination reaction zone contains at least 70 weight
51 Int. Cl. ....................... C07C 85/06; CO7C 89/02 percent monoethanolamine as well as diethanolamine
52 U.S. Cl. .................................... 564/480; 564/477; and triethanolamine, the moles of ammonia provided to
564/479;564/497; 564/498 the amination reaction exceeds the molar concentration
58 Field of Search ................ 564/477, 480, 475, 479 of alcoholic hydroxyl groups present in the amination
feed, and the feed to the amination reactor contains at
56 References Cited least a 5% increase in the concentration of monoetha
U.S. PATENT DOCUMENTS nolamine over the concentration of monoethanolamine
in the reaction product stream from the reaction of
4,123,462 10/1978 Best ..................................... 564/480 ethylene oxide and ammonia.
Primary Examiner-John Doll
Attorney, Agent, or Firm-Jean B. Mauro 8 Claims, 1 Drawing Figure
U.S. Patent Aug. 23, 1983 4,400,539
 1.
4,400,539 2
of this statement, it is to be recognized that ethylenea
PROCESS FOR THE MANUFACTURE OF mines are known to be produced from the reaction of
ETHYLENEDIAMINE ammonia and monoethanolamines. According to Arne,
this route has the advantage of virtually eliminating the
BRIEF SUMMARY OF THE INVENTION 5 environmental problems associated with the ethylene
1. Technical Field dichloride process. In characterizing the process, Arne
This invention relates to a continuous process for the states that: "It has the disadvantage of producing only
manufacture of alkyleneamines starting from the reac small quantities of polyethylene polyamines, producing
tion of ethylene oxide with ammonia to produce a mix O
instead substantial amounts of less valuable piperazine
ture of alkanolamines and the conversion of the alkanol and substituted piperazines.' What this means is that
amines by amination to ethylenediamine and other al according to Arne, polyethylene polyamines are re
kyleneamine products. garded to be valuable products and the piperazines are
2. Background Art not regarded to be valuable products because the mar
In a private report by the Process Economics Pro ket for the piperazines is not large enough compared to
gram, Report No. 138, entitled "Alkyl Amines', by 15 the capacity existing for producing the same.
Michael Arne, of SRI International, dated March 1981, According to Arne, a desirable process for the manu
there is a section which covers the production of facture of ethyleneamines would be one which would
"Ethyleneamines from Monoethanolamine' (see pps. produce substantially smaller amounts of the pipera
81-107, 116 and 117). The author considered a substan zines and larger amounts of the various polyethylene
tial collection of the prior art relating to the conversion 20 polyamines.
of monoethanolamine to, in particular, ethylenediamine. In the analysis of the prior art that Arne relied upon,
For example, the author considers Lichtenberger et al., some interesting factors which induce the manufacture
U.S. Pat. No. 3,068,290, patented Dec. 11, 1962, who of the piperazines are revealed. For example, U.S. Pat.
describe the reaction of ammonia and monoethanol No. 3,766,184 reveals in example 10 that when diethan
amine over a nickel/magnesium oxide catalyst to give 25 olamine was reacted with ammonia and water at 225 C.
ethylenediamine; Winderl et al., U.S. Pat. No. and 230 atm. in the presence of hydrogen gas and 7
3,270,059, patented Aug. 30, 1966, who describe the grams of the reduced catalyst in tablet form comprising
reaction of monoethanolamine and ammonia in the pres 3 to 4% each of nickel oxide, cobalt oxide and iron
ence of hydrogen over a cobalt/nickel catalyst at oxide, the remainder being aluminum oxide, 26% of the
150-300° C. and 200 atm.; Johansson et al., U.S. Pat. 30
diethanolamine had been converted of which 49% had
No. 3,766, 184, patented Oct. 16, 1973, who describe the formed aminoethylethanolamine, 36% formed pipera
reaction of ammonia and monoethanolamine to give zine, and 8% formed ethylenediamine. After 5 hours of
ethylenediamine; Adam et al., U.S. Pat. No. 3,520,933, reaction, the example shows that 82% of the diethanol
patented July 21, 1970, who describe the reaction be amine had been converted, at which 16% had been
tween ammonia and monoethanolamine over a cobalt 35
/nickel/copper/silver catalyst in the presence of hydro aminated to aminoethylethanolamine, 60% to pipera
gen to give ethylenediamine; Corr et al., French Pat. zine, and 10% to ethylenediamine. Thus when diethan
No. 2,065,046, published July 23, 1971, who describe olamine is reacted with ammonia, considerably more
the production of ethylenediamine from monoethanol piperazine is formed than ethylenediamine. This should
amine and ammonia by reaction over a cobalt catalyst 40 be contrasted with example 17 of the same patent which
containing phosphorus pentoxide and boric oxide; reacted ammonia with monoethanolamine in the pres
Boettger et al., U.S. Pat. No. 4,014,933, patented Mar. ence of water and obtained ethylenediamine as 60% of
29, 1977, who describe the reaction of ammonia and the yield of product, piperazine as 12% of the product
monoethanolamine over a cobalt/nickel catalyst in the yield, aminoethylpiperazine as 2% of the product yield
presence of hydrogen; Best, U.S. Pat. No. 4,123,462, 45 and hydroxyethylpiperazine as 2% of the product yield.
patented Oct. 31, 1978, who describes the reaction of When diethanolamine is combined with monoethanol
ammonia with monoethanolamine or a mixture of alka amine as a reactant in the process of that patent, we see
nolamines such as one which contains 90% by weight of from example 11 that the conversion to piperazine is
monoethanolamine, 7% by weight of diethanolamine intermediate of those conversions obtained in examples
and 3 weight percent of triethanolamine, in the presence SO 10 and 17, suggesting that the presence of diethanol
of a nickel-rhenium supported catalyst; Habermann, amine is a major factor for this increased conversion to
U.S. Pat. No. 4,153,581, patented May 8, 1979, who the unwanted piperazine.
describes the reaction of ammonia and monoethanol U.S. Pat. No. 4,014,933, in example 5, also demon
amine, in a mole ratio of about 7/1, in the presence of a strates the reaction of ammonia with diethanolamine. In
cobalt/copper/zinc oxide catalyst at 1500 psia to pro 55 that example, the patentees obtained a product composi
duce ethylenediamine; and LeGoff et al., U.S. Pat. No. tion comprising 4% ethylenediamine, 22% of pipera- .
4,209,424, patented June 24, 1980, who produce ethyl zine, 17% of aminoethylethanolamine, and 54% of un
enediamine from monoethanolamine and ammonia over reacted diethanolamine. Essentially the same results can
a nickel catalyst utilizing a rhodium promoter. be seen in example 8 of German application No.
The significance of the aforementioned report by 60 1,950,604, published Apr. 22, 1971.
