Filter aid composite material

Abstract

A composition comprising a crosslinking binder and mineral particles selected from the group consisting of i) expanded and pulverized perlite particles having a D of about 5 microns to about 40 microns, ii) diatomaceous earth particles having a D of about 10 microns to about 50 microns, and combinations thereof, wherein the mineral particles are bonded to each other by the crosslinking binder to form a composite particulate material, and the composite particulate material has a D of about 20 microns to 100 microns. 50 A composition comprising a crosslinking binder and mineral particles selected from the group consisting of i) expanded and pulverized perlite particles having a D of about 5 microns to about 40 microns, ii) diatomaceous earth particles having a D of about 10 microns to about 50 microns, and combinations thereof, wherein the mineral particles are bonded to each other by the crosslinking binder to form a composite particulate material, and the composite particulate material has a D of about 20 microns to 100 microns. 50 A composition comprising a crosslinking binder and mineral particles selected from the group consisting of i) expanded and pulverized perlite particles having a D of about 5 microns to about 40 microns, ii) diatomaceous earth particles having a D of about 10 microns to about 50 microns, and combinations thereof, wherein the mineral particles are bonded to each other by the crosslinking binder to form a composite particulate material, and the composite particulate material has a D of about 20 microns to 100 microns. 50 A composition comprising a crosslinking binder and mineral particles selected from the group consisting of i) expanded and pulverized perlite particles having a D of about 5 microns to about 40 microns, ii) diatomaceous earth particles having a D of about 10 microns to about 50 microns, and combinations thereof, wherein the mineral particles are bonded to each other by the crosslinking binder to form a composite particulate material, and the composite particulate material has a D of about 20 microns to 100 microns.

Description

Technical Field

[0001] The present disclosure relates to a composition comprising a composite particulate material and a crosslinking agent, and a method for producing the composition. The present disclosure also relates to a filter aid material comprising the composition, and a method for filtering a liquid using the composition.

Background Art

[0002] Filtering devices typically include a filter aid comprising solid particles that improve filtration efficiency. The filter aid is added to the suspension to be filtered or placed on the filter as a layer through which the liquid must pass.

[0003] Filter aids are typically composed of materials derived from volcanic glass, such as perlite or pumice. Perlite filter aids have the advantages of being lightweight, inert, imparting no taste or odor to the liquid being filtered, and being substantially insoluble in mineral and organic acids at all temperatures.

[0004] Diatomaceous earth (DE) is another useful type of filter aid material, which is a natural sand made from the fossilized remains of diatoms and is a commonly occurring material. Diatomaceous earth-based filter aids are typically used for the primary clarification of beer and wine.

[0005] Customers in the beer and wine industries are increasingly considering a shift away from standard DE-based filter aids due to health and regulatory concerns regarding crystalline silica that is commonly present. Perlite-based filter aids may also encounter problems in achieving the target clarity. Crossflow filtration devices for wine and beer generally operate at high cost. Therefore, it is considered desirable to provide a filter aid that does not contain crystalline silica, is low in cost, and achieves the clarity of standard DE-containing filter aids.

Summary of the Invention

[0006] In the following description, certain specific aspects and embodiments will become apparent. In the broadest sense, it is contemplated that these aspects and embodiments may be practiced without one or more of the features of these aspects and embodiments. It is also contemplated that these aspects and embodiments are merely illustrative.

[0007] According to a first aspect, there is provided a composition comprising a composite particulate material, the composite particulate material comprising a crosslinking agent and mineral particles selected from the group consisting of i) expanded ground perlite particles having a D 50 of from about 5 microns to about 40 microns, ii) diatomaceous earth particles having a D 50 of from about 5 microns to about 40 microns, and combinations thereof, the mineral particles being bound to each other by the crosslinking agent to form the composite particulate material, the composite particulate material having a D 50 of from about 20 microns to 100 microns, the binder being present in an amount of from 0.01 wt% to 20 wt% based on the total weight of the composition, the crosslinking agent being a reaction product of a polymer and a crosslinking agent, the polymer being selected from water-soluble synthetic polymers and natural water-soluble polymers.

[0008] According to a second aspect, there is provided a filter aid material comprising the composition according to the first aspect.

[0009] According to a third aspect, there is provided a method of filtering a liquid, comprising contacting the liquid with the filter aid material according to the second aspect.

[0010] According to a fourth aspect, there is provided a method of manufacturing the composition according to the first aspect.

[0011] One skilled in the art will understand that, unless mutually exclusive, the features described in connection with any one of the above aspects may be applied mutatis mutandis to any other aspect. Further, unless mutually exclusive, any feature described herein may be applied to any aspect and / or combined with any other feature described herein.

[0012] Here, with reference to the drawings, exemplary embodiments will be described by way of example only.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0014] Here, reference will be made in detail to the exemplary embodiments shown in the accompanying drawings.

[0015] Surprisingly, it has been found that a composition containing a composite granular material comprising a crosslinking agent and mineral particles selected from expanded and pulverized perlite particles, diatomaceous earth particles, and combinations thereof achieves excellent filtration performance results.

[0016] Expanded and pulverized perlite particles Perlite usually contains the following components: silicon dioxide, aluminum oxide, sodium oxide, potassium oxide, iron oxide, magnesium oxide, calcium oxide, water, and small amounts of other metal elements.

