CA1037487A - Process for preparing tetrahydrofuran - Google Patents
Process for preparing tetrahydrofuranInfo
- Publication number
- CA1037487A CA1037487A CA211,068A CA211068A CA1037487A CA 1037487 A CA1037487 A CA 1037487A CA 211068 A CA211068 A CA 211068A CA 1037487 A CA1037487 A CA 1037487A
- Authority
- CA
- Canada
- Prior art keywords
- silica
- mixture
- tetrahydrofuran
- diols
- diol
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for preparing tetrahydrofuran which comprises heating 1,4-butanediol in the presence of a dehydration catalyst.
A process for preparing tetrahydrofuran which comprises heating 1,4-butanediol in the presence of a dehydration catalyst.
Description
~o3!7~7 This invention relates to a process for preparing --tetrahydrofuran which comprises heating 1,4-butanediol in the presence of a dehydration catalyst.
It is known in the art that tetrahydrofuran may be made by a number of different met~ods; the more prominent methods are by the catalytic hydrogenation of furan or by the dehydration of 1,4-butanediol in the liquid phase, i.e., heating 1,4-butanediol in the liquid phase with sulfuric acid i~
at elevated temperatures.
In practice, the tetrahydrofuran is most often produced by a series of reactions starting with the reaction of formaldehyde and acetylene in the presence of a cuprous acetylide complex to form butynediol. Butynediol is converted on hydrogenation to butanediol. The 1,4-butanediol is con-verted to tetrahydrofuran as indicated above. ~, Additionally, tetrahydrofuran is prepared from maleic acid, its esters, maleic anhydride, fumaric acid, its esters, succinic acid, its esters, succinic anhydride, ~ -butyrolactone, or miYtUreS of these compounds, by hydrogenation over a hydrogenation catalyst.
Mowever, these methods in~olve considerably eYpensive equipment and often present corrosion problems.
Tetrahydrofuran is a useful solvent for natural and synthetic resins, particularly vinyls. Also, it is used as an intermediate in the manufacture of nylon, 1,4-dichlorobutane and polyurethanes.
It has been discovered that tetrahydrofuran may be efficiently prepared from l,~-butanediol by heating 1,4-butanediol in the vapor phase in the presence of a hetero- `
geneous dehydration catalyst; said dehydration catalyst selected from the group consisting of zeolites, silica, alumina, silica-aluminas, silica-magnesias and acidic clays. By this method, , '"
. '' ' ' "
; " ':
i ~
1~3~ 8OEI-2016 tetrahydrofuran is produced in essentially quantitative yields.
Also, the dehydration catalyst of the instant invention is ~
stationary and permanent and therefore may be continually ~ ;
reused The dehydration catalysts which may be employed in the practice of this invention are those which promote ring closure and removal of water. Suitable dehydration catalysts include zeolites, silica, alumina, silica-aluminas, silica-magnesias, acidic clays and the li~e.
The zeolite dehydration catalysts which may be used in the instant invention include the synthetic and natural zeolites, also known as molecular sieves. These zeolites are well known in the art and are detailed in Molecular Sieves, Charles K. Hersh, Reinhold Publishing Company, New ~orX (1961).
Pre~erably, representat:ive natural zeolitos w~ic~ may be employed in the instant invention lnclude those in ~able 3~
on page 21, of the Hersh reference while representative mole-cular sieves include those in Table 5-1, on page 54, o~ the `
Hersh reference. Additional zeolite catalysts are set forth in Orqanic Catalysts Over Crystalline Aluminosilicates, P. B. .:
Venuto and P. S. Landis, Advances in Catalysis, Vol. 18, pp. , 259 to 371 (1968). `~
The silica-alumina dehydration catalysts which may be used vary in composition from pure silica to pure alumina whereas the silica-magnesias vary in composition from pure silica to predominantly magnesia.
The acidic clay dehydration catalysts which may be used in the instant invention include clays containing the minerals kaolinite, halloysite, montmorillonite, illite, quartz, calcite, liminomite, gypsum, muscavite and the like, either in naturally acidic forms or a~ter treatment with acid. ~ `
It is known in the art that tetrahydrofuran may be made by a number of different met~ods; the more prominent methods are by the catalytic hydrogenation of furan or by the dehydration of 1,4-butanediol in the liquid phase, i.e., heating 1,4-butanediol in the liquid phase with sulfuric acid i~
at elevated temperatures.
