CA1133523A - Process for the production of tertiary alcohols - Google Patents

Abstract

ABSTRACT
Tertiary alcohols are produced by the hydration of an isoolefin in the presence as catalyst of an acidic cation exchange resin such as a sulfonated styrene-divinyl-benzene copolymer and in the presence of a neo-type poly-hydric alcohol such as neopentyl glycol or an oxy acid or lactone thereof such as .gamma.-valerolactone. The process is useful for separating isobutylene from a hydrocarbon mix-ture containing its isomers via preparation of the alcohol, separation from the unreacted hydrocarbons and dehydration of the tertiary butyl alcohol to isobutylene.

Description

PROCESS FOR THE PRODUCTION OF TERTIARY ALCOHO~S

2 Tnis invention relates to a process for producing

3 tertiary butyl alcohol (~BA~ in a higher yield than previous-

4 ly obtainable by reacting isoolefins, in particular isobutyl-ene, with water and more particularly it is concerned with a 6 process for producing TBA in a higher yield by reacting iso-7 butylene with water in the presence of a neo-type polyhydric 8 alcohol or its derivative or an oxy acid or its derivative 9 using a solid catalyst, prefera~ly, an acid-type cation ex-change resin.
11 For the production of TBA by hydration of isobutyl-12 ene, there have been proposed an indirect hydration method 13 comprising a~sorbing isobutylene in sulfuric acid and hydro-14 lyzing the formed sulfuric acid ester and a direct hydration method comprising usIng a solid acid or an acidic aqueous 16 solution as a catalyst.
17 of these methods, the method using an aqueous solu-18 tion of sulfuric acid has the disadvantage that large amounts 19 of by-products are formed through dimerization or trimeriza-tion of isobutylene and that there are problems of the cor-21 rosion of the apparatus and the treatment of the waste sul-22 furic acid. In most of the direct hydration methods using a 23 solid acid or acidic aqueous solution as a catalyst, on the 2~ other hand, some activity appears only at a high temperature such as about 200C or higher. Since the equilibrium of the 26 hydration reaction is disadvantageous for the ormation of 27 the alcohol with the rise of temperature, it is necessary to 28 conduct the reaction under a very high pressure in order to 29 obtain a sufficient yield at such a high temperature. In 3~ this respect, a sulfonic acid~type ion exchange resin is a 31 good catalyst capable of advancing the reaction at a rela-32 tively low temperature and low pressure. A number of meth-33 ods using the same have been proposed~
34 For example, 'rIndustrial and Engineering Chemistry"
Vol. 53, No. 3, page 209-211 describes a method wherein iso-36 butylene is continuously hydrated using an ion exchange res-37 in as a catalyst, but this method is not always satisfactory ;Y

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---` 1133523 ~ 2 --1 because water and isobutylene form a heterogeneous system 2 and thus give an insufficient reaction speed and yield. For 3 the purpose of solving this problem, there have been pro-4 posed a method comprising reacting isobutylene or an iso-butylene-containing hydrocarbon with an aaueous solution of 6 an organic acid using an acidic ion exchange agent as a cat-7 alyst (Japanese Patent Application [OPI~ No. 32116/1975 and 8 Japanese Patent Publication No. 1404~/1978); a method com-9 prising carrying out the reaction with addition of a mono-hydric alcohol to the reaction system and using a similar 11 catalyst (Japanese Patent Application [OPI] No. 137906/1975) 12 and a method comprising carrying out the reaction with addi~
13 ion of glycol, glycol ether or glycol diether to the reac-14 tion system (Japanese Patent Application [OPI] No. 59802/
1976 and U.S. Patent No. 4,096,194).
16 In these methods for producing TBA by directly hy-17 drating isobutylene, some improvement in~reaction rate is 18 found, but, on the other hand, by-products are formed such 19 as adducts of isobutylene with organic acids or organic sol-vents which are added to the reaction system. These by-21 products and organic solvents added to the reaction system 22 make it difficult to separate and purify T~A by distillation23 utilizing the difference of their boiling points. In the 24 case of using organic acids such as acetic acid, the appara-tus tends to become corroded.
26 Applicant has made various studies to solve the 27 above-described problems and has found that the side reac-28 tions can be suppressed and the reaction rate and conversion 29 ratio can be markedly promoted by adding a neo-type polyhy-dric alcohol or an oxy acid or derivative thereof to water 31 in the hydration reaction using an acid-type cation exchange 32 resin. The present invention is based on this finding.
33 That is to say, the present invention provides a 34 process for producing TBA comprising reacting C4 or C5 iso-olefin or an isoolefin-containing hydrocarbon mixture, pref-36 erably isobutylene or an isobutylene-containing hydrocarbon 37 mixture, with water in the presence of a solid catalyst, ..

