Patent Description:
Polyether polyols, which are often used in the manufacture of polyurethanes, such as polyurethane foams, are often manufactured using a catalyzed reaction of initiators having active hydrogen atoms with epoxides such as, for example, ethylene oxide and/or propylene oxide. Alkalinity is introduced into the polyether polyols, for example, by using alkaline metal hydroxides as catalysts.

Suitable initiators having active hydrogen atoms (sometimes referred to as "H-functional initiators") include hydroxyl group and amine group-containing compounds, and the particular H-functional initiator(s) used can impact various characteristics of the resulting polyether polyol. Amine-initiated polyether polyols, for example, are self-catalyzing and typically react faster with isocyanates (to produce polyurethane) than polyether polyols produced using H-functional initiators containing hydroxyl groups. Therefore, depending on the particular application in which the polyether polyol will be used, it may be desirable to utilize an amine-initiated polyether polyol or it may be desirable to use a hydroxyl-initiated polyether polyol. Amine-initiated polyether polyols may, for example, be particularly desirable for use in the production of rigid insulation foams, whereas hydroxyl-initiated polyether polyols, especially long-chain, relatively low hydroxyl number, polyether polyols, may be particularly desirable for use in the production of flexible foams.

In many cases, therefore, polyether polyol manufacturers produce both amine-initiated and non-amine, i.e., hydroxyl-, initiated polyether polyols. Non-amine initiated polyether polyols are, however, very sensitive to contamination from amines, especially in terms of alkalinity and color. As a result, in many cases, polyether polyol manufacturers have reactors dedicated solely to the production of amine-initiated polyether polyols. To maximize asset utilization, however, it may be desirable to have a single reactor be capable of switching between producing both amine-initiated polyether polyols and non-amine-initiated polyether polyols. <CIT> discloses a method for cleaning a polymerization reactor, used for preparing polyalkylene glycol, by means of a non-ionic surfactant solution. <CIT> discloses a process for the aqueous suspension polymerization of a vinylidene halide in reactors containing metal surfaces exposed to said suspension, wherein said polymerization is conducted in reactors wherein said metal surfaces are substantially free of adsorbed organic materials prior to introduction therein of said aqueous suspension into the reactor, whereby the amount of polymer build up on said metal surfaces during polymerization is substantially reduced. <CIT> discloses a method of removing deposits and passivating the tube-side surfaces of tube and shell type reactor equipment. The method comprises the circulation of various solutions; including inhibited acid, alkaline, and passivating solutions, through the tube-side of the reactor, with flushing steps occurring between the various chemical circulation steps. The flushing media is preferably nitrogen gas. <CIT> discloses a process for producing clear, amine-initiated polyether polyols by epoxidizing an amine in the presence of an alkali metal hydroxide catalyst. After the desired degree of epoxidation has been achieved, a hydroxy-carboxylic acid is added to the epoxidized mixture in an amount sufficient to neutralize any remaining alkali metal hydroxide. The polyols produced in this manner are particularly useful for the production of polyurethane and polyisocyanurate foams. <CIT> describes an all-purpose sanitary cleaning composition which is a mixture of water, phosphoric acid, oxalic acid, an alkylene glycol monoalkyl ether solvent, a non-ionic surfactant, a cationic surfactant comprising fluorinated alkyl quaternary ammonium halide, and an olfactory agent, in defined proportions.

As a result, it would be desirable to provide a process for removing amine contaminants from equipment used in the production of polyether polyols that allows for effective utilization of the equipment, such as a reactor, to produce both amine-initiated and non-amine initiated polyether polyols, with the non-amine initiated polyether polyols exhibiting low alkalinity levels and good color.

In certain respects, the invention described in this specification relates to methods of removing amine contaminants from equipment used in the production of polyether polyols. These methods comprise: (a) contacting the equipment with an aqueous solution of a first acid; (b) discharging the aqueous solution of the first acid from the equipment; (c) contacting the equipment with an aqueous solution of an acidic metal conditioner; (d) discharging the aqueous solution of the acidic metal conditioner from the equipment; (e) contacting the equipment with an aqueous solution of an alkali metal hydroxide; and (f) discharging the aqueous solution of the alkali metal hydroxide from the equipment. (Cleaning method.

In other respects, the invention described in this specification relates to methods of preparing polyether polyols. These methods comprise: (A) preparing an amine-initiated polyether polyol in an equipment usable in the production of polyether polyols, in particular in a reactor; (B) discharging the amine-initiated polyether polyol from the equipment (in particular the reactor); (C) cleaning the equipment (in particular the reactor) by a cleaning process comprising: (<NUM>) contacting the equipment (in particular the reactor) with an aqueous solution of a first acid; (<NUM>) contacting the equipment (in particular the reactor) with an aqueous solution of an acidic metal conditioner; and (<NUM>) contacting the equipment (in particular the reactor) with an aqueous solution of an alkali metal hydroxide; and (D) preparing a non-amine initiated polyether polyol in the equipment (in particular the reactor). The cleaning process of (C) is in particular the inventive method of removing amine contaminants from equipment used in the production of polyether polyols described in this specification, in which case step (<NUM>) comprises (a) and (b), step (<NUM>) comprises (c) and (d), and step (<NUM>) comprises (e) and (f). (Preparation method.

This specification also describes systems for producing polyether polyols. These systems comprise: (I) a reactor; (II) a source of alkylene oxide in fluid communication with the reactor; (III) a source of alkali metal hydroxide catalyst in fluid communication with the reactor; (IV) a source of amine initiator in fluid communication with the reactor; (V) a source of non-amine initiator in fluid communication with the reactor; (VI) a water source in fluid communication with the reactor: (VII) a source of a strong acid in fluid communication with the reactor; and (VIII) a source of an acidic metal conditioner in fluid communication with the reactor.

This specification also describes polyether polyols produced using the methods and systems described herein.

Various features and characteristics of the inventions described in this specification may be better understood by reference to the accompanying figure, in which:
<FIG> is an illustration of a system for manufacturing polyether polyols, which is suitable for use in the processes of this specification.

