Catalytic process for the preparation of linear polyethylenepolyamines using a titania-supported phosphamine catalyst for the preparation of linear polyethylene polyamines

Novel catalysts are disclosed which are prepared by reacting a minor amount of phosphonitrillic chloride with titania to form an intermediate reaction product that is reacted with a diamine chelating agent to provide a catalyst that can be used effectively to catalyze the reaction of monoethanolamine with ethylenediamine.

BACKGROUND OF THE INVENTION 
1. Technical Field of the Invention 
This invention relates to a process for the preparation of predominantly 
linear polyethylenepolyamines from ethylenediamine and monoethanolamine in 
the presence of unique catalyst compositions prepared from the reaction 
product of a minor amount of phosphonitrillic acid with titania. 
2. Prior Art 
Heretofore, polyethylenepolyamine compounds such as diethylenetriamine, 
triethylenetetramine and the higher homologs have been produced by the 
reaction of an alkyl halide such as ethylene dichloride with an amine such 
as ammonia or ethylenediamine at elevated temperatures and pressures. 
Normally, relatively high yields of predominantly non-cyclic 
polyethylenepolyamine compounds are obtained from this process with 
varying yields of heterocyclic amines. The large amounts of energy 
required to produce the reactants as well as the difficult separation 
procedures required to recover the more valuable linear 
polyethylenepolyamines diminish the usefulness of the ethylene dichloride 
process. The hydrohalide salts of ammonia and the polyethylenepolyamine 
products must also undergo difficult and time consuming caustic 
neutralization to yield the free polyethylenepolyamines. 
It has heretofore been known that phosphates can be used to catalyze 
reactions to produce predominantly heterocyclic rather than linear 
products. Thus, U.S. Pat. No. 3,297,701 teaches the use of aluminum 
phosphate to catalyze the reaction of ethanolamines and 
polyethylenepolyamines to yield cyclic compounds. U.S. Pat. No. 3,342,820 
discloses the use of aluminum phosphate for the preparation of 
heterocyclic compounds such as triethylenediamine. As another example, 
U.S. Pat. No. 4,103,087 also discloses the use of aluminum phosphate 
catalysts for producing heterocyclic product compounds. 
More recently, investigators have found that more linear products can also 
be obtained in a catalyst conversion. Johnson et al. U.S. Pat. No. 
4,463,193 and U.S. Pat. No. 4,578,517 are directed to the reaction of an 
alkanolamine with an alkyleneamine and ammonia in the presence of a 
catalytically effective amount of a group IIIB metal acid phosphate to 
give primarily noncyclic polyalkylene polyamine products. Thus, in Table 4 
of U.S. Pat. No. 4,463,193, Johnson et al. disclose the reaction of 
monoethanolamine with ethylenediamine and ammonia using catalysts such as 
lanthanum acid phosphate and praseodynium acid phosphate at conversions of 
about 11 to 43% of monoethanolamine to give a noncyclic selectivity of 
about 67% to 92%. In Ford et al. U.S. Pat. No. 4,503,253, phosphoric acid 
incorporated onto an inert support (silica) was used as a catalyst and in 
Table 1 of the patent, use of this type of catalyst was shown to provide 
monoethanolamine conversions of 34% to 68% with a selectivity to 
noncyclics of 62% to 86%. 
European patent application No. 0,073,520 dated August 31, 1982 for Ford 
and Johnson disclosed that the reaction of monoethanolamine with 
ethylenediamine and ammonia can be catalyzed with acidic metal phosphates, 
phosphoric or phosphorous acid or their anhydrides and alkyl or aryl 
esters (e.g., boron phosphate, ferric phosphate, aluminum phosphate, 
etc.). U.S. Pat. No. 4,314,083 discloses the reaction of ethylenediamine 
with monoethanolamine to prepare noncyclic polyalkylenepolyamines using, 
as a catalyst, a salt of a nitrogen or sulfur-containing compound. 
In inventions originating in our laboratories, Brennan et al. in U.S. Pat. 
No. 4,036,881 discloses the use of phosphorus-containing catalysts to 
catalyze the reaction of ethylenediamine with monoethanolamine. Excellent 
results were obtained when the reaction was conducted in an autoclave. 
However, when the phosphorus compound was supported on silica or 
diatomaceous earth, good results were obtained only at comparatively low 
conversions. Brennan et al. U.S. Pat. No. 4,044,053 is also relevant in 
this regard. Brennan U.S. Pat. No. 4,448,997 is directed to an alumina 
phosphate-type catalyst composition wherein the novel feature is the 
method of preparing a catalyst from alumina phosphoric acid, ammonium 
hydroxide and water. Excellent results were obtained using a catalyst of 
this nature in batch-type reactions. 
More recently, Vanderpool and co-workers in a series of U.S. patents (U.S. 
Pat. No. 4,540,822 issued Sept. 10, 1985; U.S. Pat. No. 4,578,518 and No. 
4,578,519 issued Mar. 23, 1986; U.S. Pat. No. 4,584,406 issued Apr. 22, 
1986 and U.S. Pat. No. 4,588,842 issued May 13, 1986) have disclosed that 
the reaction of monoethanolamine with ethylenediamine to provide 
essentially noncyclic polyethylenepolyamine reaction products can be 
effectively promoted with catalysts composed of a minor amount of 
phosphorus thermally, chemically bonded to a group IVb metal oxide support 
such as titania or zirconia. Also, in U.S. Pat. No. 4,555,582 issued Nov. 
26, 1983 and U.S. Pat. No. 4,524,152 issued June 18, 1985, Vanderpool used 
a zirconium silicate catalyst to promote this reaction. 
In addition, Vanderpool U.S. Pat. No. 4,540,822 issued Sept. 10, 1985 
discloses a process for making essentially linear polyethylenepolyamines 
by reacting monoethanolamine with ethylenediamine in the presence of a 
catalyst composed of a minor amount of phosphorus thermally, chemically 
bonded to a group IVb metal oxide support wherein the catalyst is 
periodically regenerated. In Vanderpool et al. U.S. Pat. No. 4,609,761 
which issued Sept. 2, 1986, a catalyst for this reaction is disclosed 
wherein a trialkyl phosphate or a trialkyl phosphite is initially 
deposited on titania as a source of phosphorus, and in Renken U.S. Pat. 
No. 4,612,397 which issued Sept. 16, 1986, a diammonium hydrogen phosphate 
is used as a source for the phosphorus in preparing the catalyst. 
Zimmerschied et. al. U.S. Pat. No. 2,921,081 discloses catalysts for use in 
the conversion of olefins that are prepared by reacting a zirconium halide 
with a designated class of phosphoric acids. 
Rylander et. al. U.S. Pat. No. 2,824,073 is concerned with the manufacture 
of a titanium-phosphoric acid catalyst that can be prepared by mixing 
titania with triphosphoric acid to form a doughy mixture which is 
thereafter dried and heated. 
The text, "Refractories", by F. H. Norton (McGraw-Hill Book Company, Inc., 
1949) in pages 318 and 319 discloses hafnium oxide, titanium oxide and 
zirconium oxides as well-known refractories. 
SUMMARY OF THE INVENTION 
Novel catalysts are disclosed which are prepared by reacting a minor amount 
of a phosphonitrillic chloride with titania to form an intermediate 
reaction product that is reacted with a diamine chelating agent such as 
ethylenediamine to provide a catalyst that can be used effectively to 
catalyze the reaction of monoethanolamine with ethylenediamine. 
Thus, the catalysts are useful in the improved production of predominantly 
linear polyethylenepolyamines from ethylenediamine and monoethanolamine. 
The novel catalysts of the claimed invention can be prepared in a manner 
to be described from titania, a phosphonitrillic chloride, a diamine 
chelating agent and an acid scavenging agent.

DETAILED DESCRIPTION 
In one aspect of the invention the catalysts of the present invention are 
used in producing essentially linear polyethylenepolyamines such as 
diethylenetriamine, triethylenetetramine, tetraethylenepentamine and 
pentaethylenehexamine from the reaction of ethylenediamine and 
monoethanolamine. 
In another aspect, the present invention is directed to an improved 
catalyst composition derived from titania, phosphonitrillic chloride and 
ethylenediamine and to the method by which it is prepared. 
