United States Patent 19 11) 4,123,462

Best 45) Oct. 31, 1978

54 AMINATION PROCESS USING 3,152,185. 10/1964, Zvejnicks ........................ 260/583 K.
NCKERHENUM CATALYSTS 3,223,735 12/1965 Scholz ............... ... 260/585 R
3,270,059 8/1966 Winderlet al. ...................... 260/.583
75 Inventor: Donald C. Best, Charleston, W. Va. 3,387,032 6/1968 Leonard ............ ... 260/585 B
3,520,933 7/1970 Adams et al. .................... 260/585 B
73 Assignee: Union Carbide Corporation, New 3,666,412 5/1972 Sowards .......................... 252/432 X
York, N.Y. 3,739,029 6/1973 Magoon et al. ... 260/585 A
21 Appl. No.: 647,065 4,036,883 7/1977 Voges et al. ..................... 260/585 B
(22 Filed: Jan. 7, 1976 FOREIGN PATENT DOCUMENTS
51) Int. Cl? ...................... C07C 85/00; C07C 85/02; 47-34181 11/1972 Japan .................................... 260/585 B
C07C 85/06; CO7C 85/08 Primary Examiner-Winston A. Douglas
52 U.S. C. ................................ 260/585 B; 252/454; Assistant Examiner-John J. Doll
252/455 R; 252/457; 252/458; 252/459; Attorney, Agent, or Firm-Robert C. Brown
252/462; 252/463; 252/465; 252/466 R; 57 ABSTRACT
252/470; 252/471; 252/472; 252/473; 252/474;
260/583 P; 260/585R, 260/585A; 260/585 C; The present invention concerns a new nickel-rhenium
260/585 D; 544/358; 544/402 catalyst and method of preparing said catalyst. The
58 Field of Search ......... 260/585 B, 268 SY, 585 R, invention also relates to the catalytic amination of lower
260/566R, 585 C; 252/455 R, 459, 466.J., 432 aliphatic alkane derivatives such as alkanemono-ols,
(56) References Cited alkanediols and alcoholamines utilizing the new nickel
rhenium catalyst.
U.S. PATENT DOCUMENTS
3,022,349 2/1962 Lemon et al. .................... 260/585 B 16 Claims, No Drawings
 4,123,462 2
1.
tion. None of these chemical processes appear to have
AMINATION PROCESS USING been operated on a commercial scale because of the
NICKEL-RHENUM CATALYSTS process requirements and costs of raw materials.
One of the most widely used commercial processes
BACKGROUND OF THE INVENTION 5 for producing ethylenediamine today involves a reac
A considerable number of methods for production of tion of ethylenedichloride with aqueous ammonia. The
alkylamine products have been proposed and a number ethylenedichloride is reacted with aqueous 30 to 40%
of them have been commercially utilized. The present ammonia to produce a dilute aqueous solution of
invention particularly concerns the production of lower amines. Sodium hydroxide is then added to neutralize
alkylamines by the catalytic amination of lower ali O the hydrochloric acid formed in the ammonia-ethylene
phatic alkane derivatives such as mono- and polyhydric dichloride reaction. This neutralization step forms addi
alcohols, alcoholamines, and compounds from which tional water and gives rise to by-product sodium chlo
these alcohols are derived, including epoxides, ketones ride. An illustration of the approximate distribution or
and alkyleneimines. profile of products produced by such a process is as
The catalytic amination of alcohols is a process 15 follows:
which has been long recognized in the prior art. It
generally concerns the reaction of alcohol with ammo
nia in the presence of a hydrogenation catalyst and Products Wt, % of Production
usually in the presence of hydrogen. Ethylenediamine (EDA) 41%
The most difficult problem in the manufacture of
amines by this and other proposed processes is that the
Diethylenetriamine (DETA)
Triethylenetetramine (TETA)
25%
10%
Tetraethylenepentamine (TEPA) 8%
chemical synthesis reactions used also form substantial Pentaethylenehexamine (PEHA) 13%
amounts of by-products, which are of considerably less Polyamine Heavies (PAH)
Piperazine (DEDA)
13%
1.5%
value and as a result often render the synthesis ineffi Aminoethylpiperazine (AEP) 1.5%
cient and not commercially feasible.
The most desirable amine products generally are 25
those products wherein an amine group replaces the About 2.5 lbs. of sodium chloride is produced per 1b.
non-amine functional group or groups in the alkyl start of the amines produced.
ing material without any further modification of the Although the product distribution is commercially
starting material. Most heavier, more highly substituted 30 feasible, the presence of chlorine in the system, includ
amines and heterocyclic nitrogen compounds can be ing in the corrosive form of hydrogen chloride, causes
further synthesized from these preferred alkylamines. A expensive maintenance costs. Moreover, recovery of
synthesis of these heavier, substituted, and heterocyclic the desired amine products from the salt-containing
amines directly from the alkyl starting materials usually aqueous solutions is difficult and the disposal of the
yields other unwanted by-products. large quantities of salt is an ever increasing environmen
The amine products produced in accordance with the 35 tal problem. The cost of the starting materials also has
present invention have many uses. In addition to their been a discouraging factor.
use as intermediates for synthesizing other chemical A method which has recently emerged commercially
materials, they are utilized, for example, in fungicides is the reduction of amino acetonitrile to form ethylene
and insecticides. diamine. Although this process, according to the litera
For convenience in the description of the invention 40 ture can be operated to produce as much as 90% ethyl
hereinbelow, the amination of ethylene glycol and enediamine in the amine yield, the expense of the start
monoethanolamine to ethylenediamine and other prod ing materials in the process and other economic consid
ucts will be most comprehensively discussed, although erations do not make this process commercially attrac
the present invention is not limited to these starting 45 tive.
materials.
The amination of ethylene glycol may be illustrated As indicated above, the catalytic amination of alkane
by the following chemical formula with the primary derivatives including aliphatic alcohols and aminoal
products usually being monoethanolamine (MEA), eth cohols has been the subject of much investigation and
ylenediamine (EDA), and piperazine (also termed di prior art literature. The applicant has now discovered a
ethylenediamine, DEDA) and aminoethylethanola- 50 new catalyst which is both more active and more selec
le: tive than previously known catalysts for carrying out
amination processes. It should be noted that there are
numerous materials which have the ability to catalyze
HOCH-OH such amination processes, but the mere ability to cata
(EG) + NH, + H.St.Ed s lyze is far from sufficient to accord a catalyst one of
HOCH-NH
MEA) 2 + H-O 2 + HOC-H-NH-CHNH
AEEA) CHNH, + commercial significance.
U.S. Pat. No. 2,861,995 describes a method of con
v verting ethanolamine to various nitrogen-containing
H-NC-H, -NH, + HN NH -- other byproducts products by using a metal hydrogenation catalyst com
(EDA) (DEDA) 60 prising one or more of nickel, cobalt, copper chromite,
catalytic noble metal such as platinum and palladium,
Numerous other chemical reactions are known for and Raney nickel and Raney cobalt. They may be sup
producing alkylamines. For example, in the synthesis of ported on a carrier such as alumina.
ethylenediamine, the following reactions have been U.S. Pat. No. 3,068,290 describes a process for con
proposed: the hydrolysis of ethylene urea; reductive 65 verting ethanolamine to ethylenediamine by using a
amination of formaldehyde cyanohydrin; the reduction hydrogenation catalyst, such as described above, in a
of cyanogen; the reduction of 1,2-dinitroethane; and the reaction which is in the liquid phase, under autogenous
amitiation of chloroacetylchloride followed by reduc pressure. The patent also describes a preferred catalyst
 4,123,462
3 4.
which is a combination of nickel and magnesium oxides It has also been found that other metals may be pres
(Ni-MgO), obtained by thermal decomposition of co ent in the catalyst in admixture with the nickel and
precipitated nickel and magnesium formates or oxalates. rhenium.
U.S. Pat. No. 3,137,730 teaches the conversion of It has additionally been discovered that the nickel
ethylene glycol by using a supported catalyst compris 5 rhenium catalyst of the present invention has surprising
ing nickel and copper. U.S. Pat. No. 3,270,059 teaches activity and selectivity in the amination of a wide range
an amination process in the presence of a supported of alkane derivatives including, for example, epoxides,
catalyst which is produced by sintering oxygen com monohydric and polyhydric alcohols, ketones, alkanei
pounds of either nickel or cobalt at temperatures in 10 mines and aminoalcohols.
excess of 700 C and reducing the sintered metal com
pound by treatment with hydrogen. U.S. Pat. No. DETAILED DESCRIPTION OF THE
3,766,184 describes a catalyst containing iron with ei PREFERRED EMBODIMENTS
ther nickel, cobalt or mixtures thereof. Ruthenium cata According to the present invention there are pro
lysts are also referred to in this and other patents as 15 vided new catalysts having high activity and selectivity
useful in amination processes. in amination processes, said catalysts comprising rhe
None of the catalysts heretofore known have been nium (atomic number 75) and nickel impregnated on a
commercially successful because of one or more inade support material selected from al-alumina, silica, silica
quacies. Modern commercial catalytic processes require aluminas, kieselguhrs or diatomaceous earths and silica
catalysts to be more than active, i.e., yield high conver 20 titania, wherein the mole ratio of the nickel to the rhe
sions in the chemical reactions they catalyze. In the case nium is in the range of from 2:1 to about 30:1 and the
of amination processes where numerous competing total nickel and rhenium metal present is in the range of
