U.S. patent application number 11/232548 was filed with the patent office on 2006-01-19 for removal of alcohols and water from a methylcyclopentadiene recycle stream in a process for the synthesis of methylcyclopentadienyl manganese tricarbonyl.
Invention is credited to Abbas Kadkhodayan, David Mark Marchand.
Application Number | 20060011542 11/232548 |
Document ID | / |
Family ID | 34838875 |
Filed Date | 2006-01-19 |
United States Patent
Application |
20060011542 |
Kind Code |
A1 |
Marchand; David Mark ; et
al. |
January 19, 2006 |
Removal of alcohols and water from a methylcyclopentadiene recycle
stream in a process for the synthesis of methylcyclopentadienyl
manganese tricarbonyl
Abstract
The field of the present invention is the synthesis of a
manganese-containing organometallic
compound--methylcyclopentadienyl manganese tricarbonyl. More
specifically, a key raw material in the synthesis process is
treated to reduce the amount of protic side products in the
material, thereby improving the yield of the overall synthesis.
Inventors: |
Marchand; David Mark; (Glen
Carbon, IL) ; Kadkhodayan; Abbas; (Collinsville,
IL) |
Correspondence
Address: |
DENNIS H. RAINEAR
CHIEF PATENT COUNSEL, ETHYL CORPORATION
330 SOUTH FOURTH STREET
RICHMOND
VA
23219
US
|
Family ID: |
34838875 |
Appl. No.: |
11/232548 |
Filed: |
September 22, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10800784 |
Mar 15, 2004 |
|
|
|
11232548 |
Sep 22, 2005 |
|
|
|
Current U.S.
Class: |
210/634 ;
210/638; 210/644; 585/21; 585/818; 585/833 |
Current CPC
Class: |
C07C 7/13 20130101; C07C
7/13 20130101; C07C 2601/10 20170501; C07C 7/10 20130101; C07C
13/08 20130101; C07C 13/08 20130101; C07C 7/10 20130101 |
Class at
Publication: |
210/634 ;
210/644; 210/638; 585/818; 585/833; 585/021 |
International
Class: |
B01D 11/00 20060101
B01D011/00 |
Claims
1. A method of extracting water and alcohol from a mixture
comprising methylcyclopentadiene, water and alcohol, comprising:
(a) providing an organic material comprising methylcyclopentadiene,
water and alcohol; (b) adding water to the organic material to
create organic and aqueous fractions; and (c) separating the
organic and aqueous fractions; wherein the separated organic
fraction comprises less water or alcohol than in the organic
material before the addition of water and separation of
fractions.
2. The method of claim 1, wherein the alcohol comprises
methanol.
3. The method of claim 1, wherein the alcohol comprises
2-methoxyethanol.
4. The method of claim 1, wherein the amount of water added to the
organic material is from about one to about ten vol. %.
5. The method of claim 1, wherein the amount of water added to the
organic material is about 2.5 vol. %.
6. The method of claim f, further comprising processing the
separated organic fraction by contacting a bed of molecular
sieve.
7. The method of claim 1, further comprising processing the
separated organic fraction by contacting a bed of activated
alumina.
8. A method of improving the purity of methylcyclopentadiene to be
added to a methylcyclopentadienyl manganese tricarbonyl synthesis
reaction, by removing water and/or alcohol contaminants therein,
said method comprising: (a) adding to methylcyclopentadiene
contaminated with water and/or alcohol an amount of water
sufficient to create methylcyclopentadiene and aqueous fractions;
(b) separating the methylcyclopentadiene and aqueous fractions;
wherein the separated methylcyclopentadiene comprised less water
and/or alcohol than the initial methylcyclopentadiene.
9. Methylcyclopentadiene produced by the method of claim 8.
10. The method of claim 8, further comprising processing the
separated organic fraction by contacting a bed of molecular
sieve.
11. The method of claim 8, further comprising processing the
separated organic fraction by contacting a bed of activated
alumina.
12. Methylcyclopentadiene of claim 11, wherein the
methylcyclopentadiene is greater than about 85%, by weight,
pure.
13. Methylcyclopentadiene of claim 12, wherein the
methylcyclopentadiene is greater than about 90%, by weight,
pure.
