MX2008009070A - Activated carbon monoliths and methods of making them - Google Patents

Abstract

Resol beads are disclosed that are prepared in high yield by reaction of a phenol with an aldehyde, with a base as catalyst, in the presence of a colloidal stabilizer, and optionally a surfactant. The resol beads have a variety of uses and may be carbonized and activated to form activated carbon monoliths.

Description

ACTIVATED CARBON MONOLITHES AND METHODS FOR MAKING THEM Field of the Invention The present invention relates to resol accounts and to methods for making and using them to form activated carbon monoliths. BACKGROUND OF THE INVENTION Phenol-formaldehyde resins are polymers prepared by reacting a phenol with an aldehyde in the presence of an acid or a base, the base-catalyzed phenolic resins which are classified as phenolic resins of resole type. A typical resol is made by reacting phenol with an excess of formaldehyde, in the presence of a base such as ammonia, to produce a mixture of methyl phenols that condense on heating to produce low molecular weight prepolymers, or resoles. . In heating the resols at elevated temperature under basic, neutral or slightly acidic conditions, a high molecular weight network structure of phenolic rings, linked by methylene groups and typically retaining methyl groups, is produced. GB 1,347,878 discloses a process in which the phenol or a phenol derivative is condensed with formaldehyde in aqueous solution, in the presence of a catalyst which is an organic or inorganic base, and in a homogeneous phase to obtain a resin in the form of a suspension of oily droplets in the reaction medium, the suspension being stabilized by the addition of a dispersing agent which prevents coalescence of the droplets. The process described results in spherical beads of phenolic resin that can be separated, washed, and dried, which are said to be useful for a variety of purposes, for example as filling material or to lighten the weight of such traditional materials as cement. or plaster. GB 1,457,013 discloses cellular, spherical accounts having a high carbon content, containing a plurality of closed cells, wherein the walls of the peripheral cells form a continuous thin layer marking the boundaries of the outer surface. The beads can be comprised of an organic precursor material, which can be a phenoplast and the process by which they are made includes a carbonization step. U.S. Patent No. 3,850,868 discloses reacting urea or phenol and formaldehyde in a basic aqueous medium to provide a prepolymer solution, mixing the prepolymer in the presence of a protective colloid forming material, subsequently acidifying the basic prepolymer solution so that the particles are formed and precipitated in the presence of a colloid forming material, such as spheroidal beads, and finally collect and, if desired, dry the particulate beads of urea or phenol formaldehyde. The resulting beads are said to have a high opacifying efficiency which makes them suitable for low gloss coating compositions. U.S. Patent No. 4,026,848 discloses aqueous resol dispersions produced in the presence of ghatti gum and a thickening agent. The dispersions are said to have increased utility in such end-use applications as coatings and adhesives. U.S. Patent No. 4,039,525 discloses aqueous resol dispersions produced in the presence of certain hydroxyalkylated gums, such as hydroxyalkylated guar gums, as interfacial agents. U.S. Patent No. 4,206,095 discloses particulate resoles produced by reacting a phenol, formaldehyde, and an amine in an aqueous medium containing a protective colloid, to produce an aqueous suspension of a particulate resole, and recovering the particulate resole from the suspension. U.S. Patent No. 4,316,827 discloses ream compositions useful as friction particles including a mixture of tri- and / or tetrafunctional and difunctional phenols, an aldehyde, an optional reaction promoter compound, a protective colloid and a rubber. In a first stage condensation reaction, the rubber can be incorporated either inside or incorporated into the surface of the particles of beef a. The condensation product is subjected to a second stage under acidic conditions, which results in a product in particulate form which is said to require no grinding or screening when used as a friction particle. U.S. Patent No. 4,366,303 discloses a process for producing particulate res ress which comprises reacting formaldehyde, phenol and an effective amount of hexamethylenetetramma or a compound containing amino hydrogen, or mixtures thereof, in an aqueous medium containing an effective amount of a protective colloid for a sufficient time to produce a dispersion of a particulate resole ream; cooling the reaction mixture below about 40 ° C; reacting the cooled reaction mixture with an alkaline compound to form alkaline dipnates; and recovering from the aqueous dispersion a ream exhibiting increased curing rates and increased sinterability. U.S. Patent No. 4,182,696 discloses molding compositions containing filler, heat reagent, solid particulate which are produced directly by reacting a phenol, formaldehyde, and an amine in an aqueous medium containing a water-soluble filler material having sites reagents on the surface thereof that chemically binds with a phenolic resin and a protective colloid to produce an aqueous suspension of a resole containing particulate filler, and recover the resole containing filler from the suspension. The filler materials can be in the form of fibrous or non-fibrous particles and can be inorganic or organic. U.S. Patent Nos. 4,640,971 and 4,778,695 disclose a process for producing a resole ream in the form of microspheres particles of a size not exceeding 500 μm by polyeprating phenols and aldehydes in the presence of a basic catalyst and an inorganic salt substantially soluble in water. Water. Preferred inorganic salts, which include calcium fluoride, magnesium fluoride, and strontium fluoride, partially or completely cover the surface of the resulting microspheres particles. U.S. Patent No. 4,748,214 discloses a process for producing micro-cured phenolic res resin particles having a particle diameter of no more than about 100 μm by reacting a novola ream, a phenol, and an aldehyde in an aqueous medium in the presence of a basic catalyst and an emulsion stabilizer. The ream novolak used in the process is obtained by heating a phenol and an aldehyde in the presence of an acidic catalyst such as hydrochloric acid or acid oxalic to carry out the polymerization, by dehydrating the polymerization product ba or reduced pressure, by cooling the product and by spraying it coarsely. U.S. Patent No. 4,071,481 discloses phenolic foams, mixtures for producing them and their manufacturing processes. The ream used is a base catalyzed polycondensation product of phenol and formaldehyde which is obtained in a substantially anhydrous, meltable, reactive, solid state. The ream is foamed and hardened by the application of heat without the use of a catalyst. Heat-sensitive blowing agents, either in liquid form or in particulate form can be mixed with the ream prior to heating. Surfactants and lubricants can be used to increase the uniformity of the voids in the foam. The resulting foams are said to be non-acidic, resistant to color changes and substantially anhydrous. U.S. Patent No. 5,677,373 discloses a process for producing a dispersion, wherein the dispersed slightly crosslinked polyamyl seed particles are swollen with an ionizing liquid, the seed particles containing covalently bonded ionizable groups cause a hmchamiento of the seed particles. by the ionizing liquid to form a dispersion of droplets, where the resulting droplets after the They have a volume that is at least five times that of the seed particles. The zing liquid can be or contain a polymerizable monomer or can be charged with such a monomer. The polymerizatof the monomers is said to take place in the droplets during or after the quenching, to form polymer particles. Chinese Patent Disclosure No. CN 1240220A discloses a method for manufacturing a spherical activated carbon based on phenol-formaldehyde ream which includes mixing together a ream of linear phenol-formaldehyde and a curing agent to form a block mixture, crushing the mixing the block to form particles of a ream raw material, dispersing the ream raw material in a dispersliquid containing a dispersing agent, emulsifying the material to form spheres, and carbonizing and activating the resulting spheres. JP 63-48320 A discloses a method for manufacturing a particulate phenolic ream, in which a particulate material obtained from a condensatproduct that is added around a core substance is produced by subjecting a phenol and an aldehyde to a condensatreactin the presence of a dispersant and the core substance. The particulate material is then dehydrated and dried. The core substance can be either an organic or inorganic material. The particulate material obtained is characterized as being relatively soluble in acetone. Japanese Patent PublicatNo. JP 10-338511A discloses a spherical phenolic resin having a particle diameter of 150 to 2,500 μm obtained by condensing phenols and aldehydes in the presence of a dispersant with a core material, by causing the product of condensatadded around the core material. A phenolic resin, glass granules, SiC, mesophase coal, alumina, graph, and phlogopite, are said to be useful as a core material. Spherical beads comprised of phenolic polymers can thus be made using various methods and have a variety of uses and, while for many uses particle size and particle size distributmay not be especially important, for some uses, the size of particle can be a very important factor, for example, when a charred product is desired to have particular transport or adsorptproperties. It may also be important to obtain particles having a relatively small particle size distribut for example when the bulk flow properties of a char are important, such as to facilitate the flow of the particles, or when The predictable packing of the particles is necessary or useful. For example, the North American patent publicat No. 2003/0154993 Al, which discloses cigars that include a tobacco rod and a filter component having a cavity filled with carbon formed into spherical beads, emphasizes the importance of obtaining point-to-point contact between the spherical beads together with the substantially complete filling of the cavity in order to produce minimal channeling of the ambulatory gas phase as well as maximum contact between the gas phase and the carbon surface of the spherical beads during smoking. For these and other uses, obtaining a desired particle size and shape and particle size distributcan be an important factor in the economic viability of a spherical polymer account in the market. There still remains a need in the art for resol resolves useful in a variety of products, which overcome the various disadvantages of those currently known in the art. BRIEF DESCRIPTOF THE INVENTIn one aspect, the inventrelates to processes for producing activated carbon monoliths, wherein the processes include: reacting a phenol with an aldehyde in a stirred aqueous medium provided with a base such as catalyst, a colloidal stabilizer, optionally a surfactant, and previously formed resol solders, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; optionally compact the aqueous dispersion of resol beads; and carbonize and activate the resol accounts to obtain a monolith of activated carbon. In another aspect, the invention relates to processes for producing activated carbon monoliths, wherein the processes include: providing a stirred aqueous reaction mixture with a phenol, a portion of an aldehyde, a portion of a base as a catalyst, a colloidal stabilizer, optionally a surfactant and previously formed resol solders; reacting in the reaction mixture for a period of time and at a temperature sufficient to produce an aqueous dispersion of partially formed resol solids; then adding a remaining portion of the aldehyde and a remaining portion of the base to obtain a resol monolith; optionally compact the resol monolith; and carbonizing and activating the resol monolith to obtain an activated carbon monolith. Still another aspect of the invention relates to processes for producing an activated carbon monolith, in which the processes include; provide a portion of a phenol, a portion of an aldehyde, and a portion of a base as a catalyst to a reaction mixture which is a stirred aqueous medium including a colloidal stabilizer, optionally a surfactant, and previously formed resol solders; reacting for a period of time and at a temperature sufficient to produce an aqueous dispersion of partially formed resol solids; then provide an additional portion of the phenol; a further portion of the aldehyde, and an additional portion of the base to the reaction mixture and reacting for an additional period of time; then adding any remaining portion of the phenol, the aldehyde, and the base for a period of time and at a temperature sufficient to obtain a resol monolith; optionally compact the resol monolith; and carbonizing and activating the resol monolith to obtain an activated carbon monolith. In yet another aspect, the invention relates to activated carbon monoliths made by processes including: reacting a phenol with an aldehyde in a stirred aqueous medium provided with a base such as a catalyst, a colloidal stabilizer, optionally a surfactant, and resol previously formed, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resol solids; optionally compact the aqueous dispersion of resol beads; and carbonize and activate the resol accounts for get a monolith of activated carbon. A further aspect of the invention relates to activated carbon monoliths made by processes including: providing a stirred aqueous reaction mixture with a phenol, a portion of an aldehyde, a portion of a base as a catalyst, a colloidal stabilizer, optionally a surfactant and previously formed resol accounts; reacting in the reaction mixture for a period of time and at a temperature sufficient to produce an aqueous dispersion of partially formed resol solids; then adding a remaining portion of the aldehyde and a remaining portion of the base to obtain a resol monolith; optionally compact the resol monolith; and carbonizing and activating the resol monolith to obtain an activated carbon monolith. Another aspect of the invention relates to activated carbon monoliths made by processes including: providing a portion of a phenol, a portion of an aldehyde, and a portion of a base as a catalyst to a reaction mixture which is a stirred aqueous medium which includes a colloidal stabilizer, optionally a surfactant, and previously formed resol counts; reacting for a period of time and at a temperature sufficient to produce an aqueous dispersion of partially formed resol solids; then provide a portion additional phenol, an additional portion of the aldehyde, and an additional portion of the base to the reaction mixture and reacting for an additional period of time; then adding any remaining portion of the phenol, the aldehyde, and the base for a period of time and at a temperature sufficient to obtain a resol monolith; optionally compact the resol monolith; and carbonizing and activating the resol monolith to obtain an activated carbon monolith. DETAILED DESCRIPTION OF THE INVENTION The present invention can be more easily understood by reference to the following detailed description of the invention, and to the examples provided. It will be understood that this invention is not limited to the specific processes and conditions described, because the specific processes and process conditions for processing articles according to the invention may vary. It is also to be understood that the terminology used is for the purpose of describing only particular modalities and is not intended to be limiting. As used in the specification and in the claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. By "comprising" or "containing" the inventors they imply that at least the compound, element, particle, etc. named must be present in the composition or article, but do not exclude the presence of other compounds, materials, particles, etc. even if such other compounds, materials, particles etc. They have the same function as the one named. In one aspect, the invention relates to resol beads comprising the reaction product of a phenol with an aldehyde, reacted in a basic stirred aqueous medium containing previously formed resol solders, a colloidal stabilizer and optionally a surfactant. The previously formed resol counts, also referred to herein as pre-formed beads and as seed particles, aid in obtaining a desired particle size and particle size distribution. The processes according to the invention can be carried out in the form of batches, in the form of semi-batches, or continuously, as is further described below. In a typical batch process, resol counts can be prepared, for example, by combining in a stirred aqueous medium a phenol and an aldehyde, in the presence of previously formed resol solders, a base such as ammonium hydroxide as a catalyst. , a colloidal stabilizer such as sodium carboxymethylcellulose, and optionally a surfactant such as sodium dodecyl sulfate. sodium, and react them together at a sufficient temperature and time to obtain the desired product. In semi-batch processes, one or more of the above may be added to the reaction mixture during the course of the reaction. In one aspect, the invention thus relates to resol beads having a desired particle size and particle size distribution, the resol beads comprising the reaction product of a phenol and an aldehyde, reacted in the presence of a base as a catalyst, for example in a stirred, basic aqueous medium that includes a colloidal stabilizer and optionally a surfactant. In yet another aspect, the invention relates to processes for producing resol beads, processes that include a step of reacting a phenol with an aldehyde, in the presence of a base as a catalyst, in a stirred aqueous medium that includes a stabilizer colloidal, and optionally a surfactant, in the presence of previously formed resol counts, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resol sols. The previously formed resol accounts can be obtained, for example, as smaller resol accounts produced in u? previous batch, or in the case of a continuous or semi-continuous process, such as recycled accounts obtained at any previous point in the process In still another aspect, the invention relates to processes for producing resol beads, the processes including: a) reacting a phenol with an aldehyde in the presence of a base as a catalyst, in a stirred aqueous medium including a colloidal stabilizer , and optionally a surfactant, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; b) recover the water-insoluble resol solids of the aqueous dispersion; c) separate the accounts below a minimum particle size; and d) recycling the beads below a minimum particle size to the aqueous medium of step a). In still another aspect, the invention relates to processes for producing resol beads, the processes including: a) reacting a phenol with an aldehyde in the presence of a base as a catalyst, in a stirred aqueous medium including a colloidal stabilizer , and optionally a surfactant, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; b) recovering insoluble resol solids in water above a minimum particle size of the aqueous dispersion; and c) retain or recycle the accounts below a minimum particle size in the aqueous dispersion of the resol accounts. In yet another aspect, the invention relates to processes for producing resol beads, the processes including: a) reacting a phenol with an aldehyde in the presence of a base as a catalyst, in a stirred aqueous medium including a colloidal stabilizer , and optionally a surfactant, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; b) recovering insoluble resol solids in water above a minimum particle size of the aqueous dispersion; and c) retaining or recycling the beads within a range of desired particle size in or to the aqueous dispersion of the resol values. The resol accounts of the invention may have a variety of particle sizes and particle size distributions. The accounts can be cured or partially cured, and then used or processed additionally, such as by carbonization and activation, to obtain, for example, activated carbon beads. In the processes according to the invention, the reagents can be combined in a batch process, or one or more of the reagents or catalysts can be added over time, alone or together, in half-batches mode. In addition, the processes according to the invention can be carried out continuously or semi-continuously, in a variety of reaction vessels and with a variety of agitation means, as is further described herein. Thus, in one aspect, the invention relates to processes for producing resol beads, processes that include a step of providing a phenol, at least a portion of an aldehyde, and at least a portion of a base as a catalyst. a reaction mixture which is a stirred aqueous medium including a colloidal stabilizer, optionally a surfactant, and previously formed resol solders; reacting them for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; and then adding any remaining portion of the base and the aldehyde for a period of time, such as about 45 minutes. Previously formed resolvable accounts can be obtained, for example, as smaller resol accounts produced in a batch prior, or in the case of a continuous or semi-continuous process, such as recycled accounts obtained at any point early in the process. In still another aspect, the invention relates to processes for producing resol accounts, processes that include a step of providing at least a portion of a phenol, at least a portion of an aldehyde, and at least a portion of a base as a catalyst to a reaction mixture which is a stirred aqueous medium including a colloidal stabilizer, optionally a surfactant, and previously formed resol solder beads; reacting them for a period of time and at a temperature sufficient to produce an aqueous dispersion of resol beads, for example up to about two hours; then an additional portion of phenol, an additional portion of the aldehyde, and an additional portion of a base as a catalyst are added to the reaction mixture and reacted, for example for an additional two hours; and then adding any remaining portion of the phenol, the aldehyde, and the base for a period of time and at a temperature sufficient to obtain the desired resol values. The previously formed resol accounts can be obtained, for example, as larger resol accounts produced in a previous batch in the case of a continuous or semi-continuous process, such as recycled accounts obtained in any previous point of the process In yet another aspect, the processes of the invention can be carried out as already described, with a further portion of an added base after the reactants have begun to react, or even when the reaction is otherwise substantially completed, the base which is the same as or different from that added to the reaction mixture as a catalyst for the reaction. Alternatively, an acid portion can be added after the reaction is initiated or substantially completed, or the processes described can be followed by a curing period at an elevated temperature. In one aspect, the invention relates to processes for producing resol beads, the processes including: a) reacting a phenol with an aldehyde in the presence of a base as a catalyst, in a stirred aqueous medium including a colloidal stabilizer, and optionally a surfactant, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; b) recover the water-insoluble resol solids of the aqueous dispersion; c) separate the accounts below a minimum particle size; and d) recycle the accounts below a size of minimum particle to the aqueous medium of stage a), wherein the accounts that are recycled are not further processed, for example by thermal curing, treatment with either an acid or a base, or by coating the beads, prior to being recycled . Thus, in one aspect, previously formed beads to be recycled are not further cured prior to recycling, for example by thermal curing. Similarly, in another aspect, the previously formed beads to be recycled are not treated, for example with an acid or a base and are at most removed from the reaction mixture and rinsed with water prior to recycling. In another aspect, the pre-formed beads to be recycled are not substantially dried prior to being recycled, but are simply provided to the reaction mixture in a wet state with water as a result, for example, of physical filtration of the material, optionally with classification carried out, based on the size of the particles. In a similar aspect, previously formed beads are not coated prior to recycling with an additional material such as, for example, a wax, carnauba wax, gum arabic, or the like, prior to recycling. In this aspect, the recycled accounts are not covered in this way prior to being recycled. In one aspect, the resol accounts of the invention, when isolated from the reaction mixture in which they are formed, and optionally washed only with water, include measurable amounts of nitrogen, derived for example from the use of ammonia or ammonium hydroxide as a catalyst, either as such or provided by hexamethylenetetramine used as a source of both ammonia and formaldehyde. In various aspects, the amount of nitrogen present in the resol counts of the invention isolated from the reaction mixture can be, for example, at least 0.5% nitrogen, or at least 0.8%, or at least 1% , up to about 2.0% nitrogen, or up to 2.5%, or up to 2.6%, or up to 3%, or more, of nitrogen. The amount of nitrogen can be measured, for example, as elemental analysis carried out using a ThermoFinnigan Elementary Analyzer FlashEA ™ 112. In a particular aspect, the amount of nitrogen is from about 1% to about 2.6%, based on elemental analysis carried out on a ThermoFinnigan FlashEA ™ 112 Elemental Analyzer. Resole beads of the invention isolated from the reaction mixture are further characterized as containing material, including phenol, hydroxymethyl phenol, and oligomers, which can be extracted in methanol. The extractable material includes nitrogen, typically in an amount less than about 1.1% nitrogen, by weight of the resol accounts The total amount of extractable material typically comprises, for example, from about 1% to about 20%, or from 3% to 15%, of the mass of the resin beads. Interestingly, the inventors have