Various embodiments are described and illustrated in this specification to provide an overall understanding of the structure, function, properties, and use of the disclosed inventions. It is understood that the various embodiments described and illustrated in this specification are non-limiting and non-exhaustive. Thus, the invention is not limited by the description of the various non-limiting and non-exhaustive embodiments disclosed in this specification. The features and characteristics described in connection with various embodiments may be combined with the features and characteristics of other embodiments. Such modifications and variations are intended to be included within the scope of this specification. The various embodiments disclosed and described in this specification can comprise, consist of, or consist essentially of the features and characteristics as variously described herein.

In this specification, other than where otherwise indicated, all numerical parameters are to be understood as being prefaced and modified in all instances by the term "about", in which the numerical parameters possess the inherent variability characteristic of the underlying measurement techniques used to determine the numerical value of the parameter. At the very least, each numerical parameter described in the present description should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Also, any numerical range recited in this specification is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of " <NUM> to <NUM>" is intended to include all sub-ranges between (and including) the recited minimum value of <NUM> and the recited maximum value of <NUM>, that is, having a minimum value equal to or greater than <NUM> and a maximum value equal to or less than <NUM>, such as, for example, <NUM> to <NUM>. Any maximum numerical limitation recited in this specification is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. All such ranges are intended to be inherently described in this specification.

The grammatical articles "one", "a", "an", and "the", as used in this specification, are intended to include "at least one" or "one or more", unless otherwise indicated. Thus, the articles are used in this specification to refer to one or more than one (i.e., to "at least one") of the grammatical objects of the article. By way of example, "a component" means one or more components, and thus, possibly, more than one component is contemplated and may be employed or used in an implementation of the described embodiments. Further, the use of a singular noun includes the plural, and the use of a plural noun includes the singular, unless the context of the usage requires otherwise.

As earlier indicated, in some implementations, this specification is directed to methods of preparing polyether polyols. Exemplary polyether polyols are polyether polyols and polyether ester polyols.

A system for manufacturing polyether polyols, which is suitable for carrying out processes of this specification, is illustrated in <FIG>, to which reference will now be made. As is seen, system <NUM> comprises reactor <NUM>. As also illustrated in <FIG>, system <NUM> comprises one or more sources of alkylene oxide(s) <NUM>, <NUM> in fluid communication with an inlet <NUM> of reactor <NUM>. Suitable alkylene oxides include any of those mentioned below, however, in some implementations, the system comprises a source of propylene oxide <NUM> and a source of ethylene oxide <NUM>. As illustrated, the ethylene oxide and propylene oxide may be mixed at or prior to reactor inlet <NUM>, though this is not required. In fact, in some implementations it may be desirable to isolate the source of propylene oxide <NUM> from the source of ethylene oxide <NUM>, which may be accomplished, for example, by dedicated piping or through appropriate valves.

The system <NUM> also includes a source of catalyst <NUM> that is in fluid communication with an inlet <NUM> of reactor <NUM>. Suitable catalysts include any material capable of catalyzing an epoxidation reaction, though, in some implementations, the catalyst source <NUM> is a source of an alkali metal hydroxide catalyst, such as any of those described below.

The system also includes a source of amine initiator <NUM> and a source of non-amine initiator <NUM>, each of which are in fluid communication with an inlet <NUM> of reactor <NUM>. Suitable amine initiators and non-amine initiators include any of those described below. It should be appreciated that, although <FIG> depicts only one source of amine initiator <NUM> and only one source of non-amine initiator <NUM>, more than one such initiator sources is of course possible, particularly where it is desirable that system <NUM> be capable of producing polyether polyols of various functionalities and molecular weights. Also, though <FIG> illustrates the possibility that two or more of amine initiator, non-amine initiator, and catalyst may be combined prior to entering inlet <NUM>, it may, and often is, desirable that the materials are not combined, particularly in the case of amine initiators and non-amine initiators. Therefore, it is of course possible that separate inlets <NUM> to reactor <NUM> are provided for each of the initiators and/or catalyst, or that other precautions are taken (such as through valves) to avoid mixing thereof.

The system <NUM> may also include a reactor pressurization source <NUM>, which may, for example, be a source of feeding pressurized nitrogen to reactor <NUM> via inlet <NUM>. In addition, system <NUM> may also include a water source <NUM> that may be a source of water to reactor <NUM> via inlet <NUM>, for example. In addition, the system may include a high pressure water source <NUM>, which may provide a source of water having a water pressure of <NUM> psi (<NUM> bar) to <NUM> psi (<NUM> bar), for example.

The system <NUM> further includes a source of a first acid <NUM> and a source of an acidic metal conditioner <NUM>. Suitable acids include any of those described below. First acid source may be in fluid communication with reactor <NUM> via inlet <NUM>. Source of acidic metal conditioner <NUM> may be in fluid communication with reactor <NUM> via inlet <NUM>, for example.

The reactor <NUM> may include discharge line <NUM> that is in fluid communication with recirculation loop <NUM>, recirculation loop <NUM>, and neutralization feed line <NUM>, in which neutralization feed <NUM> is in fluid communication with neutralization vessel <NUM>. Recirculation loop <NUM> may include external heat exchanger <NUM>. Recirculation loops <NUM> and <NUM> may be in fluid communication with reactor <NUM> via inlet <NUM>.

The source of a first acid <NUM> may also be in fluid communication with neutralization vessel <NUM>, via inlet <NUM>. In addition, water source <NUM>, which may be the same as or different from the water source <NUM>, may be in fluid communication with neutralization vessel <NUM> via inlet <NUM>. Neutralization vessel <NUM> may include a discharge line <NUM>, which may be in fluid communication with a system for further work-up of polyether polyol.

As previously indicated, an aspect of the invention described in this specification comprises preparing an amine-initiated polyether polyol in an equipment usable in the production of polyether polyols. This equipment usable in the production of polyether polyols is in particular a reactor, which term will be used in the following. A variety of amine-initiated polyether polyols can be produced according to the methods of this specification. For example, in some implementations, the amine-initiated polyether polyol produced according to the processes of this specification have a functionality of, for example, at least <NUM>, such as <NUM> to <NUM>, <NUM> to <NUM>, <NUM> to <NUM> or <NUM> to <NUM> or <NUM> to <NUM>. In certain implementations, the amine-initiated polyether polyol has a number average molecular weight of <NUM>/mol to <NUM>,<NUM>/mol, such as <NUM>/mol to <NUM>,<NUM>/mol, <NUM>/mol to <NUM>,<NUM>/mol, <NUM>/mol to <NUM>/mol, <NUM>/mol to <NUM>/mol, or <NUM>/mol to <NUM>/mol. In some embodiments, the amine-initiated polyether polyol produced according to the processes of this specification have a hydroxyl number of <NUM> to <NUM> KOH/g, <NUM> to <NUM> KOH/g, or, in some cases, <NUM> to <NUM> KOH/g.

As used herein, the term "functionality" refers to the average number of reactive hydroxyl groups, -OH, present per molecule of the polyether polyol that is being described. As used herein, the term "OH number" or "hydroxyl number" refers to the number of reactive hydroxyl groups available for reaction, and is expressed as the number of milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of the polyol, and is determined according to ASTM D4274-<NUM>. The term "equivalent weight" refers to the weight of a compound divided by its valence. For a polyol, the equivalent weight is the weight of the polyol that will combine with an isocyanate group, and may be calculated by dividing the molecular weight of the polyol by its functionality. The equivalent weight of a polyol may also be calculated by dividing <NUM>,<NUM> by the hydroxyl number of the polyol - Equivalent Weight (g/eq) = (<NUM> x <NUM>)/OH number.

The number average and weight average, Mn and Mw, respectively, molecular weights reported herein can be determined by gel-permeation chromatography (GPC) using a method described in DIN <NUM>-<NUM> of March <NUM> with a mixed bed column (Agilent PL Gel; SDVB; <NUM> micron Pore diameter: <NUM>×Mixed-E + <NUM> micron Pore diameter: 2xMixed-D), refractive index (RI) detection and calibrated with polyethylene glycol as the standard.

Amine-initiated polyether polyols that can be prepared according to certain methods of this specification can prepared by reacting an alkylene oxide with an amine-functional starter compound in the presence of an alkaline catalyst.

Suitable amine-functional starters have an amine functionality of at least <NUM>, such as <NUM> to <NUM>, or, in some cases, <NUM> to <NUM>. A primary amine, R-NH<NUM>, reacts with epoxides to give two hydroxyl groups. For example, RNH<NUM> can react with <NUM> moles of ethylene oxide to yield HO-CH<NUM>CH<NUM>-NR-CH<NUM>CH<NUM>OH. Therefore, an amine functionality of <NUM> in this case gives a polyol functionality of <NUM>.

Examples of suitable amines include, but are not limited to, aromatic amines, such as crude toluene diamine obtained by the nitration of toluene followed by reduction, <NUM>,<NUM>-toluene diamine, <NUM>,<NUM>-toluene diamine, <NUM>,<NUM>-toluene diamine, and <NUM>,<NUM>-toluene diamine or mixtures thereof; aniline; <NUM>,<NUM>'-methylene dianiline; methylene-bridged polyphenyl polyamines composed of isomers of methylene dianilines and triamines or polyamines of higher molecular weight prepared by reacting aniline with formaldehyde; ammonia; alkanol amines, such as monoethanol amine, diethanolamine, triethanolamine; aliphatic amines, such as methyl amine, ethylene diamine, diethylene triamine, and triethylene tetramine; and Mannich reaction products of phenol or substituted phenols with alkanol amines and formaldehyde or paraformaldehyde. Mixture of any two more of the foregoing amines may also be used, such as a mixture of <NUM>,<NUM>-toluene diamine and <NUM>,<NUM>-toluene diamine.

If desired, in addition to the amine-functional starter(s), other H-functional starters may be used to prepare the amine-initiated polyether polyol. In some implementations, for example, such additional starter(s) may comprise trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, <NUM>,<NUM>'-dihydroxydiphenyl-propane, sorbitol, sucrose, ethylene glycol, <NUM>,<NUM>- or <NUM>,<NUM>-propanediol, <NUM>,<NUM>-, <NUM>,<NUM>- or <NUM>,<NUM>-butanediol, <NUM>,<NUM>-heptanediol, <NUM>,<NUM>-hexanediol, <NUM>,<NUM>-cyclohexanedimethanol, <NUM>,<NUM>-cyclohexanedimethanol, <NUM>,<NUM>-cyclohexanedimethanol, <NUM>,<NUM>-cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, pentacyclopentadecanedimethanol, glycerin, pentaerythritol, <NUM>,<NUM>'-dihydroxy-diphenylpropane, or a mixture of any two or more of the foregoing. Oligomeric and/or polymeric polyols, such as polyether polyols, are also suitable starters, as are Mannich reaction products of phenol or substituted phenols with alkanol amines and formaldehyde or paraformaldehyde.

In some implementations, however, the amine, such as aromatic diamine, such as a toluene diamine (such as ortho-toluene diamine) starter is present in an amount of at least <NUM>% by weight, or, in yet other cases, at least <NUM>% by weight or at least <NUM>% by weight, based on the total weight of H-functional initiator used to prepare the amine-initiated polyether polyol.

Examples of alkylene oxides useful in producing the amine-initiated polyether polyols of certain methods of this specification include, without limitation, ethylene oxide, propylene oxide, butylene oxide, as well as mixtures of any two more thereof. The alkylene oxides may be added as mixtures or added sequentially to produce block copolymers. In some implementations, for example, first about <NUM>-<NUM>% of ethylene oxide is added, based on the total amount of alkylene oxide to be added, then about <NUM>-<NUM>% of propylene oxide is added, based on the total amount of alkylene oxide to be added.

Any material capable of catalyzing the epoxidation reaction may be used, specific examples of which include, but are not limited to, alkali metal hydroxides with <NUM> to <NUM> carbon atoms in the alkyl radical, such as, but not limited to, sodium methylate, sodium and potassium ethylate, potassium isopropylate and sodium butylate, and alkali hydroxides, such as sodium hydroxide, potassium hydroxide and cesium hydroxide. Such catalysts may be used individually or as mixtures of two or more thereof. In certain embodiments, the catalyst is used in an amount of <NUM> to <NUM> weight percent, <NUM> to <NUM> weight percent, or, in some cases, <NUM> to <NUM> weight percent, based on the weight of the finished polyether polyol.

The epoxidation reaction can occur by contacting the amine-functional starter with the alkylene oxide(s) at an elevated temperature in the range of, for example, <NUM> to <NUM>° C. under moderately elevated pressure in the presence of the catalyst.

In the cases of an alkaline-catalyzed epoxidation reaction, after the amine-initiated polyether polyol has been prepared, the resultant reaction mixture that contains the alkaline catalyst is often at least partially neutralized. In some implementations, for example, the amine-initiated polyether polyol is discharged from the reactor.

In certain implementations, the reaction mixture is neutralized with a hydroxy-carboxylic acid, though, as will be appreciated, other acids, such as inorganic acids, including sulfuric acid and/or phosphoric acid, could be used if desired. Neutralization may be accomplished by mixing the acid and reaction mixture at ambient conditions with stirring. Neutralization need not be exact neutrality. The reaction mixture may be maintained at a slight acidity or alkalinity, as desired. In some implementations, the neutralized catalyst is soluble in the polyether polyol so that the resulting amine-initiated polyether polyol may be used in polyurethane foam-forming equipment without subsequent treatment and without generating large amounts of solid waste material.

Examples of hydroxy carboxylic acids useful in the above-described neutralization step include lactic acid, salicylic acid, substituted salicylic acids, such as <NUM>-hydroxy <NUM>-methyl benzoic acid, <NUM>-hydroxy <NUM>-methyl benzoic acid and combinations thereof.

As indicated earlier, in some implementations, the processes of this specification comprise discharging the amine-initiated polyether polyol from the reactor. Various means may be used to discharge the amine-initiated polyether polyol from the reactor, such as by using a pump disposed in discharge line <NUM> or, as is the cases in the system illustrated in <FIG> the amine-initiated polyether polyol may be discharged from reactor <NUM> by pressurizing reactor <NUM> by feeding pressurized nitrogen from source <NUM>, which forces the amine-initiated polyether polyol out of reactor <NUM> via discharge line <NUM>.

Certain implementations of the processes of this specification comprise then cleaning the reactor by a cleaning process comprising: (<NUM>) contacting the reactor with an aqueous solution of a first acid; (<NUM>) contacting the reactor with an aqueous solution of an acidic metal conditioner; and (<NUM>) contacting the reactor with an aqueous solution of an alkali metal hydroxide; and (d) preparing a non-amine initiated polyether polyol in the reactor.

In certain implementations, prior to contacting the reactor with the aqueous solution of the first acid, the reactor may be conditioned to dissolve contaminants, such as residues of amine and/or the amine-initiated polyether polyol, remaining in the reactor following discharge of the amine-initiated polyether polyol. For example, in some implementations, this may be accomplished by charging water to the reactor <NUM> from water source <NUM> via inlet <NUM>. Water may be added in an amount to substantially fill the reactor <NUM>. As used herein, "substantially fill" means that sufficient water is added to the reactor to fill at least <NUM>% of the reactor volume. In some cases, sufficient water is added to fill at least <NUM>% or at least <NUM>% of the reactor volume. Heat may then be applied to the reactor <NUM> such that the water is heated to boiling, i.e., to at least <NUM>. The boiling water may then be agitated in the reactor <NUM> for a desired period of time, such as <NUM> minutes or more, before the water is discharged from reactor <NUM> and may, in some cases, be sent to wastewater, via wastewater feed <NUM>. If desired, the foregoing process may be repeated multiple times, such as at least <NUM> times, at least <NUM> times, or, in some cases, <NUM> to <NUM> times.

In addition, in some implementations, if desired, prior to contacting reactor <NUM> with the aqueous solution of the first acid, further contaminants may be removed from reactor <NUM> by applying a high pressure water wash to reactor <NUM>. This may be accomplished, for example, by spraying, via a hose and nozzle, highly pressurized (such as <NUM> psi to <NUM> psi [<NUM> bar to <NUM> bar]) water from high pressure water source <NUM> into reactor <NUM>. In some implementations, the interior of reactor <NUM> may by visually inspected (via a manway for example) and high pressure water sprayed into the reactor <NUM> in areas where visually observable contaminates are present. Water collected in reactor <NUM> from application of the high pressure water wash may be discharged from reactor <NUM>, such as to wastewater via wastewater feed <NUM>, or it may be allowed to remain in reactor <NUM> for the subsequent cleaning step.

Next, in some implementations, it may be desirable to apply a water wash to the reactor, as well as connecting piping and equipment, prior to prior to contacting reactor <NUM> with the aqueous solution of the first acid. This can be accomplished by, for example, substantially completely filling the volume of reactor <NUM> with water, which can be fed to reactor <NUM> via inlet <NUM> from water source <NUM>. As used herein, "substantially completely filling" means that water is added to reactor <NUM> in an amount sufficient to ensure that the top head of reactor <NUM> is contacted by the water, or, in other words, the entire volume of the reactor is filled with water. During the step, the water may be heated, such as to a temperature of at least <NUM> or at least <NUM> and allowed to mix in reactor <NUM> for a selected time period, such as at least <NUM> hour, at least <NUM> hours, or more, before the water is discharged from reactor <NUM> and may, in some cases, be sent to wastewater, via wastewater feed <NUM>.

As earlier indicated, the cleaning step of processes of this specification comprises contacting the reactor with an aqueous solution of a first acid. Any acid may be used for this purpose, however, in some implementations, the first acid comprises a strong acid. As used herein, the term "strong acid" refers to an acid that has a pKa of less than about -<NUM> at <NUM>. The strong acid can be an organic acid or an inorganic acid. Examples of strong acids include p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, trifluoroacetic acid, and perchloric acid. Mixtures of two or more acids can, of course, be used if desired.

In certain implementations, the aqueous solution of first acid used in the processes of this specification is a relatively dilute solution of the acid in water. For example, in some implementations, the aqueous solution of first acid comprises acid in an amount of no more than <NUM>% by weight, such as <NUM> to <NUM>% by weight, <NUM>% to <NUM> by weight, or, in some cases <NUM>% to <NUM>% by weight, based on the total weight of the aqueous solution.

The foregoing first acid treatment can be accomplished by, for example, substantially filling (as defined above) or, in some cases, substantially completely filling (as defined above), the volume of reactor <NUM> with the aqueous solution of first acid, in which the first acid may be fed to reactor <NUM> via inlet <NUM> from first acid source <NUM> and water may be fed to reactor <NUM> via inlet <NUM> from water source <NUM>. During the step, the aqueous solution of first acid may be heated, such as to a temperature of at least <NUM> or at least <NUM> and allowed to mix in reactor <NUM> for a selected time period, such as at least <NUM> hour, at least <NUM> hours, or more. In addition, the aqueous solution of first acid may be recirculated by discharging the aqueous solution out of reactor <NUM> via discharge line <NUM> and circulating it back to recirculation inlet <NUM> via line <NUM> or via line <NUM>, or via both lines <NUM> and <NUM>, by which the aqueous solution passes through heat exchanger <NUM>, thereby enabled the heat exchanger <NUM> to be exposed to the first acid treatment. The aqueous solution of first acid may then be discharged from reactor <NUM> and may, in some cases, be sent to wastewater, via wastewater feed <NUM>.

Next, according to certain implementations of the processes of this specification, reactor <NUM> is contacted with an aqueous solution of an acidic metal conditioner. As will be appreciated, acidic metal conditioners are often employed to remove oxidation and microscopically roughen a metal surface prior to painting. Acidic metal conditioners typically comprise an acid, such as phosphoric acid, and a surfactant, such as <NUM>-butoxyethanol, ethylene glycol and phosphates. In some implementations, the acidic metal conditioner may comprise <NUM>-<NUM>% by weight of phosphoric acid and <NUM>-<NUM>% by weight of surfactant, such as <NUM>-butoxyethanol, based on the total weight of the acid metal conditioner.

In some implementations, the acidic metal conditioner may also comprise a corrosion inhibitor. Any of a variety of corrosion inhibitors may be present, such as, for example, nitrogen-bases materials, sulfur-containing compounds, aldehydes, thioaldehydes, acetylenic compounds, and various alkaloids, such as papaverine, strychnine, quinine, and nicotine. A corrosion inhibitor is any component that functions to decrease or prevent the reaction of a metal with the acid that is present in the aqueous solution of acidic metal conditioner.

Any inorganic acid may be used in the acidic metal conditioner. In some implementations, however, the inorganic acid comprises a weak acid. As used herein, the term "weak acid" refers to compounds having a pKa of greater than <NUM>, such as <NUM>-<NUM>, or <NUM>-<NUM> at <NUM>. Specific examples of suitable weak inorganic acid include, but are not necessarily limited to, phosphoric acid, hydrofluoric acid, and boric acid.

Acidic metal conditioners suitable for use in the process of this specification are commercially available, one example of which is Oakite® <NUM>, commercially available from Chemetall US, Inc.

In certain implementations, the aqueous solution of acidic metal conditioner used in the processes of this specification comprises is a relatively dilute solution of the acidic metal conditioner in water. For example, in some implementations, the acidic metal conditioner is present in an amount of no more than <NUM>% by weight, such as <NUM> to <NUM>% by weight, <NUM>% to <NUM> by weight, or, in some cases <NUM>% to <NUM>% by weight, based on the total weight of the aqueous solution of acidic metal conditioner.

The foregoing acidic metal conditioner treatment can be accomplished by, for example, partially filling the volume of reactor <NUM> with the aqueous solution of acidic metal conditioner, in which acidic metal conditioner may be fed to reactor <NUM> via inlet <NUM> from acidic metal conditioner source <NUM> and water may be fed to reactor <NUM> via inlet <NUM> from water source <NUM>. As used herein, the term "partially filling" means that sufficient aqueous solution of acidic metal conditioner is added to reactor <NUM> to fill at least <NUM>% of the reactor volume, but, in some cases, less than <NUM>% of the reactor volume, such as, for example, <NUM> to <NUM>% of the reactor volume. During the step, the aqueous solution of acidic metal conditioner may be heated, such as to a temperature of <NUM> to <NUM>. In addition, the aqueous solution of acidic metal conditioner may be recirculated by discharging the aqueous solution out of reactor <NUM> via discharge line <NUM> and circulated back to recirculation inlet <NUM> via line <NUM> or via line <NUM> by which the aqueous solution passes through heat exchanger <NUM>, thereby enabled the heat exchanger <NUM> to be exposed to the acidic metal conditioner treatment. The aqueous solution of acidic metal conditioner may be allowed recirculate to reactor <NUM> for a selected time period, such as at least <NUM> hour, at least <NUM> hours, or more. The aqueous solution of acidic metal conditioner may then be discharged from reactor <NUM> and may, in some cases, be sent to wastewater, via wastewater feed <NUM>.

Next, in some implementations, reactor <NUM> may by conditioned to dissolve residues remaining from the foregoing treatments following discharge of the aqueous solution of acidic metal conditioner. For example, in some implementations, water may be charged to reactor <NUM> from water source <NUM> via inlet <NUM>. Water may be added in an amount to substantially fill the reactor <NUM> (as defined above). In some cases, sufficient water is added to fill at least <NUM>% or at least <NUM>% of the reactor volume. Heat may then be applied to the reactor <NUM> such that the water is heated to boiling, i.e., to at least <NUM>. The boiling water may then be agitated in the reactor <NUM> for a desired period of time, such as <NUM> minutes or more, before the water is discharged from reactor <NUM> and may, in some cases, be sent to wastewater, via wastewater feed <NUM>. If desired, the foregoing process may be repeated multiple times, such as at least <NUM> times, at least <NUM> times, or, in some cases, <NUM> to <NUM> times.

Next, according to implementations of the processes of this specification, reactor <NUM> is contacted with an aqueous solution of an alkali metal hydroxide. As used herein, the term "aqueous solution of an alkali metal hydroxide" refers to a solution comprising an alkali metal hydroxide and water.

Any alkali metal hydroxide may be used, however, in some implementations, the alkali metal hydroxide used comprises an alkali metal hydroxide that is also used as a catalyst in the epoxidation reaction that produces the amine-initiated polyether polyol and/or the non-amine-initiated polyether polyol that is made in reactor <NUM>. As a result, in some implementations, the aqueous solution of alkali metal hydroxide is created in reactor <NUM> by feeding an alkali metal hydroxide catalyst (which may itself comprise a solution of alkali metal hydroxide and water) to reactor <NUM> via inlet <NUM> from catalyst source <NUM> and water may be fed to reactor <NUM> via inlet <NUM> from water source <NUM>. Specific examples of suitable alkali metal hydroxides include, for example, sodium hydroxide, potassium hydroxide and cesium hydroxide.

In certain implementations, the aqueous solution of alkali metal hydroxide used in the processes of this specification is a relatively dilute solution of an alkali metal hydroxide in water. For example, in some implementations, the aqueous solution of alkali metal hydroxide comprises an alkali metal hydroxide in an amount of no more than <NUM>% by weight, such as <NUM> to <NUM>% by weight, <NUM>% to <NUM> by weight, or, in some cases <NUM>% to <NUM>% by weight, based on the total weight of the aqueous solution.

The foregoing alkaline treatment can be accomplished by, for example, at least partially filling (defined above) or substantially filling (defined above) the volume of reactor <NUM> with an aqueous solution of alkali metal hydroxide, in which the alkali metal hydroxide may be fed to reactor <NUM> via inlet <NUM> from catalyst source <NUM> and water may be fed to reactor <NUM> via inlet <NUM> from water source <NUM>. During the step, the aqueous solution of alkali metal hydroxide may be mixed and, if desired, heated in reactor <NUM>, such as to a temperature of, for example, up to <NUM>. In addition, the aqueous solution of alkali metal hydroxide may be recirculated by discharging the aqueous solution out of reactor <NUM> via discharge line <NUM> and circulated back to recirculation inlet <NUM> via line <NUM> or via line <NUM> by which the aqueous solution passes through heat exchanger <NUM>, thereby enabled the heat exchanger <NUM> to be exposed to the alkaline treatment. The aqueous solution of alkali metal hydroxide may be mixed in reactor <NUM> for a selected time period, such as at least <NUM> minutes or at least <NUM> minutes. The aqueous solution of alkali metal hydroxide may then be discharged from reactor <NUM> and may, in some cases, be sent to wastewater, via wastewater feed <NUM>.

Next, in some implementations, it may be desirable to again condition reactor <NUM> by removing residues remaining from the foregoing alkaline treatment following discharge of the aqueous solution of alkali metal hydroxide from reactor <NUM>. For example, in some implementations, this may be accomplished by charging water to the reactor <NUM> from water source <NUM> via inlet <NUM>. Water may be added in an amount to substantially fill the reactor <NUM> (as defined above). In some cases, sufficient water is added to fill at least <NUM>% or at least <NUM>% of the reactor volume. Heat may then be applied to the reactor <NUM> such that the water is heated to boiling, i.e., to at least <NUM>. The boiling water may then be agitated in the reactor <NUM> for a desired period of time, such as <NUM> minutes or more, before the water is discharged from reactor <NUM> and may, in some cases, be sent to wastewater, via wastewater feed <NUM>. If desired, the foregoing process may be repeated multiple times, such as at least <NUM> times, at least <NUM> times, or, in some cases, <NUM> to <NUM> times. In some cases, the wastewater may be analyzed for nitrogen content to determine the number of times to repeat this step. Ideally, the process is complete when no detectable nitrogen remains.

It has been discovered that the foregoing cleaning process can sufficiently eliminate amine contamination in a polyether reactor, such that the reactor is capable of being used to produce both amine-initiated polyether polyols and non-amine-initiated polyether polyols effectively. In other words, it is possible to produce non-amine initiated polyether polyols in the reactor without negatively impacted the color and alkalinity of the polyether polyol.

As a result, some implementations of the processes of this specification comprise preparing a non-amine initiated polyether polyol in the reactor. The non-amine initiated polyether polyols subject to the processes of the present invention can be prepared, for example, by a procedure in which one or more alkylene oxides having from <NUM> to <NUM> carbon atoms in the alkylene radical, such as <NUM> to <NUM> carbon atoms in the alkylene radical, and which are optionally substituted, are added to a starter molecule that contains at least <NUM>, such as <NUM> to <NUM>, or, in some cases, <NUM> to <NUM> active hydrogen atoms, in the presence of an alkaline catalyst. The processes of the present invention are suitable for removing water from a wide range of polyether polyols, in terms of their functionality, molecular weight and OH number. In certain embodiments, however, the processes of the present invention are particularly advantageous for use in connection with preparing non-amine initiated polyether polyols that have a number average molecular weight of at least <NUM>/mol, such as <NUM>/mol to <NUM>,<NUM>/mol, or, in some cases, <NUM> to <NUM>,<NUM>/mol, and a hydroxyl number of <NUM> to <NUM> KOH/gram.

Suitable alkylene oxides for preparing such non-amine initiated polyether polyols include, but are not limited to, butylene oxide, styrene oxide, ethylene oxide and propylene oxide. The alkylene oxides may be used individually, sequentially or as mixtures of two or more thereof. In certain embodiments, however, the processes of the present invention are particularly advantageous for use in connection with preparing non-amine initiated "active" polyether polyols, which, as used herein, refers to an ethylene oxide capped polyether polyol having terminal primary hydroxyl groups.

Suitable starter molecules for preparing such polyether polyols include polyols (including monomeric, oligomeric, and polymeric polyols), such as trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, <NUM>,<NUM>'-dihydroxydiphenyl-propane, sorbitol, sucrose, ethylene glycol, <NUM>,<NUM>- or <NUM>,<NUM>-propanediol, <NUM>,<NUM>-, <NUM>,<NUM>- or <NUM>,<NUM>-butanediol, <NUM>,<NUM>-heptanediol, <NUM>,<NUM>-hexanediol, <NUM>,<NUM>-cyclohexanedimethanol, <NUM>,<NUM>-cyclohexanedimethanol, <NUM>,<NUM>-cyclohexanedimethanol, <NUM>,<NUM>-cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, pentacyclopentadecanedimethanol, glycerin, pentaerythritol, <NUM>,<NUM>'-dihydroxy-diphenylpropane, or a mixture of any two or more of the foregoing. Oligomeric and/or polymeric polyols, such as polyether polyols, are also suitable starters. As will be appreciated, however, the non-amine initiated polyether polyols do not utilize a starter that has amine functionality.

In some implementations, an alkaline catalyst is used to prepare the non-amine initiated polyether polyol. Examples of such catalysts are alkali metal hydroxides with <NUM> to <NUM> carbon atoms in the alkyl radical, such as, but not limited to, sodium methylate, sodium and potassium ethylate, potassium isopropylate and sodium butylate, and alkali hydroxides, such as sodium hydroxide, potassium hydroxide and cesium hydroxide. Such catalysts may be used individually or as mixtures of two or more thereof. In certain embodiments, the catalyst is used in an amount of <NUM> to <NUM> weight percent, <NUM> to <NUM> weight percent, or, in some cases, <NUM> to <NUM> weight percent, based on the overall weight of the total reactant charge.

In some embodiments, the alkaline catalyst is neutralized in the presence of water. In certain cases, prior to any subsequent distillation, water is present in an amount of <NUM>% to <NUM>% by weight, such as <NUM>% to <NUM>% by weight, or, in some cases, <NUM>% to <NUM>% by weight or <NUM>% to <NUM>% by weight, based on the total weight of polyether polyol present.

In certain implementations, the alkaline catalyst is neutralized with an acid. Examples of suitable acids include, but are not limited to, sulfuric acid, phosphoric acid, carbonic acid, tartaric acid, lactic acid, acetic acid, citric acid, and DDBSA (dodecylbenzene sulfonic acid). The amount of acid employed is, in certain embodiments, from <NUM> to <NUM> equivalents of acid per equivalent of alkaline catalyst, such as <NUM> to <NUM> equivalent of acid per equivalent of alkaline catalyst, or, in some cases, <NUM> to <NUM> equivalent of acid per equivalent of alkaline catalyst.

After the crude polyol neutralization has ended, it may be desirable to add an antioxidant. Many antioxidants, especially those having phenolic hydroxyl groups, impart an unwanted color to alkaline crude polyols; therefore, they are usually added only after neutralization.

In some implementations, the removal of salts via filtration or sedimentation is preceded by, or conducted concurrently with, a distillation step to remove water. In some implementations, water is removed first under standard pressure and later under reduced pressure until pressure and temperature values where the residual water content in the polyol is within the specified limits have been attained, for example with the combination of a pressure of <NUM> mbar and a temperature of <NUM>. Such a distillation can also be interrupted for conduction of the filtration step, for example prior to entry into the reduced pressure phase. In this procedure, the fine distillation is conducted only after the filtration. The small amounts of water that remain after the standard pressure distillation are generally entirely soluble in the polyols, and so the salt at this time has already crystallized out virtually completely. Sometimes, quantitative salt formation is even possible virtually completely without removal of the water, for example when polyols having low equivalent molar masses are being worked up, these being entirely miscible with large amounts of water. In the workup process, it is also possible to promote salt removal via filtration through adsorbents. It may be advantageous to add such adsorbents prior to or during the removal of water, since they may be particularly effective when the polyol still has a certain water content. Adsorbents suitable for this purpose are, for example, sheet silicates (bentonite, attapulgite), diatomaceous earth (Celite) and synthetic magnesium silicate, such as AMBOSOL® or BriteSorb®.

In some implementations, the removal of the salt particles is effected via filtration and can be accomplished with the aid of a wide variety of different filtration apparatuses. On the industrial scale, what are called precoat filtrations are frequently conducted, in which the filtercake itself acts as the effective filter layer. In that case, the polyol containing salt particles is generally at first guided in circulation through the filtration apparatus until a filter cake having sufficient depth filter action has formed ("cloudy run time"), before the product, which then filters through as a clear liquid, is transferred into the final receiver. To promote the filtercake formation, a small amount of a filtration aid, for example cellulose fibers, can be added to the circulating polyol containing salt particles. Performance of such filtrations is frequently accomplished using candle filters, plate pressure filters or plate filters. Filtration operations can be optimized by the adjustment of process parameters, for example a sufficiently high pressure differential across the filter layer and a suitable viscosity controllable via the temperature. It will be appreciated that the removal of the neutralization salts formed is not restricted to the option of filtration, but can be undertaken by other methods, such as particle sedimentation, centrifugation or the like.

For salt-free and stabilized polyols which have been worked up to completion, handling and storage with exclusion of oxygen is often recommended. Inert gases suitable for this purpose are, for example, noble gases, nitrogen or carbon dioxide. The prevention of ingress of oxygen very substantially prevents product discoloration; especially at elevated temperatures, which are generally utilized to facilitate the handling of the finished products through lowering of the product viscosity. Furthermore, under an inert gas atmosphere, a much lower level of peroxide groups also arises, these contributing to cleavage of polyether chains to form further low molecular weight oxidative degradation products.

