CN1020719C - Process for recovery of phosphorus ligand from vaporized aldehyde - Google Patents
Process for recovery of phosphorus ligand from vaporized aldehyde Download PDFInfo
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- CN1020719C CN1020719C CN 85101904 CN85101904A CN1020719C CN 1020719 C CN1020719 C CN 1020719C CN 85101904 CN85101904 CN 85101904 CN 85101904 A CN85101904 A CN 85101904A CN 1020719 C CN1020719 C CN 1020719C
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- aldehyde
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- vaporization
- condensation
- boiling point
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- 239000003446 ligand Substances 0.000 title claims abstract description 120
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 80
- 239000011574 phosphorus Substances 0.000 title claims abstract description 80
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000008569 process Effects 0.000 title claims abstract description 32
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 29
- 238000011084 recovery Methods 0.000 title claims description 18
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 33
- 239000007791 liquid phase Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 18
- 239000010948 rhodium Substances 0.000 claims abstract description 18
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000006872 improvement Effects 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 100
- 230000008016 vaporization Effects 0.000 claims description 95
- 238000009833 condensation Methods 0.000 claims description 89
- 230000005494 condensation Effects 0.000 claims description 89
- 238000009834 vaporization Methods 0.000 claims description 87
- 239000006227 byproduct Substances 0.000 claims description 86
- 238000009835 boiling Methods 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000006185 dispersion Substances 0.000 claims description 40
- 150000001336 alkenes Chemical class 0.000 claims description 21
- 239000012967 coordination catalyst Substances 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
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- ZXKWUYWWVSKKQZ-UHFFFAOYSA-N cyclohexyl(diphenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZXKWUYWWVSKKQZ-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
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- 238000000926 separation method Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 150000003003 phosphines Chemical class 0.000 claims 1
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- 238000005516 engineering process Methods 0.000 description 17
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- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 9
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 3
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- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 125000004946 alkenylalkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
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- 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
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to an improved rhodium catalyzed liquid phase recycle hydroformylation process, wherein the improvement comprises the steps of selectively separating and recovering phosphorus ligand from the vaporized aldehyde product stream which is obtained after an aldehyde product is volatilized and separated from the catalyst containing reaction product solution of the hydroformylation process.
Description
The present invention is relevant a kind of method of improving rhodium catalysis liquid phase circulating aldehyde process, improvement part comprises and separates selectively and reclaims phosphorus ligand that the aldehyde product stream of this vaporization is to evaporate and separating aldehyde product gained from the catalyzer of the reaction product solution that contains hydroformylation process from the product stream of the aldehyde of vaporization.
In the prior art, ethylenically unsaturated organic compounds and carbon monoxide and hydrogen have rhodium-phosphorus coordination catalyst and free phosphorus ligand in the presence of, carrying out the method for hydroformylation production aldehyde is known by people, for example, United States Patent (USP) U.S.P.3,527,809 low pressure carbonyl hydroformylation process and United States Patent (USP) U.S.P.4,148,830 with the catalytic liquid phase round-robin of rhodium hydroformylation process.
For example, at U.S.P.3,527, in 809, disclose a kind of basic hydroformylation process, ethylenically unsaturated organic compounds and carbon monoxide and hydrogen are having rhodium-phosphorus coordination catalyst and free phosphorus ligand to exist under the situation in this method, and hydroformylation generates aldehyde with high yield under low temperature, low pressure.
Equally also known, under the reaction conditions of hydroformylation, the product of part aldehyde is combined into the by product of the higher aldehyde condensation of boiling point, for example dipolymer, trimer and tetramer.U.S.P.4,148,830 point out, the reaction solvent of the by product useful as catalysts of the liquid aldehydes condensation of these highers, and also be the good carrier of continuous liquid phase circulation technology.For example, this successive liquid phase circulation technology relates to the solution of the aldehyde product that shifts out the Partial Liquid Phase reaction from reactor, contain aldehyde product, dissolved rhodium-phosphorus coordination catalyst, free phosphorus ligand and the higher aldehyde condensation by-product of boiling point in this solution, this technology also relates to rapid evaporation aldehyde product, the product of separating aldehyde thus.Evaporable aldehyde product is separated in gas-liquid separator subsequently with the unevaporated catalyzer that contains liquid reaction solution, in separator, the aldehyde product of vaporization is flowed from top by being reclaimed, the unevaporated catalyzer through condensation that contains liquid reaction solution that stays shifts out from the bottom, and the circulation Returning reactor.
But liquid-phase catalysis circulation hydroformylation process has a weak point, is exactly, and phosphorus ligand has loss in technological process owing to the phosphorus ligand that has vaporization in the aldehyde product stream of vaporizing makes.The aldehyde product stream of vaporization is by producing in the process of fractionation by distillation aldehyde at the liquid catalyst that contains reactant solution.In industrial production, the loss of such ligand not only will be affected economically, and for further making raw material with aldehyde, in the technology with aldehyde hydrogenation production alcohol in the flow process afterwards catalyzer is destroyed, and should avoid as far as possible or reduce for this reason.As known, produce alcohol with such aldehyde through hydrogenation, because of containing phosphorus ligand, to cause the inactivation of this hydrogenation catalyst certainly.
Be purifying aldehyde product, the aldehyde product of once attempting to make vaporization, all can not address this problem as packing tower or tower tray by adopting the equipment of complicated processing entrainment.Although the liquid of carrying secretly in the vaporization aldehyde product stream may be able to be removed and be recovered in to these methods, also may impel to form the higher aldehyde condensation by-product of boiling point.Similarly with condensation and the thick aldehyde product of repetition distillatory method purifying, can only further impel the loss of aldehyde, because can form the higher aldehyde condensation by-product of more boiling point, so these separation methods, make the aldehyde loss more because of there being further condensation reaction to generate by product, shortcoming is many.