found that the extraction of this material does not substantially affect the recyclability of the accounts, that is, the use of accounts previously formed as seeds. Without wanting to be related by theory, the recyclability of the accounts appears instead to be a function of the degree of crosslinking in the resin account. Thus, in one aspect, the previously formed resol counts useful according to the invention are relatively insoluble in methanol, that is, they are soluble in amounts of up to about 15% by weight, or up to about 20% by weight, or up to about 25% by weight, in each case based on the weight of the accounts prior to the extraction with methanol. The inventors have found that the resol accounts of the invention useful as previously formed accounts are typically yellow in color, based upon visual inspection. This is contrasted with the cured beads, which typically appear to be light brown, tan-colored, or red in color. The reason for this is not clear, but this phenomenon in the same way appears to be a function of the amount of crosslinking in the resol polymer. In another aspect, the inventors have found that active beads, that is, beads that are useful as seeds, or pre-formed beads, typically have a Tg of from about 30 ° C to about 120 ° C, or from about 30 ° C to about 68 ° C, as measured by DSC. This is contrasted with accounts that have lost substantial activity such as previously formed accounts, and are characterized as having non-measurable Tg. As the solubility of methanol is found, this is observed to be a measure of the crosslinking of the resol polymer from which the beads are formed. In yet another aspect, previously formed beads that are useful as seeds are typically inflatable in DMSO to at least 110% of their original diameter. This, in the same way, is a measure of cross-linking. Previously formed accounts that have lost substantial activity as seeds typically do not swell appreciably in DMSO. Without wishing to be related by theory, this also appears to be a function of the amount of cross-linking. Resole beads of the invention, for example when isolated as an aqueous suspension of resol solids from a reaction mixture in which they are formed, are relatively insoluble in acetone. This relative insolubility in acetone in the same way can be considered as a measure of the degree of polymerization or crosslinking that has occurred in the beads. The solubility in acetone of the obtained resol solvents can thus be, for example, no more than about 5%, or no more than 10%, or no more than 15%, or no more than 20%, or no more than 25%. %, or not more than 26%, or not more than 30%, or not more than 45%, in each case as measured by the comparison of the weight of the residue produced by the evaporation of the acetone solvent to the starting weight of the accounts Alternatively, the amount of acetone solubility may be from about 5% to about 45%, or from 10% to 30%, or from 10% to 26%, in each case as measured by the comparison of the weight of the waste produced by the evaporation of the acetone solvent to the starting weight of the beads. Factors believed to affect the amount of acetone solubility include the temperatures at which the reaction is carried out, and the length of time during which the reaction is carried out. Advantages to avoid substantial amounts of acetone solubility include product handling, eg drying and storage. Accounts that have substantial acetone solubility would be expected to be difficult to process, for example by sticking with one another and forming agglomerations Resole beads of the invention are further characterized as being relatively infused, that is, resistant to melting. Thus, when the beads are heated, the resin does not flow, but eventually it produces a carbon. This property in the same way is a function of the degree of polymerization or crosslinking that has taken place in the beads, and can be considered characteristics of the resol polymers as distinguished from novolak polymers, in which substantial crosslinking requires the use of a separate crosslinking agent, often called a curing agent. Similarly, the resol cores of the invention do not deform substantially when shear is applied, but rather tend to break apart or fragment. This, likewise, is an indication of substantial cross-linking that has taken place. The density of the resolved resole beads of the reaction mixture is typically at least 0.3 g / mL, or at least 0.4 g / mL, or at least 0.5 g / mL, up to about 1.2 g / mL or up to about - 1.3 g / mL, or from approximately 0.5 to approximately 1.3 g / mL. In still another aspect, the invention relates to activated carbon beads having a size of desired particle and particle size distribution, the activated carbon beads comprising the reaction product of a phenol with an aldehyde as already described, for example carried out in the presence of a base as a catalyst, reacted in an aqueous medium agitated including a colloidal stabilizer, and optionally a surfactant, and then heat treated, stirred, charred, and activated, via one or more intermediate processing steps, as further described herein. In yet another aspect, the invention relates to methods for producing the activated carbon beads precisely described. Thus, in one aspect, the invention provides resol beads having a relatively small size distribution in high yield by the reaction of phenol, formaldehyde, and ammonia in an aqueous environment in the presence of a protective colloidal stabilizer, the improvement that is the addition of previously formed resol accounts that have a limited size distribution and a size smaller than the size of the desired product. In yet another aspect, the invention relates to processes for producing resol beads, processes that include a step of reacting a phenol with an aldehyde in the presence of a base as catalyst, in a agitated aqueous medium including a colloidal stabilizer, and optionally a surfactant, in the presence of previously formed resol solids, wherein the amount of methanol in the reaction mixture is limited. Methanol is typically present in formaldehyde solutions and acts as an inhibitor to prevent para-formaldehyde from being precipitated from the solution. The inventors have found that limiting the amount of methanol in the reaction mixture of such processes can, in some embodiments, give advantages in terms of the particle size distribution that are formed, resulting in a larger portion of larger sized beads. . These larger sized beads may be desirable for downstream processing, as they produce a carbonized product with desirable adsorption properties, and the size of the particles provides easier processing of the particles during manufacture and use. In yet another aspect, the invention relates to activated carbon monoliths made by a process in which the resol beads, which still contain a reactive surface, for example by omitting or modifying the heating step as just described, are isolated and they are dried at a relatively low temperature, for example 100 ° C or less, or at 75 ° C or less, or at 50 ° C or less, or at about 45 ° C, or even less. The accounts are then they can carbonize, for example without significant agitation, and with or without compaction, at a temperature of at least about 500 ° C, such that cross-linking occurs in the beads, and at the points of contact between the beads, resulting in the formation of a resol monolith. Other additives may be included but are not required in order to obtain the resol monolith. The resulting resol monolith can be activated, for example in steam or carbon dioxide for a period of time and at a temperature, for example from about 800 ° C to about 1,000 ° C or more, sufficient to form an activated carbon monolith with microporous solids and an interstitial network of macropores / transport pores based on the particle size and particle size distribution of the used resol counts. The carbonization and activation steps can be combined, in those cases in which the carbonization conditions are also suitable for activation. The resulting activated carbon monolith can be used, for example, for gas phase or storage adsorption, or as a gas supply system. The activated monoliths according to the invention are not particularly limited with respect to size, and the size of the monoliths can vary within a wide range. For example, the size of the monolith may be entirely a function of the lot size of the accounts of resol that is used to form the monolith, with the practical limit that is the size of the container used to contain the beads that make up the monolith, in order to form monoliths that have a diameter or width that is at least 10,000 times the size of mean particle of the resol accounts, or at least 100,000 times the average particle size of the resol accounts. Alternatively, a batch of beads can be at least partially cured and charred while in contact with each other, and then milled so that the monoliths are an aggregate of individual beads, for example having a width or diameter of 10 to 10,000 or more times the average diameter of the resol accounts from which the monolith is formed. Hitherto alternative, the monolith can be ground after or during carbonization or activation to form particles that are aggregates of individual resol values, for example having a diameter of 10 to 100 times the average particle size of the beads of individual resolves from which the monolith was formed. Based on the proposed use, these smaller monolith particles may have certain advantages over the monoliths comprised of a sizable bead of beads, with respect to size and flow properties. In yet another aspect, the invention relates to activated carbon beads having a size of desired particle and particle size distribution, the activated carbon beads comprising the reaction product of a phenol with an aldehyde carried out in the presence of a base as a catalyst, reacted in a stirred aqueous medium including a colloidal stabilizer, and optionally a surfactant, and then heat treated, with stirring, charring, and activated via one or more intermediate processing steps, as further described herein. In yet another aspect, the invention relates to processes that prevent stickiness and melting of the resol accounts during curing and carbonization, the processes include a step of heating the resol accounts under conditions whereby the resol accounts are moving. The heating can be carried out in a fluid such as a liquid or a gas, or in a vacuum.The inventors have found that, in the formation of resole beads of an aldehyde and a phenol carried out in an aqueous medium. agitated, if the beads are removed from the reaction mixture and then subjected to a stage of heating the resol accounts under conditions by which the resol accounts are in motion, the tackiness during subsequent processing in this manner can be reduced or avoid this heating stage can be carried out in a liquid, a gas, or a vacuum, but typically in a means different to the reaction medium by itself. If this heating step is omitted, a resol monolith can be obtained, as further described herein, which can be carbonized and activated to obtain an activated carbon monolith useful for gas phase or storage adsorption. Thus, in one aspect, the invention relates to resol beads having a desired particle size and particle size distribution, the resol beads comprising the reaction product of a phenol and an aldehyde, reacted in an aqueous medium. agitated, basic that includes previously formed resol counts, a colloidal stabilizer and optionally a surfactant. The processes according to the invention can be carried out in the form of batches, in the form of semi-batches, and continuously, or semi-continuously, as further described elsewhere herein. As used herein, the term "beads" is intended to refer simply to approximately spherical or round particles, in some embodiments, the shape may serve to improve the flow properties of the beads during subsequent processing or use. The resol accounts obtained according to the invention will typically be approximately spherical, but with a range of sphericity values (SPHT). The sphericity, As a measure of the roundness of a particle, it can be calculated using the following equation: SPHT = ^ U2 in which SPHT is the sphericity value obtained; U is the measured circumference of a particle; and A is the measured (projected) surface area of a particle. For an ideal sphere, the calculated SPHT would be 1.0; any of the less spherical particles would have a value SPHT less than 1. The sphericity values of the resolving accounts of the invention referred to herein, as well as those of the activated carbon accounts of the invention referred to herein, can be determined using a CamSizer, available from Retsch Technology GmbH, Haan, Germany, the CamSizer is calibrated using Glass Microspheres NIST Traceable, available from Whitehouse Scientific, Catalog Number XX025, Glass Microsphere calibration standards, 366 +/- 2 microns, 90% between 217 and 590 microns The resol accounts obtained according to the claimed invention will typically have SPHT values, for example, of at least about 0.80, or at least approximately 0.85, or at least 0.90, or even at least 0.95. Suitable ranges of sphericity values may vary, for example, from about 0.80 to 1.0, or from 0.85 to 1.0, or from 0.90 to 0.99. The term "resol" in the same way is not intended to be particularly limited, with reference to the reaction product of a phenol and an aldehyde in which the reaction is carried out in the presence of a base as a catalyst. Typically, the aldehyde is provided in molar excess. The term "resol" is not intended, as used herein, to refer only to prepolymer particles that have only a minor amount of crosslinking or polymerization that have taken place, but instead refers to the reaction product at any stage of the Initial reaction of a phenol with an aldehyde through the thermosetting step when significant crosslinking has occurred. The resol accounts according to the invention can be used for a variety of purposes for which resol accounts are known to be useful and find easy application in the formation of activated carbon accounts when they are treated and thermally subjected to carbonization and activation, as further described below for a wide range of end uses, such as in cigarette filters, in clothing for protect people from chemical and biological warfare agents such as medical adsorbents, for gas masks used in chemical spill clean-up and the like. The term "cured resol accounts" is proposed to describe accounts of resol, as just described, that have been thermally cured to reduce the tendency of the resolving beads to stick together, as is further described herein. Cured resol accounts can be useful in a variety of purposes for which resol accounts are known to be useful, including those in which the resol polymer of which the accounts are comprised have not yet been substantially reticulated, the amount of curing in some cases that is only the one needed to reduce the tendency of resol accounts to stick together. The times, temperatures, and conditions under which the resol accounts are thermally cured to obtain the cured resol accounts of the invention are as defined herein further. The general terms "phenol" and "one or more phenols" as used herein mean phenols of the type which form condensation products with aldehydes, which include, in addition to phenol (monohydroxybenzene), other monohydric and dihydric phenols such as phenol, pyrocatechol, resorcinol, or hydroquinone; substituted phenols with alkyl such as cresols or xylene; binuclear or polynuclear monohydric or polyhydric phenols such as naphthols, p, p'-dihydroxydiphenyl dimethylmethane or hydroxyanthracenes; and compounds which, in addition to containing phenolic hydroxyl groups, include such additional functional groups as phenol sulfonic acids or phenol carboxylic acids, such as salicylic acid; or compounds capable of reacting as phenolic hydroxyls, such as phenol ethers. Phenol by itself is especially suitable for use as a reagent, is readily available, and is more economical than most of the phenols just described. The phenols used according to the invention can be supplemented with non-phenolic compounds such as urea, substituted ureas, melanin, guanamine, or dicyandiamine, for example, which are capable of reacting with aldehydes as phenols do. These and other suitable compounds are described in U.S. Patent No. 3,960,761, the relevant portion of which is incorporated herein by reference. In one aspect, the phenol used is one or more monohydric phenols, present in an amount of at least 50%, based on the total weight of the phenols used, or at least 60%, or at least 75%, or at least 90%, or even at least 95% of monohydric phenols, in each case based on the total weight of the phenols used. In another aspect, the phenol used is phenol, that is, monohydroxybenzene, for example present in an amount of at least 50%, based on the total weight of the phenols used, or at least 60%, or at least 75%. %, or at least 90%, or even at least 95%, in each case based on the total weight of the phenols used. The general terms "aldehyde" and "one or more aldehydes" include, in addition to formaldehyde, polymers of formaldehyde such as paraformaldehyde or polyoxymethylene, acetaldehyde, saturated or unsaturated, monohydric or polyhydric, aliphatic or aromatic aldehydes such as butyraldehyde, benzaldehyde, salicylaldehyde, furfuraldehyde, acrolein, crotonaldehyde, glyoxal, or mixtures thereof. Especially suitable aldehydes include formaldehyde, metaldehyde, paraldehyde, acetaldehyde and benzaldehyde. Formaldehyde is particularly suitable, is inexpensive, and is readily available. Equivalents of formaldehydes for the purpose of the present invention include paraformaldehyde, as well as hexamethylenetetramine which, when used according to the invention, also provides a source of ammonia. These and other suitable aldehydes are described in U.S. Patent No. 3,960,761, the relevant portion of which is incorporated herein by reference. When formaldehyde is used as an aldehyde, It can be added as a 37% solution of paraformaldehyde in water and alcohol, called formalin. The alcohol is usually methanol, and is typically in such solutions at an average concentration of about 7-11% based on the formaldehyde sample. Methanol is a good solvent for para-formaldehyde and acts to keep para-formaldehyde from precipitating from the solution. The formalin can thus be stored and processed at low temperatures (<23 ° C) without para-formaldehyde being precipitated from the solution. However, as further described below, the inventors have found that much less methanol can be used to supply formaldehyde to the reaction that is typically used, and that solutions having less metal provide certain advantages. Thus, one aspect of the invention relates to processes for producing resol accounts in which the amount of methanol is limited. In one aspect, the aldehyde used is one or more alkyl aldehyde having one to three carbon atoms and present in an amount of at least 50%, based on the total weight of the aldehydes used, or at least 60%. %, or at least 75%, or at least 90%, or even at least 95%, in each case based on the total weight of the aldehydes used. In another aspect, the aldehyde used is formaldehyde, for example present in an amount of at least 50%, with respect to the total weight of the aldehydes used, or at least 60%, or at least 75%, or at least 90%, or even at least less 95%, in each case on the total weight of the aldehydes used. The processes according to the invention are carried out in the presence of a base as a catalyst, such that the aqueous reaction medium is typically a basic aqueous medium, that is, an alkaline medium, which has a pH, for example, higher 7, or at least 7.5, or at least 8, up to about 11, or up to about 12, or about 7 or about 12, or from 7.5 to 11. However, the processes according to the invention can be Carry out in aqueous media this is non-alkaline, for example if the ammonium chloride or the like, is used as a base. Furthermore, the pH can change during the course of the reaction, such that the pH values can be those obtained at the beginning of the processes by which the resol values of the invention are obtained. A variety of organic or inorganic bases can be used as catalysts, including but not limited to ammonia or ammonium hydroxide; amines such as diethylene diamine, diethylene triamine, hexamethylenediamine, hexamethylenetetramine, or polyethylene imine; and metal hydroxides, oxides, or carbonates, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, barium hydroxide, barium oxide, sodium carbonate; and the similar ones. It is understood that several bases used may exist in an aqueous medium as hydroxides, in whole or in part, for example ammonia or ammonium hydroxide. In the processes according to the invention, the amount of water in the aqueous medium is not particularly critical although it will be much more economical that the reaction is not carried out in a dilute aqueous medium. The amount of water used will be at least an amount that will allow the formation of a resin dispersion in phenolic water, typically at least about 50 parts by weight of water per 100 parts by weight of the obtained resol solids. There is no advantage to using a quantity of water, and in fact, the reaction will probably proceed more slowly when the excess water is used, although the invention will work even with a large excess of water. Typical levels of water with respect to organic actives will thus typically be from about 30 to about 70% by weight or from 50% by weight to 70% by weight. Thus, the amount of water can vary within a relatively wide range, for example from about 25 to about 95% by weight, or from 30 to 80% by weight, or from 35 to 75% by weight. The colloidal stabilizers useful according to the invention serve to promote or maintain a dispersion of resin in phenolic water such that the resol beads are formed in the aqueous medium during the course of the reaction. A wide variety of such agents can be used including, without limitation, naturally derived gums such as gum arabic, ghatti gum, algin gum, locust bean gum, guar gum or hydroxyalkyl guar gum; cellulosics such as carboxyl methyl cellulose, hydroxyethyl cellulose, their sodium salts, and the like; partially hydrolyzed poly alcohol; soluble starch; agar; polyoxyethylenated alkylphenols; straight chain and branched chain polyoxyethylenated alcohols; long chain alkyl aryl compounds; long chain perfluoroalkyl compounds; polymers of propylene oxide of high molecular weight; polysiloxane polymers; and the similar ones. These and other agents are further described, for example in U.S. Patent No. 4,206,095, the relevant portion of which is incorporated herein by reference. The colloidal stabilizers are used in sufficient amounts to promote the formation or stabilization of a resin dispersion in phenolic water as the resol counts are formed. They can be added at the beginning of the reaction, or they can be added after some initial polymerization has taken place. It is sufficient that the dispersion be stable while the The reaction mixture is being stirred, thus agitation helps the colloidal stabilizers to maintain the desired dispersion. It is typical to use the colloidal stabilizers in relatively small amounts, for example from about 0.05 to about 2 percent by weight, or from 0.1 to 1.5 percent by weight, in each case based on the weight of the phenol. Alternatively, the colloidal stabilizers can be used in amounts up to 2 weight percent, or up to 3 weight percent or more, based on the weight of the phenol. Typically from about 0.2 weight percent to about 1 weight percent, based on the weight of the phenol, is a good starting point for developing suitable formulations. A variety of carboxymethylcellulose can be used according to the invention as colloidal stabilizers having a variety of degree of substitution, for example, at least 0.4, or at least 0.5, or at least 0.6, up to about 1.2, or up to about 1.5, or from about 0.4 to about 1.5, or from 0.6 to 1.2, or from 0.8 to 1.1. Similarly, the molecular weight of carboxymethylcellulose can also vary, for example from about 100,000 to about 750,000, or from 150,000 to 500,000, or a typical average of about 250,000. The inventors have found sodium carboxymethyl cellulose which is especially well suited for use according to the invention. The inventors have found that products made using certain guar gums resulted in particles that were often rough texturized and contained large amounts of beads merged or agglomerated. The processes according to the invention can optionally be carried out in the presence of one or more surface active agents, then in the present surfactants, and in fact in the absence of seed particles, they can be useful to provide a surfactant at order to obtain desired properties in the formed accounts of resol. Surfactants useful according to the invention include anionic surfactants, cationic surfactants and nonionic surfactants. Examples of anionic surfactants include, but are not limited to, carboxylates, phosphates, sulfonates, sulfates, sulfoacetates, and free acids from these salts and the like. Cationic surfactants include salts of long chain amines, diamines and polyamines, quaternary ammonium salts, polyoxyethylenated long chain amines, long chain alkyl pyridinium salts, salts quaternary lanolin, and the like. Nonionic surfactants include long chain alkylamine oxide, polyoxyethylenated alkylphenols, polyoxyethylenated straight chain and branched chain alcohols, alkoxylated lanolin waxes, polyethylene glycol monoethers, dodecylhexaoxylene glycol monoethers, and the like. The inventors have found that sodium dodecylsulfate (SDS) is well suited for use according to the invention. Other ammonium surfactants are also well suited for use according to the invention, and although the surfactant can be omitted and the acceptable product having a relatively small size distribution obtained, the presence of a surfactant appears to aid in the formation of a more spherical product. In the processes according to the invention by which the resol counts are prepared, the reaction is carried out in an agitated aqueous medium, the agitation provided is sufficient to provide a dispersion of ream in phenolic water such that the resol they are obtained having a desired particle size. Agitation can be provided in a reaction vessel by a variety of methods, including but not limited to inclined blade impellers, high efficiency impellers, spiral type agitators, turbine and anchor.