[0017] The perlite particles of the present invention are in the form of expanded perlite. Generally, expanded perlite contains one or more cells, or parts of cells, which are void spaces partially or completely surrounded by glass walls and are typically formed by the expansion of gas when the glass is in a softened state. The process of expanding perlite may include heating the perlite in an expansion furnace in air to a temperature of at least about 700°C, usually 800°C to 1100°C. An exemplary method for manufacturing expanded perlite is described in US Patent Application Publication No. 2006 / 0075930, the entire content of which is incorporated herein by reference. The bulk volume of expanded perlite typically reaches up to 20 times that of the unexpanded material.

[0018] According to the present invention, the perlite is pulverized after being expanded in an expansion furnace.

[0019] Unless otherwise specified, the particle size characteristics of the perlite particles referred to in this specification are measured by the method employed in the technical field of laser light scattering using a CILAS 1064L particle size analyzer supplied by CILAS (or by other methods that basically give the same results). In the laser light scattering method, the size of particles in powders, suspensions, and emulsions can be measured using the diffraction of a laser beam based on the application of the Fraunhofer theory and Mie theory. Such a machine provides a measured value and a plot of the cumulative percentage by volume of particles having a size (referred to in the art as "equivalent spherical diameter" (e.s.d)) less than a given e.s.d value. The average particle size D 50 is the value of the particle e.s.d determined by this method at which 50% by volume of the particles have an equivalent spherical diameter less than the D 50 value.

[0020] According to the present invention, the expanded and pulverized perlite particles have a D 50 of about 10 microns to about 50 microns, for example about 15 microns to about 45 microns, or about 20 microns to about 40 microns, or about 25 microns to about 35 microns. In certain embodiments, the expanded and pulverized perlite particles have a D 50It has.

[0021] In certain embodiments, the bulk density of the expanded crushed perlite particles is from about 0.05 g / cm 3 to about 0.20 g / cm 3 , for example from about 0.06 g / cm 3 to about 0.19 g / cm 3 , for example from about 0.07 g / cm 3 to about 0.18 g / cm 3 , for example from about 0.08 g / cm 3 to about 0.17 g / cm 3 , for example from about 0.09 g / cm 3 to about 0.16 g / cm 3 , for example from about 0.10 g / cm 3 to about 0.15 g / cm 3 , for example from about 0.11 g / cm 3 to about 0.14 g / cm 3 , for example from about 0.12 g / cm 3 to about 0.13 g / cm 3 is.

[0022] In one embodiment, the perlite product is obtained from a commercially available perlite product. In another embodiment, at least one perlite product is the Harborlite™ material available from Imerys Performance Materials.

[0023] Diatomaceous earth (DE) particles Diatomaceous earth (DE) is obtained from the remains of microscopic fossilized sea or freshwater algae. DE is commonly used as a filtration aid. DE is known to have a complex and porous structure that is effective in capturing particles in a filtration process.

[0024] The starting DE material may be crude DE and may have been subjected to one or more processing steps such as physical or chemical modification. Physical modification processes include, but are not limited to, grinding, drying, and air classification. Chemical modification processes include, but are not limited to, silanization. Such modification processes are used to make the surface of DE more hydrophobic or hydrophilic using methods such as those described in U.S. Patent Nos. 3,915,735 and 4,260,498, the contents of which are incorporated herein by reference.

[0025] DE typically consists of about 80% - 90% silica, 2% - 4% alumina (mainly derived from clay minerals), and 0.5% - 2% iron oxide. The types of DE available are well known to those skilled in the art.

[0026] Unless otherwise specified, the particle size characteristics of the DE particles referred to in this specification are those measured by the method described above for expanded ground perlite particles.

[0027] According to the present invention, the DE particles have a D of about 10 microns to about 50 microns, such as about 15 microns to about 45 microns, or about 20 microns to about 40 microns, or about 25 microns to about 35 microns. 50 In certain embodiments, the DE particles have a D of about 35 microns. 50

[0028] In certain embodiments, the bulk density of the DE particles is about 0.05 g / cm 3 to about 0.46 g / cm 3 such as about 0.06 g / cm 3 to about 0.44 g / cm 3 such as about 0.07 g / cm 3 to about 0.42 g / cm 3 such as about 0.08 g / cm 3 to about 0.4 g / cm 3 such as about 0.09 g / cm 3 to about 0.38 g / cm 3 such as about 0.10 g / cm3 ~ about 0.36 g / cm 3 、 for example, about 0.11 g / cm 3 ~ about 0.34 g / cm 3 、 for example, about 0.12 g / cm 3 ~ about 0.32 g / cm 3 is.

[0029] In one embodiment, the DE particles are a commercially available diatomaceous earth product. In another embodiment, at least one natural diatomaceous earth particle is the DiaFil™ material available from Imerys Performance Materials.

[0030] Binder According to the present invention, the expanded crushed perlite particles and / or DE are bonded to each other using a crosslinking binder to form a composite particulate material. The crosslinking binder is a reaction product of a polymer and a crosslinking agent, and the polymer is selected from a water-soluble synthetic polymer and a natural water-soluble polymer.

[0031] The binder of the present invention is a permanent binder. This means, for example, when filtering beer, the binder remains within the composite particulate material product without dissolving in the liquid being filtered, and provides structural strength to the composite particulate material.

[0032] In certain embodiments, the binder consists of a single type of polymer, or in certain embodiments, the binder comprises one or more polymers.