reactions occur yielding many by-products, it is impor 3-30% by weight of the support.
tant for the catalyst to have good selectivity or the Another feature of the present invention is a process
ability to afford a high yield of useful product with a 25 for preparing said nickel-rhenium catalyst, said process
concomitant small yield of undesired product. The opti comprising (i) impregnating a mixture of metals com
mum reaction conditions including temperature, pres
sure and relative proportions of reactants, as well as prising rhenium and nickel on a support material se
reaction time, may be determined by the catalyst, and in lected from the group consisting of a-alumina, silica,
so doing may affect the economics of the whole pro 30 silica-alumina, kieselguhrs or diatomaceous earths, and
cess. The cost of the catalyst, its method of preparation silica-titanias; and (ii) activating said catalyst by heating
and its effective life as well as its physical properties the catalyst in the presence of hydrogen at a tempera
may be determinative of a successful, viable process. ture in the range of about 200-600 C for a period of
The applicant has now discovered a new catalyst about 45 minutes to about 4 hours.
containing nickel and rhenium, supported on a material 35 A further feature of the present invention is a method
selected from a-aluminas, silica, silica-aluminas, silica for producing lower aminoalkanes by the catalytic am
titanias, and kieselguhrs, or diatomaceous earths which ination of lower aliphatic alkane derivatives including
have improved properties over those catalysts hereto epoxides, alkanemono-ols, alkanediols, alkanolamines,
fore known for catalyzing the amination of aliphatic ketones, iminoalkanes and iminoalkanols and mixtures
lower alkyl derivatives. 40 thereof, said process comprising contacting said lower
SUMMARY OF THE INVENTION
alkane derivatives with ammonia at a temperature of
from 125 to 350° C and in the presence of hydrogen
This invention relates to a new catalyst comprising a and the nickel-rhenium catalyst as described herein
mixture of nickel and rhenium impregnated on various above.
support materials including a-alumina, silica, silica 45 The amination of alcohols involves a reaction be
alumina, kieselguhrs or diatomaceous earths and silica tween ammonia and alcohol in the presence of hydro
titania which are active and selective in the conversion gen gas. The amination process consists of a series of
of various alkane derivatives to desirable amine prod hydrogenation and dehydrogenation catalytic reac
ucts. It has been found that these nickel-rhenium cata
50 tions. The mechanism of these various reactions have
lysts not only exhibit excellent conversion activity but been extensively discussed in the prior art literature and
at the same time have superior selectivity in the produc are illustrated in the seven reaction formulas below:
tion of greater amounts of desired amine products yet
comparatively smaller quantities of less desired by-pro (1)
ducts. The nickel-rhenium catalyst of the present inven 55 R-CH-OHSR-CH=O + H,
tion are hydrogenation catalysts and may be used in
other processes in addition to amination processes. OH 2
The nickel-rhenium catalysts of this invention possess R-CH=O + NHR's SR-CH R" = H or Alkyl
a wide spectrum in magnitude of catalytic activity; can NHR
be used in relatively small concentrations; permit the 60 OH (3)
use of a better balance of reactants; and enable the use of
resonable reaction conditions for carrying out the pro R-CH sR-CH=NH + H.O.R = H
CSSS
NH,
4.
The applicant has further discovered that by control R-CH=NH+ His SR-CH-NH,
ling certain variables both in the preparation of the 65
catalyst and in the catalytic amination process itself, the er- - SD
NH, (5)
activity and selectivity of the amination reaction can be
even further optimized and improved.
R-CH-NH + RNHs=R-CH NH-R
 5
4,123,462
6
-continued are well-known in the art and are commercially avail
able. ..
-
NH, - SR-rH=N- (6) Support materials are not equivalent in their ability to
R CH SRR CH=N-R + NH, form active Ni-Re catalysts. For example, carbon Sup-.
NHR ported Ni-Re catalysts using CXC carbon from Na
S (7) tional Carbon Company even with large surface areas,
R-CH=N-R + His-RCH-NH-R have not shown appreciable catalytic activity in amina
tion reactions. Silica-magnesia supported Ni-Re cata
The first step in the amination process is believed to be lysts have also not shown appreciable catalytic activity
a reversible dehydrogenation of the alcohol to give an 0 in amination processes.
intermediate carbonyl 1. The aldehyde is then con Even the aforementioned support materials which
verted to an aminoalcohol 2 by reaction with ammonia have yielded active Ni-Re catalysts are not equivalent.
or an amine present in the reaction mixture. The ami Those supports which form more active catalysts yield
noalcohol then loses water to form the imine 3). The optimum amination conversions at less severe reaction
imine is then hydrogenated to the amine (4). Where the 15
conditions, e.g., lower reaction temperatures. There
intermediate aldehyde or the imine react with amines in fore, although all supports tested within the group indi
the reaction mixture, substituted and heavier amines are cated above show some catalytic activity in the amina
formed. Formulas 5, 6, and 7 illustrate the possible tion reaction, some supports within a general type have
products formed by a reaction of the intermediate imine not been considered as having strong commercial prom
with ammonia or amines present in the reaction mix 20
ise because more extreme reaction conditions, such as
ture. The products most often present in the reaction higher reaction temperatures, must be used to obtain
mixture, where ethylene glycolor monoethanolamine satisfactory conversions.
are the starting materials, include: The actual effectiveness of a material as a support in
Ethylene Glycol (EG) a Ni-Re catalyst is generally not predictable in advance.
Monoethanolamine (MEA) 25
Ethylenediamine (EDA)
However, among the general types of supports indi
Piperazine (DEDA) cated above that have been found active, there appears
to be some relationship between catalytic activity and
Diethylenetriamine (DETA) the amount of surface area of the particular support
Aminoethyl ethanolamine (AEEA) materials. . .
Aminoethyl piperazine (AEP) 30
One possible explanation for the surface area effect
One of the major shortcomings in the previously on catalyst activity is that a number of reactions in the
known techniques in synthesizing the more desirable amination process occur on the catalyst surface and are
alkylamines and diamines is the simultaneous produc therefore effected by adsorption-desorption equilibria
tion of substantial amounts of less desirable by-products. 35 of the reaction materials. The activity of a nickel
The production of excessive amounts of undesirable rhenium catalyst would therefore be effected, within
materials means an inefficient utilization of raw materi certain limits, by varying surface area of the supports
als and additional problems incurred in separating the and other surface properties including support shape,
desired products from the reaction mixture and dispos pore size, and pore volume. Generally, greater disper
ing of the waste products. A recent analysis of the cur sion of the nickel and rhenium metals on higher surface
rent and forecasted demands of the pertinent nitrogen area active supports produce more active Ni-Re cata
containing products indicates that the greatest demand lysts.
is for ethylenediamine. On the other hand, there is little Specific examples of some of the more active support
if any demand for piperazine (DEDA) and only limited materials for the Ni-Re catalyst of the present invention
demand for derivatives of piperazine like aminoethyl 45 are listed in the table below:
piperazine (AEP). As a result, the selectivity of amina TABLE 1.
tion catalysts to produce a favorable distribution of Surface Area
products is illustrated herein by comparing the amount Support General Type m/gm
of ethylenediamine (EDA) produced by the process Girder T869 Silica-alumina -60
with the amount of piperazine (DEDA) produced for a 50 Girdler T51
Girder T372
Silica-alumina
a-alumina
- 150
-40
given conversion. Girder T373 Silica-alumina 2-3
There has therefore been great demand for a catalyst Girder K306
Girder T2085
Silica-alumina
Silica-alumina
-250
-113
which has the ability to obtain high amination conver Girder KO Silica-alumina -268
sion rates yet maintain good selectivity in the products Girder T204S Kieselguhr
produced. The nickel-rhenium catalyst of the present 55 Johns-Manville
Norton LA 4102 a-alumina
Diatomaceous 10-15
invention has been sown to have these and other advan Type III silica
tages in the amination of lower alkanes having one or Grace.980-13
Grace 980-25
Silica alumina
Silica alumina
375
375
more functional groups. .. . Laboratory Silica titania -75-15
The nickel-rhenium catalysts of the present invention (SiO/TiO,
are solid catalysts wherein the nickel and rhenium met 60 Mole Ratio 9:1 to 1:9)
als are supported on certain materials many of which
have been known for use as supporting materials for In the amination reactions of the present invention,
other catalysts. Ni-Re, catalysts. comprising active supports having a
The support materials which have been found to surface area of 1 m/gm or greater are preferred.
produce the most active and selective amination cata 65 The particular size and shape of the support material
lysts are those supports which are composed of silica, has not been found to have any appreciable effect on the
silica-alumina, a-alumina, silica-titania, and kieselguhrs catalytic properties of Ni-Re catalysts formed there
or diatomaceous earths. Most of these support materials from. The support materials which may be used in mak
()(48 00:45 - 13 10-3-78 2070

4,123,462 8
7
ing the Ni-Re catalyst may be of any convenient shape step maymay not be sufficient. Although an impregnation
or size. The shape of the support usually will depend solution be prepared with the minimum amount of
upon the shape required in the particular apparatus used solvent required to dissolve the metal salts, the total
to perform the catalytic conversion reaction. Successful amount of the impregnation solution may be greater
Ni-Re catalysts have been made on support materials in beyond than that which the support material can absorb, or
the form of powders, spherical pellets and extruded the maximum absorption amount.
Strips. Impregnated spherical pellets ranging in diame In such case, a portion of the impregnation solution
ter from inch to 3/16 inch have been used. Extruded less than the maximum absorption amount is used to
initially contact the support material. After contacting,
strips of a cylindrical-type shape ranging from 1/32 O the support material is dried and then contacted with an
inch to inch in length are typical of those which can additional amount of the impregnation solution. The
be used as successful supports for Ni-Re catalysts of the sequential steps of contacting with solution and drying
present invention. are continued until all of the impregnation solution is
The particular method of impregnating or coating the used. A typical drying step can comprise heating the
nickel and rhenium metal onto the support material has 15 impregnated support to a temperature
not been found to have a significant effect on the activ several hours. Evacuation drying may ofalso120'be Cused, for
ity or selectivity of the final catalyst in amination pro
cesses. However, the amount of metal impregnated where the support is cooled under reduced pressure.
It is also advantageous to dry the support material
onto the support material and the nature of the support prior to impregnation in order to insure that the support
itself, as discussed above, does affect or vary the cata 20 will take up as much of the solution as possible. This
lytic activity and/or selectivity.
One technique for impregnating the nickel and rhe deeply intostep
pre-drying
the
also enables the metal to permeate more
support during impregnation. The pene
nium onto the support is to use a solution of salts of the tration of the metal into the support may be further
metals as a vehicle.
Various organic and inorganic nickel and rhenium increased by techniques known to those skilled in the
salts may be used in impregnation solutions. Examples 25 art such as by increasing the time the support is in
of suitable nickel-containing salts are anhydrous and contact Other
with the solution.
impregnation techniques are well known in the
hydrated nickelous nitrate hydrate: Ni(NO)6HO) art and may be utilized in the present invention. An
and nickel acetonyl acetate Ni(CHO)). Suitable other technique which can be used is often character
rhenium salts for use in the impregnating solution are
ammonium perrhenate (NHReO) and rhenium paradi 30 ized as a "sugar coating" technique where the metal is
oxane ReO3(CHO). In some cases, it is advanta predominantly port material.
present on the outer surface of the sup
geous to heat the solvent liquid to bring the metal salts This sugar coating technique differs from the impreg
into solution.
The salt solution should be prepared by considering nation process described above by the addition of a
two factors. The first concerns the amount of total 35 precipitant at the time the impregnating salt solution is
metal desired to be impregnated on a specific quantity in contactthewith the support material. The precipitant
of support. The second factor concerns the relative converts metal salt solution into a slurry. This im
pregnating vehicle reduces the penetration of the salts
atom ratio of nickel to rhenium. Both factors have been
found to affect the final properties of the catalyst. beyond the surface of the support material. The slurry
The most active catalysts have been found to be those to in contact with the support material is then evaporated
in which the Ni/Re atom ratio is between 2:1 and 30:1. dryness leaving the metal adhering predominantly to
In most cases, maximum activity occurs with a Ni/Re theAfter support surface.
the support material is impregnated with the
atom ratio between 5:1 and 20:1. Example 3 below dem desired
onstrates the effect varying Ni/Re atom ratio has on 45 pletely dried andofthen
amount nickel and rhenium metal, it is com
activated by a reduction step.
activity of the catalyst. In preparing the catalyst, the
Ni/Re atom ratio is obtained by predetermining the sufficiently evaporates theused
The drying step to be is any technique which
corresponding relative proportions of the metal salts to impregnating solution. Thevolatile drying
constituents of the
step may comprise
be present in the impregnation solution.
The total metal to be impregnated onto the support 50 The drying may be done under an inertabout
heating the catalyst to a temperature of 120' C.
atmosphere,
also has an effect on the activity of the catalyst. Exam such as nitrogen, and the catalyst may be cooled under
ple 4 demonstrates that varying the metal loading has a
different effect on a silica (Girdler T1571) and a silica reduced pressure.
The catalyst is then activated by a suitable step
alumina (Girdler T869) supported catalyst. Example 4 wherein the impregnated metal is converted into a cata
indicates that the silica supported catalyst having a high
surface area had greater activity with greater amounts 55 lytically
formation,
active form. This activation may include alloy
proper phase orientation of the metals and
of metal present. The silica-alumina supported catalyst, Mor an adjustment in the oxidation level of the metals.
with a lower surface area than the silica support, had An activation step may include a typical reduction pro
greater activity with 12.5% metal on the support as CCSS.
compared with 30% metal. In the preferred activation step the atmosphere in
Ni-Re catalysts in accordance with the present inven contact with the catalyst is hydrogen which is fed over
tion contain a total nickel plus rhenium metal content in the catalyst
the range 3-30% by weight of the support material. 200' to 600' atC an elevated temperature in the order of
Most Ni-Re catalyst exhibit maximum activity with about 4 hours. Theperiods for
specific
of from about 45 minutes to
conditions for reduction are
Ni-Re contents in the range 5-15% by weight of the 65 dependent upon the particular catalyst composition
Support. being activated.
Where relatively large amounts of metal are to be Prior to the activation step, the catalyst may be op
impregnated on supports with relatively low surface tionally calcined. In a preferred calcining step, the cata
areas or possibly high densities, a single impregnation
 . 9
4,123,462 10
lyst is heated to temperatures in the range of about 300 amine, starting materials include ethylene glycol and
to 500 C for 45 minutes to about 3 hours or more. It is monoethanol amine.
preferred that the calcining be carried out in air. The In the amination process of the present invention, the
drying step referred to above may be replaced by th alkane derivative starting material is reacted at an ele
calcining step or activating step. vated temperature with ammonia in the presence of
The nickel-rhenium catalysts of the present invention hydrogen and the nickel-rhenium catalyst. The temper
include catalysts which contain various other metals in ature for the reaction depends upon the particular start
admixture with the nickel and rhenium which do not ing material, ratios of reactants, and most importantly,
detrimentally affect the catalytic properties of catalysts the activity of the catalyst used. Generally, in processes
containing nickel and rhenium as the only impregnated 10 of the present invention, temperatures within the range
metals. These additional metals, in certain amination of 125° C to 350° C are suitable while a preferred range
processes, may actually improve selectivity and activity is 150-225 C.
of the basic Ni-Re catalyst. Certain of these metals may A relatively high pressure for the reaction is also
extend the activity life and other physical properties of 15 preferred. Normally, the increased pressure is obtained
the Ni-Re catalyst. Examples of catalysts containing by the desired amount of ammonia and hydrogen al
additional metal components include Ni-Re-La, Ni-Re ready present in the reaction vessel, which is then
Ca, Ni-Re-Mg, Ni-Re-Sr, Ni-Re-Li, Ni-Re-K, Ni-Re heated to the reaction temperature. The pressure at the
Ba, Ni-Re-Ce, Ni-Re-W, Ni-Re-Fe, Ni-Re-Ru, Ni-Re time of reaction should normally be within the range
Cu, Ni-Re-Ag, Ni-Re-Zn, Ni-Re-Co, Ni-Re-U, Ni-Re 20 from about 500 to about 5,000 psig and preferably from
Ti and Ni-Re-Mn. In order to prepare such catalysts, 800 to about 4,500 psig. The reaction may occur in a
salts of these additional metals are added in suitable single phase or in two phases where some of the ammo
amounts to the impregnation solution containing the nia and some of the alkane starting material are present
nickel and rhenium salts. in the liquid phase and some in the gaseous phase.
An indicated above, the amination of alkane deriva The ammonia employed in the reaction may be anhy
tives is a process which has been extensively investi 25 drous or may contain small amounts of water. Any
gated and is well documented in the prior art. The reac water introduced into the reaction mixture with the
tion conditions for the process to occur are generally ammonia should be considered when conversion of the
known but are particularly dependent upon the activity reaction is evaluated by the presence of water in the
of the amination catalyst present. When amination pro 30 final mixture.
cesses are catalyzed by the nickel-rhenium catalyst of Normally, the process is run in an excess of ammonia
the present invention, the conversion and activity of the to ensure reactions with ammonia and not an amine
reaction are significantly and surprisingly improved, present in the reaction mixture. This is one means of
and the reaction conditions required are generally less improving the yield of the desired aliphatic alkylamine
SeVee. 35 product. In some catalytic systems a large excess of
The alkane derivatives which may be aminated in ammonia must be present. One advantage of the present
accordance with the present invention include lower invention is that because of the exceptional selectivity
aliphatic alkane derivatives having one or more func of the nickel-rhenium catalyst of the present invention,
tional groups. Preferred lower aliphatic alkane deriva only a relatively small excess of ammonia is required.
tives include those containing one to six carbons. The 40 It has been found that increasing the mole ratio of
functional groups present may be on the primary, sec ammonia to the alkane derivative reactant decreases the
ondary or tertiary carbon atoms. At least one of the activity or conversion rate of the reaction in some types
functional groups present should be capable of being of reactors. This occurrence may be due to the fact that
replaced by an amine group in the catalytic amination excessive amounts of ammonia will reduce the amount
process of the present invention. The preferred func 45 of surface of the catalyst available for access by the
tional groups includehydroxy, amino, imino groups and alkane derivative reactant.
combinations of said groups. Illustrative examples of In the amination processes of the present invention,
preferred alkane derivative starting materials include the ammonia should be present in an amount at least
ethanol, ethylene-glycol (ethanediol), monoethanol equivalent to the stochiometric amount required by the
amine, ethyleneimine, isopropanol, propanolamines, 50 alkane derivative reactant. The ammonia should prefer
propanediols, acetone, butanols, butanediols, ably be present in an amount between 2 times and 30
aminobutanols, pentanols, pentanediols, aminopen times the stochiometric amount required.
tanols, hexanols, hexanediols and aminohexanols. The In the production of ethylene diamine from ethylene
starting materials contemplated herein also include glycol, monethanolamine or mixtures thereof, ammonia
compounds from which the aforementioned may be 55 is preferably presentin an amount to give a mole ratio of
derived. Preferably, at least one of the functional total EG and MEA to ammonia in the range of 1:4 to
groups in the starting material is a hydroxy group. 1:20,
Other functional groups which are not replaceable dur The amount of hydrogen gas present in the amination
ing amination may be present in the alkane starting process of the present invention is not critical. Usually,
material in combination or in addition to the replaceable 60 hydrogen is added in an amount sufficient to maintain
functional groups. the catalyst in an active state. A preferred amination
The particular alkane derivative starting materials to process is carried out where the hydrogen is present in
be used, of course, depends upon the particular amine an amount wherein the hydrogen to ammonia mole
product desired to be produced. Generally, the desired ratio is greater than 1 and preferably less than the ratio
aminated product differs from the alkane starting mate 65 1000:1.
rial by the amine group which replaces the non-amine Where selectivity is of primary concern in the amina
functional group or groups present in the starting mate tion process, it is preferred not to run the process to a
rial. For example, in the production of ethylene di high conversion. It has been found that selectivity to the
 4,123,462 12
11
preferred aminoalkanes decreases as conversion in to determine X at various reaction times, knowledge of
CTCSS. the reactant-alcohol concentration-time profile is re
One possible explanation for why selectivity de . quired.
The activities of the various catalysts tested have
creases as conversion increases is that the heavier and 5 been
more substituted nitrogen products are produced as a ranked by determining the amount of water pro
result of a chain of consecutive reactions. For example, duced
MEA
understandard reaction conditions. Each mole of
or EG converted produces a mole (or two moles
it has been suggested that the piperazine by-product
formed in the amination of monoethanol amine is pro in the case of EG) of water and the
duced by either route 1, 2 or 3 shown below: O NH + H2NCHCH-OH - HNCHNH + HO
(1) MEA - EDA - AEEA - piperazine (DEDA).
(2) MEA - EDA --> piperazine (DEDA) 2NH -- HOCHOH- H2NCHNH + 2HO
(3) 2MEA-> AEEA - piperazine (DEDA)
The amination process of the present invention may catalyst producing the most water is the most active.
be carried out in any conventional equipment having 15 The water produced is easily determined by Karl Fi
heating means. The process may be carried out as a scher titration of the (ammonia free) reaction mixtures.
continuous process of by batch. In continuous equip The selectivity of the catalyst is determined by ana
ment no agitating means is required as the nature of the lyzing the reaction product mixture and comparing the
continuous process causes the reactants to continually amount present of various reaction products. In the case
flow in intimate contact with the catalyst material. 20 of amination of ethylene glycol and monoethanolamine
Where high pressures are desired for the amination to produce ethylene diamine selectivity is determined
process, the equipment should have high pressure capa by comparing the amount of ethylenediamine (EDA)
bility. with the amount of piperazine produced in a given
The amount of Ni-Re catalyst present in an amination conversion. The analysis of the reaction product mix
process depends on many variables including the reac 25 ture is generally done by gas chromatographic separa
tants, the relative proportions of the reactants, reaction tion. Examples of columns which have been used in the
conditions, and the degree of conversion and selectivity gas chromatographic analysis of such reaction mixtures
include TERGITOL NP-27 on CHROMOSORB T
desired. Moreover, the amount of catalyst will depend and TERGITOL E-68 on CHROMOSORBZ. A par
also on the nature of the catalyst itself, e.g., its metal ticularly preferred column comprises Carbowax 30M
loading and activity and age. In sum, the catalyst should 30 on Chromosorb 750 having a particle size of 40-60 mesh
be present in the amination reaction in sufficient cata and wherein the column is 8 feet long having an inner
lytic amount to enable the desired reaction to occur. diameter of inch.
In the examples below, some of the materials used
were obtained from the following sources: EXAMPLE 2
Girdler supports were obtained from the Girdler 35 Comparison of Different Metals in Catalysts
Division of Chemetron Corporation, P.O. Box 337, This example concerns an evaluation of the activity
Louisville, Ky. and selectivity of various catalysts identified in Table
Norton supports were obtained from the Norton No. 2. All of the catalysts used in this example were
Company, Akron, Ohio. 40 prepared by the same general technique.
The Johns Manville supports were obtained from
Johns Manville Products Corporation, 8741 Americana Preparation of Impregnating Solutions
Blvd., Indianapolis, Ind. 86268. Stock solutions containing Ni, Cu, Pd, and Re were
Ammonium perrhenate (NHReO) was obtained prepared by dissolving a known quantity of an appro
from Cleveland Refractory Metals, 28850 Aurora 45 priate metal salt in water. The metal salts, amounts used,
Road, Solon, Ohio 44139. and the final metal concentration are tabulated below.
Nickelous nitrate Ni(NO)6HO was J. T. Baker
analytical reagent grade.
Other chemicals referred to in the examples are rea No. of
Solu- Mole Gms. Gms. Gms. Metal/
gent grade and commercially available from numerous 50 tion Meta Salt Wit. Salt HO ml solin
SOCeS.
1 Ni(NO), .6HO 290.8 66 300 05
380
EXAMPLE 1 --
2 Pd Cl 177.3 6.6 70ml 009
Analytical Method for Determining the Selectivity and COC.
Activity of an Amination Catalyst 55
3 Cu(NO), .3HO 241.6 7.6
HC
200 01.
In order to develop catalyst activity data, analytical 4 NHReO, 268.2 8 100 ,056
methods to permit the determination of the degree of
reactant conversion and the product distribution are Preparation of Catalysts
required. The degree of conversion, X, is defined by
equation (1); and Nickel on Norton a-alumina LA-4102.
The support (19 grams) was placed in a 250 ml. round
x, = 1 - =--i,
moles MEA reacted
iii. (1) botton flask, water (25 mls) and ethanol (25 mls) were
added. After swirling, 20 mls. of solution No. 1 was
65 added. A solution containing ammonium carbonate (3
where: gm) in 25 mls. of water was added dropwise to the
n = moles present at time metal-support slurry. The slurry was evaporated to
n = moles present initially dryness on a vacuum rotary evaporator. The coated
 4,123,462 14
13
catalyst was transferred to a porcelain evaporating dish, roasting, and reduction steps were conducted as de
and dried at 120° C for 2 hours. The catalyst was then scribed above.
roasted at 300 C for 2 hours in a muffle furnace, cooled Ni-Re Catalysts
to room temperature, transferred to a quartz tube and
placed in a tube furnace. The tube furnace was heated to 5 These catalysts were prepared using the procedure
300 C, and the catalyst was reduced in a stream of described for preparation of the Ni-Pd catalysts. Again,
hydrogen gas for 2 hours, 40 minutes. The quartz tube 38 grams of support was used, and after slurrying the
was purged with N, gas while cooling to room tempera supports in 50 mls, ethanol, 32 mls, of solution No. 1
ture, and the catalyst was stored under N, until tested. followed by 7.2 mls. of solution No. 4 were added. This
10 gives a Ni/Re atom ratio of approximately 11.3/1. The
Nickel on CXC Carbon, Nickel - JM - 408, and evaporation, drying, roasting and reduction steps were
Nickel-Girdler Silica, T869 as described for the Ni catalysts. Two of the reduced
* Johns Manville, Diatomaceous silica Ni-Re catalysts were pyrophoric, Ni-Re on CXC Car
These catalysts were prepared using the same proce bon and Ni-Re on JM-408 (diatomaceous silica).
dure described for the preparation of the Ni-a- alumina 15 The metal loading in each case was a maximum of 5
catalyt. The carbon used was National Carbon Compa percent by weight of the support, assuming that 100
ny's CXC 6/8 mesh. percent of the available metal was picked up by the
Support.
Nickel-Copper Catalysts The catalysts were tested in a 0.5 liter rocker auto
These catalysts were prepared using essentially the 20 clave. In each case, the catalyst (5gm.) slurried in MEA
same procedure as described above for the Ni-a- alu (25.5gm., 0.42 moles), and water (5 gm., if any), was
mina catalyst. The amount of support used was in charged to the autoclave. The autoclave was pressur
creased to 38 grams, and a 500 ml. round bottom was ized with hydrogen to the required pressure (50 or 200
used. After slurrying the support with a solution con PSIG), and finally liquid ammonia (71 gm., 4.17 mole)
taining 50 mls. HO and 40 mls. ethanol, 36 mls. of 25 was pressured into the autoclave via a hoke cylinder.
solution No. 1 followed by 20 mls. of solution No. 3 The reaction mixture was heated to the required tem
were added. This gives a Ni/Cu atom ratio of approxi perature (175 or 225) and held at reaction temperature
mately 8.7/1. A solution containing 6 gm. of ammonium for six hours.
carbonate in 50 mls. of water was then added, and the The results of the 16 tests are reported in Table 2. The
resulting slurry was evaporated to dryness using a vac- 30 analyses of the product was done by the techniques
uum rotary evaporator. The drying, roasting, and re described in Example 1. The most active catalysts tested
duction steps were conducted as described previously. was a Nickel-Rhenium based catalyst on a -alumina
The catalysts were stored under Nprior to testing. The (run No. 13) which also exhibited a high degree of selec
Ni-Cu catalysts on CXC carbon was pyrophoric. tivity (EDA/DEDA). The Ni-Re catalysts on diatoma
Ni-Pd Catalysts
35 ceous silica (JM-408) and silica (Runs 15 and 16)
showed excellent selectivity but low conversion activ
These catalysts were prepared using a slight modifi ity at the reaction conditions tested. The Ni-Re catalyst
cation of the previous procedure. The support (38 gm.) on the carbon support (Run 14) did not show any cata
was placed in a 500 ml. round bottom flask and 40 mls. lytic activity in the amination process.
TABLE 2
CONVERSION OF MONOETHANOLAMINE TO ETHYLENEDIAMENE
Approx.
Run H, MI HO %HO %MEA
Run No. CATALYST Temp. PSIG Charged in Prod. Converted Products EDA/DEDA
Ni on a-alumina 175 50 nil 1.6 5 EDA CO
2 Ni on CXC Carbon 175 200 5 1.9 6 No Products Obsd. -
3 Ni on JM-408 225 200 nil 6.4 22 EDA, DEDA 12.6
4. Ni on Girdler Silica 225 50 5 4.2 4. EDA, DEDA 5.5
5 Ni-Cu on a-alumina 175 50 nil 0.9 3 EDA o
6 Ni-Cu on CXC Carbon 175 200 5 3.6 12 No Products Obsd. -
7 Ni-Cu on JM-408 225 200 nil 4.0 13 EDA, DEDA 9.9
8 Ni-Cu on Girlder Silica 225 50 5 7.7 26 EDA, DEDA 1.0
9 Ni-Pd on a-alumina 225 200 5 4.4 15 EDA, DEDA 1.3
10 Ni-Pd on CXC Carbon 225 50 nil 4.7 16 Trace EDA and anks --
11 Ni-Pd on JM-408 175 50 5 1.7 6 No Products Obsd. -
12 Ni-Pod on Girdler Silica 175 200 nil 4.3 15 EDA ox
13 Ni-Re on on-alumina 225 200 5 14.0 48 EDA, DEDA 4.75
14 Ni-Re on CXC 225 50 nil 3.4 12 No Products Obsd. -
15 Ni-Re on JM-408 175 50 5 0.6 2 EDA OO
16 Ni-Re on Girdler Silica 175 200 nil 2.6 9 EDA OO
'Diatomaceous silica
&T869

