CA1129890A - Process for the production of tertiary butyl alcohol - Google Patents
Process for the production of tertiary butyl alcoholInfo
- Publication number
- CA1129890A CA1129890A CA359,042A CA359042A CA1129890A CA 1129890 A CA1129890 A CA 1129890A CA 359042 A CA359042 A CA 359042A CA 1129890 A CA1129890 A CA 1129890A
- Authority
- CA
- Canada
- Prior art keywords
- sulfone
- isobutylene
- reaction
- water
- butyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
Abstract
ABSTRACT
PROCESS FOR THE PRODUCTION OF TERTIARY BUTYL ALCOHOL
Isobutylene in a C4 hydrocarbon mixture with n-butenes and butanes is selectively hydrated to tertiary butyl alcohol by carrying out the reaction with water at a temperature not above 100°C. in the presence of an acidic cation exchange resin and a sulfone.
PROCESS FOR THE PRODUCTION OF TERTIARY BUTYL ALCOHOL
Isobutylene in a C4 hydrocarbon mixture with n-butenes and butanes is selectively hydrated to tertiary butyl alcohol by carrying out the reaction with water at a temperature not above 100°C. in the presence of an acidic cation exchange resin and a sulfone.
Description
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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.
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.
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 ~zg890 -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:
21 2 \ / 2 22 O~ ~O
23Dimethyl sulfone Oc the following formula:
26 ll 28Sulfonal of the following formula:
H3C \ / C2 5 333 O~ ~O 2 5 ~9~g~
1 Trional of the following formula:
2 O ~ ~ O
4 ~ C
6 O~ ~O 5 7 Diethyl sulfone of the following formula:
9 ..
12 Ethylmethylsulfone of the following formula:
17 Divinylsulfone of the following formula:
H2C = HC - S - CH - CH2 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-~l2~890 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, ~12~39V
.
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 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 2~390 , ,.
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
~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).
~ .
~lZ9890 .
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.
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.
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 ~zg890 -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:
21 2 \ / 2 22 O~ ~O
23Dimethyl sulfone Oc the following formula:
26 ll 28Sulfonal of the following formula:
H3C \ / C2 5 333 O~ ~O 2 5 ~9~g~
1 Trional of the following formula:
2 O ~ ~ O
4 ~ C
6 O~ ~O 5 7 Diethyl sulfone of the following formula:
9 ..
12 Ethylmethylsulfone of the following formula:
17 Divinylsulfone of the following formula:
H2C = HC - S - CH - CH2 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-~l2~890 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, ~12~39V
.
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 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 2~390 , ,.
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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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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Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of tertiary butyl alcohol which comprises selectively reacting isobutylene in a C4 hydrocarbon mixture with water by carrying out the reaction at a temperature not higher than 100°C. in the presence of a porous, acid-type cation exchange resin and a sulfone.
2. A process according to claim l for the production of tertiary butyl alcohol which comprises selectively hydrating iso-butylene in a C4 hydrocarbon mixture containing isobutylene, n-butenes and butanes by carrying out the reaction in the presence of a porous, acid-type cation exchange resin comprising a sul-fonated styrene-divinyl benzene copolymer having a surface area of 0.5 to 200 m2/g and an exchange capacity of 2 to 5 meq/g and a liquid mixture of water and a sulfone which has a sulfone concentration of 50 to 97% by weight, at a tempera-ture of 40 to 100°C. and a water/isobutylene molar ratio in a range of 1 to 10 under a pressure sufficient to maintain said C4 hydrocarbon mixture in the liquid state.
3. A process according to claim 1 or 2 wherein said sulfone is sulfolane, sulfolene, diethyl sulfone or dimethyl sulfone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP110,440/79 | 1979-08-31 | ||
| JP11044079A JPS5634643A (en) | 1979-08-31 | 1979-08-31 | Preparation of tertiary butyl alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1129890A true CA1129890A (en) | 1982-08-17 |
Family
ID=14535768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA359,042A Expired CA1129890A (en) | 1979-08-31 | 1980-08-26 | Process for the production of tertiary butyl alcohol |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5634643A (en) |
| CA (1) | CA1129890A (en) |
| DE (1) | DE3031702A1 (en) |
| FR (1) | FR2464241A1 (en) |
| GB (1) | GB2060616B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3628008C1 (en) * | 1986-08-19 | 1987-11-05 | Deutsche Texaco Ag, 2000 Hamburg, De | |
| JPH11193255A (en) * | 1997-12-26 | 1999-07-21 | Mitsubishi Rayon Co Ltd | Production of tertiary butyl alcohol |
| TW200514767A (en) * | 2003-08-21 | 2005-05-01 | Mitsubishi Rayon Co | Method of producing tertiary alcohols |
| DE10338581A1 (en) | 2003-08-22 | 2005-03-17 | Oxeno Olefinchemie Gmbh | Process for producing tert-butanol |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2297196A1 (en) * | 1975-01-10 | 1976-08-06 | Chaplits Donat | Isobutylene recovery from 4C hydrocarbon fractions - by intermediate conversion to tert. butanol and dehydration of the alcohol |
| GB1518461A (en) * | 1976-05-13 | 1978-07-19 | Shell Int Research | Hydration of unsaturated compounds |
| US4180688A (en) * | 1977-07-29 | 1979-12-25 | Nippon Oil Co., Ltd. | Method for continuously producing tert-butyl alcohol |
| JPS5682580A (en) * | 1979-12-07 | 1981-07-06 | Hitachi Maxell Ltd | Manufacture of button-type battery |
-
1979
- 1979-08-31 JP JP11044079A patent/JPS5634643A/en active Granted
-
1980
- 1980-08-22 GB GB8027443A patent/GB2060616B/en not_active Expired
- 1980-08-22 DE DE19803031702 patent/DE3031702A1/en not_active Withdrawn
- 1980-08-26 CA CA359,042A patent/CA1129890A/en not_active Expired
- 1980-08-29 FR FR8018789A patent/FR2464241A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2464241A1 (en) | 1981-03-06 |
| JPS5634643A (en) | 1981-04-06 |
| JPH0137379B2 (en) | 1989-08-07 |
| GB2060616A (en) | 1981-05-07 |
| DE3031702A1 (en) | 1981-03-19 |
| FR2464241B1 (en) | 1984-10-19 |
| GB2060616B (en) | 1983-10-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |