Porous aluminosilicate compositions for the removal of contaminant metals in water treatment

Abstract

The present technology provides an adsorbent material including a silicate composition, wherein the silicate composition includes a crystalline phase and may have an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having diameters of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.1 cc / g for pores having diameters of about 20 to 600 Å.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 930,133, filed November 4, 2019, which is incorporated herein by reference in its entirety.

[0002] The present technology relates generally to materials for metal contaminant removal in water treatment. More specifically, the technology relates to adsorbent materials comprising porous alumina-silicate compositions, and methods for preparing and using such adsorbent materials. Summary of the Invention [Means for solving the problem]

[0003] In one aspect, the present technology provides an adsorbent material comprising a silicate composition, the silicate composition comprising about 5 wt. % to about 95 wt. % crystalline phase, based on the total weight of the silicate composition, and the silicate composition may have an interconnected porous scaffold with a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.1 cc / g for pores having a diameter of about 20 to 600 Å.

[0004] In a related aspect, disclosed herein are adsorbent material formulations comprising silicate compositions and titanosilicate compositions as described herein in any embodiment. For example, in any embodiment disclosed herein, the adsorbent material formulation may comprise a silicate composition comprising a crystalline phase that may comprise about 20% to about 60% by weight Y-zeolite, about 5% to about 95% by weight of a non-zeolitic matrix phase, and an interconnected porous scaffold having a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å, wherein the silicate composition comprises about 5% to about 20% sodium, calculated as atomic percent, and a total nitrogen (N) pore volume of about 200 cc / g to about 0.10 cc / g for pores having a diameter of about 200 to 600 Å. 2 / g~about 500m 2 The surface composition may have a surface area of ​​1 / g.

[0005] In a related aspect, disclosed herein is an adsorbent material formulation comprising a silicate composition as described herein in any embodiment and a binder, wherein the adsorbent material formulation is a granular adsorbent material formulation. In some embodiments, the binder is kaolin clay. For example, in any embodiment disclosed herein, the adsorbent material formulation may comprise a silicate composition comprising a crystalline phase that may comprise about 20% to about 60% by weight of Y-zeolite, about 5% to about 95% by weight of a non-zeolitic matrix phase, and an interconnected porous scaffold having a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å, wherein the silicate composition comprises about 5% to about 20% sodium, calculated as atomic percent, and a total nitrogen (N) pore volume of about 200 cc / g to about 0.10 cc / g for pores having a diameter of about 200 to 600 Å. 2 / g~about 500m 2 The surface composition may have a surface area of ​​1 / g.

[0006] In another aspect, disclosed herein is a method for producing the adsorbent material described herein, the method comprising preforming precursor microspheres comprising a clay material, in situ crystallizing a zeolite in or on the preformed microspheres to provide a silicate composition as described herein in any embodiment comprising a crystalline phase, and drying the silicate composition to obtain the adsorbent material. In any embodiment herein, the silicate material obtained according to the method may comprise an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.1 cc / g for pores having a diameter of about 20 to 600 Å.

[0007] In yet another aspect, the present technology provides a method for treating a liquid containing metal contaminants, comprising contacting the liquid with an adsorbent material and / or adsorbent material formulation as described herein in any embodiment to obtain a treated liquid, wherein the contacting removes the metal contaminants from the liquid. In any embodiment disclosed herein, the liquid may be water. In any embodiment, the metal contaminant may be lead. In any embodiment, the metal contaminant may be cadmium.

[0008] In a further aspect, the present technology provides methods for treating water, comprising contacting the water with an adsorbent material and / or adsorbent material formulation as described herein in any embodiment, wherein the contacting removes metal contaminants from the water.