[0033] In certain embodiments, the polymer is selected from one or more of a water-soluble synthetic polymer and a natural water-soluble polymer. In certain embodiments, the polymer is a combination of these types of polymers.

[0034] In certain embodiments, the binder comprises a water-soluble synthetic polymer selected from, for example, polyvinyl alcohol (PVA), polyethylene glycol, urea formaldehyde, polyacrylamide, microcrystalline cellulose, polyacrylate, acrylic acid / maleic acid copolymer, and polyvinyl pyrrolidone.

[0035] In certain embodiments, the binder consists of natural water-soluble polymers such as xanthan gum, sodium alginate, potassium alginate, lignosulfonate, locust bean gum, pectin, dextran, carrageenan, agar, xanthan gum, guar gum, gum arabic (acacia), cellulose ethers such as methylcellulose and ethylcellulose, starch, or starch-based derivatives.

[0036] According to the present invention, the binder is a cross-linked binder which is a reaction product of a polymer and a cross-linking agent. Cross-linking is the formation of chemical bonds between polymer chains to form a three-dimensional network of linked molecules. The polymer can be selected from the list of polymers above. Cross-linking agents are well known in the art and can be selected according to the type of polymer. The cross-linking agent is not a self-cross-linking polymer.

[0037] In certain embodiments, the cross-linking agent is as follows: (i) Dicarboxylic acids including oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, tartaric acid, tartronic acid, aspartic acid, glutamic acid, fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoric acid, phthalic acid and its derivatives containing at least one boron atom or chlorine atom, tetrahydrophthalic acid and its derivatives containing at least one chlorine atom, isophthalic acid, terephthalic acid, mesaconic acid, and citraconic acid, (ii) Tricarboxylic acids including citric acid, tricarballylic acid, 1,2,4-butanetricarboxylic acid, aconitic acid, hemimellitic acid, trimellitic acid, and trimesic acid, (iii) Tetracarboxylic acids, including 1,2,3,4 - butanetetracarboxylic acid and pyromellitic acid, (iv) Polycarboxylic acids such as EDTA, (v) Unsaturated carboxylic acids including (ethyl)acrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2 - methylmaleic acid, fumaric acid, itaconic acid, 2 - methylitaconic acid, α,β - methyleneglutaric acid, and monoesters of unsaturated dicarboxylic acids, where the vinyl monomer is styrene optionally substituted with an alkyl group, a hydroxyl group, a sulfonyl group, or a halogen atom, (meth)acrylonitrile, C1 - C 10 (meth)acrylamide optionally substituted with an alkyl group, alkyl (meth)acrylate, glycidyl (meth)acrylate, butadiene, and vinyl ester, (vi) Inorganic acids such as boric acid and phosphoric acid, is an acid selected from one or more of the above.

[0038] In certain embodiments, the cross - linking agent is a carboxylic acid selected from dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, polycarboxylic acids, and unsaturated carboxylic acids. In certain embodiments, the carboxylic acid is a polycarboxylic acid such as citric acid or succinic acid. In certain embodiments, the carboxylic acid is an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, and maleic acid.

[0039] In certain embodiments, the binder is a reaction product of polyvinyl alcohol and citric acid. Carboxylic acids are a preferred type of cross - linking agent because of their low toxicity and low cost. Polyvinyl alcohol is also known to be non - toxic and biodegradable. The resulting cross - linked binder is insoluble in water and has a low manufacturing cost.

[0040] In certain embodiments, the binder is present in an amount of from about 0.1 wt.% to about 40 wt.%, or from about 1 wt.% to about 35 wt.%, or from about 5 wt.% to about 30 wt.%, or from about 10 wt.% to about 25 wt.%, or from about 15 wt.% to about 20 wt.%, or from about 1 wt.% to about 5 wt.% of the total wt.% of the granules.

[0041] In certain embodiments, the binder comprises a crosslinking agent in an amount of from about 1 wt% to about 30 wt%, or for example from about 2 wt% to about 25 wt%, or for example from about 3 wt% to about 20 wt%, or for example from about 4 wt% to about 15 wt%, or for example from about 5 wt% to about 10 wt% based on the total weight of the binder.

[0042] Composite granular material According to the present invention, mineral particles selected from the group consisting of expanded crushed perlite particles, diatomaceous earth particles, and combinations thereof have the above particle size and are bonded to each other using a binder to form a composite granular material. The primary powder particles aggregate to form a larger multi-particle entity called a composite granular material.

[0043] In certain embodiments, the composite granular material comprises or consists of expanded crushed perlite particles and a binder. In certain embodiments, the composite granular material comprises or consists of DE particles and a binder. In certain embodiments, the composite granular material comprises or consists of a mixture of expanded crushed perlite particles and DE particles and a binder.

[0044] The expanded crushed perlite particles and / or DE particles are bound / aggregated to each other by a binder, forming what is known as pores or interstitial spaces between the particles. In some embodiments, the pores have a measurable intrusion volume, which can be measured by the methods described in the following measurement method section. In certain embodiments, the cumulative intrusion volume is from about 2.5 mL / g to about 4.5 mL / g, or about 2.6 mL / g, or about 2.7 mL / g, or about 2.8 mL / g, or about 2.9 mL / g, or about 3.0 mL / g, or about 3.1 mL / g, or about 3.2 mL / g, or about 3.3 mL / g, or about 3.4 mL / g, or about 3.5 mL / g, or about 3.6 mL / g, or about 3.7 mL / g, or about 3.8 mL / g, or about 3.9 mL / g, or about 4.0 mL / g, or about 4.1 mL / g, or about 4.2 mL / g, or about 4.3 mL / g, or about 4.4 mL / g, or about 4.5 mL / g. In certain embodiments, the median of the intrusion volume is preferably about 3.5 mL / g.

