CN104058944A - Method for preparing aldehyde through alkene hydroformylation reaction - Google Patents
Method for preparing aldehyde through alkene hydroformylation reaction Download PDFInfo
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- CN104058944A CN104058944A CN201410169112.XA CN201410169112A CN104058944A CN 104058944 A CN104058944 A CN 104058944A CN 201410169112 A CN201410169112 A CN 201410169112A CN 104058944 A CN104058944 A CN 104058944A
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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
- C07C45/505—Asymmetric hydroformylation
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- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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- 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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
- B01J31/2471—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom
- B01J31/2476—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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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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Abstract
The invention relates to a method for preparing aldehyde through alkene hydroformylation reaction and mainly solves the problems in the prior art that the reaction activity of a rhodium catalyst based on a phosphine ligand is low, the iso-to-n ratio of a product is low and the stability of a rhodium catalyst based on a phosphite ester ligand is poor. The problems are solved by adopting the method for preparing aldehyde through the alkene hydroformylation reaction; and according to the method, alkene, carbon monoxide and hydrogen enter a hydroformylation reactor to come into contact with a catalyst at the reaction temperature of 70-120 DEG C under the reaction pressure of 1.0-4.0 Mpa to generate a product which comprises the aldehyde, wherein the catalyst comprises a rhodium-containing catalyst precursor, a double-teeth phosphine ligand and a double-teeth phosphite ester ligand. The method disclosed by the invention can be used in the alkene hydroformylation reaction.
Description
Technical field
The present invention relates to a kind of hydroformylation of olefin and prepare the method for aldehyde.
Background technology
Hydroformylation of olefin can, by basic chemical raw materials cheap and easy to get, as alkene etc. is converted into the multiple important Chemical products such as aldehydes easily and effectively, be the homogeneous catalysis process of industrial scale maximum up to now.Industrial, the hydroformylation reaction of alkene is mainly come by the various co-ordination complexs of Co, two kinds of metals of Rh that catalysis realizes, but rhodium base catalytic activity exceeds 10 than cobalt
2～10
3the individual order of magnitude; since last century the seventies; the rhodium catalyst that phosphorus-containing ligand is modified has just been dominated the hydroformylation reaction research of alkene with outstanding advantages such as its high reactivity, outstanding selectivity and gentle reaction conditionss, and progressively replaces cobalt and become the catalyzer of industrial hydroformylation technological process.Wherein, the composition and structure of phosphorus-containing ligand is the key factor of phosphorus/rhodium catalyst system reaction efficiency, and it has directly determined the important indicators such as activity, selectivity and the work-ing life of catalyzer.
The phosphorus-containing ligand of having developed is at present by the different of atom that are connected from P, can roughly be divided three classes, the phosphoramidite ligand that the phosphine part that phosphorus atom is connected with three carbon atoms, the phosphite ester ligand that phosphorus atom is connected with one or more Sauerstoffatoms and phosphorus atom are connected with one or more nitrogen-atoms etc.Rh (I)/triphenylphosphine is the synthetic widely used catalyst system of butyraldehyde of current hydroformylation of propene; but the problem existing be precious metal Rh (I) (200mg/L) and triphenylphosphine consumption large (mol ratio of triphenylphosphine and rhodium is generally 200:1), product butyraldehyde just/different ratio not high (<20).
Compare with current industrial widely used phosphine part, phosphite ester ligand can show better catalytic activity and selectivity in the hydroformylation of olefin of Rh (I) catalysis.Although the more previous technology of this catalyzer has obvious advantage and has started to be subject to the generally attention of academia and industry member; but due to the existence of the trace oxygen that is difficult in reaction system avoid or water; easily cause catalyst oxidation or hydrolysis and decompose inactivation; and and then reactive behavior and selectivity are declined rapidly, this becomes a difficult problem of olefin hydroformylation industrial technology exploitation of puzzlement bis-phosphite/rhodium catalysis.