[0009] In another aspect, the present technology provides methods for removing metal contaminants as described herein in any embodiment from water, comprising contacting the water with an adsorbent material and / or adsorbent material formulation as described herein, wherein the contacting removes the metal contaminants from the water. [Brief explanation of the drawings]

[0010] [Figure 1A] 1A and 1B show scanning electron microscope images of cut / mount / polished (CMP) sections of adsorbent materials according to the present technique, with Figure 1A providing a CMP cross-section of an adsorbent material according to Example 1A comprising a silicate composition (-170 mesh). [Figure 1B] FIG. 1B provides a CMP cross-sectional view of an adsorbent material according to Example 2, comprising a 50:50 weight ratio blend of titanosilicate (ATS) to silicate composition (-170 mesh). [Figure 1C] FIG. 1C provides a CMP cross-sectional view of an adsorbent material according to Example 2, including an 80:20 weight ratio blend of ATS to silicate composition (-170 mesh). [Figure 2A] Figure 2A shows a transmission electron microscope (TEM) image of the pores of the adsorbent material according to the present technique, showing the Y-zeolite phase and the amorphous matrix phase within the interconnected pore scaffold. Figure 2A provides a TEM image of the pores of the adsorbent material according to Example 1A, which includes a silicate composition (-170 mesh). [Figure 2B] FIG. 2B provides a TEM image of the pores of the adsorbent material according to Example 2, which includes a 50:50 weight ratio blend of ATS to silicate composition (-170 mesh). [Figure 2C] FIG. 2C provides a TEM image of the adsorbent material according to Example 2, which includes an 80:20 weight ratio blend of ATS to silicate composition (-170 mesh). [Figure 3] 1 shows X-ray powder diffraction (XRD) scans of a silicate composition (Example 1A), an 80:20 ATS / silicate composition blend (Example 2A), and ATS. DETAILED DESCRIPTION OF THE INVENTION

[0011] Various embodiments are described below. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. An aspect described in connection with a particular embodiment is not necessarily limited to that embodiment and can be implemented in any other embodiment.

[0012] As used herein, "about" will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If there are any uses of the term that are not clear to persons of ordinary skill in the art, "about" will mean up to ±10% of the particular term, given the context in which it is used.

[0013] The use of the terms "a," "an," and "the" and similar referents in the context of describing elements (particularly in the context of the claims that follow) should be construed to encompass both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is intended merely to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually listed herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better clarify embodiments and does not limit the scope of the claims, unless otherwise expressly stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0014] As used herein, the term "zeolite" refers to a crystalline aluminosilicate having a framework based on an extensive three-dimensional network of oxygen ions and having a substantially uniform pore distribution.

[0015] As used herein, the term "in situ crystallized" refers to a process in which a crystalline phase, such as a zeolite, is grown directly on or within a microsphere, e.g., in intimate association with a matrix or non-zeolitic material, as described, for example, in U.S. Pat. Nos. 4,492,902 and 6,656,347 and International Patent Application No. PCT / US2018 / 032909. For example, in any embodiment disclosed herein, a crystalline phase comprising a zeolite can be grown within the pores of a microsphere such that the zeolite is uniformly dispersed on the matrix or non-zeolitic material. The zeolite can be grown directly on or within the pores of precursor microspheres, such that the zeolite is intimately associated with and uniformly dispersed on the matrix or non-zeolitic material.

[0016] As used herein, the terms "preformed microspheres" or "precursor microspheres" refer to microspheres obtained by spray drying and calcining a clay material.

[0017] This technology provides novel adsorbent materials comprising porous aluminosilicate compositions with high surface areas and highly accessible pore structures. This highly accessible pore structure of the aluminosilicate compositions refers to a unique three-dimensional, homogeneous, interconnected pore network (i.e., an "interconnected porous scaffold") characterized by a high porosity (or total pore volume) relative to an average pore diameter in the range of 20 to 10,000 cubic centimeters (cc) / g.

[0018] The interconnected porous scaffold has been found to be advantageous for removing metal contaminants (e.g., lead) from water by cation exchange and adsorption. Specifically, the novel adsorbent material exhibits an increase in lead exchange capacity of more than 15% (e.g., more than 50%) compared to known adsorbent materials such as titanosilicates. Furthermore, unlike conventional industrial materials (e.g., titanosilicates), the clay-derived silicate composition contained in the adsorbent material of this technology does not contain chlorides, sulfates, etc., which present concerns for household and / or drinking water treatment.

[0019] Adsorbent material In one aspect, the present technology provides an adsorbent material comprising a silicate composition, the silicate composition comprising about 5 wt. % to about 95 wt. % crystalline phase, based on the total weight of the silicate composition, and the silicate composition may have an interconnected porous scaffold with a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.1 cc / g for pores having a diameter of about 20 to 600 Å.

