WO2000014081A1 - Procede de fabrication en continu d'alcools de sucre anhydres - Google Patents
Procede de fabrication en continu d'alcools de sucre anhydres Download PDFInfo
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- WO2000014081A1 WO2000014081A1 PCT/US1999/000537 US9900537W WO0014081A1 WO 2000014081 A1 WO2000014081 A1 WO 2000014081A1 US 9900537 W US9900537 W US 9900537W WO 0014081 A1 WO0014081 A1 WO 0014081A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
Definitions
- a process for producing anhydrosugar alcohols, both monoanhydrosugar alcohols and dianhydrosugar alcohols, by dehydration of the associated sugar alcohols or monoanhydrosugar alcohols using a catalyst and an organic solvent is described, wherein the organic solvent is recycled during the process, and wherein the resulting anhydrosugar alcohols are very pure.
- Anhydrosugar alcohols whether they are monoanhydrosugar alcohols or dianhydrosugar alcohols, are known to be produced with the aid of various acid catalysts by dehydration of the associated sugar alcohols or monoanhydrosugar alcohols.
- these catalysts include sulfonated polystyrenes (H form) (German Patent DE 3 041 673 C2; Canadian Patent Disclosure CA 1 178 288 Al); and various mineral acids, such as HC1 (US Patent 4,169,152; German Patent Disclosure DE 3 233 086 Al), H 3 PO 4 (East German Patent Disclosure DD 1 32 266; Can. J.
- solvents water (CA 1 178 288 Al; European Patent Disclosure EP 0 052 295 Bl) and organic solvents such as toluene or xylene (Przem. Chem. 48 (11) 665-8 (1969)) are known.
- a batch process for the formation of the dianhydrosugar alcohol isosorbide has been described in the literature as a two step process involving intramolecular dehydration of sorbitol to sorbitan (1,4- monoanhydrosorbitol), and further reaction of sorbitan to isosorbide (1,4:3,6- dianhydrosorbitol) in an acid catalyzed reaction, or dehydration, and cyclization.
- an aqueous solution of sorbitol is charged to a batch reactor.
- the temperature is increased to 130-135 °C under vacuum (35 mm Hg) to remove the water.
- a catalyst usually sulfuric acid
- the operable temperature range of the reaction is very narrow. Higher temperatures lead to decomposition and charring of the end product, while lower temperatures inhibit the reaction rate due to difficulties in removal of the water of reaction.
- This reaction produces isosorbide and a higher molecular weight byproduct. The byproduct is presumably produced by water elimination between two or more sorbitol molecules, but its exact nature is not clearly defined. See starch/ starke (1986), 38(c), 26-30 and Roland Beck, Pharm. Mfg Inc. (1996), 97-100.
- the known processes for the production of anhydrosugar alcohols are discontinuous batch processes producing a high molecular weight byproduct. There is no known teaching of performing the process continuously, or of recycling the solvent for use during the process. However, a continuous process for the production of anhydrosugar alcohols is desirable to facilitate large scale, economical production of both mono- and dianhydrosugar alcohols.
- Crude anhydrosugar alcohols contain contaminants.
- crude isosorbide contains the degradation products of sorbitol, sorbitan and isosorbide, which cause the crude isosorbide to have a light yellow to brownish color. Therefore, additional process steps for purifying the product are necessary before use.
- anhydrosugar alcohols are also of unacceptable purity for the production of polymers.
- isosorbide though purified and appearing white in its crystalline form, turns yellow or brown upon annealing to temperatures ⁇ 250 °C, which is lower than the temperature required for the formation of polymers, indicating that a resultant polymer would likely be discolored.
- a means of making a purer product than what is commercially available or available through known manufacturing processes is desired.
- Processes known for use in purification of anhydrosugar alcohols include distillation, which can occur with or without the addition of boron compounds, for example in the form of boric acid (US Patent 3,160,641) or sodium borohydride, use of an anion exchange resin (US Patent 3,160,641), and recrystallization from organic solvents such as methyl ethyl ketone or ethyl acetate (US Patent 3,454,603).
- the present disclosure relates to a process for producing very pure anhydrosugar alcohols which is economical and produces good yields, in which the formation of byproducts and contaminants is minimized, and which can be performed on a large industrial scale continuously without interruption for a relatively long time.
- a preferred embodiment provides for a process of producing anhydrosugar alcohols wherein the process includes the steps of introducing at least one sugar alcohol or monoanhydrosugar alcohol into a reaction vessel; dehydrating the sugar alcohol or monoanhydrosugar alcohol in the presence of an acid catalyst and an organic solvent to form a reaction product which is at least partly soluble in the organic solvent; removing water from the reaction vessel; removing organic solvent comprising the dissolved reaction product from the reaction vessel; separating the reaction product from the removed organic solvent; and recycling the organic solvent into the reaction vessel.
- Another preferred embodiment further includes purifying the separated reaction product by distillation, recrystallization, or a combination thereof.
