US3247264A - Method of manufacturing solid alcohols - Google Patents

Description

United States Patent 3,247,264 METHOB or MANUFACTURING some ALcorroLs Warren L. Beears, Brecksviiie, and Edward H. Eoliinger, Akron, Qhio, assignors to Goodrich-Gulf Chemicals, 1116., Cievcland, Ohio, a corporation of Deiaware No Drawing. Fiied July 22, 1960, Ser. No. 44,525

153 (Jiaims. (Cl. 260632) This invention relates to a process for producing telomer alcohols from oxidized alkyl aluminum chlorides, and particularly for producing telomer alcohols having from 12 to 30 carbon atoms from mixed oxidized telomer allryl aluminum chlorides, commonly referred to in the art as mixed telomer allroxyaluminum chlorides, which process constitutes an essential step in the production of telomer alcohols directly from alpha-olefins, such as ethylene, by chemically inserting hydrocarbon groups into mixed alkyl aluminum chlorides by chain growth, that is, by telomerization, to produce mixed telomer alkyl aluminum chlorides, the latter in turn being oxidized to produce mixed elomer alkoxyaluminum chlorides, and finally, the mixed telomer alkoxyaluminum chlorides are treated with a proton donator to convert the mixed telomer alkoxyaluminurn chlorides to telomer alcohols having the same number of carbon atoms as are contained in the telomer alkyl groups of the mixed telomer alkoxyaluminum chlorides. It is to this final step that the present process relates.

A preferred process for the production of telomer alcohols from gaseous alpha-olefins is disclosed in the copending application Serial No. 22,702, filed April 18, 1960.

In that application, the process for producing telomer alcohols, to which this invention relates, is fully set out. Briefly, it comprises a series of coordinated steps represented by the following equations:

3C H Cl+2Al Z (C H AlCl l 2 z s xA C 2 4 n an+1)x 2 n 2u+1)X y l" 2 11' 2n+l )x y (C,,H O) AlCl +xH+ xC l-1 OH-}- (4) wherein x and y represent average numerical values ranging from 2.7 to 0.3 and whose sum is 3; m represents the number of moles of (3 1-1 groups required for reaction (2); n represents the average number of carbon atoms built into the alkyl chains of the mixed alkyl aluminum chlorides to produce the mixed telomer alkyl aluminum chlorides, and which for plasticizers normally ranges from 8 to 16 carbon atoms, and for other industrial use, such as detergents, ranges from 12 to 30 carbon atoms, and even a larger number of carbon atoms are desired for some industrial uses.

In each of the above Equations 1 to 4, x and y represent the average numerical values of the constituents of the mixed reaction products. Thus, Where x and y are 1.5, the compounds are termed sesquichlorides. However, the values of x and y are commonly of the order of 1.8 to 1.2, and, as indicated above, may vary as widely as from 2.7 to 0.3, or even more widely. In the chemical industry, independently of the specific numerical values of x and y, the mixed alkyl aluminum chlorides of Equations 1 to 4 above, are termed sesquichlorides, and the term sesquichloride is sometimes herein used in that broad sense.

It is to the step (4) above, namely, the hydrolysis of the mixed oxidized telomer alkyl aluminum chlorides, or the telomer alkoxyaluminum sesquichlorides, by a proton donator, to produce the telomer alcohols, that the invention of this application primarily relates.

As described in the earlier copending application, Ser. No. 22,702, the mixed telomer alkoxyaluminum chlorides 3,247,264 Patented Apr. 19, 1966 which are to be hydrolyzed to form the telomer alcohols and which are produced by the oxidation of mixed telomer alkyl aluminum chlorides, as in Equation 3 above, (a) may be of high purity, the other chemical compounds present during the oxidation reaction (3) having been removed prior to the hydrolysis, or (b) may contain some or all of the compounds present during the oxidation reaction (3), namely (i) liquid organic anhydrous dispersant or dispersants, (ii) finely divided potassium salt, and (iii) free hydrocarbons. In either case, the hydrolyzed mixed telomer alkoxyaluminum chlorides, or telomer alcohols, may be more eitectively produced by the process of the invention of this application, as will be presently described.