PREATION OF POLYETHYLENEPOLYAMINES 
The novel catalyst compositions catalyze the reaction of ethylenediamine 
with monoethanolamine at a temperature of from about 250.degree. C. to 
about 400.degree. C., preferably from about 270.degree. C. to about 
320.degree. C. and a pressure of from about 500 (34.47 bar gauge) to about 
3000 psig. (206.8 bar gauge) and preferably from about 1000 (68.9 bar 
gauge) to about 2000 psig. (137.8 bar gauge). Higher temperatures and 
pressures can be used, if desired, but there is no particular advantage in 
using such higher temperatures and/or pressures. 
The pelleted catalyst compositions of the present invention are preferably 
employed as a fixed bed of catalyst in a continuous reaction system. In a 
continuous process of this nature, the time of contact of the reactants 
with the catalyst is one of the interrelated factors that those skilled in 
the art will adjust, along with temperature, pressure, bed geometry, 
pellet size, etc. in order to obtain a desired rate of reaction and, 
hence, a desired percentage of conversion of the reactants. Thus, in a 
continuous process, it is not necessary to drive the reaction to 
completion because unreacted feedstock components can be recycled to the 
reactor. 
It is customary to use cylindrically-shaped catalyst pellets having a 
diameter essentially equal to the length thereof, such as diameters and 
lengths ranging from about 0.794 mm (1/32 inch) to about 9.525 mm (3/8 
inch). It will be understood that the shape and dimensions of the pellets 
are not critical to the present invention and that pellets of any suitable 
shape and dimensions may be used as desired, by one wishing to practice 
the process of the present invention. 
When cylindrical pellets of catalyst of the type described above are used, 
the weighted hourly space velocity may be varied within wide limits (e.g., 
0.1 to 5 w/hr/w) in order to obtain a desired rate of conversion, as 
explained above. Normally, space velocities of about 0.5 to 2 w/hr/w will 
be employed. 
Catalyst life is an important factor in conducting a continuous reaction. 
For example, if a catalyst is easily poisoned, or if catalyst pellets do 
not have good structural properties, the economics of the process will be 
seriously and adversely affected. 
The catalysts of the present invention are not particularly susceptible to 
poisoning so this normally does not present a problem. However, under the 
reaction conditions employed, amines of the type used and formed herein 
have the potential capability of leaching or otherwise adversely affecting 
the structural integrity of the pellets. In an extreme instance, catalyst 
pellets having good initial crush strength and surface hardness will be 
reduced to fines very rapidly when used under reaction conditions such as 
those employed herein. 
As a consequence, the catalyst compositions of the present invention are 
advantageously used for a continuous process for the continuous production 
of essentially linear polyethylenepolyamine reaction products from 
monoethanolamine and ethylenediamine. Such catalyst compositions can be 
used for prolonged periods without the need for regeneration (e.g., 1,000 
hours or more). Nevertheless, with the passage of time deactivation will 
tend to slowly occur. Deactivation can be measured qualitatively as the 
increase of temperature required to maintain an essentially constant 
conversion rate for the monoethanolamine and ethylenediamine. 
CATALYST PREATION 
The catalyst compostions of the present invention are prepared from titania 
and a phosphonitrillic chloride using a diamine chelating agent and an 
acid scavenging agent. In the first step, titania pellets are immersed in 
an organic solvent solution of a phosphonitrillic chloride and an acid 
scavenging agent and heated at about 80.degree. to about 150.degree. C. 
for about 1 to about 24 hours to thereby at least partially react said 
phosphonitrillic chloride with a portion of said titania and to scavenge 
liberated chloride with said scavenging agent to form titania pellets 
containing an intermediate reaction product of said phosphonitrillic 
chloride with a portion of said titania. As a consequence, a binding of 
the phosphonitrillic chloride to the titania will occur. The exact nature 
of the reaction that occurs and the exact nature of the reaction product 
that is formed are not known. 
