U.S. patent application number 13/007858 was filed with the patent office on 2011-06-09 for apparatus for the hydroformylation of olefins.
This patent application is currently assigned to LG CHEM, LTD.. Invention is credited to JAE-Hui Choi, Sung-Shik Eom, Moo-Ho Hong, Dae-Chul Kim, Dong-Hyun Ko, O-Hark Kwon, Sang-Gi Lee, Sang-Oeb Na.
Application Number | 20110135544 13/007858 |
Document ID | / |
Family ID | 40075281 |
Filed Date | 2011-06-09 |
United States Patent
Application |
20110135544 |
Kind Code |
A1 |
Hong; Moo-Ho ; et
al. |
June 9, 2011 |
Apparatus For The Hydroformylation Of Olefins
Abstract
The present invention relates to a method for preparing
aldehydes by reacting olefins with a synthesis gas including carbon
monoxide and hydrogen, and to an apparatus therefore. More
particularly, the present invention relates to a method for
preparing aldehydes, characterized by spraying and supplying
olefins, synthesis gas including carbon monoxide and hydrogen, and
a catalyst composition into an oxo reactor through a nozzle, and to
an apparatus therefore. According to the present invention, the
hydroformylation efficiency can be improved, thereby obtaining
desirable aldehydes with a high yield.
Inventors: |
Hong; Moo-Ho; (Daejeon
Metropolitan City, KR) ; Ko; Dong-Hyun; (Daejeon
Metropolitan City, KR) ; Na; Sang-Oeb; (Seoul,
KR) ; Eom; Sung-Shik; (Daejeon Metropolitan City,
KR) ; Lee; Sang-Gi; (Daejeon Metropolitan City,
KR) ; Kwon; O-Hark; (Daejeon Metropolitan City,
KR) ; Kim; Dae-Chul; (Daejeon Metropolitan City,
KR) ; Choi; JAE-Hui; (Daejeon Metropolitan City,
KR) |
Assignee: |
LG CHEM, LTD.
Seoul
KR
|
Family ID: |
40075281 |
Appl. No.: |
13/007858 |
Filed: |
January 17, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12601858 |
Nov 25, 2009 |
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PCT/KR2008/003029 |
May 29, 2008 |
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13007858 |
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Current U.S.
Class: |
422/235 ;
422/234 |
Current CPC
Class: |
B01J 10/00 20130101;
B01J 2219/0011 20130101; Y02P 20/582 20151101; B01J 19/2465
20130101; B01J 4/002 20130101; C07C 45/50 20130101; C07C 45/50
20130101; C07C 47/02 20130101 |
Class at
Publication: |
422/235 ;
422/234 |
International
Class: |
B01J 10/00 20060101
B01J010/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 29, 2007 |
KR |
10-2007-0051868 |
Claims
1.-12. (canceled)
13. An apparatus for the hydroformylation of olefins, comprising an
oxo reactor provided with a nozzle which is connected with a
venturi; an olefin feed line and a synthesis gas feed line for
feeding a synthesis gas including hydrogen and carbon monoxide,
which are connected to the nozzle, respectively; a recycling line
for supplying the reaction mixture Which is recovered from the oxo
reactor, into the nozzle provided in the oxo reactor; a separation
line branching off from any position in the recycling line; a
catalyst/aldehyde separator connected to the separation line; a
catalyst solution feed line connected to any position in the
catalyst/aldehyde separator and recycling line; and an aldehyde
recovery line which is connected to the catalyst/aldehyde
separator.
14. The apparatus for the hydroformylation of olefins according to
claim 13, wherein the nozzle is provided at the top portion inside
the oxo reactor.
15. The apparatus for the hydroformylation of olefins according to
claim 13, wherein the oxo reactor is a venturi-loop reactor.
16. The apparatus for the hydroformylation of olefins according to
claim 13, wherein the nozzle has a diameter of 0.1 mm to 100
cm.
17. The apparatus for the hydroformylation of olefins according to
claim 13, wherein a circulating pump is provided at any position of
the recycling line.
18. The apparatus for the hydroformylation of olefins according to
claim 13, wherein a heat exchanger is provided at any position of
the recycling line.
Description
TECHNICAL FIELD
[0001] The present invention relates to a process for the
preparation of aldehydes by hydroformylation of olefins and an
apparatus therefore. This application claims priority from Korea
Patent Application No. 10-2007-0051868 filed on May 29, 2007 in the
KIPO, the disclosure of which is incorporated herein by reference
in its entirety.
BACKGROUND ART
[0002] The hydroformylation or oxo process is known as a method for
the production of saturated aldehydes from olefins, carbon
monoxide, and hydrogen in the presence of a catalyst, in which the
method involves addition of one hydrogen atom and one formyl group
(--CHO) onto a C.dbd.C bond. Generally, these aldehydes are
subjected to condensation, followed by hydrogenation to give the
corresponding alcohols with the longer chain.
[0003] The hydroformylation can be exemplified by the preparation
of octanol (2-ethylhexanol) from propylene using a rhodium
catalyst.
[0004] Octanol is mainly used as a raw material for obtaining
plasticizers for PVC, such as DOP, and used as an intermediate in
the preparation of synthetic lubricants, surfactants or the like.
Propylene is injected together with a synthesis gas (H.sub.2+CO)
into an oxo reactor using a catalyst to generate n-butylaldehyde
and iso-butylaldehyde. The produced aldehyde mixture and catalyst
mixture are sent to a separation system, and are separated into
hydrocarbons and catalyst mixture. Then, the catalyst mixture is
recycled to the reactor, and the hydrocarbons are sent to a
stripper. The hydrocarbons in the stripper are stripped with the
fresh synthesis gas, and the unreacted propylene and synthesis gas
are recovered to the oxo reactor. Butylaldehydes are sent to a
fractionation column, and separated into n-butylaldehyde and
iso-butylaldehyde, respectively. The n-butylaldehyde is introduced
from the bottom of the fractionation column into an aldol
condensation reactor, followed by condensation and dehydration to
give 2-ethylhexenal. The 2-ethylhexenal is sent to a hydrogenation
reactor, and thus octanol (2-ethylhexanol) is produced by
hydrogenation. The reactants in the outlet of the hydrogenation
reactor are sent to a fractionation column; followed by separation
of light/heavy ends to give octanol products.
[0005] The hydroformylation may be performed in a continuous,
semi-continuous, or batch types, and a typical hydroformylation
reaction system is a gas or liquid recycle system. On the other
hand, in the hydroformylation, it is important to increase reaction
efficiency by improvement in contact between liquid and gaseous
starting materials, which has been conventionally accomplished by
using a continuous stirred tank reactor (CSTR). In addition, in
U.S. Pat. No. 5,763,678, disclosed is a hydroformylation process in
a series of loop-type reactors which functions as a continuous
stirred tank reactor, However, there are limitations in the
improvement of the hydroformylation efficiency by the above
methods, and it is hard to obtain desirable aldehyde products using
a single reactor. Thus, desirable aldehyde products can be
generally produced by a longer reaction retention time or two or
more reactors connected in series.
DISCLOSURE
Technical Problem
[0006] In order to solve the above problems, it is an object of the
present invention to provide a method for the preparation of
aldehydes from olefins, carbon monoxide, and hydrogen, in which the
hydroformylation efficiency is improved to obtain aldehydes with a
high yield, and an apparatus used therefore.
Technical Solution
[0007] In the present invention, provided is a method for the
hydroformylation of olefins, comprising the step of spraying and
supplying olefins and a synthesis gas including hydrogen and carbon
monoxide through a nozzle into an oxo reactor provided with the
nozzle.
[0008] In the method for the hydroformylation of olefins, the
olefins and synthesis gas may be sprayed and supplied in a molar
ratio of 95:5 to 5:95.
[0009] In the method for the hydroformylation of olefins, the
olefins and synthesis gas may be sprayed and supplied into an oxo
reactor through a nozzle in a pressure of 5 to 200 bar,
respectively.
[0010] In the method for the hydroformylation of olefins, a venturi
may be connected to the nozzle.