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~33~3 1 preferably an acid^type cation exchange resin, characterized 2 in that a neo-type polyhydric alcohol or derivative thereof 3 or an oxy acid or derivative thereof i`s included in the reac 4 tion system.
The quantity of isobutylene or the iso~utylene 6 content in an isobutylene-contai~ing hydrocarbon mixture, 7 used in the present invention, is not particularly limited.
8 Generally, the isobutylene-containing hydrocarbon mixture 9 comprises predominantly C4 hydrocar~ons, for example, isobu-10 tylene, n--butylene and butane and, optionally, some amounts 11 of C3 or Cs hydrocarbons. On a commercial scale, iso~utylene 12 containing C4 hydrocarbon mixtures obtained by steam cracking 13 or catalytic cracking of petroleum fractions, are used.
14 The accompanying drawings are flow diagrams, Fig.
15 1 and Fig. 2, which illustrate carrying out the process of 16 the present invention continuously.
17 The neo-type polyhydric alcohol or derivative 18 thereof used in the present ivention is i.llustrated in the 19 following:
The neo-type polyhydric alcohol is represented by 21 the following general formula, 22 Xl 23 ~ CH2 24 2 CH2-lc-cH2oH

226 Cl H2 x3 28 in which Xl, X2 and X3 are selected from the group consisting 29 of hydrogen, hydroxyl group and organic groups suc~ as alkyl, 30 especially methyl, aryl, alkoxy, substituted alkoxy and ester 31 groups and at least one of Xl, X2 a~d X3 is a hydroxyl group 32 or a hydroxyl-containïng group. Preferred polyh~dric alco-33 hols are those in which at least one of Xl, X2 and X3 is a 34 hydroxyl gxoup, or their ethers with th.e same or a different 35 alcohol. Examples of the polyhydric alcohol having such a 36 structure are:
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_~ ~1335Z3 1 ~1) Pentaerythritol 4 CH2OH _ (2) Trimethylolpropane g CH2H
(3) Trimethylolethane 11 '' ' ' CH 2 0~1 12 3 ~

14 (4 ? Neopentyl glycol CH
~OCH2-C-CH2OH

18 (5) Dipentaerythritol CH OP CH OH

(6) Dineopentyl glycol CH CH

HOCH2-~-CH2-o-cH2-c-cx2oH ' '1~' C~3 CH3 26 As the derivative of the neo-type polvhy-dric alcohol, there 27 can be used esters or partially esterified products thereof 28 or their ethers such as t~e ether-dimers as described above. -29 The neo-type polyhydric alcohols or their derivatives can of course be used in combination.
31 - The neo-type polyhydric alcohol or derivative 32 thereof is ordînarily used in the form of a solution in 33 water but it is not always required that it hould be com-34 pletely dissolved therein. As the added quantity of the neo-type polyhydric alcohol or derivative thereof is in-36 creased, in general, the rate of formation of. ~R~ increases 37 but the viscosity of the solution becomes greater also.