Arne is its evaluation of the prior art and its interpreta The aforementioned examples which clearly demon
tion, on the basis of his evaluation of the prior art, of a strate the propensity of diethanolamine to react with
process for the manufacture of ethylenediamine from ammonia to produce a disproportionate amount of pip
monoethanolamine and ammonia. According to Arne, erazines is further demonstrated in U.S. Pat. No.
BASF and Berol are currently producing ethylenea 65 3,766,184. By comparing examples 11 and 17 of the
mines in Europe from monoethanolamine and ammonia patent, we find that the presence of diethanolamine and
and Union Carbide has announced a plant expansion triethanolamine in the reaction feed, as demonstrated in
based on the same process. Regardless of the accuracy example 11, contribute to the formation of a dispropor
 4,400,539
3 4
tionate amount of piperazine. It should be noted in the stream contains ammonia in an amount such that the
case of example 17 that the feed was ammonia with number of moles thereof substantially exceeds the molar
monoethanolamine and the amount of the piperazines concentration of alcoholic hydroxyl groups present in
which were formed constituted essentially 1/10th the the stream. The process also involves providing a con
amount of the ethylenediamines formed. In example 1 1, tinuous recycle stream consisting essentially of mono
the piperazines, which were formed constituted about ethanolamine, provides for an amination zone compris
1/5th the amount of the ethylenediamine which was ing a solid amination catalyst, and a separation zone for
formed. However, in example 17 the process was oper separating monoethanolamine from the amination prod
ated in such a manner as to favor the formation of piper uct stream removed from the amination zone. The
azine; note that the monoethanolamine conversion in 10 monoethanolamine which is separated from the amina
example 17 was 55% which indicates a longer reaction tion product stream forms the aforesaid recycle stream.
time thus favoring high conversions which "leads to The recycle stream is fed under pressure to the amina
lower selectivity to the desired ethylenediamine and to tion zone by combining it with the aforesaid fluid
more of the undesirable piperazine', see Arne, pg. 83, stream to form a continuous amination feed stream
Supra. 15 which is under pressure. This amination feed stream is
This would suggest that the presence of diethanol supplied to the amination zone which is maintained at a
amine and/or triethanolamine in the feed along with superatmospheric pressure but sufficiently below the
monoethanolamine contributes to the formation of an pressure of the amination feed stream to assure flow
amount of piperazine which exceeds that which would thereof through the amination zone and to form an
be obtained from monoethanolamine alone. It also sug amination product stream containing ethyleneamines
gests that the amount of the piperazines formed exceeds therein. The ethyleneamines are continuously recov
that amount which the amount of diethanolamine and ered from the aforesaid amination product stream. The
/or triethanolamine, perse, would form under the reac amination feed stream provided contains at least 70
tion conditions employed. This being the case, it it logi weight percent of monoethanolamine based on the
cal to assume that diethanolamine and/or triethanol 25 weight of the ethanolamines contained therein. The
amine are in some manner reacting with monoethanol moles of ammonia in the amination feed stream exceeds
amine or inducing the unfavorable reaction of monoeth the molar concentration of alcoholic hydroxyl groups
anolamine so as to form increased amounts of the un in said amination feed stream. The amination feed
wanted piperazines. stream also contains at least a 5% increase in the con
The foregoing analysis also suggests that while the 30 centration of monoethanolamine over that which is
manufacturing of alkyleneamines from monoethanol contained in the aforesaid homogeneous fluid stream.
amine reaction with ammonia is sound, if one were to The process of this invention provides a number of
utilize a reaction feed of monoethanolamine combined advantageous novel features. For example, one may
with diethanolamine and/or triethanolamine, more of utilize in the amination reaction a product stream ob
the unwanted piperazines would be produced and this 35
tained directly from an ethanolamines reactor (which
would constitute an economic loss. involves the reaction of ethylene oxide with ammonia as
However, the use of monoethanolamine alone is not aforedescribed) and thereby reduce significantly the
without its disadvantages. It is known that monoetha raw material and energy costs attendant in the forma
nolamine is formed by the reaction of ammonia and tion of alkyleneamines. As a consequence of doing this,
ethylene oxide and the products of that reaction consti 40
there is provided to the amination reaction a feed stream
tute a mixture of monoethanolamine, diethanolamine which contains diethanolamine and triethanolamine.
and triethanolamine. If monoethanolamine has to be This invention gives recognition to the fact that by
isolated before it is utilized in the manufacture of the maintaining a concentration of monoethanolamine in
alkyleneamines, it means that the monoethanolamine the feed stream to the amination zone at a level greater
must be distilled from the product mixture in which it is 45
than is provided by the reaction of ethylene oxide and
formed and this adds to the cost of the monoethanol ammonia, that one can enhance the capacity in the am
amine. Moreover, such monoethanolamine, when re ination zone to reduce the formation of the piperazines.
covered, is brought to room temperature and when it is This is believed to occur by virtue of diluting the prod
subsequently utilized in the formation of the ethylenea uct stream from the ethylene oxide and ammonia reac
mines, it has to be heated and pressurized to the condi 50
tor, i.e., the homogeneous fluid stream, with monoetha
tions utilized for the manufacture of the alkyleneamines. nolamine whereby to materially reduce the affect that
Consequently, there is a considerable energy cost in diethanolamine and/or triethanolamine have on en
volved in the effective utilization of monoethanolamine hancing the formation of the piperazines.
per se. It should also be appreciated that the ammonia The process of this invention achieves a production
which is utilized in the reaction to produce the mono 55
cost advantage of at least 20% over the production cost
ethanolamine is not directly available for the reaction to of producing ethyleneamines by the ethylene dichlo
produce the alkyleneamines unless it is subjected to the ride-ammonia process. Giving proper credits for pipera
same treatment of heating and pressurization as is the zines, the process of this invention gives substantially
monoethanolamine.
greater return on investment and net income, even on
DISCLOSURE OF INVENTION an after tax basis, than the ethylene dichloride-ammonia
process.
There is described herein a continuous process for the
manufacture of ethylenediamine, as well as other DETAILS OF THE INVENTION
ethyleneamines, which comprises providing a continu Reaction Between Ethylene Oxide and Ammonia to
ous homogeneous fluid stream under pressure, which 65
Form Alkanolamines
stream comprises ammonia, monoethanolamine, dieth
anolamine and triethanolamine as produced by the di The process which may be employed to provide a
rect reaction of ethylene oxide and ammonia. The product stream of alkanolamines by the reaction of
 4,400,539
5 6
ethylene oxide and ammonia, viz. the aforementioned thereby maximizes the production of the desired etha
continuous homogeneous fluid stream, may be any one nolamines, minimizing the formation of higher molecu
of the processes described in the prior art which involve lar weight ethanolamine products. The preferred pro
the reaction of ethylene oxide with ammonia to produce cess for making the ethanolamines involves reacting a
a mixture of monoethanolamine, diethanolamine and 5 homogeneous stream of a mixture of ethylene oxide and
triethanolamine. A desirable process from the stand ammonia in a molar ratio of ammonia to ethylene oxide
point of this invention is one which produces a mixture within the range between about 15:1 and about 50:1.
in which monoethanolamine is present in amounts The stream is maintained in a single, homogeneous,
greater than 50 weight percent of the total concentra supercritical fluid phase by maintaining a temperature
tion of alkanolamines. Illustrative of such processes are 10 and pressure which creates such a phase. The tempera
those described in U.S. Pat. No. 2,196,554, U.S. Pat. No. ture for effecting the supercritical fluid is that tempera
3,697,598, and U.S. Pat. No. 3,723,530. ture which constitutes the minimum critical tempera
The process in U.S. Pat. No. 2, 196,554 to Guinot ture for the fluid composition. Typically, the supercriti
involves preparing monohydroxylethylamines in yields cal fluid phase has a density of at least 15 pounds per
of 90%-95% by reacting at least 30 parts by weight of 15
ammonia with l part of ethylene oxide in a liquid phase cubic
for a
foot. This supercritical fluid phase is maintained
period of time sufficient to permit the reaction to
reaction. Relatively dilute aqueous ammonia solutions proceed to completion and thus to form a product mix
are employed and the patent discloses that steam gener ture containing predominantly monoethanolamine (fre
ated during concentration of the reaction product mix quently at least about 70 weight percent of the composi
ture is used for heating subsequent reaction product 20 tion of the ethanolamines) and small amounts of the di
mixtures to separate ammonia gas therefrom, thus re and triethanolamine.
ducing the heat energy requirements for the process. In In practicing this preferred process for making the
the practice of the instant invention, when utilizing the ethanolamines, the temperatures employed to carry out
reaction of this patent it will not be necessary to sepa the reaction between ethylene oxide and ammonia is
rate the ammonia gas from the product mixture since 25
arinmonia gas will be utilized in the amination step re preferably above the critical temperature of the reac
tion mixture. When maintained at that temperature, a
sulting in the formation of the ethyleneamines.
Another process for preparing ethanolamines with single the
supercritical fluid phase is achieved within which
reaction between ethylene oxide and ammonia will
extremely high yields of monoethanolamines and only occur. The reaction proceeds when the reaction mix
small amounts of the di- and triethanolamines by react- 30 ture is maintained above its critical temperature to
ing ethylene oxide with large excess amounts of ammo achieve the single supercritical fluid phase. If one in
nia in a liquid phase reaction system is disclosed in U.S.
Pat. No. 3,697,598 to Weibull, et al. The relative molar creases the pressure of the reaction zone, then there will
ratio of ammonia to ethylene oxide used in the process be a consequent increase in the reaction rate. An in
is within the range of 10:1 to 80:1 with the reaction 35 crease in pressure is reflected by an increase in the den
being carried out in the presence of a cation exchange sity of the supercritical fluid phase. The degree of in
resin catalyst. The process of this patent is described as crease in the density of the reaction mixture is only
being a continuous process which is capable of being important as it relates to the reaction rate, but in terms
run isothermally or, preferably adiabatically, at temper of practicing the preferred process for making the etha
atures in the range of 20° C. to 250° C. when pressures 40 be nolamines it is only necessary that the reaction mixture
are employed that are high enough to keep the reactants maintained as a single phase supercritical fluid. In the
and reaction products in the liquid phase throughout typical case, the density of the single phase supercritical
the reaction. fluid will be at least 15 pounds per cubic foot (240
U.S. Pat. No. 3,723,530 to Goetze et al. also discloses kg/m3).
a process for preparing a mixture of alkanolamines by 45 The reaction may be carried out under isothermal or,
the liquid phase reaction of ethylene oxide and a large preferably adiabatic conditions, and while no catalyst is
excess of ammonia. In this patent the mole ratios of required the presence of a small amount of water in the
ammonia to ethylene oxide are from 14:1 to 40:1. The reaction mixture has an advantageous catalytic effect.
patent describes the process as being capable of being In the most preferred embodiment, it is desirable to
run continuously, either isothermally or adiabatically. 50 effect the reaction in a plug-flow type reactor by feed
When operated continuously, the reaction is carried out ing a stream comprising ammonia and ethylene oxide to
in the liquid phase at temperatures in the range from 60 one end of a tubular plug-flow type reactor and with
C. to 150° C. and pressures of 20 to 120 atm., and the drawing the effluent containing the desired alkanola
monoethanolamine content of the product mixture gen mines from the other end thereof. It is also very desir
erally does not exceed 70% by weight. 55 able in the practice of the invention to maximize the
The preferred method for making ethanolamines is plug-flow characteristics of the reactor and for this
set forth in copending applications Ser. Nos. 247061, reason the geometry of the reactor should be such as to
filed Mar. 24, 1981, and 259,899, filed May 4, 1981. minimize any backmixing or recycling that might occur
These applications disclose processes for preparing as a consequence of improper reactor design or im
alkanolamines in which high yields of monoalkanola 60 proper fluid velocities.
mines are obtained. The processes involve the reaction In making the ethanolamines, it is preferred that a
of, e.g., ethylene oxide with a large excess of ammonia large excess of ammonia relative to the ethylene oxide
in a single supercritical fluid phase. The process dis be used in the reaction to obtain yields of monoe
closed in said applications is capable of being run batch thanolamines of at least 65 weight percent, preferably at
wise or continuously under isothermal or adiabatic con 65 least 70 weight percent and worst. In a typical practice
ditions. When the process is operated as a continuous of the invention in order to obtain these desirable yields
process, the desired reactor is of a design which pro of monoethanolamine, one may employ between about
vides for the minimization of produce recycle and 15 to about 50 moles, and preferably between about 20
 4,400,539, 8:
7.
to 35 moles, of ammonia for each mole of ethylene employed and indeed, in the typical case, they should be
oxide. - - - - - - - avoided to climit the energy requirements needed to
As indicated above, the temperature at which the separate water from the product mixture. . . .
reaction between ethylene oxide and ammonia is carried In this embodiment, before, carrying out the reaction,
out is important if one operates the reaction such that of ethylene oxide with ammonia, the process (as pointed
the reaction mixture is maintained in single supercritical out previously) is carried out continuously under iso
fluid phase during the course of the reaction. As pointed thermal or, preferably adiabatic conditions, in a plug
out previously, the temperature should be above the flow type reactor or a series of reactors which in combi
critical temperature for the reaction mixture in order to nation achieve the results of a plug-flow type reaction
achieve the supercritical fluid phase. The temperature 10 system. A turbulent single directional flow of the reac
should be above 130 C. and may be as high as 225 C. tion mixture through a plug-flow type reactor, under
though the upper limit of the reaction temperature is. plug-flow type reaction conditions, results in the flow
not critical so long as the critical temperature of the of the stream through the reactor with a minimum
reaction mixture is exceeded. In the most preferred amount of backmixing and thermal stratification. This
embodiment, the reaction temperature is within the 15 results in essentially eliminating hot spots in the reactor.
range from about the critical temperature of the reac which will affect the reaction rates and product distri
tion mixture, generally from about 130 C. to about 225 bution, i.e., as between monoethanolamine, diethanol
C. Under isothermal conditions, since the reaction is amine and triethanolamine, and minimize the reaction of
strongly exothermic, it is necessary to withdraw heat ethylene oxide with already formed ethanolamines.
from the reaction mixture to keep the temperature ap 20
proximately constant. ,, , ; , THE AMINATION REACTION
In cases where the reaction is to be carried out under The amination reaction employed in carrying out the
adiabatic or nearly adiabatic conditions, the reactants process of this invention is not narrowly limited pro
are preheated to a temperature which is at least suffi vided that the objectives of the invention are obtained.
cient to effect an interreaction between the reactants, 25
To that extent, one may employ the technology of Arne
such as a temperature as low as 20° C. and higher. It Lichtenberger et al., Winderl et al., Johansson et al.,
should be understood that if one attempts to effect the Adam et al., Corr et al., Boettger et al., Habermann and
reaction at such low temperatures as 20° C. that such LeGoff et al. to produce ethylenediamine from the
will not occur with the reaction mixture being in a product mixture derived from the reaction of ethylene
single supercritical fluid phase and therefore it will be 30
oxide with ammonia, as hereinabove described.
necessary to preheat and/or utilize the exotherm of the However, in the preferred practice of this invention,
reaction to achieve conditions which would bring the the amination process is carried out in such a manner as
reaction mixture under supercritical fluid conditions as to favor the selectivity of the reaction towards the pro
aforestated. However, in the desirable practice of this duction of ethylenediamine. This is accomplished by
invention the reactant mixture is introduced at a tem 35
perature such that they achieve a supercritical fluid utilizing the nickel-rhenium catalyst which are de
condition. Under such conditions, the reaction occurs scribed in the aforementioned Best patent and U.S. Pat.
rapidly with a strong exotherm. In the typical case, the No. 4,111,840, patented Sept. 5, 1978, to Best.
reactant mixture is heated and introduced to the reac Broadly speaking, the objective of the amination
tion zone at a temperature sufficient to achieve the reaction is to convert the products of the reaction of
supercritical fluid conditions. The pressure of the reac ethylene oxide and ammonia, which products contain,
tion zone, coupled with its temperature, should be such inter alia, monoethanolamine, diethanolamine and tri
as to achieve the supercritical fluid state. Desirably, the ethanolamine, to ethyleneamines. In the typical practice
pressure throughout the course of the reaction main of the invention, the amination reaction serves to con
tains the single phase supercritical fluid state. The pres 45 vert such products to, inter alia, ethylenediamine. As
sures applied in the reaction of ammonia with ethylene mentioned above the reaction of ethylene oxide and
oxide is within the range of about 2000 pounds per ammonia produces a stream which contains essentially
square inch absolute (psia) to about 5000 pounds per ammonia, monoethanolamine, diethanolamine and tri
square inch absolute (psia). ethanolamine. The amount of ammonia in the product
Though the reaction of ethylene oxide and ammonia 50 mixture is subject to the amount of ammonia which is
under supercritical fluid conditions need not be carried utilized in the reaction with ethylene oxide. In the typi
out in the presence of any particular catalyst, it has been cal case the amount of ammonia which will be used will
found advantageous as characterized in the aforemen be vastly in excess of the stoichiometry of the reaction
tioned copending applications to effect that reaction in to produce the product mixture and therefore the avail
the presence of a small amount of water incorporated 55 able ammonia which is used in the reaction between
with the reaction mixture. It has been found that such a ethylene oxide and ammonia will in large part be ade
small amount of water has an advantageous catalytic quate for the subsequent amination reaction to produce
effect on the reaction rate for forming ethanolamines the ethyleneamines. The aforementioned mixture of
though it does not appear to affect the yield of mono ammonia, monoethanolamine, diethanolamine and tri
ethanolamine in the product mixture. The amount of 60 ethanolamine will comprise the continuous homogene
water than can be used to affect catalytic activity is not ous fluid stream mentioned previously. The homogene
a critical amount, and therefore only small amounts of ous fluid stream can be supplied directly to the amina
water are utilized to effect this kind of result. In general tion reaction. In practicing the process of this invention
from about 0.5% to about 5% by weight of water based there is provided with the homogeneous fluid stream
on the weight of the reaction mixture may be utilized to 65 additional monoethanolamine as described above and
catalytically induce the reaction. Though greater that additional amount of monoethanolamine with the
amounts of water may be desirable, or useful to affect homogeneous fluid stream when provided to the amina
the aforementioned catalysis, such amounts need not be tion reaction will comprise the amination feed stream.
 4,400,539
9 10
As mentioned previously, the amination feed stream from each mole of ethanolamine provided in the amina
is supplied to the amination zone at a pressure which is tion feed stream and the utilization of at least 20 moles
equal to or somewhat lower than the pressure of the of ammonia for each mole of monoethanolamine which
homogeneous fluid stream. Consequently, the amina is present in the amination feed stream being the most
tion reaction Zone is at a pressure which is essentially highly preferred embodiment. The amination feed
equivalent to the pressure of the amination feed stream stream may also possess a limited amount of water. The
as it exists when introduced to the amination reaction water that is present will typically be that which is
ZOC. - provided as a result of the ethylene oxide-ammonia
In the typical case the amination feed stream will be reaction. The water content in the amination feed
composed of the components of the homogeneous fluid 10 stream may range between 0 weight percent to 10
stream, recycled monoethanolamine and, optionally, weight percent, basis the weight of the amination feed
hydrogen and/or ammonia. In the preferred operation stream and preferably the water content is kept between
of the process of this invention the amination feed 0-5 weight percent, based on the total weight of the
stream is supplied to the amination reaction as a single amination feed stream.
phase supercritical fluid stream. However, the pressure 15 In further characterizing the amination feed stream,
of that supercritical fluid stream will be less than the the preferred monoethanolamine content thereof is at
pressure of the continuous homogeneous fluid stream least 90% of the weight of the total ethanolamines con
which is removed from the reaction between ethylene tained therein, while the diethanolamine content of the
oxide and ammonia, even though the latter stream is amination feed stream is typically at least 3% of the
also in the typical case a single phase supercritical fluid weight of the aforementioned total ethanolamines con
stream. tent. Usually the triethanolamine content of the amina
The amination zone comprises as an essential ingredi tion feed stream is at least 0.5% by weight of the total
ent in order to effect the amination reaction a catalyst ethanolamines content.
material which will convert the aforementioned amina The reaction which involves the amination feed
tion feed stream into a stream containing ethylenea 25 stream to produce ethyleneamines is accomplished in
mines, preferably containing inter alia ethylenediamine. the amination zone. This zone contains the solid catalyst
Such material effects the production of the ethylenea in the form of a fixed bed and has a temperature and
mines, as aforedescribed, preferably favoring the forma pressure sufficient to cause the amination feed stream to
tion of ethylenediamine. Though the catalysts which react to form the ethyleneamines, such as ethylenedi
are generally described in the prior art as capable of 30 amine, etc. The amination zone contains the appropriate
converting a mixture of ammonia and monoethanol catalysts for the amination reaction, as described above,
amine in the vapor state to ethylenediamine may be the amination feed stream, hydrogen and ammonia.
utilized in the practice of this invention, the preferred When hydrogen and ammonia are not components of
catalyst is a solid material comprising nickel and rhe the amination feed stream in the appropriate propor
nium on a support as described in the aforementioned 35 tions, optionally, they are added separately,
Best patents. Such catalyst is characterized as having The hydrogen may be supplied to the reaction zone
high activity and selectivity in amination processes and as a separate feed stream into the amination zone or as a
comprises rhenium and nickel impregnated on a support component of the amination feed stream. Hydrogen
material such as alpha-alumina, silica, silica-aluminas, serves the purpose of a promoter for the catalyst. When
kieselguhrs or diatonaceous earths, and silica-titania, in 40 hydrogen is not provided in the reaction zone and the
which the mole ratio of nickel to the rhenium is in the catalyst is a nickel-rhenium catalyst as described above,
range of 2:1 to about 30:1 and the total nickel and rhe the catalyst life is greatly shortened and the rate of
nium metal present is in the range of 3 to 30 percent by amine production is materially reduced. By providing
weight of the support. Such catalysts are discussed at hydrogen in the amination zone, the catalyst is continu
length in U.S. Pat. No. 4,123,462 and such disclosure for 45 ously promoted to effectively cause the amination of the
their manufacture is incorporated herein by reference, ethanolamines to produce the desired products. It is
and in particular that disclosure set forth in column 4, believed that hydrogen acts in part as a continuously
lines 24-34, that disclosure starting at column 5, line 59, supplied inert to keep available sites at the catalyst sur
all of columns 6, 7, and 8 to line 23 of column 9, Exam face for the desired reaction between ammonia and the
ples 2, 3, 4, 5, 6, 7, 8, 9, 10 and 12. The same disclosure 50 ethanolamines and preclude the stabilization of the cata
can be found in U.S. Pat. No. 4,111,840, patented Sept. lyst sites by ethyleneamines and/or ammonia. Inerts
5, 1978, and that disclosure is also incorporated herein which can also be supplied to the reaction are inert
by reference. gases such as nitrogen, helium, methane, and the like.
The amination feed stream contains at least 70 weight Such inert gases can be utilized to help in the control of
percent monoethanolamine based on the total ethanol 55 the reaction temperature and assist in maintaining the
amines content, not more than about 30 weight percent desired pressure conditions during the course of the
diethanolamine, same basis, not more than 15 weight reaction. Suitable inert solid diluents for the catalyst can
percent of triethanolamine determined on the same be any of the aforementioned support materials utilized
basis, and the sum of the diethanolamine and triethanol in the manufacture of the catalyst and preferably is a
amine does not exceed 30 weight percent of the total 60 material such as alpha-alumina, silicon carbide, silica,
ethanolamine content thereof. The amination feed glass shot or balls, and the like. Such solid inert materi
stream also contains ammonia in an amount which is in als serve the purpose of adequately diluting the bed for
stoichiometric excess of the alcoholic hydroxyl groups the purpose of controlling gas flow characteristics
which are present in the amination feed stream. In the within the catalyst bed as well as assisting in the control
preferred case there is contained at least 10 moles of 65 of the temperature within the reaction zone.
ammonia for each mole of ethanolamine present in the As mentioned immediately above, the catalyst is pro
amination feed stream. In the most preferred embodi vided in the reaction zone in the form of a bed of parti
ment there is provided at least 15 moles of ammonia cles. Typically, such beds are supported upon distribu
 4400,539 12
tion plates or screens which allow for the passage of : gases, to the extent that such are not included with the
gases or fluids through the bed. in this respect, the amination feed stream) to the reaction zone. The better
process is carried out utilizing standard fluid-solid het interdispersion of the various components of the amina
erogeneous catalytic techniques. - tion feed stream (as well as hydrogen, ammonia and
Also supplied to the amination zone is an amount of 5 other gases supplied to the amination zone) the better
monoethanolamine in addition to that which is supplied will be the overall effectiveness of the amination reac
to the amination feed stream from the homogeneous tion. -

fluid stream. This monoethanolamine is provided to the After the fluids are removed from the amination
amination zone in admixture with the amination feed Zone, they are subjected to a variety of separation steps
stream, and therefore becomes a part thereof either 10 for the purpose of removing the various components
immediately prior to the feeding of the amination feed contained therein. For example, the effluent gas stream
stream to the amination zone or at some point further from the amination zone will be subjected to distillation
upstream of the amination zone. to remove water, ammonia ethylenediamine, monoetha
As mentioned previously, hydrogen is supplied as a nolamine (which will be recycled as described above),
promoter for the catalyst. The amount of hydrogen that hydroxyethylpiperazine, aminoethylethanolamine, tet
should be present in the amination feed stream should raethylenepentamine, diethylenetriamine, aminoethyl
be from about one mole percent to about 30 mole per piperazine, piperazine, triethylenetetramine, diethanol
cent based on the total moles in the amination feed amine and triethanolamine. Because of the vast differ
stream. Preferably the amount of hydrogen which is ences between the boiling points of monoethanolamine,
provided in the amination zone is from about 2 to about 20 diethanolamine and triethanolamine, the separation of
15 mole percent based on the total moles in the amina monoethanolamine from the composition is very readily
tion feed stream. obtained and an extremely pure stream of monoethanol
The temperature of the amination zone in the usual amine can be produced by simple distillation. In the
case is selected based upon the temperature characteris normal course, the monoethanolamine which can be
tics of the catalyst which is utilized for the amination 25 obtained by distillation will contain at least 99 weight
reaction. When employing the nickel-rhenium catalyst percent of monoethanolamine with extremely small
mentioned above, this temperature is about 120° C. to amounts of piperazine, diethylenetriamine, aminoethyl
about 225 C., preferably in a range of about 150 to piperazine, hydroxyethylpiperazine, and the like, being
about 215 C. It should be mentioned that in carrying present.
out the process in its most desirable embodiment, the 30 HIGH PRESSURE SEPARATION
stream within the amination zone is under supercritical
fluid or vapor phase conditions, preferably under super In a preferred embodiment of this invention, the ho
critical fluid conditions as described above. Therefore, mogeneous fluid stream which comprises the effluent
the pressure within the reaction zone should be corre from the reaction of ethylene oxide and ammonia is
lated with the temperature so as to achieve either the 35 introduced to a high pressure separator which serves
supercritical fluid conditions or a vapor phase condi the purpose of producing an amination feed stream
tion. It is most desirable to avoid the presence of any which is enriched in respect to its monoethanolamine
liquid on the catalyst. That is, the catalyst should be content without creating a significant energy loss result
essentially free of any liquid deposition on its surface. If ing from a large pressure reduction. In essence, what
such deposition occurs, it will very rapidly cause the 40 occurs is that the homogeneous fluid stream is passed to
dissolution of the catalyst on the surface of the sup a simple separation tank in which a modest phase sepa
ported used with it and consequently the catalyst will ration occurs resulting in the removal from the tank of
become liquefied and be carried away with the effluent a gaseous stream which is richer in monoethanolamine
from the amination zone. As that occurs, the catalyst than the homogeneous fluid stream which is provided
within the zone will contain less and less of the desired 45 to the tank. Withdrawn from the bottom of the tank is a
nickel and rhenium, and consequently its activity will stream which contains a smaller content of monoetha
decrease to such an extent that eventually it will no nolamine. In a preferred embodiment of the invention,
longer activate the amination reaction. this high pressure separation is practiced as follows.