14. Methylcyclopentadienyl manganese tricarbonyl produced by the
method comprising providing the methylcyclopentadiene of claim
9.
15. A composition comprising a hydrocarbonaceous fuel and
methylcyclopentadienyl manganese tricarbonyl of claim 14.
16. The composition of claim 15, wherein the hydrocarbonaceous fuel
is selected from a group consisting of a gasoline fuel and a diesel
fuel.
17. An internal combustion engine containing the composition of
claim 15.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This patent application is a continuation-in-part of patent
application Ser. No. 10/800,784 filed Mar. 15, 2004, which is
hereby incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The field of the present invention is the synthesis of a
manganese-containing organometallic
compound--methylcyclopentadienyl manganese tricarbonyl. More
specifically, a key raw material in the synthesis process is
treated to reduce the amount of protic side products in the
material, thereby improving the yield of the overall synthesis.
BACKGROUND OF THE INVENTION
[0003] Methylcyclopentadiene ("MCP") is a key raw material in the
synthesis of methylcyclopentadienyl manganese tricarbonyl ("MMT").
The first step of the reaction sequence involves reacting excess
MCP with sodium metal in an ether solvent to generate a process
intermediate complex, MCP-Na. For economic reasons, the excess MCP
is recovered in the product distillation step, blended with fresh
MCP, and finally recycled back to the initial reaction step.
[0004] The ether solvent used in this first step in a MMT synthesis
process is a dimethyl carbitol ("DMC") solvent. This solvent,
commonly known as "diglyme" or diethylene glycol dimethylether
belongs to a class of solvents capable of sufficiently solubilizing
alkali metals, metal compounds, and their salts. One way to make
"glymes" is by a controlled polymerization of ethylene epoxide with
sodium methoxide and then capping the desired chain product with
methyl halide. This solvent is thought to be the source of the
alcohol contaminants in the MMT crude that end up distilling over
with the unreacted MCP. At the elevated reaction temperature stages
of generating the MCP-Na the sodium is thought to cleave a small
amount of the DMC solvent to give the alkoxides of methanol and
2-methoxyethanol. These alcohols are reconstituted further down the
MMT synthesis steps at the stage where the MMT crude is washed with
an aqueous solution to remove the salts before feeding this crude
to the distillation columns. This is how the water is introduced
into the MMT crude, and the water together with the alcohols end up
distilling over with the MCP stream.
[0005] In the MMT synthesis process, the water- and alcohol-laden
MCP stream is recycled back and reacted with sodium metal in the
DMC solvent to give the MCP nucleophile, MCP-Na. At the same time
the sodium will react with the alcohol contaminants methanol and
2-methoxyethanol to give the corresponding sodium alkoxides, and
with the contaminant water to give sodium hydroxide. These
alkoxides and hydroxide will compete with MCP-Na chemistry further
down the process for making MMT, hence compromising overall MMT
yield. Finally they will be reconstituted back to their original
methanol, 2-methoxyethanol, and water form at the aqueous wash of
the MMT crude before being sent to the columns. These contaminants
then recycle back into the MMT synthesis process as part of the MCP
recycle stream. The kind of cycle these contaminants are exhibiting
in this MMT process can be termed as a catalytic cycle of
destroying the reactant sodium metal. If allowed to continue, this
can become expensive because the levels of these contaminants in
the process are being boosted as more are generated from DMC
cleavage each cycle. Therefore, there is a need for a purification
process that efficiently removes the contaminants from the MCP
recycle stream.
BRIEF SUMMARY OF THE INVENTION
[0006] One aspect of the invention relates to a method of
extracting water and alcohol from a mixture comprising
methylcyclopentadiene, water and alcohol, comprising (a) providing
an organic material comprising methylcyclopentadiene, water and
alcohol; (b) adding water to the organic material to create organic
and aqueous fractions; and (c) separating the organic and aqueous
fractions; wherein the separated organic fraction comprises less
water or alcohol than in the organic material before the addition
of water and separation of fractions. In one embodiment of the
invention, the method further comprises processing the separated
organic fraction by contacting a bed of molecular sieve, such as a
bed of activated alumina. In another embodiment of the invention,
the organic and aqueous fractions are separated using a
liquid/liquid extraction, optionally utilizing centrifugation.
[0007] A second aspect of the invention relates to a method of
improving the purity of methylcyclopentadiene to be added to a
methylcyclopentadienyl manganese tricarbonyl synthesis reaction by
removing water and/or alcohol contaminants therein, said method
comprising (a) adding to methylcyclopentadiene contaminated with
water and/or alcohol an amount of water sufficient to create
methylcyclopentadiene and aqueous fractions; and (b) separating the
methylcyclopentadiene and aqueous fractions; wherein the separated
methylcyclopentadiene comprises less water and/or alcohol than the
initial methylcyclopentadiene. In one embodiment, the
methylcyclopentadiene and aqueous fractions are separated using a
liquid/liquid extraction, optionally utilizing centrifugation.
[0008] A third aspect of the invention relates to
methylcyclopentadiene purified by the method comprising (a)
providing an organic material comprising methylcyclopentadiene,
water and alcohol; (b) adding water to the organic material to
create organic and aqueous fractions; and (c) separating the
organic and aqueous fractions; wherein the separated organic
fraction comprises less water or alcohol than in the organic
material before the addition of water and separation of fractions.
In one embodiment of the invention, the method further comprises
processing the separated organic fraction by contacting a bed of
molecular sieve, such as a bed of activated alumina. In another
embodiment of the invention, the organic and aqueous fractions are
separated using a liquid/liquid extraction, optionally utilizing
centrifugation.
[0009] A fourth aspect of the invention relates to
methylcyclopentadienyl manganese tricarbonyl produced by the method
comprising providing methylcyclopentadiene that had been purified
by a method involving (a) providing an organic material comprising
methylcyclopentadiene, water and alcohol; (b) adding water to the
organic material to create organic and aqueous fractions; and (c)
separating the organic and aqueous fractions; wherein the separated
organic fraction comprises less water or alcohol than in the
organic material before the addition of water and separation of
fractions. In one embodiment of the invention, the method of
purifying the methylcyclopentadiene further comprises processing
the separated organic fraction by contacting a bed of molecular
sieve, such as a bed of activated alumina. In another embodiment of
the invention, methylcyclopentadiene is further purifying by
separating the organic and aqueous fractions using a liquid/liquid
extraction, optionally utilizing centrifugation.
[0010] A fifth aspect of the invention relates to a hydrocarbon
composition comprising methylcyclopentadienyl manganese tricarbonyl
produced by the method comprising providing methylcyclopentadiene
that had been purified by a method involving (a) providing an
organic material comprising methylcyclopentadiene, water and
alcohol; (b) adding water to the organic material to create organic
and aqueous fractions; and (c) separating the organic and aqueous
fractions; wherein the separated organic fraction comprises less
water or alcohol than in the organic material before the addition
of water and separation of fractions. In one embodiment of the
invention, the method of purifying the methylcyclopentadiene
further comprises processing the separated organic fraction by
contacting a bed of molecular sieve, such as a bed of activated
alumina. In another embodiment of the invention,
methylcyclopentadiene is further purifying by separating the
organic and aqueous fractions using a liquid/liquid extraction,
optionally utilizing centrifugation.
[0011] Further embodiments, features, and advantages of the present
invention, as well as the structure and operation of the various
embodiments of the present invention, are described in detail below
with reference to the accompanying figure.
BRIEF DESCRIPTION OF THE FIGURE
[0012] The accompanying figure, which is incorporated herein and
forms a part of the specification, illustrates one of the
embodiments of the present invention and, together with the
description, further serves to explain the principles of the
invention and to enable a person skilled in the pertinent art to
make and use the invention.
[0013] FIG. 1 illustrates the amounts of DMC (diamonds),
2-methoxyethanol ("2MeEthOH") (circles), water (squares), and
methanol (triangles) in the MCP recycle stream following a
liquid/liquid extraction utilizing centrifugation.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The disclosed process is directed to removing protic
contaminants that inevitably result during the processes and
synthesis of methylcyclopentadienyl manganese tricarbonyl ("MMT").
Specifically, as noted earlier herein, the intermediate product
methylcyclopentadiene ("MCP"), when reacted with sodium metal in an
ether solvent, generates protic contaminant side products including
methanol, water and 2-methoxyethanol. Treatment of the recycle
crude MCP with a water wash and optionally a molecular sieve bed
removes most of the contaminants. Alternatively, a liquid/liquid
extraction, optionally utilizing an ultracentrifugation step, may
be utilized during the MCP recycling process to remove most of the
contaminants.
[0015] A method of extracting water and alcohol from a mixture
comprising methylcyclopentadiene, water and alcohol, comprises
providing an organic material comprising methylcyclopentadiene,
water and alcohol; adding water to the organic material to create
organic and aqueous fractions; and separating the organic and
aqueous fractions; wherein the separated organic fraction comprises
less water or alcohol than the organic material before the addition
of water and separation of fractions. In one embodiment of the
invention, the method further comprises processing the separated
organic fraction over, through, or otherwise contacting a bed of
molecular sieve, such as a bed of activated alumina. In another
embodiment of the invention, the organic and aqueous fractions are
separated using a liquid/liquid extraction, optionally utilizing
centrifugation.
[0016] The MCP recycle stream may contain in one embodiment one or
more of the following contaminants: about 0.1 to about 0.8%
methanol, about 0.1 to about 0.8% water, and about 0.1 to about
1.1% 2-methoxyethanol. The amount of any of these contaminants may
be decreased utilizing the method of the present invention.
Optimally, the amount of methanol may be decreased by about 50 to
about 85%, the amount of water may be decreased by about 0 to about
60%, and the amount of 2-methoxyethanol may be decreased by about
50 to about 90%. In one embodiment, the water or any alcohol
contaminant in the purified MCP recycle stream is present in an
amount less than about 1%, by weight. In another embodiment, the
water or any alcohol contaminant in the purified MCP recycle stream
is present in an amount less than about 0.5%, by weight. In a third
embodiment, the water or any alcohol contaminant in the purified
MCP recycle stream is present in an amount less than about 0.1%, by
weight.
[0017] One method of decontaminating the MCP recycle stream from
methanol, 2-methoxyethanol, and water side product contaminants of
the MMT synthesis process is to include a step consisting either of
a water wash or a molecular sieve bed in the MCP purification
process. If lower levels of these protic contaminants are required
than what can be achieved by either one of the two individual
methods above, then the two purification methods may be installed
together in series, first the water wash followed by the molecular
sieve bed.
[0018] In one embodiment of the present disclosure, the MCP recycle
stream being recovered from the crude product by column
distillation and recycled back into the MMT synthesis process
contains at least the three detrimental protic components methanol,
water and 2-methoxyethanol in levels of about 0.361, 0.39, and
1.087 wt % respectively. On washing the MCP organic layer with 2.5%
vol/vol water, these contaminants are pulled into the aqueous phase
and their levels are lowered in the organic phase by 82.8, 55.9,
and 64.7% respectively. An even higher level of purification is
achieved by running this same organic layer over, through or
otherwise contacting UOP AZ molecular Sieve. In one example the
three contaminants are lowered by 79.4, 97.1, and 77.2% for
methanol, water, and 2-methoxyethanol, respectively. Recycled MCP
thus purified results in significant process savings and improved
MMT yield.
[0019] The amount of water that is added to the MCP recycle stream
may vary. It has been determined that relatively small amounts of
water are effective to wash the contaminants from the MCP recycle
stream. In one example, the addition of about one to about ten
volume percent of water may be added to the organic MCP recycle
stream and then separated from it. In another example, about 2.5
volume percent may be added. For processing efficiencies, the less
water that can be added to remove the contaminant side products,
the better.
[0020] In some examples, the MCP recycle stream may be further
treated by passing it over, through, or otherwise contacting a
molecular sieve bed or over activated alumina to remove still
further water and other protic side products from the stream. This
step is performed alone on an MCP recycle stream, or in one
example, is performed in series after the washing step described
otherwise herein. For best processing efficiency, this step is done
after the washing step, because then there is less water to remove.
The result is that the sieve bed or the activated alumina will not
need to be regenerated as often than if it was used to extract
higher volumes of water and protic side products.