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4 The oxy aci.d or derivative thereof used i.n the present invention is illustrated in the follo~in.g:
6 Examples of the oxy acid are C2-C5 oxy acids such 7 as oxyacetic acid ~HOCH2COOH)) lactic acïd (:OE3CHCOH~COOHl, 8 3-oxypropionic acid CHOCH2CH2COOH~ trichlorolactic 9 ~cid CCl3CCHcOH~COOHlt oxypival,c acid CHOCH2CcCH3~2COOH~
y-oxy~utyr}c acid CHOCH2CH2CH2COOHl. and th.e li~e.
11 As a typical example of the derivative of hydroxy 12 acids, lactones corresponding to the intramolecularly con-13 densed hydroxy acids are preferable, but other oxv acid 14 esters may be used particularly the lower alkyl esters such as the methyl and eth~l esters. Useful examples of the lac~
16 tone are ~-propiloactone CH~-CH2, ~ dimethylpropiolactone 17 o - CO

18 CH3~ C - CH2, y-butyrolactone C~2-CH2, y-valerolactone 19 CH3 0 - CO ~H2 CO
2Q \ 0/
21 CH2-lCH2, ~-valerolactone CH2CH2CH2CH2COO, diglycolide 3 \ /

24 ~ CO - O \ /0 - ~0\
CH2 / CH2, lactide CH3CH CHCH3 and the likeO
26 ~ O - CO CO - O
27 ~seful examples of the oxy acid esters are glycollc acla 28 methyl ester HOCH2COOCH3, glycolic acid ethyl ester 29 ~OCH2COOC2H5 and~th.e like. Thus the oxy acids particularly 30 of C2-C5, straight or branched-chain alkyl type, and the 31 derivatives thereof, viz., the oxy acid lower alkyl esters, 32 the lactones, lactides, the halogen, especially chlorine, 33 substituted derivatives, or mixtures of these, may be 34 employed.
The oxy acid or derivative thereof is ordinarily used 36 in the form of a solution in water, but it is not always 1 required that it should ~e.completelv dissolved therein~ As 2 the added quantity of the o~y acid or derivative thereof is 3 increased, in general, the rate of formation of TBA increas-4 es but if too large an excess is added, the e~ficiency of a reactor is lowered. Accordingly~ the said compound is gen-6 erally added in a proporti.on o:E Q~l to 200 parts, preferably 7 Q.3 to 50 parts by weight, to 1 part by weight of wat~r.
8 The solid catalyst used in th.e present inventi~n 9 includes preferably strongly acid cation exchange resins, for example, sulfonated polystyrene resins in whlch sulfonic 11 acid groups are introduced into a base of a copolymer of sty- -12 rene and divinylbenzene; phenolsulfonic acid resins in which 13 sulfonic acid groups are introduced into a condensate of 14 phenol and formaldehyde; and perfluorosulfonic acid resins consisting of copolymers of sulfonated vin~l ether fluoride 16 and fluorocar~on, which.are preferably of a gel type, macro-17 porous type of macroreticular type-. Supported ion exchange 18 resins may be used. In addition, other solid catalysts for 19 hydration can be used; for example, oxide type catalysts such as alumina, silica alumina, silica ~el, zeolites, mor-21 danites, ~aolin; oxides of metals such as tungsten, thorium, 22 zirconium, molybdenum, zinc, titanium and chromium; support-23 ed ones of these oxides7 m~neral acid catalysts such as sup-24 ported phosphoric acid; heteropoly acid catalysts such as supported silicotungstic acid; sulfides such as sulfides of 26 nickel and nickel-tungsten or supported ones of these sul-27 fidesr and metal sulfates s~ch as aluminum sulfate~
28 The ~uantity of the catalyst depends upon how it is 29 used, that is, whether it is used in the form of a suspen-sion or a fixed bed. In the former case, the quantity of 31 the catalyst is preferably 0.1 to lQ~ by weight of an aque .. . . . . . .
32 ous solution of a neo-type polyhydric alcohol or of an oxy 33 acid or dcrivativc thereof.
34 The molar ratio of water to isobutylene ranges preferably from 1 to 10 since ;f less than 1, t~e conversion 36 ratio is lowered, while if too large, the efficiency of a 37 reactor is lowered.

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1 The reaction temperature is generally 30 to 150C, 2 prefera~ly 5Q to 120C.
3 The reaction pressure may be normal pressure, but 4 the reaction is preferablv operated under a pressure corres-ponding to the vapor pressure of a hydrocarbon mixture as 6 starting maierial at the reaction temperature or under a 7 pressure somewhat higher than the vapor pressure.
8 The form of reactor to be used may be of a batch 9 type, but, in general, it is of a continuous type using an acid-type cation exchange resin in the form of a fixed bed.
11 The reaction time is generally in the range of 20 12 minutes to 10 hours in the case of a batch type and a suit-13 able liquid hour space velocity (LHSV) of a hydrocarbon is 14 ordinarily Q.3 to 10 hr~l in the case of a continuous type.
Embodiments of the process of the present inven-16 tion will now be illustrated with reference to the accompany-17 ing drawings. In these embodiments, isobutylene from an iso-18 butylene containing hydrocarbon mixture is continuouslv con-19 verted into TBA and separated.
20 With reference to Fig. 1, the system comprises !' 21 mainly first and second reactors 101 and lQ3 filled with a 22 catalyst, distilling columns 102 and 104 for the separation 23 of unreacted hydrocarbons, a distilling column 105 for the 24 separation of TBA and a storage tank 106 of an aqueous solu-tion of neo-type polyhydric alcohol. A starting hydrocarbon 26 mixture and an aqueous solution of neo-type polyhydric alco-27 hol are fed to the first reactor respectively from a pipe 1 28 and a pipe 2. The reaction liquor containing TBA is with-29 drawn from the bottom of the first reactor 101 and fed through a pipe 3 to the distilling column 102 for the separa-31 tion of unreacted hydrocarbons. A hydrocarbon mixture con-32 taining unreacted isobutylene is withdrawn from distilling 33 column 102 through a pipe 4 and fed with the aqueous solu-34 tion of neo-type polyhydric alcohol from a pipe 6 to the second reactor 103. A TBA-containing reaction liquor is dis-36 charged from the bottom of the second reactor 103 and fed to 37 the distilling column 104 for the separation of hydrocarbons 38 via a line 7 r from which an unreacted hydrocarbons ` ' . ;

~L33523 1 mixture is taken via line 8. TBA-containing liquors with-2 drawn from lines 5 and 9 are fed to the distilling column 3 105 for the separation of TBA, from which crude TsA is taken 4 through line 10. An aqueous solution of neo-type polyhydric alcohol is taken via line 11, mixed with water from line 12 6 and reused for the reaction through the storage tank 106.
7 Removal of water from the crude TBA is carried out in con-8 ventional manner.
9 In reference to Fig. 2, the system comprises main-ly first and second hydration reactors 101 and 104 filled 11 with a catalyst, a separator 102 for the separation of an 12 unreacted hydrocarbon layer and aqueous layer, a distilling 13 column 103 for the separation and recovery of TBA and a dis-14 tilling column 105 for the separation of unreacted hydro-carbons.
16 To the first hydration reactor 101 are respectively 17 fed a st~ing hydrocarbon mLxture from a pipe line 1, water from 18 a pipe line 2 and an aqueous solution containing an oxy acid 19 or derivative thereof and TsA from a pipe line 3. The reac-tion liquor is fed to the separator 102 via a pipe line 4 21 from the bottom of the first hydration reactor 101. From the 22 separator 102, the separated hydrocarbon mixture containing 23 unreacted isobutylene is withdrawn via a pipe line 5 and fed 2~ to the second hydration reactor 104 with an aqueous solution containing the oxy acid or derivative thereof via a pipe line 26 8. The reaction liquor containing TBA is discharged from the 27 bottom of the second hydration reactor 104 and fed through a 28 pipe line 9 to the distilling column 105, from which an un-29 reacted hydrocarbon mixture is withdrawn via a pipe line 10 at the top and the aqueous solution containing the oxy acid 31 or derivative thereof and TBA is taken via the pipe line 3 32 at the bottom, which is again fed to the first hydration 33 reactor 101. The aqueous solution containing TBA and the oxy 34 acid or derivative thereof, separated in the separator 102, is fed via a pipe line 6 to the distilling column 103, from 36 which crude TBA is recovered via a pipe line 7 at the top and 37 the aqueous solution containing the oxy acid or derivative ., ................. . :
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li33523 .

g 1 thereof is withdrawn via the pipe line 8 at the bottom, 2 followed by feeding again to the second hydration reactor 3 104. Removal of water from the crude TBA is carried out in 4 conventional manner.
According to the process of the present invention, 6 the rate of the hydration reaction of isobutylene and the 7 conversion ratio thereof can be increased markedly with 8 suppression of side reactions, thus allowing obtaining TBA
9 in high yield. Moreover, a neo-type polyhydric alcohol or an oxy acid or derivative having a much higher boiling 11 point than TBA can readily be separated by distillation and 12 thus the reuse thereof is simplified.
13 By means of the present process isobutylene can be 14 isolated from an isobutylene-containing hydrocarbon mixture.
That is to say, isobutylene in an isobutylene-containing 16 hydrocarbon mixture is preferentially converted into TBA
17 according to this process and the unreacted hydrocarbon mix-18 ture is then separated, after which TBA is dehydrat~ed in 19 known manner to give isobutylene. Isobutylene of high purity can be obtained in this way.
21 The present invention will be further illustrated 22 in detail by the following examples and comparative examples, 23 in which parts are by weight and percentages are by mole un-24 less otherwise indicated.

26 Using an autoclave equipped with a stirrer and a 27 cation exchange resin of macroreticular type (Amberlite 15, Z8 commercial name) consisting of a sulfonated styrene-divinyl-29 ben~ene copolymer as a catalyst, hydration reactions of iso-butylene (99.5%) and an isobutylene-containing C4 hydrocarbon 31 (isobutylene 41.0%, n-butylenes 43.0%, butanes 16.0%) were 32 carried out with solutions of neo-type polyhydric alcohols 33 in water under conditions as shown in Table 1. After the 34 reactions, the reaction products were rapidly cooled and sub-jected to analysis by gas chromatography to obtain the yields 36 of TBA and by-products. The results are shown in Table 1.
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-~ ~133S23 1 Comparative Examples 1-8 2 In the hydration reaction of isobutylene using the 3 same reactor, catalyst and starting hydrocarbon as those of 4 Examples 1-9, comparison tests were carried out with no addi-tion of organic solvent to the reaction system and with addi-

6 tion of organic solvents in place of the neo-type polyhydric

7 alcohols. The experimental conditions and results are shown

8 in Table 2.

