U.S. patent application number 12/408722 was filed with the patent office on 2010-03-18 for hydroformylation process.
This patent application is currently assigned to INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE. Invention is credited to Mao-Lin HSUEH, Kuo-Chen SHIH, Tsai-Tien SU, Hao-Hsun YANG.
Application Number | 20100069678 12/408722 |
Document ID | / |
Family ID | 42007794 |
Filed Date | 2010-03-18 |
United States Patent
Application |
20100069678 |
Kind Code |
A1 |
HSUEH; Mao-Lin ; et
al. |
March 18, 2010 |
HYDROFORMYLATION PROCESS
Abstract
The disclosed is about a hydroformylation of a cyclic olefin
with rhodium catalyst, and specifically about the recovering of the
rhodium catalyst. Aldehyde and the cyclic olefin are added into a
rhodium catalyst solution to process a hydroformylation, thereby
forming the product cycloalkyl aldehyde. Afterwards, the result is
divided into two layers. The upper layer is substantially rhodium
catalyst solution, and the lower layer is substantially cycloalkyl
aldehyde and the aldehyde. After separation, the upper layer is
reserved to process next hydroformylation reaction with newly added
cyclic olefin.
Inventors: |
HSUEH; Mao-Lin; (Pingtung
County, TW) ; YANG; Hao-Hsun; (Tainan City, TW)
; SHIH; Kuo-Chen; (Kaohsiung City, TW) ; SU;
Tsai-Tien; (Hsinchu City, TW) |
Correspondence
Address: |
PAI PATENT & TRADEMARK LAW FIRM
1001 FOURTH AVENUE, SUITE 3200
SEATTLE
WA
98154
US
|
Assignee: |
INDUSTRIAL TECHNOLOGY RESEARCH
INSTITUTE
Hsinchu County
TW
|
Family ID: |
42007794 |
Appl. No.: |
12/408722 |
Filed: |
March 23, 2009 |
Current U.S.
Class: |
568/444 |
Current CPC
Class: |
C07C 45/50 20130101;
C07C 45/82 20130101; C07C 2601/16 20170501; C07C 45/80 20130101;
C07C 45/80 20130101; C07C 45/80 20130101; C07C 45/82 20130101; C07C
45/50 20130101; C07C 45/50 20130101; C07C 45/50 20130101; C07C
45/82 20130101; C07C 2603/52 20170501; C07C 45/80 20130101; C07C
45/82 20130101; C07C 47/445 20130101; C07C 47/32 20130101; C07C
47/445 20130101; C07C 47/32 20130101; C07C 47/347 20130101; C07C
47/445 20130101; C07C 47/347 20130101; C07C 47/32 20130101; C07C
47/347 20130101 |
Class at
Publication: |
568/444 |
International
Class: |
C07C 45/49 20060101
C07C045/49 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 16, 2008 |
TW |
097135460 |
Claims
1. A hydroformylation process, comprising: (i) reacting a cyclic
olefin with carbon monoxide and hydrogen in the presence of an
aldehyde and a rhodium catalyst at a temperature of 40.degree.C. to
160.degree. C. to obtain a hydroformylation product liquid
containing cycloalkyl aldehyde; (ii) cooling the hydroformylation
product liquid to room temperature, and letting the
hydroformylation product liquid stand until it divides into a first
layer and a second layer, wherein the first layer comprises
substantially the rhodium catalyst and a the second layer comprises
substantially the aldehyde and the cycloalkyl aldehyde; and (iii)
separating the first layer from the second layer.
2. The hydroformylation process as claimed in claim 1, wherein the
rhodium catalyst is dissolved in a solvent comprising alkane or
cycloalkane.
3. The hydroformylation process as claimed in claim 1, wherein the
cyclic olefin has single or multi carbon-carbon double bonds.
4. The hydroformylation process as claimed in claim 1, wherein the
step of separating the first layer from the second layer is
performed at a pressure from atmospheric pressure to 10 MPa.
5. The hydroformylation process as claimed in claim 1, wherein the
carbon monoxide and hydrogen have a pressure of 0.5 MPa to 15
MPa.
6. (canceled)
7. The hydroformylation process as claimed in claim 1, wherein the
aldehyde is C.sub.1-12 aldehyde.
8. The hydroformylation process as claimed in claim 1, further
comprising distilling the second layer to separate the aldehyde and
the cycloalkyl aldehyde.