[0020] The silicate composition comprises a crystalline phase. For example, in any embodiment disclosed herein, the crystalline phase can comprise a zeolite. Suitable zeolites in the crystalline phase can include, but are not limited to, X, Y-zeolite, ZSM-5, beta zeolite, ZXM-11, ZSM-14, ZSM-17, ZWM-18, ZSM-20, ZSM-31, ZSM-34, ZSM-41, ZSM-46, mordenite, chabazite, or a mixture of two or more thereof. In any embodiment disclosed herein, the crystalline phase can be a Y-zeolite crystalline phase. In any embodiment disclosed herein, the zeolite can be grown throughout the silicate composition (i.e., within the interconnected porous scaffold and on the surface).

[0021] The crystalline zeolite phase may be a residue of a zeolite crystallization process of a clay material as described herein in any embodiment. For example, in any embodiment described herein, the clay material may be calcined clay. Suitable clay materials in any embodiment described herein may include, but are not limited to, metakaolin, kaolin clay, or a mixture of any two or more thereof. In any embodiment described herein, the clay material may comprise about 30% to about 60% metakaolin by weight, based on the total weight of the clay material. Suitable amounts of metakaolin by weight may include, but are not limited to, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, or any ranges including and / or between any two of the foregoing values. In any embodiment described herein, the clay material may comprise about 40% to about 70% kaolin clay by weight, based on the total weight of the clay material. Suitable amounts of kaolin clay based on the total weight of the clay material may include, but are not limited to, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, or any ranges between and / or including any two of the foregoing values. In any embodiment herein, the clay material may be substantially calcined through its characteristic exotherm. In any embodiment disclosed herein, the crystalline zeolite phase may be a crystalline Y-zeolite phase.

[0022] In any embodiment herein, the silicate composition may comprise from about 5% to about 95% by weight of crystalline phase, based on the total weight of the silicate composition. Suitable amounts of crystalline phase present in the silicate composition may include, but are not limited to, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95% by weight (based on the total weight of the silicate composition), or any ranges therebetween, including any two of these values. In any embodiment disclosed herein, the silicate composition may comprise from about 20% to about 60% by weight of crystalline phase, based on the total weight of the silicate composition. For example, in any embodiment disclosed herein, the crystalline phase can be present in an amount of about 20 wt%, about 22 wt%, about 24 wt%, about 26 wt%, about 28 wt%, about 30 wt%, about 32 wt%, about 34 wt%, about 36 wt%, about 38 wt%, about 40 wt%, about 42 wt%, about 44 wt%, about 46 wt%, about 48 wt%, about 50%, about 52%, about 54%, about 56%, about 58%, about 60 wt%, or any range including and / or between any two of these values ​​(based on the total weight of the silicate composition).

[0023] In any embodiment herein, the silicate composition may further comprise a non-zeolitic matrix phase. In any embodiment disclosed herein, the non-zeolitic matrix phase may be amorphous, crystalline, or a combination thereof. In any embodiment disclosed herein, the non-zeolitic matrix phase may be amorphous. For example, in any embodiment disclosed herein, the amorphous non-zeolitic matrix phase may comprise, but is not limited to, an amorphous aluminosilicate, mullite, spinel, or a combination thereof. In any embodiment disclosed herein, the silicate composition may comprise from about 5 wt. % to about 95 wt. % of the non-zeolitic matrix phase, based on the total weight of the silicate composition. Suitable amounts of non-zeolitic matrix phase present in the silicate composition can include, but are not limited to, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95% by weight (based on the total weight of the silicate composition), or any two of these values, and / or any range therebetween.

[0024] The silicate composition may have an interconnected porous scaffold that may include pores that may be microporous, mesoporous, macroporous, or a mixture thereof. For example, in any of the embodiments described herein, the interconnected porous scaffold of the silicate composition may have a mercury pore volume of about 0.01 cc / g to about 0.25 cc / g for pores with diameters of about 200 to 10,000 Å. Suitable mercury pore volumes as described herein in any of the embodiments include about 0.01 cc / g, about 0.02 cc / g, about 0.03 cc / g, about 0.04 cc / g, about 0.05 cc / g, about 0.06 cc / g, about 0.07 cc / g, about 0.08 cc / g, about 0.09 cc / g, about 0.10 cc / g, about 0.11 cc / g, about 0.12 cc / g, about 0.13 cc / g, and the like. The mercury pore volume may be about 0.14 cc / g, about 0.15 cc / g, about 0.16 cc / g, about 0.17 cc / g, about 0.18 cc / g, about 0.19 cc / g, about 0.20 cc / g, about 0.21 cc / g, about 0.22 cc / g, about 0.23 cc / g, about 0.24 cc / g, about 0.25 cc / g, or any range between and including any two of the foregoing values. In any embodiment herein, the mercury pore volume may be about 0.10 cc / g to about 0.25 cc / g for pores having diameters of about 200 to 10,000 Å.

