WO1996020972A2 - A PROCESS FOR THE REMOVAL OF A pH-BASIC MATERIAL FROM A POLYETHER POLYOL - Google Patents

A PROCESS FOR THE REMOVAL OF A pH-BASIC MATERIAL FROM A POLYETHER POLYOL Download PDF

Info

Publication number
WO1996020972A2
WO1996020972A2 PCT/US1995/016244 US9516244W WO9620972A2 WO 1996020972 A2 WO1996020972 A2 WO 1996020972A2 US 9516244 W US9516244 W US 9516244W WO 9620972 A2 WO9620972 A2 WO 9620972A2
Authority
WO
WIPO (PCT)
Prior art keywords
emulsion
polyether polyol
polymerizate
inorganic salt
coalescer
Prior art date
Application number
PCT/US1995/016244
Other languages
French (fr)
Other versions
WO1996020972A3 (en
Inventor
Mark R. Kratz
Robert P. Yeater
David A. Balister
Robin E. Tirpak
Lewis S. Newman
Richard B. Steitle
Mark S. Solomon
Ronald B. Timm
Original Assignee
Bayer Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer Corporation filed Critical Bayer Corporation
Publication of WO1996020972A2 publication Critical patent/WO1996020972A2/en
Publication of WO1996020972A3 publication Critical patent/WO1996020972A3/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30Post-polymerisation treatment, e.g. recovery, purification, drying

Definitions

  • the present invention relates to a process for the removal of a pH-basic material from a polyether polyol.
  • Polyether polyols are reacted with polyisocyanates to produce polyurethanes.
  • These polyether polyols are produced by polymerization reactions catalyzed by alkaline materials such as potassium hydroxide. These alkaline materials must be removed or at least substantially removed from the product polyether polyol to avoid adverse effects upon the characteristics of polyurethane plastics and foams produced from the polyol.
  • alkaline materials are often removed by simply adding acid to the polyol polymerizate containing alkali metal catalyst to neutralize the alkaline catalyst. An insoluble salt is formed. This insoluble salt may then be removed from the polyol by filtration.
  • U.S. Patent 3,582,491 discloses a method for removing inorganic catalyst from polyols in which a mixture of water, water- insoluble polyether, and a solvent which is substantially immiscible in water is subjected to electrostatic coalescence. Two phases are generated. The first phase is an aqueous phase containing water -soluble materials such as the inorganic catalyst present in the polyol. The second phase is an organic phase in which both the polyether and the water-immiscible solvent are present. This second organic phase must be further treated (e.g., by distillation or vacuum distillation) to remove the organic solvent from the polyether polyol.
  • Patent 3,715,402 discloses a process for the removal of catalysts from polyols in which a mixture of water, polyether, a solvent in which the polyether is soluble and an acid is subjected to electrostatic coalescence or centrifugation. Two streams are recovered by this process.
  • the first stream is an aqueous stream in which the water soluble materials, including the catalyst, are present.
  • the second stream is a solution of the polyether polyol in the solvent. This second stream must be further treated (e.g., by distillation or vacuum distillation) to separate the polyether polyol from the solvent.
  • Patent 4,029,879 discloses a process for the removal of catalysts from polyether polyols in which from 1 to 5% (based on polyether polyol) of water, is added to an adsorbent synthetic magnesium silicate-polyol mixture. The resultant mixture is heated for at least one hour at a temperature of from about 80 to about 130 ⁇ C and then filtered to remove the adsorbent which contains the catalyst. The polyol is then stripped of water and other volatile materials by heating at 80 to 130°C (1 to 10 mm mercury pressure).
  • U.S. Patent 4,129,718 also discloses a process for removal of catalysts from polyether polyols.
  • crude polyol, an adsorbent and water are mixed at a temperature of from about 80 to 130°C for at least 45 minutes and treated with carbon dioxide just prior to filtration. After filtration, the polyol is stripped of water and other volatile materials present.
  • the destabilized emulsion is then passed through a sheet-formed structure made of fine fibers to separate the aqueous phase from the organic phase. Residual alkaline material is then removed from the organic phase by, for example, adding an acid or adsorbent to the organic phase and then distilling off any solvent or water which is still present.
  • One of the disadvantages of this process is that it requires a significant amount of time to destabilize the emulsion prior to separation of the organic and aqueous phases.
  • Another disadvantage of this disclosed process is that only certain types of polyether polyols may be treated effectively.
  • U.S. Patent 3,919,081 discloses a process for separating an emulsion of water and an insoluble hydrocarbon in which a tank having a solid medium in granular form is employed.
  • the solid medium disclosed in this patent is activated carbon.
  • U.S. Patent 4,661,227 discloses an apparatus for the removal of inorganic aqueous solutions from organic solvents in which a coalescer is employed.
  • the coalescer is a vertical housing having a central electrode which is constructed of conical members that define a tortuous flow path.
  • the two phases formed in the coalescer are (1) an aqueous phase containing the pH-basic material and (2) an organic phase containing the polyether polyol. These phases exit the coalescer at different points and are directed to different retaining vessels.
  • the polyether polyol-containing phase may then be further treated with an acid to precipitate out an insoluble salt of the pH-basic material.
  • Figure 1 is a schematic representation of the process of the present invention.
  • Figure 2 illustrates one arrangement of equipment useful for the practice of the present invention in which the coalescer is a vertical packed column.
  • FIG. 3 illustrates an arrangement of equipment suitable for the process of the present invention in which the coalescer is a T- shaped, two-stage coalescer.
  • the present invention relates to a process for removing a pH- basic material, particularly an alkaline catalyst, from a polyether polyol polymerizate in which the amount of solid waste product to be disposed of is significantly reduced.
  • a polyether polyol polymerizate in which a pH-basic material is still present is combined with water and, if the difference between the specific gravity of the organic phase and the specific gravity of the aqueous phase is less than 0.1, an inorganic salt in a manner such that an emulsion forms.
  • the inorganic salt is preferably used in the form of an aqueous solution..
  • the emulsion is then passed directly through a coalescer to cause separation into two phases.
  • One phase is an aqueous phase containing a substantial amount of the alkaline catalyst.
  • the second phase is an organic phase containing the polyether polyol. No organic solvent is added to the polyether polyol polymerizate either prior to formation of the emulsion or passage through the coalescer.
  • Polyether polyols are generally produced by adding alkylene oxides, particularly propylene oxide and/or ethylene oxide, to a starting material having acidic hydrogen atoms (e.g., water, polyalcohols or polyamines) in the presence of a pH-basic catalyst (generally, an alkali metal hydroxide).
  • a pH-basic catalyst generally, an alkali metal hydroxide.
  • the amount of catalyst generally used in such processes is from about 0.1 to about 1.0%, by weight.
  • the polyether polyol polymerizate is treated to remove as much of the basic catalyst as possible. Usually, about 0.0005% (5 ppm) or less of the catalyst remains after such treatment.
  • the basic catalyst is removed by (a) neutralization of the polyether polymerizate with a dilute acid, (2) distilling off water, (3) precipitation of the inorganic salts formed by the acid-base reaction, and (4) filtering off the precipitated salt.
  • the polyether polyol polymerizate is emulsified and the resultant emulsion is passed through a coalescer to separate off an aqueous layer containing 90% or more of the pH-basic catalyst which was initially present in the polyether polyol polymerizate.
  • the organic phase recovered from the coalescer may then be treated by known techniques. For example, dilute acid may be added to the polyether polyol recovered as the organic phase from the coalescer to neutralize any remaining pH- basic material. Water present in the polyether polyol/acid mixture may then be distilled off and the precipitated salt removed by filtration. The amount of polyether polyol lost through distillation and precipitation is substantially reduced by this process. The amount of solid waste generated by this process is also significantly reduced.
  • a polyether polyol polymerizate containing a pH-basic material is combined with water and optionally, a minor amount of an inorganic salt.
  • the inorganic salt is used when the difference between the specific gravity of the organic phase and the specific gravity of the aqueous phase is less than 0.1.
  • An inorganic salt may also be added to polyether polyol polymerizates in which the specific gravity differential between the polyol phase and aqueous phase is greater than 0.1, but such addition of salt is not required.
  • an inorganic acid salt will generally be added to a polymerizate treated in accordance with the process of the present invention.
  • any inorganic salt which is capable of producing an aqueous solution having a specific gravity greater than the density of water is suitable.
  • An inorganic salt which forms an insoluble salt when reacted with any acid to be used in subsequent treatments is preferred.
  • the inorganic salt be the same as the pH-basic catalyst which was used in the alkoxylation reaction to produce the polyether polyol.
  • useful inorganic salts include: sodium chloride, potassium chloride, potassium sulfate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, barium hydroxide, and strontium hydroxide.
  • the preferred inorganic salts include: sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, barium hydroxide and strontium hydroxide. Potassium hydroxide is the most preferred inorganic salt.
  • the inorganic salt When an inorganic salt is used, the inorganic salt is generally added to water prior to combination with the polyether polyol polymerizate. However, the inorganic salt may be added simultaneously with or subsequent to addition of the water to the polyether polyol polymerizate.
  • the amount of inorganic salt to be added depends on the stability of the emulsion generated when combining the aqueous phase and the polyol polymerizate. If the specific gravity differential between the polyol polymerizate and water is sufficient to allow easy phase separation, little, if any, salt will be required. Where the specific gravities of the polyol polymerizate and water are close, larger amounts of salt will be needed to aid coalescence and phase separation.
  • the inorganic salt may be used in amounts of from 0 weight % up to saturation, based on the amount of water added to the polyether polyol polymerizate. For most of the commercially produced polyether polyols, from about 1 to about 15 weight % inorganic salt are preferred. Amounts of from about 2 to about 6 weight % of inorganic salt are most preferred.
  • the amount of water to be added to the polyether polyol polymerizate depends on the amount of pH-basic catalyst to be removed from the polymerizate. It is preferred that the minimum amount of water necessary to remove almost all of the pH-basic catalyst be used. Use of only the necessary amount of water minimizes the amount of water which must be removed by distillation after coalescence. Amounts of from about 5 to about 65% by weight, based on the weight of the total weight of the emulsion are generally useful, with amounts of from about 12 to about 26% by weight being preferred.
  • the water, polyether polyol polymerizate, and any inorganic acid salt are combined under conditions such that an emulsion is formed at a temperature of from about 80 to 100°C, preferably from about 90 to 100°C, and most preferably about 95°C.