Ethanol (200 proof) was added, followed by 32 mls. of 60

solution No. 1 and 43 mis. of solution No. 2. This gives EXAMPLE 3
a slurry
rry containing3. a Ni/Pd atom ratio of approximatel
pp y Ni/Re Atom Ratio
7/1. Powdered ammonium carbonate was then added
portion wise until the PH of the slurry increased to For this example ten nickel-rhenium catalysts have
approximately 8 (Hydrion paper). The slurry was then 65 been prepared on two support materials including Gir
evaporated to near dryness using a vacuum rotary evap dler supports T372 and T869.
orator. The mass was reslurried in 50 mls. of fresh abso All of these catalysts were prepared by the same
lute ethanol and evaporated to dryness. The drying, general procedure. A solution containing Ni(NO3).
 4,123,462
15 16
6HO and NHReO dissolved in 12 mls of distilled shows that the T869 supported catalysts with a 10/1 and
water was prepared. 15/1 Ni/Re atom ratio are more active than those with
The impregnation procedure involved adding the a 30/1 Ni/Re atom ratio. Also, the T869 supported
nickel-rhenium solution to 19 grams of dried, evacuated catalysts are more active than the T372 supported cata
support material via a syringe. The impregnated sup lysts.
port was dried in an oven at 120 C for several hours, EXAMPLE 4
and then placed in a muffle oven at a specified tempera
ture (calcining temperature) for 3 hrs. to calcine the Varying The Ni-Re Loading
catalyst. After calcining, the catalyst was placed in a
quartz tube and purged with a continuous nitrogen flow 10 This example illustrates the effect on activity and
(10-20 cc/min.) while being heated to a record specified selectivity of varying the total weight % of nickel--A
temperature. Upon reaching this temperature (reduc rhenium metal impregnated on the catalyst support.
tion temperature) the flow of nitrogen was interrupted Four catalysts were prepared having different
and hydrogen was fed at 10-20 cc/min through the tube amounts of total nickel and rhenium metal on Girdler
for 3 hrs, to reduce the metal oxides and activate the 15 T869 and T1571 supports.
catalyst. After this activation, the flow of hydrogen was 12.5% Ni-Re on Girdler T1571
interrupted and nitrogen was fed through the quartz
tube and the catalyst was permitted to cool to room A solution containing 18.8 gms. of Ni(NO3), 6HO
temperature (25 C). The activated catalyst was stored and 1.73 gms. NHReC) dissolved in 52 mls. of water
under nitrogen until used. 20 was prepared. 35 gms. of T1571 support was dried in an
The above procedure is a general one and was used to oven at 120° C and evacuated. 26 mls. of the above
prepare the ten nickel-rhenium catalysts. Ni-Resolution was slurried with the dried, evacuated
These catalysts differed by the Ni/Re ratio, the cal support. The impregnated support was then dried, evac
cining temperature, the reduction temperature, and the uated, and impregnated with a second 26 ml portion of
support used as shown in the Table 3. The amounts of 25 the Ni-Resolution. The support was again dried, cal
Ni(NO). 6HO and NHReO used to prepare the cined, and reduced at 300 C for 3 hours in a stream of
above catalysts were varied to give in each case a cata hydrogen.
lyst containing the desired Ni/Re atom ratio. All of the
catalysts were prepared to contain 5 wt.% total metal
30% Ni-Re on T1571 Support
(Ni - Re) on the support. 30 A solution containing 45.12 gm Ni(NO). 6H2O and
The above catalysts were tested for activity to con 4.12 gm of NHReO dissolved in 62 mils of water was
vert monoethanolamine to ethylenediamine using a 0.5 prepared and used to impregnate 28 grams of Girdler
liter Parr rocker autoclave constructed of stainless steel. T1571 support. The impregnation procedure was simi
The test procedure involved charging 5 grams of the lar to that described for the 12.5% Ni-Re catalyst ex
appropriate catalyst, 26 gm (0.5 mole) of monoethanol 35 cept that 21 mls of the above Ni-Resolution was used
amine, and 200 PSIG of hydrogen to the autoclave. per impregnation. A total of 3 impregnations were re
Next, 72 grams of anhydrous ammonia was pressured quired to absorb all of the Ni-Re on the support. The
into the autoclave, and the autoclave was heated to 200 impregnated support was calcined at 300°C for 3 hours,
C. The reaction temperature was maintained at 200 C and then reduced for 3 hours at 300° C in hydrogen.
for 1 hour and then the autoclave was allowed to cool 40 30% Ni-Re on T869 Support
to room temperature (~23° C). The excess ammonia
was slowly vented from the autoclave, and the products A solution prepared by dissolving 45.12 gm Ni(-
were recovered essentially ammonia-free. NO). 6HO and 4.12 gm NHReOH in 59 mls of water
The crude, ammonia-free products were first ana was used to impregnate 28 gms of Girdler T869 support.
lyzed for water content using the Karl Fisher titration 45 The impregnation required 4 coatings with 15 mls of the
method to determine the extent of monoethanolamine Ni-Resolution per coating. The impregnated support
reacted. was calcined at 300 C for 3 hours and then reduced in
TABLE 3 a stream of hydrogen for 3 hours at 300 C.
Cat-
alyst Ratio Calcining Temp. C
Girdler
Support EDA 50
12.5% Ni-Re on T869 Support
No. Ni/Re Temp. C Reduction Used % HO DEDA A solution of 18.8gm of Ni(NO). 6HO and 1.73 gn.
15/1 300 300 T869 3.5 Not of NHReO4 in 37 mls of water was prepared, and use:
2 3O/ 300 600 T869 5.0
t
5.4
to impregnate 35 gms. of Girdler T869 support. The
3 15/1 300 600 T372 4.2 EDA impregnation required 2 coatings with 18.5 mls of the
4 30/1 300 300 T372 5.7
only
24
55 Ni-Resolution per coating. The impregnated catalysi
5 15/1 600 600 T372 3.9 EDA was calcined for 3 hours at 300 C and reduced for 3
only hours at 300' .
6 30/1 600 300 T372 3,3 Not The above four catalysts were tested for activity an
7 15/1 600 300 T869 10.3 7.7 selectivity in the conversion of ethylene glycol to eitiy.
8 30/1 600 600 T869 5.3 Not 60 enediamine, monoethanolamine, and piperazine in a 0.
9 10/1 300 300 T869 16.7 3.2 1 Parr rocker autoclave constructed of stainless ::: ee
10 10/1 300 300 T372 7.4 Not The procedures used to charge the autoclave, and ana.
lyze the products were identical to those described i:
Example 2 above. The specific reaction conditions f,
The data analysis of the products, namely the water 65 set forth in the table below. The reaction time fo: r2?.
content and product ratio of EDA to DEDA also ap experiment was 45 minutes where the reaction tin;
pears in Table No. 3. The results indicate a clear depen were measured after the reaction mixture reached f:
dence of catalyst activity on Ni/Re atom ratio. The data desired reaction temperature.
 4,123,462
17 18
TABLE 4 ated support through an addition funnel. After slurrying
Weight the support with the Ni-resolution, the impregnated
Girder 2, support was dried at 120 C and then calcined for 3 hrs.
Cata-
lyst
Total
Metal Feed Reac-
Weight
%
at 300° C. Finally, the catalyst was activated by reduc
Sup- On the Mole tion HO Product tion in a stream of hydrogen for 3 hrs. at 300 C. After
Exp. port Sup- Ratio Temp. in 6- Ratio cooling to room temperature, the catalyst was stored
No. Used port NH/EG C duct EDAADEA under nitrogen prior to testing.
1 T571 2.5 13/ 200 10.3 3.0
2
3
: T869
T1571
12.5
300
13/1
3/1
225
225
30.8
32.2
0.6
0.7
Preparation of 5% Ni-re on Girdler T1571 Support
4.
5
T869
T157
30.O.
12.5
3/1
20/1
200
225
10.9
0.3
4.3
2.4 .
O A solution of 7.51 gms of Ni(NO3), 6HO and 0.6926
6 T869 12.5 20/1 200 7.3 . 13.0 gm. of NHReO in 29 mls of water was prepared. The
7 T1571 300 20/1 200 9.2 10.6 slurry was warmed to dissolve the salts. The support
8 T869 300 20/ 225 15.7 4.4 was prepared for ingregnation by drying for 3 hrs. at
120 C, and then cooled to room temperature under
The respective feeds of reactants in each of the exper 15 vacuum. The Ni-Resolution was added to the evacu
imental runs are as follows: ated support via an addition funnel. The impregnated
support was dried. Calcined and reduced as described
Gms.
previously for the preparation of Ni-re on T869 sup
Exp. Nos. Gms NH Gms. EG Catalyst Initial H. Press port.
1,2,3,4 68.0 19.0 5.0 200 PSG B. Amination Reaction
5,6,7,8 104.0 9.0 5.0 200 PSG
Using the above prepared catalysts, a series of eight
Analysis of the data from the eight experimental runs experiments outlined in the following table were con
ducted.
- Table 5
Feed Mole : Initial Wit. 2% Product
Exp. Ratio Reaction Catalyst Hydrogen HO in Ratio
No. NH/EG Time (min). Support Pressure Product EDAMDEDA
15/1 45 T869 200 100 5.7
2 25/1 45 . T869 300 . 8.7 0.6
3 15/1 90 T869 300 11.7 5.3
4 25/1 90 T869 200 8.6 12
5 15/1 45 T1571 300 3.3 Only MEA
6 25/1 45 T157 200 2.5 Only MEA
7 15/1 90 T57 200 7.6 7.5
8 25/1 90 T157 300 5.8 2