[0045] The measured pore volume has advantageously been found to be more than 25% larger than that of conventionally used perlite products or DE products. Such a larger pore volume means a larger volume per mass that can pass through the filter. This makes it possible to increase the solids holding capacity with an equivalent dosage of filter aid.

[0046] In certain embodiments, the composite particulate material comprises expanded crushed perlite particles and diatomaceous earth particles, and at least one pore of the porous structure is filled with at least one unbonded diatomaceous earth particle.

[0047] In certain embodiments, the ratio of expanded crushed perlite to DE can be from about 5:1 to about 1:4, or from about 5:1 to about 1:3, or from about 5:1 to about 1:2, or from about 5:1 to about 1:1, or from about 5:1 to about 2:1, or from about 5:1 to about 1:3, or from about 4:1 to about 1:4, or from about 4:1 to about 1:3, or from about 4:1 to about 1:2, or from about 4:1 to about 1:1, or from about 4:1 to about 2:1, or from about 4:1 to about 1:3.

[0048] According to the present invention, the composite granular material has a D value by the laser diffraction method of 50 from about 150 microns to about 2000 microns, for example, from about 200 microns to about 1900 microns, or from about 300 microns to about 1800 microns, or from about 400 microns to about 1700 microns, or from about 500 microns to about 1600 microns, or from about 600 microns to about 1500 microns, or from about 700 microns to about 1400 microns, or from about 800 microns to about 1300 microns, or from about 900 microns to about 1200 microns, or from about 1000 microns to about 1100 microns, or from about 200 microns to about 600 microns, for example from about 350 microns to about 550 microns, or from about 400 microns to about 500 microns, or from about 600 microns to about 1900 microns, for example from about 700 microns to about 1800 microns, or from about 800 microns to about 1600 microns, or from about 900 microns to about 1500 microns, or from about 1000 microns to about 1400 microns, or from about 1100 microns to about 1300 microns. The composite granular material has a D value by laser of 50 from about 200 microns to about 1000 microns, or from about 300 microns to about 900 microns, or from about 400 microns to about 800 microns, or from about 500 microns to about 700 microns may also be sufficient.

[0049] In certain embodiments, the bulk density of the composite granular material is from about 0.1 g / cm 3 to about 0.50 g / cm 3 , for example from about 0.15 g / cm 3 to about 0.45 g / cm 3 , for example from about 0.20 g / cm 3 to about 0.40 g / cm 3 , for example from about 0.20 g / cm 3 to about 0.35 g / cm 3 , for example from about 0.25 g / cm 3 to about 0.30 g / cm 3 .

[0050] The composite granular material of the present invention may have a measurable BET surface area. The BET specific surface area refers to the surface area of the particles of the composite granular material per unit mass and is determined by the amount of nitrogen that adsorbs on the surface of the particles to form a monolayer that completely covers the surface according to the BET method (measured in accordance with the BET method, AFNOR standards X11-621 and 622, or ISO 9277). Details of the BET specific surface area measurement method used in the preparation of this application are described in the examples.

[0051] The BET specific surface area of the composite granular material is about 1.5 m 2 / g or more, for example, about 1.6 m 2 / g or more, or about 1.7 m 2 / g or more, or about 1.8 m 2 / g or more, or about 1.9 m 2 / g or more, or about 2.0 m 2 / g or more, or about 2.5 m 2 / g or more, or about 3.0 m 2 / g or more, or about 5.0 m 2 / g or more, or about 10 m 2 / g or more (for example 10.0 m 2 / g), or about 20 m 2 / g or more (for example 11.0 m 2 / g) may be. The BET specific surface area of the composite granular material is about 50 m 2 / g or less (for example 50.0 m 2 / g), for example, about 40 m 2 / g or less (for example 40.0 m 2 / g), or about 30 m 2 / g or less (for example 30.0 m 2 / g), or about 20 m 2 / g or less (for example 20.0 m 2 / g), or about 15 m 2 / g or less (for example 15.0 m 2 / g), or about 12 m 2 / g or less (for example 12.0 m 2 / g), or about 11 m 2 / g or less (for example 11.0 m 2 / g), or about 10 m 2 / g or less (for example 10.0 m 2 / g), or about 8.0 m2 less than or equal to about 7.0 m / g, or 2 less than or equal to about 6.0 m / g, or 2 it may be less than or equal to about 5.0 m / g. The BET specific surface area of the composite granular material is about 1.5 m 2 / g to about 50 m 2 / g (e.g., 50.0 m 2 / g), for example, about 2 m 2 / g to about 40 m 2 / g (e.g., 40.0 m 2 / g), or about 5 m 2 / g to about 30 m 2 / g (e.g., 30.0 m 2 / g), or about 10 m 2 / g to about 20 m 2 / g (e.g., 20.0 m 2 / g) and may be acceptable.

[0052] In certain embodiments, the composite granular material has an angle of repose of about 5° to about 35° when measured by the angle of repose (funnel method) using an EFT-01 powder flow tester, the composite granular material has an absorption capacity of at least 150% when measured using the Westinghouse method described in the experimental section of this specification and utilizing dioctyl adipate as the absorbent, and has a dust content of less than 10 when measured by a DustmonRD 100 dust analyzer.

[0053] The angle of repose of a material is the steepest descent angle, i.e., the inclination angle, with respect to the horizontal plane at which the material can be deposited without collapsing. The morphology of the material affects the angle of repose. When a bulk granular material is poured onto a horizontal plane, a conical pile is formed. The internal angle between the surface of the pile and the horizontal plane is known as the angle of repose and is related to the density, surface area and shape of the particles, and the coefficient of friction of the material. Materials with a small angle of repose form flatter piles than materials with a large angle of repose. For this reason, smooth and rounded sand grains cannot be deposited at as steep a gradient as coarse sand that interlocks with each other. The method for calculating the angle of repose will be described in more detail in the following experimental section.

[0054] In certain embodiments, the angle of repose (of the dried product) is from about 5° to about 35°, such as from about 10° to about 30°, such as from about 15° to about 25°.

[0055] In certain embodiments, the composite particulate material advantageously has a low dust content (measured using a Dustmon RD 100 dust analyzer (available from Retsch™)), less than 10, such as less than 9, or 8. The method of calculating the value of the dust content will be described in more detail in the experimental section.

[0056] Composition According to the present invention, a composition comprising a composite particulate material is provided. The composite particulate materials are bound to each other using a cross-linking agent.

[0057] In certain embodiments, the composition comprises an additional inorganic mineral component. Examples of additional inorganic mineral components include natural or synthetic silicate or aluminosilicate materials, pumice powder, natural glass, cellulose, activated carbon, feldspar, nepheline syenite, sepiolite, zeolite, and clay. Examples of clay minerals include halloysite, kaolinite, and bentonite. The additional inorganic mineral component can be added in an amount of about 0.01 part to about 10 parts, such as about 0.5 part to about 5 parts, per part of expanded ground perlite and / or DE.

[0058] The composition is prepared by dry mixing one or more mineral particles (dried powders of expanded ground perlite and / or DE, and any other desired additional inorganic materials), and then spray drying the one or more mineral particles together with a binder to form aggregates. The binder is first prepared by dissolving the binder component in water.

[0059] In the case of spray drying, an aqueous binder mixture is supplied to the inlet of a spray dryer and sprayed onto the dry-mixed mineral particles. As an example of a suitable spray drying device, there is a Niro Minor spray drying unit. This machine is equipped with a cylindrical drying chamber with a diameter of 800 mm and a height of 600 mm provided with a conical shape at the bottom, and an air-driven disk type atomizer is attached. The atomizer can be operated at a speed of 30,000 rpm.

[0060] Next, a curing step (crosslinking step) is carried out in a kiln at a temperature of about 80°C to 120°C. The curing step is usually carried out for a time sufficient for the granules to dry and the binder to cure. After the curing step is carried out, the moisture content of the granules is less than about 5 wt% of the granules, for example less than about 3 wt%, or less than about 2 wt%. The curing step is carried out for a time sufficient for the moisture content to reach the desired level described above, and may take 12 hours, or 8 hours, or 4 hours.

[0061] This is a much lower temperature than that for standard production in DE where the kiln temperature may exceed 1400°C. By avoiding the use of such high temperatures and keeping the temperature low, it is possible to prevent the undesirable formation of crystalline silica such as quartz or cristobalite. The presence of cristobalite in the filter aid is generally undesirable because it is known to be potentially harmful to health at high concentrations.

[0062] In certain embodiments, the total content of crystalline silica present in the composition is about 0.2 wt% or less of the total wt.% of the composition. In certain embodiments, the composition contains from about 0 wt% to about 0.2 wt%, for example from about 0.01 wt% to about 0.1 wt% of crystalline silica present in the composition. In certain embodiments, the composition does not contain crystalline silica, meaning that crystalline silica is not detected.

[0063] The method for measuring the cristobalite content can be measured using techniques known to those skilled in the art, including the specific methods described in International Publication No. WO 2010 / 042614.

[0064] Filter aid material According to the present invention, there is provided a filter aid material comprising the composition described herein. The filter aid composition can be formed into a sheet, pad, cartridge, or other product used to perform a filtering function.

[0065] The filter aid of the present invention can be used in various processes and compositions, as well as various filtering methods. In certain embodiments, the filter aid material is applied to a filter membrane to protect it and / or improve the clarity of the liquid being filtered in a filtering process. In another embodiment, the filter aid composition is added directly to the beverage being filtered to increase the flow rate and / or extend the filtering cycle. In another embodiment, a method of precoating at least one filter element with the filter aid material and contacting at least one liquid to be filtered with at least one coated filter element, or a method of using in a body feed method, or a method of using both precoating and body feed methods is provided.

[0066] The filter aid material of the present invention can also be used in various filtering methods. In one embodiment, the filtering method includes precoating at least one filter element with the composition of the present invention and contacting at least one liquid to be filtered with at least one coated filter element. In such an embodiment, the contacting may include passing the liquid through the filter element. In another embodiment, the filtering method includes suspending the filter aid material in at least one liquid containing particles to be removed from the liquid and then separating the filter aid material from the filtered liquid.

