CN100412046C - Method for the continuous production of aldehydes - Google Patents
Method for the continuous production of aldehydes Download PDFInfo
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- CN100412046C CN100412046C CNB2004800312101A CN200480031210A CN100412046C CN 100412046 C CN100412046 C CN 100412046C CN B2004800312101 A CNB2004800312101 A CN B2004800312101A CN 200480031210 A CN200480031210 A CN 200480031210A CN 100412046 C CN100412046 C CN 100412046C
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- hydrogen
- aryl
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- 238000000034 method Methods 0.000 title claims abstract description 67
- 150000001299 aldehydes Chemical class 0.000 title abstract description 29
- 238000010924 continuous production Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 216
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 140
- 239000000203 mixture Substances 0.000 claims abstract description 89
- 239000010948 rhodium Substances 0.000 claims abstract description 71
- 150000001336 alkenes Chemical class 0.000 claims abstract description 66
- 239000007789 gas Substances 0.000 claims abstract description 49
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 47
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003446 ligand Substances 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 24
- 239000004711 α-olefin Substances 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 55
- 239000001257 hydrogen Substances 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 40
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- 125000001072 heteroaryl group Chemical group 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- 238000006317 isomerization reaction Methods 0.000 claims description 14
- 230000009466 transformation Effects 0.000 claims description 14
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000004437 phosphorous atom Chemical group 0.000 claims description 11
- 125000002252 acyl group Chemical group 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 10
- 125000001118 alkylidene group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 8
- 230000022244 formylation Effects 0.000 claims description 8
- 238000006170 formylation reaction Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 150000008300 phosphoramidites Chemical class 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000002912 waste gas Substances 0.000 claims description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 229910021386 carbon form Inorganic materials 0.000 claims description 4
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 4
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 4
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 4
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 19
- 238000004519 manufacturing process Methods 0.000 abstract description 4
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- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 133
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 15
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 8
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Images
Abstract
The invention relates to a method for the continuous production of aldehydes comprising between 5 and 21 carbon atoms, by the isomerising hydroformylation in a homogenous phase of olefin compositions comprising between 4 and 20 carbon atoms and containing alpha-olefins and olefins with internal double bonds, by means of a synthesis gas, in the presence of a homogeneous rhodium catalyst that is complexed with an organophosphorus ligand containing oxygen atoms and/or nitrogen atoms and a free ligand. Said production is carried out at high temperature and high pressure in a multi-stage reaction system consisting of at least two reaction zones. According to said method, the olefin composition is first reacted in a first reaction zone or a group of several first reaction zones at a total pressure of between 10 and 40 bar, using a synthesis gas with a CO/H2 molar ratio of between 4:1 and 1:2 until a 40 to 95 % conversion of the alpha-olefins is obtained. The hydroformylation product from the first reaction zone or group of several first reaction zones is then reacted in a subsequent reaction zone or group of several reaction zones at a total pressure of between 5 and 30 bar, using a synthesis gas with a CO/H2 molar ratio of between 1:4 and 1:1000. The total pressure in the subsequent reaction zone or zones is respectively 1 to (G1-Gf) bar lower than that of the preceding reaction zone, whereby G1 represents the total pressure in the respective preceding reaction zone and Gf represents the total pressure in the respective reaction zone that succeeds said first reaction zone or zones, with the proviso that the difference between G1 and Gf is greater than 1 bar and the partial CO pressure in the subsequent reaction zone or zones is respectively lower than that of the preceding reaction zone.
Description
The present invention relates to a kind of by in comprising the reaction of high order system of at least 2 reaction zones, under the temperature and pressure that raises, with homogeneous rhodium catalyst and free ligand that the organophosphor ligand that contains aerobic and/or nitrogen cooperates in the presence of, by synthetic gas, containing alpha-olefin and having in the homogeneous phase of compositions of olefines of alkene of internal double bonds and carrying out the isomery hydroformylation and the continuous method for preparing aldehyde with 5-21 carbon atom with 4-20 carbon atom.
The hydroformylation of alkene also is known as carbonylic preparation method, and in nineteen ninety, world's annual production of the product that is obtained by the hydroformylation of alkene is estimated as about 700 ten thousand tonnes.Although at the homogeneous catalyst of the initial stage of carbonylic preparation method industrial application great majority use based on cobalt; be used for industry from the seventies in 20th century more and more based on the homogeneous hydrogenation formylation catalyzer of rhodium; because compare with the situation of cobalt catalyst; they can carry out more economical operation under lower temperature and particularly lower pressure, and realize high n/i selectivity in the hydroformylation with the alkene of terminal double link (alpha-olefin).For this reason, respectively by ethene and propylene industrial preparation C
3And C
4In the method for aldehyde, use the low pressure hydroformylation of the rhodium complex of triphenylphosphine modification in fact to substitute the high-pressure hydrogenation formylation that uses cobalt carbonyl catalyst fully usually.Yet, even use the high-pressure hydrogenation formylation of cobalt carbonyl catalyst still to have outstanding industrial significance, particularly in the hydroformylation of long-chain olefin with internal double bonds in today.This class alkene can obtain in a large number, for example (comes leisure to remove or select hydrogenated diene hydrocarbon such as 1,3-butadiene and the C that removes based on iso-butylene as Residual oil II
4The C of the steam cracker behind the mixture
4Cut, it contains 1-butylene and 2-butylene) or from dimerizing olefins technology and three polymerizing technologies or from olefin metathesis equipment and fischer-tropsch equipment, and its products of oxo synthesis is as the raw material of other Industrial products of preparation such as softening agent or tensio-active agent alcohols.Because their mode of production, these alkene are relevant alpha-olefin usually and have the isomer mixture form of the corresponding construction isomer of internal double bonds, and with the raw material of this form as carbonylic preparation method.For the present invention, to should be its pair key (different with alpha-olefin) mutually be not the alkene of portion at the end of olefin hydrocarbon molecules but within it to " interior " alkene.
Although require higher temperature and the pressure of Geng Gao when using cobalt catalyst, for described than the long-chain olefin mixture hydroformylation and have that the reason of preferred use cobalt catalyst may be the different catalytic properties of catalyst metal cobalt and rhodium for the hydroformylation of various olefin(e) compounds of internal double bonds.In the hydroformylation of alpha-olefin, depend on that the CO molecule adds to position on two keys according to equation (1),
Can form linear aldehyde A (being known as n-aldehyde) or branching aldehyde B (also being known as iso-aldehyde).Usually, in hydro formylation products, need a high proportion of n-aldehyde, by the expression of n/i ratio, the i.e. mol ratio of n-aldehyde and iso-aldehyde in the reaction product.Although rhodium in the hydroformylation of short chain alpha-olefin-triphenylphosphine catalyst system produces high n selectivity, this catalyst body ties up to above-mentioned alkene mixture or has in the hydroformylation of alkene of internal double bonds has shortcoming.At first; rhodium-triphenylphosphine catalyst system only demonstrates very low hydroformylation activity for internal double bonds; the result is that this " interior " alkene does not react; perhaps have only and when using uneconomic long reaction times, just can be reacted to acceptable economically degree; second; this catalyst system also turns to internal double bonds with terminal double link significance degree ground isomery under the condition of hydrogenation formyl reaction; this fact makes described shortcoming become more serious; therefore when rhodium-triphenylphosphine catalyst system being used for the hydroformylation of industrial olefin isomer mixture of this class or inner alkene, only obtain not satisfied olefin conversion and not satisfied internal olefin utilizes degree.
For can alpha-olefin and internal olefin than the hydroformylation of the hydroformylation of long-chain olefin mixture and internal olefin in utilize the intrinsic advantage of the low pressure hydroformylation of using rhodium catalyst; various effort have been carried out for a long time; with exploitation rhodium catalytic " isomery " hydroformylation process; that is, the n-aldehyde ratio in the reaction product that is obtained by the hydroformylation of the mixture of internal olefin or alpha-olefin and internal olefin is higher than the method for the desired ratio of double-bond isomerization that ratio and rhodium-triphenylphosphine catalyst system by terminal double link in the starting olefin and internal double bonds produce.For realizing that research that this target is carried out concentrates at present by suitable part and/or process engineering measure rhodium catalyst character is improved.Yet, also need to improve successfully to be used for the isomerizing hydrogenation formylation of industrial practice economically significantly.
As the rhodium catalytic system that is fit to the isomery hydroformylation; for example can mention the rhodium of description among the US-A 3,527 809 and title complex, the US-A 4 of organophosphite part; the rhodium of describing among the rhodium of describing in 668,651 and the title complex of the organic phosphite ester ligand of chelating and WO 01/58589 and the WO 02/83695 and the title complex of organic phosphorous acid amides (phosphoramidite) part and organophosphite or organic phosphinate part.
Because the n/i selectivity in the olefin hydroformylation is subjected to the influence of many parameters, this class catalyzer is used for the isomery hydroformylation must the combined process engineering measure and relate to the measure of reaction conditions, to reach gratifying economically result.By people such as d ' Oro, LA CHIMICA ETL ' INDUSTRIA
62, the parameter that 572 (1980) the n/i selectivity of confirming in the hydroformylation that uses rhodium-triphenylphosphine catalyst system have a remarkably influenced is the CO dividing potential drop in the hydroformylation reactor.Although find to reduce the CO dividing potential drop in this case the n selectivity is improved, reduce the CO dividing potential drop used hydrogenation of olefin speed is increased greatly, and therefore a large amount of paraffinic hydrocarbons that forms.
