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Definitions

• TITLE PROCESS FOR THE PRODUCTI ON OF ALDEHYDES
• the present invention relates to a process for the production of aldehydes from alpha-olefins. More specifically, the invention relates to a process for producing aldehydes from alpha-olefins by use of rhodium-containing catalysts.
• a process using cobalt catalyst has been used commercially to form aldehydes, i.e., the socalled "cobalt oxo process".
• cobalt oxo process a cobalt catalyst is mixed with alpha-olefin, carbon monoxide, and hydrogen in a ligand phase. Under high temperature and pressure, a hydroformylation reaction occurs to form aldehydes containing one more carbon atom than the olefin.
• the cobalt catalyst is then separated from the reaction mixture by chemical reaction and the catalyst is subsequently regenerated prior to recycle back to the original reaction vessel for further treatment with fresh alphs-olefin, hydrogen and carbon monoxide.
• the aldehyde is then separated by distillation. This aldehyde is converted subsequently to a dimer aldehyde, e.g., butyraldehyde from propylene is converted to 2-ethyl hexanal, by aldol condensation. In this process, only normal mono-aldehydes are useful for the aldol condensation step.
• the cobalt oxo process is, however, subject to a number of disadvantages.
• the process requires high temperatures and pressures.
• a number of side reactions occur resulting in a relatively high proportion of undesirable branched chain mono-aldehydes, a high proportion of paraffin and unwanted alcohols.
• the cobalt catalyst tends to decompose during the process, and typically 10%-20% of the cobalt is lost with each pass of the catalyst through the reaction system.
• One commercial multi-step process for the manufacture of higher alcohols is via hydroformylation of high purity, lower molecular weight olefins.
• olefin containing n carbon atoms is converted to an aldehyde with n+1 carbon atoms, followed by external condensation t aldehydes containing 2 (n+1) carbon atoms.
• high purity propylene may be distilled from a steam cracked material, (2) this propylene is hydroformylated to butyraldehydes,
• n-butyraldehyde is then separated from the mixture of isomers and subsequently, (4) n-butylaldehyde is condensed to 2-ethyl hexenal, (5) 2-ethyl nexenal is then hydrogenated to the saturated aldehyde, and finally (6) 2-ethyl hexenal is reduced to the desired 2-ethyl hexanol (2-EH) containing eight carbon atoms.
• 2-EH is a major raw material for the preparation of phtalic acid esters which are used as plasticizers and the like.
• Another commercial multi-step process for the manufacture of higher oxoalcohols is via hydroformylation of higher olefins.
• lower molecular weight olefins must be first polymerized.
• catalytic or steam cracked propylene/butene-1 mixtures are polymerized to the desired extent, the higher molecular weight c 6 -C 13 olefins are then distilled to obtain feedstocks having the desired olefin in purified form and these feedstocks are subjected to hydroformylation individually to C 7 -C 14 aldehydes. These aldehydes are then hydrogenated to the corresponding oxo alcohols.
• cobalt catalyst is used commercially for this route because higher olefins obtained via polymerization step are branched, which branched olefins cannot be easily and economically hydroformylated using rhodium catalysts.
• Cobalt and rhodium are both used commercially as catalysts in the hydroformylation step for the first multi-step process described above.
• the high cost of high purity feed for this process in addition to the limited commercial availability of pure feed, has restricted its use in the manufacture of 2-ethyl hexanol starting with propylene feed.
• 3-methylpentanol may be manufactured from pure ethylene feed in a similar fashion, the high cost of ethylene has made this route economically unattractive.
• the multi-step rhodium based oxo process has had severe problems when using liquid phase reaction conditions with a homogeneous rhodium catalytic complex because of the difficulties encountered in separating aldehyde product from the liquid phase reaction media.
• these problems arise because the normal aldehydes of interest, e.g., C 8 -C 13 aldehydes, require elevated temperatures for sufficient volatilization so that they can be removed from the liquid reaction media by distillation, stripping or the like.
• the rhodium based oxo processes of the prior art suffer from destablization, decomposition, deactivation or loss of selectivity.
