CA1225194A - Regenerative process for the preparation of linear polyethylenepolyamines using a supported catalyst - Google Patents

Abstract

REGENERATIVE PROCESS FOR THE PREPARATION OF LINEAR
POLYETHYLENEPOLYAMINES USING A SUPPORTED CATALYST
(Docket No. 80,256-F) ABSTRACT OF THE DISCLOSURE

This invention is directed to a regenerative process for preparing predominantly linear polyethylenepolyamines from ethylenediamine and monoethanolamine using a catalyst comprising a phosphorous compound deposited on a group IVb transition metal oxide support.

Description

go REGENERATIVE PROCESS FOR TOE PREPARATION OF LINEAR
POLYETHYLENEPOLYAMINES USING A SUPPORTED CATALYST
(Docket No. 80,256 -F) BACKGROUND OF THE INVENTION

Technical Field of the Invention This invention relates to a continuous process for the preparation of predominantly linear polyethylenepolyamines from ethylenediamine and monoethanolamine in the presence of unique thermally pelleted activated catalyst compositions having phosphorous deposited on a group Ivy transition metal oxide and to the use ox oxygen to regenerate the catalyst when it has become at least partially deactivated during the course of the reaction.

Prior art Heretofore, polyethylenepolyamine compounds such as diethylenetriamine, triethylenetetramine and the higher homology have been produced by the reaction of an alkyd halide such as ethylene dichlorides with an amine such as ammonia or ethylenediamine at elevated temperatures and pressures. Normally, relatively high yields of predomi-neonatal non-cyclic polyethylenepolyamine compounds are - obtained from this process with varying yields of hotter-cyclic amine. 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 dichlorides 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 hotter-S cyclic rather than linear products. Thus, US. Patent No.
3,297,701 leaches the use of aluminum phosphate to catalyze the reaction of ethanolamines and polyethylenepolyamines to yield cyclic compounds. So Patent No. 3,342,820 discloses the use of aluminum phosphate for the preparation of hotter-cyclic compounds such as triethylenediamine~ As another example, US. Patent No. aye 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.
thus, Ford et at. US. Patent No. 4,316,840 discloses the preparation of polyalkylenepolyamines from ethylene Damon utilizing a metal nitrate or sulfate as a catalyst. US.
Patent No. 4,314,083 discloses the reaction of ethylene Damon with monoethanolamine to prepare non cyclic polyalk~-lenepolyamines using, as a catalyst, a salt of a nitrogen or sulfur-containing compound.
In inventions originating in our laboratories, Brennan et at. in US. Patent No 4,036,881 discloses the use of phosphorous containing catalysts to catalyze the reaction of ethylenediamine with monoethanolamine. Excellent results were obtained when the reaction was conducted in an auto-crave. However, when the phosphorous compound was supported on silica or diatomaceous earth, good results were obtained only at comparatively low conversions. Brennan et at. USE

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Patent No. 4,044,053 is also relevant in this regard. United States Patent No. 4,448,907 of Brennan, filed December 27, 1982, 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. Brennan United States 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 1963, discloses the preparation of granulated zirconium phosphate and its use as an ion-exchange resin. Wrinkler et at in a 1966 publication [Douche Cody. Wits., Berlin, Germany, Z. Anorg.
Allen. Chum. 346 (1-2), 92-112 (1966)] disclose compounds of the general formula HXVP2O3 wherein X represents 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 Bra Apcn. 2,092,467 published August 18, 1982, modifies iron phosphate catalysts disclosed in Coveter United States Patent 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 titanic or zircon can also be used.

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Tail et. at. U. S. Patent No. 4,025,608 is directed to the reaction of a zirconium salt with phosphoric acid or a phosphate to prepare granular zirconium phosphate for use as an ion exchanger. 3immerschied et. at. U. S. Patent No.
S 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. Bates U. S.
Patent No. 2,3~9,243 shows treatment of hydrocarbons with a zirconium phosphate prepared by reacting a phosphoric acid with a soluble salt ox zirconium such as the nitrate, sulk-ate, chloride or oxychloride. Styles et. at. in U. S.
Patent No. 3,416,~84 prepare crystalline zirconium pros-plates by thermally treating zirconium phosphate with pros-phonic acid to provide products that are useful as ion exchangers and catalysts. Dyer et. at. U. S. Patent No.
3,130,147 is concerned with cracking hydrocarbons using an acidic catalyst comprising oxides of aluminum, zirconium and phosphorous prepared by reacting water soluble salts of aluminum and zirconium with certain oxyacids of phosphorous and the salts thereof.
Inn et. at. U. S. Patent No. 4,018,706 is directed to the purification of exhaust gases using a support containing an oxide complex of titanium, phosphorous and aluminum.
The complex is prepared by mixing a water soluble titanium compound such as titanium tetrachloride or titanium sulfate with a water soluble phosphorous compound such as phosphoric acid In Holy U. S. Patent No. 3,448,164 catalysts are disclosed that can contain titanic and can be prepared, for example, by coprecipitating titanium mutilates or a titan-I'm oxide with aluminum phosphate. Relaunder et. at. U. S.

