Note: Descriptions are shown in the official language in which they were submitted.
~:~9~342~
CATALYSIS OF CONDENSAT10~ REACTIONS
This application is related to copending Canadian Patent
Application No.~c~/~2Q~ filed March 31, 1982.
TECHNICAL FIELD OF THE INVENTION
_ _ ~
The present invention relates to organic condensation
reactions effected in the presence of novel pyrophosphate
and hydrogen phosphate catalysts and is more particularly
concerned with the production of amine compounds in enhanced
yields.
BACKGROUND OF THE PRIOR ART
Organic synthesis by condensation reactions resulting
in the loss of a molecule of water or of ammonia are well
known in the art. Certain of such reactions are generally
effected in the presence of acidic catalysts. An important
area in which such acid catalysis has bee~ employed is in
cyclization reactions as in the synthesis of triethylenediamine
and its C-substituted homologues. The catalysts more generally
used or proposed for use in such cyclization reactions are
solid products of the Lewis acid type.
Triethylenediamine, also called diazab-icyclo -[2.2.2]-
octane, has been widely employed commercially as a catalyst
in organic isocyanate reactions with compounds containing
labile hydrogen, as in the production of urethane polymers.
Triethylenediamine (somet.mes hereinafter referred to as
TEDA) was initially prepared
34~3
i~ significant ~uantities by methods such as that
descri~ed in U.S. Patent No. 2,937,176, by passing
aliphatic amines in vapor phase over acidic cracking
catalyst, such as silica-alumina dried gel or acid
activated clays. Numerous other feed stocks as well as
other catalysts are disclosed in subsequent patents for
preparation of TEDA as well as C-alkyl derivatives
thereo~.
Typical among these are U.S. Patents 2,985,658 and
1~ 3,166,558 employing preferably silica-alumina type
catalyst, but listing also other useful solid acid
catalysts that can be employed such as alumina in which
phosphate or fluoride ion is incorporated (U.S. 2,9~5,658).
Among other catalysts proposed in the patent art
for preparation of triethylene diamine and/or C-alkyl
homologues thereof, are certain phosphate compounds,
particularly aluminum phosphate.
The use of aluminum phosphate as a catalyst in the
preparation of heterocyclic compounds from aliphatic
amines ~las early disclosed in U.S. Patent 2,467,205,
particularly for the preparation of piperazine from
ethylenediarnine or from polyethylene polyamine. The
use of aluminum phosphate as catalyst in the preparation
of triethylenediamine accompanied by piperazine among
other by-products is further described in U.S. Patent
3,172,891; while U.S. Patent 3,342,820 describes the
use of complex phosphates of alkali metal and trivalent
metals in the preparation of C-alkyl TEDA.
U.S. Patent 3,297,701 discloses as catalysts for
preparation of TEDA and C-alkyl TEDA, in addition to
the preferred aluminum phosphate stated to be superior,
other phosphate compounds including calcium and iron
phosphates among other listed metal phosphates. In the
conversion of N-aminoethylpiperazine to triethylenedi-
amine over aluminum phosphate catalyst, at most up to39 mol% triethylenediamine is said to be obtained.
Other o~ the named metal phosphate catalysts in the
1~9~'~2b~
examples of the Ratent obtain yields of less than 10 mol % T~DA.
Acid metal phosphate catalysts, particularly phosphates of boron,
aluminum and trivalent iron, have also been proposed for use in intra-
molecular cyclic dehydration reactions and other condensation reactions
involving amino compounds. Examples of such reactions are found in U.S.
Patent 4,117,227, which discloses conversion of an N-substituted diethanol-
amine to the corresponding N-substituted morpholine. U.S. Patent
4,036,881 describes preparation of non-cyclic polyalkylene polyamines by
condensation of an alkylene diamine with an ethanolamine. N-hydroxethyl-
morpholine is condensed with morpholine in the presence of aluminum
phosphate catalyst to form dimorpholino ethane according to U.S. Patent
4,103,087. Similarly, dimorpholinodiethyl ether is obt~ined by condensation
of hydroxyethyl morpholine with aminoethyl morpholine over iron, aluminum
or boron phosphate in U.S. Patent 4,095,022. Reaction of piperazine
with ethanolamine over such acidic metal phosphate produces N-aminoethyl
piperazine according to U.S. Patent 4,049,657. U.K. Patent 1,492,359
discloses the preparation of morpholine compounds by reacting an amino-
alkoxyalkanol compound over phosphoric acid and similar types of phosphorus-
containing substances.