  • the emulsion is then heated to a temperature of from about 90 to 150°C, preferably from about 115 to about 130°C, and most preferably about 130°C before entering the coalescer.
  • an aqueous solution of the inorganic salt is heated to a temperature of from about 80 to 100°C, preferably from about 90 to 100°C, and most preferably about 95°C before it is combined with the polymerizate which is maintained at a temperature within the same preferred ranges.
  • the emulsion is then heated to a temperature of from about 90 to 150°C, preferably from about 115 to about 130°C, and most preferably about 130°C before entering the coalescer.
  • any of the known techniques for generating an emulsion may be used in the practice of the present invention. It is, however, preferred that both heating and mixing be done in-line, particularly where the process is to be conducted as a continuous flow process. The time necessary to heat the materials to the necessary temperature will be dependent upon the flow rate and starting temperatures of the streams being fed to the coalescer.
  • Mixing is preferably achieved using a static mixer.
  • An example of a suitable static mixer is a portion of piping equipped with inserts designed to induce turbulence and mixing.
  • Such static mixers are commercially available from Koch Engineering Company, Chemineer, Inc., TAH Industries and Sulzer Brothers, Ltd.
  • water, inorganic salt and polyether polyol polymerizate be combined in a static mixer under conditions such that the shear force will generate an emulsion.
  • Examples of other devices for generating emulsions which could be used in the process of the present invention include: pin mixers, stirred tanks, in-line agitators, impingement mixers, sonic mixers, orifice or nozzle mixers, and centrifugal pumps.
  • coalescer Any of the known coalescing devices may be used in the practice of the present invention. Specific examples of commercially available coalescers which may be used in the practice of the present invention include those available from: Otto York, Inc.; ACS Industries, Inc.; Fluid Technology Group of Facet Enterprises, Inc.; and Osmonics, Inc.
  • coalescing media or packing materials having (1) a high surface area or a high surface area to volume ratio and (2) sufficient surface activity that the formation of droplets during the coalescing process is not impeded may be used in the practice of the present invention.
  • Coalescing media which are resistant to degradation under the highly pH-basic conditions of the process of the present invention are preferred.
  • a coalescer in which a metal mesh coalescing medium (or packing material) is present has been found to be particularly useful. It is preferred that the metal mesh be made of stainless steel or of stainless steel through which a fibrous material such as polytetrafluoroethylene or a polyester (such as that which is commercially available under the name Dacron) is interwoven.
  • Traditional coalescing materials having the required surface area and surface activity such as activated carbon may also be used in the practice of the present invention.
  • the coalescer used in the process of the present invention may have one, two or more beds of coalescing medium present therein.
  • the emulsion is generally passed through the coalescer at a rate such that the emulsion will separate into two phases.
  • the specific rate to be used will be dependent upon the particular coalescer being used. Suitable rates may be readily determined by those skilled in the art.
  • Some polyether polyols (e.g., those made from propylene oxide only) will require a very short residence time in the coalescer (e.g., 5- 10 minutes). However, most of the commonly used polyether polyols will require an average residence time of at least 30 minutes. An average residence time of from about 35 to about 420 minutes is generally sufficient. The preferred average residence is from about 50 to about 240 minutes, most preferably about 60 minutes.
  • the emulsion is maintained at a temperature of from about 90 to about 150°C, preferably from about 90 to about 130°C, and most preferably about 130°C as it is passed through the coalescer.
  • the mesh provides a high surface area medium on which the water is forced together (i.e., coalesced) to form droplets.
  • These water droplets have a density which is sufficiently different from that of the polyol to induce their separation from the emulsion by gravity.
  • the small amount of polyol which is soluble in the aqueous phase is also coalesced into droplets which separate by gravity.
  • the aqueous potassium hydroxide (at a concentration of 4%) will have a density of 0.97 g/ml compared to the polyol density of 0.94 g/ml (at approximately 130°C).
  • the aqueous potassium hydroxide phase would, therefore, exit the coalescer at the bottom and the less dense polyether polyol phase would exit the coalescer at some point above the phase interface level.
  • the volume in the coalescer downstream of the mesh may be used as a settling chamber.
  • the interface level between the two phases is generally maintained at a level which provides optimum residence time for each phase. This level may be monitored by an ultrasonic or capacitance instrument and controlled by restriction of the flow out of the bottom of the coalescer.
  • further separation may be achieved by means of additional beds of coalescing medium (preferably high surface area mesh material) located at points above and below the first bed of mesh material through which the emulsion is initially passed.
  • additional beds of coalescing medium preferably high surface area mesh material
  • Each of the separated phases would then be subjected to a second coalescing step.
  • This embodiment is schematically illustrated in Figure 3 which will be discussed in greater detail below.
  • the pressure in the coalescer is maintained above atmospheric pressure to insure that the boiling point of the aqueous phase is greater than the operating temperature of the coalescer. This prevents boiling in the coalescer that would cause undesirable mixing of the aqueous and polyol phases and disrupt the phase separation.
  • the pressure is maintained using restrictions in the lines by which the aqueous phase and the polyether leave the coalescer. For example, at an operating temperature of 130°C, the pressure in the coalescer is advantageously maintained at a level of from about 45 to about 55 psig.
  • Polyether polyol leaving the coalescer may be further treated to remove any residual pH-basic catalyst by, e.g., acid neutralization and filtration to remove precipitated salt.
  • the aqueous phase containing 90% or more of the pH-basic catalyst and any other inorganic material leaving the coalescer may be used, for example, to neutralize acidic solutions.
  • the aqueous phase exiting the coalescer is diluted with water until it has an inorganic salt concentration corresponding to that of the inorganic salt solution added to the polymerizate to be coalesced.
  • the diluted aqueous phase may then be recycled into the process. This recycled stream may replace or supplement the aqueous solution of inorganic salt to be mixed with the polyol polymerizate to form an emulsion.
  • the process of the present invention may be carried out batchwise or on a continuous basis. It is preferred that this process be carried out on a continuous basis.
  • FIG. 1 illustrates the embodiment of the present invention in which water (stream 2) is combined with a solution of inorganic salt (stream 3) in mixer A to generate a dilute solution of inorganic salt (stream 4).
  • the polyether polyol polymerizate (stream 1) is combined with the dilute solution of inorganic salt (stream 4) as both streams are fed to static mixer B.
  • the resulting emulsion (polymerizate/salt stream) exiting mixer B (stream 5) is then passed through coalescer C.
  • the less dense phase exiting coalescer C (stream 6) is the polyether polyol phase.
  • the more dense phase exiting coalescer C (stream 7) is the aqueous phase.
  • FIG. 2 illustrates an embodiment of the present invention in which the polyether polyol polymerizate (stream 21) is combined with an aqueous solution of inorganic salt (stream 22) to form stream 23.
  • Stream 23 is then passed through static mixer B to form an emulsion (stream 24).
  • Stream 24 is then passed through coalescer C which is equipped with coalescing medium 25.
  • the coalesced stream 26 is then separated into its aqueous phase (stream 28) and polyether polyol phase (stream 27).
  • Figure 3 illustrates an embodiment of the present invention in which the polyether polyol polymerizate (stream 31) is combined with an aqueous solution of inorganic salt (stream 32) to form stream 33.
  • Stream 33 is then passed through static mixer B to form the emulsion (stream 34).
  • Stream 34 is then passed through coalescer C which is equipped with three separate beds of coalescing medium 35.
  • the polyol phase exits coalescer C as stream 36.
  • the aqueous phase
  • the process of the present invention generally removes at least 90% of the pH basic catalyst which was initially present in the polyether polyol polymerizate. In many cases, 95% or more of the pH basic catalyst is removed.
  • FIG. 1 shows the general configuration of the equipment and process materials used in each of these Examples.
  • Stream 1 was a polyether polyol alkaline polymerizate which had been prepared by the reaction of ethylene and/or propylene oxide with a starting material containing active hydrogen (starter) under potassium hydroxide (KOH) catalysis.
  • the nominal temperature of stream 1 was 95°C.
  • Stream 2 was water at ambient temperature.
  • Stream 3 was a 45% aqueous solution of potassium hydroxide at ambient temperature.
  • Streams 2 and 3 were combined in mixer A at a controlled ratio to provide a dilute potassium hydroxide solution (stream 4). The ratio was varied over a range of from about 74:1 to about 10:1 parts of stream 2 to parts of stream 3.
  • the dilute KOH solution (stream 4) was heated to 90°C and combined with stream 1 , the alkaline polyether polymerizate. This mixture (stream 5) was emulsified by passing it through static mixer B. Stream 5 was heated to the final operating temperature and then passed through the coalescer C. As coalescing took place, the more dense material (usually the aqueous phase) settled to the bottom of the coalescer C while the less dense material (usually the polyether) rose to the top.
  • a phase interface was formed and the more dense phase (stream 7) exited the coalescer at an outlet below the interface level.
  • the polyether polyol, usually stream 6, was then further processed using techniques common to commercial polyether production.
  • the finished product was a polyether polyol suitable for use in reactions with isocyanates to form polyurethanes. This process can be run continuously for a long period of time. For the specific examples characterized by the data in the table below, run times of from about 90 to 900 minutes were used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

A process for removing a pH-basic material from a polyether polyol polymerizate in which a polymerizate containing polyether and an alkaline material is combined with water and, if the difference between the specific gravity of the poymerizate and water is less than 0.1, an inorganic salt at a temperature and under conditions such that an emulsion forms. No organic solvent is required. The emulsion is heated to a temperature of from about 90 to about 150 °C. The heated emulsion is then passed through a coalescing medium at a rate such that the residence time is sufficient to separate the emulsion into an aqueous phase containing the pH-basic material and an organic phase containing a polyether polyol which is substantially free of pH-basic material.

Description

A PROCESS FOR THE REMOVAL OF A pH-BASIC MATERIAL FROM A POLYETHER POLYOL
BACKGROUND OF THE INVENTION
The present invention relates to a process for the removal of a pH-basic material from a polyether polyol.
Polyether polyols are reacted with polyisocyanates to produce polyurethanes. These polyether polyols are produced by polymerization reactions catalyzed by alkaline materials such as potassium hydroxide. These alkaline materials must be removed or at least substantially removed from the product polyether polyol to avoid adverse effects upon the characteristics of polyurethane plastics and foams produced from the polyol. These alkaline materials are often removed by simply adding acid to the polyol polymerizate containing alkali metal catalyst to neutralize the alkaline catalyst. An insoluble salt is formed. This insoluble salt may then be removed from the polyol by filtration.
U.S. Patent 3,582,491 discloses a method for removing inorganic catalyst from polyols in which a mixture of water, water- insoluble polyether, and a solvent which is substantially immiscible in water is subjected to electrostatic coalescence. Two phases are generated. The first phase is an aqueous phase containing water -soluble materials such as the inorganic catalyst present in the polyol. The second phase is an organic phase in which both the polyether and the water-immiscible solvent are present. This second organic phase must be further treated (e.g., by distillation or vacuum distillation) to remove the organic solvent from the polyether polyol. U.S. Patent 3,715,402 discloses a process for the removal of catalysts from polyols in which a mixture of water, polyether, a solvent in which the polyether is soluble and an acid is subjected to electrostatic coalescence or centrifugation. Two streams are recovered by this process. The first stream is an aqueous stream in which the water soluble materials, including the catalyst, are present. The second stream is a solution of the polyether polyol in the solvent. This second stream must be further treated (e.g., by distillation or vacuum distillation) to separate the polyether polyol from the solvent. U.S. Patent 4,029,879 discloses a process for the removal of catalysts from polyether polyols in which from 1 to 5% (based on polyether polyol) of water, is added to an adsorbent synthetic magnesium silicate-polyol mixture. The resultant mixture is heated for at least one hour at a temperature of from about 80 to about 130βC and then filtered to remove the adsorbent which contains the catalyst. The polyol is then stripped of water and other volatile materials by heating at 80 to 130°C (1 to 10 mm mercury pressure).
U.S. Patent 4,129,718 also discloses a process for removal of catalysts from polyether polyols. In this disclosed process, crude polyol, an adsorbent and water are mixed at a temperature of from about 80 to 130°C for at least 45 minutes and treated with carbon dioxide just prior to filtration. After filtration, the polyol is stripped of water and other volatile materials present.
Each of these known procedures is disadvantageous in that a significant amount of neutralization salt or adsorbent-containing alkaline catalyst must be disposed of as waste. These procedures also reduce the yield of polyol because residual polyol present in the neutralization salt or on the adsorbent is lost. The polyether polyol must also be further treated to remove solvent. U.S. Patent 4,482,750 discloses a process for removing alkaline catalysts from polyether polyols in which water and optionally an inert organic solvent are added to an alkaline polyether polyol to form an emulsion. The emulsion is maintained at a temperature of at least 70°C for at least 30 minutes with little or no stirring in order to destabilize the emulsion. The destabilized emulsion is then passed through a sheet-formed structure made of fine fibers to separate the aqueous phase from the organic phase. Residual alkaline material is then removed from the organic phase by, for example, adding an acid or adsorbent to the organic phase and then distilling off any solvent or water which is still present. One of the disadvantages of this process is that it requires a significant amount of time to destabilize the emulsion prior to separation of the organic and aqueous phases. Another disadvantage of this disclosed process is that only certain types of polyether polyols may be treated effectively.
Devices for separating mixtures such as the polyether polyol poiymerizates discussed above are also known. These devices generally require specialized media, electricity or complicated flow paths. U.S. Patent 3,919,081, for example, discloses a process for separating an emulsion of water and an insoluble hydrocarbon in which a tank having a solid medium in granular form is employed. The solid medium disclosed in this patent is activated carbon.
U.S. Patent 4,661,227 discloses an apparatus for the removal of inorganic aqueous solutions from organic solvents in which a coalescer is employed. The coalescer is a vertical housing having a central electrode which is constructed of conical members that define a tortuous flow path. A process for removing a pH-basic material from a polyether polyol in which large amounts of neutralization salt are not generated, organic solvents are not needed, specialized adsorbent materials are not required and simple, standard coalescers could be used would, therefore, be an improvement over the current commercial processes.
SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for removing a pH-basic material, particularly an alkaline catalyst, from a polyether polyol. It is another object of the present invention to provide a process for removing a pH-basic material from a polyether polyol in which significantly less solid waste is generated than in prior art processes.
It is a further object of the present invention to provide a process for the removal of alkaline materials from polyether polyols in which 90% or more of the residual pH-basic material is removed prior to addition of a neutralizing acid.
It is another object of the present invention to provide a process for removing alkaline materials from polyether polyols in which the polyol/water emulsion need not be destabilized prior to passage through the coalescer.
It is also an object of the present invention to provide a polyether polyol having improved color characteristics in which substantially all pH-basic material has been removed prior to traditional purification treatments.
These and other objects which will be apparent to those skilled in the art are accomplished by combining (a) a polymerizate made up of a polyether polyol and a pH-basic material with (b) water and, if the difference in specific gravity of the organic phase and the aqueous phase is less than 0.1, (c) an inorganic salt (preferably in the form of an aqueous solution of the inorganic salt) at a temperature of from about 90 to about 150°C under conditions such that an emulsion forms. This emulsion is then passed directly through a coalescer at a rate which ensures the formation of two phases. The optimum residence time in the coalescer will vary depending on specific process conditions and the type of polyether polyol used. For most of the common commercial polyether polyols, a residence time of at least 30 minutes is required. The two phases formed in the coalescer are (1) an aqueous phase containing the pH-basic material and (2) an organic phase containing the polyether polyol. These phases exit the coalescer at different points and are directed to different retaining vessels. The polyether polyol-containing phase may then be further treated with an acid to precipitate out an insoluble salt of the pH-basic material.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of the process of the present invention.
Figure 2 illustrates one arrangement of equipment useful for the practice of the present invention in which the coalescer is a vertical packed column.
Figure 3 illustrates an arrangement of equipment suitable for the process of the present invention in which the coalescer is a T- shaped, two-stage coalescer. DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention relates to a process for removing a pH- basic material, particularly an alkaline catalyst, from a polyether polyol polymerizate in which the amount of solid waste product to be disposed of is significantly reduced. In this process, a polyether polyol polymerizate in which a pH-basic material is still present is combined with water and, if the difference between the specific gravity of the organic phase and the specific gravity of the aqueous phase is less than 0.1, an inorganic salt in a manner such that an emulsion forms. If used, the inorganic salt is preferably used in the form of an aqueous solution.. The emulsion is then passed directly through a coalescer to cause separation into two phases. One phase is an aqueous phase containing a substantial amount of the alkaline catalyst. The second phase is an organic phase containing the polyether polyol. No organic solvent is added to the polyether polyol polymerizate either prior to formation of the emulsion or passage through the coalescer.
Polyether polyols are generally produced by adding alkylene oxides, particularly propylene oxide and/or ethylene oxide, to a starting material having acidic hydrogen atoms (e.g., water, polyalcohols or polyamines) in the presence of a pH-basic catalyst (generally, an alkali metal hydroxide). The amount of catalyst generally used in such processes is from about 0.1 to about 1.0%, by weight. Upon completion of the alkoxylation reaction, the polyether polyol polymerizate is treated to remove as much of the basic catalyst as possible. Usually, about 0.0005% (5 ppm) or less of the catalyst remains after such treatment.
In many of the known procedures, the basic catalyst is removed by (a) neutralization of the polyether polymerizate with a dilute acid, (2) distilling off water, (3) precipitation of the inorganic salts formed by the acid-base reaction, and (4) filtering off the precipitated salt.
In the process of the present invention, the polyether polyol polymerizate is emulsified and the resultant emulsion is passed through a coalescer to separate off an aqueous layer containing 90% or more of the pH-basic catalyst which was initially present in the polyether polyol polymerizate. The organic phase recovered from the coalescer may then be treated by known techniques. For example, dilute acid may be added to the polyether polyol recovered as the organic phase from the coalescer to neutralize any remaining pH- basic material. Water present in the polyether polyol/acid mixture may then be distilled off and the precipitated salt removed by filtration. The amount of polyether polyol lost through distillation and precipitation is substantially reduced by this process. The amount of solid waste generated by this process is also significantly reduced.
In the process of the present invention, a polyether polyol polymerizate containing a pH-basic material is combined with water and optionally, a minor amount of an inorganic salt. The inorganic salt is used when the difference between the specific gravity of the organic phase and the specific gravity of the aqueous phase is less than 0.1. An inorganic salt may also be added to polyether polyol polymerizates in which the specific gravity differential between the polyol phase and aqueous phase is greater than 0.1, but such addition of salt is not required. Because most of the commercially produced polyether polyols do not have a specific gravity which is sufficiently higher or lower than the specific gravity of the aqueous phase of the polymerizate, an inorganic acid salt will generally be added to a polymerizate treated in accordance with the process of the present invention.
Any inorganic salt which is capable of producing an aqueous solution having a specific gravity greater than the density of water is suitable. An inorganic salt which forms an insoluble salt when reacted with any acid to be used in subsequent treatments is preferred. For practical reasons, it is most preferred that the inorganic salt be the same as the pH-basic catalyst which was used in the alkoxylation reaction to produce the polyether polyol. Examples of useful inorganic salts include: sodium chloride, potassium chloride, potassium sulfate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, barium hydroxide, and strontium hydroxide. The preferred inorganic salts include: sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, barium hydroxide and strontium hydroxide. Potassium hydroxide is the most preferred inorganic salt.
When an inorganic salt is used, the inorganic salt is generally added to water prior to combination with the polyether polyol polymerizate. However, the inorganic salt may be added simultaneously with or subsequent to addition of the water to the polyether polyol polymerizate. The amount of inorganic salt to be added depends on the stability of the emulsion generated when combining the aqueous phase and the polyol polymerizate. If the specific gravity differential between the polyol polymerizate and water is sufficient to allow easy phase separation, little, if any, salt will be required. Where the specific gravities of the polyol polymerizate and water are close, larger amounts of salt will be needed to aid coalescence and phase separation. The inorganic salt may be used in amounts of from 0 weight % up to saturation, based on the amount of water added to the polyether polyol polymerizate. For most of the commercially produced polyether polyols, from about 1 to about 15 weight % inorganic salt are preferred. Amounts of from about 2 to about 6 weight % of inorganic salt are most preferred. The amount of water to be added to the polyether polyol polymerizate depends on the amount of pH-basic catalyst to be removed from the polymerizate. It is preferred that the minimum amount of water necessary to remove almost all of the pH-basic catalyst be used. Use of only the necessary amount of water minimizes the amount of water which must be removed by distillation after coalescence. Amounts of from about 5 to about 65% by weight, based on the weight of the total weight of the emulsion are generally useful, with amounts of from about 12 to about 26% by weight being preferred.
The water, polyether polyol polymerizate, and any inorganic acid salt are combined under conditions such that an emulsion is formed at a temperature of from about 80 to 100°C, preferably from about 90 to 100°C, and most preferably about 95°C. The emulsion is then heated to a temperature of from about 90 to 150°C, preferably from about 115 to about 130°C, and most preferably about 130°C before entering the coalescer.
In a preferred embodiment of the invention, an aqueous solution of the inorganic salt is heated to a temperature of from about 80 to 100°C, preferably from about 90 to 100°C, and most preferably about 95°C before it is combined with the polymerizate which is maintained at a temperature within the same preferred ranges. The emulsion is then heated to a temperature of from about 90 to 150°C, preferably from about 115 to about 130°C, and most preferably about 130°C before entering the coalescer.
Any of the known techniques for generating an emulsion may be used in the practice of the present invention. It is, however, preferred that both heating and mixing be done in-line, particularly where the process is to be conducted as a continuous flow process. The time necessary to heat the materials to the necessary temperature will be dependent upon the flow rate and starting temperatures of the streams being fed to the coalescer. Mixing is preferably achieved using a static mixer. An example of a suitable static mixer is a portion of piping equipped with inserts designed to induce turbulence and mixing. Such static mixers are commercially available from Koch Engineering Company, Chemineer, Inc., TAH Industries and Sulzer Brothers, Ltd.
It is preferred, that the water, inorganic salt and polyether polyol polymerizate be combined in a static mixer under conditions such that the shear force will generate an emulsion.
Examples of other devices for generating emulsions which could be used in the process of the present invention include: pin mixers, stirred tanks, in-line agitators, impingement mixers, sonic mixers, orifice or nozzle mixers, and centrifugal pumps.
The emulsion is then passed directly through a coalescer to cause the separation of (1) an aqueous phase containing the pH- basic catalyst and added inorganic salt and (2) an organic phase which is made up primarily of polyether polyol. Any of the known coalescing devices may be used in the practice of the present invention. Specific examples of commercially available coalescers which may be used in the practice of the present invention include those available from: Otto York, Inc.; ACS Industries, Inc.; Fluid Technology Group of Facet Enterprises, Inc.; and Osmonics, Inc.
Any of the known coalescing media or packing materials having (1) a high surface area or a high surface area to volume ratio and (2) sufficient surface activity that the formation of droplets during the coalescing process is not impeded may be used in the practice of the present invention. Coalescing media which are resistant to degradation under the highly pH-basic conditions of the process of the present invention are preferred. A coalescer in which a metal mesh coalescing medium (or packing material) is present has been found to be particularly useful. It is preferred that the metal mesh be made of stainless steel or of stainless steel through which a fibrous material such as polytetrafluoroethylene or a polyester (such as that which is commercially available under the name Dacron) is interwoven. Traditional coalescing materials having the required surface area and surface activity such as activated carbon may also be used in the practice of the present invention. The coalescer used in the process of the present invention may have one, two or more beds of coalescing medium present therein.
The emulsion is generally passed through the coalescer at a rate such that the emulsion will separate into two phases. The specific rate to be used will be dependent upon the particular coalescer being used. Suitable rates may be readily determined by those skilled in the art.
Some polyether polyols (e.g., those made from propylene oxide only) will require a very short residence time in the coalescer (e.g., 5- 10 minutes). However, most of the commonly used polyether polyols will require an average residence time of at least 30 minutes. An average residence time of from about 35 to about 420 minutes is generally sufficient. The preferred average residence is from about 50 to about 240 minutes, most preferably about 60 minutes. The emulsion is maintained at a temperature of from about 90 to about 150°C, preferably from about 90 to about 130°C, and most preferably about 130°C as it is passed through the coalescer. In a coalescer having a metal mesh packing material, the mesh provides a high surface area medium on which the water is forced together (i.e., coalesced) to form droplets. These water droplets have a density which is sufficiently different from that of the polyol to induce their separation from the emulsion by gravity. The small amount of polyol which is soluble in the aqueous phase is also coalesced into droplets which separate by gravity. For example, in a system where potassium hydroxide is the pH-basic catalyst to be removed and also the inorganic salt added to the polyether polyol polymerizate, the aqueous potassium hydroxide (at a concentration of 4%) will have a density of 0.97 g/ml compared to the polyol density of 0.94 g/ml (at approximately 130°C). The aqueous potassium hydroxide phase would, therefore, exit the coalescer at the bottom and the less dense polyether polyol phase would exit the coalescer at some point above the phase interface level.
The volume in the coalescer downstream of the mesh may be used as a settling chamber. The interface level between the two phases is generally maintained at a level which provides optimum residence time for each phase. This level may be monitored by an ultrasonic or capacitance instrument and controlled by restriction of the flow out of the bottom of the coalescer.
In one embodiment of the present invention, further separation may be achieved by means of additional beds of coalescing medium (preferably high surface area mesh material) located at points above and below the first bed of mesh material through which the emulsion is initially passed. Each of the separated phases would then be subjected to a second coalescing step. This embodiment is schematically illustrated in Figure 3 which will be discussed in greater detail below. The pressure in the coalescer is maintained above atmospheric pressure to insure that the boiling point of the aqueous phase is greater than the operating temperature of the coalescer. This prevents boiling in the coalescer that would cause undesirable mixing of the aqueous and polyol phases and disrupt the phase separation. The pressure is maintained using restrictions in the lines by which the aqueous phase and the polyether leave the coalescer. For example, at an operating temperature of 130°C, the pressure in the coalescer is advantageously maintained at a level of from about 45 to about 55 psig.
Polyether polyol leaving the coalescer may be further treated to remove any residual pH-basic catalyst by, e.g., acid neutralization and filtration to remove precipitated salt. The aqueous phase containing 90% or more of the pH-basic catalyst and any other inorganic material leaving the coalescer may be used, for example, to neutralize acidic solutions. In a preferred embodiment of the present invention, the aqueous phase exiting the coalescer is diluted with water until it has an inorganic salt concentration corresponding to that of the inorganic salt solution added to the polymerizate to be coalesced. The diluted aqueous phase may then be recycled into the process. This recycled stream may replace or supplement the aqueous solution of inorganic salt to be mixed with the polyol polymerizate to form an emulsion.
The process of the present invention may be carried out batchwise or on a continuous basis. It is preferred that this process be carried out on a continuous basis.
Figure 1 illustrates the embodiment of the present invention in which water (stream 2) is combined with a solution of inorganic salt (stream 3) in mixer A to generate a dilute solution of inorganic salt (stream 4). The polyether polyol polymerizate (stream 1) is combined with the dilute solution of inorganic salt (stream 4) as both streams are fed to static mixer B. The resulting emulsion (polymerizate/salt stream) exiting mixer B (stream 5) is then passed through coalescer C. The less dense phase exiting coalescer C (stream 6) is the polyether polyol phase. The more dense phase exiting coalescer C (stream 7) is the aqueous phase.
Figure 2 illustrates an embodiment of the present invention in which the polyether polyol polymerizate (stream 21) is combined with an aqueous solution of inorganic salt (stream 22) to form stream 23. Stream 23 is then passed through static mixer B to form an emulsion (stream 24). Stream 24 is then passed through coalescer C which is equipped with coalescing medium 25. The coalesced stream 26 is then separated into its aqueous phase (stream 28) and polyether polyol phase (stream 27). Figure 3 illustrates an embodiment of the present invention in which the polyether polyol polymerizate (stream 31) is combined with an aqueous solution of inorganic salt (stream 32) to form stream 33. Stream 33 is then passed through static mixer B to form the emulsion (stream 34). Stream 34 is then passed through coalescer C which is equipped with three separate beds of coalescing medium 35. The polyol phase exits coalescer C as stream 36. The aqueous phase exits coalescer C as stream 37.
The process of the present invention generally removes at least 90% of the pH basic catalyst which was initially present in the polyether polyol polymerizate. In many cases, 95% or more of the pH basic catalyst is removed.
Having thus described our invention, the following Examples are given as being illustrative thereof. All parts and percentages given in these Examples are parts by weight and percentages by weight, unless otherwise indicated.
EXAMPLES Example 1-1Q Figure 1 shows the general configuration of the equipment and process materials used in each of these Examples.
Stream 1 was a polyether polyol alkaline polymerizate which had been prepared by the reaction of ethylene and/or propylene oxide with a starting material containing active hydrogen (starter) under potassium hydroxide (KOH) catalysis. The nominal temperature of stream 1 was 95°C. Stream 2 was water at ambient temperature. Stream 3 was a 45% aqueous solution of potassium hydroxide at ambient temperature.
Streams 2 and 3 were combined in mixer A at a controlled ratio to provide a dilute potassium hydroxide solution (stream 4). The ratio was varied over a range of from about 74:1 to about 10:1 parts of stream 2 to parts of stream 3. The dilute KOH solution (stream 4) was heated to 90°C and combined with stream 1 , the alkaline polyether polymerizate. This mixture (stream 5) was emulsified by passing it through static mixer B. Stream 5 was heated to the final operating temperature and then passed through the coalescer C. As coalescing took place, the more dense material (usually the aqueous phase) settled to the bottom of the coalescer C while the less dense material (usually the polyether) rose to the top. A phase interface was formed and the more dense phase (stream 7) exited the coalescer at an outlet below the interface level. The less dense phase (stream 6) exited above the level of the interface. The polyether polyol, usually stream 6, was then further processed using techniques common to commercial polyether production. The finished product was a polyether polyol suitable for use in reactions with isocyanates to form polyurethanes. This process can be run continuously for a long period of time. For the specific examples characterized by the data in the table below, run times of from about 90 to 900 minutes were used.
Figure imgf000019_0001
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Claims

