Note: Descriptions are shown in the official language in which they were submitted.
~ 3 ~ 3
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This invention relates to an improved
process for making ether carboxylic acids and more
particularly to processes for makin~ ether carboxylates
prepared by a calcium ion catalyzed reaction in
alkaline medium of maleic acid salt and a carboxylate
salt containing a reactive hydroxyl group. Such
reactions are of the type typically referred to as
Michael condensation reactions.
Polycarboxylic acids have long been known to
be useful, usually in the salt form, as detergent
builders or sequestrants. Also, ether carboxylates
useful as metal sequestering and detergent builders
have been known and are most desirable for their
beneficial effects in laundering applications.
While many carboxylate compounds in the
prior art have utility as a builder or sequesterant in
laundry detergent formulations, it has been found that
certain ether carboxylates are more attractive and
cost effective for such utility. In the field of
detergent builders and se~uesterants for laundry
detergent formulations low cost of the components is
extremely important because it is in a very competitive
market. While many ether carboxyla-te compounds have
been found to be useful there is needed more economical
manufacturing processes whereby such compounds can be
economically produced in large volume.
One example of ether carboxylates is a
mixture of polycarboxylic acids or salts thereof,
particularly the sodium salts, of l-hydroxy-3-oxa-
1,2,4,5-pentane -tetracarboxylic acid (HOPTC) and
3,6-dioxa-1,2,4,5,7,8-octane hexacarboxylic acid
(DOOHC) which is highly useful in detergent formula-
tions as a sequesterant or builder. This mixture is
.~
~3~2~23
-2- 05-21 ( 6906 )A
prepared by reaction of a combination of D,L-tartrate
salts with maleate salts catal~zed by calcium ions.
The production of builders or sequesterants
for the detergent industry usually involves large
5 volumes of materials. Also, the reaction of oryanic
materials generally provides by-products unwanted or
undesired and cost is incurred for their removal.
The unwanted by-produc-ts often become waste products
requiring disposal thereby presenting environmental
issues. It is therefore desired to have processes
for manufacture which reduce or eliminate by-product
disposal re~uirements and associated costs, particu-
larly in large scale production such as is encountered
in the production of builders or sequesterants for
use in detergent formulations.
SUMMARY OF THE INVENTION
In accordance with this invention, there is
provided a process for preparin~ HOPTC and DOOHC
by the reaction of the salts of maleic acid and a
tartaric acid (solids content~ said reaction catalyzed
by calcium ions and conducted under alkaline conditions
wherein unwanted fumarate by-product is reduced. Such
reduction is achieved by concentrating the reaction
mixture to a solids content of above 60%, by weight,
prior to initiation of the reaction. More preferably,
the reaction mixture is concentrated by removal of
water to a range of from about 62% to about 70% and
more particularly to about 62% to about 65% solids.
While the process of this invention achieves
the objective of reduc~d by-product formation in the
ranges of solids content as noted above, it is most
desired to operate the process of this invention in the
preferred range 65% solids content or below because
calcium tartrate has been found -to precipitate in
smaller crystals at higher solids content concentra-
tion. While small crystals are not less pure,
~3:~ 2~3
-3- 05-21 ( 6906 )A
processin~ steps such as fil-tration, etc. become more
difficul-t with smaller crystals.
various embodiments oE -this invention may be
employed to achieve the concen-tra-tion of the reaction
mixture which has been found to provide advantageous
reduction of by-product. In one embodiment concentra-
tion of the reaction mix-ture is provided by holding
the reaction mix-ture for a period of time at moderate
temperature while sweeping the reactor with an inert
gas such as air to remove water. In another embodiment,
the reaction mixture is heated to an elevated temp-
erature such as the reaction tempera-ture or even
boiling prior to adding the required amount of base -to
initiate a reaction thereby removing water at a more
rapid rate. I-t is preferred to subjec-t the reaction
mixture to reduced pressure -to achieve efficient
concentra-tion oE the reaction mixture prior to adding
-the re~uired amount of base to initiate the reaction.
Because there are provided various recycle
systems whereby unreac-ted starting materials are
recovered and reused in subsequen-t reactions process
efficiency is maintained even at high reactor solids
concentration.
