WO2015046924A1 - 히드로포밀화 반응용 촉매 조성물 및 이를 이용한 올레핀의 히드로포밀화 방법 - Google Patents
히드로포밀화 반응용 촉매 조성물 및 이를 이용한 올레핀의 히드로포밀화 방법 Download PDFInfo
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- WO2015046924A1 WO2015046924A1 PCT/KR2014/008978 KR2014008978W WO2015046924A1 WO 2015046924 A1 WO2015046924 A1 WO 2015046924A1 KR 2014008978 W KR2014008978 W KR 2014008978W WO 2015046924 A1 WO2015046924 A1 WO 2015046924A1
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- hydroformylation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Definitions
- the present invention relates to a catalyst composition for hydroformylation reaction and a method for hydroformylation of olefins using the same, and more particularly, to specific phosphine ligands and transition metal catalysts used for hydroformylation of olefinic compounds, and further stable ligands.
- a catalyst composition comprising an agent and a method for hydroformylation of an olefin using the same.
- Hydroformylation reaction commonly known as OXO reaction
- OXO reaction is an industrially important reaction for homogeneous catalysis, and various aldehydes containing about 12 million tonnes of alcohol derivatives worldwide are currently available through the oxo process. Production and consumption ( SRI report , November 2012, 7000I page 10).
- oxo alcohol which is widely used industrially such as solvents, additives, raw materials of various plasticizers, synthetic lubricants.
- the catalyst of the hydroformylation reaction is known to have a metal-carbonyl compound catalyst, and industrially used catalysts mainly include cobalt (Co) and rhodium (Rh) series. These catalysts vary in N / I selectivity (ratio of linear (normal) to branched (iso) isomers), activity and stability of the aldehydes produced, depending on the type of ligand applied and the operating conditions.
- the core metals of the oxo catalyst are iridium (Ir), ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe) and nickel (Ni). Transition metals such as) can be applied.
- the metals are known to exhibit catalytic activity in the order of Rh »Co> Ir, Ru>Os>Pt>Pd>Fe> Ni.
- CO, Rh, Pt and Ru are metals belonging to Group 8 transition metals and exhibit high catalytic activity in the oxo reaction. Pt and Ru are only applied to academic research. Currently, most commercial oxo processes are based on rhodium and cobalt.
- HCo (CO) 4 , HCo (CO) 3 PBu 3 and HRh (CO) ( PR 3 ) 3 is a representative example.
- phosphine Phosphine, PR 3 , R is C 6 H 5 , or nC 4 H 9
- phosphite phosphine oxide
- TPP triphenylphosphine
- rhodium (Rh) metal is used as a catalyst and TPP is applied as a ligand, and in order to increase the stability of the catalyst system, TPP as a ligand is known to apply more than 100 equivalents of the catalyst.
- the present inventors continue to study to solve the above problems, while applying a specific phosphine ligand and a specific stabilizer to the hydroformylation reaction of the olefin improves the stability of the catalyst while improving the selectivity of the isoaldehyde It has been found that the amount of ligand used can be reduced and the present invention has been completed.
- an object of the present invention is a catalyst composition comprising a specific phosphine ligand, a transition metal catalyst and a ligand stabilizer to improve the selectivity of isotype aldehyde while increasing the stability of the catalyst and reducing the amount of ligand used while exhibiting high catalytic activity. And it is to provide a method for hydroformylation of olefins using the same.
- the present invention provides a catalyst composition for hydroformylation reaction comprising a triphenyl phosphine compound having a substituent in the para position, a diphenyl phosphine compound and a transition metal catalyst as means for solving the above problems.
- the present invention comprises the step of reacting the olefin compound and synthetic gas (CO / H 2 ) in the presence of the above-described catalyst composition to obtain an aldehyde having a normal / isoselectivity (N / I) of 6 or less; A hydroformylation method of a system compound is provided.
- the catalyst composition according to the present invention and the hydroformylation method reacting with the same include a specific ligand for the transition metal catalyst and a stabilizer for the ligand in combination with the hydroformylation reaction of the olefin. While improving the stability of the catalyst to maintain a high catalytic activity and provides an effect of reducing the amount of ligand used.
- the ligands and stabilizers also have the advantage that they can be directly applied to the commercialized oxo process in the aldehyde recovery process of the hydroformylation continuous process.
- the catalyst composition for hydroformylation reaction according to the present invention is characterized by comprising a triphenyl phosphine compound, a diphenyl phosphine compound and a transition metal catalyst having a substituent in the para position.
- the triphenyl phosphine compound having a substituent at the para position may be, for example, a compound having a substituent independently selected from an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 5 carbon atoms at the para position.
- the triphenyl phosphine compound having a substituent at the para position may be a compound having one substituent selected from an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 5 carbon atoms at the para position.
- the triphenyl phosphine-based compound having a substituent in the para position may be tri-p-tolylphosphine (TPTP), tri-p-ethylphenylphosphine (TPEtPP), tris-p- Methoxyphenyl phosphine (TPPPP) and tri-p-isopropoxyphenyl phosphine (TIPPP) It may be one or more selected from.
- TPTP tri-p-tolylphosphine
- TPEtPP tri-p-ethylphenylphosphine
- TPPPP tris-p- Methoxyphenyl phosphine
- TIPPP tri-p-isopropoxyphenyl phosphine It may be one or more selected from.
- the triphenyl phosphine compound having a substituent in the para position may act as a ligand for the transition metal catalyst in the present invention.
- an appropriate ligand can be selected and introduced into the reactor, thus providing the advantage that it is easy to apply to the actual process, as well as diphenyl-cycloalkyl.
- a phosphine-based compound it is possible to increase the stability of the catalyst and lower the amount of the ligand while improving the selectivity of isoaldehyde.
- the content of the triphenyl phosphine compound having a substituent in the para position is preferably 0.5 to 200 mole fraction, 1 to 100 mole fraction, or 5 to 50 mole fraction with respect to 1 mole of the central metal of the transition metal catalyst. . If it is less than the lower limit, there is a fear that the reactivity of the catalyst may not appear due to the lack of an appropriate ligand, and if it exceeds the upper limit, it may not be advantageous in terms of reaction rate due to the presence of excess.
- the content of the triphenyl phosphine compound having a substituent in the para position may be in the range of 0.5 to 6.0 wt%, or 1.0 to 5.0 wt%, based on the total weight of the catalyst composition. If it is below the lower limit, there is a problem in the stability of the catalyst system, and if the upper limit is exceeded, there is a problem in that the cost increases due to the excessive use of expensive compounds.
- the triphenyl phosphine-based compound having a substituent in the para position may include tri-p-tolylphosphine (TPTP) in the range of 1.0 to 5.0 wt%, or 1.0 to 4.0 wt% based on the total weight of the catalyst composition.
- TPTP tri-p-tolylphosphine
- the diphenyl phosphine compound may include, for example, n-alkyl having 1 to 6 carbon atoms, branched alkyl having 2 to 6 carbon atoms, tert-alkyl having 3 to 6 carbon atoms, or a cycloalkyl group having 5 to 6 carbon atoms.
- diphenyl phosphine-based compound examples include, for example, n-alkyl having 1 to 6 carbon atoms, branched alkyl having 2 to 6 carbon atoms, tert-alkyl having 3 to 6 carbon atoms, or cycloalkyl group having 5 to 6 carbon atoms. It may have a substituent independently selected from an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 5 carbon atoms in the para position of phenyl.
- the diphenyl phosphine-based compound may be n-alkyl diphenylphosphine, branched alkyl diphenylphosphine, tert-butyl diphenylphosphine, cyclohexyldiphenylphosphine, cyclohexylditolyl phosphine and cycloheptyldi It may be at least one selected from phenylphosphine.
- the diphenyl phosphine-based compound may be at least one selected from cyclohexyldiphenylphosphine, cyclohexylditolyl phosphine, and cycloheptyldiphenylphosphine.