CN200610147735.2 is by using phosphorous acid ester additive agent; a kind of hydroformylation of propene system of rhodium (I)/triaryl phosphine catalysis of improvement is provided; the just different selectivity that compares of butyraldehyde in the activity of raising Rh (I)/triaryl phosphine catalyzer and product; and the work-ing life of significant prolongation bisphosphite ligands; reduce the consumption of triaryl phosphine; but the activity of this catalyst system, far below the catalyst activity of Rh (I)/bis-phosphite, needs higher catalyst concn to maintain reactive behavior.
CN101332437A uses rhodium-triaryl phosphine complex compound and the catalyzer of at least one diphosphite ester catalyst as butene hydroformylation; for synthesizing of valeral; the activity that same this catalysis of discovery embodies is far below the catalyst activity of Rh (I)/bis-phosphite; although the reaction result of patent report is high; but in experimentation because temperature control is improper; reactive behavior fluctuation is large, causes active result higher.
Summary of the invention
Technical problem to be solved by this invention be in prior art taking phosphine part as the reactive behavior of basic rhodium catalyst low; just different from low in product; the problem of the poor stability taking phosphite ester ligand as rhodium catalyst, provides a kind of new hydroformylation of olefin to prepare the method for aldehyde.This catalyzer is for hydroformylation of olefin, have taking phosphine part as the reactive behavior of basic rhodium catalyst high, just different from high in product, the advantage of the good stability taking phosphite ester ligand as rhodium catalyst.
For addressing the above problem; the technical solution used in the present invention is as follows: a kind of hydroformylation of olefin is prepared the method for aldehyde; alkene, carbon monoxide and hydrogen enter hydroformylation reaction device; be that 70～120 DEG C, reaction pressure are to contact with catalyzer under 1.0～4.0Mpa in temperature of reaction; generation comprises the product of aldehyde, and described catalyzer comprises rhodium-containing catalyst precursor, bidentate phosphine ligands and bidentate phosphite ester ligand.
In technique scheme, preferably, the general structure of described bidentate phosphine ligands is:
in at least one, the integer that wherein n is 1～5, Ar is the aromatic group of 6～22 carbon atoms, and described Ar group is identical or not identical, P is phosphorus, R
1, R
2for alkyl group or cyclic group; The general structure of described bidentate phosphite ester ligand is:
Wherein: X is C
6～C
28replacement or unsubstituted organic divalence bridging arylidene, Y
1, Y
2, Z
1or Z
2for hydrogen, the tertiary butyl or methoxyl group.
In technique scheme, preferably, described bidentate phosphine ligands has the structural formula of following L1～L10:
In technique scheme, preferably, described bidentate phosphite ester ligand has the structural formula of following L11～L16:
In technique scheme, preferably, described rhodium-containing catalyst precursor is rhodium metal, rhodium dicarbonyl acetylacetonate (I), acetylacetonatodicarrhodium rhodium (I), Rh (OAc)
3, Rh
2o
3, Rh
4(CO)
12, Rh
6(CO)
16in at least one.
In technique scheme, preferably, described bidentate phosphine ligands, the mol ratio of bidentate phosphite ester ligand and rhodium is 0.1～10:0.1～10:1, more preferably, is 1～8:1～8:1.
In technique scheme, preferably, the concentration range of described rhodium is 10～500mg/L, more preferably, is 20～200mg/L.
In technique scheme, preferably, described alkene is ethene, propylene, 1-butylene, 2-butylene; Oxygen level in alkene is less than 10ppm.
In technique scheme, preferably, the volume ratio of described alkene, carbon monoxide, hydrogen is 1:0.5～2:0.5～2.
On-the-spot formation in the catalyzer of olefin hydroformylation of the present invention has both been included in reaction system, also can comprise previously preparedly, if needed, can also use the mixture of this class catalyzer.Catalyzer of the present invention can generate in hydroformylation of olefin device, rhodium catalyst precursor, and bidentate phosphite ester ligand, bidentate phosphine ligands joins in reactor, stirs for some time generation in the atmosphere of CO, hydrogen and alkene under certain temperature.