In practice, the tetrahydrofuran is most often produced by a series of reactions starting with the reaction of formaldehyde and acetylene in the presence of a cuprous acetylide complex to form butynediol. Butynediol is converted on hydrogenation to butanediol. The 1,4-butanediol is con-verted to tetrahydrofuran as indicated above. ~, Additionally, tetrahydrofuran is prepared from maleic acid, its esters, maleic anhydride, fumaric acid, its esters, succinic acid, its esters, succinic anhydride, ~ -butyrolactone, or miYtUreS of these compounds, by hydrogenation over a hydrogenation catalyst.
Mowever, these methods in~olve considerably eYpensive equipment and often present corrosion problems.
Tetrahydrofuran is a useful solvent for natural and synthetic resins, particularly vinyls. Also, it is used as an intermediate in the manufacture of nylon, 1,4-dichlorobutane and polyurethanes.
It has been discovered that tetrahydrofuran may be efficiently prepared from l,~-butanediol by heating 1,4-butanediol in the vapor phase in the presence of a hetero- `
geneous dehydration catalyst; said dehydration catalyst selected from the group consisting of zeolites, silica, alumina, silica-aluminas, silica-magnesias and acidic clays. By this method, , '"
. '' ' ' "
; " ':
i ~
1~3~ 8OEI-2016 tetrahydrofuran is produced in essentially quantitative yields.
Also, the dehydration catalyst of the instant invention is ~
stationary and permanent and therefore may be continually ~ ;
reused The dehydration catalysts which may be employed in the practice of this invention are those which promote ring closure and removal of water. Suitable dehydration catalysts include zeolites, silica, alumina, silica-aluminas, silica-magnesias, acidic clays and the li~e.
The zeolite dehydration catalysts which may be used in the instant invention include the synthetic and natural zeolites, also known as molecular sieves. These zeolites are well known in the art and are detailed in Molecular Sieves, Charles K. Hersh, Reinhold Publishing Company, New ~orX (1961).
Pre~erably, representat:ive natural zeolitos w~ic~ may be employed in the instant invention lnclude those in ~able 3~
on page 21, of the Hersh reference while representative mole-cular sieves include those in Table 5-1, on page 54, o~ the `
Hersh reference. Additional zeolite catalysts are set forth in Orqanic Catalysts Over Crystalline Aluminosilicates, P. B. .:
Venuto and P. S. Landis, Advances in Catalysis, Vol. 18, pp. , 259 to 371 (1968). `~
The silica-alumina dehydration catalysts which may be used vary in composition from pure silica to pure alumina whereas the silica-magnesias vary in composition from pure silica to predominantly magnesia.
The acidic clay dehydration catalysts which may be used in the instant invention include clays containing the minerals kaolinite, halloysite, montmorillonite, illite, quartz, calcite, liminomite, gypsum, muscavite and the like, either in naturally acidic forms or a~ter treatment with acid. ~ `
- 2 - `
': ' ' ' 8C~-2016 ~3~
The catalyst~is preferably used in the form of a bed through which the reactants are passed.
The temperatures at which the process can be carried out varies widely. Temperatures ranging from about 125C. to about 300C. are generally adequate although higher temperatures can be used. Preferably, the reaction is carried out at a temperature of from about 180C. to about 270 C. The maximum depends upon destruction of the product, olefin formation occurring under too rigorous conditions.
Although only atmospheric pressure is normally required, it will be of course apparent to those skilled in the art that superatmospheric pressure or subatmospheric pressure may be used where conditions and concentrations so dictate.
The process may be lllustrated by the following equation:
( 2 4 ~ ~ CH2 ~ l~I2 2 C ~ / 2 \ 0 /
In Canadian application Serial ~o. 203,212 of William E. Smith, filed June 24, 1974 and assigned to the same assignee as the present in~ention, there is disclosed `
and claimed a process for making butanediols by reacting `;
propylene, oxygen and a carbo~ylic acid to produce an allyl carboYylate which is then hydroformylated to produce the mixture o~ the corresponding aldehydes. Hydrogenation of the mi~ture produces a mixture of the esters of the corresponding diols. The diol esters are de-esterified by alcoholysis or hydrolysis to produce the following diols: 1,4-butanediol, 2-methyl-1,3-propanediol and 1,2-butanediol. In Canadian
': ' ' ' 8C~-2016 ~3~
The catalyst~is preferably used in the form of a bed through which the reactants are passed.
The temperatures at which the process can be carried out varies widely. Temperatures ranging from about 125C. to about 300C. are generally adequate although higher temperatures can be used. Preferably, the reaction is carried out at a temperature of from about 180C. to about 270 C. The maximum depends upon destruction of the product, olefin formation occurring under too rigorous conditions.
Although only atmospheric pressure is normally required, it will be of course apparent to those skilled in the art that superatmospheric pressure or subatmospheric pressure may be used where conditions and concentrations so dictate.
The process may be lllustrated by the following equation:
( 2 4 ~ ~ CH2 ~ l~I2 2 C ~ / 2 \ 0 /
In Canadian application Serial ~o. 203,212 of William E. Smith, filed June 24, 1974 and assigned to the same assignee as the present in~ention, there is disclosed `
and claimed a process for making butanediols by reacting `;
propylene, oxygen and a carbo~ylic acid to produce an allyl carboYylate which is then hydroformylated to produce the mixture o~ the corresponding aldehydes. Hydrogenation of the mi~ture produces a mixture of the esters of the corresponding diols. The diol esters are de-esterified by alcoholysis or hydrolysis to produce the following diols: 1,4-butanediol, 2-methyl-1,3-propanediol and 1,2-butanediol. In Canadian
- 3 - ;
8CH-2Ql6 ~
: "
;~37~
application Serial No. 195,~892 of William E. Smith, filed /. ::
March 25, 1974 and assigned to the same assignee as the present .~ ~
.; :. : .
invention, there is disclosed and claimed a process wherein the hydrogenation is accomplished concurrently with the . .
hydroformylation reaction. Deesterification of the diol ester .
mixture by alcoholysis or hydrolysis produces the same ~`
mixture of diols indicated above.
Tet.rahydroEuran may be prepared from a mixture o~
diols; the procedures disclosed in Canadian appl:Lcations Serial Nos. 203,212 and 19$,892 may he used to obtain this .`
diol mixture. This process involves heating a mixture of 1,4-butanediol, 1,2-butanediol and 2-methyl-1,3-propanediol ..
in the vapor phase in the presence of a heterogeneous de-hydration catalyst; said dehydration catalyst being selected from the group consisting of zeolites, silica, alumina, silica-aluminas, silica-magnesias and acidic clays.
The reaction may be carried out by passing a mixture of 1,4-butanediol, 1,2-butanediol and 2-methyl-1,3-propanediol -.
in the vapor phase through a heated catalyst bed. The 1,4- ;.
butanedio1 is converted to tetrahydroiuran and water. The :
,,:,, r- :
~ ~ 8C~I-2016 other diols come through unchanged or are converted to ole~inic dehydration products. Well-known techniques of separating tetrahydrofuran from its water azeotrope are employed.
lrhe following examples are set forth to illustrate more clearly the principle and practice of this invention to those s~illed in the art. Unless otherwise specified, where parts or percents are mentioned, they are parts or percents by weight.
A vertical hot tube reactor (16 mm ID x 70 cm effective length) is constructed from heavy wall glass, with 24/40 male and female joints. Vigreaux points are indented ~ust above the male joint to support catalyst pellets. Thermo-couple leads are fastened into three ot~er Vigreaux in-dentations at points along t~e length. ~hree 4 ~t. ~ 1 in.
Briskheat glass insulated heating tapes are wound onto the tube, covered with glass wool and glass tape, and connected to separate variable transformers. The tube exit is connected by a gooseneck (also heated) to an efficient condenser and collection vessel. A three-nec~ed flask serves as the evaporator, with the reactants added from an additional funnel in a side neck. A nitrogen carrier gas is employed to provide a contact time in t~e 3-10 second range. ;
The tube as described above is charged with 110 grams ;
of alumina catalyst (Harshaw 1/8 in. pellets, Al-0104T) and operated at 250-270C. while 51 grams of 1,4-butanediol is passed through over a 15 minute period. Collected at about the same rate as input is 51 grams of liquid effluent, which ;
is found by glpc analysis to be composed of tetrahydrofuran and water only, in 1:1 molar ratio (guantitative yield and .. . .
conversion).
The tube as described in Example 1 is charged with 89 grams of silica-alumina catalyst (87% silica-- 13% alumina, 3/16" x 3/16" pills, Davison Chemical grade 970) and operated at 250C. while 90 grams of 1,4-butanediol is passed through over a one hour period. The effluent collected (86 grams) contains, as shown by glpc analysis, 70 grams of tetrahydro~
furan (97% yield) and not more than a trace of 1,4-butanediol.
The tube and cataly~t as described in Example 2 is operated at 250C. while 100 grams of diol mixture containing 84 grams of 1,4-butanediol, 11 grams of 1,2-butanediol and 5 grams of 2-methyl-1,3-propanediol is passed through over a one hour period. Quantitative glpc anaylsis of the effluent reveals the presence of 67 grams of tetrahydrofuran (100%
yield), as well as the water, the other diols, and their olefinic dehydration products.
The tube as described in Example 1 is charged with 85 grams of silica-magnesia catalyst (70% silica--30% magnesia, 3/16" x 3/1~" pills, Davison C~emical) and operated at 250C.
while 100 grams of the diol mixture described in Example 3 is passed through over a one hour period. Analysis of the effluent by glpc indicates the presence of about 5 grams of unconverted 1,4-butanediol (6% recovery), 63 grams of tetra-hydrofuran (100% yield based on 94% conversion), 4 grams of 1,2-butanediol, 3 grams of 2-methyl-1,3-propanediol, and small amounts of olefinic dehydration products.
It should, of course, be apparent to t~ose skilled in the art that changes may be made in the particular embodiments of the invention described w~ich are within the full intended scope of the invention as defined by the appended claims.
8CH-2Ql6 ~
: "
;~37~
application Serial No. 195,~892 of William E. Smith, filed /. ::
March 25, 1974 and assigned to the same assignee as the present .~ ~
.; :. : .
invention, there is disclosed and claimed a process wherein the hydrogenation is accomplished concurrently with the . .
hydroformylation reaction. Deesterification of the diol ester .
mixture by alcoholysis or hydrolysis produces the same ~`
mixture of diols indicated above.
Tet.rahydroEuran may be prepared from a mixture o~
diols; the procedures disclosed in Canadian appl:Lcations Serial Nos. 203,212 and 19$,892 may he used to obtain this .`
diol mixture. This process involves heating a mixture of 1,4-butanediol, 1,2-butanediol and 2-methyl-1,3-propanediol ..
in the vapor phase in the presence of a heterogeneous de-hydration catalyst; said dehydration catalyst being selected from the group consisting of zeolites, silica, alumina, silica-aluminas, silica-magnesias and acidic clays.
The reaction may be carried out by passing a mixture of 1,4-butanediol, 1,2-butanediol and 2-methyl-1,3-propanediol -.
in the vapor phase through a heated catalyst bed. The 1,4- ;.
butanedio1 is converted to tetrahydroiuran and water. The :
,,:,, r- :
~ ~ 8C~I-2016 other diols come through unchanged or are converted to ole~inic dehydration products. Well-known techniques of separating tetrahydrofuran from its water azeotrope are employed.
lrhe following examples are set forth to illustrate more clearly the principle and practice of this invention to those s~illed in the art. Unless otherwise specified, where parts or percents are mentioned, they are parts or percents by weight.
A vertical hot tube reactor (16 mm ID x 70 cm effective length) is constructed from heavy wall glass, with 24/40 male and female joints. Vigreaux points are indented ~ust above the male joint to support catalyst pellets. Thermo-couple leads are fastened into three ot~er Vigreaux in-dentations at points along t~e length. ~hree 4 ~t. ~ 1 in.
Briskheat glass insulated heating tapes are wound onto the tube, covered with glass wool and glass tape, and connected to separate variable transformers. The tube exit is connected by a gooseneck (also heated) to an efficient condenser and collection vessel. A three-nec~ed flask serves as the evaporator, with the reactants added from an additional funnel in a side neck. A nitrogen carrier gas is employed to provide a contact time in t~e 3-10 second range. ;
The tube as described above is charged with 110 grams ;
of alumina catalyst (Harshaw 1/8 in. pellets, Al-0104T) and operated at 250-270C. while 51 grams of 1,4-butanediol is passed through over a 15 minute period. Collected at about the same rate as input is 51 grams of liquid effluent, which ;
is found by glpc analysis to be composed of tetrahydrofuran and water only, in 1:1 molar ratio (guantitative yield and .. . .
conversion).
The tube as described in Example 1 is charged with 89 grams of silica-alumina catalyst (87% silica-- 13% alumina, 3/16" x 3/16" pills, Davison Chemical grade 970) and operated at 250C. while 90 grams of 1,4-butanediol is passed through over a one hour period. The effluent collected (86 grams) contains, as shown by glpc analysis, 70 grams of tetrahydro~
furan (97% yield) and not more than a trace of 1,4-butanediol.
