U.S. patent application number 10/143443 was filed with the patent office on 2002-12-19 for method and apparatus for the preparation of ketones.
This patent application is currently assigned to EagleView Technologies, Inc.. Invention is credited to Warren, Jack S..
Application Number | 20020193638 10/143443 |
Document ID | / |
Family ID | 26806798 |
Filed Date | 2002-12-19 |
United States Patent
Application |
20020193638 |
Kind Code |
A1 |
Warren, Jack S. |
December 19, 2002 |
Method and apparatus for the preparation of ketones
Abstract
A method and apparatus for continuously producing a ketone in a
tube reactor at elevated weight hourly space velocities and in the
presence of a catalyst from feed material comprised of a first
carboxylic acid or aldehyde or their derivatives and a second
carboxylic acid and a method for using the ketone production method
to produce herbicidal or other agricultural compounds.
Inventors: |
Warren, Jack S.;
(Blountville, TN) |
Correspondence
Address: |
Patrick J. O'Connell, Esq.
Popovich & Wiles, PA
IDS Center, Suite 1902
80 South 8th Street
Minneapolis
MN
55402
US
|
Assignee: |
EagleView Technologies,
Inc.
|
Family ID: |
26806798 |
Appl. No.: |
10/143443 |
Filed: |
May 10, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10143443 |
May 10, 2002 |
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09394583 |
Sep 13, 1999 |
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6392099 |
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60109261 |
Nov 19, 1998 |
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Current U.S.
Class: |
568/354 |
Current CPC
Class: |
C07C 45/48 20130101;
C07C 45/00 20130101; C07C 45/48 20130101; C07C 49/293 20130101;
C07C 49/293 20130101; C07C 45/00 20130101; C07D 261/08
20130101 |
Class at
Publication: |
568/354 |
International
Class: |
C07C 045/72 |
Claims
1. A method of preparing a desired ketone comprising the steps of:
providing a catalytic bed; providing a raw material feed comprised
of a first carboxylic acid or aldehyde or their derivatives and a
second carboxylic acid in the ratio of from 1:2 to 1:20; passing
said raw material feed through said catalytic bed at a temperature
of between about 350.degree. C. and 500.degree. C. at a weight
hourly space velocity greater than two; and separating said desired
ketone.
2. The method of claim 1 including determining the optimum bed
reaction temperature for said raw material feed and preheating said
catalytic bed to said optimum bed reaction temperature.
3. The method of claim 1 wherein said desired ketone is an
unsymmetrical ketone.
4. The method of claim 3 wherein said desired ketone is a
cyclopropyl ketone and said aldehyde is cyclopropylaldehyde.
5. The method of claim 3 wherein said desired ketone is a
cyclopropyl ketone and said first carboxylic acid is
cyclopropanecarboxylic acid.
6. The method of claim 5 wherein said second carboxylic acid is
acetic acid and said desired ketone is methyl cyclopropyl
ketone.
7. The method of claim 1 wherein said catalytic bed includes a
CeO.sub.2/ZrO.sub.2 catalyst structure in the range of about 1 to
5% CeO.sub.2 per gram of ZrO.sub.2.
8. The method of claim 1 including maintaining said raw material
feed in said catalytic bed at a pressure in the range of 10 to 200
psi as said raw material passes through said catalytic bed.
9. The method of claim 1 wherein said weight hourly space velocity
is about 5-20.
10. The method of claim 1 wherein said first carboxylic acid and
said second carboxylic acid are different.
11. A method of preparing a desired ketone comprising the steps of:
providing a catalytic bed; providing a raw material feed comprised
of a first carboxylic acid or aldehyde or their derivatives and a
second carboxylic acid in the ratio of from 1:2 to 1:20; passing
said raw material feed through said catalytic bed in a vertically
upward direction at a temperature of between 350.degree. C. and
500.degree. C.; and separating said desired ketone.
12. The method of claim 11 including determining a preferred bed
reaction temperature for said raw material feed and preheating said
catalytic bed to said preferred bed reaction temperature.
13. The method of claim 11 wherein said desired ketone is an
unsymmetrical ketone.
14. The method of claim 13 wherein said desired ketone is methyl
cyclopropyl ketone.
15. The method of claim 11 wherein said catalytic bed includes a
CeO.sub.2/ZrO.sub.2 catalyst structure in the range of about 1 to
5% CeO.sub.2 per gram of ZrO.sub.2.
16. A method of preparing a ketone comprising: providing a
plurality of tube reactors, each having a catalytic bed; providing
a raw material feed comprised of first and second raw materials
which react in a ketone production reaction to produce said ketone;
selectively passing said raw material feed through the catalytic
bed of one of said plurality of tube reactors and not the other(s)
of said plurality of tube reactors at a temperature of between
350.degree. C. and 500.degree. C.; and recovering said ketone.
17. The method of claim 16 including determining a preferred bed
reaction temperature for said raw material feed and preheating said
catalytic bed of said one tube reactor to said preferred bed
reaction temperature.
18. The method of claim 16 including selectively stopping the
passage of raw material feed through the catalytic bed of said one
tube reactor and passing said raw material feed through the
catalytic bed of one of the other(s) of said tube reactors and
passing said raw material feed through the catalytic bed of said
one of the other(s) of said tube reactors.
19. The method of claim 16 including providing a single ketone
recovery means selectively connectable to said one tube reactor or
said one of the other(s) of said tube reactors for recovering said
ketone wherein said means is connected with said one tube
reactor.
20. The method of claim 19 including selectively stopping the
passage of raw material feed through the catalytic bed of said one
tube reactor and connecting the raw material feed through the
catalytic bed of said one of the other(s) of said tube reactors and
disconnecting said recovery means from said one tube reactor and
connecting said recovery means to said one of the other(s) of said
tube reactors.
21. The method of claim 20 including regenerating the catalytic bed
of said one tube reactor.