• Pruett et al. in U.S. Patent No. 3,527,809 disclose a process in which an alpha-olefin is contacted with carbon monoxide and hydrogen in the presence of a rhodium-containing complex catalyst and tertiary organo-containing ligands.
• British Patent No. 1,387,657 discloses a process for hydroformylation of an olefin containing up to five carbon atoms in which the olefin is catalytically reacted with hydrogen and carbon monoxide in a primary reaction zone so that an aldehyde or aldehyde and alcohol is produced and some olefin remains unconverted.
• the aldehyde or aldehyde and alcohol produced is withdrawn from the reaction mixture as vapor along with other gases, including unconverted olefin. The gases thus withdrawn are separated.
• Part of the separated gases, including some unconverted olefin, are then recycled to the primary reaction zone, the other part of the unconverted olefin is hydroformylated in a secondary reaction zone and further aldehyde dor aldehyde and alcohol product is separated from the secondary reaction zone without further recycling of the remaining separated gases.
• Other variations of such processes are described in British Patent No. 1,228,201 and Wilkinson U.S. Patent No . 4 , 108 , 905 .
• 3,511,880 discloses a process in which an olefin is converted to n+1 aldehydes by hydroformylation in the presence of carbon monoxide and hydrogen in a liquid phase reaction medium containing a Group VIII noble metal, a biphyllic ligand and, for example, an alkali metal hydroxide.
• 3,821,311 teaches a single-stage process in which an alpha-olefin is reacted with hydrogen, carbon monoxide and a liquid solution phase comprising (a) a hydroxylic organic solvent, (b) a rhodium complex, (c) a triaryl phosphine, triaryl arsine or triaryl stibine and (d) an aldol condensation catalyst, such as KOH.
• the desired product is said to be a saturated aldehyde containing
• 3,278,612 to Greene discloses a process for the production of C n+ 1 and C 2n+ 2 alcohols from C n olefins in the presence of certain complex transition metal-phosphorouscontaining catalytically active materials, including certain cobalt, rhodium and ruthenium complexes, in systems containing certain organic Lewis bases, i.e., electron-sharing doners, such as amines.
• None of the above prior art processes provides a one-step reaction for the production of the aldehydes containing 2n+2 carbon atoms from the alpha-olefins containing n carbon atoms in which one can readily recover the product as a vapor.
• Such a one-step reaction process is highly desirable since the higher molecular weight materials are, in many cases, the ultimate product which is sought from the hydroformylation process.
• the aldehyde containing n+1 carbon atoms are first separated from the reaction mixture and subsequently an aldol condensation with the n+1 aldehyde is conducted for form the aldehyde containing 2n+2 carbon atoms. If desired, hydrogenation to the alcohol can then also be carried out.
• tripenyl phosphine based rhodium-containing complex catalyst Most of these prior techniques employ a tripenyl phosphine based rhodium-containing complex catalyst, and they are therefore also subject to a number of other disadvantages.
• the triphenyl phosphine based rhodium catalysts are subject to some degree of decomposition, expecially at higher temperatures, e.g., about 125-135oC. Since rhodium is extremely expensive, even a small amount of decomposition is very undesirable. Also, even at lower temperatures, the rhodium catalysts are subject to deactivation because of the presence of acid.
• rhodium based catalyst systems have generally provided more efficient production of aldehyde than cobalt, e.g., the reaction rate with Rh-based catalyst can be about 1000 times as fast as with a Co-based catalyst, rhodium is much more expensive than cobalt and is likely to increase in cost as more and more processes switch from cobalt to rhodium. Moreover, any deactivation or decomposition of the Rh-catalyst is extremely disadvantageous. Thus, methods which produce the desired aldehyde product in one step while decreasing rhodium decomposition or deactivation are extremely desirable both from an efficiency and from an economic point of view.