9 The yields of TBA and by-products were obtained in a manner analogous to Examples 1-9.

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:: :. :, ~ 33523 1 EX~PLE 10 2 This example describes a process comprising con-3 tinuously hydrating isobutylene is an isobutylene-containing 4 C4 hydrocarbon mixture and separating TBA using the apparatus shown in Fig. 1.
6 To a first reaction 101 were respectively fed a 7 starting C4 hydrocarbon mixture (isobutylene 19.8%, n-butenes 8 32.0%, butanes 48.2%), obtained from a catalytic cracking 9 apparatus, at a rate of 8415 parts/hr. from a pipe 1 and a 55% by weight aqueous solution of neopentyl glycol at a 11 rate of 7200 parts/hr. from a pipe 2. The first reactor 101 12 was filled with the same catalyst as that used in Examples 13 1-9 and the hydration reaction was carried out under condi-14 tions of a temperature of 90C., pressure of 16 Kg/cm and liquid space velocity of LHSV 2.0 hr 1 A liquor containing 16 11.6% of TBA, discharged from the first reactor 101, was fed 17 at a rate of 15615 parts/hr. to a first distilling column 102 18 for the separation or hydrocarbons via a pipe 3. An unreacted 19 hydrocarbon mixture via a pipe 4 and an aqueous neopentyl glycol solution containing 21.1% of TAB via a pipe 5 at a 21 rate of 8566 parts/hr. were respectively withdrawn. The un-22 reacted isobutylene-containing hydrocarbon mixture (isobuty-23 lene 4.3%, n-butenes 38.2%, bùtanes 57.5%) via the pipe 4 at 24 a rate of 7049 parts/hr. and the 55% by weight aqueous solu-tion of neopentyl glycol via a pipe 6 at a rate of 3600 parts/
26 hr. were respectively fed to a second reactor 103 (filled 27 with the same catalyst as that of the first reactor 101) in 28 which the hydration reaction was carried out under conditions 29 of a temperature of 70C., pressure of 11 Kg/cm2 and liquid space velocity ~HSV of 1.0 hr . A liquor containing 3.1%
31 of TBA, discharged from the second reactor 103, was fed 32 via line 7 at a rate of 10649 parts/hr. to a second dis-33 tilling column 104 for the separation of hydrocarbons, from 34 which an unreacted hydrocarbon mixture (isobutylene 0.6%, n-butenes 39,6%, butanes 59.8%) via line 8 at a rate of 6797 36 parts/hr. and an aqueous neopentyl glycol solution containing 37 8.6% of TBA via line 9 at a rate of 3852 parts/hr. were , . . . .
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~335;;~3 1 respectively withdrawn. The liquors containing TBA withdrawn 2 via the line 5 from the first distilling column 102 and via 3 line 9 from the second distilling column 104 were combined 4 and fed to a third distilling column 105 for the separation of TBA, from which a crude TBA ~TBA 88.2%, water 11.8%) via 6 line 10 at a rate of 2456 parts/hr. and an aqueous solution 7 of neopentyl glycol via line 11 at a rate of 9994 parts/hr.
8 were respectively withdrawn. The aqueous solution of neo-9 pentyl glycol withdrawn via line 11 was mixed with water at a rate of 806 parts/hr. via line 12, delivered to a storage 11 tank 106 of the 55% by weight aqueous solution of neopentyl 12 glycol and then recycled to each of the reactors.
13 The yields of TBA were 82.0% for the first reactor 14 101 and 84.0% for the second reactor 103.

16 With the use of an autoclave equipped with a stirrer 17 and a cation exchange resin of highly porous type consisting 18 of a sulfonated styrene-divinylbenzene copolymer as a cata-19 lyst, hydration reactions of isobutylene (99.5~) and an iso-butylene-containing C4 hydrocarbon (isobutylene 41.0%, n-21 butylenes 43.0%, butanes 16.0%) were carried out with solu-22 tions of oxy acids or derivatives thereof in water under con-23 ditions as shown in Table 3. After the reactions, the reac-24 tion products were rapidly cooled and subjected to analysis by gas chromatography to obtain the yields of TBA and by-26 products. The results are shown in Table 3.

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1 CO~ARATIVE EXAMPLES 9-15 2 In the hydration reaction of isobutylene with the 3 same reactor, catalyst and starting hydrocarbon as those of 4 Examples 11-22, comparison tests were carried out with no addition of organic solvent and with addition of organic 6 solvents in place of the oxy acids or derivatives thereof.
7 The experimental conditions and results are shown in Table 4.
8 The yields of TBA and by-products were obtained in 9 a manner analogous to Examples 11-22.

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2 This example describes a process comprising con-3 tinuously hydrating isobutylene in an isobutylene-containing 4 C4 hydrocarbon mixture and separating TBA using the apparatus shown in Fig. 2.
6 To a first hydration reactor 101 were respectively 7 fed a starting hydrocarbon mixture (isobutylene content:
8 36.2%) via a pipe line 1 at a rate of 1000 mols/hr., water 9 via a pipe line 2 at a rate of 527 mols/hr. and an aqueous solution of TBA and y-butyrolactone (TBA: 17.6% water:
11 18.7%; y-butyrolactone: 63.7%) via a pipe line 3 at a rate 12 of 471 mols/hr. The reaction mixture from the first reactor 13 101 was separated into a hydrocarbon layer and an aqueous 14 layer in a separator 102. To a second hydration reactor 104 l; were respectively fed the hydrocarbon layer (isobutylene 16 content: 12.4%) at a rate of 729 mols/hr and aqueous solu-17 tion of y-butyrolactone content: 63.7%) at a rate of 471 18 mols/hr. The first and second hydration reactors were filled 19 with the same catalyst of the sulfonic acid-type cation ex-change resin as that of Examples 11-22. In the first hydra-21 tion reactor 101, a temperature of 90C. and LHSV of 4 hr 1 22 were maintained and in the second hydration reactor 104, a 23 temperature of 70~C. and LHSV of 2 hr 2 were maintained. The 24 reaction mixture from the second hydration reactor 104 was 2; fed to a distilling column 105 from which unreacted hydro-26 carbons (isobutylene content: 1.1%) were separated and re-27 covered at a rate of 645 mols/hr. The aqueous layer in the 28 separator 102 was fed to a distilling column 103 for the 29 separation of TBA from which crude TBA (TBA content: 67.4%) was recovered at a rate of 527 mols/hr. The yield of TBA
31 from the isobutylene in the starting hydrocarbon mixture was 32 98.1%.

':,;

, ` ' ' : ~

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. In a process for the production of tertiary alcohols by causing an isoolefin or a hydrocarbon mixture containing an isoolefin to react with water in the presence of an acidic cation exchange resin catalyst, the improvement which comprises carrying out the reaction in the presence of a neo-type polyhydric alcohol having the general formula in which X1, X2 and X3 are selected from the group con-sisting of hydrogen hydroxyl, alkyl, aryl, alkoxy, sub-stituted alkoxy and ester groups and at least one of Xl, X2 and X3 is a hydroxyl or hydroxyl-containing group; or the esters or partially esterified products thereof or ethers thereof; or in the presence of a C2 to C5 oxy acid or the lactones, lactides, methyl or ethyl esters thereof, or the halogen substituted deriva-tives of these materials, or mixtures thereof.

2. The process as set forth in claim 1 in which X1, X2 and X3 are selected from the group consisting of hydrogen, hydroxyl and methyl and at least one is hydroxyl.

3. The process as set forth in claim 1 in which the polyhydric alcohol is selected from the group consist-ing of pentaerythritol, trimethylolpropane, trimethylol-ethane, neopentyl glycol, the ether-dimers of said poly-hydric alcohols and mixtures thereof.

4. A process according to claim 1 in which the oxy acid is selected from the group consisting of oxyacetic acid, lactic acid, 3-oxypropionic acid, .beta., .beta., .beta.-trichloro-lactic acid, oxypivalic acid and .gamma.-oxybutyric acid.

5. A process according to claim 1 in which the lactone is selected from the group consisting of .beta.-propio-lactone, .beta.,.beta.-dimethylpropiolactone, .gamma.-butyrolactone, .gamma.-valerolactone and .delta.-valerolactone.

6. A process according to claim 1 in which the lactide is selected from the group consisting of digly-colide and lactide.

7. A process according to claim 1 in which the oxy acid ester is selected from the group consisting of glycolic acid methyl ester and glycolic acid ethyl ester.

8. The process as set forth in claim 1 in which the resin used is a sulfonated resin.

9. The process as set forth in claim 1 in which the resin used is a sulfonated styrene-divinylben-zene copolymer.

10. The process as set forth in claim 1 in which the feed contains isobutylene and tertiary butyl alcohol is recovered as product.

11. The process as set forth in claim 1 in which the feed comprises isobutylene in a hydrocarbon mix-ture, the resin used is a sulfonated styrene-divinylbenzene copolymer and tertiary butyl alcohol produced by hydration is recovered in a substantially purified form.

12. The process as set forth in claim 1 in which the hydrocarbon mixture comprises predominantly C4 hydrocarbons including isomers of isobutylene.