- Yet another preferred embodiment provides for a process of producing anhydrosugar alcohols wherein the process includes the steps of introducing at least one sugar alcohol or monoanhydrosugar alcohol into a reaction vessel; dehydrating the sugar alcohol or monoanhydrosugar alcohol in the presence of an acid catalyst and a solvent to form a reaction product which is at least partly soluble in the solvent; removing water from the reaction vessel; removing solvent comprising the dissolved reaction product from the reaction vessel; separating the reaction product from the removed solvent; and recycling the solvent into the reaction vessel, wherein the steps of introducing in the starting materials, removing water, removing solvent and recycling the solvent occur simultaneously.
- the solvent be an organic solvent
- the acid catalyst be a soluble acid or an acid anion exchange resin
- the reaction product be separated from the solvent by means of extraction.
- other materials and methods are contemplated for use, as disclosed herein.
- Fig. 1 illustrates a preferred embodiment of the continuous process of the invention
- Fig. 2 illustrates the solubility of sorbitol, sorbitan and isosorbide in xylene
- Fig. 3 illustrates a preferred embodiment of the invention wherein the continuous process for the production of anhydrosugar alcohol includes purification.
- the present disclosure describes a process for the production of mono- and dianhydrosugar alcohols, preferably of extremely high purity.
- the process is directed toward the production of anhydrosugar alcohols and generally includes the steps of introducing at least one sugar alcohol or monoanhydrosugar alcohol into a reaction vessel; dehydrating the sugar alcohol or monoanhydrosugar alcohol in the presence of an acid catalyst and a solvent to form a reaction product which is at least partly soluble in the solvent; removing water from the reaction vessel; removing solvent comprising the dissolved reaction product from the reaction vessel; separating the reaction product from the removed solvent; and recycling the solvent into the reaction vessel.
- the process may further include an additional purification step.
- the process may be continuous such that the steps of introducing in the starting materials, removing water, removing solvent comprising the dissolved reaction product and recycling the solvent after separation from the reaction product occur simultaneously.
- Typical sugar alcohols in particular pentites and hexites, are suitable for use in the process as starting materials.
- the starting materials may be sugar alcohols, monoanhydrosugar alcohols, or a mixture thereof.
- preferred starting materials include arabinitol, ribitol, D-glucitol (also known as D-sorbitol or sorbitol), D-mannitol (mannitol), galactitol and iditol.
- sorbitol is particularly desirable because sorbitol is readily available and can be obtained on a large industrial scale by the reduction of glucose with hydrogen, as known to one of ordinary skill in the art.
- the catalysts used to facilitate the dehydration reaction are acid catalysts.
- acid catalysts include soluble acids. Examples of such acid catalysts include sulfur ic acid, phosphoric acid, p-toluene sulfonic acid, methanesulfonic acid and the like. Sulfuric acid is a preferred catalyst from this class.
- acid anion exchange resins may also be used, such as sulfonated polystyrenes.
- a preferred acid anion exchange resin is AG50W-X12 from BioRad.
- Inorganic ion exchange materials may also be used, such as acidic zeolites. In particular, H-beta zeolite from Degussa may be used in the process disclosed herein.
- acid catalyst may be used in the process described herein.
- soluble acids such as sulfuric acid provide long term catalytic stability during the reaction, permitting the process to continue for long periods of time without recharging the catalyst.
- these catalysts also tend to promote the formation of an unwanted byproduct, a dark colored oligomeric residue which may be produced in amounts up to about 10%, and sometimes even greater.
- acid ion exchange resins produce little or no residue but do not at this time provide long term catalytic stability. Therefore, either type of acid catalyst may be selected with its specific limitations and advantages in mind, allowing the formation of a process with long term stability or minimal byproduct production.
- the solvent useful for the process described herein preferably forms an azeotropic mixture with water, or has a boiling point greater than that of water (100°C). Desirably, the solvent has a boiling point of 120-150°C, preferably at least 130 °C.
- Preferred solvents include organic solvents but exclude esters, such as ethyl acetate (EtOAc), because an ester may form undesirable transesterification products during the dehydration reaction.
- EtOAc ethyl acetate
- the solvents of the invention perform a dual function by facilitating the removal of water from the reaction mixture and acting as a solvent for the reaction product.
- the reaction product should be much more soluble in the solvent than the starting material, catalyst or any byproducts or intermediates of the reaction.
- the solubility of the starting material, catalyst and any potential reaction intermediates or byproducts is as low as possible in the organic solvent of the process in order to assure a high degree of purity in the reaction product.
- suitable organic solvents include, but are not limited to, xylene, anisole, dichlorobenzene, nonane, n-octane, cumene, butyl ether and ethyl benzene.
- the solvent of the process is selected from xylene, anisole, dichlorobenzene and nonane. More preferably, the solvent is selected from xylene and anisole, with xylene being the most preferred solvent.
- reaction it is possible to perform one or two dehydrations of the starting sugar alcohol during the reaction, producing a mono- or dianhydrosugar alcohol.
- the reaction further may be controlled so as to produce a combination of mono-and dianhydrosugar alcohols by adjusting either the reaction conditions or the starting materials, which may contain both sugar alcohols and monoanhydrosugar alcohols.
- the dehydration is desirably performed at elevated temperatures between 80°C and 180°C, preferably at temperatures between 120°C and 140°C, and most preferably between 130°C and 140°C. It is advantageous to perform the dehydration under a protective or non-reactive gas atmosphere, particularly nitrogen.
- the dehydration can be performed at atmospheric pressure, although elevated or reduced pressures can also be used with minor adjustments to process parameters such as time and temperature, as known to one of ordinary skill in the art.
- the reaction mixture is preferably kept under reflux conditions in order to remove water by azeotropic distillation. Water may also be removed by other methods known in the art, such as evaporation.
- the dehydration reaction in the reaction vessel can be performed in various ways. For instance, it is possible to keep the quantity of supplied starting material, compared with the organic solvent present, so high that two or more phases form in the reaction vessel. These phases comprise at least a lower aqueous phase comprising molten sugar alcohol and/or anhydrosugar alcohol, and an organic phase above the aqueous phase in which the reaction product that has formed dissolves rapidly.
- the organic phase is removed from the reaction vessel along with the dissolved reaction product by pumping, decanting or other methods known in the art.
- Such two phase systems are demonstrated in the Examples herein, particularly Examples 2-6, which exemplify the use of various solvents, catalysts, dosages of starting materials and solvent recirculation rates.
- the organic solvents useful in the dehydration reaction may have a density lower than that of the aqueous phase, as described above, or higher than that of the aqueous phase. If organic solvents with higher densities than the aqueous phase are used, the aqueous phase forms the upper layer and the dissolved product is present in the lower organic layer. It is possible to use a relatively large quantity of organic solvent into which the sugar alcohols or the monoanhydrosugar alcohols, catalyst and water are metered. In this case, it is unnecessary to allow the development of two phases in the reaction chamber.
- the solvent in which the reaction product is dissolved be drawn off continuously, causing the dehydration to be done in a steady state of equilibrium wherein the moles of starting materials metered in and the moles of dissolved reaction product removed are equivalent to one another.
- the continuous drawing off of the reaction product in the organic solvent from the reaction vessel drives the reaction forward and greatly increases yield and productivity.
- the dehydration can be performed in such a way that the catalyst is added in the requisite quantity once, and further catalyst is added only when necessary. However, it is also possible to add the catalyst in dosed fashion continuously during the dehydration.
- the high temperature of the dehydration reaction promotes rapid dehydration of the starting materials. However, it may also promote the formation of byproducts and/or the further conversion of the desired mono- or dianhydrosugar alcohols to undesired secondary products over time. Therefore, for both one phase and two phase reactions, it is desirable to divert the resultant reaction product from the reaction chamber rapidly to protect it against further decomposition.
- the reaction product is drawn off from the reaction vessel continuously during the course of the dehydration reaction.
- the acid catalyst may be deactivated and/or removed from the solvent containing the reaction product, which preferably has been removed from the reaction vessel.
- the deactivation may be accomplished by any method known in the art, such as addition of a metal hydroxide base to form an insoluble salt which will precipitate out of solution.
- a metal hydroxide base to form an insoluble salt which will precipitate out of solution.
- calcium hydroxide may be used in the process disclosed herein.
- Polymeric or inorganic ion exchange materials may be recovered by filtration. Before reuse, reactivation may be necessary.
- the reaction product may be recrystallized from the solvent.
- a liquid-to-liquid extraction can be performed instead of the recrystallization using water or lower aliphatic alcohols such as ethanol or methanol, and may be conducted as part of the continuous process.
- the solvent containing the reaction product may be removed from the reaction vessel and combined with water or a lower aliphatic alcohol, such as methanol or ethanol.
- the reaction product is extracted from the solvent into the water or aliphatic alcohol, which is then decanted or otherwise separated from the solvent.
- the reaction product can be recrystallized from the water or lower aliphatic alcohol, while the solvent is recycled for use in the reaction vessel. It is preferable that the solvent and the water or lower aliphatic alcohol form a two phase system in order to facilitate separation of the solvent for reuse in the process of the invention.
- the extraction of the reaction product by the organic solvent from the reaction mixture under reaction conditions is a reactive extraction which removes the reaction product from the reaction mixture and which furthermore aids in purifying the reaction product.
- the reaction product is separated from unreacted starting material, reaction intermediates and reaction byproducts.
- the organic solvent comprising the dissolved reaction product is drawn off from the reaction vessel.
- the dissolved reaction product is then separated from the drawn-off organic solvent by cystallization or by means of liquid-liquid extraction with water or lower aliphatic alcohols like methanol or ethanol. If separated by crystallization, the reaction product is obtained as a solid. If separated by liquid-liquid-extraction, the reaction product is obtained as a solution in water or lower aliphatic alcohols like methanol or ethanol.
- the reaction product obtained by the reactive extraction described above may be purified further if desired.
- the continuous process described herein comprises intrinsic purification steps resulting in a more pure reaction product than would otherwise result from batch processes as known heretofor in the art.