[0067] The filter aid material comprising the composition of the present invention can also be used to filter various types of liquids. Those skilled in the art can easily recognize the liquids that may desirably be filtered in a process comprising a filter aid comprising at least one diatomaceous earth product disclosed herein. In one embodiment, the liquid is a beverage. Exemplary beverages include, but are not limited to, vegetable-based juices, fruit juices, distilled spirits, and malt-based liquids. Exemplary malt-based liquids include, but are not limited to, beer and wine. In another embodiment, the liquid is one that tends to form turbidity when cooled. In a further embodiment, the liquid is a beverage that tends to form turbidity when cooled. In yet another embodiment, the liquid is beer. In still a further embodiment, the liquid is oil. In yet another embodiment, the liquid is cooking oil. In still a further embodiment, the liquid is fuel oil. In another embodiment, the liquid is water, including, but not limited to, wastewater. In a further embodiment, the liquid is blood. In yet another embodiment, the liquid is liquor. In still a further embodiment, the liquid is a sweetener such as, for example, corn syrup or molasses.

Examples

[0068] Details of the comparative DE sample, comparative perlite sample, and novel composite of DE and expanded crushed perlite used in the following examples are shown in Table 1 below.

[0069]

Table 1

[0070] Example 1 The novel composite material 1 (Sample F) was prepared using 80 g of expanded and pulverized perlite (Harborlite™ 500 - Sample C, available from Imerys). This perlite was placed in a mixer (Kitchen Aid mixer) together with 20 g of natural diatomaceous earth (DiaFil™ 615 - Sample E), and the powders were dry - mixed at the lowest setting for 5 minutes. 1.5 g of polyvinyl alcohol (PVA) and 4.5 g of citric acid were dissolved in 50 g of water. The final weight % of the binder was 6 wt% of the total composite particulate matter. The binder composition was then sprayed onto the dry - mixed powders to form composite particulate matter by agglomeration. It took 3 minutes to transfer all of the solution to the Kitchen Aid mixer. The composite particulate matter was then cured by heating in an oven at a temperature of 120 °C for 85 minutes. The novel composite material 1 was subjected to X - ray diffraction, Walton solid - liquid filtration, and mercury intrusion porosimetry by the methods described below, and the results are shown in Figures 1, 2, and 3, respectively.

[0071] Example 2 The novel composite material 2 (Sample G) was prepared using 66 g of expanded and pulverized perlite (Harborlite™ 500 - Sample C, available from Imerys). This perlite was placed in a mixer (Kitchen Aid mixer) together with 33 g of natural diatomaceous earth (DiaFil™ 615 - Sample E), and the powders were dry - mixed at the lowest setting for 5 minutes. 1.5 g of polyvinyl alcohol (PVA) and 4.5 g of citric acid were dissolved in 50 g of water. The final weight % of the binder was 6 wt% of the total composite particulate matter. The binder composition was then sprayed onto the dry - mixed powders to form composite particulate matter by agglomeration. It took 3 minutes to transfer all of the solution to the Kitchen Aid mixer. The composite particulate matter was then cured by heating in an oven at a temperature of 120 °C for 85 minutes. The novel composite material 2 was subjected to Walton solid - liquid filtration and mercury intrusion porosimetry by the methods described below, and the results are shown in Figures 2 and 3, respectively.

[0072] The filtration performance of the novel composite 1 and the novel composite 2 is demonstrated to be comparable to that of the standard grade DE shipped from the facilities in Lombok when tested with a Walton filter (vertical tank, single horizontal leaf, positive pressure, Ovaltine as the suspended substance). The novel composite 1 and the novel composite 2 are representative of the compositions of the present invention described herein, and it is demonstrated that the compositions of the present invention described herein provide the clarity of Hyflo (Sample A) while suppressing the pressure increase over time. As shown in Figure 2, compared with perlite, the compositions of the present invention described herein far exceed H500 (Sample C) in terms of clarity at the same pressure and exceed H200 (Sample D) in terms of clarity at a considerably lower pressure.

[0073] In addition to the filtration performance, as shown in Figure 3, for the novel composite 1 and the novel composite 2, it is also important to note the increase in pore volume for each relative to Hyflo (Sample A - 3.1 mL / g) and Standard Supercel (Sample B - 2.8 mL / g), which are the standard DE grades in Lombok. The pore volume of the normal fired and flux-fired DE grades is approximately 2.8 mL / g when measured with a mercury porosimeter. The pore volume of the novel composite 1 is measured to be 3.7 mL / g, a 25% increase over the normal DE. This enables a larger solids retention capacity with the same dosage of filter aid.

[0074] Measurement method PSD laser The particle size distribution (PSD) was determined using a Mastersizer 3500S by Malvern instruments.

[0075] D 50 is the average particle size (D measured by laser diffraction (NFX - 11 - 666 or ISO 13320 - 1 standard) as described above and in the examples. 50) is the value. Refer to the paper by G. Baudet and J. P. Rona, Ind. Min. Mines et Carr. Les techn. June, July 1990, pp 55-61, which shows that the lamellarity index is correlated with the average ratio of the maximum dimension to the minimum dimension of the particles.

[0076] Density The bulk density of the sample was evaluated by placing it in a test tube, measuring the volume of the sample, and comparing the volume of the sample with the mass of the sample.

[0077] Specific surface area (SSA - B.E.T m 2 / g) The BET specific surface area was determined using the method based on the NF X 11-621 standard entitled "Determination de l'aire massique (surface specifique) des poudres par adsorption de gaz - Methode B.E.T. - Mesure volumetrique par adsorption d'azote a basse temperature (Determination of mass area (specific surface) of powders by gas adsorption - BET Methods - Volumetric measurement by nitrogen adsorption at low temperature)".