[0025] In any of the embodiments described herein, the interconnected porous scaffold of the silicate composition can comprise a nitrogen pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å. For example, in any of the embodiments described herein, the interconnected porous scaffold of the silicate composition can have a nitrogen pore volume of about 0.02 cc / g, about 0.03 cc / g, about 0.04 cc / g, about 0.05 cc / g, about 0.06 cc / g, about 0.07 cc / g, about 0.08 cc / g, about 0.09 cc / g, about 0.10 cc / g, or a range inclusive of and / or between any two of the foregoing values.

[0026] The silicate composition of the adsorbent material also has a high surface area. For example, in any of the embodiments described herein, the silicate composition has a surface area of ​​about 200 m 2 / g~about 500m 2 / g. Suitable surface area values ​​for the silicate composition include a surface area of ​​about 200 m 2 / g, approx. 210m 2 / g, approx. 220m 2 / g, approx. 230m 2 / g, approx. 240m 2 / g, approx. 250m 2 / g, approx. 260m 2 / g, approx. 270m 2 / g, approx. 280m 2 / g, approx. 290m 2 / g, approx. 300m 2 / g, approx. 310m 2 / g, approx. 320m 2 / g, approx. 330m 2 / g, approx. 340m 2 / g, approx. 350m 2 / g, approx. 360m 2 / g, approx. 370m 2 / g, approx. 380m 2 / g, approx. 390m 2 / g, approx. 400m 2 / g, approx. 410m 2 / g, approx. 420m 2 / g, approx. 430m 2 / g, approx. 440m 2 / g, approx. 450m 2 / g, approx. 460m 2 / g, approx. 470m 2 / g, approx. 480m 2 / g, approx. 490m 2 / g, approx. 500m 2 / g, or any range including and / or between any two of the foregoing values. In any embodiment described herein, the surface area is about 200 m 2 / g~about 500m 2 / g, approx. 200m 2 / g ~ approx. 350m 2 / g, approx. 225m 2 / g~about 300m 2 / g, approx. 255m2 / g ~ approx. 275m 2 / g, or any range inclusive of and / or between any two of the foregoing values.

[0027] The silicate composition of the adsorbent material may further comprise a surface composition of at least about 5% to about 20% sodium, calculated as atomic percent. For example, in any embodiment described herein, the surface composition of the silicate composition may comprise sodium, calculated as atomic percent, of about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, or any range including and / or between any two of the foregoing values. In any embodiment herein, the surface composition may be about 7% to about 12% sodium, calculated as atomic percent. In any embodiment herein, the surface composition may comprise about 9% to about 11% sodium, calculated as atomic percent.

[0028] The silicate composition of the adsorbent material has a highly negatively charged surface, as confirmed by other surface charge analysis methods, such as cation exchange capacity or zeta potential measurements. Without being bound by theory, it is believed that the excessive negative charge on the surface of the silicate composition is the result of the substitution of silicon for aluminum within the structure, allowing it to act as a cation adsorbent / exchanger for metal contaminants (e.g., Pb, Zn, Cr, Cd, Cu, Mn, Fe, etc.) in liquids such as water. The inventors have discovered that the adsorbent material of the present invention, including the silicate composition, can exhibit an increase in lead (Pb) exchange capacity of more than 15% compared to conventional water filtrate materials based on titanosilicates. In any embodiment herein, the silicate composition of the adsorbent material can exhibit an increase in lead exchange capacity of about 15% to about 150%. For example, in any embodiment disclosed herein, the lead exchange capacity can be about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 100%, about 105%, about 110%, about 115%, about 120%, about 125%, about 130%, about 135%, about 140%, about 145%, about 150%, or any range inclusive of and / or between any two of these values.

