CN1303049C - Process for producing isononyl aldehyde from mixed octene and synthetic gas - Google Patents
Process for producing isononyl aldehyde from mixed octene and synthetic gas Download PDFInfo
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- CN1303049C CN1303049C CN 200410062259 CN200410062259A CN1303049C CN 1303049 C CN1303049 C CN 1303049C CN 200410062259 CN200410062259 CN 200410062259 CN 200410062259 A CN200410062259 A CN 200410062259A CN 1303049 C CN1303049 C CN 1303049C
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- isononyl aldehyde
- synthetic gas
- phosphine oxide
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Links
- 238000000034 method Methods 0.000 title claims abstract description 51
- WTPYRCJDOZVZON-UHFFFAOYSA-N 3,5,5-Trimethylhexanal Chemical compound O=CCC(C)CC(C)(C)C WTPYRCJDOZVZON-UHFFFAOYSA-N 0.000 title claims abstract description 42
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 28
- 239000010941 cobalt Substances 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- 239000002904 solvent Substances 0.000 claims description 41
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- -1 olefin hydrocarbon Chemical class 0.000 claims description 8
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 3
- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical compound CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 claims description 3
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical group CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007037 hydroformylation reaction Methods 0.000 description 10
- 229910052703 rhodium Inorganic materials 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- IUZCCOPYZPLYBX-UHFFFAOYSA-N cobalt;phosphane Chemical compound P.[Co] IUZCCOPYZPLYBX-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing isononyl aldehyde from mixed octene and a synthetic gas under the existence of cobalt/phosphine oxide catalysts, which belongs to the field of fine petrochemical industry. The method is characterized in that the compound of cobalt is used as the precursor of a catalyst, phosphine oxide is used as the ligand of the catalyst, and then the catalyst system of cobalt/ phosphine oxide is formed. The synthetic gas is the mixture of carbon monoxide (CO) and hydrogen (H2), and the ratio of CO to H2 in the synthetic gas is 1: 2. Isononyl aldehyde is prepared from the mixed octene and the synthetic gas under a moderate condition that the reaction temperature is between 120 DEG C and 200 DEG C and the pressure of the synthetic gas is from 4 to 20 MPas. The method for preparing isononyl aldehyde from the mixed octene and the synthetic gas, which is provided by the present invention, has the advantages of simple technology, low cost, moderate reaction condition and high yield of isononyl aldehyde, and is suitable for industrialization.
Description
Technical field
The present invention relates in the presence of cobalt/phosphine oxide catalyzer to make the method for isononyl aldehyde, belong to the Speciality Petrochemicals field from mixed octene and synthetic gas.
Background technology
Isononyl aldehyde is important organic chemicals, and isononyl aldehyde is after being hydroconverted into isononyl alcohol, and direct and phthalate makes diisononyl phthalate.Diisononyl phthalate is the softening agent of excellent property.
On industrial production, aldehyde can make through the hydroformylation process from alkene and synthetic gas.Since fritz rowland at the end of the thirties (O.Roelen) has been invented hydroformylation catalyst; hydroformylation catalyst and reaction process thereof a large amount of R and D have been carried out both at home and abroad; existing multiple catalyst system and technological process are applied to suitability for industrialized production, mainly contain the cobalt carbonyl catalyst and the rhodium phosphine catalyst of cobalt carbonyl catalyst, tertiary phosphine modification.As the modification cobalt method (cobalt phosphine catalyst, US Pat.3239566) of shell (Shell) company, connection carbon (UCC) company and Mitsubishi change into the rhodium-tertiary phosphine method (US Pat.3527809, USPat.4247486, US Pat.5105018) of company.On activity, rhodium catalytic system will be higher than cobalt catalyst.Though the rhodium catalyst of phosphine-modified is applied to have excellent catalytic performance in the hydroformylation of low-carbon (LC) (carbon atom quantity＜4) alkene; but in higher olefins is especially branched in the hydroformylation reaction of alkene; rhodium-triphenylphosphine catalyzer fails to demonstrate good performance (speed of response is slower, and transformation efficiency and yield are all lower).Cobalt catalyst also has application in the hydroformylation of high-carbon (carbon atom quantity＞5) alkene, but is confined to hold the hydroformylation of the higher olefins of two keys.
