United States Patent (19) 11 4,032,578 Savini (45) June 28, 1977

54 PROCESS FOR THE MANUFACTURE OF 3,432,557 3/1969 Wile ...... 260/601 R AND HDA AND OTHER FOREIGN PATENTS OR APPLICATIONS BY ALDOL CONDENSATON 2,058,532 5/1971 France ...... 260/638 B 75 Inventor: Charles G. Savini, Warren, N.J. Primary Examiner-Joseph E. Evans 73) Assignee: Exxon Research and Engineering Company, Linden, N.J. Attorney, Agent, or Firm-C. Leon Kim 57 ABSTRACT Filed: Jan. 7, 1976 (22) A new process for the manufacture of aldehydes by (21) Appl. No.: 647,150 using a feed consisting of crude, high conversion, demetalled conventional oxo product Related U.S. Application Data is described. In another embodiment a new process for (63) Continuation-in-part of Ser. No. 547,475, Feb. 6, the manufacture of hexadecyl and related alco 1975, abandoned, which is a continuation of Ser. No. hols using the above-described feed is also set forth. 317,615, Dec. 22, 1972, abandoned. The process is a uniphase aldol condensation process utilizing small quantities of basic catalyst and operating (52) U.S. C...... 260/601 R; 260/638 B above certain minimum threshold temperatures. The (51) Int. C.’...... C07C47/02; C07C 45/00; process is operable with crude oxo feeds that contain as CO7C 29/14 much as 40% by weight acetals. Process conditions are (58) Field of Search ...... 260/601 R, 638 B described which enable reversion of the acetals to alde (56) References Cited hydes and alcohols thereby allowing concurrent con densation of reactive components with high selectivi UNITED STATES PATENTS ties to the product alcohols and aldehydes. The prod 2,485,989 10/1949 Smith ...... 260/601 R ucts of the process, such as hexadecyl alcohol, are well 2,757,200 7/1956 Jones et al...... 260/638 HF 2,809,220 10/1959 Mertzweiller et al...... 260/638 HF known and have many uses, such as in the formulation 2,810,762 10/1957 Ernst et al...... 260/635 A of cosmetic products. 2,848,498 8/1958 Mention ...... 260/638 B 3,148,218 9/1964 Heimsch et al...... 260/601 R 8 Claims, 1 Drawing Figure

SOLUBLITY OF WATERN Cs OXO PRODUCT

O 90% - Conversion Oxo Product 75%-Conversion Oxo Product O50%-Conversion Oxo Product O25% -Conversion Oxo Product

OO 2OO 3OO 400 SOO 6OO 700

TeMPERATURE (F) U.S. Patent June 28, 1977 4,032,578

SOLUBLITY OF WATER IN Cs OXO PRODUCT 4O

3O O 90% - Conversion Oxo Product 75%-Conversion Oxo Product O 50%-Conversion Oxo Product O 25% - Conversion Oxo Product

O

O

O2 OO 2OO 3OO 4OO 5OO 6OO 7OO

TEMPERATURE (F) 4,032,578 2 Also, U.S. Pat. No. 2,820,067 describes a process for PROCESS FOR THE MANUFACTURE OF the preparation of high molecular weight alcohols from ALDEHYDES AND HDA AND OTHER ALCOHOLS low molecular weight olefins by a novel modification of BY ALDOL CONDENSATION the synthesis reaction. This modification re sides in the treatment at elevated temperatures and low CROSS-REFERENCE TO RELATED pressures of the aldehyde products from the carbonyla APPLICATIONS tion process in the presence of zinc salts for extended This application is a continuation-in-part of pending periods which is then followed by to U.S. Ser. No. 574,475, filed Feb. 6, 1975, now aban produce high yields of dimeric primary alcohols. U.S. doned, which is in turn a continuation of U.S. Ser. No. 10 Pat. No. 3,248,428 discloses a process for producing 317,615 filed Dec. 22, 1972, now abandoned. alpha, betaunsaturated carbonyl compounds of in creased molecular weight by the condensation of car FIELD OF THE INVENTION bonyl compounds of relatively low molecular weight at This invention relates to a novel process for the man elevated temperatures with a catalyst comprising an ufacture of hexadecyl alcohol via aldol condensation 5 insoluble reaction product of molybdenum oxide and using crude, high conversion, demetalled, conventional magnesium oxide. Finally, U.S. Pat. No. 2,848,498 oxo product as feed followed by hydrogenation and describes a process for the production of aldols, ketols purification. More particularly, the invention relates to and unsaturated oxo compounds from one or more an improved aldol condensation process which repre saturated oxo compounds as feeds. The process com sents a viable alternative to presently employed aldox 20 prises mixing a stream of a saturated oxo compound or processes. compounds with a stream of an aqueous alkaline con densation agent. For the most part, the abovedescribed BACKGROUND OF THE INVENTION processes result in selectivities considerably less than The manufacture of hexadecyl alcohol and related 100% and during operation require significant controls alcohols is presently commercially produced via the 25 to avoid undesirable side reactions and may require aldox process whereby overall produce yields are ap catalyst recycle and the use of