of Table 4 show that the 12.5% metal catalyst supported

on T869 is more active than the 30% metal catalyst All of the experiments outlined in the above table
supported on T869. Conversely the 30% metal catalyst were conducted in a 0.51 Parr autoclave constructed of
supported on T1571 is more active than the 12.5% stainless steel. In each experiment 5 grams of the speci
metal catalyst supported on T1571. The data confirms 40 fied catalyst and 18.6 grams of ethylene glycol were
that the degree of ethyleneglycol conversion can be
increased either by increasing the reaction temperature charged to the autoclave. Next the autoclave was pres
surized with hydrogen to the specified initial pressure
from 200 C to 225 C, or by decreasing the NH/EG (PSIG), and then the required amount of ammonia was
feed mole ratio from 20/1 to 13/1. forced into the autoclave under nitrogen pressure. The
EXAMPLE 5 45 amount of ammonia charged was either 76 gm or 128
Amination Reaction Conditions gms depending upon the desired NH/EG feed mole
ratio; 76 grams was charged for experiments 1, 3, 5, 7
This example demonstrates that Ni-Re based catalysts and 128 grams was charged for experiments 2, 4, 6, 8.
are active for converting ethylene glycol to ethylene After charging the ammonia the autoclave was
diamine, monoethanolamine, and piperazine. Also 50 heated, while being rocked, to 200 C. Upon reaching
shown is the effect of the various reaction variables on 200 C, the reaction temperature was maintained for the
the conversion of ethylene glycol, specified time, and then the autoclave heater was turned
off. The autoclave was allowed to cool to room temper
A. Preparation of Catalysts ature, and the excess ammonia was slowly vented to
Two batches of nickel-rhenium based catalysts sup 55 reduce the pressure in the autoclave to atmospheric
ported on Girdler supports T869 and T1571 were pre pressure.
pared. Each of the catalyst supports was impregnated In Table 5 above, for each experiment, the wt.%
with 5 weight 2% total metal (as Ni' -- Re") having a water in the final product (NH-free basis) is tabulated
Ni/Re atom ratio of 10/1. The supports were impreg together with the area-ratio of EDA to DEDA ob
nated as described below. 60 tained from gas-chromatographic analysis of the reac
Preparation of 5% Ni-Re on Girdler T869 tion mixtures. In all experiments the reaction mixtures
were found to contain monoethanolamine and some
A solution containing 24.7gm of Ni (NO3)6H2O and unreacted ethyleneglycol. In experiments 1, 2, 3, 4, 7
2.278 gms. of NHReO in 67 mls. of water was pre and 8 the reaction mixture also contained ethylenedi
pared. 130gms Girdler T869 support ( inch extrusions) amine and piperazine. m
was prepared for impregnation by drying for 3 hours in The data reported in Table 5 confirms that T869
a 120' Coven, and then allowed to coolin an evacuated supported catalysts are more active than the T1571
flask. The Ni-Resolution was added to the dried, evacu catalysts and that degree of ethylene glycol conversion
 19 4,123,462 20
increases with increasing reaction time. Also shown is HO, 5.95gms of NHReO, and 1.37 gm of HBO. The
that the selectivity to ethylenediamine decreases as the impregnated support was dried in an oven at 125 C for
conversion of ethylene glycol increases. 3 hrs., calcined at 300 C for 3 hrs., and finally reduced
The data demonstrates the effect of varying the feed in a stream of hydrogen for 3 hrs. at 300 C. The acti
mole ratio of ammonia to ethylene glycol. Increasing 5 vated catalyst was stored under nitrogen until used.
the NH/EG feed mole ratio from 15/1 to 25/1 de All aminations were conducted in an 0.51. rocker
creased the degree of ethylene glycol conversion. How autoclave constructed of stainless steel. Five grams of
ever, the increase in the NH/EG mole ratio increased the Ni-Re catalyst on K306 was placed in a rocker
the selectivity of the reaction to form ethylenediamine bomb autoclave which had been flushed out with nitro
as compared with the piperazine product. O gen. The alcohol or ketone was placed in a test tube
The conversion of ethylene glycol does not appear to attached to a dip tube which fitted into the bomb auto
be effected by the hydrogen pressure within the ranges clave. The bomb was sealed and pressurized to 200 psig
examined in these experiments. with hydrogen. Next, the bomb was placed in the heat
EXAMPLE 6 ing jacket of the rocking device, and the desired amount
15 of liquid ammonia was pressured into the bomb via
Ni-Re-B Catalyst nitrogen pressurized Hoke cylinder. The NH-catalyst
This example illustrates that a beneficial effect on H mix was then heated to 190 C., and the rocker was
activity can be obtained by adding Boron to a nickel switched on. On the first down-stroke the bomb was
rhenium catalyst. This is accomplished by adding boric tipped sufficiently to permit the alcohol or ketone to
acid to the Ni(NO3)2.6H2O and NHReOaqueous solu 20 dump from the test-tube, and come into contact with
tion used to impregnate Girdler T869 support as de the catalyst 3-Hamixture. The reaction timer was started
scribed more fully below. at this point. The particular reaction conditions for each
A solution containing 5.13 gm Ni(NO)6H2O, 0.47 of the three aminations are summarized in the following
gms NHReO and 1.3 gm HBO in 19 ml of distilled 25 table:
water was prepared. 18 gms of predried Girdler T869
support was placed in a 250 ml round bottom flask, and C.
the flask was equipped with a vacuum adapter. The Run Amination of Gms. Gns. Gms. Rxn. Rxn.
flask was evacuated by means of a vacuum pump, and No. (compound) Catalyst NH, Compound Temp. Time
then 9.5 mls of the above aqueous solution containing Ethanol 5 79 21.3 190 2 hr.
Ni-Re and HBO was added to the support via a sy 30 23 2-Propanol Acetone
5
5
39.5
79
27.8
27
190 2 hr.
190 2 hr.
ringe. The impregnated support was re-dried at 120 C
for 3 hours and impregnated as described above with a
second 9.5 mils of the Ni/Re/B solution. The com After the desired reaction time, the liquid contents of
pletely impregnated support was dried at 120 C for 3 the bomb were vented into a cold trap. After warming
hours, calcined at 300 C in a muffle furnace for 3 hours, 35 to room temperature, samples of the reaction products
and finally reduced at 300 C for 3 hours in a stream of were analyzed by gas chromatography to determine the
hydrogen. products of the reaction. The results obtained are tabu
The above catalyst was tested for activity to convert lated below.
ethylene-glycol to ethylene diamine, monoethanol
amine and piperazine using the 0.5 l Parr autoclave 40 . Run 1 Run 2 Run 3
described above. The experiments conducted are out Products Ethanol 2-Propanol Acetone
lined in Table 6 below. For comparison purposes, a Ammonia 4.0 5.2 1.4
similar catalyst prepared on T869 support except that it Water 3.07 15.67 37.4
contained only nickel and rhenium was tested under the Ethylamine 13.82 -