Pyrophosphates of lithium, sodium, strontium and barium have been
used as dehydration catalysts; see U.S. Patent 3,957,900. Phosphates
and pyrophosphates of strontium and nickel have been used for the dehydrogenation
of, for example, n-butene to butadiene under the conditions described in
U.S. Patent 3,54].,172.
SUMMARY OF THE INVENTION
In its broadest aspect the present application is concerned with
the provision in methods for the synthesis of organic compounds by
condensation reactions in the presence of phosphate catalysts, of the
improvement which comprises the use as such of catalysts which are
selected from the group consisting of the pyrophosphate, monohydrogen
A'~ _ 3 _
~19~2~
phosphate and dihydrogen phosphate of strontium, copper, magnesium,
calcium, barium, zinc, lanthanum, aluminum, cobalt, nickel, cerium,
neodymium, and mixtures thereof, subject to the exclusion of the
pyrophosphate, monohydrogen phosphate and dihydrogen phosphate of strontium
per se, and mixtures ~hereof.
DETAILED DESCRIPTION OF THE INVENTION
The monohydrogen and dihydrogen phosphate catalysts of the present
invention are prepared by reaction of a mono- or diphosphate of an alkali
metal or ammonium with a soluble salt of strontium, copper, magnesium,
calcium, barium, æinc, aluminum, lanthanum, cobalt, nickel, cerium or
neodymium at ambient temperatures. The highest purity and best yields
of the present invention are obtained when using the soluble metal salts
of a strong acid such as the metal nitrates, in substantially stoichiometric
proportion to the phosphate. In aqueous media under these conditions,
t'ne reaction mixture is at a pH of about 3.5 to 6.5. In general, to
obtain a precipitate of desired high content of the metal monohydrogen
or dihydrogen phosphate, the ratio of phosphate to metal salt in the
reaction mixture should be such as to have a pH of 5 + 3, or the mixture
should be adjusted to that pH range.
The pyrophosphate form of the catalysts of the present invention
are prepared by heat treating the metal monohydrogen or dihydrogen
phosphate product at temperatures above about 300C up to 750C in the
presence of a mixture of steam and air, preferably at least about 20% by
~olume of steam.
For use as a catalyst, the metal pyro-, monohydrogen or dihydrogen
phosphate product may be employed in the form of irregular particles of
the desired size range prepared by breaking up the washed and dried
filter cake or in the form of regular shaped pellets obtained by known
methods of casting or extruding or the product
-,~
_~ ~ - 4 -
~3L9~
may be deposited or otherwise impreynated into the
pores of a microporous substrate such as alumina,
silica, silica-alumina, and the like. In using the
catalyst of the present invention to catalyze organic
condensation reactions, substan~ially the same conditions
may be employed as when using the known catalysts for
the particular synthesis. For optimum results, however,
some adjustment in temperature, diluent and/or space
rate may be found beneficial.
Some specific examples of the type of organic
compounds selectively obtained by the method of this
invention include TEDA, the aliphatic a]kylamines such
as methylamine, methylethylamine, dimethylethylamine,
morpholine, and dimethylaminoethylmorpholine. In the
production of these compounds, the temperature is in
the range of about 285 to 420C, the pressure is in
the range of about 0.1 to 1.5 atmospheres, and the
liguid hourly space velocity (LHSV) of the organic feed
stock per volume of catalyst is in the range of about
0.05 to 1.5. Preferabl~ depending on the particular
reaction, the temperature is in the range of about 300
to 400C, the pressure is in the range o about 0.3 to
1.O atmospheres and the LHSV is in the range of about
0.1 to ~.3 to obtain the highest yields and most econom-
ical process. The operable ratio of the organic feedsto water diluent i5 about 10 to 90% on a weight basis
and preferably, 20 to 80% by weight. The optimum yield
of these compounds is likely to be obtained using the
highest temperature in the preferred range at the
lowest LHSV.
In the preparation of TEDA, the preferred catalyst
is selected from the group consisting of monohydrogen
phosphate of calcium, magnesium, zinc, mixtures of
strontium and barium in the ratio of Sr to Ba of about
1 to 5 to 5 to 1 and mixtures of lanthanum and strontium
in the ratio of La to Sr of about 15 to 1 to 15. The
organic feed stock used in this reaction to produce
~842~
TEDA is a substituted piperazine compound selected from
the group consisting of hydroxyethylpiperazine and
aminoethylpiperazine. The catalysts of this invention
are relatively unef~ected by the purity of the feed
stock. For example, high conversion and good yields
can be obtained from crude hydroxyethylpiperazine which
contains minor quantities of piperazine and bis hydroxy-
ethylpiperazine.