At US-A 4,885, illustrated in 401, when using rhodium-chelating phosphite catalysts system, in hydroformylation reactor, reduce the CO dividing potential drop speed of reaction is increased and CO/H
2Than being preferably 1: 1 to 1: 10.
US-A 4,885, and 401 embodiment 12 relates to the 2-butylene hydroformylation, although it is pointed out when reducing CO/H
2Than the time speed of reaction raise, but the n/i of the aldehyde that forms is than reducing.
US-A 4; 885; 401 summaries have been mentioned the possibility of the mixture of alpha-olefin and internal olefin being carried out hydroformylation in a series of different reactors; and the words that need; in each reactor, set optimum reaction condition separately, but the concrete instruction of the guidance of relevant operating method and optimization measure is not provided.
US-A 4,599, and 206 comprise about with different CO/H
2Use rhodium-organic single phosphite ester ligand catalyzer to come the embodiment of hydroformylation 1-butylene/2-butylene mixture in two reactors in succession of mol ratio operation.Yet, the reaction conditions that the change of these embodiment is bigger can not from each result, discover any relevant how to carry out the isomery hydroformylation with the high n/i that realizes product aldehyde than and the inducible instruction of high butene conversion.
EP-A 188 426 has described a kind of olefin hydroformylation method, wherein will infeed in second reactor assembly with the first reactor assembly decoupling, to finish hydroformylation from the alkene waste gas that contains of first reactor assembly.The reaction conditions that adopts in second reactor assembly of decoupling can be different from those that adopt in first reactor assembly, wherein particularly can adopt different catalyst systems.Allegedly using these isolating reactor assemblies is for more effective and utilize the alkene infeed more fully.EP-A 188 426 does not relate to the hydroformylation under isomerization conditions, and the embodiment in the document is corresponding is confined to use in the hydroformylation of propylene rhodium-triphenylphosphine catalyst system.In addition, not instruction about when using internal olefin, can how to improve the n/i ratio as raw material.
(US-A 5 for WO 97/20801; 744; 650) hydroformylation speed in using the hydroformylation of rhodium-organic polyphosphite catalyzer and the relation between the carbon monoxide pressure of tension have specifically been illustrated; prevent or reduce the inactivation of rhodium in hydroformylation process-organic polyphosphite catalyzer; prevent and/or reduce carbon monoxide pressure of tension in hydroformylation process; the hydrogen dividing potential drop; the reaction stagnation pressure; the cyclic fluctuation of hydroformylation speed and/or temperature; and the carbon monoxide pressure of tension when having advised carrying out hydroformylation as the solution of these problems should make: hydroformylation speed raises and hydroformylation speed reduction when carbon monoxide pressure of tension raises when carbon monoxide pressure of tension reduces, and has also advised satisfying one or more in the following condition:
A) use temperature makes the temperature head between reaction product liquid temperature and the coolant inlet temperature be lower than 25 ℃,
B) the carbon monoxide transformation efficiency is less than 90%,
C) transformation efficiency of hydrogen is higher than 65%,
D) transformation efficiency of alefinically unsaturated compounds is higher than 50%.
For carbon monoxide pressure of tension n/i is optionally influenced, WO 97/20801 only observes to operate in having the scope of following feature and will cause high isomery ratio, in described scope; about carbon monoxide pressure of tension; hydroformylation has negative reaction progression, that is, and and under higher carbon monoxide pressure of tension.
Continue partial monopoly US-A 5 874 639 with US-A 5,744,650 theme expands to and uses the catalyzer that contains organic many phosphorus-metal complexess.
US-A 5 728 893 relates to and uses the staged reactor that is used for hydroformylation with particular configuration, and its purpose is to realize such reaction conditions, every pound/inch of the variation of n selectivity of product in this condition
2CO dividing potential drop be no more than 0.2% reaction conditions of (approximating every crust CO dividing potential drop is 2.9%).Unique embodiment in this patent relates to use rhodium-triphenylphosphine catalyst system and uses from beginning with regard to excessive hydrogen with traditional hydroformylation ethene and propylene.According to the data from embodiment, rising CO dividing potential drop reduces hydroformylation speed.Do not provide the information of the butyraldehyde n/i ratio that produces in the propene hydroformylation of relevant embodiment 2.
According to JP-A 143 572 (2000), hydroformylation should carry out under such condition, and in fact the carbon monoxide pressure of tension under this condition in the reactor does not influence speed of reaction.
People such as Reinius (J.Mol.Cat.A:Chemical (Journal of Molecular Catalysis magazine, chemistry is collected)
158, 499 (2000)) and studied the hydroformylation of use rhodium-methyl (thienyl) diphenylphosphine title complex as the methyl methacrylate of catalyzer, and the conclusion that draws is the H that increases in the synthetic gas
2Dividing potential drop can not change the n/i selectivity of hydrogenation formyl reaction, and these are different as the situation of catalyzer with use triphenylphosphine-rhodium complex.
People such as Yang, Catalysis Today (contemporary catalysis)
74, H has been described in 111 (2002)
2With of the influence of CO dividing potential drop to the catalytic activity of three sulfonic acid rhodium complexs of triphenylphosphine in propene hydroformylation.Under the situation of this catalyst system, find that hydroformylation speed is along with H
2The rising of dividing potential drop and raise and reduce along with the rising of CO dividing potential drop.
EP-A 423 769 relates to the combination of using two different reactors that connect into reactor cascade in the multistage hydroformylation of alkene.According to the embodiment of this patent application, use syngas mixture in the presence of traditional rhodium-triphenylphosphine catalyst system, to carry out the hydroformylation of propylene, wherein the ratio of hydrogen is higher than the ratio of carbon monoxide in first and second conversion zones.EP-B 423 769 does not provide the information about the isomery hydroformylation.
EP-A 1 008 580 relates to the reactor cascade that comprises at least 2 reactors that uses the pressure stage that is divided into hydroformylation, the wherein H in first (m-1) pressure stage equally
2And the relation character between the corresponding dividing potential drop in CO dividing potential drop and downstream second (m) pressure stage closes at least one following inequality,
p
CO(m-1)＜p
CO(m)
p
H2(m-1)＜p
H2(m)
p
CO(m-1)+p
H2(m-1)＜p
CO(m)+p
H2(m)
P wherein
COAnd p
H2Be CO and the H in each pressure stage or the conversion zone
2Dividing potential drop.This operating method allegedly improves hydroformylation speed and improves the n/i selectivity.According to the embodiment among the EP-A 1 008 580, this is by setting 50kg/cm in first conversion zone
2Pressure and in second conversion zone, set 170kg/cm
2Pressure and use CO/H
2Mol ratio is the hydroformylation that 1: 1 synthetic gas is realized octene mixture.Hydroformylation catalysts is the carbonyl hydrogenation Rh that does not cooperate that produces on the spot in reactor as used herein.Although in the explanation of EP-A 1 008 580, point out; this method also is applicable to uses the cobalt cooperate with various phosphorous acid esters or phosphine part and the hydroformylation of rhodium catalyst; but the n/i of the aldehyde that produces during for the catalyzer that uses with the different in kind that does not cooperate rhodium is than the aspect, lacks the information of the influence of the specific embodiment of this method and relevant this method.
For the 1-octene hydroformylation that is undertaken by the rhodium catalyst that cooperates with single sulfonated phosphine, US-A 4,716, and the CO that 250 (embodiment 9) also disclose the CO dividing potential drop in being higher than first conversion zone divides to depress and carries out second conversion zone.For the CO/H in each conversion zone
2All there is excessive hydrogen in ratio in first and second conversion zones.Yet, when in first and second stages, using the CO dividing potential drop that approximately equates and in first and second conversion zones, all using high H
2During/CO mol ratio, the n/i that in the scheme that is different from embodiment 9, has realized at formation aldehyde C-9 than aspect optimum (n/i than=12.3).
WO 02/68371 relates to the isomery hydroformylation process in reactor cascade, wherein uses traditional rhodium-triphenylphosphine catalyzer and use rhodium catalyst by chelating two phosphine-modifieds with xanthene skeleton in first conversion zone in second conversion zone.When using CO/H
2During than the synthetic gas that is 1: 1, according to embodiment, second conversion zone in the document also carries out under the pressure that is higher than pressure in the fs, and this presses corresponding to the branch in the fs increases CO and H
2Dividing potential drop.Yet it is complicated using different catalyst systems, and this significantly increases the cost of this method.
The objective of the invention is to find the hydroformylation process of the mixture of a kind of internal olefin and alpha-olefin; although speed of reaction and n-aldehyde selectivity are pressed with opposite dependency to the CO branch as shown in the prior art, this method can prepare aldehyde by this alkene mixture economically with high n selectivity and high space-time yield.For this reason, the isomerization of the two keys of the internal double bonds terminad in the internal olefin that exists in the alkene mixture should be promoted and simultaneously alpha-olefin should be inhibited to the double-bond isomerization of internal olefin because the latter owing to internal olefin fundamentally than the reactive low total space-time yield that reduces this method of alpha-olefin.
We find that this purpose is achieved by the method that following a kind of continuous preparation has the aldehyde of 5-21 carbon atom; this method is by in comprising the reaction of high order system of at least 2 reaction zones; under the temperature and pressure that raises; with homogeneous rhodium catalyst and free ligand that the organophosphor ligand that contains aerobic and/or nitrogen cooperates in the presence of; by synthetic gas; carry out the isomery hydroformylation containing alpha-olefin and have in the homogeneous phase of compositions of olefines of alkene of internal double bonds with 4-20 carbon atom, wherein compositions of olefines at first in one or more first reaction zone groups under the stagnation pressure that 10-40 clings to CO/H
2Mol ratio be 4: 1 to 1: 2 synthesis gas reaction reaching the alpha-olefin transformation efficiency of 40-95%, and in one or more downstream reactions district group, under the stagnation pressure of 5-30 crust, make hydroformylation mixture and CO/H from described one or more first reaction zone groups
2Mol ratio is 1: 4 to 1: 1000 a synthesis gas reaction, stagnation pressure in wherein said one or more downstream reactions district clings to (T1-Tf) than the stagnation pressure in the reaction zone of front low 1 in each case at least, wherein T1 is the stagnation pressure in the reaction zone of front, and Tf is the stagnation pressure in the reaction zone in described one or more first reaction zone downstreams, condition be the difference of T1-Tf greater than 1 crust, and the CO dividing potential drop in described one or more downstream reactions district is lower than the CO dividing potential drop in the reaction zone of front in each case.
The inventive method is based on many results of study of relevant isomery hydroformylation.Therefore especially find:
A) in two reactors that are connected in series and in the Residual oil II continuous hydrogenation formylation that carries out under the identical situation of other condition in these two reactors, by at constant CO/H
2Reduce synthetic gas pressure under the mol ratio or by at the low CO/H of constant total drops
2Mol ratio and the CO dividing potential drop that realizes reduces causes the aldehyde productive rate in the hydro formylation products mixture to raise and the rising of n-valeral ratio;
B) in the hydroformylation in batches of 2-butylene, reduce the CO dividing potential drop aldehyde productive rate and n-valeral ratio are raise; And
C) in the hydroformylation in batches of 1-butylene, reduction CO dividing potential drop makes does not wish that the 1-butylene that takes place increases to the isomerization of 2-butylene, and the result makes the n/i ratio of the space-time yield that forms aldehyde and the valeral that forms so reduces.
Set processing parameter owing to use measure of the present invention and according to the present invention; the result; the most of conversion of the alpha-olefin that exists in compositions of olefines in one or more first reaction zone groups according to the present invention (is the transformation efficiency of 40-95%; the transformation efficiency of preferred 70-95%) be corresponding n-aldehyde; and the isomerization of the terminal double link of significance degree to internal double bonds do not take place; therefore; the olefin hydroformylation that in one or more downstream reactions district group, under the best hydroformylation condition of internal double bonds terminad double-bond isomerization, has internal double bonds in the mode simplified greatly in compositions of olefines; and do not cause the remarkable isomerization of unborn alpha-olefin in the compositions of olefines, thereby finally obtain having the aldehyde product of high n/i ratio by compositions of olefines with high space-time yield.The degree of not wishing the inside isomerisation of olefin of alpha-olefin that takes place in one or more first reaction zone groups under the hydroformylation condition should remain on alap level, and is no more than 80%, preferably is lower than 50%, especially preferably is lower than 30%.
Therefore the very popular transformation efficiency that is generally 50-99% of the alpha-olefin that exists in the compositions of olefines can be realized at single first reaction zone or in a plurality of first reaction zones.For the present invention, the statement of " one or more first reaction zone group " is used in reference to this single first reaction zone or a plurality of first reaction zone.This is equally applicable to single reaction zone or a plurality of reaction zone in one or more first reaction zone group downstreams.In this " one or more downstream reactions district group ", main purpose is to treat the isomery hydroformylation of the internal olefin in the compositions of olefines of hydroformylation.
Therefore, the inventive method is at pressure and CO/H
2Be different from than the aspect and by cascade (being classification) reaction zone the alkene mixture that contains alpha-olefin and internal olefin carried out progressively the prior art of hydroformylation (for example US-A 4 716 250; EP-A 1 008 580), because CO dividing potential drop in one or more downstream reactions district group and stagnation pressure all are lower than CO dividing potential drop and stagnation pressure in one or more first reaction zone groups, wherein said one or more first reaction zone groups are usually than the higher CO/H of described one or more downstream reactions district's group
2Mol ratio and significantly higher stagnation pressure operation down.
In the methods of the invention, at stagnation pressure, CO/H
2The hydroformylation that has the compositions of olefines of terminal double link and internal double bonds in the reaction of high order system of mol ratio and these processing parameter aspect cascades of CO dividing potential drop; this reaction of high order system also comprises a plurality of reaction zones that are connected in series; for example 2-10, preferred 2-4, preferred especially 2 reaction zones, wherein each reaction zone main CO/H in different stagnation pressures, CO dividing potential drop and the words that need, reaction zone
2These aspects of mol ratio differ from one another.Therefore, each reaction zone may reside in each reactor that is connected in series in reactor cascade, perhaps single reaction zone can also comprise the reactor that a plurality of serial or parallel connections connect and satisfy standard, promptly substantially the same stagnation pressure and the CO dividing potential drop of each reaction zone of the present invention.On the contrary; can single hydroformylation reactor segmentation be formed a plurality of reaction chambers that can set reaction conditions therein separately by suitable internals; thereby make one or more these reaction chambers form reaction zone; and, make one or more downstream reactions chamber of reactor form second reaction zone or a plurality of downstream reactions district according to the processing parameter setting in each chamber.Therefore, if the downstream chamber of reactor than the stagnation pressure of low at least 1 crust in the chamber of front and lower CO dividing potential drop and needs, at lower CO/H
2Operate under the mol ratio, then downstream chamber forms new reaction zone with respect to the chamber of front.Similarly implication is applicable to the reaction conditions in each reactor that is connected in series.
Reactor for the inventive method; can use the reactor of all suitable hydrogenation formyl reactions in principle; stirred reactor for example; for example as US-A 4 778 929 described bubble-column reactors; for example as EP-A 1 114 017 described recirculation reactors; for example as EP-A 423 769 described tubular reactors; in this case; each reactor in the serial reaction device can have different mixed characteristics, and for example as EP-A 1 231 198 or US-A 5 728 893 described locellus reactors.
If reaction zone comprises a plurality of reactors, then can in this reaction zone, use identical or different type of reactor, and can between each reaction zone, use identical or different type of reactor equally.Preferably in each reaction zone, use identical type of reactor, for example recirculation reactor or stirred vessel.
In one or more first reaction zone groups, the inventive method is carried out under the stagnation pressure of 10-40 crust, preferred 10-30 crust, preferred especially 10-25 crust usually, and in one or more reaction zone groups in one or more first reaction zone group downstreams, the inventive method is carried out under the stagnation pressure of 5-30 crust, preferred 5-20 crust, preferred especially 9-20 crust usually.Stagnation pressure in each reaction zone is the following stated dividing potential drop sum: reactant gases carbon monoxide (CO) and hydrogen (H
2) dividing potential drop; Treat the dividing potential drop of the aldehyde that produces in various alkene in the compositions of olefines of hydroformylation and the hydroformylation process; And the dividing potential drop of formed by product in any impurity that trace exists in other component that exists in the reaction mixture such as stable hydrocarbon, rare gas element such as nitrogen, auxiliary agent such as solvent or free ligand, any stablizer such as tertiary amine or azine (add in the reaction mixture and make it to avoid taking place DeR to stablize used part) and the raw material such as carbonic acid gas and the hydroformylation process.Usually, by introducing reactant gases CO and H
2And/or by under each temperature of reaction, reaction mixture decompression being set stagnation pressure in each reaction zone to remove volatile constituent.
According to the present invention, set the stagnation pressure in each reaction zone so that low at least 1 crust of the reaction zone of the overall pressure ratio front in the downstream reaction district clings to (T1-Tf), wherein T1 is the reaction zone R of front
mIn stagnation pressure, at reaction zone R
mCan also there be one or more reaction zones such as R in the front
l, R
kDeng, and Tf is the reaction zone R in downstream, previous reaction district
nIn stagnation pressure, at reaction zone R
nCan also there be other reaction zone (R the back
o, R
pDeng), the stagnation pressure in this other reaction zone is followed and reaction zone R
mAnd R
nBetween identical relation.At this, be suitable for the condition of the difference of T1-Tf greater than 1 crust.Usually, downstream reaction district R
nIn the low 1-25 crust of reaction zone of overall pressure ratio front, preferably low 1-15 crust, especially preferably low 1-10 crust.The reference point of the stagnation pressure in each reaction zone is the stagnation pressure in the reactor in each case; If perhaps a plurality of reactors form reaction zone together, then be the stagnation pressure in last reactor of reaction zone of front; If perhaps a plurality of reactors form reaction zone together, then be the stagnation pressure in first reactor in downstream reaction district.Corresponding implication is applicable to that wherein one or more each reaction chambers form the locellus reactor of reaction zone.Under the situation of tubular reactor, stagnation pressure and the stagnation pressure in the ingress that enters downstream tubular reactor or other reactor in the exit of first tubular reactor form the reference point of determining each reaction zone.If reactor that two or more are connected in series or the total pressure head between the reaction chamber are lower than 1 crust, then these reactors or reaction chamber form reaction zone together.
Temperature of reaction in each reaction zone is generally 50-200 ℃, and preferred 50-150 ℃, preferred 70-130 ℃ especially.
In the methods of the invention, the CO/H of the synthetic gas in one or more first reaction zone groups
2Mol ratio is generally 4: 1 to 1: 2, and preferred 4: 1 to 2: 3, preferred especially 3: 2 to 2: 3 (CO: H
2), and the CO/H in one or more reaction zone groups in described one or more first reaction zone group downstreams
2Mol ratio is generally 1: 4 to 1: 1000, and preferred 1: 4 to 1: 100, preferred especially 1: 9 to 1: 100 (CO/H
2), wherein the CO dividing potential drop in the downstream reaction district is set at the value of the main CO dividing potential drop in the previous reaction zone that is lower than this reaction zone next-door neighbour.Usually, the CO dividing potential drop in the reaction zone in one or more first reaction zone downstreams is set at divide and forces down the 1-20 crust, preferably low 1-10 crust, the value of especially preferably low 2-7 crust than the main CO in next-door neighbour's the previous reaction zone.
For the reference point of determining the CO dividing potential drop in each reaction zone, be suitable for above-mentioned similarly for the explanation of determining the stagnation pressure in each reaction zone.
Best stagnation pressure in each reaction zone of the inventive method, best CO/H
2Mol ratio and best CO dividing potential drop depend on the type and the composition of the compositions of olefines for the treatment of hydroformylation; for example treat the chain length of the alkene of hydroformylation; the ratio of terminal double link and internal double bonds, the position of internal double bonds and the degree of branching that may also have alkene.Therefore; according to the present invention; advantageously in conventional preliminary experiment or mathematics processing simulation to the hydroformylation catalysts of specific compositions of olefines and use with these processing parameter optimizations, to find in the optimal conditions economically that in the aldehyde product, realize very high n/i ratio under the very high space-time yield.
Similarly implication is applicable to the reaction zone quantity in the inventive method.Therefore, for the present invention, what come in handy is to be routed to many 10 cascade reaction districts to realize n/i ratio and space-time yield best combination economically.Because the high fund cost of gained and/or equipment cost and running cost that may be higher, this may offset by improving the economic advantages that n/i ratio and space-time yield obtain.For this reason; the inventive method advantageously is being generally 2-8; preferred 2-4; carry out in preferred especially 2 reaction zones that are connected in series, wherein the best economically quantity of reaction zone is advantageously determined as the type of the compositions of olefines for the treatment of hydroformylation and the function of composition and used hydroformylation catalysts by normal experiment or mathematics processing simulation in various situations.
Can before entering the subsequent reaction district, will isolate the aldehyde of formation, and unreacted alkene be sent into the next one treat in the reaction zone of hydroformylation from the hydro formylation products mixture decompression of a reaction zone.According to the present invention preferably, before entering next reaction zone, do not carry out described aftertreatment from the hydro formylation products mixture of a reaction zone, and with its directly decompression enter in the next reaction zone.The stagnation pressure that the favourable embodiment of this of the inventive method is lower than by the stagnation pressure in the downstream reaction district in the reaction zone of front is achieved.
By regulating the waste gas materials flow from each reaction zone, the stagnation pressure in each reaction zone is set at the function of amount of the synthetic gas of fresh introducing usually, and this waste gas materials flow mainly is made up of unreacted synthetic gas, rare gas element and hydrocarbon usually.If there is not default CO/H with needs
2Mol ratio is with CO/H
2Mixture is introduced in each reaction zone, in order to set required CO/H in each reaction zone
2Mol ratio maybe advantageously, is used to have about 1: 1 traditional C O/H
2The synthetic gas of mol ratio and CO or H by being metered into other amount
2In each reaction zone, set required CO/H
2Mol ratio.At this moment, there is favourable economically chance, that is, mainly contains CO or H from other method by using
2Waste gas to regulate CO/H
2Mol ratio and the inventive method and other method are integrated.Therefore, containing CO waste gas and can be used to increase CO/H for example from methyl-formiate production
2Mol ratio is perhaps from being the H that contains of corresponding saturated alcohol with aldehyde or olefine aldehydr prepared therefrom (for example 2-ethyl hexenal or 2-propyl group heptenal) hydrogenation
2Waste gas can be used as H
2The source is to reduce the CO/H in each reaction zone
2Mol ratio.The CO dividing potential drop can also be by reducing CO/H in the downstream reaction district
2Pressure and reducing.
The inventive method is fit to preferably containing the aliphatic C that can be linearity or branching with internal double bonds and terminal double link
4-C
20The compositions of olefines of alkene carries out hydroformylation.The example of this class compositions of olefines is as the industrial 1-butylene that obtains/2-butylene mixture, for example Residual oil II.Term Residual oil II is meant the C from steam cracker
4Obtain C after isolating divinyl and acetylene in the cut and isolating iso-butylene subsequently
4Olefin fraction.It has following composition usually:
0.5-5 the Trimethylmethane of weight %,
The normal butane of 5-20 weight %,
The trans-2-butene of 20-40 weight %,
The cis-2-butene of 10-20 weight %,
The 1-butylene of 25-55 weight %,
0.5-5 the iso-butylene of weight %,
And the gas of trace such as 1,3-butadiene, propadiene, propylene, cyclopropane, methyl cyclopropane and vinylacetylene.
Other suitable compositions of olefines for example is the amylene mixture that for example forms in acid catalyzed ethene and propylene codimerization, by acid or the catalytic propylene dimerization of nickel (Dimersol method) or the hexene mixture that obtains by for example EP-A 1 069 101 and EP-A 1 134 271 described metathesis process, the heptene mixture that obtains by acid or the catalytic propylene of nickel and butylene codimerization for example, octene mixture for example as obtaining by butene dimerization as described in the US-A 5,849 972, the nonene mixture that obtains by acid catalyzed propylene trimerization for example, the decene mixture that obtains by acid catalyzed amylene dimerization for example, the undecylene mixture that obtains by amylene and hexene codimerization for example, for example gather by US-A 5 849 927 described acid catalyzed propylene four, butene mixture trimerization and/or the dodecylene mixture that for example obtains by the dimerization of WO 00/53546 described hexene mixture, for example by the US-A 5 849 972 described butene mixture four poly-cetene mixtures that obtain, the vaccenic acid mixture that obtains of union alkene mixture dimerization for example, and/or by decene mixture dimerization or the amylene mixture four poly-eicosylene mixtures that obtain.Much less, can also use the composition that contains alkene in the methods of the invention with different carbonatomss.This composition with alkene of different carbonatomss for example can be by obtaining as EP-A 1 134 271 and EP-A 1 069 101 described butylene metathesiss or by SHOP method or Fischer-Tropsch process.Can be for example at Weissermel, Arpe:Industrielle Organische Chemie, the 82-99 page or leaf, the 5th edition, Wiley-VCH finds preparation to contain the summary of various appropriate method of the composition of higher alkene among the Weinheim 1998.The aldehyde that can be obtained by these compositions of olefines according to the present invention for example is suitable as the raw material of preparation softening agent and surfactant alcohols; these softening agent and surfactant alcohols can be for example by aldehyde hydrogenation is directly obtained or is obtained by acetalation and step of hydrogenation by it for alcohol, for example the 2-propyl enanthol can make by valeral (hydroformylation by Residual oil II obtains) being carried out acetalation and subsequently acetal product 2-propyl group heptenal is carried out hydrogenation.
For illustrative purposes, rather than in order to provide enumerating of any limit, only list by way of example below can exist with described compositions of olefines in the representative olefinic compounds of part:
Butylene such as 1-butylene, 2-butylene and iso-butylene, amylene such as 1-amylene, the 2-amylene, 2-methyl-1-butene alkene and 2-methyl-2-butene, hexene such as 1-hexene, the 2-hexene, the 3-hexene, the 2-Methyl-1-pentene, 2-methyl-2-amylene, 3-methyl-2-amylene and 3-Methyl-1-pentene, heptene such as 1-heptene, the 2-heptene, the various isomer of 3-heptene and methyl hexene, octene such as 1-octene, the 2-octene, the 3-octene, 4-octene and have internal double bonds or the branched octenes of terminal double link, nonene such as 1-nonene, the 2-nonene, the 3-nonene, 4-nonene and have internal double bonds or the branching nonene of terminal double link, decene such as 1-decene, the 2-decene, the 3-decene, the 4-decene, 5-decene and have internal double bonds or the branching decene of terminal double link, undecylene such as 1-undecylene, the 2-undecylene, the 3-undecylene, the 4-undecylene, 5-undecylene and have internal double bonds or the branching undecylene of terminal double link, dodecylene such as 1-dodecylene, the 2-dodecylene, the 3-dodecylene, the 4-dodecylene, the 5-dodecylene, 6-dodecylene and have internal double bonds or the branching dodecylene of terminal double link.Tetradecene, 15 carbenes, cetene, heptadecene, vaccenic acid, 19 carbenes and eicosylene are suitable equally.
The compositions of olefines that can be used for the inventive method can also comprise diolefine, for example α-ω-diolefine such as 1,3-butadiene, 1, the 4-pentadiene, 1, the 5-hexadiene, 1, the 6-heptadiene, 1, the 7-octadiene, 1,8-nonadiene or 1,9-decadiene, and the diolefine such as the 1,3-pentadiene that have internal double bonds and terminal double link simultaneously, 1, the 3-hexadiene, 1, the 4-hexadiene, 1, the 3-heptadiene, 1, the 4-heptadiene, 1, the 5-heptadiene, 1, the 3-octadiene, 1, the 4-octadiene, 1, the 5-octadiene, 1, the 6-octadiene, 1, the 3-nonadiene, 1, the 4-nonadiene, 1, the 5-nonadiene, 1, the 6-nonadiene, 1, the 7-nonadiene, 1, the 3-decadiene, 1, the 4-decadiene, 1, the 5-decadiene, 1, the 6-decadiene, 1, the 7-decadiene, 1, the 8-decadiene.
Hydroformylation process of the present invention use uniform dissolution in reaction medium and the rhodium catalyst that cooperates with phosphorus-containing ligand carry out, and this phosphorus-containing ligand can also and only have the less trend that the terminal double link isomery is turned to internal double bonds at the isomerisation of olefin that will have internal double bonds under the reaction conditions of the present invention and hydroformylation under reaction conditions of the present invention.With respect to rhodium, advantageously excessive use part uses with part/Rh mol ratio of 2-300, preferred 2-20, preferred especially 2-10 usually.
Rhodium concentration in the liquid reaction mixture is generally the 10-500 ppm by weight, preferred 30-350 ppm by weight, preferred especially 50-300 ppm by weight.As the rhodium source, can use for example rhodium salt such as rhodium acetate, rhodium chloride or rhodium nitrate, rhodium complex such as acetyl acetone rhodium and/or rhodium carbonyl compound such as Rh (CO)
2Acac, Rh
4(CO)
12Or Rh
6(CO)
16(acac: the methyl ethyl diketone root).The rhodium Source Type that uses is not crucial usually for the result of the inventive method.
In order to carry out hydroformylation, will be dissolved in as the rhodium compound in rhodium source or be suspended in the reaction mixture usually, and also handle part to be used similarly.Under the hydrogenation formyl reaction condition, in hydroformylation reactor, form on the spot then the activated rhodium complex of hydroformylation, that is, form by the rhodium compound reaction that makes carbon monoxide and hydrogen and be combined with phosphorus-containing ligand.Certainly preformed rhodium catalyst title complex can also be joined in the reaction mixture.
The inventive method is carried out in homogeneous phase; promptly in treating the alkene of hydroformylation, carry out; the aldehyde of rhodium hydroformylation catalysts, free ligand and the formation of uniform dissolution in reaction mixture is present in the liquid phase; that is, the inventive method is not provided at the hydroformylation in two liquid phases of existence arranged side by side.
Hydroformylation process of the present invention can advantageously carry out in the presence of solvent.As solvent, preferred use the aldehyde that in the hydroformylation of each alkene, forms and they have more high boiling downstream reaction product, i.e. an aldol condensation product.Same suitable solvent is aromatic substance such as toluene and dimethylbenzene, can be used to dilute the hydrocarbon or the hydrocarbon mixture of above-mentioned aldehyde, and the downstream product of aldehyde.Other possible solvent is the ester of aliphatic carboxylic acid and alkanol, for example ethyl acetate or
Ether such as t-butyl methyl ether and tetrahydrofuran (THF).Under the situation of enough hydrophilic parts, can use alcohol as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, ketone such as acetone and methylethylketone etc.Can also be with " ionic liquid " as solvent.These are liquid salt, N for example, N '-dialkylimidazolium salt such as N-butyl-N '-methylimidazole salt, tetraalkylammonium salt such as tetra-n-butyl ammonium salt, N-Fixanol such as normal-butyl pyridinium salt, Si Wan Ji phosphonium salt is as three hexyls (tetradecyl) phosphonium salt, for example a tetrafluoro borate, acetate, tetrachloro aluminate, hexafluorophosphate, muriate and tosylate.
The inventive method advantageously uses liquid discharging method to carry out.At this moment, from the hydroformylation reactor of first reaction zone, take out continuously liquid hydroformylation mixture and it is sent in the hydroformylation reactor of next reaction zone.Because the downstream reaction district operates under than the lower stagnation pressure in the district of front, in the hydroformylation reactor in the downstream reaction district of the hydro formylation products mixture from the reaction zone of front advantageously can being reduced pressure.Usually, the hydro formylation products mixture from first reaction zone did not carry out aftertreatment before it enters in the subsequent reaction district.Operation downstream reaction district under the selected reaction conditions of the reaction conditions of the reaction zone that is different from the front.Usually from the hydroformylation reactor in this downstream reaction district, take out the liquid hydroformylation mixture continuously; and its pressure that reduces pressure is hanged down in the pressure reduction vessel that 1-35 clings to, preferred 3-10 clings to remove wherein dissolved gases, as unreacted CO/H than the pressure in the hydroformylation reactor usually
2Mixture perhaps needs, and it is sent in other downstream reaction district as mentioned above.The gas that in pressure reduction vessel, discharges, particularly unreacted CO/H
2The words that mixture needs can be recycled in one of reaction zone of front with further reaction, in this case maybe advantageously, in interchanger to this gas circulation materials flow carry out scrubbing or intermediate condensation with the aldehyde that removes deentrainment and/or alkene or with the sub-materials flow discharging of this recycle stream to avoid the accumulation of rare gas element in reactor.The liquid hydroformylation mixture that contains hydro formylation products, is dissolved in wherein alkene, higher-boiling compound, catalyzer and free ligand that remains in the pressure reduction vessel can be fed degassing tower subsequently, to reclaim unreacted alkene.Subsequently; can be with the hydro formylation products that contains from degassing tower; higher-boiling compound; the bottoms of catalyzer and free ligand feeds distillation tower; here with hydro formylation products and higher-boiling compound; catalyzer separates with free ligand and can further use; the words that need simultaneously; with higher-boiling compound; the materials flow of catalyzer and free ligand concentrate and with sub-materials flow discharging with after avoiding higher-boiling compound and in reactor, accumulating; advantageously be recycled in the reactor of one of reaction zone of front, in the reactor of preferred first reaction zone.The aldehyde product can be handled by the whole bag of tricks of prior art, for example handles by the method described in US-A 4,148,830, US-A 6,100,432 or the WO01/58844.
As can be with the catalyzer of double-bond isomerization, for the present invention, the title complex of preferred rhodium and the organic phosphoramidite of chelating or organophosphite or organic phosphinate part.In these parts, one or more phosphorus atom can be substituted by arsenic and/or antimony atoms, but preferably use phosphorus-containing ligand.
Be applicable to that the isomery hydroformylation catalysts in the inventive method for example is the title complex of the phosphoramidite ligand of rhodium and formula I,
Wherein
Q is the bridged group of following formula:
Wherein
A
1And A
2Be O, S, SiR separately independently of each other
aR
b, NR
cOr CR
dR
e, R wherein
a, R
bAnd R
cBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other,
R
dAnd R
eBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other, perhaps connect carbon atom and form cycloalkylidene, perhaps radicals R with 4-12 carbon atom with them
dWith other radicals R
dTogether or radicals R
eWith other radicals R
eForm intramolecular bridged group D together,
D is selected from following divalent bridging group,
Wherein
R
9And R
10Be hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylic acid ester groups or cyano group independently of each other separately, or the formation C that mutually combines
3-C
4Alkylidene bridge,
R
11, R
12, R
13And R
14Be hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylic acid ester groups, cyano group, alkoxyl group, SO separately independently of each other
3H, sulfonate group, NE
1E
2, alkylidene group-NE
1E
2E
3+X
-, acyl group or nitro,
C is 0 or 1,
Y is a chemical bond,
R
5, R
6, R
7And R
8Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, COOR separately independently of each other
f, COO
-M
+, SO
3R
f, SO
3 -M
+, NE
1E
2, NE
1E
2E
3+X
-, alkylidene group-NE
1E
2E
3+X
-, OR
f, SR
f, (CHR
gCH
2O)
xR
f, (CH
2N (E
1))
xR
f, (CH
2CH
2N (E
1))
xR
f, halogen, trifluoromethyl, nitro, acyl group or cyano group,
Wherein
R
f, E
1, E
2And E
3Be the identical or different group that is selected from hydrogen, alkyl, cycloalkyl and aryl,
R
gBe hydrogen, methyl or ethyl,
M
+Be positively charged ion,
X
-Be negatively charged ion and
X is the integer of 1-120,
Perhaps
R
5And/or R
7Two adjacent carbonss that connect phenyl ring with them form the fused rings system with 1,2 or 3 other ring,
A and b are 0 or 1 separately independently of each other,
P is a phosphorus, and
R
1, R
2, R
3And R
4Be heteroaryl, heteroaryloxy, alkyl, alkoxyl group, aryl, aryloxy, cycloalkyl, cycloalkyloxy, Heterocyclylalkyl, heterocycle alkoxyl group or NE separately independently of each other
1E
2Group, condition are R
1And R
3Connect by the nitrogen-atoms that is connected to the pyrrole group on the phosphorus atom P, perhaps R
1With R
2Together and/or R
3With R
4Form divalent group E together, this group E contains at least one and is connected to the pyrrole group on the phosphorus atom P and is had following formula by the nitrogen on the pyrroles:
Py-l-W，
Wherein
Py is a pyrrole group,
L is chemical bond or O, S, SiR
aR
b, NR
cOr CR
hR
i,
W is cycloalkyl, cycloalkyloxy, aryl, aryloxy, heteroaryl or heteroaryloxy, and
R
hAnd R
iBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other,
Perhaps form the connection pyrrole group, this group is connected on the phosphorus atom P by nitrogen-atoms and has following formula:
Py-l-Py。
Preferred phosphoramidite ligand is the part of formula Ia:
Wherein
R
15, R
16, R
17And R
18Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, W ' COOR separately independently of each other
k, W ' COO
-M
+, W ' (SO
3) R
k, W ' (SO
3)
-M
+, W ' PO
3(R
k) (R
1), W ' (PO
3)
2 -(M
+)
2, W ' NE
4E
5, W ' (NE
4E
5E
6)
+X
-, W ' OR
k, W ' SR
k, (CHR
1CH
2O)
yR
k, (CH
2NE
4)
yR
k, (CH
2CH
2NE
4)
yR
k, halogen, trifluoromethyl, nitro, acyl group or cyano group,
Wherein
W ' is singly-bound, heteroatoms or the divalent bridging group with 1-20 bridge atom,
R
k, E
4, E
5And E
6Be the identical or different group that is selected from hydrogen, alkyl, cycloalkyl and aryl,
R
1Be hydrogen, methyl or ethyl,
M
+Be the positively charged ion Equivalent,
X
-Be the negatively charged ion Equivalent and
Y is the integer of 1-240,
Two adjacent R wherein
15, R
16, R
17And R
18Group can also form the fused rings system with 1,2 or 3 other ring with the carbon atom that they connect pyrrole ring,
Condition is R
15, R
16, R
17And R
18In the group at least one is not hydrogen, and R
19And R
20Do not interconnect,
R
19And R
20Be cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other,
A and b are 0 or 1 separately independently of each other,
P is a phosphorus atom,
Q is the bridged group of following formula:
Wherein
A
1And A
2Be O, S, SiR separately independently of each other
aR
b, NR
cOr CR
dR
e, wherein
R
a, R
bAnd R
cBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other,
R
dAnd R
eBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other, perhaps connect carbon atom and form cycloalkylidene, perhaps radicals R with 4-12 carbon atom with them
dWith other radicals R
dTogether or radicals R
eWith other radicals R
eForm intramolecular bridged group D together,
D is selected from following divalent bridging group,
Wherein
R
9And R
10Be hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylic acid ester groups or cyano group independently of each other separately, or the formation C that mutually combines
3-C
4Alkylidene bridge,
R
11, R
12, R
13And R
14Be hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylic acid ester groups, cyano group, alkoxyl group, SO separately independently of each other
3H, sulfonate group, NE
1E
2, alkylidene group-NE
1E
2E
3+X
-, acyl group or nitro,
C is 0 or 1,
R
5, R
6, R
7And R
8Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, COOR separately independently of each other
f, COO
-M
+, SO
3R
f, SO
3 -M
+, NE
1E
2, NE
1E
2E
3+X
-, alkylidene group-NE
1E
2E
3+X
-, OR
f, SR
f, (CHR
gCH
2O)
xR
f, (CH
2N (E
1))
xR
f, (CH
2CH
2N (E
1))
xR
f, halogen, trifluoromethyl, nitro, acyl group or cyano group,
Wherein
R
f, E
1, E
2And E
3Be the identical or different group that is selected from hydrogen, alkyl, cycloalkyl and aryl,
R
gBe hydrogen, methyl or ethyl,
M
+Be positively charged ion,
X
-Be negatively charged ion and
X is the integer of 1-120,
Perhaps
R
5And/or R
7Two adjacent carbonss that connect phenyl ring with them form the fused rings system with 1,2 or 3 other ring.
Described part is the theme of WO 02/083695, and the document is incorporated herein by reference at this comprehensively, and has wherein also described the preparation of these parts.Preferred part in this class part for example is a following compounds, and this is only enumerated for illustration purpose, and the part that can adopt is not applied any restriction.
Et: ethyl
Me: methyl
For using rhodium complex also to comprise the phosphoramidite ligand of describing among WO 98/19985 and the WO 99/52632 as the suitable phosphoramidite ligand of the isomery hydroformylation of catalyzer; this class part has to have by nitrogen-atoms and is connected to 2 of heteroaryl on the phosphorus atom such as pyrryl or indyl; 2 '-dihydroxyl-1; 1 '-biphenylene or 2; 2 '-dihydroxyl-1; 1 '-Ya binaphthylyl bridged group, for example following part:
1 of these parts, 1 '-biphenylene or 1,1 '-Ya binaphthylyl bridged group can also pass through methylene radical (CH
2-), 1,1-ethylidene (CH
3-CH＜) or 1,1-propylidene (CH
3-CH
2-HC＜) by 1,1 further bridging.
For using rhodium complex as the part of describing in the suitable phosphinate part of the isomery hydroformylation of catalyzer especially WO 98/19985, for example:
For using rhodium complex also to comprise for example as WO 01/58589 described phosphorous acid ester and phosphinate part as the suitable part of the isomery hydroformylation of catalyzer.Only, can mention following part for example for illustration purpose:
Is for example as WO 02/068371 and EP-A 982314 described phosphine parts with xanthenyl-two (phosphorus is for xanthenyl) skeleton for using rhodium complex as fine other the suitable part of the isomery hydroformylation of catalyzer.Only for illustration purpose, below enumerated some these class parts for example:
For the rhodium complex that uses the chelating phosphite ester ligand part that for example is formula II, III and IV as this suitable class part of the isomery hydroformylation of catalyzer.
Wherein G is replacement or the unsubstituted divalent organic bridging base group with 2-40 carbon atom, and M is selected from-C (R
w)
2-,-O-,-S-, NR
v, Si (R
t)
2-and-divalent bridging group of CO-, wherein radicals R
wIdentical or different and each hydrogen, alkyl or phenyl, tolyl or anisyl naturally with 1-12 carbon atom, radicals R
vBe hydrogen or replacement or unsubstituted alkyl with 1-12 carbon atom, radicals R
tIdentical or different and each hydrogen or methyl naturally, m is 0 or 1, identical or different and each aryl that does not replace or replace naturally of group Ar, subscript k is 0 or 1, radicals R
xIdentical or different and each monovalent alkyl or aryl that does not replace or replace naturally, and R
yIt is the divalent organic group that is selected from replacement and unsubstituted alkylidene group, arylidene, arylidene-alkylidene group-arylidene and two arylidene.Only do not apply any restriction, can mention the following chelating phosphite ester ligand that can be used for the inventive method for example for illustration purpose.
This class bis-phosphite chelating ligand and other bis-phosphite chelating ligand are the theme of EP-A 213369 and US-A 4 769 498 and the preparation of wherein having described them.
Substitute above-mentioned bis-phosphite chelating ligand, can also use the monodentate list phosphite ester ligand of following formula V to cooperate to form the rhodium hydroformylation catalysts in the methods of the invention and as free ligand:
P(OR
S)(OR
T)(OR
U) V
The title complex of the well-formedness of known this class part and they and rhodium is as the catalyzer of isomery hydroformylation.In single phosphite ester ligand of formula IV, radicals R
S, R
TAnd R
UBe to have 1-30 usually, the identical or different organic group of preferred 5-30 carbon atom, for example replacement or unsubstituted alkyl, aryl, arylalkyl, cycloalkyl and/or heteroaryl independently of each other.Because they have higher hydrolysis and stability to degradation, particularly preferred example such as EP-A 155508 described sterically hindered single phosphite ester ligands.Only, can mention down the phosphite ester ligand structure of itemizing for example for illustration purpose.
Be also included within the bidentate ligand that except the phosphorous acid ester group, also has phosphinate (phosphinite) or phosphine groups in the ligand molecular for the known part of isomery hydroformylation that uses rhodium complex as catalyzer.This class part especially is described in WO 99/50214.Only, below show some examples of this class part for illustration purpose:
Bu
t: the tertiary butyl
Ph: phenyl
Part type described above can be in the methods of the invention used with the title complex of they and rhodium and/or as the form of free ligand.Preferably use rhodium and the title complex of phosphoramidite ligand described in WO 02/083695 as the isomery hydroformylation catalysts in the inventive method with xanthene skeleton.
According to the present invention; the inventive method can obtain corresponding aldehyde with the compositions of olefines hydroformylation with alkene of internal double bonds with containing alpha-olefin; this method and make gained n/i and be higher than the space-time yield that can obtain by traditional method than being higher than corresponding to the ratio of alpha-olefin in the compositions of olefines and space-time yield, and needn't set up cascade to form two or more reaction zones.
Below by embodiment the inventive method is described.
Embodiment
Synthesizing of part 53
28.5g (218mmol) 3-skatole (skatole) is placed in the reaction vessel with about 50ml dry toluene, and under reduced pressure steaming desolventizes to remove the water of trace by component distillation.Repeat this program once.In argon gas, be cooled to-65 ℃ then with 700ml dry toluene absorption of residual excess and with this mixture.Successively slowly add 14.9g (109mmol) PCl down at-65 ℃ then
3And 40g (396mmol) triethylamine.In 16 hours, make reaction mixture reach room temperature, refluxed then 16 hours.Will be at the 19.3g in the 300ml dry toluene (58mmol) 4,5-dihydroxyl-2,7-di-t-butyl-9,9-dimethyl xanthene adds in the reaction mixture, then this mixture was refluxed 16 hours, and after cool to room temperature, the sedimentary colorless solid of suction strainer (triethylamine hydrochloride), steam desolventize and from hot ethanol with twice in resistates recrystallization.Drying under reduced pressure obtains 36.3g (theoretical value 71%) colorless solid.
31p-NMR(298K)：δ＝105。
The hydroformylation of 1-butylene, CO: H
2Mol ratio=1: 1
Difference weighing 5.5mg Rh (CO)
2Acac (acac=methyl ethyl diketone root) and 200mg part 53 are dissolved in the 5g toluene separately, mixing and following to the 10 synthetic gas (CO: H that cling at 90 ℃
2=1: 1) handle (pre-activation).After 1 hour, mixture is reduced pressure.Add the 9.9g 1-butylene by Prssure lock then, by synthetic gas (CO: H
2=1: 1) stagnation pressure is set at 17 crust, and under 90 ℃, carries out 2 hours (109ppm Rh of hydroformylation; The mol ratio of part 53: Rh approximately=10: 1).Shown in after the reaction times, the cooling autoclave is by the careful exhaust of cold-trap, and the mixture of reaction products of collecting by gc analysis (reactor and cold-trap).Transformation efficiency is 99%, the productive rate of valeral be 92% and the linear lag (ratio of n product) be 98.5%.The productive rate of 2-butylene (isomerization product) is 7%.
CO and H during the reaction beginning
2Dividing potential drop respectively is 6 crust.
The linear lag (ratio of n product) be defined as the n-valeral divided by n-valeral and i-valeral and multiply by 100 amount again.
The hydroformylation of 1-butylene, CO: H
2Mol ratio=1: 2
Difference weighing 5.4mg Rh (CO)
2Acac (acac=methyl ethyl diketone root) and 200mg part 53 are dissolved in the 5g toluene separately, mixing and following to the 10 synthetic gas (CO: H that cling at 90 ℃
2=1: 2) handle (pre-activation).After 1 hour, mixture is reduced pressure.Add the 10.1g 1-butylene by Prssure lock then, and by synthetic gas (CO: H
2=1: 2) stagnation pressure is set at 17 crust.Then gas feed is converted to synthetic gas (CO: H
2=1: 1) in reactor, to guarantee 1: 2 constant CO: H
2Mol ratio.Under 90 ℃, carry out 2 hours (105ppm Rh of hydroformylation subsequently; The mol ratio of part 53: Rh approximately=10: 1).Transformation efficiency is 98%, the productive rate of valeral be 49% and the linear lag (ratio of n product) be 95.8%.The productive rate of 2-butylene (isomerization product) is 46%.
CO dividing potential drop during the reaction beginning is 4 crust, and reacts the H when beginning
2Dividing potential drop is 8 crust.
The hydroformylation of 2-butylene, CO: H
2Mol ratio=1: 1
Difference weighing 5.0mg Rh (CO)
2Acac (acac=methyl ethyl diketone root) and 176mg part 53 are dissolved in the 5g toluene separately, mixing and following to the 10 synthetic gas (CO: H that cling at 90 ℃
2=1: 1) handle (pre-activation).After 1 hour, mixture is reduced pressure.Add the 11.3g 2-butylene by Prssure lock then, by synthetic gas (CO: H
2=1: 1) stagnation pressure is set at 17 crust.Under 90 ℃, carry out 4 hours (93ppm Rh of hydroformylation subsequently; The mol ratio of part 53: Rh approximately=10: 1).Transformation efficiency is 12%, the productive rate of valeral be 10% and the linear lag (ratio of n product) be 88.5%.
CO and H during the reaction beginning
2Dividing potential drop respectively is 6 crust.
The hydroformylation of 2-butylene, CO: H
2Mol ratio=1: 2
Difference weighing 5.0mg Rh (CO)
2Acac (acac=methyl ethyl diketone root) and 176mg part 53 are dissolved in the 5g toluene separately, mixing and following to the 10 synthetic gas (CO: H that cling at 90 ℃
2=1: 2) handle (pre-activation).After 1 hour, mixture is reduced pressure.Add the 11.2g 2-butylene by Prssure lock then, by synthetic gas (CO: H
2=1: 2) stagnation pressure is set at 17 crust.Then gas feed is converted to synthetic gas (CO: H
2=1: 1) in reactor, to guarantee 1: 2 constant CO: H
2Mol ratio.Under 90 ℃, carry out 4 hours (93ppm Rh of hydroformylation subsequently; The mol ratio of part 53: Rh approximately=10: 1).Transformation efficiency is 34%, the productive rate of valeral be 32% and the linear lag (ratio of n product) be 93%.
CO dividing potential drop during the reaction beginning is 4 crust, and reacts the H when beginning
2Dividing potential drop is 8 crust.
The hydroformylation of 2-butylene, CO: H
2Mol ratio=1: 9
Difference weighing 5.0mg Rh (CO)
2Acac (acac=methyl ethyl diketone root) and 176mg part 53 are dissolved in the 5g toluene separately, mixing and following to the 10 synthetic gas (CO: H that cling at 90 ℃
2=1: 9) handle (pre-activation).After 1 hour, mixture is reduced pressure.Add the 11.2g 2-butylene by Prssure lock then, by synthetic gas (CO: H
2=1: 9) stagnation pressure is set at 17 crust.Then gas feed is converted to synthetic gas (CO: H
2=1: 1) in reactor, to guarantee 1: 9 constant CO: H
2Mol ratio.Under 90 ℃, carry out 4 hours (93ppm Rh of hydroformylation subsequently; The mol ratio of part 53: Rh approximately=10: 1).Transformation efficiency is 64%, the productive rate of valeral be 46% and the linear lag (ratio of n product) be 96%.
CO dividing potential drop during the reaction beginning is 1.2 crust, and reacts the H when beginning
2Dividing potential drop is 10.8 crust.
Embodiment 6
The hydroformylation of trans-2-butene, CO: H
2Mol ratio=1: 1
Difference weighing 5.0mg Rh (CO)
2Acac (acac=methyl ethyl diketone root) and 187mg part 53 are dissolved in the 5g toluene separately, mixing and following to the 10 synthetic gas (CO: H that cling at 90 ℃
2=1: 1) handle (pre-activation).After 1 hour, mixture is reduced pressure.Add the 10.4g trans-2-butene by Prssure lock then, by synthetic gas (CO: H
2=1: 1) stagnation pressure is set at 12 crust.Under 90 ℃, carry out 4 hours (97ppm Rh of hydroformylation subsequently; The mol ratio of part 53: Rh=10: 1).Transformation efficiency is 33%, the productive rate of valeral be 30% and the linear lag (ratio of n product) be 95%.
CO and H during the reaction beginning
2Dividing potential drop respectively is 3.5 crust.
Embodiment 7
Use 53 couples of Residual oil II of Rh/ part to carry out the continuous hydrogenation formylation
Comprising that as shown in drawings the liquid capacity separately that is connected in series is in the continuous operation equipment of the container (4) of the decompression of two agitated autoclave (1 and 2), Pressure separator (3), separation of C 4 hydrocarbon of 1L and heating and the wiped film evaporator (5) that separates the high boiling point phase that contains catalyzer from product mutually; use rhodium and part 53 as catalyzer to the Residual oil II (1-butylene of 29 weight %; the 2-butylene of 52 weight %, the butane of 19 weight % and other C4 hydrocarbon) carry out hydroformylation.From distillation (5) turn back to reactor catalyzer to return materials flow be about 130g/h, and resid feed speed is about 70g/h.In the mol ratio of part/metal is that (mole: mole) rhodium concentration in the reactor was about 100ppm down, and the temperature of first reactor is that the temperature of 70 ℃ and second reactor is 90 ℃ in about 10: 1.With CO: H
2Mol ratio be 1: 1 synthetic gas infeed first reactor and about 22 the crust stagnation pressures under operate.Under about 20 crust, in second reactor, additionally introduce H
2The CO content that can make synthetic gas is adjusted to any value of about 50%CO to the about 1%CO scope via exhaust gas concentration.In second reactor at CO: H
2Mol ratio is (first reactor: CO: H under 1: 25 the steady state operation
2Mol ratio=1: 1), through 13 days representative time, obtain 49% aldehyde productive rate and 96.1% n proportion of products.
Claims (7)
1. a continuous preparation has the method for the aldehyde of 5-21 carbon atom; it is by in comprising the reaction of high order system of at least 2 reaction zones; under 50-200 ℃ temperature of reaction and pressure; with homogeneous rhodium catalyst and free ligand that the organophosphor ligand that contains aerobic and/or nitrogen cooperates in the presence of; by synthetic gas; in the homogeneous phase that contains the alpha-olefin and the compositions of olefines with 4-20 carbon atom of alkene, carry out the isomery hydroformylation with internal double bonds; described organophosphor ligand can will have the isomerisation of olefin of internal double bonds and hydroformylation and only have the less trend that the terminal double link isomery is turned to internal double bonds under reaction conditions under reaction conditions, wherein compositions of olefines at first in one or more first reaction zone groups under the stagnation pressure of 10-40 crust with CO/H
2Mol ratio be 4: 1 to 1: 2 synthesis gas reaction reaching the alpha-olefin transformation efficiency of 40-95%, and in one or more downstream reactions district group, under the stagnation pressure of 5-30 crust, make hydroformylation mixture and CO/H from described one or more first reaction zone groups
2Mol ratio is 1: 4 to 1: 1000 a synthesis gas reaction, stagnation pressure in wherein said one or more downstream reactions district 1 clings to (T1-Tf) than always forcing down in the reaction zone of front in each case, wherein T1 is the stagnation pressure in the reaction zone of front, and Tf is the stagnation pressure in the reaction zone in described one or more first reaction zone downstreams, condition be the difference of T1-Tf greater than 1 crust, and the CO dividing potential drop in described one or more downstream reactions district is lower than the CO dividing potential drop in the reaction zone of this reaction zone front in each case.
2. the method that requires as claim 1 is wherein set CO/H in described one or more first reaction zones
2Mol ratio is 3: 2 to 2: 3, and sets CO/H in described one or more downstream reactions district
2Mol ratio is 1: 9 to 1: 100.
3. as claim 1 or 2 methods that require, this method is carried out in two reaction zones.
4. as the method for any one requirement among the claim 1-3, wherein will be used for from the hydrogeneous waste gas of aldehyde and olefine aldehydr hydrogenation process setting CO/H at described one or more reaction zones in the described first reaction zone downstream
2Mol ratio.
5. as the method for any one requirement among the claim 1-4, use therein homogeneous hydrogenation formylation catalyzer is the title complex of the phosphoramidite ligand of rhodium and formula I:
Wherein
Q is the bridged group of following formula:
Wherein
A
1And A
2Be O, S, SiR separately independently of each other
aR
b, NR
cOr CR
dR
e, wherein
R
a, R
bAnd R
cBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other,
R
dAnd R
eBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other, perhaps connect carbon atom and form cycloalkylidene, perhaps radicals R with 4-12 carbon atom with them
dWith other radicals R
dTogether or radicals R
eWith other radicals R
eForm intramolecular bridged group D together,
D is selected from following divalent bridging group,
Wherein
R
9And R
10Be hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylic acid ester groups or cyano group independently of each other separately, or the formation C that mutually combines
3-C
4Alkylidene bridge,
R
11, R
12, R
13And R
14Be hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylic acid ester groups, cyano group, alkoxyl group, SO separately independently of each other
3H, sulfonate group, NE
1E
2, alkylidene group-NE
1E
2E
3+X
-, acyl group or nitro,
C is 0 or 1,
Y is a chemical bond,
R
5, R
6, R
7And R
8Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, COOR separately independently of each other
f, COO
-M
+, SO
3R
f, SO
3 -M
+, NE
1E
2, NE
1E
2E
3+X
-, alkylidene group-NE
1E
2E
3+X
-, OR
f, SR
f, (CHR
gCH
2O)
xR
f, (CH
2N (E
1))
xR
f, (CH
2CH
2N (E
1))
xR
f, halogen, trifluoromethyl, nitro, acyl group or cyano group,
Wherein
R
f, E
1, E
2And E
3Be the identical or different group that is selected from hydrogen, alkyl, cycloalkyl and aryl,
R
gBe hydrogen, methyl or ethyl,
M
+Be positively charged ion,
X
-Be negatively charged ion and
X is the integer of 1-120,
Perhaps
R
5And/or R
7Two adjacent carbonss that connect phenyl ring with them form the fused rings system with 1,2 or 3 other ring,
A and b are 0 or 1 separately independently of each other,
P is a phosphorus atom, and
R
1, R
2, R
3And R
4Be heteroaryl, heteroaryloxy, alkyl, alkoxyl group, aryl, aryloxy, cycloalkyl, cycloalkyloxy, Heterocyclylalkyl, heterocycle alkoxyl group or NE separately independently of each other
1E
2Group, condition are R
1And R
3Connect by the nitrogen-atoms that is connected to the pyrrole group on the phosphorus atom P, perhaps R
1With R
2Together and/or R
3With R
4Form divalent group E together, this group E contains at least one and is connected to the pyrrole group on the phosphorus atom P and is had following formula by the nitrogen on the pyrroles:
Py-l-W，
Wherein
Py is a pyrrole group,
L is chemical bond or O, S, SiR
aR
b, NR
cOr CR
hR
i,
W is cycloalkyl, cycloalkyloxy, aryl, aryloxy, heteroaryl or heteroaryloxy, and
R
hAnd R
iBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other, perhaps form the connection pyrrole group, this group is connected on the phosphorus atom P by nitrogen-atoms and has following formula:
Py-l-Py。
6. as the method for any one requirement among the claim 1-5, use therein homogeneous hydrogenation formylation catalyzer is the title complex of the phosphoramidite ligand of rhodium and formula Ia:
Wherein
R
15, R
16, R
17And R
18Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, W ' COOR separately independently of each other
k, W ' COO
-M
+, W ' (SO
3) R
k, W ' (SO
3)
-M
+, W ' PO
3(R
k) (R
1), W ' (PO
3)
2 -(M
+)
2, W ' NE
4E
5, W ' (NE
4E
5E
6)
+X
-, W ' OR
k, W ' SR
k, (CHR
1CH
2O)
yR
k, (CH
2NE
4)
yR
k, (CH
2CH
2NE
4)
yR
k, halogen, trifluoromethyl, nitro, acyl group or cyano group,
Wherein
W ' is singly-bound, heteroatoms or the divalent bridging group with 1-20 bridge atom,
R
k, E
4, E
5And E
6Be the identical or different group that is selected from hydrogen, alkyl, cycloalkyl and aryl,
R
1Be hydrogen, methyl or ethyl,
M
+Be the positively charged ion Equivalent,
X
-Be the negatively charged ion Equivalent and
Y is the integer of 1-240,
Two adjacent R wherein
15, R
16, R
17And R
18Group can also form the fused rings system with 1,2 or 3 other ring with the carbon atom that they connect pyrrole ring,
Condition is R
15, R
16, R
17And R
18In the group at least one is not hydrogen, and R
19And R
20Do not interconnect,
R
19And R
20Be cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other,
A and b are 0 or 1 separately independently of each other,
P is a phosphorus atom,
Q is the bridged group of following formula:
Wherein
A
1And A
2Be O, S, SiR separately independently of each other
aR
b, NR
cOr CR
dR
e, R wherein
a, R
bAnd R
cBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other,
R
dAnd R
eBe hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl separately independently of each other, perhaps connect carbon atom and form cycloalkylidene, perhaps radicals R with 4-12 carbon atom with them
dWith other radicals R
dTogether or radicals R
eWith other radicals R
eForm intramolecular bridged group D together,
D is selected from following divalent bridging group,
Wherein
R
9And R
10Be hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylic acid ester groups or cyano group independently of each other separately, or the formation C that mutually combines
3-C
4Alkylidene bridge,
R
11, R
12, R
13And R
14Be hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylic acid ester groups, cyano group, alkoxyl group, SO separately independently of each other
3H, sulfonate group, NE
1E
2, alkylidene group-NE
1E
2E
3+X
-, acyl group or nitro,
C is 0 or 1,
R
5, R
6, R
7And R
8Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, COOR separately independently of each other
f, COO
-M
+, SO
3R
f, SO
3 -M
+, NE
1E
2, NE
1E
2E
3+X
-, alkylidene group-NE
1E
2E
3+X
-, OR
f, SR
f, (CHR
gCH
2O)
xR
f, (CH
2N (E
1))
xR
f, (CH
2CH
2N (E
1))
xR
f, halogen, trifluoromethyl, nitro, acyl group or cyano group, wherein
R
f, E
1, E
2And E
3Be the identical or different group that is selected from hydrogen, alkyl, cycloalkyl and aryl,
R
gBe hydrogen, methyl or ethyl,
M
+Be positively charged ion,
X
-Be negatively charged ion and
X is the integer of 1-120,
Perhaps
R
5And/or R
7Two adjacent carbonss that connect phenyl ring with them form the fused rings system with 1,2 or 3 other ring.
7. as the method for claim 1 requirement, use therein compositions of olefines is Residual oil II.
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| CN101293818B (en) * | 2007-04-28 | 2010-07-07 | 中国石油化工股份有限公司 | Two-stage reaction method for mixed butylene hydroformylation |
| EP2740535A1 (en) * | 2012-12-04 | 2014-06-11 | Dow Technology Investments LLC | Bidentate ligands for hydroformylation of ethylene |
| WO2014156776A1 (en) | 2013-03-27 | 2014-10-02 | 株式会社クラレ | Method for producing dialdehyde |
| CN105001046A (en) * | 2015-07-09 | 2015-10-28 | 武汉工程大学 | Nonyl alcohol synthesis process |
| KR101962094B1 (en) * | 2015-09-30 | 2019-03-26 | 주식회사 엘지화학 | Catalyst composition for hydroformylation and hydroformylation process using the same |
| CN107915758B (en) * | 2017-11-15 | 2019-10-29 | 万华化学集团股份有限公司 | Phosphoramidite ligand, catalyst and the method for preparing 4- acetoxyl group butyraldehyde |
| CN109020791A (en) * | 2018-09-13 | 2018-12-18 | 广东新华粤石化集团股份公司 | A method of alcohol is prepared using the olefin hydroformylation of Co catalysts Direct Regeneration reuse |
| US20220402835A1 (en) * | 2019-12-19 | 2022-12-22 | Dow Technology Investments Llc | Processes for preparing isoprene and mono-olefins comprising at least six carbon atoms |
| CN113385235B (en) * | 2021-06-16 | 2022-11-25 | 上海华谊（集团）公司 | Preparation of 2-methylbutanal hydroformylation catalyst composition, method and use |
| CN113385236B (en) * | 2021-06-16 | 2023-02-03 | 上海华谊（集团）公司 | Olefin hydroformylation catalyst composition and hydroformylation method |
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|---|---|---|---|---|
| EP1008580A1 (en) * | 1998-12-10 | 2000-06-14 | Mitsubishi Chemical Corporation | Process for preparing aldehydes and alcohols |
| WO2002006837A1 (en) * | 2000-07-14 | 2002-01-24 | Matsushita Electric Industrial Co., Ltd. | Particle-labeled protein and immuno-chromatograph using the same |
-
2004
- 2004-10-14 CN CNB2004800312101A patent/CN100412046C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1008580A1 (en) * | 1998-12-10 | 2000-06-14 | Mitsubishi Chemical Corporation | Process for preparing aldehydes and alcohols |
| WO2002006837A1 (en) * | 2000-07-14 | 2002-01-24 | Matsushita Electric Industrial Co., Ltd. | Particle-labeled protein and immuno-chromatograph using the same |
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|---|---|
| CN1871199A (en) | 2006-11-29 |
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