The present invention relates to a catalyst
10 composition for hydroformylation reaction and a method of
hydroformylating an olefin using the same. More particular,
the present invention relates to a catalyst composition
comprising a specific phosphine ligand, a transition metal
catalyst, and further a ligand stabilizer used in
15 hydroformylation reaction of an olefin, and a method of
hydroformylating olefin using the same.
【Background Art】
Hydroformylation generating linear (normal) and
branched (iso) aldehydes, in which the number of carbons
20 increases by 1, by reacting a variety of olefins with a
mixture of carbon monoxide (CO) and hydrogen (H2) generally
called synthesis gas and in the presence of a homogeneous
organometal catalyst and a ligand was first discovered by
Otto Roelen of Germany in 1938.
2
Hydroformylation also known as oxo syntheisis is a
very important reaction in connection with a homogeneous
catalyst reaction. At present, approximately 12 million tons
of a variety of aldehydes comprising alcohol derivatives are
produced and consumed through oxo synthesis 5 worldwide (SRI
report, November 2012, 7000I page 10).
In oxo synthesis, a variety of aldehydes is oxidized
or hydrogenated after condensation such as aldol and the
10 like, thereby being transformed into a variety of acids and
alcohols comprising long alkyl groups. In particular,
hydrogenated alcohols of aldehydes through oxo synthesis are
called oxo alcohols. Oxo alcohols are widely used in
industry as solvents, additives, raw materials of a variety
15 of plasticizers, synthetic lubricating oils, and the like.
As a catalyst of the hydroformylation reaction,
activity of a metal carbonyl compound catalyst was known.
Cobalt (Co) and rhodium (Rh) based catalysts are mainly used
in industry. An N/I selectivity (ratio of linear (normal) to
20 branched (iso) isomers), activity, and stability of the
aldehydes depend on ligand types applied to these catalysts
and driving conditions.
At present globally, 70% or more of oxo process25
related plants use a low pressure oxo process, in which a
3
large amount of a phosphine ligand is applied to a rhodium
based catalyst, due to advantages such as high catalyst
activity, a high N/I selectivity, and a relatively easy
reaction conditions, in spite of drawbacks such as high
catalyst costs, catalyst activity reduction due 5 to poisoning,
and the like.
As a central metal of an oxo catalyst, in addition to
cobalt (Co) and rhodium (Rh), transition metals such as
10 iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt),
palladium (Pd), iron (Fe), nickel (Ni), and the like may be
used. However, each of the metals is known to have the
following catalyst activity relationship: Rh ≫ Co > Ir, Ru
> Os > Pt > Pd > Fe > Ni. CO, Rh, Pt, and Ru, which are
15 Group VIII transition metals, exhibit high catalyst activity
in an oxo reaction. Pt and Ru are only used in academic
research. At present, rhodium and cobalt are mainly used in
most industrial oxo processes. As representative examples,
there are HCo(CO)4, HCo(CO)3PBu3 and HRh(CO)(PR3)3.
20
As ligand types used in an oxo process, there are
phosphine (PR3, where R is C6H5, or n-C4H9), phosphine oxide
(O=P(C6H5)3), and phosphite. When rhodium is used as a
central metal, triphenylphosphine (TPP) as a ligand in
25 connection with catalyst activity and stability is
4
considered to be the best option. Therefore, in most oxo
processes, rhodium (Rh) as a catalyst is used and TPP as a
ligand is applied. In addition, it is known that TPP as a
ligand is applied in an amount of 100 equivalents or more of
a catalyst to improve catalyst sta5 bility.
Generally, linear aldehyde derivatives of aldehydes,
products of an oxo reaction are valuable and, as such, most
research on catalysts has focused on increasing a ratio of
linear aldehydes.
10 However, there is an urgent need for technology to
improve catalyst stability and reduce a use amount of
ligands while improving selectivity for iso-aldehydes.
【Disclosure】
【Technical Problem】
15 Accordingly, inventors of the present invention
confirmed that, when a specific phosphine ligand and a
specific stabilizer are applied to hydroformylation of
olefin, stability of catalyst is improved and a use amount
of a ligand is reduced while improving selectivity for iso20
aldehyde, during watchful research to overcome the above
problems, thus, completing the present invention.
