Note: Descriptions are shown in the official language in which they were submitted.
BACKGROUND OF THE INVENTION ~,,
Technical Field of the Invention ''
This invention relates to the preparation of pre- ,
dominatly linear polyethylenepolyamines from ~,he starting
reagents of ethylenediamine and monoethanolamine in the
presence of unique thermally activated catalyst compositions ; ,
, comprising a group IVb transition metal oxide support and
phosphorous derived from phosphorous bromide or phosphoryl '`-~'
chloride.
. . .
,
Prior Art
;~ Heretofore, polyethylenepolyamine compounds such as
~ . . -
diethylenetriamine, triethylenetetramlne and the higher ,:
; lS ~ homologs have been produced by the reaction of an alkyl ',~
halide such as ethylene dichloride with an amine such as ,~
ammonia or e~hylenediamine at elevated temperatures and
pressures. Normally, relatively high yields of predominatly
non-cyclic polyethylenepolyamine compounds are obtained from
this process with varying yields of heterocyclic amines.
The large amounts of energy required to produce the reac-
tants as well as the difficult separation procedures ,'-
required to recover the more valuable linear polyethylene- '~
polyamines diminish the usefulness of the ethylene
dichloride process. The hydrohalide salts of ammonia and
~he polyethylenepolyamine products must also undergo diffi-
cult and time consu'ming caustic neutraliza~ion to yield the
free polyethylenepolyamines.
It has heretofore been known that phosphates can be
used to catalyze reaction products to produce predominately
r -
~P7'~6
heterocyclic rather than llnear produc~s. Thus, U.S. Patent No.
3,297,701 teaches the use o~ aluminum phosphate to catalyse the
reaction of ethanolamines and polyethylenepolyamines to yield
cyclic compounds. U.S. Patent No. 3,342,820 discloses the use
of aluminum phosphate for the preparation of heterocyclic com-
pounds such as triethylenediamine. As another example, U.S.
Patent No. 4~103,087 also discloses the use of aluminum phosphate
catalysts ~or producing heterocyclic product compounds.
More recently, investigators have found that more
linear products can also be obtained in a catalyst conversion.
Thus, Ford et. al. U.S. Patent No. 4,316,840 discloses the pre-
paration of polyalkylenepolyamines from ethylene diamine utiliz-
ing a metal nitrate or sulfate as a catalyst. U.S. Patent No.
4,314,083 discloses the reaction of ethylene diamine with mono-
ethhanolamine to prepare noncylcic polyalkylenepolyamines using,
as a catalyst, a salt of a nitrogen or sulfur-containing com-
pound.
In inventions originating in our laboratories,
Brennan et. al. in U.S. Patent No. 4,036,881 discloses the use
of phosphorous-containing catalysts to catal~ze the reaction of
ethylenediamine with monoethanolamine. Excellent results were
obtained when the reaction was conducted in an autoclave~ ~ow-
ever, when the phosphorous compound was supported on silica or
diatomaceos earth, good results were obtained only at compara-
tively low conversions. Brennan et. al. U.S. Patent No. 4,044,
053 is also relevant in this regard. A recently ~iled Brennan
copending application which issued to U.S. Patent No. 4,448,997
on May 15, 1984 entitled "Preparation of Linear Polyethylene-
polyamines With an Aluminum Phosphate Catalyst" is directed to
an aluminum phosphate catalyst. Excellent results were obtained
~Z~77~6
using a catalyst of this nature in batch-type reactions. Brennan
U.S. Patent No. 4,103,087 discloses the use of pelleted aluminum
phosphate to prepare di-(N,N-disubstituted amino)alkanes.
French Patent No. 1,317,359 dated February 8, 1963,
discloses the preparation of granulated zirconium phosphate
and its use as a ion-exchange resin. Winkler et al. in a 1966
publication [Deutsche akad. Wiss., Berlin, Germany, Z. Anorg.