In the prior processes of hydrolyzing the mixed telomer alkoxyaluminurn chlorides, the hydrolyzing medium is an aqueous solution of hydrochloric or sulfuric acids, or water alone. While the hydrolyzing medium is being vigorously stirred, the anhydrous telomer vallroxyaluminum chlorides are added thereto so as to bring the telomer alkoxyaluminum chlorides into intimate agitative reactive contact with the aqueous hydrolyzing medium, thus efiecting within the resulting admixture the production of the telomer alcohols in accord with the Equation 4 above. Thereupon, the mixture is separated, as by settling, into two portions, an upper organic portion containing the telomer alcohols and a lower aqueous portion. The latter is drawn off and the telomer alcohols recovered from the upper organic portion. The telomer alcohols are said to be sprung from the telomer alkoxyaluminum chlorides.

The prior process, while commercially operative for telomer alcohols having up to 12 carbon atoms, is not economically effective for telomer alcohols having from 12 to 30 or more carbon atoms, all of which are solids at room temperatures, namely, 20 (3., since it is very difiicult to obtain by settling a good clean and complete phase eparation between the organic and aqueous phases of the admixture, for the reason that solid gels of the solid telomer alcohols form in the admixture and cloudy, difiicultly separable phases result, requiring more time and generally further separation operations that cause low product yields and increased cost of the separation operation.

Extensive experimentation and tests have shown that as the chain length of the solid telomer alcohols increases, the difiiculty of phase separation because of gelation is increasingly greater, that better separations are obtained at higher temperatures than at lower temperatures, but that at higher temperatures the telomer alcohols decompose and discolor and that even colorless telomer alcohols hydrolyzed at higher temperatures give straw-colored plasticizers when esterified with phthalic anhydride.

The object of this invention is to effect economically in a short time and at relatively low temperatures a good clean and practically complete phase separation by settlin of the two-phase admixture resulting from the hydrolysis of higher telomer alkoxyaluminum chlorides by an aqueous hydrolyzing medium.

Applicants have in the invention of this application discovered a novel, highly effective and economical process for overcoming the inadequacies of the prior processes enumerated in the preceding paragraphs, which novel process makes commercially practical (a) a good clean and practically complete phase separation at reasonably low temperatures in a few minutes of time with a hi h yield of solid telomer alcohols, (b) colorless solid telomer alcohols, and (c) colorless plasticizers when the telomer alcohols are esterified with phthalic anhydride.

In carrying out the invention of this application, there is employed a novel hydrolyzing medium comprising Water, or water and an acid, and an alcohol liquid at normal temperatures and having a boiling point lower than that of the solid telomer alcohol being produced, these alcohols a's' a"c1ass being referred to. as liquid alcohols and alcohols having from 2 to 10 carbon atoms being herein for convenience termed liquid low-boil alcohols. The liquid alcohol is present in proportions ranging from 4 to 100 parts byweight of alcohol to 100 parts of the telomer alkoxyaluminum chlorides, normally from 30 to '75 parts by weight of the liquid alcohol are employed, the ratio of liquid alcohol to the telomer is not critical and preferably increases as the number of carbon atoms in the telomer alcohol increases. The hydrolyzing medium may also contain small proportions of sulfuric and hydrochloric acid, as in the prior processes, but it has been ascertained by extensive testing that these acid con stituents are not essential to the invention of this application and may be omitted.

The telomer a koxyalurninum chlorides from which the telomer alcohols are sprung, may be dispersed in the liquid organic anhydrous dispersant in which the telomer alkoxyaluminum chlorides were produced. These dispersants include the liquid alkanes, the liquid mixed alkanes, such as Deobase kerosene and those resulting from the Fischer-Tropsch process, the liquid cycloalkanes, the liquid benzene hydrocarbons, tetrahydrofuran, isopropyl ether and the like. Also included may be other compounds present at the end of the oxidation step producing the telomer alkoxyaluminum chlorides. Alternatively, the telomer alkoxyaluminum chlorides may be practically free of any other compounds.