That is, the present invention has been made in view
of the above problems, and it is one object of the present
25 invention to provide a catalyst composition comprising a
5
specific phosphine ligand, a transition metal catalyst, and
a ligand stabilizer to exhibit superior catalyst activity
and improve selectivity of iso-type aldehyde while improving
stability of a catalyst and reducing a use amount of a
ligand, and a method of hydroformylating 5 ing olefin using the
same.
【Technical Solution】
In accordance with one aspect of the present
invention, provided is a catalyst composition for
10 hydroformylation, comprising a triphenyl phosphine-based
compound having a substituent group at a para position, a
diphenyl phosphine-based compound, and a transition metal
catalyst.
15 In accordance with another aspect of the present
invention, provided is a method of hydroformylating an
olefin comprising reacting an olefin and synthesis gas
(CO/H2) in the presence of the catalyst composition
described above to obtain aldehyde having a normal/iso (N/I)
20 selectivity of 6 or less.
【Advantageous effects】
As apparent from the fore-going, the present
invention advantageously provides a catalyst composition and
a hydroformylation method using the same, which may maintain
25 catalyst activity through improvement of catalyst stability
6
and reduce a use amount of a ligand while improving
selectivity for iso-aldehyde, by using a specific ligand to
a transition metal catalyst and a ligand stabilizer together
in hydroformylation of olefins.
Furthermore, the ligand and the stabilizer may b5 e
directly applied to a continuous hydroformylation process to
recover aldehyde and oxo synthesis industry.
【Best mode】
Hereinafter, the present invention will be described
10 in more detail.
Since a catalyst composition for hydroformylation of
the present invention comprises a specific one-coordinated
phosphine compound as a ligand, stability of a catalyst is
improved and a use amount of a ligand is reduced in
15 hydroformylation of olefin. As a result, selectivity for
iso-aldehydes is improved.
In particular, the catalyst composition for
hydroformylation according to the present invention
20 comprises a triphenyl phosphine-based compound having a
substituent group at a para position, a diphenyl phosphinebased
compound, and a transition metal catalyst
In one embodiment, the triphenyl phosphine-based
25 compound having the substituent group at the para position
7
may be a compound having a substituent group independently
selected from a C1 to C3 alkyl group and a C1 to C5 alkoxy
group at the para position.
As a specific embodiment, the triphenyl phosphinebased
compound having the substituent group 5 at the para
position may be a compound having, at the same time, a
substituent group type selected from a C1 to C3 alkyl group
and a C1 to C5 alkoxy group at the para position.
As another embodiment, the triphenyl phosphine-based
10 compound having the substituent group at the para position
may be one or more selected from tri-p-tolylphosphine (TPTP),
tri-p-ethylphenylphosphine (TPEtPP), tris-p-methoxyphenyl
phosphine, and tri-p-isopropoxyphenyl phosphine (TIPPP).
15 In particular, the triphenyl phosphine-based compound
having the substituent group at the para position may
function as a ligand to the transition metal catalyst in the
present invention. In particular, since continuous
consumption occurs in an aldehyde recovery process of a
20 hydroformylation continuous process, a selected proper
ligand may be added to a reactor. Accordingly, it is easy to
apply the triphenyl phosphine-based compound to an actual
process. In addition, stability of catalyst may be improved
and a use amount of the ligand may be reduced while
8
improving selectivity for iso-aldehyde through combination
with a diphenyl-cycloalkyl phosphine-based compound.
The amount of the triphenyl phosphine-based compound
having the substituent group at the para 5 ra position is
preferably 0.5 to 200 mole fraction, and may be 1 to 100
mole fraction or 5 to 50 mole fraction, with respect to 1
mol of a central metal of the transition metal catalyst.
When the amount of the triphenyl phosphine-based compound is
10 smaller than the lowest amount, reactivity of the catalyst
may not be exhibited due to lack of the ligand. On the other
hand, when the amount of the triphenyl phosphine-based
compound is larger than the largest amount, a reaction rate
may not be improved due to a large amount of the compound.
15
In one embodiment, the amount of the triphenyl
phosphine-based compound having the substituent group at the
para position may be 0.5 to 6.0 wt%, or 1.0 to 5.0 wt% with
respect to a total weight of the catalyst composition. When
20 the amount of the triphenyl phosphine-based compound is
smaller than the lowest amount, catalyst stability may be
affected. On the other hand, when the amount of the
triphenyl phosphine-based compound is larger than the
largest amount, costs increase due to overuse of the
25 expensive compound.
9
The triphenyl phosphine-based compound having the
substituent group at the para position may comprise tri-ptolylphosphine
(TPTP) in an amount of 1.0 to 5.0 wt%, or 1.0
to 4.0 wt%, with respect to a total weight of the catalyst
composition5 .
Meanwhile, when a triphenyl phosphine-based compound
(TPP), that is not substituted at the para position, is used,
improved selectivity for iso-aldehyde may not be
accomplished whenever the triphenyl phosphine-based compound
10 (TPP) is used alone or with the diphenyl phosphine-based
compound as a stabilizer.
In one embodiment, the diphenyl phosphine-based
compound may comprise a C1 to C6 n-alkyl group, a C2 to C6
15 branched alkyl group, a C3 to C6 tert-alkyl group, or a C5
to C6 cycloalkyl group.
As a specific embodiment, the diphenyl phosphinebased
compound comprises a C1 to C6 n-alkyl group, a C2 to
C6 branched alkyl group, a C3 to C6 tert-alkyl group, or a
20 C5 to C6 cycloalkyl group, and may have a substituent group
independently selected from a C1 to C3 alkyl group and a C1
to C5 alkoxy group at the para position of diphenyl.
As another embodiment, the diphenyl phosphine-based
compound may be 1 or more selected from n-alkyl
25 diphenylphosphine, branched alkyl diphenylphosphine, tert10
butyl diphenylphosphine, cyclohexyldiphenylphosphine,
cyclohexylditolyl phosphine, and
cycloheptyldiphenylphosphine.
As yet another embodiment, the diphenyl phosphinebased
compound may be 1 or more selected 5 from
cyclohexyldiphenylphosphine, cyclohexylditolyl phosphine,
and cycloheptyldiphenylphosphine.
In particular, the diphenyl phosphine-based compound
10 of the present invention may function as a ligand stabilizer.
The amount of the diphenyl phosphine-based compound
is preferably 1 to 250 mole fraction, and may be 10 to 100
mole fraction or 10 to 60 mole fraction, with respect to 1
mol of a central metal of the transition metal catalyst.
15 When the amount of the diphenyl phosphine-based compound is
smaller than the lowest amount, effects of stabilizing the
ligand may be insignificant. On the other hand, when the
amount of the diphenyl phosphine-based compound is larger
than the largest amount, a reaction rate may not be improved
20 due to a large amount of the compound.
In one embodiment, the amount of the diphenyl
phosphine-based compound may be 0.5 to 6.0 wt% or 1.0 to 5.5
wt%, with respect to a total weight of the catalyst
25 composition. When the amount of the diphenyl phosphine-based
11
compound is smaller than the lowest amount, catalyst
stability may be deteriorated. On the other hand, when the
amount of the diphenyl phosphine-based compound is larger
than the largest amount, costs increase due to overuse of
the expensive 5 ive compound.
The diphenyl phosphine-based compound may comprise
cyclohexyldiphenylphosphine (CDHP) in an amount of 1.0 to
5.5 wt% or 1.0 to 5.0 wt%, with respect to a total weight of
the catalyst composition.
10
In one embodiment, the transition metal catalyst may
be represented by Formula 1 below:
[Formula 1]
M(L1)x(L2)y(L3)z
15 wherein M is rhodium (Rh), iridium (Ir) or cobalt
(Co), and
L1, L2 and L3 are each independently hydrogen, CO,
cyclooctadiene, norbornene, chlorine, triphenylphosphine, or
acetylacetonate, x, y and z are each independently integer
20 of 0 to 5, and at least one of x, y and z is not 0.
As a specific embodiment, the transition metal
catalyst may be one or more selected from cobalt carbonyl
[Co2(CO)8], acetylacetonate dicarbonyl rhodium
25 [Rh(AcAc)(CO)2], acetylacetonate carbonyl triphenylphosphine
12
rhodium [Rh(AcAc)(CO)(TPP)], hydrido carbonyl
tri(triphenylphosphine)rhodium [HRh(CO)(TPP)3],
acetylacetonate dicarbonyl iridium [Ir(AcAc)(CO)2], and
hydrido carbonyl tri(triphenylphosphine)iridium
[HIr(CO)(TPP)5 3].
The amount of a central metal of the transition metal
catalyst may be 10 to 1000 ppm, or 50 to 500 ppm based on a
weight or volume of the central metal of the catalyst
10 composition. The amount of the central metal of less than 10
ppm is industrially undesirable since hydroformylation rate
reduces. On the other hand, when the amount of the central
metal is larger than 1000 ppm, costs increase due to
expressive central metal and a reaction rate may not be
15 proper.