[0021] Another method of decontaminating the MCP recycle stream
from methanol, 2-methoxyethanol, and water side product
contaminants of the MMT synthesis process is by a liquid/liquid
extraction. A liquid/liquid extraction is a process that allows the
separation of two or more components due to their unequal
solubilities in two immiscible liquid phases, such as an organic
and an aqueous fraction. Optionally, the liquid/liquid extraction
utilizes centrifugation to separate the two immiscible liquid
phases.
[0022] In an embodiment of the invention, the liquid/liquid
extraction utilizes a liquid/liquid Separator to remove the
methanol, 2-methoxyethanol, and water side product contaminants
from the MCP recycle stream. In this embodiment, the liquid/liquid
Separator may be installed across the MCP recycle stream coming off
of the distillation column. The MCP recycle stream coming off the
distillation column may be mixed with an immiscible solvent, e.g.
water that has a different density than the MCP recycle stream to
yield a liquid/liquid dispersion. The liquid/liquid dispersion may
then be separated by centrifugal force using a liquid/liquid
Separator. Optionally, the liquid/liquid extraction steps may be
repeated one or more times to increase the purity of the isolated
MCP.
[0023] Any amount of immiscible solvent may be added to the MCP
recycle stream to form the liquid/liquid dispersion. If the
immiscible solvent is water, then, optimally, the amount added will
be minimized to decrease the amount of water that may later be
processed to remove any extracted DMC. In one embodiment, the
amount of water added to the MCP recycle stream is about 0 to about
10%, by weight. In another embodiment, the amount of water added to
the MCP recycle stream is about 2 to about 8%, by weight. In a
third embodiment, the amount of water added to the MCP recycle
stream is about 4%, by weight.
[0024] The MCP purified by the method of the present invention may
then be utilized in synthesizing MMT. The synthesized MMT may then
be incorporated into a hydrocarbonaceous fuel, such as gasoline,
diesel fuel, fuel oil, biofuels, and synfuels or into hydrocarbon
containing wastes and coals. In one embodiment, the synthesized MMT
is incorporated into a hydrocarbon composition that is gasoline or
diesel to be utilized in an internal combustion engine, such as an
internal combustion engine of an automobile. In another embodiment,
the synthesized MMT is incorporated into home heating equipment
burning fuel oil, an industrial furnace, or utility power furnaces
burning fuel oil or stationary burners. In a third embodiment, the
synthesized MMT is used in waste incinerators.
[0025] The following examples are illustrative, but not limiting,
of the methods of the present invention. Other suitable
modifications and adaptations of the variety of conditions and
parameters normally encountered in the field, and which are obvious
to those skilled in the art, are within the spirit and scope of the
invention.
[0026] All patents and publications cited herein are fully
incorporated by reference herein in their entirety.
EXAMPLES
Example 1
[0027] An MCP recycle stream from a MMT purification system was
found to contain 0.361 wt % methanol, 0.39 wt % water and 1.078 wt
% 2-methoxyethanol. To an aliquot of this organic material was
added 2.5 vol % water. The resulting biphasic product was agitated
to extract the three protic impurities into the aqueous layer. The
liquid mixture was allowed to settle and the organic layer
separated from the aqueous layer. Analysis of the organic layer
showed a dramatic decrease in methanol of 82.8%, water of 55.9%,
and 2-methoxyethanol of 64.7%. The process was repeated on a fresh
aliquot of recycle MCP, but this time the wash was carried out with
5 vol % water. This doubling of the water layer did not
significantly improve on the purification process (see Table 1).