For this reason, in liquid-phase catalysis circulation aldehyde reaction, need a kind of simple and efficient, method of can be selectively the phosphorus ligand that is included in the vaporization in the aldehyde product stream of vaporization of continuous liquid phase circulation rhodium catalytic hydroformylation reaction process gained being shifted out and reclaims.
Have now found that, separate and reclaim the phosphorus ligand of vaporization in the aldehyde product stream of the vaporization that can in continuous liquid phase rhodium catalytic cycle hydroformylation process process, obtain selectively.Separate and recovery method is that described aldehyde product stream contact with a kind of dispersive liquid phase, so that the phosphorus ligand that condensation is vaporized from described aldehyde steam selectively, reclaim the also use on demand of phosphorus ligand of condensation then.
More particularly, the invention describes the hydroformylation process of an improved liquid phase circulation rhodium catalytic production aldehyde, in this hydroformylation process, a kind of olefinic compounds, carbon monoxide and hydrogen, dissolved rhodium-phosphorus ligand catalyzer is being arranged, the higher aldehyde condensation by-product of free phosphorus ligand and boiling point exists under the situation, reaction generates aldehyde, in the technology this aldehyde is separated from the solution of liquid reactive aldehyde product and reclaim, in this aldehyde product solution, contain aldehyde, dissolved rhodium-phosphorus coordination catalyst, the aldehyde condensation byproduct that free phosphorus ligand and boiling point are higher, this solution shifts out from hydroformylation reactor, the aldehyde product that obtains vaporizing by the aldehyde product that evaporates in the described solution flows, this aldehyde product stream mainly is by vaporization aldehyde product, the phosphorus ligand of having vaporized and the higher aldehyde condensation byproduct of boiling point of vaporization are formed, this liquid phase reaction aldehyde product solution in separator with not the vaporization, the catalyst separating that contains liquid reacting product solution, this catalyzer reclaims and Returning reacting system from the separator bottom.Improvements of the present invention comprise: (a) separate the phosphorus ligand in the aldehyde by-product stream be contained in described vaporization and the higher aldehyde condensation by-product of boiling point of vaporization selectively, method is that the low dispersion liquid of air-flow and a kind of its boiling point aldehyde condensation by-product more higher than described boiling point is contacted, thereby make the phosphorus ligand and the higher aldehyde condensation by-product condensation of boiling point of the vaporization that contains in the above-mentioned aldehyde product stream of having vaporized, (b) the aldehyde product from vaporization flows back to the higher aldehyde condensation byproduct of boiling point that receipts are condensed, said dispersion liquid employing is the form of droplet, and its consumption is that separated percentage ratio with the phosphorus ligand that reclaims like this at least will be than the while is separated and the percentage ratio of the aldehyde by product that the boiling point of recovery is higher is high 1.2 times.
The aldehyde reaction that the present invention can be used for improving any continuous liquid phase circulation rhodium-phosphorus ligand complex catalysis generates the technology of aldehyde, and this technology is to carry out under the situation that has the free organophosphates ligand.This type of carbonylation process and reaction conditions all are known in the prior art, as United States Patent (USP) 4,148, and the 830 continuous liquid phase circulation technologies that proposed.Generally be with a kind of olefinic compounds and carbon monoxide and H-H reaction generation aldehyde in these methods, be reflected in the liquid phase reaction medium and carry out, contain the higher aldehyde condensation by-product of dissolved rhodium-phosphorus ligand catalyzer, free organophosphates ligand and boiling point in the reaction medium, the aldehyde reaction condition is that temperature of reaction is approximately from 50 ℃ to 200 ℃, the stagnation pressure of hydrogen, carbon monoxide and olefin(e) compound is about 1 to 10,000 pound/square inch (absolute pressure).
Of course it is to be understood that for the present invention the concrete mode and the concrete reaction conditions that carry out aldehyde reaction are not strict, it can change with dealing with various requirements widely and produce required concrete aldehyde product.
Therefore, meeting the olefinic initial reactant of processing requirement of the present invention, can be unsaturated link(age) to be arranged or in the centre unsaturated link(age) is arranged in terminal, can be straight chain, side chain or ring texture.This alkene can contain 2 to 20 carbon atoms, can contain one or more vinyl unsaturated groups.In addition, this alkene also can be with various groups or substituting group, and these groups or substituting group have no adverse effect substantially to aldehyde reaction, for example carbonyl, carbonyl oxygen base, oxygen base, hydroxyl, oxygen carbonyl, fontanel element, alkoxyl group, aryl, fontanel alkyl or the like.The example of unsaturated olefinic compound comprises alpha-olefin, unsaturated link(age) is at intermediary alkene, alkyl olefin(e) acid ester, the alkenyl alkyl acid esters, alkenyl alkyl ethers, alkenols or the like, for example, ethene, propylene, 1-butylene, the 1-amylene, the 1-hexene, the 1-octene, 1-decene, the 1-laurylene, the 1-octadecylene, 2-butylene, 2-methacrylic (iso-butylene), isopentene, the 2-amylene, the 2-hexene, the 3-hexene, the 2-heptene, tetrahydrobenzene, propylene dimer, propylene trimer, the propylene tetramer, 2-ethyl-1-hexene, vinylbenzene, 3-phenyl-1-propylene, 1, the 4-hexadiene, 1, the 7-heptadiene, 3-cyclohexyl-1-butylene, allyl alcohol, hexenyl-1-4-alcohol, 1-octenyl-4-alcohol, vinyl acetate, the allyl acetic acid ester, 3-acetic acid butene esters, the vinylacrylic acid ester, the allyl group propionic ester, the allyl group butyric ester, the methyl methacrylic acid ester, 3-butenyl acetic ester, EVE, vinyl methyl ether, allyl ethyl ether, n-propyl-7-octene acid esters, 3-butenyl cyanogen, 5-hexene acid amides or the like.Of course it is to be understood that if needed the mixture of different alkene also can be used in the hydroformylation process that the present invention relates to.In alkene, better be to use the alpha-olefin that contains 2 to 8 carbon atoms and contain the middle alkene of 4 to 8 carbon atoms, in addition can also be with the mixture of these alpha-olefins and middle alkene.Best olefin feedstock is ethene, propylene, butene-1, butene-2 (cis and/or trans), iso-butylene and their different mixture.
Equally, can use any known rhodium-phosphorus coordination catalyst, this type of Catalysts and its preparation method all is known in the prior art.These rhodiums-phosphorus coordination catalyst comprises up to now for improving any rhodium-organic phosphine or the rhodium-organophosphite complexing hydroformylation catalyst of hydroformylation process.If needed, also can use this class mixture of catalysts.In addition, the amount of required complex catalyst is only required and metal rhodium is reached can use in reaction and concentration can be low as far as possible in the reaction medium of certain reaction technology, and reaction is normally carried out.In general, the concentration of metal scope about 10ppm to 1000ppm(in metal), this concentration all is fit to most of aldehyde reaction, be preferably adopt 10 to 500ppm, be more preferably 25 to 350ppm rhodium (in metal).
Proposed in front, hydroformylation process of the present invention is carried out having in the presence of the free phosphorus ligand, and promptly this part ligand and used rhodium coordination catalyst are not complexings.In general, free ligand is not necessarily identical with the phosphorus ligand of rhodium-phosphorus coordination catalyst, can use various ligand in given technology.For coordination catalyst, can arbitrary existing organic phosphine coordination body and function make free ligand, these ligands and preparation method are known in the prior art.This class free phosphorus ligand can comprise any development organic phosphine that is used for aldehyde reaction or organophosphite ligand so far.Certainly, if desired, also can use the mixture of this type of ligand.Like this, aldehyde reaction of the present invention can be carried out having in the presence of the excessive free phosphorus ligand, and for example, every mole of rhodium metal has one mole free phosphorus ligand to exist at least in reaction medium.The amount of used free phosphorus ligand, general only relevant with the product of required aldehyde and used alkene and coordination catalyst.Generally speaking, the amount of the free phosphorus ligand in reaction medium and the ratio of every mole of rhodium are about more than 1 to 300 the scope or 300, and this is fit to for most applications.For example, generally with a large amount of free triaryl phosphine ligands, as the ratio of triphenylphosphine ligand and every rhodium greater than 50, or be more preferably greater than 100, so that obtain satisfied catalytic activity and catalytic stability, and other phosphorus ligand, help the catalytic stability and the activity that reach suitable as alkylaryl phosphine and cycloalkyl aryl phosphine, and do not lower the yield that conversion of olefines becomes aldehyde, this situation is the free amount of ligand in reaction medium to be that every mole of rhodium is 1 to 100 mole, when being more preferably 15 to 60 moles.
In United States Patent (USP) 3,527,809; 4,148,830; 4,283,562; 4,400,548, Europe patent specification publication number 96,986; 96,987 and 96,988(is open in December 28 nineteen eighty-three); PCT patent application specification publication number WO80/01690(1980 August 21 is open) and U. S. application numbers 581,352(1984 applied for February 17) in the example of more special rhodium-phosphorus coordination catalyst and free phosphorus ligand is disclosed.Wherein ligand and coordination catalyst have preferably: United States Patent (USP) 3,527,809 and 4, triphenylphosphine ligand in 148,830 and rhodium-triphenylphosphine coordination catalyst, United States Patent (USP) 4,283, the two organophosphite ligands and the rhodium-two organophosphite coordination catalyst of the Application No. 581,352 of 562 rhodium-alkyl phenyl phosphine and rhodium-cycloalkyl Phenylphosphine coordination catalyst and application on February 17th, 1984.
Also once pointed out the front, aldehyde reaction is to carry out in the presence of the aldehyde condensation by-product that higher is arranged, producing the higher aldehyde by product (as dipolymer, trimer and tetramer) of boiling point in the aldehyde reaction process is the characteristic of the continuous aldehyde reaction of this class, as at United States Patent (USP) 4,148, in 830 and 4,247,486 explanation is more fully arranged.The byproduct of this aldehyde is the liquid-phase catalysis circulation technology, and a kind of good carrier is provided.Certainly, can when beginning, successive reaction use any suitable solvent (aldehyde cpd corresponding to desirable aldehyde product is better) when needing, main solvent is general to be made up of aldehyde product and the higher aldehyde condensation by-product of boiling point simultaneously, and this is the characteristics that are suitable for this class continuous processing.Certainly the aldehyde condensation by-product also can correspondingly be used.The limit of the amount that can exist at the higher aldehyde by product of reaction medium mid-boiling point can be very wide, generally only is subjected to equipment and the restriction of the product of the particular aldehyde that will produce.For example, when aldehyde reaction begins, can do not have or only have the higher aldehyde condensation byproduct of a spot of boiling point in the presence of (making the solvent of rhodium coordination catalyst) react, or reaction can be in 70%(weight), perhaps even under as many as 90% or the more condensation by-product carry out (in the amount of whole liquid phase mediums), in general, the ratio of the aldehyde condensation by-product that aldehyde and boiling point are higher, its scope is about 1: 4 to 4: 1(weight), big portion situation all is suitable for.Simultaneously, be understandable that, in reaction medium, also can have a spot of other known organic cosolvents when needing.
Although aldehyde reaction condition discussed above generally can change in wide range, but present method better is the total gas pressure at hydrogen, carbon monoxide and unsaturated olefin reaction raw materials is lower than 1500 pounds/square inch, preferably can be lower than 500 pounds/square inch, react under the situation of absolute pressure.The minimum stagnation pressure of reactant there is no particular determination, mainly only is decided by for will obtaining required speed of response, and the amount of necessary reaction mass.More specifically, the carbon monoxide pressure of tension of hydroformylation process of the present invention is better approximately from 1 to 120 pound/square inch, and more preferably approximately from 3 to 90 pounds/square inch, the hydrogen dividing potential drop is better approximately from 15 to 160 pounds/square inch, more preferably approximately from 30 to 100 pounds/square inch.H
2: the scope of the mol ratio of CO is approximately from 1: 10 to 100: 1 or higher, and better the mol ratio of hydrogen and carbon monoxide is approximately from 1: 1 to 10: 1.