In one embodiment, a method of hydroformylating the
olefin using the catalyst composition may comprise obtaining
aldehyde having a normal/iso (N/I) selectivity of 6 or less
20 by reacting an olefin and synthesis gas (CO/H2) in the
presence of the catalyst composition.
In one embodiment, the olefin may comprise a compound
represented by Formula 2 below:
25 [Formula 2]
13
wherein R4 and R5 are each independently hydrogen, a
C1 to C20 alkyl group, fluorine (F), chlorine (Cl), a bromo
(Br) group, trifluoromethyl group(-CF3) or a C6 to C20 aryl
group having 0 to 5 substituent 5 nt groups, and
a substituent group of the aryl group is a nitro (-
NO2) group, fluorine (F), chlorine (Cl), bromine (Br), a
methyl group, an ethyl group, a propyl group, or a butyl
group.
10
As a specific embodiment, the olefin may be one or
more selected from ethene, propene, 1-butene, 1-pentene, 1-
hexene, 1-octene, and styrene.
15 The synthesis gas used in the method of preparing
aldehyde of the present invention is mixed gas of carbon
monoxide and hydrogen. A mixing ratio of CO:H2 may be 5:95
to 70:30, 40:60 to 60:40, or 50:50 to 40:60, but the mixing
ratio is not limited thereto. When the mixing ratio is
20 outside these ranges, unused gas is accumulated in a reactor
and, as such, reactivity of the catalyst may be deteriorated.
14
In addition to the method of hydroformylating the
olefin according to the present invention, other reaction
conditions may be carried out through generally known
methods.
In the method of preparing aldehyde 5 of the present
invention, a reaction temperature of the olefin and the
synthesis gas (CO/H2) in the presence of the catalyst
composition may, for example, be 20 to 180℃, 50 to 150℃,
or 75 to 125℃, but the present invention is not limited
10 thereto. When the reaction temperature is less than 20℃,
hydroformylation does not proceed. On the other hand, when
the reaction temperature is larger than 180℃, stability of
the catalyst is seriously damaged and, as such, activity of
the catalyst is deteriorated.
15 In addition, pressure of the reaction may, for
example, be 1 to 700 bar, 1 to 300 bar, or 5 to 30 bar. When
the reaction pressure is less than 1 bar, the
hydroformylation reaction proceeds too slowly. On the other
hand, when the reaction pressure is larger than 700 bar, an
20 expensive reactor must be used to prevent explosion, without
improvement of activity, and, thus, industrialization may be
difficult.
When the process of hydroformylating the olefin
25 according to the present invention is schematically
15
described, the triphenyl phosphine-based compound having the
substituent group at the para position, a transition metal
catalyst (b), and a diphenyl-cycloalkyl phosphine-based
compound are dissolved in a solvent such as benzene, toluene,
ethanol, pentanol, octanol, texanol, butyraldehyde, penty5 l
aldehyde, or the like, to prepare a mixed solution.
Subsequently, the olefin, and the synthesis gas of carbon
monoxide and hydrogen with the mixed solution are added to
the reactor and then hydroformylation is proceeded by
10 elevating temperature and applying pressure, while stirring.
As a result, iso-aldehyde having improved selectivity,
particularly having a normal/iso (N/I) selectivity of 6 or
less may be obtained.
15 Concrete ingredients and contents of the catalyst
composition according to the present invention are the same
as described above. The catalyst composition of the present
invention may be prepared by dissolving in the solvent
described above. A solvent used in the present invention is
20 preferably one or more selected from aldehydes comprising
propane aldehyde, butyraldehyde, pentyl aldehyde, valer
aldehyde, and the like; ketones comprising acetone, methyl
ethyl ketone, methyl isobutyl ketone, acetophenone,
cyclohexanone, and the like; alcohols comprising ethanol,
25 pentanol, octanol, texanol, and the like; aromatic compounds
16
comprising benzene, toluene, xylene, and the like;
halogenated aromatic compounds comprising orthodichlorobenzene,
and the like; ethers comprising
tetrahydrofuran, dimethoxyethane, dioxane, and the like;
halogenated paraffins comprising methylene chloride and 5 the
like; and paraffin hydrocarbons comprising heptane and the
like, but the present invention is not limited thereto. In
particular, the solvent may be an aldehyde generated through
hydroformylation.
10
In accordance with the catalyst composition and the
method of hydroformylating olefin using the same of the
present invention, although the ligand is used in a smaller
amount than a conventionally used amount, an N/I selectivity
15 of aldehyde is 3.1 to 3.7 and, thus, selectivity for isoaldehyde
is improved. In addition, a stabilization value of
the catalyst is 60 to 61% after 15 hr, 72 to 80 % after 5 hr,
and 78 to 92% after 2.5 hr, based on a catalyst activity
value of 116 to 138% during supply of fresh.
20
Hereinafter, preferred examples will be provided for
better understanding of the present invention. It will be
apparent to those skilled in the art that these examples are
only provided to illustrate the present invention and
25 various modifications and alterations are possible within
17
the scope and technical range of the present invention. Such
modifications and alterations fall within the scope of
claims included herein.

250 ppm of rhodium (Rh) as a transition metal
catalyst, 2.0 wt% of a triphenyl phosphine-based compound
(tri-p-tolylphosphine), a substituent group at a para
position of which is methyl, as a ligand to the catalyst,
10 and 2.0 wt% of a diphenyl phosphine-based compound
(cyclohexyl diphenyl phosphine) having a C6 cycloalkyl group,
as a ligand stabilizer were dissolved in butylaldehyde to
prepare 100 g of a total solvent.
Mixed gas of propene:CO:H2 mixed in a molar ratio of
15 1:1:1 was added to the catalyst solution, and stirred for 1
hour at 90 ℃ while maintaining pressure of the reactor at 8
bar such that a reaction was carried out.
Activity (%) of the fresh catalyst used in the
reaction and a normal/iso selectivity of aldehyde prepared
20 were measured according to methods described below. In
addition, a degree of stability of the catalyst was measured
maximally up to 15 hr through a stability test. Results are
summarized in Tables 1 and 2.

18
*Catalyst activity (%): a total amount of aldehyde
generated in the reaction was measured by dividing into a
molecular weight of butyraldehyde, a concentration of the
used catalyst, and reaction time. A unit was
mol(BAL)/5 /mol(Rh)/h.
*Normal/iso selectivity of aldehyde: resultant values
are values obtained by dividing the amount of normalbutyraldehyde
generated from the reaction into the amount of
iso-butyraldehyde. A generation amount of each aldehyde was
10 measured through gas chromatography (GC).
*Stability test (againg test): mixed gas of CO and H2
mixed in a molar ratio of 1:1 was added to the solution to
maintain pressure of the reactor pressure at 10 bar and an
aging test was carried out while stirring at 120 ℃. Aging
15 activity change of the catalyst was recorded in %.

An experiment was carried out in the same manner as
in Example 1, except that 1.0 wt% of the triphenyl
20 phosphine-based compound (tri-p-tolylphosphine), in which a
substituent group at a para position is methyl, and 2.5 wt%
of the diphenyl phosphine-based compound (cyclohexyl
diphenyl phosphine) having a C6 cycloalkyl group, as a
ligand stabilizer were used. Measured results are summarized
25 in Tables 1 and 2.
19

An experiment was carried out in the same manner as
in Example 1, except that 4.0 wt% of the triphenyl
phosphine-based compound (tri-p-tolylphosphine), in which 5 a
substituent group at a para position is methyl, was used and
the diphenyl phosphine-based compound (cyclohexyl diphenyl
phosphine) having a C6 cycloalkyl group, as a ligand
stabilizer was not added. Measured results are summarized in
10 Tables 1 and 2.

An experiment was carried out in the same manner as
in Example 1, except that 6.0 wt% of triphenyl phosphine, in
15 which a substituent group does not exist at a para position,
was used instead of the triphenyl phosphine-based compound
(tri-p-tolylphosphine), in which a substituent group at a
para position is methyl, and the diphenyl phosphine-based
compound (cyclohexyl diphenyl phosphine) having a C6
20 cycloalkyl group, as a ligand stabilizer was not added.
Measured results are summarized in Tables 1 and 2.
【Table 1】
Ciloans sificat Ligand Sotfa bliilgiaznedr
F(caacr%tte)aislvhyi stty
Nosto eyrl meaclti/viis
Example 1 Triphenyl Diphenyl- 116 3.7
20
Example 2
phosphin-cisnapibonuttosam b s spsimeottewgduiithrp ntohioadunycure,e lhpa
owcapccgnpsshynauyoroopicdrbcmotshcl aslpu iiho torptein aiai ixneltlsoi ,kukensw yeystdhlnl oi tpaCec ht6sh
138 3.1
CEoxmapmaprlaet i1v e
-
98 6.4
CEoxmapmaprlaet 2i ve
Tp,wsndepprh hutoxaoioib eirspscsssaihpht t tgeh i irnitoonynunuaoilee pttn
100 9.1
【Table 2】
Ciloans sificat Ligand Sotfa bliilgiaznedr
Ctaetsatl y(satg ing tsitmaeb)i lity
Fresh 2h.r5 5hr.0 1h5r.0
Example 1
Tobcisgppmrsaonuraoeipsm borstphepsuaihhidotp tyen ui ilnento wy-dunhl,e ip naichttsh
capDcowcgnpsynayshuioroocdrcpibpmotsl alhcshpu io oihterpteiaan ini ixnlletyso ikk,ulenswyy es-tdhlln oi ptaCech t6sh
116 78 72 60
Example 2 138 92 80 61
CEoxmapmaprlaet i1v e
-
98 63 59 54
CEoxmapmaprlaet 2i ve
Topwsgnarshurotoipibot sphcsu ihihtpten i inetoey,undxpl e oiapnesrihtstan
100 56 48 28
As shown in Tables 1 and 2, it can be confirmed that,
in Example 1 to 2 using the specific ligand and the
5 stabilizer to the ligand together of the present invention,
21
iso-aldehyde selectivity of aldehyde, an N/I selectivity of
which is 3.1 to 3.7, is improved, and catalyst stability is
dramatically improved showing 60 to 61% after 15 hr, 72 to
80 % after 5 hr, and 78 to 92% after 2.5 hr, based on a
catalyst activity value of 116 to 138% during 5 supply of
fresh.
On the other hand, it can be confirmed that, in
Comparative Example 1 using only the ligand, without the
stabilizer, in a total amount of the ligand and the
10 stabilizer used in Examples 1 to 2, an N/I selectivity of
aldehyde is 6.4 (an N/I selectivity of less than 6 is
impossible) due to relative reduction of iso-aldehyde
selectivity, and a stability value of the catalyst is
reduced indicating 54% after 15 hr, 59 % after 5 hr, and 63%
15 after 2.5 hr, based on a catalyst activity value of 98%
during supply of fresh.
Furthermore, it can be confirmed that, in Comparative
Example 2 using only triphenylphosphine in which a
substituent group does not exist at a para position,
20 conventionally used instead of the ligand used in Examples 1
to 2, normal aldehyde selectivity is improved indicating an
aldehyde N/I selectivity of 9.1, and a stability value of
the catalyst poorly is 28% after 15 hr, 48% after 5 hr, and
56% after 2.5 hr, based on a catalyst activity value of 100%
25 during fresh supply.
22

What is claimed is:
1. A catalyst composition for hydroformylation
reaction, comprising a triphenyl phosphine-based compound
having a substituent group at a para position, a 5 diphenyl
phosphine-based compound, and a transition metal catalyst.
2. The catalyst composition according to claim 1,
wherein the triphenyl phosphine-based compound having the
10 substituent group at the para position is a compound having
a substituent group independently selected from a C1 to C3
alkyl group and a C1 to C5 alkoxy group at the para position.
3. The catalyst composition according to claim 2,
15 wherein the triphenyl phosphine-based compound having the
substituent group at the para position is a compound having,
at the same time, a substituent group type selected from a
C1 to C3 alkyl group and a C1 to C5 alkoxy group at the para
position.
20
4. The catalyst composition according to claim 1,
wherein the diphenyl phosphine-based compound comprises a
functional group selected from a C1 to C6 n-alkyl group, a
C2 to C6 branched alkyl group, a C3 to C6 tert-alkyl group,
25 and a C5 to C6 cycloalkyl group.
23
5. The catalyst composition according to claim 4,
wherein the diphenyl phosphine-based compound comprises a
substituent group selected from a C1 to C3 alkyl group and a
C1 to C5 alkoxy alkyl at the para 5 a position.