The amine-initiated and non-amine initiated polyether polyols described in this specification may be used in a variety of applications. For example, such polyols may be reacted with one or more isocyanates to provide polyurethane products including, but not limited to, coatings, adhesives, sealants, elastomers, foams, including flexible foams, and the like. Suitable organic polyisocyanates for forming such polyurethanes include unmodified isocyanates, modified polyisocyanates, and isocyanate prepolymers. Such organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanates of the type described, for example, by <NPL>. Examples of such isocyanates include those represented by the formula:.

in which n is a number from <NUM>-<NUM>, such as <NUM>-<NUM>, and Q is an aliphatic hydrocarbon group; a cycloaliphatic hydrocarbon group; an araliphatic hydrocarbon group; or an aromatic hydrocarbon group.

As should be apparent from the foregoing description, in some respects, this specification relates to methods of removing amine contaminants from equipment used in the production of polyether polyols. These methods comprise: (a) contacting the equipment with an aqueous solution of a first acid; (b) discharging the aqueous solution of the first acid from the equipment; (c) contacting the equipment with an aqueous solution of an acidic metal conditioner; (d) discharging the aqueous solution of the acidic metal conditioner from the equipment; (e) contacting the equipment with an aqueous solution of an alkali metal hydroxide; and (f) discharging the aqueous solution of the alkali metal hydroxide from the equipment.

As should also be apparent from the foregoing description, in some respects, this specification relates to systems for producing polyether polyols. These systems comprise: (I) a reactor; (II) a source of alkylene oxide in fluid communication with the reactor; (III) a source of alkali metal hydroxide catalyst in fluid communication with the reactor; (IV) a source of amine initiator in fluid communication with the reactor; (V) a source of non-amine initiator in fluid communication with the reactor; (VI) a water source in fluid communication with the reactor: (VII) a source of a strong acid in fluid communication with the reactor; and (VIII) a source of an acidic metal conditioner in fluid communication with the reactor.

An ortho-toluenediamine-initiated polyether polyol (functionality of <NUM> and hydroxyl number of about <NUM>/KOH g) was prepared using a system as generally depicted by <FIG>. The ortho-toluenediamine-initiated polyether polyol was prepared in reactor <NUM> and then discharged. Reactor <NUM> was filled with water to a level of about <NUM>% with agitation and the water in reactor <NUM> was heated to boiling, e.g., to around <NUM>. The boiling water was recycled to reactor <NUM> by passing via lines <NUM>, <NUM> and <NUM> for <NUM> minutes. Thereafter, the water was emptied to wastewater via line <NUM>. Reactor <NUM> was then opened and visually inspected. A high pressure spray water wash of reactor <NUM> was then conducted by spraying the inside of reactor <NUM> with <NUM>-<NUM> psi (<NUM>-<NUM> bar) water via a hose inserted inside the manway of reactor <NUM>. Then, reactor <NUM> was overfilled (reactor <NUM> was filled to a <NUM>% level and then allowed to overfill into connected piping and equipment to ensure that the top head surface of reactor <NUM> and seals were all touched with water) with water and the water was agitated and heated to around <NUM> for about <NUM> hours. Thereafter, the water was emptied to wastewater via line <NUM>.

A glycerine-initiated polyether polyol (functionality of <NUM> and hydroxyl number of about <NUM>/KOH g) was then prepared in reactor <NUM>. The resulting polyol had a cloud point of <NUM>, an alkalinity, determined by visual titration, of <NUM>, and an APHA color of <NUM>.

Following discharge of the glycerine-initiated polyether polyol, reactor <NUM> was charged with a water/dilute sulfuric acid solution (e.g. <NUM>-<NUM>% sulfuric acid) to a level higher than the level of any product recipe used in reactor <NUM>. Thereafter, the water/dilute sulfuric acid solution was emptied to wastewater via line <NUM>.

Reactor <NUM> was then filled a level of about <NUM>% with a mixture of water of Oakite® <NUM> (which is a mixture of phosphoric acid and <NUM>-butoxyethanol), using a ratio of about <NUM> gallons (<NUM><NUM>) of Oakite to <NUM>,<NUM> lb (<NUM>,<NUM>) water. The mixture was heated to about <NUM>-<NUM> and circulated through the recycle loop and external heat exchanger (via lines <NUM>, <NUM> and <NUM>) for about <NUM> to <NUM> hours. Thereafter, the Oakite/water mixture was emptied to wastewater via line <NUM>.

Reactor <NUM> was then filled with water to a level of about <NUM>% with agitation and the water in reactor <NUM> was heated to boiling, e.g., to around <NUM>. The boiling water was recycled to reactor <NUM> by passing via lines <NUM>, <NUM> and <NUM> for <NUM> minutes. Thereafter, the water was emptied to wastewater via line <NUM>.

A mixture of <NUM>% potassium hydroxide (about <NUM> pounds (<NUM>)) and water (about <NUM>,<NUM> pounds (<NUM>,<NUM>)) was then charged to reactor <NUM> and mixed for about <NUM> minutes. The potassium hydroxide/water mixture was then emptied to wastewater via line <NUM>.

Reactor <NUM> was then again filled with water to a level of about <NUM>% with agitation and the water in reactor <NUM> was heated to boiling, e.g., to around <NUM>. The boiling water was recycled to reactor <NUM> by passing via lines <NUM>, <NUM> and <NUM> for <NUM> minutes. Thereafter, the water was emptied to wastewater via line <NUM>. This process was repeated <NUM>-<NUM> times.

Claim 1:
A method of removing amine contaminants from equipment used in the production of polyether polyols, comprising:
(a) contacting the equipment with an aqueous solution of a first acid;
(b) discharging the aqueous solution of the first acid from the equipment;
(c) contacting the equipment with an aqueous solution of an acidic metal conditioner;
(d) discharging the aqueous solution of the acidic metal conditioner from the equipment;
(e) contacting the equipment with an aqueous solution of an alkali metal hydroxide; and
(f) discharging the aqueous solution of the alkali metal hydroxide from the equipment.