US2658083A

US2658083A - Selective hydrogenation of oxoprocess aldehydes

Info

Publication number: US2658083A
Application number: US223124A
Authority: US
Inventors: Donald E Burney; William J Cerveny
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1951-04-26
Filing date: 1951-04-26
Publication date: 1953-11-03
Anticipated expiration: 1970-11-03

Description

Nov. 3, 1953 D. E. BURNEY Er Al. 2,658,083

SELECTIVE HYDROGENATION OF OXO-PROCESS ALDEHYDES Filed April 26, 1951 2 Sheets-Sheet l Product Dona/d E Burney Wil/iam J. Cerveny TTOIPA/EY 2,658,083 SELECTIVE HYDROGENATION OF OXO-PROCESS ALDEHYDES Filed April 26 1951 Nov. 3, 1953 D. E. BURNEY Er AL 2 Sheets-Sheet 2 vm Bi INVENTORS gasp?.

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Patented Nov. 3, 1953 SELECTIVE HYDROGENATION TOF OXO- PROCESS ALDEHYDES Donald E. Burney, Griffith, Ind., and William J. Cerveny,fLansing, Ill., assignors to Standard Oil Company, Indiana Chicago, Ill., a corporation of Application April 26, 1951, Serial No. 223,124

10 Claims.

Our invention relates to the selective hydrogenation of carbonyl groups in the presence of olenic double bonds. More particularly, it relates to the conversion of carbonyl compounds into alcohols in the presence of oleiinic compounds without simultaneously effecting the saturation of the olenic linkages in said olenic compounds.

Numerous attempts have been made in the past to convert organic compounds containing carbonyl groups into the corresponding alcohols by hydrogenation, without simultaneously saturating oleiinic double bonds present in the charging stock, either in the same compound with the carbonyl groups, or in different compounds. For example, Adkins (Reactions oi Hydrogen, University of Wisconsin Press, 'Madison, Wisconsin, 1937) failed in attempting to selectively hydrogenate the carbonyl group of alde hydes and ketones which also contained olefinic double bonds. Now, however, we have discovered an effective technique for the selective hydro-v genation of carbonyl groups in certain carbonylolefin combinations.

In one embodiment of our invention, we have succeeded in preparing alcohols and highermolecular weight olens from a mixture of secondary olens and tertiary olens, by a combination process including an acid-copolymerization step, a treatment with carbon monoxide and hydrogen according to the so-called Oxo process, and our selective hydrogenation technique. A mixture of n-butyl'ene and isobutylene, for example, may be copolymerized with sulfuric acid to give a mixture of isooctenes, the isooctenes are then reacted with carbon monoxide and hydrogen by means of the carbonylation step of the Oxo process,

I l -(2=+ CO H3 Cf|3 oHo to give a mixture of nonyl aldehydes and isooctenes, and the resulting mixture is then contacted with hydrogen in the presence of a cobalt catalyst at elevated temperature and pressure, the aldehydes being thereby converted into the corresponding nonyl alcohols,

l---l-H CHO Onion and the isooctenes remaining unaiected` The selective hydrogenation step of our invention offers the important advantage that it avoids the necessity of isolating the aldehydes `from the canbonylation product of the Oxo process, an operation that is known to result in large losses of aldehydes through aldol condensation and other `undesired reactions. Our selective hydrogenation step also avoids the heat effects that would be produced if the olefins `were reduced to paraliins in the same operation, and the problem of temperature control within the reactor is thereby made less diflicult. Our selective hydrogenation step has the additional important advantage that it permits the recovery and utilization or recycling of non-carbonylated olens, which would be converted to parains inthe conventional hydrogenation procedure.

One object of our invention is to provide 'a means for converting carbonyl compounds into alcohols in the presence of olenic dou-ble bonds, Without simultaneously saturating the double bonds. Another object of our invention is to provide a means for hydrogen'ating carbonyl compounds resulting from the carbonylation step of the Oxo reaction, while simultaneously leaving non-carbonylated olenic constituents unaffected, so that the latter may be recycled to the l carbonylation step. IOther objects of our invention, and its advantages over the prior art, will be apparent from the following description and examples.

Our process is especially suitable for the selective hydrogenation of the products resulting from the carbonylation of secondary olefin-ten tiary olen copolymers, such as copolymers of mixtures containing at least one olen from the group comprising propylene, l-butene, Z-butene, and secondary amylenes, and at least Vone olen from the group comprising isobutylene, 2-methyl-l-'butena and Z-methyl-Z-butene. Thus, our process Ais suitable for treating the mixture of nonyl aldehydes and isooctenes obtained from n-butylene-isobutylene codimer, the `mixture of octyl aldehydes and isoheptenes obtained from propylene-isobutylene copolymer, the mixture of nonyl aldehydes and isooctenes obtained from prop ylene and 2-'methylbutenes, vthe mixture of decyl aldehydes and isononenes obtained from secondary amylenes and isobuty'lene, the mixture of undecyl aldehydes and isodecenes obtained from secondary amylenes and a Z-methylbutene, and similar mixtures of aldehydes and olens.

The copolymerization of olefin mixtures lmay be effected by various processes, most of which employ acidic catalysts, such as sulfuric acid, phosphoric acid, or hydrogen fluoride; `or 2potentially acidic catalysts such as copper pyrophosphate or boron fluoride; or ,solid tcatalysts such as silica-alumina or acid-treated bentonite. Hot sulfuric acid, for example, absorbs both secondary and tertiary olefins at temperatures around 140-194 F. and converts them into copolymers, comprising chiey the various isomeric dimers. In a particularly successful copolymerization process, secondary butylenes and isobutylene are passed over a solid granular catalyst, comprising phosphoric acid adsorbed on clay or other inert material, at 350-500c F. and around 40 atmospheres. Under these conditions, when the charge stream contains 30% of secondary butylenes and 15% of isobutylene, approximately 67% of the olens are converted into a product, of which 85% is dimer and 15% is trmer. Fractional distillation of the crude product yields a dimer fraction having properties and composition as in the following illustrative example:

Butylene-Isobutylene Codimer: Properties and Total isooctene content, percent Over 98. Distribution of isooctenes, percent by weight:

2,2,3-trimethylpentenes 21 2,2,4-trimethylpentenes 10. 2,3,3-trimethylpentenes 11. 2,3,4-trimethylpentenes 47. Dimethylhexenes 10.

The resulting mixture may be subjected to carbonylation by contact with a mixture of hydrogen and carbon monoxide having a molar ratio between about 0.5:1 and 5:1 at a temperature between about 200 and 500 F., a pressure between about 50 and 300 atmospheres, and a liquid space velocity between about 0.05 and 10 per hour, in the presence of a catalyst comprising cobalt or iron, as disclosed in the copending joint application of Donald E. Burney and Bernard H. Shoemaker, Serial No. 788,845, filed November 29, 1947, now U. S. Patent No. 2,628,981. Under these conditions, between 20 and 60 percent of the n-butylene-isobutylene codimer is converted into nonyl aldehydes, plus a minor proportion of nonyl alcohols, in a reaction time between about 30 and 120 minutes.

We have now found that mixtures of aldehydes and olens, such as those produced by the reaction of secondary olefin-tertiary olen copolymers with carbon monoxide and hydrogen in the Oxo process, may be selectively hydrogenated over a cobalt catalyst at an elevated pressure, suitably above about 500 pounds per square inch and preferably below about 4000 pounds per square inch, a temperature between about 150 and 700 F., and a liquid space velocity between about 0.1 and 5.0 volumes of charging stock per volume of reaction zone per hour, the aldehydes being thereby converted into the corresponding alcohols, without the simultaneous saturation of any substantial proportion of the olefinic compounds in the charging stock. The hydrogenation may be carried out in conventional batchtype autoclaves; or the liquid charging stock may be passed upward concurrently with hydrogen through a continuous reactor in contact with the catalyst, suitably at a temperature between about 350 and 600 F.; or the liquid charging stock may be passed as a continuous phase downward through a. reactor countercurrent to the hydrogen. In the preferred form of our invention, the mixture of olefin and carbonyl compound is trickled downward over a granular or pelleted catalyst in a continuous atmosphere of hydrogen at a temperature between about 350 and 600 F., a pressure between about 500 and 1500 pounds per square inch, and a liquid space velocity between about 0.2 and 2.0 per hour.

Catalysts comprising cobalt as the active con stituent are suitable for the selective hydrogenation reaction of our invention. Pure cobalt may be used as the catalyst in finely divided form, or in the form of granules, fragments, or shaped masses having finely divided surfaces; or the meta1 may be supported on powdered, pelleted, or granular inert carriers, such as silica, bonded silica (for example, Filtros), pumice, alumina, Carborundum, glass kieselguhr, and the like; and it may be combined with various promoters, such as thoria, magnesia, and the like. We prefer to use supported catalysts containing between about 5 and 15 per cent cobalt, but the proportion of cobalt is not a critical variable in our process.

Freshly prepared cobalt catalysts, when first used in our process, may sometimes exhibit a tendency to hydrogenate both the carbonyl groups and the olenic double bonds of our charging stock. However, in such cases, we have found that the activity of the catalyst toward olefnic double bonds is lost very rapidly during exposure to the charging stock and operating conditions of our process.

Prior to the hydrogenation step, the liquid product from the carbonylation step of the Oxo process should preferably be treated to remove substantially all cobalt carbonyl and carbon monoxide therefrom, since it is known that carbon monoxide tends to retard the hydrogenation. The purification may be accomplished, for example, by purging the liquid with hydrogen or an inert gas, or by washing the liquid successively with an acid and with water.

For the same reason, the hydrogen that is supplied to the hydrogenation reactor should preferably contain less than about 2 percent of carbon monoxide, and should be substantially free from catalyst poisons such as hydrogen suldc and the like.

After the Y selective hydrogenation has been completed, the reaction product contains alcohols, olefins, and a small proportion of saturated hydrocarbons. This mixture may be separated by techniques that are well known in the art. For example, the alcohols will ordinarily be substantially higher-boiling than the hydrocarbon constituents; the hydrocarbons may therefore be distilled out, and may be recycled to the carbonylation step in whole or in part, if desired: and the remaining alcohols may then be subjected to further purification by fractional distillation. Alternatively, the alcohols may be selectively extracted from the reaction product, suitably by use of an extractant medium comprising a glycol, a lower aliphatic alcohol, or a hydroxy ether. Or, the reaction product may be subjected to extractive distillation with a suitable solvent such as a member selected from the groups named above, the hydrocarbon constituents being thereA by removed as an overhead fraction. AS a :Ellic-A ther alternative, the reaction mixtures may be subjected to an esterification procedure, suitably with boric acid, phthalic anhydride, or the like, in order to convert the alcohols therein to the corresponding esters, and the hydrocarbon constituents may then be conveniently distilled out. The esters may afterwards be separated and used as such, or may be hydrolyzed to regenerate the alcohols. These constitute particularly advantageously embodiments of our invention, since the selective-hydrogenation step permits the recycle oi unreacted olens to the carbonylation step, whereas in the usual hydrogenation procedure they would become saturated and uns-uitable for recycling. As a still further alternative, the entire reaction product may be subjected to dehydration, suitably in the vapor phase at around TO-900 F. and one atmosphere over an alumina catalyst, in order to reconvert the alcohols therein to oleflns having one more carbon atom than the olens in the charging stock prior to the carbonylation reaction,

Prior to either the carbonylation step or the selective hydrogenation step, we may optionally add to the liquid charging stock an inert liquid as a diluent and as a mutual solvent for the reactants and reaction products. As illustrations of such liquids, the following may be cited: aliphatic, aromatic, and naphthenic hydrocarbons; others; and alcohols, in particular the lower aliphatic alcohols, benzyl alcohol, tetrahydrofurfuryl alcohol, and the like.

Figure 1 illustrates an embodiment of our invention employing batch-type equipment. An olen copolymer charging stock is supplied through line II to mixing and metering tank I2 equipped with agitator I3, wherein a quantity of powdered catalyst, suitably 3 to 5% of cobalt on kieselguhr, is suspended in `the liquid. The susl pension is withdrawn through line I4 by pump I 5 and delivered through heat exchanger vI6 into reactor II. A now of gases is maintained through the reactor during the lling operation at a rate sufficient to maintain the solid catalyst in suspension, and the liquid charge may be recirculated from the bottom of reactor I'I through heat exchanger it by way oi line I8, valve I9, and pump I5 in order to bring the charge up to reaction temperature, optimally around 350 F. When the desired liquid level is reached in the reactor, the vessel is closed and a mixture of carbon monoxide and hydrogen in approximately 1:1 molar ratio is introduced through line 20, compressor 2l, and sparger lines 22 until the pressure reaches approximately 200 atmospheres, From the top of the reactor, gas emerges through cooler 23 and is expanded through valve 24 into separator 25, :from which a portion is purged through valve 20 as required to prevent excessive build-up of non-reactive gases, and the remainder is recycled through valve 21 and compressor 2l to the reactor. The recycle and makeup gases ordinarily have a temperature below about 100 F., and are distributed to various points in the reactor, as indicated in the drawing, to maintain an approximately uniform temperature.

After the reactive components of the olefin copolymer have reacted to the desired extent with carbon monoxide and hydrogen, the supply of gas to compressor 2| is stopped, and the gas remaining in the system is released through purge valve 2B. The reactor contents are adjusted to a temperature between about 375 and 425 F. by withdrawingr a stream. of the reaction mixture through cooler 2,8 .and recycling it through valve. 29, pump I5, and heat exchanger It. Hydrogen, substantially free from carbon monoxide, is then introduced into the reactor through line 20 and compressor 2 I, and is purged through valve. 2.3 until the system contains little or no carbon monoxide. The hydrogen pressure is then raised to between about 500 and 1500 pounds per square inch, and hydrogen is recycled through cooler 23, valve 24, separator 25, valve 2^?, compressor 2|, and sparger lines 2 2 to the reactor to maintain the catalyst in suspension and to help in controlling the reaction temperature. Under the described conditions,y the reduction of aldehydes to alcohols takes place readily,

with little or no reduction of oleiins that failedto react with carbon monoxide and hydrogen in the carbonylation step. When the hydrogenation has been completed, the supply of hydrogen is stopped, the pressure is released through valve 26 to approximately 5 or 10 atmospheres, and the reactor charge is forced by the residual pressure through cooler 2.8, valve 30, separator 25, valve 3I, and filter 32, where the suspended catalyst is removed. The recovered catalyst may be washed from the filter through line 33, suitably with filtered product, and subsequently reused. The filtered product is withdrawn through line 34 and subjected to further process steps, such as fractional distillation (apparatus not illustrated) to separate the various components thereof.

Figure 2 illustrates a continuous process for carrying out our invention.

An olen charging stock, supplied through line Ii I, is introduced by pump II2 through heat exchanger II3 into the top of carbonylation reactor l I4, where it is contacted at a pressure be,` tween about and 300 atmospheres, preferably about 200 atmospheres, and a temperature between about 200 and 500 F., preferably between about 32,5 and 375 F., with an equimolar mixture 0f carbon monoxide and hydrogen, introduced through line II5 and compressor III. The rate of injection of copolymer is suitably between about 0.05 and l0 volumes per hour per unit volume of reaction zone, and preferably between about 0.5 and 2 per hour. The reactor is packed with a suitable carbonylation catalyst, such as metallic cobalt supported on an inert siliceous. material, arranged in such manner that efcient contact is obtained between the liquid hydrocarbon and the reactant gases. Makeup catalyst, suitably metal carbonyls, such as cobalt or iron carbonyl, or oil-soluble organicacid salts, such as iron or cobalt stearato or' naphthenate, may be added through line Ill to` the oleiin stream in line III, in order to compensate for any loss of catalyst from the reactor as dissolved carbonyl or entrained solids in the product stream. Alternatively, solid catalyst may be omitted from the reactor altogether, and the total catalyst requirements may be supplied with the charging stock in the form of metal carbonyls (suitably between about 0.1 and .2 percent by Weight) or metal salts of organic acids (suitably between about 0.1 and 10 percent by weight). The processed liquid stream and the unreacted gases are withdrawn from the base of the reactor through line IIB to high-pressure separator II9.

The gas stream from separator H2 flows through Valve I2!! and cooler I2I into low-pressure separator 122, where condensed liquids are removed. The gas stream emerging from sepa 7 arator |22 through line |23 is divided, part of it flowing through valve |24 to compressor ||6, from which it is recycled to reactor I |4, and the remainder being purged through line |25, or sent to suitable gas reprocessing equipment.

The liquid stream from separator ||9 ows into cooler |26, and is divided into two streams. One stream is recycled through valve |21, pump |28, line |29, and heat exchanger ||3 to reactor |14, where it serves to regulate the temperature of the exothermic reaction between the olefin stream, hydrogen, and carbon monoxide. The rate of recycle may be adjusted to maintain the desired temperature, the cooling liquid being introduced at the top of the reactor or at such points within it as may be required to control localized heating. The remainder of the liquid stream from cooler |26 ows through valve |30 to low-pressure separator |3|, where the liquid is freed of dissolved gases. The gases are combined in line |23 with the gases from separator |22.

The liquid streams from separators |22 and |3| are combined and transferred by pump |32 through line |33 and heat exchanger |34 into selective hydrogenation reactor |35. This liquid comprises a mixture of aldehydes and unreacted olens, together with minor proportions of alcohols and saturated hydrocarbons, and it ordinarily contains minor proportions of the catalyst from the carbonylation reaction, in the form of the metal carbonyl, oil-soluble metal salts, or suspended solids. The catalyst may be removed, if desired, before the liquid is introduced into reactor |35. For example, the liquid stream may be treated with hydrogen or other inert gases at elevated temperatures, suitably above about 150 F., in order to destroy metal carbonyl and to strip out the liberated carb-on monoxide, and the precipitated metal may then be removed by filtration or centrifugation; or the liquid stream may be scrubbed with a dilute acid, such as sulfuric acid, and then with water (apparatus not shown). The hydrogenation reactor |35 contains a selective hydrogenation catalyst comprising cobalt as the 'active component, preferably on an inert support, such as Filtros (a bonded silica), or pumice. Hydrogen, preferably containing not more than about 2 percent of carbon monoxide is supplied by compressor' |56 through line |31 into the bottom of reactor |35. The hydrogen passes upward through the downwardflowing liquid stream, the pressure within the reactor being maintained around 800 pounds per square the temperature around 550 F. Under these conditions, the aldehydes are converted into alcohols, while the olefins are substantially unaiected. Excess hydrogen is withdrawn at the top of reactor |35 through valve |33 and cooler |39 into low-pressure separator |40, from which the gas phase is withdrawn and purged through line Uil to prevent the accumulation of inert constituents within the reactor; or the gas phase may be recycled Wholly or in part to gas processing equipment, not shown.

From the bottom of reactor |35, the selectively hydrogenated liquid is withdrawn through cooler |42, and the stream is then divided, part of it being recycled through valve |43, pump IM, line |33, and heat exchanger |34 to reactor |35 for use in regulating the reaction temperature therein at the desired level, while the remainder of the liquid stream from cooler |42 is reduced in pressure to around one atmosphere through valve |45 and allowed to flow into low-pressure separator |46, from which the dissolved gases are removed and purged or recycled as desired.

The liquid streams from separators |4|l and |46 are combined and transferred to a fractionation system, where the hydrocarbons and alcohols may be segregated and purified. For this purpose, Figure 2 illustrates a two-stage fractionation method:

The liquid streams from separators |550 and |46 are transferred by pump |41 through heater |48 into fractionating column |49 at an intermediate point. The hydrocarbon constituents, being lower boiling than the alcohols, are fractionally distilled overhead through condenser |59 into separator |5i, from which a portion is reuxed through valve |52 to the top of column |49, and the remainder is withdrawn through valve |53 to storage, or to further purification. The hydrocarbon stream, comprising mainly olens, may be recycled to reactor le, either with or without an intermediate purification stage. In the event that recycling is employed, a small proportion of the recycle stock is preferably withdrawn from the process in order to prevent the accumulation therein of saturated constituents and other constituents which will not undergo the carbonylation reaction.

1t will be noted that reactor H4 is shown with liquid and gas flowing concurrently downward, Whereas in reactor |55 the liquid stream flows downward countercurrent to the gas stream. It is intended that either of these flow systems may be used in either reactor. Moreover, a third modification, in which the liquid and gas flow upward in parallel, may also be used in either reactor.

The following specic examples will more fully illustrate our invention.

Example I A solution of cobalt nitrate was prepared by mixing 120 grams of the hexahydrate (ce (No3) 2.61120) with 50 milliliters of water and heating nearly to boiling. To the hot solution were added T grams of 4-8 mesh Filtros (a bonded silica), and the mixture was stirred continuously and heated until substantially all of the water had evaporated. In this way, the cobalt nitrate was deposited uniformly on the Filtros. The heating was then continued, and the cobalt nitrate was decomposed into cobalt oxide, as evidenced by the evolution of red fumes of nitrogen peroxide. After the evolution of red fumes had ceased, the material was cooled and screened to remove the nes. The oxide Was then reduced with hydrogen at atmospheric pressure and 700 F. for five hours. A yield of 192 grams of catalyst containing 5.4 percent cobalt was obtained. After reduction, the catalyst was handled under an inert atmosphere.

A charging stock was prepared by contacting a n-butylene-isobutylene codimer with carbon n'onoxide and hydrogen according to the car bonylation step of the Oxo process. The resulting product, containing 34 percent by volume of nonyl aldehydes, 8 percent nonyl alcohols, 516 per- 1G EampleIII An x0-process carbonylation-step reaction product, prepared from a n-butylene-isobutylene codimer, and containing 24 percent by volume cent isooctenes, and .2 percent high-boiling ma- 5 of .nonyl aldehydes 7 percent Yrmnyl alhols terials, was trickled downward at the rate of 209 55 rpercent sooctenes, and 9 percent high boilers, m1. per hour through a reactor having Yarl ill-51de was trickled downward over 645 milliliters of diameter of 1.5 inches and a catalyst zone packed 4 8 mesh AFiltros, mpregnated with approxi with cobalt catalyst, prepared as described ,aboveg mately 4 9 percent of reduced cobalt according t0 a depth 0f 2-5 feet 'A temperature of 380A@ w to the general procedure outlined in Example l F. and a hydrogen pressure of 7750-856 pounds The reacton conditions were as follows: per square inch were maintained in the reactor. a After two passes over the catalyst V(equivalent to Temperature Catalyst mldsectlOL 609g E 2 a. space velocity of 0.115/hr.), the product COH- Hydrogen praSSure--`*^- 800 1b/m" sisted of 35 percent by Volume nonyl alcohols, 3.5 15 Feed rate------n-W 492 mL/hr' percent nonyl aldehydes, 50 percent hydlocal'- Space Veloclty hquld M (L8/hr' bons having a bromne number 0f 134, 'COlT- On fractional distillation, the product was :found sponding to an unsaturation of over` 90 percent, to contain 34 pel-Cent .nonyl alcohols', correspondand the remainder high-.boiling materials. ing ,to 38 percent conversion of the aldehydes Example II originally present, 3 percent nonyl aldehydes, 47 percent hydrocarbons having a bromine A hydrogenation reactor having yan inside Ad1 number of 132 Corresponding to 96 percent un ameter of 1.5 inches and a reaction Zone 25 saturation andpercent high boilers. inches in length was charged with 645 milliliters of unreduced cobalt oxide catalyst, prepared as Example IV described in Example I, and `the catalyst was .A series of selective hydrogenation experi- IeduCed in place With hydrogen at aIOund 800 ments was carried out on a charging stock con F. for six hours. taining `2,1 percent by volume of nonyl alde- A Il-butyleIlS-sobutylehe @Odimr having a hydes, 7 percent nonyl alcohols, 60 percent `isobI'OmIlS number 0f 137 `WaS subjected O CalbOh- 30 octenes, 7 percent high ,boiler-s, and 0 6 mg, S01- ylaton under OXO process Conditions, and a uble cobalt compounds per milliliter, that had product was obtained consisting of 21 percent been prepared by Contacting a n buty1ene is0 by volume of nonyl aldehydes, 7 percent 1101134 butylene codimer with carbon Vmonoxide and alCOhOlS, 65 percent SOOGteIleSy and 7 'percent hydrogen under 0x0-process carbonylation-step high-boiling materials- The CalbOIlyatGnDrOdconditions. 'The carbonylat'ion product was uct Was fed HO '611612010 0f the lllydiogenation trickled downward over 645 milliliters Aoi .ll-8 IEBJCOI at a rate Of 193 milliliter-S per 110111 and mesh Filtros, 'impregnated with approximately contacted with hydrogen and cobalt catalyst at 4.9 percent of reduced cobalt according to the about 415 F. and 800 pounds Der square inch. general procedure outlined in Example I, and The reactor effluent was Cooled, flashed 170 at- 40 contained in a, zone measuring 25 inches in mospheric pressure, and fractionally distilled length in a hydrogen-filled reactor having an under reduced pressure. The product consisted inside diameter of 115 inches. of 27 percent by volume of nonyl alcohols, 2 The experiments were continued for one hour percent nonyl aldehydes, 63 percent hydrocarat each set of reaction conditions before the bons having a bromine number of 137, correproduct Was collected for evaluation, Analysis sponding to 100 percent unsaturation, and 8 of the liquid products was by fractional distilpercent high-boiling materials. Thus, 90.5 perlation. The reaction conditions and results were cent of the aldehydes had been reduced to the as follows:

Product composition Hydrogen Feed Space sicognfle- Pressure, Tgrp" rate, vvmtty Alcc- AldevHydro- H'igh hydes to lb./1n.2 ml./hr. ,1g 1, hols, hydes, cartoons, boilers, alcohols, vol. vol. vol. vol. percent percent percent Apercent percent 415 19s 0.a 27 2 5s s o1 405 363 o. 6 27 .5 6o 5 ve 402 54o o. s 19 11 63 i 4s 505 51o os so 2 so 2 91 557 o as 29 2 `to 5 91 corresponding alcohols, while the oleiins were Bromine titration of the hydrocarbon fractions unchanged. of the products indicated that all of them were When a similar n-*butylene-isobutylene codibetween.96 and 100 percent oleiinic. mer which had not been subjected to carbonyl- *Example V ation was fed at a rate of 192 milliliters per hour into the same reactor, containing the same An OXO-process carbonylation-step reaction catalyst, and contacted with hydrogen at Soo product prepafed from al; Il-butyleILe-.sobutylpounds per square inch and an average temperen@ Codlme and Contammg 17 Percent by ature of 396 F., the product was 100 percent Volume 0f IIODYI aldehydes, 7 Percent DOIlyl al- Cs hydrocarbons having a bromine number of cohols, 71 percent isooctene, and 5 percent high 5, which indicated that 96 percent of the olens bOlerS, Was passed llDWald through 645 milli- Originauy present in the codimer had been hylitcrs of 4-8 mesh Filtros, impregnated with 4.9 drogenated to the corresponding parains. 75 Weight percent of reduced cobalt, in a reactor having an inside diameter of 1.5 inches and a catalyst bed 25 inches in length. The reaction conditions were as follows:

Temperature, catalyst mid-section-. 550 F.

Hydrogen pressure 800 lb./in2. Excess hydrogen rate 1.0 ft.3/hr. Feed rate 323 ml./hr. Space velocity, liquid 0.5/hr.

Example VI A propylene-butylene copolymer was fractionally distilled, and from it was separated a C7 fraction having a bromine number of 158. The C7 fraction was mixed with 0.1 percent by weight of cobalt in the form of cobalt tallate, and the resulting solution was subjected to carbonylation by contact with a 1: 1 mixture of carbon monoxide and hydrogen at 325 to 250 F., 3000 pounds per square inch, a liquid space velocity of (L5/hour, and an excess gas rate of 200 percent of the theoretical quantity necessary for complete carbonylation. The conversion was 52 percent, molar basis, of the C7 olens, yielding a product having the following composition:

Mole-percent C7 hydrocarbons (Br No., 130.4) 48 Cc aldehydes 36 Ca alcohols l2 Bottoms 4 The total product liquid was washed at 80 F. with 25 percent by volume of aqueous 5% sulfuric acid, then twice with the same proportion of water. The washed product liquid was steamdistilled, and all of the organic materials except the bottoms were withdrawn overhead as a distillate fraction. The distillate fraction was passed downward over a reduced 12 percent cobalt-on-pumice catalyst at 375 F., 3000 pounds per square inch, and a liquid space velocity of derstood that we do not wish to be limited to the specific charging stocks and operating conditions described therein, since our invention is broadly applicable, as defined elsewhere in the specification. In general, it may be said that any modications or equivalents that would ordinarily occur to those skilled in the art are to be considered as lying within the scope of our invention.

The products of our invention are alcohols of a wide range of chemical and physical properties. They are useful as solvents and as ingredients of hydraulic uids, and are capable of being converted into a wide variety of chemical derivatives. For example, they may be oxidized to aldehydes and carboxylic acids; they may be reacted with ammonia to form amines, and with other amines to form secondary and tertiary mixed amines; they may be dehydrated to form olens and ethers; they may be used to alkylate aromatics; and they may be converted by conventional methods into esters. Especially useful esters may be prepared from the mixed octyl alcohols obtainable from propylene-butylene copolymers and from the mixed nonyl alcohols obtainable from n-butylene-isobutylene codimer according to our invention. Among such esters may be cited the phthalates, phosphates, sebacates, adipates, stearates, citrates, and the like, which are useful as plasticizers for numerous plastics, elastomers, and resins, including vinyl polymers, butadiene-styrene rubbers, and cellulose plastics; the sulfates, which are useful as wetting agents; and the acrylates and methacrylates, which, after being polymerized, are excellent viscosity index improvers for lubricating oils.

This application is a continuaticn-in-part of our application Serial No. 788,847, filed November 29, 1947, now abandoned.

In accordance with the foregoing specication, we claim as our invention:

1. In a process for selectively hydrogenating aldehydes in a mixture containing aldehydes and olens obtained by subjecting a secondary olefin-tertiary olefin copolymer to reaction with carbon monoxide and hydrogen, the step which comprises contacting said mixture with hydrogen at a temperature between about and 700 F. an elevated pressure above about 500 pounds per square inch, and a liquid space velocity between about 0.1 and 5.0 volumes of charging stock per Volume of reaction zone per hour in the presence of a cobalt catalyst.