6. The catalyst composition according to claim 1,
wherein the transition metal catalyst is represented by
Formula 1 below:
10 [Formula 1]
M(L1)x(L2)y(L3)z
wherein M is rhodium (Rh), iridium (Ir) or cobalt
(Co), and
L1, L2 and L3 are each independently hydrogen, CO,
15 cyclooctadiene, norbornene, chlorine, triphenylphosphine, or
acetylacetonate, x, y and z are each independently integer
of 0 to 5, and at least one of x, y and z is not 0.
7. The catalyst composition according to claim 1,
20 wherein the transition metal catalyst is one or more
selected from cobalt carbonyl [Co2(CO)8], acetylacetonate
dicarbonyl rhodium [Rh(AcAc)(CO)2], acetylacetonate carbonyl
triphenylphosphine rhodium [Rh(AcAc)(CO)(TPP)], hydrido
carbonyl tri(triphenylphosphine)rhodium [HRh(CO)(TPP)3],
25 acetylacetonate dicarbonyl iridium [Ir(AcAc)(CO)2], and
24
hydrido carbonyl tri(triphenylphosphine)iridium
[HIr(CO)(TPP)3].
8. The catalyst composition according to claim 1,
wherein an amount of a central metal of the transition 5 ition metal
catalyst is 10 to 1000 ppm based on a weight or volume of
the catalyst composition.
9. The catalyst composition according to claim 1,
10 wherein an amount of the triphenyl phosphine-based compound
having the substituent group at the para position is 0.5 to
200 mole fraction with respect to 1 mol of a central metal
of the transition metal catalyst.
15 10. The catalyst composition according to claim 1,
wherein an amount of the triphenyl phosphine-based compound
having the substituent group at the para position is 0.5 to
6.0 wt% based on a total weight of the catalyst composition.
20 11. The catalyst composition according to claim 1,
wherein the triphenyl phosphine-based compound having the
substituent group at the para position comprises tri-ptolylphosphine
(TPTP) in an amount of 1.0 to 5.0 wt% with
respect to a total weight of the catalyst composition.
25
25
12. The catalyst composition according to claim 1,
wherein an amount of the diphenyl phosphine-based compound
is 1 to 250 mole fraction with respect to a 1 mol of a
central metal of the transition metal catalyst.
5
13. The catalyst composition according to claim 1,
wherein an amount of the diphenyl phosphine-based compound
is 0.5 to 6.0 wt% with respect to a total weight of the
catalyst composition.
10
14. The catalyst composition according to claim 1,
wherein the diphenyl phosphine-based compound comprises
cyclohexyldiphenylphosphine in an amount of 1.0 to 5.5 wt%
with respect to a total weight of the catalyst composition.
15
15. A method of hydroformylating an olefin, the
method comprising obtaining aldehyde having a normal/iso
(N/I) selectivity of 6 or less by reacting an olefin and
synthesis gas (CO/H2) in the presence of the catalyst
20 composition according to any one of claims 1 to 14.
16. The method according to claim 15, wherein the
olefin comprises a compound represented by Formula 2 below:
[Formula 2]
26
wherein R4 and R5 are each independently hydrogen, a
C1 to C20 alkyl group, fluorine (F), chlorine (Cl), a bromo
(Br) group, trifluoromethyl group(-CF3) or a C6 to C20 aryl
group having 0 to 5 substituent 5 nt groups, and
a substituent group of the aryl group is a nitro (-
NO2) group, fluorine (F), chlorine (Cl), bromine (Br), a
methyl group, an ethyl group, a propyl group, or a butyl
group.
10
17. The method according to claim 15, wherein the
olefin is one or more selected from ethene, propene, 1-
butene, 1-pentene, 1-hexene, 1-octene, and styrene.
15 18. The method according to claim 15, wherein a molar
ratio of the synthesis gas (Co:H2) is 5:95 to 70:.
19. The method according to claim 15, wherein the
catalyst composition is added to a next reaction after
20 dissolving in a solvent or more selected from propane
aldehyde, butyraldehyde, pentyl aldehyde, valer aldehyde,
acetone, methyl ethyl ketone, methyl isobutyl ketone,
27
acetophenone, cyclohexanone, ethanol, pentanol, octanol,
texanol, benzene, toluene, xylene, ortho dichlorobenzene,
tetrahydrofuran, dimethoxyethane, dioxane, methylene
chloride, and heptane.
5
20. The method according to claim 15, wherein the
reaction is carried out at 20 to 180℃ at a pressure of 1 to
700 bar.