Titania, a solid, normally inert material, is used as one of the starting 
materials of the present invention. It is preferably in the form of 
pre-formed high surface area pellets, such as pellets having a surface 
area of from about 2 to about 250M.sup.2 /gram. This is particularly 
desirable when the finished catalyst is to be used to catalyze a 
continuous process, such as one wherein monoethanolamine and 
ethylenediamine are continuously passed in liquid phase over a fixed bed 
of catalyst. However, if desired, the titania may be used in powdered 
form. This will be advantageous when the catalyst is to be used to 
catalyze a batch process. It is within the scope of the present invention 
to prepare the catalyst compositions using powdered titania as a starting 
material and to thereafter form the powdered catalyst into pellets using 
pelleting procedures known to those skilled in the art, such as procedures 
wherein the powdered titania is mixed with a minor amount of graphite and 
then compressed under pressure in a pellet-forming machine. 
Titania is characterized as having the formula TiO.sub.2. However, it is 
believed that hydroxyl groups are present on the surface of the titania 
and that, surprisingly, the hydroxyl groups will react with a 
phosphonitrillic chloride, at least to the extent that reaction products 
containing from about 0.1 to about 6 wt. % of phosphorus are formed. This 
is surprising because titania is essentially insoluble in water and 
organic solvents. However, organic solvent solutions of a phosphonitrillic 
chloride, and particularly aromatic solvent solutions apparently have the 
capacity to wet the surface of the titania at least to an extent to permit 
a limited reaction of the titania with the phosphonitrillic chloride. It 
is believed that the reaction may proceed as follows: 
##STR1## 
Any appropriate non-reactive organic solvent may be used, such as an 
aliphatic or an aromatic solvent such as benzene, toluene, xylenes, 
cyclohexane, n-heptane, pyridine, chloroform, diethyl ether, ethyl 
acetate, etc. The solvent should be one in which the phosphonitrillic 
chloride is soluble to an extent sufficient to permit the formation of an 
organic solvent solution containing from about 0.1 to about 50 wt. % of 
phosphonitrillic chloride. 
Chloride is liberated during the course of the reaction forming one 
equivalent of hydrogen chloride for each P-Cl bond broken, so an acid 
scavenging agent which is soluble in the solvent and which will not form a 
precipitate should be used. Examples of suitable acid scavenging agents 
include hetero aromatic bases, trialkyl amines, etc. Representative of the 
trialkyl amines that may be used as acid scavenging agents are the C.sub.1 
to C.sub.8 trialkyl amines such as trimethyl amine, tribuyl amine, 
trioctyl amine, etc. Representative examples of other acid scavenging 
agents that may be used include pyridine, lutidine, quinoline, etc. 
In general, at least about 2 to about 25 wt. % phosphonitrillic chloride, 
based on the weight of the titania should be employed, and preferably, 
about 2 to about 10 wt. % of phosphonitrillic chloride, based on the 
weight of the titania. Larger quantities may be used, if desired, but 
there is no apparent adantage in doing so because the amount of phosphorus 
that will bind to the titania is limited. Thus, irrespective of the amount 
of the excess of the phosphonitrillic chloride that is employed, not more 
that about 6 wt. % of phosphorus will bind to the titania. 
The amount of acid scavenging agent that is employed should be adequate to 
react, at least, with all of the hydrogen chloride that is liberated. 
Normally, from about 50 to about 300 wt. % of acid scavenging agent, based 
on the weight of the phosphonitrillic chloride will be adequate. In 
accordance with a preferred form of the present invention, from about 35 
to about 200 wt. % of the acid scavenging agent will be used. 
The reaction between the titania and the phosphonitrillic chloride will 
normally take place when the suspension of the titania in the solution is 
heated at a temperature of about 20.degree. to about 150.degree. C. More 
preferably, the temperature will be within the range of about 50.degree. 
to about 110.degree. C. The reaction time suitably may be within the range 
of about 1 to about 24 hours, and more preferably from about 1 to about 8 
hours. There is no need to use an imposed pressure, so the reaction is 
preferably conducted at autogenous (atmospheric) pressure. 
After the reaction between the titania and the phosphonitrillic chloride 
has been completed, the intermediate reaction product that is formed by 
the reaction should be recovered in any appropriate manner, such as for 
example, by decantation, draining, filtration, centrifugation, etc., and 
washed free of reaction by-products and unreacted acid scavenging agent 
and phosphonitrillic chloride. 
The thus-recovered intermediate reaction product is then reacted with a 
diamine chelating agent to form the final catalyst composition of the 
present invention. Again, the solid intermediate product is immersed or 
otherwise suspended in an organic solvent solution of the reactants. 
The amount of diamine chelating agent to be used should be an amount 
sufficient to react with all of the chlorine present in the intermediate 
reaction product of the titania with the phosphonitrillic chloride, and 
therefore is preferably used in molar excess. Thus, from about 1.1 to 
about 4 mole equivalents, based on the chloride originally present in the 
phosphonitrillic chloride, should be used, and more preferably, from about 
1.2 to about 2 mole equivalents of diamine chelating agent per mole 
equivalent of chloride originally present in the phosphonitrillic chloride 
should be used. 
The diamine chelating agent is dissolved in a suitable organic solvent, 
such as a solvent of the type described above. The amount of solvent to be 
used suitably will be sufficient to form about a 0.1 to 100 wt. % solution 
of the ethylenediamine in the solvent, and more preferably, about a 10 to 
about a 50 wt. % solution. An acid scavenging agent will also be present, 
and may be the same or different from the acid scavenging agent used 
during the reaction of the titania with the phosphonitrillic chloride. 
Again, a molar excess of acid scavenging agent should be present, so the 
amount of acid scavenging agent to be used should be at least a two molar 
amount, based on the diamine chelating agent, and more preferably will 
comprise from about 2 to about 4 moles of acid scavenging agent per mole 
of diamine chelating agent. 
The reaction conditions to be employed in the second reaction step are 
suitable within the same ranges specified for the first reaction step 
(i.e., a reaction at atmospheric pressure at a temperature within the 
range of about 20.degree. to about 150.degree. C., such as about 
50.degree. to about 110.degree. C., and a reaction time within the range 
of about 1 to about 24 hours, such as about 1 to about 8 hours to thereby, 
e.g., at least partially react said ethylene diamine with said 
intermediate reaction product to form a final pelleted reaction product). 
The exact composition of the final reaction product that is formed as a 
result of the reaction of the ethylenediamine with the second reaction 
product is not known. However, it is believed that the ethylenediamine 
reacts with the residual chlorine present in the intermediate reaction 
product in the following manner: 
##STR2## 
At the end of the second reaction step the final reaction product is 
separated and recovered from the organic solvent solution in any 
appropriate manner, such as by draining, decantation, filtration, 
centrifugation, etc., and is then washed with solvent (e.g., toluene) and 
dried. 
The pelleted catalyst compositions of the present invention should be 
calcined. They can be calcined prior to use or calcined in situ when used 
as catalysts at temperatures in excess of about 100.degree. C. When the 
catalysts are to be calcined prior to use, calcination is suitably 
conducted for 2 to 24 hours such as about 1 to about 8 hours at a 
temperature of at least 100.degree. C. but below the temperature at which 
thermal alteration of the catalyst occurs. This can be determined by 
routine experimentation for a particular catalyst. Temperatures above 
about 500.degree. C. should be avoided. A suitable calcining temperature 
range is normally about 200.degree. to about 500.degree. C. and, more 
preferably, 300.degree. to 400.degree. C. 
In any event, in-situ calcining will occur when the pelleted compositions 
are used to catalyze the reaction of monoethanolamine with ethylenediamine 
at 250.degree. to 400.degree. C. 
There are many compounds which can be formed from the reaction of 
ethylenediamine and monoethanolamine besides the preferred linear 
polyethylenepolyamines such as diethylenetriamine, triethylenetetramine, 
tetraethylenepentamine and pentaethylenehexamine. Less desirable cyclics 
and other compounds, such as piperazine, N-(2-aminoethyl)ethanolamine and 
N-(2-aminoethyl)piperazine, are also formed. The more desired linear 
polyethylenepolyamines can be easily recovered from the reaction product 
mixture by conventional methods such as distillation. Such distillation 
recovery methods are well known in the art. An outstanding advantage of 
the claimed invention is that the lower molecular weight 
polyethylenepolyamines recovered from the reaction mixture can be further 
reacted with monoethanolamine to produce a larger percentage of the higher 
molecular weight linear polyethylenepolyamines. 
The following examples will further illustrate the preparation of 
predominantly linear polyethylenepolyamines from ethylenediamine and 
monoethanolamine by the use of the catalyst compositions of the present 
invention. They are given by way of illustration and not as limitations on 
the scope of the invention. Thus, it will be understood that reactants, 
proportions of reactants, and time, temperature and pressure of the 
reaction steps may be varied with much the same results achieved. 
For purposes of convenience and brevity, the reactant compounds employed 
and the products obtained have been abbreviated in the following examples 
and tables. The abbreviations employed for these various compounds are: 
EDA--ethylenediamine 
MEA--monoethanolamine 
PIP--piperazine 
DETA--diethylenetriamine 
TETA--triethylenetetramine 
TEPA--tetraethylenepentamine 
AEEA--N-(2-aminoethyl)ethanolamine 
AEP--N-(2-aminoethyl)piperazine 
HEP--N-(hydroxyethyl)piperazine 
DIAEP--diaminoethylpiperazine 
PEEDA--piperazineoethyl-ethylenediamine 
AETETA--aminoethyltriethylene tetramine. 
WORKING EXAMPLES 
The present invention will be further illustrated by the following working 
examples. 
I. Catalyst Preparation (6147-10) 
A preformed pelleted titanium dioxide catalyst support (225 g, 220 cc) was 
placed in a roundbottom flask. A solution of phosphonitrillic chloride 
(11.5 g) and tributyl amine (20.1 g) in 95 cc of dry toluene was added. 
The mixture was heated in an oil bath at 100.degree. C. for 4 hours then 
cooled and rinsed three times with dry toluene. The drained carrier was 
then treated with a solution of ethylenediamine (7.2 g) and tributyl amine 
(45.8 g) in 100 cc of dry toluene, heated and rinsed as before. The 
catalyst was then dried for 1 hr at 150.degree. C. and calcined 2 hr at 
350.degree. C. It contained 1.3% P by AA (atomic absorption analysis). 
II. Use as a Catalyst for Formation of Ethyleneamines (6147-12) 
The above catalyst was placed in a stainless steel tube in an aluminum 
heating block (100 cc of catalyst). Through the tube was passed a mixture 
of EDA (2 pbw) and MEA (1 pbw) at a rate of 100 cc per hour. The apparatus 
was held at a series of temperatures 3 to 4 hours to allow equilibration 
and samples were taken for analysis by GLC. The area % analysis along with 
the calculated % MEA conversion, % EDA conversion, DETA/Piperazine ratio, 
and percent non-cyclic products in the TETA range as well as the relevant 
selectivities among the observed products is presented for each of the 
samples in Table I-A, Table I-B and Table I-C. 
TABLE I-A 
__________________________________________________________________________ 
Ethyleneamines Continuous Reactor Products 
Cyclic Phosphamine on Titania 
Catalyst 6147-10 
2 3 4 5 6 7 8 9 10 11 12 
1 Temp. 
Area Area % MEA 
Area % Selec. 
Area % Selec. 
% Conv. 
Area 
% Selec. 
Sample 
.degree.C. 
% EDA 
% MEA Conv. 
% PIP 
to PIP 
% BAEE 
to BAEE 
of EDA 
DETA to 
__________________________________________________________________________ 
DETA 
Feed 65.23 
34.76 
6147-12-1 
300 56.58 
17.75 48.92 
0.22 1.08 0.00 0.00 13.26 17.74 
86.91 
6147-12-2 
299 59.36 
20.59 40.76 
0.20 1.20 0.00 0.00 9.00 17.07 
87.49 
6147-12-3 
306 57.73 
17.97 48.30 
0.40 1.72 0.00 0.00 11.50 19.22 
81.29 
6147-12-4 
280 62.09 
27.15 21.88 
0.03 0.35 0.00 0.00 4.82 10.35 
96.57 
6147-12-5 
281 64.30 
24.95 28.20 
0.14 1.37 0.00 0.00 1.43 10.07 
94.28 
6147-12-6 
290 61.90 
22.74 34.56 
0.23 1.51 0.00 0.00 5.11 13.54 
89.30 
6147-12-7 
290 61.62 
23.54 32.26 
0.21 1.43 0.00 0.00 5.54 13.09 
89.33 
6147-12-8 
299 59.18 
20.30 41.59 
0.35 1.76 0.00 0.00 9.28 16.66 
83.78 
6148-12-9 
300 59.85 
19.37 44.26 
0.35 1.73 0.00 0.00 8.25 16.64 
82.27 
6147-12-10 
311 55.17 
14.22 59.07 
0.63 2.16 0.02 0.09 15.42 21.58 
73.99 
6147-12-11 
310 56.12 
14.04 59.60 
0.60 2.12 0.02 0.08 13.96 21.49 
75.28 
6147-12-12 
320 55.23 
13.34 61.62 
0.76 2.49 0.06 0.20 15.33 21.77 
70.89 
6147-12-13 
321 55.99 
3.44 90.09 
1.08 2.92 0.04 0.12 14.16 25.25 
67.97 
6147-12-14 
321 55.90 
3.76 89.18 
1.03 2.83 0.04 0.12 14.30 24.77 
67.71 
6147-12-15 
299 60.37 
19.01 45.30 
0.33 1.69 0.00 0.00 7.44 16.96 
85.75 
6147-12-16 
301 56.58 
22.24 36.00 
0.22 1.08 0.00 0.00 13.26 17.74 
86.91 
__________________________________________________________________________ 
TABLE I-B 
__________________________________________________________________________ 
15 
13 14 Ratio: 16 17 18 19 20 21 22 
1 Area % 
% Selec. 
Obsv. DETA/ 
Area % 
% Selec. 
Area % Selec. 
% of 
Area % 
% Selec. 
Sample 
AEEA to AEEA 
Obsv. PIP 
of AEP 
of AEP 
% NTEA 
to NTEA 
NC to TETA 
of 
__________________________________________________________________________ 
TETA 
6147-12-1 
0.21 1.07 80.27 0.23 1.13 0.18 0.89 100.00 
1.81 8.90 
6147-12-2 
0.28 1.45 72.64 0.19 1.01 0.17 0.88 100.00 
1.54 7.93 
6147-12-3 
0.24 1.04 47.35 0.24 1.05 0.28 1.22 99.36 
3.16 13.39 
6147-12-4 
0.17 1.70 279.75 0.04 0.36 0.01 0.13 36.36 
0.03 0.25 
6147-12-5 
0.18 1.70 69.00 0.03 0.35 0.01 0.13 19.18 
0.03 0.31 
6147-12-6 
0.32 2.15 58.87 0.09 0.62 0.08 0.56 100.00 
0.88 5.83 
6147-12-7 
0.35 2.44 62.04 0.09 0.64 0.08 0.59 100.00 
0.81 5.54 
6147-12-8 
0.35 1.77 47.47 0.18 0.93 0.21 1.06 100.00 
2.12 10.68 
6147-12-9 
0.34 1.69 47.29 0.18 0.90 0.20 0.99 100.00 
2.49 12.32 
6147-12-10 
0.27 0.96 34.21 0.47 1.63 0.47 1.61 89.75 
4.62 15.82 
6147-12-11 
0.23 0.81 35.47 0.45 1.58 0.43 1.51 87.77 
4.32 15.13 
6147-12-12 
0.08 0.28 28.38 1.00 3.25 0.45 1.47 86.25 
5.11 16.65 
6147-12-13 
0.12 0.33 23.25 1.05 2.83 0.64 1.73 96.11 
7.40 19.93 
6147-12-14 
0.12 0.33 23.91 1.02 2.79 0.64 1.75 96.46 
7.32 20.02 
6147-12-15 
0.31 1.59 50.49 0.20 1.05 0.17 0.86 100.00 
1.78 9.02 
6147-12-16 
0.21 1.07 80.27 0.23 1.13 0.18 0.89 100.00 
1.81 8.90 
__________________________________________________________________________ 
TABLE I-C 
__________________________________________________________________________ 
23 24 25 26 27 28 29 30 31 
1 Area % % Selec. 
Area % % Selec. 
Area % % Selec. 
Area % 
% Selec. 
Total 
Sample 
of DIAEP 
of DIAEP 
of PEEDA 
of PEEDA 
of AETETA 
to AETETA 
of TEPA 
of TEPA 
Product 
__________________________________________________________________________ 
6147-12-1 
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 20.41 
6147-12-2 
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 19.51 
6147-12-3 
0.02 0.09 0.00 0.00 0.00 0.00 0.05 0.19 23.67 
6147-12-4 
0.07 0.65 0.00 0.00 0.00 0.00 0.00 0.00 10.72 
6147-12-5 
0.19 1.85 0.00 0.00 0.00 0.00 0.00 0.00 10.69 
6147-12-6 
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 15.16 
6147-12-7 
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 14.65 
6147-12-8 
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 19.89 
6147-12-9 
0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.06 20.23 
6147-12-10 
0.39 1.34 0.18 0.65 0.23 0.80 0.27 0.95 29.18 
6147-12-11 
0.43 1.52 0.22 0.79 0.18 0.65 0.13 0.48 28.55 
6147-12-12 
0.57 1.86 0.31 1.01 0.25 0.84 0.30 1.00 30.70 
6147-12-13 
0.17 0.46 0.15 0.41 0.41 1.12 0.79 2.15 37.15 
6147-12-14 
0.14 0.39 0.14 0.40 0.42 1.16 0.89 2.44 36.58 
6147-12-15 
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 19.78 
6147-12-16 
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 20.41 
__________________________________________________________________________ 
III. Use of Reference Catalyst to Prepare Ethyleneamines 
In order to provide a comparison of the improvement in catalyst activity 
that is obtainable with the catalysts of the present invention, a 
reference catalyst was also used to catalyze the reaction of 
ethylenediamine with monoethanolamine in the manner and in the equipment 
described above in Example II. The reference catalyst was a 
titania-supported phosphorus catalyst prepared by immersing titania 
pellets in concentrated phosphoric acid, after which the immersed titania 
was drained of excess liquid and then calcined. The reference catalyst had 
been used for extensive pilot plant studies of the process under 
consideration and had been found to be the most consistantly active 
catalyst of all of the catalysts that were tested. 
The results of this series of test were was follows: 
TABLE II 
______________________________________ 
Selectivity to Linear Polyethylenepolyamines 
Reference Catalyst 
% of Linear 
Temp. % MEA Polyethylene- 
.degree.C. Conv. polyamines 
______________________________________ 
300 38.3 87.8 
305 45.9 80.7 
311 59.4 79.4 
314 64.3 77.8 
320 65.9 75.4 
322 73.2 77.0 
326 99.9 73.2 
______________________________________ 
TABLE III 
______________________________________ 
Selectivity to Linear Polyethylenepolyamines 
Catalyst 6147-10 
of the Present Invention 
% of Linear 
Temp. % MEA Polyethylene- 
.degree.C. Conv. polyamines 
______________________________________ 
299 41.6 92.6 
299 45.3 91.8 
300 44.3 93.2 
301 36.0 93.3 
310 59.6 88.4 
311 59.1 86.6 
320 61.6 87.9 
321 90.1 84.1 
321 89.2 83.4 
______________________________________ 
Turning now to the drawings and especially to FIG. 2, where the data from 
Tables II and III has been plotted to show the selectivity to linear 
amines obtained with the catalyst of the present invention, as compared 
with the reference catalyst, it will be noted that an almost constant 10% 
increase in selectivity to linear ethyleneamines was obtained with the 
catalyst of the present invention. This result was surprising and 
unexpected, because the reference catalyst was the most effective catalyst 
known to the inventors prior to their discovery of the catalyst 
compositions of the present invention. Also, it is surprising that the 
enhanced selectivity was obtained over such a wide range of 
monoethanolamine conversion. 
Turning now to FIG. 1, wherein the selectivity to linear ethyleneamines is 
plotted relative to reaction temperature, it will be noted that the 
catalyst composition of the present invention again demonstrated 
surprising and unexpected results. Although the catalyst of the present 
invention was only slightly superior to the reference catalyst at the 
lower end of the temperature range, the superiority became more pronounced 
as the temperature was increased, amounting to about a 10% increase in 
selectivity at a reaction temperature of about 330.degree. C. 
The foregoing examples have been given by way of illustration and not as 
limitations on the scope of this invention, as defined by the appended 
claims.