In carrying out this process, in a preferred embodi The homogeneous fluid stream which is removed from
ment utilizing a nickel-rhenium catalyst which also 50 the reaction between ammonia and ethylene oxide is
contains boron, as described in the aforementioned Best passed as a supercritical fluid to admixture with mono
patents, the pressure is in the range of about 1500-3000 ethanolamine recycle introduced at a temperature sub
psi, with the preferred pressure being approximately stantially below that of the homogeneous fluid stream.
2250 psia. When operating at such pressures, the tem As a result, the temperature of the homogeneous fluid
perature is in the range of about 150-215 C. and the 55 stream is reduced and the resulting stream that is
fluid velocity through the amination zone is carried out formed from admixture with the recycled monoethanol
to effect a residence time in the reactor of from about 3 amine is no longer in a supercritical fluid condition.
to 8 minutes. That stream is thereafter passed to a heat exchanger and
The amination reactor which provides the amination the temperature of the stream is raised to a temperature
zone may be any reactor configuration ranging fron a 60 which allows the enriched amination feed stream which
fixed bed tubular reactor to a backmixed fixed bed reac is taken from the high pressure separator tank to be
tor. in view of the fact that the amination reaction does again a supercritical fluid stream. For example, if the
not provide a significant exotherm, it is not necessary effluent from the ethylene oxide-ammonia reaction,
for one to utilize a fuid bed reactor. However, one may which comprises the continuous homogeneous fluid
utilize a fluid bed reactor if such is desired. One impor 65 stream, is at 170° C., it will be cooled by recycled mono
tant feature of a reactor is that it should be designed to ethanolamine which is at about 45 C. to form a lower
provide for a uniform flow distribution of the amination pressure stream having a temperature of about 143° C.
feed streatin (and hydrogen, ammonia, and the like which is no longer a supercritical fluid. That stream is
 4,400,539
13 14
thereafter heated to form an effluent from the high carrying out this invention which includes the separa
pressure separator tank having a temperature of 160° C. tion of products from the amination reaction to the
and consequently being further heated to a stream hav extent necessary to allow for the recovery of monoetha
ing a temperature of 180° C., and possessing the condi nolamine for recycle.
tions of a supercritical fluid. It also follows that by Excluded from the drawing is the recovery of other
introducing the recycled monoethanolamine into the components of the amination reaction as well as dieth
fluid stream followed by high pressure separation that anolamine and triethanolamine. Their individual separa
there is a loss of pressure from that at which the homo tion is effected by conventional distillation techniques
geneous fluid stream is at when taken as an effluent from and the order of their separation is predicated upon the
the ethylene oxide-ammonia reaction. As described O respective volatilities of such components.
previously, that reaction is carried out at pressures As shown in the drawing, ethylene oxide for the
within the range of about 2000 pounds per square inch reaction is fed through line 16 into admixture with am
absolute to about 5000 pounds per square inch absolute. , monia recycle fed through line 18. Makeup of ammonia
For example, should the effluent from the ethylene is supplied through line 15 into line 18 on an as needed
oxide-ammonia reaction be at 3000 psi, it typically will 15 basis. The admixture of ammonia and ethylene oxide is
be reduced to a pressure of about 2200 psi before it is fed achieved simply by connecting the respective lines for
to the high pressure separator tank and reheated each and they are pumped (not shown) with a high
through a heat exchanger to a temperature which pressure feed pump to heat exchanger 14.
achieves a supercritical fluid condition. In order to effectively utilize the energy resources of
The high pressure separator tank is nothing more 20 the process, the reaction mixture stream comprising
than a simple tank containing therein a demister pad at ethylene oxide and ammonia are fed through a high
its upper area to remove any liquid components trapped pressure feed pump (not shown) to a shell and tube heat
in the volatile components removed from the upper exchanger 14, which is supplied with heat by passing
portion of the tank. The liquid body which is created in the effluent from the catalytic reactor 36, that is the
the tank as a result of the phase separation occurring 25 effluent fed through line 33 or line 45 for a bottom feed,
therein will be removed from the bottom thereof and to the shell side of the heat exchanger 14. As a result,
will be richer in diethanolamine and triethanolamine the ethylene oxide-ammonia reaction mixture is heated
than is the homogeneous fluid stream minus any amount by passage through the tube side of the heat exchanger
of ethanolamine which has been added to such stream 14 to a temperature which is considered desirable for
prior to its addition to the high pressure separator tank. effecting the adiabatic reaction of ethylene oxide with
The monoethanolamine recycle which is provided ammonia under supercritical fluid conditions. For ex
can be an amount which is equivalent to the amount of ample, the feed stream to the reactor is brought to a
monoethanolamine not converted in the amination zone temperature of about 136 C. and 3,000 psia. It is then
to ethyleneamines. The monoethanolamine recycle can fed into tubular reactor 10 having, for example, a length
be introduced before or after the aforementioned high 35 to diameter ratio of 40:1 and which contains in the entry
pressure separation, but at least, in any case prior to the port thereof a swirling device as described in copending
amination zone in admixture with the amination feed application Ser. No. 259,899, filed May 4, 1981. The
stream. If it is introduced prior to the amination zone to continuous homogeneous fluid stream removed from
the components of the amination feed stream, then for reactor 10 is in the form of a supercritical fluid. The
the purposes of this invention, it is considered a part of 40 temperature and pressure of the fluid is sufficient to
the amination feed stream and to the extent that the effect the supercritical state, such as a temperature of
previous discussion refers to a supply of an amination 170° C. and a pressure of 3,000 psia. The pressure in the
feed stream to the reaction zone, such additional mono stream is controlled by a pressure reducing valve, not
ethanolamine is considered a component part thereof. shown, and is fed to interconnect with the fluid from
In the preferred practice of this invention, the monoeth 45 line 19. The fluid from line 19 can contain the monoeth
anolamine is removed from the product stream effluent anolamine recycle or a mixture of monoethanolamine
from the amination zone after the removal of pipera recycle and ammonia which is also recycled or simply
zine, and this monoethanolamine recycle is reduced in ammonia from recycled ammonia. In the preferred
temperature from about 60° C. to about 25 C. and has practice of the invention, the monoethanolamine recy
a purity as aforedescribed. The monoethanolamine is 50 cle is mixed with some of the ammonia recycle and the
recycled back to a point in the reaction chain prior to combination is fed through line 19 to effect admixture
the high pressure separator to effect admixture with the with the effluent from reactor 10, that is the homogene
homogeneous fluid stream as described previously. It is ous fluid stream. The control of ammonia recycle to line
also possible to instead recycle at least a part of the 19 is effected by valve 13 located in line 21. The control
monoethanolamine stream subsequent to the high press 55 for monoethanolamine addition to line 21 is effected by
sure separation step so that it is not necessary to reduce valve 23 located in line 20. If it is desired to introduce .