The reaction mixture can be stirred at a relatively low speed, which is dependent in part on the size of the container, with, for example, a stirring paddle in the form of an anchor. Alternatively, agitation can be provided, for example, by mixing caused by flow induced by internal or external circulation, by co-current flow or countercurrent flow, for example with respect to a flow of reagents, or by flowing medium of reaction by passing one or more stationary mixing devices, such as static mixers. An advantage of the present invention, as described herein, is the ability to obtain a desired particle size and particle size distribution. The particle size distribution of the resol values obtained according to the invention, as defined herein, may be that measurement following the isolation techniques described below. After the reactions are complete and the resol counts are obtained, the resol values of useful size are obtained by cooling the product mixture to a temperature of about 20 ° C to about 40 ° C, and the suspension is drained of the reactor in a transfer vessel having a stirring device so that the solids can be suspended in the vessel when desired. The contents of the container are first left settle for a period of about 15 to about 60 minutes (without agitation) to allow a bed of particles to form at the base of the container. A clear separation between the lower bed of the particles and the upper liquid phase will be visible when the settling process has been completed, typically, the liquid has a milky appearance and has a viscosity in the range of 0.10 to 20 cP. The presence of a large number of sub-5 micron particles gives the liquid phase this milky appearance. From the settled milky suspension, the liquid phase is decanted from the upper part of the vessel until the separation line between the settled bed of the particles has been reached. This decanting process will remove most of the liquid in the container. The amount that remains in the bed of the particles will be from about 5% to about 30% of the total amount of the liquid originally present in the suspension. A large amount of sub-5 micron particles are contained in the decanted liquid phase and are still suspended in the liquid phase that will be removed from the container. This amount of suspended solids represents from about 0.10% to about 5% of the total yield of the process solids. To the bed of the solids, a quantity of water It adds that it is approximately equivalent to the amount of decanted liquid removed from the container. The contents of the container are then resuspended using a stirring device such that the concentration of the solid phase is homogeneous throughout the container. Mixing is typically continued for at least 10 minutes. The impeller is then turned off and the suspension is allowed to settle once again to form a bed of solids at the base of the container. The suspension is allowed to settle for about 15 to about 60 minutes until a discrete interface between the bed of the solids and the liquid can be observed. The procedure for washing the solids described in the above is repeated 2 to 4 additional times until the liquid phase is substantially clear and free of any of the suspended solids. The suspension is then resuspended, using the agitator, and the contents of the container are poured over a filter. Once the suspension has been poured on the filter, vacuum is applied to the bed of the solids to separate the liquid phase from the solid phase. The vacuum is maintained until the liquid has been removed from the cake. The time required to do this will depend on the strength offered by the solids bed and the filtration medium. Typically, for particle sizes in the range of 100 at 700 um and a filter element having an average pore size of 40 um, this process will take from about 5 to about 60 minutes. After the liquid has been removed from the cake, the nitrogen gas at room temperature and pressure is fed to the top of the cake. The gas is removed through the cake using the vacuum located at the base of the bed. The gas is removed through the cake from 1 to 12 hours, until the bed of solids has been dried. The moisture content of the cake should be below 1% on a total solids basis. The dry solids are removed from the filter. The particle size distribution of the dry solids can be determined by a number of methods. For example, a sieve solution can be used to fractionate the solids into separate groups. For example, for a distribution containing particles in the size range of 50 to 650 um, the initial screen fraction will be between 50 and 150 um. The second could be between 150 and 250 um, and so on in increments of 100 um up to 650 um. Alternatively, the screen fractions should be selected to produce fractions of 50 um instead of 100 um. By fractionating the solids into different fractions, a size distribution of The particle can be generated that expresses the fraction (volume or weight) of the distribution present in the average size of each screen fraction. In the screening procedure, sufficient time must be allowed to allow the mass of particles in each fraction to reach a permanent state mass. For this a time of about 1 to about 24 hours is typically required, or sufficient time such that the mass on each screen reaches 99% of its final permanent state value, or until the mass on each screen does not change by more than 0.10. % of the mass on that fraction of screens during a period of 5 hours, for example. Another method to measure the particle size distribution is to use a direct laser light scattering device. Such a device can produce a volume distribution of particle size as a function of particle size. The device operates by passing a particle sample suspended in a non-absorbent liquid medium in the path of a laser beam. A particle modifies the laser light that falls on it through the two basic mechanisms of dispersion and absorption. The light scattering includes the diffraction of light around the edges of the particle surface, reflection of the particle surface, and refraction through the particle. The result of the refraction of light through the particle results in a distribution of scattered light in all directions. The scattered light is focused on a photodiode detector array that is located at a distance from the measurement plane. The detector is comprised of an array of discrete photodiodes arranged in a semicircular fashion. The diffraction angle of the incident light is inversely proportional to the size of the particle that diffracts the light. Therefore, the farthest diodes reconnect the signals of the smallest detectable particles and the innermost diodes collect the signals of the largest detectable sizes. From an understanding of the theory of light scattering and an understanding of system geometry, a particle size distribution can be reconstructed from the diffraction pattern in terms of the volume distribution number. An example of a useful device for such measurements is the Malvern Mastersizer 2000 which measures in the size range of 0.20 to 2000 microns and is sold by Malvern Instruments Ltd. (Malvern, United Kingdom). Another such instrument is the Beckman Coulter LS 230 which can measure in the range of 0.02 to 2000 microns and is sold by Beckman Coulter Inc. (Fullerton, California, USA). Both instruments operate on the previous principle and are sold with proprietary companion software.

From the determined distribution of any of the above techniques, certain characteristic sizes of the distribution can be calculated. Characteristic sizes are used to compare particle distributions from different experiments to determine the effect of processing conditions on the size distribution of the particles produced. For example, the characteristic size of 10% (given) of a distribution can be determined. The characteristic size of d10 represents a particle size in which 10% of the volume of all the particles is composed of smaller particles than the established diode and vice versa, the size in which 90% of the volume of all the particles is It consists of particles larger than the established d? 0. Similarly, the characteristic size dgo represents a particle size in which 90% of the volume of all the particles is composed of smaller particles than the established dgo and the inverse is the size in which 10% of the volume of all the particles It consists of particles larger than the established dgo. Similarly, the size at 50% (dso) is the size below and above which 50% of the volume of all solids in the lot is located. The dso is also called the average size. To represent the determined particle size distribution of a screening procedure, the Average size of a screening fraction is determined. The determined particle size distribution of a screening technique is a mass-based distribution, which for a system with uniform density is equivalent to a volume-based distribution. The average size (d50) of the distribution is the size above and below in which 50% of the volume of the particles (V50) is located. The largest particle diameter in a screening fraction is the diameter of the screen opening in the upper screening fraction (dupPer) and the smallest particle diameter in a screening fraction is the diameter of the aperture the sieve in the lowest screening fraction (d? OWer) • The volume of the smallest particles in a screening fraction can thus be calculated from the following general formula: lower 'r lower' The average size of a screening fraction is obtained from the following formula that expresses the volume up and down which 50% of the volume in the screen fraction is located,? P_p_er + V l.o.wer Terms of cancellation in the above equation, the following formula for the average size of screening can be derive, For the examples described in the present application, the average screen size is used when plotting the mass distribution of the particles as a function of size. To calculate the dio or the dgo of a distribution, a cumulative graph of the distribution is plotted with the average screen size of each fraction of screens on the x axis and the cumulative mass fraction on the y axis. The sizes given or the dgo can be read from the graph by reading the size corresponding to 10% and 90% of the cumulative total of mass fraction or volume on the graph. For a particle size distribution measured by laser light scattering, a similar procedure is used to determine dio and dgo sizes. The mass fraction or cumulative volume is plotted against the size reported and the size corresponding to 10% and 90% of the cumulative total of the fraction in mass or volume on the graph can be read. The particle size distribution, as used herein to define the size distribution of the resol account or size distribution of the activated carbon account, can be expressed by a "space" (S) ", where S is calculated by the following equation: where d90 represents a particle size in which 90% of the volume is composed of particles smaller than the dong; and dio represents a particle size in which 10% of the volume is composed of particles smaller than the established dio; and d5o represents a particle size in which 50% of the volume is composed of particles larger than the established dso value, and 50% of the volume is composed of particles smaller than the established d50 value. A range of particle size distributions can be obtained according to the invention by following the isolation techniques just described. For example, space values of about 25 microns to about 750 microns can be achieved, or from about 50 to about 500 microns, or from about 75 microns to about 375 microns, the space defined in the above as the size of DGO particle minus the particle size dio- Typical particle size values dso for the precisely described spaces could be from about 10 um to about 2 mm or more, or from 50 microns to 1 mm, or from 100 micras to 750 microns, or from 250 microns to 650 microns. Alternatively, space values of 100 to 225 microns can be achieved in which greater than 20% of the distribution is in the size range greater than 425 microns. In a further alternative, a space of 100 to 160 microns in which at least 50% of the weight of the distribution, or at least 65% by weight, or at least 75% by weight are present as particles greater than 425 Microns can be achieved by following the isolation techniques described. In a modality, the resol beads according to the invention can be prepared, for example, by reacting in a stirred aqueous medium a phenol and an aldehyde, in the presence of a base such as ammonium hydroxide provided as a catalyst, a colloidal stabilizer such as sodium carboxymethylcellulose (for example having a degree of substitution of about 0.9), and optionally a surfactant such as sodium dodecylisulfate. The processes described herein will generally be carried out for a period of time and at a temperature sufficient to produce an aqueous dispersion of resol beads. Thus, the reaction can be carried out, for example, at a temperature from about 50 ° C to about 100 ° C, or from 60 ° C to 95 °, or from 75 ° C to 90 ° C. Similarly, the duration of time that the reaction it is allowed to run based on the temperature for example, from about 1 hour, or less, to about 10 hours, or more, or from 1 hour to 10 hours, or from 1 hour to 8 hours, or from 2 hours to 5 hours. In certain embodiments, the inventors have kept the reaction mixture at a temperature of about 70 ° C for about 5 hours, and then have raised the temperature to about 90 ° C for about 1 hour. Alternatively, the inventors have kept the reaction mixture at a temperature of about 85 ° C for about 4 hours, and then have raised the temperature to about 90 ° C for about 30 minutes to 1 hour. Another alternative would be to maintain the reaction mixture at a temperature of about 85 ° C for about 2 hours, and then raise the temperature to about 90 ° C for about 1 hour. The use of substituted phenols may require higher reaction temperatures than when phenol is used, ie, monohydroxybenzene. The processes according to the invention will typically be carried out at temperatures such as those already described, and at temperatures at which the emulsion polymerizations are typically carried out. It may be advantageous in some cases for the reaction pressure to be maintained, at pressures greater than one atmosphere, in order to obtain beads having a higher density than the obtained at lower reaction pressures. This is because, if the gas byproduct bags are trapped inside the beads, it is reasonable to expect that higher reaction procedures will decrease the volume of the gas bags and result in a denser product. The particle sizes of the resol values prepared according to the invention can vary within a wide range as measured using the measurement techniques already described, for example, having an average particle size, or of 50, or of 10. μm up to 2 mm, or up to 3 mm, or more, especially in those cases in which the beads are recycled, the beads typically develop at a rate of up to about 200 micras per step. Alternatively, the average particle size can fall within the range of 25 μm to 1,500 μm, or 50 μm to 1,000 μm, or 100 μm to 750 μm, or 250 μm to 500 μm. With the average particle sizes precisely described, the space could be, for example, from 25 microns to 750 microns, or from 50 to 500 microns, or from 75 microns to 375 microns, or from 75 microns to 200 microns, or as It is described. The beads may alternatively be grown at a rate of about 25 microns to about 250 microns, or 50 microns to 200 microns, or 100 microns to 200 microns, in each case by passage through a reaction medium. A range of particle sizes and Particle size distributions can be achieved according to the invention, and the inventors have found that the use of previously formed resol counts as seed particles allows more control of these variables than the processes of the prior art. Thus, in one aspect, the resol accounts according to the invention may have a relatively large particle size, and a relatively small particle size distribution, when compared to what has hitherto been achieved, as already described. . When the previously formed resol accounts are used as seed particles, the size of the previously formed resol accounts used may vary within a wide range or fraction of given size, and will be selected based on available sizes or fractions, as well as about the desired particle size and the particle size distribution of the final resolves. Thus, the average particle size or d.sub.50 of the previously formed resolves can be, for example, at least about 1 μm, or at least 10 μm, or at least 50 or up to 500 μm, or up to 1. mm, up to 1.5 mm, or even up to 2 mm or greater. Alternatively, the average particle size of the previously formed beads may be in the range of about 1 μm to about 2 mm, or 10 μm to 1 500 μm, or 50 μm to 1,000 μm, or from 100 μm to 750 μm, or from 125 μm to 300 μm. The appropriate particle size for the previously formed resol plants will be selected based on the desired particle size of the finished particle. Similarly, previously formed resolves having a range of particle size distributions are useful according to the invention, the selected distribution that is based on parts on the available size fractions, the need for a relatively uniform particle size. in obtained resol accounts, and waste avoidance when using accounts that have a range of particle size distributions. Thus, previously formed resol counts having space values of about 25 microns to about 750 microns can be used, or from about 50 to about 500 microns, or from about 75 microns to about 250 microns, the space defined in above as the difference between the particle size dgo and the particle size gave • In practice, in those modalities in which previously formed accounts are going to be provided to subsequent reaction mixtures and in which an average particle size of approximately 300 μm to about 425 μm is desired, beads can be formed as described elsewhere herein, and then drying and screening in fractions, for example, four fractions: those greater than about 425 μm (> 425-μm); those from about 300 μm to about 425 μm (> 300 <425-μm); those of about 150 μm to about 300 μm (> 150 <300-μm); and those less than about 150 μm (< 150-μm). By this means, the material < 300-μm can be recycled to a subsequent batch. In the subsequent batch, the material > 300-μm in this way can be substantially increased, resulting in a smaller size distribution. Without wishing to be related by any theory, it seems that the smaller beads that are recycled to the reaction develop in size, thus increasing the product yield in a range of size 300 - 425 μm. Through the use of pre-formed beads, a total material yield in the size range 300 - 425 μim over 5 batches can be achieved that is similar to the total yield of the product minus the yield of the material < 300-μm initially produced. The inventors have found that the final average count size is dependent in part on the size of the previously formed resol accounts used as recycle seeds. Thus, the processes according to the invention provide the flexibility of adjustment to the size of the desired account by varying the size of the recycled seed. that is used. For example, the inventors found that the use of seeds smaller than 150 microns results in increased yield of the product of 150-350 microns, while seeds of 150-300 microns will increase the yield of accounts greater than 425 microns. The inventors have also found that the reactivity of the seeds is affected if the count is allowed to cure. Therefore, it may be useful to avoid curing or only partial curing, for example when heating, the seeds to be recycled. The inventors found that when the seeds to be recycled are cured in a separate stage at elevated temperature, they do not appear to develop in size during the reaction as much as the uncured seeds. When the resol accounts according to the invention are prepared, the average size of the beads can vary as a function of the agitation rate and type of agitator, used during the reaction. In general, rapid agitation results in smaller account size while slow agitation results in larger scores. Slow agitation speeds using a conventional tilted turbine blade or arc blade can result in nucleation on the walls of the reactor due to poor movement, leading to undesirable amounts of cake formation and excessive buildup on the walls of the reactor. This problem can be avoided by using an anchor-type stirrer which, even at slow speeds, will sweep the walls of the reactor by reaction. However, while the agitation speed provides some control over the average size of the beads, it typically does not provide as much control over the particle size distribution. The previously formed resol counts can therefore be used according to the invention, in order to provide a measure of control over the particle size and the particle size distribution. A variety of particle sizes and particle size distributions can be used according to the invention as the previously formed resol counts, as already described, and the size and size distribution can be selected in order to achieve the size of the desired particle and the particle size distribution in the resol accounts of the final product in view of the present description. Although seeds having a variety of particle sizes and particle size distributions can be used according to the invention, the inventors have found that in some applications, the amount of recycle accounts can be selected as a function. of the ratio of the external surface area of the recycled beads to the amount of phenol used in the reaction. The external surface area of the seeds was calculated using the average diameter of the loaded seeds. For example, for a monodisperse particle distribution where the maximum diameter of any particle is "d", the maximum cross-sectional area (Area) of the particle taken through the meridian plane of the particle can be calculated from the following formula: Area = nd2 (m2) The above formula calculates the surface area of an individual particle that has a size of d. For example, if the value of d was 250 microns, the surface area would then be calculated as: . = t (250.10-06) 2 = 1,964. * 10"07 m2 The inventors have found that, it should be desirable to avoid the formation of an excessive amount of small particles (fines), the total surface area of the recycled accounts provided (in m2) can desirably be, for example, at least five times higher that, or at least six times greater than, or at least seven or eight times greater than the amount of phenol (in kg).

The inventors have found that, if the ratio is less than about eight, for example, there is substantially more nucleation of new particles than the development of existing particles. The ratio in number of more particles generated during the reaction (of nucleation) is plotted against the surface area of the recycled beads charged to the unit mass by reaction of the charged phenol. When the surface area of the seeds is less than about 5 m2 per kg of phenol, the number of new particles can be markedly increased. These new particles will be mainly small and present as fine, undesirable dust. Thus, if it is desirable to ensure that the growth of the initial seeds is promoted in the container and the nucleation of fine particulate materials is removed, sufficient seeds of the appropriate size can be charged to the reactor such that the surface area (in m2) of the seeds added to the reactions at least 5 times the amount of phenol added to the container (in kg). These two measures: forming seed with the desired particle size, and providing sufficient surface area, can produce a product having a larger proportion of product in a desired size range. The temperature history of previously formed beads used as seeds can be significant, in order to ensure that the surface of the accounts remains active. For example, a limited curing stage implemented at the end of each reaction in batches at a temperature of about 90 ° C lasting 45 minutes will typically be sufficient when the beads are going to be recycled. The inventors found that if treated in water at a temperature of 100 ° C, the surface of the beads will obviously be deactivated, making it difficult for them to function as seeds to develop larger beads. Thus, in one aspect, the resol accounts according to the invention may have a relatively large particle size, a relatively small particle size distribution, when compared to those hitherto achieved. For example, when particles having a size range of about 425 to about 600 um are desired, particles smaller than 425 um may be considered suitable for use as seeds to be recycled for successive batches. However, particles in the size range of 150 to 300 μm may be more desirable for use as seeds, since they can give a product yield of 60 to 80% in the desired size range (425 to 600 um) during a given lot. The other 20 to 40% of the performance is present as bills above (>; 600 um) or smaller (< 425 um). The inventors they expect that some of the smaller beads will be formed as a result of the nucleation that has occurred during the batch formation, and that some of the smaller accounts are the original seeds that have not been developed at sizes exceeding 425 um. Larger accounts are probably the result of seed particles growing at sizes larger than 600 um. Thus, the amount of accounts of smaller or larger size produced can be a function of several factors such as nucleation speed, the activity of the accounts, and the performance of the process. When these relatively large particles are desired, the particles in the size ranges of 1 to 150 μm could be well considered too fine for use as seeds. They result in a small yield of product size particles. Particles in the size range of 300 to 425 um are also considered less suitable, since they will typically produce particles larger than 600 um and do not give the required performance of the product. Because a relatively wide particle distribution is produced from each batch, it may not be practical to select an extremely reduced distribution as seed particles and still have material in the size class of 150 to 300 um to act as seed.

For this reason, a seed distribution is typically selected for seed in each batch. Thus, in practice, a relatively monodisperse seed amount can be added to each reaction batch to act as sites for the growth of a phenolic resin bed. The surface area of the seeds can be used to determine an appropriate amount of seeds to be used for example, for each kg of phenol loaded to the batch reactor, the surface area, of the seeds, (in m2) can be, for example, at least 5 times the weight of the phenol (in kg) charged to the reactor, or at least 6 times the weight, or at least 7 times the weight of phenol used, calculated as already described. When the previously formed resol accounts are used as seeds to prepare the resol accounts of the invention, the following steps can be used, for example, to produce the resol accounts: a) Charge all or part of a reaction mixture of a phenol an aldehyde such as formaldehyde, and a base such as ammonia (for example as ammonium hydroxide or hexamethylenetetramine) to a stirred aqueous medium containing colloidal stabilizer and optionally a surfactant. b) Load a quantity of previously formed resol accounts into the reaction mixture that they have surface reactive functionality with one or more of the phenol or formaldehyde monomers. The amount of seeds used may be sufficient. For example, to provide a surface exceeding 5 m2 per kg of phenol added. c) Heat the reaction mixture to a temperature of about 75 ° to 30 to about 85 ° C and add any of the remaining reagents (phenol, formaldehyde, ammonia) to the vessel in the semi-batches mode during the course of the reaction . d) Contain the reaction mixture at that temperature for about 5 hours or more. e) Heat the reaction mixture to about 90 ° C for about 45 minutes, f) Cool the reaction mixture to between about 10 ° C to about 50 ° C and separate the resultant resol solids from liquid in the reaction mixture. Alternative times and temperatures can be used as described elsewhere in the present. Typically, with each step through the process, if a particle is present that originates from a previously formed proportioned account or from a resol particle source, more reaction product is deposited Over the surface. Thus, a particle increases in size each time it passes through the process. The inventors have found that during a typical reaction conducted according to the invention, a particle size can be increased, for example, by approximately 100 to 200 μm, or as already described. The processes according to the invention can be carried out in the form of batches, in which all the reagents are provided to the reaction mixture together. Alternatively, the processes can be carried out using various additions in semi-batches as described further herein. Without wishing to be related to any particular theory, the following discussion exposes the mechanism by which the resol accounts of the invention appear to be formed. The condensation reaction of an aldehyde such as formaldehyde with a phenol in the presence of a base as a catalyst in an aqueous environment stirred at elevated temperatures, for example at least 60 ° C, leads to the formation of a two-phase mixture. , the aqueous phase containing unreacted formaldehyde, phenol, ammonia and lower order alcohols, the second phase containing non-crosslinked, higher order polymeric species formed as a result of the condensation reaction ofm. resol. The resol compounds are oiled from the solution due to their high molecular weight. When using a colloidal stabilizer, the oily phase forms beads of polymeric material which are suspended in the stirred vessel as discrete droplets. Through the course of time, the action of the formaldehyde cross-linking that diffuses into the liquid droplets causes a further increase in the molecular weight of the polymer. The increase in molecular weight leads to the solidification of the oil droplets to form resol beads that can be filtered, washed and recovered for use as a dry polymeric material. The colloidal stabilizer and optional surfactant can be present in the reaction mixture from the start of phenol / aldehyde condensation, or else the condensation reaction can be conducted to the stage where a low viscosity resin is produced, the stabilizer Colloidal and the surfactant are then added with more water if necessary. Sufficient water will typically be provided such that a phase inversion takes place, producing a resin dispersion in water, with water being the continuous phase. The concentrations of resol solids can vary within a wide range, since the amount of water is not critical, with a typical solids content up to about 40 or 50 weight percent, based on the weight retained in the solids in the drying An adequate dispersion of the resin in water during the early stages of the process is achieved by applying agitation to the aqueous medium, the use of an agitator which is a convenient way to provide the necessary agitation in batch and semi-continuous processes, in such devices as in-line mixing devices that are suitable for continuous processes. Resolved beads are substantially insoluble in water, resins typically having a weight average molecular weight of at least about 4 about 300, or at least 400, or at least 500, or up to about 2,000, or even 2,500, or up to 3,000 or more. Of course, it can be difficult as a matter of practice determines the molecular weight when a significant amount of crosslinking has taken place. Depending on the proposed end use, it may be desirable to subject the resole to an elevated temperature for a controlled period of time, optionally with an intervention neutralization step. While the inventors have found that batch processes result in usable accounts, the inventors have found that, in some cases, several additions of semi-batches of reagents can result in a higher yield of the desired particle size and particle size distribution. Alternatively, continuous processes may provide certain advantages such as increased yield in product uniformity obtained. According to further aspects of the invention, various modes of semi-batches and operating steps can be used, for example, in order to improve performance or the particle size distribution obtained, such as to increase the amount of desired particles (> 425 um) or to decrease the number of unwanted fine particles (<150 um) made during the reaction of the resol. As an example, the following strategies can be used to produce advantages either in product performance or product quality (size), or both: (i) Instead of adding all reagents to the reactor in batch mode , some or all of the phenol, surfactant, colloidal stabilizer, seed particles, and only a portion of the base and aldehyde can be added to the reactor at the start of the reaction, and the remaining aldehyde and the base added in the semi-mode -Lots for a period, for example, 45 minutes. This strategy can minimize the generation of fines and maximize the distribution of average size as measured by screening the dry product. (ii) In processes similar to those above in (i), reactions can be conducted in stages. In such processes, perhaps a quarter of all reagents are charged to the reactor with about half the aldehyde and base that are added in the semi-batches mode. The reaction is allowed to proceed for two hours, before perhaps an additional quarter of the ingredients is added to the reactor in the same manner as the first charge to the vessel with half the aldehyde and base that are added in semi-batches mode. The two remaining charges of materials can be added in intervals of 2 additional hours to the reactor in the same way. The seed particles are added during the first loading, the amount added corresponding to the amount of phenol added in the first loading room, as already described. This type of strategy represents a process step formation in order to develop a smaller amount of seeds to a larger size, and would be useful, for example, when only a small amount of seeds is available for use. (iii) In additional embodiments, similar to those described in (i) above, an additional charge of a base, such as ammonia, is made, for example approximately 2 hours after the entire initial base has been added to the ciner. The base is added to the ciner in the semi-batches mode and the amount used can be approximately the same as it was originally charged to the reactor. Thus, in one aspect, the invention relates to processes for producing resol beads, processes that include a step of providing a phenol, a portion of an aldehyde, and a portion of a base as a catalyst to a reaction mixture that is an agitated aqueous medium including a colloidal stabilizer, optionally a surfactant, and previously formed resol solders; reacting for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; and then adding a remaining portion of the base and the aldehyde over a period of time, such as about 45 minutes. Resolves accounts previously formed can be obtained, for example, as smaller resol accounts produced in a previous batch, or in the case of a cnuous or semi-cnuous process, such as recycled accounts obtained at any point early in the process . In yet another aspect, the invention relates to processes for producing resol beads, processes that include a step of providing a portion of a phenol, a portion of an aldehyde, and a portion of a base as a catalyst to a reaction mixture. which is an agitated aqueous medium that includes a colloidal stabilizer, optionally a surfactant, and previously formed resol counts; reacting them for a period of time and at a temperature sufficient to produce an aqueous dispersion in resol accounts, for example up to about two hours; then an additional portion of the phenol, an additional portion of the aldehyde, and an additional portion of a base as a catalyst are added to the reaction mixture and reacted, for example for an additional two hours; and then adding any remaining portion of the phenol, the aldehyde, and the base for a period of time and at a temperature sufficient to obtain the desired resol values. Resolves accounts previously formed can be obtained, for example, as smaller resol accounts produced in a previous batch, or in the case of a cnuous or semi-cnuous process, such as recycled accounts obtained at any point early in the process . In yet another aspect, the processes of the invention can be carried out as already described, with a further portion of an added base after the reactants have begun to react, or even when the reaction is otherwise substantially completed, the base which is the same as or different from that already added to the reaction mixture as a catalyst for the reaction. It will be easily appreciated that any of the Processes described herein may be modified as already described, such as by charging only a portion of a phenol, an aldehyde, such as formaldehyde, and a base such as ammonia (for example as ammonium hydroxide or hexamethylene tetramine) to a stirred aqueous medium containing a colloidal stabilizer and optionally a surfactant, loading a quantity of seed particles, and then reacting for a time, adding any resulting portion of the phenol, formaldehyde, or ammonia to the container in the half-life mode. lots during the additional course of the reaction. In additional aspects, the processes by which resol accounts are formed can be continuous processes. Thus, in several aspects, continuous processes are devised according to any of the following. A vessel containing a stirring device and operating at a temperature, for example, from about 75 ° C to about 85 ° C, is provided with four continuous feed streams. In a stream, a mixture of phenol and water are fed into the vessel. The amount of phenol and water charged may comprise the total amount of these two compounds charged to the process. A second stream comprises a mixture of formaldehyde and ammonia. The amount of each corresponds to the amount of the phenol / water stream. The amount of formaldehyde and ammonia charged to the first reactor comprises from about 10% to 100% of the total amount of formaldehyde and ammonia charged to the process. The amount of ammonia and formaldehyde charged to the reactor can be independent of each other. A third feed stream comprises a colloidal agent such as soluble sodium carboxymethyl cellulose, water, and optionally a surfactant such as sodium dodecylisulfate. A fourth feed stream comprises seed particles. The velocity of the fourth stream may be such that the area velocity (in m2 / sec) is charged to the reactor proportional to the mass velocity of the phenol being charged (in kg / sec). The ratio of these two amounts can be, for example, equal to or greater than 4 m2 of the seed surface area per kg of charged phenol. The precisely described streams are mixed in the reactor to facilitate the growth of the resol particles. The residence time in this first reactor can be, for example, from about 1 hour to about 3 hours. The product of this reactor can then be fed to a second reactor also maintained at a temperature of about 75 ° C to about 85 ° C. Any remaining formaldehyde and ammonia not charged in the first reactor are charged to this second reactor continuously. The residence time of the second reactor can be, for example, from about 1 to about 3 hours.