- Further purification of the crude reaction product may occur by distillation, recrystallization, melt recrystallization or a combination thereof, as described in detail in copending application [Atty Docket No. 032358-018], filed on even date herewith.
- a combination of distillation and recrystallization from an aliphatic alcohol such as methanol or ethanol is preferred in order to minimize the number of purification steps while maximizing the purity of the reaction product.
- This purification of the reaction product may occur as part of the continuous process or in a separate process.
- the purity of the resultant anhydrosugar alcohol should be at least 99.0%, preferably at least 99.5%, most preferably at least 99.8%, and preferably meets the purity requirements for use in polymer production, as set forth at least in copending application [Atty. Docket No. 032358-018], filed on even date herewith.
- the most effective way to purify the reaction product is a combination of vacuum distillation and recrystallization from lower aliphatic alcohols, preferably methanol or ethanol.
- hydride ions such as in the form of sodium borohydride, NaBH 4 , or lithium aluminum hydride
- At least the steps of introducing the starting materials, removing water from the reaction, removing solvent and recycling the solvent to the reaction flask are performed simultaneously, creating a continuous process for the formation of anhydrosugar alcohols.
- the process of the invention described herein has the surprising and unexpected result of furnishing an economical large scale method of manufacturing anhydrosugar alcohols. It is a further surprising result that the anhydrosugar alcohols made by the process of the invention are exceptionally pure.
- FIG. 1 A preferred process of the invention will now be described in relation to Figure 1.
- the dehydration takes place in a vessel (1), which is provided with supply lines for the starting materials such as sugar alcohol or aqueous sugar alcohol solution, as well as the organic solvent and acid catalyst.
- sugar alcohol or aqueous sugar alcohol solution and, if necessary, a catalyst is supplied from the supply vessel (5) via a pump (6) and a heater (9) to vessel (1) by a single line (13).
- Vessel (1) is heated by means of an oil bath (2) to temperatures of about 80-180°C, preferably 120-160°C, most preferably 130-140°C.
- the reaction mixture thus formed in vessel (1) is mixed during the dehydration reaction by means of an agitator (16).
- a distillation head with a cooler (14) is used to distill off the water that results from, in part, the dehydration process. This water is condensed in the cooler and any organic solvent that may have been jointly distilled in the distillation is separated from it. The water and solvent form two different layers, which can easily be separated, such as in the water separator (15).
- the water can be drained off, and the solvent, which is preferably lighter than water, flows continuously back into the reaction chamber.
- a heatable drain line (11) is used for continuously drawing off solvent from the reaction chamber by means of a pump (8).
- This solvent containing dissolved reaction product, is carried to a recrystallization vessel (3) which is at a lower temperature than the reaction chamber, preferably below 10° C.
- the low temperature is maintained by ice bath (4).
- the recrystallization vessel may be provided with an agitator (17) and with other typical measurement instruments such as temperature sensors and the like.
- the crystals can be carried off continuously or discontinuously.
- the solvent can be drawn off continuously, optionally reprocessed, and returned to the dehydration mixture via line (12) and pump (7). It is advantageous to heat the solvent to a suitable temperature before returning it to the dehydration mixture, for example, by passing it through a heat exchanger (10).
- the process is preferably performed under conditions in which the resultant reaction product has substantially better solubility in the solvent than the starting material or catalyst. It can be seen from Fig. 2 that the differences in solubility between sorbitol and the desired end product isosorbide are considerable at temperatures of 80 °C and higher.
- the dehydration temperature of the process is optimally between 80 °C and
- the temperature of dehydration may vary from these ranges as required by changes in starting material, reaction pressure or other process parameters, as known to one of ordinary skill in the art. It is understood that a favorable temperature range for dehydration will be selected on the basis of a few preliminary experiments with suitable solvents and catalysts using the desired starting material, as known to one of ordinary skill in the art.
- the pressure of the reaction may be changed from atmospheric pressure if desired, with appropriate corresponding changes in the temperature of the reaction as known to those skilled in the art.
- isosorbide produced by this invention is of such high quality as to be used for making polymers, in particular polyesters, and products made therefrom, such as fibers, containers, sheets, films and optical disks, as described for example in copending U.S.
- polymers incorporating the anhydrosugar alcohols produced by the process described herein may be formed by polycondensation of the anhydrosugar alcohol with multi-functional containing materials such as poly carboxy lie monomers, poly carboxy lie acid halides such as acid chloride, polycarbonate monomers such as diphenylcarbonate or phosgene, isocyanates such as toluene diisocyanate and methylene diphenylisocyanate, and dicarboxylic acids, such as terephthaloyl moieties, or dimethyl esters thereof and, optionally, aliphatic diols, such as ethylene glycol. All references cited herein are incorporated in their entirety by reference.
- Example 1 In a continuous process of the invention, a reaction flask is loaded with xylene as solvent, water, and H 2 SO as catalyst. The stirring rate is adjusted to 150 rpm. The precipitation flask is loaded with xylene, and the stirring rate is adjusted to 300 rpm. Both flasks are purged with inert gas (nitrogen) to prevent oxidation of the sugar derivatives by air. An oil bath is heated to about 170 °C, and a cooling bath is cooled to about -15°C. Pumps are started, and the pumping rates are adjusted to maintain the xylene amounts in the reaction flask and precipitation flask at a rate of at least 2 to 1, respectively. Heaters are switched on for heating materials entering the reaction flask.
- inert gas nitrogen
- the temperature of the xylene/reaction product mixture is 85°C-95°C, while the temperature of xylene returning to the reaction flask after separation from the reaction product is about 120 °C.
- the inner temperature of the xylene/reaction product transport line has to be above the melting point of isosorbide to prevent precipitation of isosorbide and thus blocking of the line, and is below a temperature at which evaporation of the xylene/product mixture occurs because reduced pressure in the reaction line just before the pumping head may cause gas bubbles within the pumping head, leading to pump failures.
- a pump and heater are switched on to feed aqueous sorbitol to the reaction flask.
- the temperature of the aqueous sorbitol feed is about 95°C. After a period of 15- 30 minutes, isosorbide precipitation is observed in the precipitation flask. At the beginning of the reaction, a minor amount of low-density brown flakes, which are degradation products located at the surface of the xylene layer, are formed which agglomerate after 60-90 minutes. Compared to the flakes, the agglomerates have higher density and combine with the aqueous layer. It is therefore advantageous to pump out the xylene/product solution in a region apart from the surfaces of the xylene layer where the flow velocity is low in order to avoid collection of the agglomerates.
- Example 2 The process as described in Example 1 is repeated, except that the reaction product dissolved in xylene is added to a solution of methanol and then further purified, as demonstrated generally in Figure 3.
- Figure 3 depicts a process diagram of the reaction, wherein the sugar alcohol, acid catalyst and solvent are fed into a reactor. As the reaction product is generated, it is recovered in the product recovery area. Here, the crude reaction product is separated from the solvent, which is recycled for use in the reactor. The crude reaction product is then further purified in the stage of product purification, resulting in a highly purified anhydrosugar alcohol.
- the xylene solvent and methanol form a two-part solution at room temperature in the product recovery stage, wherein the reaction product is extracted into the methanol layer.
- the methanol layer containing the reaction product is then separated from the xylene by decanting.
- the methanol containing the reaction product is distilled, and the distillation product is recrystallized.
- the resulting isosorbide has a purity of > 99.8% .
- the starting material (educt) solution employed is an aqueous sugar alcohol solution of the kind produced as a product in the hydrogenation of glucose.
- the sorbitol used is a commercial product of Aldrich having about 97% purity.
- the duration of the reaction is approximately 4 hours.
- Amounts of sorbitol, isosorbide, and intermediates are shown in Table 1. Table 1
- Example 4 This example demonstrates the use of various catalysts in the dehydration reaction.
- the duration of the reaction is approximately 4 hours.
- Amounts of sorbitol, isosorbide, and intermediates are shown in Table 2.
- Example 5 This example demonstrates the effect of different dosages of the starting material sugar alcohol.
- a reaction as described in Example 1 is performed with 1 ml H 2 SO 4 cone, catalyst; 2100 ml xylene; a xylene recirculation rate of 3000 ml/h; a reaction flask temperature of 130° to 140°C; and a precipitation flask temperature of ⁇ 0 °C.
- the duration of the reaction is approximately 4 hours.
- Amounts of sorbitol, isosorbide and intermediates are shown in Table 3. Table 3
- Example 6 This example demonstrates the effect of varying the recirculation rate of the solvent.
- the duration of the reaction is approximately 4 hours.
- Amounts of sorbitol, isosorbide and intermediates are shown in Table 4.
- the duration of the reaction is approximately 4 hours, over which time the catalyst is added in a continuous dosage.
- Example 8 Separation of the reaction product from the organic solvent may be done by liquid/liquid extraction. For example, at 80°C, 200 ml of a 1.1 % solution of isosorbide in xylene is extracted with 20 ml of water. The isosorbide is extracted almost entirely into the aqueous phase, and the xylene layer retains only about 0.04% isosorbide.
- Example 9 The phase behavior of a three-component system of mixed xylenes, methanol and isosorbide was studied.
- a three component mixture of isosorbide, methanol and mixed xylenes (20 g total) was prepared by one of two methods. a) Isosorbide was placed in a small vial and the vial immersed in a preheated ( ⁇ 80 °C) oil bath until the isosorbide melted. To the molten isosorbide was added first methanol and then xylene.
- Table 5 contains composition information for samples that remained as one phase on standing.
- Table 6 contains composition information for samples that separated into two phases on standing.
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Abstract
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/786,716 US6639067B1 (en) | 1998-09-09 | 1999-01-11 | Continuous process for the production of anhydrosugar alcohols |
AU21112/99A AU2111299A (en) | 1998-09-09 | 1999-01-11 | Continuous process for the production of anhydrosugar alcohols |
KR1020017002972A KR20010079763A (ko) | 1998-09-09 | 1999-01-11 | 무수당 알콜의 연속 제조 방법 |
CA002340348A CA2340348A1 (fr) | 1998-09-09 | 1999-01-11 | Procede de fabrication en continu d'alcools de sucre anhydres |
EP99901410A EP1119558A4 (fr) | 1998-09-09 | 1999-01-11 | Procede de fabrication en continu d'alcools de sucre anhydres |
JP2000568839A JP2002524455A (ja) | 1998-09-09 | 1999-01-11 | アンヒドロ糖アルコール類の連続的製造方法 |
BR9913612-0A BR9913612A (pt) | 1998-09-09 | 1999-01-11 | álcool de açúcar anidro, processo de produção deálcool de açúcar anidro, polìmero e produto |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19841032.8 | 1998-09-09 | ||
DE19841032A DE19841032A1 (de) | 1998-09-09 | 1998-09-09 | Verfahren zur Herstellung von Anhydrozuckeralkoholen |
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WO2000014081A1 true WO2000014081A1 (fr) | 2000-03-16 |
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PCT/US1999/000537 WO2000014081A1 (fr) | 1998-09-09 | 1999-01-11 | Procede de fabrication en continu d'alcools de sucre anhydres |
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EP (1) | EP1119558A4 (fr) |
JP (1) | JP2002524455A (fr) |
KR (1) | KR20010079763A (fr) |
CN (1) | CN1317001A (fr) |
AU (1) | AU2111299A (fr) |
BR (1) | BR9913612A (fr) |
CA (1) | CA2340348A1 (fr) |
DE (1) | DE19841032A1 (fr) |
ID (1) | ID28701A (fr) |
TR (1) | TR200100701T2 (fr) |
WO (1) | WO2000014081A1 (fr) |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2001092266A2 (fr) * | 2000-05-26 | 2001-12-06 | E.I. Dupont De Nemours And Company | Procede de production d'alcools de sucre au moyen d'une purge gazeuse |
WO2001092246A2 (fr) * | 2000-05-26 | 2001-12-06 | E.I. Dupont De Nemours And Company | Procede de fabrication en continu d'alcools de sucre anhydres et reacteur utile a cet effet |
FR2832407A1 (fr) * | 2001-11-20 | 2003-05-23 | Roquette Freres | Procede de preparation d'une composition contenant au moins un produit de deshydratation interne d'un sucre hydrogene |
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WO2016105106A2 (fr) * | 2014-12-23 | 2016-06-30 | 에스케이이노베이션 주식회사 | Procédé de production en continu d'alcool de sucre anhydre |
US10414776B2 (en) | 2014-12-23 | 2019-09-17 | Sk Innovation Co., Ltd. | Efficient method for producing and purifying anhydrous sugar alcohol |
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JP6852263B2 (ja) * | 2016-02-08 | 2021-03-31 | 三菱ケミカル株式会社 | アンヒドロ糖アルコールの製造方法 |
CN109134485B (zh) * | 2017-06-16 | 2021-02-09 | 中国科学院大连化学物理研究所 | 一种制备异山梨醇的方法 |
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KR102152693B1 (ko) * | 2020-02-28 | 2020-09-08 | 주식회사 삼양사 | 수율이 개선된 무수당 알코올의 디에테르 제조 방법 |
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JP2003535085A (ja) * | 2000-05-26 | 2003-11-25 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | アンヒドロ糖アルコールの連続的製造方法およびそれに有用な反応器 |
WO2001092246A2 (fr) * | 2000-05-26 | 2001-12-06 | E.I. Dupont De Nemours And Company | Procede de fabrication en continu d'alcools de sucre anhydres et reacteur utile a cet effet |
WO2001092246A3 (fr) * | 2000-05-26 | 2002-04-04 | Du Pont | Procede de fabrication en continu d'alcools de sucre anhydres et reacteur utile a cet effet |
WO2001092266A3 (fr) * | 2000-05-26 | 2002-04-25 | Mark Allen Andrews | Procede de production d'alcools de sucre au moyen d'une purge gazeuse |
US6407266B2 (en) | 2000-05-26 | 2002-06-18 | E. I. Du Pont De Nemours And Company | Continuous process for the manufacture of anhydro sugar alcohols and reactor useful therefor |
US6689892B2 (en) * | 2000-05-26 | 2004-02-10 | E. I. Du Pont De Nemours And Company | Process for the manufacture of anhydro sugar alcohols with the assistance of a gas purge |
WO2001092266A2 (fr) * | 2000-05-26 | 2001-12-06 | E.I. Dupont De Nemours And Company | Procede de production d'alcools de sucre au moyen d'une purge gazeuse |
JP4729238B2 (ja) * | 2000-06-09 | 2011-07-20 | ロケット・フルーレ | 少なくとも1つの水素添加糖の内部脱水生成物を含む組成物の精製方法 |
JP2003535866A (ja) * | 2000-06-09 | 2003-12-02 | ロケット・フルーレ | 少なくとも1つの水素添加糖の内部脱水生成物を含む組成物の精製方法 |
US7122661B2 (en) | 2000-06-09 | 2006-10-17 | Roquette Freres | Method for purifying a composition containing at least one internal dehydration product of a hydrogenated sugar |
EP1627878A1 (fr) * | 2000-06-09 | 2006-02-22 | Roquette Freres | Composition contenant au moins un produit de déshydratation interne d'un sucre hydrogéné |
EP1287000B1 (fr) * | 2000-06-09 | 2005-10-12 | Roquette Frˬres | Procede de purification d'une composition contenant au moins un produit de deshydratation interne d'un sucre hydrogene |
US7439352B2 (en) | 2000-11-01 | 2008-10-21 | Archer-Daniels-Midland Company | Process for the production of anhydrosugar alcohols |
US6849748B2 (en) | 2000-11-01 | 2005-02-01 | Archer-Daniels-Midland Company | Process for the production of anhydrosugar alcohols |
JP2005509667A (ja) * | 2001-11-20 | 2005-04-14 | ロケット・フルーレ | 少なくとも1の水素化糖の内部脱水生成物を含む組成物の製造方法 |
KR100939431B1 (ko) * | 2001-11-20 | 2010-01-28 | 로께뜨프레르 | 수소화 당의 내부 탈수 생성물 1종 이상을 함유하는조성물의 제조 방법 |
US8008477B2 (en) | 2001-11-20 | 2011-08-30 | Roquette Freres | Method for preparing a composition containing at least one internal dehydration product for a hydrogenated sugar |
WO2003043959A1 (fr) * | 2001-11-20 | 2003-05-30 | Roquette Freres | Procede de preparation d'une composition contenant au moins un produit de deshydratation interne d'un sucre hydrogene |
FR2832407A1 (fr) * | 2001-11-20 | 2003-05-23 | Roquette Freres | Procede de preparation d'une composition contenant au moins un produit de deshydratation interne d'un sucre hydrogene |
WO2003089420A3 (fr) * | 2002-04-17 | 2003-12-04 | Du Pont | Recuperation et purification d'alcools de sucre dianhydro a partir d'un courant de vapeur |
WO2003089436A1 (fr) * | 2002-04-17 | 2003-10-30 | E. I. Du Pont De Nemours And Company | Procede continu integre permettant de fabriquer de l'alcool de sucre anhydre |
US6864378B2 (en) | 2002-04-17 | 2005-03-08 | E. I. Du Pont De Nemours And Company | Integrated continuous process for anhydro sugar alcohol manufacture |
US6831181B2 (en) | 2002-04-17 | 2004-12-14 | E. I. Dupont De Nemours And Co. | High yield byproduct recycle process for anhydro sugar alcohols |
US6818781B2 (en) * | 2002-04-17 | 2004-11-16 | E. I. Du Pont De Nemours And Company | Simultaneous reaction and separation process for the manufacture of dianhydro sugar alcohols |
WO2003089445A3 (fr) * | 2002-04-17 | 2003-12-31 | Du Pont | Processus de reaction et separation pour la fabrication d'alcools de sucres dianhydro |
WO2003089445A2 (fr) * | 2002-04-17 | 2003-10-30 | E.I. Du Pont De Nemours And Company | Processus de reaction et separation pour la fabrication d'alcools de sucres dianhydro |
WO2003089420A2 (fr) * | 2002-04-17 | 2003-10-30 | E. I. Du Pont De Nemours And Company | Recuperation et purification d'alcools de sucre dianhydro a partir d'un courant de vapeur |
US6867296B2 (en) | 2002-04-17 | 2005-03-15 | E. I. Du Pont De Nemours And Company | Recovery and purification of anhydro sugar alcohols from a vapor stream |
WO2003089435A1 (fr) * | 2002-04-17 | 2003-10-30 | E.I. Du Pont De Nemours And Company | Processus de recyclage de sous-produit de haut rendement pour des alcools de sucre anhydro |
WO2007089510A2 (fr) * | 2006-01-26 | 2007-08-09 | Battelle Memorial Institute | Procédés de déshydratation de sucres |
US7772412B2 (en) | 2006-01-26 | 2010-08-10 | Battelle Memorial Institute | Methods for dehydration of sugars and sugar alcohols |
WO2007089526A1 (fr) * | 2006-01-26 | 2007-08-09 | Battelle Memorial Institute | Procédé de déshydratation du sucre et de traitement d'un catalyseur |
US7615652B2 (en) | 2006-01-26 | 2009-11-10 | Battelle Memorial Institute | Two-stage dehydration of sugars |
US7649099B2 (en) | 2006-01-26 | 2010-01-19 | Battelle Memorial Institute | Method of forming a dianhydrosugar alcohol |
WO2007089510A3 (fr) * | 2006-01-26 | 2008-01-17 | Battelle Memorial Institute | Procédés de déshydratation de sucres |
US7728156B2 (en) | 2006-01-26 | 2010-06-01 | Battelle Memorial Institute | Method of performing sugar dehydration and catalyst treatment |
US7420067B2 (en) | 2006-03-09 | 2008-09-02 | Archer-Daniels-Midland Company | Process for the production of anhydrosugar alcohols |
WO2007103586A3 (fr) * | 2006-03-09 | 2008-01-31 | Archer Daniels Midland Co | Procédé de production d'alcools de sucre anhydres |
US8445704B2 (en) | 2008-03-13 | 2013-05-21 | Bioecon International Holding N.V. | Process for converting polysaccharides in an inorganic molten salt hydrate |
EP2100972A1 (fr) | 2008-03-13 | 2009-09-16 | BIOeCON International Holding N.V. | Procédé pour convertir les polysaccharides dans un hydrate de sel fondu |
US9765084B2 (en) | 2008-04-10 | 2017-09-19 | Iowa Corn Promotion Board | Recovery and refining of dianhydrosugars |
KR101631928B1 (ko) | 2008-04-10 | 2016-06-20 | 아이오와 콘 프로모션 보드 | 이무수당 제조 방법 |
US9120806B2 (en) | 2008-04-10 | 2015-09-01 | Iowa Corn Promotion Board | Dianhydrosugar production process |
KR20110003529A (ko) * | 2008-04-10 | 2011-01-12 | 아이오와 콘 프로모션 보드 | 이무수당 제조 방법 |
WO2010106055A1 (fr) | 2009-03-17 | 2010-09-23 | Bioecon International Holding N.V. | Procédé de transformation de polysaccharides dans un hydrate de sel fondu inorganique |
WO2010106053A2 (fr) | 2009-03-17 | 2010-09-23 | Bioecon International Holding N.V. | Processus de conversion de polysaccharides en hydrate de sel fondu inorganique |
US8440845B2 (en) | 2009-03-17 | 2013-05-14 | Bioecon International Holding N.V. | Process for converting polysaccharides in an inorganic molten salt hydrate |
WO2010106052A1 (fr) | 2009-03-17 | 2010-09-23 | Bioecon International Holding N.V. | Procédé de transformation de polysaccharides dans un hydrate de sel fondu inorganique |
WO2010106057A1 (fr) | 2009-03-17 | 2010-09-23 | Bioecon International Holding N.V. | Procede pour la conversion de polysaccharides dans un hydrate de sel fondu inorganique |
WO2012015616A1 (fr) | 2010-07-30 | 2012-02-02 | Archer Daniels Midland Company | Synthèse assistée par rayonnement microondes des dérivés de sucres déshydratés hydroxyméthylfurfural, acide lévulinique, alcools de sucre anhydres et leurs éthers |
EP2615093A1 (fr) | 2012-01-16 | 2013-07-17 | BIOeCON International Holding N.V. | Isolement de sucres hexitols anhydres par des adsorbants sélectifs |
WO2013169029A1 (fr) | 2012-05-11 | 2013-11-14 | 주식회사 삼양제넥스 | Procédé de préparation d'alcools d'anhydrosucre à pureté élevée par distillation en couche mince |
US9290508B2 (en) | 2012-05-11 | 2016-03-22 | Samyang Genex Corporation | Method for preparing high purity anhydrosugar alcohols by thin film distillation |
WO2014070371A1 (fr) | 2012-10-31 | 2014-05-08 | Archer Daniels Midland Company | Procédé perfectionné de fabrication de produits de déshydratation interne d'alcools de sucre |
EP2933256B1 (fr) | 2012-12-14 | 2019-05-22 | Samyang Corporation | Procédé d'élaboration d'un alcool d'anhydrosucre au moyen d'hydrol |
WO2016137833A1 (fr) | 2015-02-24 | 2016-09-01 | Archer Daniel Midland Company | Production d'isoidide et purification |
WO2017158303A1 (fr) | 2016-03-16 | 2017-09-21 | Roquette Freres | Procede de fabrication de dianhydrohexitol avec une etape de distillation sur un evaporateur a couche mince |
EP4219505A1 (fr) | 2016-03-16 | 2023-08-02 | Roquette Freres | Procede de fabrication de dianhydrohexitol avec une etape de distillation sur un evaporateur a couche mince |
US10526340B2 (en) | 2016-04-25 | 2020-01-07 | Roquette Freres | Process for manufacturing dianhydrohexitol crystals with a step of evaporative crystallization of the first crystallization mother liquors |
Also Published As
Publication number | Publication date |
---|---|
JP2002524455A (ja) | 2002-08-06 |
EP1119558A1 (fr) | 2001-08-01 |
CA2340348A1 (fr) | 2000-03-16 |
TR200100701T2 (tr) | 2001-07-23 |
DE19841032A1 (de) | 2000-03-16 |
ID28701A (id) | 2001-06-28 |
CN1317001A (zh) | 2001-10-10 |
EP1119558A4 (fr) | 2002-01-09 |
BR9913612A (pt) | 2001-10-30 |
AU2111299A (en) | 2000-03-27 |
KR20010079763A (ko) | 2001-08-22 |
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