2. The process of claim 1 wherein said catalyst consists essentially of metallic cobalt and an inert carrier.

3. The process of claim 1 wherein said copolymer is a copolymer of an olefin selected from the group consisting of prcpylene, 1-butene, 2-butene, and the secondary amylenes, and an olefin selected from the group consisting of isobutylene, 2- methyl-l-butene, and Z-methyl-Z-butene.

4. In a process for selectively hydrogenating aldehydes in a mixture containing aldehydes and oleiins obtained by subjecting a secondary olefin-tertiary olen copolymer to reaction with carbon monoxide and hydrogen, the step which comprises contacting said mixture with hydrogen at a temperature between about 150 and 700 F., an elevated pressure between about 500 and 4000 pounds per square inch, and a liquid space velocity between about 0.1 and 5.0 volumes of charging stock per Volume of reaction zone per hour in the presence of a cobalt catalyst.

5. The process of claim 4 wherein said copolymer is a propylene-butylene copolymer.

6. The process of claim 4 wherein said copolymer is a n-butylene-isobutylene codimer.

7. In a process for selectively hydrogenating aldehydes in a mixture containing aldehydes and olens obtained by subjecting a secondary olefin-tertiary olefin copolymer to reaction with ,A carbon monoxide and hydrogen, the step which comprises passing said mixture downward over a supported cobalt catalyst in an atmosphere of hydrogen at a temperature between about 350 and 600 F., a pressure between about 500 and 4000 pounds per square inch, and a liquid space velocity between about 0.2 and 2.0 volumes of i3 charging stock per volume of catalyst zone per hour.

8. In a process for the preparation of alcohols from a secondary olefin-tertiary olen copolymer. the steps which comprise subjecting said copolymer to reaction with carbon monoxide and hydrogen in a carbonylation zone, contacting the resulting product with hydrogen at an elevated pressure between about 500 and 4000 pounds per square inch, at a temperature between about 150 and 700 F., and a liquid space velocity between about 0.1 and 5.0 volumes of charging stock per volume of reaction zone per hour in the presence of a cobalt catalyst, separating alcohols and unreacted olens from the resulting product, and recycling part of said unreacted olens to said carbonylation zone.

9. In a process for selectively hydrogenating aldehydes in a mixture containing nonyl aldehydes and isooctenes obtained by subjecting a 20 n-butylene-isobutylene codimer to reaction with carbon monoxide and hydrogen, the step which comprises contacting said mixture with hydrogen at a pressure between about 500 and 4000 pounds per square inch, a temperature between about 350 25 and 600 F., and a space velocity between about 0.2 and 2.0 volumes of liquid per volume of reaction zone per hour in the presence of a cobalt catalyst.

10. In a process for selectively hydrogenating aldehydes in a mixture containing octyl aldehydes and isoheptenes obtained by subjecting a propylene-isobutylene copolymer to reaction with carbon monoxide and hydrogen, the step which comprises contacting said mixture with hydrogen at a pressure between about 500 and 4000 pounds per` square inch, a temperature between about 350 and 600 F., and a space velocity between about 0.2 and 2.0 volumes of liquid per volume of reaction zone per hour in the presence of a cobalt catalyst.

DONALD E. BURNEY. WILLIAM J. CERVENY.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,327,066 Roelen Aug. 17, 1943 2,414,276 Sensel et al Jan. 14, 1947 2,437,000 Gresham et al Mar. 9, 1948 2,464,916 Adams et al Mar. 22, 1949

Claims

1. IN A PROCESS FOR SELECTIVELY HYDROGENATING ALDEHYDES IN A MIXTURE CONTAINING ALDEHYDES AND OLEFINS OBTAINED BY SUBJECTING A SECONDARY OLEFIN-TERTIARY OLEFIN COPOLYMER TO REACTION WITH CARBON MONOXIDE AND HYDROGEN, THE STEP WHICH COMPRISES CONTACTING SAID MIXTURE WITH HYDROGEN AT A TEMPERATURE BETWEEN 150 AND 700* F. AN ELEVATED PRESSURE ABOVE ABOUT 500 POUNDS PER SQUARE INCH, AND A LIQUID SPACE VELOCITY BETWEEN ABOUT 0.1 AND 5.0 VOLUMES OF CHARGING STOCK PER VOLUME OF REACTION ZONE PER HOUR IN THE PRESENCE OF A COBALT CATALYST.