22. The method of claim 16 wherein said catalytic bed includes a
CeO.sub.2/ZrO.sub.2 catalyst structure in the range of about 1 to
5% CeO.sub.2 per gram of ZrO.sub.2.
23. An apparatus for producing a ketone from first and second feed
materials via a ketone production reaction comprising: a feed
material source for providing said first and second feed materials;
a plurality of tube reactors, each having an inlet end, an outlet
end and a catalytic bed therebetween; means for selectively
supplying said first and second feed materials to the inlet end of
one of said plurality of tube reactors in a predetermined ratio and
preventing the supply of said first and second feed materials to
the inlet end of the other(s) of said plurality of tube
reactors.
24. The apparatus of claim 23 wherein said means for supplying
includes a selection valve positioned between said feed material
source and said plurality of tube reactors.
25. The apparatus of claim 23 wherein said plurality of tube
reactors are mounted to facilitate vertically upward flow of said
first and second feed materials through the catalytic bed of said
one tube reactor.
26. A method of preparing a desired ketone comprising the steps of:
providing a catalytic bed; providing a raw material feed comprised
of a first carboxylic acid or aldehyde or their derivatives and a
second carboxylic acid in the ratio of from 1:2 to 1:20; passing
said raw material feed through said catalytic bed at a temperature
of between about 100.degree. C. and 500.degree. C. and at a
pressure in the range of about 10 psig to about 200 psig; and
separating said desired ketone.
27. The method of claim 26 wherein said pressure is in the range of
about 20 psig to 100 psig.
28. A process for the preparation of a compound of formula (I)
12wherein: R.sup.1 is cycloalkyl having from three to six ring
carbon atoms which is unsubstituted or which has one or more
substituents selected from the group consisting of R.sup.4 and
halogen; R.sup.2 is halogen; straight- or branched-chain alkyl
having up to six carbon atoms which is substituted by one or more
--OR.sup.5; cycloalkyl having from three to six carbon atoms; or a
member selected from the group consisting of nitro, cyano,
--CO.sub.2R.sup.5, --NR.sup.5R.sup.6, --S(O).sub.pR.sup.7,
--O(CH.sub.2).sub.mOR.sup.5, --COR.sup.5,
--N(R.sup.8)SO.sub.2R.sup.7, --OR.sup.7, --OH, --OSO.sub.2R.sup.7,
--(CR.sub.9R.sup.10).sub.tSO.sub.qR- .sup.7a, --CONR.sup.5R.sup.6,
--N(R.sup.8)--C(Z)Y, --(CR.sup.9R.sup.10)NR.- sup.8R.sup.11 and
R.sup.4; n is zero or an integer from one to three; when n is
greater than one, then the groups R.sup.2 are the same or
different; m is one, two or three; p is zero, one or two; q is
zero, one or two; t is an integer from one to four; R.sup.3 is
straight- or branched-chain alkyl group containing up to six carbon
atoms which is unsubstituted or which has one or more substituents
selected from the group consisting of halogen, --OR.sup.5,
--CO.sub.2R.sup.5, --S(O).sub.pR.sup.7, phenyl or cyano; or phenyl
which is unsubstituted or which has one or more substituents
selected from the group consisting of halogen, --OR.sup.5 and
R.sup.4; R.sup.4 is straight- or branched-chain alkyl, alkenyl or
alkynyl having up to six carbon atoms which is unsubstituted or is
substituted by one or more halogen; R.sup.5 and R.sup.6, which are
the same or different, are each hydrogen or R.sup.4; R.sup.7 and
R.sup.7a independently are R.sup.4, cycloalkyl having from three to
six ring carbon atoms, or --(CH.sub.2).sub.w-phenyl wherein phenyl
is unsubstituted or is substituted by from one to five R.sup.12
which are the same or different; w is zero or one; R.sup.8 is
hydrogen; straight- or branched-chain alkyl, alkenyl or alkynyl
having up to ten carbon atoms which is unsubstituted or is
substituted by one or more halogen; cycloalkyl having from three to
six ring carbon atoms; --(CH.sub.2).sub.w-phenyl wherein phenyl is
unsubstituted or is substituted by from one to five R.sup.12 which
are the same or different; or --OR.sup.13; R.sup.9 and R.sup.10
independently are hydrogen or straight- or branched-chain alkyl
having up to six carbon atoms which is unsubstituted or is
substituted by one or more halogen; R.sup.11 is --S(O).sub.qR.sup.7
or --C(Z)Y; R.sup.12 is halogen; straight- or branched-chain alkyl
having up to three carbon atoms which is unsubstituted or is
substituted by one or more halogen; or a member selected from the
group consisting of nitro, cyano, --S(O).sub.pR.sup.3 and
--OR.sup.5; Y is oxygen or sulphur; Z is R.sup.4,
--NR.sup.8R.sup.13, --NR.sup.8--NR.sup.13R.sup.14, --SR.sup.7 or
--OR.sup.7; and R.sup.13 and R.sup.14 independently are R.sup.8, or
an agriculturally acceptable salt or metal complex thereof, which
process comprises: (i) reacting a compound of formula (II) 13
wherein R.sup.15 is a straight- or branched-chain alkyl group
having up to six carbon atoms with a compound of formula (III) 14
in an aprotic solvent in the absence of a base to form a compound
of formula (IV) 15(ii) reacting a compound of formula (IV) with a
compound that contains a leaving group L [such as alkoxy or
N,N-dialkylamino, esp. ethoxy and CH(OCH.sub.2CH.sub.3).sub.3]to
form a compound of formula (V) 16(iii) reacting a compound of
formula (V) with hydroxylamine or a salt of hydroxylamine to form a
compound of formula (I), wherein the process further comprises
producing the compound of formula (III) by: providing a catalytic
bed; providing a raw material feed comprised of a R.sup.1COOH or
R.sup.1COH and a second carboxylic acid in the ratio of from 1:2 to
1:20; passing said raw material feed through said catalytic bed at
a temperature of between about 350.degree. C. and 500.degree. C. at
a weight hourly space velocity greater than two; and separating the
compound of formula (III).
29. The process of claim 28, wherein the second carboxylic acid is
acetic acid.
30. A process for the preparation of a compound of formula (X)
17comprising: (iii) reacting a compound of formula (XI) 18 with a
compound of formula (XII) 19 to form a compound of formula (XII)
20(iv) reacting a compound of formula (XIII) with
CH(OCH.sub.2CH.sub.3).sub.3 to form a compound of formula (XIV)
21(iii) reacting a compound of formula (XIV) with hydroxylamine or
a salt of hydroxylamine to form a compound of the formula (XV)
22(iv) reacting a compound of formula (XV) with chloroperbenzoic
acid [or an equivalent] to form a compound of the formula (X)
wherein the process further comprises producing the compound of
formula (XII) by: providing a catalytic bed; providing a raw
material feed comprised of cyclopropane carboxylic acid or
cyclopropane aldehyde and acetic acid in the ratio of from 1:2 to
1:20; passing said raw material feed through said catalytic bed at
a temperature of between about 350.degree. C. and 500.degree. C. at
a weight hourly space velocity greater than two; and separating the
compound of formula (XII).
Description
[0001] This application claims the benefit of provisional
application Serial No. 60/109/261 filed Nov. 19, 1998.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to the preparation
of ketones and more particularly to a method and apparatus for
preparing unsymmetrical ketones such as methyl cyclopropyl ketone
(MCPK). The invention also relates to a method of using such ketone
preparation method in the preparation of a herbicidal or other
agricultural compounds.
[0004] 2. Description of the Prior Art
[0005] In general, unsymmetrical ketones are useful as
intermediates for the production of numerous specialty chemicals.
More specifically, methyl cyclopropyl ketone (MCPK) has a variety
of current and potential future uses including, among others, the
production of specialty agricultural and pharmaceutical
compounds.
[0006] Numerous literature references cite and disclose various
well-known processes for the preparation of ketones. These
processes include oxidation of secondary alcohols, Friedel-Crafts
acylation, reaction of acid chlorides with organo cadmium
compounds, acetoacetic ester synthesis and decarboxylation from
acids, among others.
[0007] Text and literature references also detail problems
associated with using these processes to produce ketones. These
include problems such as the unavailability and/or cost of raw
materials, the requirement of multi-stage processing, the low
conversion of the raw materials and/or the low selectivity of the
desired ketones, and the production of corrosive or hard to
separate products.
[0008] Ketone production processes have also been described in the
patent literature. For example, U.S. Pat. Nos. 4,528,400 and
4,570,021 disclose a process for the preparation of unsymmetrical
ketones by a catalytic vapor phase reaction using reactants such as
ketones with carboxylic acids. However, laboratory trials using
acetone and cyclopropanecarboxylic acid resulted in the production
of high quantities of gamma-butyrolactone, several pentenones and
pentanones, but no MCPK.
[0009] U.S. Pat. Nos. 3,410,909 and 3,453,331 disclose processes
for the preparation of symmetrical and unsymmetrical ketones from
aldehydes containing up to 8 carbons in a non-cyclic saturated
aliphatic chain.
[0010] German Patent Disclosure No. P36 37 788.0 (1986) discloses a
specific condensation reactor process for the preparation of methyl
cyclopropyl ketone (MCPK) from cyclopropanecarboxylic acid or its
derivatives. However, although examples from this patent show raw
material conversion of from 58 to 99 percent and selectivity to
MCPK of 42 to 75 percent, the liquid hourly space velocity (LHSV)
or weight hourly space velocity (WHSV) values of less than 1 (i.e.,
0.25 to 0.99) minimize the industrial usefulness of this
condensation reactor process.
[0011] European Patent Application No. 0 085 996 also discloses
processes for the preparation of unsymmetric aliphatic ketones at
atmospheric pressures (or slightly above) and at relatively low
WHSV.
[0012] Still further, a reported disadvantage of all vapor phase
tube reactor processes is the "coking" or deactivation of the
catalyst and consequential "plugging" of the reactors. This results
in the loss of production hours while the catalyst is being
regenerated or replaced.
[0013] Accordingly, there is a need in the art for a method and
apparatus for the production of ketones, and particularly
unsymmetrical ketones such as methyl cyclopropyl ketone (MCPK)
which utilizes readily available and inexpensive raw materials,
which eliminates or minimizes reactor plugging, which provides for
high conversion rates and high selectivity to MCPK and which
dramatically improves the rate of production.
SUMMARY OF THE INVENTION
[0014] In contrast to the prior art, the present invention relates
to a method and an apparatus for producing ketones, and in
particular unsymmetrical ketones such as MCPK which overcome the
limitations of the prior art. Specifically, the method and
apparatus of the present invention utilizes readily available and
inexpensive raw materials, minimizes reactor plugging, results in
high conversion and selectivity rates and provides for increased
production of the desired ketone. Generally, the raw materials used
in the method and apparatus of the present invention include an
acid or aldehyde or their derivatives and a carboxylic acid.
[0015] More specifically, the present invention involves the
preparation of methyl cyclopropyl ketone (MCPK) utilizing a tube
reactor provided with a suitable catalyst ranging from about 1
percent to 25 percent by weight. The preferred raw materials or
feed materials include cyclopropylaldehyde or its derivatives (such
as cyclopropanecarboxylic acid) and acetic acid which are readily
available through processes known in the art. These raw materials
are fed into a catalytic tube reactor where they are exposed to the
catalyst and react to produce the desired ketone and various
co-products. Preferably, the new raw materials are fed from the
bottom to the top so that the reactant materials flow vertically
upwardly through the reactor. To minimize undesired co-products as
well as "coking" of the catalyst and thus "plugging" of the
reactor, the optimum reaction temperature of the reactant feed
stream is determined and the catalyst bed is preheated to such
optimum temperature prior to the introduction of the reactant
materials.
[0016] To further minimize downtime of the production process
during the regeneration of catalyst or during reactor maintenance
or repair, multiple or side-by-side reactors are provided with
means for selectively directing the reactant materials to one or
the other and removing product and co-products from such selected
reactor. This permits the non-selected reactor or reactors to be
repaired and/or maintained and the catalyst therein to be
regenerated, if needed.
[0017] In the preferred embodiment and method of the present
invention, the reactor is a vapor phase tube reactor in contrast to
a condensation reactor or a batch stirred reactor. Further, the
reactant materials in the method and apparatus of the present
invention are preferably fed into the bottom of the reactor and
caused to flow upwardly through the reactor over the catalyst. With
this configuration, it is possible to dramatically increase the
LHSV or WHSV. This results in dramatically increased production
rates.
[0018] Accordingly, an object of the present invention is to
provide an improved method and apparatus for the preparation of
ketones and in particular unsymmetrical ketones such as methyl
cyclopropyl ketone (MCPK).
[0019] Another object of the present invention is to provide a
method and apparatus for preparing MCPK in a tube reactor with a
minimized incidence of reactor plugging.
[0020] Another object of the present invention is to provide a
method and apparatus for the preparation of MCPK utilizing
inexpensive and readily available reactant or feed materials.
[0021] A further object of the present invention is to provide an
improved method and apparatus for the preparation of MCPK at high
conversion rates and high selectivity to MCPK, with minimal
undesirable co-products.
[0022] A still further object of the present invention is to
provide a method and apparatus for the preparation of MCPK at high
production rates so as to result in an economically attractive
process.
[0023] A still further object of the present invention is to
provide a method of using the above-described ketone preparation
method to prepare a herbicidal or other agricultural compound.
[0024] These and other objects of the present invention will become
apparent with reference to the drawing, the description of the
preferred embodiment and the appended claims.
DESCRIPTION OF THE DRAWING
[0025] The single figure is a schematic illustration of the method
and apparatus of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT AND METHOD
[0026] Reference is first made to the drawing which illustrates a
schematic of the system or apparatus of the present invention and a
flow diagram of the process in accordance with the present
invention. While the apparatus and method are applicable to a wide
variety of ketones and more specifically unsymmetrical ketones,
they are particularly applicable to methyl cyclopropyl ketone
(MCPK). Accordingly, the preferred embodiment and method will be
described with respect to MCPK and a system and process used to
make MCPK. Unless otherwise indicated all percentages are by
weight.
[0027] In the drawing, the primary reaction members comprise a pair
of vapor phase tube reactors 11 and 12. If desired or needed, more
than two reactors could be provided to accommodate the specific
reaction time or life cycle of the selected feed materials and the
regeneration time of the selected catalyst. These reactors 11 and
12 are preferably conventional stainless steel catalytic tube
reactors which are filled with various combinations of an inert
filler material and a catalyst. In the preferred embodiment, the
inert filler material is comprised of glass beads between about
3-10 mm in diameter, although it is contemplated that various other
materials can be used as well such as stainless steel beads, lava
rock and sand, among possible others. A portion of the reactors are
also filled with a catalytic material to promote the desired
reaction of the reactant materials. A variety of catalysts known in
the art are useful in the production of ketones. These preferably
include a catalyst carrier or support, which has been impregnated
with a catalyst. Possible supports include metal or metal oxides
such as alumina, silica, titania, zirconia and mixtures thereof and
naturally occurring clay material such as montmorillonite or
kaolin. Possible catalysts include, but are not limited to, metal
or metal oxides such as oxides of cerium (CeO.sub.2 or CeO.sub.3),
zirconium (ZrO.sub.2), or other lanthanides, and the group III B,
IV B and V B metal or metal oxides. The preferred catalysts are
cerium oxide (CeO.sub.2 or CeO.sub.3), zirconium oxide (ZrO.sub.2)
or zinc oxide (ZnO). In the preferred method of the present
invention, the catalytic material is CeO.sub.2 provided on an
aluminum oxide (Al.sub.2O.sub.3) or a zirconium support oxide
(ZrO.sub.2) support material.
[0028] One method of preparing the catalyst in accordance with the
invention is by impregnating the porous support material with
cerium acetate hydrate, Ce(O.sub.2CCH.sub.3).sub.3.1.5H.sub.2O.
This gives 1.0 g of CeO.sub.2/2.0 g of this precursor. The hydrate
is dissolved as 200 g/L aqueous solution. The catalyst support is
dried at 450 C for twelve (12) hours. Impregnation is by the
incipient wetness method (drop-wise), at ambient temperature. The
aqueous solution can be divided to obtain the actual amount of
catalyst necessary for the impregnation. Odd percentages can be
obtained by using 10 milliliters of the solution for each one (1)
gram of actual catalyst needed. For 5 wt % CeO.sub.2 catalyst, 50
milliliters of this saturated aqueous solution is used per 100
grams of catalyst support. For impregnation of catalyst on the
catalyst support greater than 5%, multiple applications should be
used, with an intermediate drying step at 120 C, to insure uniform
coverage. For 10 wt % CeO.sub.2 catalyst, two (2) 50 milliliter
solutions are used. The resulting catalyst support with impregnated
catalyst is then oven-dried at 450 C for twelve (12) hours, prior
to pretreatment in the reactor. Other precursors, such as cerium
nitrate and techniques, such as spray or tumble-drying, known to
those skilled in the art, can be used to apply the catalyst.
[0029] The concentration of the catalyst in the reactors 11 and 12
is preferably in the range of 1 to 25 percent by weight, with the
preferred range being 1 to 20 percent by weight. Such catalyst
range, however, will vary with the particular catalyst and catalyst
support and support configuration being used. For example, with a
CeO.sub.2 catalyst on a Al.sub.2O.sub.3 support having an exposed
or effective surface area of about 178 m.sup.2/g, the preferred
range is 10 to 20% and more preferably 15 to 20%. For a CeO.sub.2
catalyst on a ZrO.sub.2 support having an exposed or effective
surface area of about 34 m.sup.2/g, the preferred range is less
than 5% and more preferably about 2 to 5%.
[0030] The distribution of the catalyst within the reactors 11 and
12 can vary. Preferably, however, the bottom 1/3 of the reactor is
filled with inert material in the form of glass beads, the middle
third of the reactor is filled with catalyst and the top 1/3 of the
reactor could be empty or filled with inert material in the form of
glass beads.
[0031] In the preferred embodiment as shown, the reactors 11 and 12
are vertically oriented so that the feed materials pass vertically
upwardly from the bottom to the top of the reactors. However, the
benefits of the invention can also be realized with reactors having
different orientations so that the feed materials flow downwardly
or laterally through the reactors. These latter orientations are
not as preferred, however, because of an increased tendency to
plug.
[0032] The raw or reactive materials in accordance with the present
invention are provided from a reactant material source or reservoir
14. In general, these reactant or feed materials will comprise a
mixture of (1) a carboxylic acid or aldehyde or their derivatives
and (2) a second carboxylic acid or its derivatives. As used
herein, a derivative is a chemical substance or compound which is
derived from another. For example, because the OH of a carboxylic
acid can be replaced by a number of groups such as Cl, H, OR or
NH.sub.2 to yield acid chlorides, aldehydes, esters and amines,
respectively, these are all considered derivatives of carboxylic
acid. In the preferred embodiment, the reactant materials comprise
a mixture of acetic acid and cyclopropylaldehyde or its derivatives
(such as cyclopropanecarboxylic acid). The molar ratio of the
acetic acid to the cyclopropanecarboxylic acid which makes up the
feed stream or feed material is preferably in the range of 2:1 to
20:1. More preferably, the ratio of acetic acid to
cyclopropanecarboxylic acid is about 3:1 to 8:1 and most preferably
within a range of 3:1 to 5:1. The most preferred ratio is about
4:1. If desired, the feed materials can be provided in separate
reservoirs or from separate sources and then combined in the
desired feed ratio.
[0033] The feed material is fed from the reservoir 14 through a
conduit 15 to a pump or pressure member 16 which discharges the
feed material into the conduit 18 at an elevated pressure greater
than atmospheric. The pressure is selected to optimize the reaction
conditions (conversion and selectivity) and to maintain the feed
materials in a gaseous state at the selected reaction temperature.
In the preferred method and apparatus, the feed material is
pressurized to a range of about 10 psig to about 200 psig, and more
preferably to a pressure of about 20 psig to 100 psig. Most
preferably, the pressure is provided at about 40 psig to 50
psig.
[0034] From the pump 16, the feed material is directed through the
conduit 18 to a valve complex 19, which selectively directs the
feed material either to the reactor feed conduit 20 or the reactor
feed conduit 21. As shown, the feed conduits 20 and 21 are
connected respectively, to the bottom ends of the reactors 11 and
12. The reactor feed conduits 20 and 21 include shutoff valves 22
and 24, respectively, for isolating the reactors 11 and 12 from the
feed materials and facilitating the flow of purging or other
materials, if desired. If more than two reactors are utilized, the
valve complex 19 is modified and additional reactor feed conduits
and shutoff valves are provided so that the flow of the feed
materials can be selectively directed to each reactor, while
selectively isolating one or more of the others.
[0035] The system of the present invention also includes a supply
of purging and/or regeneration materials 25 and 26. Such materials
may be provided from any available source such as a reservoir or
the like. In the preferred embodiment, the materials 25 and 26
comprise air and nitrogen, respectively, although other materials
known in the art can be used as well such as hydrogen and methane.
The materials are used during purging or preheating of the reactors
11 or 12 or during regeneration of the catalyst within the reactors
11 and 12. The materials 25 and 26 are provided to the valve 19
through the conduits 28 and 29, respectively. The conduits 28 and
29 are also provided with a plurality of shut-off valves 30, 31 and
32 to selectively control the flow of materials 25 and 26 to the
valve 19. Pressure regulators 34 and 35 are associated with the
valves 30 and 32. The valve 19 functions to selectively direct the
flow of materials 25 and/or 26 to either the reactor feed conduit
20 or the reactor feed conduit 21. The conduits 20 and 21 are
provided with temperature gauges 36 and 38, respectively, upstream
of the valves 22 and 24
[0036] The reactors 11 and 12 are also provided with heating means
41 and 42 and means in the form of the temperature control and
regulators 44 for selectively controlling the heaters 41 and 42.
Means for monitoring the temperature and pressure within the
reactor are also provided on each reactor 11 and 12 in the form of
the pressure and temperature monitors 45.
[0037] Outflow or product exit conduits 46 and 48 are connected
with the top or upper ends of the reactors 11 and 12, respectively,
for directing the outflow from the reactors to a product separation
means 51. Connected with each of the conduits 46 and 48 is a
secondary or waste conduit 49 and 50, respectively, for purging or
regeneration material, which is not desired to be, directed to the
recovery means 51. Appropriate valves 52, 53, 54 and 55 are
provided in the conduits 49, 50,46 and 48, respectively, for
controlling the flow of the product and waste streams. If more than
two reactors are provided, additional exit conduits, waste conduits
and associated valves are also provided.
[0038] The product recovery means 51 includes a receiver, a
precipitation or distillation column 56 and a pressure means or
pump 58 to recover the preferred product, namely, methyl
cyclopropyl ketone (MCPK) from the exit stream. In FIG. 1, the MCPK
is recovered through the conduit 60, with the other materials or
co-products being recovered through the conduit 59.