Catalyzer also can be prepared in advance; by suitable rhodium catalyst precursor is mixed with described bidentate phosphine ligands, bidentate phosphite ester ligand in optional suitable solvent; pass into the gas mixture of CO and hydrogen; can prepare for the preparation of hydroformylation of olefin of the present invention the method for aldehyde, its consumption only need provide required a certain amount of rhodium concentration in propene hydroformylation reaction medium.Described solvent is all generally solvent used in hydroformylation reaction, everyly can not bring the suitable solvent of too much disadvantageous effect all can use to reaction.Representative appropriate solvent comprises those for example disclosed solvents in US4668651.If needed, can use the mixture of one or more different solvents.First-selected the is solvent of dissolved olefin, rhodium catalyst precursor, bidentate phosphine ligands, bidentate phosphite ester ligand preferably, preferred solvent is toluene, aldehyde compound.
Catalyzer of the present invention can be intermittently or is applied in a continuous manner the hydrogen firstization reaction of alkene, comprises the hydroformylation reaction of ethene, propylene, 1-butylene, 2-butylene.In the industrial production of continuous mode, in can described rhodium catalyst precursor, bidentate phosphine ligands, bidentate phosphite ester ligand and reaction solvent etc. being added to reactor in an operation steps, start continuous production method, be heated to after desired reaction temperature, in above-mentioned reaction mixture, import alkene, carbon monoxide and hydrogen with continuous or mode intermittently.In the effluent of reactor, contain the rhodium catalyst of aldehyde compound, hydroformylation, free bidentate phosphine ligands and bidentate phosphite ester ligand, by product as aldehydes condensation product, unreacted alkene, carbon monoxide, hydrogen and reaction solvent etc.Effluent exports to vaporizer/separator from reactor, by being decompressed to for example 0.1MPa, gaseous reactant carbon monoxide and hydrogen are separated from mixture, and required aldehyde product can be separated in one or more separating step from liquid reaction mixture and collection in the usual way.Then the rhodium catalyst of remaining hydroformylation, free bidentate phosphine ligands and bidentate phosphite ester ligand, by product are turned back in hydroformylation of olefin device as circulations such as aldehydes condensation products, and be reused in method of the present invention.Adopt any this area professional person isolation technique in common knowledge can be by such as propionic aldehyde of described aldehyde compound, butyraldehyde, valeral product is separated from reaction mixture, such as method of evaporation etc.
Method of the present invention needs regularly or continuously to monitor the concentration of above-described bidentate phosphine ligands and described bidentate phosphite ester ligand to the reaction system moved, if find that described concentration is lower than described value, may cause due to reasons such as oxidation or degradeds the loss of described compound, now bidentate phosphine ligands and described bidentate phosphite ester ligand added in the reaction mixture of use.
The method that hydroformylation of olefin in this patent is prepared aldehyde can significantly improve the just different selectivity that compares of existing Rh (I)/bidentate phosphite ester or Rh (I)/bidentate phosphine ligands; and can maintain higher catalytic activity; extend the work-ing life of bisphosphite ligands and catalyzer thereof; be conducive to improve the economy of technique; after reducing, the separating energy consumption of system and the consumption of rhodium catalyst, obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[comparative example 1]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with 1 of 0.04mmol, two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 2.2 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 2.8mol/Lh.
[comparative example 2]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) and the L15 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 23.2 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.5mol/Lh.
[comparative example 3]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the triphenylphosphine of 0.04mmol and the L15 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 24.2 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 1.5mol/Lh.