The front pointed out yet that aldehyde reaction of the present invention can be carried out from 50 ℃ to 200 ℃ approximately in temperature of reaction.Generally speaking, the aldehyde reaction temperature is preferably about 90 ℃ to 110 ℃ approximately from 70 ℃ to 120 ℃.This is a temperature range preferably for most of olefin starting material.
Pointed out already, aldehyde reaction technology of the present invention is a relevant continuous liquid-phase catalysis circulating system, a part of liquid reactions aldehyde product solution shifts out from reactor in this system, contain the aldehyde product in this solution, dissolved rhodium-phosphorus coordination catalyst, the aldehyde condensation by-product that free phosphorus ligand and boiling point are higher, wherein required aldehyde product is through a step or multistep evaporation or distillation, at normal pressure, reduce pressure or add to depress from liquid-phase reaction solution and separate, condensation also collects a product collector, product can be further purified, the not evaporable catalyzer that contains liquid reacting product solution that stays is returned in the reactor if needed.Continuous hydroformylation system of this class and method are known by the people in known technology, need not give unnecessary details at this.In general, the aldehyde product of vaporization can be separated with any suitable gas-liquid separator, and the aldehyde product of vaporization is discharged on top, and the not evaporable that stays contains the liquid catalyst of reaction product solution, collect in the separator bottom, and Returning reacting system.Evaporation aldehyde product can carry out with any currently known methods.Better also can be with vaporizer or vaporizer, these equipment are influential to the residence time, the residence time weak point of these equipment can be avoided or reduce to greatest extent in the material of reaction product the more sensitive rhodium of ratio of specific heat-phosphorus coordination catalyst being produced the degree of decomposing, if can allow the aldehyde product at high temperature experience several minutes or be more preferably steam several seconds, to reduce damage to the more sensitive catalyzer of ratio of specific heat.Vaporization temperature in general can be up to 150 ℃ or higher, but vaporization temperature is better to be lower than 150 ℃ when possible, the example of suitable vaporizer comprises falling-film evaporator, thin-film evaporator, Rota-film evaporator, scrapes surface-type vaporizer etc., and is for referencial use with used in practice falling-film evaporator.Though the aldehyde product of vaporization can be from the residual not evaporable liquid catalyst that contains reaction product solution, with industrial use, complicated separating with the high gas-liquid separator of price, use a kind of uncomplicated capture separator but generally be preferably, the aldehyde product vapor is passed through on the top of this separator, with the required aldehyde product of last recovery.Usually also have the aldehyde product vapor by an entrainment treatment unit, this device has a demist plate, makes to be entrained in the steam and any liquid that shifts out is got back in the separator.But the catalyzer that contains reaction product solution that stays self-separation device bottom then reclaims simply and turns back to reaction system, if needed, can be before the Returning reacting system with liquid circulation by a water cooler, as falling film cooler, and/or if needed, after any other purifying or process catalyst regeneration step.In addition, hydroformylation process of the present invention also can comprise other any known treatment steps when needing, but does not influence novelty of the present invention, for example, from liquid reacting product solution, evaporate before the required aldehyde product, low-boiling-point substance flash distillations such as unreacted alkene, alkane, carbon monoxide, hydrogen.
Have now found that, the above-mentioned continuous liquid-phase catalysis circulation hydroformylation process of discussing, available selection separates and reclaims that contained phosphorus ligand is improved in the aldehyde product vapor of vaporization of this type of reaction, otherwise this ligand since volatilization lose with the aldehyde product of vaporization.In addition, it is that low dispersive liquid contacts well with the aldehyde product vapor of vaporization that improvement step of the present invention is with a kind of boiling point aldehyde condensation by-product more higher than boiling point, the phosphorus ligand of vaporization is condensed into the droplet of the phosphorus ligand of liquid, and reclaims said liquid phosphorus ligand.
As previously mentioned, from the aldehyde product stream of the isolated vaporization of liquid catalyst that contains aldehyde product solution, mainly contain the aldehyde product of vaporization, the phosphorus ligand of vaporization and the higher aldehyde condensation by-product of boiling point of vaporization, the concentration that is contained in ligand in the aldehyde product stream of above-mentioned vaporization and by product be stored in product liquid in the amount of ligand and by product relevant.Certainly, low-boiling-point substance that also may poor vaporization in the aldehyde product of said vaporization stream, as contain unreacted alkene, alkane, an oxidation carbonyl, hydrogen etc., but this is unimportant to the present invention.
The applicant now invents, contact completely with vaporization aldehyde product with a kind of suitable dispersion liquid, make the callable drop of the not only condensable one-tenth of phosphorus ligand of wherein contained vaporization, and with the method for amount of the used dispersion liquid of control, the percentage ratio that can make the phosphorus ligand of isolating is selectively apparently higher than the percentage ratio that is condensed from said vaporization aldehyde product stream equally with the higher aldehyde by product of isolating boiling point.Therefore unique distinction of the present invention is to separate and to reclaim contained phosphorus ligand in the aldehyde product stream of vaporizing selectively.And the amount of simultaneously that the boiling point that be separated by this method equally and reclaim is higher aldehyde product is reduced to minimum.
Though do not plan to make an explanation with the theory of what profundity, the phlegma that in the aldehyde product stream of vaporization, contains the phosphorus ligand of vaporizing, be because the aldehyde product stream of vaporization approximately is to contact with the dispersion liquid drop at its dew point to cause, and almost immediately with dispersive droplet evaporation or part evaporation, and aldehyde product stream is cooled to it below dew point, make the heavy component in the above-mentioned logistics, be that the higher aldehyde condensation byproduct of phosphorus ligand and boiling point is condensed into droplet, and can be reclaimed with arbitrary appropriate means.The ligand of this condensable vaporization and the inventive method of by product also can make the liquid phosphorus ligand and/or the higher aldehyde condensation by-product aggegation of boiling point that initially are entrained with become big and more segregative drop.
