CA1055519A - Manufacture of butenediol diacetates - Google Patents
Manufacture of butenediol diacetatesInfo
- Publication number
- CA1055519A CA1055519A CA223,200A CA223200A CA1055519A CA 1055519 A CA1055519 A CA 1055519A CA 223200 A CA223200 A CA 223200A CA 1055519 A CA1055519 A CA 1055519A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- tellurium
- platinum
- antimony
- ene
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE: But-2-ene-1,4-diol diacetate and/or but-1-ene-3,4-diol diacetate are manufactured from butadiene, oxygen and acetic acid using a platinum catalyst (particularly a platinum catalyst supported on active charcoal) which in addition contains a metal of main group 5 or 6 of the periodic table of elements.
Description
The invention relates to a process for the manufacture of butenediol diacetates, especially but-2-ene-1,4-diol diacetate and but-l-ene-3,4-diol diacetate, by reaction of butadiene with oxygen and acetic acid, in the gas phase or liquid phase, over a solid catalyst which consists of platinum and an element of main group 5 or 6.
According to German application DOS 2,217,452 published on October 26, 1972 in the name of Mitsubishi Chemical butadiene can be reacted in the liquid phase with oxygen and acetic acid, in the presence of solid catalysts containing palladium to give butenediol diacetates. The reaction can also be carried out in the gas phase over catalysts which contain palladium and alkali metal salts as promoters (see German application DOS 2,200,124 published on July 5, 1973 in the name of Kuraray). A disadvantage of the liquid phase method is the low rate of reaction. A disadvantage of the conventional gas phase reaction is that undesired by-products such as l-acetoxy-1,3-butadiene are formed, and that the reaction has to be carried out at low butadiene concentrations so as not to reduce the catalytic activity of the catalyst.
We have now found that butenediol diacetates, especially but-2-ene-1,4-diol diacetate, are obtained in high yield and with high space-time yield by reaction of butadiene, oxygen and acetic acid, preferably in the gas phase, over a solid catalyst if the catalyst 105~519 O.Z. 30,500 i8 platinum containing one or more elements of main group 5 or 6 selected from the group comprising phosphorus, arsenic, antimony, bismuth, selenium and telluriumO
The catalyst is preferably a supported catalyst and may be obtained by the conventional methods for producing supported platinum catalysts.
The catalyst may be manufactured, eg~, by dispersing a carrier in a solution obtained by dissolving a platinum compound and one or more compounds of phosphurus, arsenic, antimony, bismuth, tellurium and selenium in a suitable solvent, eg. water, then evaporating off the solvent so as to deposit the above components on the carrier and reducing the mass in a stream of gas containing hydrogen or a reducing compound, or by means of conventional reducing agents, such as hydrazine, methanol or formalin. The catalyst may also be manufactured by adding a precipitant (eg. an alkaline reagent) to a mixture of the carrier and the solution and then carrying out a reduction by the above processO Platinum and antimony, phosphorus, arsenic, bismuth, tellurium and selenium can in each method be deposited on the carrier either simultaneously or succes-sively; in some cases, the carrier can be added in the rorm of asoluble compound and then be co-precipitated with the active metal.
It is possible to use any reduction method by which platinum and arsenic, antimony, bismuth, tellurium and/or selenium are reduced to the metal state.
Carriers which may be used are active charcoal, silica gel, silicic acid, alumina, clay, bauxite, magnesia, kieselguhr, pumice and the like. The carriers may be activated by conventional methods, eg. by treatment with acids.
The choice of the platinum compound used to manufacture the catalyst is not a decisive ~actor though a halogen co~pound of platinum, such as platinum-II chloride or platinum-IV chloride, a salt o~ an organic acid, such as platinum acetate, platinum nitrate, platinum oxide and the like are preferred for cost reasons. However, other platinum compounds, eg. hexachloroplatinic acid or sodium - lOSSSl9 Z. 30,500 ~tinosulrate can of course also bc used.
In general, the concentration of platinum on the carrier is from 0.1 to 20% by weight~though higher and lower concentrations are not excluded.
The arsenic, antimony, bismuth, tellurium and selenium com-pounds used as the other components for the manufacture of the catalyst are also not subject to special limitations; it is possible to use the halides, nitrates, sulfates, oxides and other compounds of this type. Suitable compounds containing phosphorus are, inter alia, o- and m-phosphoric acid, alkali metal phosphates and alkaline earth metal phosphates~
Though the amounts Or phosphorus, arsenic, antimony, bismuth, tellurium and selenium compounds deposited on the carriers may be varied within wide limits and still prove effective, amounts of from 0.05 to 30~ by weight are generally appropriate.