[comparative example 4]
In continuous propene hydroformylation reaction device, the gas in hydroformylation reaction device, vaporizer and gas stripping column taking nitrogen replacement volume as 10L.In the container of a 15L, [Rh (acac) (CO) for handle
2], Isosorbide-5-Nitrae-bis-(diphenylphosphine) butane L4 bidentate phosphine ligands is dissolved in 10L butyraldehyde-n, the concentration that makes Rh (I) is 100mg/L, Rh/1, the mol ratio of two (diphenylphosphine) butane of 4-is 1:4.By interim pipeline, catalyst solution is driven into hydroformylation reaction device through recycle pump, keeping the useful volume of hydroformylation reaction device is 5L; And make successively 1# vaporizer, 2# vaporizer and gas stripping column bottom respectively maintain the solution of 0.7L, after completing, remove interim pipeline.Propylene is sent into hydroformylation reaction device with the speed of 6.66g/min, and carbon monoxide and hydrogen enter gas stripping column with the speed of 4.44g/min and 0.32g/min respectively, and then enters hydroformylation reaction device.Reactor temperature is 100 ± 1 DEG C, and the total gaseous tension of hydrogen, carbon monoxide and propylene is 1.9 ± 0.1MPa.Propylene, carbon monoxide and hydrogen react the propane that generates butyraldehyde-n and isobutyric aldehyde and trace under the catalysis of Rh/P1; the mixing solutions that contains reaction product and catalyzer flow into 1# vaporizer from hydroformylation reaction device; in mixing solutions, part propylene, propane and a small amount of butyraldehyde are evaporated; remaining solution enters 2# vaporizer and evaporates part butyraldehyde and micro-propylene, propane again, and the remaining solution that contains catalyzer is circulated back in hydroformylation reaction device.The butyraldehyde evaporating is condensed into the liquid that is dissolved with propylene and propane, then by being pumped into gas stripping column.Adopt carbon monoxide and hydrogen gas mixture that the propylene and the propane flammable gas that are dissolved in are wherein put forward, and together enter hydroformylation reaction device, at the bottom of gas stripping column tower, receive butyraldehyde-n and the isobutyric aldehyde of mixing with the speed of 9.7 ± 0.1g/min.The liquid level of hydroformylation reaction device, 1# vaporizer, 2# vaporizer and gas stripping column bottom keeps constant.Measure the mol ratio of butyraldehyde-n and isobutyric aldehyde by gas-chromatography (GC).
Reaction is carried out 780 hours altogether continuously, and the mol ratio of butyraldehyde-n/isobutyric aldehyde of receiving at the bottom of gas stripping column tower kept constant after 120 hours, and remained 2.8 always.
[comparative example 5]
According to condition and step described in comparative example 4; just in reaction system, adopt bisphosphite ligands L15 to replace 1; two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-; the mol ratio of Rh:L15 is 1:4; the system concentration of Rh maintains 100mg/L, and hydroformylation reaction temperature is 100 ± 1 DEG C.
Propylene is sent into hydroformylation reaction still with the speed of 9.99g/min; carbon monoxide and hydrogen enter gas stripping column with the speed of 6.66g/min and 0.48g/min respectively; then enter reactor, at the bottom of gas stripping column tower, receive butyraldehyde-n and the isobutyric aldehyde of mixing with the speed of 14.7 ± 0.1g/min.In hydroformylation reaction device, the concentration of L15 is monitored by liquid chromatography, along with carrying out continuously of reaction, finds that L15 constantly reduces.For keeping the constant concentration of L15, need in reaction response device, to add 1.2g L12 in every 24 hours.The method of adding is: 1.2g L5 is dissolved in to butyraldehyde-n and the isobutyric aldehyde mixing solutions at the bottom of 0.5L gas stripping column tower, received, by interim pipeline, solution is driven into hydroformylation reaction device through recycle pump, remove interim pipeline after completing.Reaction is carried out 610 hours altogether continuously, and the mol ratio of butyraldehyde-n/isobutyric aldehyde of receiving at the bottom of gas stripping column tower kept constant after 120 hours, and remained 24 always.
[comparative example 6]
According to condition and step described in comparative example 4; just in reaction system, adopt bisphosphite ligands L15 and triphenylphosphine ligand (TPP); the mol ratio of Rh:L15:TPP is 1:4:4, and the system concentration of Rh maintains 100mg/L, and hydroformylation reaction temperature is 100 ± 1 DEG C.
Propylene is sent into hydroformylation reaction still with the speed of 5.00g/min; carbon monoxide and hydrogen enter gas stripping column with the speed of 3.33g/min and 0.24g/min respectively; then enter reactor, at the bottom of gas stripping column tower, receive butyraldehyde-n and the isobutyric aldehyde of mixing with the speed of 7.3 ± 0.1g/min.Reaction is carried out 720 hours altogether continuously, and the mol ratio of butyraldehyde-n/isobutyric aldehyde of receiving at the bottom of gas stripping column tower kept constant after 120 hours, and remained 25 always.
