CA1207746A - Modified catalysts and preparation of linear polyethylenepolyamines therewith - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

This invention is directed to pelleted catalyst compositions suppor-ted on group IVb transition metal oxides that contain phosphorous derived from phosphoryl chloride or phosphorous bromide and their use in the production of predominantly linear polyethylenepolyamines from ethylenediamine and monoeth-anolamine.

Description

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 ~' ~$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 ` ~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.

~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. - ---.

~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 ~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.

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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. .

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~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 .:
.

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~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--

Claims (22)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. 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 phos-phorous derived from phosphoryl chloride or phosphorous bromide.

2. As a new composition of matter, a pelleted catalyst composition com-prising a group IVb metal oxide having thermally, chemically bonded thereto from about 0.5 wt.% to about 10 wt.% of phosphorous derived from phosphoryl chloride or phosphorous bromide.

3. A composition as in claim 1 or 2, wherein the group IVb metal oxide is titania.

4. A composition as in claim 1 or 2, wherein the group IVb metal oxide is zirconia.

5. A method of preparing a catalyst composition which comprises treat-ing pellets of a group IVb metal oxide with a liquid containing phosphoryl chloride 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.

6. A method of preparing a catalyst composition which comprises impreg-nating pellets of a group IVb metal oxide by maintaining said pellets in con-tact with a phosphorous halide selected from the group consisting of phosphoryl chloride and phosphorous bromide at about reflux temperature for a period of time ranging 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 catalyst composition comprising said group IVb metal oxide having from about 0.5 to about 10 wt.% of phosphorous thermally chemically bonded thereto.

7. A method as in claim 5 or 6, wherein the group IVb metal oxide is titania.

8. A method as in claim 5 or 6, wherein the group IVb metal oxide is titania and the source of phosphorous is phosphoryl chloride.

9. A method as in claim 5 or 6, wherein the group IVb metal oxide is titania and the source of phosphorous is phosphorous bromide.

10. A method as in claim 5 or 6, wherein the group IVb metal oxide is zirconia.

11. A method as in claim 5 or 6, wherein the group IVb metal oxide is zirconia and the source of phosphorous is phosphoryl chloride.

12. A method as in claim 5 or 6, wherein the group IVb metal oxide is zirconia and the source of phosphorous is phosphorous bromide.

13. In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a phosphorous containing catalyst to provide an essentially 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 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 400°C and a pressure of about 500 to about 3000 psig. to obtain an essentially noncyclic reaction product.

14. In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a phosphorous containing catalyst to provide an essentially 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 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 400°C and a pressure of about 500 to about 3000 psig. to obtain an essentially noncyclic reaction product.

15. A method as in claim 13 or 14, wherein the group IVb metal oxide is titania.

16. A method as in claim 13 or 14, wherein the source of phosphorous is phosphoryl chloride.

17. A method as in claim 13 or 14, wherein the source of phosphorous is phosphorous bromide.

18. A method as in claim 13 or 14, wherein the group IVb metal oxide is zirconia.

19. A method as in claim 13 or 14, wherein the group IVb metal oxide is zirconia and the source of phosphorous is phosphoryl chloride.

20. A method as in claim 13 or 14, wherein the group IVb metal oxide is zirconia and the source of phosphorous is phosphorous bromide.

21. A method as in claim 13 or 14, wherein the reaction product is frac-tionated to obtain at least a fraction comprising diethylenetriamine and wherein at least a portion of said diethylenetriamine is recycled to the reac-tion zone together with the said feedstock.

22.