Platinum catalyst of the above type which contain active charcoal as the carrier and abou-t from 0.1 to 5% Or tellurium or antimony in addition to from 0.1 to 10~ of platinum (based on the total weight of catalyst) have proved exceptionally suitable and are particularly preferred.
Higher concentrations of platinum than those stated can also ~e used but do not afford any economic advantage, since it was found that the space-time yield and the olefin conversion do not increase proportionately to the increase in concentration Or the metal.
The reaction which is to be catalyzed can be carried out by any conventional process, continuously or batchwise, eg. using a fixed bed, a fluidized bed or a three-phase fluidized bed, the chosen state Or aggregation Or the reaction medium being the deciding factor.
The reactlon temperature in the gas phase is in general from 100 to 180C, preferably from 120 to 150C. The reaction pressure is determined by the method used and is in general from atmospheric pressure to about 100 bars.
In the liquid phase, the temperature is in general from 70 to 110~ and the pressure is in general again from 1 to 100 bars without ; -3-A
being limited thereto since, eg., pressures of up to 1,000 bars or more do not hinder the operation of the process.
The butenediol diesters which may be manufactured by the process of the invention are valuable intermediates for, eg., the manufacture of butenediol and butanediol. Butenediol 3,4-diacetate (vinylglycol acetate), generally formed in minor amounts, is an intermediate for the manufacture of vitamins and other biologically active compounds.
25 mmoles (8.43 g) of platinum chloride and 25 mmoles of tellurium oxide (3.99 g) are dissolved in 200 ml of 6N hydrochloric acid; 50 g of active charcoal (0 1-0.4 mm particle diameter) which has beforehand been boiled with 15% strength nitric acid, are added and the mixture is slowly evaporated to dryness on a water-bath. After additional drying, for which purpose a stream of nitrogen at 150C is passed through the catalyst, in a tube, for 2 hours, the material is reduced by saturating the stream of nitrogen with methanol at room temperature and passing it over the catalyst at a rate of 5 l/min for 4 hours at 200C and 2 hours at 400C.
25 g of the catalyst thus produced and 540 g of acetic acid are introduced into a stirred flask. A mixture of 3 l (~TP)/hr of butadiene and 3 l (STP)/hr of oxygen is passed in at 85C and after 4 hours the reaction is discontinued, the catalyst is separated off, the solution is concentrated and the residue is distilled. 36.8 g Or diacetates are obtained, the butadiene conversion being 33%.
The distillate contains 81.2% of but-2-ene-1,4-diol diacetate and 18.8% of but-1-ene-3,4-diol diacetate.
250 mmoles (84.3 g) of platinum chloride and 32.5 mmoles (5.2 g) of tellurium dioxide are dissolved in 2,000 ml of 6N hydro-chloric acid, 500 g of active charcoal (particle diameter 4 mm) are added and the mixture is slowly evaporated to dryness on a waterbath.
From then onward, the procedure described above is followed.
370 ml (144 g) of the catalyst obtained are introduced into a 1055519 o z. 30,500 double-walled tube (32 mm diameter; L = 50 cm). 10.5 l (STP) of butadiene, 10.5 l (STP) of oxygen and 250 g of acetic acid vapor are introduced hourly at 130C. The vapor is at 130C.
Sample~ are taken hourly and fractionated by distillation.
Analysis Or the distillate shows that the proportion of butenediol diacetate formed iB over 99% (based on the component present in the lesser amount). The space-time yield after 4, 11 and 32 hours are shown in the table.
time 4 11 32 g of BEDA/kg od catalyst x hr 43 43 42.5 g of BEDA/l of reaction space x hr 17 17 16.7 BEDA = but-2-ene-1,4-diol diacetate
According to German application DOS 2,217,452 published on October 26, 1972 in the name of Mitsubishi Chemical butadiene can be reacted in the liquid phase with oxygen and acetic acid, in the presence of solid catalysts containing palladium to give butenediol diacetates. The reaction can also be carried out in the gas phase over catalysts which contain palladium and alkali metal salts as promoters (see German application DOS 2,200,124 published on July 5, 1973 in the name of Kuraray). A disadvantage of the liquid phase method is the low rate of reaction. A disadvantage of the conventional gas phase reaction is that undesired by-products such as l-acetoxy-1,3-butadiene are formed, and that the reaction has to be carried out at low butadiene concentrations so as not to reduce the catalytic activity of the catalyst.
We have now found that butenediol diacetates, especially but-2-ene-1,4-diol diacetate, are obtained in high yield and with high space-time yield by reaction of butadiene, oxygen and acetic acid, preferably in the gas phase, over a solid catalyst if the catalyst 105~519 O.Z. 30,500 i8 platinum containing one or more elements of main group 5 or 6 selected from the group comprising phosphorus, arsenic, antimony, bismuth, selenium and telluriumO
The catalyst is preferably a supported catalyst and may be obtained by the conventional methods for producing supported platinum catalysts.