[comparative example 7]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L), the L15 bidentate phosphite ester ligand of the triphenylphosphine of 0.04mmol and 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the 1-butylene of 20g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 38 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 1.8mol/Lh.
[comparative example 8]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L), the L13 bidentate phosphite ester ligand of the triphenylphosphine of 0.04mmol and 0.04mmol and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the 2-butylene of 20g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 20 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 1.5mol/Lh.
[comparative example 9]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.015mmol, 3.75mg, 100mg/L), the L15 bidentate phosphite ester ligand of the triphenylphosphine of 0.06mmol and 0.06mmol and 15mL dry toluene, connect gas tube, after argon replaces gas reactor three times, (1-butylene accounts for weight ratio 87.9% to the mixed butene of importing 15g, cis-2-butene accounts for 4.7%, Trans-2-butene 6.2%, butane 1.2%), be heated to 80 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 3h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 65 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.1mol/Lh.
[embodiment 1]
Under air atmosphere, be equipped with and in manometric stainless steel autoclave, add rhodium dicarbonyl acetylacetonate (I) [Rh (acac) (CO) to 200mL
2] (0.01mmol, 2.5mg, concentration is 103mg/L) and 0.04mmol 1, the L15 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-and 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 75.0 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.5mol/Lh.
[embodiment 2]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L5 bidentate phosphine ligands of 0.04mmol and the L13 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 58.0 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 4.5mol/Lh.
[embodiment 3]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L3 bidentate phosphine ligands of 0.04mmol and the L15 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 50.0 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.8mol/Lh.
[embodiment 4]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L4 bidentate phosphine ligands of 0.04mmol and the L13 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 48.0 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 4.2mol/Lh.
[embodiment 5]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L6 bidentate phosphine ligands of 0.04mmol and the L12 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 95.0 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 2.8mol/Lh.
[embodiment 6]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L7 bidentate phosphine ligands of 0.04mmol and the L11 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 97.0 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 2.7mol/Lh.
[embodiment 7]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L1 bidentate phosphine ligands of 0.04mmol and the L14 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 47.0 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.2mol/Lh.
[embodiment 8]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L2 bidentate phosphine ligands of 0.04mmol and the L16 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the propylene of 15g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 65.0 than (mol ratio of butyraldehyde-n/isobutyric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 2.9mol/Lh.
[embodiment 9]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with 1 of 0.04mmol, the L15 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-and 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the 1-butylene of 20g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 108.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 4.0mol/Lh.
[embodiment 10]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with 1 of 0.04mmol, the L13 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-and 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the trans-2-butene of 20g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) gas mixture to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the gas mixture of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 55.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 2.5mol/Lh.
[embodiment 11]
According to condition and step described in comparative example 4; just in reaction system, adopt bisphosphite ligands L15 and 1; two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-; the mol ratio of Rh:L15:L4 is 1:4:4; the system concentration of Rh maintains 100mg/L, and hydroformylation reaction temperature is 100 ± 1 DEG C.
Propylene is sent into hydroformylation reaction still with 9.99g/min; carbon monoxide and hydrogen enter gas stripping column with the speed of 6.66g/min and 0.48g/min respectively; then enter reactor, at the bottom of gas stripping column tower, receive butyraldehyde-n and the isobutyric aldehyde of mixing with the speed of 14.8 ± 0.1g/min.Reaction is carried out 720 hours altogether continuously, and L15 is stable during this time, does not add L15, and the mol ratio of butyraldehyde-n/isobutyric aldehyde of receiving at the bottom of gas stripping column tower kept constant after 120 hours, and remained 76 always.
[embodiment 12]
According to condition and step described in comparative example 4; just in reaction system, adopt bisphosphite ligands L13 and 1; two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-; the mol ratio of Rh:L13:L4 is 1:4:4; the system concentration of Rh maintains 100mg/L, and hydroformylation reaction temperature is 100 ± 1 DEG C.