Used dispersion liquid can be any suitable liquid among the present invention, and this liquid evaporates or partly evaporation under the dew point of the aldehyde product stream of vaporizing when contacting with vaporization aldehyde product stream.Certainly, dispersion liquid should should be able to dissolve each other with aldehyde product and catalyst solution, so it can not produce bad influence to aldehyde product and catalyst solution, even ligand that will reclaim thus and by product turn back in the reactor system.Simultaneously, liquid should be pure preferably, and do not corrode used diverting device or reclaim the separator that required phosphorus ligand is used, be more preferably, dispersion liquid has satisfied volatility under the dew-point temperature of the aldehyde product stream of vaporization, under this dew-point temperature, dispersion liquid contacts with aldehyde product stream, even turn back in the reactor assembly, also can not be focused in catalyst solution influences catalyzer or its processing performance inadequately and need be provided with to separate and shift out step.
The example of this class dispersion liquid can comprise and contain to 3 to 20, be preferably 3 to 8 carbon atoms aldehydes, contain 3 to 20, be preferably the alcohols, water of 3 to 8 carbon atoms etc., if needed, above these mixtures of liquids of a class or a class also can be used.These flowing fluid ratios are preferably the product aldehyde that comprises the concrete hydroformylation process that relates to and the corresponding alcohol of product aldehyde, are best dispersion liquid with product aldehyde.For example, under the situation of producing propionic aldehyde, butyraldehyde and valeral, dispersion liquid is respectively propionic aldehyde, butyraldehyde and valeral preferably.Certainly, it should be understood that because C
3Generate the mixture of aldehyde with the hydroformylation of olefins technology of higher carbon bond, generate the mixture of butyraldehyde-n and isobutyric aldehyde as the propylene hydroformylation, when making dispersion liquid, generally just use the mixture of aldehyde, though also can use the aldehyde of one of them to make dispersion liquid separately when needing with product aldehyde.Also be like this when making dispersion liquid with the corresponding alcohol of product aldehyde.The general pure aldehyde product that preferably aldehyde reaction is obtained is at last made dispersion liquid and is used.Do like this and be easy to accomplish that the dispersion liquid that is provided can not produce detrimentally affect to aldehyde reaction.
The dispersion of the used dispersion liquid that contacts with the aldehyde product stream of vaporization can adopt different devices to finish and produce drop, because the size of drop is not strict in the present invention among the present invention.This class device comprises nozzle, fog nozzle, jet tray, orifice or any allied equipment.This device can have different design shape, its role is to make through dispersive liquid and from the liquid-phase catalyst that contains aldehyde product solution the logistics of isolated vaporization aldehyde product contact or mix.Generally, be preferably a kind of nozzle of use, this nozzle is encapsulated in the pipe or in the container, it can be used as the spray thrower of drop, and by this nozzle, aldehyde product stream can flow through, and can fully contact and mix with aldehyde product stream and make through dispersive liquid.In addition, although dispersion to dispersion liquid, can with the aldehyde product stream of the vaporization that flows into cocurrent flow, adverse current or cross-current to mode carry out, but preferably in pipeline, use nozzle, this nozzle has the aldehyde product stream of the isolated vaporization of liquid catalyst that contains aldehyde product solution from separator certainly, and the form of nozzle arrangement is to make dispersant liquid drop be adverse current to the steam flow of coming in.If needed, also available more than more than one nozzle.In addition, to the specific design of nozzle, do not have strict restriction, certainly, the aldehyde product that preferably can be easier to control dispersive liquid and vaporization flows contacted amount.Also have, flow the also not strict restriction of temperature of contacted dispersant liquid drop with the aldehyde product of vaporization, the temperature of dispersion liquid is very little to the influence of the recovery of the higher aldehyde condensation by-product of phosphorus ligand and boiling point, because contact with dispersion liquid and to reduce vapor temperature, major influence factors is owing to evaporating the cooling performance that dispersion liquid causes fully or partly.For this reason, being about 20 ℃ to 80 ℃ in most situation dispersion liquid temperature all is fit to.
Through cooled phosphorus ligand and the higher aldehyde condensation by-product of boiling point that obtains with the drop form, can adopt suitable vapour-liquid separator then, from the product stream of the vaporization that stays, separate and reclaim, preferably with a kind of separator that flow rate of liquid is reduced there, by gravity solution-air just takes place and separate, for example blade type impingement separator like this.Except this a kind of initial tripping device, preferably also adopt the entrainment treatment unit, so that make full use of recovery system, to increase total effect of recovery system.For example, aldehyde product evaporization process also can produce to be carried secretly adhering to of some catalyst solution, and the present invention can make the entrained drip of any steam product stream be gathered into big drop with dispersion liquid and the technology that the aldehyde product stream of vaporization contacts.Therefore, this entrainment treatment unit is the main additional unit of initial tripping device, can increase the solution-air separating effect.And, generally preferably use a kind of candle formula of removing mist to filter entrainment trap.Its effect is to collect any liquid droplets of staying in the vapour stream.Certainly, other entrainment tripping device commonly used or their coupling apparatus can be used for the present invention equally, for example, use common mechanism to change, and comprise the device of gravity, inertia impact, centripetal force, centrifugal force, pedesis etc.
The aldehyde product of isolated vaporization like this can pass through the top then, and be reclaimed by any way from the aldehyde condensate by product of the higher of the liquid phosphorus ligand of condensation and condensation.If needed, the above-mentioned aldehyde product that is recovered can be further purified with any method, as condensation or redistillation.What need emphatically point out is, is further purified the product of required aldehyde this moment, just more favourable and effective, and this is the subsidiary result who improves step of the present invention.
