Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR THE PRODVCTION OF TERTIARY BUTY1 ALCOHOL
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1 BACKGROUND OF THE INVENTION
2 This invention relates to a process for the pro-
3 duction of tertiary butyl alcohol (TBA) in a high yield
4 from a C4 hydrocarbon mixture containing isobutylene
More particularly, the present invention relates
6 to a process for the production of TBA in a high yield by
7 selectively reacting isobutylene in a C4 hydrocarbon mix-
8 ture containing isobutylene with water in the presence of
9 a porous, acid-type cation exchange resin and a sulfone.
~arious processes have heretofore been proposed
11 concerning the preparation of alcohols by hydrating corres-
12 ponding olefinic unsaturated compounds in the presence of
13 an acid-type cation exchange resin and a solvent. For
14 example, there can be mentioned a process in which iso-
butylene or an isobutylene-containing hydrocarbon mixture
16 is reacted with an aqueous solution of an organic acid in
17 the presence of an acidic ion exchange agent as a catalyst
18 (Japanese Patent Application OPI No. 32116/75 and Japanese
19 Patent Publication No. 14044/78), a process in which a mono
hydric alcohol is added to the reaction system and the reac-
21 tion is carried out by using a similar catalyst (Japanese
22 Patent Application OPI No. 137906/75) and a process in which
23 glycol, glycol ether or glycol diether is added to the reac-
24 tion system and the reaction is similarly carried out (Jap-
anese Patent Application OPI No. 59802/76 and U~S. Patent
26 No. 4,096,194).
27 In addition to these processes for preparing TBA
28 by reacting water with isobutylene, there has been proposed
29 for preparing secondary butyl alcohol ~SBA) a method of
reacting water with an olefinic unsaturated compound, par-
31 ticularly butene-l and/or butene-2, in the presence of an
32 acidic ion exchange resin and a sulfone at a temperature of
33 100 to 220C. (Japanese Patent Application OPI No. 7605/78
34 equivalent to British Patent 1,518,461).
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1 These known processes for preparing TBA by hy-
2 drating isobutylene have the disadvantage of producing by-
3 products such as addition products of isobutylene and the
4 organic acid or organic solvent adaed to the reaction sys-
tem, although the reaction rate is improved to some extent.
6 Since these by-products and added solvents have a boiling
7 point close to or lower than that of TBA, separation and
8 recovery of TBA from these by-products and solvents are
9 very difficult and large operating costs are necessary for
recovery of TB~. Although the process for preparing SBA
11 by reacting water with butene-l and butene-2 at a tempera-
12 ture of 100 to 220C.shows good stability of the solvent
13 used, it is impossible to produce T~A in a high yield by
14 selectively hydrating isobutylene because isobutylene-
bearing C~ hydrocarbon feed reacts with water and forms iso-
16 butylene dimer and SBA cocurrently with the formation of
17 TBA.
18 SUMMARY OF THE INVENTION
19 Applicants have made various studies with a view
to eliminating the above defects and disadvantages involved
21 in the conventional techniques and have found that when iso-
22 butylene is caused to react with water in the presence of
23 a specific ion exchange resin and a sulfone at a temperature
24 not higher than 100C., the reaction speed and conversion
can be remarkably enhanced while occurrence of side reac-
26 tions is inhibited.
27 DETAILED DESCRIPTION
28 More specifically, in accordance with the present
29 invention there is provided a process for preparing tertiary
butyl alcohol by reacting water with iso~utylene selectively
31 from a C4 hydrocarbon mixture containing isobutylene, said
32 process being characterized in that the reaction is carried
33 out at a temperature not higher than 100C. in the presence
34 of a porous acid-type cation exchange resin and a sulfone.
The composition of the iso~utylene-containing C4
36 hydrocarbon mixture used in the present invention is not
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1 particularly limited but will usually include n-butenes.
2 Ordinarily, a mixture containing hydrocarbons having 4
3 carbon atoms, such as isobutylene, butene-l, butene-2,
4 isobutane and n-butane is used, but this mixture may con-
tain small amounts of C3 or C5 hydrocarbons. C4 fractions
6 containing isobutylene, obtained by steam cracking or cata-
7 lytic cracking of petroleum, are preferably employed from
8 the industrial viewpoint.
9 Non-cyclic and cyclic sulfones are suitably used
in the present invention. For example, the following sul-
11 fones may be used.
12Sulfolane of the following formula:
13 H2C, C,H2
14 H2C \ CH2
16 O~ ~
18Sulfolene o the following formula:
19 HC - CH
21 2 \ / 2
22 O~ ~O
23Dimethyl sulfone Oc the following formula:
24 O
H3C - S - CH3
26 ll
27 O
28Sulfonal of the following formula:
29 O 4 O
H3C \ / C2 5
333 O~ ~O 2 5
34
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1 Trional of the following formula:
2 O ~ ~ O
4 ~ C
6 O~ ~O 5
7 Diethyl sulfone of the following formula:
8 O
9 ..
H5 C2 S -C2 H5
12 Ethylmethylsulfone of the following formula:
13 O
14 H5C2 - S CH3
16
17 Divinylsulfone of the following formula:
18 O
19
H2C = HC - S - CH - CH2
21
22 These sulfones may be used singly or in the form
23 of a mixture of two or more of them. Ordinarily, the sul-
24 fone is used in the state dissolved in water. The amount
used of the sulfone is preferably 100 to 3000 parts by
26 weight, especially 200 to 2000 parts by weight, per 100
27 parts by weight of water.
28 A strongly acidic cation exchange resin is pre-
29 ferably used as the porous, acid-type cation exchange resin
in the present invention. For example, there may be used a
31 sulfonated polystyrene-type resin formed by introducing sul-
32 fonic acid groups into a styrene-divinyl benzene copolymer
33 base, a phenol-sulfonic acid type resin formed by introducing
34 sulfonic acid groups into a phenol-formaldehyde condensate
and a perfluorosulfonic acid type resin formed by intro-
36 ducing sulfonic acid groups into a vinyl ether fluoride-
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1 fluorocarbon copolymer. ~ porous resin characterized by a
2 surface axea of at least 0.5 m2/g (dry weight) and an ex-
3 change capacity of at least 2.0 meq/g (dry weight), is
4 prefe~red.
The amount of the catalyst used in the suspended
6 state differs from the amount used in a fixed bed, and in
7 the ~ormer case it is preferred to use the catalyst in an
8 amount of 0.1 to 10~ by weight based on the aqueous solution
9 of the sulfone.
When the molar ratio of water to isobutylene is
11 lower than 1, the conversion is lowered, and if the molar
12 ratio of water to isobutylene is too high, the efficiency
13 of the reaction vessel is reduced. It is preferred that
14 the molar ratio of water to isobutylene be in the range o~
from 1 tc 10.
16 The reaction is carried out at a temperature not
17 higher than 100C., preferably 40 to 100C.
18 The reaction may be carried out under atmospheric
19 pressure, but preferably under the vapor pressure of the
starting hydrocarbon mixture at the reaction temperature or
21 a pressure slightly higher than said vapor pressure.
22 The reaction may be conducted batchwise but ordin-
23 arily is conducted in a continuous manner by using a fixed
24 bed of the porous, acid-type cation exchange resin.
The reaction time is usually 20 minutes to 10 hours
26 when the reaction is conducted batchwise and when conducted
27 in a continuous manner, the liquid hourly space velocity
28 (LHSV) of the hydrocarbon mixture is preferably from 0.3 to
29 10 hr 1.
In accordance with a preferred embodiment of the
31 present invention, the hydration reaction is carried out in
32 the presence of a porous, acid-type cation exchange resin,
33 e.g., a sulfonated styrene-divinyl benzene copolymer having
3~ a surface area of 0.5 to 200 m2/g, especially 3 to 200 m2/g,
and an exchange capacity o~ 2.0 to 5.0 meq/g, especially 2.7
36 to 5.0 meq/g, and a liquid mixture of water and sulfolane,
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1 sulfolene, diethyl sulfone or dimethyl sulfone having a
2 sulfone concentration of 50 to 97~ by weight, especially
3 60 to 95~ by ~eight, at a temperature of 40 to 100C., es-
4 pecially 60 to 100C., and a water/isobutylene molar ratio
of from 1.0 to 10. O, preferably from 1.6 to 6.0, in a C4
6 hydrocarbon mixture containing isobutylene, n-butenes and
7 butanes, under a pressure sufficient to keep said C4 hydro-
8 carbon mixture in the liquid state, preferably a pressure
9 of 7 to 18 Kg/cm .
When the sulfonated styrene-divinyl benzene co-
11 polymer is an ordinary gel-type resin having a surface area
12 smaller than 0.1 m2/g, even if the exchange capacity is
13 higher than 2.0 meq/g, the catalytic activity is low, and
14 when the exchange capacity is lower than 2.0 meq/g, even if
the surface area is larger than 0.5 m2/g, the catalytic
16 activity is low. If the sulfone concentration is 50 to 97%
17 by weight, the hydration reaction is promoted at a water/
18 isobutylene molar ratio of from 1 to 10. However, even in
19 this case, if the reaction temperature is above 100 to
200C., dimerization of isobutylene and hydration of n-
21 butenes are promoted and diisobutylene and SBA are formed.
22 Accordingly, a temperature of 40 to 100C. is effective for
23 selective reaction of isobutylene with water.
24 The starting C4 hydrocarbon mixture containing iso-
butylene is reacted with the aqueous solution of the sulfone
26 in a catalyst packed reaction vessel, and the resulting mix-
27 ture of hydration reaction products is subjected to distilla-
28 tion and separated into the unreacted hydrocarbon mixture
29 and the TBA-containing aqueous solution of the sulfone. The
recovered aqueous solution is subjected to distillation to
31 separate it into crude TBA (TBA/water azeotropic mixture)
32 and the aqueous solution of the sulfone. ~later is removed
33 from crude TBA according to customary procedures to obtain
34 substantially pure TBA, and the separated unreacted hydro-
carbon mixture and the aqueous solution of the sulfone may
36 be recycled to the reaction vess~l and used for the hydration
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1 reaction~ .
2 According to the present invention for selectively
3 hydrating isobutylene in a C4 hydrocarbon mixture containing
4 isobutylene, the reaction rate and the conversion of iso-
butylene are remarkably increased and TBA can be prepared in
6 a high yield while occurrence of side reac~ions is inhibited.7 Furthermore, the boiling points of the sulfones used in the
8 present invention are considerably higher than the boiling
9 point of TBA. Accordingly, the sulfones can be separated
very easily by distillation and can be reused without diffi-
11 culty.
12 When the process of the present invention is utilized,
13 isobutylene can be effectively isolated from a C4 hydrocarbon
14 mixture containing isobutylene. More specifically, according
to ~e process o~ the present invention, isobutylene in a C4
16 hydrocarbon mixture containing isobutylene is selectively
17 converted to T~A; the reaction mixture is separated into the
18 TBA-containing aqueous solution of the sulfone and the unre-
19 acted hydrocarbon mixture, TBA is isolated from the TBA-
containing aqueous solution of the sulfone, and isobutylene
21 is obtained by dehydrating TBA according to known procedures,22 by which high purity iso~utylene can be produced.
23 The present in~ention will now be described in detail
24 with reference to the following examples and co~parative
.25 examples.
26 ~
27 In an autoclave equipped with a stirrer, a C4 hydro-
28 carbon mixture containing isobutylene (40.0~ of isobutylene,
29 40.0~ of n-butenes and ~0.0% of butanes) was hydrated with
an aqueous solution of a sulfone in the presence of a highly
31 porous cation exchange resin of a sulfonated styrene-divinyl
32 benzene copolymer as a catalyst under conditions indicated
33 in Table 1. After completion of the reaction, the reaction
34 mixture was rapidly cooled, and the reaction product was
analyzed by gas chromatography to deter~ine conversions of
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1 isobutylene and n-butene and selectivities to TBA and SBA.
2 The results obtained are shown in Table 1. ,'.
3 Comparatlve Examples ~ "
4 In the same reaction vessel as used in Examples 1
5 through 6, hydration of isobutylene was carried out in the
6 same manner as described in Examples 1 through 6 except that .^
7 the sulfone was not added, a catalyst having a surface area
8 smaller than 0.5 m2~g or an exchange capacity lower than
9 2.0 meq/g was used or the reaction temperature was higher :
10 than 100C. The reaction conditions and results obtained are
11 shown in Table 2.
12 The conversions of isobutylene and n-butene and the
13 selectivities to TBA and SBA were determined in the same
14 manner as described in Examples 1 through 6.
l_ Note (For Ta~le 1 and Table 2)
16 (1) The selectivity to TBA is expressed in terms of
17 mol ~ of formed TBA based on reacted isobutylene.
18 ~2) The selectivity to SBA is expressed in terms of
19 mol ~ of formed SBA based on reacted n-butene.
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