FI80899C - FOERFARANDE FOER BEHANDLING AV ZEOLITMALMER FOER AVLAEGSNANDE AV FAERGFOERORENINGAR UR DEM OCH FOERBAETTRANDE AV LJUSHETEN HOS DEM ANVAENDNINGEN AV GENOM FOERFARANDET FRAMSTAELLD ZEOLITPRODUKT S - Google Patents

Description

1 80899

The present invention relates to processes for the treatment of zeolite ore, such as clinoptilolite. relates in particular to processes for converting zeolites into high-grade, high-brightness pigments, extenders or fillers which are comparable to high-grade commercial kaolin clay pigments and fillers, but which have a bulk density of only about half the kaolin clay pigment in bulk or packaged.

20 Natural zeolites belong to a group of at least 34 minerals that are chemically crystalline, hydrated aluminosilicates of alkali and alkaline earth metals, usually sodium, potassium, magnesium, calcium, strontium and barium. Structurally, the minerals are lattice-structured aluminosilicates formed by unrestricted A104 and SiO4 tetrahedral space networks. Tetrahedrons are interconnected through all oxygen atoms. Zeolite minerals are aluminosilicates of alkali and alkaline earth metals, mainly sodium and calcium, forming three-dimensional lattice, containing widely varying amounts of water in the pores in the lattice. Zeolite materials are open-structure and the cavities connected by their pores and channels contain water molecules. When the zeolite minerals Akti-35 can be heated above 100 ° C, the crystal structure remains unchanged and the cations coordinate with the oxygen atoms on the inner surfaces of the on-fish. Upon activation, the zeolite crystal becomes a porous solid with up to 50% pore space through which a cavity penetrates. These are connected by 5 channels with a diameter of 2-7 A. The structure formed is a natural equivalent to a synthetic molecular sieve, as evidenced by the size of the channels, the ability to absorb gases, and the efficiency of separating gas mixtures into their components.

Zeolite strata are believed to have formed from 10 volcanic ash and lava flows that came into contact with seawater, freshwater lakes, groundwater, or shallow, saline lakes. The alkalinity of the water and the type and concentration of the ions it contained determined the zeolite variety formed. Zeolite-15 deposits may have formed wherever volcanic activity has taken place in the vicinity of table salt or alkaline water and sufficient time has elapsed for the formation of minerals. Extensive zeolite deposits are found in Europe, the Far East, Australia, South America and 20 in Africa. Of the more than forty natural zeolite minerals identified, only six have been reported to be present in such quantities and purity (80-90% purity) that they are of serious commercial interest. The six most notable zeolites are cabazite, mordenite-25 ti, clinoptilolite, erionite, phillipsite, and Analite. Typical natural zeolites also include fer rierite, heulandite and lumontite.

Due to their ion exchange capacity, natural zeolites are mined, processed and used for the purification of acid-containing gases, such as methane containing hydrogen sulphide or natural gas, for the decontamination of radioactive effluents to recover radioactive materials, eg Cs-137, from nuclear reactor effluents or and wastewater treatment. The processing of natural zeolites 3 80899 prior to use involves grinding, sorting and calcination to expel water from the pores.

Natural zeolites can also be used as starting materials in the production of synthetic zeolites. U.S. Patents 4,401,633 and 4,401,634 describe methods for preparing synthetic zeolite A by heating heulandite or clinoptilolite in aqueous sodium hydroxide solution, filtering and reacting the filtrate with sodium aluminate to precipitate zeolite A. A similar process is published in a Russian article by A. Yu. Kruppenikova et al., (English) Phase Transitions in the Recrystallization of Clinoptilolite, published by the Institute of Physical and Organic Chemistry of the Georgian Academy of Sciences. The preparation of synthetic zeolite A by hydrothermal treatment of clinoptilolite in a suspension of sodium aluminate and aqueous sodium hydroxide is disclosed in U.S. Patent 4,247,524.

Attempts to improve zeolite content primarily in cabazite ores by sizing in a wet-20 hand cyclone and vibratory table are described in Beneficiation of Natural Zeolites from Bowie, Arizona: A Preliminary Report by K.D. Mondale, F.A. Mumpton and F.F. Apian, pp. 527-537, Zeolite '76, published by State University College, Brockport, New York, 1976.

U.S. Patent 3,189,557 describes a process for removing caustic from montmorillonite ore by dry grinding, screening to remove calcite fines, forming an aqueous slurry, centrifuging the slurry to remove fines, adding a wetting agent and a drum-dry wetting agent-containing slurry. A water-absorbent material is rapidly re-formed which can be used as a beer stabilizer and detergent or as an iron starch additive.

U.S. Patents 2,173,909 and 3,902,993 disclose air foaming for treating zeolite ores so that the zeolite can be separated from the side rock present in said ores.

Synthetic zeolites have been used as catalysts and water softeners. Numerous patents and other prior art publications address methods for regenerating or recovering zeolite particles from catalyst waste or water softener. These include U.S. Patent 1,570,854, JP Patent 5,369 (1954) and East German Patent 8,072 (1971).

10 It has been reported that finely ground clinoptilolite has been prepared in Japan and sorted by dry cyclonization to a product of -10 μm with a brightness of 80 (Takasaka in Funsai, 1975, 20, pp. 127-134, 142). It has been reported that ground zeolite ore (Kokai 73,099,402; Kokai 70,041,044) has been used in papermaking in Japan. Kobor et al. reported in Papirpar, 1968, 12 (2), 44-50 (in Hungarian) that Hungarian zeolite is not suitable for the production of wood-free paper, that the zeolite has an average brightness of 20 and a high degree of dispersion, and that paper containing zeolite as a filler the specific volume (bulk) has increased and the elasticity has decreased. Due to the low brightness of these materials, they cannot be used in the production of paper that must meet the quality requirements of the United States and the rest of the world.

We have invented a method for purifying natural zeolites which are badly defective in color by organic and inorganic color contaminants so as to be able to remove color contaminants and obtain finely divided zeolite pigments, fillers or extenders with a TAPPI brightness before zeolite. We have also discovered a method for treating zeolite ores in such a way as to be able to remove harmful impurities, improve their scale, ion exchange capacity and surface area, and reduce their particle size. The novel zeolite pigments, extenders and fillers of this invention are also known to retain the lattice structure of natural zeolites. Quite surprisingly, the fine grinding steps used in the process of this invention have not destroyed or detectably impaired the crystalline lattice structure. This means that the ion exchange capacity of the zeolite-10 titanium products formed in the processes of the process of this invention has remained unchanged. It is noteworthy that the relatively low bulk densities of bulk and packaged product compared to the bulk density of the finest kaolin clay pigments as bulk and packaged product make the products of this invention very suitable for the production of lightweight papers and other lightweight products.

The novel zeolite products of the present invention provide quality papers filled with them, and the products provide useful coating materials for use as paints 20 and coatings, e.g., for paper. The invention also provides novel coated papers containing novel zeolite products.

The curves in Figure 1 show the TAPPI brightness for the two papers as a function of percentage pigment content. The filler of the second paper is the zeolite product of Example 1 and the second is a commercial grade, uncalcined, delaminated Kao clay clay.

The curves in Figure 2 show the TAPPI opacity as a function of percentage pigment content for two papers. The filler of the second paper is the zeolite product of Example 1 and the other is the same uncalcined, delaminated kaolin clay.

The process of the invention comprises the steps of: (a) mixing finely ground zeolite ore.

6,80899 a dispersant (e.g. from the group of tetrasodium pyrophosphate, sodium silicate and polyacrylates) and water for dispersing said zeolite and forming an aqueous zeolite slurry; 5 (b) removing coarse material having a particle size of 44 μm or more from said zeolite water slurry; (c) removing fines having at least 50% of the particles smaller than 2 μm or less in size and containing said coefficient 10 from said zeolite slurry. , (d) a mixture of the zeo-slurry slurry and the fine grinding medium after the fines removal step (c) is vigorously mixed to finely grind said zeolite to particles having at least 20% of a size of less than 2 μm, and said grinding medium is removed from said fines. (e) removing at least 40% of the fines having a particle size of less than 2 μm or less and containing 20 color impurities from the finely ground zeolite slurry; (f) if desired, passing a second zeolite slurry through the fine grinding medium obtained in (e) above. grinding with a fine grinding medium by vigorously mixing said slurry and a fine grinding medium to grind said zeolite with a fine grinding medium into particles of at least 60% smaller than 2 μm and removing fines having at least 80% of the particles smaller than 2 μm in size and containing a fine grinding medium (g) after said fines removal step (e) or (f), said finely ground zeolite slurry is subjected to a magnetic separation to remove magnetic color impurities, 35 (h) if desired, 780899 obtained from (g) above. the zeolite slurry undergoes a final grinding with a fine grinding medium by vigorously mixing said slurry and a fine grinding medium to grind said zeolite with a fine grinding medium into particles, at least 90% of which are of all sizes; e 2 pm, (i) bleaching the zeolite slurry formed and, if desired, (j) isolating the zeolite from the dry slurry formed.

The zeolite is preferably finely ground twice and any suitable equipment available to the ore processor, such as ball mills, hammer mills, fine grinders, etc., can be used. or a dispersant belonging to the group of polycarboxylate salts such as polyacrylate salts, e.g. sodium, ammonium, potassium or lithium polyacrylate salt of polyacrylic acid, preferably dispersants in the form of 20 acrylate salts having an average molecular weight of 500 to 10,000, preferably 500 to 10,000, other suitable and available dispersants, and the nature of the dispersant is not critical to the practice of this invention. The dispersant and finely ground zeolite can be mixed in any suitable mixing device, e.g. blunger.

In many cases, the finely ground zeolite is washed with acid prior to dispersion, thereby reducing the amount of dispersant required to obtain a suitable dispersion. It has been theorized that some zeolites are rich in calcium sulfate, which consumes large amounts of dispersant. In such cases, the finely ground zeolite may be acid washed by mixing water and an acid, e.g. hydrochloric acid β 80899, sulfuric acid, nitric acid, phosphoric acid or some other suitable inorganic acid. For example, it is possible to mix the finely ground ore, water and acid in such amounts that the formed slurry contains 2-20% by weight of acid (based on the liquid component), followed by mixing the formed aqueous, acidic zeolite slurry. The acid is believed to dissolve some of the gypsum (CaSO 4 · 2H 2 O) precipitated in the zeolite ore matrix. The finely ground zeolite is then separated from the mixture of water and acid by appropriate means. The aqueous, acidic zeolite slurry can, for example, be allowed to stand for a certain time, during which the finely ground zeolite settles to the bottom. The aqueous, acidic liquid on top is then removed by decantation and discarded. The remaining precipitated slurry is then separated by filtration, the resulting filter cake is diluted with a further amount of water, mixed in a slurry and filtered again. This filtration-slurry cycle is repeated enough times to remove the acid from the zeolite as accurately as practicable. It has been found that usually two or three filtration-slurry cycles are sufficient. A basic substance such as sodium hydroxide is usually added to the final aqueous slurry to neutralize the acid residues in the zeolite slurry. After neutralization of the slurry, the above-mentioned suitable dispersant is added to disperse the slurry.

The coarse material is conveniently removed from the zeolite aqueous slurry dispersed by means of a suitable dispersant by sieving the slurry and removing the coarse material. Such a coarse material, i.e. gravel, has an average particle size of 44 μm (microns) or more. Typical equipment includes Sweco vibrating screens, shaking and vibrating screens, and vibrating screens.

In the next step, fines having a particle size of less than 2 μm or less and also containing color impurities are removed by suitable means from the dispersed zeolite slurry from which the coarse material has been removed and discarded. For example, a centrifuge is preferably used, although all fines removal procedures such as fractional sedimentation, decantation and the like can be used. The fines are removed in a centrifuge and discarded and the coarser material remains and is fed to the next step.

After removal of the fines, the zeolite slurry 10 is mixed with a fine grinding medium in a ratio of 30 to 70% by weight of the grinding medium in the mixture, and the mixture is stirred vigorously, whereby the zeolite particles of the slurry are finely ground.

The grinding medium is then finely removed from the ground zeolite slurry. The grinding medium includes sand, porcelain balls, metal balls, e.g. iron balls, rubber coated iron balls, nickel balls or rubber coated nickel balls, alumina beads such as Alumasand A or zirconia beads bearing the trade name Z-Beads. The particles of such a medium are considerably larger in size than the zeolite particles in the slurry and can be in the form of pellets with a diameter of 0.79 to about 6.4 mm. preferably 1.6 to about 3.2 mm. The grinding medium may be in any suitable form, e.g. beads, pellets, etc. For example, Alumasand A contains mainly (85-90% by weight) alumina, particle size -8 to +12 mesh. Z-Beads consist of zironium oxide beads with a nominal size of 16 mesh. The grinding step or steps with fine grinding medium (FMM 30 I) are performed with zeolite in the form of an aqueous slurry in any suitable grinder such as a Denver disc grinder or a Chicago Boiler Company Dynomill type KD-5 grinder.

After grinding the zeolite particles with a fine grinding medium, it is recommended to remove and discard the fines containing color impurities by a procedure similar to that described in point 3 above. This step is called the second fines removal step FR II. The slurry obtained from step FR II is preferably allowed to undergo 5 second grinding steps with fine grinding medium (FMM II), which is carried out in the same way as the first grinding step with fine grinding medium (FMM I) above. The slurry obtained from the second grinding step with the fine grinding medium (FMM II) can be passed through the additional fines removal steps with and without filtration and slurry without filtration or slurry, and further grind with the fine grinding medium. In fact, it may be desirable to use more than one or two grinding steps with a fine grinding medium to minimize the loss of zeo-15 composite particles in the fines that are removed in subsequent fines removal steps.

The finely ground zeolite slurry formed after removal of the fines is subjected to a magnetic separation step MS I to remove magnetic color impurities. Any suitable hardware can be used, of which there are several available and widely used. The slurry can be fed through the magnetic separator more than once, e.g., two, three or more times to remove magnetic dirt contaminants more and more accurately. If the slurry from the above 25 grinding steps with the fine grinding medium and the second fines removal step (FR II) is too dilute, it can be filtered and the resulting filter cakes diluted with fresh water and mixed by slurrying into a slurry having an appropriate solids content, etc.

After undergoing magnetic separation once, twice or several times, it can be oxidatively bleached with, for example, ozone, sodium hypochlorite, ammonium persulphate or potassium persulphate. The amount of ha-35 deceptive bleach used is 0.01 to 0.1% by weight based on the dry weight of the aqueous 80899 zeolite feed. By adding basic reagents, the pH of the dispersion is adjusted to 4.5 to 7.0, preferably 6-7. The oxidizing bleach is allowed to react for the time required to reach maximum brightness. Other oxidizing bleaching agents may be used, e.g., water-soluble inorganic or organic compounds having a readily released, bleaching oxygen molecule. Examples of such compounds include ammonium persulfate, potassium permanganate, hydrogen peroxide and the like. However, prior to bleaching, it may be desirable to allow the slurry obtained from the magnetic separation step or steps to undergo additional fines removal steps, e.g., FR III, FR IV and / or FR V and / or additional fines removal steps to improve the stability of the zeolite in the slurry. In such cases, the fines removal steps are performed in the same manner as the fines removal steps I and II described above.

In some cases, reductive bleaching can improve the whiteness and brightness of the material. A commonly used reducing bleach is sodium dithionite, which is usually added to the slurry in the pH range of 2-5. In some cases, sodium dithionite may be used as the sole bleaching agent or may be used after the oxidative bleaching described above.

Prior to the bleaching described above, it may be desirable to further reduce the size of the zeolite particles in the slurry. In this case, it may be necessary to increase the solids content of the slurry. This can be accomplished by filtering the slurry and slurrying the formed filter cake 30 to the desired solids content suitable for grinding with a fine grinding medium. But prior to milling, the slurry is dispersed with a polyacrylate salt and sodium carbonate or other suitable dispersant or combination of dispersants. The second and third grindings can then be performed with a fine grinding medium 12 80899 to further reduce the particle size of the zeolite. After this fine grinding with a grinding medium, the slurry is oxidatively and / or reductively bleached and then the zeolite particles are separated from the slurry and the bleaching agents. This separation can take place by filtering the slurry, slurrying the formed cake cakes and spray-drying the slurry. If desired, other procedures can be used to separate the zeolite particles from the slurry and bleaches.

According to our invention, one preferred method of treating zeolite ores so as to remove harmful impurities, improve their brightness, ion exchange capacity and surface area and reduce their particle size consists of the steps of: 15 (1) mixing finely ground (100% less than 75 μm) zeolite; a dispersing agent and water to disperse said zeolite and form an aqueous zeolite slurry, (2) removing 20 coarse material from said zeolite water slurry to remove coarse material having a particle size of 44 μm or greater, (3) removing fines having at least 50% or at least 70% is less than 2 μm in size and typically 60% is less than 2 μm and the fines contain 25 color impurities from said coarse-grained zeolite slurry, (4) after the fines removal step (3) a mixture of zeolite slurry and fine grinding medium vigorously mixing to finely grind said zeolite to particles of at least about 20%, preferably 25% of less than 2 μm in size, (5) removing fines of which at least 40% or at least 80% or 90% of the particles are less than 2 μm in size, and typically at least 85% is less than 2 μm and typically at least 85% is less than 2 μm and contains color impurities from the zeolite slurry ground by means of a fine grinding medium, (6) the zeolite slurry obtained in (5) above is passed through another, above grinding with a fine grinding medium as described in (4) to reduce the particle size so that at least 60% or at least 75% or 85% of the particles are less than 2 μm in size, (7) removing fines having at least 80% or at least 85% or 95 % less than 2 10 μm in size and containing colors derived from zeolite slurry ground by means of a fine grinding medium (8) after the fines removal step (7), said zeolite slurry ground with a fine grinding medium is subjected to magnetic separation to remove magnetic color impurities, (9) the zeolite slurry obtained in (8) above and to reduce the particle size of the slurry 20 so that at least 90% of the particles are less than 2 μm in size, (10) bleaching the formed zeolite slurry and (11) isolating the zeolite product from the dry formed slurry.

The dry finely ground zeolite product of the novel processes of this invention has a very small particle size, i.e. at least 85% of the particles are less than 2 microns in size and are characterized by a TAPPI brightness of at least 90. These products are quite suitable as pigments or fillers in papermaking and are very suitable. together with all papermaking materials.

Zeolite products with a brightness value of 83-90% but slightly coarser particle size (e.g. 30-80% less than 2) have excellent retention capacity when used as a paper filler and also improve the brightness and opacity of the filler-containing sheet 1480899. Such pigments also have use in the manufacture of coated sheets of paper that have been rendered or unpolished.

The ion exchange properties 5 of the products of this invention are quite useful in the production of carbonless copy paper, e.g., pressure sensitive copy paper, although those products can also be used for heat-sensitive carbonless paper.

Carbonless paper is a type of copy paper that does not require carbon paper. It has a structure of at least two parts: a coated back (CB) coated on the underside with microcapsules containing a colorless dye precursor or cursors or color former (s) in a solvent, and a bottom sheet (CF = 15 coated front) which contains a reagent (commonly referred to as a co-reactant and having e.g. acid activated bentonite, attapulgite clay, phenolic resin or substituted zinc salicylate). When the topsheet is subjected to a pressure that breaks the microcapsules, the reagent reacts with the color former (s) to form a dye or dyes. Multi-copy structures may have interleaved sheets with a top and bottom surface coated (CFB).

We have found that the zeolite product described above is an excellent co-reactant for such a carbonless paper which, upon contact with the dye precursors of the CB sheet, immediately produces a strong color. The zeolite product can be used as the sole pigment in the CF sheet coating or can be used in admixture with uncalcined and / or calcined kaolin clays or other commonly used coating pigments. Conventional latex or starch adhesives can be used to bond the zeolite product or the mixture of zeolite product and clay to the paper sheet. Prior to use, the zeolite product can be ion-exchanged with zinc and with such a sin-35 kilo ion-exchanged zeolite (containing e.g.

is 80899 2% zinc as zinc oxide) in carbonless paper develops a more intense color. The zeolite can be ion-exchanged with other ions, such as nickel or cobalt ions, to react with certain dye precursors 5 and / or to provide color balance when using multiple dye precursors (e.g., generating "black" dyes, which may consist of a mixture of two or more dyes). throughout the visible spectrum and the end result is gray, black or neutral).

The zeolite product of the present invention is an excellent paper filler (pigment) that improves the opacity and brightness of a paper sheet more than even the best non-calcined, delaminated kaolin products (which are known to be excellent as paper fillers). The curves in Figure 1 show the TAPPI brightness for the two papers as a function of percentage pigment content. The filler (pigment) of the second paper is the zeolite product of Example 1 and the second is a commercial grade, uncalcined, delaminated kaoli-20 nisava (pigment). The curves in Figure 2 show the TAPPI opacity for two papers as a function of the percentage filler (pigment) content. The filler (pigment) of the second paper is the zeolite product of Example 1 and the second is a commercial grade, uncalcined, delaminated kaolin-25 clay (pigment). The method of making the filled papers, the values of which are based on the curves of Figures 1 and 2, is the same as that described in Example 8, Part A. These values indicate that the new zeolite product surprisingly improves TAPPI opacity at all filler concentrations compared to one of the best commercial grade kaolin clays. Similarly, Figure 2 shows that when the filler content is the same, the new zeolite product improves the TAPPI opacity compared to one of the best commercial grade clay fillers. When used as a component of paper coatings, the zeolite product of this invention also improves gravure properties in a highly desirable manner. When used in paper coatings and paints, it also improves the degree of brightness and opacity to a rare degree.

5 The following are examples of abbreviations: s second min minute h hour 10 lb in pounds t ton, 1000 kg pm micron (micrometer) ft foot M mesh, US standard sieve set 15 ml milliliter gal US gallon g gravity acceleration% percent, by weight, unless otherwise stated 20 kG kilogass, magnetic flux density temperature “C, unless otherwise indicated luminance TAPPI luminance measured with a light meter Technidyne model S-4% -2 pm percentage of particles less than 2 pm measured with a Micromeritics Sedigraph 5000% coarse matter Percentage of particles in the sample with a size of more than 30 μm (325M) F / BI first filtration and slurry cycle as described F / B II second filtration and slurry cycle as described 35 F / B III third filtration and slurrying cycle as described 17 80899 F / B IV fourth filtration and slurrying cycle as described F / BV Fifth filtration and slurrying cycle as described 5 Vatu as such F / B VI sixth filtration and slurry cycle as described N / D neutralization and dispersion as described 10 FR I first fines as described FR II second fines as described FR III third fines as described FR IV fourth fines removal as described FR V Fifth removal of fines as described 20 FMM I first grinding with fines as described FMM II second grinding with fines as described FM III third grinding with fines as described MS I first magnetic separation as described MS II second magnetic separation as described 30

Example 1 A. A 243.3 kg batch of zeolite ore with 55% clinoptilolite, 10% feldspar, 8% quartz, 7% gypsum, 2% clay minerals and 18% mordenite (separated by 35) was finely ground twice to a nominal size of 100. % - 18 80899 200M (75 μm). An acid wash solution was prepared by adding 42.6 L of a 36% HCl solution to 568.5 liters of water to give a 1.99% HCl solution. 240.6 kg of finely ground ore and acid washing solution were combined in a tank to give 5 slurries with a solids content of 30.5%. The slurry was stirred slowly for about two hours at ambient temperature (27-32 ° C). The consistency of the slurry was 26.5% solids, pH 0.85 and the amount of solids was 201.1 kg.

The slurry was allowed to settle for 1.25 hours and was removed by decanting 45.5 L of clear liquid. The remaining slurry was subjected to F / B I, whereupon it was pressure-filtered to a solids content of 55-60% and the resulting filter cakes were diluted to approximately the original volume with water alone and slurried for 0.5 hours. The consistency of the resulting slurry was 26.5% solids, pH

1.7 and the amount of solids was 197.0 kg. This slurry was subjected to Section F / B II as described for Step F / B I. The mass consistency of the formed slurry was 26% of the solids and the amount of solids was 193.0 kg. The slurry from section 20 F / B II was subjected to section F / B lii, which was similar to sections F / B I and F / B II. The pH of the resulting slurry was 2.04. The sludge consistency was 30% solids and its solids content was 192.0 kg.

The slurry from section F / B III was allowed to go through a period of 25 N / D while slurrying, first adding 7.5 kg / t NaOH in solids (1.36 kg NaOH pellets). After slurrying for 10 minutes, the pH was 4.2 and an additional 0.45 kg of NaOH (0.25 kg / ton) was added. After a further 10 minutes of slurry, the pH was 7.0 and 7.5 kg / t (1.36 kg of TSPP powder) of tetrasodium pyrophosphate (TSPP) dispersant was added. After a further 10 minutes of slurry, a dispersed slurry was obtained.

The coarse material was removed from the dispersed slurry with a 122 cm (48 ") Sweco vibrating screen with a 325M sieve-35 fabric. After the first screening, the first product slurry with a consistency of 25% and a solids content of 117.6 kg passed through the sieve 80899. From the first screening the resulting coarse (sludge) slurry was diluted to a solids content of 29%, re-screened to give a second product slurry which was added to the first product slurry to give a combined descaled product slurry having a sludge consistency of 23% solids, and amount of solids 137.1 kg.

10 The descaled slurry was allowed to pass the FR I section by feeding the slurry at 7.6 rpm into a Bird centrifuge equipped with a 46 cm (18 ") diameter and 71 cm (28") length slurry. ) on a solid rotor and operating at 2000 rpm. The fines fraction (overflow) was discarded and the coarse fraction (underflow) was recovered as a product slurry with a consistency of 44% solids and a solids content of 122.6 kg.

Table 1 below shows the TAPPI brightness of each step described in Part A,% -2,% coarse material 20 and% Fe 2 O 3 by weight.

table 1

Separate pin-%%% coarse% ratio_lightness_pm_aines_Fe, Q, 25 Feed - 0 60 4.0

Fine grinding 70 41 9 3.7

Acid wash 73 - F / B I 74 38 6 - F / B II 74 42 - - 30 F / B III 75 42 - - N / D 72 42 - 3.9

Removal of coarse material 75 40 0 4,2 FR I 79 20 0 2,0 35 20 80899 B. Batch of 454 kg of zeolite ore mined from the same site as the ore in Part A and containing 50% clinoptilolite, 8% feldspar, 16% quartz, 7% gypsum, 3% clay minerals and 16% mordenite (separated) was finely ground twice as in Part A to give 447.6 kg of material -200M. The finely ground material was slurried and reacted as in Part A in 2.1% HCl with a slurry consistency of 20% solids. After the reaction, a slurry with a consistency of 16 10% solids and a solids content of 349.6 kg was obtained in 1990.

The wash solution was removed by first allowing the slurry to settle over the weekend (ca. 65 hours) and then removing by decanting 454.8 L of clear liquid. The remaining slurry was allowed to go through section F / B I as above with the filter cakes slurried in water. The slurry with a consistency of 23% solids, a total volume of 1304 L and a solids content of 340.5 kg was diluted back to the original volume in 1990 1. The diluted slurry was allowed to go through Section F / B II, slurrying at a consistency of 23% solids. Saa-20 tu 1493 L of slurry with 331.4 kg of solids was re-diluted to a volume of 1990 1. The diluted slurry from Section F / B II was then passed through Section F / B III, slurrying at 25% solids.

The dispersed slurry obtained from section F / B III, which contained 321.9 kg of solids in a volume of 800 l, was allowed to go through section N / D by adding 8 kg / t of NaOH to give a pH of 5.5 and adding then TSPP in a ratio of 5 kg / t solids. The coarse slurry with 321.9 kg solids and a consistency of 25% solids was removed as coarse as in Part A, except that the material was screened only once through a 200M (74) sieve. The sludge from which the coarse material had been removed was allowed to pass through the FR I Bird centrifuge as in Part A, with the difference that a higher speed (3000 35 2000 instead of 2000) was used. In this case, the coarse product contained 21,80899,263.3 kg of solids.

Table 2 below shows the TAPPI brightness,% -2,% coarse, and% Fe 2 O 3 for each of the steps described in Part B.

5 Table 2

Separate- TAPPI-% -2% coarse-% ration_blightness pm_for Fe, Q,

Feed - 10 Fine grinding 74 - - 1.9

Acid wash 74 F / B I 78 47 12 F / B II 75 46 - 2.1 F / B III 75 52 - 2.3 15 N / D -

Removal of coarse material 76 43 - 1.8 FR I 80 23 6 0.8 20 C. The coarser sludge fractions isolated by centrifugation in parts A and B were combined into a slurry with a consistency of 36% solids and a solids content of 384.5 kg. The slurry combination was allowed to pass through the FMM I two-compartment 57-liter Denver disc mill in one compartment using 45.4 kg of Diamonite A (ceramic spheres 1.7 mm in diameter) as the medium. At a feed rate of 300 ml / min, a product slurry was obtained which contained 364.1 kg of solids and had a particle size of 53% -2.

The ground slurry was diluted to a solids content of about 30% before section FR II using a high speed (8700 rpm) Merco Model H-9 plate nozzle centrifuge. The feed rate was about 4.5 l / min. The product slurry contained 335.5 kg solids. This slurry was subjected to Section F / B IV by first adjusting the pH to about 3 with a concentrated sulfur-35 pad and then pressure filtration. Filter cakes 22 8 0 8 9 9 were slurried to a solids content of 35%, neutralized to pH 5 with NaOH and then dispersed at 5 kg TSPP per tonne of solids.

The sludge thus dispersed was allowed to pass the cycle FMM II 5 in a five-liter refiner Chicago Boiler Co. model KD 5 Dynomill with 6.8 kg 1.3 mm Norton Z-Beads (zirconia) as a grinding medium. The grinding feed rate was 45.5 l / h to give a product with a particle size of 84% -2. The product slurry contained 306.5 kg solids and had a consistency of 30% solids.

This ground slurry was allowed to go through the MS I cycle by passing it through a high magnetic flux density (12 kG) wet wet separator with a 10.2 cm diameter vessel (separation chamber) with 8% by volume of medium coarse stainless steel wool. The feed speed was 26.2 cm / min. The recovered slurry, with a consistency of 22% solids and 283.3 kg solids, was allowed to undergo MS II under the same conditions. The consistency of the recovered slurry was 17% solids and it contained 243.3 kg solids.

The product slurry from section MS II was allowed to pass through sections FR III, IV and V in succession. Each treatment was performed with the Merco centrifuge used above, but at a lower speed (6700 rpm). In the three fines 25 discharges, the feed rate was 3.8 l / min. The coarse fraction (product) slurry from section FR III had a consistency of 24% solids and contained 208.4 kg solids. The product sludge from section FR IV had a consistency of 32% solids and contained 196.1 kg solids. The product-30 slurry from section FR V had a consistency of 38% solids and contained 166.6 kg solids.

The product slurry from section FR V was then allowed to go through section F / B V. F / B V was the same as F / B IV with the difference that the former was performed at a solids content of 40%. 35 The thus neutralized and dispersed slurry was passed through a 23 80 8 99 son FMM III 5-liter Dynomill at a feed rate of 38 l / h to give a product with a particle size of 91% -2 μιη.

The powdered slurry thus obtained was bleached by first diluting to a solids content of 20% and lowering the pH of the slurry 5 to 3.0 with 0.68 kg of concentrated sulfuric acid. The slurry was stirred slowly for about 2 hours and after the addition of bleach sodium dithionite (K-brite) at a ratio of 6.5 kg / t solids (0.68 kg K-brite). The pH of the slurry was maintained at 3.0 during bleaching by the addition of an additional 0.23 kg of concentrated sulfuric acid.

The bleached slurry contained 80.4 kg of solids and had a TAPPI brightness of 95. The bleached slurry was then passed through F / B VI by filtration first as in F / B IV and V. The filter cakes were slurried to a solids content of 40%. The resulting slurry was neutralized and simultaneously dispersed with a mixture of 15% sodium polyacrylate dispersant (C-211) and 30% sodium carbonate dissolved in water. The addition ratio was 25 kg of mixture per ton of solids. The final slurry thus dispersed was fed to a spray dryer at a rate of 94.5 l / h (about 45.4 kg / h) to give 68.1 kg of a final product with a TAPPI brightness of 94 and a particle size of 89.5% -2.

Table 3 below shows the TAPPI brightness,% -2 μm and% Fe 2 O 3 of the product recovered after each separate operation described in Part C.

Table 3

Separate- TAPPI-%% 30 raatio_lightness_-2 pm_Fe? Q,

Consolidation 81 22 0.8 FMM I 81 53 0.9 FMM II 82 53 0.9 F / B IV 83 56 35 FMM II 83 84 0.8 24 80899 MS I 88 84 0.7 MS II 90 84 0.7 FR III 92 82 0.5 FR IV 93 80 0.3 5 FR V 94 78 0.2 FMM III 94 91

Bleaching 95 - F / W VI -

Spray drying 94 90 0.2 10

X-ray fluorescence analysis of the final product and the zeolite crude ores (starting materials) is shown in Table 4 below.

15 Table 4

Component New product (%) Crude zeolite ore (%)

A_B

SiO 2 66 68 20 Al 2 O 3 12 6.9

Fe 2 O 3 0.23 3.7 1.9

TiO 2 0.08 0.20 0.36

Na 2 O 1.7 2.0

CaO 1.1 2.0 1.6 MgO 0.84 1.8 1.6 K20 2.3 1.6

ZnO 0.02 0.01 0.01

The final zeolite product contained 48% clinoptilolite, 30% quartz, 12% feldspar, 9% gypsum, 3% clay minerals and 16% mordenite (as a difference).

The new zeolite material prepared in this example with a particle size distribution is quite competitive with commercial No. 1 paper coating grade kaolin product 35 as shown in Table 5.

25 80899

Table 5 5 Particle size% Powdered zeo- New zeolite- Commercial (less than (pm) composite ore tituote_kaolin product 44 90 100 100 6.9 - 100 100 5.0 56 99 99 10 2.0 41 90 90 1.0 - 65 74 0.5 - 39 55 0.25 - 22 32

Avg. particle size (pm) 3.3 0.68 0.44

Electron micrographs show that the fibrous components normally found in zeolite crude ore are absent from the novel zeolite products that have been comminuted using the fine grinding medium of the process of this invention. Thus, it is likely that the novel zeolite products of this invention, when inhaled, will cause less lung damage.

Based on its characteristics, the new zeolite end product is well suited for the use of pigments, extenders or fillers. Its color and other physical characteristics are competitive with those of a commercial, high brightness, calcined kaolin pigment as shown in Table 6.

30 35 26 80899

Table 6

Kaolinite with good brightness

Parameter_product_product_ 5 Color: (1) L * 97.37 98.2 a * -0.02 -0.43 b * 1.24 2.88 GYI (2) 2.40 5.15

Brightness: PIN 93.9 93.2 10 "Twist" (3) 93.9 93.2 IS0 <4) 91.9 91.8

Bulk density: (5) bulk 362 657 (kg / m3) (6) packed 413 897

Density'7 '2.17 2.69

15 DTA (8) exotherm exotherm 500 ° C

350 and 900 ° C exotherm 900 ° C TGA (% loss to 1100 ° C 15.4 approx. 0.5% up to '9')

Wear and tear '10 '(mg) 13 20-25 (calcined) 20 Ö1 grain absorption (11) (g / 100 g) 74 60-110

Hegman {12) 3 3

Moisture113 '(%) 3.1 pH (10% solids) 5.0 6.8 25 Footnotes: (1) Determined according to the CIE 1976 formula (L * a * b *) as described in "Color research and application" , butter. 2, No. 1, Spring 1977, pp. 7-11, John Wiley & Sons, Inc.

(2) German yellowness index, calculated from L *, a * and 30 b *.

(3) Determined by measuring the TAPPI brightness after rotating the cylinder containing the sample and the piston by 30 to 45 ° while applying a pressure of 2.1 kp / cm 2 to the sample.

(4) TAPPI Provisional Method (1976) T 534, Appendix, using a filter marked with the letter "A".

27 80 8 99 (5) Determined by adding 20 g of the sample to a 100 ml graduated beaker and reading the volume.

(6) Determined by sealing the sample in a cylinder (6) 300 times with a Numinco automatic sealer.

5 (7) The values are based on the weight of the constant volume of the massive sample material, whereby the pore volume has been reduced by calculation.

(8) Differential thermal analysis using a DuPont System 94 Analyzer, where when the fine sample is heated, the energy release appears as exothermic peaks and the energy absorption as endothermic peaks.

(9) Thermogravimetric analysis measuring the weight changes (due to decomposition or oxidation) during heating of the sample.

15 (10) Measured with an Einlehner consumption meter and the method TAPPI Useful Method 603.

(11) ASTM D 281-31.

(12) Measured by mixing the dry sample with crude linseed oil, placing the mixture in a small well, scraping the mixture from the well down the trough with equal length segments marked 0-8, and noting the segment where the coarse-grained area stands out. an area with as little coarse material as possible.

25 (13) Measured with an Ohaus moisture determination scale.

The surface area of the new final zeolite product was measured and the value was found to be 78 m 2 / g, which is considerably higher than that of the zeolite ore used as starting material, which had a surface area of 33 m 2 / g in part B. In Part A, the area was approximately the same as in Part B.

The ion exchange capacity of the new zeolite product and also of the zeolite ore used as starting material in Part B was measured. These cation exchange capacity results are shown below.

35 28 80899

Cation exchange capacities in milliequivalents per gram (meq / g)

cation

Total Ca Mg K Cu 5 Raw countries! (1) 1.71 0.54 0.19 1.06 0.39

Zeolite product (2) 1.76 0.98 0.14 1.31 0.67

Synthetic Z4a (3) 4.02 1.98 0.36 3.41 0.39

Zn_AI Sr Cs Na 10 Crude ore) 0.78 0.17 0.16 0.82 1.18

Zeolite product12 ’0.92 0.25 0.45 0.87 1.33

Synthetic Z4a <3) 1.18 0.04 1.35 1.61 4.07 (1) Zeolite ore from Part B 15 used as raw material (2) New zeolite end product from Example 1 (3) Synthetic zeolite 4A which is Sylosiv-100 , manufactured by WR Grace Co.

The cation exchange capacity of the new product is in most cases higher than the 20 ore used as raw material. In some cases, e.g. for copper and aluminum, the ion exchange capacity of the new product was better than that of the synthetic zeolite, which is specifically defined as a cation exchanger. The superiority of the cation exchange capacity of the new product is all the more convincing given the large amounts of quartz, feldspar, clay minerals, gypsum and possibly other materials with low ion exchange capacity. After removal of these materials, the cation exchange capacity of the new product would be (by weight) substantially higher.

Example 2 A 34.1 kg batch of zeolite ore mined from a different location than the ore of Example 1 and containing 33% mordenite, 23% clinoptilolite, 23% feldspar, 15% quartz, 2% melilite and 4% clay minerals. the powder was finely ground twice to a nominal size of 200M (75). The finely ground ore was naturally dispersed in a slurry containing 15% solids when mixed with water. The slurry thus prepared was subjected to the F / R I cycle by feeding it at a speed of 7.6 1 / min into a Bird centrifuge equipped with a 46 cm (18 ") diameter and 71 cm (28") solid rotor operating at 3000 rpm. The coarse fraction was recovered as a product slurry with a consistency of 30% solids and a solids content of 28.6 kg.

The product slurry from section F / R I was allowed to go through section FMM 10 I in a five-liter refiner Chicago Boiler Co. model KD 5 Dynomill with 1.3.7 kg of 1.3 mm Norton Z-Beads acting as grinding medium. The grinding feed rate was 170 l / h to give a product with a particle size of 65% -2. The product slurry contained 27.7 kg solids and had a consistency of 28% solids.

The ground slurry was diluted to a solids consistency of 15% prior to treatment in a F / R II Merco centrifuge at 6700 rpm. Section F / R II was performed in two steps. The first run was performed at a feed rate of 272 kg / h 20 (1701 1 / h), with the coarse fraction (product) accounting for 30% of the feed solids. The second run was performed using the fine fraction from the first run at a feed rate of 136 kg / h (851 1 / h), whereby 80% of the feed solids were recovered as a coarse fraction. The coarse fraction from each of the 25 runs was combined into a single F / R II product that accounted for 65% by weight of the feed solids (18.2 kg).

The product slurry from section F / R II was allowed to pass through the section in an FMM II mill at a Dynomill feed rate of 45.4 l / h to give a product with a particle size of 78% -2. The product slurry had a consistency of 30% solids and contained 15.7 kg solids.

This powdered slurry was diluted to a solids content of 7-8% prior to treatment in an F / R III Merco centrifuge at 35,600 rpm. In section F / R III, the centrifuge was fed at 80899 at 11.3 l / min (54.5 kg / h) and 56% was recovered (coarse fraction). The consistency of the product slurry was 11.4% solids and contained 8.6 kg solids.

The product from section F / R III was subjected to section 5 MS I by passing it through a high magnetic flux density (12 kg) wet magnetic separator with a 5 cm diameter vessel (separation chamber) with 8% by volume of medium coarse stainless steel wool. The feed speed was 52.3 cm / min. The recovered slurry with a consistency of 10.9% solids and 6.8 kg solids was allowed to undergo MS II under the same conditions. The product from MS II was a slurry with a consistency of 3.2% solids and 5.0 kg solids.

The product slurry from section MS II was then subjected to section F / B I where it was acidified to pH 2.0-2.5 with sulfuric acid and then removed by decantation and filtration with enough water to give a solids content of 60%. The filter cakes were slurried with water alone to a slurry having a consistency of 30% solids and a volume of 19 to 20 liters. The slurry from section F / B I was subjected to section FMM III, where it was fed to a Dynomill refiner at a rate of 45.4 l / h and the particle size became 93.5% -2. The product slurry from FMM III with a volume of 19 liters, a consistency of 30% solids and containing 4.1 kg of solids was then bleached. The pH of the slurry was adjusted to 3 with sulfuric acid before 0.027 kg (7.5 kg / t) of sodium dithionite (K-brite) was added. Bleaching was done by slowly stirring the slurry one hour after the addition of K-brite.

30 The sludge from the bleaching operation was subjected to stage F / B II, which was the same as stage F / BI, except that the filter cakes were dried in an oven at 105 ° C for a total of about 24 hours to obtain 3.6 kg of product with a TAPPI brightness. was 91.3 and the particle size was 89.5% -2.

35 Table 7 below shows, for example, the TAPPI brightness of the product recovered after each step of the operation described in Example 80899, 5 -2 μm and% Fe 2 O 3.

Table 7 5

Separate- TAPPI-% -2 pm% Fe 2 O 3 operation_lightness_

Grinding 75.3 33 0.71 F / R I 78.8 38 0.93

10 FMM I N / A 62.5 N / A

F / R II 83.9 47.5 0.55

FMM II 85.4 82 N / A

F / R III 86.1 78 0.45 MS I 89.7 82 0.35

15 MS II 91.9 N / A N / A

F / B I N / A N / A N / A

FMM III 91.9 93.5 N / A

Bleaching 92.5 N / A N / A

F / B II N / A N / A N / A

20 Drying 91.3 89.5

Example 3 A 0.23 kg sample of zeolite ore containing 20% clinoptilolite, 22% cabazite, 19% thompsonite + 25 offretite, 11% erionite, 15% quartz, 10% feldspar and 3% clay minerals was finely ground three times in a small Micropul in a refiner with a nominal size of 100% less than 200M (75% less than 325M and 20% -2 pm). The TAPPI brightness of the ore thus finely ground was 59.

30 The finely ground ore was subjected to FMM I.

45 minutes in a laboratory disc mill with a charge of 0.23 kg of ore, 0.68 kg of medium Diamonite Alumasand B (0.8 mm ceramic balls, medium to ore ratio 3: 1) and 0.45 kg of water (slurry consistency 33% solids). The stirring speed was 1300 rpm. The resulting slurry had a particle size of 46% -2 μιη and a TAPPI brightness of 72. The ground slurry was subjected to a F / RI cycle of 3,000 rpm for one minute (approximately 100,000 g-second). des-laboratory centrifuge. The coarse fraction was recovered as 5 products with a TAPP brightness of 73 and a particle size of 40% -2. The fine (mud) verse was rejected.

The coarse product obtained from section F / R I was diluted to a solids content of 33% and was allowed to go through section FMM II, which was the same as section FMM I, except that the preparation time was longer, i.e. 2.5 hours. The product slurry from FMM II had a particle size of 86% -2 μm and a TAPPI brightness of 73.

The doubly ground slurry was allowed to go through period F / R II, which was the same as period F / R I. The particle size of the product slurry was 77% -2 μm and the TAPPI brightness was 81.

The product slurry from section F / R II was bleached by treating (slowly stirring for 10 minutes) 5 kg of sodium dithionite (K-brite) per ton of solids. The TAPPI brightness of the bleached product was 84.

20 Table 8 is a summary showing the TAPPI brightness,% -2 μm and% Fe 2 O 3 of each of the separate operations described above.

Table 8 25

Separate- TAPPI-% -2% coarse-% operation_luminance pm_for Fe, 0,

Fine grinding 59 20 25 3.2 FMM I 72 46 5 - 30 F / R I 73 40 7 2.5 FMM II 73 86 0 - F / R II 81 77 0 1.4

Bleaching 84 - - - 35 Thus, the treatment improved the TAPPI brightness by about 25 units, reduced the iron content to well below 50% of the initial concentration, and gave a product that was fine enough to be used as a pigment, filler, or extender.

Example 4 A 0.23 kg batch of zeolite ore, mainly consisting of analyte, was finely ground three times as in Example 3. The finely ground material had a TAPPI brightness of 27, a content of 30% coarse material and a particle size of 10-30% -2.

The finely ground product was subjected to FMM I as described in Example 3. The stirring time was 1.5 hours. The product from section FMM I had a particle size of 50% -2 μm and a TAPPI brightness of 52. This product was subjected to the F / R I procedure described in Example 15 in Example 3. The product from section F / RI had a TAPPI brightness of 58 and a particle size of 43% - 2 pm.

The product from section F / R I was allowed to go through section FMM II as described above. The length of stay was five hours. The product obtained from the FMM II section had a TAPPI brightness of 72 and a particle size of 95% -2 μm. The product from section FMM II was allowed to go through section F / R II, which was the same as section F / R I. The TAPPI + brightness of the product from section F / R II was 77 and the particle size was 92% -2.

The TAPPI brightness of the product from Section F / R II was increased to 80 by bleaching as in Example 3 5 kg of sodium dithionite (K-brite) per ton of solids. Alternatively, removal of the highly magnetic material from the F / R II product with a magnetic laboratory stir bar increased the brightness of the product to 30 81 (without bleaching).

Table 9 shows the TAPPI brightness,% coarse material,% -2 μm and% Fe 2 O 3 for each of the separate operations described above.

35 34 80899

Table 9

Separate- TAPPI-% -2% coarse-% operation on luminance_of_Substance Fe, Q, 5 Fine grinding 27 30 30 2.43 FMM I 52 50 5 - F / RI 58 43 6 2.0 FMM II 72 95 0 - F / R II 77 92 to 0.7 10 MS I 81 - - - or bleaching 80 - -

Thus, the treatment improved the TAPPI brightness by more than 50 units and reduced the iron content threefold, and a particle size was achieved that allowed use as a pigment, filler or extender.

Paper applications

Paper coating dyes were prepared by adding a new zeolite product to water with or without clays and other pigments and mixed into a homogeneous slurry. If necessary, a dispersant such as tetrasodium pyrophosphate, sodium polyacrylate or a mixture of sodium carbonate and sodium polyacrylate was added. The latex (e.g., Dow 620) or starch dispersion was then slowly mixed in and the coating dye was applied to the paper sheet with either a laboratory blade coater or stencil rods. The coated sheets were conditioned at 21 ° C and 50% RH (relative humidity), machine calendered, and tested for the desired properties.

30 Ion exchange can be used to add various ions to a new zeolite product. If zinc ions are to be exchanged in the product, the new zeolite product can be treated in the form of a slurry with, for example, a single molar solution of zinc chloride, zinc acetate or other soluble zinc salt, followed by filtration and washing off excess zinc ions. In the same way, a zeolite containing nickel, cobalt or other metal ions can be prepared by ion exchange. In some cases, an appropriate metal oxide, e.g., ZnO, can be mixed with the new zeolite product to provide an improved ceramic reactant for carbonless copy paper.

Example 5 This example describes the preparation of carbonless copy paper using a new zeolite product. Following the general procedure outlined above, a coating dye having a solids content of 48% and containing 15 parts of Dow 620 latex per 100 parts of zinc ion-exchanged zeolite product was prepared. A second set was prepared containing 100 parts of a zeolite product mixture and 2% ZnO. Mixture 15 was diluted to a solids content of 25% and applied to rice with 15.4 kg / 307 m2 (34 lb / 3300 ft2) of uncoated hard paper on the felt side of the paper. The sheets were coated (unilaterally only) at 2.3, 3.2 and 4.1 kg / rice. The coated sheets were then dried and machine calendered.

The sheets were compared to a standard sheet of Mead Carbonless CF sheet and all sheets were printed on a sheet of Mead black CB sheet. A pressure of 70 kp / cm2 was used to make copies from the CB sheet. The print intensity (blackness) was determined by measuring the reflectivity of the print area. A decrease in value means a blackening or darkening of the color and it is desirable to achieve the lowest possible value.

30 35 36 80899

Table 10 Coating weight Heij penetration kg / rice)

Control (Standard 5 Mead CF sheet) 2.3 - 3.2 43.6

Zeolite product, ion-exchanged 2.3 with zinc 3.2 40.8 4.1 40.6 10 Zeolite product, containing 2.3 39.8% 2% ZnO 3.2 37.8 4.1 38.0 These results clearly show that new 15 zinc ion-exchanged zeolite products achieve a higher printing intensity, i.e. blackness.

Example 6 This example describes the manufacture and use of paper coated with a novel zeolite product. Text-20 targets were intaglio and carbonless icing paper.

A second set of paper coatings was prepared containing varying amounts of zeolite product (ion-exchanged with zinc). Other pigment components were No. 2 standard choline coating clay and high brightness, wear-resistant calcined standard clay. The coatings were applied to rice on 15.4 kg / 307 m2 (34 lb / 3300 ft2) of uncoated hard paper on the felt side of the paper in an amount of 2.3 kg / 307 m2 (5 lb / 3300 ft2) of rice. The sheets were then machine calendered and tested for intaglio printability and suitability as a non-carbonless copy paper co-reactant. The sheets were coated at a solids content of 46% using a motor-driven laboratory swab knife coater.

35 37 80899

Table 11

Parts by weight

Coating composition A_B_C_D

Part of zeolite product 15 30 60 100 5 Part No 2 Kaolin coating clay 45 30 40 0

Knows calcined kaolin clay 40 40 0 0

Knows Dow 620 latex (binder) 15 15 15 15 10 Sheet properties Coating weight (CIS, kg / 307 m2) 2.2 2.2 2.3 2.2

The TAPPI brightness of the sheet is 84.9 85.5 85.2 86.3

Opacity 86.7 86.7 86.0 86.1 * Helium test, mm 46 56 91 110+ 15 Carbon-free copy paper, 49.7 45.3 40.8 37.8 reflectivity ** ♦ Superiority increases as numerical value increases ♦♦ Superiority increases as the numerical value decreases, resulting in a more intense, blacker, or darker print 20

Helio test values indicate the length of a test strip printed in millimeters (print weight 76 kg) that is missing twenty dots. A higher value means qualitatively better gravure printing (a value of 110+ means 25 that no dots are missing from the printed ribbon).

The results in Table 11 clearly show the excellent quality achieved when printing in gravure or carbonless copy paper11a on papers made to contain more novel zeolite product. Example 7 Uncoated paper containing about 45% wood pulp and weighing 10.9 kg / 307 m2 (24 lb / 3300 ft2) of rice was coated at about 2.3 kg / one side of the rice (one-sided coating). ) of the 35 coating color formulations described in Table 12.

38,80899 Coatings were applied at a solids content of 48% to 10.9 kg / 307 m2 (24 lb / 3300 ft2) of base paper on the edge of the paper with a motor-powered drag knife coater. The coated sheets were conditioned and then calendered at a temperature of 66 ° C and a pressure of 56 kp / cm 2 in four runs (each surface twice). The values for the base paper and the finished sheet are shown in Table 12.

Table 12 10 Coating- Bottom- Print-section composition of paper

_kalsinoim. ) _E_F_G_H

Zeolite-15 Product of Example 1 15 30 60 100 No. 2 Coating Clay (Freeport Columbia 45 30 40 0

Coating Clay)

Calcined clay, high 40 40 00 20 brightness, good abrasion resistance, Freeport Nuopague)

Latex binder 15 15 15 15 (Dow 620) 25 Sheet properties Coating weight (kg / 370 m2) - 2.3 2.3 2.3 2.3

Gloss 7.6 46.4 44.2 48.1 40.3

Sheet TAPPI Brightness 64.7 69.9 70.7 68.9 71.2 30 Opacity 78.9 82.4 82.9 81.7 83.7 These results demonstrate the ability of the new zeolite product to improve the brightness and opacity of the paper sheet.

The sheets were tested as receiving sheets of carbonless copy paper 35 using a standard CB size. Ars 39 8 0 899 immediately gave an intense trace of the same intensity as that obtained on the CF control sheet. As the amount of new zeolite product was increased, there was little difference in color tone, but the intensity of the print 5 (darkness) intensified as the zeolite content increased.

Example 8

Part A. Pulps containing 50% bleached softwood sulfate pulp and 50% bleached hardwood sulfate pulp were prepared by grinding to about 400 CSF (TAPPI 10 T227n-58) in a Valley grinder. The test excipients were added in the amounts shown in Table 13 below as aqueous slurries with a solids content of 15%, and stirring was continued. 0.5% resin glue (based on the total amount of dry fiber and solid fillers) was then added as a 5% aqueous solution. Stirring was then added, continuing 1.25% aluminum sulfate hydrate (based on the total amount of dry fiber and dry pigment binders) as a 10% aqueous solution. Cationic retention aid (Percol 292) was then added at a rate of 0.25 kg / t dry fiber. The resulting stock was diluted with water to a concentration of 0.5% (based on the dry weight of the fiber and filler) and the pH was adjusted to 4.5 with sulfuric acid or sodium hydroxide. 200 g of stock was removed and dried in an oven for ash determination. 25 Sheets of paper were made from the stock in a sheet mold and each sheet was pressed twice, dried, weighed and tested. The types and amounts of filler used are shown in Table 13 below, which also shows the ash content in percent, basis weight, GE brightness, 30 TAPPI opacity, Mullen strength, and tear strength.

The values in Table 13 show that the zeolite products of the present invention, and in particular the final, dried zeolite product of Example 2, compete well with both commercial, uncalcined, delaminated Kao-35 linseed clay and commercial high brightness alloyed kaolin clay. In particular, the final, dried zeolite product of Example 2 improves the brightness and opacity of the sheet more than a commercial, very high brightness delaminated kaolin clay product and is thus optically more effective than commercial delaminated kaolin clay. The product from Section II of Example 2 of the present invention, the product from Section FMM I and the product from Section FR I each give a slightly lower sheet brightness than the commercial delaminated product, but the products of sections FMM I and FR I achieve greater opacity than the commercial product. the delaminated kaolin tint and the zeolite product of section FR II achieve approximately the same opacity as the commercial delaminated kaolin clay. In addition, sheets filled with the product of Section FR II and commercial delaminated clay have a slightly higher Mullen strength than sheets filled with other fillers.

Part B. Pulps were prepared as described in Part A, but with the difference that 30% of each of the fillers listed in Table 14 below was added as aqueous slurries with a solids content of 15%. In addition, varying amounts of cationic retention aid (Percol 292) were used as shown in Table 14. In each of the 25 sheets prepared, the ash content of the stock as a percentage, the ash content of the sheets as a percentage and the retention ash content as a percentage of the first run were determined in Table 14. The values in Table 14 show that the ash retention in the first run is very good in FR II, FMM I of the present invention. and FR I products as well as a commercial, uncalcined delaminated kaolin clay product and a calcined clay product. The ash retention of the final, dried product of Example 2 in the first run is less than 40% using 35 0.25 kg of Percol 292 per ton of dry fiber.

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Table 14% first- Fill-% sulp-% for canning run

Driving agent- Percol 292 putty- ash retentions type kg / ton; kaa_ kaa_ ash_ 5 5 FR II 0 28.2 4, 4 15.6 0.06 28.2 12.2 43 ^ 3 0.13 28.2 14.0 49.6 0.19 28.2 16.2 57, 4 0.25 28.2 17.8 63.1 0.38 28.2 19.1 67.7 10 6 FMM I 0 28.4 6.0 21.1 0.06 28.4 15.5 54 6 0.13 28.4 16.1 56.7 0.19 28.4 17.9 63.0 0.25 28.4 19.0 66.9 0.38 28.4 19.2 67.6 7 FR I 0 27.9 2.3 8.2 15 0.06 27.9 9.9 35.5 0.13 27.9 13.3 47.7 0.19 27.9 13.8 49.5 0 .25 27.9 13.8 49.5 0.38 27.9 15.9 57.0 8 final 0 27.5 1.7 6.2 20 dry product o .06 27.5 7.2 26.2 0 , 13 27.5 8.3 30.2 0.19 27, 5 9.6 34, 9 0.25 27.5 10.5 38.2 0.38 27, 5 12, 0 43.6 D Delam. 0 25.6 5.4 21.1 clay 0.06 25, 6 13, 8 53.9 25 0.13 25.6 15.0 58.6 0.19 25.6 16.1 62.9 0, 25 25.6 16, 3 63, 7 0.38 25, 6 17.2 67.2 E Calcium ** 0 28.9 12.7 43.9 clay 0.06 28.9 17 * 7 61.2 30 0.13 28.9 18.0 62.3 0.19 28.9 19.2 66.4 0.25 28.9 20.1 69.6 _____ 0.38 28.9 20.9 72.3

Delaminated kaolin clay with very high brightness * ^

Fine, High Brightness Calcined Kaoli - ^ 8 Nisavi ** 80 899 Use in Paints The novel zeolite products of this invention can also be used to make coating materials such as paints. The abrasion resistance, opacity and brightness of paints 5 containing new zeolite products are excellent and comparable to the values achievable with commercial calcined kaolin-Vella. The coating materials containing the novel zeolite products of this invention also contain a binder, which may be of any known type commonly used in connection with certain types of coating materials. In addition, any known thinner used for current coating materials can be used. For example, organic diluents or water-based diluents can be used by known techniques commonly used and known in the coating industry. It is, of course, desirable for the thinner to be volatile. In addition, the known coating materials described in the novel coating materials described and claimed herein, in particular water-based paints, can be used. Other ingredients such as dispersants, defoamers, thickeners, preservatives, and the like may be used in the novel coatings described and claimed herein.

Example 9 25 Part A. Three separate pigment systems, i.e. paints, were prepared by first mixing the following ingredients: 30 35 45 80899

Table 15

Ingredient Weight of CMC thickener (2% aqueous solution) 75 5 Water 50

Ethylene glycol 5

Taraol 731 dispersing wave 2

Defoamer (Colloid 681-F) 2 Preservative (phenylmercuric acetate-10, PMA 30) 0.3

Pigment 100

Uncalcined, delaminated clay was used as the pigment in the first pigment paint. The zeolite product prepared in Example 1 was used in the second 15 paints. In the third paint, calcined clay was used as the pigment.

The resulting mixture was ground for 10 minutes, then the stirring speed was reduced, 25 parts by weight of water and 50 parts by weight of vinyl acrylic plastic water emulsion (Wave 375, sold by Air Co.), 55% solids, were added, slow mixing was continued and three different pigment system paints were obtained. The painting was then performed and the properties shown in Table 17 below were measured.

Part B. In addition, three 55 PVC paints were prepared (pigment volume concentration was calculated by dividing the pigment volume by the sum of the pigment volume and the binder volume) by first mixing the following ingredients: 30 35 46 8 0 8 9 9

Table 16

Ingredient parts by weight of CMC thickener (2% aqueous solution) 50

Water 55 5 Ethylene glycol 6

Carbitol acetate 3.8

Tamol 731 dispersant 2.5

Texanol (Eastman Kodak) 1.5 melting agents 10 Defoamer (Colloids AF-100) 1 PMA 30 preservatives 0.3

Windgale White Calcium Carbonate 75 T102 75

Test fragment (ie delaminated clay, zeolite product or calcined clay)

In the first case, uncalcined, delaminated clay was used as the test pigment. The second paint used the zeolite product prepared in Example 1 as a test pigment, and the third paint used calcined clay as a test pigment.

The resulting mixture was ground for about 10 minutes, then 60 parts by weight of water, 37.5 parts by weight of CMC thickener (2% aqueous solution) and 109 parts by weight of vinyl latex emulsion, 55% solids, were added, and the ingredients were mixed with the resulting mixture. to the mixture at low speed. Painting was then performed with each paint and different properties were measured. The results obtained are shown in Table 17 below. These values indicate that the paint prepared with the novel zeolite product described in Example 1 had excellent abrasion resistance.

35 47 8 0 8 9 9

Table 17

Land Values Calcined New Zeo- Delamin.

A. SPS clay_ composite clay_ 5

Contrast ratio% 96.5 93.3 91.1

White reflectance 88.5 86.5 81.0 85 ° gloss 13.4 18.4 30.4

Viscosity: Krebs- 102 107 107 10 units

B. 55 PVC

Wingdale White CaCO3 150 150 150 R-901 TiO2 150 150 150 15 Test pigment 150 124.5 150

Contrast ratio% 97.9 97.8 97.9

White reflectivity 90.3 90.4 88.5 85 ° gloss 5.1 5.9 4.0 20 Color reflectance 47.0 48.9 46.4 (2% carbon black)

Viscosity: Krebs- 90 92 103 units 25 Abrasion values (5% soap solution)

Rubbing cycle of paint 1500 1870 1030 onset

Wash removable ink 520 430 400 30

Pencil No. 2 200 175 170 Crayon 600 400 360

Lipstick 230 190 50

Mercury chromium 1200 1400 600 35

Claims (20)

A process for treating zeolite ores for removing color contaminants and for improving their whiteness properties, characterized in that (a) blends a finely ground zeolite ore, a dispersant (e.g. from the tetrasodium pyrophosphate, sodium equilibrium group). and polyacrylates) and water for dispersing said zeolite and for forming a zeolite water slurry, (b) removing from said zeolite water slurry coarse material having a particle size of 44 microns or more, (c) removing fines of at least 50% of particles. a size below 2 µm and containing 15 color impurities from the zeolite slurry from which the coarse material has been removed, (d) subjecting a mixture of the zeolite slurry, after removal of the fine material in step (c), and a fine grinding medium for fine grinding of fine grit to particles, of which at least 20% have a size below 2 µm, and reject nos (e) removes fine material in which at least 40% of particles have a size below 2 µm and which contains color impurities from the finely ground zeolite slurry; (f) if desired, exposes it above in the step. (e) obtaining the zeolite slurry milled with fine grinding medium for a further grinding with a fine grinding medium by subjecting said slurry and a fine grinding medium to vigorous stirring to effect a grinding of the zeolite to particles, of which at least 60% have a size below 2 µm. and removes fine material in which at least 80% of particles have a size below 2 µm and which contains color contaminants from the zeolite slurry painted with the fine grinding medium, subjecting the finely ground zeolite slurry after said fine material removal step (e) (f) for magnetic separation to remove magnetic paint-f (h) exposes the zeolite slurry obtained in step 1 (g) to a final grinding with a fine grinding medium by subjecting said slurry and a fine grinding medium to vigorous stirring to grinding said zeolite with the fine grinding medium to particles of which at least 90% have a size below 2 µm, (i) bleach the resulting zeolite slurry, and if desired (j) isolate the zeolite in dry form from the resulting slurry. 15 Process according to Claim 1, characterized in that the slurry after removal of the fine material in step (e) is filtered and slurried with water and mixed with a fine grinding medium and subjected to vigorous stirring to obtain a second fine grinding of said zeolite. . 3. A process as claimed in claim 1 or 2, characterized in that the zeolite slurry after the magnetic separation step (g) is subjected to a second magnetic separation to remove further magnetic paint impurities, followed by optionally following a fine material removal step for removal. of fine material, in which at least 80% of particles have a size below 2 microns containing color contaminants, and the zeolite slurry after this third step of removal of fine material is optionally mixed with a dispersant (e.g., a mixture of sodium polyacrylate and sodium carbonate ) for dispersing said zeolite and subjected to a third grinding with a fine grinding medium, wherein said zeolite slurry is mixed with a fine grinding medium and subjected to vigorous stirring for grinding said zeolite to particles of which at least 90% have a size play during 2 p.m. 4. A process according to claim 1 or 2, characterized in that the slurry is filtered after the magnetic separation and the resulting filter cakes are slurried in water to a zeolite slurry and the resulting slurry mixed with a fine grinding medium and the mixture. is subjected to vigorous stirring for fine grinding of said zeolite, after which said grinding medium 10 is removed from said finely ground zeolite slurry and the resulting zeolite slurry is then subjected to a bleaching step. 5. A method according to claim 1, characterized in that the magnetically separated separation step 15 precedes the step of removing fine material after grinding (f) with the second fine grinding medium. 6. A process according to claim 1, characterized in that, after the magnetic separation step (g), the zeolite slurry is subjected to a second magnetic separation to remove further magnetic paint impurities. Process according to any of the preceding claims, characterized in that the bleaching step is carried out using an oxidative or reductive bleaching agent (eg ozone, sodium hypochlorite, potassium monopersulfate, sodium dithionite, thiourea dioxide or chlorine). or by using an oxidative bleaching agent and then a reductive bleaching agent. Process according to any of the preceding claims, characterized in that, before mixing with dispersant and water in step (a), the finely ground zeolite is washed with water and acid (eg hydrochloric acid, sulfuric acid or phosphoric acid ), the concentration of which is preferably 2-20% by weight acid in water, and the zeolite is separated from the water and acid by filtration (optionally 56 80899 after the slurry of zeolite, water and acid settles and the resulting supernatant liquid decanted), washed with water and neutralized. 9. A method according to any of the preceding claims, characterized in that said zeolite ore consists mainly of one or more of the following: clinoptilolite, chabasite, mordenite, erionite, phyllipsite and analsite. Process according to any of the preceding patent claims, characterized in that the isolation step consists of the steps of filtering the zeolite slurry after the bleaching step and slurrying the resulting filter cakes with water and a dispersant (eg a mixture of sodium polyacrylate). and sodium carbonate into a zeolite slurry and then spray drying the resulting zeolite slurry. 11. A process according to claim 1, characterized in that the insulation step consists of the steps of filtering the zeolite slurry after the bleaching step and drying the resulting filter cakes in a convection oven at a temperature not exceeding 105 ° C. Method according to any of the preceding patent claims, characterized in that products having a TAPPI whiteness of 80 or greater and a particle size of 20 - 89% -2 µm are recovered from some intermediate stage beginning with the step. (c) for removing fine material. Use of zeolite powder prepared by the method of any one of claims 1-12 as a filler together with a binder in a coating composition. Use according to claim 13, characterized in that the coating composition contains an evaporable diluent, preferably a volatile organic liquid, and optionally also water as a diluent. = 7 80899 Use according to claim 13, characterized in that the coating material is a paper coating. Use according to claim 15, characterized in that the coating also contains one or more of the following: finely divided kaolin clay, finely divided titanium dioxide, zinc oxide, nickel oxide and cobalt oxide. Use according to claim 15 or 16, characterized in that the zeolite material has been ion exchanged with zinc ions, nickel ions or cobalt ions. Use of zeolite powder prepared by the method of any of claims 1-12 as a filler in paper. Use according to claim 18, characterized in that a pulp is formed, in the pulp, the said zeolite powder is added and makes sheets of the pulp for obtaining paper. Use according to claim 18, characterized in that the paper further contains finely divided kaolin clay and / or finely divided titanium dioxide as filler.