identical experimental conditions. In both experiments 45 Diethylamine
Triethylamine
0.21
0.30
-
-
the reaction temperature was 200 C and the initial Ethanol 68.5 O
hydrogen pressure was 200 PSIG. The data in Table 6 Acetone
2-Propanol
-
-
0.1
51.31
6.95
12.06
shows that nickel-rhenium-boron containing catalyst is Isopropylamine -- 27.42 28.14
more active than the nickel-rhenium catalyst. Diisopropylamine -- 0.34 2.36
TABLE 6 SO
Pro
duct
The high selectivity to the aminated products ethyl
Wt. 2 Ratio amine and isopropylamine, are clear from the data. It is
Exp. Gms Gms Gms Rxn HO in EDA noted that in the case of acetone there is a substantial
No. Catalyst Catalyst NH, EG Time Prod. DEDA amount of the intermediate 2-propanol present in the
1 Ni-Re-B 5 76. 19 . 1 hr 15.7 is 55 reaction mixture but this is an expected intermediate in
on T869
2. Ni-Re 5 76. 19 1 hr 9.5 6.8 the ultimate production of the isopropylamine.
on T869
EXAMPLE 8
1,3-Propanediol Conversion
EXAMPLE 7 60
The nickel-rhenium based catalyst are also active
Amination of Ethanol, 2-Propanol, and Acetone catalysts for the conversion of higher molecular weight
A nickel-rhenium catalyst, further containing boron, diols such as 1,3-propane-diol to diamines. This experi
was prepared to test its effectiveness in aminating etha ment shows that 1,3-propanediol is converted to a mix
. nol, 2-propanol, and acetone. 65 ture of 1,3-propanediamine and 3-hydroxypropylamine
A nickel-rhenium catalyst was prepared by impreg over a nickel-rhenium catalyst.
nating 200 gms Girdlers's K306 support with 100 mls of A nickel-rhenium catalyst was prepared by impreg
an aqueous solution containing 64.5gms of Ni(NO),6- nating 130 grams of Girdler support T869 with 67 mls
 21
4,123,462 22
of an aqueous solution containing 24.7 gm of Ni(-
NO)6H2O and 2.28 gms of NHReO. The impreg- EXAMPLE 10
nated catalyst support was dried at 120 C for several Preparation and Testing of Ni-Re Catalysts on
hours, calcined at 300 C for 3 hours, and reduced in a Silica-Titania Supports s
stream of hydrogen at 300 C for 3 hours. Three supports were prepared having SiO/TiO,
Five grams of the above catalyst was charged to a 0.5 mole ratios of 1/9,s 1/1 and 9/1,, respectively.
res Appropri
Sea. ity g A.d 32 gm of it.
propanediol. Ine autoclave was sealed, and pressurize
ate amounts of TiCl, and Si(OCHCH) were mixed
together in an addition funnel, and added dropwise to a
to 200 PSIG with hydrogen. Next, 107 gm of anhydrous rapidly stirring flask containing 550 grams of 28% NH3
ammonia was pressured into the autoclave. Theo auto- 10 wesi (4.4as moles. NHOH).
4. w After the addition
clave was heated to 200 C and maintained at 200 C for was complete, the slurry was heated to 90' C, and stir
2 hours. After cooling to room temperature the excess ring was continued for 1 hour. The slurry of SiO-TiO
ammonia was vented from the autoclave, the autoclave woodoomperature and fiered. f s
Was R the reaction H. WaS E. 1 O-TiO, was washed with portions of distilled water
Analysis of the reaction mixture by gas chromatogra- 15 tilth washings gave a negative test for chloride ion
phy showed that significant amounts of 1,3-propanedia- with silver nitrate. The SiO, TiO, was air dried, then
nine and 3-hydroxypropylamine were produced during died in an oven at 100 Cf20 hours and finally cal
the reaction. Analysis of the crude reaction mixture for cined at 500 C for 3 hours. The surface area of the
water content by Karl Fisher titration showed that the powdered product was determined. The specific data
reaction mixture contained 15.2 wt.% water. This 20 a
amount of water indicates that about 45% of the 1,3- EE Each of the three supports is indicated
propanediol charged had been converted to products.
EXAMPLE 9 -
PreparationCo,
andBTesting of Catalysts Containing Ni, Re, 25 -storio, E.
on Girdler T869 Support
E. -"X"-...,-
Active catalysts containing nickel, rhenium, cobalt 5. s is 38
and boron have been prepared. The presence of boron
in these catalysts has been shown not to be essential to
the activity or selectivity although boron may play a Three catalysts were prepared having the same 10%
role in the life of these catalysts. bw. total Ni-Re content on each of the three SiO/-
Three catalysts have been prepared from a solution TiO2 supports described above. An impregnating solu
containing Ni(NO)6HO, Co(NO3)6H2O, NH.ReO4. tion containing 7.521 gms of Ni(NO), 6H.O and 0.693
and HBO, in distilled water which was used to impreg. gms of NH4ReO4 in 21 mls of water was prepared and
nate a T869 catalyst support. The amounts of the metal used to impregnate 18 grams of each SiO2/TiO, Sup
salts used and the reduction temperature and time in the port. Each catalyst was thereafter calcined at a temper
preparation of each catalyst is shown in Table 7 below. ature of 300 C for 3 hours and thereafter reduced under
Each catalyst was calcined at 300° C for 3 hours prior to
reduction.
hydrogen at a temperature of 300 C for 3 hours.
These catalysts were tested for activity to convert
The aforementioned three catalysts were tested for either ethyleneglycolor monoethanolamine, to ethyl
activity to aminate either ethyleneglycolor a mixture of enediamine. Each test was conducted by charging 5
monoethanolamine, diethanolamine, and triethanol- grams of the respective catalyst together with an appro
amine. The amination experiments were conducted in a priate amount of NH3 alcohol, and hydrogen to an 0.5
0.5 liter rocker autoclave. The reagents, conditions and 45 1therocker
results are outlined in Table 8 below:
bomb autoclave. The reactants were heated to
desired reaction temperature. After a desired period
Table 7
Exp. Ni(NO)2.6HO NHReO Co(NO), .6HO HBO, Reduction
No. grams grams grams grams HO mls. Temp "C. Time
3.062 0.282 0.919 18 300 3 hrs.
2 2.64 0.487 5.288 0.337 18 300 3 hrs.
3 2.749 0.3512 2,115 0.072 18 400 177 min.
*Two impregnations were required, each using 9 mls of the metal solution, where the support was dried at 125' C between each
impregnation.
of time, the contents of the bomb were analyzed for
composition via a combination of gas chromatography,
and Karl Fisher titration. Specific details of the tests are
tabulated in the following Table 8.
In runs 1-3 significant amounts of MEA were present
in the reaction mixture.
Table 8
Exp. Alcohol, Rxn Wt % HO Product Ratio
No. grams NH, grams H. psig Temp C Rxn Time in prod. EDAMDEDA
1 EG, 19 76 200 200 2 hrs. 11.05 4.94
2 EG, 19 76 200 200 2 hrs. 13.12. 4.75
3 MDT, 19 106 200 185 1 hr. 7.12 7.01
Mixture: 90% wt. MEA; 7% wt. DEA; 3% wt., TEA
 4,123,462
23 24
Table 9
Exp. Support Grams Grams RSn Time Wt.% Product Ratio
HO
No. SiO/TiO, Alcohol Alcohol NH, psig H, Temp C (hours) in Prod. EDA/DEDA
9/1 EG 9 76 200 200 2 14.4 2.87
2 1/1 EG - . 19 76 200 200 2 19.2 3.65
3 1/9 EG 19 76 200 200 2 22.5 2.92
4. 1/9 MEA 19 76 200 185 .75 17.99 3.2
5 9/ MDT 19 06 200 185 5 10.5 8.68
MDT is 90 wit% MEA, 7 wt.% diethanolamine, and 3 wit?, triethanolamine.