Allgen. Chem. 346 (1-2)~ 92-112 (1966)] disclose compounds of
the general formula HXVP2O3 wherein X represent arsenic, antimony
and mixtures thereof. Also disclosed are compounds of the
general formula H2XiVP2O3, wherein X represents silicon,
germanium, tin, lead, titanium and zirconium. It is shown -that
the group IV phosphates have cation exchange properties.
Daniel Br. Apcn. 2,092,467 pub. August 18, 1982,
modifies iron phosphate catalysts disclosed in Cavaterra U.S.
Pat. 3,948,959 for making methacrylic acid from isobutyric acid.
Daniel uses such catalysts in admixture with a support prepared
by calcining the dried powder recovered from a slurry of silica
with phosphoric acid. Daniel teaches that the support is inert
and that titania or ~irconia can also be used.
SUMMARY OF THE INVENTION
A method of preparing novel catalyst compositions is
disclosed. The catalyst is extremely useful in the improved
production of predominatly linear polyethylenepolyamines
~L~$~7~
from ethylenediamine and monoethanolamine reactants. me novel catalysts of
the claimed invention can be prepared by treating a group IVb metal oxide sup-
port with phosphoryl chloride or phosphoxous bromide such that, in a thermally
activated condition, the phosphorous is chemically bound to the support. m ese
; novel catalyst compositions can be used to catalyze the reaction of monoethan-
olamine with ethylenediamine to provide essentially linear polyethylenepoly-
amine reaction products.
DETAILED DESCRIPTION
In one aspect the invention is directed to improved catalyst compo-
sitions comprising a group IVb metal oxide to which phosphorous derived from
phosphoryl chloride or phosphorous bromide has been chemically bonded by -ther-
mal activation. In another aspect the catalysts are used in producing essen-
tially linear polye-thylenepolyamines such as diethylenetriamine, triethylene-
tetramine, tetraethylenepentamine and pentaethylenehexamine from the reaction
of ethylenediamine and monoethanolamine. The inventor is unaware of the pre-
cise structural differences between the claimed catalysts and previous phos-
phate catalysts that have been tried in such reactions, but is cognizant of
substantially higher rates of conversion to linear polyethylenepolyamines with
the claimed catalysts.
According to one aspect of the present invention there is provided
as a new composition of matter, a pelleted composition comprising a group IVb
metal oxide having deposited thereon at least about 0.5 wt.% of phosphorous
derived from phosphoryl chloride or phosphorous bromide.
According to another aspect of the present invention there is provi-
ded as a new composition of matter, a pelleted catalyst composition comprising
a group IVb metal oxide having thermally, chemically bonded khereto from about
0.5 wt.% to about 10 wt.% of phosphorous derived from phosphoryl chloride or
phosphorous bromide.
According to a further aspect of the present invention there is pro-
vided a method of preparing a catalyst composition which comprises treating
pellets of a group IVb metal oxide with a liquid containing phosphoryl chloride
--4--
~'
~$7~
or phosphorous bromide for a period of time ranging from about 0.5 to about 5
hours and thereafter recovering and drying the thus -treated pellets.
According to another aspect of the present invention there is provi-
ded a method of preparing a catalyst composition which comprises impregnating
pellets of a group IVb metal oxide by maintaining said pellets in contact with
a phosphorous halide selected from the group consisting of phosphoryl chloride
and phosphorous bromide at abou-t reflux temperature for a period of time rang-
ing from about 0.5 to about 5 hours and thereafter hydrolysing said halide,
and recovering and drying the thus treated pellets to thereby provide a cata-
lyst composition comprising said group IVb metal oxide having from about 0.5
to about 10 wt.~ of phosphorous thermally chemically bonded thereto.