the temperature of the monoethanolamine prior to its the monoethanolamine recycle at a later stage, then
reintroduction as a recycle stream into the ethanolamine valve 23 can be closed thereby diverting flow of the
feed going to the amination zone. In such a case, where monoethanolamine recycle through line 27. In such a
there is effected monoethanolamine enrichment by the 60 case, valve 25 will be opened and allow the flow of the
utilization of a high pressure separation step, as de monoethanolamine recycle to a later stage in the pro
scribed above, then the homogeneous fluid stream is cess scheme. The admixture of the monoethanolamine
cooled by heat exchanger to a temperature low enough recycle and the homogeneous fluid stream is achieved
to take it from a supercritical fluid stream to a liquid upon contact of line 19 with line 11 through which the
stream which allows separation to occur in the high 65 homogeneous fluid stream is passed. The admixture is
pressure separation tank. thereafter fed to heat exchanger 12 for the purpose of
Coming now to the drawing, the drawing illustrates a further reducing the temperature of the mix stream in
schematic flow diagram of an integrated process for line 11 to a desired temperature for the gas-liquid phase
 4,400,539
15
separation to be effected in the high-pressure separator distillation column 50 maintained at a temperature suffi
30. The temperature reduction is effected by both the cient to remove the water contained in the reaction
reduced temperature of the monoethanolamine recycle, through line 49. The heavies from the reaction are re
stream and any ammonia which is also recycled there covered from distillation column 50 through line 44 and
with into line 19 and thereafter into line. 11. Further 5 passed to still 52 for the recovery of ethylenediamine by
reduction in the temperature may be thereafter obtained way of line 51. The heavies from that distillation are
by heat exchanger 12 to effect the desired temperature removed through line 54 into piperazine still, 56 from
for effective gas-liquid separation under the conditions which piperazine is recovered through, line 57. The
of high pressure which are existing in separator 30. The bottoms from that separation are removed through line
pressure in line 11 and separator 30 is controlled so as to 10 53 and passed to still 58 for the recovery of monoetha
effect, in coordination with the temperature therein, nolamine which is recycled by way of line 20 for even
separation of the homogeneous fluid stream from reac tual addition to the homogeneous fluid stream either
tor 10. The effluent vapor taken from the top of separa prior to or after the high pressure separator 30. The
tor 30 is fed through line 34 to a heat exchanger (not bottoms of that separation are passed from line 59 into a
shown) whereby to increase the temperature of the 15 series of refining columns for recovering each of the
effluent stream which at this instance is characterized as various components of the stream.
the amination feed stream. By increasing the tempera
ture, while maintaining a pressure of from about 1500 to DETAILED DESCRIPTION
about 2500 psi, and preferably about 2200 psia from the EXAMPLE 1.
amination feed stream, the amination feed stream is 20
converted into a supercritical fluid stream. This super The reaction system and apparatus shown in the
critical fluid stream is fed through line 34 into the top of drawing and discussed above, comprising an adiabatic,
amination reactor 36 which contains a fixed bed of tubular ethylene oxide/ammonia reactor, an amination
rhenium-nickel catalyst containing boron supported catalytic reactor, and associated equipment, is used in
upon a diatomaceous earth particulate support. 25 this run. In this run, a liquid ethylene oxide feed of 220
Alternatively, the amination feed stream may be ad moles per hour is mixed with a liquid ammonia-water
vantageously fed through line 33 controlled by valve 55 mixture (98 percent NH3, 2 percent water) to give an
into the bottom of amination reactor 36 so as to effect an ammonia to ethylene oxide mole ratio of 30:1. The
upward flow of the amination feed stream through the mixed ammonia/ethylene oxide feed is pumped into the
catalyst bed contained therein during the amination 30 first reactor stage of reactor 10, which is a four stage
reaction. adiabatic, tubular reactor having a 40:1 length to diame
In order to provide the necessary hydrogen promoter terratio, after preheating to a temperature of about 135°
to the reaction, hydrogen which is within the system is C. The pressures in the reactor stages are controlled to
recycled through hydrogen compressor 24 into the maintain the flowing stream in a single, swirling, super
upper portion of the high pressure separator 30 through 35 critical fluid phase having an average reaction mixture
line 22 and is thereafter carried with the amination feed density of 21.5 lbs/ft3. The pressure at the outlet of the
stream through line 34, or alternatively line 33, into final reactor stage of reactor 10 is 3000 psig (204 atm.)
reactor 36. . and the temperature of the product mixture is 170 C.
The effluent from reactor 36 is passed into line 33, or after a residence time within the reactor of about 20
alternatively line 45, and thereafter through the shell 40 minutes.
side of the heat exchanger used for preheating the am The homogeneous product mixture stream from the
monia-ethylene oxide reaction mixture as described ethylene oxide/ammonia reactor 10 contains about 95
previously, designated in the drawing as heat exchanger mole percent ammonia, 1.9 mole percent water, 2.4
31, for convenience sake. Heat exchanger 31 depicts the mole percent monoethanolamine, 0.4 mole percent di
shell side of the same heat exchanger previously charac 45 ethanolamine and less than 0.1 mole percent triethanol
terized as heat exchanger 14 which characterizes the amine. The homogeneous fluid stream in line 11 is de
tube side thereof. The reaction product effluent from pressurized to 2200 psig (150 atm.) and is mixed with a
reactor 36 is thereafter passed through line 35 into an monoethanolamine recycle stream carried in line 19
ammonia flash tank 38 for the purpose of separating from line 20 containing 99 mole percent monoethanol
ammonia and hydrogen from the effluent liquid stream. 50 amine and an ammonia recycle stream containing about
The ammonia and hydrogen are taken off through line 98 mole percent ammonia and 2 mole percent water
28 and subsequently separated whereby the ammonia is carried in line 19 from lines 18 and 21, and then pre
fed through ammonia recycle compressor 26 and then heated to a temperature of 155° C. before being fed to a
into line 18 for subsequent recycle or it is passed to line 32 foot diameter high pressure separator, 30, which is
29 for eventual introduction into line 18, also for ammo 55
nia recycle, as described previously. The hydrogen is maintained at a pressure of 2200 psig (150 atm.). A
fed into a recycle compressor 24 so that the hydrogen recycle stream containing about 80 mole percent hydro
can be recycled to separator 30 as described previously. gen and 20 mole percent ammonia is also fed to the
The bottoms from flash tank 38 are fed through line 39 product mixture in high pressure separator 30 through
into which the bottoms from high pressure separator 30 60 line 22.