The product suspension of the second reactor can then be pumped to a third reactor operating at 90 ° C. None of the feed currents need to be fed to this container. The residence time can be, for example, from about 30 minutes to about 2 hours. The product stream from the third reactor can then be pumped to a fourth reactor operating at 25 ° C. Sufficient residence time is provided in this vessel to cool all of the feed stream below about 40 ° C. The product from this container is fed to a solid-liquid separation device in order to recover the solids fraction. One section of the solid-liquid separation can be used for washing the solids fraction and another section is used to dry the solids by using a stream of hot gas to remove adhesion moisture. In a further embodiment, the reactants are added to a batch reactor to form an aqueous reaction mixture that is stirred. Approximately four-fifths of formaldehyde and ammonia can be retained to make additions to a later point in half-batches mode. The reactor in batches with the contents can then be heated to a temperature of about 75 ° C to about 85 ° C. After the batch reactor reaches the operating temperature, the solution of The resulting formaldehyde and ammonia can then be added to the container in semi-batches mode for example for a period of 45 minutes or more. The mixture can be maintained at this temperature for 5 hours or more. The mixture is then heated to about 90 ° C for about 45 minutes. The mixture is then cooled to a temperature of about 10 ° C to about 50 ° C and the separated solids form the liquid by filtration. Additional variations of the processes described include those in which two or more of the feed streams in a continuous process are combined prior to being added to the reaction medium. The mixing or stirring can be achieved, for example, by a rotating stirrer inside the vessel, by flow induced by external or internal circulation, by co-current or countercurrent flow provided in or to the reaction vessels, or by the medium flow of reaction passing stationary mixing devices (static mixers). The number of the containers can be varied from one to several containers to vary the nature of the mix of fully backmixed to the approximation of the plug flow, limited by the practicality and economy of providing multiple containers. In addition, the temperatures of one or multiple vessels can be varied to adjust the reaction rates or the discharge temperature of the suspension. Alternatively, a continuous process can be used in which the resol values above a minimum particle size are recovered from the reactor medium, and the resol values below a minimum particle size are retained or recycled to the reaction medium. Thus, in still another aspect, the invention relates to processes for producing resol accounts, processes that include: a) reacting a phenol with an aldehyde in the presence of a base as a catalyst, in a stirred aqueous medium including a colloidal stabilizer, and optionally a surfactant, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; b) recovering insoluble resol solids in water above a minimum particle size of the aqueous dispersion by any means; and c) retain or recycle the accounts below the minimum particle size in or to the aqueous dispersion of the resol accounts. In yet another aspect, the invention relates to processes for producing resol accounts, processes that include: a) reacting a phenol with an aldehyde in the the presence of a base as a catalyst, in a stirred aqueous medium including a colloidal stabilizer, and optionally a surfactant, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; b) recovering insoluble resol solids in water above a minimum particle size of the aqueous dispersion by any means; and c) retaining or recycling the beads within a range of desired particle size in or in the aqueous dispersion of the resol values. Various configurations for the solid-liquid separation of any of the above continuous processes, or recovery of counts above a minimum particle size, are possible, for example, where the solids are fractioned according to size before being separated. of the liquid of the reaction mixture. Fractionation can be achieved by using devices integral to one of the containers or in a separate device. Such size separation can be achieved by various methods, such as by the use of a fixed physical aperture, such as a screen, slots or holes in a plate, through which some solids pass and others are retained according to their ability to pass through the hole. Alternatively, the severity You can use, with or without counterflow liquid flow, such as in a settlement tank, or an elutriation column. As a further alternative, centrifugal force may be used, such as that provided by a hydrocyclone or a centrifuge. The separation techniques just described can be repeated on the liquid suspension to create multiple streams of solids fractionated by size classes. The solids may or may not require washing and drying, according to the proposed use of the accounts. Alternative methods for providing seed particles, in those cases where the seed particles are provided, include those in which the dry seeds are fed into the first container by the use of a mechanical regulating device. Alternatively, the seeds may be fed as a suspension, with or without combination with all or part of one of the three liquid streams in the above description. Seeds can be recycled from the continuous process of operation by one of the solid-liquid separation or fractionation processes described above, or the seed can be generated in a separate process. Of course, if the size fractionation of the solid particles is carried out inside the reaction vessel, the smaller particles can be retained and serve as a particle of seed, such that a continuous external feed stream of seeds is not required. In that event, the larger sized particles are separated from the reaction mixture and the smaller sizes retained serve as seeds during the continuous process in which the reagents are added continuously. In still another aspect, the invention relates to processes along the lines already described, wherein the amount of methanol provided to the reaction mixture is limited. Formaldehyde is typically provided as a 37% solution of para-formaldehyde in water and alcohol and is called formalin. The alcohol is usually methanol and is present at an average concentration of about 6-14% based on the formaldehyde sample. Methanol is a good solvent for para-formaldehyde and acts to keep para-formaldehyde from precipitating from the solution. The formalin can thus be stored and processed at low temperatures (<23 ° C) without the para-formaldehyde that precipitates from the solution. However, the inventors have found that the use of formaldehyde solutions with much less methanol that formaldehyde is typically used to adequately supply the reaction and that these solutions have performance advantages from the larger particle point of view. Thus, according to this aspect of the invention, a Batch reaction can be conducted using water, a phenol such as phenol, a base such as ammonia as a catalyst, a colloidal stabilizer such as carboxymethyl cellulose, an optional surfactant such as sodium dodecyl sulfonate or the like, and formaldehyde in the form of a water / methanol solution. A number of previously formed resol accounts in the size range of 150 to 300 um can be suitably added to the batch. The amount of seeds added can be such that, for example, their neutral surface area is approximately 5.79 m2 per kg of the phenol added to the batch. This will ensure that growth is a dominant mechanism in the formation of accounts during the lot. To each batch, an amount of methanol can also be added, but remember that the amount of methane is limited. The following steps can then be used, for example to form a solid resin count product: a) the above reagents are added to a batch reactor to form an aqueous reaction mixture that is stirred. Approximately four-fifths of formaldehyde and all ammonia can be retained to be added to a later point in the semi-batches mode. b) The reactor in batches with the contents can then be heated to 75 to 85 ° C. c) After the batch reactor reaches the Operating temperature, the remaining formaldehyde solution and ammonia can then be added to the container in the semi-batches mode for example for a period of 45 minutes or more. d) The mixture is kept at its temperature for at least 5 hours. e) The mixture is then heated at 90 ° C for 45 minutes. f) The mixture is then cooled to between 10 and 50 ° C and the separated solids form the liquid by filtration. The amount of methanol contained in the formalin thus used may vary. In order to stabilize the formaldehyde in solution, a methanol concentration as low as 0.50% can be used, but can be as high as 13% or more. At low levels of methanol, the solution may become unstable and formaldehyde may be precipitated from the solution, particularly at lower temperatures (<30 ° C), where formaldehyde is less soluble than the water-methanol mixture. The. Methanol concentration may thus be present up to about 0.50% or more, or up to about 2% or more, or up to about 7%, or up to 13% or more, or from 0 to 5%, or from 0.50% to 13%, in each case with respect to the concentration of methanol in the formalin solution. The resolution accounts thus obtained can be Use for a variety of purposes for example, when curing, carbonizing, and activating the material so that it can be used as an adsorbent. Both thermal curing prior to carbonization and activation after carbonization can be achieved integral with carbonization, if the appropriate activation processing parameters are present during carbonization, such as a gaseous atmosphere that is selected that is suitable to achieve all three of those objectives, as described further below, or else curing, carbonization, and activation can be accomplished in two or more discrete stages. In those cases in which the stickiness of the particles to each other is acceptable, a discrete thermal curing step can be omitted completely. Obtaining the appropriate particle size of the carbonized product can be important in obtaining the desired transport and adsorption properties, and in those cases, ideally, in which a high yield of the larger sized beads particles is desired, example greater than 425 um, very few fines are obtained or retained that are less than 150 um. The heating of resol accounts such as those already described can generate carbonized beads that have substantially the same shape as the original target, but with a higher density. So, in the carbonization and activation, a resol account will produce an activated carbon count in a substantially similar manner but typically with a smaller diameter than the starting resin. During the curing and carbonization of the resol accounts, the stickiness and agglomeration of the particles may occur as the temperature increases. This is an aggravation in the experimental work, and represents a serious impediment to the successful improvement of a rotary kiln process. During a curing experiment with resin beads produced by a resol process, the beads began to stick together to the walls of the reactor as they were heated to 71 ° C. In subsequent experiments to traditionally characterize this phenomenon in a rocking quartz reactor, it was observed that the beads were bonded together in a single mass to the inner wall of the vessel. The beads remained similar until a temperature of 425-450 ° C was reached, corresponding to the region of temperature during carbonization where significant devolatilization occurs. At this point, the agglomerations break from the wall of the container. The subsequent agitation in the rotation vessel breaks many of the agglomerations in their constituent accounts, but the agglomerations remained in the final product even after hours of processing additional . Although stickiness and agglomeration can not be a major problem in batch operations, it can be a serious problem in an ascending furnace. For efficiency, these processes typically run continuously. Low temperature solids are fed into one end of the furnace and progressed first through a heating zone and subsequently into a high temperature section where the carbonization is complete. For example, the 70-450 ° C region could be confined to a special zone in the reactor. If the beads stick together and to the internal parts of the reactor in this section, it could be difficult to pass materials through the container. The reactor could still be completely blocked by the mass of agglomerated resin, requiring a stoppage and cleaning of the equipment. Without wishing to be related by any theory, it seems that this stickiness or agglomeration results from the formation of bridges between the particles during heating, with the material formed by the bridges coming from the particles by themselves. Head space GC analysis of uncured resol accounts indicates the presence of phenol and residual formaldehyde. Thus, methods to reduce the amount of phenol and formaldehyde to prevent this agglomeration from occurring can be carried out in such a way that the formation of bridges through the Curing reactions are prevented during the phenol and formaldehyde removal process. Thus, in another aspect, the invention relates to controlled thermal processing conducted under conditions whereby the resin particles are in motion. This technical processing is sufficient to create a sufficient amount of crosslinking such that the surface of the beads is less reactive, reducing the stickiness and agglomeration of the beads together during the carbonization. In one aspect, the resol beads can be stirred in a liquid such as water and heated to curing temperatures, for example about 95 ° C, or at least about 85 ° C, or at least about 90 ° C. C, or from about 85 ° C to about 95 ° C, or from about 88 ° C to about 98 ° C. Typically, the liquid will be different from that in which the reaction was carried out, and in fact, the inventors have found that the thermal curing according to the invention when carried out in the reaction medium results in accounts that they may tend to adhere to each other, indicating that the proposed cure has not been satisfactorily achieved. In another aspect, the resol counts are agitated, as already described, in the presence of vapor.

In still another aspect, the resol beads are shaken and dried, as already described, in a vacuum dryer. In still a further aspect, the resol beads are stirred and heated, as already described, in an inert gas. According to the above, resol accounts are less likely to stick and agglomerate or merge together during curing and additional charring, since they are treated or partially cured while in motion. The particles are typically adjusted in motion or agitation before the heating process is initiated. The container containing the particles can be adjusted for movement such as by rotation or agitation. Alternatively, the container may be stationary and the particles may be adjusted in motion by an internal mechanical movement device such as an agitator, or by the action of a fluid of movement, either a liquid or a gas. If the fluid is a gas, the process can be operated as a fluidized bed. Nitrogen, air, and steam are all satisfactory gases. Gases such as natural gas can be used with the proviso that they do not significantly chemically degrade the resin. A variety of suitable inert gases are used, the term inert is intended to describe a gas that can be provided that does not chemically degrade or otherwise alter or adversely affect the desired properties of the particles. Similarly, liquid fluids must not significantly damage the resin chemically. Water is an example of a suitable fluid fluid. If the fluid is a liquid, the particles can be adjusted in motion by shaking, shaking or otherwise moving the liquid, by boiling the liquid or by a combination of agitation, otherwise shaking movement and boiling. The mechanical intensity of the movement is sufficient as long as the stickiness of the particles does not occur during the heating process. The pressures at which the process can be carried out can vary widely depending on the fluid medium used. If no fluid is used, the pressure can be in a vacuum, such that volatile reagents can be easily removed. If liquid fluids are used, the pressure may be above an atmosphere, if such conditions are necessary or useful in order to achieve the desired temperature. Otherwise, atmospheric pressure is generally satisfactory for gas or liquid fluids. The process is generally operated from ambient starting temperature (20-25 ° C) to approximately 90-110 ° C finish temperature. Higher temperatures are possible, but the curing of the resin accelerates as the temperature increases further. The partial or extensive curing of the resin does not significantly affect the amount of the product produced in the carbonization reaction. Normally, the temperature is increased from the environment to the highest temperature at a rate that allows the removal of unreacted phenol and formaldehyde from the moving particles without the particles sticking together. Satisfactory results have been obtained by fluidizing the particles in nitrogen and increasing the ambient temperature to 105 ° C in 80 minutes and maintaining at 105 ° C for 60 minutes. Thirty minutes in agitated reflux water also gives satisfactory results. When liquid water is the fluid, the volume of water is not critical with the condition that efficient movement is achieved. Particles treated with liquid fluids may require a subsequent washing step to completely remove the dissolved phenol and formaldehyde. The resol accounts produced according to the invention can be used in a variety of ways, for example by curing, carbonization, and activation to obtain activated carbon beads. The resol accounts can be cured as is described, the amount of curing obtained varies depending on the temperature of the treatment, the medium in which the beads are cured, and the duration of the treatment. The resolution beads precipitated according to the invention have some degree of branching and partial crosslinking. Heating of these resol solids precipitated at low temperatures, for example from about 95 ° C to about 115 ° C, typically induces a partial cure. However, rapid heating of the formaldehyde phenol resol solvents at room temperature through the partial curing region just described, for example at 95-115 ° C in less than 20 minutes in an inert gas, can cause Accounts stick together to form a merged mass with the linked accounts where they are touched. Tackiness together may be acceptable or even desirable in those cases in which discrete counts are not desired, such as in the formation of a resol monolith, but it is a distinct disadvantage where the sphericity and a relatively uniform particle size are desired. As already described, the inventors have found that a partial cure can increase the glass transition temperature from less than about 50 ° C to greater than about 90 ° C. If the partial curing is carried out under sufficient stirring conditions to keep the particles moving with respect to each other, the Stickiness of accounts can be eliminated. Thus, in one aspect, the present invention relates to thermal processing of resolvable accounts that accounts are in motion, in order to prevent subsequent stickiness of the accounts during any further processing. The heating rate and the time of the partial cure temperature may vary depending on the properties of the starting resole and the heating medium used. The beads can be completely cured and carbonized without the separate partial curing stage already described, but, since the beads will probably stick together, they may need to be mechanically separated from a mass that can be difficult to break. Complete curing of the material can be achieved, for example, in the temperature region from about 120 ° C to about 300 ° C with the maximum velocity typically occurring at about 250 ° C. During such curing the resin becomes highly crosslinked, and water and some unreacted monomers are typically involved. During carbonization, reticulated resol solids decompose to form oxidation products different from the starting materials, leaving a product with an increased carbon content. The carbonization is believed to begin as the cured resin is heated above about 300 ° C. The Most weight loss (typically between 40 and 50 weight percent) typically occurs in the temperature range of about 300 ° C to about 600 ° C. Water, carbon monoxide, carbon dioxide, methane, phenol, cresols and methylene bisphenols are typically the much more abundant species involved. During the carbonization process, the beads also contract, but retain their spherical shape. The minimum density is typically achieved at approximately 550 ° C. As the carbonization temperature increases beyond 600 ° C, very little weight loss occurs, but the particles continue to contract. This continued reduction in size without significant weight loss results in an increase in density as the temperature increases further. The reduction in the diameters of particular typically ranges from about 15 to about 50%, or from 15 to 30%, and the highest reduction results from the highest final carbonization temperatures. Generally the carbonization temperatures are from about 800 ° C to about 1,000 ° C. The final carbonized product is also called carbon. Microporosity (pores having diameters of 20 angstroms or less) generally develop at temperatures above 450 ° C. However, carbonization by itself usually produces a material in which microporosity it is not fully accessible, and the material is then activated additionally to produce accessible porosity. If an activated product is desired, the maximum carbonization temperature is usually close to the activation temperature that will be used. Carbonization temperatures above 1,000 ° C are possible if a high surface area material is not the ultimate goal. The excessive carbonization temperature causes additional graphing of the material, the process where the amorphous carbon begins to turn into a bulk graphite phase, causing the density of the particles to increase. The carbonization reactions are generally carried out in a non-oxidizing atmosphere, to prevent • excessive degradation of the material. Common atmospheres include nitrogen and oxygen-depleted combustion gases. Thus the atmosphere can include water, carbon oxide, and hydrocarbons, and the gas burned from the fuel to provide the heat for the carbonization reaction can provide a suitable atmosphere for carbonization. The carbonization can be carried out in a vapor and / or atmosphere rich in carbon dioxide, in which case the carbonization can be carried out in the same equipment and in the same gaseous atmosphere as the subsequent activation. Similarly, the carbonization step can be advantageously combined with the thermal curing step and running on the same equipment and on the same gaseous atmosphere. If desired, a preliminarily partial cure may also frequently be performed on the same equipment as curing and carbonization, provided there is sufficient agitation. Generally the beads move during curing and carbonization, but it is a requirement, as long as some agglomeration or stickiness is acceptable. Carbonized product accounts merged under static conditions can be broken to provide free flowing accounts if necessary. However, keeping the accounts provides better heat transfer and gives a more uniform product. Rotary kilns and fluidized beds are suitable reactors for the curing and carbonization reactions. The term "activation" as used herein is intended to encompass any treatment that serves to increase the accessible surface area of a carbonized material, and typically involves treating the carbonized material with steam, carbon dioxide, or a mixture thereof. , in an endothermic reaction that removes a portion of the carbon. The activation process makes more of the inherent micropore system of the accessible carbonized material. Carbon monoxide is a primary product when carbon is reacted with carbon dioxide, and Carbon monoxide and hydrogen are among the gases produced when water reacts with carbon. The combustion of product gases can be used to provide heat to the process. This endothermic activation reaction is typically performed at elevated temperature, the rate of activation that increases with temperature. The speeds are significant in the range of about 800 to about 1,000 ° C. Excessively high activation temperatures (typically above about 900 ° C) can produce a non-uniformly activated product that over-activates on the outside and becomes active on the inside. This results from the reaction rate of the activation gas that is greater than the rate of diffusion of the gas in the particle. The activation speed also increases with the partial pressure of the activation gas. It is generally preferable to minimize the presence of molecular oxygen during the activation process unless a non-uniform product is desired. If molecular oxygen is present, an exothermic oxidation occurs causing local heating and the reaction will continue to occur in the hot spot region resulting in a non-uniform product. In fact, the endothermic nature of the activation helps to control the uniformity of the product since the reaction produces local cold spots and also the reaction occurs in a region, of a different higher temperature. If the sphericity and the controlled particle size are desired, the quanta will remain in motion during the activation, but this is not a requirement for the reaction. If the beads are kept in motion, both mass and heat transfer are facilitated, and a more uniform product can be produced. Rotary kilns and fluidized beds are suitable reactors. The combustion gases can be used to provide both the heat and the activation gas to the reactor. For the convenience of the process, the carbonization process can be combined with the activation process in the same reactor with the same gas composition, that is, in the same gaseous atmosphere. The activated carbon product of the activation process maintains its spherical shape and is normally essentially the same or similar in size as the starting carbon. Excessively small bills can be consumed entirely during activation, and are performed at elevated temperatures, with the smallest bills activated at high speeds. This can change the particle size distribution to a larger average size than the starting carbon. The activation produces an account that can be highly porous and has a very high surface area depending on the degree of activation. Thus the activated product will have lower density than the carbon that comes from it. The surface area per unit weight, the pore volume and the pore volume per cent due to micropores can be determined by the method developed by Brunauer, Emmett and Teller (commonly called the BET method). Activation of a 300-350 micron coal with poorly accessible pores (surface area of less than 1 m2 / g) at 900 ° C in 50% volume steam-50% by volume nitrogen for two hours in a fluidized bed typically produces an activated carbon with a BET surface area above 800 m2 / g. The activated carbon beads produced by the processes of the invention can be highly porous and also have high surface areas. The phenol-formaldehyde resole beads produced in the absence of a pore-forming component are carbonized and activated to surface areas of up to about 1,500 m2 / g have generally 95% or greater of the pore volume due to the micropores. In addition activation to the higher surface area reduces the percentage of the micropores, and a material with a BET surface area of 1,800 m2 / g can have approximately 90 percent of its pores in the micropore region. The incorporation of a pore forming component in the resol account can produce an account of activated carbon that possesses mesopores (20 to 500 angstroms in diameter) in addition to the micropore structure. Suitable pore forming agents include ethylene glycol, 1, -butanediol, diethylene glycol, Methylene glycol, gammabutyrolactone, propylene carbonate, dimethylformamide, N-methyl-2-pyrrolidinone, and nonoethanolamine. The presence of mesopores can be advantageous in cases where the mass transfer of species and / or out of the activated beds and needs to be increased. The particle size can be measured with a particle size distribution meter of laser diffraction type, or optical microscopy methods, as already described. Alternatively, the particle size can be correlated by the percentage of particles screened through a mesh. For example, the beads may be poured onto a U.S. standard screen 30 and the material passing through the U.S sieve number 30 of U. S. is dropped onto a No. 40 standard U.S sieve screen. The material retained from the U.S sieve of number 40 of the standard sieve would then have particle diameters of 420 to 590 microns. The resulting activated charcoal beads can be characterized in a variety of ways, such as by pore size; surface area; absorbent capacity; average, medium, or average particle size. These properties will depend in part on the degree of activation and pore structure of the starting resin, as well as if any additional pore forming material has been added, as already described. The surface area per unit weight, the pore volume and the pore volume per cent due to micropores can be determined by the method developed by Brunauer, Emmett and Teller (commonly called the BET method). The particle size can be measured with a particle size distribution meter of laser diffraction type, or optical microscopy methods. Alternatively, the particle size can be correlated by a percentage of particles derived through a mesh. The bulk density is. can be determined by ASTM Method D 2854-96 entitled "Standard Test Method for Apparent Density of Activated Carbon". Some typical values for these characteristics are set forth below, the given formation which is typical of the activated carbon beads made of resol beads according to the invention formed in the addition of significant amounts of additional pore-forming material. The BET surface areas of the activated carbon beads of the invention may vary within a relatively wide range, for example from about 500 m2 / g to about 3,000 m2 / g, or from 600 m2 / g to 2,600 m2 / g, or from 650 m2 / g to 2,500 m2 / g. Similarly, the pore volume of the carbon accounts activated of the invention can vary within a relatively broad range, for example from about 0.2 to about 1.1 cc / g, or from 0.25 to 0.99 cc / g, or from 0.30 cc / g to 0.80 cc / g. In addition, for example, from about 85% to about 99% of the pores can have diameters below 20 angstroms, or from about 80% to 99%, or from 90% to 97%. The apparent density of activated carbonaceous beads of the invention may also vary within a relatively broad range, for example from about 0.20 g / cc to about 0.95 g / cc, or from 0.25 g / cc to about 0.90 g / cc, or from 0.30 cc / g to 0.80 cc / g. Thus, the inventively developed carbonized resin beads to a relatively low degree could have a BET surface area of about 500 m2 / g to about 1,500 m2 / g, a pore volume of about 0.30 cc / g to 0.50 cc / g. , and with approximately 99% to approximately 95% of the pores having diameters below 20 angstroms. The apparent density could be from 0.90 g / cc to approximately 0.60 g / cc. However, even lower degrees of activation could be well achieved. Material that has been activated to a relatively high degree could, for example, have a BET surface area of about 1,500 m2 / g to about 3,000 m2 / g, a pore volume of about 0.7 cc / g at 1.0 cc / g or more, with from about 85% to about 99% of the pores having diameters below 20 angstroms. The apparent density could be from about 0.25 to about 0.60 g / cc. Relatively high degrees of activation are possible if they have been achieved, for example about 2,600 m2 / g. Typically, the activated material will have for example, a BET surface area of about 750 m2 / g to about 1,500 m2 / g, corresponding to a pore volume of 0.30 cc / g to 0.70 cc / g, and 95% to 99% of its pore volume of pores of less than 20 angstroms. The apparent density would be from about 0.50 g / cc to about 0.75 g / cc. The inventors have found that the average particle size of the activated particles is typically about 30% or less than that of the resol beads from which they are formed. Thus, a resol account having an average particle size of 422 microns provides an activated product with an average particle size of 295 microns, a BET surface area of 1260 m2 / g, a pore volume of 0.59 cc / g, 97% pore volume of pores less than 20 angstroms and density = 0.63 g / cc after carbonization and activation in 50% steam / 50% nitrogen at 900 ° C for 2 hours. The inventions can be further illustrated by the following examples of the preferred embodiments, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated. EXAMPLES Test Methods Test Method to Determine Particle Size (PS) and Particle Size Distribution (PSD) of Phenolic Resol Accounts: Unless otherwise indicated, the particle size analysis of the accounts was performed using a Wild PHotomakroskop M400, to acquire images of accounts, while the processing and analysis of images was performed using the software Visilog v 5.01 (Noesis). The beads were scattered on glass slides and the images were captured in magnifications ranging from 10X to 100X, depending on the range of particle size. Each increase was calibrated using micrometer standards. The images were recorded in the bitmap format and processed using the Visilog software to measure the particle diameters. The number of processed images varied from 20 to 40 and depended on the particle size and the increase with the objective of collecting on a few thousand particles in order to ensure that a statistically insignificant number of particles were captured and measured. He JMP statistical analysis software was subsequently used to calculate particle size distribution and particle statistics such as mean and standard deviation. The pore volume and pore size distributions were measured on a Micromeritics ASAP 2000 physisorption apparatus using N2 at 77 K. The adsorption isotherm was measured at a relative pressure of 10"3 to 0.995. needed for the low end of the pore size distribution, the adsorption isotherm was also measured for C02 at 0 ° C from a relative pressure of 10"4 to .03. The total pore volume for the sample was calculated from the total gas adsorption at a relative pressure of 0.9. The pore size distribution was calculated from the adsorption isotherm according to the Horvath-Kawazoe groove pore geometry model. See ebb, P.A., Orr, C; "Methods in Fine Particle Technology", Micromeritics Corp, 1997, p. 73. EXAMPLE 1 To a 500 mL 3-necked flask equipped with an arc-shaped mechanical stirring paddle, thermal well, heating mantle and reflux condenser were added phenol in water (54-g of 88%; mol), stabilized formaldehyde solution (97 g of 37%, 1196 mol), concentrated ammonium hydroxide (4.3 g, 0.070 mol), water (25 g) mL), sodium dodecylsulfate (0.122-g), sodium carboxymethylcellulose (0.500-g, substitution degree = 0.9, average MW 250,000). The resulting mixture was mixed well and stirred at 50-rpm, and 25-g of pre-formed beads (made using the same process) in the size range of 150-300 μm were added. The mixture was heated at 75 ° C for 4.5-h, and at 90 ° for 45-min. The mixture was cooled to 32 °, and allowed to settle, and the mother liquor was decanted. The residue was washed three times with 150-mL portions of water (decanted the first two washes) and filtered. The product was dried overnight at room temperature in a fluid bed dryer in a stream of nitrogen passed through the bottom of the bed, and a sample was analyzed for the particle size distribution. The product was screened into four size groups as listed in Table 1. The numerical particle size distribution is given in Table 2. Table 1 - Particle size distribution by weight Example 2 The procedure described in Example 1 was followed except that none of the previously formed accounts were added to the mixture. The weights of the screened fractions are given in Table 1, and the numerical particle size distribution is given in Table 2. Table 2 - Numerical particle size distribution.

EXAMPLE 3 A 500-mL 3-necked flask equipped with an arc-shaped mechanical stirring vane, thermal well, heating mantle, and reflux condenser was charged with phenol (54-g 88%, 0.506-mol) stabilized formaldehyde solution (97-g of 37%; 1,196-mol), concentrated ammonium hydroxide (4.3 g, 0.070-mol), water (25-mL), sodium dodecylisulfate (0.122-g), sodium carboxymethylcellulose (0.500-g; degree of substitution = 0.9; and average MW 250,000). The resulting mixture was mixed well and stirred at 50-rpm and heated at 75 ° C for 4.5-h, and at 90 ° C for 45-min. The mixture was cooled down to 32 ° C, allowed to settle, and the mother liquor decanted. The residue was washed three times with 150-mL portions of water (decanted from the first two washes) and filtered. The product was dried overnight in a fluidized bed dryer in a nitrogen flow. The product was screened in four groups of size comprised of beads having a diameter of > 425-μm; < 425-μm but > 300-μm; < 300-μm but > 150-μm; and < 150-μm. Example 4 The procedure of Example 3 was followed except that the beads having a size (diameter) of < 300-μm produced in Example 3 were charged to the mixture before heating to 75 ° C. Example 5 The procedure of Example 3 was followed, except that the beads having a size (diameter) of < 300-μm produced in Example 4 were charged to the mixture before heating to 75 ° C. Example 6 The procedure of Example 3 was followed, except that the beads having a size (diameter) of < 300-μm produced in Example 5 were charged to the mixture before the heating at 75 ° C. Example 7 The procedure of Example 3 was followed, except that the beads having a size (diameter) of < 300-μm produced in Example 6 were charged to the mixture before heating to 75 ° C. The results of Examples 3-7 are summarized in Table 3. Note that the yield of the product in the size range of 300-425 μm was increased by the addition of the smaller counts, and that the total yield of. 300 - 425 μm counts approximates the total throughput of all account sizes. The cumulative total weight listed in Table 3 represents the total weight of the product in all the size intervals produced in successive batches at that point. The total% yield of the accounts in the size range of 300 - 425 μm represents the number of accounts of this size range produced in the example added to the quantity produced in the previous examples. The total% yield is the total weight of the counts of all the size ranges produced in the example and previous examples divided by the total weight of the phenol used in the example and the previous examples. The total weight of the product of each sample is similar to the sum of the recycled accounts and the total weight of the product of example 3. The quantity of the product in the 300 - 425 μm size range produced in each reaction is always greater than the amount of recycled beads, always greater than the amount of recycled beads, which indicates that the 150 - 300 μm beads grew to the size range of 300 - 425 during the reaction. or Table 3 - Recycling of size accounts < 300 um produced in a batch to the next batch a) cumulative total weight is the weight of the entire product of successive lots less the recycled accounts b)% of total return of the accounts is the sum of the weight of the accounts of 300-4215 um of successive lots divided by the total amount of phenol of the successive lots c)% of total yield is the sum of the weight of all the sizes of successive lots divided by the total amount of phenol of the successive lots Examples 8-12. Five reactions were carried out under similar conditions. The only difference was that the amount of seeds in terms of unit mass per surface area of the phenol charged to each experiment was varied. Each experiment had the same loading details in terms of the amount of formaldehyde (37%), phenol (88%), ethanol, Na-CMC (2.76 g), SDS (0.66 g), water and ammonia. The formaldehyde solution used contained 7.5% methanol to inhibit the formaldehyde precipitation. This was equivalent to 40.21 grams of methanol as shown in Table 4. Each experiment was conducted in semi-batches mode, that is, all of the reagents were charged to the reactor except for 436.15 grams of formaldehyde and all (23.77 grams ) of the ammonia were pumped into the reactor at a rate of 6 mls / min started at a time when the reactor temperature reached the target operating temperature. Each experiment lasted a period of 5 hours after 85 ° C was reached. The batch was subsequently heated to 90 ° C for 45 minutes and then cooled to room temperature and subjected to a series of suspensions where the mother liquor was replaced by fresh water four times. The difference between the experiments was the amount of seeds added to the container in each experiment. Table 4a shows the amount of seeds loaded both in terms of its mass, the range of particle size and the surface area charged per unit mass of phenol charged to the container. The particle size distributions of the product that resulted from the batches are shown in Table 4b. It can be seen that the lots that had a unit mass per phenol surface area of 1.45 m2 / kg, produced a large fraction of particles that were in the lowest size class (0-150 μm). This fine material is undesirable in thermal processing, since it will produce a very small product size and have dusting problems. In addition to producing fine materials, it was found that a small seed surface area ratio in a batch can produce a large number of agglomerates in some experiments. The effectiveness of using a small amount of seeds is also reflected in the calculated space value of each distribution. For experiment 8, this had a value of 332 μm and for experiment 12, it had a value of 279 μm while experiments 9, 10 and 11 had values less than 228 μm. The dgo value of example 8 is comparable to that of example 9 but the value given is much lower than any of experiments 9, 10 or 11. The dio and d90 was the lowest of all the five experiments in experiment 12 which had the lowest seed surface area 1.45 m2 / kg of phenol. or Tables 4a and 4b - Recycling beads (seeds) in terms of their mass, the range of particle size and the surface area charged per unit mass of phenol charged to the container Table 4a or Table 4b Example 13 (5-gallon batch) To a 5-gallon jacketed reactor equipped with an anchor impeller and a reflux condenser were added phenol (8860-g of 88%, 45.5-mol), stabilized formaldehyde solution (8740-g). 37%; 107.7-mol), ammonium hydroxide (390-g; 6.35-mol), water (2800-mL), sodium dodecylisphate (11-g), sodium carboxymethylcellulose (45-g, degree of substitution = 0.9). The resulting mixture was mixed well and stirred at 25 rpm, and 1200 g of beads in the size range of 150-300 μm was added. The mixture was heated at 75 ° C for 4 hours, and for 45 minutes at 88 ° C. The mixture was cooled to 32 °, allowed to settle, the mother liquor was decanted. The residue was washed three times with 12 liter portions of water (decanted from the first two washes) and filtered. The product was dried overnight in a fluidized bed dryer, and a sample was analyzed for particle size dissolution. Example 14 (5-gallon semi-continuous) The procedure of Example 8 was followed except that the formaldehyde and the ammonia solution were fed continuously for two hours, at 75 ° C, to the reaction mixture containing phenol, carboxymethylcellulose, water and sodium dodecyl sulfate. After two hours of feeding time, the reaction mixture was maintained at 75 ° C for two additional hours, and at 88 ° C for 45 minutes. There was no significant difference of Example 13 in product performance or account size distribution. Example 15 A kettle of 1-L oil-enrobed resin with a round bottom equipped with an anchor-shaped stirring paddle, stainless steel, reflux condenser, thermal well and formaldehyde feed line was charged with liquefied phenol (162 -g; 1.517-mol), solution of 2% guar gum in water (77-g), sodium dodecyl sulfate (345-mg, 1.2-mmol), and previously uncured resin beads having a diameter of 120-250 μm (57-g). The resulting mixture was heated to 80 ° C, and a solution of concentrated ammonium hydroxide (14.1- g, 0.241-mol) dissolved in 37% aqueous formaldehyde (291-g; 3.589-mol) stabilized with methanol (12%) it was added at a rate of 2.7 mL / min. The temperature was raised to 85 ° C during the addition and maintained at 85 ° C for 4 h, and heated at 90 ° C for 45 min. After cooling to 30 ° C, the solid product did not settle. The mixture was diluted with 300 mL of distilled water, allowed to settle and the water layer was decanted. This procedure was repeated three times. The solid product was isolated by vacuum filtration and dried in a fluidized dryer. The performance of the accounts was 223-g. The product contained a large amount of small beads that stuck to the larger ones giving them a rough surface.