[0078] In this method, a Micromeritics measuring device (available from Micromeritics Instrument Corp. (USA)) equipped with a vacuum pump, a VacPrep 061 degassing section, a Tristar 3000S measuring section and a sample holder, a Mettler AG204 scale with an accuracy of 0.1 mg, a Dewar flask, a nitrogen adsorption gas and a helium carrier gas was used.

[0079] The sample was weighed near an empty sample holder (accuracy 0.1 mg), and its mass M0 was recorded in g. Subsequently, the pre-homogenized powder sample was introduced into the sample holder using a funnel. A sufficient space (dead volume) was left between the sample and the upper part of the sample holder to allow free circulation of gas. The sample holder was placed in one of the degassing stations and degassed at 250 °C for about 20 minutes under a primary vacuum of 10 Pa. After degassing, a sufficient amount of nitrogen was added to the sample holder to prevent air from mixing when transferring the sample holder from the degassing station to the measurement station.

[0080] Subsequently, the sample holder was attached to the measurement station, and a Dewar flask filled with liquid nitrogen was placed around the sample holder. BET measurement was started using the device control software. Then the device automatically performed the following operations: Vacuum removal of the nitrogen introduced for the transfer of the sample holder, Leak test, Addition of helium carrier gas, Measurement of the dead volume at ambient temperature, Measurement of the cold dead volume using liquid nitrogen, Vacuum removal of helium, Leak test, Addition of nitrogen at 950 mmHg and measurement of the saturation pressure, Obtaining of the analytical values.

[0081] The BET line converted from the five measured adsorption points was plotted using the data acquisition and processing software of the instrument. The Dewar flask and then the sample holder were removed. After returning the apparatus to ambient temperature, the sample was weighed again near the sample holder (accuracy 0.1 mg), and the weight was recorded in g as M2. The mass M of the tested portion of the sample was calculated as follows (in g): M = M2 - M0

[0082] Subsequently, the value M was input into the software calculation program, and the BET specific surface area of the sample was automatically calculated in m 2 / g.

[0083] Void fraction The void fraction is the ratio of the interstitial space within the granular material. The void fraction is calculated using the following formula: Φ = V V / V T

[0084] where Φ is the void fraction, V V is the void volume, and V T is the total volume.

[0085] The void fraction was measured using the mercury intrusion method, which determines the characteristics of the void fraction by pressing mercury into the pores. The method used for void fraction measurement was the standard test of the mercury intrusion method specified in ASTM D4404-18.

[0086] Angle of repose The angle of repose was measured using a manual powder flow tester (EFT-01) in accordance with ISO 8398:1989. The angle of repose is calculated as follows: Θ = tan -1 h / r

[0087] where Θ is the angle of repose, h is the height (cm) of the conical pile, and r is the radius (cm).

[0088] Supplementary measurements for the angle of repose are the dynamic angle of repose (or flow angle) measured using Granudrum. The GranuDrum apparatus (available from GRANUTOOLS™) is an automatic powder flowability measurement method based on the principle of a rotating drum. The drum is horizontally cylindrical with transparent side walls and is half-filled with a powder sample.

[0089] The drum rotates about its axis at angular velocities taking various values from 2 rpm to 70 rpm. In this case, the angular velocity is measured at 10 rpm, and a large number of snapshots are taken with a CCD camera. For the measured rotational speed, the dynamic aggregation index is measured from the fluctuations of the interface, and the flow angle, also called the "dynamic angle of repose" in the literature, is calculated from the average interface position. The smaller the value of the flow angle, the correspondingly better the fluidity.

[0090] XRD X-ray diffraction is used to identify and quantify mineral species, such as crystalline and inorganic species. A powder sample of approximately 1 gram is filled into a sample holder and attached to an XRD instrument called Rigaku Empyren that uses a Ge monochromator to generate CuK α radiation. The scan range at the 2θ angle is from 2° to 70°.

[0091] Crystalline silica ("CS") has a dominant main peak near 21.5°. Hyflo shows a very characteristic primary peak, along with the characteristic secondary and tertiary peak signals of CS, with a low count intensity. Perlite (H500) and novel composite 1 and novel composite 3 show very weak signals in this range even at very high count intensities.

[0092] Walton A 4L solid suspension consisting of 5 g / L of Ovaltine dissolved in deionized water was prepared as a model solid solution using Ovaltine. This was hydrated for 45 minutes. The pressure vessel was filled with deionized water, and a Hyflo precoat (2.0 g in 50 mL) was applied at 20 cm 2Applied to a stainless-steel Dutch weave screen. This precoat was added at a flow rate of 150 mL / min. After applying the precoat, the turbidity was monitored by measuring the NTU using a turbidimeter, aiming for the NTU to be less than 1. After hydrating Ovaltine for 45 minutes, each filter aid sample was added to 4 L of a solid suspension at a concentration of 2 g / L. The suspension of Ovaltine and the filter aid is called the body feed. The body feed was administered to the pressure vessel at 60 mL / min for 30 minutes. The pressure and turbidity were monitored every minute. The pressure rise was measured from 10 minutes to 20 minutes, and the turbidity after 20 minutes was reported on the Walton graph in Figure 2.

[0093] The perlite grades (H500 and H200) show higher turbidity compared to diatomaceous earth (Hyflo and Standard Supercel) as well as novel composite 1 and novel composite 2. The perlite grades show a higher pressure rise compared to novel composite 1 and novel composite 2. The diatom grades show a higher pressure rise compared to novel composite 1 and novel composite 2. Furthermore, the turbidity of Hyflo is higher than that of novel composite 1 and novel composite 2. All of these are shown in Figure 2.

Claims

1. A composition comprising a composite granular material, wherein the composite granular material comprises a crosslinking binder and i) D particles of approximately 5 microns to approximately 40 microns. ５０ ii) Expanded and ground perlite particles having a diameter of approximately 10 microns to approximately 50 microns ５０ It comprises diatomaceous earth particles having and mineral particles selected from the group consisting of combinations thereof, The mineral particles are bonded together by the crosslinking binder to form a composite granular material, and the composite granular material has a diameter of approximately 20 to 100 microns. ５０ A composition having the following characteristics: the binder is present in an amount of 0.1 wt% to about 40 wt% of the total weight of the composition, the crosslinking binder is a reaction product of a polymer and a crosslinking agent, and the polymer is selected from water-soluble synthetic polymers and natural water-soluble polymers.

2. The aforementioned crosslinking agent is as follows: (i) Dicarboxylic acids including oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, tartaric acid, tartonic acid, aspartic acid, glutamic acid, fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoric acid, phthalic acid and derivatives thereof containing at least one boron or chlorine atom, tetrahydrophthalic acid and derivatives thereof containing at least one chlorine atom, isophthalic acid, terephthalic acid, mesaconic acid, and citraconic acid, (ii) Tricarboxylic acids, including citric acid, tricarbaryl acid, 1,2,4-butanetricarboxylic acid, aconitic acid, hemimeltic acid, trimellitic acid and trimesic acid, (iii) Tetracarboxylic acid comprising 1,2,3,4-butanetetracarboxylic acid and pyromellitic acid, (iv) Polycarboxylic acids such as EDTA, (v) Unsaturated carboxylic acids including ethylene acrylic acid copolymer, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2-methylmaleic acid, fumaric acid, itaconic acid, 2-methylitaconic acid, α,β-methylene glutaric acid and monoesters of unsaturated dicarboxylic acids, styrene optionally substituted with alkyl groups, hydroxyl groups or sulfonyl groups or halogen atoms, (meth)acrylonitrile, C １ ~C １０ (Meth)acrylamides, alkyl (meth)acrylates, glycidyl (meth)acrylates, butadienes, and vinyl esters optionally substituted with alkyl groups. (vi) Inorganic acids such as boric acid and phosphoric acid, The composition according to claim 1, wherein the acid is selected from one or more of the following.

3. The composition according to claim 2, wherein the binder is a reaction product of polyvinyl alcohol and an acid.

4. The composition according to claim 3, wherein the acid is citric acid.

5. The composition according to claim 1, wherein the composite granular material is bonded by a crosslinking binder to form a porous structure containing pores having a pore volume of 2.5 mL / g to 4.5 mL / g.

6. The composition according to claim 5, wherein the composite granular material comprises expanded and crushed perlite particles and diatomaceous earth particles.

7. The composition according to claim 6, wherein at least one pore of the porous structure is filled with at least one unbound diatomaceous earth particle.

8. When measured using the EFT-01 powder flow tester by the angle of repose (funnel method), the angle of repose is approximately 5° to approximately 30°. When measured using the Westinghouse method described herein and dioctyl adipic acid as the absorbent, an absorption capacity of at least 150% is observed, and The composition according to claim 1, having a dust content of less than 10 when measured by a Dustmon RD 100 dust analyzer.

9. The aforementioned expanded and pulverized perlite particles are approximately 15 microns in size D ５０ The composition according to claim 1, having the following characteristics.

10. The aforementioned diatomaceous earth particles are approximately 35 microns in size D ５０ The composition according to claim 1, having the following characteristics.

11. The aforementioned composite granular material is approximately 30 microns to approximately 40 microns in size. ５０ The composition according to claim 1, having the following characteristics.

12. The composition according to claim 1, wherein the composite granular material contains both expanded and crushed perlite particles and diatomaceous earth particles in a ratio of 5:1 to 1:

4.

13. The composition according to claim 1, wherein the crystalline silica present in the composition is about 0.2 wt% or less of the total wt% of the composition.

14. A filtration aid material comprising the composition described in claim 1.

15. A method for filtering a liquid, comprising contacting the liquid with the filter aid material described in claim 14.

16. A method for producing a composition containing a composite granular substance, (a) i) Expanded and pulverized perlite particles having a D of about 5 microns to about 40 microns ５０ ii) Diatomaceous earth particles having a D of about 10 microns to about 50 microns ５０ and mineral particles selected from the group consisting of combinations thereof are spray-dried together with a cross-linking binder to form a composite particulate material. Here, the composite granular material is approximately 20 microns to 100 microns in size D ５０ The composition has the following properties: the binder is present in an amount of 0.01 wt% to 20 wt% of the total weight of the composition, the crosslinking binder is a reaction product of a polymer and a crosslinking agent, and the polymer is selected from water-soluble synthetic polymers and natural water-soluble polymers; (b) curing the composition in a kiln, Methods that include...

17. The method according to claim 16, wherein the curing process is carried out in a kiln at a temperature of 80°C to 300°C.

18. The method according to claim 17, wherein the curing process is carried out for 4 to 12 hours.

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