• aldehydes can be produced in a one-stage reaction in which at least one alphaolefin containing n carbon atoms, wherein n is an integer of 2 or greater, is reacted in the liquid phase with a mixture of carbon monoxide and hydrogen in the presence of complex rhodium-containing catalyst, free ligand and Lewis base to thereby form aldehyde containing 2n+2 carbon atoms, wherein the reaction is conducted at a temperature and pressure sufficient to remove at least part of the product from the reaction mixture by vaporization or stripping, i.e., by product flash-off.
• n+1 aldehydes having an improved normal to iso isomer ration and that improved stabilization of a rhodium based catalyst are provided by a process in which at least one alpha-olefin containing n carbon atoms, wherein n is an integer of 2 or more, is reacted in the liquid phase with a mixture of carbon monoxide and hydrogen in the presence of complex rhodium-containing catalyst not containing halogen, free ligand and Lewis base to thereby form the aldehyde containing n+1 carbon atoms, wherein the reaction is conducted at a temperature and pressure sufficient to remove at least part of the product from the reaction mixture by vaporization or stripping .
• up to about 60% of the olefin is converted to aldehyde product in one pass through the reactor system.
• the first of these processes provides a one-stage reaction of the production of aldehydes containing 2n+2 carbon atoms by a product flash-off technique.
• the rhodium catalyst does not have to leave the reactor vessel and, accordingly, there is less chance of lost of the rhodium catalyst or of poisoning of the catalyst because the rhodium is "protected" by a continuous olefin partial pressure.
• the presence of the Lewis base has been found to stabilize the rhodium catalyst, resulting in less chance of a catalyst deactivation caused by acid and water present in the reaction mixture.
• the alpha-olefins suitable for use in the present invention include those containing from 2 to 12 carbon atoms, e.g., ethene, propene, butene-1, pentene-1, hexene-1 and octene- 1. Mixtures of such olefins can also be used.
• the alpha-olefin can be a mixture of propene and butine-1; a mixture of ethene and propene: and/or a mixture of propene and pentene-1.
• the presence of acid in the hydroformylation reaction mixture causes deactivation of the rhodium-containing catalyst.
• the CO partial pressure has a detrimental effect on the rhodium-containing catalyst activity.
• the water from the condensation of the aldehydes to the trimer glycol ester by-product can react with CO to produce formic acid.
• Suitable bases for includsion in the reaction mixture of the present invention include Lewis bases, e.g., inorganic bases such as KOH and organic bases such as triethanol amine.
• Lewis bases e.g., inorganic bases such as KOH
• organic bases such as triethanol amine.
• the aldol condensation reaction is desired to produce the aldehydes containing 2n+2 carbon atoms from the olefin starting materials via the aldol condensation reaction, the base should be an effective basic aldol condensation catalyst.
• Suitable such aldol cndensation catalysts include the alkali metal and alkaline earth metal oxides and hydroxides such as KOH, NaOH and Sr(OH) 2 and stronger organic bases such as tetrabutyl phosphonium acetate, which if used can also act as the solvent for the reaction mixture.
• the concentration of the base in the reaction mixture can vary greatly and should be in an amount effective to stabilize the rhodium-containing catalyst or if desired, in an amount effective to catalyze the aldol condensation t the aldehyde dimer product. If only stabilization of the catalyst is desired, of course, a lower concentration of the base is desirable. If the dimer aldehyde is the product desired, a higher concentration of base is normally chosen.
• any rhodium-containing catalyst not containing halogen which is stable at the desired reaction temperature and conditions can be used.
• a temperature of only about 90oC. at appropriate pressure is required and therefore any rhodium-containing catalyst not containing halogen known in the art to be stable at this temperature will be appropriate.
• Such non-halogen containing rhodium catalysts provide higher n/i isomer ratios than those catalysts which contain halogen, which n/i ratios are even further improved in the presence of the Lewis base.
• any rhodium-containing catalyst thermally stable at the desired reaction temperature will be suitable.
• rhodium-containing catalysts not containing halogen are also preferred in the process of the invention.
• the rhodium-containing catalysts in the processes of the present invention should also have a sufficient reaction rate with the olefin at the desired temperature to make the reaction process economically feasable.
• the rhodium-containing catalyst should also be one that will produce a high normal to iso isomer ratio for the product of the process, e.g., a normal to iso molar ratio of at least about 5/1 and preferably from about 5/1 to about 90/1.
• a rhodium-containing catalyst which is thermally stable at the desired reaction temperatures must be used.
• the reaction temperature should be about 130oC. at an appropriate pressure, and accordingly, the rhodiumcontaining catalyst should be stable at this temperature.
• rhodium-containing catalysts for operating the process of the invention in the temperature range of from about 100oC. to 125oC. include, for example, RhHCO(PPh 3 ) 3 and RhHCO(AsPh 3 ) 3 in which Ph represents a phenyl group.
• the preferred catalysts are, however, those which exhibit high thermal stability. These thermally stable catalysts include
• n is an integer of two or more, as the ligand is also suitable higher temperature reactions.
• concentration of rhodiumcontaining catalyst in the reaction mixture can vary greatly, e . g., from about 10 ppm to about 10,000 ppm. preferably from about 20 ppm to about 5,000 ppm.
• the product flash-off processes of the present invention can employ any organic solvent in which the base is sufficiently soluble to allow the desired reaction t occur.
• Suitable solvents include tributyl phosphate, pentadiol, tetrabutyl phosphonium acetate, trimer glycol ester (i.e., the timer by-product of the aldol condensation reation) and diethylene glycol.
• the reaction mixture employed in the processes of the present invention also preferably contains free ligand.
• This ligand is not necessarily the same ligand that is attached to the complex rhodium-containing catalyst.
• suitable ligands include any ligands that are capable of complexing with rhodium to form a rhodium-containing catalyst which is stable at the temperature at which the reaction will be run.
• Suitable such ligands for the higher temperature product flash- off process of the present invention include [Rh(CO) 3 (PPh 3 ) 2 ] + BPh 4 -, Ph 2 P(CH 2 ) n P + Ph 2 (CH 2 P)Bph 4 - and Ph 2 P(CH 2 ) n SiR 3 wherein
• Ph represents a phenyl group: n is an integer of 2 or more, preferably, from 2 to 6; and R is an alkyl group.
• ligands which will complex with the rhodium may be used, e.g., triphenyl phosphine and tripenyl arsine.
• concentration of the ligand in the reaction mixture can vary depending upon the concentration of the catalyst to form a desirable range of ligand to catalyst molar ratios.
• the ligand to rhodium molar ratio can vary from about 2/1 to about 2000/1 and preferably from about 2/1 to about 1000/1.
• Carbon monoxide and hydrogen can be fed into the reaction vessel at various pressures depending upon the product that is desired from the reaction.
• the molar ratio of hydrogen to carbon monoxide is a factor which helps determine the product produced by the product flash-off technique of the present invention.
• the molar ratio of H 2 to CO in the process of the present invention can vary from about .5/1 to about 50/1 and preferably from about 2/1 to about 15/1.
• more hydrogen will be required for a simple hydroformylation than for a hydroformylation-aldol condensation process since excess hydrogen is necessary to react with the enal form which is produced by the latter process. This is illustrated by the following reaction formulas:
• the temperature range used in the processes of the present invention varies depending upon the reactants used, the termal stability of the rhodium-containing catalyst, and the product desired from the reaction.
• the temperature should be sufficient to remove at least part of the product from the reaction mixture by vaporization or stripping at a desired process pressure condition.
• Typical temperature ranges for the process of the present invention are from about 90 to 200oC, preferably 100 to 200o, such as from about 120 to about 180oC.
• a temperature of about 140oC. and pressure about 150 psi can be used.
• the pressure ranges for the processes of the present invention can vary depending upon the reactants used and the products which are desired therefrom.
• a lower pressure is desired, e.g., a pressure of from about 50 psi to about 700 psi and preferably from about 50 psi to about 400 psi.
• the combined temperature and pressure conditions for the product flash-off technique should be such that the desired aldehyde product will be stripped or vaporized by the feed gases at a rate corresponding to the product's formation.