- the diphenyl phosphine compound in the present invention may act as a stabilizer for the ligand.
- the content of the diphenyl phosphine compound is preferably 1 to 250 mole fraction, 10 to 100 mole fraction, or 10 to 60 mole fraction with respect to 1 mole of the central metal of the transition metal catalyst. Below the lower limit, the effect of stabilizing the ligand may be insignificant, and when the upper limit is exceeded, it may not be advantageous in terms of reaction rate due to the presence of excess.
- the content of the diphenyl phosphine-based compound may be in the range of 0.5 to 6.0 wt%, or 1.0 to 5.5 wt%, for example, based on the total weight of the catalyst composition. If it is below the lower limit, there is a problem in the stability of the catalyst system, and if the upper limit is exceeded, there is a problem in that the cost increases due to the excessive use of expensive compounds.
- the diphenyl phosphine-based compound may include cyclohexyldiphenylphosphine (CDHP) in the range of 1.0 to 5.5% by weight or 1.0 to 5.0% by weight based on the total weight of the catalyst composition.
- CDHP cyclohexyldiphenylphosphine
- the transition metal catalyst may be represented by the following Formula 1, for example.
- M is rhodium (Rh), iridium (Ir) or cobalt (Co),
- L 1 , L 2 and L 3 are each independently hydrogen, CO, cyclooctadiene, norbornene, chlorine, triphenylphosphine or acetylacetonato , x, y and z are each independently integers of 0 to 5, and x, y and z are not 0 at the same time.
- the transition metal catalyst may be cobalt carbonyl [Co 2 (CO) 8 ], acetylacetonatodicarbonyldium [Rh (AcAc) (CO) 2 ], acetylacetonatocarbonyltriphenylphosphinedium [ Rh (AcAc) (CO) (TPP)], hydridocarbonyltri (triphenylphosphine) rhodium [HRh (CO) (TPP) 3 ], acetylacetonatodicarbonyliridium [Ir (AcAc) (CO) 2 ] and hydridocarbonyltri (triphenylphosphine) iridium [HIr (CO) (TPP) 3 ].
- the transition metal catalyst may use a core metal content in the range of 10 to 1000 ppm, or 50 to 500 ppm based on the weight or volume of the catalyst composition. If the core metal content is less than 10 ppm, the hydroformylation reaction rate is slowed down, and thus commercially undesirable. If the core metal content is higher than 1000 ppm, the core metal is expensive, so the cost may not be increased and may not be appropriate in terms of reaction rate.
- the hydroformylation method of an olefin compound using the catalyst composition described above may react with an olefin compound and a synthetic gas (CO / H 2 ) in the presence of the catalyst composition to give a normal / isoselectivity (N / I) of 6. It may include the following; obtaining an aldehyde below.
- the olefinic compound may include a compound represented by the following Formula 2, for example.
- each R 2 independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, fluorine (F), chlorine (Cl), bromine group (Br), trifluoromethyl group (-CF 3 ) or 6 to 5 carbon atoms having 0 to 5 substituents. It is an aryl group of 20 to,
- the olefin compound may be at least one selected from ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, and styrene.
- the synthesis gas used in the aldehyde production method of the present invention is a mixed gas of carbon monoxide and hydrogen, the mixing ratio of CO: H 2 is not limited thereto, 5:95 to 70:30, 40:60 to 60:40 Or 50:50 to 40:60. Any deviation from the ranges indicated above may result in the accumulation of unused gas in the reactor and consequently deteriorate the reactivity of the catalyst.
- reaction conditions may generally use a known method.
- the reaction temperature of the olefin-based compound and the synthetic gas (CO / H 2 ) in the presence of the catalyst composition is, for example, 20 to 180 ° C, 50 to 150 ° C, or 75 to May be 125 ° C. If it is less than 20 °C hydroformylation reaction does not proceed, there is a problem that the catalyst activity is reduced rather than 180 °C stability of the catalyst is greatly impaired.
- a triphenyl phosphine compound having a substituent at the para position, a transition metal catalyst (b), and a diphenyl-cycloalkyl phosphine compound may be selected from benzene, toluene,
- a mixed solution is prepared by dissolving in a solvent such as ethanol, pentanol, octanol, texanol, butylaldehyde or pentylaldehyde.
- the catalyst composition of the present invention can be prepared by dissolving the aforementioned components in a solvent.
- Solvents usable in the present invention are not limited thereto, but are preferably aldehydes including propane aldehyde, butyl aldehyde, pentyl aldehyde, or baler aldehyde; Ketones including acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone and the like; Alcohols such as ethanol, pentanol, octanol and tensanol; Aromatics including benzene, toluene, xylene and the like; Halogenated aromatics including ortho-dichlorobenzene and the like; Ethers including tetrahydrofuran, dimethoxyethane, dioxane and the like; Halogenated paraffins including
- the N / I selectivity of the aldehyde is improved to 3.1 to 3.7 with improved ligand content, and the fresh ( fresh), based on the range of 116 to 138% catalyst activity, the catalyst had a stabilization value of 60 to 61% after 15 hr, 72 to 80% after 5 hr, and 78 hr after 2.5 hr. To 92%.
- rhodium (Rh) as a transition metal catalyst
- 2.0 wt% of a cyclohexyl diphenyl phosphine compound having a cycloalkyl group was dissolved in a butylaldehyde solvent to make a total solution of 100 g, and then added to a 600 ml autoclave reactor.
- a mixed gas having a propene: CO: H 2 molar ratio of 1: 1: 1 was injected into the catalyst solution to maintain a reactor pressure of 8 bar, and reacted for 1 hour while stirring at 90 ° C.
- Catalytic activity (%) The total amount of aldehyde produced in the reaction was measured by dividing the molecular weight of butylaldehyde, the concentration of the catalyst used, and the reaction time, and the unit is mol (BAL) / mol (Rh) / h.
- Aging test A aging experiment was carried out while injecting a gas having a molar ratio of CO: H 2 of 1: 1 to the solution to maintain a reactor pressure of 10 bar and stirring at 120 ° C. Recorded in units.
- Example 1 1.0% by weight of a triphenyl phosphine compound (tri-p-tolylphosphine) having a substituent in the para position, and a diphenyl phosph having a cycloalkyl group having 6 carbon atoms as a stabilizer for the ligand
- a pinhexyl compound cyclohexyl diphenyl phosphine
- Example 1 4.0% by weight of a triphenyl phosphine compound (tri-p-tolylphosphine) having a substituent in the para position, and a diphenyl phosph having a cycloalkyl group having 6 carbon atoms as a stabilizer for the ligand Except that the pin-based compound (cyclohexyl diphenyl phosphine) was not added, the same experiment as in Example 1 was repeated and measured results are summarized in Table 1 and 2, respectively.
- a triphenyl phosphine compound tri-p-tolylphosphine
- diphenyl phosph having a cycloalkyl group having 6 carbon atoms
- Example 1 6.0% by weight of triphenyl phosphine (triphenyl phosphine) having no substituent in the para position instead of tri-p-tolylphosphine having a substituent in the para position methyl, the ligand
- triphenyl phosphine triphenyl phosphine
- the diphenyl phosphine compound having a cycloalkyl group having 6 carbon atoms as a stabilizer was not added.
- the N / I selectivity of the aldehyde is in the range of 3.1 to 3.7, and the isoaldehyde selectivity is improved.
- the stability value of the catalyst was 60 to 61% after 15 hr, 72 to 80% after 5 hr, and 78 to 92% after 2.5 hr. As a result, it was confirmed that remarkably improved.
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Abstract
Description
구분 | 리간드 | 리간드의 안정화제 | 프레쉬 촉매 활성(%) | 노말/이소 선택도 |
실시예 1 | 파라 위치 치환기가 메틸인 트리페닐포스핀계 화합물 | 탄소수 6인 시클로알킬을 포함하고 파라 위치 치환기가 없는 디페닐-시클로알킬포스핀 | 116 | 3.7 |
실시예 2 | 138 | 3.1 | ||
비교예 1 | - | 98 | 6.4 | |
비교예 2 | 파라 위치 치환기가 없는 트리페닐포스핀 | 100 | 9.1 |
구분 | 리간드 | 리간드의 안정화제 | 촉매 안정성 시험(aging time) | |||
프레쉬(fresh) | 2.5 hr | 5.0 hr | 15.0 hr | |||
실시예 1 | 파라 위치 치환기가 메틸인 트리페닐포스핀계 화합물 | 탄소수 6인 시클로알킬을 포함하고 파라 위치 치환기가 없는 디페닐-시클로알킬포스핀 | 116 | 78 | 72 | 60 |
실시예 2 | 138 | 92 | 80 | 61 | ||
비교예 1 | - | 98 | 63 | 59 | 54 | |
비교예 2 | 파라 위치 치환기가 없는 트리페닐포스핀 | 100 | 56 | 48 | 28 |
Claims (20)
- 파라 위치에 치환기를 갖는 트리페닐 포스핀계 화합물, 디페닐 포스핀계 화합물 및 전이금속 촉매를 포함하는 히드로포밀화 반응용 촉매 조성물.
- 제1항에 있어서,상기 파라 위치에 치환기를 갖는 트리페닐 포스핀계 화합물은 파라 위치에 탄소수 1 내지 3의 알킬기, 및 탄소수 1 내지 5의 알콕시기 중에서 독립적으로 선택된 치환기를 갖는 화합물인 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물
- 제2항에 있어서,상기 파라 위치에 치환기를 갖는 트리페닐 포스핀계 화합물은 파라 위치에 탄소수 1 내지 3의 알킬기, 및 탄소수 1 내지 5의 알콕시기 중에서 선택된 1종의 치환기를 동시에 갖는 화합물인 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물
- 제1항에 있어서,상기 디페닐 포스핀계 화합물은 탄소수 1 내지 6의 n-알킬, 탄소수 2 내지 6의 분지 알킬, 탄소수 3 내지 6의 tert-알킬, 혹은 탄소수 5 내지 6의 시클로알킬기 중에서 선택된 1종의 작용기를 포함하는 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물
- 제4항에 있어서,상기 디페닐 포스핀계 화합물은 파라 위치에 탄소수 1 내지 3의 알킬기 및 탄소수 1 내지 5의 알콕시기 중에서 독립적으로 선택된 치환기를 갖는 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물
- 제1항에 있어서,상기 전이금속 촉매는 하기 화학식 1로 표시되는 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물.[화학식 1]M(L1)x(L2)y(L3)z(상기 화학식 1에서,M은 로듐(Rh), 이리듐(Ir) 또는 코발트(Co)이고,L1, L2 및 L3은 각각 독립적으로 수소, CO, 시클로옥타디엔(cyclooctadiene), 노보넨(norbornene), 염소(chlorine), 트리페닐포스핀(triphenylphosphine) 또는 아세틸아세토네이토(acetylacetonato) 이며, x, y 및 z는 각각 독립적으로 0 내지 5의 정수이고, x, y 및 z가 동시에 0은 아니다.)
- 제 1 항에 있어서,상기 전이금속 촉매는 코발트카보닐[Co2(CO)8], 아세틸아세토네이토디카보닐로듐[Rh(AcAc)(CO)2], 아세틸아세토네이토카보닐트리페닐포스핀로듐[Rh(AcAc)(CO)(TPP)], 하이드리도카보닐트리(트리페닐포스핀)로듐[HRh(CO)(TPP)3], 아세틸아세토네이토디카보닐이리듐[Ir(AcAc)(CO)2] 및 하이드리도카보닐트리(트리페닐포스핀)이리듐[HIr(CO)(TPP)3] 중에서 선택되는 1종 이상인 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물.
- 제 1 항에 있어서,상기 전이금속 촉매의 중심 금속 함량은 촉매 조성물의 무게 또는 부피를 기준으로 10 내지 1000 ppm인 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물.
- 제 1 항에 있어서,상기 파라 위치에 치환기를 갖는 트리페닐 포스핀계 화합물은 상기 전이금속 촉매의 중심금속 1몰에 대하여 0.5 내지 200몰 분율인 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물.
- 제 1 항에 있어서,상기 파라 위치에 치환기를 갖는 트리페닐 포스핀계 화합물은 촉매 조성물 총 중량 기준으로 0.5 내지 6.0 중량% 범위 내인 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물.
- 제 1 항에 있어서,상기 파라 위치에 치환기를 갖는 트리페닐 포스핀계 화합물은 트리-p-톨릴포스핀(TPTP)을 촉매 조성물 총 중량에 대하여 1.0 내지 5.0 중량% 범위 내로 포함하는 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물.
- 제 1 항에 있어서,상기 디페닐 포스핀계 화합물은 상기 전이금속 촉매의 중심금속 1몰에 대하여 1 내지 250 몰 분율인 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물.
- 제 1 항에 있어서,상기 디페닐 포스핀계 화합물은 촉매 조성물 총 중량에 대하여 0.5 내지 6.0 중량% 범위 내인 것을 특징으로 하는, 히드로포밀화 반응용 촉매 조성물.
- 제 1 항에 있어서,상기 디페닐 포스핀계 화합물은 시클로헥실디페닐포스핀을 촉매 조성물 총 중량에 대하여 1.0 내지 5.5 중량% 범위 내로 포함하는 것을 특징으로 하는 히드로포밀화 반응용 촉매 조성물.
- 제 1 항 내지 제 14항 중 어느 한 항에 따른 촉매 조성물의 존재 하에서 올레핀계 화합물 및 합성기체(CO/H2)를 반응시켜 노말/이소 선택도(N/I)가 6 이하인 알데히드를 수득하는 단계;를 포함하는 올레핀계 화합물의 히드로포밀화 방법.
- 제 15항에 있어서,상기 올레핀계 화합물은 에텐, 프로펜, 1-부텐, 1-펜텐, 1-헥센, 1-옥텐 및 스티렌 중에서 선택된 1종 이상인 것을 특징으로 하는 올레핀계 화합물의 히드로포밀화 방법.
- 제 15항에 있어서,상기 합성기체(CO:H2)의 혼합비율은 5:95 내지 70:30의 몰비인 것을 특징으로 하는 올레핀계 화합물의 히드로포밀화 방법.
- 제 15항에 있어서,상기 촉매 조성물은 프로판 알데히드, 부틸 알데히드, 펜틸 알데히드, 발러 알데히드, 아세톤, 메틸 에틸 케톤, 메틸 이소부틸 케톤, 아세토페논, 시클로헥사논, 에탄올, 펜탄올, 옥탄올, 텐산올, 벤젠, 톨루엔, 크실렌, 오르소디클로로벤젠, 테트라히드로푸란, 디메톡시에탄, 디옥산, 메틸렌 클로라이드 및 헵탄 중에서 선택된 1 이상의 용매에 녹인 다음 반응에 투입되는 것을 특징으로 하는 올레핀계 화합물의 히드로포밀화 방법.
- 제 15항에 있어서,상기 반응은 20 내지 180℃ 온도 및 1 내지 700 bar 압력 하에 수행되는 것을 특징으로 하는 올레핀계 화합물의 히드로포밀화 방법.
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EP14838850.7A EP2881173B1 (en) | 2013-09-30 | 2014-09-25 | Catalyst composition for hydroformylation reaction and method for hydroformylation of olefin using same |
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US14/426,074 US9616422B2 (en) | 2013-09-30 | 2014-09-25 | Catalyst composition for hydroformylation reaction and method of hydroformylating olefin using the same |
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