Then, be collected in separator bottom through the liquid phosphorus ligand of condensation with through the higher aldehyde condensation by-product of the boiling point of condensation, mode that can any needs is reclaimed.In general, mode is directly the liquid phosphorus ligand of condensation and the higher aldehyde condensation by-product of boiling point of condensation to be turned back in the used separator preferably, this separator is in order to isolate the aldehyde product of vaporization in the nonvolatile liquid-phase catalyst that contains product solution certainly, catalyzer is recycled and turns back to reactor system, so that the loss of costly phosphorus ligand reduces to minimum.
The present invention has found the method with the amount of the used dispersion liquid of control uniquely, condensation and the percentage ratio that separates phosphorus ligand from the aldehyde product stream of vaporization can be improved selectively, the percentage ratio that is condensed with the aldehyde condensation by-product of isolating boiling point minimum can be reduced to simultaneously.In addition, the ratio and the relative volatility that reclaim the phosphorus ligand aldehyde condensation by-product higher with reclaiming boiling point are relevant, and promptly the vapour pressure of higher aldehyde by product is relevant with the relative concentration that the ratio (vapour pressure with the aldehyde condensation by-product gets divided by the vapour pressure of phosphorus ligand) of the vapour pressure of the phosphorus ligand of being correlated with reaches each composition in the aldehyde product method of vaporization.The higher aldehyde condensation by-product of mid-boiling point of the present invention can be about 10 to 5,000 for the relative volatility scope of phosphorus ligand.
As from through finding out that the relative volatilization that the higher aldehyde condensation by-product of boiling point is compared with phosphorus ligand is high more the example that calculates, the ratio of percentage ratio that then reclaims the percentage ratio of the phosphorus ligand aldehyde condensation by-product higher with reclaiming boiling point is also high more.In addition, for the vaporization aldehyde product of certain flow stream, the amount of used dispersion liquid low more (using 1 pound of dispersion liquid as 1,000 pound of aldehyde product vapor stream) the then ratio of the higher aldehyde condensation by-product rate of recovery of the rate of recovery and the boiling point of phosphorus ligand is also big more.
Therefore, the ratio of the higher aldehyde condensation by-product rate of recovery of control and the vaporization aldehyde product amount that the flows contacted dispersion liquid phosphorus ligand rate of recovery that can in a very wide processing range, obtain broad and boiling point.This makes the present invention can be fit to arbitrary given situation.For example, in a hydroformylation process, the amount of the free ligand in the system is very little, be less than 70 moles ligand and require the higher aldehyde condensation by-product of boiling point in the reactant solution to keep lower concentration as every mole of rhodium, as be about 0.25 to 2% weight, the present invention can in aldehyde product autoreaction thing solution, evaporate and separation period between, return the method for system by selectable recovery and circulation, make the loss amount of ligand reduce to minimum, can make the phosphorus ligand that contains high percent in the aldehyde product stream of vaporization, and the percentage ratio that is contained in the aldehyde condensation by-product of the higher in the vaporization aldehyde product stream can be limited in minimum simultaneously, recovery and circulation along with the liquid ligand, this aldehyde condensation by-product equally is recovered and circulates, and like this, helps to avoid producing the higher aldehyde condensation by-product of unwanted boiling point in system.
Therefore, when the relative volatility of comparing with phosphorus ligand when the higher aldehyde condensation by-product of boiling point is relatively lower, for the percentage recovery that reaches higher ligand ratio, then the amount of dispersion liquid to be reduced widely the percentage yield of the higher aldehyde condensation by product of boiling point.
In general, in of the present invention improving one's methods, the amount of employed dispersion liquid preferably be enough to make the percentage of isolated phosphorus ligand from vaporization aldehyde product stream be at least 1.2 times to, be more preferably at least 1.5 times of percentage ratios to the higher aldehyde condensation by-product of same separated boiling point.Certainly, be understandable that, high like that in the example that the result of gained generally is not so good as to be calculated in practice, however select top condition and running parameter, to obtain best result, much relations are arranged with the experience of using improvement technology of the present invention.For a certain specified criteria, only need very a spot of test, just can reach optimal results.For example, per hour generally can consider 5 to 60, preferably 10 to 40 pounds dispersion liquid is 1000 pounds a vaporization aldehyde product stream to flow per hour, can obtain the ratio of the rate of recovery of the higher aldehyde condensation by-product of the higher phosphorus ligand rate of recovery and boiling point under most situation.
In addition, if needed, vaporization aldehyde product stream and the contacted improvement technology of dispersion liquid involved in the present invention, separate selectively and reclaim wherein contained phosphorus ligand with a kind of dispersion liquid, also separate simultaneously and reclaim the higher aldehyde condensation by-product of boiling point, equally also available gasiform aldehyde product stream carries out when needing, when this logistics with gaseous state when reactor comes out, can in gas phase circulates hydroformylation process, carry out in order to obtain similar effects.
Following example is to be used for explaining the present invention, rather than to a kind of restriction of the present invention.Except that specializing, all hereinafter and the umber of being mentioned in the claim, percentage ratio, all by weight.
Example 1-6
To containing 97.7%(weight) propionic aldehyde, 0.5%(weight) the higher aldehyde condensation by-product of boiling point, and phosphorus ligand, the surplus of different amounts (ppm) are light component, relevant steam as unreacted alkene, alkane, hydrogen and carbon monoxide has carried out series of computation, described vapour stream contacts with dispersion liquid propionic aldehyde (40 ℃) under the cloud point temperature, propionic aldehyde sprays from nozzle, and per hour the propionic aldehyde amount changes with respect to the flow of the aldehyde product stream of per hour 1000 pounds of vaporizations.The relative volatility that the higher aldehyde condensation by-product of boiling point is as calculated compared with phosphorus ligand, and the percentage number average of the aldehyde condensation by-product of the percentage ratio of the phosphorus ligand that can separate from the aldehyde product stream of vaporization and reclaim as calculated and higher is listed in the table 1.
Table 1
The isolated aldehyde of joining that the used liquid vapour stream of example ligand relative separation goes out contracts
The amount of body
1The dew point volatility
2Position body weight % closes by product wt%
15 pound 117 148 55 2 of 1 PDPP*
50 pound 117 148 98 45 of 2 PDPP*
10 pound 115 260 49 1 of 3 CHDPP*
40 pound 115 260 98 40 of 4 CHDPP*
10 pound 133 1,730 44 0.1 of 5 TPP***
50 pound 133 1,730 96 0.5 of 6 TPP***
1. the poundage of the used liquid of flow of the aldehyde product of per 1000 pounds of vaporizations
2. the aldehyde condensation by-product is to the relative volatility of used ligand
* PDPP=propyl group diphenylphosphine (100ppm)
* CHDPP=cyclohexyl diphenylphosphine (50ppm)
* * TPP=triphenylphosphine (30ppm).
Example 7-10
To containing 87.6%(weight) butyraldehyde, 0.3%(weight) the higher aldehyde condensation by-product of boiling point and various phosphorus ligands, the surplus of different amounts (ppm) be light component, carried out series of computation as the various vapour streams of unreacted alkene, alkane, hydrogen and carbon monoxide.Described vapour stream contacts with dispersive liquid butyraldehyde (40 ℃) under dew-point temperature, and butyraldehyde liquid sprays from nozzle, and per hour the butyraldehyde amount is different with respect to the aldehyde product stream of per hour 1000 pounds of vaporizations.The higher aldehyde condensation by-product of boiling point as calculated is to the relative volatility of phosphorus ligand, and the percentage ratio that is contained in the phosphorus ligand that also can from the aldehyde product stream of vaporization, separate and reclaim in the described vapour stream of calculating, with the corresponding percentage ratio that is contained in the higher aldehyde condensation by-product of boiling point separable and that reclaim in the described steam of calculating, all list in table 2.
Table 2
The isolated aldehyde of joining that the used liquid vapour stream of example ligand relative separation goes out contracts
The amount of body
1The dew point volatility
2Position body weight % closes by product wt%
10 pound 146 224 32 0.2 of 7 PDPP*
60 pound 146 224 93 2 of 8 PDPP*
10 pound 138 375 38 0.2 of 9 TPP**
60 pound 138 375 99 3 of 10 TPP**
1. the poundage of the used liquid of flow of the aldehyde product stream of per 1000 pounds of vaporizations
2. the aldehyde condensation by-product is to the relative volatility of used ligand
* PDPP=propyl group diphenylphosphine (125ppm)
* TPP=triphenylphosphine (50ppm).
Example 11-16
To containing 91.8%(weight) valeral, 0.5%(weight) the higher aldehyde condensation by-product of boiling point and various phosphorus ligands (ppm), the surplus of different amounts be light component, as unreacted alkene, alkane, the different vapour stream of hydrogen and carbon monoxide has carried out a series of calculating, described vapour stream contacts with dispersive liquid valeral (40 ℃) under dew-point temperature, valeral liquid sprays from nozzle, and per hour the amount of valeral is different with respect to the flow of the aldehyde product stream of per hour 1000 pounds of vaporizations.The higher aldehyde condensation by-product of boiling point as calculated is to the relative volatility of phosphorus ligand, and the percentage ratio that is contained in the phosphorus ligand that also can from the aldehyde product stream of vaporization, separate and reclaim in the described steam that calculates, with corresponding calculate be contained in the percentage ratio that the higher aldehyde condensation by-product of boiling point in the described steam is separable and reclaim, all list in table 3.
Table 3
The isolated aldehyde of joining that the used liquid vapour stream of example ligand relative separation goes out contracts
The amount of body
1The dew point volatility
2Position body weight % closes by product wt%
10 pound 145 15 47 14 of 11 PDPP*
50 pound 145 15 91 68 of 12 PDPP*
10 pound 144 18 53 16 of 13 CHDPP**
40 pound 144 18 90 60 of 14 CHDPP**
10 pound 149 80 53 3 of 15 TPP***
50 pound 149 80 98 52 of 16 TPP***
1. the poundage of the used liquid of flow of the aldehyde product of per 1000 pounds of vaporizations
2. the aldehyde condensation by-product is to the relative volatility of used ligand
* PDPP=propyl group diphenylphosphine (150ppm)
* CHDPP=cyclohexyl diphenylphosphine (100ppm)
* * TPP=triphenylphosphine (80ppm).
Example 17
In a continuous liquid phase circulating aldehyde process, butene-1 and carbon monoxide and hydrogen hydroformylation generate aldehyde, have been reflected at rhodium-phosphorus coordination catalyst, free cyclohexyl diphenylphosphine ligand and the higher C of boiling point
5Carry out more than three days under the existence of aldehyde condensation by-product.Contain C
5The rhodium catalyst of aldehyde product reaction soln is evaporated after shifting out from hydroformylation reactor, obtains the C through vaporization
5Aldehyde product stream estimates to contain 91.8%(weight) valeral and the C of 2 methyl butyraldehyde
5Aldehyde mixture, 0.35%(weight) the higher C of boiling point
5Aldehyde condensation by-product and 100ppm cyclohexyl diphenylphosphine ligand, this product stream is the reaction soln that contains from staying in a separator, separates in the unevaporated liquid catalyst.Described reaction soln recirculation is returned in the hydroformylation reactor.The C that boiling point is higher
5The aldehyde condensation by-product is 18 to the relative volatility of the cyclohexyl diphenylphosphine ligand in the described solution.The C of described vaporization
5The aldehyde product circulates into a pipe, (condensation and backflow) the liquid C behind some purifying
5The aldehyde product is under 40 ℃, through a nozzle, with the C of vaporization
5Aldehyde generates the mode that logistics is adverse current and is sprayed onto in the pipe, and speed be to flow per hour about 26 pounds C for 1000 pounds the aldehyde product of vaporization per hour
5The aldehyde product.