special materials which proximately 20%. Additionally, the commercially em resist corrosion of the high caustic concentrations. ployed process produces severe operating problems There is, therefore, a need for an efficient, highly selec and significantly reduces the production of the conven tive route to aldehydes and their corresponding hydro tional oxo alcohol. Alternate conventional systems 30 genated aldol saturated alcohols which avoids many of employ low temperature two-phase and additionally the processing problems of conventional systems. may be characterized as high basicity systems. Selec tivities for the conventional systems have never appre SUMMARY OF THE INVENTION ciably exceeded about 60% due to the side reactions In accordance with the present invention, a twostep which occur at process conditions required to achieve 35 process for the manufacture of aliphatic alcohols is acceptable reaction rates. described. The process comprises contacting an alde hyde or acetal-containing feedstream with a lower level DESCRIPTION OF THE PRIOR ART of basic catalyst selected from the group consisting of Aldolization processes are well known in the art and Groups I-A and II-A hydroxides, soaps, alkoxides, provide a ready means for preparing aldehydes and 40 phenoxides; quaternary ammonium hydroxides, cho alcohols from compounds containing olefinic unsatura line and the like. The contacting is carried out in the tion. These processes generally involve condensation of presence of a controlled amount of water and a temper two moles of aldehyde to produce a hydroxy aldehyde. ature in excess of 200 F. to thereby provide a uniphase The lower aldols are readily dehydrated to the corre reaction media whereby aldolization of the aldehyde sponding unsaturated aldehyde which upon reduction 45 feedstream takes place. The amount of water present in forms the saturated alcohol. One of such processes is the aldolization media must be controlled such that it described adequately in U.S. Pat. No. 3,454,649 where does not exceed the water solubility of said media so as high molecular weight alcohols containing 2 or more to maintain a homogeneous liquid-phase aldolization carbon atoms than twice the number in the olefin feed mixture. The product from this step is then hydroge are produced. The feed employed is the oxo reaction 50 nated over Raney-nickel catalyst at temperatures of product which is mixed with an oil soluble Group II 300' to 400' F. and hydrogen partial pressures of 1-40 metal compound such as magnesium oleate. The com atm. to produce a yield of saturated alcohols. bined feed is then passed to a heating zone where di By the term "aldolization" as used above is meant the meric aldehydes are produced. After demetalization, condensation reaction in which two molecules of alde the reaction product is hydrogenated under conven 55 hyde react and bond one to the other in a way such that tional hydrogenating conditions in the presence of hy the alpha carbon of the first aldehyde molecule be drogenation catalysts to provide dimeric alcohols. In comes attached to the carbonyl carbon of the second. U.S. Pat. No. 2,810,762, a process for the preparation The following illustrative equation demonstrates this of glycols and dimeric alcohols from aldehydes is de aldol condensation and subsequent dehydration. scribed wherein the aldehyde feedstocks employed are 60 feedstocks contaminated with minor amounts of alco hols and other impurities. The decobaited and dried H H crude aldehyde products from an oxo process are CH-CRO + CH-CEO passed to a reaction vessel and mixed with a slurry of le sodamide in a temperature range of about 100-250 F 65 where aldolization occurs. The crude condensation ch-h-ch-cho A ch,-ch=ch-cHo ; ho product is then converted to mono- and dihydric alco OH hols under conventional hydrogenation conditions. 4,032,578 - 3 The extent of aldol dehydration is dependent upon the specific process conditions of the reaction system. As H H described above, the feed may broadly be referred to as any aldehyde-containing feedstream. More particu R-CRO -- 2ROH 2 r--or + HO larly, feedstreams such as pure aldehyde or dilute feed OR streams containing aldehydes with or without asso aldehyde alcohol acetal ciated impurities may be used in the present invention. The basic catalyst employed is one generally to be Preferably, the feedstream employed is a crude, deme described as a weak to moderate base or a dilute solu talled, high conversion oxo product stream from a typi O tion of a strong base. Typically, Groups I-A and I-A cal oxo reactor. Such a crude oxo feedstream typically hydroxides are employed. Equally operable are Groups contains 20% hydrocarbons, 40% aldehydes, 20% alco I-A and II-A soaps, such as sodium stearate. Moreover, hols, and 20% acetals. Group I-A and II-A alkoxides and phenoxides are appli The novelty and improvement of the present inven cable. Alkoxides may be described as having the for tion over conventional aldol methods resides in the 15 mula RO-Na' where R is an alkyl group while phenox substitution of high temperatures for the conventional ides may be described as having the formula PhO-Na' high basicity concentration requirement. By using where Ph is a phenyl group. Nonlimiting representative higher temperatures, such as will be described herein examples of suitable catalysts include Groups I-A and after in the presence of a controlled amount of water, II-A oleates, stearates, octoates, and tallates; Group I-A lower levels of basic catalysts may be employed; and 20 and I-A acetates; sodium hydroxide, potassium hy higher aldehyde conversions to the aldol product will droxide, quaternary ammonium hydroxides and the be generated because of the reversion of the acetal like. species present in the feed and the avoidance of unde Catalyst demands are extremely small and conse sirable side reactions. It has unexpectedly been discov quently, the need for catalyst recycle operations is ered that acetal reversion to the aldehyde precursor 25 avoided. Low catalyst concentration has other benefi can be effectively carried out under slightly basic con cial effects, included among these are high product ditions in the presence of a controlled amount of water. selectivity. In fact, materials such as sodium acetate or An additional advantage gained by the operation of the sodium stearate, can be used in the aldol condensation present inventive process is that impure aldehyde feeds to give product with the equivalent selectivity and reac may be employed without substantially affecting over 30 tivity as a caustic sodium hydroxide base system. While all selectivities. any of the above-referred to materials may be used as a Another embodiment of the present invention is the catalyst, preferred as a catalyst is the use of dilute caus employment of a uniphase reaction system. This uni tic. phase system, which is obtained by monitoring process 35 As described above, where acetals are present in the ing conditions, such as water levels, temperature, and feedstream, the addition of water in a limited amount is the like, has distinct advantages in the operation of an critical to bring about the reversion of the acetal spe aldol condensation process. Some of the advantages of cies to the aldehyde. the uniphase oxoaldol processing at preferred process In a preferred embodiment of the instant invention, conditions, (hereinafter described as UFOA) not oth 40 an aqueous solution of a basic catalyst, which solution erwise obtainable with conventional technology are as contains water in an amount within the solubility limit follows: (1) The elimination of emulsions in the aldol of the aldolization mixture, is used to obtain a uniphase reactor and in subsequent processing steps; (2) sub aldolization media. The water solubility in the aldoliza stantial lower energy costs because of minimal mixing tion mixture depends on various factors such as the requirements since the reaction takes place in a single 45 specific feed employed and the reaction temperature. phase; (3) higher selectivity to the desired product as As shown in the attached diagram, the water solubility well as the use of relatively inexpensive materials of in a crude Coxoproduct, which may be used as the construction for equipment fabrication due to the low aldol feedstock, increases with the temperature. In caustic levels required; (4) plug flow reactors, e.g., general, the water solubility in a crude, demetalled Cn tubular or packed-fed reactors, may be used if desired; 50 oxo product (n=5.6, . . . , 12) increases by aproxi (5) catalyst recovery, recycle and associated handling mately one weight percent per unit decrease in the are eliminated since small quantities of catalyst are olefinic feed carbon number, as summarized in Table a used in a single pass system; (6) pure aldehyde feeds given below. TABLE a can be processed with high selectivity; and (7) finally 55 there is markedly lower investment and operating costs WATER SOLUBLITY IN CRUDE OXO PRODUCT per given plant capacity. ATSOOF. As described above, the contact of the aldehyde-con Oxo Product Solubility Oxo Product Solubility CHO 13.5 CHO s 9.5 taining feedstream with the basic catalyst may take CHO 12.5 CHO 8.5 place in the presence of a controlled amount of water 60 CHO ES 1.5 CHO se 7.5 where the aldehyde-containing feedstream also con CHO 10.5 CHO 6.5 tains a certain amount of acetal. The amount of water Notes: present in the aldolization mixture should be within the 'Data pertain to "high conversion"oxoproduct; i.e., 