According to a still further aspect of the present invention there
is provided in a method wherein monoethanolamine is reacted with ethylenedi-
amine in the presence of a phosphorous containing catalyst to provide an ess-
entially noncyclic product comprising polyethylenepolyamines, the improvement
for conducting said process on a continuous basis which comprises:
a. using! as a catalyst, a pelleted group IVb metal oxide having
deposited thereon phosphorous derived from phosphoryl chloride or phosphorous
bromide,
b. continuously contacting a mixture of ethylenediamine and monoeth-
anolamine in a molar ratio of about 1 to 5 moles of ethylenediamine per mole
of monoethanolamine with said pelleted catalyst at a temperature of about 250
to about 400C and a pressure of about 500 to about 3000 psig. to obtain an
essentially noncyclic reaction product.
According to yet another aspect of the present invention there is
provided in a method wherein monoethanolamine is reacted with e-thylenediamine
in the presence of a phosphorous containing catalyst to provide an essen-tially
noncyclic product comprising polyethylenepolyamines, -the improvement for con-
ducting said process on a continuous basis which comprises:
a. using, as a catalyst, a pelleted group IVb metal oxide having
thermally chemically bonded thereto from about 0.5 wt.% to about 10 wt.% of
-4a-
-
12~ 779~;
phosphorous derived from phosphoryl chloride or phosphorous bromi.de,
b. continuously contacting a mixture of ethylenediamine and monoeth-
anolamine in a molar ratio of about 1 to 5 moles of ethylenedlamine per mole
of monoethanolamine with said pelleted catalyst at a temperature of about 250
to about 400C and a pressure of about 500 to about 3000 psig. to obtain an
essentially noncyclic reaction product.
The novel catalyst compositions catalyze the reaction of ethylenedi-
amine with monoethanolamine at a temperature of from about 250C to about
400C, preferably from about 300C to about 350C and a pressure of from about
500 to about 3000 psig. and preferably from about 1000 to about
-4b-
" ~ ,
:
~2$779L~;
2000 psig. Higher temperatures and pressures can be used ,- ;
but there is no particular advantage in using higher
? ~ '; .
temperatures and/or pressures.
The pelleted catalyst compositions of the present
invention are normally 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 adjus~, 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 i5 not necessary to drive the reaction to
compIetion 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
.
thereo~, such as diameters and lengths ranging from about
1/32" o about 3/8". 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
--5--
` ~Z~77~S
poisoned, or if catalyst pellets do not have good structural ; ,
properties, the economlcs of the process will be seriously , ;-
~ ,_ ..~
and adversely affected.
The catalysks of the present invention are not
S 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. -
It is a feature of the present invention that the `~
pellated catalyst compositions have improved resistance to
physical degradation when used to catalyse the reaction of
monoethanolamine with ethylenediamine.
,
The catalyst compositions of the present invention are
:
prepared by depositing a phosphorus compound on a support
comprising an oxide of a group IVb transition metal oxide.
The group IVb transition metal oxides include the oxides of
titanium, zirconium, hafnium and thorium. Pellets of the
group IVb metal oxide may be prepared by extrusion or by
compaction in conventional pelleting apparatus using a
pelleting aid such as graphite. It is also within the scope
of the present invention to deposit the phosphorus compound
on a powdered IVb metal oxide followed by pelleting and
calcination.
Phosphoryl chloride (POC13) or phosphorous bromide
tPBr3) is used as a source for the phosphorous.
~Z~779~6
When the ca~alyst composition is to be prepared by
impregnating a preformed pellet, a suitable procedure to be
used is to heat the phosphoryl chloride or phosphorous
bromide to reflux temperature (e.g., about 105C.) and to
then add pellets in an amount abollt equal to the volume of
the heated liquidO Thereafter heating is continued. This
treatment should be continued from about 0.5 to about 5 :
hoursO At the end of that time, the resulting slurry may be
cooled. When the resulting mixture is treated with water
the phosphoryl chloride and/or phosphorous bromide is
hydrolysed. When hydrolysis is complete the mixture of
pellets and liquid is decanted to remove excess liquid
followed by water washing to substantially completely remove
unabsorbed liquid. Thereafter the composition may be dried ` -~
and calcined at an appropriate temperature such as a
temperature of about 200C. to about 800C.