TABLE-US-00001 TABLE 1 Removal of protic contaminants methanol,
water, and 2-methoxyethanol from MCP recycle stream in a commercial
scale MMT production process by washing the organic material with
water Impurity Initial 2.5% H.sub.2O Impurity 5.0% H.sub.2O
Impurity Component wt % Wash Removed (%) Wash Removed (%) Methanol
0.361 0.062 82.8 0.054 85 Water 0.39 0.172 55.9 0.146 62.6
2-Methoxyethanol 1.078 0.38 64.7 0.264 75.5
Example 2
[0028] An MCP recycle stream from one of the MMT purification
systems was found to contain 0.68 wt % methanol, 0.69 wt % water
and 1.62 wt % 2-methoxyethanol. This material was contacted with a
bed of UOP AZ molecular sieve. Subsequent analysis of the sieve
treated MCP recycle showed a significant decrease in methanol of
79.4%, water of 97.1%, and 2-methoxyethanol of 77.2%. (see Table
2). TABLE-US-00002 TABLE 2 Removal of protic contaminants methanol,
water, and 2-methoxyethanol from MCP recycle stream in a commercial
scale MMT production process by treating the organic with UOP AZ
molecular sieve. UOP AZ Impurity Initial Molecular Impurity
Component wt % Sieve Removed (%) Methanol 0.68 0.14 79.4 Water 0.69
0.02 97.1 2-Methoxyethanol 1.62 0.37 77.2
[0029] It is to be understood that the reactants and components
referred to by chemical name anywhere in the specification or
claims hereof, whether referred to in the singular or plural, are
identified as they exist prior to coming into contact with another
substance referred to by chemical name or chemical type (e.g.,
solvent, etc.). It matters not what chemical changes,
transformations and/or reactions, if any, take place in the
resulting mixture or solution or reaction medium as such changes,
transformations and/or reactions are the natural result of bringing
the specified reactants and/or components together under the
conditions called for pursuant to this disclosure. Thus the
reactants and components are identified as ingredients to be
brought together either in performing a desired chemical reaction
(such as formation of the organometallic compound) or in forming a
desired composition (such as an additive concentrate or additized
fuel blend). Accordingly, even though the claims hereinafter may
refer to substances, components and/or ingredients in the present
tense ("comprises", "is", etc.), the reference is to the substance,
components or ingredient as it existed at the time just before it
was first blended or mixed with one or more other substances,
components and/or ingredients in accordance with the present
disclosure. The fact that the substance, components or ingredient
may have lost its original identity through a chemical reaction or
transformation during the course of such blending or mixing
operations or immediately thereafter is thus wholly immaterial for
an accurate understanding and appreciation of this disclosure and
the claims thereof.
[0030] Applicant does not intend to dedicate any disclosed
embodiments to the public, and to the extent any disclosed
modifications or alterations may not literally fall within the
scope of the claims, they are considered to be part of the
invention under the doctrine of equivalents.
Example 3
Optimization of Water Amount into the Liquid/Liquid Separator
[0031] The LX 204 Liquid/Liquid Extractor (Rousselet Robatel,
Annonay, France) was fed with a MCP stream contaminated with 2.87%
DMC, 0.57% 2-methoxyethanol, 0.02% water, and 0.08% methanol. The
LX 204 Liquid/Liquid Extractor was run with the water wash stream
in batches of 0.0%, 0.75%, 2.00% and 4.00%, respectively. As the
amount of water in the secondary stream into the Extractor
increases, the level of contaminants in the MCP stream exiting the
Extractor decreases, as shown in FIG. 1.
Example 4
Optimization of the Number of Stages Utilized in the Liquid/Liquid
Separator
[0032] The LX 204 Liquid/Liquid Extractor (Rousselet Robatel,
Annonay, France) was utilized to optimize the number of stages
required to yield highly purified MMT. The rotor speed of the
Extractor used was 2700 rpm. The MCP stream was fed into the
Extractor at a rate of 230 lbs/hr, with a corresponding secondary
feed stream of water of 7.9%
[0033] The purity of MCP from each successive liquid/liquid
extraction stage was analyzed for the weight percent of each of
methanol, 2-methoxyethanol, water, and DMC. The results are shown
in Table 3 below. TABLE-US-00003 TABLE 3 Liquid/Liquid Extractor
use in removal of contaminants from the MCP recycle stream in a MMT
synthesis method. Methanol 2-Methoxyethanol Water DMC (%) (%) (%)
(%) Original Level 0.16 0.60 0.17 8.12 Stage 1 0.09 0.48 0.15 7.45
Stage 2 0.00 0.31 0.13 6.48 Stage 4 (Final) 0.00 0.22 0.13 6.38
[0034] As shown in Table 3, the levels of contaminants decrease
with an increasing number of liquid/liquid extractions utilizing
centrifugation to separate the two immiscible liquids. After four
liquid/liquid extraction steps, the methanol had decreased by 100%,
the methoxyethanol by 63%, and the water by 24%. The DMC level in
the MCP stream being recycled was not an issue because DMC was the
solvent used in the process.
* * * * *