The catalyst may be manufactured, eg~, by dispersing a carrier in a solution obtained by dissolving a platinum compound and one or more compounds of phosphurus, arsenic, antimony, bismuth, tellurium and selenium in a suitable solvent, eg. water, then evaporating off the solvent so as to deposit the above components on the carrier and reducing the mass in a stream of gas containing hydrogen or a reducing compound, or by means of conventional reducing agents, such as hydrazine, methanol or formalin. The catalyst may also be manufactured by adding a precipitant (eg. an alkaline reagent) to a mixture of the carrier and the solution and then carrying out a reduction by the above processO Platinum and antimony, phosphorus, arsenic, bismuth, tellurium and selenium can in each method be deposited on the carrier either simultaneously or succes-sively; in some cases, the carrier can be added in the rorm of asoluble compound and then be co-precipitated with the active metal.
It is possible to use any reduction method by which platinum and arsenic, antimony, bismuth, tellurium and/or selenium are reduced to the metal state.
Carriers which may be used are active charcoal, silica gel, silicic acid, alumina, clay, bauxite, magnesia, kieselguhr, pumice and the like. The carriers may be activated by conventional methods, eg. by treatment with acids.
The choice of the platinum compound used to manufacture the catalyst is not a decisive ~actor though a halogen co~pound of platinum, such as platinum-II chloride or platinum-IV chloride, a salt o~ an organic acid, such as platinum acetate, platinum nitrate, platinum oxide and the like are preferred for cost reasons. However, other platinum compounds, eg. hexachloroplatinic acid or sodium - lOSSSl9 Z. 30,500 ~tinosulrate can of course also bc used.
In general, the concentration of platinum on the carrier is from 0.1 to 20% by weight~though higher and lower concentrations are not excluded.
The arsenic, antimony, bismuth, tellurium and selenium com-pounds used as the other components for the manufacture of the catalyst are also not subject to special limitations; it is possible to use the halides, nitrates, sulfates, oxides and other compounds of this type. Suitable compounds containing phosphorus are, inter alia, o- and m-phosphoric acid, alkali metal phosphates and alkaline earth metal phosphates~
Though the amounts Or phosphorus, arsenic, antimony, bismuth, tellurium and selenium compounds deposited on the carriers may be varied within wide limits and still prove effective, amounts of from 0.05 to 30~ by weight are generally appropriate.
Platinum catalyst of the above type which contain active charcoal as the carrier and abou-t from 0.1 to 5% Or tellurium or antimony in addition to from 0.1 to 10~ of platinum (based on the total weight of catalyst) have proved exceptionally suitable and are particularly preferred.
Higher concentrations of platinum than those stated can also ~e used but do not afford any economic advantage, since it was found that the space-time yield and the olefin conversion do not increase proportionately to the increase in concentration Or the metal.
The reaction which is to be catalyzed can be carried out by any conventional process, continuously or batchwise, eg. using a fixed bed, a fluidized bed or a three-phase fluidized bed, the chosen state Or aggregation Or the reaction medium being the deciding factor.
The reactlon temperature in the gas phase is in general from 100 to 180C, preferably from 120 to 150C. The reaction pressure is determined by the method used and is in general from atmospheric pressure to about 100 bars.
In the liquid phase, the temperature is in general from 70 to 110~ and the pressure is in general again from 1 to 100 bars without ; -3-A
being limited thereto since, eg., pressures of up to 1,000 bars or more do not hinder the operation of the process.
The butenediol diesters which may be manufactured by the process of the invention are valuable intermediates for, eg., the manufacture of butenediol and butanediol. Butenediol 3,4-diacetate (vinylglycol acetate), generally formed in minor amounts, is an intermediate for the manufacture of vitamins and other biologically active compounds.
25 mmoles (8.43 g) of platinum chloride and 25 mmoles of tellurium oxide (3.99 g) are dissolved in 200 ml of 6N hydrochloric acid; 50 g of active charcoal (0 1-0.4 mm particle diameter) which has beforehand been boiled with 15% strength nitric acid, are added and the mixture is slowly evaporated to dryness on a water-bath. After additional drying, for which purpose a stream of nitrogen at 150C is passed through the catalyst, in a tube, for 2 hours, the material is reduced by saturating the stream of nitrogen with methanol at room temperature and passing it over the catalyst at a rate of 5 l/min for 4 hours at 200C and 2 hours at 400C.
25 g of the catalyst thus produced and 540 g of acetic acid are introduced into a stirred flask. A mixture of 3 l (~TP)/hr of butadiene and 3 l (STP)/hr of oxygen is passed in at 85C and after 4 hours the reaction is discontinued, the catalyst is separated off, the solution is concentrated and the residue is distilled. 36.8 g Or diacetates are obtained, the butadiene conversion being 33%.
The distillate contains 81.2% of but-2-ene-1,4-diol diacetate and 18.8% of but-1-ene-3,4-diol diacetate.
250 mmoles (84.3 g) of platinum chloride and 32.5 mmoles (5.2 g) of tellurium dioxide are dissolved in 2,000 ml of 6N hydro-chloric acid, 500 g of active charcoal (particle diameter 4 mm) are added and the mixture is slowly evaporated to dryness on a waterbath.
From then onward, the procedure described above is followed.
370 ml (144 g) of the catalyst obtained are introduced into a 1055519 o z. 30,500 double-walled tube (32 mm diameter; L = 50 cm). 10.5 l (STP) of butadiene, 10.5 l (STP) of oxygen and 250 g of acetic acid vapor are introduced hourly at 130C. The vapor is at 130C.
Sample~ are taken hourly and fractionated by distillation.
Analysis Or the distillate shows that the proportion of butenediol diacetate formed iB over 99% (based on the component present in the lesser amount). The space-time yield after 4, 11 and 32 hours are shown in the table.
time 4 11 32 g of BEDA/kg od catalyst x hr 43 43 42.5 g of BEDA/l of reaction space x hr 17 17 16.7 BEDA = but-2-ene-1,4-diol diacetate
Claims (7)
1. A process for the production of but-2-enediol-1,4-diacetate and/or but-1-ene-diol-3,4-diacetate which comprises reacting butadiene, oxygen and acetic acid in the gas or liquid phase in the presence of a solid catalyst which consists of platinum metal and an element selected from the group consisting of phosphorus, arsenic, antimony, bismuth, selenium and tellurium.
2. A process as claimed in claim 1, wherein the catalyst is applied to a carrier selected from the group consisting of active charcoal, silica gel, silicic acid, alumina, clay, bauxite, kieselguhr and pumice.
3. A process as claimed in claim 2, wherein the catalyst is deposited on active charcoal.
4. A process as claimed in claim 3, wherein the platinum content of the catalyst is from 0.1 to 20% by weight.
5. A process as claimed in claim 4, wherein the element is selected from antimony and tellurium.
6. A process as claimed in claim 5, wherein the amount of tellurium or antimony applied to said carrier is from 0.1 to 5% based on the total weight of catalyst.
7. A process as claimed in claim 6, wherein the element is tellurium.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742417658 DE2417658A1 (en) | 1974-04-11 | 1974-04-11 | PROCESS FOR THE PRODUCTION OF BUTENEDIOL DIACETATE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1055519A true CA1055519A (en) | 1979-05-29 |
Family
ID=5912738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA223,200A Expired CA1055519A (en) | 1974-04-11 | 1975-03-25 | Manufacture of butenediol diacetates |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE827837A (en) |
| CA (1) | CA1055519A (en) |
| DE (1) | DE2417658A1 (en) |
| GB (1) | GB1494430A (en) |
| SU (1) | SU641872A3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2847068A1 (en) | 1978-10-28 | 1980-05-08 | Basf Ag | METHOD FOR PRODUCING BUTEDIOL DIACETATES AND BUTANDIOL |
| DE2854154A1 (en) | 1978-12-15 | 1980-07-03 | Basf Ag | METHOD FOR PRODUCING VINYL GLYCOLESTERS |
| JPS608864B2 (en) * | 1980-01-24 | 1985-03-06 | 東亜燃料工業株式会社 | Production method of catalyst for diacyloxyalkene synthesis |
| DE3309168A1 (en) * | 1983-03-15 | 1984-09-20 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING DIACYLOXIBUTENES |
| US6111134A (en) * | 1997-09-25 | 2000-08-29 | Mitsubishi Chemical Corporation | Process for producing unsaturated glycol diester using tellurium and rhodium catalyst |
-
1974
- 1974-04-11 DE DE19742417658 patent/DE2417658A1/en not_active Withdrawn
-
1975
- 1975-03-25 CA CA223,200A patent/CA1055519A/en not_active Expired
- 1975-04-10 GB GB1472775A patent/GB1494430A/en not_active Expired
- 1975-04-11 BE BE155323A patent/BE827837A/en unknown
- 1975-11-10 SU SU752121910A patent/SU641872A3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| GB1494430A (en) | 1977-12-07 |
| DE2417658A1 (en) | 1975-10-30 |
| BE827837A (en) | 1975-10-13 |
| SU641872A3 (en) | 1979-01-05 |
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