Mixed octene is an alkene in the high-carbon side chain, and the octene molecule has 1～3 branched chain methyl, and two key is in the end position, so the reaction activity of hydroformylation is lower.At alkene in the high-carbon side chain, the new catalyst system that United States Patent (USP) is invented a kind of rhodium/triphenylphosphine oxide No. 4528403, and be applied to the hydroformylation process of mixed octene.Though this method is under 130 ℃, 200 normal atmosphere, 4 hours reaction conditions, the yield of the higher aldehyde C-9 mixture that can obtain, stablize rhodium catalyst but in carrying out the isolating still-process of catalyzer and product, will add triphenylphosphine in addition, and must after peroxidation, just can recycle with the rhodium catalyst that contains triphenylphosphine after product separates.In addition, rhodium metal costs an arm and a leg.Therefore still to exist processing step many for this method, severe reaction conditions (200 normal atmosphere), problem such as unfavorable economically.
Summary of the invention
The purpose of this invention is to provide a kind of have industrial application value, be catalyst system, make the method for isononyl aldehyde from mixed octene and synthetic gas with cobalt/phosphine oxide.
The method that the present invention proposes from mixed octene and synthesis gas preparation isononyl aldehyde, it is characterized in that: described method adopts the precursor of the compound of cobalt as catalyzer, with the part of phosphine oxide as catalyzer, form cobalt/phosphine oxide catalyst system, under the condition of gentleness, from mixed octene and synthesis gas preparation isononyl aldehyde, its preparation process is followed successively by:
(1) in autoclave, adds a certain amount of Cobaltous diacetate, part (phosphine oxide), mixed octene and solvent;
(2) reactor is airtight is placed in the process furnace, with synthetic gas (CO/H
2=1/1) behind the air in the replacement reaction kettle, reactor is heated to temperature of reaction;
(3) under given temperature of reaction, charge into synthetic gas (CO/H to reactor
2=1/1) to reaction pressure;
(4) after reaction finishes, reactor is taken out from process furnace, be cooled to room temperature after, reacting kettle inner pressure is reduced to normal pressure, open kettle cover, take out the reaction solution that contains the isononyl aldehyde product, reaction solution is carried out underpressure distillation, obtain the product isononyl aldehyde.
In the above-mentioned method for preparing isononyl aldehyde, the compound of described cobalt is the inorganic salt of cobalt or the organic compound of cobalt, as Cobaltous diacetate, cobalt chloride, Xiao Suangu, cobalt octacarbonyl, tetracarbonylhydrocobalt.
In the above-mentioned method for preparing isononyl aldehyde, described phosphine oxide part is triphenylphosphine oxide, tributylphosphine oxide, trioctyl phosphine oxide.
In the above-mentioned method for preparing isononyl aldehyde, described mixed octene is to be obtained by the n-butene oligomerisation, mainly contains alkene in the side chains such as 2,4,4-Trimethyl-1-pentene, dimethyl hexene, methyl heptene.
In the above-mentioned method for preparing isononyl aldehyde, described solvent can be alkane solvents such as aromatic hydrocarbon solvents such as ether solvents such as ketones solvents such as esters solvents such as alcoholic solvents such as methyl alcohol, ethanol, ethyl acetate, acetone, ether, toluene, hexanaphthene.
In the above-mentioned method for preparing isononyl aldehyde, described synthetic gas is carbon monoxide (CO) and hydrogen (H
2) gas mixture, CO/H
2Ratio be CO/H
2=1/1.
In the above-mentioned method for preparing isononyl aldehyde, the ratio of described step (1) Cobaltous diacetate and mixed octene is Co atom/olefin hydrocarbon molecules=1/10000～25/1000; The ratio of described step (1) Cobaltous diacetate and phosphine oxide is Cobaltous diacetate/phosphine oxide (mol ratio)=1/1～1/10; The ratio of described step (1) mixed octene and solvent is mixed octene/solvent (volume ratio)=2/1～1/2.
In the above-mentioned method for preparing isononyl aldehyde, described step (2) temperature of reaction is generally 120～200 ℃, is preferably 140～180 ℃.
In the above-mentioned method for preparing isononyl aldehyde, the pressure of described step (3) synthetic gas is generally 4～20MPa, is preferably 6～15MPa.
In the above-mentioned method for preparing isononyl aldehyde, described step (3) is reflected in the autoclave carries out, and raw material olefin can continuously feeding, also can intermittently feed in raw material; When reacting with intermittent mode, the reaction times was generally 1～10 hour, was preferably 2～8 hours.
Method technology provided by the invention is simple, and cost is low, the reaction conditions gentleness, and product isononyl aldehyde yield height is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further.
Preparation process of the present invention is:
(1) in 70 milliliters of autoclaves, adds a certain amount of Cobaltous diacetate, part (phosphine oxide), mixed octene and solvent.
(2) reactor is airtight is placed in the process furnace, with synthetic gas (CO/H
2=1/1) behind the air in the replacement reaction kettle, reactor is heated to temperature of reaction (120～180 ℃).
(3) under given temperature of reaction (120～180 ℃), charge into synthetic gas (CO/H to reactor
2=1/1) to reaction pressure (6～15MPa).Under temperature of reaction and reaction pressure, under agitation reacted 1～10 hour.In reaction process, Lian Xu supplies the Give synthetic gas and keeps reaction pressure stable.
(4) after reaction finishes, reactor is taken out from process furnace, be cooled to room temperature after, reacting kettle inner pressure is reduced to normal pressure.Open kettle cover, take out the reaction solution that contains the isononyl aldehyde product.Reaction solution is carried out underpressure distillation, obtain the product isononyl aldehyde.
Cobalt is the activity of such catalysts component in the present invention, and phosphine oxide is the part of cobalt.By adding cobalt compound, phosphine oxide part and mixed octene and feed synthetic gas in reactor, hydroformylation catalyst can generate in reaction process and catalytic mixing octene and synthesis gas reaction generation isononyl aldehyde " original position ".
The compound of cobalt can be the inorganic salt of cobalt or the organic compound of cobalt, as Cobaltous diacetate, cobalt chloride, Xiao Suangu, cobalt octacarbonyl, tetracarbonylhydrocobalt etc.
The present invention uses phosphine oxide to do part, as triphenylphosphine oxide, tributylphosphine oxide, trioctyl phosphine oxide etc.
The mixed octene that the present invention uses is to be obtained by the n-butene oligomerisation, mainly contains alkene in the side chains such as 2,4,4-Trimethyl-1-pentene, dimethyl hexene, methyl heptene.
The solvent that the present invention uses can be alkane solvents such as aromatic hydrocarbon solvents such as ether solvents such as ketones solvents such as esters solvents such as alcoholic solvents such as methyl alcohol, ethanol, ethyl acetate, acetone, ether, toluene, hexanaphthene.
The synthetic gas that the present invention uses is carbon monoxide (CO) and hydrogen (H
2) gas mixture, CO/H
2Ratio be CO/H
2=1/1.
By the above-mentioned reaction that method of the present invention is carried out, the ratio of Cobaltous diacetate and mixed octene is Co atom/olefin hydrocarbon molecules=1/10000～25/1000.
By the above-mentioned reaction that method of the present invention is carried out, the ratio of Cobaltous diacetate and phosphine oxide is Cobaltous diacetate/phosphine oxide (mol ratio)=1/1～1/10.
By the above-mentioned reaction that method of the present invention is carried out, the ratio of mixed octene and solvent is mixed octene/solvent (volume ratio)=2/1～1/2.
Carry out above-mentioned reaction by method of the present invention, under heating, carry out.Temperature of reaction is generally 120～200 ℃.Be higher than ceiling temperature, catalyzer easily decomposes and loses activity, and is lower than lower limit temperature, and then speed of response is too slow.Be preferably 140～180 ℃
Carry out above-mentioned reaction by the inventive method, carry out adding to depress.The pressure of synthetic gas is generally 4～20MPa, is preferably 6～15MPa.In reaction process, supply with synthetic gas continuously and keep the synthetic gas pressure-stabilisation.
By the above-mentioned reaction that the inventive method is carried out, in autoclave, carry out, raw material olefin can continuously feeding, and also intermittently (disposable) is reinforced.When reacting with intermittent mode, the reaction times was generally 1～10 hour, was preferably 2～8 hours.
Be embodiments of the invention below.
Embodiment 1
At internal volume is in the stainless steel autoclave of 70ml, adds 0.2345g Cobaltous diacetate (Co (CH
3COO)
24H
2O, the sharp fine chemicals of Beijing benefit company product), 1.3130g triphenylphosphine oxide (Ph
3PO, the grand space in Beijing chemical company product), 15ml (10.5g) mixed octene and 5ml methyl alcohol (solvent).Behind the closed reactor, charge into synthetic gas (CO/H to reactor
2=1/1) to 3MPa, pressure release is to normal pressure again, and three times with the air in the replacement reaction kettle so repeatedly.Reacting by heating still to 160 ℃ under normal pressure fills synthetic gas (CO/H again in reactor
2=1/1) to 8MPa, 160 ℃, stir under reaction 2.5 hours, supply with synthetic gas in the reaction process continuously and keep pressure-stabilisation in 8MPa.Reaction stops pressure feed after finishing, and reactor is cooled to room temperature and the still internal pressure is reduced to normal pressure, reaction solution is taken out carry out underpressure distillation again, obtains the product isononyl aldehyde.Reaction result is listed in table 1.
Embodiment 2
Except that temperature of reaction is 140 ℃, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 3
Except that temperature of reaction is 180 ℃, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 4
Except that synthetic gas pressure was 6MPa, other was operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 5
Except that synthetic gas pressure was 10MPa, other was operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 6
Except that synthetic gas pressure was 12MPa, other was operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 7
Except that the reaction times is 1 hour, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 8
Except that the reaction times is 5 hours, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 9
Except that the reaction times is 8 hours, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 10
Except that the consumption of Cobaltous diacetate is the 0.1190g, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 11
Except that the consumption of Cobaltous diacetate is the 0.0236g, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 12
Except that the consumption of Cobaltous diacetate is the 0.5870g, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 13
Except that the triphenylphosphine oxide consumption was 0.5259g, other was operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 14
Except that the triphenylphosphine oxide consumption was 0.2630g, other was operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 15
Except that the triphenylphosphine oxide consumption was 2.6268g, other was operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 16
Except that using 5ml ethanol to replace the methyl alcohol among the embodiment 1 to do the solvent, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 17
Except that using 5ml acetone to replace the methyl alcohol among the embodiment 1 to do the solvent, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 18
Methyl alcohol in using 5ml substituted ether embodiment 1 is done the solvent, and other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 19
Except that using 5ml toluene to replace the methyl alcohol among the embodiment 1 to do the solvent, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 20
Except that using the 5ml hexanaphthene to replace the methyl alcohol among the embodiment 1 to do the solvent, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 21
Remove and use 0.4125g tributylphosphine oxide (Bu
3PO, Beijing Chemical Plant's product) replace the triphenylphosphine oxide among the embodiment 1 to do outside the part, other is operated with embodiment 1.Reaction result is listed in table 1.
Embodiment 22
Remove and use 0.7410g trioctyl phosphine oxide ((C
8H
17)
3PO, U.S. ACROS ORGANICS company product) replace the triphenylphosphine oxide among the embodiment 1 to do outside the part, other is operated with embodiment 1.Reaction result is listed in table 1.
Comparative example 1
Except that without the phosphine oxide part, other is operated with embodiment 1.Reaction result is listed in table 1.
Comparative example 2
Except that being 140 ℃ without phosphine oxide part and temperature of reaction, other is operated with embodiment 1.Reaction result is listed in table 1.
Comparative example 3
Except that being 180 ℃ without phosphine oxide part and temperature of reaction, other is operated with embodiment 1.Reaction result is listed in table 1.
Comparative example 4
Remove and use 0.4933g triphenylphosphine ((C
6H
5)
3P, Beijing Chemical Plant's product) replace the triphenylphosphine oxide among the embodiment 1 to do outside the part, other is operated with embodiment 1.Reaction result is listed in table 1.
Comparative example 5
Except that not using the methanol solvate, other is operated with embodiment 1.Reaction result is listed in table 1.
Table 1
| The reaction example | Cobaltous diacetate consumption (g) | Phosphine part consumption (g) | Mixed octene consumption (g) | Cobalt alkene compares Co/CH | The cobalt phosphine compares Co/P | Quantity of solvent (5ml) | Temperature (℃) | Pressure (MPa) | Time (h) | Aldehyde yield (%) |
| Embodiment 1 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Methyl alcohol | 160 | 8.0 | 2.5 | 51.0 |
| Embodiment 2 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Methyl alcohol | 140 | 8.0 | 2.5 | 46.7 |
| Embodiment 3 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Methyl alcohol | 180 | 8.0 | 2.5 | 45.1 |
| Embodiment 4 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Methyl alcohol | 160 | 6.0 | 2.5 | 46.6 |
| Embodiment 5 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Methyl alcohol | 160 | 10.0 | 2.5 | 45.5 |
| Embodiment 6 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Methyl alcohol | 160 | 12.0 | 2.5 | 38.1 |
| Embodiment 7 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Methyl alcohol | 160 | 8.0 | 1.0 | 42.2 |
| Implement | 0.2345g | (C 6H 5) 3PO | 10.5g | 1/100 | 1/5 | Methyl alcohol | 160 | 8.0 | 5.0 | 57.6 |
| Example 8 | 1.3130g | |||||||||
| Embodiment 9 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Methyl alcohol | 160 | 8.0 | 8.0 | 58.4 |
| Embodiment 10 | 0.1190g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/200 | 1/5 | Methyl alcohol | 160 | 8.0 | 2.5 | 46.4 |
| Embodiment 11 | 0.0236g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/1000 | 1/5 | Methyl alcohol | 160 | 8.0 | 2.5 | 44.8 |
| Embodiment 12 | 0.5870g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/40 | 1/5 | Methyl alcohol | 160 | 8.0 | 2.5 | 51.8 |
| Embodiment 13 | 0.2345g | (C 6H 5) 3PO 0.5259g | 10.5g | 1/100 | 1/2 | Methyl alcohol | 160 | 8.0 | 2.5 | 42.1 |
| Embodiment 14 | 0.2345g | (C 6H 5) 3PO 0.2630g | 10.5g | 1/100 | 1/1 | Methyl alcohol | 160 | 8.0 | 2.5 | 41.1 |
| Embodiment 15 | 0.2345g | (C 6H 5) 3PO 2.6268g | 10.5g | 1/100 | 1/10 | Methyl alcohol | 160 | 8.0 | 2.5 | 49.7 |
| Embodiment 16 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Ethanol | 160 | 8.0 | 2.5 | 43.0 |
| Embodiment 17 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Acetone | 160 | 8.0 | 2.5 | 40.2 |
| Embodiment 18 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Ether | 160 | 8.0 | 2.5 | 44.1 |
| Embodiment 19 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Toluene | 160 | 8.0 | 2.5 | 34.7 |
| Embodiment 20 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Hexanaphthene | 160 | 8.0 | 2.5 | 41.8 |
| Embodiment 21 | 0.2345g | (C 4H 9) 3PO 0.4125g | 10.5g | 1/100 | 1/2 | Methyl alcohol | 160 | 8.0 | 2.5 | 43.0 |
| Embodiment 22 | 0.2345g | (C 8H 17) 3PO 0.7410g | 10.5g | 1/100 | 1/2 | Methyl alcohol | 160 | 8.0 | 2.5 | 38.1 |
| Comparative example 1 | 0.2345g | Do not have | 10.5g | 1/100 | 1/5 | Methyl alcohol | 160 | 8.0 | 2.5 | 40.7 |
| Comparative example 2 | 0.2345g | Do not have | 10.5g | 1/100 | 1/5 | Methyl alcohol | 140 | 8.0 | 2.5 | 19.9 |
| Comparative example 3 | 0.2345g | Do not have | 10.5g | 1/100 | 1/5 | Methyl alcohol | 180 | 8.0 | 2.5 | 30.0 |
| Comparative example 4 | 0.2345g | (C 6H 5) 3P 0.4933g | 10.5g | 1/100 | 1/5 | Methyl alcohol | 160 | 8.0 | 2.5 | 1.2 |
| Comparative example 5 | 0.2345g | (C 6H 5) 3PO 1.3130g | 10.5g | 1/100 | 1/5 | Do not have | 160 | 8.0 | 2.5 | 0 |
Annotate: " cobalt alkene is than Co/CH " refers to the ratio of Co atom/olefin hydrocarbon molecules in the table 1; " the cobalt phosphine is than Co/P " refers to Cobaltous diacetate/phosphine oxide (mol ratio).
Claims (11)
1, from the method for mixed octene and synthesis gas preparation isononyl aldehyde, it is characterized in that: described method adopts the presoma of the compound of cobalt as catalyzer, with the part of phosphine oxide as catalyzer, form cobalt/phosphine oxide catalyst system, under the condition of gentleness, from mixed octene and synthesis gas preparation isononyl aldehyde, its preparation process is followed successively by:
(1) in autoclave, adds a certain amount of Cobaltous diacetate, phosphine oxide part, mixed octene and solvent;
(2) reactor is airtight is placed in the process furnace, uses CO/H
2Behind the air in=1/1 the synthetic gas replacement reaction kettle, reactor is heated to temperature of reaction, described temperature of reaction is 120～200 ℃;
(3) under given temperature of reaction, charge into CO/H to reactor
2=1/1 synthetic gas is to reaction pressure, and the pressure of described synthetic gas is 4～20MPa;
(4) after reaction finishes, reactor is taken out from process furnace, be cooled to room temperature after, reacting kettle inner pressure is reduced to normal pressure, open kettle cover, take out the reaction solution that contains the isononyl aldehyde product, reaction solution is carried out underpressure distillation, obtain the product isononyl aldehyde.
2, according to the described method for preparing isononyl aldehyde of claim 1, it is characterized in that: the compound of described cobalt is Cobaltous diacetate, cobalt chloride, Xiao Suangu, cobalt octacarbonyl, tetracarbonylhydrocobalt.
3, according to the described method for preparing isononyl aldehyde of claim 1, it is characterized in that: described phosphine oxide part is triphenylphosphine oxide, tributylphosphine oxide, trioctyl phosphine oxide.
4, according to the described method for preparing isononyl aldehyde of claim 1, it is characterized in that: described mixed octene is to be obtained by the n-butene oligomerisation, mainly contains alkene in 2,4,4-Trimethyl-1-pentene, dimethyl hexene, the methyl heptene side chain.
5, according to the described method for preparing isononyl aldehyde of claim 1, it is characterized in that: described solvent is alcoholic solvent, esters solvent, ketones solvent, ether solvent, aromatic hydrocarbon solvent, alkane solvents.
6, according to claim 1 or the 5 described methods that prepare isononyl aldehyde, it is characterized in that: described alcoholic solvent is that methyl alcohol, ethanol, described esters solvent are that ethyl acetate, described ketones solvent are that acetone, described ether solvent are that ether, described aromatic hydrocarbon solvent are that toluene, described alkane solvents are hexanaphthenes.
7, according to the described method for preparing isononyl aldehyde of claim 1, it is characterized in that: the ratio of described step (1) Cobaltous diacetate and mixed octene is Co atom/olefin hydrocarbon molecules=1/10000～25/1000; The mol ratio of described step (1) Cobaltous diacetate and phosphine oxide is Cobaltous diacetate/phosphine oxide=1/1～1/10; The volume ratio of described step (1) mixed octene and solvent is mixed octene/solvent=2/1～1/2.
8, according to the described method for preparing isononyl aldehyde of claim 1, it is characterized in that: described step (2) temperature of reaction is 140～180 ℃.
9, according to the described method for preparing isononyl aldehyde of claim 1, it is characterized in that: the pressure of described step (3) synthetic gas is 6～15MPa.
10, according to the described method for preparing isononyl aldehyde of claim 1, it is characterized in that: described step (3) is reflected in the autoclave carries out, the raw material olefin continuously feeding, or intermittently reinforced; When reacting with intermittent mode, the reaction times is 1～10 hour.
11, according to the described method for preparing isononyl aldehyde of claim 1, it is characterized in that: described step (3) is reflected in the autoclave carries out, the raw material olefin continuously feeding, or intermittently reinforced; When reacting with intermittent mode, the reaction times is 2～8 hours.
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| CN114656343B (en) * | 2020-12-23 | 2024-05-17 | 中国石油化工股份有限公司 | Method for preparing aldehyde and alcohol |
| CN115701418B (en) * | 2021-08-02 | 2024-05-17 | 中国石油化工股份有限公司 | Aldol composition and preparation method thereof, and method for continuously preparing aldehyde and alcohol |
| CN114100541A (en) * | 2021-11-23 | 2022-03-01 | 上海簇睿低碳能源技术有限公司 | Method for synthesizing isononanal by microchannel reaction device |
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