It will be understood that the phosphorous that is
present on a thus-treated pellet is not present as-elemental ;~
phosphorous, but rather as phosphorous that is chemically
bound, probably as an oxide, to the group IVb metal oxide
support. This is demonstrated by the fact that repeated
washing will not remove all of the phosphorous. However, --
the exact nature of the bonding is not completely
unders~ood.
The amount of phosphorous that is bonded or otherwise
adheres to the support is a function of heating and other
conditions used in the treating step and is also a function
of the chemical identity of the phosphorous compound that is
used as a source of phosphorous. Under the treating
conditions exemplified above, at least about 2.5 wt~ of
~%~7~;
phosphorous is caused to bond or otherwise permanently ~-
adhere to the pellets. There is an upper limit to the
amount of phosphorous that bonds or otherwise permanently
adheres to the support. This upper limit is, as indicated,
a function of both the treating conditions and the chemical
used as a source of the phosphorous. Normally, the maximum
amount of phosphorous that can be caused to bond or other- -
wise permanently adhere to the pellets is within the range
; of about 5 to 10 wt~.
When the pellets are impregnated with the phosphorous
compound at a temperature of at least about 100C~, there is
no absolute need to calcine the catalyst composition before
use. However, the pellets can be calcined, if desired, as a
precautionary measure and/or in order to still further
improve the physical properties of the pellets. The pelle~s
are suitably calcined at a temperatuxe of about 200C to
about 800C for a period of time within the range of 2 to 24
hours; more preferably at a temperature of about 500C to -~
about 700C for about 4 to 16 hours.
Other procedures can be used in adding phosphorous to --
the group IVb metal oxide. For example, the pellets can be
treated with the phosphorous compound at ambient tempera-
tures or at more modest elevated temperatures of less than
about 100C. In this situation, however, it is necessary to
thermally activate the treated pellets by calcining under
the conditions recited aboveO
Alternatively, the group IVb metal oxide can be treated
with the phosphorous-containing compound in powdered form
and the powder can thereafter be pelleted. If the treatment
is conducted at a temperature of about 100C or more,
7~74Çi
thermal activation will normally have been obtained and it r; ;i`~
will not be absolutely necessary to perform a calcining V5 -
operation. If lower treating temperatures are used, - '~
calcining is a desired operation. The calcining operation
can be conducted prior to or subsequent to the pelleting
step. Any appropriate pelleting procedure of the type known
; ~:
to those skilled in the art mày be used. For example, the
treated powdered qroup IVb metal oxide can be mixed with
graphite and/or other binders and compacted or extruded -- -
under conventional conditions.
There are many compounds which can be formed from the
reaction of ethylenediamine and monoethanolamine besides the
preferred linear polyethylenepolyamines such as diethylene- ~-
triamine, triethylenetetramine, tetraethylenepentamine and
pentaethylenehexamine. Less desirable cyclics and other
compounds, such as piperazine, N-(2-aminoethyl)ethanolamine
and N~(2-aminoethyl)piperazine, are also ~ormed. The more
desired linear polyethylanepolyamines 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
~7~
given by way of illustration and no~ as limitatlons 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
; 5 ~he same results achieved.
For purposes of convenience and brevity, the ractant
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 - pipera~ine
D~TA - diethylenetriamine
. -- . .
TETA - triethylenetetramine ~- -
TEPA - tetraethylenepentamine
AEEA - N-(2-aminoe~hyl)ethanolamine
AEP - N-(2-aminoethyl)piperazine
HEP - N-~hydroxyethyl)piperazine ^~
Example I
1. Titania Catalyst Preparation
A sPries of pelleted catalysts were prepared by
depositing phosphorous on a titania support.
a Phosphoric Acid
Titania supported phosphoric acid catalysts were
prepared by heating about 100 cc of phosphoric acid to about
130C. under an inert atmosphere in a flask fitted with a
condenser. 105 cc of titania pellets were slowly added
through the condenser and the temperature was maintained for
the desired period of time.
-10-
~Z~ 6
Thereafter the catalyst was recovered by first
decanting the excess phosphoric acid followed by the
addition to the pellets of a large quantity of water. The
pellets and water were slowly stirred to dissipate heat. -
The pellets were washed several times with copious amounts
of water and dried.
b. Phosphoryl Chloride ~:
(Phosphorou_ Oxychloride~ on Tl nia
When using phosphoryl chloride as ~he source of
phosphorus, a slight modification of the above identified
procedures was necessary. The phosphoryl chloride was
refluxed at 105C. The heat was turned off and the reflux
was maintained by the addition of titania pellets at a rate
sufficient to maintain a strong reflux. -~
~When the resulting reaction mixture was treated with ~ -
water the phosphoryl chloride was hydrolysed. Constant ~-
stirring was very important in order to malntain good heat
dissipation. Phosphorus bromide was also used as a source ~,
o~ phosphorus using ~he procedure outlined above for
phosphoryl chloride.
For convenience, the catalyst prepared and a brief
description of the same is set forth herein as Table I. - ---
.
11-
~2~
TABI,E I
TITANIA CATALYST COMPOSITIONS
, '; ~.' :,
- Type Number C~osition
A 5464-72 40 wt.% Phosphate on alumina
A 5494-4 Titania (TiO2)
A 5494-16 Titania treated with phosphoric acid
(H3PO4) for ~ hour
A 5494-5 Titania treated with phosphoric acid
for 2 hours
, -,...:.
A 5494-17 Titania treated with phosphoric acid
for 12 hours
A 5494-95 Titania treated with phosphoric acid
for 2 hours
A 5494-96 Titania treated with phosphoric acid
for 4 hours
B 494-13 Titania treated with phosphoryl
chloride (POC13~ for 4 hours
B 5494-23 Titania treated with phosphoryl
chloride for 4 hours and then
calcined
B 5494-31 Titania calcined at 600~C., then
treated with phosphoryl chloride ~'~
` and recalcined
C 5494-20 Titania treated with phosphorous _::'t'~;"'`;
bromide (PBr3) for 2 hours ~ ~`
Pre~aration of Polyethvlenepolvamines from Ethvlenediamine
and Uonoethanolamine Using Titania Supported_Phos~horus
Catalysts_
The catalysts described in Table I were utilized for
the conversion of ethylenediamine and monoethanolamine to a
polyethylenepolyamine reac~tion product in a 100 cc
continuous reactor system. Pellets were placed in the
reactor and the feedstock that was fed to the reactor was a
mixture of ethylenediamine and monoethanolamine in a molar
-12-
~2~7~
ratio of about two moles of ethylenediamine per mole of
monoethanolamine.
In order to obtain a basis for comparison, the
reaction temperature was varied so as to obtain about a 65%
conversion of the monoethanolamine feedstock.
The reaction product was periodically sampled and
analyzed by gas chromatographic analysis of the crude reactor
effluentO Results were calculated on a feed-free basis.
The catalysts tested and results obtained in the
series of tests are set forth in Table II. In general, each
feedstock was run for at least 2 1/2 hours to make sure that
reaction conditions had stabilized.
Referriny now to Table II it will be seen that the
reference catalyst composition (5464-72) which comprised a
commercially available 40 wt.% phosphate on aluminia catalyst
of the type disclosed in Brennan U.S. Patent No. 4,103,087 at
column 8, lines 50-54 gave less satisfactory results than those
obtained with the catalysts of the present invention. This
run shows that with a pelleted aluminum phosphate catalyst, and
in a continuous reaction, the results obtained are not so
favorable as those reported for batch reactions in the
abo~e mentioned U.S. Patent 4,448,997.
In particular, note that only about 77% of the
triethylenetetramine fraction was noncyclic with this run.
In contrast, with the catalyst of the present invention the
noncyclic content was normally in excess of 90%. Note also
that there was also a significantly smaller yield of
diethylenetriamine with the reference catalyst.
:
The second reference tests (5494-4) was untreated
titania pellets and it is seen that they were essentially
inert insofar as conversion of monoethanolamine and
ethylenediamine is concerned.
