Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Reexamination Certificate
2001-07-09
2004-01-13
Shah, Mukund J. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
Reexamination Certificate
active
06677481
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to production of pivalic acid and methyl pivalate. More particularly, the present invention is directed to a method for producing pivalic acid and methyl pivalate by cracking C
9
and C
13
carboxylic acids to pivalic acid or methyl pivalate.
2. Description of Related Art
Pivalic acid (2,2-dimethylpropanoic acid) is widely used as a starting material for various agrochemical, pharmaceuticals, aroma chemicals, specialty chemicals, and polymer additives.
Current processes produce pivalic acid in yields of approximately 74% pivalic acid or less. The by-products are mainly higher molecular weight oligomeric carboxylic acids with carbon numbers of C
9
and C
13
and higher. The carboxylic acids are typically separated by phase separation from the boron trifluoride dihydrate catalyst and further purified by distillation resulting in the following components:
In the neo acid process, a hydrocarbon feed or a compound capable of forming a reactive hydrocarbon intermediate, carbon monoxide and recycled catalyst are fed to a continuous process to manufacture an &agr;,&agr;-branched quaternary carboxylic acid. The term “hydrocarbon feed” as used herein includes, but is not limited to, olefins, alcohols and ethers which are capable of forming a reactive hydrocarbon intermediate. The catalyst is a strong acid, typically hydrates of boron trifluoride and occasionally containing a co-catalyst such as phosphoric acid. Other possible catalysts include Lewis acids, zeolite or modified zeolite catalysts, hydrofluoric acid, sulfuric acid, and solid acid catalysts.
One such conventional process for the preparation of pivalic acid is set forth in U.S. Pat. No. 5,241,112 (Sanderson et al.), which is incorporated herein by reference. Sanderson et al. specifically relate to a process for the production of pivalic acid from branched olefins, particularly isobutene and carbon monoxide using a solid acid catalyst and, optionally, with minor amounts of a Lewis acid, such as boron trifluoride. The solid acid catalyst is typically a compound comprising sulfonic acid and phosphonic acid groups, where the phosphonic acid groups are covalently bonded to a polymeric chain.
An example of a typical process for manufacturing pivalic acid is shown in FIG.
1
. In reaction step I, conduits
2
and
3
continuously feed isobutylene and carbon monoxide, respectively, to a back mixed, stirred tank reactor 5 having a boron trifluoride dihydrate catalyst disposed therein. Step II, the catalyst recovery step, occurs when the reactor effluent is contacted with water
1
in separator
6
to provide crude pivalic acid, and to extract the boron trifluoride dihydrate catalyst, which is recycled back via conduit
4
to reactor
5
. The crude pivalic acid product is fed to distillation tower via conduit
10
, where it is then purified in distillation step III. Pivalic acid is separated from the C
9
and C
13
acids and oligomeric acids with more than 13 carbons. The pivalic acid is removed from tower
7
via conduit
21
and the oligomeric acids are removed as bottoms via conduit
23
. C
9
and C
9
and C
13
acids are separated from pivalic acid and oligomeric acids with more than 13 carbons via a conduit
22
. Depending on a variety of process conditions, significant amounts of C
8
and C
12
oligomers are also formed from the oligomerization of the feed olefin before carboxylation occurs. Increasing the reaction temperature reduces these unwanted by-products, but also undesirably increases the rate of corrosion. Since these by-product acids occur with carbon numbers that differ by four, they are easily separated by distillation. However, under low temperature conditions, which is preferred to minimize corrosion, selectivity to the desired pivalic acid product is adversely affected.
The present invention addresses these problems and is directed to a novel and unique process for increasing the yield by back cracking oligomeric carboxylic acids to pivalic acid or methyl pivalate. The present invention is able to increase the yield by separating the C
9
and C
13
acids from the crude pivalic acid product and either recycling them back to the pivalic acid reactor or by post-treatment. These C
9
and C
13
acids break down to form pivalic acid (C
5
), thus increasing the effective selectivity. Using the novel approach according to the present invention, lower temperatures can be used to achieve selectivity to pivalic acid, which was heretofore only attainable at higher, more corrosive temperatures. An additional benefit of the process according to the present invention is that the recycled C
9
and C
13
acid stream acts as a diluent in the feed isobutylene, which further inhibits oligomerization of the isobutylene.
SUMMARY OF THE INVENTION
A method for the production of pivalic acid which comprises: (a) reacting an oligomeric neo carboxylic acid with a source of carbon monoxide at a temperature of less than about 200° C, preferably between about 90° C. to about 200° C. more preferably between about 90° C. to about 150° C. in the presence of a catalyst to produce a C
5
carbocation product; and (b) reacting the C
5
carbocation product with water; thereby producing pivalic acid. Preferably, step (a) comprises the steps of: (i) decarbonylating the neo-carboxylic acid to form a C
n−1
carbocation, wherein n is equal to the number of carbon atoms present in the neo-carboxylic acid; (ii) cracking the C
n−1
carbocation to form a C
4
carbocation; and (iii) reacting the C
4
carbocation with the source of carbon monoxide to form the C
5
carbocation product. The partial pressure of carbon monoxide is preferably in the amount from about 50 psig to about 2000 psig, more preferably about 500 psig to about 1500 psig.
Another embodiment according to the present invention is a method for production of alkyl pivalate comprising: (a) reacting an oligomeric neo-carboxylic acid with a source of carbon monoxide at a temperature of less than about 200° C. preferably between about 100° C. to about 160° C. in the presence of a catalyst to produce a C
5
carbocation product; and (b) reacting the C
5
carbocation product with alcohol; thereby producing the alkyl pivalate.
A further embodiment according to the present invention comprises a method of controlling the oligomerization of pivalic acid comprising: (a) producing pivalic acid, wherein a by-product of producing pivalic acid is an oligomeric neo-carboxylic acid; (b) separating the by-product oligomeric neo-carboxylic acid from the pivalic acid; (c) reacting the oligomeric neo-carboxylic acid with a source of carbon monoxide at a temperature of less than about 200° C. in the presence of a catalyst to produce a C
5
carbocation product; and (d) reacting the C
5
carbocation product with water; thereby producing pivalic acid having an overall yield of at least 80 wt. %.
Still a further embodiment according to the present invention comprises a method for production of pivalic acid comprising: (a) reacting isobutylene, carbon monoxide, and a catalyst to produce a reaction mixture; (b) contacting the reaction mixture with water to regenerate catalyst and/or to produce a crude acid product having pivalic acid and oligomeric neo-carboxylic acid; (c) separating the pivalic acid from the oligomeric neo-carboxylic acid; (d) reacting the oligomeric neo-carboxylic acid with a source of carbon monoxide at a temperature of less than 200° C. in the presence of a catalyst to produce a C
5
carbocation product; and (e) the C
5
carbocation product reacting with water; thereby producing pivalic acid having an overall yield of at least 80 wt. %.
According to still another embodiment of the present invention, a method for production of alkyl pivalate comprising: (a) reacting isobutylene, carbon monoxide, and a first catalyst to produce a reaction mixture, (b) contacting the reaction mixture with an alcohol to regenerate the first catalyst and to produce a crude product having alkyl pivalate and an oligomeric neo-carboxyl
Beck Carl Robert
Broadbelt Linda J.
Davoren Dennis J.
Haubein Ned C.
Mozeleski Edmund J.
ExxonMobil Chemical Patents Inc.
Kubena Linda A.
Shah Mukund J.
Tucker Zachary C.
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