WHAT IS CLAIMED IS:
1. A process for removing a pH-basic material from a polyether polyol polymerizate comprising: a) combining 1) a polymerizate containing polyether and an alkaline material with
2) water and if the difference between the specific gravity of polymerizate 1) and the specific gravity of water 2) is less than 0.1,
3) an inorganic salt at a temperature of from about 80 to about 100°C in amounts and under conditions such that an emulsion forms, in the absence of an organic solvent, b) heating the emulsion formed in a) to a temperature of from about 90 to about 150°C, c) passing the heated emulsion directly through a coalescing medium at a rate such that the residence time of the emulsion is sufficient to separate the emulsion into
4) an aqueous phase containing the pH-basic material and any inorganic material and
5) an organic phase containing polyether polyol which is substantially free of pH-basic materials. 2. The process of Claim 1 in which the water 2) and an inorganic salt 3) are combined to form an aqueous solution before being combined with the polyether polyol polymerizate. 3. The process of Claim 2 in which the aqueous solution of inorganic salt used in step a) is present in an amount such that the solution constitutes from about 5 to about 65% by weight of the emulsion generated. 4. The process of Claim 2 in which the inorganic salt is the same as the pH-basic material present in the polymerizate to be treated.
5. The process of Claim 1 in which step a) is carried out in a static mixer under shear conditions sufficient to generate an emulsion.
6. The process of Claim 1 in which step b) is carried out at a temperature of from about 90 to about 130°C.
7. The process of Claim 1 in which the pH-basic material being removed is potassium hydroxide.
8. The process of Claim 1 in which the average residence time of the emulsion in the coalescer is from about 35 to about 420 minutes.
9. The process of Claim 1 in which the average residence time of the emulsion in the coalescer is about 60 minutes.
10. The process of Claim 2 in which the concentration of the inorganic salt in the aqueous phase combined in step a) is from about 2 to about 6% by weight.
11. The process of Claim 10 in which the inorganic salt is potassium hydroxide.
12. The process of Claim 2 in which the aqueous solution of inorganic salt is used in step a) in an amount such that the aqueous solution constitutes from about 12 to about 24% by weight of the emulsion which forms.
13. The process of Claim 1 in which the coalescer has a metal mesh as the contact surface present therein.
14. The process of Claim 1 in which pH-basic material is removed from a polyether polyol polymerizate on a continuous basis.
15. The process of Claim 1 in which the separated aqueous phase 4) is recycled to step a).
16. The process of Claim 15 in which the separated aqueous phase 4) is diluted to the desired concentration of inorganic salt prior to being recycled.
17. A polyether polyol which is substantially free from residual alkaline catalyst which has been recovered from the process of Claim 1.
PCT/US1995/016244 1995-01-05 1995-12-08 A PROCESS FOR THE REMOVAL OF A pH-BASIC MATERIAL FROM A POLYETHER POLYOL WO1996020972A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US36921495A 1995-01-05 1995-01-05
US08/369,214 1995-01-05