~he type A titania supported catalysts ~herein the
source of phosphorus was phosphoric acid gave uniformly good
results. The best pellet strength was obtained with the
type B cata,yst based on phosphoryl chloride.
Thus, Table II demonstrates that with titania supported
pelleted catalyst in a continuous reaction system, it is
po~sible to obtain excellent results in the reaction of
monoethanolamine with ethylenediamine. The percentage of
noncyclic reaction products is very high, being over 30% in
all cases except for type G (when phosphorus bromide was the
source of phosphorus). Note, however, that when phosphorous
bromide was the source of the phosphorous, the yield of
noncyclic reaction products was a distinct improvement in
CompariSoD with catalyst 5464-72. Diethylenetriamine yislds
of from ahout 55 to about 65% were obtained with this group
of catalysts. Uniformly good yields of triethylenetetramine
were also obtained.
r
--14--
~7~g~
.
~ ~ ~ ~ ~ ~ ~ m ~ m c~
~E~ '
~ ~ :- '
:s
o ~ a~
,, ~1
P~
U~
.
E~
OP : -
..
O ~ ~ ~ u~ In ~ ~ r-
E~ H 1` r~ O
~ a ~ . .
cn
~,
r
u~ ~ ~ ~ c~J ~I ~ ~ ~ ~r
I¢ 1~ ~ ~ A
~¢ t~ O U') Ltl ~10 00 0 ~
u~ E-~ .I ..... ...
~ 1:~ co
;t; E~ ~ ~ ,~ ~1
H 14 ~1 Pl ~1 ~ I - - - . . .
~ ~ t:~ 5 'r ~1 ~ r-~ N ~1 N .--1 ~ In ~.
~C O ~
1~ a) ~ . ~ .... ...
~ a ,1 ~ ~ oOoo 0O~
E~ E~ u~ ~ ... ;
O ~: u~
E~ . I ..... ... . .;.. ,
::~ ~ ~ ~ n "" ,,,,,,.,,~
. r~ D ~ N Lt~ Il) ~ ~) ~r O
H ~ . I ..... ...
H Pl ~D ~ N N N N N N N U-)
~ ~_)
O d~ ~
U~ O ~ ~\ CO ~D ~1 ~~ ~r ~ n
) ~ I ~) N O ~ ~ ~ 1 N ~ --
::
~ ~: ~:
O ' N N N ~) 11~ .
h ~_ ... ..
O ~ ~P ~ ~ ~ U~ U~
.
~ ~ a~ u~
rn ~ 3 . .
C o - J
~4
U~ ~ o
~ l l l l l l l l l l l
~L2~7~
Exarnple II . -
Zirconia Sup~orted Phosphorus Containing Catalyst
Compositions
A series of phosphorus containing zirconia supported
catalyst compositions were prepared using the procedure
outlined above in Example I. The pelleted catalysts were : -
tested in ~he 100 cc continuous reactor described in
Example I using the same conversion conditions. The
catalyst compositions that were prepared are given in
Table III. The results obtained with this group of
catalysts is set out in Table IV. .
~: "'.,- . '
: .
:' '
~
r
. .
-16-
~2~ 6
q~ABLE I I I
` ., . , ,:
Zirconia Catalyst Co ~
:~-.;,;,'..^
~y~ Number Composition
: 5464-72 40 wt% Phosphate on alumina
5484-37 Zirconia
. .
: D 5484-6 Zirconia treated with 11 wt% phos-
phorlc acid (H3PO4) for 1 hour at
125C.
D 5484-63 Pelleted zirconia treated with`.,;;,~
phosphoric acid for 1 hour a~ 125C. ` `
D 5484~17 Zirconia treated with 22 wt~ pho~-
phoric acid for 1 hour at 125C.
D 5484-83 Zirconia treated with 11 wt% phos- :
phoric acid for 1 hour at 125C.
,
D 5484-84 Zirconia treated with 11 wt~ phos-
phoric acid for 2 hours at 125C.
D 5484-8S Zirconia treated with 11 wt~ phos-
phoric acid for 4 hours at 125C.
: D 5494-71 : Zirconia treated with 11 wt% phos-
, phoric acid for 24 hours at 125C. : ~
E : 54~4-29 Zirconia treated with phosphoryl i
chlor.ide for 4 hours .
E 5494-30 No. 5494-29 calcined at 600C. for
16 hour 5 .
.... ~ ..
F 5494-8~ Zirconia treated with phosphorous
bromide for 2 hours
.:
.
--17--
~7~6
~ a)
~ ~ x ~ x ~ x ~, æ a . .
C~ ~ . - :
~ ~ " ^ ~
~J r- o ~ o
~, ~ . . .
a~ u~
a) s~ ~1
P~
E~ . ~ I ~9 ~ ~ ~ ~
~I Z r~
E~
~ . ~, .
.. ~r
o f~ P~ co r~Ln ~ o u~ u~ r- ~
PJ
~ Cl
t~ R
u~ ~ r~ ~ ~o~r oo r-
P~ I I .... .. . ~,
r~ ~ ~(~1~ ~o-n ~ ~
t~ ?
~¢ I` ~I co oo 11') ~ ~r Ir) U~
:~ E~ .I ....... .. . ~
~n ~1 ~ ~ 0 3
~ ~ ~1 ~ ~ ~1 ~ ~ ~ ~1 ~ ~ ~
~ ~ ~ S~
O ~ ~) ~ L~ rl N O ~ D ~ 5
> .C -1 1~ ~i
H U~ ~ ~ P
:,~ ~ ~ ~ ~ ~ ~ r ~ o ~r ~ ~ CL
P~ Q~ ~ I
~1 ~ ~ o~ooo~l ~o
a
s~ ~ ~n ~ ~ ~ co o ~ ~Lr~
O E~ , I ....... .. ~ C
Q ¦~i ~4 ~D ~D O ~ U') ~1
~Q C l t~')Ir~ U'l 11') Ir~ 11-1 Il-) t~ Lr) U') ~D
U~
~ r~ ~ ~ co ~co o~9
0 Q
O P~
J-~ U O
ri ~ Il~ ~)
~;, O 0~0 ~ . ,a
,n C ~ ~D ~0 ~ ~ O ~ ~~0 ~ ~ .
~7 ~ o
~,
~ u~
~ s~
E~
~o)
o
, ~ - ~ ~
o ~ ~o a~ ~ o ~
) . . :~
~ ~ o ~l ~
3 ~
o o-- U~
P~
~ 3
ai ~1 ~ oD ~ r m l o o 1
~ r--~ ~ ~9 ~ co co co ~ ~ ~co ~
~ II IIIIIIi II I ~
~r ~~r er ~ ~r ~r ~ ~r ~r ~r
~9 oo~ co co o~ a~ oo ~ ~ ~C~
--18 -
~77~
With reference to Table IV, it will be seen tha t once
again there was a good conversion of the monoethanolamine and
ethylenediamine to noncyclic products characterized by good
ylelds of diethylenetriamine and triethylenetetramine.
This series of tests demonstrates that the ~irconia
supported catalysts give results equivalent to those obtained
with titania.
There are times when it is desirable to obtain greater
yields of the higher polyethylenepolyamines such as triethylene-
tetramine or tetraethylpentamine than those reported herein.
In such instances, the diethylenetriamine can be recycled by
substituting diethylenetriamine for all or a part of the
ethylenediamine feedstock.
This specification includes data related to the inven-
tion disclosed and claimed herein and also, for comparative
purposes, data is disclosed in this specification that is also
disclosed and claimed in copending ~anderpool Canadian patent
application S.N. 444,530, entitled "Catalysts and Preparation
of Linear Polyethylenepolyamines Therewith" (D#80047).
The foregoing examples of the present invention have
been given by way of illustration only and are not intended as
limitations on the scope of the invention which is defined by
the following claims.
~19--