The inventors attribute this to the guar gum used as a colloidal stabilizer. EXAMPLE 16 A kettle of resin jacketed with 1-L oil with a round bottom equipped with an anchor-shaped stirring paddle, stainless steel, reflux condenser, thermal well and formaldehyde feed line was charged with liquefied phenol ( 162-g; 1517-mol), 2% sodium carboxymethyl cellulose solution (degree of substitution = 0.9, and average of 250,000) in water (76-g), and previously uncured resin beads having a diameter of 120-250 μm (57-g). The resulting mixture was heated to 80 ° C, and a solution of concentrated ammonium hydroxide (14.3-g, 0.244-mol) dissolved in 37% aqueous formaldehyde (291-g; 3.589-mol) stabilized with methanol (12%) was added at a rate of 2.7 mL / min. The temperature was raised to 85 ° C during the addition and maintained at 85 ° C for 4 h, and heated at 90 ° C for 45 min. After cooling to 35 ° C, the mixture was allowed to settle and the mother liquor was decanted the product was washed 3 times with 300-mL portions of water and was isolated by vacuum filtration and dried in a fluidized dryer. The performance of the accounts was 202-g. The product was screened through screens to separate according to size: 6.5-g > 600-μm; 62.4-g > 425-μm (< 600-μm); 98.7-g > 300-μm; 29.4-g > 250-μm; and 24.1-g > 150-μm.

Examples 17-18 (Addition of semi-batches of formaldehyde and ammonia to the reactor) In experiments 17 and 18, a 1.2 liter jacketed reactor with suitable agitation was used to suspend the phenolic resole beads. The amounts of the material shown in Table 5 were loaded in each experiment. In the case of example 17, all reagents were added to the reactor while in example 18, only a portion of the formaldehyde (100 grams) and none of the ammonia were added to the reactor. These were added instead in the semi-batches mode at a rate of 6 mls / min once the reactor temperature had reached the operating temperature (85 ° C). 30 grams of ethanol were added to each experiment. The 40.21 grams in experiment 17 are contained in the formaldehyde solution. About 40 additional grams of methanol were added in the experiment in Example 18. The materials in the reactor were heated to the reaction temperature (85 ° C) and kept at this temperature for 5 hours. In the case of the semi-batches experiments, the formaldehyde / ammonia mixture was pumped into the reactor at a rate of 6 mls / min. It took about 1 hour and 15 minutes to pump the formaldehyde / ammonia mixture into the reactor. After the reaction has been completed, the The contents of the vessel were heated to 90 ° C or higher and kept for a minimum of 40 minutes and then cooled to near room temperature. The suspension was resuspended in water 4 times to wash the particles and displace the mother liquor. The suspension was then filtered and dried with air. A direct light scattering instrument was used to determine the particle size distribution of the product. The results of the analyzes are shown in Table 5. The distribution produced by the semi-batches method produced a smaller distribution containing few fine particles (<250 um) and few large particles (> 350 um). This is reflected in the space values for both distributions. The space calculated for example 17 (case of lots) was 125 μm and for example 18 (case of semi-lots), it was 93 μm. This type of distribution is advantageous for the downstream processing and for the use of the final product. In addition, the performance of the batch experiment (example 17) was 77.14% while the yield of the semi-batches experiment (example 18) was 83.43%. Thus, the operation in the semi-batches mode has advantages of the quantity of the product made as well as the quality of the particle size distribution.

NJ NJ or Table 5 Experimental description and results of experiments with addition of lots or semi-batches of formaldehyde and ammonia NJ NJ Examples 19-22 (Addition of batches in parts) Of the experiments listed in Table 6 (examples 19 to 22), three are conducted in half-batches mode (examples 19, 20, 21) while the other experiment (example 22) is conducted in batch mode. For each experiment, the amount of seeds added in relation to the amount of phenol added remained constant. The type of seeds added to each experiment was also the same, being in the size range of 150 to 300 microns. The full charge details are shown in Table 6. The ethanol was not added to the experiment in Example 22. The formaldehyde containing 7.5% methanol was used in each experiment. Experiments 19 and 21 were conducted in the same way, a 1.2 liter jacketed reactor with adequate stirring to suspend phenolic resole beads was used. The amounts of material shown in Table 6 were loaded to each experiment. Only a portion of the formaldehyde (100 grams) and no ammonia were added to the reactor. These, however, were added in semi-batches mode at a speed of 6 mls / min once the reactor temperature had reached the operating temperature (85 ° C). The materials in the reactor were heated to the reaction temperature (85 ° C) and kept in this state. temperature for 5 hours. The formaldehyde / ammonia mixture was pumped into the reactor at a rate of 6 mls / min. It took about 1 hour and 15 minutes to pump the formaldehyde / ammonia mixture into the reactor. After the reaction has been completed, the contents of the vessel were heated to 90 ° C or higher and maintained for a minimum of 40 minutes and then cooled to near room temperature. The suspension was allowed to settle and the liquid layer was decanted. Fresh water was added to the washing of the solids. This washing procedure was repeated two additional times. The suspension was finally filtered and dried in air. A number of screens were used to separate the dry particles in a number of fractions. The results of the analyzes are shown in Table 6. Experiment 20 was conducted in two stages. Each stage uses half of each ingredient as it is listed for experiment 20 in Table 6. The first stage was conducted in the same manner as experiments 19 and 21 were done. The experiment was continued for 3 hours instead of 5 hours (as in experiments 19 and 21). After 3 hours, the batch was cooled to 40 ° C and 324.21 grams were removed from the container. The remaining contents were reheated to 85 ° C and the second part of the experiment was started. As in the first part, all the ingredients except for 436.15 grams of formaldehyde and 23.77 grams of ammonia were charged to the reactor. The remaining formaldehyde and ammonia were loaded at a rate of 6 mls / min. The second part of the experiment was continued for 3 hours before being heated to 90 ° C for at least 40 minutes. The batch was then cooled to 40 ° C. The suspension was allowed to settle and the liquid layer was decanted. Fresh water was added to wash the solids. This washing procedure was repeated two additional times. The suspension was finally filtered and dried in air. A number of screens were used to separate the dry particles in a number of fractions. The results of the analysis are shown in Table 6. Example 22 was conducted in batch mode. All of the ingredients shown in Table 6 were charged to the reactor and heated to 85 ° C. The contents were maintained at 85 ° C for 5 hours before being heated at 90 ° C for at least 40 minutes. The batch was then cooled to 40 ° C. The same washing, filtering and drying as defined for examples 19, 20 and 21 were used for example 22. The results of the screening are shown in Table 6. Of the 4 experiments described in the above, the two stage experiments Individuals conducted in the semi-batches mode resulted in the highest d? 0 value and lowest space values of all four experiments. The experiment conducted in batch mode (example 22) had the lowest value given and the second largest space (except for experiment 20). This indicates that for single-stage experiments, the operation of semi-batches produced smaller distributions with significantly less fine particles. The experiment conducted in 2 stages (example 20) had the largest space, due to the presence of more large particles in the distribution but had very few fine materials that the experiment in batches, having a size of 115 microns. In addition, Example 22 showed the lowest performance value of all four experiments at 55% compared to the next closest value of 90% for Example 21.

NJ NJ O Table 6 Operating conditions and results of particle size distribution for experiments done in parts NJ Examples 23-29 (Addition of batch in parts) Examples 23 and 24 represent separate steps of a two-step experiment. The amounts listed for Example 23 were charged to the reactor in batch mode except that 436.15 grams of formaldehyde (37%, 7.5% methanol) and all of the ammonia (23.77 grams) were fed to the reactor at a rate of 6 mls / min. . Feeding was started once the reactor had reached 85 ° C. After a reaction time of 5 hours, the batch was heated at 90 ° C for 40 minutes. Then it was cooled to 40 ° C. Half of the lot was drained from the container; the drained portion was allowed to settle and the liquid layer was removed from the container. The solids were suspended with water three times to wash the solids. The suspension was then filtered and dried by passing air at room temperature through the bed of solids until dried. This powder was screened and the results are shown in Table 7. In Example 24, the material remaining in the reactor of Example 23 was reheated to 85 ° C and the ingredients listed in Table 6 were added to the reactor. Again, 168.07 grams of the formaldehyde (37%) and all of the ammonia (11.8 grams) were charged in the semi-batches mode to the container. All other quantities were loaded in batch mode. In Example 24, no seeds were added to the container since the particles already present acted as seed material for the charge for Example 24.

After 5 hours at 85 ° C, the reaction was cooled to 40 ° C. The suspension was drained from the container and allowed to settle in a vessel; the liquid layer was removed from the glass. The solids were resuspended with water three times in order to wash them. The suspension was then filtered and dried by passing air at room temperature through the bed of solids until dried. The solids yield of the process was 89.82%. Table 7 provides the particle size distributions of Examples 23 and 24. The advantages of operation in the two stages as opposed to a stage can be seen from the particle size distribution. In example 24, the particle size distribution had grown such that there are no larger particles present (> 500 um) and few small particles present (<300 um) than in example 23. This mode of operation is advantageous for a process in which the majority of large particles and few fine particles are desired. The increase in the number of large particles comes at the expense of the generation of very few fines. This is reflected in the change in the value of the space. For experiment 23, it was 210 μm whereas for experiment 24, it was 242 μim. The results of another one-step experiment (example 25) are also shown in Table 7. This experiment was conducted in half-batches mode with all the ingredients that are added to the reactor except for 436.15 grams of formaldehyde (37%) and 23.77 grams of ammonia. These were added in the semi-batches one mode. time the reactor reached 85 ° C. The experiment was continued for 5 hours when the suspension was heated to 90 ° C for at least 40 minutes and then cooled to 40 ° C. The suspension was drained from the reactor and washed 4 times with water using a decanting / resuspension procedure. The solids finally filtered, they were washed with water and dried using air at room temperature. The results for example 25 are shown in Table 7. The results show that by doing an experiment in parts, a larger amount of large particles can be generated as evidenced by the larger dgo value in example 24 (418.10 μm) compared to examples 23 (334.70 μm) and 25 (331.50 μm). The yield of particles greater than 425 μm in Example 24 is 25.69% while for Examples 23 and 25 it is 7.93% and 4.43% respectively. In Examples 26-29, the second group of experiments, four experiments are compared for their ability to develop the smallest particle size generated from the reaction (0-150 μm). All experiments were done in semi-batches mode. The first three experiments (example 26, 27, 28) were made in one stage, while the final experiment (example 29) was done in four stages. A much smaller amount of seeds was used in the final experiment, since the seeds were rationed to the amount of phenol charged to the reactor as part of the first stage charges to the vessel. However, on a seed surface area per amount of phenol charged to the container, it is comparable to the amount of seed surface area in Examples 27 and 28. Example 26 was used twice the amount of seed that was used. in the other three experiments. In examples 26, 27 and 28, 138 grams of water, 0.66 grams of SDS and 2.76 grams of CMC were added to the reactor together with 298.18 grams of phenol (88%) and 100 grams of formaldehyde (37%, 7.5% methanol ). 436.15 grams of formaldehyde and 23.77 grams of ammonia were added in semi-batches mode. In Example 29, a total of 857.84 grams of formaldehyde, 477.08 grams of phenol, 220.8 grams of water, 38 grams of ammonia, 4,416 grams of Na-CMC, 1.04 grams of SDS were added to the reactor. 30 grams of ethanol were added to each experiment except for the experiment in Example 29. Each of these quantities was divided into four equal portions. During each stage of operation, a portion of each reagent was added to the reactor. For the formaldehyde portion (214.46 grams), 40 grams were added to the reactor and 174.46 grams were added to the reactor. mode of semi-batches at a speed of 6 mls / min. All of the ammonia for each stage (9.5 grams) was added along with the formaldehyde. In Example 29, the first stage was conducted in a manner similar to Examples 26, 27 and 28. The mixture of formaldehyde and ammonia was added once the reaction temperature reached 85 ° C. The reaction was continued for 3 hours before the next stage was started. Phenol, formaldehyde, Na-CMC, SDS, water and part of the formaldehyde were added to the reactor in one charge and the remaining formaldehyde and ammonia were added in the semi-batches mode at a rate of 6 mls / min. After 3 additional hours the third stage was conducted in the same way as the second and after 3 additional hours, the fourth stage was completed in the same way. After the fourth stage was complete (3 hours) the vessel was heated to 90 ° C for at least 40 minutes and subsequently cooled to 40 ° C. The formed suspension was filtered, washed with water and dried with air for 12 hours. The particle size distribution formed was written and the results are shown in Table 8. The comparison of all the examples shows that conducting a four-stage experiment was superior to conducting it in a single stage when the amount of seed initially added is equivalent in terms of weight I JJ added per unit of phenol or any other reagent added. When compared in terms of the amount of large particles produced, example 29 produced particles much larger than any example 26, 27 or 28. The value given for all experiments was comparable while the d90 value for the step experiment was much larger. The results also show that the achieved performances are comparable by both methods of operation. t t Table 7a and Table 7b. Experimental description and results of experiments with the addition of reagents by parts Table 8a Operating conditions for examples 26, 27, 28 and 29 t o Table 8b Results for examples 26, 27, 28 and 29 Examples 30-31 Table 9 shows the operating conditions and the results of two experiments, examples 30 and 31. The first is a standard semi-lot experiment using the ingredients given in Table 9. Similar to the previous examples, 436.15 grams of formaldehyde (7.5%) and all of the ammonia (23.77 grams) were added in the semi-batches mode at a rate of 6 ml / min, starting when the target operating temperature reached (85 ° C). In Example 31, the same procedure was used as in Example 30 except that an additional amount of ammonia (23.77 grams) was pumped into the reactor 30 minutes after the formaldehyde and the ammonia had been added to the reactor. The ammonia was added at a rate of 6 mls / min. To each experiment, 138 grams of water, 0.66 grams of SDS and 2.76 grams of CMC were also added in the batch mode at the beginning of the experiment. In both cases, 80 grams of seeds were used in the size range of 150 to 300 um. The use of the additional ammonia resulted in a larger number of large beads compared to the case where no additional ammonia was added. Although the total yield of the product of Example 31 was lower than Example 30 (87.47% vs. 100.77%), the performance of the particles above a size of 425 μm was much larger (78.45% vs. 4.43%). This increase in the larger particle amount enters only a minor increase in space from a value of 163 μm to 188 μm. This reflects the ability of supplemental ammonia to develop particles of all sizes. t to O Table 9a and 9b Experimental description and results of experiments with supplementary addition of ammonia Table 9a Table 9b Examples 32-35 In Table 10, the details of Examples 32-35 are given, from which it can be seen that the loading of materials to each batch was equivalent except for the amount of methanol present. In Example 32, the added formalin contained 1% methanol which was equivalent to 5.26 grams of methanol. The formalin in Example 33 contained 7.5% methanol equivalent to 40.21 grams of methanol. The 7.5% solution was used in Examples 34 and 35 as well but the additional methanol was added so much that the experiments in Examples 34 and 35 contained 70.21 grams and 100.21 grams of methanol respectively. All quantities in Table 10, including 80 grams of seed material, were charged to the batch reactor except for 436.15 grams of formaldehyde and 23.77 grams of ammonia. These materials were then added to the container in the semi-batches mode. Each charge was heated to 85 ° C and maintained for 5 hours. Once the reaction mixture had reached 85 ° C, the remaining formaldehyde formation and the ammonia were added to the reactor in the semi-batches mode over a period of 45 minutes. After 5 hours, the formed suspension was heated at 90 ° C for 45 minutes, after which it was cooled to 30 ° C. The suspension was subsequently submitted to Three stages of solvent exchange with water before the suspension leaked. The recovered solids were dried at room temperature for 12 hours and screened using a series of perforated screen plates. The mass retained on each screen plate is shown in Table 10. Also shown in Table 10 are product performance and product yield in the size ranges above 425 um. The space is also shown in Table 10. It shows a maximum value when the content of methanol is grams (320 μm) and with 5.36 grams, it has a value of 157 μm. The results in Table 10 show that while the total total yield of the product does not directly correlate with the amount of methanol in the reactor, the change in total product yield above 425 um increases with a decrease in the amount of methanol in the lot. t o Table 10a Load quantities for each experiment to t o Table 10b: Results in terms of the distribution of particle size, yield and space 4-.