• the product flash-off processes of the present invention can be controlled to produce either the aldehydes containing n+1 carbon atoms or the aldehydes containing 2n+2 carbon atoms by employing a proper concentration of rhodium and/or basic aldol catalyst.
• rhodium catalyst concentrations with a relatively higher base concentration produce predominantly aldehydes containing 2n+2 carbon atoms
• higher rhodium catalyst concentrations with a relatively low base concentration produce predominantly aldehyde containing n+1 carbon atoms.
• any factors that affect the ratio of the hydroformylation reaction or aldol condensation reaction will also have an effect on the product that is formed.
• the rhodium catalyzed hydroformylation rates are increased with higher hydrogen pressures and decreased with higher CO partial pressures and higher ligand concentrations.
• the rate of aldol condensation is affected by the solvent used. Therefore, any changes in this factors will have an effect on the product produced.
• Figure 1 is a schematic representation of an apparatus for performing a "product flash-off" process in accordance with the present invention.
• reactor 1 contains a liquid reaction medium 2 which includes base, an appropriate rhodium-containing catalyst and free ligand.
• the reaction medium 2 is maintained at a temperature sufficient to vaporize or strip any of the desired product that is formed at the reaction pressure.
• CO and H 2 are introduced through line 3 and alpha-olefin through line 4 into the reactor 1.
• the CO, H 2 and alphaolefin are dispersed in the reaction medium by use of a sparger 5.
• the reaction medium 2 is also stirred vigorously with stirrer 6.
• the alpha-olefin disperses through the reaction medium, it is converted into the desired product, and along with unreacted CO, H 2 and olefin, the product is directed through line 7 to a condensor 8.
• the condensable product is condensed before entering gas-liquid separator 9.
• the non-condensable gases, such as unreacted CO, H 2 and alpha-olefin, are withdrawn from the top of the separator 9 and recycled back via line 10 and compressor
• the condensable product including the desired aldehyde
• the condensable product is continuously discharged from the base of the separator 9 and passes to a secondary liquid-liquid separator 14 via line 13.
• the solvent upon settling, is separated by phase separation and discharged from the separator by line 15.
• the solvent containing the major portion of the water produced by the reaction is dried in a bed 17 via pump 16 to remove its water.
• the solvent is combined with make-up solvent introduced by line 18, which solvent is recovered from the aldehyde product.
• the aldehyde product is collected from the liquid-liquid separator 14 via line 19.
• the condensable product is transferred via line 13 to a distillation column (not shown) where separation of aldehyde and solvent is conducted.
• the solvent recovered from the distillation is recycled back to reactor 1 and steps 14-17 are eliminated.
• the reaction mixture is analyzed by gas chromatography.
• Example 1 The procedure of Example 1 is repeated using RhHCO(PPh 3 ) 3 as a catalyst, a reaction temperature of 100oC., and an olefin feed of about 20 g.
• the solvent (60-70 cc.), reaction time, and olefin charge are varied as indicated in columns 2-4 of Table II below.
• the results are analyzed as in Example 1 and are set forth in columns 5-7 of Table II.
• a 300 cc capacity autoclave is charged with 20.3 grams of butene-1, 73.2 grams of diethylene glycol (DEG), 1 gram of KOH, 3.95 grams of diphenyl phosphino ethyl trimethyl silane and 0.097 grams of tris-(diphenyl phosphino ethyl trimethyl silane) rhodium carbonyl hydride.
• DEG diethylene glycol
• KOH potassium phosphino ethyl trimethyl silane
• tris-(diphenyl phosphino ethyl trimethyl silane) rhodium carbonyl hydride The air in the autoclave is flushed out with nitrogen, while the contents of the autoclave are stirred with a turbine sparger at 1500 rpm.
• the reactor is then heated to about 140oC.
• the autoclave is pressurized with a 4/1-H 2 /CO molar ratio synthesis gas (CO and H 2 ) to about 500 psig.
• the agitation is resumed and simultaneously a preblended synthesis gas having a H 2 /CO molar ratio of 1.5/1.0 is admitted to the reactor.
• the run is concluded after 8 minutes starting from the time when synthesis gas valve is opened to allow gas flow to reactor.
• the progress of the oxonation is monitored on the basis of the amount of CO and H 2 consumed.
• the H 2 /CO feed valve is shut off and the autoclave is immediately cooled with dry ice to about 0oC. Prior to depressing the autoclave, a large gas sample is taken.
• Example 3 The same procedure outlined in Example 3 is repeated except that propylene is used in place of butene-1. Charges to the autoclave are: propylene 22 grams, diethylene glycol 116.8 grams, KOH 1 gram, diphenyl phosphino ethyl trimethyl silane 5.846 grams and tris-(diphenyl phosphino ethyl trimethyl silane) rhodium carbonyl hydride 0.144 grams. The calculated rhodium concentration in solution is 102 ppm. The reaction temperature and pressure are respectively
• Example 3 The same procedure outlined in Example 3 is again repeated except that a mixed feed of propylene and butene-1 is used rather than just butene-1. Charges to the autoclave are: propylene 8.7 grams, butene-1
• the autoclave is charged with 20.2 grams of butene-1, 74.1 grams of diethylene glycol, 1 gram of KOH, 3.14 grams of phosphinophosphonium ligand having the chemical formula of:
• RhH(CO) AsPh 3 ) 3
• Ph a phenyl group
• the rhodium concentration in solution is 102 ppm and ligand to rhodium molar ratio is 40 to 1.
• the run is carried out at 120oC. and 700 psig until 100% conversion, based on carbon monoxide consumption, is reached (35 minutes).
• the data (solvent and ligand free basis) are summarized in Table VI below.
• An autoclave is charged with 110 cc. of diethylene glycol, 0.095 g. of [Rh(CO) 3 (PPh 3 ) 2 ] + BPh 4 -,
• reaction mixture is analyzed for n-pentanal, iso-pentanal, 2-propyl heptanal, 2-propyl heptenal, 2-propyl-methyl-hexenal, % conversion and % dimer conversion and the results are summarized in Table VII below.
• a 2 liter stainless steel reactor equipped with agitator, sparge inlet and appropriate outlet arrangments for continuous hydroformylation operation is charged with the following materials:
• the rhodium used is tris-(diphenyl phosphino ethyl trimethyl silane) rhodium carbonyl hydride.
• the reactor is pressurized to about 250 psig and heated to about 140oC.
• the rhodium concentration is increased from 14.7 ppm to 100 ppm (ligand/rhodium ratio of 143).
• the conversion rate of olefin to liquid oxo product is 6 to 7 times faster.
• Gas chromatography of the liquid sample showed 21.6% monoaldehydes and 62.2% dimer aldehydes, with a selectivity toward dimer aldehydes of 83.8%.
• Examples 8 and 9 demonstrate that the process of the present invention provides a one stage reaction by which aldehydes containing 2n + 2 carbon atoms can be prepared from the alpha-olefins containing n carbon atoms. Also, the example demonstrates that the catalyst was thermally stable.
• a mixture of gaseous butene-1, hydrogen and carbon monoxide together with recycle gases is fed continuously via the sparge inlet to the liquid reaction medium maintained at the above temperature and pressure.
• Reactor effluent gases are withdrawn therefrom, and include unreacted feeds, product aldehydes and solvent. These gases leave the top of the reactor and pass through a condenser, where product and solvent are condensed before entering a gas-liquid separator.
• Non-condensable gases are withdrawn from the top of the separator and recycled to the reactor via a compressor. A small portion of these gases is purged through a valve.
• the condensable product withdrawn from the separator is continuously discharged from the base of the separator and passed to a secondary liquid-liquid separator, where the solvent DEG, upon settling, is separated by phase separation (DEG is the bottom layer).
• the aldol product is collected.
• the discharge DEG removed from separator, containing major portion of product water, is dried in a bed via a pump to remove the water therein. This dried DEG is then combined with make-up DEG recovered from aldehyde product, prior to returning to the reactor. Rates and weight compositions of feed, product and recycled streams are detailed below in Table XI.
• the presence of acidic compounds during the hydroformylation reactions causes deactivation of the complex rhodium-containing catalyst.
• water from the condensation reaction of aldehydes reacts with CO to give formic acid.
• hydrolysis of the trimer aldehyde by-product of the condensation reactions can yield acidic compounds. While these acidic conditions should be avoided, in the event of deactivation conditions, the complex rhodium catalyst can be regenerated by the addition of base.
• a continuous hydroformylation reaction using butene-1 was run in a 2 liter autoclave, with 20% trimer aldehyde, n-pentanal, RhHCO(PPh 3 ) 3 catalyst (about 170 ppm) and triphenyl phosphine ligand in a molar ratio to the catalyst of 210/1.
• the reaction was conducted at a temperature of about 97.5oC. and a pressure of about 114 psia.
• the H 2 /CO ratio varied from 8/1 to 10/1.
• a series of. such runs were made.
• the acid value (i.e., the amount of KOH needed to neutralize any acid present) of the reaction mixture in each case was measured initially and after a certain reaction time as indicated in columns 1-4 of Table XII below. Analyses of the samples taken from the reactors were found to contain formic acid and valeric acid. The above results deomonstrate that acid deactivates the catalyst, but that activity can be regenerated by treatment with base.
• the catalyst from run c above was recovered and used in a series of batch hydroformylation reactions in a 300 cc reactor at a pressure of about 300 psi and a temperature of about 100oC.
• the H 2 /CO was pressurized into the react at a molar ratio of 4/1 and during the run was fed at a molar ratio of 1/1.
• the system is treated with KOH prior to conducting the hydroformylation reaction.
• the acid value before and after the run, the reaction rate and the normal to iso product molar ration was measured. The results are set forth below in Table XIII.
• COMPARATIVE ACCELERATED EXPOSURE TEST A series of side by side tests were run to demonstrate the temperature instability of RhH(CO) (PPh 3 ) at higher temperatures to show that the presence of base increases the normal to iso isomer ratio of the product produced by the process of the invention.
• the test procedure is basically the same as that described for Examples 1-33 of Netherlands Patent No. 78-00856, which corresponds to U.S. Application No. 762,336 filed January 27, 1977 of Bryant et al.
• a first 250 ml stainless steel vessel is charged with 0.089g of RhH(CO)) (PPH 3 ) in which Ph represents a phenyl group, 3.57g of triphenyl phosphine, 75. Og (67ml) of diethylene glycol, and 1.0g of KOH.
• a second such vessel is charged with the same materials, except the KOH is omitted. Both vessels are heated to the same selected temperature as indicated in column 3 of Table XIV below by use of an oil bath.
• a mixture of H 2 and CO in a molar ratio of 1/1 is introduced into each vessel to a total pressure of 85 psig.
• a slight CO/H 2 gas flow is maintained in each vessel, i.e., about 1 bubble/sec.
• a series of such comparative exposures are conducted at the various selected temperatures indicated in column 3 of Table XIV below. The time for each exposure test is indicated in column 2 of Table XIV.
• each vessel After the exposure indicated in columns 2 and 3, the contents of each vessel are cooled to ambient temperature and transferred to a 300 cc autoclave, and a hydroformylation or a combined hydroformylation/aldol condensation reaction is conducted.
• the temperature of the autoclave is increased to 120oC.
• Butene-1 and H 2 /CO mixture in a molar ratio of 1.5/1 and a total pressure of 600 psig are added to the autoclave.
• the rhodium concentration is 100 ppm and the ligand to rhodium molar ratio is about 140/1 in each instance.
• reaction rates (activity) relative to a non-exposed system i.e., exposure A in Table XIV
• results are set forth in columns 4 and 5 of Table XIV.
• the n/i ratio of the product of each process is also determined.
• the process of the present invention can be used to produce dimeraldhydes which are particularly suited for use as intermediates in the production of plasticizers.

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