GENERAL EXAMPLE It is to be understood that the invention of this application is not limited to any particular apparatus for the carrying out'of the process thereof. A suitable hydrolyzing reactor comprises a fluid tight reaction vessel, such as a jacketed Pfaudler kettle, equipped with an electrically driven rotary stirrer; a thermometer; inlet and outlet connections, including an inlet for delivering to the hydrolyzer'the hydrolyzing medium, preferably in measured amount, as through a recording liquid meter, from a source of supply, as a storage tank; and an inlet for delivering the telomer alkoxyaluminum chlorides, preferably in measured amount as through a recording liquid meter to indicate rate and amount of flow; a reflux condenserfor venting vapors from the top of the hydrolyzer and for condensing and returning condensed vapors to the hydrolyzer; and a valved outlet connection from the bottom of the hydrolyzer. There is also provided means for heating or cooling the hydrolyzer contents, such as the outside heat-transfer jacket or inside heat-transfer coils, or both, for maintaining a desired range of temperatures of the hydrolyzer contents. Alternatively, the reflux condenser may be of the closed type, in which case the pressure within the hydrolyzer should be kept at a low level, and should not exceedlS to 20 p.s.i.g.

The hydrolyzing medium comprising water, or water and acid, and a liquid alcohol is charged into a hydrolyzer of the type hereinabove described and the stirrer placed in operation. The hydrolyzing medium may be, but is not necessarily, heated to near, but not much above, the reflux temperature, of lowest boiling constituent of the hydrolyzing medium. The I telomer alkoxyaluminum chlorides which may be, but are not necessarily, preheated to about the temperature of the hydrolyzing medium, are fed slowly into the hydrolyzer, with the agitation continuing'until the hydrolyzing action is completed, the exothermic heat of hydrolysis being removed by the cooling means. The hydrolyzing action is almost instantaneous as the telomer alkoxyaluminum chlorides are stirred into the hydrolyzing medium. The stirrer is turned off and the organic phase and the aqueous phase allowed to separate. Good clean and complete separation of the two phases is obtained in about 5 to minutes. 5 minutes is suflicient. The heavier aqueous phase is withdrawn from the bottom of the hydrolyzer through Usually a valved outlet connection, Then the lighter organic phase, which includes the sprung telomer alcohols, is withdrawn for further processing and recovery of the telomer alcohols. This is accomplished by the neutralizing, drying and filtering of the sprung telomer alcohols. Where it is desired to separate mixed telomer alcohols into the individual telomer alcohols, this further step is accomplished in the usual way by fractional distillation under vacuum of the mixed telomer alcohols.

EXAMPLE I The following example is illustrative of the process of this invention. Utilizing the apparatus and procedure described in the General Example and starting with a tel omer alkoxyaluminum sesquichloride of the formula (C l-i O AlCl wherein theaverage value of n is 14, and with a hydrolyzing medium comprising 140 grams of n-butanol admixed with 280 grams of distilled water, first, charge the hydrolyzing'rnedium into the hydrolyzer, and place the stirrer in operation, then, add gradually and slowly into the top of the hydrolyzer 440 grams of the said telomer alkoxyaluminum sesqui'chloride, the heat. of hydrolysis raising the temperature of the hydrolyzer contents which for highest efficiency should be maintained at about C. to C., i.e., at a temperature not higher than about the boiling point of any constituent in the hydrolyzer, by' carrying away the heat of hydrolysis through the heat-transfer devices.v Higher or'lower temperatures, however, may be employed. When the hydrolyzing reaction, which is normally very rapid, is completed, the stirrer is turned off and the hydrolyzer contents allowed to stand to separate it into two phases, a lighter upper organic phase which contains the telomer alcohols as well as a major part of the n-butanol, and a heavier aqueous phase. The lighter organic phase is then isolated and the telomer alcohols recovered therefrom, as

by fractional distillation, and analyzed with the following results:

Table I .T elomer alcohols yield EXAMPLES 11 TO v Several different telomer alkoxyaluminum sesquichlorides (TAS) were isolated and each'hydrolyzed separately with a hydrolyzing medium (HM) consisting of n-butanol and water, followingthe procedure of Example I, the data of each of these operations being tabulated below.

EXAMPLE II Parts by weight, grams (a) TAS=(C1ZH25O)L5AICIL5 (b)HM= n-Butanol 15 And water 50 Phase separation time, 10 minutes Percent yield C H OH=98.8.

EXAMPLE III Recipe:

(a) TAS: I

n-Butanolfi 20- And' water Phase separation time, 10 minutes.

Percent yield C H O H:98.8.

5 EXAMPLE IV Parts by Weight, grams Recipe:

(a) TAS:

24 49 )1.5 1,5 (b) HM:

n-Butanol 50 And water 75 Phase separation time, 10 minutes. Percent yield C H OH=98.5.

EXAMPLE V Recipe:

(a) TAS:

3u e1 )1.5 1.5 100 (b) HM:

n-Butanol 60 And Water 100 Phase separation time, 10 minutes. Percent yield C I-i OI-I==97.8.

EXAMPLES VI TO VIII In the following series of tests, a number of telomer alkyl aluminum sesquichlorides were oxid zed in a liquid dispersant comprising heptane and potassium chloride to produce telomer alkoxyaluminum sesquichloride dispersed in the liquid dispersant and the letter was hydrolyzed as described in Example I in a hydrolyzing medium comprising water, n-butanol and sulfuric acid, producing telomer alcohols, all as indicated below:

EXAMPLE VI Parts by Recipe: weight, grams (a) TAS:

( 10 21 )1.5 1.5 100 Heptane 30 KCl 10 E (b) HM:

Water 150 n-Butanol 4 Sulfuric acid 20 174 Phase separation time, 5 minutes. Percent yield C I-I OH=98.4.

EXAMPLE VII Recipe:

(a) TAS:

12 25 )1.5 1.5 100 Heptane 32 KCl m (b) HM:

Water 130 n-Butanol 5 Sulfuric acid 20 155 Phase separation time, 5 minutes. Percent yield C H OH=98.9.

EXAMPLE VIII Recipe:

(a) TAS:

31 )1.5 1.5 190 Heptane 35 KCl 10 m (b) HM: Water 120 n-Butanol 10 Sulfuric acid 150 Phase separation time, 5 minutes. Percent C15H31OH:99.3-

It is clearly demonstrated in the above Examples II to VIII that the hydrolysis of telomer alkoxyaluminum sesquichlorides, including the separation of the organic and aqueous phases, is by the process of this invention carried out in a short time to produce a high yield of telomer alcohols.

As has been hereinabove indicated, the longer the alkyl chain of the telomer alcohol the more difficult it is to effect the phase separation essential to spring the telomer alcohols from the hydrolyzing medium. To illustrate the effectiveness of the hydrolyzing medium comprising other low-boil alcohols and water, the following series of tests were run utilizing telomer alkoxyalurninum sesquichloride having 24 carbon atoms, namely,

EXAMPLE IX Parts by Recipe: Weight, grams 24 49 )L5 l.5 1% (b) HM:

Water Ethanol (B.P. 78.5 C.) 75

175 Phase separation time, 5 minutes. Percent yield C H OH=99.2.

EXAMPLE X Recipe 24 9 )1.5 1.5 lQQ (b) HM: Water 100 n-Propanol (B.P. 972 C.) 40

Phase separation time, 5 minutes. Percent yield C H OH=98.7.

EXAMPLE XI Recipe:

(b) HM: Water 100 n-Pentanol (B.P. 137.8 C.) 60

Phase separation time, 5 minutes. Percent yield C H OH:98.5.

EXAMPLE XII Recipe:

( 24 49 )1.5 1.5 w (b) HM: W'ater 100 n-Hexanol (B.P. 157 C.) 40

140 Phase separation time, 5 minutes. Percent yield C H OH:99.3.

EXAMPLE XIII Recipe:

( TAS: 24 4Q )1.5 1.5 E (b) HM: Water 100 n-Heptanol (B.P. 156 C.) 75

Phase separation time, 5 minutes. Percent yield C H OH=981 Percent yield C I-I, H:98.7.'

As is clearly shown in Examples I to XIV, above, the added low boiling liquid alcohols may be added in amounts as low as 4% to as high as 100%, by weight,

of the telomer alkoxy-aluminum sesquichloride (TAS) to yield from 98% to as high as 99.7% of the desired solid alcohol. A summary of Weights of'constituents disclosed in the above Examples I to XIV clearly demonstrates this wide variability in the percentages of low boiling alcohol needed.

ployed may be varied, and that equivalent materials may 7 be employed where desirable, without departing from the spirit and scope of the invention as defined in the appended claims.

What we claim is: 1. A process for the manufacture of higher alkyl hydrocarbon alcohols that are solids at room temperatures, which process comprises stirring alkoxyaluminum sesquichlorides of the'empirical formula (C H O) AlCl in which x and y are each numerical values ranging from 2.7 to 0.3 and whose sum is 3 and in which n ranges from 12 to 30, into a hydrolyzing liquid medium consisting essentially of (i) water and (ii) an alcohol which is liquid at room temperatures selected from the class consisting of alkyl monohydric hydrocarbon alcohols having from 2 to 10 carbon atoms; the said liquid alcohol being present in from 4% to 100% by weight of the alkoxyaluminum sesquichloride; continuing the stirring until all of the alkoxyaluminum sesquichloride has been intimately admixed into the hydrolyzing liquids, then allowing the resulting mixture to stand, in which condition it quickly 7 7 Table of weights of constituents used in Ex. I to XIV TAS A W HM A/TAS, A/HM, HM/TAS, Ex. Sesqui- Liquid Water Hydropercent percent percent chloride alcohol lyzing 1 medium Other added liquid alcohols than the liquid low-boil alcohols referred to in the above specific examples are operable in the process of the invention of this application to bring about a clean and complete separation of the organic phase and theaqueous phase of the mixture produced in the hydrolysis of telomer alkoxyaluminum chlorides. The ease of separating out of the added liquid alcohols from the telomer alcohols produced may be determinative of the specific added alcohol to be employed. Experience has indicated that the added liquid alcohol should have a boiling point at least 25 C. lower than that of the telomer alcohols being produced and that the liquid low-boil normal alcohols having from 2 to 8 carbon atoms are preferable in the production of the process of this invention of telomer alcohols which are solids at normaltemperatures, viz. the C and higher alcohols.

Other liquid alcohols which have been found to be effective in the process of the invention of this application, not specifically mentioned in the above examples, are the monohydric alcohols, such as 2-propanol, B.P. 82.4 C.; sec-butanol, B.P. 99.5 C.; tert.-butanol, B.P. 825 C.; tert.-pentanol, B.P l0l.8 C.; 2-ethylbutanol, B.P. 148.9 C.; 3-heptanol, B.P. 156 C.; 2-octanol, B.P. 178.2 C.; n-nonanol, B.P. 215 C.; n-decanol, B.P. 232j C.; and also polyhydric alcohols, such as ethylene glycol, B.P. 197.2" C.; propylene glycol, B.P. 182 C.; 1,3-butylene glycol, 207 C.; hexylene glycol, B.P. 198 C.; glycerol,

' B.P. 290 C.; and the like.

separates into two distinct layers, namely, an upper liquid organic portion containing the higher solid alcohol produced and a lower aqueous layer; and fractionally distilling the said upper organic portion to isolate the higher solid alcohols thus produced.

2. The process defined in claim 1 in which the liquid 7 V ous liquid of the hydrolyzing liquid is water. I

, 6. The process defined in claim 1 in which the liquid alcohol of the hydrolyzing liquid is a butanol and the aqueous liquid of the hydrolyzing liquid is water.

