USOO523222A

United States Patent (19) 11 Patent Number: 5,231,222

Papa et al. (45. Date of Patent: Jul. 27, 1993
(54) ESTERIFICATION PROCESS Acid' by V. Peterka in Prumysl Potravin, vol. 27, No. 2,
pp. 115-116, (1976) (English Translation).
75) Inventors: Anthony J. Papa, St. Albans; David "Studies of the Rate of Oleic Acid Esterification with
R. Bryant, South Charleston, both of Methanol' by A. Cybulski in Chemica Stosowana, vol.
W. Va. 26, No. 1, pp. 85-97, (1982), Institute of Chem. Warsaw
(English Translation).
73 Assignee: Union Carbide Chemicals & Plastics Chapter 8 of "Sulphonation and Related Reactions" by
Technology Corporation, Danbury, E. E. Gilbert, Interscience Pub., (1965) pp. 425-431.
Conn. "Esterification of Butanol and Acetic Acid' by C. E.
Leyes and D. F. Othmer, Ind. Eng. Chem., vol. 37, pp.
21 Appl. No.: 724,811 968–977 (1945).
"Cause of the Slowdown of the Esterification Reaction
22 Filed: Jul. 2, 1991 Catalyzed by Aromatic Sulfonic Acids,' B. I. Chare
51) Int. Cli.............................................. C07C 67/08 lishvili et al in Kinetika i Kataliz, vol. 19. No. 4, pp.
52 U.S.C. ..................................... 560/265; 560/205 899-903 (1977); English Translation, pp. 715-718
58 Field of Search ................... 560/205, 265; 562/91 (1978).
Primary Examiner-José G. Dees
56 References Cited Assistant Examiner-B. Frazier
U.S. PATENT DOCUMENTS Attorney, Agent, or Firm-R. J. Finnegan
3,071,604 1/1963 Bloomfield et al. ............. 260/410.6 57 ABSTRACT
3,692.822 9/1972 Hay et al. ............ ... S60/265 An improved esterification process for producing vola
4,698,440. 10/1987 Blair et al. ........................... 560/205 tile product esters by reacting a lower linear hydro
FOREIGN PATENT DOCUMENTS carbyl carboxylic acid with an alcohol containing from
138788 4/1970 Czechoslovakia .
2 to 10 carbon atoms, in a substantially non-aqueous
193282 9/1985 Canada ................................ 560/205 medium, the improvement comprising minimizing the
009886 4/1980 European Pat. Off. . amount of acidic sulfate contained in the product ester
0158499 10/1985 European Pat. Off... by employing as the esterification catalyst a long chain
1173089 12/1969 United Kingdom . alkylbenzene sulfonic acid catalyst, the alkyl radical
1262645 2/1972 United Kingdom. containing from 8 to 20 carbon atoms, or mixtures of
such catalysts.
OTHER PUBLICATIONS
"Effect of Catalysts on the Esterification of Stearic 22 Claims, 1 Drawing Sheet
WATER
MAKEUP

14 REFENED TO
PRODUCT REACTOR
ESTER

ALCOBOL
CATALYST 3
U.S. Patent July 27, 1993 5,231,222

WATER
24 MAKEUP

30 18
7
31
22
9 Z 27 (Z)
(Z)
12
17 21
|% y

19

15

23
8

14 14 TO
REFINED
D PRODUCT
ESTER
REACTOR
19

ACD
ALCOHOL 2
CATALYST 3
 5,231,222
1. 2
derived from the esterification of the acid catalysts
ESTERIFICATION PROCESS themselves with the alcohol present in the reaction
medium. Thus the production of product esters contain
FIELD OF THE INVENTION ing as little of such acidic sulfate as possible is very
This invention relates to an improved process for desirable to the product ester manufacturer.
producing a product ester by the esterification of a SUMMARY OF THE INVENTION
lower hydrocarbyl carboxylic acid with an alcohol in
the presence of an esterification catalyst, wherein the It has now been discovered that the presence of such
improvement comprises employing as the catalyst a acidic sulfate in product esters produced by the above
10 described esterification procedure can be easily mini
long chain alkyl substituted benzene sulfonic acid.
BACKGROUND OF THE INVENTION
mized by employing as the esterification catalyst, a long
chain alkyl substituted benzene sulfonic acid.
Methods for producing a product ester by the esterifi Thus it is an object of this invention to provide an
cation of a lower hydrocarbyl carboxylic acid with an 15 improved esterification process for producing such
alcohol in the presence of an esterification catalyst are product esters wherein the amount of acidic sulfate in
well known in the art. A preferred conventional process the product ester is minimized by employing a long
for the manufacture of such product esters comprises chain alkyl substituted benzene sulfonic acid as the
esterifying the carboxylic acid and alcohol in a reactor esterification catalyst, thereby obtaining product esters
containing a substantially anyhydrous reaction medium having excellent storage stability. Other objects and
which also contains the esterification catalyst; obtaining 20 advantages of this invention will become readily appar
a volatilized product ester-water azeotrope from a dis ent from the following written description and ap
tillation column connected to the reaction vessel, and pended claims.
recovering the product ester via phase separation of the Accordingly, a generic aspect of this invention can be
product ester-water azeotrope in a separate vessel. For described as an improved process for producing a prod
instance, British Patents 1,173,089 and 1,262,645 dis 25 uct ester having the formula
close such a process using sulfuric acid or para-toluene
sulfonic acid as the esterification catalyst. Moreover, if RCOOR
desired, a dialkyl sulfate such as dimethyl sulfate or
diethylsulfate may be employed as a catalyst precursor wherein R is a hydrocarbyl radical having from 1 to 4
to form an in situ hydrolyzed catalytic equilibrium mix 30 carbon atoms and wherein R' is an alkyl radical having
ture of monoalkyl sulfate and sulfuric acid. Further from 2 to 5 carbon atoms, said process consisting essen
European Patent Publication No. 009886 also teaches tially of (1) continuously feeding substantially equino
the use of a strong mineral acid such as sulfuric acid or lar amounts of carboxylic acid of the formula
p-toluene sulfonic acid as the catalyst in such a process,
while European Patent Publication No. 158,499 advo 35 RCOOH
cates that the catalyst be an alkyl sulfonic acid of the
formula RSO3H wherein R is a C1 to C12 substituted or and an alkanol of the formula
unsubstituted aliphatic hydrocarbyl group with the
added proviso that the alkyl sulfonic acid have a desul ROH
fonation temperature in excess of 186' C., the preferred 40
catalyst being methanesulfonic acid (CH3SO3H). wherein R and R' are the same as defined above, to a
However, it has been found that the presence of reaction vessel containing a substantially anhydrous
acidic sulfate (SO42) in the product ester can be highly reaction medium that contains the carboxylic acid, alka
detrimental to the storage capabilities of such product nol, product ester, an esterification catalyst, and not
esters. For instance, the presence of even a fairly mod 45 more than about 5 percent by weight water; (2) remov
erate amount of acidic sulfate in the product ester has ing product ester and water from said reaction vessel by
been surprisingly found to be the cause of product ester distillation to a distillation column; (3) adding water to
instability with regard to unacceptable carboxylic acid said distillation column to aid in forming a product
formation via decomposition of the product ester upon ester-water azeotrope; and (4) phase separating said
storage. For example a product butyl acetate containing 50 product ester-water azeotrope in a separate vessel to
about 0.70 ppm SO4-2 and having an initial carboxylic obtain said product ester; the improvement comprising
acidity of about 0.010 percent acetic acid at 24°C., was minimizing the amount of acidic sulfate contained in
found to have increased in said acidity to 0.05 percent said product ester by employing as said esterification
after days of storage; to 0.125 percent after 43 days and catalyst an alkylbenzene sulfonic acid of the formula
to 0.175 percent after 69 days. Such high amounts of 55
acetic acid obtained upon storage would render the
stored product ester unacceptable to the customer.
The acidic sulfate found in the product ester is be
lieved to catalyze hydrolysis of the product ester back
to the carboxylic acid and alcohol starting materials
thus limiting or shortening the shelf life or storage capa
bility of the product ester. It is further believed that the wherein R" is an alkyl radical having from 8 to 20 car
source of such acidic sulfate in the product esters is bon atoms.
derived from thermal decomposition of the correspond
ing in situ formed sulfonate esters of the acid catalyst 65 BRIEF DESCRIPTION OF THE DRAWINGS
employed during the esterification process to sulfur The drawing schematically illustrates a flow diagram
oxides (e.g. SO2/SO3) which appear in the product as embodiment of the esterification process of this inven
acidic sulfate (i.e., SO42). The sulfonate esters are tion, wherein product ester and water are conveyed
 5,231,222
3
from the reactor to a distillation column, a product
ester-water azeotrope is obtained, the product ester ROH
water azeotrope is then phase separated in a decanter to
obtain crude product ester which may be refined if wherein R' represents an alkyl radical having from 2 to
desired. 5 carbon atoms. Illustrative alcohols include ethanol,
n-propanol, iso-propanol, n-butanol, iso-butanol, sec
DESCRIPTION OF THE PREFERRED butanol, tert-butanol, amyl alcohols such as 1-pentanol,
EMBODIMENTS 2-methyl-1-butanol, 3-methyl-1-butanol, and mixtures
Accordingly the subject invention encompasses the thereof, and the like. The preferred alcohols are n
carrying out of any known esterification process for 10 propanol, iso-propanol, n-butanol, and iso-butanol, es
producing a product ester, wherein an alcohol contain pecially n-butanol. It is of course to be understood that
ing from 2 to 5 carbon atoms is reacted with a hydro while it is more preferred to employ purified single
carbyl carboxylic acid containing from 1 to 4 carbon alcohol starting materials, mixtures of alcohols, prefera
atoms in the hydrocarbyl radical in a substantially anhy bly those having the same number of carbon atoms, may
drous reaction medium in the presence of an esterifica 15 be employed if desired. For example, amyl alcohol is
tion catalyst, said product ester being recovered via commonly commercialized in the form of mixed Cs
phase separation from a product ester-water azeotrope, alcohols.
the improvement comprising employing the long chain As noted above the esterification catalysts employ
alkyl substituted benzene sulfonic acid catalysts dis able in this invention are long chain alkylbenzene sul
closed herein to minimize the formation of undesirable 20 fonic acids of the formula
acidic sulfate in the product ester.
Thus the generic reaction conditions and processing
techniques of this invention are not narrowly critical
and may correspond, if desired and appropriate, to any
of the known conditions heretofore employed in such 25
conventional esterification processes. Indeed such reac
tion conditions and processing techniques may be var wherein R" represents an alkyl radical having from 8 to
ied widely and tailored to meet individual needs and 20 carbon atoms. Such acids as well as methods for their
produce the particular product ester desired. preparation are well known. Of course it is to be under
For instance, product esters of this invention are 30 stood that as employed herein, said formula is to be
those of the formula considered as encompassing mixtures the individual
RCOOR." acid compounds represented by said formula, as well as
the individual acid compounds themselves. For exam
wherein R represents a linear hydrocarbyl radical hav 35 plese,
in addition to employing such individual acids per
it may be more convenient or desirable to employ
ing from 1 to 4 carbon atoms and wherein R' represents the commercial or technical grade compounds of such
an alkyl radical having from 2 to 5 carbon atoms. Illus acids (i.e. a mixture of such individual acids where in
trative product esters include ethyl acetate, n-propyl the alkyl radical shown
acetate, iso-propyl acetate, n-butyl acetate, iso-butyl representing an averageasnumber R' is commonly expressed as
of carbon atoms in the
acetate, amyl acetates, such as n-pentyl acetate, 2-meth range of from 8 to 20, e.g. those normally used in manu
yl-1-butyl acetate and 3-methyl-1-butyl acetate, ethyl facturing detergents). Thus illustrative alkyl substituted
propionate, n-propyl propionate, iso-propyl propionate, benzene sulfonic acids, include n-octylbenzene sulfonic
n-butyl propionate, iso-butyl propionate, amyl propio acid, n-nonylbenzene sulfonic acid, n-decylbenzene
nates, such as n-pentyl propionate, 2-methyl-1-butyl sulfonic acid, n-undecylbenzene sulfonic acid, n-diode
propionate and 3-methyl-1-butyl propionate, ethyl acry 45 cylbenzene sulfonic acid, n-tridecylbenzene sulfonic
late, n-propyl acrylate, iso-propyl acrylate, n-butyl ac acid, n-tetradecylbenzene sulfonic acid, n-pentadecyl
rylate, iso-butyl acrylate, amyl acrylates, n-propyl
methacrylate, n-butyl methacrylate, n-butyl butyrate, benzene sulfonic acid, n-hexadecyl benzene sulfonic
acid, n-heptadecylbenzene sulfonic acid, n-octadecyl
and the like. The preferred product esters this invention benzene sulfonic acid, n-nonyldecyl benzene sulfonic
are the propyl and butyl acetates and propionates, the 50 acid, n-eicosylbenzene
more preferred esters being the acetates, especially sulfonic acid, and mixtures
n-butyl acetate. thereof. Illustrative commercial grade mixtures of the
Thus the carboxylic acid starting materials employ alkyl benzene sulfonic acids of the above formula avail
able in this invention are those of the formula able to the Public include Bio-Soft (RS-100 which has
55 an equivalent weight of about 318 and wherein R" rep
RCOOH resents an average alkyl chain length of about 11.5 car
bon atoms (Stepan Co), AAS-98S a linear alkylbenzene
wherein R represents a hydrocarbyl radical having sulfonic acid with an average alkyl chain length of
from 1 to 4 carbon atoms. Illustrative carboxylic acids C11-C12 (Continental Chemical Co.), Vista SA697 and
include acetic acid, propionic acid, butanoic acid, Vista SA 597 a C13 linear alkyl benzene sulfonic acid
isobutanoic acid, acrylic acid and methacrylic acid. The (average mol. wt. 342) and a C11 linear alkylbenzene
preferred carboxylic acid starting materials are acetic sulfonic acid (average mol wt. 318), respectively, (both
and propionic acid, especially acetic acid. Most prefera products of the Vista Chemical Co.), Stepantan (RH
bly the carboxylic acid starting materials are purified 100 la branched dodecylbenzene sulfonic acid (Stepan
single carboxylic acids, although mixtures of such acids 65 Co.), a linear alkyl benzene sulfonic acid wherein the
could be employed if desired. alkyl radical (R") constitutes about 1% C10, 40% C1,
The alcohol starting materials employable in this 28% C12 and 31% C13+ (Alfa Products Co.), and the
invention are those of the formula like. The more preferred alkylbenzene sulfonic acid
 5,231,222
5 6
catalysts of the above formula are those wherein R' advance the reaction rate of the process. However,
represents an alkyl radical having from 10 to 14 carbon preferably the catalyst should obviously produce a
atoms, the most preferred catalyst being the commercial rapid reaction. This the concentration of the alkyl sub
Bio-Soft (R) S-100 described above. stituted benzene sulfonic acid esterification catalysts of
The esterification process of this invention is a well this invention in reaction medium of the esters batch
known mildly exothermic equilibrium reaction. The still reactor may be in the range of about 0.1 to about 5.0
basic process can be carried out in a conventional esters wt.% acidity, calculated as wt.% H2SO4. Preferably it
batch still kettle reactor wherein product ester and is maintained in the range of from about 0.1 to to about
water are removed from the equilibrium esterification 2.0 wt.% and more preferably from about 0.2 to about
reaction as a mixture of binary and ternary heteroge 10 0.8 wt.% calculated as wt.% H2SO4. Preferably the
neous azeotropes between the ester, alcohol, and water catalyst level should remain constant and may be moni
in a conventional esters batch still distillation column tored daily by titration. If the acidity level should drop
and allowed to phase separate in a decanter. Any suit below an acceptable level, makeup catalyst may be
able conventional esters type reactor and distillation added to the reactor to achieve whatever reaction rate
column can be employed herein. However in view of 15 is desired.
possible acid corrosion problems over time it is pre The esterification process of this invention may be
ferred to employ corrosion resistant type materials, e.g. operated at any suitably known reaction temperatures
316 stainless steel, of construction for such units. More and pressures. For instance, the process described
over, it is further preferred that the ester batch still herein may be operated at pressures ranging from atmo
distillation column consist of at least 30 Oldershaw trays 20 spheric pressure to about 75 psia, or higher if desired;
or plates the upper number of said trays or plates, being preferred pressures ranging from atmospheric pressure
constrained only by practical considerations. to about 45 psia. For example in the case of producing
A preferred startup procedure is to begin by adding a butyl acetate it is generally preferred to maintain the
conventional feed ratio of substantially equimolar reactor and distillation column at a pressure slightly
amounts of alcohol and acid to an initially charged 25 above atmospheric, e.g. 16 to 20 psia. Likewise the
reactor. An illustrative initial charge might consist for esterification reaction may be generically conducted at
example of 35-50 wt.% acetic acid, 10-50 wt % buta a temperature ranging from about 80 C. to 180° C. and
nol, 0-50 wt.% butyl acetate and 0-5 wt.% water. preferably from about 85°C. to about 140 C. Of course
Once the initial charge has been added to the reactor, the most preferred reaction conditions in any one indi
the esterification catalyst should be added. The reaction 30 vidual circumstance will depend to a large extent upon
contents are then slowly heated and the esters batch still the particular product ester and processing efficiency
distillation column brought up on total reflux. Equilib desired by the operator and such conditions should be
rium should be achieved in a very short time (e.g. less readily determinable by one skilled in the art following
than one hour) by this technique. the more preferred aspects of this invention as explained
Another startup procedure is to start near equilibrium 35 herein and/or through simple routine experimentation.
condition to enhance the steadiness of the operation. For example with Bio Soft (R) S-100 catalyst it has been
For instance in the case of butyl acetate this may be found that butyl acetate can be readily obtained at a
achieved with an approximate starting composition of reactor temperature of about 120° C. and atmospheric
35 wt.% acetic acid, 10 wt.% n-butanol, 50 wit, % pressure while at a pressure slightly above atmospheric
butyl acetate and 5 wt.% water followed by addition of 40 pressure (e.g. about 16-20 psia) one can efficiently em
the esterification catalyst. When such a steady-state ploy a reactor temperature of about 135C. Of course it
composition is charged to the reactor the esters batch is desirable not to force too high a reaction temperature
still distillation column can be rapidly line-out to con in order to maintain low overhead carboxylic acid acid
stant conditions in about one-half hour. Additions as ity and high crude product ester purities. Most prefera
desired to the distillation column can be commenced 45 bly the esterification process of this invention is carried
without delay. Such a startup procedure can save time out at steady-state operating conditions so as to promote
in a plant depending upon the specific conditions such as much consumption of the alcohol as possible in order
as type of equipment any availability of crude product to prevent alcohol from entering the distillation column
ester. and to prevent it from passing overhead as a low boiling
As mentioned, once the esters distillation column is 50 water azeotrope and/or etherifying into a dialkyl ether
brought to total reflux it is allowed to line out to con by-product. Thus it is preferred to monitor the carbox
stant conditions. During equilibration the reactor tem ylic acid acidity in the reaction medium e.g. by titration
perature lowers somewhat due to the formation of the and to maintain said acidity level at a steady state.
product ester and water. Lining out of the reactor and The subject esterification process of this invention
distillation column temperature is a good indication that 55 involves a substantially anhydrous reaction medium, i.e.
equilibrium has been achieved, one containing no more than about 5 wt.% water, in
After equilibrium has been achieved the alcohol and the reactor, and preferably one in which the reaction
acid are fed continuously to the reactor, preferably in a medium contains less than about 3 wt.% water. Limit
substantially equimolar ratio. As employed herein the ing the amount of water in the reactor to such minor
expression substantially equimolar ratio includes molar 60 amounts permits high react on rates and assures maxi
ratios of alcohol to acid in the range of from about 1 to mum product ester concentration in the reactor. Such
1.5:1. Of course such includes equimolar ratios of such low concentrations of water are achievable because
reactants and higher or lower alcohol to acid ratios may while the esterificaton process produces water as a
also be employed if desired. In general it is preferred to by-product, both the product ester and water formed
employ a slight excess of alcohol to the acid (e.g., about 65 are readily distilled from the reactor and conveyed to a
a 1.05:1 molar ratio of n-butanol to acetic acid). distillation column wherein aqueous azeotropes are
The quantity of esterification catalyst employed in formed, of which water makes up a large percentage
this invention can be any catalytic amount that will (e.g. about 25-30%).
 5,231,222
7 8
In general it is also preferred to add some water to the least of which is the production of product esters that
distillation column to aid in forming the product ester are very stable against carboxylic acid formation upon
water azeotrope, since the amount of water normally storage as described herein. As noted this stability is
distilled from the reactor is not generally sufficient to considered to be the result of the fact that the long chain
ensure a satisfactory aqueous azeotrope with the prod alkylbenzene sulfonic acid catalysts of this invention
uct ester. On the other hand if the water content of the resist formation of unstable sulfonic esters (e.g. from the
product ester-water azeotrope is too high such is also reaction of an alcohol and the catalyst itself), thus pre
not desirable. Nor is it desirable to employ too low or venting the appearance of acidic sulfate in the product
high a temperature in the distillation column for re ester and the corresponding carboxylic acid acidity
moval of the product ester-azeotrope overhead. For O problems on storage of the product. It has also been
example, if the temperature in the distillation column is surprisingly found that the presence of certain neutral
too high above the boiling point of the product ester acidic sulfate such as that which might be derived from
water azeotrope, excessive carboxylic acid may be car glass apparently does not cause an increase in carbox
ried overhead and if said temperature is too low (such as ylic acid acidity upon storage. Indeed it was found that
might be caused by excessive water being added to the 15 the carboxylic acid acidity of n-butyl acetate did not
distillation column) then the crude product ester may be change with time when stored in a glass container,
contaminated with excessive alcohol carryover. Thus despite having increased in sulfate content. This in
the temperature in the distillation column, is preferably crease in sulfate is believed to have been caused by
monitored at any suitable point (e.g. slightly above the contamination from the glass (typically the sulfate con
lower addition point of water to the distillation column) tent of small ester samples stored in glass vessels have
in the distillation column to control it right at or near been found to increase from 1 to 5 ppm). Thus such
the boiling point of the product ester-water azeotrope. sulfate originating from the glass is apparently not cata
The amount of water added to the column is preferably lytic in causing hydrolysis of the ester to its carboxylic
that amount which will achieve the most efficient re acid in contrast to that hydrolysis caused by acidic
sults in terms of both the amount of product ester ob 25 sulfate that originates from reaction of the alcohol and
tained and its crude product purity. Moreover, while sulfonic acid catalyst itself. In addition to the major
water is preferably added to a tray close to the bottom advantage of minimizing the amount of acidic sulfate
of the distillation column to aid in product ester re contained in the product ester that is obtainable by
moval from the reactor as an azeotrope, it is also pre employing the subject invention, numerous other ad
ferred to add some water to a tray at or near the top of 30 vantages may be attributed to the use of the particular
the distillation column along with some portion of the alkylbenzene sulfonic acid catalysts of this invention.
crude product ester obtained from the decanter upon For example, such very stable catalysts exhibit high
phase separation of the product ester-water azeotrope in catalytic activity and also help provide for a very stable
order to establish a reflux and minimize the amount of reaction medium in the reactor. Indeed it is considered
carboxylic acid in the crude product taken overhead. 35 that the catalysts of the subject invention should greatly
Moreover, while it is preferred herein that the water minimize the present need for frequent catalyst makeup
added to the distillation column be derived from the additions during the esterification process such as com
decanter upon phase separation of the product ester monly required with heretofore conventional catalysts.
water azeotrope, such need not be the case. The water Moreover it is considered that the long chain alkylben
added to the distillation column may be fresh water if 40 zene sulfonic acid catalysts of this invention will mini
desired, such as from the same fresh water source pref. nize corrosion problems and also do not appear to
erably added to the decanter to aid in the phase separa cause charring or fouling of the heating coils during
tion of the product ester-water azeotrope. In any event esterification. Further due to the excellent stability of
water purity can exhibit a significant effect on product the catalyst of this invention, at the completion of a
quality and productivity. Thus it is preferred that the 45 particular product ester production campaign it is con
fresh water source be deionized water or some other sidered that the reactor kettle residues containing the
high purity type of water. Moreover it is obviously used long chain alkylbenzene sulfonic acid catalyst may
generally preferred to employ sufficient water flow be readily stripped from the reactor (e.g. when it is
rates, to the upper and lower locations of the distillation desired to start a new production run directed to a
column to achieve a highly efficient steady-rate esterifi 50 different product ester using the same production equip
cation system, e.g., in the case of butyl acetate water ment and facilities), stored and then reused, thus allow
flow rates of about 0.5 and 0.3 lbs., respectively, per lb. ing recycling of the catalyst residues from one product
of butanol feed, may be sufficient. ester production campaign to another, when desired.
As noted the addition of some of the crude product Indeed it is anticipated that reactor kettle residues con
ester obtained upon phase separation of the product 55 taining the catalysts of this invention may be recycled
ester-water azeotrope to the top part of the distillation 2-3 times before disposal (although some makeup cata
column is preferred to produce a reflux that aids in lyst may be required to restore full activity). In general
keeping carboxylic acid from going overhead and con kettle residues containing heretofore conventional es
taminating the product ester. In general it is preferred to terification catalysts are not readily reuseable due to
return at least a sufficient amount of such crude product 60 variable amounts of char and metals from corrosion
ester (along with water) so as to maintain about a 1:1 contained in the used catalyst composition.
reflux ratio at the top of the distillation column. Of Finally the product esters of the esterification process
course higher amounts of product ester can be recycled of this invention have a wide range of utility that is well
to obtain higher reflux ratios (e.g. up to 3:1 or more) if known and documented. For example esters such as the
desired. alkyl acetates and alkyl propionates are especially useful
Beneficial factors involved in the employment of the e.g. as solvents in paints and as raw materials for agri
alkyl substituted benzene sulfonic acid catalysts in the cultural applications such as insecticides, herbicides,
esterification process of this invention are many, not the etc.; while esters such as the alkyl acrylates and methac
 5,231,222
10
rylates are especially useful as monomers for polymers tions referred to herein and in the appended claims are
and resins used in coatings, adhesives and plastics, as by weight unless otherwise indicated.
well as in textiles and leather finishes and in paints.
Accordingly a preferred embodiment of this inven SULFATE DETERMINATIONS
tion can be further illustrated by reference to the draw The process employed by this invention in determin
ing which schematically shows a diagrammatic flow ing the amount of acidic sulfate (SO42), measured as
procedure suitable for practicing this invention. Na2SO4, in the process and product ester is by ion chro
Shown in said drawing is a reactor (5) (i.e. a conven matography (IC) as follows:
tional esters batch still kettle) to which the carboxylic The principal in detecting the acidic sulfate in the
acid (1) and alcohol (2) may be continuously fed at a O water immiscible product ester involves extracting a
temperature sufficient to vaporize the product ester and sample of the product ester with a dilute solution of
water to a distillation column (4) (e.g. a conventional sodium hydroxide. For example the butyl acetate vol
ester batch still distillation column). The catalyst (3) une is three times the volume of the dilute base result
(i.e. the alkyl substituted benzene sulfonic acid) is pres 15
ing in a three fold concentration of the sulfate in the
ent in the alcohol/carboxylic acid reaction medium of dilute base layer. The dilute base extract is then injected
the reactor and make up catalyst may be added incre into an ion chromatograph to measure the sulfate con
mentally to the esterification reaction if required or centration. Recovery of sulfate by this method is 97 to
desired. 103 percent.
Product ester may be removed from the equilibrium 20
esterification reaction system as a mixture of binary and INSTRUMENT PARAMETERS
ternary heterogeneous azeotropes between the ester, Instrument Dionex Model 202i, or equivalent
alcohol and water from said distillation column (4) via Columns Dionex AG4A and AS4A and AMMS
line (9) which is equipped with a cooler or condenser Inline Filter Dionex Column
(7). The condensed liquid may then be conveyed to a 25
Temperature
Detector
Ambient
Dionex conductivity CDM
conventional ester-water azeotrope decanter (6) in Mobile Phase 2.5 mM sodiurn carbonate and
which phase separation is allowed to occur. The crude 1.5 mM sodium bicarbonate in H20
product ester rich top layer of decanter (6) may be fed Flow 1.5 mL/min
via lines to a conventional product ester refining still Pressure
Regenerate
1000 psig
25 mN H2SO4
(11) to distill off lights and obtain the desired refined 30 Flow 3-4 in L/min
product ester via line (16). A portion of said crude prod Regenerate Press. 5 psig
uct ester rich top layer of decanter (6) may be returned Conductivity 16-18. Siemens background
via line (12) to the top of distillation column (4) to main Sample loop 50 liters
tain the desired reflux ratio. REAGENTS
The bottom aqueous layer of decanter (6) may be 35 Water ASTM type I Water conductivity
exceeded 16.7 megohms resistance.
added via lines (8) and (13) to the distillation column (4) The sulfate concentration in the
in order to satisfy the azeotropic water requirements for deionized water should be less
product ester removal and to minimize carboxylic acid NaOH
than 50 ppb as measured by IC.
50% liquid high purity low
from distilling overhead with the product ester-water carbonate solution
azeotrope mixture via line (9). Na2CO3 ACS Reagent grade (Am. Chem. Soc.)
Fresh make-up water line (24) may be added' to de NaHCO3 ACS Reagent grade (Am. Chem. Soc.)
canter (6) via line (9) to aid in the phase separation and Na2SO4
H2SO4
ACS Reagent grade (Am. Chem. Soc.)
high purity low metals content
provide sufficient water for distillation column (4). Fur 0.01 N. NaOH 50% NaOH, 0.8 g diluted to 1 L.
ther line (9) may contain a vent gas line 27, while reac
tor (5) may be connected to a stripped storage residues 45
tank (not shown) if desired. Excess water may be STANDARD PREPARATION
purged downstream e.g. via line (14).
The lights, e.g., carboxylic acid and alcohol obtained Prepare a standard stock solution in water containing
via line (17) from the top of refining still (11) may be approximately 1000 ppm sulfate, as SO42, from so
reworked by condensing them in cooler (30) and allow 50 dium sulfate. Prepare a second standard containing
ing them to phase separate in a second conventional approximately 1 ppm sulfate in the 0.01N NaOH. Chro
decanter (26) so that the carboxylic acid enriched top matograph the standard along with the samples and
layer of said decanter (26) may be recycled via line (19) blanks.
to reactor (5). Line (17) may contain a vent gas line (18). SAMPLE PREPARATION (E.G, BUTYL
The bottom layer of said decanter (26) may be con 55 ACETATE)
veyed via line (20) to line (14) carrying the water from
the first decanter (6) to a final conventional refining or a) Because the levels of sulfate in the samples may be
stripping still (15). The vaporized gases e.g. product in the parts per billion (ppb) range, contamination
ester, etc. obtained via line (21) from the top of said should be a constant concern. The samples should be
stripping still (15) may be condensed via cooler (31) and taken and handled in containers that are relatively free
added to recycle line (19) or discarded via vent gas line of sulfate. Samples and dilutions should be stored in
(22), as desired. Finally the excess water recovered plastic bottles, because glass bottles usually contain
from the bottom of said stripping still (15) via line (23) several ppm sulfate. To test for sulfate in the containers,
can be disposed of as desired in any suitable environ add deionized or other high purity water, shake vigor
mentally correct manner. 65 ously and analyze the water for sulfate. Regardless of
The following examples are illustrative of the present the containers used, blank analyses are essential to cor
invention and are not to be regarded as limitive. It is to rect for sulfate brought in the analysis by the reagents,
be understood that all parts, percentages and propor containers and other sources.
 11
5,231,222
12
b) Analyze each sample in duplicate. Some process EXAMPLE 1.
samples may contain two layers. The upper layer is
mostly butyl acetate and the bottom layer is mostly A continuous process to produce n-butyl acetate was
water. Either layer can be analyzed for sulfate. The carried out using an esterification system corresponding
dilute base lower layer of the sample can be analyzed to the schematic flow diagram of the subject drawing.
directly or with dilution. The organic part cannot be A 35 Oldershaw tray distillation column was employed.
injected directly into the ion chromatograph (IC) with The esterification reactor kettle was charged with a
out damaging the columns. Use the extraction proce mixture of n-butanol and acetic acid at a 1:1 molar ratio
dure in step (c) for the upper butyl acetate layer. and 1.0 wt-% of Bio Soft (R) S-100 was employed as the
c) Refined butyl acetate samples and the upper layers O esterification catalyst. The reactor contents were
from unit process samples should be analyzed as fol heated to 115 to 120° C. while the distillation column
lows. Shake thirty, 30-1, grams of each organic sample and reactor were maintained at about 18-20 psia by
with ten, 10-it, grams of 0.01 NaOH in 50 mL polyeth pressuring with nitrogen gas. Esterification equilibrium
ylene plastic bottles. Soon after the layers separate care 5 was achieved within 0.5 hours as determined by con
fully remove some of the bottom dilute base layer and mencing of n-butyl acetate overhead reflux in the distil
inject into the IC. lation column and by kettle analysis which showed a
d) Repeat in duplicate using the reagents and contain constant acetic acid content. The catalyst concentration
ers but no sample to provide two blanks for the IC was 0.29 wt.% calculated as sulfuric acid.
analysis. An esterification feed mixture of acetic acid and n
20 butanol in a molar ratio of about 1.00:1.05 was fed con
e) Samples should be run in random order if possible.
The analysis of the samples should be corrected for tinuously to the reactor kettle at a temperature of 110
sulfate found in the 0.01N NaOH blank chromatograms. to 120° C. at 18-20 psia which was sufficient to vaporize
The 0.01N NaOH will probably contain between 10 and the product ester/water azeotrope while maintaining
50 ppb sulfate. 25 kettle equilibrium. The kettle composition remained
essentially constant during the process, while the cata
ACIDITY DETERMINATIONS lyst concentration ranged from 0.29% to 0.32% calcu
The process employed by this invention is determin lated as sulfuric acid (the slight variation was due to
ing the amount of carboxylic acidity in the process and variation in kettle liquid level).
product ester is as follows. 30 The product ester left the top of the distillation col
(a) Introduce 60 mL (60 g) of the sample into a 250 umn, as a mixture of binary and ternary heterogeneous
mL Erlenmeyer flask by means of a suitable transfer azeotropes between n-butyl acetate, n-butanol and wa
graduate. ter, and was allowed to phase separate into product
(b) Add a few drops of 1.0 percent alcoholic phe ester-rich upper and a water-rich lower layers in a de
nolphthalein indicator and titrate with standard 0.1N 35 canter, after passing through a cooler. The average
alcoholic potassium hydroxide to a pink end point per composition of the decanter lower water layer was
manent for at least 15 seconds. found to contain 300 ppb (0.30 ppm) of acidic sulfate.
(c) Calculation: mL KOHX0.01 = acidity, 9% by About one-half of the crude product ester upper
weight, e.g., as acetic acid. phase recovered from the decanter was conveyed to a
refining still, while the other half of said crude product
CATALYST CONCENTRATIONS ester was added back at the head of the distillation
DETERMINATIONS column to maintain about a 1:1 reflux.
The process employed by this invention in determin ofInn-butanol this process run, about 1.1 to 1.6 lb. of water per lb.
was continuously fed to the top of the
ing the alkyl benzene the acid catalyst concentration in 45 distillation column and about 0.9 to 1.1 lb. of water per
the reaction kettle in terms of sulfuric acid involves
lb. of n-butanol
tritration with a base. This method actually determines (tray 17) of the column.was added to the lower water feed point
sulfuric acid as the monobasic acid, monobutyl sulfo from The water layer recovered
the decanter was not
nate, but the results are reported as percent sulfuric acid umn, but instead fed to a water recycled to distillation col
for convenience. The procedure is as follows: stripping column for
50 recovery of n-butyl acetate and unreacted butanol and
1. Into each of two 250 mL. glass-stoppered flasks
pipet 10 mL of sample and add 8 to 10 drops of thymol acetic cation
acid, which were returned to the reactor. Purifi
of the water made it suitable for disposal.
blue-xylene cyanol FF indicator.
Indicator: 3.0 grams of thymol blue (Na salt from n-butyl average
The
acetate
acidic sulfate content of the refined
recovered from refining still and pro
Baxter Scientific Products) and 0.8 grams of xylene 55 duced by this process run was 20 ppb and the acetic acid
cyanol FF (from Fisher, catalog #1131069) dissolved in acidity was 0.009 wt-%. After standing at 42 C. (107.6
1 liter of DMF. F.) for 23 days, the acetic acid acidity of the refined
2. Add 100 mL of neutralized anhydrous isopropanol n-butyl acetate was still found to be 0.009 wt-%, and
to each of the flasks. after 49,78 and 119 days at 42 C., said acidity was 0.011
3. Immediately titrate the contents of each flask with wt-%, 0.016 wt.% and 0.015 wt.%, respectively, show
standard 0.1N morpholine in isopropanol to a color ing that the obtained n-butyl acetate product ester was
change from purple to green. Approach the end point very stable against acetic acid formation upon storage.
dropwise using a 25 mL buret.
4. Calculation: EXAMPLE 2
Sulfuric Acid, % by weigh 65 A continuous process to produce n-butyl acetate was
t=AXNX 9.81/10X Sp.Gv. carried out using an esterification system corresponding
A=ML of N normal morpholine solution required to the schematic flow diagram of the subject drawing.
for the sample. A 43 Oldershaw tray distillation column was employed.
 5,231,222 14
13
The reactor kettle was initially charged with acetic Sufficient fresh water was added to the decanter to
acid followed by Bio-Soft (R) S-100 as the esterification maintain a sharp liquid level in the decanter and provide
catalyst and finally with n-butanol (about a 1.3:1.0 for the water added to distillation column.
molar ratio of acetic acid to n-butanol) and heating The average acidic sulfate content of the refined
commenced. The amount of catalyst added calculated n-butyl acetate produced by this process run was 25 ppb
to be about 1.1 wt-%, while the catalyst content in the and the average acetic acid acidity was 0.006 wt-%.
reactor was 0.37% calculated as sulfuric acid. Addi EXAMPLE 3
tional acetic acid and butanol were added at 1:1 molar
ratio to obtain the desired kettle level. The following experimental data in Table I, illustrates
Heating the reactor was commenced while the distil 10 the reactive consumption of various acid catalysts, i.e.
lation column and reactor were maintained at about 30 methane sulfonic acid (MSA), p-toluene sulfonic acid
psia by pressuring with nitrogen gas. After heating 1.5 (p-TSA), sulfuric acid (H2SO4), Bio-Soft (R) S-100 (re
hours, a reactor temperature of 105 C. had been ferred to in this example as dodecylbenzene sulfonic
reached and esterification equilibrium achieved as de acid or DBSA) and p-octylbenzene sulfonic acid
termined by commencing of n-butyl acetate overhead 15 (OBSA) with n-butanol at 115° C. with regard to form
reflux in the distillation column and a constant acetic ing sulfonate ester.
TABLE I
- MSA - - PTSA - - HSO4- - DBSA- OBSA
Time Wt. 2 Acid Tine Wt, %. Acid Time Wt, %. Acid Tine Wt. 9, Acid Time Wt. 9, Acid
Hrs. Reacted Hrs. Reacted Hrs. Reacted Hrs. Reacted Hrs. Reacted
1.0 0000 4.00 00.00 4.00 100.00 7.00 1.84 7 2.85
7.0 11.11 13.00 21.85 11.50 96.78 12.50 4.79 13 2.31
13.0 22.22 20.00 24.65 19.00 98.95 13.50 0.00 21 1.76
20,0 20.94 27.00 21.85 36.00 99.52 2.00 2.58 29 1.49
28.0 22.22 40,50 15.41 59.00 99.59 28.50 l, 39 0.68
42.0 29.05 48.00 6.25 85.80 92.41 34.50 0.00 6. 1.22
49.50 27.35 88.00 21.0 92.50 88.22 41.00 0.00 92 1.76
72.00 2009 97.50 85.53 49,50 0.00
89.50 19.23 105.00 88.03 7100 0.00
112.00 92.05 94.50 0.00
12.00 84.2

The above data shows that p-TSA and MSA reacted

acid concentration in the reactor.
with n-butanol (to the extent of 20-25% in less than 25
hours) forming the corresponding sulfonate esters
An esterification feed mixture of acetic acid and n 35 (butyl p-toluene sulfonate and butyl methane sulfonate
butanol in a molar ratio of about 1.00:1.05 was fed con respectively). Continued heating at 115 C. up to about
tinuously while maintaining the reactor temperature at 88 hours showed no further reaction suggesting equilib
about 125 to 135° C. at 19-22 psia. Water addition was rium had been achieved under the reaction conditions.
simultaneously commenced to the distillation column in The data also shows that mixing H2SO4 and n-butanol
sufficient quantity to form the ester/water azeotrope formed mono-n-butylsulfate virtually instantaneously
while maintaining reactor equilibrium throughout the (within 30 seconds at 110° C). In contrast the DBSA
process. The average catalyst concentration during the catalyst showed little or no reaction with the n-butanol
process was 0.3 wt-% calculated as H2SO4. The catalyst even after heating at 115° C. for over 90 hours, while
neither exhibited loss by decomposition nor required only a slight degree of esterification to the sulfonate
makeup additions during this process which was run 45 ester was observed for the OBSA catalyst over 90 hours
continuously for several weeks. at 115 C. Such data indicates that the long chain alkyl
The overhead product ester-water azeotrope leaving benzene sulfonic acid catalysts of this invention should
the column was condensed by a cooler and phase sepa be much more resistant than other esterification cata
rated in a decanter vessel. The average acidic sulfate lysts to the formation of those unstable sulfonic esters
content of the crude n-butyl acetate rich top layer 50 that can occur during the acid-alcohol esterification
stream was determined to be 25 ppb. The average acidic because of reaction between the alcohol and catalyst
sulfate content of the decanter lower water layer was itself. Moreover, such undesirable sulfonic ester by-pro
300 ppb. ducts are readily decomposable to sulfur oxides during
Some of the upper product ester-rich layer from the esterification and are considered to be the root cause of
decanter was fed to refining still to produce refined 55 carboxylic acid formation upon storage of product es
n-butylacetate product and the remainder was returned tes,
to the head of the distillation column to maintain about
a 1:1 reflux. EXAMPLE 4
About 1.6 lb to 1.8 lb of the decanter water phase per In a laboratory-scale glass esterification system corre
lb of n-butanol fed to the system was returned to the 60
sponding to that used in Example 2, five different cata
head of the distillation column, and about 0.40 lb to 0.65 lyst were tested for comparable acidic sulfate genera
lb of the decanter water layer per lb of n-butanol was tion in the crude product ester. The five catalyst were:
fed to the lower point (tray 4) on the distillation col
umn. The remaining water from the decanter was fed to
a water stripping column for recovery of n-butyl ace
tate and unreacted butanol and acetic acid, which were Catalyst Example
returned to the reactor. Purification of the water made Diethyl Sulfate A.
it suitable for disposal. Sulfuric Acid B
 5,231,222
15 16
-continued acid (C), 1-decanesulfonic acid (E) and diethyl sulfate
Catalyst Example (A).
p-Toluenesulfonic Acid C EXAMPLE 5
Bio-Soft (R) S-100 D A continuous esterification process was carried out
1-Decanesulfonic Acid E
using the esterification system and general procedure
described in Example 1. In this production run propi
The esterification processes were conducted under onic acid was esterified with n-butanol to produce n
typical raw material feed rates to provide comparable butyl propionate.
distillation column and kettle operation temperatures. O
The reactor was charged with a mixture of n-butanol
The feed ratio rates employed and temperatures ob and propionic acid to give a 25% excess of propionic
served during a 6 hour run for each experiment were as acid on a molar basis. The acid was added first followed
follows: by the n-butanol. During addition of butanol, Bio
15 Soft (R) S-100 (0.88 wt.%) was added to the reactor.
EXAMPLE The kettle contents were heated to 105 C. at 18-20
A to C D to E psia and n-butanol and propionic acid fed at 1.05:1.00
n-Butanol to Acetic Acid, :05 :10S
molar ratio, respectively. Water addition to the distilla
molar ratio tion column was commenced after the reactor had been
n-Butanol feed rate, g/hr S4.4 81.6 charged and the reaction temperature achieved.
Acetic Acid feed rate, g/hr 42.0 63.0 The reaction kettle achieved equilibrium within
H2O to Top of Column 0.50 0.33 about two hours. Analysis showed a high equilibrium
(g/g n-butanol) ester content in the reactor. The lack of di-n-butyl ether
H2O to Low Part of Column 0.28 0.18
(g/g n-butanol) in the reaction medium showed the high catalyst selec
H2O to decanter 0.39 0.26 25 tivity.
(g/g n-butanol) The esterification was carried out at an average kettle
Kettle Temp., "C. 16 20-122
Overhead Column Temp., C. 90.3-90.4 90.3-90.8 temperature of 105-110° C. and a distillation column
Column Control Temp., C. 92.0-92. 92.8-100.5 overhead temperature of about 97 C. Sufficient fresh
water (not decanter water) was added to the top and
bottom of the distillation column to obtain the desired
Appropriate catalyst concentrations were employed 30 product ester-water azeotrope.
to provide comparable esterification rates. The kettle The product ester-water azeotrope obtained from the
catalyst concentrations (as % of H2SO4) and results distillation column overhead was phase separated in a
observed for the various crude product ester composi decanter.
tions of the product ester-rich top layer of the decanter After refining the crude product ester top layer, n
and the acidic sulfate content found in both the product butyl propionate was obtained having a purity in excess
ester-rich top layer and the bottom water-rich layer of of 99.5%. The average acidic sulfate content of the re
the decanter, were as follows: fined n-butyl propionate was found to be 26 ppb and the
acetic acid acidity was 0.010 wt.%. After standing at
- Example - 40 42 C. for 41 and 96 days, said acidity was found to be
A. B C D E 0.007 wt.% and 0.019 wt.%, respectively.
Kettle H2SO4, 26 0.30 0.37 0.15 0.2 0.18 EXAMPLE 6
Kettle Acidity, as 26.0 28.5 25.8 32.5 34.5
Acetic Acid, 2.
Kettle H2O, 7% 1.65 1.38 48 2.05 0.49 45
n-Propyl acetate was prepared from reaction of
n-Butyl Acetate, top 97.02 97.64 97.03 98.8 98.03 acetic acid with n-propanol in the presence of Bio
layer, 2. Soft (R) S-100 catalyst. The esterification system and
N-Butanol, top layer, 2.20 2.33 2.49 1.12 1.43 general procedure described in Example 2 were em
%
Acidity, top layer, 2% 0.00 0.001 0001 000 0.00
ployed.
H2O in top layer, 9% 1.28 00 1.5 106 0.68 50 The reactor was first filled with acetic acid followed
n-Butyl Acetate, ave, 93.3 89.2 88.3 107.5 98.3 by addition of n-propanol (1.3:1.0 molar ratio of acidic
mL/hr acid to n-propanol). While adding the alcohol Bio
H2O Collected, ave, 62.5 67.5 65.8 74.2 80 Soft (R) S-100 catalyst (2.6 wt.%) was introduced into
in Mhr
Sulfate in top layer, 80 83 78 53 98 the reactor. The kettle contents were heated to 120 C.,
ppb 55 which gave reflux in the distillation column. Additional
Sulfate in bottom
layer, ppb.
220 69 149 80 205 acetic acid and n-propanol in a 1:1 molar ratio was
introduced into the reactor kettle to obtain the desired
liquid level. Analysis of the kettle at this point gave an
From the above data and, in particular, from the acid catalyst concentration of 0.683%, calculated as
determined acidic sulfate content in both the top prod H2SO4.
uct ester-rich decanter layer and the bottom water-rich Heating was continued while water addition to the
decanter layer in each experiment, it is clear that cata lower distillation column side and top distillation col
lyst "D", the long chain alkylbenzene sulfonic acid umn trays was initiated. At about this time the column
catalyst, i.e., Bio-Soft (R) S-100 of this invention was was taken off full reflux and some overhead azeotrope
comparatively far superior in minimizing the amount of 65 flow was permitted into the decanter. Water flows to
acidic sulfate contained in said crude product ester and the distillation column were stabilized at about 0.03 lb
separated aqueous layer, than that achieved when using and 0.25 lb per lb of n-propanol feed at the upper and
such catalysts as sulfuric acid (B), p-toluene sulfonic lower feed points on the column, respectively.
 5,231,222
17 18
The esterification achieved stable operation at a reac 3. A process as defined in claim 1, wherein R' is an
tor temperature of 120 C. and at distillation column tail alkyl radical having from 10 to 14 carbon atoms.
and head pressures of 24 and 21 psia respectively. 4. A process as defined in claim 1, wherein the alco
The catalyst concentration in the reactor was con hol is propanol or butanol.
stant at an average of 0.55% acidity as H2SO4 and did 5 5. A process as defined in claim 4, wherein the car
not require additional catalyst, which attests to a high boxylic acid is acetic acid.
degree of catalyst stability. 6. A process as defined in claim 4, wherein the car
The product ester-water azeotrope obtained over boxylic acid is propionic acid.
head from the distillation column was condensed in a O 7. A process as defined in claim 4, wherein the alco
hol is n-butanol and the carboxylic acid is acetic acid.
decanter to obtain a crude n-propyl acetate rich upper 8. A process as defined in claim 4, wherein the alco
phase layer and an aqueous bottom layer phase. hol is n-butanol and the carboxylic acid is propionic
Various modifications and variations of this invention acid.
will be obvious to a worker skilled in the art and it is to 9. A process as defined in claim 2, wherein the mix
be understood that such modifications and variations 15 ture of said alkylbenzene sulfonic acids is one in which
are within the purview of this application and the spirit R" represents an alkyl radical having an average of
and scope of the appended claims. about 11.5 carbon atoms.
What is claimed is: 10. A process as defined in claim 11, wherein the
1. An improved process for producing a product ester alcohol is n-butanol and the carboxylic acid is acetic
20 acid.
having the formula
11. A process as defined in claim 1, wherein the alkyl
RCOOR benzene sulfonic acid catalyst is dodecylbenzene sul
fonic acid.
wherein R is a linear hydrocarbyl radical having from 1 12. A process as defined in claim 1, wherein the water
25 added to the distillation column is derived from the
to 4 carbon atoms and wherein R' is an alkyl radical phase separation of the product ester-water azeotrope,
having from 2 to 5 carbon atoms, with the proviso that and wherein a portion of the product ester of said phase
said product ester is not an acrylate or a methacrylate, separation is recycled to the distillation column.
said process consisting essentially of (1) continuously 13. A process as defined in claim 12, wherein the
feeding substantially equimolar amounts of carboxylic 30 esterification catalyst comprises a mixture of individual
acid of the formula alkylbenzene sulfonic acids represented by the formula
RCOOH

and an alkanol of the formula 35

ROH

wherein R and R are the same as defined above, to a

reaction vessel containing a substantially anhydrous wherein R' is an alkyl radical having from 8 to 20 car
40 bon atoms.
reaction medium that contains the carboxylic acid, alka 14. A process as defined in claim 12, wherein R' is an
nol, product ester, an esterification catalyst, and not alkyl radical having from 10 to 14 carbon atoms.
more than about 5 percent by weight water; (2) remov 15. A process as defined in claim 12, wherein the
ing product ester and water from said reaction vessel by alcohol is propanol or butanol.
distillation to a distillation column; (3) adding water to 45
16. A process as defined in claim 15, wherein the
said distillation column to aid in forming a product carboxylic acid is acetic acid.
ester-water azeotrope; and (4) phase separating said 17. A process as defined in claim 15, wherein the
product ester-water azeotrope in a separate vessel to carboxylic acid is propionic acid.
obtain said product ester; the improvement comprising 50 18. A process as defined in claim 15, wherein the
minimizing the amount of acidic sulfate contained in alcohol is n-butanol and the carboxylic acid is acetic
said product ester by employing as said esterification acid.
catalyst an alkylbenzene sulfonic acid of the formula 19. A process as defined in claim 15, wherein the
alcohol is n-butanol and the carboxylic acid is propionic
acid.
55
20. A process as defined in claim 13, wherein the
mixture of said alkylbenzene sulfonic acids is one in
which R" represents an alkyl radical having an average
of about 11.5 carbon atoms.
60
21. A process as defined in claim 12, wherein the
wherein R" is an alkyl radical having from 8 to 20 car alcohol is n-butanol and the carboxylic acid is acetic
bon atoms. acid. w
2. A process as defined in claim 1, wherein the esteri 22. A process as defined in claim 12, wherein the
fication catalyst comprises a mixture of individual alkyl alkylbenzene sulfonic acid catalyst is dodecylbenzene
benzene sulfonic acids represented by the formula in sulfonic acid.
claim 1.