In the preparation of dimethylaminoethylmorpholine
(DMAEM), the preferred catalys~ is a mixture of strontium
and nickel monohydrogen phosphate in the ratio of Sr to
Ni of about 1 to 5 to 5 to 1. The feed stock is morpholine
and dimethylethanolamine in the ~olar ratio in the
range of about 1 to 3 and 3 to 1. Preferably, the
reaction takes place in the presence of hydrog n in the
molar ratio of hydrogen to organic feed of about 1 to 1
to 20 to 1 and an inert gas such as nitrogen, argon or
helium in the molar ratio of inert gas to organic feed
of about 1 to 1 to 20 to 1.
In the preparation of morpholine compounds, e.g.
morpholine and alkyl morpholine, wherein the alkyl
group has from 1 to ~ carbon atoms, diglycolamine
compounds, e.g. diglycolamine and alkyl diglycolamines,
wherein the alkyl group has from 1 to 6 carbon atoms
are preferably carried out in the presence of strontium
monohydrogen phosphate at about 300 to 370C with the
other conditions remaining the same as that discussed
above. This reaction also preferably takes place in
the presence of the inert gas in ratios of 2 to 1 to 10
to 1 inert gas to liquid organic feed stock.
The methods and catalysts of this invention are
also capable of reacting an alcohol and a nitrogen-
containing compound selected from the group consisting
of ammonia, aliphatic primary and secondary amines, and
aromatic primary and secondary amines to selectively
convert this compound to the corresponding symmetrical
or unsymmetrical higher molecular weight amine with
little, if any, conversion to the corresponding by-products
of thermodynamic amine equilibration. The amines and
alcohol ln the feed stock each contain 1 to 20 carbons
per molecule. Preferably, the catalyst is lanthanum or
coppex monohydrogen phosphate and the molar ratio of
alcohol to nitrogen-containing compound ranges from
about 1 to 6 to 6 to 1.
CATALYST PREPARATION
Example 1
-
200 grams of strontium nitrate [Sr(N03)2] was
dissolved in distilled water and brought to a total
volume of 800 cc with distilled water. To this solution
there was added 10 cc of 85% phosphoric acid followed
by 34.5 cc of 50% sodium hydroxide added rapidly with
vigorous stirring. The resultant fine white precipitate
was stixred for 10 minutes, vacuum-filtered and water-
washed. The obtained filter cake was air dried in a
static oven at approximately 110~C and extruded into
1/8 inch pellets for evaluation.
The obtained product had a surface area of 10-15
m2/g. By X-ray diffraction the principal component was
identified as ~ -Sr~P04 with minor quantities of Sr5(0H)
(P04)3 and unreacted Sr(NO3)2. Infrared spectroscopy
showed a spectrum consistent with SrHP04. (Ref:
Richard A. Nygurst and Ronald O. Kagel, "Infrared
spectra of Inor~anic Compounds", page 163, 1971).
Example 2
195 grams of barium nitrate --Ba(NO3)2-- and 53
grams of strontium nitrate --Sr(NO3)2-- were dissolved
in distilled water and diluted to 500 cc. 132 grams o
dibasic ammonium phosphate --(N~4)2HPO4-- were dissolved
in distilled water and diluted to 500 cc with heat.
The three salt solutions were then combined with heat
and stirred for about 10 minutes. The combined solution
119842~3
was vacuum filtered and the resulting precipitate was
washed with distilled water and air dried overnight in
a static oven at approximately 110C. The filter cake
was broken up into small (1/8 to 1/4 inch) irregular
granules for evaluation. The resulting product had a
surface pH of 4-5 as determined by acid base indicators
and the ratio of strontium to barium in the product was
found to be 1 to 3.5.
Example 3
The procedure for preparing the Example 2 was
carried out except that 130 grams of Ba(N03)2 and 106
grams of Sr(N03)2 were dissolved in distilled water in
place of the 195 and 53 grams respectively. The product
had a surface pH of 4-5 and a Sr/Ba ratio of 2/1 mol/mol.
The resulting catalyst was in the form of a fine powder
and was deposited on an inert, low surface area Alundum
silica-alumina core using a powder-coating step. The
step comprised placing the amount of catalyst to be
coated into a jar with the Alundum spheres and rotating
on a jar-mill for several days to cause the catalyst
powder to adhere to the spheres. The resulting coated
spheres contained 25% of the active catalyst and 75%
-- inert.
Example 4
212 grams of Sr(N03)2 were dissolved in distilled
- water and diluted to 500 cc. 115 grams of ammonium
dihydrogen phosphate --NH4H2P04-- were dissolved in
distilled water and diluted to 500 cc. The remaining
steps of the catalyst procedure of Example 2 were
carried out. The resulting catalyst was believed to
contain less than 5% strontium dihydrogen phosphate
--Sr(H2P04)2-- with the balance being SrHP04. The
surface pH of this catalyst mixture was 4-4.6 in compar-
ison to substantially pure strontium monohydrogen
phosphate which has a surface pH of 4.8-5.4. Sub-
stantially pure strontium dihydrogen phosphate was
found to have a surface pH of 0.2-1.2; see Example 21.
The product of this example was deposited on the
S silica-alumina spheres in the same manner as set forth
under Example 3.
Example 5
The same procedure for preparing the catalyst of
Example 1 was carried out except that 236 grams of
calcium nitrate --Ca(NO3)2.4H2O-- and 115 grams of
NH4H2P04 were combined. The resulting dried catalyst
particles were coated on the silica-alumina spheres in
the same manner as that of Example 3. The analysis of
the catalyst formed by this procedure indicated that it
consisted essentially of calcium monodihydrogen phosphate
with a Ca/P ratio of 1.009 and a surface pH of 4-6. In
contrast, substantially pure calcium monohydrogen
phosphate had a surface pH of 5-5.5; see Example 16
below. The presence of a very small amount of calcium
dihydrogen phosphate may account for the difference in
the surface pH value of this catalyst.
Example 6
The catalyst preparation procedure of Example 2
was repeated except that 212 grams of Sr(NO3)2 were
dissolved in place of the mixed barium and strontium
nitrate salts and the resulting strontium monohydrogen
phosphate catalyst had a surface pH of 4.8-5.2.
Examples 7-15
The following salts were combined and catalysts
were prepared in the manner set forth under Example 2:
1~ 984~ZB
CatalystSurface
Example Salt _o utions ~ormulation pH _
(~ (b)
7 168g. Nd(N03)3.5H20 80g- (NH4)2 4 2 4 3
8 217g. Ce(N03)3.6H20 ggg- (NH4)2 4 2 4 3 0.2-1.2
9 415g. ~a(N03)3-5H20 198g- (NH4)2HP4 La2(HP4)3 0.2-1.8
202g. Sr(N03)2+ 132g- (NH4)2HP04 SrHP04/LaHP0 4-5
20 grams of (Sr/La=14.9/~)
La(N03)3.5H20
10 11 291g. Co(N03)2.6H20 132g. (NH4~2 4 4 4.6-4.8
12 291g. Ni(N03)2.6H~0 132g- (NH4)2HP 4 4 6.2-6.8
13 242g. CuC12.2.5H20 132g- (NH4)2 4 4
14 297g. Zn(N03)2.6H20 132g- (NH4)2 4 4 6.2-6.5
125g. Al(N03)3.9H20 66g. (NH4)2H 4 2 4 3 2
*Colored product, pH N.A.
Example 16
160 grams of Ca(NO3)4 were dissolved in distilled
water and diluted to 800 cc. 20 cc. of phosphoric acid
~88% by wt. in water) were added with agitation.
34.5 cc-. of sodium hydroxide solution (50% by wt. NaOH
in water) were added to precipitate the CaHPO4 which
was filtered, washed, dried and granulated as in Example 2.
The resulting product had a surface-pH of 5-5.5.
Controls 1-3
The following salts were also combined in the
manner of the Example 1 preparation.
~ 91~42~3
Catalyst
Con~rol Salt Solutions Formulation
, .
~a) (b)
1 261g. ~a(N03)2 230g. NH4HS04 BaS04
2 75g. CsCl 40g. (NH4)2HP04 CsHP04-~
3 106g. Sr(N03)2 40g. 50% NaOH+ SrHAsO4
80g- (NH4)2H2A54
*Did not form a precipitate.
Control 4
200 grams of Sr(NO3~2 were dissolved in distilled
water and diluted to 400 cc. 92 grams of H2SO4 were
diluted in 200 cc. of distilled H20 75 grams of 50
wt. % NaOH solution were diluted to 200 cc. with distilled
water. The H2SO~ and NaOH solutions were mixed together
slowly. ~he Sr(N03)2 solution was stirred into the
solution containing H2SO4 and NaOH. The solution was
stirred for 10 minutes and the precipitate was filtered,
washed and dried. The surface pH of the resulting
catalyst was less than 3 which was believed to be
substantially all SrSO4.
Example 17
71 grams of Na2HP04 were dissolved in 500 cc. of
distilled water. 101.7 grams of MgC12.6H20 were dis-
solved in 500 cc. of distilled H2O. Both solutions
were mixed together and the precipitate was filtered,
washed and dried. The surface pH of the MgHPO4 product
was 7-8.
Example 18
71 grams of Na2HP04 and 130.7 grams of Ba(NO3)2
were each separately dissolved in 500 cc. of distilled
H2O The 2 solutions were mixed and the precipitate
was filtered, washed and dried. The resulting BaHP04
had a surface pH of 8-9.
2~
12
Each of the products resulting from the procedures
of Examples 17 and 18 above were coated on the silica-
alumina spheres in the same manner as indicated in
Example 3.
Example 19
The SrHP04 catalyst of Example 6 was heat treated
for 2 hours in the presence of a mixture 20% by volume
steam and the balance air at 350C. The resulting
strontium pyrophosphate (Sr2P2O7) had a crushing strength
of 0.47 kg./mm of length and a packed bulk density of
1.01 kg./l.
ExamPle 20
The ZnHP04 catalyst product of Example 14 above
was coated on the silica-alumina spheres in the manner
set forth in Example 3.
Example 21
132.5 grams of strontium hydroxide octahydrate
--Sr(OH)2.8H2O-- were dissolved in a solution of 750
cc. of 85% phosphoric acid and 1500 cc. of distilled
water. The resulting solution was slowly evaporated to
a total volume of about 900 cc. with the temperature
being maintained at 25 to 30~C. The solution was
cooled to 5C overnight and a whi-te precipitate was
recovered by vacuum filtration. The resulting Sr(H2PO4)2
precipitate was washed with 5-300 cc. portions of
anhydrous ethanol and with 2-200 cc. portions of anhy-
drous ether. The product was dried at room temperature
under vacuum for 6 hours. An elemental analysis of the
product showed a P/Sr mol ratio of 2.04 and the surface
pH was found to be 0.2-1.2. The fine powder was pressed
into tablets the size of a typical"Aspirin" (registered
trade mark) tablet and crushed to granules 1~8 to 1/4 inch
in size.
34Z~
13
Example 2_
The fine powder of the catalyst prepared in accor-
dance with Example 21 was deposited on silica-alumina
spheres in the manner set forth in Example 3.
Example 23
2000 grams of Sr~NO3)2 were dissolved in 2000 cc
-, of deionized water and the solution diluted to 4000 cc
with deionized water after dissolution of the Sr(N03)2
was complete.
In another container, 1342.3 grams of Na2HP04 were
dissolved in 2000 cc of deionized water. After solution
of the na2HP04 was complete, the solution was diluted
to 4000 cc with deionized water. The pH of this solution
was approximately 8.~3.
Precipitation of SrHP04 was effected by slowly
adding the Na2HP04 solution to the Sr(NO3)2 solution
with rapid stirring. The white SrHP04 precipitated
rapidly from solution forming a rather thick slurry.
This slurry was mixed for one hour, after which time
the pH ~as measured to be about six.
The solid SrHP04 was recovered by filterir.g on an
eight frame filter press using cloth filters. It was
washed with deionized water. After filtering and
washing, the solid was dried in a circulating hot air
oven at 250F for four hours. The yield of SrHPO4 was
1680 grams. The solid was wetted and formed into
pellets by extrusion through a 3.1 mm die plate and
cutting the extrudates to about 1/4 inch in length.
After drying the extrudate at 250F for four hours in a
circulating hot air oven, they were heat treated at
662F for two hours in a 20% steam, 80% air atmosphere.
Example 24
106 grams o~ Sr(N03)2 and 145 grams of Ni (N03)2
6H2O were dissolved in distilled water and diluted to
~9~342~3
14
500 cc. 132 grams of (NH4)2HP04 were dissolved in
distilled water and diluted to 50~ cc. the remaini~g
steps of Example 1 were carried out to yield a ~Sr-Ni)HPO4
catalyst having a surface pH of 5.4-7Ø
USE OF CATAL~STS
Examples 25-62
Each o~ the prcducts prepared in accordance with
Examples 1 through 22 and Controls 1 and 3-5 above were
evaluated for catalytic performance for the preparation
of TEDA with either a feed mixture containing hydroxy-
ethylpiperazine (HEP) or N-aminoethylpiperazine (AEP)
in accordance with the following test procedure:
(a) 20 cc (approximately 6.2g.) of the
catalyst was loaded into a 3/4 " diameter
stainless steel reactor.
(b) The reactor was placed in a conventional
tube furnace such that the catalyst bed was near
the furnace center and therefore could be heated
to a constant and uniform temperature.
(c~ The catalyst bed temperature was raised
to a temperature of 340-400C over a period of 15
to 30 minutes while a small flow of gaseous nitroyen
was maintained through the reactor to aid in the
removal of water vapor.
(d) A feed mixture containing HEP and water
such that the organic component made up 60% of the
mixture was then allowed to flow through the
catalyst bed at a rate of 6.5-7.0 cc/hour; the
nitrogen flow was discontinued.
(e) The catalyst bed temperature indicated
in the tables set forth below was maintained
during the run and the product samples were collected
and analyzed. Analyses were performed using
well-established gas chromatographic techniques.
4Z8
The yields of TEDA and piperazine (PIP)
as well as the conversion obtained from the catalysts
of Examples 1-22 in Table 1 can be compared with
those of Control Catalysts 1 and 3-5 in Table 2
below.
16
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The results set forth in Table 1 where the catalysts
of the examples demonstrate a unique ability to convert
over 50 ~ol.% of the feed to prod-~cts the majority of
which is TEDA. Depending on the particular feed stock,
the yield of TEDA ranged from 6% in the worst case
using Ni to approximately 84% in the best mode using 1
part SrHP04 to 3.5 parts BaHP04, see Example 1 above.
The former being the use of NiHPo4 with an aminoethyl-
piperazine feed. When the feed over NiHPo4 was changed
to hydroxyethylpiperazine, the yield increased 6 fold
with a corresponding increase in the conversion from
appro~imately 57% to 82%. The BaHPO4 catalysts per se
did not meet the criteria for an effective catalyst for
the conversion of HEP to TEDA. However, when approxi-
mately four parts of this catalyst were combined withone part of SrHPO4 as in the Example 2, the yield of
TEDA and the conversion increased based on a synergistic
effect over that of the SrHPO4 catalyst.
Exam~le 63
The catalyst of Example 23 was tested in the
conversion of crude HEP to TEDA. The reaction was
carried out at atmospheric pressure, at a liquid hourly
space velocity of 0.3 and at the temperatures indicated
in Table 3 below.
TABLE 3
Initial After 78 DaYs
Bed Temp., C 360 368
HEP Conversion, wt. % g9+ 99+
TEDA Yield, wt. % 40.5 43.0
PIP Yield, wt. % 13.5 18.5
Example 64
The ca~alyst of Example 23 was tested for the
conversion of diethanolamine to TEDA. The test was
carried out at 370C using a feed consisting of diethan-
11'9f342B
21
olamine and water (2.0 to 1.0 mole ratio) pumped intothe reactor at a rate of 4.4 liquid cc/hr along with
helium diluent at a rate of 25 cc/minute. The diethanol-
amine was in completely converted to TEDA, as the only,
i.e. about 26 mol. %, recovered product.
Example 65
A 64% by weight solution of N-aminoethyl piperaæine
in water was passed over a catalyst composition consisting
essentially of SrHP04 at 380C and at a liquid hourly
space velocity of 0.3 volumes of liquid per volume of
catalyst. In a first pass operation there was obtained
96.8 mol. % conversion of the feed compound, obtaining
a yield of 34.8% by weight (40.1 mol. %) TEDA and 27.1%
by weight ~40.6 mol. %) PIP.
Other typical condensation reactions in which
SrHP04 may be employed as a catalyst include the formation
of amines by amination of the corresponding alcohols
with ammonia and the formation of polyamines from
glycols and diamines.
It is believed that the key to the properties of
the SrHP04 as a highly selective catalyst is due to the
presence of a specific structure, which provides a
narrow range of acidity. This narrow acidity range-
displayed by SrHP04 may be optimum for promoting certain
types of acid catalyzed reactions, in contrast to such
catalysts as alumina, silica-alumina and the like which
have acid sites of widely varying strength, and hence
show relatively low selectivity for the desired reaction.
Example 65
Diethyleneglycol was passed over the SrHP04 catalyst
of Example 23 in the presence of water at a temperature
of 370C and at a contact time of 6.7 seconds. The
feed contained 57 v~l. % diethyleneglycol and 43 vol.
% H20. The reaction product contained 33 wt. % 1,4-dioxane,
corresponding to a yield of 47 mol. %.
22
The addition of water to the organic feeds may be
desir~ble to prevent loss of catalyst activity as a
result of dehydration of the SrHP04 to the pyrophosphate.
Example 67
The SrHP04 catalyst of Example 23 was tested for
the conversion of 1, 4-butanediol to tetrahydrofuran.
The test was carried out at 350C using a feed consisting
of 20 percent by volume of water and 80 percent by
volume of 1, 4-butanediol pumped to the tubular reactor
at a rate of 4.4 cc/hr. Helium dilutent was also fed
at the rate of 30 cc/min. Under these conditions, the
diol was completely converted to tetrahydrofuran.
Example 68
-
The CaHP04 catalyst of Example 5 was recovered in
a fine, powdered state and was deposited on inert
alumina spheres instead of the silica-alumina spheres
in the same manner as set forth under Example 3. 20 cc
of the resulting coated alumina contained 2 gms. of
CaHP04. The performance of this catalyst was evaluated
for the preparation of an alipathic secondary amine
with a feed mixture of monoethylamine (EA) and methanol
using the general procedure used in Examples 25-62 for
the preparation of TEDA. Specifically, 1 mol. of the
primary amine and 1 mol. of the alcohol were reacted at
350C, 1 atmosphere pressure ancl an LHSV of 0.15/hr.
The conversion was 23.9 mol. % of the ME to the secondary
aliphatic amine. The yield of methylethylamine (MEA)
was 16.5 mol. % of the amine feed with a selectivity of
69 mol. %. The only oth~r product in any significant
c~antity was dimethylethylamine (DMEA) with a yield of
5.4 mol. % and a selectivity of 22 mol %.
34~
23
Example 69
The procedure of Example 68 was followed except
that 1 mol. of die~lylamine (DEA) was substituted for 1
mol. of EA. 27.6 mol. % of this primary amine in the
feed was convexted for the most part to a single secondary
~mine, i.e. diethylmethylamine (DEMA) and a trace
amount of a tertiary amine, i.e. triethylamine. The
yield of DEA fed was 23 mol. % DEMA with a selectivity
of 83.3 mol. %.
Examples 70-71
3 grams of the La2(HP04)3 catalyst of Example 9
were coated onto alurnina spheres and the procedures of
Example 60 and 69 were followed. The results from
these reactions are summarized in Table 4 below.
Examples 72-73
The SrHP04 catalyst of Example 6, was used to
convert methanol and either monoethylamine (Example 72)
or diethylamine (Example 73) in the same manner set
forth under Example 68.
The results of these Examples 72-73 are summarized
and compared with the other Examples 68-71 in Table 4
below.
TABLE 4
ALIPHATIC AMINE PROD~CTION
Amine Yield, mol. % Selectivity, Mol. % Conversion
Feed MEA DMEA DEMA MEA DMEA DEMA _ Mol. %
Example
68 EA 16.5 5.4 - 69 22 - 23.9
69 DEA - - 23 - - 83.3 27.6
30 70 EA 27 25 - 47 44 - 57
71 DEA - - 39 - - 66 59
72 EA 22 17 - 55 17 - 40
73 DEA 1.4 6.9 41 2.8 13.8 82 50
~7)
Dimethylethylamine.
~8~2~3
24
The data of Table 4 above illustrates the unexpect-
edly high selectivities to the corresponding aliphatic
amine without the formation of the corresponding by-
products of thermodynamic amine equilibration. The
relatively low conversion to product of Examples 6B-71
can be attributed to the fact that only 2 gms. of
CaHPO4 or 3 gms. La2(HPO4)3 were used in Examples 68-71
in comparison to about 20 gms. of SrHP04 that were used
in Examples 72 and 73.
Example 74
The CuHPO4 catalyst of Example 13 was coated onto
alumina spheres and the procedure of Example 68 was
followed except that 1 mol. of a~onia was substituted
for 1 mol. of EA. The results from this reaction were
a 65 mol. % yield of monomethylamine (MA) based on the
methanol, an 87 mol.% selectivity to MA and a methanol
conversion of 75 mol. %.
ExamPle 75
The La2(HPO4~3 catalyst of Example 9 was deposited
on alumina spheres and the procedure of Example 74 was
followed. The results were yields based on the methanol
in the feed of 13 mol. % trimethylamine (TMA), 2.8 mol.
% dimethylamine (DMA) and 3 mol. % monomethylamine
(MA), selectivities based on the methanol of 69 mol. %
TMA, 14.9 mol. % DMA and 16 mol. % MA, and a methanol
conversion of 52 mol. %.
It has also been found that MgHPO4 and BaHPO4 were
effective in selectivity converting amines to the
corresponding higher molecular weight amine.
Examples 76-82
~ he ~Sr-Ni)HPO4 catalyst of Example 24 was evaluated
for the preparation of N-(2-dimethylaminoethyl)morpholine
~DMAEM) with a feed mixture of morpholine (MOR), dimethyl-
2~3
ethanolamine (DMEA), distilled water, hydrogen andhelium in the amounts shown below in Table 5 using the
general procedure used in Examples 25-62 for the TEDA
preparation. Specifically the condensation reaction
was carried out at 340C, 1 atmosphere of pressure and
an LHSV in the range of 0.31-0.44~1r. as shown in
Table 5 in the presence of 20 cc. of the (Sr-Ni)HPC4
catalyst granules.
Examples 83-86
The SrHPO4 catalyst of Example 6 was used in place
of the (Sr-Ni)HPO4 catalyst of Example 24 and the
condensation reactions were carried out in the same
manner as described under Examples 76-82. The results
of these runs are summarized and compared with the
Examples 76-82 feed, yield and conversion data in
Table 5 below.
TABLE 5
DMAEM PRODUCTION
Example Feed, LHSV, Yield, Mol. % Conversion,
20 _ Vol. % hr. MOR Mol. %
76 MOR 60 , 0.31 100 16
DMEA 20
H O 20
H2e (20 cc/min)
H2 (20 cc/min)
77 MOR 60 0.44 63 23
DMEA 20
H O 20
He (20 cc/min)
H2 (20 cc/min)
78 MOR 40 0.31 53 43
DMEA 40
H O 20
He (20 cc/min)
H2 (20 cc/min)
~9~34Z~
26
TABLE 5 - (Cont'd)
DMAEM PRODUCTION
Example Feed, LHSV, Yield, Mol. % onversion,
Vol. %h -1 MOR Mol. %
79 MOR 40 0.21 58 48
DMEA 40
H2O 20
He (20 cc/min)
H2 (20 cc/min)
MOR 20 0.31 52 60
DMEA 60
H O 20
He (20 cc/min)
H2 (20 cc/min)
81 MOR 20 0.21 58 75
DMEA 60
H O 20
He (20 cc/min)
H2 ~20 cc/min)
82 MOR 40 0.31 97 21
DMEA 20
H O 40
H2e (20 cc/min)
H2 (20 cc/min)
83 MOR 40 0.21 42 32
DMEA 20
H2O 20
He (20 cc/min)
84 MOR 40 0.21 37 28
DMEA 40
H O 20
He (20 cc/min)
MOR 60 0.21 43 22
DMEA 20
H2O ~
He (20 cc/min)
86 MOR 20 0.21 33 45
DMEA 60
H O 20
H2e (20 cc/min)
42~
~7
Examples 87-91
The catalyst product of Example 1 was evaluated
for cataly-tic performance for the preparation of morpho-
line from diglycolamine at 1 atmosphere in accordance
with the following test procedure:
(a) 10 cc (approximately 3.1 g.) of Sr~O4
was loaded into a 3/4 " diameter stainless
steel reactor.
(b) The reactor was placed in a conventional
tube furnace such that the catalyst bed was near
the furnace center and therefore could be heated
to a constant and uniform temperature.
(c) The catalyst bed temperature was slowly
raised to a temperature of 250C over a period of
15 to 30 minutes while a small flow of gaseous
helium was maintained through the reactor in three
of the examples.
(d) A feed mixture containing DGA and water
(excépt for Examples 88 and 90) in the ratio set
forth in Table 6 below was then allowed to flow
through the catalys-t bed at an LHSV of 0.21 to
0.88; the helium flow was continued through the
run ~except for Examples 90-91).
(e) The catalyst bed temperature indicated
in Table 6 below were maintained throughout -the
run and the product samples were collected and
analyzed. Analyses were performed using well-
established gas chromatographic techniques.
The operating conditions and yields
obtained from the catalyst of Example 1 are summarized
in Table 6 below.
342~
28
Table 6
Example 87 88 89 90 91
F~ed, DGA/H20, Vol. % 80/20100~080/20 100/0 50/50
Helium Diluent, cc/min. 34.5 34 28.5 None None
Temp., C 320 320 370 350 330
Contact Time, sec. 12 55 12 13 22
LHSV 0.21 0.21 0.44 0.88 0.21
Yield of Morpholine, mol. ~ 85 63 37 46 75
Selectivity to Mo~pholine % 85 74 37 57.5 75.6
Conv. of DGA mol. %100 85 100 80 99
Dioxane Yield, mol. % ~-- less than 1%
In each of the Examples 87-91, it was unexpectedly
found that DGA could be to selectively converted to
morpholine without the conversion of appreciable quantities
of dioxane, tar or other high molecular weight components.
It would be expected that the reaction product from DGA
conversion would contain substantially equal amounts of
dioxane and morpholine.
~,
` Examples 92-118
- The test procedure set forth in Examples 87-91 was
followed in Examples 92~118 in the presence of the
Example 1 catalyst. Table 7 below sets forth the feed
mixture, operating conditions and the product yields
fQr each example.
.,
29
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