The tube and cataly~t as described in Example 2 is operated at 250C. while 100 grams of diol mixture containing 84 grams of 1,4-butanediol, 11 grams of 1,2-butanediol and 5 grams of 2-methyl-1,3-propanediol is passed through over a one hour period. Quantitative glpc anaylsis of the effluent reveals the presence of 67 grams of tetrahydrofuran (100%
yield), as well as the water, the other diols, and their olefinic dehydration products.
The tube as described in Example 1 is charged with 85 grams of silica-magnesia catalyst (70% silica--30% magnesia, 3/16" x 3/1~" pills, Davison C~emical) and operated at 250C.
while 100 grams of the diol mixture described in Example 3 is passed through over a one hour period. Analysis of the effluent by glpc indicates the presence of about 5 grams of unconverted 1,4-butanediol (6% recovery), 63 grams of tetra-hydrofuran (100% yield based on 94% conversion), 4 grams of 1,2-butanediol, 3 grams of 2-methyl-1,3-propanediol, and small amounts of olefinic dehydration products.
It should, of course, be apparent to t~ose skilled in the art that changes may be made in the particular embodiments of the invention described w~ich are within the full intended scope of the invention as defined by the appended claims.
Claims (4)
1. In a process for the conversion of propylene to tetrahydrofuran, said process including the steps of (a) reacting propylene, oxygen and a carboxylic acid to form an allyl carboxylate, (b) converting said allyl carboxylate under hydro-formylation conditions to produce the corresponding aldehyde (c) hydrogenating said aldehyde to produce a diol monocarboxylate (d) hydrolyzing said diol monocarboxylate to give a mixture of the corresponding diols, said mixture of diols comprising the tetrahydrofuran precursor 1,4 butane diol, and as impurities therein 1,2 butane diol and 2 methyl 1/3 propane diol, said precursor being difficultly separable from said impurities, the improvement which comprises heating said mixture of diols to a temperature in the range of about 180°C to about 270°C
in the vapour phase in the presence of a heterogeneous dehydra-tion catalyst selected from the group consisting of natural zeolites, synthetic zeolites, silica, alumina, silica-aluminas, silica magnesias and acidic clays to form a second mixture com-prising tetrahydrofuran, olefinic dehydration products of said 1,2 butane diol and 2 methyl 1, 3 propanediol, unconverted diols and water, from which second mixture the desired tetrahydrofuran is readily separable.
in the vapour phase in the presence of a heterogeneous dehydra-tion catalyst selected from the group consisting of natural zeolites, synthetic zeolites, silica, alumina, silica-aluminas, silica magnesias and acidic clays to form a second mixture com-prising tetrahydrofuran, olefinic dehydration products of said 1,2 butane diol and 2 methyl 1, 3 propanediol, unconverted diols and water, from which second mixture the desired tetrahydrofuran is readily separable.
2. The process of claim 1 wherein said dehyration catalyst is silica alumina.
3. The process of claim 1 wherein said dehydration catalyst is silica-magnesia.
4. The process of claim 1 wherein said dehydration catalyst is alumina.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42085273A | 1973-12-03 | 1973-12-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1037487A true CA1037487A (en) | 1978-08-29 |
Family
ID=23668098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA211,068A Expired CA1037487A (en) | 1973-12-03 | 1974-10-09 | Process for preparing tetrahydrofuran |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1037487A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4656297A (en) * | 1985-03-11 | 1987-04-07 | Amoco Corporation | Coproduction of butanediol and tetrahydrofuran and their subsequent separation from the reaction product mixture |
| WO2015038548A1 (en) * | 2013-09-10 | 2015-03-19 | Invista Technologies S.A R.L. | Improved process for manufacture of tetrahydrofuran |
-
1974
- 1974-10-09 CA CA211,068A patent/CA1037487A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4656297A (en) * | 1985-03-11 | 1987-04-07 | Amoco Corporation | Coproduction of butanediol and tetrahydrofuran and their subsequent separation from the reaction product mixture |
| WO2015038548A1 (en) * | 2013-09-10 | 2015-03-19 | Invista Technologies S.A R.L. | Improved process for manufacture of tetrahydrofuran |
| CN105531266A (en) * | 2013-09-10 | 2016-04-27 | 因温斯特技术公司 | Improved process for manufacture of tetrahydrofuran |
| CN105531266B (en) * | 2013-09-10 | 2018-01-19 | 因温斯特技术公司 | For manufacturing the improved method of tetrahydrofuran |
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