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Patent No. 2,824,073 is concerned with the manufacture of a titanium-phosphoric acid catalyst that can be prepared by mixing titanic with triphosphoric acid to form a doughy mixture which is thereafter dried and heated.
This invention is related to Canadian Patent Application Serial No. 444,530, filed December 30, 1983 and entitled "Catalysts and Preparation of Linear Polyethylene-polyamides Therewith".
This specification includes data related to the invention disclosed and claimed herein and also, err comparative purposes, data is disclosed herein that is also disclosed and claimed in copendlng Canadian patent applications as follows:

Application Filing Docket Serial No. Date Inventors No. Title 444,475 12/30/83 Vanderpool 80,067 Calcined Catalyst & Watts and Preparation of Linear Polyethylene-polyamides Therewith 444,539 12/30/83 Vanderpool 80,068 Linear Polyethylene-& Larking polyamide Preparation and Catalyst 444,537 12/30/83 Vanderpool 80,069 Modified Catalysts & Renken and Preparation of Polyethylenepoly-amine Therewith 444,538 12/30/83 Vanderpool 80,142 Preparation of & Watts Linear Polyamlnes from Novel Catalysts 444,531 12/30/83 Renken 80,158 Supported Catalysts and Preparation of Linear Polyethylene-polyamlnes Therewith I
SUMMARY OF THE INVENTION
A method of preparing novel catalyst compositions is disclosed. The catalyst is extremely useful in the improved pro-diction of predominantly linear polyethylenepolyamines from ethyl-enediamine and monoethanolamine. The novel phosphate catalysts of the claimed invention can be prepared by treating a group Ivy metal oxide support with a phosphorous compound such that, in a thermally activated condition, the phosphorous is chemically bound to the support. These novel compositions can be used to catalyze the reaction of monoethanolamine with ethylenediamine to provide essentially linear polyethylenepolyamine reaction products. to has also been discovered that the novel catalyst compositions when at least partially deactivated in the continuous production of linear polyethylenepolyamine reaction products from month-nolamine and ethylenediamine can be regenerated by treatment with oxygen under controlled regeneration conditions.
DETAILED DESCRIPTION

_ According to one aspect of the present invention there is provided in a method wherein monoethanolamine is continuously reacted with ethylenediamine in a reaction zone in the presence of a pelleted catalyst to provide an essentially non cyclic react lion product comprising polyethylenepolyamines, wherein the cay Tolstoy comprises a group Ivy metal oxide support having a minor amount of phosphorous thermally bonded to at least the surface thereof and wherein said pelleted catalyst becomes at least par-tidally deactivated with the passage of time:
the improvement which comprises:
a) regenerating said catalyst for further use in said continuous process by contacting said partially deactivated catalyst at a catalyst activating temperature of less than about 700C with an oxygen-containing gas for a period of time within I

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the range of about 2 to 12 hours sufficient to regenerate and no-active said catalyst; and b) thereafter again initiating the continuous no-action of monoethanolamine with ethylenediamine in said reaction zone in the presence of said thus regenerated catalyst to provide an essentially non cyclic product comprising polyethylenepolyami-nest According to another aspect of the present invention there is provided a continuous process for the manufacture of an essentially non cyclic reaction product comprising polyethylenepo-luminous by continuously contacting monoethanolamine with ethyl-enediamine in a reaction zone in the presence of a pelleted gala-lust comprising a group Ivy metal oxide support having phosphorous deposited thereon under conversion conditions comprising a tempo-nature within the range of about 250 to about ~00C, a pressure of about 500 to about 3000 prig and wherein the mow ratio of ethyl-enediamine to monoethanolamine is in the range of about 1 to about 5 mows of ethylenediamine per mow of monoethanolamine, whereby, with the passage of time, said catalyst becomes at least partial-lye deactivated:
the improvement which comprises) passing an inert gas through said catalyst bed to purge said reaction bed of unrequited feed stock and reaction products;
b) contacting said catalyst bed at a temperature within the range of about ~50 to about 550C with a mixture of oxygen and an inert gas containing from about 1 to about 20 mow percent of oxygen for a period of time within the range of about 0.5 to about 10 hours; and c) thereafter again bringing monoethanolamine and ethylenediamine into contact with said catalyst under said relation pa-~%25~
conditions to again provide an essentially non cyclic product come prosing polyethylenepolyamine.
According to a further aspect of the present invention there's provided a method wherein monoethanolamine is continuously catalytically reacted with ethylenediamine in a reaction zone us don conversion conditions including a temperature of about 250 to about 400C and a pressure of about 500 to about 3000 prig in the mow ratio of about 1 to 5 mows of ethylenediamine per mow of monoethanolamine to thereby provide an essentially non cyclic no-action product comprising polyethylenepolyamines and wherein the pelleted catalyst comprises a pelleted group Ivy metal oxide sup-port having about 0.5 to about 10 wt.% of phosphorous thermally bonded to at least the surface thereof, whereby, with the passage of time said catalyst will become at least partially deactivated:
the improvement which comprises:
a) discontinuing the passage of feed stock over said catalyst bed;
b) passing a stream of nitrogen through said bed while heating the same to a temperature of about 450C;
c) next charging a mixture of air and nitrogen eon-twining from about 1 to about 3 mow percent of oxygen over said catalyst for a period of time within the range of about 1 to 2 hours at a temperature of about 400 to about 450C;
d) next charging a mixture of air and nitrogen con-twining about 4 to about 20 mow percent of oxygen over said gala-lust bed for about 2 to 10 hours at a temperature ox about 450 to 550C;
e) next charging air over said catalyst bed for about

2 to 3 hours; and : f) again contacting said catalyst with a mixture owe monoethanolamine and ethylenediamine under said conversion of -6b-conditions to again provide an essentially linear reaction pro-duct comprising polyethvlenePolyamines.
The invention is related to improved catalyst compost-lions comprising a group Ivy metal oxide to which phosphorous has been chemically bonded by thermal activation. The catalysts are used in producing essentially linear polyethylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepenta-mine and pentaethylenehexamine from the reaction of ethylenedi-amine and monoethanolamine. The inventor is unaware of the pro-else structural differences between the claimed catalysts and pro-virus phosphate catalysts that have been tried in such reactions, but is cognizant of -6c-- =:

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substantially higher rates of conversion to linear polyeth-ylenepolyamines with the claimed catalysts.
The novel catalyst compositions catalyze the reaction of ethylenediamine with monoethanolamine at a temperature of from about 250C to about 400C, preferably from about 300 to about 350C and a pressure of from about 500 to about 3000 prig and preferably from about Tao about 2000 prig. 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 invent lion 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 gala-lust 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 convert soon of the reactants Thus, in a continuous process, it is not necessary to drive the reaction to completion because unrequited feed stock 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 , 25 1/32" to 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 dime-sons may be used as desired, by one wishing to practice the process of the present invention.

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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 worry) in order to obtain a desired rate of conversion, as explained above. Normally, space velocities of about 0.5 to 2 worry will be employed.
Catalyst life is an important factor in conducting a continuous reaction. For example, if a catalyst it 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 portico-laxly susceptible to poisoning so this normally does not present a problem. However, under the reaction conditions employed, amine 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 pelleted catalyst compositions have improved resistance to physical degradation when used to catalyze the reaction of monoethanolamine with ethylenediamine.
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 monoethanol-amine and ethylenediamine. As shown herein such catalyst So compositions can be used for prolonged periods without the need for regeneration. Thus, in Example IV it is shown that a representative catalyst of the present invention was used for over 2,000 hours with good results. 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.
When a catalyst composition of the present invention ha become deactivated, or at least partially deactivated, in the sense that the temperature required to maintain a desired conversion level is considered to be excessive, the catalyst Jay be regenerated with ease with oxygen under controlled regeneration conditions.
The minimum regeneration temperature is the temperature required, for the catalyst employed, both to burn impurities from the catalyst and to again thermally activate the gala-lust. This can be determined experimentally (see Example IVY and is normally in excess of 400C (e.g., 450C). The maximum regeneration temperature is the temperature at which the catalyst employed is thermally deactivated. The better practice is to use a temperature well blow the deactivation temperature range of about 700C to 900C (e.g., 550C).
Pure oxygen can be used, but it is preferably used in a concentration of about 1 to 20%, the balance being an inert ; gas ego. nitrogen, flue gas, eta). The catalyst bed is preferably preconditioned with a lean regeneration gas (e.g., 1-3% oxygen) for about 0.5 to 5 hours (e.g., I
hours). Thereafter the oxygen concentration in the regeneration gas can be progressively increased or I=

increased in stages to a concentration of from about 3% to about 20~ oxygen while adjusting the temperature, if desired, to a temperature within the range of about 450 to 550C.
The oxygen treatment may be continued in this fashion suite-by for about 2 to 10 hours. Thereafter the catalyst bed is flushed with an inert gas until it is cooled and it may then be restored to service.
The catalyst compositions of the present invention are prepared by depositing a phosphorus compound on a support comprising an oxide of a group Ivy transition metal oxide.
The group Ivy transition metal oxides include the oxides of titanium, zirconium, hafnium and thorium. Pellets of the group Ivy metal oxide may be prepared by extrusion or by compaction in conventional pelleting apparatus using a pot-feting aid such as graphite. It is also within the scope of the present invention to deposit the phosphorus compound on a powdered Ivy metal oxide followed by pelleting and calcination.
Any appropriate liquid or liquefiable phosphorus compound can be used as a source of the phosphorus. For convenience, phosphoric acid will normally be used. How-ever, other phosphorus compounds such as phosphoryl chloride pickle), phosphorous acid, polyphosphoric acid, phosphorus halides, such as phosphorus bromide, alkyd phosphates and alkyd phosphates such as trim ethyl phosphate, triethyl pros-plate, trim ethyl phosphate, triethyl phosphate, etc. may be utilized.
Preferably the catalyst composition is prepared by impregnating a preformed pellet. A suitable procedure to be - Jo ~2;2~

used is to heat a liquid containing the liquid or liquefiable phosphorus compound at a temperature of about 100 to about 150C and to then add pellets in an amount about equal to the volume of the heated liquid. This treatment should be continued from about 0.5 to about 5 hours. At the end of that time, the resulting mixture of pellets and liquid is cooled, decanted to remove excess liquid followed by washing with an amount of winter adequate to substantially completely remove unabsorbed liquid. Temperatures above 150C can be used, if desired, but there is no particular advantage in doing so.
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 Ivy 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 understood.
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 it also a function of the chemical identity of the phosphorous compound that is used as a source of phosphorous. Under the treating condo-lions exemplified above, at least about 2.5 wit% of pros-US porous is caused to bond or otherwise permanently adhere to the pellets. Theresa 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 ox ~%~

phosphorous that can be caused Jo bond or otherwise per ma-neatly adhere to the pellets is within the range of about 5 to 10 White As a matter of convenience, the normal practice is to use only one chemical as a phosphorous source (e.g., pros-phonic acid). However, mixtures of two or more such reagents may be used, if desired.
Calcining is not mandatory if the pellets are impregnated at least at about 100C, but the pellets can be calcined, if desired. Calcining is conducted for 2 to I
hours at a temperature of 100C but below the temperature at whisk thermal destruction of the phosphorus bonding occurs This can be determined experimentally for a particular catalyst twig., Example IV-B). Temperatures above 900C
should be avoided. A suitable calcining temperature range is normally 200 to 800C and, more preferably, 500 to Other procedures can be used in adding phosphorous to the group Ivy metal oxide. For example, the pellets can be treated with the phosphorous compound at ambient temperature or at more modest elevated temperatures of less than about 100C. In this situation, however, it is necessary to then-Sally activate the treated pellets by calcining under the conditions recited above.
I Alternatively, the group Ivy 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, thermal activation will normally have been obtained and it will not I be absolutely necessary to perform a calcining operation.

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If lower treating temperatures are used, calcining is nor-molly a desired operation. The calcining operation can be conducted prior to or subsequellt to the pelleting step. Any appropriate pelleting procedure of the type known to those skilled in the art may be used. For example, the treated powdered group Ivy metal oxide can be mixed with graphite and/or other binders and compacted or extruded under Canaan-tonal conditions.
There are many compounds which can be formed from the reaction of ethylenediamne and monoethanolamine besides the preferred linear polyethylenepolyamines such as diethylene-thiamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamin2. Less desirable cyclic and other compounds such as piperazine, N-(2-amin~ethyl)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 polyp ethylenepolyamines recovered from the reaction mixture can be further reacted with monoethanolamine to produce a larger percentage ox the higher molecular weight linear polyethylenepolyaminesO
- I 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 Swahili 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 S compounds employed and the products obtained have been abbreviated in the following examples and tables. The abbreviations employed for these various compounds are:
ETA - ethylenediamine ME - monoethanolamine PIP - piperazine DELTA - diethylenetriamine THETA - triethylenetetramine TEA - tetraethylenepentamine AREA - ~-(2-aminoethyl)ethanolamine ASP - N-(2~aminoethyl)piperazine HOP - N-(hydroxyethyl)piperazine Example I
1. Titanic Catalyst erosion A series of pelleted catalysts were prepared by deposit-in phosphorus on a titanic support.
a Phosphoric Acid r Titanic supported phosphoric acid catalysts were pro-pared 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 titanic pellets were slowly added through the condenser and the temperature was maintained for the desired period of time.
Thereafter the catalyst was recovered by first decanting the excess phosphoric acid followed by the addition to the I=

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 on Titan When using phosphoryl chloride as the source of phosphorus, a slight modification of the above identified procedures was necessary. The phosphoryl chloride was reflexed at 105~C. The heat was turned off and the reflex was maintained by the addition of titanic pellets at a rate sufficient to maintain a strong reflex. thereafter, heat was used to maintain the temperature When the resulting reaction mixture was tweaked with water the phosphoryl chloride was h~drolysed. Constant stirring was very important in order to maintain good heat dissipation. Phosphorus bromide was also used as a source of phosphorus using the procedure outlined above for phosphoryl chloride.
For convenience, the catalysts prepared and a brief description of the same is set forth herein as Table I.

TABLE I
TITANIC COOLEST compositions Type N~ber Composition A 5464-72 40 White Phosphate on alumina A 5494-4 Titanic (Shea) A 5494-16 Titanic treated with phosphoric acid (H3PO4) for hour A 5494-S Titanic treated with phosphoric acid four 2 hours A 5494-17 ~itania treated with phosphoric acid for 12 hours A 5494-95 Titanic treated with phosphoric acid for 2 hours A 5494-96 Titanic treated with phosphoric acid for 4 hours B 5494-6 Titanic treated with phosphoric acid for 2 hours and then calcined at 600C for 16 hours B 5494-65 Titanic treated with phosphoric acid, pelleted and then calcined at 600C for ours C 5494-11 Titanic treated with phosphoric acid, aluminum nitrate (Allen) then calcined at 600C for 16 hours C 5494-76 Titanic treated with phosphoric acid, aluminum nitrate and then calcined at 600 C for 16 hours C 5494-77 Titanic treated with phosphoric acid, alum m us nitrate and then calcined at Ç00C for 16 hours D 5494-13 Titanic treated with phosphoryl chloride (PCC13) for 4 hours D 5494-23 Titanic treated with phosphoryl chloride for 4 hours and then calc.ined at 600C for 16 hours D 5494-31 Titanic calcined at 600C, then treated with phosphoryl chloride and recalcined at 600C for 16 hours E 5494-19 Titanic treated with phosphorous acid (POW) for 2 hours 5494-78 Titanic treated with phosphorous acid for 2 hours and then calcined at 600C for 16 hours F 5494-18 Titanic treated with pol~phosphoric acid POW) for 2 hours F 5494-87 Titanic treated with polyphosphoric acid for 2 hours and then calcined at 600C for 16 hours G 5494-20 Titanic treated with phosphorous bromide ~PBr3) for 2 hours ~Z2~
Preparation of Polyethylenepolyamines from ~thylenediamine and Monoethanolamine Using Titanic Supported Phosphorus Catalysts.
The catalysts described in Table I were utilized for the conversion of ethylenediamine and monoethanolamine to a polyethylenepolyamine reaction product in a lo cc continuous reactor system. Pellets were placed in the reactor and the feed stock that was fed to the reactor was a mixture of ethylenediamine and monoethanolamine in a molar ratio of about two moles of ethylenediamine per mole of monoethanolamine.
lo In order to obtain a basis for comparison, the reaction temperature was varied so as to obtain about a 65%
conversion of the monoethanolamine feeds-toclc.
The reaction product was periodically sampled and analyzed by gas chromatographic analysis of the crude reactor effluent. Results were calculated on a feed-free basis.
The catalysts tested and the results obtained in the series of tests are set forth in Table II. In general, each feed stock was run for at least I hours to make sure that reaction conditions had stabilized.
Referring now to Table II it will be seen that the reference catalyst composition (5464-72) which comprised a commercially available 40 wt. % phosphate on alumina catalyst of the type disclosed in Brennan United States Patent No.
4,103,087 at column 8, lines 50-54 gave results which were improved upon in all instances. 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 United States Patent No.
4,448,907.

In particular, note that only about 77% of the triethylenetetramine fraction was non cyclic with this run.
In contrast, with the catalyst of the present invention the non cyclic content was normally in excess of 90~. Note also that there was also a significantly staller yield of diethylenetriamine with the reference catalyst.
The second reference catalyst ~5494-4) was untreated titanic pellets and it is seen that they were essentially inert insofar as conversion of monoethanolamine and ethylene-Damon is concerned.
The type A titanic supported catalysts wherein the source of phosphorus was phosphoric acid gave uniformly good results. Essentially equivalent results were obtained with the type B catalyst, however, the pellets were not quite so strong. The same comment applies to type C catalysts wherein the support was treated with phosphoric acid and thereafter there was an additional treatment with aluminum nitrate.
The best pellet strength was obtained with the type D gala-lust based on phosphoryl chloride.
Thus, Table II demonstrates that with titanic supported pelleted catalyst in a continuous reaction system, it is possible to obtain excellent results in the reaction of monoethanolamine with ethylenediamine. The percentage of non cyclic reaction products is very high, being over 90% in all cases except for type G (when phosphorus bromide was the source of phosphorus). Diethylenetriamine yields of from about 50 to about 70~ were obtained with this group of catalysts. Uniformly good yields of triethylenetetramine were also obtained I
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Analysis of Catalyst Pellets In an attempt to obtain a better understanding of the catalytic phenomena involved, three of the catalyst compost-. lions of Table II were subjected to a detailed analysis utilizing a scanning electron microscope (SUM).
The results of the first series of analyses is riven instable III attached. Note that with catalyst 5494-6, the phosphorus was concentrated in the initial 50 microns of the pellet surface.
In addition, the exterior surface at the end of the pellet was also analyzed and the results of this analysis are set forth in Table IV.
In respect of catalyst 5494-11, wherein the titanic was treated with aluminum nitrate and phosphoric acid and then calcined, an analysis of the interior of the surface is given in Table V.
The scanning electron microscope analysis of the surface of catalyst 5494-11 is given in Table VI.

TABLE III
Analysis off /Ti_~/Calcined (5494-6) Interior Surface of recaptured Pellet Wright % of Dejected Elements 50~ lo in From in Fur Outer 39~ 50~ 100~ Opposite opposite Element Edge in. in. in. Sonnetized _ _ Side No 2.4 0.7 0 0 0 0 1.5 I 2.7 1.9 0 0 0 0 0 So I 1.5 0 0 0 0 P 35.3 10.8 if if 0.2 0 20.4 Of 5.3 I 0 0 0 0 0 K. 7.3 2.0 0 0 0 0 0 C a D 9 1.6 1.5 0.9 2.0 2.0 0.5 Tao 79.3 98.5 9g.1 97.~ 98.0 77.6 100.0 99.9 100.0 Lowe 100.0 Lowe 100.0 Above data indicate that the phosphorus is concentrated at the surface of the catalyst pellet in a layer less Han 50 microns thick.

~22~g~

ALE rev Analysis of ~I3PD~/T~0~/Calc m Ed (5494-6), Continued Exterior Surface no of Pellet _ _ Concentration, Weight of Detected Elements Element 1 2 3 4 5 6 7 No 1.1 0.8 0.9 0.6! 1.0 1.1 0.8 Al 0.1 0.2 0.7 0.1 3.2 3.3 0.2 So 1.4 1.2 1.6 1.1 2.8 3.0 1.7 S O O O O O . I
I 0 0 0 0 0 0 0.8 K 0 0 0 0 0 0 1.2 Cay 0 1.0 0.5 0.5 3.7 3.1 0.8 To 66.3 68.6 67.1 72.161.3 60.5 62.0 P 31.0 28.2 29.3 25.52709 29.0 31.3 99.9 100.0 100.1 99.9 99.9 99.g 100.0 Above data indicate that the phosphorus concentration is relatively constant across the ~xkerior surface of the pellet.

I

BLUE V
Analysis of H3PO~/TiO~/Al(NO3)/Calcined Sans No. 4 (5494-ll) - Interior Surf go (Fractured of Pellet Concentrations, White of Detected Elements Event 1 I _ 3 I 2.5 0.88 1.5 P 1.7 0 0 Cay 1.2 0.82 1.5 To 94.6 ~8.3 97.0 owe OWE 100.~

age of fractured pellet was very rough, so that the closest analysis to the edge was 7 microns away. At this location, the "P" concentration was very low. Comparing this with data m Table VI, it is evident that the phosphorus exists within a very thin surface layer, much thinner than that for P04~TiO2/calcined, and that the 'I" concentrations are lower than those for the E3PO4~riO4/calcined catalysts.

I=

I

EYE TV
No3)3/calcined Sample No. 4 (5494-11), Continued - Exterior Surface (End Essay) of Pellet _ _ Concentration Weight of Detected Elements Element 1 * 2 3 4 5 6 7 _ _ _ _ No O O O O '0.4 0.3 0.1 Al 0 1.0 1.2 1.9 1.5 1.2 1.1 So 0 0.4 0.4 0 0 0 0 P 5.312~5 Lola 12.S 15.8 10.0 12.9 Cay 0 0.5 0.6 1.0 0.8 0.2 0.7 To 94.785.6 87.0 84.7 81.6 88.3 85.3 100.0100.0100.0 100.1 100.1 100.0 100.1 *Values suspect me above data indicate that 'I" concentrations are relatively constant across the end surface of the pellet. No reason can be offered for the low value on analysis #1. All 'I" concentrations are lower than those Pro the H3PO4/TiO2/calcmed catalysts.

In the case of the preceding analysis, it was demon-striated that the phosphorus was concentrated near the surface of the pellet. When catalyst 5494-13 was analyzed using the scanning electron microscope, different results were obtained, as is shown by Table VII.

I

TABLE VII
Analysis of Pool Shea Sample No. 5 (5494-13) Interior fracture) Surface of Pellet Concentration, Wit% of Detected Elements Element 1 2 3 4 5 So 0.3 1.5 0.6 1.0 0.7 P 6.8 I 7.2 So 8.5 Of 0.6 0.8 lo 1.2 1.2 K 0.1 0 0 0 Cay 0.9 0.6 0.4 0.6 0.5 To 91.4 89.0 90.7 88.589.2 100 . 1 100 . 1 100 . O 100 . O 100 . 1 The above data indicate that the "P" concentration is approximately constant throughout the bulk of the catalyst particle, rather than being limited to a thin layer at the surface as in H3PO4/TiO2/calcined and H3PO4/TiO2/~l(NO3)3/
calcined.

Further, when the exterior surface was analyzed, as set forth in Table VIII, it was found that the phosphorus was concentrated more in the interior of the catalyst than on the exterior. This demonstrates the need for caution when extrapolating from one catalyst composition to another in - reactions of this nature.

TALE VOWS
Analysis of POCl~/TiO~
Sample No. 5 (5494-13) Continued Exterior Surface tend of Pellet Concentration, White of Detected Elements _ Element 1 2_ 3 I 5 So 0.1 Go 0.3 /0.6 0.5 P 3.7 I 4.5 6.1 6.6 Of 1.8 1.1 24.7* 0.7 1.1 Cay 0.8 I 0.4 0.7 0.6 To 93.7 91.5 70.1 91.9 91.2 100.1 OWE 100.9 100.0 *Value suspect The above data indicate that "P" is distributed rather evenly across the exterior surface of the catalyst pellet, but is lower in concentration on the surface than inside the pellet. It it interesting that the lowest "P" concentration above corresponds to the lowest concentration within the pellet.

The catalyst compositions were also analyzed by X-ray detraction in bulk and after being powdered.
The results of the X-ray examination indicated that the titanic that was used was in a single phase, namely as anatasen Phospha~ing of the titanic with phosphoric acid produced the well known compound Taipei OWE. In add-lion, an unknown Taipei compound was also detected. The X-ray detraction pattern was quite similar to that of three known triphosphates, namely AgTi2(PO4)3, BaFeTi(PO4)3 and GeNb(PO4)3. Accordingly, the unknown was identified as a triphosphate possibly formed by the following reaction:
Shea 2Tl(HPO4)3 ) 2EITi2(PO4)3 -I OWE

Lo Indexing of the unknown's pattern is given in Table IX, which follows:

TABLE IX
indexing of Tip POX Unknown Pattern d-Spacings, A Miller intensity Obsd Calculated / Indices w 6.05 6.11 (01~) w 4.35 4.41 (014) w 4.20 4.23 (110) m 3.68 3.68 (006) s 3.50 3.48 (202) Shea also m 3.32 3.29 (106) w 3.22 3.16 (007) w 3.03 3.05 (024) m 2.75 2.75 (211) m 2.03 2.04 (036) w 1.95 1.96 (128) w 1.83 1.84 ~0-0-12) w 1.60 1.60 (140) w 1.28 1.28 (514) w 1.25 1.25 (3-1-14) Calculated using l/d =~4/3(1/a2)(h2-~hk+k2)+(1/c2)Q2, where ho are Miller indices, a and c are lattice constants, 8.474 and AYE, respectively.

the X-ray detraction analysis studies further indicated that calcining converted essentially all of the Taipei to the new compound. The crystal size of the latter was determined to be about AYE. However, with respect to catalyst 5494-11 it was found that only a part of the Taipei was converted to the new compound. The new come pound was not detected in sample 5494-13.
The results obtained from the catalyst pellet analysis are extremely interesting in a number of respects. First, it is clearly demonstrated that new catalyst compositions were obtained in the case of the samples 5494-6 and 5494-11.

-27~

I=

go Otherwise the new phosphorus compound would not have been found.
Further, the superior activity obtained with a titanic . support is not solely attributable to the presence of the new compound as shown by the results obtained in Table II.
Finally, the interaction between the phosphorus and the titanic support will vary depending upon the chemical nature of the source of the phosphorus but, again as shown by Table II, uniformly good results are obtained when titanic it used as a catalyst support for a phosphorus containing compound.

Zircon Sup sorted Phosphorus Containing Catalyst Compositions A series of phosphorus containing zircon supported catalyst compositions were prepared using the procedure outlined above in Example I. The pelleted catalysts were tested in the 100 cc continuous reactor described in Exam-pie I using the same conversion conditions The catalyst compositions that were prepared are given in Table X. The results obtained with this group of catalysts is set out in table XI.

I

a 2;~S~9 AL `

'ABLE X
Zircon m a Catalyst Positions YO-YO Number Cb~osi~ion 5464-72 40 wit% Phosphate on alumina 5484-37 Zircon 5484-6 Zircon treated with 11 wit% phosphoric acid (H3PO4) for 1 hour at 125C
H 5484-63 Pelleted zircon treated with phosphoric acid for 1 hour at 125C
H 5484-17 Zircon treated with 22 wit% phosphoric acid for 1 hour at SKYE
H 5484-83 Zircon treated with 11 White phosphoric acid for 1 hour at 125C
H 5484-84 Zircon treated with if wit% phosphoric acid for 2 hours at 125C
H 5484-85 Zircon treated with 11 wit% phosphoric acid for 4 hours at 125C
5494-71 Zircon treated with 11 wit% phosphoric acid for 24 hours at 125C
J 5484-64 Jo. 5484-63 calcined at 600C for 16 hours J AYE Zircon treated with 10 White phosphoric acid for 1 hour at 125C and then calcined at 600C for 16 hours J 5484-56 No. AYE after 300 hours of reaction time J 5484-46 Zircon treated with 15 wit% of phosphoric a d d and then calcined for 16 hours at 600C
J AYE Zirsonia treated with 11 wit% of phosphoric acid for 1 hour at SKYE and then calcined at 600C for 16 .
K 5494-79 Zircon treated with phosphorous acid POW) for 2 hours L 5494-83 No. 5494-79 calcined at 600C for 16 hours M 5494-29 Zircon a treated with phosphoryl chloride for 4 hours N 5494-30 No. 5494-29 calcined at 600C for 16 hours 0 5494-86 Zircon a treated with polyphosphoric acid (PUPA) for 2 hours P 5494-88 No. 5494-86 calcined at 600C for 16 hours Q 5494-81 Zircon treated with phosphorous brcnide for 2 hours ~2~g~

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n LnLn Lo Lo Lo Lo Lo Lo Lo us Inn Lo no Lo Lo Lo Lo ~30-With reference to Table XI, it will be seen that once again there was a good conversion of the monoethanolamine and ethylenediamine to non cyclic products characterized by good yields of diethylenetriamine and triethylenetetramine~
This series of tests demonstrates thaw the zircon supported catalysts give results equivalent to those obtained with titanic.
An attempt to analyze the zircon supported catalysts using a scanning electron microscope were unsuccessful because the phosphorus content of the PI - emission line waive length, AYE is very close to the ZrL - emission line, AYE. These two lines could not be resolved using the electronic discriminator with which the scanning elect iron microscope was fitted.
Insofar as X-ray detraction analysis is concerned, it was determined that the zircon was an equimix of monoclinic zircon, baddeleyite and a tetragonal phase usually formed at higher temperatures.
Surface scrapings from the zircon catalyst that had been treated with the phosphorous compound contained some rather large crystals of ZrP2O7. Because of their low - surface area, it is doubtful that this ZrP2O7 is responsible for the excellent activity of the zircon supported gala-lust. The ZrP2O7 X-ray pattern it wear, indicating that ZrP2O7 represents a small fraction of the phosphorus pros-en. It is probable that another phosphorous compound that is amorphous is the catalytically active species.

Example III
Recycle Studies The It metal oxide supports tend Jo shift product distribution towards diethylenetriamine. There are times when it is desirable to obtain greater yields of triethylene-tetramine or tetraethylenepentamine. Accordingly, a series of recycle tests were run to determine the feasibility of recycle of diethylenetriamine. The reaction sequence described above or the 100 ml. reactor was used for the recycle studies. However, 20 White of the ethylenediamine in the feed was replaced with diethylenetriamine in two runs and all of the monoethanolamine was replaced with diethylene-thiamine in the other two runs.
The catalyst compositions that were used are identified in Table XII and the results of the simulated recycle tests are set out in Table XIII.

TALL
Catalyst Com~osLtions, S mutated Recycle I
Type Number Description A 5494-7 Titanic treated with phosphoric acid for 2 hours A 5494-8 Titanic treated with phosphoric acid for 2 hours H 5494-2 Zircon treated with phosphoric acid for 2 hours H 5494-3 Zircon treated with phosphoric acid for 2 hours I

a) En I Ed a Q I a O do O
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Lo Lo In Lo ~-33--As will be seen from Table XIII, with both titanic and zircon, the very high selectivity to non cyclic products was once again obtained. There was a significant increase in the yield of triethylenetetramine and also an improvement in the yield of tetraethylenepentaMine.

Example IV-A
This example is illustrative of the long term stability and activity of catalyst compositions of the present in invention and ox the low susceptibility of such catalyst compositions to poisoning.
A fresh batch of catalyst ~5544-20) was prepared using the procedure of Example It to prepare a catalyst as set forth in Example I in respect of catalyst 5494-23.
Catalyst 5544-20 was used for a prolonged life study using the equipment and procedures of Example I. In this instance, however, more severe reaction temperature condo-lions were used in order to accelerate the effects of long term usage. For this purpose a monoethanolamine conversion of 80% was established and maintained throughout about 2000 hours of reaction time. At the end of that time the run was arbitrarily terminated. Representative results of the test are set forth in Table XIV-A.

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As can be seen from Table XIV-A, the catalyst had good initial selectivity and the selectivity remained good throughout the run.
The temperature required to maintain ME conversion at 80~ increased from 315C to about 335C during the first 1000 hours of operating, indicating a slight loss in active-try. The use of a temperature of 335C at the end of the run indicates an overall moderate loss of activity.

Example lob Catalyst Regeneration A titania-supported phosphate catalyst prepared in accordance with Example I was charged to a 100 cc continuous reactor and subjected to an accelerated aging test using, as a feed a mixture of ethylenediamine and monoethanolamine in a ratio of 2 mows of ethylenediamine per mow of monoethanol-amine The feed was charged at a liquid hourly at the rate of about 1 volume of liquid feed per hour per volume of catalyst. Pressure was held at lS00 lobs. and the tempera lure was adjusted to give about an 80% ME conversion. At the beginning of the run at a temperature of about 325C, - analysis indicated a conversion of monoethanolamine of about 78~, a ratio of diethylenetriamine to piperazine of about 19 and a reaction product containing about 94% non cyclic come pounds in the triethylenetetramine fraction. In a duplicate run at 325 the initial ME conversion is found to be about 81~ and the ratio of diethylenetriamine to piperazine was found to be about 17; the percent of non cyclic products in the triethylenetetramine traction was fund to be about 93~.
In order to simulate a prolonged run, an accelerated aging I

procedure was used wherein the catalyst bed was held at reaction conditions without feed for a period of about 2 weeks. After the 2 week period, a temperature of about 345C was required to obtain about an 80~ conversion of monoethanolamineO In a specific run, after two weeks of accelerated aging, ME conversion was 83~, the ratio of DELTA
to PIP was 7 with only about 72% non cyclic products in the THETA fraction.
Thereafter, the catalyst was regenerated in accordance with the following procedure:
l) The catalyst bed was heated to about 450C;
2) A mixture of about 100 cc per minute of air in 700 cc per minute of nitrogen was passed through the kowtow lust bed for about 1 hour;
3) Next a mixture of about lo cc per minute of air and 300 cc per minute of nitrogen was passed over the gala-lust bed for about l hour;

4) Thereafter air was charged without inert gas at the rate of lo cc per minute for 2 hours; and

5) The catalyst bed was flushed with nitrogen while cooling over night.
After regeneration the catalyst was again tested for activity and at a temperature of 325C the monoethanolamine conversion was about 77%; the ratio ox diethylenetriamine to US piperazine was about 19 and the percentage of non cyclic products in triethylenetetramine fraction was once again 94%. Thus, regeneration had been successfully performed.
When the preceding regeneration procedure was attempted at 350C, regeneration was unsuccessful while at 400C the results were unsatisfactory.

An attempt to regenerate the catalyst by heating at 350C in a nitrogen stream was unsuccessful.
An attempt to regenerate the catalyst by washing at 250C with feed was also ineffective.