7. The process for the manufacture of a higher alkyl 7 alcohol that is solid at room temperature and is within the empirical formula C H OH, in which n ranges from 12 to 30, which process comprises admixing with stirring an alkoxyaluminum sesquichloride of the empirical formula (C H O) AlCl in which x and y are numerical values ranging from 2.7 to 0.3 and whose sum is 3 and in which n ranges from 12 to 30, into a hydrolyzing liquid medium consisting essentially of (i) an aqueous liquid selected from the class consisting of water and dilute water solutions of'amineral acid, and (ii) liquid alcohol selected from the class consisting of alkyl monohydric hydrocarbon alcohol'having from 2 to 10 carbon atoms; the ratio of the weight of liquid alcohol to the weight of hydrolyzing liquid medium ranging from 2.5 parts by weight of the liquid alcohol to 75 parts by weight of the said hydrolyzing medium; continuing the stirring until all of the alkoxyaluminum sesquichloride has been intimately admixed with the hydrolyzing medium; then allowing the resulting admixture to stand until there is a practically complete and rapid phase separation thereof into an upper organic portion and a lower aqueous portion; isolating the said upper organic portion and recoven'ng from said upper organic portion the solid higher alcohol thus produced.

8. The process defined in claim 7 in which the liquid alcohol of the hydrolyzing liquid is ethanol.

9. The process defined in claim 7 in which the liquid alcohol of the hydrolyzing liquid is butanol.

10. The process defined in claim 7 in which the aqueous liquid is water.

References Cited by the Examiner UNITED STATES PATENTS 7/1957 Sonntag 260632 12/ 1958 Kirshenbaum et al. 260-632 X FOREIGN PATENTS 12/ 1958 Great Britain.

LEON ZITVER, Primary Examiner.

15 C. B. PARKER, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,247,264 April 19, 196

Warren L. Beears et a1.

ror appears in the above numbered pat- It is hereby certified that er the said Letters Patent should read as ent requiring correction and that corrected below.

Column 4, line 16, for [C H O A1c1 read (C H 0) A1Cl EXAMPLE II, insert Recipe: as a heading to the first column; line 65, for "C H OH=98.8"

read (C H O) l A1Cl 1 5 line 75 for "C H OH=98 8" read C H OH=98.8 column 5, line 75, after "Percent" insert Yield Signed and sealed this 14th day of November 1967 (SEAL) Attest:

EDWARD J. BRENNER Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer

Claims (1)

1. A PROCESS FOR THE MANUFACTURE OF HIGHER ALKYL HYDROCARBON ALCOHOLS THAT ARE SOLIDS AT ROOM TEMPERATURES, WHICH PROCESS COMPRISES STIRRING ALKOXYALUMINUM SESQUICHLORIDES OF THE EMPIRICAL FORMULA (CNH2N+1O)XALCLY, IN WHICH X AND Y ARE EACH NUMERICAL VALUES RANGING FROM 2.7 TO 0.3 AND WHOSE SUM IS 3 AND IS WHICH N RANGES FROM 12 TO 30, INTO A HYDROLYZING LIQUID MEDIUM CONSISTING ESSENTIALLY OF (I) WATER AND (II) AN ALCOHOL WHICH IS LIQUID AT ROOM TEMPERATURES SELECTED FROM THE CLASS CONSISTING OF ALKYL MONOHYDRIC HYDROCARBON ALCOHOLS HAVING FROM 2 TO 10 CARBON ATOMS; THE SAID LIQUID ALCOHOL BEING PRESENT IN FROM 4% TO 100% BY WEIGHT OF THE ALKOXYALUMINUM SESQUICHLORIDE; CONTINUING THE STIRRING UNTIL ALL OF THE ALKOXYALUMINUM SESQUICHLORIDE HAS BEEN INTIMATELY ADMIXED INTO THE HYDROLYZING LIQUIDS, THEN ALLOWING THE RESULTING MIXUTRE TO STAND, IN WHICH CONDITION IT QUICKLY SEPARATES INTO TWO DISTINCT LAYERS, NAMELY, AN UPPER LIQUID ORGANIC PORTION CONTAINING THE HIGHER SOLID ALCOHOL PRODUCED AND A LOWER AQUEOUS LAYER; AND FRACTIONALLY DISTILLING THE SAID UPPER ORGANIC PORTION TO ISOLATE THE HIGHER SOLID ALCOHOLS THUS PRODUCED.