75-90 percent olefin conver 'sion in oxo solubility limit of said mixture so as to maintain a uni Solubility expressed as wt. percent HO; specific gravity of oxo product - 0.8 vs. phase reaction media. The following equilibrium shows 65 1.0 for water at ambient temperatures. that the presence of water helps bring about the acetal reversion to the aldehyde precursor and consequently The invention is operable over a wide range of pro higher yields of aldol product: cess conditions as described herein. However, the most 4,032,578 S 6 critical process variable is process temperature. In trolled amount of water, into the feedstream. If the order to achieve reactivity and maximum selectivities, feedstock is preheated in a separate container before it sufficient for a good commercial operation in the ab is fed into the aldolization reactor, the aqueous catalyst sence of the conventional high base concentration re solution can be homogeneously mixed with the feed quirements, a minimum threshold temperature of ap stock in this preheater with the use of a static mixer or proximately 200' F. is necessary. In general, however, other contacting devices known in the art. the process is operable from 150-1,000°F., preferably The overall process may be more readily understood from 300-800° F., most preferably 500-700°F. by reference to a typical process for manufacture of The amount of base to be employed, as described hexadecyl alcohol. Feed for the process is the crude, above, is the minimal amount necessary to bring about 10 demetalled Caldehyde stream produced in a conven the desired reactivity and selectivity. However, in gen tional oxo alcohol plant using UOP heptenes as the eral, the amount of base present during the course of a olefin feed source. Feedstream composition for HDA reaction will be from 0.01 to 3.0 wt.%, preferably from 0.05 to 2.0 wt.%, and most preferably from 0.1 to 1.0 manufacture via UFOA processing is as follows: lights wt.% based on amount of feed. 15 (10 wt.%), CHO (49 wt.%), COH (24 wt.%), Cs (1 Residence times, in general, depend upon process wt.%), C acetal (16 wt.%), and trace heavy compo conditions such as temperature, water level, etc. How nents. ever, satisfactory yields are obtainable with residence Aldolization is carried out in the following manner. times of between about 0.08 to 5 hours, preferably Three volume percent of 2.5 normal sodium hydroxide, from about 0.25 to 1.5 hours. The process is carried out 20 which contains water below the solubility limit of the at the autogeneous pressure of the reaction system and feed at the chosen temperature, i.e. 600°F., is continu is temperature dependent. Additionally, however, the ously added to a crude, CHO feedstream. This com process may be carried out at pressures which are sub posite stream is pumped through a reactor preheater to atmospheric or superatmospheric. attain a temperature of 600°F. A static mixer is em The hydrogenation of the aldol product to produce 25 ployed to promptly bring the mixture to a homoge the saturated alcohol is carried out under conventional neous state. Effluent from the preheater enters an insu conditions and using conventional catalysts. For exam lated, packed-bed reactor operated in the down-flow ple, hexadecyl alcohol precursor is effectively hydroge configuration. Space velocity through the condensation nated at 2800 psig with a Harshaw 3250T supported reactor is 2 v?hr/v. Composition of the reactor product nickel catalyst. may be carried out 30 stream is: lights (10 wt.%), CHO (24 wt.%), COH using any of the conventional hydrogenation catalysts (34 wt.%), C (30 wt.%), C acetal (2 wt.%), and including materials such as Raney-type nickel at pres trace heavy components. sures of from 400-600 psig. The products of the two Quenching and washing of the aldol product stream step process are saturated alcohols having twice the is carried out by a single unit operation. Water at ambi number of carbon atoms as the original aldehyde feed. 35 For example, octylaldehyde is the feed employed when ent temperature is continuously injected into the aldol hexadecyl alcohol is the alcohol desired. reactor effluent stream at a concentration of 10 volume It should be noted that the overall solubility of water percent based on the reactor flow volume. A static in an aldolization mixture does not, in general, change mixer in the transfer line from the condensation reactor significantly with the extent of aldolization, if the aldol 40 to a settling drum provides adequate contacting of the ization is conducted at a higher temperature, i.e., above product and water streams. Phase separation occurs in about 300 F., and a crude oxo product, which contains the disengaging drum which operates with a residence a substantial quantum of acetals, is employed. This is time of 5 minutes. Process temperature in the settling partly because a possible decrease in the water solubil drum is 350 F. ity due to the formation of aldols is largely counterbal 45 Aqueous phase from the settling drum is sent to the anced by an increase in the water solubility attributable oxoplant environmental conservation stream treat to the alcohols generated by the acetal reversion. Fur ment facilities in order to remove all pollutants. The thermore, as indicated in the accompanying Figure, the organic phase from the drum is compressed and trans water solubility of an aldolization mixture tends to ferred to hydrogenation facilities. converge to a limit point, regardless of its composition, 50 Hydrogenation is carried out in fixed bed reactors as the mixture temperature increases. operating at 2800 psig over NiWS catalyst at 350 F. In addition, the level of water present in the aldoliza and with a space velocity of 1.0 v./hr./v. Composition tion mixture remains substantially constant throughout of hydro product is as follows: lights (11 wt.%), CHO the aldolization process, for the portion of water con (trace), COH (59 wt.%), COH (30 wt.%), and trace sumed in reverting the acetals back to aldehydes and 55 heavy components. alcohols is substantially replenished by the water gener Separation and purification of hydro product is car ated by the alcohol dehydration. However, should one desire to continuously monitor the water solubility and ried out in a standard distillation train operating under the water content of the aldolization mixture at a given WaCUll. conversion and a chosen temperature, a standard Karl 60 Overall yields obtained with the UFOA process Fischer titration method as described in Example 7 scheme are 57 lbs, isooctyl alcohol and 28 lbs. hex may be employed. adecylalcohol per 100 lbs. of crude oxo feed of the Widely practiced means of introducing water may be composition stated above. employed in order to readily obtain a uniphase aldol To further illustrate the process of the present inven ization media. For example, a sparger or a quench 65 tion, the following examples are provided; however, it distributor, which may be provided in the aldolization is to be understood that the details thereof are not to be reactor, can be utilized in introducing an aqueous solu regarded as limitations as they may be varied as will be tion of a basic catalyst, which solution contains a con understood by one skilled in the art. 4,032,578 7 8 amount of water is within the solubility limit of the EXAMPLE 1. reaction mixture. Crude, demetalled, oxo product produced from UOP Run II was carried out in a 2000 ml round bottomed heptene polymer was the feedstream for all reactions glass flask continuously purged with a very small summarized in Table I. Feed and product compositions 5 amount of inert gas (N) to eliminate oxygen from the for the experiments described herein were determined system. A reflux condenser was fitted to the top of the by G.C. using n-nonane as an internal standard for reaction flask and chilled water was circulated through instrument calibration. Pertinent analyses are pres the shell side and its internal cooling coils in order to ented below. eliminate loss of organic components from the system. Water, catalyst, and feed were mixed in the amounts 10 The reaction system was vented through the reflux shown and the composite mixture was charged to a 1 condenser, and the N purge leaving the reflux con liter autoclave at ambient pressure and temperature. denser was discharged at essentially atmospheric pres After the reactor was flushed with inert gas, it was Ste. sealed and rapidly heated to 500 F., forming a uni Procedures used for Run II were as follows: Approxi phase mixture. Temperature was controlled (+5 F.) at 15 mately 500 cc of aqueous caustic solution was prepared this level by standard control instrumentation. Sam by slowly dissolving reagent grade NaOH (164 gms) in pling of the reaction product was carried out at the water (418 gms). This caustic solution was added to the process temperature and residence time shown in glass reaction vessel through a feed port located on the Table I and the compositions of the product streams top of the 3-necked, round bottom flask. Crude oxo were determined according to the G.C. procedure pre 20 feed (500 cc) of composition shown in Table II was viously described. also added to the reaction vessel through the feed port. Results show: (1) aldehyde components in a crude, The reaction vessel was sealed, purged with inert gas, demetalled, C oxo feedstream can be condensed at and heated by an electrical heating mantel surrounding high temperature with small quantities of base catalyst the flask. Vigorous stirring was provided by a standard in a single phase reaction environment with high selec 25 flask mixer powered by an external air motor. The tivity; (2) aldolization to the desired dimers is effec reaction was conducted at 195 F. for 4 hours. It should tively catalyzed by small amounts of base; thermal be noted that the amount of water present in the reac treatment of crude oxo product does not produce sig tion mixture exceeded the solubility limit of the reac nificant yields of C dimers (Run I vs. Run III); (3) tion mixture; hence, a two-phase reaction media was acetal components in the crude feedstream revert to 30 formed. Product was sampled at process temperature alcohol and aldehyde at the above process conditions and analyzed by the G.C. procedure previously de and concurrent production of commercially valued fined. products is achieved; and (4) the reaction can be car Run III was carried out with crude, demetalled oxo ried out with different classes of base catalyst (e.g., product of composition shown in Table II. A single 0.02 wt.% NaOH on feed and 1.07 wt.% benzyl tri 35 phase reaction environment was employed through the methyl ammonium hydroxide on feed). use of an alcohol diluent. TABLE I HDA PRODUCTION FROM CRUDE, HIGH CONVERSION, DEMETALLED, C, OXO PRODUCT WIA. UFOA PROCESSING Aldol Step Run Run Run 8 Reaction Conditions: + Reactor Type Batch Batch Batch + lsothermal Reaction Temperature (F) 500 500 500 -- Res. Time (hrs) 5 4 4. O Feed: + CHO Hydro Feed (cc) 500 500 500 + HO (gms) 25 15 25 + Catalyst (type) NaOH (dbCH)N(CH)OH None + Catalyst (gms) 0, 4.3 m Aldol Feed and Product Compositions C-Pct. by weight-e- Component Aldol Feed Run Prod. Run I Prod, Run Prod. lights 0.5 9.6 10.3 10.8 CHO 49.0 22.2 34.7 44.3 COH 24.0 33.9 33.1 29.8 C Prod. 2.6 32.4 7.5 6.5 C 14.0 2. 2.7 4.8 ob = phenyl. Procedures employed for Run III follow. Base cata 60 lyst was mixed with the alcohol and the oxo product EXAMPLE 2 componenty of the feed was added and thoroughlyp Crude, demetalled, oxo product produced from UOP mixed. The composite reaction feed was placed in a polymer was the feed for all reactions (Runs I, II and standard 3 liter steel rocker bomb and purged with III) shown in Table II. Feed and product analyses for inert gas (N). The closure of the reaction vessel was these experiments were determined by the standard 65 sealed and the vessel placed within a standard rocker G.C. procedure set forth in Example 1. cradle. Rapid heating was provided by an electrical Run 1 was carried out in a 1 liter autoclave according heating mantel surrounding the reaction vessel. Tem to the procedures set forth in Example I wherein the perature was maintained (5 F.) by conventional con 4,032,578 9 10 trol instrumentation at the desired process temperature EXAMPLE 3 for the time interval shown below. After the desired residence time was reached, the reaction vessel was Feed materials for the experiments summarized in rapidly cooled by chilled water flowing through an Table III were crude, demetalled, oxo products pro internal cooling coil. The product was removed from 5 duced from various molecular weight fractions of a the reactor and analyzed by G.C. commercial UOP polymer stream. Compositions of Results show: (1) yields of valued product (C. alco feed and product streams were obtained by G.C. in the hol and dimer alcohol precursor) are substantially manner as set forth in Example 1. Analyses are pres greater using the claimed UFOA process technique; ented below. conventional 2-phase aldolization (Run II) using the 10 Each experiment was carried out using 1500 cc of high basicity required to attain reasonable reactivity oxo feed. The procedure of Example 2, Run III was and the uniphase reaction system (Run III) using an utilized for each run except that water was employed in alcohol solubilizing diluent give substantially lower place of isopropyl alcohol, and the reactions were per product yields; (2) stable emulsions characteristic of formed in the same process equipment. Oxo product conventional two-phase aldolization reaction systems 15 feed was mixed with aqueous caustic in the amounts using C," aldehyde feeds (e.g., Run II) are not formed shown below and the composite feed was placed within in the UFOA process claimed herein (e.g., Run I); 3) a 3000 cc steel rocker bomb. These reactions where acetals contained in crude oxo feed do not revert to then performed in the rocker bomb according to the alcohol and aldehyde precursors in conventional aldol procedures set forth in Example 2, Run III. reaction systems (e.g., Runs II and III) and further- 20 The results of this Example are set forth in summary more, the classical aldolization reaction systems using fashion in Table III and show that the UFOA condensa high basicity catalysts generate measurable quantities tion carried out by the present invention is applicable of heavy boiling components. to a wide molecular weight range of crude oxo product streams used as feedstreams. TABLE II NEWALDOL PROCESS VS. CONVENTIONAL ALDOL CONDENSATON UFOA Run Run Run o Reaction Conditions: (Batch Reactions) + Isothermal Reaction Temperature (F) 500 95 180 + Res. Time (hrs.) 5 4. 4 O Feed: + CHO Hydro Feed (cc) 500 SOO 500 + HO (gms) 25 418 82 + Naoh Catalyst (gms) 0.1 164 -- + KOH Catalyst (gms) an 82 + Isopropyl Alcohol (gms) O 410 8 Feed and Product Compositions (% by wt.) C-RunUFOA I-D C-Run II-D C-Run III-e Component Feed Product Feed Product Feed Product lights 0.5 9.6 22.6 23.9 23.1 25.7 CHO 49.0 22.2 45.7 4.5 49. 4.5 COH 24.0 33.9 17.0 15.8 17.8 10.7 C Prod. 2.6 32.4 3.4 3.2cs 1.9 34.33 C Acetal 14.0 2. 1,4 14.5 7.2 13.0 Heavies None Detected None Heavies Present- 0.9 11.8 Detected Amt. Unknown e Product Selectivities and Yields; Run Run Run + C Selectivity" - 97 57 max 5 + (C + C) Alcohol Yield' 98t 67 max 40 Notes: "The product composition shown is on a heavies-free basis. Bottoms have been detected (by G.C.) in product produced by the conventional aldol reaction system; however, selectivity to heavies is not presently known. 'For Run Il, ca. 30% of the components identified as C. Prod. do not correspond to com ponents contained in the C fraction obtained via the Aldox route to HDA or the new UFOA aldol process. These materials may not be alcohols or aldehydes, 'For Run III, ca. 25% of the components identified as C. Prod. do not correspond to com ponents contained in the C fraction obtained via the Aldox Route to HDA or the UFOA aldol process. 'Product reported on an IPA free basis. Net C Product Formed 'C SelectivityE (Aid. -- Acetal) decrease x 100: (COH Precursor + CHO + Net COH) Prod. (C + C).w Alc. Yield E (COH Precursor + CHO + Acetal) Feed X 100: where: Net COH = COH in Prod. - COH in Feed. 'Selectivity and Yield reported on heavies-free basis. Therefore, estimates represent maximum possible selectivity and yield for Run Il. 4,032,578 11 12 TABLE III Wt. 2 Prod. Distribution via. G.C. wt.% Product Feed Run No. Cat. Lights CHO CHO Car Acetal Selectivity (%) CHO Feed 5.6 54.7 15.4 7.4 16 --- CHO IIl- 0.14 4.5 18.8 27.0 46.6 3.1 100. CHO Feed 10.5 49.0 24.0 2.6 40 CHO III-2 0.04 O 25. 29.6 32.5 1.8 00, CHO Feed -- 6.5 16.6 29.6 7.4 37.3 CHO III-3 0.18 17.5 10.7 4.1.1 27.5 3. 00. Notes: Reaction Conditions: 'Prod. Selectivity = percentage o Reactor Type-Batch of converted components to sale- oType = 500 F able product. 8Res. Time = 5 hrs. OHO = 5 vol.% on feed except Wt.% Cat. = Wt.% NaOH on feed. = 3 vol. (Run -3) Trace heavy components detected in feeds and products.

EXAMPLE 4 EXAMPLE 5 In this Example carried out in the manner described In the manner described for Example 3 above, a for Example 3 above, the effect of catalyst source on series of experiments were carried out to determine the selectivity was investigated. 20 sensitivity of selectivity and integral product yield to The results found in Table IV show: (1) sodium hy reasonable variations in the ratio of aqueous base cata droxide, acetate, or soaps (stearate, tallates, etc.) can lyst to oxo product feed. The results of these runs may be effectively employed as catalyst in UFOA reaction be found in Table V and show that product selectivity systems giving comparable integral reaction rates and is not measurably effected by varying aqueous catalyst product selectivities; (2) selectivity to dimer alcohol 25 to oxo product feed ratio ca. 20% around a desired precursor much greater than 100% can beachieved process operating point (e.g., conditions set forth in (selectivity based on aldehyde content in feed, e.g., Run V-2 below). TABLE V CHANGES IN HOICATALYST CONCENTRATION DO NOT MARKEDLY ALTER UFOA CONDENSATION SELECTIVITY, INTEGRAL REACTION RATE, OR PRODUCT YELD Vol. of 0.1N Prod. Distribution via G.C. wit. Product Feed Run No, NaOH on Feed ights CHO CHO Cis Acetal Select. (%) CHO Feed 10.5 49.0 24.0 2.6 40 CHO W. 34 10.9 27.5 28.8 29.4 3.4 100. CHO W-2 50 10.4 27.8 29.9 29.2 2.6 00. CHO W.3 6.7 13.7 21.9 28.8 33.5 2.2 00. Notes: Reaction Conditions: Product Selectivity = percentage o Reactor Type-Batch of converted components to o, Tse 500 F saleable product. o Res. Time as 5 hours Trace heavy components detected in feeds and products, Run No. IV-1 with feed composition shown) with p ) EXAMPLE 6 UFOA processing; (3) oxo feedstreams containing high 45 acetal content can be efficiently utilized by UFOA In the manner described for Example 1 above, a processing; and (4) the precursor of octadecyl alcohol series of runs were carried out to determine the effect can be readily produced by employing the claimed of primary process variables on UFOA selectivity and invention using a crude oxo plant stream available reactivity. Data are presented in Table VI. Results during isononyl alcohol production. indicate UFOA condensation of aldehydes can be car ried over a broad range of temperature and catalyst levels without incurring measurable selectivity loss. TABLE IV CATALYSTS FOR UFOA CONDENSATION Prod. Distribution via G.C. wit. Product Feed Run No. Catalyst Lights CHO COH Cis Acetal Selectivity (%) CHO Feed 16.5 16.6 29.6 7.4 37.3 CHO V-1 Na Stearate 17.4 9. 40.9 27.2 4. 100. CHO V-2 Na Acetate 17.5 10.6 4.6 26.8 3.5 100. CHO V-3 NaOH 7.3 0.4 4. 26.9 4.2 100. Notes: Reaction Conditions: 'Product Selectivity = percentage o Reactor Type-Batch of converted components to oT = 500 F saleable product. oP = 550 psig Res. Times 5 hours Cat. = 0.16 wt.% NaOH on HO s 3 vol% on feed feed or equivalent Trace heavy components detected in feed and products. 4,032,578 13 14 TABLE VI - - -m-rh UFOA CONDENSATION GVES HIGH SELECTIVETY WHLOW RESIDENCE TIME React. Res. Prod. Wt. Vol. 1) Prod. Distribution via G.C. Wit. Temp. Time Select. %(1) Feed Run No. NaOH HO Lights CHO COH C, Acetal Heavy (F) (hrs) (%) CHO Feed -- wn 5.7 4.7 21.2 44 17.1 trace - ro- - CHO V- 0.45 20 3.0 15.8 35.3 32.7 3.3 trace 600. 15 100. CHO Feed - 10.5 49.0 24.0 2.6 4.0 trace -- - w CHO W-2 0.2 4.0 6.02) 30.5 29.6 31.3 2.6 trace 500. 1.5 100. CHO WI-3 0. 2.0 7.5(2) 36.6 26.1 26.5 3.3 trace 550. 0.5 100. Notes: Catalyst and water levels based on CHO Feed 'Lights lost during sampling

EXAMPLE 7 temperature ranging from about 300' F. to about Example 7 illustrates a method of measuring the 1,000 F. to achieve a uniphase aldolization mixture. maximum level of water solubilizable in a crude oxo 2. The process of claim 1 wherein said basic catalyst product, or an aldolization mixture, at a given tempera is selected from the group consisting of sodium hydrox ture. 20 ide, potassium hydroxide, sodium stearate, sodium A 1,000 cc. static cell was charged with approxi acetate and benzyl trimethyl ammonium hydroxide. mately 150 cc of water and 350 cc of an oxo product 3. The process of claim 2 wherein said basic catalyst having a given conversion level, e.g., 25%, 50%, 75%, is sodium hydroxide. or 90%. The cell was rocked in a constant temperature 4. The process of claim 1 wherein said aldehyde-con bath to attain an equilibrium. After the equilibration, 25 taining feed is a crude-demetalled oxo product. the agitation was stopped; and two phases, i.e. oil-rich 5. The process of claim 4 wherein said oxo product and water-rich, were allowed to separate. Subse comprises an acetal. quently, a sample was withdrawn from the oil-rich 6. The process of claim 1 wherein said aldolization phase for an analysis. The water content in this sample temperature ranges from about 500F. to about 700°F. was then determined by a standard Karl Fischer titra 30 7. A process for producing an aliphatic alcohol which tion method. Such measurements were conducted on a comprises: series of Coxo products having the conversion rates a. contacting an aldehyde-containing feed with a of 25%, 50%, 75% and 90% at various temperature catalyst, in an amount ranging from about 0.01 to levels. about 3 weight percent based on the aldehyde-con The data plotted on the accompanying Figure show 35 taining feed, selected from the group consisting of that the water solubility in a C oxo product rises hydroxides, soaps, alkoxides and phenoxides of rapidly with the increase in the temperature; and that Groups I-A and I-A metals, quaternary ammonium the water solubilities in the C oxo products of the hydroxides and choline in the presence of water in four different conversion levels essentially converge to an amount substantially within the solubility limit a maximal point at a temperature near 700°F. 40 of the aldehyde-containing feed at a temperature What is claimed is: ranging from about 300 F. to about 1000 F. to 1. An aldolization process which comprises contact achieve a uniphase aldolization mixture; and, ing an aldehyde-containing feed with a catalyst, in an thereafter, amount ranging from about 0.01 to about 3 weight b. hydrogenating the aldol product produced in (a) percent based on the aldehyde-containing feed, se 45 above under conventional conditions and using lected from the group consisting of hydroxides, soaps, conventional catalysts to produce said aliphatic alkoxides and phenoxides of Groups I-A and II-A met alcohol. als, quaternary ammonium hydroxides and choline in 8. The process of claim 7 wherein said aliphatic alco the presence of water in an amount substantially within hol product comprises hexadecyl alcohol. the solubility limit of the aldehyde-containing feed at a 50 k ak k k :

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