[0011] In the method for the hydroformylation of olefins, the oxo
reactor may be a venturi-loop reactor.
[0012] In the method for the hydroformylation of olefins, the
nozzle may have a diameter of 0.1 mm to 100 cm.
[0013] In the method for the hydroformylation of olefins, the flow
rate of reaction liquid which is circulated by a pump may be 0.01
to 20 times of charging capacity of the reactor per minute.
[0014] In the method for the hydroformylation of olefins, the oxo
reactor may be maintained at a temperature of 50 to 200.degree. C.
and pressure of 5 to 50 bar.
[0015] In the method for the hydroformylation of olefins, the
olefin may be propylene, the aldehyde may be butylaldehyde, and the
catalyst solution may be a rhodium catalyst solution.
[0016] The method for the hydroformylation of olefins may further
comprise the step of recovering the reaction mixture from the oxo
reactor.
[0017] The method for the hydroformylation of olefins may further
comprise the step of separating aldehydes from the reaction
mixture.
[0018] The method for the hydroformylation of olefins may further
comprise the step of supplying the catalyst mixture, which is
resulting from the separation of aldehydes from the reaction
mixture, through a nozzle provided in the oxo reactor.
[0019] In addition, the present invention provides an apparatus for
the hydroformylation of olefins, comprising an oxo reactor provided
with a nozzle; an olefin feed line and a synthesis gas feed line
for feeding a synthesis gas including hydrogen and carbon monoxide
which are connected to the nozzle, respectively; a recycling line
for recovering the reaction mixture which is recovered from the oxo
reactor to supply into the nozzle provided in the oxo reactor; a
separation line branching off from any position in the recycling
line; a catalyst/aldehyde separator connected to the separation
line; a catalyst solution feed line connected to any position in
the catalyst/aldehyde separator and recycling line; and an aldehyde
recovery line which is connected to the catalyst/aldehyde
separator.
[0020] In the apparatus for the hydroformylation of olefins, the
nozzle may be provided at the top portion inside the oxo
reactor.
[0021] In the apparatus for the hydroformylation of olefins, a
venturi may be connected to the nozzle.
[0022] In the apparatus for the hydroformylation of olefins, the
oxo reactor may be a venturi-loop reactor.
[0023] In the apparatus for the hydroformylation of olefins, the
nozzle may have a diameter of 0.1 mm to 100 cm.
[0024] In the method for the hydroformylation of olefins, the flow
rate of reaction liquid which is circulated by a pump may be 0.01
to 20 times of charging capacity of the reactor per minute.
[0025] In the apparatus for the hydroformylation of olefins, a
circulating pump may be provided at any position of the recycling
line which connects the bottom portion of the oxo reactor with the
nozzle.
[0026] In the apparatus for the hydroformylation of olefins, a heat
exchanger may be provided at any position of the recycling line
which connects the bottom portion of the oxo reactor with the
nozzle.
Advantageous Effects
[0027] The present invention provides a method for the preparation
of aldehydes by hydroformylation of olefins, in which the
hydroformylation efficiency is improved, thereby obtaining
desirable aldehydes with a high yield.
DESCRIPTION OF DRAWINGS
[0028] FIG. 1 is a schematic diagram showing the process for the
hydroformylation of olefins according to one embodiment of the
present invention.
DESCRIPTION OF MARKS OF THE DRAWINGS
TABLE-US-00001 [0029] 10: Olefin feed line 11: Synthesis gas feed
line 12, 13, 14, 15, 16: Recycling line 17: Separation line 18:
Aldehyde recovery line 19: Catalyst solution feed line 20: Nozzle
30: Venturi 40: Circulating pump 50: Catalyst/aldehyde separation
apparatus 60: Heat exchanger 100: Oxo reactor
Best Mode
[0030] Hereinafter, the present invention will be described in
detail.
[0031] Preferred examples of the olefins used in the present
invention include ethylene, propylene, butene, 1-hexene, 1-octene,
1-nonene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene,
1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene,
1-nonadecene, 1-eicosene, 2-butene, 2-methyl propene, 2-pentene,
2-hexene, 2-heptene, 2-ethyl hexene, 2-octene, styrene,
3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene,
3-cyclohexyl-1-butene, allyl acetate, allyl butyrate, methyl
methacrylate, vinyl methyl ether, vinyl ethyl ether, allyl ethyl
ether, n-propyl-7-octenoate, 3-butenenitrile, 5-hexenamide,
4-methyl styrene, 4-isopropyl styrene.
[0032] The typical process according to the present invention
includes the hydroformylation of propylene into n- and
iso-butylaldehydes using a rhodium catalyst.
[0033] The prepared aldehydes according to the present invention
may be subjected to hydrogenation, and thus converted into
corresponding alcohols which may be used as a solvent and for the
preparation of plasticizer.
[0034] In the hydroformylation of olefins, homogeneous catalysts
using a group VIII transition metal including rhodium (Rh), cobalt
(Co), and iridium (Ir) as a main ingredient may be used, and
hydride (H.sup.-), carbonyl (CO), tripenylphosphine (TPP) may be
used as a ligand, but are not limited thereto, any one known in the
art may be used. The rhodium catalyst is highly expensive, but
provides more stable reaction conditions, excellent catalytic
activity and high selectivity during the hydroformylation process,
compared to the cobalt or iridium catalyst. Thus, the rhodium
catalyst is generally employed in the commercialized process.
[0035] Olefins, as a starting material, are sprayed and supplied
together with a synthesis gas (syn gas) including carbon monoxide
and hydrogen through the nozzle which is provided in the oxo
reactor. The nozzle is preferably provided at the top portion
inside the oxo reactor. The nozzle which is provided in the oxo
reactor may have various diameters depending on the size of the
reactor, 0.1 mm to 100 cm, and preferably 1 mm to 50 cm. The nozzle
may consist of multiple nozzles of two or more.
[0036] The olefins and synthesis gas are sprayed and supplied into
the oxo reactor through the nozzle at a feeding pressure of 1 to
200 bar, respectively. The molar ratio of olefin:synthesis gas
supplied into the oxo reactor is about 95:5 to 5:95, and more
preferably 75:25 to 25:75. The hydroformylation reaction is
performed at a temperature of 50 to 200.degree. C. and a pressure
of 5 to 100 bar, and more preferably at a temperature of 50 to
150.degree. C. and a pressure of 5 to 50 bar.
[0037] Unlike the conventional hydroformylation process using a
continuous stirred tank reactor (CSTR), a continuous reactor
equipped with the nozzle or both nozzle and venturi of the present
invention facilitates gas-liquid contact during the
hydroformylation reaction, thereby greatly increasing the reaction
efficiency.
[0038] In particular, in the case of using a continuous reactor
equipped with nozzle and venturi (venturi-loop reactor), the
starting materials, olefins and synthesis gas (CO+H.sub.2) are
spayed into the venturi through the nozzle to more facilitate
gas-liquid contact, thereby maximizing the reaction efficiency.
[0039] In the case of using a circular type reactor for the
hydroformylation reaction, some of the products (reaction mixture)
may be reused as a reactant (starting material). The reaction
mixture recovered from the bottom portion of the oxo reactor
contains aldehydes, unconverted olefins and catalyst solution. The
desired aldehydes may be separated from the reaction mixture using
a separator. The separated aldehydes are recovered, and the
catalyst mixture, resulting from the separation of aldehydes from
the reaction mixture, is sprayed and supplied into the oxo reactor
through the nozzle provided in the oxo reactor.
[0040] The preferred process using the method of the present
invention may be understood more readily by reference to the
accompanying drawings. In FIG. 1, omitted are practical standard
installations such as a valve, a temperature sensor, and a pressure
sensor, which are easily recognized by those skilled in the
art.
[0041] FIG. 1 is a schematic diagram showing the process for the
hydroformylation of olefins according to one embodiment of the
present invention. Olefins (e.g., propylene) and synthesis gas
(carbon monoxide+hydrogen) are supplied into the nozzle 20, which
is provided at the top portion of the oxo reactor 100 charged with
the catalyst solution, through the olefin feed line 10 and the
synthesis gas feed line 11, respectively.
[0042] In order to improve the efficiency of the gas-liquid
reaction, the nozzle 20 and the venturi 30 which is connected to
the nozzle are installed inside the oxo reactor 100, and the
supplied olefins and synthesis gas are continuously sprayed and
supplied into the venturi 30 through the nozzle 20. As such, the
oxo reactor 100 may be a reactor equipped with the nozzle or both
nozzle and venturi for the purpose of improving the efficiency of
the gas-liquid reaction, preferably venturi-loop reactor. The
olefins and synthesis gas, which had been sprayed into the oxo
reactor, undergo hydroformylation in the presence of a catalyst to
generate the reaction mixture. The reaction mixture contains
unconverted olefins, by-products, and the catalyst solution, in
addition to the desired aldehydes (e.g., n- and
iso-butylaldehydes).
[0043] The reaction mixture containing the aldehydes is recovered
through a recycling line 12 using a circulating pump 40, and then
circulated through the recycling line 13 into the nozzle 20
provided in the reactor, in which some of the circulated reaction
mixture may be sent to a catalyst/aldehyde separator 50 through a
separation line 17 branching off from the recycling line 13 in
order to separate aldehydes.
[0044] As the catalyst/aldehyde separator 50 for the separation of
aldehydes, any means capable of separating the aldehydes from the
reaction mixture may be used without limitations. The recovered
aldehydes may be sent to the separation/recovery device and the
like (not shown) through the aldehyde recovery line 18, and various
aldehydes and condensation products may be separated, recovered by
the conventional distillation apparatus and the like. For example,
during the hydroformylation process of producing butylaldehydes
from propylenes, the recovered butylaldehydes recovered from the
oxo reactor are sent to the fractionation column, and separated
into n- and iso-butylaldehydes, respectively. The n-butylaldehydes
in the bottom of the fractionation column are introduced into an
aldol condensation reactor, followed by hydrogenation to give
octanol (2-ethyl hexanol).
[0045] The residual catalyst mixture, resulting from separation of
the desired aldehydes from the reaction mixture, is supplied into
the recycling line 15 of the oxo reactor 100 through a catalyst
solution recycling line 19.
[0046] The reaction mixture of the reactor which is combined with
the recycled catalyst mixture is passed through a heat exchanger
60, and sprayed and supplied through the nozzle provided in the oxo
reactor 100 into the oxo reactor 100 together with the olefins and
synthesis gas which are supplied through the olefin feed line 10
and synthesis gas feed line 11.
[0047] The recirculation of the catalyst mixture, from which the
desired materials are removed, maybe continuously performed. If
necessary, some of the recirculating reaction mixture maybe
discharged to regenerate the catalyst or a fresh catalyst solution
or reactivated catalyst solution may be added to the recirculating
stream of the reaction mixture. FIG. 1 shows an example of
introducing the residual catalyst solution or the reactivated
catalyst solution into the reactor system by connecting the
catalyst solution recycling line 19 between the recycling lines 14
and 15.
[0048] The heat exchanger 60 may be provided between the recycling
lines (15 and 16), but the position is not particularly limited.
The heat exchanger 60 functions to maintain the temperature of the
reaction mixture, which is recirculated into the oxo reactor 100,
within a range suitable for hydroformylation reaction.
Mode for Invention
[0049] Hereinafter, the present invention will be described in more
detail with reference to preferred Examples. However, these
Examples are for illustrative purposes only, and the invention is
not intended to be limited by these Examples.
EXAMPLE 1
[0050] As shown in FIG. 1, a venturi-loop reactor having a capacity
of 3 liters was manufactured and installed. Instead of an external
heat exchanger, the internal temperature of the reactor was
maintained by flowing heat transfer oil in a jacket. The
venturi-loop reactor was equipped with a nozzle having a diameter
of 1.7 mm, and the expansion tube had a diameter of 8.0 mm and a
length of 200 mm. 48 g of triphenylphosphine (TPP) and 0.8 g (by
weight) of rhodium (triphenylphosphine)acetylacetonatecarbonyl
(ROPAC) were dissolved in 800 g of refined n-butylaldehyde to
prepare a n-butylaldehyde catalyst solution. The prepared catalyst
solution was injected into the reactor, and the circulating pump
was operated to slowly circulate the catalyst solution at a rate of
2 liter per minute. The entire system was purged with the refined
nitrogen gas through the nozzle at the top portion of the reactor
three times. While maintaining the external circulating pump at a
rate of 2 liter per minute, the internal temperature of the reactor
was increased and maintained at 90.degree. C. by flowing heat
transfer oil in an external jacket of the venturi-loop reactor.
When the temperature was stably maintained at 90.degree. C.,
propylene was supplied at a speed of 12 g/min until the reactor was
pressurized to 16.2 barg. After confirming that the internal
temperature of the venturi-loop reactor was maintained at
90.degree. C. for 5 min, the synthesis gas (mixed gas of carbon
monoxide and hydrogen at a molar ratio of 50:50) was supplied into
a neck of the nozzle (10 in FIG. 1) at a pre-set feeding pressure
of 18.8 barg and the reaction was simultaneously initiated. While
the internal temperature of the venturi-loop reactor was maintained
at 90.degree. C. by using an automatic temperature control device
connected to the reactor, the flow rate of the synthesis gas
supplied into the reactor was measured. After 2 hrs, the mixed gas
was cut off, and then the operation of circulating pump was
immediately stopped. The reactor temperature was reduced to room
temperature, and then the pressure was released. The mixture of
total catalyst solution and products was recovered through a
separation line, and its weight was measured. As a result, the
weight of total solution (after reaction) was found to be 1,265 g,
and thus the weight of the resulting butylaldehyde was found to be
465 g. In addition, the total amount of consumed synthesis gas was
measured using an integrated flow meter installed in the synthesis
gas feed line. During reaction, the maximum consumption rate of the
synthesis gas was found to be 5.4 liter per minute.
EXAMPLE 2
[0051] The experiment was performed in the same manners as in
Example 1, except that the circulating rate of the circulating pump
was reduced to 1.0 liter per minute. After 2 hrs, the total weight
of the obtained catalyst solution and products was found to be
1,225 g, and thus the weight of the resulting butylaldehyde was
found to be 420 g. During reaction, the maximum consumption rate of
the synthesis gas was found to be 4.1 liter per minute.
EXAMPLE 3
[0052] The experiment was performed in the same manners as in
Example 1, except that the diameter of the nozzle installed in the
venturi-loop reactor was changed to 4mm. After 2 hrs, the total
weight of the obtained catalyst solution and products was found to
be 1,240 g, and thus the weight of the resulting butylaldehyde was
found to be 440 g. During reaction, the maximum consumption rate of
the synthesis gas was found to be 4.6 liter per minute.
COMPARATIVE EXAMPLE 1
[0053] The experiment was performed in the same manners as in
Example 1, except for supplying the synthesis gas into the
circulating line (16 in FIG. 1) at the top portion of the nozzle
instead of the neck of the nozzle (10 in FIG. 1) in the
venturi-loop reactor as in Example 1. The weight of the resulting
butylaldehyde was found to be 412 g. During reaction, the maximum
consumption rate of the synthesis gas was found to be 4.0 liter per
minute.
COMPARATIVE EXAMPLE 2
[0054] While supplying the synthesis gas in the same manners as in
Example 1 and maintaining the stirrer at a speed of 1000 rpm, the
experiment was performed for 2 hrs, except for using an autoclave
reactor having a capacity of 3 liters instead of the venturi-loop
reactor of Example 1. The weight of the resulting butylaldehyde was
found to be 403 g. During reaction, the maximum consumption rate of
the synthesis gas was found to be 3.9 liter per minute.
INDUSTRIAL APPLICABILITY
[0055] The present invention provides a method for the preparation
of aldehydes by hydroformylation of olefins, in which the
hydroformylation efficiency is improved, thereby obtaining
desirable aldehydes with a high yield.
* * * * *