DETA I LED DE S CR I PT I ON OF THE I NVENT I ON
Calcium catalyzed reactions for the produc-
tion of ether carboxylates are known. A typical
example of such a process is disclosed in U.S.Patent
4,663,071 to Bush et al.
The U.S. Pa-tent discloses a process for
preparing a mixture of HOPTC and DOOHC referred to
above. In such process the mixture is obtained by
the reaction of maleic acid and tartaric acid salts.
This disclosure is a typical example of the reaction
of maleic acid with tartaric acid said reaction being
catalyzed by calcium ions and conducted in alkaline
,~
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medi~m. Such reactions are known in the art as
Michael condensation reactions. It is typical of the
Michael condensation reactions -to provide the most
effective e~uilibrium state for -the production of the
desired compound or mixture by control of the reactant
ratio.
It has been found that D,L-tartaric acid
salts possess different solubility characteristics
than do either the D- or L- isomers such that the
D,L- isomer conveniently precipitate from solution at
a pH in the range of from about 7 to about 9.5 while
the calcium salts of HOPTC and DOOHC remain in solution
and can be purified for use as a builder combination
in detergent formulations.
The recovery of unreacted maleate salts from
calcium catalyzed reactions of maleic acid salts with
salt of tartrate salts in alkaline medium is conveni-
ently achieved by acidifying the reaction product so
as to reduce the pH to within the range of about 4 to
below about 6.
A particular advantage of the process of
this invention, whereby unreacted maleate salt is
recovered, is the abilit~ to regulate the reac-tant
ratios more freely sirlce convenient recovery and
recycle is possible. Loss of unreacted maleate salt
is insignificant and its reco~ery economical, parti-
cularly when maleic acid is employed to reduce the
pH of the reaction product of the condensation
reaction.
In accordance with one embodiment of this
invention the unreacted D,L-tartrate and maleate
starting materials are removed by precipitation ~rom
the reaction mass prior to the removal of calcium from
the system. Specifically, calcium D,L-tartrate and
mono sodium malea-te are precipitated from the reac-tion
mix-ture by adjustment of the p~l o~ the reaction
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solution in two steps. The precipitate of calcium
D,L-tartrate and mono sodium maleate is then returned
to a subsequent condensation synthesis reaction. It
has been found that the small amounts of by-products
such as malate and fumarate and residual amounts of
HOPTC and DOOHC trapped in the precipitate are not
deleterious to the use of this recycled precipitate in
subsequent condensation synthesis reaction.
FORMATION OF HOPTC/DOOHC MIXTURES
The first step is the synthesis of
HOPTC/DOOHC mix-tures by the reaction in aqueous medium
of maleate and D,L-tartrate reactants comprising both
monovalent cation and calcium salts of maleic acid and
D,L-tartaric acid. As noted above, the total amount
of maleate plus D,L-tartrate reactants in the aqueous
reaction mixture will generally range from about ~0%
to about 70% by weight of the mixture, more preferably
from about 55% to about 65% by weight. Calcium maleate
is provided by first reacting maleic acid with calcium
hydroxide or calcium carbonate the later preferably
provided at least in part by recycle from earlier
reactions. The D,L-tartrate is typically provided by
epoxidation of maleic acid (from maleic anhydride) in
the presence of a catalyst and hydrogen peroxide by
known means followed by hydrolysis of the epoxide.
one portion of the D,L-tartaric acid employed in the
synthesis reaction is -taken from the neutralized
hydroxylation reaction product. Another portion of
the needed D,L-tartrate is provided by the recycled
calcium D,L-tartrate provided by earlier reactions as
will be more fully described below.
The molar ratio of maleic acid -to D,L-tartaric
acid in the reaction mixture provided from all the
sources noted above will generally range from about
0.5:1 to 8:1, more preferably from about 0.8:1 to
about 1.2:1. The ratio of reactants will control
the ratio of HOPTC/DOOHC in the final product.
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As noted above the synthesis reaction takes
place in the presence of a catalyst comprising calcium
ions. To provide the necessary amount of calcium
cation, several sources can be used. Calcium mal~ate,
prepared from recycled calcium carbonate and maleic
acid, may provide one calcium ion source. Previously
used but unreacted calcium D,L-tartrate recovered in
the process of this invention provides another major
calcium ion source. Any additional needed calcium ions,
usually a very small amount, is typically provided
by an additional calcium ion source such as calcium
hydroxide added either as a solid or as a slurry.
Other water soluble calcium salts can be employed, but
calcium hydroxide possesses the additional advantage
of supplying needed hydroxide ions. The total amount
of calcium ion present provides a total molar ratio of
calcium cation to maleate of 1:1. However, the amount
of calcium cation can vary greatly and may be such
that the ratio of moles of calcium cations to total
moles of maleic and D,L-tartaric acids in solution can
approach, but be less than 1.
The hydroxide o~ a monovalent cation is also
essentially added to the reaction mixture as a source
of alkalinity. This neutralizing agent is usually
added in an amount such that the ratio of moles of
monovalent cations to total moles of D,L--tartaric acid
plus the moles of maleic acid minus the moles of
calcium cations ranges from about 2.1:1 to about
3.8:1. More preferably this ratio ranges from about
2.2:1 to about 3.3:1. The monovalent cation-
containing neutralizing agent can be any hydroxide
which upon addition to water yields monovalent
n~utralizing cations in solution. Such neutralizing
agents include, for example, alkali metal, ammonium or
substituted ammonium hydroxide. Sodium hydroxide is
highly preferred.
h, ;3
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Su~ficient neutralizing agent which, in
combination with calcium hydroxide, is added to the
synthesis reaction mixture to insure that the reaction
mixture is over-neutralized. Thus, the reaction
mixture in the process of this invention will general-
ly have a pH within the range of from about 8.5 to 13,
more preferably from about 10.5 to about 12.5. The
aqueous reaction mixture, after the appropria-te
amounts of reactants, catalysts and n~utralizing agent
are combined, is maintained at a temperature of from
about 20C. to about 120C., preferably from about
70C. to about 95C. for a period of time sufficient
to form a reaction product mixture containing the
desired amounts of ~OPTC and DOO~C. Reaction times of
from about 0.5 -to 50 hours, more preferably from about
1 to 4 hours, would generally be suitable for realiz-
ing acceptable yields of the 2 components of the
desired mixture. Reaction time is highly affected by
temperature whereby higher temperature increases the
rate of reaction. The mole ratio of reactants in the
reaction mixture, that is, tartrate, maleate, calcium
and free hydroxide is 1.1/1.0/0.85/0.50 respectively.
At completion of the reaction the mixture is
quenched with water to cool it to a temperature in the
range of 80C. Addition of water also improves the
handling of the viscous reaction mass.
MONOSODIUM MALEATE AND D, L-TARTRATE PREC IP ITA~ION
The reaction mixture containing mixed salts
of HOPTC and DOOHC also contains relatively large
amounts of unreacted maleic and tartrate acid salt.
These salts are recovered and recycled to provide
higher efficiency of utilization of this valuable raw
material.
The recovery of these salts is achieved by
a two step method of lowering of the pH of the reaction
mixture whereby sodium hydrogen maleate or monosodium
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maleate and calcium -tartrate precipitate. In the
preferred embodiment the reaction mixture is cooled
and diluted with water. An acidic material such as
sulfuric acid, or an organic acid such as formic acid
is combined with the reaction mixture in sufficient
amount to bring the combined synthesis mass and acid
to an initial pH in the range of from abou-t 6 to
about 9, preferably slightly below 7. Then, with
further addition of suitable acid the pH of the
reaction mixture is relatively more rapidly acidified
further to a pH in the range of from about 4.5 to
below 6, preferably to about 4.8 -to about 5.2.
Any number of acidic materials can be
employed to lower the pH of the reaction mixture.
Combinations of acidic materials may also be employed.
Typical examples of such acids are sulfuric acid,
hydrochloric acid, nitric acid, formic, acetic,
propionic, butyric and D,L-tartaric, carbonic,
phosphoric, sulfonic, sulfurous, boric, phosphorous,
adipic, benzoic, citric, fumaric, glycolic, malic,
maleic, malonic, oxalic, succinic, sorbic, nitrilo-
triacetic, long chain fatt~ acids, etc.
In the process of this invention, the acid
substance may be added to the crude reaction mass.
Alternately, the reaction mass may be added to a heel
containing the acid substance~ In a further process
of this invention, the acid substance and the reaction
mass may be added concurrently into a mixing vessel.
Sufficient water is added to the reaction mass and/or
acid material so that the final concentration of
desired ether carboxylate in the completed mixture
is about ~0%.
Sufficient acid is added to reach a
preferred pH of near 5.0 and the precipitated reaction
mass is cooled to below 50~C., preferably from just
above the freezing point of the mixture to about
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40C. most practically to from about 20C. to about
30C. to obtain usable filtration rates in large scale
production. In a preferred mode, cooling the reaction
product from the 80C. reaction temperature to 65C.
over 30 minutes is ~ollowed by slow cooling to from
about 30C. to about 40C. The suspension is then
allowed to rest for about 30 minutes. The slurry is
preferably cooled slowly with mild or slow agitation
so as to grow particles which can be filtered in an
appropriately short time. Other methods of acid
addition such as are noted above can also be employed
with appropriate adjustment of precipitation conditions.
In the process of this invention wherein
HOPTC and DOOHC are produced it has been found that
both unreacted starting acids, D,L-tartaric acid and
maleic acid can be recovered in their salt ~orm.
Also, it has been found that the calcium salt of
D,L-tartaric acid precipitates from the reaction
mixture at a pH in the range of from about 7 to about
12 and is typically of smaller crys-tal habit than
the maleate salt. However, according to this
invention the two acid salts may be precipitated
in a two step procedure which produces globular
particles including both acid salts.
When a mixed acid solution is employed to
precipitate tartrate and maleat~ in the process o~
this invention, the acids may be added either
sequentially or concurrently. In one mode of
operation, the reaction mass at a temperature of about
80C., is added to a heel of aqueous acid, typically
formic acid, and then a solution of maleic acid
is added to the partly neutralized reaction mass.
It has been found that when the pH of the
reaction mixture is in the abo~e-stated range calcium
D,L-tartrate precipitates when such mixture is
diluted with water or cooled to a temperature in the
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range of from about at least above freezing to about
70C. The reaction mixture is typically diluted with
water in amounts up to about 200 percent by weight.
Greater dilution may be accomplished but additional
amounts o~ water are not beneficial due to increased
solubility or the salts being precipitated and also
would probably require removal later. Dilution of
the reaction mixture by about 30 to about 80 percent,
by weight, is typical and usually both cooling and
dilution are employed to provide maximum amount of
tartrate precipitation.
In the process of this invention, there is
employed, in conjunction with the above-noted stepwise
reduction of pH, the use of crystal seeding whereby
small particles of calcium tartrate/monosodium maleate
recovered from previous production of mixtures of
HOPTC and DOOHC are added to the reaction mixture.
Thus, when the temperature of the reaction mixture is
first reduced to about 80C. by diluting the reaction
mixture as noted above, crystals of calcium tartrate/
sodium maleate from a previous batch are introduced
into the reaction mixture. Amounts of crystals in the
range of up to about 30 percent of the expected weight
of the fresh precipitate may be added. When crystals
are employed from the previous filter cake there is
provided seed crystals of monosodium maleate. These
crystals dissolve leaving calcium tartra-te. However,
the dissolved monosodium tartrate buffers the solution
to a pH of about 6. When the pH is reduced in the
second step dissolved monosodium maleate begins to
precipitate below about 5.~.
Following the addition of crystals, the pH
of the reaction mixture is then slowly reduced by
combining the reaction mixture with acid to provide a
reaction mixture having a pH in the range of about 7
to about 9 without prior seeding as described above.
:~3~23
~ 05-21~906)A
However, with seedin~ as noted above it is more
preferable to reduce the pH of the reaction mixture
in the first step of pH reduction to from about 6 to
about 7. While lowering the pH of the reaction
mixture i~ is also cooled to a temperature in the
range of from above the freezing point of the mixture
to about 50C. It has been surprisingly found that,
in the second step of pH reduction when the pH of the
reaction mixture is reduced rapidly, or over a brief
period of time, for example up to about one minute to
about 10 minutes, unexpectedly large agglomerates of
the combined salts of calcium tartrate and monosodium
maleate are created. Throughout pH reduction, cooling
is required to maintain the temperature of the reaction
mixture in the desired range of from above freezing to
about 35C. As noted above, the reaction mixture is
held for about 30 to about 40 minutes after final pH
reduction to allow crystal formation. It is preferred
to allow a short rest period between steps whereby -the
reaction mixture, at a pH above about 6, rests for
about 10 minutes before the second step of pH reduction
is performed. The larger agglomerates are more easily
separated from the reaction mixture.
Removal of the precipitated acid salt may
take any form practical and typically is performed by
continuously drawing the slurry from the precipitator
to a belt or drum filter or centrifuge. Other forms
of removal such as decantation, etc. may also be
employed. The filtrate contains the ether carboxylate
in salt form. In a preferred embodiment the filtrate
is transferred to another precipitator for removal of
the calcium cations in the form of calcium carbonate.
In the production the HOPTC/DOOHC mixture
filter cake is discharged and, in one embodiment,
reslurried with water. The slurry is ~ecycled directly
or indirectly to the synthesis reactor to supply a
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portion o~ the required D,L-tartrate and maleate
salts. Pxeferably the recovered maleate salt and/or
D,L-tartrate salt is slurried with water and mixed
with calcium maleate for recycle into the synthesis
reaction.
CALCIUM CARBONATE PRECIPI TATION
After removal of the insoluble acid salt
or salts as described above, the ~iltrate from such
operation is recovered and purified for use as deter-
gent builder. In a preferred embodiment, calcium is
removed either batchwise or preferably continuously.
Typically, the filtrate from the above-mentioned step
is pH adjusted with a base, preferably sodium hydroxide,
as it is being fed into a calcium carbonate precipitator
to bring the pH of the solution into a range of from
about 10 to about 12, preferably from about 10 to
about 10.5. The pH adjustment may be performed either
in the precipitator or in a separate vessel if desired.
The pH adjusted material is maintained in -the range of
from about 75C. to about 110C., preferably at about
90C. to 100C. Concurrently a solution o~ a basic
carbonate, preferably sodium carbonate, preferably at
a concen-tration of about 25%, is added to the precipi-
tator to provide an overall mole ratio of carbonate to
calcium o~ 1.3:1.
Alternatively, calcium carbonate is removed
by increasing the mole ratio of carbonate ion to
calcium ion without change in pH.
Although this invention is described with
respect to carbonate precipitation using the preferred
sodium cation, it is to be understood that other
suitable cations may also be employed to obtain
precipitation of calcium carbonate. Other cations
useful in the process of this invention include
potassium, ammonium or organo substituted ammonium.
Other salts may be employed to obtain the calcium
~3~ 2~
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carbonate precipitate and includes sodium bicarbonate
and mixtures of carbonates and bicarbonates.
During the precipitation of calcium carbonate
it is preferred that watex is continuously removed
from the slurry to maintain the concentration of the
organic acid salts in the range of from about 30% to
about 50% by weight. Filtration of the precipitated
calcium carbonate may take any form practical and
typically is performed by continuously drawing the
slurry from the precipitator to a centrifuge or to a
belt or drum filter. The filtrate contains the
desired ether carboxylate mostly as the alkaline salt
along with minor amounts of raw material and by-products.
In the preparation of HOPTC/DOOHC mixtures, the
by-products comprise typically less than ~0% by weight
of the HOPTC and DOOHC present.
The wet cake from the separation is mechani-
cally reslurried with water to form an approximately
50% calcium carbonate slurry for recycle to the
synthesis reac-tion. The recovered carbonate may be
added directly to the ether carboxylate synthesis
reactor or together with recovered, unreacted tartrate
and maleate. Preferably, the recovered calcium carbonate
is converted to calcium maleate in a separate vessel
before return to the synthesis reaction.
CALCIUM MALEATE FORMATION
Before introduction into the synthesis
reaction, the calcium carbonate precipitate obtained
from the product as described above is preferably
converted to calcium maleate by reac-t.ion with maleic
acid. Prefera~ly, the maleic acid is prepared in
situ. In one embodiment, the maleic acid is prepared
by charging molten maleic anhydride to water heated
to 65C. to 75C. After hydrolysis of the maleic
anhydride to maleic acid is complete, the slurry of
calcium carbonate solids is added at a rate slow
2 .-~ 2 ?3
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enough to avoid uncontrolled foaming due to the
evolution of carbon dioxide. During the addition
of calcium carbonate the reaction mass is heated to a
temperature in the range of from about 90C. to about
100C. and preferably to about 95C.
In the production of HOPTC and ~OOHC it is
preferred that calcium D,L-tartrate and monosodium
maleate slurry obtained from the tartrate/maleate
removal step is added to the calcium maleate while
heating to a boil at atmospheric pressure. The
mixture is held at boiling for about 15 minutes to
ensure conversion of all of the calcium carbonate to
the maleate. The mixture is then charged to the
synthesis reactor for the preparation of additional
HOPTC and DOOHC. During transfer to the synthesis
reactor water may be evaporated to reduce volume.
Although the above described process follows a
particular scheme, it is obvious that other schemes or
flow charts may also be followed. For example, hold
tanks, mixing tanks and transfer tanks may be employed
which are not described above. Other variations will
occur to those knowledgeable in the art.
EXTRACTION
The filtrate obtained from the procedure to
remove calcium carbonate is purified by extraction
with methanol and water. Such purification in the
production of HOPTC and DOOHC mixtures is shown in
U.S. Patent 4,633,071 referred to above.
According to such patent the solution
obtained after removal of calcium carbonate is
thoroughly mixed with methanol. After settling, two
layers ~orm because the desired solution of HOPTC and
DOOHC is less soluble in methanol than the impurities
to be removed. The undesired solution is decanted
and stripped of residual methanol. The residue is
dissolved in water and extracted again with methanol.
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After purification the product is
concentrated so as to provide the desirable concentra-
tion of ether carboxylate solution fox use as detergent
builder or sequestrant. The concentrated material
5 may also be dried by ~ny typical means such as by
spray drying, etc. to provide granular or particulate
material which is the form traditionally employed.
To further illustrate the process of the
present invention there is desGribed below non
limiting preferred em~odiments. In the following
examples all percentages are by weight unless
otherwise noted.
EXAMPLE 1
Into a round bottom 1ask equipped with a
thermometer, addition funnel, condenser and mechanical
stirrer there were placed 39.4g of maleic anhydride
and 200g of water. The mixture was heated to 70C.
to form maleic acid to which was added 50.lg of
calcium carbonate. Then wet filter cake, 350g, from
a previous run together with 100g of water were
added to the flask. The w~t cake contained the
following in weight percent:
Disodium meso tartrate - O.3~1
Calcium D,L-tartrate - 19.62
Disodium Malate - 1.27
HOPTC - 13.24
DOOHC - 0.7
Monosodium Maleate - 15.71
After addition of wet cake 62.95g of
D,L-tartaric acid and 550g of disodium tartrate
solution obtained by hydrolysis of epoxysuccinate
were added to the reaction. This mixture was heated
to 90C. with stirring. Air was swept through the
reactor to remove about 760g of water during a period
35 of 70 minutes after the reaction mass reached 90C.
Then 127.9g of sodium hydroxide, 50% solution, was
-16- 05-21(6906)A
added to the mixture. Heating at 90C. was continued
for another 90 minutes. The reaction mixture was
quenched with 126g of water to reduce the organic
solids content from 65% to 54% thereby cooling the
reaction mass from 90C. to about 80C. The resulting
mixture, a clear solution, was then divided into 2
parts with Portion A containing 566g and Portion B
containing 280g.
A
Into this portion of the reaction mixture
40g of ~ilter cake from a previous reaction containing
both calcium tartrate and sodium hydrogen maleate
together with 160g of watex were added and the reaction -
mass held at 60C. After holding for 10 minutes at
that,temperature formic acid was added over 20 minutes
to lower the p~ to 5.9. After reducing the pH the
reaction mixture was cooled to 35C. over 30 minutes.
The reaction mixture was then held at 35C. for an
additional 30 minutes. A sample was taken for a
filtration rate test (A-l). Th~n a 40% maleic acid
solution was added to adjust the pH to 4.85 over a
period of about 5 minutes and the system again held at
35C. for an additional 30 minutes. Another sample
was taken (A-2).
B
In this portion of the reaction mixture
there were added 15g of calcium tartrate filter cake
as described above in Part A together with 80g of
water. The diluted reaction mixture was then
cooled to 35C. Then formic acid was added over a
period of 20 minutes to adjust the pH to 6. The
reaction mixture at the lower pH value was held at
35C. for 45 minutes and a sample taken for a filtra-
tion rate test (B-1). A 40% maleic acid solution was
added to adjust the p~ to 4.8 with relatively rapid
addition and the system held at 35C. for an additional
~3~2 ~
-17- 05~21(6906)A
30 minutes. Another sample was taken for a filtration
rate test ~B-2). The results of -these tests are
presented below in Table I. As shown in Table 1, the
filtration rates of both samples in Part B are much
lower than the samples in Part A. This is believed to
be due to the addition of greater amounts of crystal
seed material from the previous filter cake in Part A.
The filtration rate reported in Table I below was
measured at a cake thickness of 12.7 mm.
TABLE I
Sample A-l A-2 B-l B-2
pH during filtration 5.9 4.85 6.0 4.8
Filtration rate423711,407 1263 3259
liters/hr/meter2
The filtrates were analyzed to determine
their components. The results of the analyses are
shown in Table II below. The results indicate that
the maleate salt is mostly removed from the system
at the lower pH even though maleic acid is employed to
20 acidify the reaction mixture.
TABLE II
Analyses A-l A-2 B-1 B-2
Disodium tartrate 2.2 1.9 2.0 1.6
Disodium malate O.3 0.3 0.O O.O
Disodium maleate4.6 0.7 4.3 0.5
Disodium fumarate 1.1 1.2 1.1 1.O
HOPTC 21.0 21.5 20.4 20.0
DOOHC 3.2 3.3 3.1 3.3
~L3~2$2~
~18- 05-21(6906)A
EXAMPLE 2
(Prior Art)
A sodium tartrate solution, 385 g (analysis
below), diluted with 115 g. water was charged to a 2
liter 4-necked reactor fitted with a mechanical stirrer,
condenser, thermometer and addition funnel. In a
separate vessel, maleic anhydride, 92.5 g, was mixed
with 200 g. of water and heated to 60C. to form
maleic acid. Then 47 ~. of calcium carbonate was
added to form calcium maleate. This mixture was then
added to the reactor containing the sodium tartrate
solution. Calcium tartrate filter cake from a previous
reaction, 275 g. (analysis below) was then charged
to the reactor. 50% sodium hydroxide, 173 g, and
D,L-tartaric acid, 49.5 g, were also added to the
reactor. The analyses of these materials are given
below in Table III.
TABLE III
COMPONENT SODIUM TARTRATE CALCIUM TARTRATE FINA~
(WEIGHT %)SOLUTIONFILTER CAKEREACTION CHARGE
Tartrate 29.6 42.1 23.9
Malate 0.9 0.4 0.4
Maleate 7.3 2.7 15.2
Fuma~ate 0.5 0.7 0 3
HOPTC --- l1.1 2.5
DOOHC --- 1.1 0.2
The mole ratio of reactants at the start
of the reaction was tartrate/maleate/calcium/hydroxide
= 1.3/1.0/0.9/l.O.
The reaction mixture was stirred at 120 rpm
and heated at 90~3C. for three hours while sweeping
air across the reaction to remove water from the
system. [Final total solids concentration was
60- 65%.] At the end of the reaction, 185 g. of
water was added to quench the reaction. Then 45 g of
1312~?~
-19- 05-21(6906)A
88% formic acid and 60 g water was added and khe
reaction mixture allowed to cool to room temperature.
The final pH after the addition of formic acid was 5.2.
After filtration to remove the crystallized calcium
tartrate and sodium hydrogen maleate, the filtrate
was analyzed and the results shown below in Table IV.
TABLE IV
Com~onent Weight %
disodium tartrate 1.8
disodium malate 0.6
disodium maleate 0.4
disodium fumarate 2.0
HOPTC 28.0
DOOHC 5.7
Total diacids, 4.8% or 14.2% of ~OPTC ~ DOOHC
Fumarate, 2.0% or 5.9% of HOPTC+DOOHC
This example shows the use of a 'istandard"
procedure for the synthesis of HOPTC~DOOHC that
employs recycle of a previously produced filter cake0 of calcium tartrate and sodium hydrogen maleate.
EXAMPLE 3
The procedure of Example 1 was repeatd
except that after all the charges were added the
reaction mixture was held at 78~3C. for 1.5 hours
while removing the excess water by sweeping with air.
When the reaction mixture had reacted 60-65% solids
level it was heated to 85C. and held for an additional
hour. The reaction was treated as in Example 1.
Final pH was 5Ø The filtrate was analyzed as
shown below in Table V.
~ 3 ~ 3~
-20-05-21(6906)A
TABLE V
Component Weight %
disodium tartrate 1.3
disodium malate 0.4
disodium maleate 0.4
disodium fumarate 1.0
HOPTC 24.1
DOOHC 5.1
Total diacids, 3.1% or 10. 6% of HOPTC+DOOHC
Fumarate, 1.0% or 3.4% of HOPTC~DOOHC
This example shows that a significant
reduction of fumarate content is achieved by
concentrating the reaction mixture at a lower
temperature prior to heating to the desired reaction
temperature.
EXAMPLE 4
This example demonstrates the disadvantage
of cooling the reaction mixture before reducing the pH
by combining the mixture with acid. A reaction
mixture obtained in accordance with the procedure of
Example 1 was obtained and divided into four equal
portions of 180g, then each was querlched with 40g of
water. A heel comprising 10g of formic acid, 88%, and
40g of water was prepared for each portion.
A
One portion of the reaction mixture at
52C. was added to the acid heel thereby lowering the
pH of the mix~ure to about 6.9 while cooliny continued
over a period of about 32 minutes. Cooling was then
continued until the reaction mixture and the combined
heel reached about 34C. The maleic acid mixture,
40%, was then added over a period of about 5 minutes
with continued cooling to maintain the reaction
mixture at about 34C. and lowering the pH to 5Ø
~t~
-21- 05-21(6906)A
Globular precipitate formed and the mixture was then
filtered to recover the precipitate.
B
The reaction mixture was cooled to 43c.
before being added to the heel. The combined heel
and reaction mixture was further cooled to a
temperature of about 30C. during combination which
produced a p~ of about 7.1 after holding at the noted
temperature and pH for about 10 minutes. Maleic
acid was then added to the solution over a period
of 6 minutes lowering the pH to 5Ø The resulting
mixture was then filtered to recover the precipitate.
The filtration rate of each precipitate was
measured during filtration and the results appear in
Table III below.
TABLE VI
Cake Thickness - mm Filtration Rate - liters/hr/M2
A B
9.5 2770.3 1751.~
12.7 2077.7 1495.1
15.8 1670.7 1197.7
The data in Table III above indicates that
combining the reaction mixture with ~he acid heel at5 higher temperature improves the filtration rates.
EXAMPLE 5
A reaction mixture obtained in accordance
with the procedure of Example 1, 360g, was quenched
with 80g of water and cooled to about 80C. An acid
heel was prepared by combining 23g of 88% formic acid
and 80g of water. Into this heel was charged the
quenched reaction mixture; however, the pH was lowered,
with cooling to about 35C. as it was combined with
the acid heel in the one step whereby the pH of the
combination reached about 6.3. Maleic acid, 40%,
was added over a period of one hour r~sulting in a
-22- 05-21 ( 6906 )A
final pH of 5Ø Cooling was continued for an addi-
tional one hour and 40 minutes to obtain a final
temperature of 32C. The precipitate was recovered
by filtration and the filtration rates at the varying
filter cake thicknesses are reported below.
TABLE VII
Cake Thickness - mm Filtra-tion Rate - liters/hr/M2
9.5 1222 . 2
12 . 7 937
1015.8 774
By comparing the data presented in Tables
II and IV the improvement in product by means of
reduced by-product formation in accordance with this
invention is clearly shown.
There has been described a novel process
of general application for the production of ether
carboxylates. While the process has been described
with reference to specific compounds no intention is
made by such reference to limit the scope of this
invention unless expressly stated. Various modifica-
tions may be made in the materials and sequence of
process steps as well as process combinations which
are adapted to suit the various reactants and products
without departing from this invention.