[0039] Having described the apparatus and system of the present
invention in detail, the ketone production method may be understood
best as follows. First, one of the reactors 11 and 12 is selected
for initial use in the process of the present invention. For
purposes of describing the preferred method of the present
invention, the reactor 11 will be selected. In such case, the other
reactor 12 is isolated from the system by closing the valves 24, 53
and 55. The reactor 11 is then prepared for preparation of the
ketone, specifically MCPK, by activating the heater 41 and
providing a purging gas from the sources 25 and/or 26, through the
valve 19 and into the lower end of the reactor 11. In accordance
with the preferred method, the reactor 11 is preheated by the
heater 41 to a temperature in the range of 350.degree. C. to
500.degree. C. and more preferably in the range of 400.degree. C.
to 440.degree. C. Most preferably, in accordance with the present
invention, the preferred reaction temperature is first determined
and the reactor is heated to this temperature. This preferred
temperature will vary to some extent with the composition of the
feed stream, the concentration and type of catalyst, the liquid or
weight hourly space velocity at which the reactor will be run, etc.
The reactor 11 is then heated to this preferred temperature.
[0040] When the preferred temperature is reached, the valve 19 is
actuated to stop the flow of the purging or other gas to the
reactor 11 and to provide feed material of the desired composition
from the reservoir or source 14. In the preferred embodiment, this
feed material is a mixture of acetic acid and
cyclopropanecarboxylic acid in the ratios set forth above. This
pressurized feed stream is supplied to the bottom of the reactor 11
so that the vaporized feed materials enter the reactor from the
bottom and flow upwardly through the glass beads, the catalyst and
the glass beads before exiting through the top of the reactor 11.
During this process, the material in the feed stream and the
conduit 20 is sufficiently pressurized as set forth above by the
pressure means 16 to maintain the feed materials in a gaseous state
at the reaction temperature. The feed materials are fed through the
reactor 11 at a rate sufficient to provide a liquid or weight
hourly space velocity in excess of 1, more preferably in excess of
2 and most preferably in the range of 5-20 or 10-20. As used herein
and as known in the art, weight (or liquid) hourly space velocity
(WHSV or LHSV) is the amount of raw material (unit weight or
volume) per unit weight or volume of catalyst per hour.
[0041] During the passage of feed materials through the reactors,
the temperature within the reactors is maintained at the preferred
temperature. This temperature will vary depending upon the feed
materials, the ketone being produced and the pressure within the
reactors, among other possible factors. In general, the temperature
and pressure are selected to achieve a desired reaction yield and
to maintain the feed reactants in their gaseous form. Normally, the
reaction temperatures for ketone produciton will be in the range of
100.degree. C. to 500.degree. C. For a MCPK production process, the
reaction temperature will be in the range of 350.degree. C. to
500.degree. C. and more preferably 400.degree. C. to 440.degree.
C.
[0042] Within the reactor 11, the feed material reacts in the
presence of the catalyst and at the preferred temperature, to
produce MCPK or other desired ketone along with other byproducts or
co-products including acetone and dicyclopropyl ketone. With the
valve 52 closed and the valve 54 open, this exit or product stream
is then directed via the conduit 46 to the recovery means 51 where
the MCPK and other co-products are separated from one another.
Preferably, this separation/recovery process is a precipitation or
distillation process known in the art.
[0043] With the method and apparatus as described above, conversion
rates in excess of 80% can be achieved with conversion rates
commonly in the range of 95%-99%. Also, with the above method and
apparatus, selectivity of the converted feed stream to MCPK in
excess of 50% and commonly in the range of 70%-80% can be
achieved.
[0044] In the event the reactor 11 requires maintenance or for some
reason the reactor becomes plugged or the catalyst needs
regeneration, the second reactor 12 can be quickly and easily
utilized without resulting in downtime and thus loss of production
or production rate. To accomplish this conversion to the reactor
12, the reactor 12 can be brought up to the optimum temperature and
the valve 24 can be opened to allow the flow of purging or other
gas into the bottom of the reactor 12 through the reactor and out
through the conduit 50. Once the optimum temperature has been
reached and the reactor 12 has been sufficiently purged, the valve
19 is adjusted to direct the feed material from the reservoir 14
into and through the conduit 21 and through the reactor 12. When
this is done, the valves 53 and 54 are closed and the valve 55 is
opened. The previously used reactor 11 is then isolated from the
feed materials and can be isolated entirely from the system by
closing the valve 22 or can be provided with purging or
regeneration material from the sources 25 and 26 if desired.
[0045] In the MCPK process of the preferred embodiment, the
reaction time or reaction life cycle is greater than the catalyst
regeneration time. Thus, a pair of reactors 11 and 12 is sufficient
to provide a continuous ketone production process. As used herein,
the term "reaction time" or "reaction life cycle" is the time
during which acceptable reaction conditions exist (i.e., before
catalyst regeneration is needed or plugging occurs) for the
selected feed materials and selected catalyst at the specific
reaction variables of temperature, pressure, WHSV and the like. The
term "regeneration time" is the time needed to regenerate the
selected catalyst. If the specific feed materials, catalyst and
reaction variables are such that the reaction time or life cycle is
less than the regeneration time. More than two reactors are needed
to maintain a continuous ketone production process.
[0046] Having described the method and apparatus of the present
invention in detail, the present invention can be further
understood by reference to the following examples.
EXAMPLES
[0047] Results of examples are shown in Tables 1 and 2 below for
various feed composition ratios, operating temperatures and
pressures and weight hourly space velocities and at various
concentrations of catalysts. Specifically, Table 1 reflects a 10
percent CeO.sub.2/Al.sub.2O.sub.3 catalyst, while Table 2 reflects
a 15 percent CeO.sub.2/Al.sub.2O.sub.3 catalyst.
[0048] In the examples for the data in Tables 1 and 2, 1/2 inch
I.D. stainless steel tube reactors were filled with glass beads,
CeO.sub.2/Al.sub.2O.sub.3 catalyst, and glass beads (of
approximately 1/3, 1/3, 1/3). The reactor was preheated with
flowing air at a temperature of 520 to 560 C. An internal
thermocouple was located at the catalyst bed for monitoring the
temperature. A standard controller was used for temperature control
of the surrounding clamshell furnace and pressure was controlled
using a diaphragm-type backpressure regulator.
[0049] Feed material in a molar ratio of 4:1 (acetic
acid:cyclopropanecarboxylic acid) was fed into the reactor. For
each example, the temperature, pressure and weight hourly space
velocity was controlled to maintain "steady state" operation.
Samples were taken from the output of the reactor and analyzed for
cyclopropanecarboxylic acid (CPA) and MCPK for the purpose of
calculating conversion and selectivity.
[0050] The CeO.sub.2 containing catalyst was prepared by
impregnating Al.sub.2O.sub.3 with cerium acetate hydrate via the
incipient wetness method (drop-wise) at ambient temperature. The
support was dried at 450 C for eight (8) hours. For the five weight
percent CeO.sub.2 catalyst one solution was used, for the ten
weight percent CeO.sub.2 catalyst, two solutions were used, and for
the fifteen weight percent CeO.sub.2 catalyst, three solutions were
used, each with an intermediate drying step at 120 C. The catalyst
was then oven dried on the support at 450 C for eight (8) hours
prior to pre-treatment in the reactor.
[0051] The results were as follows:
1TABLE 1 Example Molar Temperature Pressure Conversion Selectivity
No. Ratio C. psig WHSV CCA % MCPK % M-11-1A 4:1 421 15 6-7 92 79
M-11-6A 4:1 435 35 5-6 91 62 M-11-7A 4:1 431 44 3-4 98 64 M-11-8A
4:1 431 52 3-4 98 70 M-11-9A 4:1 434 59 2-3 99 67 M-11-12B 4:1 433
48 3-4 96 76 10% CeO.sub.2/Al.sub.2O.sub.3 (Engelhard) Pretreated
at 560 C., (Flowing Air)
[0052]
2TABLE 2 Example Molar Temperature Pressure Conversion Selectivity
No. Ratio C. psig WHSV CCA % MCPK % M-50-48 4:1 430 40 5-6 94 50
M-50-64 4:1 405 40 5-6 99 70 M-50-80 4:1 410 40 2-4 99 65 M-50-96
4:1 405 40 4 98 72 M-50-112 4:1 420 40 6-8 99 71 M-50-128 4:1 410
40 6-8 96 72 M-50-144 4:1 440 40 13-16 95 68 15%
CeO.sub.2/Al.sub.2O.sub.3 (Engelhard) Pretreated at 520 C.,
(Flowing Air) Ratio: Acetic Acid: Cyclopropanecarboxylic Acid WHSV:
(Weight Hourly Space Velocity) Grams Raw Material per Gram Catalyst
per Hour CCA: Cyclopropanecarboxylic Acid MCPK: Methyl Cyclopropyl
Ketone
[0053] In the examples for the data in Tables 3, 4 and 5, yield
data (conversion and selectivity is shown for a CeO.sub.2/ZrO.sub.2
catalyst structure of 2%, 3% and 4%. In these examples, the
temperature was in the range of 410-450 C, the pressure was about
30 psig and the feed ratio of acetic acid to cyclopropanecarboxylic
acid was 4:1. The other reaction conditions and equipment were
similar to that of the CeO.sub.2/Al.sub.2O.sub.3 example above.
3TABLE 3 2% CeO.sub.2/ZrO.sub.2 Conversion Selectivity R.sub.1M
USK.sub.1 WHSV % % 2 78 60 4 87 74 6 85 72 8 82 65 10 75 55
[0054]
4TABLE 4 3% CeO.sub.2/ZrO.sub.2 Conversion Selectivity R.sub.1M
USK.sub.1 WHSV % % 2 86 82 4 90 83 6 91 85 8 91 86 10 92 83
[0055]
5TABLE 5 4% CeO.sub.2/ZrO.sub.2 Conversion Selectivity R.sub.1M
USK.sub.1 WHSV % % 2 78 55 4 82 62 6 84 63 8 86 68 10 80 62
[0056] The ketones produced by the apparatus and method of the
present invention can be utilized and combined with other processes
to produce various herbicidal or other agricultural compounds.