1-butylene is sent into hydroformylation reaction still with 16.33g/min; carbon monoxide and hydrogen enter gas stripping column with the speed of 8.16g/min and 0.59g/min respectively; then enter reactor, at the bottom of gas stripping column tower, receive valeraldehyde and the isovaleric aldehyde of mixing with the speed of 17.8 ± 0.1g/min.Reaction is carried out 720 hours altogether continuously, and L12 is stable during this time, does not add L12, and the mol ratio of valeraldehyde/isovaleric aldehyde of receiving at the bottom of gas stripping column tower kept constant after 120 hours, and remained 81 always.
[embodiment 13]
According to condition and step described in comparative example 4; just in reaction system, adopt bisphosphite ligands L13 and 1; two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-; the mol ratio of Rh:L13:L4 is 1:4:4; the system concentration of Rh maintains 100mg/L, and hydroformylation reaction temperature is 100 ± 1 DEG C.
Trans 2-butylene is sent into hydroformylation reaction still with 5.44g/min; carbon monoxide and hydrogen enter gas stripping column with the speed of 2.72g/min and 0.20g/min respectively; then enter reactor, at the bottom of gas stripping column tower, receive valeraldehyde and the isovaleric aldehyde of mixing with the speed of 5.6 ± 0.1g/min.Reaction is carried out 720 hours altogether continuously, and L10 is stable during this time, does not add L10, and the mol ratio of valeraldehyde/isovaleric aldehyde of receiving at the bottom of gas stripping column tower kept constant after 120 hours, and remained 54 always.
[embodiment 14]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L4 bidentate phosphine ligands of 0.04mmol and the L12 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the cis-2-butene of 20g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 68.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 2.2mol/Lh.
[embodiment 15]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L5 bidentate phosphine ligands of 0.04mmol and the L15 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the trans-2-butene of 20g, be heated to 110 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 45.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 2.8mol/Lh.
[embodiment 16]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L7 bidentate phosphine ligands of 0.04mmol and the L12 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, (1-butylene accounts for weight ratio 50% to the mixed butene of importing 20g, cis-2-butene accounts for 25%, Trans-2-butene 25%), be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 88.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.0mol/Lh.
[embodiment 17]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L4 bidentate phosphine ligands of 0.08mmol and the L12 bidentate phosphite ester ligand of 0.08mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, (1-butylene accounts for weight ratio 50% to the mixed butene of importing 20g, cis-2-butene accounts for 25%, Trans-2-butene 25%), be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 90.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.2mol/Lh.
[embodiment 18]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L8 bidentate phosphine ligands of 0.02mmol and the L11 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, import the 1-butylene of 20g, be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 105.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.1mol/Lh.
[embodiment 19]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L9 bidentate phosphine ligands of 0.04mmol and the L14 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, (1-butylene accounts for weight ratio 50% to the mixed butene of importing 20g, cis-2-butene accounts for 25%, Trans-2-butene 25%), be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 68.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.2mol/Lh.
[embodiment 20]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with the L10 bidentate phosphine ligands of 0.04mmol and the L15 bidentate phosphite ester ligand of 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, (1-butylene accounts for weight ratio 40% to the mixed butene of importing 20g, cis-2-butene accounts for 20%, Trans-2-butene 40%), be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) mixed air to stagnation pressure is 2MPa, and maintain reaction pressure at 2MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 92.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.2mol/Lh.
[embodiment 21]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with 1 of 0.04mmol, the L15 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-and 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, (1-butylene accounts for weight ratio 30% to the mixed butene of importing 20g, cis-2-butene accounts for 35%, Trans-2-butene 35%), be heated to 80 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) mixed air to stagnation pressure is 2.5MPa, and maintain reaction pressure at 2.5MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 75.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 2.6mol/Lh.
[embodiment 22]
Under air atmosphere, be equipped with in manometric stainless steel autoclave to 200mL and add that [Rh (acac) (CO)
2] (0.01mmol, 2.5mg, 103mg/L) with 1 of 0.04mmol, the L15 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-and 0.04mmol, and 70mL dry toluene, connect gas tube, after nitrogen replacement gas reactor three times, (1-butylene accounts for weight ratio 60% to the mixed butene of importing 20g, cis-2-butene accounts for 20%, Trans-2-butene 20%), be heated to 100 DEG C of the interior temperature of reactor, with the mechanical stirrer stirring of electromagnetic drive, passing into hydrogen and carbon monoxide (volume ratio 1:1) mixed air to stagnation pressure is 1.5MPa, and maintain reaction pressure at 1.5MPa, the carbon monoxide and the hydrogen that consume with mass flowmeter metering reaction, after reaction 1h, stop passing into the mixed air of hydrogen and carbon monoxide.Reactor is cooling with frozen water, and in stink cupboard, emptying residual gas, weighs, and drives still, and it is 68.0 than (mol ratio of valeraldehyde/isovaleric aldehyde) that sampling is measured just different by gas-chromatography (GC), and the space-time yield of reaction is 3.2mol/Lh.
[embodiment 23]
According to condition and step described in embodiment 1, just with acetylacetonatodicarrhodium rhodium (I) replacement, [Rh (acac) (CO)
2], add 1 of 0.01mmol acetylacetonatodicarrhodium rhodium (I) (concentration is 103mg/L) and 0.08mmol, the L15 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-and 0.08mmol, the mol ratio of butyraldehyde-n/isobutyric aldehyde is 74.0, and the space-time yield of reaction is 3.3mol/Lh.
[embodiment 24]
According to condition and step described in embodiment 1, just use Rh
4(CO)
12[Rh (acac) (CO) in replacement
2], add 0.01mmol Rh
4(CO)
12isosorbide-5-Nitrae-bis-(diphenylphosphine) butane L4 bidentate phosphine ligands of (concentration is 103mg/L) and 0.4mmol and the L15 bidentate phosphite ester ligand of 0.4mmol, the mol ratio of butyraldehyde-n/isobutyric aldehyde is 72.0, the space-time yield of reaction is 3.2mol/Lh.
[embodiment 25]
According to condition and step described in embodiment 1, just with acetylacetonatodicarrhodium rhodium (I) replacement, [Rh (acac) (CO)
2], add 1 of 0.1mmol acetylacetonatodicarrhodium rhodium (I) (concentration is 1030mg/L) and 0.01mmol, the L15 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-and 0.01mmol, the mol ratio of butyraldehyde-n/isobutyric aldehyde is 38, and the space-time yield of reaction is 4.8mol/Lh.
[embodiment 26]
According to condition and step described in embodiment 1, just with acetylacetonatodicarrhodium rhodium (I) and Rh (OAc)
3mixture replace [Rh (acac) (CO)
2], add 0.05mmol acetylacetonatodicarrhodium rhodium (I) and 0.05mmolRh (OAc)
31 of (concentration is 1030mg/L) and 0.01mmol, the L15 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligandses of 4-and 0.01mmol, the mol ratio of butyraldehyde-n/isobutyric aldehyde is 72.0, and the space-time yield of reaction is 4.6mol/Lh.
[embodiment 27]
According to condition and step described in embodiment 1, just bidentate phosphine ligands is the mixture of L4 and L8, and [Rh (acac) (CO) to add 0.05mmol rhodium dicarbonyl acetylacetonate (I)
2] the L15 bidentate phosphite ester ligand of (concentration is 515mg/L), the L4 bidentate phosphine ligands of 0.1mmol and the L8 bidentate phosphine ligands of 0.1mmol, 0.1mmol, the mol ratio of butyraldehyde-n/isobutyric aldehyde is 82, the space-time yield of reaction is 4.9mol/Lh.
[embodiment 28]
According to condition and step described in embodiment 11; when propylene is sent into hydroformylation reaction still with 9.99g/min; carbon monoxide and hydrogen are respectively with 13.32g/min and 0.48g/min; enter gas stripping column; and then enter hydroformylation reaction device; oxygen level <1ppm in propylene, in product, the mol ratio of butyraldehyde-n/isobutyric aldehyde is 45, the space-time yield of reaction is 3.2mol/Lh.
[embodiment 29]
According to condition and step described in comparative example 4; propylene is sent into hydroformylation reaction device with the speed of 9.99g/min; carbon monoxide and hydrogen enter gas stripping column with the speed of 6.66g/min and 0.96g/min respectively; and then enter hydroformylation reaction device; oxygen level <1ppm in propylene; in product, the mol ratio of butyraldehyde-n/isobutyric aldehyde is 115, and the space-time yield of reaction is 3.6mol/Lh.
[embodiment 30]
According to condition and step described in comparative example 4; propylene is sent into hydroformylation reaction device with the speed of 20.0g/min; carbon monoxide and hydrogen enter gas stripping column with the speed of 6.66g/min and 0.48g/min respectively; and then enter hydroformylation reaction device; oxygen level <1ppm in propylene; in product, the mol ratio of butyraldehyde-n/isobutyric aldehyde is 78, and the space-time yield of reaction is 3.7mol/Lh.
[embodiment 31]
According to condition and step described in comparative example 4; propylene is sent into hydroformylation reaction device with the speed of 9.99g/min; carbon monoxide and hydrogen enter gas stripping column with the speed of 13.32g/min and 0.96g/min respectively; and then enter hydroformylation reaction device; oxygen level <1ppm in propylene; in product, the mol ratio of butyraldehyde-n/isobutyric aldehyde is 82, and the space-time yield of reaction is 3.6mol/Lh.
Claims (11)
1. a hydroformylation of olefin is prepared the method for aldehyde; alkene, carbon monoxide and hydrogen enter hydroformylation reaction device; be that 70～120 DEG C, reaction pressure are to contact with catalyzer under 1.0～4.0Mpa in temperature of reaction; generation comprises the product of aldehyde, and described catalyzer comprises rhodium-containing catalyst precursor, bidentate phosphine ligands and bidentate phosphite ester ligand.
2. hydroformylation of olefin is prepared the method for aldehyde according to claim 1, it is characterized in that the general structure of described bidentate phosphine ligands is:
in at least one, the integer that wherein n is 1～5, Ar is the aromatic group of 6～22 carbon atoms, and described Ar group is identical or not identical, P is phosphorus, R
1, R
2for alkyl group or cyclic group; The general structure of described bidentate phosphite ester ligand is:
Wherein: X is C
6～C
28replacement or unsubstituted organic divalence bridging arylidene, Y
1, Y
2, Z
1or Z
2for hydrogen, the tertiary butyl or methoxyl group.
3. hydroformylation of olefin is prepared the method for aldehyde according to claim 1, it is characterized in that described bidentate phosphine ligands has the structural formula of following L1～L10:
4. hydroformylation of olefin is prepared the method for aldehyde according to claim 1, it is characterized in that described bidentate phosphite ester ligand has the structural formula of following L11～L16:;
5. hydroformylation of olefin is prepared the method for aldehyde according to claim 1, it is characterized in that described rhodium-containing catalyst precursor is rhodium metal, rhodium dicarbonyl acetylacetonate (I), acetylacetonatodicarrhodium rhodium (I), Rh (OAc)
3, Rh
2o
3, Rh
4(CO)
12, Rh
6(CO)
16in at least one.
6. hydroformylation of olefin is prepared the method for aldehyde according to claim 1, it is characterized in that described bidentate phosphine ligands, and the mol ratio of bidentate phosphite ester ligand and rhodium is 0.1～10:0.1～10:1.
7. hydroformylation of olefin is prepared the method for aldehyde according to claim 5, it is characterized in that described bidentate phosphine ligands, and the mol ratio of bidentate phosphite ester ligand and rhodium is 1～8:1～8:1.
8. hydroformylation of olefin is prepared the method for aldehyde according to claim 1, and the concentration range that it is characterized in that described rhodium is 10～500mg/L.
9. hydroformylation of olefin is prepared the method for aldehyde according to claim 7, and the concentration range that it is characterized in that described rhodium is 20～200mg/L.
10. hydroformylation of olefin is prepared the method for aldehyde according to claim 1, it is characterized in that described alkene is at least one in ethene, propylene, 1-butylene, 2-butylene; Oxygen level in alkene is less than 10ppm.
11. according to claim 1 hydroformylation of olefin prepare the method for aldehyde, it is characterized in that the volume ratio of described alkene, carbon monoxide, hydrogen is 1:0.5～2:0.5～2.
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