DE3029739A1 - Tertiary alcohol prepn. - by reacting iso-olefin or hydrocarbon mixt. contg. iso-olefin with water in the presence of a catalyst - Google Patents

Abstract

Tert. alcohol is prepd. by allowing isoolefin or a hydrocarbon mixt. contg. it to react with water in the presence of a solid catalyst. Improvement is that neo type polyhydric alcohol or its deriv. is present. The velocity of hydration of isobutylene and the conversion are promoted, and tert. butyl alcohol can be obtd. in high yield while suppressing undesirable side-reaction. A neo type polyhydric alcohol has a considerably higher b.pt., which makes it easy to separate from tert. butyl alcohol, therefore, the polyhydric alcohol can be used repeatedly. Isobutylene can be isolated from a hydrocarbon mixt. contg. isobutylene by the above method.

Description

The present invention relates to a process for the production of tertiary butyl alcohol in a higher yield than has hitherto been achieved in the reaction of olefins, in particular isobutylene, with water. The invention relates in particular to a process for the preparation of tertiary butyl alcohol in increased yield by reacting isobutylene with water in the presence of a polyhydric alcohol of the neo type or one of its derivatives or an oxyacid or a derivative thereof, using a solid catalyst, preferably an acidic one Cation exchange resin.

To make tertiary butyl alcohol by change of water on isobutylene an indirect hydration method has been proposed, in which isobutylene in sulfuric acid, is absorbed and hydrolyzed the resulting sulfuric acid ester; a direct hydration process is also known, which used a solid acid or an acidic aqueous solution as a catalyst

The one working using an aqueous sulfuric acid solution Process has the disadvantage that large amounts of by-products are formed by dimerization or Primerization of isobutylene; creates further difficulties the corrosion of the system and the processing of the used sulfuric acid. Most direct hydration processes On the other hand, with a solid acid or acidic aqueous solution as a catalyst, a certain activity is achieved only at high temperatures of around 200 ° C or more. Because the equilibrium of the hydration reaction for alcohol formation is unfavorable as the temperature rises, the reaction must be carried out under a very high pressure, in order to be able to do so at such a high pressure Temperatures to achieve sufficient yields. In this

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Respect is a sulfonic acid type ion exchange resin a good catalyst that favors the reaction to proceed at relatively low temperature and pressure. Numerous methods using this catalyst have been proposed.

For example, in "industrial and engineering chemistry", Volume 53, No. 3, pp. 209-211, a method described in the isobutylene is continuously hydrated using an ion exchange resin as a catalyst However, the process is not always satisfactory because water and isobutylene form a heterogeneous system and thus provide inadequate reaction rates and yields .. To solve this problem, a process proposed that isobutylene or an isobutylene-containing hydrocarbon with an aqueous solution of a organic acid is converted using an acidic ion exchanger as a catalyst (JP-PA J OPI] 3211.6 / 1975 and JP-PS I4o44 / 197 & ^. Furthermore, a method has been proposed in which the reaction is carried out with the addition of a monohydric alcohol and using a similar catalyst is carried out (JP-PA [OPI] 137906/1975) and a method in which glycol, glycol ether or glycol diether is added to the reaction system (JP-PA [OPI] 59802/1976 and U.S. Patent 4,096,194).

In this process for the production of tert-butyl alcohol some improvement in the rate of reaction is noted, however, by direct hydration of isobutylene on the other hand, by-products are formed such as adducts of isobutylene and organic acids or organic solvents, added to the reaction system. These by-products and organic added to the reaction system Solvents make the separation and purification of the tert-butyl alcohol by distillation due to the lower boiling point.

-y-h

divorced difficult. If organic acids such as acetic acid are used, the corrosion of the system is also increased.

It has now been found that the side reactions are suppressed and the rate of reaction and degree of conversion are considerable can be improved by using a polyhydric alcohol of the Neo type or an oxyacid or a derivative thereof, in which a hydration reaction using an acidic cation exchange resin occurs. The present invention is based on this observation.

The present invention thus provides a method of manufacture of tertiary butyl alcohol, in which a Cji, - or C -isoolefin or an isoolefin-containing hydrocarbon mixture, preferably isobutylene or an isobutylene-containing hydrocarbon mixture, with water in the presence of a solid Catalyst and preferably an acidic cation exchange resin is implemented. The method is characterized in that a neo type polyhydric alcohol is added to the reaction system or a derivative thereof or an oxyacid or a derivative thereof is incorporated.

The amount of isobutylene or the isobutylene content of an isobutyl-containing hydrocarbon mixture are not particularly limited. In general, the isobutylene-containing hydrocarbon mixture consists mainly of Cu hydrocarbons, for example isobutylene; n-Butylene and butane and, if appropriate, smaller amounts of C ^ - or (^ -hydrocarbons. Technically, an isobutylene-containing Cj, hydrocarbon mixture obtained by steam cracking or catalytic cracking of petroleum fractions is used.

-y-2.

T he accompanying drawings, Figure 1 and Figure 2 show flow charts that illustrate the continuous execution of the erfindurfsgemässen method.

The polyhydric alcohol of the neo-type corresponds to the following general formula

CH ₂ . _r

^: x ^ ch ₂ -c-ch ₂ oh1

where X ,, X _? and X, hydrogen, hydroxyl groups or organic radicals such as alkyl radicals, in particular methyl, aryl-alkoxy, substituted alkoxy or ester radicals, where at least one of the radicals X, X or X is a hydroxyl group or a radical containing hydroxyl groups. Preferred polyhydric alcohols are those in which at least one of the radicals X 1, X 1 and X represents a hydroxyl group, or their ethers with the same or a different alcohol. Examples of polyhydric alcohols of this type are:

(1) pentaerythritol

CH-OH
HIGH ₂ -C-CH ₂ OH

CH ₂ OH ■! __

(2) trimethylol propane

: CH ₃ CH ₂ -C-CH ₂ OH

CH ₂ OH

Trimethylolethane! - CH ₂ OH

CH 1 -C -CH ₀ OH; 3, 2

CH ₀ OH ι 2

Neopenty! Glycol CH ₃

(5) dipentaerythritol

CH ₂ OH • CH ₂ OH

j HIGH ₀ -C-CH ₀ -O-CH ₀ -C-CH ₀ Oh! ί \ 2 2,

S. CH ₀ OH CH ₀ OH ι 2

(β) 'dineopentyl glycol

^CH 3 ■. CH, - ·· -

^CH 3 CH ₃

Derivatives of these polyhydric alcohols can be their esters or partially esterified products or their ethers such as those above Use the ether dimers described. Of course you can use polyhydric alcohols and their derivatives in a mixture.

The polyhydric alcohol of the neo type or its derivative is usually used in the form of a solution in water, but it must not be completely dissolved in it. As the amount of polyhydric alcohol or its derivative increases, the

Rate of formation of tertiary butyl alcohol, however, the viscosity of the solution also increases. Accordingly, this compound is generally used in an amount from 5 to 800 and preferably from 10 to 400 parts by weight per 100 parts by weight of water.

Examples of oxyacids which can be used according to the invention are the Cp-C ₁ -hydroxy acids such as hydroxyacetic acid (HOCHpCOOH),

- "όχόώϊοπ * ™ lactic acid (CH ^ CH (OH) COOH), ^ -HyiöroxysSurfe (HOCH ₂ CH ₀ COOH), β, β, β-trichlorolactic acid (CI-CCH (OH) COOH), HydroxyvalinsMure (HOCH ₂ C ( CEL) ₂ COoH), ^ -hydroxybutyric acid (HOCHgCH CHgCOOH) and the like.

As a typical example of hydroxy acid derivatives, lactones which correspond to intramolecularly condensed hydroxy acids are preferred, but other oxy acid esters can also be used, in particular the lower alkyl esters such as methyl and ethyl esters. Suitable lactones are the ß-propiolactone CH ₂ -CH ₂ , ß, ß-dimethylpropriolactone
0-0

^ fW «^ _ f u. eggs

_; CH α «—CO ^ butyrolactone CH -CH _n , ^ -VaIerolacton te- ^J L 2 ί 2

CH ^ CO

m f2p ₂

.CH - CH CO t9-valerolactone CH ₀ CH ₀ CH ₀ CH ₀ COO, diglycolide

'> ^: .m- -. η ■ - 1.1

ψΓ - '. y:. \ Lactide CH, CH CHCH,

CH, .CH. 5 ν / 3

& - ':' ν η - rn CO - 0

and the same.

- \ y- /? /). '■ - "'-" - 3023739

Examples of suitable oxy acid esters are methyl glycolate HOCH ₂ COOCHg, ethyl glycolate HOCHgCOOCgH and the like. It is thus possible to use the oxyacid with a straight or branched Cg-C, alkyl chain and derivatives thereof, ie lower alkyl esters of hydroxy acids, lactones, lactides, halogen and, in particular, chlorine-substituted derivatives or mixtures thereof.

The oxyacid or its derivative is usually in the form of a Solution in water used, in which, however, it does not always have to be completely dissolved. If you increase the amount added of oxyacid or its derivative, the rate of formation of tertiary butyl alcohol generally increases however, the output of the reactor becomes too great a surplus lowered. Such a compound is therefore generally used in an amount from 0.1 to 200, and preferably from 0.3 to 50 parts by weight per part by weight of water were added.

The solid catalysts used in the present invention include preferably strongly acidic cation exchange resins, e.g. sulfonated polystyrene resins, in which sulfonic acid groups in a basic copolymer of styrene and divinylbenzene were introduced, phenol sulfone resins in which sulfonic acid groups in a condensate of phenol and formaldehyde have been introduced, and perfluorosulfonic acid resins composed of copolymers sulfonated vinyl ether fluoride and fluorocarbon, the are preferably gel-like, macroporous or macro-crosslinked. Supported ion exchange resins can also be used. It is also possible to use other solid hydration catalysts, for example oxidic catalysts such as alumina, silica / alumina. Silica gel, zeolite, mordenite, kaolin, "oxides of metals such as tungsten, thorium, zirconium, molybdenum, zinc,

Titanium and chromium, such supported oxides, mineral acid catalysts such as phosphoric acid on a carrier, heteropolyacids such as silicotungstic acid on a carrier, sulfides such as Nickel and nickel / tungsten sulfide, optionally on supports, and metal sulfates such as aluminum sulfate.

The amount of catalyst depends on how the catalyst is used, ie in the form of a suspension or a bed of plague. In the former case, the amount of catalyst is preferably from 0.1 to 10 wt.% Of an aqueous solution of the polyhydric alcohol from the neo-type, or an oxy acid or its derivative. ■. .

The molar ratio of water to isobutylene is preferably in Range from 1 to 10, since if the ratio is less than 1, the degree of conversion is reduced, while if the ratio is too high, the efficiency '·; of the reactor decreases.

The reaction temperature is generally from JO to 150 and preferably from 50 to 120 ^° C.

Normal pressure is suitable as the reaction pressure. However, the reaction is preferably carried out under a pressure which is The vapor pressure of the hydrocarbon feedstock is equal to or slightly above the reaction temperature.

The plant can operate batchwise, but a continuous reactor is generally used acidic cation exchange resin in a fixed bed layer.

The reaction time is generally from 20 minutes to 10 hours in the case of a discontinuous procedure and in the case of a continuous procedure A suitable space velocity (LHSV) is the procedure

ORIGINAL INSPECTED

- γ- η

liquid hydrocarbons usually at 0.3 to 10 hours " ¹ .

Embodiments of the method according to the invention are will now be explained with reference to the accompanying drawings. In these embodiments, isobutylene is made from one containing isobutylene Hydrocarbon mixture continuously converted into tert-butyl alcohol and separated off.

The system according to FIG. 1 contains the first and second reactors 101 and 103, which are filled with catalyst, distillation columns 102 and 104 for separating unreacted hydrocarbons _, a distillation column 105 for separating the tert-butanol and a storage container ΙΟβ for an aqueous solution of neo-type polyhydric alcohol. The hydrocarbon mixture used as the starting material and the aqueous solution of the polyhydric alcohol are fed to the first reactor via line 1 and line 2. The liquid reaction mixture containing tert-butyl alcohol is drawn off at the bottom of the first reactor 101 and fed via line 3 to the distillation column 102, where unconverted hydrocarbons are separated off. A hydrocarbon mixture containing unreacted isobutylene is drawn off from the distillation column 102 via line 4 and fed from line 6 to the second reactor 103 together with the aqueous solution of the polyhydric alcohol. A liquid mixture containing tert-butanol is drawn off at the bottom of the second reactor 103 and fed to the distillation column 104 via line, this column emitting a mixture of unconverted koaiene hydrogen via line 8. The tert-butanol-containing mixtures withdrawn via lines 9 and 9 are fed to the distillation column 105, which emits crude tert-butyl alcohol on line 10. An aqueous solution of the "polyvalent

3029733

Alcohol is delivered to line 11, mixed with water from line 12 and via the storage container 106 of the recycled. The removal of-water from the crude tert-butyl alcohol takes place in conventional Way.

The system of Figure 2 includes the first and second Hydration reactors 101 and 104, which are filled with catalyst, a separator 102 for separating unreacted Hydrocarbon and aqueous phase, a distillation column 103 for separating and isolating the tert-butyl alcohol and a distillation column 105 for Separation of unreacted hydrocarbon.

The first hydration reactor 101 receives the starting hydrocarbon mixture through 'line 1, water through line 2 and an oxyacid or its derivative and Aqueous solution containing tert-butanol through "line 3 fed. The product is fed to the separator 102 via line 4 from the bottom of the first hydration reactor. A hydrocarbon mixture containing unreacted isobutylene is drawn off from the separator 102 via line 5 and fed to the second hydration reactor 104, together with an aqueous solution containing the oxyacid or whose derivative contains and originates from line 8. Tert-butanol-containing liquid reaction product is at the bottom of the second hydration reactor io4 withdrawn and fed via line to the distillation column 105, from the unreacted. Hydrocarbon mixture is withdrawn via line 10 at the top, while the oxyacid or its derivative and the

Tert-butyl alcohol-containing aqueous solution is removed at the bottom via line 3 and from there again to the first

Hydration reactor 101 arrives. The aqueous solution that contains tert-butanol and the oxy acid or its derivative and separated in the separator 102, passes via line 6 into the distillation column 103, from which crude tertiary butyl alcohol via line 7 wins, while the oxy acid or its derivative containing aqueous solution on Soil in line 8 is withdrawn and fed to the second hydration reactor 104. Eliminating the water out the crude tertiary butyl alcohol is carried out in a conventional manner.

According to the invention, the rate of the hydration reaction of isobutylene and the degree of conversion can be increased noticeably, while side reactions are suppressed, so that the tertiary butyl alcohol is obtained in high yield. Further, the polyhydric alcohol of the Neo type or a Oxy acid or its derivative with a significantly higher boiling point than tertiary butyl alcohol is easily separated off by distillation which simplifies their reuse.

Using the process according to the invention, isobutylene be isolated from an isobutylene-containing hydrocarbon mixture. The isobutylene is in the isobutylene-containing hydrocarbon mixture according to the invention converted into tertiary butyl alcohol and this is from the unreacted hydrocarbon mixture separated off and then dehydrated in a known manner, obtaining isobutylene of high purity.

In the following examples, parts are amounts by weight

and percentages are to be understood as Mol- #, unless otherwise is specified.

ORIGfNAL INSPECTED

Examples 1 to 9

In a stirrer and a macroreticular cation exchange resin (trade name Amberlite 15) made of sulfonated! Styrene / divinylbenzene copolymer are equipped autoclave hydration reactions of isobutylene (99 * 5%) and a C ^ -hydrocarbon isobutylenhaltigen ^(2-J 1.0% isobutylene, 43.0 fo n-butylenes, 16.0% butanes) using of aqueous solutions of polyhydric alcohols

"Out of;""theconditions" according to Table V. After the reaction, the reaction products are rapidly cooled and analyzed by gas chromatography, the yields of tertiary butyl alcohol and by-products being obtained. The results are summarized in Table 1:

Eg «alcohol

Tabel

Alcohol Water Isobutylene (g) (g) Fe content Starting hydrocarbon mixture

CO O K)

Next to-

Isobu ~ Cata- React- React- Reak- Austylen lysation- tion- prey products (Mol) (g) temp, pressure ₂ time TBA O _n (kg / cm) (hours)

1 neopentyl glycol 200

2 neopentyl glycol 300

3 trimethylolpro-

pan '200

4 trimethylol propane 100

5 pentaerythritol 40

6 trimethylolpro-

pan 100

Neopentyl glycol 150

200 100

200

300 360

99.5 99.5

99.5 99.5

150 41.0

3.0 20 ■ 80 12th 0.5 25.3 0.1 3.0 20th 70 9 0.5 18.5 0.1 1.0 20th 80 12th 0.5 19.5 0.1 3.0 20th 80 12th 1.0 29.2 track 3.0 20th 80 12th 1.0 16.1 no

1.0.

20th

70

0.5 17.3 0.3

7 trimethyl-

propane 200 200 99.5 3.0

8 neopentyl glycol 250 150 99.5 3.0

9 pentaerythritol 50 150 41.0 1.0 neopentyl glycol 200

+ TBA = tert-butanol Yield: MoI- ^, based on isobutylene used

80. 12
6fr. V7>
80 12

4.0 92.1 0.3 53 Pi "93.2 0.4 5.0 80.2 0.5

Comparative Examples 1 to 8

Reaction vessel, catalyst and starting hydrocarbons corresponded to Examples 1 to 9. The comparative experiments were carried out without the addition of organic solvents and with the addition of organic solvents instead of the polyhydric alcohols. Table 2 shows the test conditions and results. The yields of tertiary butanol and by-products were as in the Examples 1 to 9 determined *

Table 2

E.g. solvents

Solution water jobuty _isobuty . _Kata . _Rea k- Reak- Reak- Off Off

™ i ™ / ^ T? S! 2iiL ^len ( ^Mo1 ) lysatortions-prey

quantity (g) x.output- fa _{tefflp # pressure time TBA additional} .

(o "^ (kg / cm) (Std) ($) prod

without 200 • 400 Hydrocarbon 3.0 without 200 400 mixture of substances 1.5 1 Methanol 200 200 .99.5 3.0 2 Ethyleellosolve 200 200 41.0 3.9 3 Ethylene glycol 200 200 99.5 3.0 Diethylene glycol 200 200 99.5 3.0 5 Neopentyl alcohol 200 99.5 3.0 6th acetic acid 200 99.5 3.0 7th 99.5 8th 99.5

c)

20th

15 20 20 20 20 20 20

80
80
80
80
80
80
80
80

12 12 12 12 12 12 12 12

1.0 8.0 1.0 1.0 1.0 1.0 1.0 1.0

8.3 25.1 16.7 10.7

6.2

7.9 6.8 17.2

0.5 1.3 4.5 2.4

1.4 '

0.2

2.4

Yield: MpI $, based on isobutylene used approx

CD

CD

CO CD

Example 10

This example describes a process for continuously hydrating isobutylene in an isobutylene-containing Cj, hydrocarbon mixture and separating off the tertiary butyl alcohol, a device according to FIG. 1 being used became.

A first reactor 101 is the C ^ hydrocarbon mixture (19.8 % isobutylene, 32.0 % n-butenes, 48.2 % ■ butanes, obtained by catalytic cracking) in an amount of 8415 parts per hour via line 1 and a 55 wt .- ^ aqueous solution of neopentyl glycol in an amount of 7200 parts / hour. supplied via line 2. The first reactor 101 is filled with the same catalyst that was used in the processes of Examples 1-9. The accumulation of water takes place at a temperature of 90 C, a pressure of 16 kg / cm and a space velocity LHSV of 2.0 hours ". A liquid with 11.6 % tertiary butyl alcohol obtained from the first reactor 101 is in an amount of 15,615 parts / hour of a first distillation column 102 for the purpose of separating off the hydrocarbons via line 3. Unreacted hydrocarbon mixture is drawn off via line 4, and line 5 gives an aqueous neopentyl glycol solution with 21.1 % tertiary butyl alcohol in an amount of 8566 Parts / hour. The unreacted isobutylene-containing hydrocarbon mixture (4.3 % isobutylene, 38.2 % n-butenes, 57 * 5- ^ butanes) passes through line 4 in an amount of 7049 parts / hour and the 55 wt .- ^ neopentyl glycol aqueous solution through line 6 in an amount of 3 600 parts / hr. to the second reactor I03 (contains the same catalyst as the first reactor 101), in the hydration reaction at 70 ⁰ C, a pressure of 11 kg / cm and a space velocity LHSV of 1.0 hours. A 3.1 % tertiary butyl alcohol containing, from the

Second reactor 103 obtained liquid is via line 7 ■ ■ · in an amount of IO 649 parts / hour. a second distillation column 104 is fed and separated from hydrocarbons there. This column is unreacted hydrocarbon mixture (0.6 % isobutylene, 39.6 % n-butenes, 59.8 % butanes) via line 8 in an amount of 6,797 parts / hour. and an aqueous neopentyl glycol solution with 8.6 % tertiary butyl alcohol via line 9 in an amount of 3852 tilines / hour. ' away. The liquids containing tert-butanol in line 5 from the first distillation column 102 and line 9 from the second distillation column are combined and fed to a third distillation column 105 for the purpose of separating out the tertiary butyl alcohol. This column delivers crude tertiary butyl alcohol (88.2 % TBA, 11.8 % v / water) in line 10 at a rate of 2,456 parts / hour. and an aqueous neopentyl glycol solution in line 11 at a rate of 9,994 parts / hour. The. aqueous neopentyl glycol solution in line 11 is mixed with water in an amount of 806 parts / hour. mixed from line 12, fed to a storage container IO6 with 55% strength by weight aqueous neopentyl glycol solution and then again circulated to the three reactors.

The yields of tert-butanol were 101 82.0% in the first reactor and I03 84.0% in a second reactor ,

Examples 11-22

In a flask equipped with a stirrer and a highly porous Xationenaustauscherharz of a sulfonated styrene / divinylbenzene copolymer are autoclave hydration of 99.5 ^ sodium isobutylene and isobutylenhaltigem C ^ -hydrocarbon mixture (4l, 0% isobutylene ,. 43.0 fo n-Butylene, 16, 0 fo butanes) carried out using aqueous solutions of oxy acids or their derivatives,

working under the conditions according to table j5
became. After the respective reactions, the reaction products were rapidly cooled and analyzed by gas chromatography, the yields of tert-B butanol and by-products being obtained. The results are shown in Table 3.

Table 3

E.g . Oxy acid Amount of ' 200 350 ■ 200 water isobu- style Iso 3.0 Va 1-Q React
■ f "" 1 r \ V \ Ct mm D λ Q Λ * " Reak the end the end ta. or their Oxy acid tf'-oxybutyric acid 250 392 375 (G) salary buty
len 3.0 Λαϊα "
lysa-
+ · / NVl rteatc—
Ή "ϊ Ο7Π Cf mm. ions prey prey 0 derivative or derivative f- valerolactone 300 300 i.Aus
gangs material (mole) 1.5 l / U L
(G) T ^ tt * Jm f J tf
⁰ C U ± CJiIo ■ " Time
(Hours.) TBA Next to-
prod. K) (G) / f-Valerolac ton 375 99.5 0.5 kg / cm (*) to vf-butyrolactone 200 99.5 ■ 3.0 20th 80 0.5 39.7 0.2 OJ 11 & -Valerolactone / -Butyrolactone 100 200 41.0 1.5 10 70 12th 0.5 37.3 0.2 co 12th # "- butyrolactone 3-oxypropionic acid 150 150 41.0 1.5 10. 70 9 0.5 28.1 0.1 13th ß-propiolactone '<T-Valerolac ton 50 99.5 3.0 5 70 9 0.5 24.6 0.1 14th ^ -Butyrolactone 8th 41.0 3.0 10 ^ O 9 0.5 25.3 - 15th fl-butyrolactone 100 41.0 3.0 5 70 9 0.5 15.3 0.1 16 25th 99.5 0.75 20th 80 9 1.0 38.2 0.1 17th 200 99.5 1.5 20th 80 12th 1.0 26.7 0.1 18th 300 99.5 Yield: MoI- ^, based on isobutylene used 10 .80 12th 1.0 21.6 0.2 19th 250 41.0 20th 80 12th 4.0 92.5 0.3 20th 200 41.0 10 80 12th 5.0 88.7 0.2 21st 25th 20th 60 12th 5.0 84.0 0.2 22nd 100 7th

Comparative Examples 9 to 15

For the hydration of isobutylene, the same reactor, catalyst and hydrocarbon feedstock as in Examples 11 to 22 were used. The comparative experiments however, were carried out without the addition of organic solvents and with the addition of organic solvents instead of Oxy acids or their derivatives. Test conditions and results are shown in Table 4.

The yields of tert-butanol and by-products were as determined in Examples 11-22.

Table 4

Ver
^ easy
ex.
solvent SSf! "- leobuty- Ko- Kata-
^ ^s '^<s' material 400 99.5 3.0 20th Reak-Reak *
tion-tion
temp. pressure
o _c kg / cm ^ 12th Reak
ions
Time
Hours. the end
prey
TBA
* the end
prey
Secondary prod. I. 9 without 400 41.0 1.5 15th 80 12th 1.0 8.5 0.5 10 Without 200 99.5 3.0 20th 80 12th 8, .p. "· 25.8 1.3 11 methanol 200 200 99.5 3.0 20th 80 12th 1.0 16.9 4.6 I »» f 12 ethyl cellosolve 200 200 99.5 3.0 20th 80 12th 1.0 10.9 2.4 13 acetic acid 200 200 99.5 3.0 20th 80 12th 1.0 17.5. O 14 methyl acetate 200 350 99.5 3.0 20th 80 12th 1.0 18.1 JJ
Q
j?
> 15 ethyl acetate 50 Yield: mol #, based on isobutylene used 80 1.0 10.1 L. IHSPEC

CD K) CD - ^ I CO CD

0029739

Example 23

This example describes a process for continuous Hydration of isobutylene in an isobutylene-containing C ^ - Hydrocarbon mixture and separation of the tertiary butyl alcohols using a device according to FIG. 2.

In a first reactor 101, the hydrocarbon mixture (isobutylene content 36.2 %) in an amount of 1,000 mol / hour, via line 2 527 mol of water / hour. and via line 3 an aqueous solution of tert-baiaeol and Y ^ -butyrolactone (17 * 6 % TBA, 18.7 % water, 63.7 % ^ -butyrolactone (in an amount of 471 mol / hour. The The mixture leaving the first reactor 101 is separated into a hydrocarbon phase and an aqueous phase in the separator 102. The hydrocarbon phase (isobutylene content 12.4 %) is fed to a second hydration reactor 104 in an amount of 729 mol / hour aqueous solution of Y ^ butyrolactone (content of Y ^ -butyrolactone 63.7 %) in an amount of 471 mol / hour. The first and second reactors were filled with the same catalyst made of sulfonic acid cation exchange resin, which was used in the processes of Examples II to 22 was used. in the first reactor 101, a temperature of 90 ⁰ C and a LHSV of 4 h and in the second reactor 104, a temperature is maintained of 70 C and a LHSV of 2 h. the reaction mixture from the second reactor 104 is a distillation column 105 supplied, in which unreacted hydrocarbons (isobutylene content 1.1 %) separated and in an amount of 645 mol / hour. be won. The aqueous phase of the separator 102 is fed to a distillation column 103, from which crude tertiary butyl alcohol (TBA content 67.4 fo) in an amount of 527 mol / hour. is obtained. The yield of tertiary butyl alcohol, based on the isobutylene in the starting hydrocarbon mixture, was 98.1 %.

For: Toa Nenryo Kogyo K.K., Chiyoda-ku, Tokyo / Japan

Dr H Rech

r.Beil sanwalt

Claims (1)

Lawyers' 05 Aug 1980 ADELONSTRASSE 58 6230 FRANKFURT AM MAIN 80 35 058 d / ga Toa Nenryo Kogyo K.K. Chiyoda-ku, Tokyo / Japan Jj ^ j j ΐ. "ΊΓ ΓΓ" i - ^ r ¹ J Ejjuj j ^^^ ΐΓίΧϊ ^ ίί ^ 3 ^^ ί ^ Sm Γ ^ Τ Γ ^? ^ -? * '! Process for the production of tertiary alcohols j patent pending; Process for the production of tertiary alcohols by reacting an isoolefin or an isoolefin-containing one Hydrocarbon mixtures with water in the presence of a solid catalyst, characterized in that one the reaction in the presence of a neo-type polyhydric alcohol or a derivative thereof or an oxyacid or a derivative thereof. 2. The method according to claim 1 for producing a tertiary alcohol by converting an isoolefin or an isoolefin-containing hydrocarbon mixture with water in the presence of an acidic cation exchange resin, characterized in that the reaction is carried out in the presence of a polyhydric alcohol of the Neo type the general formula ? ^H 2 CH ₂ OH -C-
I. V - ΓΉ CH_ ^X 3 wherein X ₁ , X 2 and X represent hydrogen, hydroxyl groups, alkyl, aryl, alkoxy, substituted alkoxy or ester groups and at least one of the radicals X ₁ , X 2 or X is a hydroxyl group or a radical containing hydroxyl groups , or an ester, partially esterified product thereof or ether. 35. ■ The method according to claim 2, characterized in that ■ X ₁ , X ₂ and. X, represent hydrogen, the hydroxyl group or methyl and at least one of the radicals is a hydroxyl group. 4. The method according to claim 2, characterized in that the polyhydric alcohol trimethylolpropane, trimethylolethane, Pentaerythritol, Neopenty! Glycol, the ether dimers these polyhydric alcohols or mixtures thereof are used. Process according to Claim 1 for the preparation of tertiary alcohols by reacting an isoolefin or an isoolefin-containing hydrocarbon mixture with water in the presence of an acidic cation exchange resin, characterized in that the reaction is carried out in the presence of a C ₀ to C oxyacid, of lactones, lactides, Methyl or ethyl esters of this acid or halogen-substituted derivatives thereof or mixtures thereof. 6 «. Method according to claim 5 * characterized in that one as oxyacids - ;;. Hydroxyacetic acid, lactic acid, 3-hydroxypropionic acid ^ ßjß-trichlorolactic acid, Hydroxypivalic acid or T ^ hydroxybutyric acid used. 7. The method according to claim 5, characterized in that one as lactone J3-propiolactone, β, β-dimethylpropiolactone, . ^ -Butyrolactone, ^ Valerolactone or £ -VaIerolacton used. 8. The method according to claim 5 *, characterized in that man- used as lactide diglycolide or lactide. 9. The method according to claim 5, characterized in that Glycolsäureme.thylester or Glycolic acid ethyl ester is used as the oxy acid ester. 10. The method according to claim 2 or 5, characterized in that a sulfonated resin is used as the exchange resin. 11. The method according to claim 2 or 5 » characterized in that a sulfonated styrene / divinylbenzene copolymer is used as the exchange resin. 12. The method according to claim 1, 2 or 5, characterized. that the feed contains isobutylene and that tertiary butyl alcohol is obtained as the product. IJ. Method according to claim 2 or 5 *, characterized in that that the feed is isobutylene in a hydrocarbon mixture contains, the resin from a sulfonated! Styrene / divinylbenzene copolymer and the tertiary butyl alcohol produced by hydration is essentially • isolated in purified form. .14. Process according to Claim 1, 2 or 5, characterized in that the hydrocarbon mixture mainly contains Cu hydrocarbons, including isobutylene isomers.