Example V
This example is illustrative of the utility of hyphen as a support in the preparation and use of the catalyst compositions of the present invention.
The amount of hyphen available was insufficient to permit the preparation of the number of pellets required for a continuous evaluation using the equipment and reaction conditions of Example I. However, enough hyphen was avail-bye to permit a batch evaluation using powdered catalyst.
Catalyst Preparation Typically, these catalysts were prepared by addition of 50 g of the metal oxide powder to 150 cc of 85% H3PO4 at 130C. This temperature was maintained for approximately five hours. The solids were then separated by filtration through a frilled glass funnel; filter paper systems were not adequate as the phosphoric acid caused disintegration of the paper and subsequent product loss. The product was then washed to remove excess phosphoric acid and dried.
General Experimental Procedures All batch reactions were carried out in a 300 cc stain-less steel, rocking autoclave. They were used with glass liners to minimize the effects of catalyst derived impure ties from the crave walls.
The general procedure consisted of placing 6.1 g ~20 wit% basis MEAT of catalyst in a liner followed by addition I

I

I

of 60.5 g of a 1.1 EDEMA mixture (30 g ETA and 30.5 g MOE The liner was placed in the reactor, the system was purged with nitrogen, and finally heated to 315C for 2 hours. The crude xeac~ion product was filtered from the catalyst and analyzed by GO using an OVA chromatography column.
The supports used for this series of tests included titanic, zircon and hyphen. Powdered T1067 was also run to provide a basis for comparison.
The results are set forth in Table XV.

TABLE XV
Batch Run Evaluation of $itania, Zircon and Hyphen as Catalyst supports lo Ratio:
Catalyst Conversion Selectivity DWIGHT
Support EDEMA PIP DELTA AREA PIP
Titanic 51 83 I
Zircon 3.55.2 5.1 ~afnia 5.86.4 4.7 65.7 5.4 14.0 T-1067 6.317.7 3.0 53.7 17.9 17.7 Batch tests such as those summarized in Table XV are characterized by poor reproducibility. However, they do provide a qualitative measure of catalyst suitability.
It can be concluded from the results of Table XV that pelleted thermally activated catalyst compositions comprise in hyphen having phosphorous derived from phosphoric acid deposited thereon will give results analogous to those obtained in Example I and Example II where titanic and zircon, respectively, were used as supports I

I

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.

Claims (8)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows;

1. In a method wherein monoethanolamine is continu-ously reacted with ethylenediamine in a reaction zone in the presence of a pelleted catalyst to provide an essentially noncyclic reaction product comprising polyethylenepoly-amines, wherein the catalyst comprises a group IVb metal oxide support having a minor amount of phosphorous thermally bonded to at least the surface thereof and wherein said pelleted catalyst becomes at least partially deactivated with the passage of time:
the improvement which comprises:
a) regenerating said catalyst for further use in said continuous process by contacting said partially deactivated catalyst at a catalyst activating temperature of less than about 700°C with an oxygen containing gas for a period of time within the range of about 2 to 12 hours sufficient to regenerate and reactive said catalyst; and b) thereafter again initiating the con-tinuous reaction of monoethanolamine with ethylenediamine in said reaction zone in the presence of said thus regenerated catalyst to provide an essentially noncyclic product com-prising polyethylenepolyamines.

2. A method as in claim 1 wherein said group IVb metal oxide support is titania.

3. A method as in claim 1 wherein said group IVb metal oxide support is zirconia.

4. In a continuous process for the manufacture of an essentially noncyclic reaction product comprising poly-ethylenepolyamines by continuously contacting monoethanol-amine with ethylenediamine in a reaction zone in the presence of a pelleted catalyst comprising a group IVb metal oxide support having phosphorous deposited thereon under conversion conditions comprising a temperature within the range of about 250° to about 400°C, a pressure of about 500 to about 3000 psig and wherein the mol ratio of ethylene-diamine to monoethanolamine is in the range of about 1 to about 5 mols of ethylenediamine per mol of monoethanolamine, whereby, with the passage of time, said catalyst becomes at least partially deactivated:
the improvement which comprises:
a) passing an inert gas through said cata-lyst bed to purge said reaction bed of unreacted feedstock and reaction products;
b) contacting said catalyst bed at a temperature within the range of about 450° to about 550°C
with a mixture of oxygen and an inert gas containing from about 1 to about 20 mol percent of oxygen for a period of time within the range of about 0.5 to about 10 hours; and c) thereafter again bringing monoethanol-amine and ethylenediamine into contact with said catalyst under said reaction conditions to again provide an essen-tially noncyclic product comprising polyethylenepolyamine.

5. A method as in claim 4 wherein said group IVb metal oxide support is titania.

6. A method as in claim 4 wherein said group IVb metal oxide is zirconia.

7. A method as in claim 4 wherein the inert gas is nitrogen.

8. In a method wherein monoethanolamine is con-tinuously catylitically reacted with ethylenediamine in a reaction zone under conversion conditions including a temperature of about 250° to about 400° C. and a pressure of about 500 to about 3000 psig in the mol ratio of about 1 to 5 mols of ethylenediamine per mol of monoethanolamine to thereby provide an essentially noncyclic reaction product comprising polyethylenepolyamines and wherein the pelleted catalyst comprises a pelleted group IVb metal oxide support having about 0.5 to about 10 wt.% of phosphorous thermally bonded to at least the surface therof, whereby, with the passage of time said catalyst will become at least partially deactivated:
the improvement which comprises:
a) discontinuing the passage of feedstock over said catayst bed;
b) passing a stream of nitrogen through said bed while heating the same to a temperature of about 450°C;
c) next charging a mixture of air and nitrogen containing from about 1 to about 3 mol percent of oxygen over said catalyst for a period of time within the range of about 1 to 2 hours at a temperature of about 400°
to about 450°C;
d) next charging a mixture of air and nitrogen containing about 4 to about 20 mol percent of oxygen over said catalyst bed for about 2 to 10 hours at a temperature of about 450° to 550°C;
e) next charging air over said catalyst bed for about 2 to 3 hours; and f) again contacting said catalyst with a mixture of monoethanolamine and ethylenediamine under said conversion conditions to again provide an essentially linear reaction product comprising polyethylenepolyamines.