Examples 36-45 The following examples illustrate various thermal treatments of phenol / formaldehyde resins resin beads prepared in an aqueous environment using an ammonia catalyst, in a manner as already described. The precipitated beads of the aqueous reaction mixture at the end of the reaction were washed with water, and then dried at room temperature. EXAMPLE 36 This example illustrates the hydrothermal treatment of resole resin beads and subsequent carbonization. The initial accounts of 425-500 microns were analyzed by DSC and showed a Tg of principle at 47 ° C. 600 g of these beads were refluxed in 3000 g of water (~ 97 ° C) with stirring at ambient pressure for 30 minutes and subsequently washed with 3000 ml of water. A portion of these beads were dried with air at room temperature while the rest was left humid. DSC of the dry accounts showed that the start Tg has changed to 94 ° C. The wet and dry samples were subsequently carbonized in a rotary laboratory oven under nitrogen using a 2-hour rise at 1000 ° C. In both cases, the accounts were not stuck or agglomerated by all the carbonization. The carbonized products of the wet and dry starting materials were subsequently activated for 2 hours at 50% in volume of steam in nitrogen at 900 ° C in a fluidized bed reactor resulting in BET surface areas of 814 and 852 m2 / g, respectively. EXAMPLE 37 This example illustrates an escalated version of the hydrothermal process and subsequent carbonization. 17.1 kg (37 pounds) of resin beads of 400-500 microns were suspended in 25 L of water in a 50 L flask. The beads were heated to reflux and kept for one hour. They were then cooled, filtered and washed with an equal weight (-38 pounds, 17.2 kg) of water. The beads were left wet in water with no additional drying. Approximately one pound of these beads were carbonized in nitrogen at 1000 ° C in a rotary laboratory reactor and activated in the same reactor at ~ 878 ° C for 3 hours at 50% steam volume (total gas feed rate L / min 3). There was no indication of stickiness or agglomeration in the carbonization or subsequent activation. The resulting activated material had a BET surface area of 443 m2 / g. EXAMPLE 38 This example illustrates that insufficient agitation results in agglomeration when the resin is treated with steam. A 2-inch ID stainless steel reactor that It contains a gas inlet line that leads to the base of a frit at the bottom of the reactor was heated under nitrogen (1.0 SLPM) at 120 ° C. The gas inlet line was also heated to 120 ° C. The flow of nitrogen was then discontinued, and the liquid water was fed at 4,333 mL / minute and vaporized in the gas inlet line at 120 ° C. The steam flow was continued for 5 minutes to purge the nitrogen from the lower region of the reactor. The uncured resin beads (74.2 g) were loaded into a glass tube containing a thick frit. The upper part of the tube was fitted with a septum that allowed a stainless steel tube of H inch to move up and down in the cylinder. The stainless steel tube was connected to the inch bellows pipe. The other end of the bellows pipe was attached to another stainless steel pipe that was fitted through the existing thermocouple fit over the top of the 2-inch ID stainless steel reactor and extended about an inch below the region where the reactor head was attached to the reactor. The base of the glass tube was attached to a supply of nitrogen. The nitrogen supply was used to introduce the material into the tube and then to fluidize it in the glass tube at the desired time. The lowering of the stainless steel tube in the uncured fluidized beads allowed the beads to be transferred from the tube to the 2-inch ID reactor due to the speed linearly significantly increased in the small tube. The configuration of the reactor was such that the vapor and the nitrogen carrier left the reactor at a point upstream where the solids entered the reactor thus minimizing the mixing of nitrogen with the vapor at the base of the reactor. The resin beads were added to the steam stream in the 2-inch ID reactor in 7 minutes. The steam treatment was continued at 120 ° C for an additional 48 minutes. The steam flow was terminated and the reactor was maintained for an additional hour in slow nitrogen flow (42 SCCM) during which time the water was continued to be emitted from the reactor. The reactor was then allowed to cool to nitrogen (1.0 SLPM). The isolated material from the reactor (62.8 g) bound very loosely together and broke easily, but was not free flowing. The vapor velocity during this example was below the fluidization rate of the resin beads. EXAMPLE 39 This example illustrates the use of a vacuum rotary cone drier [model, source] and the subsequent carbonization of the product. 54.4 kg (120 pounds) of beads were dried at 50 ° C for 8 hours in a rotary cone dryer operating under vacuum, approximately 70 mm Hg. The resulting dry product was screened, and the cut of 400-500 microns was transferred back to the same dryer and heated at 100 ° C and remained there for 2 hours, all under vacuum (approximately 70 mm Hg). 335 g of these beads were carbonized in 6 L / min of nitrogen at 900 ° C in a laboratory rotary reactor and activated in 90% steam in the same reactor at ~ 878 ° C for 2 hours in 90% by volume steam (total gas feed rate of 6 L / min standard). No sign of stickiness or agglomeration was observed in carbonization or subsequent activation. EXAMPLE 40 This example illustrates that tackiness occurs in the absence of a high final temperature, with the use of a rotary cone dryer. 54.4 kg (120 pounds) of beads were dried at 50 ° C for 8 hours in a rotary cone dryer operating under full vacuum. The resulting dry product was screened and a portion of the cut of 400-500 microns was used as found without further treatment. 346 g of these beads were carbonized in 6 L / min of nitrogen at 1000 ° C in a laboratory rotary reactor and activated in 90% steam in the same reactor at ~ 878 ° C for 2 hours in 90% by volume steam (total gas feed rate 6 L / min standard). During the carbonization, the beads were observed to stick together and adhere to the inner wall of the reactor between the oven temperatures of ~ 150 to ~ 450 ° C. EXAMPLE 41 This example illustrates a process of the invention and subsequent curing using a fluidized bed. A 2-inch ID stainless steel fluidized bed reactor equipped with a thermocouple and a gas dispersion frit was charged with resin beads of 420-590 microns. (303.1 g). The resin beads were fluidized in nitrogen (29 SLPM). The temperature was increased from room temperature to 105 ° C for 80 minutes, maintained at 105 ° C for 60 minutes, increased to 150 ° C for 90 minutes and maintained at 150 ° C for 60 minutes. In cooling the material recovered from the reactor (266.5 g) was free flowing. EXAMPLE 42 This example illustrates that agglomeration can occur, even with agitation, if the appropriate temperatures are not maintained for a sufficient time. A 2 inch ID stainless steel fluidized bed reactor equipped with a thermocouple and a gas dispersion frit was charged with resin beads of 420-590 microns (301.2 g). The resin beads were fluidized under nitrogen (29.8 SLPM). The temperature was increased from ambient to 150 ° C for 60 minutes, maintained at 150 ° C for 60 minutes, increased to 250 ° C for 60 minutes and maintained at 250 ° C for 60 minutes. In the cooling, the material recovered from the reactor (247.0 g) was melted in a cylinder sticking to the thermocouple, to the walls of the reactor and to the gas dispersion frit. EXAMPLE 43 This example illustrates that the process of the invention can be integrated with the carbonization reaction in a single reactor. A 2-inch ID stainless steel fluidized bed reactor equipped with a thermocouple and a gas dispersion frit was charged with resin beads of 420-590 microns (301.8 g). The resin beads were fluidized in nitrogen (29 SLPM). The temperature was increased from room to 105 ° C for 80 minutes, maintained at 105 ° C for 60 minutes, and then allowed to cool and kept fluidized over the weekend in nitrogen (29 SLPM). The material was then heated under nitrogen (29 SLPM) at 1000 ° C for 300 minutes and maintained at 1000 ° C for 15 minutes. In cooling, the carbonized material recovered from the reactor (168.8 g) was free flowing. EXAMPLE 44 This example illustrates the formation of activated carbon beads by the process of the invention which characterizes carbonization in nitrogen and activation in 50% steam-50% nitrogen in a fluidized bed. 350.1 g of wet resin beads with water of Example 37 were charged to a 2-inch ID stainless steel reactor containing a gas inlet line that leads to the base in a frit at the bottom of the reactor and a 5-element thermocouple mounted on the resin bed. Nitrogen was fed to the reactor at 29 SLPM, and the reactor was heated in a vertically mounted electric three-element tube furnace at room temperature to 105 ° C for a period of 20 minutes and maintained at 105 ° C for 60 minutes. The nitrogen flow rate was then reduced to 10.8 SLPM and the temperature was increased to 900 ° C over a period of 120 minutes. Upon reaching a bed temperature of 900 ° C the nitrogen flow was reduced to 5.4 SLPM, and the water was fed to the reactor at a rate of 4,333 mL liquid / minute through an input line heated to 120 ° C to vaporize the water before it entered the reactor. The steam-nitrogen feed was continued at an oven temperature of 900 ° C for 120 minutes. During activation, an endotherm of 4-5 ° C was measured by the 5-element thermocouple. At the completion of the 120 minute activation, the water feed was terminated, the nitrogen flow was adjusted to 10.8 SLPM, and the reactor allowed to cool. 116.8 g of activated carbon beads were isolated from the reactor. The activated product had a bulk density = 0.66 g / cc, an average particle size of approximately 380 microns, a surface area BET = 1032 m2 / g, pore volume = 0.468 cc / g, and 98% of the pores were less than 20 Angstroms in diameter. EXAMPLE 45 This example illustrates the formation of activated carbon beads by the process of the invention which characterizes a carbonization and activation both carried out at 50% steam-50% nitrogen in a fluidized bed. 196.4 g of wet resin beads in water of Example 37 were charged to a 2 inch ID stainless steel reactor containing a gas inlet line leading to the bottom of a frit at the bottom of the reactor and a thermocouple to the bottom of the reactor. Elements mounted on the resin bed. Nitrogen was fed into the reactor at 29 SLPM, and the reactor was heated in a three-element electric vertically mounted tube furnace at room temperature at 105 ° C for a period of 20 minutes and maintained at 105 ° C for 60 minutes . The nitrogen flow was reduced to 5.4 SLPM, and the water was fed to the reactor at a speed of .333 mL liquid / minute through an inlet line heated to 120 ° C to vaporize the water before it entered the reactor. The reactor was then heated to 900 ° C for a period of 120 minutes. The steam-nitrogen feed was continued at an oven temperature of 900 ° C for 120 minutes. During activation, an endotherm of 4-8 ° C was measured by the 5-element thermocouple. At the completion of the 120 minute activation, the water supply was finished, the flow of nitrogen was adjusted to 10.8 SLPM, and the reactor allowed to cool. 50.3 g of activated carbon beads were isolated from the reactor. The activated product had a bulk density = 0.60 g / cc, an average particle size of 381 microns, a surface area BET = 1231 m2 / g, pore volume = 0.576 cc / g, and 97% of the pores were lower that 20 angstroms in diameter.

Claims (7)

CLAIMS 1. A process for producing an activated carbon monolith, the process characterized in that it comprises: reacting a phenol with an aldehyde in a stirred aqueous medium provided with a base such as a catalyst, a colloidal stabilizer, optionally a surfactant, and resol solvents. previously formed, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; optionally compact the aqueous dispersion of resol beads; and carbonize and activate the resol accounts to obtain a monolith of activated carbon. 2. The process according to claim 1, characterized in that the activated carbon monolith has a diameter that is at least 10,000 times the average particle size of the resol solids in the aqueous dispersion. 3. The process according to claim 1, characterized in that the activated carbon monolith has a diameter that is at least 1,000 times the average particle size of the resol solids in the aqueous dispersion. 4. The process according to claim 1, characterized in that the carbonization and activation is
1. They perform in separate stages. 5. The process according to claim 1, characterized in that the carbonization and activation are carried out in a single step in the same gas atmosphere. 6. The process, in accordance with the claim 1, characterized in that the previously formed resol counts have an average particle size of about 10 μm to about 1,500 μm. The process according to claim 1, characterized in that the previously formed resol counts have an average particle size of about 125 μm to about 300 μm. 8. The process according to claim 1, characterized in that the resol solids obtained have an average particle size of about 10 μm to about 2,000 μm. 9. The process according to claim 1, characterized in that the carbonization and activation are carried out at a temperature of about 500 ° C to about 1,500 ° C. 10. The process according to claim 1, characterized in that the phenol comprises monohydroxybenzene. 11. The process according to claim 1, characterized in that the aldehyde comprises formaldehyde. 12. The process according to claim 1, characterized in that the base comprises one or more of ammonia or ammonium hydroxide. The process according to claim 1, characterized in that the previously formed resol counts are provided in an amount of at least 10% by weight, based on the weight of the phenol. The process according to claim 1, characterized in that the molar ratio of the aldehyde to the phenol is from about 1.1: 1 to about 3: 1. 15. The process according to claim 1, characterized in that the colloidal stabilizer comprises a salt of carboxymethyl cellulose. 16. The process according to claim 1, characterized in that the temperature is from 75 ° C to 90 ° C. 17. The process according to claim 1, characterized in that the surfactant is present and comprises one or more of: sodium dodecyl sulfate or sodium dodecyl benzene sulfonate. 18. The process in accordance with the claim 1, characterized in that the base comprises one or more of: ammonia or hexamethylenetetramine. 19. The process according to claim 1, characterized in that the methanol is present in the aldehyde provided to the reaction mixture in a amount of no more than about 2%, based on the total weight of the aldehyde. 20. A process for producing an activated carbon monolith, the process characterized in that it comprises: providing a stirred aqueous reaction mixture with a phenol, a portion of an aldehyde, a portion of a base as a catalyst, a colloidal stabilizer, optionally a surfactant and previously formed resol accounts; reacting in the reaction mixture for a period of time and at a temperature sufficient to produce an aqueous dispersion of partially formed resol solids; then adding a remaining portion of the aldehyde and a remaining portion of the base to obtain a resol monolith; optionally compact the resol monolith; and carbonizing and activating the resol monolith to obtain an activated carbon monolith. 21. A process for producing an activated carbon monolith, the process characterized in that it comprises: providing a portion of a phenol, a portion of an aldehyde, and a portion of a base as catalyst to a reaction mixture which is a stirred aqueous medium which includes a colloidal stabilizer, optionally a surfactant, and previously formed resol counts; reacting for a period of time and at a temperature sufficient to produce an aqueous dispersion of partially formed resol solids; then providing an additional portion of the phenol, an additional portion of the aldehyde, and an additional portion of the base to the reaction mixture and reacting for an additional period of time; then adding any remaining portion of the phenol, the aldehyde, and the base for a period of time and at a temperature sufficient to obtain a resol monolith; optionally compact the resol monolith; and carbonizing and activating the resol monolith to obtain an activated carbon monolith. 22. The process according to claim 21, characterized in that at least one quarter of the total charge of formaldehyde and ammonia is charged to the reactor and the remainder is charged in half-batches mode. 23. The process in accordance with the claim 21, characterized in that the aldehyde and the base are added to the reaction mixture over a period of from about 15 minutes to about 180 minutes. 24. The process according to claim 21, characterized in that the addition of formaldehyde and
2. Ammonia to the reaction mixture starts from about 5 minutes to about 180 minutes after the initial loading of reactants into the reactor. 25. An activated carbon monolith, characterized in that it is made by a process comprising: reacting a phenol with an aldehyde in a stirred aqueous medium provided with a base such as a catalyst, a colloidal stabilizer, optionally a surfactant, and previously resole beads formed, for a period of time and at a temperature sufficient to produce an aqueous dispersion of resole beads; optionally compact the aqueous dispersion of resol beads; and carbonize and activate the resol accounts to obtain a monolith of activated carbon. 26. The process according to claim 25, characterized in that the activated carbon monolith has a diameter that is at least 10,000 times the average particle size of the resol solids in the aqueous dispersion. 27. The process according to claim 25, characterized in that the activated carbon monolith has a diameter that is at least 1,000 times the average particle size of the resol solids in the aqueous dispersion. 28. The process according to claim 25, characterized in that it further comprises grinding the activated carbon monolith to obtain monolith particles having an average particle size of about 10 times to about 10,000 times the average particle size of the resole beads of the aqueous dispersion. 29. The activated carbon monolith according to claim 25, characterized in that the carbonization and activation are carried out in separate stages. 30. The activated carbon monolith according to claim 25, characterized in that the carbonization and activation are carried out in the same gas atmosphere. 31. The activated carbon monolith according to claim 25, characterized in that the previously formed resol counts have an average particle size of about 10 μm to about 1,500 μm. 32. The activated carbon monolith according to claim 25, characterized in that the resol solids obtained have a mean particle size of about 10 μm to about 2,000 μm. 33. The activated carbon monolith according to claim 25, characterized in that the carbonization and activation are carried out at a temperature of about 500 ° C to about 1,500 ° C.
3. 3 . The activated carbon monolith according to claim 25, characterized in that the phenol comprises monohydroxybenzene. 35. The activated carbon monolith according to claim 25, characterized in that the aldehyde comprises formaldehyde. 36. The activated carbon monolith according to claim 25, characterized in that the base comprises one or more of ammonia or ammonium hydroxide. 37. The activated carbon monolith according to claim 25, characterized in that the molar ratio of the aldehyde to the phenol is from about 1.1: 1 to about 3: 1. 38. The activated carbon monolith according to claim 25, characterized in that the colloidal stabilizer comprises a salt of carboxymethyl cellulose. 39. The activated carbon monolith according to claim 25, characterized in that the temperature is from 75 ° C to 90 ° C. 40. The activated carbon monolith according to claim 25, characterized in that the surfactant is present and comprises one or more of: sodium dodecyl sulfate or sodium dodecyl benzene sulfonate. 41. The activated carbon monolith in accordance with claim 25, characterized in that the base comprises one or more of: ammonia or hexamethylenetetramine. 42. The activated carbon monolith according to claim 25, characterized in that the methanol is present in the aldehyde provided to the reaction mixture in an amount of not more than about 2%, based on the total weight of the aldehyde. 43. An activated carbon monolith, characterized in that it is made by a process comprising: providing a stirred aqueous reaction mixture with a phenol, a portion of an aldehyde, a portion of a base as a catalyst, a colloidal stabilizer, optionally a surfactant and previously formed resol accounts; reacting in the reaction mixture for a period of time and at a temperature sufficient to produce an aqueous dispersion of partially formed resol solids; , then add a remaining portion of the aldehyde and a remaining portion of the base to obtain a resol monolith; optionally compact the resol monolith; and carbonizing and activating the resol monolith to obtain an activated carbon monolith. 4
4. 4. An activated carbon monolith, characterized because it is made by a process comprising: providing a portion of a phenol, a portion of an aldehyde, and a portion of a base as catalyst to a reaction mixture which is a stirred aqueous medium that includes a colloidal stabilizer, optionally a surfactant , and previously formed resol accounts; reacting for a period of time and at a temperature sufficient to produce an aqueous dispersion of partially formed resol solids; then providing an additional portion of the phenol, an additional portion of the aldehyde, and an additional portion of the base to the reaction mixture and reacting for an additional period of time; then adding any remaining portion of the phenol, the aldehyde, and the base for a period of time and at a temperature sufficient to obtain a resol monolith; optionally compact the resol monolith; and carbonizing and activating the resol monolith to obtain an activated carbon monolith. 4
5. 5. The activated carbon monolith according to claim 44, characterized in that at least one quarter of the total charge of formaldehyde and ammonia is charged to the reactor and the remainder is charged in half-batches mode. 4
6. 6. The activated carbon monolith in accordance with claim 44, characterized in that the aldehyde and the base are added to the reaction mixture for a period of about 15 minutes to about 180 minutes. 4
7. 7. The activated carbon monolith according to claim 44, characterized in that the addition of formaldehyde and ammonia to the reaction mixture starts from about 5 minutes to about 180 minutes after the initial loading of reactants into the reactor.