C
5The liquid droplets of aldehyde is volatilized, and makes C
5Aldehyde product vapor stream is cooled under its dew point, forms cyclohexyl diphenylphosphine ligand and the higher C of boiling point
5The droplet of aldehyde condensation by-product.The steam that contains the described droplet that is condensed feeds a gas-liquid separator.Steam filters entrainment trap through a candle formula of removing mist then, thereby isolate the C of vaporization in described phlegma at first by a blade type impingement separator in separator
5Aldehyde product stream, these droplets are collected from the bottom of described gas-liquid separator, and through in the pipe, are circulated to separator, the C that vaporizes in this separator
5The aldehyde product is separated with the unevaporated liquid catalyst that contains reaction product solution.Separated C
5After leaving described gas-liquid separator, aldehyde product stream gives condensation, so that reclaim thick C
5The aldehyde product.Analyze thick C
5The different samples of aldehyde product show, contain cyclohexyl diphenylphosphine and about 0.23 to the 0.33%(weight of the 26ppm that has an appointment) the higher C of boiling point
5The aldehyde condensation by-product.These analyses are pointed out, about 74% cyclohexyl diphenylphosphine ligand and the higher C of about boiling point of 6 to 34%
5The aldehyde condensation by-product is from the C of vaporization
5Separated and shift out in the aldehyde product stream, and C that should vaporization
5Aldehyde product stream is isolating from the liquid catalyst that contains reaction product solution.
When using C
5The product liquid of aldehyde and when slightly aldehyde product liquid spray carries out aldehyde reaction, then can find to contain cyclohexyl diphenylphosphine and the about 0.35%(weight of 100ppm) the higher C of boiling point
5The aldehyde condensation by-product.
To various improvement of the present invention with to change for the experienced staff of this professional domain is conspicuous, so this class is improved and is changed in the authority that should be included in this specification sheets and in the main points and scope of claims.
Claims (7)
1, a kind ofly produce the catalytic hydroformylation process of liquid phase circulation rhodium that aldehyde is used, wherein, olefin(e) compound, carbon monoxide and hydrogen are at dissolved rhodium-phosphorus coordination catalyst, react under the existence of the aldehyde condensation by-product that free phosphoric acid position body and boiling point are higher and generate the aldehyde resultant, described aldehyde is from containing the aldehyde resultant, dissolved rhodium-phosphorus coordination catalyst, separate in the solution of the liquid reactive aldehyde resultant of the aldehyde condensate that free phosphorus ligand and boiling point are higher and reclaim, step is to shift out said aldehyde resultant solution from hydroformylation reactor, evaporate aldehyde resultant contained in the described solution and obtain an aldehyde generation logistics of vaporizing, this aldehyde generates logistics basically by the aldehyde resultant, the phosphorus ligand of vaporization and the higher aldehyde condensation by-product of boiling point of vaporization are formed, the generation logistics of this aldehyde is separated with the unevaporated catalyzer that contains the liquid phase reaction resultant solution that stays in a separator, catalyzer self-separation device bottom is reclaimed, and circulation turns back in the reaction system
Its improvement part is that the aldehyde that (a) separates described vaporization selectively generates contained phosphorus ligand in the logistics, it is low dispersion liquid that method is to use the higher aldehyde condensation by-product of the more described boiling point of a kind of boiling point, making itself and described aldehyde generate logistics contacts fully, thereby make aldehyde generate the phosphorus ligand of vaporization contained in the logistics and the higher aldehyde condensation by-product condensation of boiling point of vaporization in above-mentioned vaporization, (b) obtain in the aldehyde generation logistics of recovery by described vaporization, phosphorus ligand that is condensed and the higher aldehyde condensation by-product of the boiling point that is condensed, described dispersive liquid uses with droplet form, and its consumption uses the per hour dispersion liquid of 5-60 pound for 1000 pounds the aldehyde of vaporization per hour generates logistics.
2,, it is characterized in that olefin(e) compound is the alkene that contains 2 to 8 carbon atoms according to the method for claim 1.
3, according to the method for claim 2, the consumption that it is characterized in that dispersion liquid uses per hour about 10 to 40 pounds dispersion liquid for 1000 pounds the aldehyde of vaporization per hour generates logistics.
4,, it is characterized in that phosphorus ligand is three organic phosphine compounds according to the method for claim 3.
5,, it is characterized in that ligand is a triphenylphosphine according to the method for claim 4.
6,, it is characterized in that ligand is the cyclohexyl diphenylphosphine according to the method for claim 4.
7, according to the method for claim 3, it is characterized in that generating isolated the logistics, the phosphorus ligand of condensation and the higher aldehyde condensation by-product of boiling point of condensation through reclaiming from the aldehyde of vaporization, separator is returned in circulation, separates in the liquid-phase catalyst of not vaporizing of the self-contained resultant solution that responds of aldehyde generation logistics of vaporizing described in this separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101904 CN1020719C (en) | 1984-03-30 | 1985-04-01 | Process for recovery of phosphorus ligand from vaporized aldehyde |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59540884A | 1984-03-30 | 1984-03-30 | |
| CN 85101904 CN1020719C (en) | 1984-03-30 | 1985-04-01 | Process for recovery of phosphorus ligand from vaporized aldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101904A CN85101904A (en) | 1987-01-17 |
| CN1020719C true CN1020719C (en) | 1993-05-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101904 Expired - Lifetime CN1020719C (en) | 1984-03-30 | 1985-04-01 | Process for recovery of phosphorus ligand from vaporized aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1020719C (en) |
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1985
- 1985-04-01 CN CN 85101904 patent/CN1020719C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN85101904A (en) | 1987-01-17 |
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