EXAMPLE 11 -continued
P reparation off an Active
ctive Ni-Re
Ni-Re Catal
Cat yst With
Without Component Test 2.
Area 1 Test %
Area 2
Calcining DEDA 929 S6.
32
An aqueous solution containing 3.46 gm Ni(NO)6. Ees f. .1
HO, 0.199 gm NHReO, and 1.129 gm HBO dis
solved in 19 mls of distilled water was prepared. The
above solution was used to impregnate 18 grams of 20 EXAMPLE 12
Girdler T869 support. The impregnation was con Variables in Catalyst Preparation
ducted in two steps, 9 mls of the above solution was
used to impregnate 18 grams of the support. After dry In order to determine if the activity of Ni/Re based
ing at 125 C, the support was reimpregnated with the catalysts is effected by changing either the Ni/Re atom
remaining 9 mls of solution. The fully impregnated 25 ratio, the method of supportimpregnation, the calcining
support was dried at 125 C, and then reduced for 3 temperature, or the reduction temperature, a series of
hours in a stream of hydrogen at 300° C followed by an eight experiments have been conducted. A fifth variable
additional 1 hour at 350 C. The reduced catalyst was also included in the experimental set was the support
grey in color and was stored under nitrogen until tested used; both Girdler T869 and Girdler T372 were exam
for activity. 30 ined. The experiments conducted are outlined in Table
The above prepared catalyst was tested under two 0.
sets of conditions. The catalysts were prepared as required for testing.
Test For example, for experiment number 1 a catalyst was
prepared by precipitating Ni and Re on Girdler T372
A 0.5 liter stainless steel rocker autoclave bomb was 35 support. The metals were precipitated from an aqueous
charged with 5 grams of the above catalyst (15-DCB solution containing Ni(NO)6HO, NHReO4 (2 to 1
133) and 19 grams of a mixture of monoethanolamine, mole ratio), and Girdler T372 by the addition of ammo
diethanolamine, and triethanolamine (90 wit% MEA, 7 nium carbonate. After carbonate addition, the resulting
wt% DEA, and 3 wit% TEA). The bomb was sealed slurry was evaporated to dryness to give the metal
and then pressurized to 200 psig with hydrogen and 106 coated support. The dried support was placed in a muf.
grams of liquid ammonia was then added into the auto fle oven and calcined for 3 hours at 300 C, and finally
clave via a hoke cylinder. the catalyst was activated by reduction for 3 hours at
The bomb was heated to 185 C and rocked for 45 300 C in a stream of hydrogen.
minutes. The preparation of the catalysts without a precipitan
Test 2 45 were conducted as described above except that thr
addition of ammonium carbonate to the metal-suppor:
The apparatus and procedure used for Test 2 was the slurry was omitted.
same as that for Test 1 except the reaction temperature For each experiment 5 gms catalyst (5% total meta:
was 200 C, and the reaction time was 1 hour. After the on support listed on the table), 26 gms MEA, 72 gms
reaction period for each test, a sample of the product 50 ammonia, and 200 psig hydrogen gas were charged to
was removed from the bomb and analyzed by gas chro 500 ml rocker autoclave. The reaction time was 6 hour:
matography. The compositions of the samples for Tests and reaction temperature was 225 C.
1 and 2 are tabulated in the table below. The data obtained for the 8 runs are tabulated i1.
Table 10. The water analysis was by Karl Fisher titra
Test Test 2 55 tion. Two values for the 9% water are shown for ruins
Component Area 26 Area % 3, 5, and 7 as these experiments were repeated by usia
Water 7.2 15.25 new batches of the catalysts prepared as described ea:
EDA 9.0 23.2 lier.
Table 10
Exp. Ratio Precipitant Calcining Reduction Support
No. NiARe Used Temp C Temp C Used 7% Water?
1 2/1 (NH)CO, 300 300 T372 8.7, 1.6, 9.u
2 20/1 (NH)CO, 30) 600 T372 26.8
3 2/1 None 300 600 T869 9.09:, 24.8
4 20/1 None 300 300 T869 33.5
5 2A1 (NH)CO, 500 600 T869 28.9, 30.98
6 20/1 (NH),CO, 500 300 T869 30.2
7 2A None 500 300 T372 8.0, 8.69
 4,123,462
25 26
Table 10-continued
Exp. Ratio Precipitant Calcining Reduction Support
No. Ni/Re Used Temp C Temp C Used 9% Water"
8 20/ None 500 600 T372 29.3
The value 909 is considered a blunder, the correct value being 24.88. A statistical analysis of all the
results and the value 24.88 from the second repeated run confirm this,

ometric amount required by the alkane derivative co

What is claimed is: reactant,
1. In the process for aminating a lower aliphatic al 10 11. A process for producing lower aminoalkanes by
kane derivative with ammonia in the presence of a solid the catalytic amination of lower aliphatic alkane deriva
catalyst wherein the products comprise both economi tives selected from lower alkanemono-ols, lower al
cally desirable alkylamines and undesirable by-products kanediols, lower alkanolamines, and mixtures thereof,
of lesser economic significance, the improvement in said process comprising the step of reacting said alkane
selectivity and increased conversion, evidenced by the 15 derivatives with ammonia under pressure, at a tempera
production of a substantially greater amount of said ture of from 125° C to 350 C, and in the presence of
valuable alkylamines together with concomitant reduc hydrogen and an active nickel-rhenium catalyst, said
tion in the yield of undesirable by-products from a given catalyst comprising rhenium and nickel impregnated on
alkane charge, which comprises reacting under amina a support material selected from the group consisting of
tion conditions said alkane charge with ammonia in the 20 aluminas, silicas, silica-aluminas, kieselguhrs or diato
presence of hydrogen and a nickel-rhenium catalyst maceous earths, and silicatitanias, wherein the nickel
comprising rhenium and nickel impregnated on a sup and rhenium metal content is from 3-30% by weight of
port material selected from the group consisting of the support material and the atom ratio of the nickel to
aluminas, silicas, silica-aluminas, kieselguhrs or diato the rhenium present is in the range from about 2:1 to
maceous earths and silica-titanias, wherein said catalyst 25 about 30:1, and wherein said catalyst is present in a
has a total nickel and rhenium metal content of 3-30% catalytic amount.
by weight of the support and the atom ratio of the 12. The process of claim 11 wherein the catalyst is
nickel to the rehnium present is in the range from about activated by heating it in the presence of hydrogen in
2:1 to about 30:1. the temperature range 200-600 C.
2. The process of claim 1 wherein said alkane deriva 30 13. The process of claim 11 wherein the pressure
tive contains from one to six carbon atoms and at least during the reaction is in the range of 500 to 5,000 psig,
one functional group capable of being replaced by an 14. The process of claim 11 wherein the lower ali
amino group by the catalytic amination process. phatic alcohol is 1,3-propanediol. w
3. The process of claim 1 wherein said alkane deriva 15. The process of claim 11 wherein the lower ali
tive contains from one to six carbon atoms and at least 35 phatic alcohol is selected from ethanol and 2-propanol.
one hydroxy functional group. 16. A process for producing ethylenediamine by the
4. The process of claim 1 wherein the desirable alkyl catalytic amination of a compound selected from the
amine product is ethylenediamine and the alkane deriv group consisting of ethylene glycol, monoethanol
ative is selected from the group consisting of ethylene amine, ethyleneoxide, ethyleneimine, and mixtures
glycol, monoethanolamine, and mixtures thereof. thereof, said process comprising reacting said com
5. The process of claim 1 wherein said catalyst is pound with ammonia in the presence of hydrogen and a
comprised of boron in addition to nickel and rhenium. Ni-Re catalyst comprising rhenium and nickel impreg
6. The process of claim 1 wherein said catalyst is nated on a support material selected from the group
comprised of boron and cobalt in addition to nickel and consisting of aluminas, silicas, silica-aluminas, kiesel
rhenium. 45 guhrs or diatomaceous earths, and silica-titanias, said
7. The process of claim 1 wherein said support mate catalyst having a total nickel and rhenium metal content
rial is an a-alumina. ; of 3-30% by weight of the support and a nickel to rhe
8. The process of claim 1 wherein said support mate nium atom ratio in the range from about 2:1 to about
rial is a silica-alumina. : 30:1 and wherein said catalyst is activated in the pres
9. The process of claim 4 wherein the ammonia is 50 ence of hydrogen at elevated temperature, and wherein
present in an amount greater than the stochiometric the temperature of the amination reaction is in the range
amount required by the alkane derivative coreactant 125'-350 C, the pressure is 500-5000 psig and the
that is present. amount of ammonia present is in excess of 2 times the
10. The process of claim 9 wherein the ammonia is stochiometric amount required by the compound.
present in an amount in the range 2-15 times the stochi 55

65
 UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 4,123,462 Dated October 31, 1978
Inventor(s) D. C. Best

It is certified that error appears in the above-identified patent

and that said Letters Patent are hereby corrected as shown below:

Column 5, line 56 "sown" should read "shown".

20, line 21 "3-H" should read "NH-H".
signed and Sealed this
Thirteenth Day of March 1979
SEAL
Attest:

RUTH C. MASON DONALD W. BANNER

Attesting Officer Commissioner of Patents and Trademarks