Preferably, the ketone production method of the present invention
can be used, in combination with other process steps, to prepare
such a compound of the formula (I) 1
[0057] wherein:
[0058] R.sup.1 is cycloalkyl having from three to six ring carbon
atoms which is unsubstituted or which has one or more substituents
selected from the group consisting of R.sup.4 and halogen;
[0059] R.sup.2 is halogen; straight- or branched-chain alkyl having
up to six carbon atoms which is substituted by one or more
--OR.sup.5; cycloalkyl having from three to six carbon atoms; or a
member selected from the group consisting of nitro, cyano,
--CO.sub.2R.sup.5, --NR.sup.5R.sup.6, --S(O).sub.pR.sup.7,
--O(CH.sub.2).sub.mOR.sup.5, --COR.sup.5,
--N(R.sup.8)SO.sub.2R.sup.7, --OR.sup.7, --OH, --OSO.sub.2R.sup.7,
--(CR.sub.9R.sup.10).sub.tSO.sub.qR.sup.7a, --CONR.sup.5R.sup.6,
--N(R.sup.8)--C(Z)Y, --(CR.sup.9R.sup.10)NR.sup.8R.s- up.11 and
R.sup.4;
[0060] n is zero or an integer from one to three; when n is greater
than one, then the groups R.sup.2 are the same or different;
[0061] m is one, two or three;
[0062] p is zero, one or two;
[0063] q is zero, one or two;
[0064] t is an integer from one to four;
[0065] R.sup.3 is straight- or branched-chain alkyl group
containing up to six carbon atoms which is unsubstituted or which
has one or more substituents selected from the group consisting of
halogen, --OR.sup.5, --CO.sub.2R.sup.5, --S(O).sub.pR.sup.7, phenyl
or cyano; or phenyl which is unsubstituted or which has one or more
substituents selected from the group consisting of halogen,
--OR.sup.5 and R.sup.4;
[0066] R.sup.4 is straight- or branched-chain alkyl, alkenyl or
alkynyl having up to six carbon atoms which is unsubstituted or is
substituted by one or more halogen;
[0067] R.sup.5 and R.sup.6, which are the same or different, are
each hydrogen or R.sup.4;
[0068] R.sup.7 and R.sup.7a independently are R.sup.4, cycloalkyl
having from three to six ring carbon atoms, or
--(CH.sub.2).sub.w-phenyl wherein phenyl is unsubstituted or is
substituted by from one to five R.sup.12 which are the same or
different;
[0069] w is zero or one;
[0070] R.sup.8 is hydrogen; straight- or branched-chain alkyl,
alkenyl or alkynyl having up to ten carbon atoms which is
unsubstituted or is substituted by one or more halogen; cycloalkyl
having from three to six ring carbon atoms;
--(CH.sub.2).sub.w-phenyl wherein phenyl is unsubstituted or is
substituted by from one to five R.sup.12 which are the same or
different; or --OR.sup.13;
[0071] R.sup.9 and R.sup.10 independently are hydrogen or straight-
or branched-chain alkyl having up to six carbon atoms which is
unsubstituted or is substituted by one or more halogen;
[0072] R.sup.11 is --S(O).sub.qR.sup.7 or --C(Z)Y;
[0073] R.sup.12 is halogen; straight- or branched-chain alkyl
having up to three carbon atoms which is unsubstituted or is
substituted by one or more halogen; or a member selected from the
group consisting of nitro, cyano, --S(O).sub.pR.sup.3 and
--OR.sup.5;
[0074] Y is oxygen or sulphur;
[0075] Z is R.sup.4, --NR.sup.8R.sup.13,
--NR.sup.8-NR.sup.13R.sup.14, --SR.sup.7 or --OR.sup.7; and
[0076] R.sup.13 and R.sup.14 independently are R.sup.8,
[0077] or an agriculturally acceptable salt or metal complex
thereof,
[0078] The process for preparing a compound of the above formula
(I) comprises:
[0079] (i) reacting a compound of formula (II) 2
[0080] wherein R.sup.15 is a straight- or branched-chain alkyl
group having up to six carbon atoms with a compound of formula
(III) 3
[0081] in an aprotic solvent in the absence of a base to form a
compound of formula (IV) 4
[0082] (ii) reacting a compound of formula (IV) with a compound
that contains a leaving group L [such as alkoxy or
N,N-dialkylamino, esp. ethoxy and CH(OCH.sub.2CH.sub.3).sub.3]to
form a compound of formula (V) 5
[0083] (iii) reacting a compound of formula (V) with hydroxylamine
or a salt of hydroxylamine to form a compound of formula (I),
[0084] wherein the process further comprises producing the compound
of formula (III) by:
[0085] providing a catalytic bed;
[0086] providing a raw material feed comprised of a R.sup.1COOH or
R.sup.1COH and a second carboxylic acid in the ratio of from 1:2 to
1:20;
[0087] passing said raw material feed through said catalytic bed at
a temperature of between about 350.degree. C. and 500.degree. C. at
a weight hourly space velocity greater than two; and
[0088] separating the compound of formula (III).
[0089] In the above process, the compound of formula (III) is a
ketone produced in accordance with the ketone production method of
the present invention.
[0090] The ketone production method of the present invention can
also be used, in combination with other process steps, to prepare a
compound of the following formula (X) 6
[0091] The specific process steps comprise:
[0092] (i) reacting a compound of formula (XI) 7
[0093] with a compound of formula (XII) 8
[0094] to form a compound of formula (XIII) 9
[0095] (ii) reacting a compound of formula (XIII) with
CH(OCH.sub.2CH.sub.3).sub.3 to form a compound of formula (XIV)
10
[0096] (iii) reacting a compound of formula (XIV) with
hydroxylamine or a salt of hydroxylamine to form a compound of the
formula (XV) 11
[0097] (iv) reacting a compound of formula (XV) with
chloroperbenzoic acid [or an equivalent] to form a compound of the
formula (X)
[0098] wherein the process further comprises producing the compound
of formula (XII) by:
[0099] providing a catalytic bed;
[0100] providing a raw material feed comprised of cyclopropane
carboxylic acid or cyclopropane aldehyde and acetic acid in the
ratio of from 1:2 to 1:20;
[0101] passing said raw material feed through said catalytic bed at
a temperature of between about 350.degree. C. and 500.degree. C. at
a weight hourly space velocity greater than two; and
[0102] separating the compound of formula (XII).
[0103] In the above process, the compound of formula (XII) is
methyl cyclopropyl ketone (MCPK) produced in accordance with the
ketone production method of the present invention.
[0104] Further details of compounds of formula (I) and formula (X)
described above are known in the art and described in one or more
of PCT Publication No. WO 99/02476, U.S. Pat. No. 5,366,957 and
U.S. Pat. No. 5,849,928, the substance of which is incorporated
herein by reference.
[0105] Although the description of the preferred embodiment and
method have been quite specific, it is contemplated that various
modifications could be made without deviating from the spirit of
the present invention. Accordingly, it is intended that the scope
of the present invention be dictated by the appended claims rather
than by the description of the preferred embodiment.
* * * * *