Publications (2)

Publication Number Publication Date
WO1996020972A2 true WO1996020972A2 (en) 1996-07-11
WO1996020972A3 WO1996020972A3 (en) 1996-09-12

Family

ID=23454566

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/016244 WO1996020972A2 (en) 1995-01-05 1995-12-08 A PROCESS FOR THE REMOVAL OF A pH-BASIC MATERIAL FROM A POLYETHER POLYOL

Country Status (2)

Country Link
CA (1) CA2165140A1 (en)
WO (1) WO1996020972A2 (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998017708A1 (en) * 1996-10-18 1998-04-30 Mdv Technologies, Inc. Process for the fractionation of polyoxyalkylene block copolymers
EP0926183A2 (en) * 1997-12-24 1999-06-30 Bayer Corporation A process for the removal of alkalinity in the manufacture of polyether polyols and the reuse of this alkalinity in the manufacture of polyether polyols
WO2001014456A1 (en) * 1999-08-25 2001-03-01 The Dow Chemical Company Process for purifying polyethers
WO2002010252A1 (en) * 2000-07-27 2002-02-07 Huntsman International Llc Polyol processing
DE102007038436A1 (en) 2007-08-16 2009-02-19 Bayer Materialscience Ag Process for the preparation of polyols
DE102008011683A1 (en) 2008-02-28 2009-09-03 Bayer Materialscience Ag Process for the preparation of polyols
DE102008028555A1 (en) 2008-06-16 2009-12-17 Bayer Materialscience Ag Process for the preparation of polyols
DE102009043616A1 (en) 2009-09-29 2011-03-31 Bayer Materialscience Ag Process for the preparation of amino-containing polyols
US20110112332A1 (en) * 2008-07-23 2011-05-12 Dow Global Technologies Inc. Process for increasing the coalescence rate for amine-initiated polyethers
EP2365019A1 (en) 2010-03-13 2011-09-14 Bayer MaterialScience AG Method for manufacturing polyether polyols
EP2770009A1 (en) 2013-02-22 2014-08-27 Bayer MaterialScience AG Method for manufacturing polyether polyols
US8987529B2 (en) 2013-02-22 2015-03-24 Bayer Materialscience Ag Process for preparing polyether polyols
WO2017194709A1 (en) 2016-05-13 2017-11-16 Covestro Deutschland Ag Method for the preparation of polyoxyalkylene polyols
EP3741788A1 (en) 2019-05-24 2020-11-25 Covestro Deutschland AG Method for the preparation of polyoxyalkylenpolyol mixtures
EP3747929A4 (en) * 2018-11-02 2021-03-24 Jiahua Chemistry (Binzhou) Co., Ltd Polyether polyol refining method and refining apparatus
EP3838963A1 (en) 2019-12-17 2021-06-23 Covestro Deutschland AG Method for producing polyoxyalkylene polyesterpolyols
CN114031764A (en) * 2021-10-22 2022-02-11 南京清研新材料研究院有限公司 Polyether purification method
WO2023057328A1 (en) 2021-10-07 2023-04-13 Covestro Deutschland Ag Process for preparing polyoxyalkylene polyester polyols

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10150837B2 (en) 2016-06-23 2018-12-11 Covestro Llc Processes for removing water from a polyether polyol
CN108341942B (en) * 2017-01-22 2020-05-26 山东蓝星东大化工有限责任公司 Refining method of polyether polyol for alkali metal catalytic synthesis

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3357738A (en) * 1965-10-11 1967-12-12 Bourlier Jean Automobile top
US3492358A (en) * 1968-04-10 1970-01-27 Dow Chemical Co Purification of ethers
US3823145A (en) * 1968-07-26 1974-07-09 Basf Wyandotte Corp Removal of impurities from polyols
EP0038983A2 (en) * 1980-04-25 1981-11-04 Bayer Ag Process for working up polyether polyols

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3263450B2 (en) * 1992-11-27 2002-03-04 三井化学株式会社 Purification method of crude polyoxypropylene polyol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3357738A (en) * 1965-10-11 1967-12-12 Bourlier Jean Automobile top
US3492358A (en) * 1968-04-10 1970-01-27 Dow Chemical Co Purification of ethers
US3823145A (en) * 1968-07-26 1974-07-09 Basf Wyandotte Corp Removal of impurities from polyols
EP0038983A2 (en) * 1980-04-25 1981-11-04 Bayer Ag Process for working up polyether polyols

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent Publications Ltd., London, GB; AN 94-222044(27) XP002007410 & JP,A,06 157 743 (MITSUI TOATSU CHEM INC) *
XP002007409 *

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998017708A1 (en) * 1996-10-18 1998-04-30 Mdv Technologies, Inc. Process for the fractionation of polyoxyalkylene block copolymers
EP0926183A2 (en) * 1997-12-24 1999-06-30 Bayer Corporation A process for the removal of alkalinity in the manufacture of polyether polyols and the reuse of this alkalinity in the manufacture of polyether polyols
EP0926183A3 (en) * 1997-12-24 2001-05-16 Bayer Corporation A process for the removal of alkalinity in the manufacture of polyether polyols and the reuse of this alkalinity in the manufacture of polyether polyols
WO2001014456A1 (en) * 1999-08-25 2001-03-01 The Dow Chemical Company Process for purifying polyethers
US6376625B1 (en) 1999-08-25 2002-04-23 The Dow Chemical Company Process for purifying polyethers
JP2003507550A (en) * 1999-08-25 2003-02-25 ザ ダウ ケミカル カンパニー Method for purifying polyether
WO2002010252A1 (en) * 2000-07-27 2002-02-07 Huntsman International Llc Polyol processing
US6762279B2 (en) 2000-07-27 2004-07-13 Huntsman International Llc Polyol processing
DE102007038436A1 (en) 2007-08-16 2009-02-19 Bayer Materialscience Ag Process for the preparation of polyols
EP2028211A1 (en) 2007-08-16 2009-02-25 Bayer MaterialScience AG Process for producing polyols
US8865945B2 (en) 2007-08-16 2014-10-21 Bayer Materialscience Ag Process for the preparation of polyols
DE102008011683A1 (en) 2008-02-28 2009-09-03 Bayer Materialscience Ag Process for the preparation of polyols
DE102008028555A1 (en) 2008-06-16 2009-12-17 Bayer Materialscience Ag Process for the preparation of polyols
US8501904B2 (en) 2008-06-16 2013-08-06 Bayer Materialscience Ag Method for producing polyols
US20110112332A1 (en) * 2008-07-23 2011-05-12 Dow Global Technologies Inc. Process for increasing the coalescence rate for amine-initiated polyethers
DE102009043616A1 (en) 2009-09-29 2011-03-31 Bayer Materialscience Ag Process for the preparation of amino-containing polyols
WO2011039145A1 (en) 2009-09-29 2011-04-07 Bayer Materialscience Ag Method for producing polyols that contain amino groups
WO2011113729A1 (en) 2010-03-13 2011-09-22 Bayer Materialscience Ag Method for producing polyether polyols
EP2365019A1 (en) 2010-03-13 2011-09-14 Bayer MaterialScience AG Method for manufacturing polyether polyols
US8987529B2 (en) 2013-02-22 2015-03-24 Bayer Materialscience Ag Process for preparing polyether polyols
US9006499B2 (en) 2013-02-22 2015-04-14 Bayer Materialscience Ag Process for preparing polyether polyols
EP2770009A1 (en) 2013-02-22 2014-08-27 Bayer MaterialScience AG Method for manufacturing polyether polyols
US10961346B2 (en) 2016-05-13 2021-03-30 Covestro Deutschland Ag Method for the preparation of polyoxyalkylene polyols
WO2017194709A1 (en) 2016-05-13 2017-11-16 Covestro Deutschland Ag Method for the preparation of polyoxyalkylene polyols
US11938416B2 (en) 2018-11-02 2024-03-26 Jiahua Chemistry (Binzhou) Co., Ltd. Polyether polyol refining method and refining apparatus
EP3747929A4 (en) * 2018-11-02 2021-03-24 Jiahua Chemistry (Binzhou) Co., Ltd Polyether polyol refining method and refining apparatus
WO2020239525A1 (en) 2019-05-24 2020-12-03 Covestro Intellectual Property Gmbh & Co. Kg Process for producing polyoxyalkylene-polyol mixtures
EP3741788A1 (en) 2019-05-24 2020-11-25 Covestro Deutschland AG Method for the preparation of polyoxyalkylenpolyol mixtures
EP3838963A1 (en) 2019-12-17 2021-06-23 Covestro Deutschland AG Method for producing polyoxyalkylene polyesterpolyols
WO2021122401A1 (en) 2019-12-17 2021-06-24 Covestro Intellectual Property Gmbh & Co. Kg Process for preparing polyoxyalkylene polyester polyols
WO2023057328A1 (en) 2021-10-07 2023-04-13 Covestro Deutschland Ag Process for preparing polyoxyalkylene polyester polyols
CN114031764A (en) * 2021-10-22 2022-02-11 南京清研新材料研究院有限公司 Polyether purification method

Also Published As

Publication number Publication date
WO1996020972A3 (en) 1996-09-12
CA2165140A1 (en) 1996-07-06

Similar Documents

Publication Publication Date Title
WO1996020972A2 (en) A PROCESS FOR THE REMOVAL OF A pH-BASIC MATERIAL FROM A POLYETHER POLYOL
US4482750A (en) Process for removing alkaline catalysts from polyether polyols
EP0711819B1 (en) Process for recovering organic sulfur compounds from fuel oil and equipment therefor
EP0188119B1 (en) Method for desalting crude oil
US3617546A (en) Removal of organic compounds by liquid membrane
US4645512A (en) Continuous process for removing water-soluble particles from organic liquids
US4283290A (en) Purification utilizing liquid membrane with electrostatic coalescence
EP1212370B1 (en) Process for preparing polyethers
CN110291061B (en) Process for co-production of oxide/styrene by upgrading waste stream in propylene
US6331656B1 (en) Hydroformylation process
US4689177A (en) Use of tridithiocarbamic acid compositions as demulsifiers
US5098993A (en) Method for removing alkali metal compound from crude high-molecular weight substance
JPH08301803A (en) Desalting method for phenol tar
US5039429A (en) Hypochlorite removal from waste stream effluents
WO2022054783A1 (en) Acetic acid recovering method
US3562348A (en) Production of aluminum-free hydrocarbon
JP3437737B2 (en) Supercritical water reactor
US5093029A (en) Breaking emulsions of alkanesulfonyl chlorides in aqueous hydrochloric acid
US3953582A (en) Process for the separation of sodium azide
EP0058074A1 (en) Liquid-liquid contacting process
CA1100094A (en) Recovery of dissolved species from aqueous solutions by a liquid membrane technique
KR930003816B1 (en) Simultaneous coffee hydrolysis and oil extraction
US3157463A (en) Extraction of plutonium and uranium values from aqueous solution
JP4065714B2 (en) Method for purifying 1,2-dichloroethane
EP1628734B1 (en) Method for purifying spent acid

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): BR CN JP KR

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: A3

Designated state(s): BR CN JP KR

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase