WO2001032559A1

WO2001032559A1 - Process for producing ultra finely-divided zeolite powder

Info

Publication number: WO2001032559A1
Application number: PCT/US2000/030019
Authority: WO
Inventors: Patrick C. Hu; Conrad J. Langlois, Jr.; Ronald L. Camp
Original assignee: Albemarle Corporation
Priority date: 1999-10-29
Filing date: 2000-10-30
Publication date: 2001-05-10

Abstract

Particulate synthetic zeolite is micronized in a liquid organic medium to form a micronized zeolite product having an average (mean) particle size about 2 microns or less and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns. Preferably, the micronized zeolite product has a mean particle size of 1 micron or less, and at least 90% by weight of the zeolite product, based on the dry weight of the zeolite product, if isolated, has a particle size of 2 microns or less. Further advantages accrue by calcining particulate zeolite to a water content of 10 wt% or less as determinable by thermal gravitional analysis, and then micronizing the calcined zeolite in a liquid organic medium to form a micronized zeolite product having a content of volatiles of less than about 10 wt%, an average (mean) particle size of about 2 microns or less, and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns. Preferably, the micronized zeolite product has a low crystallinity, a low rehydration capability, a mean particle size of 1 micron or less, and at least 90% by weight of the zeolite product, based on the dry weight of the zeolite product, if isolated, has a particle size of 2 microns or less. The liquid organic medium used is (a) inert or substantially inert, (b) devoid or substantially devoid of water, and (c) devoid of a dispersant.

Description

PROCESS FOR PRODUCING ULTRA FINELY-DIVIDED ZEOLITE POWDER

BACKGROUND

A need has arisen for a process capable of producing ultra finely-divided synthetic zeolite powder for use in the production of detergent powder compositions and as a thermal stabilizer and/or blocking agent for certain polymer compositions. Generally speaking, there are two approaches for producing synthetic zeolites of small particle size. One approach is to synthesize the zeolite in a very dilute aqueous medium. Unfortunately, attempts to recover the finely-divided zeolite product by removing the water from the aqueous medium have proven unsuccessful. Under the conditions used, the finely- divided zeolite particles agglomerated thereby producing a product of undesirably large, average particle size.

The other method involves physical subdivision of preformed particulate zeolite by use of milling procedures. Because of the relative low density of zeolites, the only known feasible method for effecting such subdivision has been ball milling of the zeolite in water containing a substantial amount of a dispersant. See in this connection McLaughlin, U.S. Pat. No. 5,704,556. Unfortunately, it was not possible to recover the finely-divided zeolite from the aqueous medium of the McLaughlin patent without experiencing substantial agglomeration of the particles. In fact, attempts to effect such separation have resulted in formation of zeolite particles having an average particle size larger than the zeolite as it existed prior to ball milling. In addition, the presence of the dispersant almost always leaves undesirable residues in the recovered product rendering it unsuitable, without further purification, for certain end use applications.

Japan kokai 01-153514, laid open on June 15, 1989, describes formation of "submicron" A-type zeolite by a forming an aqueous solution from aluminum hydroxide and sodium hydroxide at 35° C or less. A second aqueous solution of colloidal silica is formed, again at 35 ° C or less. These solutions are mixed at 35 ° C or less with agitation for a period of time (e.g., 5 hours) for nuclei to form, and the resultant slurry is then agitated for 24 hours at 35-38 ° C for crystal growth to occur. It is indicated that the maximum particle size of the zeolite formed in this manner is 0.4 micron or less. However, the particle size of zeolite as reported by the kokai was determined by SEM (Scanning Electron Microscopy, see Table 1, thereof) which is useful in determining the particle size of zeolite crystals, but not useful in determining the size of particles. The difference is that each particle consists of several zeolite crystals (or zeolite crystal particles). The particle size defined hereinafter is the size of particles determined under a dispersed state. In sum, when using an electron microscope, one can distinguish the boundary of crystals, hence the crystal size. But one cannot distinguish particle boundary which is necessary for zeolite particle size determination.

Furthermore, to conduct a process such as described in the kokai, it is not possible to use as the starting material synthetic zeolite produced in existing plant facilities. Thus one or more conventional zeolite products plus the zeolite product of the kokai cannot be produced in an existing plant using conventional zeolite synthesis technology. Instead, to use the process of the kokai either new synthesis facilities are required, or the normal operation of the existing synthesis facilities, if adaptable for use in conducting the special process of the kokai, must be interrupted so as carry out such special process. PCT publication WO/0015553, published 23 March 2000, discloses a special process for synthesizing small size zeolite particles. While suitable for small-scale laboratory operation, the technology described is not suitable for industrial production of small size particulate zeolite because of the difficulty of filtering slurries of such particles. The document further describes the step of shock annealing such specially prepared small particle size zeolites in order to achieve phase transformation on the outer surface of the particle shell.

As soon as the particle reaches the desired elevated temperature it is rapidly cooled to limit the phase transformation. Thus this step requires rapid heating and rapid cooling operations and thus if conducted on an industrial scale would require expensive equipment for conducting these operations. In addition experience has shown that heating particulate zeolite to such elevated temperatures results in fusion among the particles with consequent loss of the initial small particle size.

BRIEF SUMMARY OF THE INVENTION

This invention is deemed to provide effective and efficient ways of circumventing all of the foregoing difficulties whereby isolatable ultra fine synthetic zeolite powder can be effectively produced from synthetic zeolite that has been produced using conventional synthesis technology. New synthesis plant facilities are unnecessary. And the operation of existing synthesis plant facilities need not be interrupted in order to form finely-divided zeolite powder. Instead, the synthesis process can be carried out at the same time special finely-divided synthetic zeolite is being formed from conventional synthetic zeolite already produced. Moreover, the equipment required for conducting the process technology of this invention is readily available for purchase, if not already available at plant site. Moreover, finely-divided zeolite powder with true ultra-fine particle size are produced. Particle size is not determined by SEM, and thus erroneous particle size determinations are not obtained or utilized. In accordance with one of its embodiments, this invention provides a process for producing ultra-finely divided synthetic zeolite which comprises micronizing particulate synthetic zeolite in an inert or substantially inert liquid organic medium that is devoid or substantially devoid of water, and devoid of dispersant, to form a micronized zeolite product having an average particle size of about 2 microns or less and containing at least 90% by weight, based on the total weight of the zeolite product (i.e., the weight of the zeolite solids if removed from the organic medium and dried), of particles no larger than about 5 microns. In other words, the weight percentage of the micronized zeolite product that fulfills this requirement of having an average particle size of about 2 microns or less is based on the dry weight of the zeolite product, as if it were in isolated form. Another embodiment of this invention is a dry, finely-divided synthetic zeolite powder having an average (mean) particle size of about 2 microns or less, and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns. In a preferred embodiment, the mean particle size of the dry, finely- divided synthetic zeolite powder is 1 micron or less, and at least 90% by weight of the finely- divided zeolite powder (assuming the powder has been isolated and dried) has a particle size of 2 microns or less. The preferred zeolite in these compositions is zeolite- A, zeolite-X, or zeolite-Y, or a mixture of any two or all three of these. More preferred zeolites are zeolite-A and zeolite-X. Zeolite-A is the most preferred zeolite of this embodiment of the invention.

Still another embodiment is a composition comprising a mixture of (i) finely-divided anhydrous or substantially anhydrous synthetic zeolite having an average (mean) particle size of about 2 microns or less, and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns, and (ii) a liquid organic medium. The organic medium constitutes a continuous liquid phase in the mixture. In preferred compositions of this type, the mean particle size of the finely-divided anhydrous or substantially anhydrous synthetic zeolite is 1 micron or less, and at least 90% by weight of such zeolite has a particle size of 2 microns or less. The preferred synthetic zeolite in these compositions is zeolite-A, zeolite-X, or zeolite- Y, or a mixture of any two or all three of these. More preferred zeolites are zeolite-A and zeolite-X. Zeolite-A is the most preferred zeolite for use in the practice of this embodiment of the invention. The synthetic zeolite used in forming these compositions must either be totally anhydrous or, if it contains water, its water content must be below the amount corresponding to the theoretical quantity of water of hydration for that particular zeolite. Preferably the zeolite will contain a total amount of water that is no more than 90 wt% of the theoretical quantity of water of hydration, and most preferably will contain no more than 20 wt% of this theoretical quantity. The water content of the zeolite being used in forming the foregoing compositions should be determined, in any case where the actual water content is not already known, by measuring the weight loss of a sample of such zeolite after the sample has been maintained at 800 °C for 1 hour.

To reduce the total quantity of water present in the zeolite to be used in forming the compositions described in the immediately preceding paragraph, it is preferable to preheat the particulate zeolite to a temperature in the range of 40 to 200 ° C, with or without application of reduced pressure.

Further embodiments are the compositions as described in the penultimate paragraph above wherein (ii) is a liquid organic medium having a viscosity at 20 ° C of at least 0.1 poise. The relatively viscous liquid organic medium in these compositions is preferably a liquid medium that has plasticizing properties for polymers, such as, for example, a synthetic ester. The preferred zeolite in these compositions is zeolite-A, zeolite-X, or zeolite-Y, or a mixture of any two or all three of these. More preferred zeolites are zeolite-A and zeolite-X. Zeolite- A is the most preferred zeolite for use in the practice of this embodiment.

In each of the above embodiments of this invention the synthetic zeolite used can be a partially or totally ion-exchanged zeolite. The cations of these exchanged zeolites can be zinc, calcium, magnesium, or other similar metallic cations. The preferred ion-exchanged zeolites are zeolite-A, zeolite-X, and zeolite-Y having a content of exchanged zinc or calcium cations. Non-ion-exchanged synthetic zeolites, however, are more preferred than ion- exchanged zeolites.

In addition, it has now been found possible to still further improve the micronizing or grinding efficiency of a synthetic zeolite whereby it is possible to form a synthetic zeolite product having a content of volatiles (e.g., water) of less than about 10 wt%> and an average particle size of about 2 microns or less, and containing at least 90%> by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns. Moreover, it is possible pursuant to this invention to conduct the process to produce a micronized zeolite product having a crystallinity of less than about 5%.

More particularly, this aspect of the invention involves, inter alia, the further unprecedented discovery that by calcining the starting zeolite material prior to micronizing, particularly important advantages can be achieved, especially if fine particle size zeolite powders with low volatile content are the targeted products. These advantages are even more desirable since fine particle zeolite with low re-hydration capability can be economically produced, eliminating the need for expensive containers to keep the content of volatiles low.

Still another remarkable feature of this aspect of the invention is that it makes possible the formation of an anhydrous micronized zeolite that is resistant to reabsorption of water.

Indeed, this invention can provide a micronized synthetic zeolite that is characterized by having a rehydration capability of no more than 10 wt% as determinable by the amount of water absorbed in 60 hours at 23 °C from air of 65% relative humidity. Thus, the highly desired reduction in re-hydration capability of fine particle powder zeolite can be achieved when the starting particular zeolite was properly calcinated prior to micronizing. This discovery suggests that the expensive "shock annealing" processes previously described can be replaced with conventional calcining equipment, such as rotary kilns and the like. The ability to produce such anhydrous micronized zeolites that are resistant to reabsorption of water in turn means that such micronized zeolite is ideally suited for use as an additive component for various compositions. For example such a zeolite product can be used as a reinforcing agent or filler for plastics such as poly( vinyl chloride); poly( vinylidene chloride); polyolefins such as ethylene and/or propylene homopolymers and copolymers; engineering thermoplastics such as thermoplastic polyesters (PET or PBT), thermoplastic nylon polymers (e.g., nylon 6, nylon 6,6, or nylon 6,12), thermoplastic poly(phenylene ethers) and blends thereof with styrenated polymers such as polystyrene and high-impact polystyrene; and many more such materials.

Accordingly, this invention provides as one of its embodiments a process for producing ultra-finely divided zeolite which comprises:

A) micronizing calcinated particulate zeolite in a liquid organic medium which is ( 1 ) inert or substantially inert to the zeolite, (2) devoid of water, and (3) devoid of a dispersant, to form a slurry of finely-divided zeolite in the liquid organic medium, said calcinated particulate zeolite having a water content of about 10 wt% or less, as determinable by thermal gravitational analysis, and then

B) removing the liquid organic medium from the slurry to thereby provide a micronized zeolite product having a content of volatiles of less than about 10 wt% based on the total weight of the micronized zeolite product, and an average (mean) particle size of 5 microns or less, and preferably of 2 microns or less, and containing at least about 90%) by weight, based on the dry weight of the micronized zeolite product, of particles no larger than 5 microns, and preferably no larger than 2 microns. In other words, the weight percentage of the micronized zeolite product that fulfills this requirement of having an average particle size of 5 microns or less and preferably 2 microns or less is based on the dry weight of the zeolite product, as if the dry zeolite were in isolated form.

Another embodiment is a process for producing ultra-finely divided zeolite which comprises: a) calcining particulate zeolite to a water content of about 10 wt% or less as determinable by thermal gravitational analysis, b) micronizing such calcinated particulate zeolite in a liquid organic medium which is

(1) inert or substantially inert to the zeolite, (2) devoid of water, and (3) devoid of a dispersant, to form a slurry of finely-divided zeolite in the liquid organic medium, and then c) removing the liquid organic medium from the slurry to thereby provide a micronized zeolite product having a content of volatiles of less than about 10 wt% based on the total weight of the micronized zeolite product, and an average (mean) particle size of 5 microns or less, and preferably of 2 microns or less, and containing at least about

90% by weight, based on the dry weight of the micronized zeolite product, of particles no larger than 5 microns, and preferably no larger than 2 microns. In other words, the volume percentage of the micronized zeolite product that fulfills this requirement of having an average particle size of 5 microns or less and preferably 2 microns or less is based on the dry volume of the zeolite product, as if the dry zeolite were in isolated form.

Water content of a zeolite is determined thermal gravitational analysis, in which the weight loss of a sample of the zeolite is measured after the sample has been maintained at 800 °C for 1 hour.

The particulate zeolite that is used in step A) above or that is calcinated in step a) above can be a natural zeolite, but preferably is a synthetic zeolite. Type A zeolite (a.k.a. zeolite-A), type X zeolite (a.k.a. zeolite-X), type P zeolite (a.k.a. zeolite-P), and hydroxy- sodalite, as well as a mixtures of any two or more of these, are more preferred. Type A zeolite is most preferred.

Another embodiment of this invention is the provision of a finely-divided zeolite that (i) has a content of volatiles of less than about 10 wt% based on the total weight of the finely- divided zeolite, (ii) has an average (mean) particle size of 5 microns or less, and preferably of 2 microns or less, and (iii) contains at least about 90% by weight, based on the dry weight of the finely-divided zeolite, of particles no larger than 5 microns, and preferably no larger than 2 microns.

A further embodiment of this invention is the provision of a finely-divided zeolite that (i) has a crystallinity of less than about 5% based on the total weight of the finely-divided zeolite, (ii) has an average (mean) particle size of 5 microns or less, and preferably of 2 microns or less, and (iii) contains at least about 90% by weight, based on the dry weight of the finely-divided zeolite, of particles no larger than 5 microns, and preferably no larger than 2 microns.

Yet another embodiment of this invention is the provision of a finely-divided zeolite that (i) has a rehydration capability of no more than about 10 wt% based on the total weight of the finely-divided zeolite, such rehydration capability being determinable by the amount of water absorbed by the finely-divided zeolite in 60 hours at 23 °C from air of 65% relative humidity, (ii) has an average (mean) particle size of 5 microns or less, and preferably of 2 microns or less, and (iii) contains at least about 90% by weight, based on the dry weight of the finely-divided zeolite, of particles no larger than 5 microns, and preferably no larger than 2 microns. A still further embodiment of this invention is the provision of a finely-divided-zeolite that has (i) a crystallinity of less than about 5% based on the total weight of the finely-divided zeolite; and (ii) a rehydration capability of no more than about 10 wt% based on the total weight of the finely-divided zeolite, such rehydration capability being determinable by the amount of water absorbed by the finely-divided zeolite in 60 hours at 23 °C from air of 65% relative humidity.

A preferred embodiment of this invention provides a finely-divided zeolite that has (i) a content of volatiles of less than about 10 wt% based on the total weight of the finely- divided zeolite, (ii) an average (mean) particle size of 5 microns or less, and preferably of 2 microns or less, and (iii) a rehydration capability of no more than about 10 wt% based on the total weight of the finely-divided zeolite, such rehydration capability being determinable by the amount of water absorbed by the finely-divided zeolite in 60 hours at 23 °C from air of 65% relative humidity. In a more preferred embodiment, this finely-divided zeolite contains at least about 90% by weight, based on the dry weight of the finely-divided zeolite, of particles no larger than 5 microns, and preferably no larger than 2 microns. Another preferred embodiment of this invention provides a finely-divided zeolite that has (i) a content of volatiles of less than about 10 wt% based on the total weight of the finely- divided zeolite, (ii) an average (mean) particle size of 5 microns or less, and preferably of 2 microns or less, (iii) a crystallinity of less than about 5%; and (iv) a rehydration capability of no more than 10 wt% as determinable by the amount of water absorbed by the finely-divided zeolite in 60 hours at 23 °C from air of 65% relative humidity. In a more preferred embodiment, this finely-divided zeolite contains at least 90% by weight, based on the dry weight of the finely-divided zeolite, of particles no larger than 5 microns, and preferably no larger than 2 microns.

In each of the above embodiments in the immediately preceding six (6) paragraphs, the finely-divided zeolite is preferably a synthetic zeolite powder. Type A zeolite and type

X zeolite are preferred. Type A zeolite is most preferred. Still another embodiment is a composition comprising a mixture of (A) finely-divided anhydrous or substantially anhydrous synthetic zeolite having a content of volatiles of less than about 10 wt% based on the total weight of the finely-divided zeolite, an average (mean) particle size of about 2 microns or less, and containing at least 90%> by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns, and

(B) a liquid organic medium. The organic medium constitutes a continuous liquid phase in the mixture. In preferred compositions of this type, the mean particle size of the finely- divided anhydrous or substantially anhydrous synthetic zeolite is 1 micron or less, and at least 90% by weight of such zeolite has a particle size of 2 microns or less. The preferred synthetic zeolite in these compositions is zeolite-A, zeolite-X, or zeolite-Y, or a mixture of any two or all three of these. More preferred zeolites are zeolite-A and zeolite-X. Zeolite-A is the most preferred zeolite for use in the practice of this embodiment of the invention. The synthetic zeolite used in forming these compositions must either be totally anhydrous or, if it contains water, its water content must be below the amount corresponding to the theoretical quantity of water of hydration for that particular zeolite. Preferably the zeolite will contain a total amount of water that is no more than 90 wt% of the theoretical quantity of water of hydration, and most preferably will contain no more than 20 wt% of this theoretical quantity. The water content of the zeolite being used in forming the foregoing compositions should be determined, in any case where the actual water content is not already known, by measuring the weight loss of a sample of such zeolite after the sample has been maintained at 800 °C for 1 hour.

To reduce the total quantity of water present in the zeolite to be used in forming the compositions described in the immediately preceding paragraph, it is preferable to preheat the particulate zeolite to a temperature in the range of 40 to 200 °C, with or without application of reduced pressure. Further embodiments are the compositions as described in the penultimate paragraph above wherein (B) is a liquid organic medium having a viscosity at 20 °C of at least 0.1 poise. The relatively viscous liquid organic medium in these compositions is preferably a liquid medium that has plasticizing properties for polymers, such as, for example, a synthetic ester. The preferred zeolite in these compositions is zeolite-A, zeolite-X, or zeolite-Y, or a mixture of any two or all three of these. More preferred zeolites are zeolite-A and zeolite-X. Zeolite-

A is the most preferred zeolite for use in the practice of this embodiment. In each of the above embodiments of this invention the synthetic zeolite used can be a partially or totally ion-exchanged zeolite. The cations of these exchanged zeolites can be zinc, calcium, magnesium, or other similar metallic cations. The preferred ion-exchanged zeolites are zeolite-A, zeolite-X, and zeolite-Y having a content of exchanged zinc or calcium cations. Non-ion-exchanged synthetic zeolites, however, are more preferred than ion- exchanged zeolites.

Other embodiments, features, and advantages of this invention will become still further apparent from the ensuing description and the appended claims.

FURTHER DETAILED DESCRIPTION The calcining of zeolite prior to micronizing in accordance with processes of this invention may be carried out at various elevated temperatures and over various amounts of time. Typically, the higher the temperature, the less amount of time is required to achieve the desired level of volatile content and/or crystallinity in the end product. The desired level of crystallinity for the end product, if isolated from the organic medium, will be less than 40%, more preferably less than 20%, even more preferably less than 10%, and most preferably less than 5%, as determinable by x-ray diffraction. The calcining typically is conducted at a temperature of at least 500°C, more preferably at least 600°C, and most preferably at a temperature in the range of 600°C to 1000°C. Using these temperature ranges, typically the calcining will be carried out for a period of time in the range of 5 minutes to 240 minutes, measured from the point in time when the pre-selected temperature is reached. Normally, the calcining step is carried out at or near atmospheric pressure, although sub- or super- atmospheric pressures also may be employed. The water content of the calinated zeolite should be 10 wt% or less, more preferably 3 wt% or less, and most preferably 1 wt% or less. The calcination can be carried out as a direct or indirect process using direct calciners, e.g., fluid bed or flash calciners; indirect calciners, e.g., those which utilize steam bundle technology or tube furnace technology; mechanical convection ovens; rotary kilns; high temperature furnaces and the like. It will be noted that the calcining operation pursuant to this invention does not require use of extraordinary measures in order to rapidly cool the zeolite.

Unlike the McLaughlin patent cited above, processes of this invention are conducted in the absence of a dispersant. Even though a dispersant is absent, the ultra fine zeolite particles do not coalesce or agglomerate to any appreciable extent during or after separation of the zeolite particles from the liquid organic medium. Thus the particles in the slurry in the organic medium are different in character from the particles formed by grinding a zeolite in water and a dispersant. Moreover, since no dispersant is used in the process of this invention, the cost and contamination problems associated with use of a dispersant are eliminated.

McLaughlin also teaches that mean particle size of the starting zeolite feedstock in those processes should be 1 micron or less, whereas the mean particle size of starting zeolite forms no limitation for processes of the present invention, such that the mean particle size of starting zeolite in processes of this invention may be more or less than 1 micron, and typically will be 2 to 5 microns or more. It is also important to observe that while the McLaughlin patent mentions that the liquid vehicle used in that process can be water or an organic solvent, there is no suggestion or indication in the patent that anything beneficial could or might result from using an organic liquid instead of water. Instead, the patent indicates that as long as the liquid has a reasonably low viscosity and does not adversely affect the chemical or physical characteristics of the particles, the choice of the fluid vehicle is optional. In fact, water is indicated to be the preferred liquid, and the Examples of the patent all employ water as the liquid medium. Since the process of that patent is incapable of preparing a zeolite product which, if separated from the water, would have the particle size attributes of the zeolites that can be produced pursuant to this invention, the process of this invention is deemed to represent an unprecedented advance in the art. In short, the ultra fine particles of this invention possess an unexpected beneficial property which could not have been foreseen, namely, the capability of being separated from the liquid medium in which the ultra fine particles have been formed without undergoing any appreciable coalescence or agglomeration.

It will be understood that in the practice of this invention it is not necessary to separate the ultra fine particles from the organic liquid medium in which such particles have been formed by the ball milling step. The ultra fine particles while dispersed or suspended in a liquid organic medium always possess the unique capability of being separated from the liquid medium without undergoing appreciable coalescence or agglomeration. It will also be appreciated that solvent exchange procedures can be utilized wherein the ultra fine particles which are initially produced in a first liquid organic medium are in effect transferred to another liquid organic medium. As noted above, a variety of synthetic zeolites can be subjected to the practice of this invention. Processes for the manufacture of such materials are well known and reported in the literature. Many zeolites, including the preferred zeolites such as zeolite-A, zeolite-X, zeolite-Y, zeolite-P and hydroxysodalite, are available in the marketplace as articles of commerce. The particle size of the initial zeolite used in the process of this invention is not critical as long as the particles are susceptible to ball milling in the particular ball milling equipment being utilized. Typically, the particle size of the starting zeolite will be in the range of 2 to 5 microns. In any case where the initial zeolite particles are too large to be suitably milled in a ball mill, such particles can be reduced into a suitable size for ball milling by use of other grinding equipment such as a hammer mill, mortar and pestle, or the like.

Various types of liquid organic media can be used in the ball milling operation pursuant to this invention. The liquid organic medium can have a viscosity at 20 ° C of 5 poise or less, preferably 1 poise or less, and more preferably 0.05 poise or less. The media will typically have a boiling point of 200° C or less, more preferably about 100°C or less, and a dielectric constant at 25 ° C in the range of 10 to 40, more preferably in the range of 15 to 20.

Among suitable materials are alcohols, esters, and ethers, (including mixtures thereof) which are in the liquid state of aggregation at the grinding temperature being utilized, and preferably also at a temperature at least as low as 20 °C. Examples of suitable alcohols, including polyols, are methanol, ethanol, ethylene glycol, l-propanol,2-propanol, 2-methyl-l-propanol, propylene glycol, 1 -butanol, 3-pentanol, cyclopentanol, 2-hexanol, 2-heptanol, 1 -octanol, and analogous alcohols or polyols. Suitable esters include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate and analogous liquid esters. Ethers suitable for use include di ethyl ether, ethyl n-propyl ether, diisopropyl ether, tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, cyclohexylmethyl ether, glyme (the dimethyl ether of ethylene glycol), diglyme (the dimethyl ether of diethylene glycol), triglyme, and tetraglyme.

Hydrocarbons can be used as the liquid organic media but are less preferred because of the tendency of at least certain zeolites to undergo some clumping when dispersed in a liquid hydrocarbon medium.

In a highly preferred embodiment of this invention the liquid organic medium used in the ball milling operation is a liquid of lubricating viscosity having plasticizing properties.

Examples of such liquids are poly-alpha-olefms, such as hydrogenated oligomers of 1 -decene; alkyl esters of dicarboxylic acids; complex esters of dicarboxylic acid, polyglycol and alcohol; alkyl esters of carbonic or phosphoric acids; polysilicones; fluorohydrocarbon oils; and similar materials often sold either as plasticizers or as synthetic lubricating oils for use in gasoline engines. A few such synthetic esters include dibutyl adipate, di(2-ethylhexyl) adipate, didocyl adipate, di(tridecyl) adipate, di(2-ethylhexyl) sebacate, dilauryl sebacate, dihexylfurmate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, and analogous synthetic esters. These compositions are of particular utility as plasticizers for use in synthetic polymers.

The initial liquid organic medium used should be anhydrous or substantially anhydrous. Those skilled in the art of chemistry will readily understand that the term

"substantially anhydrous" means that the amount of water present should not be enough to materially interfere with the efficacy of the operation which is being conducted in that medium. In the real world, it is practically impossible to exclude a few molecules of water from entering into what purports to be an anhydrous solvent. Anyone unfamiliar with the art of chemistry should consult a person skilled in the art, e.g., a manufacturer of the given solvent, to determine what they would regard as being anhydrous or substantially anhydrous. Organic solvent manufacturers operate with various sets of specifications on water contents for most organic solvents. As an alternative, one can simply conduct a test experiment using the proposed liquid organic medium to determine whether it is suitable or not in the operation. If it is not suitable because of its initial water content, the solvent is not "substantially anhydrous".

The particular design of the ball mill utilized in the practice of this invention is not critical. Thus, any of a wide variety of commercially available ball mills can be utilized. The balls or spheres utilized in the device will often be within a size range recommended by the particular manufacturer of the ball mill. Typically, the balls or spheres will be in the range of 0.012 to 0.5 inches (0.03 to about 1.27 centimeters) in diameter. The balls or spheres can be formed from any material of sufficient hardness and wear resistance, such as ceramics, metals, plastics, composites, or like materials of suitable physical properties and inertness.

In the ball milling operation, the initial slurry of the zeolite in the liquid organic medium will typically contain in the range of 5 to 40 wt% of the zeolite based on the total weight of the slurry. Slurries containing in the range of 15 to 30 wt% of the zeolite based on the total weight of the slurry are preferred.

Ordinarily, the ball milling operation will be conducted at ambient room temperature conditions. However, the operation can be conducted at temperatures either below or above room temperature. If desired, the temperature can be changed during the course of the ball milling. For example, during the ball milling the temperature can be changed from room temperature to an elevated temperature below the boiling temperature of the liquid organic medium in use. Conversely, the ball milling can initially be conducted at an elevated temperature below the boiling temperature of the liquid organic medium and can be progressively reduced in temperature as the ball milling progresses. In short, any suitable temperature conditions can be employed.

The ball milling operation is conducted for a period of time sufficient to produce a particle size distribution in the zeolite product meeting the requirements of this invention. Ordinarily, the time period for ball milling will be at least about 5 minutes and in some cases can extend to as much as 72 hours or longer. In practice, the length of time to be used in any given set of circumstances should be determined by performing a few pilot experiments to optimize the grinding conditions, including time, in any situation where the optimum conditions are not already known.

It has been pointed out above that upon completion of the ball milling step, the ultra fine zeolite can be maintained in the liquid organic medium for subsequent use or the ultra fine zeolite can be isolated in powder form by separating the ultra fine zeolite product and the liquid organic medium from each other. It is also possible to conduct a solvent exchange operation on the slurry of the ultra fine zeolite produced in the ball milling operation. In this case, the liquid organic medium in which the ball milling was conducted is replaced by another suitable liquid organic medium to thereby form a slurry of the ultra fine zeolite in the new diluent.

If it is desired to isolate the ultra fine zeolite from a liquid organic medium, various physical separation procedures are available for use. For example, the slurry can be subj ected to filtration, centrifugation, decantation, or like procedure. The isolated finely-divided zeolite is then dried such as in a circulating air oven, a vacuum dryer, a spray dryer, a drum dryer, a tray dryer, or similar drying apparatus. In some cases, it is desirable to physically agitate the dried ultra fine zeolite in order to produce a free flowing ultra fine powder.

The following Examples illustrate the practice and advantages of this invention. These Examples are not intended to limit and should not be construed to limit this invention inasmuch as they are presented for purposes of illustration and not limitation. Comparative Example 1, which forms no part of this invention, presents the results of a group of experiments demonstrating the impossibility of isolating ultra fine zeolite particles prepared in an aqueous medium.

COMPARATIVE EXAMPLE 1

Particulate zeolite-A (Albemarle Corporation) containing approximately 20 wt% of water of hydration was used to prepare a 30 wt% slurry in water. This slurry was charged into a 0.5 liter ball mill together with one-fourth inch diameter alumina balls (produced by Coors

Ceramics Company). Typically the quantity of balls used was such as to extend for about three-fourths of the height of the cylinder-shaped ball mill when the cylinder was in a vertical position. In other words, the "apparent" volume of the balls in the cylinder (i.e. , ignoring the volume of the space within the zone occupied by the balls) was approximately 75% of the total volume of the cylinder. Into the mill was then charged the 30 wt% zeolite slurry in an amount just sufficient to immerse all of the balls within the liquid phase of the slurry. After grinding for 72 hours, the milled slurry was then removed from the mill and subjected to the following steps: 1) The slurry was centrifuged to separate the zeolite from the water, and the water was discarded.

2) The zeolite solids were re-slurried in a 1 wt% aqueous sodium hydroxide solution.

3) The resultant slurry was centrifuged to separate the zeolite solids from the aqueous caustic solution, which solution was discarded. 4) Water-wet and dry portions of the processed zeolite were subjected to particle size analysis. In particular, aportion of the zeolite solids from step 3) was subjected, while

® wet with water, for particle size analysis using a MICROTRAC FRA Model No.

9240-4-10-1 particle size analyzer manufactured by Leeds & Northrup. Another portion of the zeolite solids from step 3) was dried in an oven at 115 °C for 2 hours and subjected to particle size analysis in the same particle size analyzer. Step 4) as initially conducted provided particle size determinations on a first pair of zeolite samples, one being a dry sample and the other being a water-wet sample.

The remainder of the zeolite solids collected in step 3) above was subjected to steps

2) and 3) for a second time, and then water-wet and dry portions of this processed zeolite were subjected to particle size analysis as in step 4). This provided a second set of particle size determinations, one on a dry sample and one on a water- wet sample. The procedure of this paragraph was repeated for a third time using the residual zeolite solids remaining from step

3) when conducted for the second time. This provided particle size determinations on a third pair of zeolite samples, one being a dry sample and the other being a water-wet sample. Finally, the foregoing procedure was repeated for a fourth time using the residual zeolite solids remaining from step 3) when conducted for the third time. This provided particle size determinations of a fourth pair of zeolite samples, one being a dry sample and the other being a water-wet sample.

For control purposes, a sample of the zeolite-A from the initial slurry prior to milling was also subjected to particle size analysis using the same particle size analyzer. The results of these determinations are summarized in Table 1.

TABLE 1

Example 2 illustrates the practice of this invention wherein the organic liquid medium used in the ball milling operation was 1 -propanol.

EXAMPLE 2

The procedure used in this Example involved milling a sample of dehydrated zeolite-A in 1 -propanol. Dehydration was effected by maintaining the zeolite at 150°C for 4 hours.

Three pairs of samples were prepared. The first pair of samples prepared pursuant to this invention was formed by grinding 40 grams of the dehydrated zeolite with 60 grams of 1- propanol in the 0.5 liter mill for 64 hours. One sample was subjected, while wet with 1- propanol, to particle size analysis using the particle size analyzer referred to in Comparative Example 1. Another sample was subjected to this particle size analysis after drying in a vacuum oven at 115 °C for 2 hours. The second pair of samples was formed in the same manner except that 480 grams of the dried zeolite was ground in a 6 liter mill together with 720 grams of 1 -propanol for 64 hours. The third pair of samples involved subjecting a portion of the slurry remaining from the second pair of samples to grinding in a 2 liter mill for another 42 hours. In each case, one-fourth inch diameter alumina balls from Coors Ceramics

Company were used and the mill was charged in the same manner as in Comparative Example 1 except that the slurry was made from 1 -propanol rather than water.

The results of these particle size determinations are summarized in Table 2.

TABLE 2

It can be seen from the results in Table 2 that in sharp contrast to the results in Table 1, the finely-divided zeolite produced pursuant to this invention in an organic medium (1- propanol) could be isolated from the organic liquid medium without undergoing any appreciable agglomeration. In short, the finely-divided zeolite of this invention could be isolated without losing its ultra fine particle size.

Examples 3-7 further illustrate the practice and advantages of this invention. Various liquid organic media were used in these Examples. Also, ball mills of different sizes were used. In Example 3, the synthetic zeolite used was Zeolite-A which had been partially ion exchanged with zinc prior to the ball milling step.

EXAMPLE 3

The zinc-containing zeolite was prepared by adding 40 grams of zinc sulfate heptahydrate to 600 grams of zeolite-A slurried in 1800 grams of water at room temperature for 4 hours under agitation. After the zinc ion exchange, the slurry was filtered and the filter cake was washed with deionized water on a 5-inch rotary centrifuge. The filter cake was collected and oven dried at 150°C for 8 hours under vacuum to form the partially ion- exchanged zinc zeolite. 1 -Propanol was used as the liquid organic grinding medium. Into a 5-liter ball mill j ar, partially filled with one- fourth inch alumina balls, from Coors Ceramics

Company, as in Comparative Example 1, was charged a 30 wt% slurry of the partially ion- exchanged zinc zeolite in 1 -propanol, the amount of the slurry being such that the balls were totally immersed in the liquid phase of the slurry. After grinding the slurry in the ball mill jar for 94 hours, the slurry was filtered and the residual solvent on the filter cake was removed in a vacuum oven at 150° C for 24 hours. After drying, the filter cake was pulverized in a

Waring blender. A particle size determination was then performed as in Comparative Example 1 on a sample of the resultant zinc zeolite powder of this invention.

EXAMPLE 4

A zeolite-A sample was prepared by grinding a commercially available zeolite-A (Albemarle Corporation). The starting zeolite powder was first dried in a convection oven at 60 °C for 72 hours. 1 -Propanol was added to the zeolite to form a slurry with a solid content of approximately 30 wt%. The zeolite slurry was then poured into a 5-liter ball mill equipped with one-fourth inch alumina balls, from Coors Ceramics Company, as in Comparative Example 1, and ground for 92 hours. After the grinding, the slurry was filtered and the residual solvent on the filter cake was removed by placing the propanol-wet zeolite filter cake in a vacuum oven at 60 °C for 24 hours. A particle size determination was then performed as in Comparative Example 1 on a sample of the finely-divided zeolite-A of this invention so produced and isolated.

EXAMPLE 5

In this operation, 1 -hexanol was used at the liquid organic medium for the ball milling operation. In particular, 40 grams of another portion of the dried starting zeolite powder of Example 4 was blended with 200 grams of 1 -hexanol to form a slurry. The slurry was ground for 92 hours in a 1 -liter ball mill using one-fourth inch alumina balls in the manner of

Comparative Example 1. After milling, the zeolite was filtered and the zeolite filter cake was dried in a vacuum oven at 100° C for 24 hours. A sample of the finely-divided zeolite-A of this invention so produced and isolated, was subjected to a particle size determination as in Comparative Example 1.

EXAMPLE 6

The liquid organic medium used in this operation was ethanol. In this operation, 4540 grams of the another portion of the dried starting zeolite powder of Example 4 and 6265 grams of anhydrous ethanol were blended to form a slurry. The slurry was poured into the jar of a 25-liter ball mill filled to an apparent volume of 75-80% (i.e., the balls extended to 75-80% of the height of the j ar in a vertical position) with one-fourth inch diameter alumina balls from Coors Ceramics Company. The zeolite in the slurry was ground for 92 hours. After milling, the zeolite slurry was filtered and the zeolite filter cake was dried in a vacuum oven at 100° C for 24 hours. A sample of the finely-divided zeolite-A of this invention so produced and isolated, was subjected to a particle size determination as in Comparative Example 1. EXAMPLE 7

In these operations, another portion of the dried starting zeolite of Example 4 was added to n-heptane to form a slurry of 40 wt% solids. It was noted that the zeolite did not disperse as well in the n-heptane medium an in alcoholic media. Some of the zeolite powder tended to form clumps. In one operation (Case 1), the slurry was ground in a 0.5-liter ball mill for 8 hours using one-fourth inch alumina spheres from Coors Ceramics Company. After grinding, the bulk of the n-heptane was removed by means of filtration, and the filter cake was then oven-dried at 150 ° C for 4 hours under vacuum. In a second operation (Case 2), the same procedure as in Case 1 was followed except that the grinding time was 64 hours. A sample of each of the two finely-divided zeolite-A products of this invention so produced and isolated, was subjected to a particle size determination as in Comparative Example 1.

Table 3 summarizes the results of the particle size determinations on the finely-divided zeolite products produced and isolated in Examples 3-7. All sizes given in Table 3 are in microns.

TABLE 3

Examples 8-14 and Examples 15-38 present the results of a group of experiments demonstrating characteristics of products and processes of this invention which employ a calcined zeolite or in which a zeolite calcining step is carried out. These particular examples were carried out using the following sample preparation and evaluation procedures.

Sample Preparing Procedures

All micronized zeolite samples for Examples 8-14 and Examples 15-38 described herein were produced using a zeolite A powder obtained from Albemarle Corporation as the staring particular zeolite. All samples were produced following the sequence of calcining the particular zeolite, slurrying the dried zeolite in isopropanol at a zeolite to isopropanol weight ratio of 20/80, grinding the slurry in a Netzsch LMZ-2 medium mill, removing most of the grinding liquid medium in an rotarvap, and removing the rest of organic liquid grinding medium in a vacuum oven. Calcining was carried out in either a Blue M, mechanical convection oven produced by General Signal or a Thermo lyne high temperature furnace, type 46200. Grinding was carried out in a Netzsch LMZ-2 mill. The LMZ-2 grinder was operated at 2000 RPM with 90 % of the grinding chamber filled with 0.2 mm diameter zirconium beads. In all cases, the zeolite/isopropanol slurries were fed into the grinder continuously at a constant rate of 500 mL/minute. The slurry feeding system formed a closed loop with the grinder chamber such that multiple passes through the grinding chamber of Netzsch LMZ-2 mill could be executed. The rotarvap was operated at 100°C under vacuum. The vacuum oven drying was carried out by leaving samples at 150 °C for 2 hours at about 50 mm Hg vacuum as generated by a mechanical pump.

Evaluation Procedures

Particle size determinations for Examples 8- 14 and Examples 15-38 were carried with a Coulter7 counter particle size analyzer, model LS 230. All measurements were carried out after samples were dispersed and sonicated in water. Re-hydration evaluations were carried out by monitoring sample weight gains, at 23 °C and 65 % relative humidity, after the samples were dehydrated. Sample dehydration was accomplished either by treating sample in the vacuum oven at 200 °C for 4 hours or placing sample in the Thermodyne high temperature furnace at 500 °C for various time periods.

Acid neutralization experiments were carried out by monitoring the pH changes of an HCl solution after the introduction of zeolite samples, under agitation. The experimental procedure for acid neutralization tests is described below:

1. Standardize a pH meter equipped with a proper pH probe using pH buffers of 4 and 10.

2. Add 500 ml of de-ionized water into a 600 ml flask equipped with an 1.5 inch magnetic stirring bar. The beaker is placed on a magnetic stirrer operating at about 500 RPM.

3. Pipette 10 ml of a standardized 0.0100 N HCL solution to the beaker.

4. Weigh exactly 1 gram of zeolite sample and add it to the acid solution under agitation, at time zero.

5. Record pH as a function of time.

The samples in Examples 8-14 and Examples 15-38 are also given sample identification as run-i-j-kx, wherein i denotes the pre-milling calcining conditions, j denotes the number of passes through the LMZ-2 mill, k denotes the time, in hours, the milled and dried sample was exposed to dehydration processes, and x is either V or F. When x is V, the dehydration was carried out in the vacuum oven and when x is F, the dehydration was conducted in the furnace. Thus, Run-1 means that the zeolite was dried in the Blue M oven at 250 °C for 24 hours prior to milling. The pre-milling calcining for runs 2 to 5 was carried out in the Thermo lyne type 46200 high temperature furnace. In all calcining processes, about

400 grams of the particular zeolite was used as the starting material. For run-2 the particular zeolite was heated in the furnace for 4 hours at 500 °C. In runs 3, 4, and 5, 400 grams of the particular EZA7 zeolite was placed in the furnace for one hour at the respective temperatures of 600 °C, 700 °C and 800 °C. The LMZ-2 mill was operated at 2000 RPM with 90 % of the grinding chamber filled with 0.2 mm diameter zirconium beads. For examples, run-3-12 indicates that the sample was prepared by calcining the starting zeolite at 600 °C for one hour prior to milling, the zeolite particles, on the average, passed the milling chamber about 12 times, and the liquid grinding medium was removed through routine rotarvap and vacuum oven operations. Run-4-24-4V is used to describe a sample which was prepared by calcining the starting zeolite at 700 °C for one hour prior to milling, zeolite particles, on the average, passed the milling chamber about 24 times, and after the liquid grinding medium was removed through routine rotarvap and vacuum oven operations, the sample was dehydrated in the vacuum oven for an additional 4 hours at 200 °C. Run-5-3-lF is used to describe a sample which was prepared by calcimng the starting EZA7 zeolite at 800 °C for one hour prior to milling, zeolite particles, on the average, passed the milling chamber about 3 times, and after the liquid grinding medium was removed through routine rotarvap and vacuum oven operations, the sample was dehydrated in the furnace for one hour at 500 °C.

Several samples (Examples 8-14) were also prepared without the benefit of pre- grinding calcimng. These powder samples are given sample identification by a prefix of Msas. Three of the samples, Msas-13, Msas-1015, andMsas-18 were selected for comparison purposes. One of the samples, Msas-18, was also dehydrated at 500 °C for various time periods to generate Msas-18-1F, Msas-18-2F, and Msas-18-4F. For example, Msas-18-1F denotes that the starting zeolite did not receive pre-grinding calcining and after it was micronized, the powder was dehydrated in the furnace for 1 hour at 500 °C.

EXAMPLES 8-14

The particle size, and crystallinity as determined by X-ray Diffraction ("XRD") generated from the runs for comparison samples Msas- 10, Msas- 1015, Msas- 18,Msas-18-lF, Msas-18-2F, and Msas-18-4F, before and after dehydration at 500 °C, are given in Table 4. TABLE 4

> π

(a) Crystallinity is reported in Table 4 as % of type A zeolite determined by X-ray diffraction with respect to a reference standard.

The data of Table 4 show that samples generated from the above mentioned milling/drying powder-production-processes are capable of producing micronized powder zeolites. It also suggests that the crystallinity of the zeolite is reduced significantly through milling. The smaller mean particle size corresponds to lower zeolite crystallinity. Also, significant agglomeration occurred when Msas- 18 was heated at 500 °C.

The acid (HCl) neutralization capability data for the comparison examples are given in Table 5 as a function of slurry time. All numerical values in Table 5, other than times, are pH.

TABLE S

The data suggests that the micronized zeolites, Msas-13, Msas-1015 and Msas-18, are just as effective as the starting zeolite in neutralizing HCl, even though the crystallinities of the micronized zeolites are noticeably lower than that of the starting particular zeolite. It was also noted that the dehydration process which was carried out by drying the Msas-18 sample at 500 °C for various time periods (1, 2, and 4 hours), all resulted in significant reductions in the capability of neutralizing HCl. This suggests that if one follows the previously known production sequence of milling/drying/calcining, one could very well produce micronized zeolite which would not have the combination of both small average particle size and acid scavenging capabilities. When comparing the particle size data before and after Msas-18 samples were dehydrated in furnace at 500 °C, one may conclude that sintering between zeolite particles may occur during furnace dehydration at 500 °C.

EXAMPLES 15-38

To illustrate the unexpected findings underpinning the present invention with respect to calcining prior to micronizing, the particle size data for starting material and 20 samples prepared following the production sequence of calcination followed by milling and then drying are given in Table 6 below. All sizes given in Table 6 are in microns.

TABLE 6

The particle size data given in Table 6 suggest that pre-milling calcination imparts no adverse effects on milling efficiency. On the contrary, one may conclude that calcining at 800 °C prior to grinding improves grinding efficiency. This conclusion is supported by the relatively smaller particle size data associated with samples generated in the run-5 series, when comparing to that of others. It was also recognized that there were only minor increases in mean particle size after samples were dehydrated in vacuum oven at 200 °C for 4 hours. Table 7 is a collection of re-hydration data for 15 of the above mentioned samples and for the starting material sample. All data are presented in Table 7 as percent weight gain at 23 °C and 65% relative humidity. TABLE 7

The re-hydration data given in Table 7 revealed that the calcining/milling/drying preparation procedure does indeed produce samples with reduced re-hydration capability. As a reference, the re-hydration measurement conducted on a sample, Example 35 (starting-4V), which was prepared by dehydrating the starting zeolite for 4 hours at 200 °C in the vacuum oven, is also inserted into Table 7. The data in Table 7 suggests that the re-hydration capability of the fine particle size zeolite is a function of pre-grinding calcining conditions, and the number of passes through the milling chamber. When comparing data generated from samples producing in any given calcination conditions (as identified by the first digit following the ran), the higher the number of passes corresponds to the lower re-hydration capability. When everything else is equal, it appears that the higher the calcination temperature corresponds to the lower re-hydration capability. The number of passes through the milling chamber appears to be a more dominant factor as compares to the pre-grinding calcining temperatures. Since the particle size is directly related to the number of passes, one can also conclude that the rehydration capability is related to particle size.

To explore the reason behind the loss of re-hydration capability, all the samples were examined by X-ray diffraction. The data, expressed as % of crystallinity as compare to a reference type A zeolite sample, is given in Table 8.

TABLE 8

When comparing the crystallinity data given in Table 8 to the re-hydration data given in Table 7, it was not surprising to find that the reduction of re-hydration capability of micronized zeolites following this invention is related to the loss of crystallinity. When comparing XRD data between samples before and after de-hydration (4 hours in vacuum oven), it is clear that vacuum oven de-hydration imparts no significant crystallinity reduction. This is quite different from the data given in Table 4 where the crystallinity of Msas-18 reduced from 39 to 12 after dried in a furnace thermostat at 500 °C for 4 hours.

Samples were examined for their HCl scavenging capability. The pH of HCl solution after the addition of zeolite was measured at various time intervals. The pH data is given in Table 9. TABLE 9

Surprisingly, despite all the losses in crystallinity, there is essentially no reduction in the zeolite's ability to neutralize HCl. The pH data indicates that micronized zeolite powder prepared according to the calcination/milling/drying sequence of this invention meets all the acid scavenging expectations for type A zeolite.

Data given in Table 4 above indicates that agglomeration occurred when a sample, Msas-18, produced following a previously known procedure, was heated in an oven thermostated at 500°C. The oven treatment was repeated on run-5 zeolite samples produced following a process of this invention. Although, there are indications of agglomeration occurring during heating at 500 °C, the degree of agglomeration was several orders smaller than what was observed in runs employing the previously known process, e.g., Msas-18. The following Table 10 sets for the determined particle size on Run-5 zeolite samples before and after furnace dehydration. All numerical values are given in microns.

TABLE 10

The foregoing demonstrates that calcining the starting detergent grade particular zeolite prior to milling yields tremendous benefits, especially if fine particle size zeolite powders with low volatile content are the targeted products. It is also reasonable to conclude that this invention provides fine particle zeolite with low volatile content in combination with low re-hydration characteristics, all using economically viable processes. Moreover, utilizing the processes of this invention, agglomeration of the fine particle powder zeolite caused by sintering, which can occur during the practice of other processes which use a high temperature drying step, is greatly reduced.

In connection with this invention, particle size determination must not be based on use of scanning electron microscopy. Instead a MICROTRAC® FRA Model No. 9240-4-10-1 particle size analyzer manufactured by Leeds & Northrap, or other particle size analyzer of at least equivalent accuracy and precision is to be used.

Compounds referred to by chemical name or formula anywhere in this document, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another component or a solvent). It matters not what preliminary chemical changes, if any, take place in the resulting mixture or solution, as such changes are the natural result of bringing the specified substances together under the conditions called forpursuant to this disclosure. Also, even though the claims may refer to substances in the present tense (e.g. , "comprises" or "is"), the reference is to the substance as it exists at the time just before it is first contacted, blended or mixed with one or more other substances in accordance with the present disclosure.

This invention is susceptible to considerable variation in its practice. Therefore the foregoing description is not intended to limit, and should not be construed as limiting, the invention to the particular exemplifications presented hereinabove. Rather, what is intended to be covered is as set forth in the ensuing claims.

Claims

CLAIMS:

1. A process for producing ultra-finely divided zeolite which comprises micronizing particulate zeolite in a liquid organic medium, wherein said medium is (a) inert or substantially inert, (b) devoid or substantially devoid of water, and (c) devoid of a dispersant, to form a micronized zeolite product having an average particle size of about 2 microns or less and containing at least 90%> by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns.

2. A process according to Claim 1 further comprising separating the organic medium and said micronized zeolite product from each other.

3. A process according to Claim 1 wherein the micronizing is effected by ball milling.

4. A process according to Claim 1 wherein the balls used in the ball milling are ceramic balls.

5. A process according to Claim 1 wherein the particulate zeolite is micronized to form a micronized zeolite product wherein the mean particle size is 1 micron or less, and wherein at least 90% by weight of said product, based on the dry weight of the zeolite product, if isolated, has a particle size of 2 microns or less.

6. A process according to Claim 1 wherein said organic medium is at least one substantially non-volatile liquid plasticizer, and wherein said micronized zeolite product is in the form of a slurry in said plasticizer.

7. A process according to Claim 1 wherein said organic medium has a viscosity at 20 °C of about 0.05 poise or less, and a boiling point of 100° C or less, and wherein said micronized zeolite product and said organic medium are separated from each other under substantially inert, anhydrous conditions such that the micronized zeolite product being separated does not undergo any appreciable agglomeration during the separation.

8. A process according to Claim 7 wherein said separation comprises subjecting a slurry of said micronized zeolite product in said organic medium to filtration, centrifugation, or decantation under substantially inert, anhydrous conditions, and evaporating the residual organic medium from the resultant micronized zeolite product.

9. A process according to Claim 8 wherein said organic medium is at least one alcohol.

10. A process according to Claim 9 wherein said at least one alcohol is one or a mixture of alkanols having in the range of 1 to about 6 carbon atoms in the molecule.

11. A process according to Claim 8 wherein after evaporating the residual organic medium from the resultant micronized product, the zeolite product is subjected to agitation to produce a free-flowing powder having an average particle size of about 2 microns or less and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns.

12. A process according to Claim 5 wherein said organic medium has a viscosity at 20 °C of about 0.05 poise or less, and a boiling point of 100° C or less, and wherein said micronized zeolite product and said organic medium are separated from each other under substantially inert, anhydrous conditions such that the micronized zeolite product being separated does not undergo any appreciable agglomeration during the separation.

13. A process according to Claim 12 wherein said separation comprises subj ecting a slurry of said micronized zeolite product in said organic medium to filtration, centrifugation, or decantation under substantially inert, anhydrous conditions, and evaporating the residual organic medium from the resultant micronized zeolite product.

14. A process according to Claim 13 wherein said organic medium is at least one alcohol.

15. A process according to Claim 14 wherein said at least one alcohol is one or a mixture of alkanols having in the range of 1 to about 6 carbon atoms in the molecule.

16. A process according to Claim 13 wherein after evaporating the residual organic medium from the resultant micronized product, the zeolite product is subjected to agitation to produce a free-flowing powder wherein the mean particle size is 1 micron or less, and wherein at least 90% by weight of said product, based on the dry weight of the zeolite product, if isolated, has a particle size of 2 microns or less.

17. A process according to Claim 1 wherein the particulate zeolite to be micronized is zeolite-A, zeolite-X, or zeolite-Y.

18. A process according to Claim 1 wherein the particulate zeolite to be micronized is substantially free from water other than water of hydration.

19. A process according to Claim 1 wherein the micronizing is performed at least at one temperature in the range of 20 °C to 100°C.

20. A process according to Claim 19 wherein prior to the micronizing, the particulate zeolite to be micronized is heated in the absence of said organic medium to a temperature in the range of 30 ° C to 100 ° C to remove water from the zeolite, and wherein the micronizing is performed at a temperature no higher than the temperature at which said zeolite was heated in the absence of said organic medium to remove water therefrom.

21. A process according to Claim 20 wherein the particulate zeolite is zeolite-A.

22. Finely-divided synthetic zeolite powder having an average particle size of about 2 microns or less, and containing at least 90% by weight, based on the dry weight of the zeolite powder, of particles no larger than about 5 microns.

23. Synthetic zeolite powder according to Claim 22 wherein the average particle size of the dry, finely-divided synthetic zeolite powder is 1 micron or less, and at least 90% by weight of the finely-divided zeolite powder, based on the dry weight of the zeolite powder, has a particle size of 2 microns or less.

24. Synthetic zeolite powder according to Claim 22 or 23 wherein the zeolite is zeolite-A, zeolite-X, or zeolite-Y, or a mixture of any two or all three of these zeolites.

25. Synthetic zeolite powder according to Claim 22 or 23 wherein the zeolite is zeolite-A.

26. A composition comprising a mixture of (A) finely-divided anhydrous or substantially anhydrous synthetic zeolite having an average (mean) particle size of about 2 microns or less, and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns, and (B) a liquid organic medium of lubricating viscosity having plasticizing properties, said medium constituting a continuous liquid phase in said mixture.

27. A composition according to Claim 26 wherein the mean particle size of the finely-divided anhydrous or substantially anhydrous synthetic zeolite is 1 micron or less, and wherein at least 90% by weight of such zeolite has a particle size of 2 microns or less.

28. A composition according to Claim 26 or 27 wherein the synthetic zeolite is zeolite-A, zeolite-X, or zeolite-Y, or a mixture of any two or all three of these zeolites.

29. A composition according to Claim 26 or 27 wherein the synthetic zeolite is zeolite-A.

30. A process for producing ultra-finely divided zeolite which comprises: a) calcimng particulate zeolite to a water content of 10 wt% or less as determinable by thermal gravitational analysis, b) micronizing said calcinated particulate zeolite in a liquid organic medium which is ( 1 ) inert or substantially inert to the zeolite, (2) devoid of water, and (3) devoid of a dispersant, to form a slurry of finely-divided zeolite in the liquid organic medium, and then c) removing the liquid organic medium from the slurry to thereby provide a micronized zeolite product having a content of volatiles of less than about 10 wt% and an average particle size of about 2 microns or less, and containing at least 90% by weight, based upon the dry weight of the zeolite product, if isolated, of particles no larger than about

5 microns.

31. A process according to Claim 30 wherein steps a), b) and c) are conducted such that said micronized zeolite product is further characterized by having a crystallinity of less than about 40%..

32. A process according to Claim 30 wherein steps a), b), and c) are conducted such that said micronized zeolite product is further characterized by having a rehydration capability of no more than 10 wt% as determinable by the amount of water absorbed in 60 hours at 23 °C from air of 65% relative humidity.

33. A process according to Claim 30 wherein steps a), b) and c) are conducted such that said micronized zeolite product is further characterized (i) by having a crystallinity of less than about 40%; and (ii) by having a rehydration capability of no more than 10 wt% as determinable by the amount of water absorbed in 60 hours at 23 ° C from air of 65% relative humidity.

34. A process according to Claim 30 wherein the calcining in a) is conducted at a temperature of at least about 500 °C.

35. A process according to Claim 30 wherein the calcining in a) is conducted at a temperature of at least about 600 ° C.

36. A process according to Claim 30 wherein the calcining in a) is conducted at a temperature in the range of 600° C to 1000°C.

37. A process according to Claim 30 wherein the calcining in a) is conducted for a period of at least about 5 minutes.

38. A process according to Claim 30 wherein the calcining in a) is conducted for a period of at least about 10 minutes.

39. A process according to Claim 30 wherein the calcining in a) is conducted for a period in the range of 10 to 240 minutes.

40. A process according to Claim 30 wherein step a) is conducted at a temperature of at least about 600 ° C for a period of at least about 60 minutes, and wherein steps b) and c) are conducted to form a micronized zeolite product having a content of volatiles of less than about 5 wt% and an average particle size of about 1 micron or less, and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 3 microns.

41. A process according to Claim 30 wherein step a) is conducted at a temperature in the range of 800 to 1000°C for a period in the range of 10 to 240 minutes, and wherein steps b) and c) are conducted to form a micronized zeolite product having a content of volatiles of less than about 4 wt%, an average particle size of about 0.7 micron or less, a crystallinity of less than about 20%, a rehydration capability of no more than about 8 wt% as determinable by the amount of water absorbed in 60 hours at 23 °C from air of 65% relative humidity, and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 2 microns.

42. A process according to Claim 30 wherein step a) is conducted at a temperature in the range of 800 to 900 ° C for a period in the range of 10 to 240 minutes, and wherein steps b) and c) are conducted to form a micronized zeolite product having a content of volatiles of less than about 4 wt%, an average particle size of about 0.5 microns or less, a crystallinity of less than about 10%, a rehydration capability of no more than about 4 wt% as determinable by the amount of water absorbed in 60 hours at 23 °C from air of 65% relative humidity, and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 2 microns.

43. A process according to Claim 30 wherein said organic medium has a viscosity at 20 °C of about 1 poise or less, a boiling point of 200° C or less, and a dielectric constant at 25 ° C in the range of 10 to 40.

44. A process according to Claim 30 wherein said organic medium has a viscosity at 20 ° C of about 0.05 poise or less, a boiling point of 100 ° C or less, and a dielectric constant at 25 ° C in the range of 10 to 40.

45. A process according to Claim 30 wherein said organic medium is an alkanol having a viscosity at 20 °C of about 0.05 poise or less, a boiling point of 100° C or less, and a dielectric constant at 25 °C in the range of 15 to 20.

46. A process according to Claim 30 wherein said organic medium has a viscosity at 20 °C of about 1 poise or less, a boiling point of 200° C or less, and a dielectric constant at 25 °C in the range of 10 to 40; and wherein in conducting step c) said liquid medium is vaporized or stripped from said slurry, optionally under reduced pressure, followed by drying in a vacuum oven at a temperature in the range of 200 to 500 °C.

47. A process according to Claim 30 wherein said organic medium has a viscosity at 20 ° C of about 0.05 poise or less, a boiling point of 100 ° C or less, and a dielectric constant at 25 °C in the range of 10 to 40; and wherein in conducting step c) said liquid medium is vaporized or stripped from said slurry, optionally under reduced pressure, followed by drying in a vacuum oven at a temperature in the range of 400 to 500 °C.

48. A process according to Claim 30 wherein said organic medium is an alkanol having a viscosity at 20 °C of about 0.05 poise or less, a boiling point of 100° C or less, and a dielectric constant at 25 °C in the range of 15 to 20; and wherein in conducting step c) said liquid medium is vaporized or stripped from said slurry, optionally under reduced pressure, followed by drying in a vacuum oven at a temperature in the range of 400 to 500 °C.

49. A process according to any of Claims 30-48 wherein said zeolite is selected from the group consisting of type A zeolite, type X zeolite, type P zeolite, hydroxysodalite, and a mixture of any two or more of the foregoing.

50. A process according to any of Claims 30-48 wherein step a) is carried out so that said particulate zeolite has a water content of about 3 wt% or less.

51. A process according to Claim 50 wherein the water content is about 1 wt% or less.

52. A process according to Claim 30 wherein:

1) said zeolite is type A zeolite;

2) the calcining of the particulate type A zeolite is conducted to achieve a water content of 1 wt% or less as determinable by thermal gravitational analysis;

3) said organic medium is an alkanol having a viscosity at 20 ° C of about 0.05 poise or less, a boiling point of 100 ° C or less, and a dielectric constant at 25 ° C in the range of l5 to 20;

4) in conducting step c) said alkanol is vaporized or stripped from said slurry, optionally under reduced pressure, followed by drying in a vacuum oven at a temperature in the range of 400 to 500 °C; and 5) steps a), b) and c) are conducted such that the micronized type A zeolite product has a content of volatiles of less than about 4 wt%, an average particle size of about 0.7 micron or less, a crystallinity of less than about 5%, and a rehydration capability of no more than about 8 wt%> as determinable by the amount of water absorbed in 60 hours at 23 ° C from air of 65% relative humidity, and contains at least 90% by weight, based on the dry weight of the type A zeolite product, if isolated, of particles no larger than about 2 microns.

53. A process according to Claim 52 wherein the particulate zeolite in a) has an average particle size in the range of 2 to 5 microns.

54. A process according to Claim 30 wherein the particulate zeolite in a) has an average particle size in the range of 2 to 5 microns.

55. Finely-divided synthetic zeolite powder having a content of volatiles of less than about 10 wt%, a crystallinity of less than about 40%, an average particle size of about 2 microns or less, and containing at least 90% by weight, based on the dry weight of the zeolite powder, of particles no larger than about 5 microns.

56. Synthetic zeolite powder according to Claim 55 wherein the average particle size of the dry, finely-divided synthetic zeolite powder is 1 micron or less, and at least 90% by weight of the finely-divided zeolite powder, based on the dry weight of the zeolite powder, has a particle size of 2 microns or less.

57. Synthetic zeolite powder according to Claim 55 or 56 wherein the zeolite is selected from the group consisting of zeolite-A, zeolite-X, zeolite-Y, zeolite-P, hydroxysodalite and a mixture of any two or more of these zeolites.

58. Synthetic zeolite powder according to Claim 55 or 56 wherein the zeolite is zeolite-A.

59. A composition comprising a mixture of (A) finely-divided anhydrous or substantially anhydrous synthetic zeolite having a content of volatiles of less than about 10 wt%, a crystallinity of less than about 40%, an average (mean) particle size of about 2 microns or less, and containing at least 90% by weight, based on the dry weight of the zeolite product, if isolated, of particles no larger than about 5 microns, and (B) a liquid organic medium of lubricating viscosity having plasticizing properties, said medium constituting a continuous liquid phase in said mixture.

60. A composition according to Claim 59 wherein the mean particle size of the finely-divided anhydrous or substantially anhydrous synthetic zeolite is 1 micron or less, and wherein at least 90%) by weight of such zeolite has a particle size of 2 microns or less.

61. A composition according to Claim 59 or 60 wherein the synthetic zeolite is selected from the group consisting of zeolite-A, zeolite-X, zeolite-Y, zeolite-P, hydroxysodalite and a mixture of any two or more of these zeolites.

62. A composition according to Claim 59 or 60 wherein the synthetic zeolite is zeolite-A.

63. A process for producing ultra-finely divided zeolite which comprises: a) micronizing calcinated particulate zeolite in a liquid organic medium which is ( 1 ) inert or substantially inert to the zeolite, (2) devoid of water, and (3) devoid of a dispersant, to form a slurry of finely-divided zeolite in the liquid organic medium, said calcinated particulate zeolite having a water content of about 10 wt% or less as determinable by thermal gravitational analysis, and then b) removing the liquid organic medium from the slurry to thereby provide a micronized zeolite product having a content of volatiles of less than about 10 wt% based on the total weight of the micronized zeolite product, and an average (mean) particle size of about 5 microns or less, and containing at least about 90% by weight, based on the dry weight of the micronized zeolite product, of particles no larger than about 5 microns.

64. A process according to Claim 63 wherein the micronized zeolite product in b) has an average (mean) particle size of about 2 microns or less.

65. A process according to Claim 64 wherein the micronized zeolite product in b) contains at least about 90% by weight, based on the dry weight of the micronized zeolite product, of particles no larger than about 2 microns.

66. A process according to Claim 63 wherein the micronized zeolite product in b) contains at least about 90% by weight, based on the dry weight of the micronized zeolite product, of particles no larger than about 2 microns.

67. A process according to Claim 63 wherein said organic medium has a viscosity at 20 °C of about 1 poise or less, a boiling point of 200° C or less, and a dielectric constant at 25°C in the range of 10 to 40.

68. A process according to Claim 63 wherein said organic medium has a viscosity at 20°C of about 0.05 poise or less, a boiling point of 100°C or less, and a dielectric constant at 25 °C in the range of 10 to 40.

69. A process according to Claim 63 wherein said organic medium is an alkanol having a viscosity at 20°C of about 0.05 poise or less, a boiling point of 100°C or less, and a dielectric constant at 25 °C in the range of 15 to 20.

70. A process according to Claim 63 wherein said organic medium has a viscosity at 20 °C of about 1 poise or less, a boiling point of 200° C or less, and a dielectric constant at 25 °C in the range of 10 to 40; and wherein in conducting step c) said liquid medium is vaporized or stripped from said slurry, optionally under reduced pressure, followed by drying in a vacuum oven at a temperature in the range of 200 to 500°C.

71. A process according to Claim 63 wherein said organic medium has a viscosity at 20 °C of about 0.05 poise or less, a boiling point of 100° C or less, and a dielectric constant at 25 °C in the range of 10 to 40; and wherein in conducting step c) said liquid medium is vaporized or stripped from said slurry, optionally under reduced pressure, followed by drying in a vacuum oven at a temperature in the range of 400 to 500 °C.

72. A process according to Claim 63 wherein said organic medium is an alkanol having a viscosity at 20°C of about 0.05 poise or less, a boiling point of 100°C or less, and a dielectric constant at 25 °C in the range of 15 to 20; and wherein in conducting step c) said liquid medium is vaporized or stripped from said slurry, optionally under reduced pressure, followed by drying in a vacuum oven at a temperature in the range of 400 to 500°C.^~

73. A process according to any of Claims 63-72 wherein said zeolite is selected from the group consisting of type A zeolite, type X zeolite, type P zeolite, hydroxysodalite, and a mixture of any two or more of the foregoing.

74. A process according to Claim 73 wherein said zeolite is type A zeolite.