9. The hydroformylation process as claimed in claim 1, wherein the
aldehyde and the cycloalkyl aldehyde have same chemical
formula.
10. The hydroformylation process as claimed in claim 1, wherein the
cyclic olefin comprises dicyclopentadiene, tricyclopentadiene,
dicyclohexadiene, or cyclohexene.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This Application claims priority of Taiwan Patent
Application No. 097135460, filed on Sep. 16, 2008, the entirety of
which is incorporated by reference herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a hydroformylation process
of cyclic olefins in the presence of a metal catalyst, and in
particular relates to the separation of the desired products from
the metal catalyst by phase separation.
[0004] 2. Description of the Related Art
[0005] It is known in the art that compared to a heterogeneous
catalyst, the homogeneous catalyst has advantages such as high
reactivity, high selectivity, and a relatively milder reaction
condition. However, many homogeneous catalyst systems cannot be
commercially applied mainly due to difficulties in separating,
recovering, and reusing the homogeneous catalysts, as it is well
known.
[0006] It is known in the art that distillation is one of the
favorable methods for the separation of catalysts and products. If
the volatility of the product is low, the temperature required to
separate the product by distillation should be higher. Most
homogeneous catalysts, however, are thermal sensitive, such that
the homogeneous catalyst may decompose during higher distillation
temperatures and fail to be recovered for reuse. Other methods for
recovering the homogeneous catalyst, e.g. chromatography, are
inefficient. Accordingly, an effective and low cost separation
process is critical for development of the homogeneous
catalyst.
[0007] Hydroformylation of olefins with carbon monoxide
(hereinafter CO) and hydrogen (hereinafter H.sub.2) to form
aldehydes is an important homogeneous catalytic reaction. The
catalysts used for the hydroformylation of olefins are usually
rhodium or cobalt catalysts, especially the rhodium catalysts due
to their high reactivity and selectivity. Although rhodium
catalysts have higher reactivity, their cost is much higher than
the cobalt catalysts. The effective recovery and reuse of the
rhodium catalysts determines their realization in the industry. If
the volatility of the hydroformylation products (less than C5) is
relatively low, the low temperature distillation method can be used
to separate the products and the catalysts without significantly
decomposing the catalysts. On the other hand, if the volatility of
the hydroformylation products is high, the abovementioned
distillation method for separation is unfavorable, due to the
higher temperatures decomposing the catalyst such that the catalyst
cannot be recovered and reused, thus increasing costs.
[0008] As described above, the products from hydroformylation of
cyclic olefins have a higher boiling point. If the product and
catalyst are separated by vacuum distillation, a higher
distillation temperature is needed, thereby decomposing the rhodium
catalyst.
[0009] In WO 93/02024, a mixture of first alcohol having 1 to 3
carbon atoms and water is reported to be used as an extraction
solution to separate the rhodium catalyst and high boiling-point
aldehydes from hydroformylation. The efficiency of this method is,
however, not good, and a better method for the efficient separation
of the hydroformylation products and catalyst is still needed.
BRIEF SUMMARY OF THE INVENTION
[0010] The invention provides a hydromormylation process,
comprising: (i) Reacting a cyclic olefin with carbon monoxide and
hydrogen in the presence of an aldehyde and a rhodium catalyst to
obtain a hydroformylation product liquid containing cycloalkyl
aldehyde; (ii) the hydroformylation product liquid is then divided
into a first layer and a second layer, wherein a substantial part
of the first layer comprises the rhodium catalyst and a substantial
part of the second layer comprises the aldehyde and the cycloalkyl
aldehyde; and (iii) Separating the first layer from the second
layer.
[0011] A detailed description is given in the following
embodiments.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The following description is of the best-contemplated mode
of carrying out the invention. This description is made for the
purpose of illustrating the general principles of the invention and
should not be taken in a limiting sense. The scope of the invention
is best determined by reference to the appended claims.
[0013] The invention provides a hydroformylation process. First, a
rhodium compound and an organophosphorus compound are mixed in an
appropriate solvent. The rhodium compound includes rhodium
trichloride hydrate (RhCl.sub.3.xH.sub.2O), dicarbonyl
acetylacetone rhodium (Rh(acac)(CO).sub.2), bis(dicarbonyl chloro
rhodium ((RhCl(CO).sub.2).sub.2), carbonyl rhodium
(Rh.sub.6(CO).sub.16 or Rh.sub.4(CO).sub.12), rhodium (III) nitrate
(Rh(NO.sub.3).sub.3, and the likes. The rhodium catalyst solution
has a concentration of 10 ppm to 1000 ppm, and preferably 100 ppm
to 600 ppm. The organophosphorous compound can be any
phosphorous-containing organics, such as
tris(2,4-di-tert-butylphenyl) phosphite, triphenylphosphite,
tris(3-methyl-6-tert-butylphenyl) phosphite,
tris(2,4-di-tert-butylphenyl) phosphate,
di(2-tert-butylphenyl)-tert-butylphosphite, trialkyl phosphine or
other suitable phosphorous-containing organics. The rhodium
compound and the organophosphorous compound have a molar ratio of
1:1 to 1:300, and preferably 1:10 to 1:150. The solvent used for
the catalytic reactions can be alkane, cycloalkane, or other
solvent with low polarity. In one embodiment, the solvent is
n-hexane.
[0014] Subsequently, cyclic olefin and aldehyde are added the
rhodium catalyst solution to process hydroformylation. The aldehyde
serves as an extraction liquid, which may dissolve the cycloalkyl
aldehyde product after the hydrofomylation and separated from the
rhodium catalyst solution. The aldehyde can be C.sub.1-12 alkyl or
aromatic aldehyde compound. The aldehyde and the cycloolefin have a
weight ratio of 1:2 to 1:20. In one embodiment, the aldehyde and
the cyclic olefin has a weight ratio of 1:5 to 1:10.
[0015] The described mixture is charged in a high pressure reaction
vessel to undergo a hydroformylation reaction under high pressure
of H.sub.2 and CO to obtain the cycloalkyl aldehyde product. The
molar ratio of H.sub.2 and CO in this reaction is 1:10 to 10:1, and
preferably of 1:3 to 3:1. The reaction temperature is at 40.degree.
C. to 160.degree. C., and preferably 70.degree. C. to 140.degree.
C. The pressure of the H.sub.2 and CO is between 0.5 MPa and 15
MPa, and preferably 2 MPa to 10 MPa. The cyclic olefin may have one
carbon-carbon double bond or multiple carbon-carbon double bonds,
such as dicyclopentadiene (hereinafter DCPD), tricyclepentadiene
(hereinafter TCPD), dicyclohexadiene (hereinafter DCHD),
cyclohexene, cyclohexene-1-carbaldehyde, (abbreviated CHCA),
1,2,3,6-tetrahydrobenzaldehyde, or other cyclic olefin such as
methyl-3-cyclohexene-1-carboxaldehyde,
methyl-4-cyclohexene-2-carboxaldehyde,
3-cyclohexene-1-carbonitrile, 3-cyclohexene-1-methanol, methyl
3-cyclohexene-1-carboxylate, 3-cyclohexene-1-carboxylate,
4-acetyl-1-cyclohexene, 1-methyl-4-cyclohexene-2-carboxylate,
1-phenyl-4-cyclohexene-2-carboxaldehyde, 1,2,3,6-tetrahydrophthalic
anhydride.
[0016] The cycloalkyl aldehydes formed from cyclic olefins such as
DCPD, TCPD, DCHD, cyclohexene, CHCA by hydroformylation reactions
are shown in Formulae I-8.
##STR00001## ##STR00002##
[0017] The R in Formula 8 can be hydrogen or a substituent selected
from alkyl, alcohol, aldehyde, carboxylic acid, or other functional
groups.
[0018] After the hydroformylation reaction process, the resulting
hydroformylation product liquid is standing charged until the
mixture of rhodium catalyst solution, the cycloalkyl aldehyde
product, the aldehyde compound divided into two layers. The upper
layers is substantial rhodium catalyst and its solvent, and the
lower layer is substantial the cycloalkyl aldehyde product and the
aldehyde compound. The phase separation phenomenon is happened in a
pressure between atmospheric pressure to 10 MPa and a temperature
between 0.degree. C. to 100.degree. C. The described two layers
were separated to complete the so-called separation of the
cycloalkyl aldehyde product and the rhodium catalyst solution.
[0019] The separated rhodium catalyst solution can be added another
cyclic olefin to undergo another hydroformylation reaction. The
separation method described recovers and reuses the rhodium
catalyst, and efficiently separates the rhodium catalyst solution
and the cycloalkyl aldehyde with high boiling point.
[0020] After separation, the cycloalkyl aldehyde product and the
aldehyde compound can be distillated to further separate the
cycloalkyl aldehyde product and the aldehyde compound. In one
embodiment, the aldehyde compound and the cycloalkyl aldehyde
product have same chemical formula, wherein the aldehyde compound
comes from the product of the late hydroformylation process. In
this situation, the additional purification such as purification
for separating the cycloalkyl aldehyde product and the aldehyde
compound can be omitted.
[0021] The cycloalkyl alcohols can be formed from cycloalkyl
aldehydes through the hydrogenation reaction are shown in Formulae
9 to 15.
##STR00003## ##STR00004##
EXAMPLES
Example 1
[0022] Rh(acac)(CO).sub.2 (114 mg; 0.435 mmol),
tris(2,4-di-tert-butylphenyl) phosphite (5.625 g; 8.7 mmol), and
tricyclodecanedialdehyde (5.0 g) were added into a flask, followed
by the addition of dry n-hexane (50 g) in the dry box. A high
pressure reaction vessel was heated to 80.degree. C., followed by
vacuum and recharging with nitrogen for three times, and cooled to
room temperature. The aldehyde compound and the rhodium solution
were transferred to the high pressure reaction vessel, and the
nitrogen in the high pressure reaction vessel was replaced with a
mixture of CO/H.sub.2(1:1). The pressure inside the vessel was
built-up to 40 atm, the reaction vessel was heated to 100.degree.
C., and the pressure was then built to 50 atm.
[0023] DCPD (30 g; Fluka) and dry n-hexane (10 g) were weighted and
charged into a feeding bottle. The DCPD was then fed into the high
pressure reaction vessel (20 mL/hours) from the feeding bottle with
a feeding time of about 2 hours. The total pressure of the
CO/H.sub.2 was maintained at 50 atm, and the reaction temperature
was also maintained at 100.+-.2.degree. C. throughout the reaction.
Two hours after the complete of the DCPD feeding, the temperature
of the reaction vessel was decreased to the room temperature, and
the resulting mixture was phase separated into two layers. The
layers were separated and then analyzed by a gas chromatograph (GC)
and an inductively coupled plasma mass spectrometry (ICP-MS).
According to the GC data, the cycloalkyl aldehyde had a yield of
98% and a partition coefficient between the upper and lower layer
layers of 9.6. According to the ICP-MS data, the partition
coefficient of the rhodium catalyst between the upper and lower
layers was 14.6.
Example 2
[0024] Rh(acac)(CO).sub.2 (107 mg; 0.407 mmol),
tris(2,4-di-tert-butylphenyl) phosphite (5.625 g; 8.7 mmol), and
tricyclodecanedialdehyde (4.1 g) were added into a flask, followed
by the addition of dry n-hexane (50 g) in the dry box. A high
pressure reaction vessel was heated to 80.degree. C., followed by
vacuum and recharging with nitrogen for three times, and cooled to
room temperature. The aldehyde compound and the rhodium solution
were transferred to the high pressure reaction vessel, and the
nitrogen in the high pressure reaction vessel was replaced with a
mixture of CO/H.sub.2(1:1). The pressure inside the vessel was
built-up to 40 atm, the reaction vessel was heated to 100.degree.
C., and the pressure was then built to 50 atm.
[0025] DCPD (30 g; Fluka) and dry n-hexane (10 g) were weighted and
charged into a feeding bottle. The DCPD was then fed into the high
pressure reaction vessel (20 mL/hours) from the feeding bottle with
a feeding time of about 2 hours. The total pressure of the
CO/H.sub.2 was maintained at 50 atm, and the reaction temperature
was also maintained at 100.+-.2.degree. C. throughout the reaction.
Two hours after the complete of the DCPD feeding, the temperature
of the reaction vessel was decreased to the room temperature, and
the resulting mixture was phase separated into two layers. The
layers were separated and then analyzed by a gas chromatograph
(GC). According to the GC data, the cycloalkyl aldehyde had a yield
of 99% and a partition coefficient between the upper and lower
layer layers of 9.8.
[0026] While the invention has been described by way of example and
in terms of the preferred embodiments, it is to be understood that
the invention is not limited to the disclosed embodiments. To the
contrary, it is intended to cover various modifications and similar
arrangements (as would be apparent to those skilled in the art).
Therefore, the scope of the appended claims should be accorded the
broadest interpretation so as to encompass all such modifications
and similar arrangements.
* * * * *