are also fed by way of line 32 and the admixture is fed The overhead stream from the high pressure separa
into a second flash separator, 37, for additional separa tor is heated to 170° C. to form a homogeneous single
tion of ammonia to be recycled through line 18 by way phase before being fed to the catalytic amination reactor
of line 43 and ammonia recycle compressor 26. The 36. The overhead stream from the separator 30, con
bottoms from separator 37 is fed to an ammonia strip 65 tains about 7.2 mole percent hydrogen, 87.0 mole per
ping still 40 through line 41 for final removal of ammo cent ammonia, 1.4 mole percent water, 4.3 mole percent
nia from the amine reaction product mixture. The bot monoethanolamine, 0.1 mole percent diethanolamine
toms from the still 40 is passed through line 42 into and less than 0.01 mole percent triethanolamine.
 4,400,539
17 18
Amination reactor 36 is a 7 foot diameter vertical per hour of diethylenetriamine and about 7.0 moles per
reactor containing an 1100 ft. bed of solid catalyst hour of aminoethylethanolamine. About 23 moles per
comprising 7.0% nickel; 1.86% rhenium; 1.44% boron hour of diethanolamine is also recovered.
on a silica-alumina support. The feed stream enters the We claim:
bottom thereof through line 33 and valve 55 and flows 5 1. A continuous process for the manufacture of ethyl
upward through the catalyst bed while being main enediamine which comprises:
tained in a single supercritical fluid phase at a tempera (A) providing (1) a continuous homogeneous fluid
ture of 170° C. and a pressure of 2200 psi (150 atm.). stream under pressure, which stream comprises
The effluent taken from the top of the amination ammonia, monoethanolamine, diethanolamine and
reactor 36 through line 45 comprises a single phase fluid 10 triethanolamine as produced by the direct reaction
stream containing about 7.2 mole percent hydrogen, 85 of ethylene oxide and ammonia in which the num
mole percent ammonia, 3.1 mole percent water, 1.3 ber of moles of ammonia substantially exceeds the
mole percent ethylenediamine, 0.1 mole percent dieth molar concentration of alcoholic hydroxyl groups
ylenediamine (piperazine), 0.1 mole percent diethylene present in such steams; (2) a continuous recycle
triamine, 2.6 mole percent monoethanolamine, 0.1 mole 15 stream consisting essentially of monoethanolamine;
percent diethanolamine and less than 0.01 mole percent (3) an amination zone comprising a solid amination
each of aminoethylpiperazine, aminoethylethanola catalyst; and (4) a separation Zone for separating
mine, and triethanolamine. This stream is cooled to 150 monoethanolamine from the amination product
C. and depressurized to 400 psia (27.2atm.) before being stream removed from the amination zone which
fed through a 6 foot diameter flash separator 38 where 20 monoethanolamine forms said recycle stream;
unreacted ammonia is recovered for recycling back to (B) feeding said recycle stream under pressure to said
the ethylene oxide-ammonia reactor 10 and recovered fluid stream to form a continuous amination feed
hydrogen is recycled back to the high pressure separa stream under pressure;
tor 30, respectively. The liquid bottoms from the flash (C) feeding the amination feed stream to the amina
separator 38 contains about 70 mole percent ammonia, 25 tion zone under sufficient pressure to assure flow
12 mole percent water, 5.3 mole percent ethylenedi through the amination zone but at lower pressure
amine, 0.4 mole percent piperazine, 10.5 mole percent than said homogeneous fluid stream and to form an
monoethanolamine, 0.3 mole percent diethylenetri amination product stream containing ethylenedi
amine, 0.04 mole percent aminoethylpiperazine, 0.3 amine therein;
mole percent aminoethylethanolamine, 0.36 mole per (D) separating monoethanolamine from the amina
cent diethanolamine and less than 0.05 mole percent of tion product stream to form said recycle stream;
other amine products. This stream is combined in line 39 and
with the liquid bottoms product from the high pressure (E) continuously recovering ethylenediamine from
separator, 30, containing about 61 mole percent ammo
nia, 4.3 mole percent water, 24.7 mole percent monoeth 35 said amination product stream; wherein said amina
anolamine, 4.1 mole percent diethanolamine and 0.6 tion feed stream contains at least 70 weight percent
mole percent triethanolamine, depressurized to 225 psia monoethanolamine, based on the weight of the
(15.3 atm.) and heated to 80° C. in a flash separator, 37, ethanolamines therein; the moles of ammonia in the
where about 80 percent of the remaining unreacted amination feed stream exceeds the molar concen
ammonia is removed and recycled to the ethylene ox 40 tration of alcoholic hydroxyl groups in said amina
ide/ammonia reactor 10, through line 18. tion feed stream; and the amination feed stream
The liquid bottoms from the flash separator 37 is fed contains at least a 5% increase in the concentration
to ammonia stripping still 40, a standard distillation of monoethanolamine over that contained in said
column operating with a pressure of 50 psia to remove fluid stream.
the remaining unreacted ammonia and about 40 percent 45 2. The process of claim 1 wherein said ethylene ox
of the water for recycle. ide-ammonia product mixture stream is in a single, su
The bottom stream from the distillation column 40, percritical fluid phase.
comprising the mixed products contains about 24 mole 3. The process of claim 1 wherein the amination feed
percent water and 18 mole percent ethylenediamine, 1.3 stream in the amination zone is a homogeneous fluid.
mole percent piperazine, 1.2 mole percent diethylenetri 50 4. The process of claim 1 wherein the amination feed
amine, 0.1 mole percent aminoethylpiperazine, 0.1 mole stream in the amination zone is in a single, supercritical
percent hydroxyethylpiperazine in addition to 50 mole fluid phase.
percent monoethanolamine, 1.0 mole percent of amino 5. The process of claim 1 wherein the solid amination
ethylethanolamine, 3.5 mole percent of diethanolamine catalyst in the amination zone comprises nickel.
and less than 0.5 mole percent of triethanolamine. This 55 6. The process of claim 1 wherein the solid amination
stream is then separated by standard distillation tech catalyst in the amination zone comprises nickel-rhenium .
niques into component alkanolamines and alkylema on a support medium.
mines for recovery or recycle. Monoethanolamine is 7. The process of claim 1 wherein said continuous
recycled through line 20 to and mixed with the homo amination feed stream contains hydrogen.
geneous fluid product mixture in line 11. The run pro 60 8. The process of claim 6 wherein the amination feed
duces about 115 moles per hour of ethylenediamine, stream contains hydrogen.
ak is k. : k
about 8 moles per hour of piperazine, about 7.6 moles

65