[0029] In any embodiment described herein, the silicate composition can have a particle size of about 10 microns to about 150 microns. In any embodiment disclosed herein, the particle size can be about 40 microns to about 150 microns. For example, in any embodiment disclosed herein, the particle size can be about 10 microns, about 20 microns, about 30 microns, about 40 microns, about 50 microns, about 60 microns, about 70 microns, about 80 microns, about 90 microns, about 100 microns, about 110 microns, about 120 microns, about 130 microns, about 140 microns, about 150 microns, or any range inclusive of and / or between any two of these values.

[0030] In any embodiment described herein, the silicate composition can have an average particle size distribution of about 10 microns to about 60 microns. For example, in any embodiment described herein, the average particle size distribution can be about 10 microns, about 15 microns, about 20 microns, about 25 microns, about 30 microns, about 35 microns, about 40 microns, about 45 microns, about 50 microns, about 55 microns, about 60 microns, or any range inclusive of and / or between any two of the foregoing values. In any embodiment herein, the average particle size distribution is about 45 microns to about 55 microns. In any embodiment, the average particle size distribution can be about 50 microns or less, about 45 microns or less, about 40 microns or less, about 35 microns or less, about 30 microns or less, about 25 microns or less, about 20 microns or less, about 15 microns or less, about 10 microns or less, or any range inclusive of and / or between any two of the foregoing values. The average particle size distribution can be measured via a particle size analyzer, such as a Microtrac S3500 particle size analyzer. For example, in any embodiment disclosed herein, the silicate composition may have an average particle size distribution of from about 10 microns to about 60 microns as measured by a Microtrac S3500 particle size analyzer.

[0031] In any embodiment described herein, the adsorbent material formulation may comprise about 20% to about 60% by weight of a crystalline phase, which may comprise Y-zeolite, about 5% to about 95% by weight of a non-zeolitic matrix phase, the interconnected porous scaffold may have a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å, and the silicate composition may have about 5% to about 20% sodium, calculated as atomic percent, and about 200m 2 / g~about 500m 2 / g and a surface area of ​​0.15 to 0.25 μm.

[0032] The adsorbent material of the present technology may further include an additional adsorbent for adsorbing metal contaminants. For example, in any embodiment disclosed herein, the additional adsorbent may include titanosilicate, non-zeolitic molecular sieve, activated carbon, porous glass, clay, metalloaluminate, metallophosphate, layered silicate, or a combination of two or more thereof. In any embodiment described herein, the additional adsorbent may be titanosilicate.

[0033] In any embodiment herein, the sorbent material can have a weight ratio of silicate composition to additional sorbent (weight ratio of silicate composition to additional sorbent) of about 99:1 to about 1:99. For example, in any embodiment herein, the weight ratio of silicate composition to additional sorbent can be about 99:1, about 95:5, about 90:10, about 85:15, about 80:20, about 75:25, about 70:30, about 65:35, about 60:40, about 55:45, about 50:50, about 45:55, about 40:60, about 35:65, about 30:70, about 25:75, about 20:80, about 15:85, about 10:90, about 5:95, about 1:99, or any range inclusive of and / or between any two of the foregoing values. In any embodiment herein, the weight ratio can be from about 80:20 to about 20:80, from about 80:20 to about 50:50, from about 50:50 to about 20:80, or any range inclusive of and / or between any two of the foregoing values.

[0034] In a related aspect, disclosed herein are adsorbent material formulations comprising the silicate and titanosilicate compositions as described herein in any embodiment. For example, in any embodiment disclosed herein, the adsorbent material formulation may comprise a silicate composition comprising a crystalline phase that may comprise about 20% to about 60% by weight Y-zeolite, about 5% to about 95% by weight of a non-zeolitic matrix phase, and an interconnected porous scaffold having a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å, wherein the silicate composition comprises about 5% to about 20% sodium, calculated as atomic percent, and a total nitrogen (N) pore volume of about 200 cc / g to about 0.10 cc / g for pores having a diameter of about 200 to 600 Å. 2 / g~about 500m 2 The surface composition may have a surface area of ​​1 / g.

[0035] In any embodiment herein, the adsorbent material formulation can have a weight ratio of silicate composition to titanosilicate of about 99:1 to about 1:99. For example, in any embodiment herein, the weight ratio of silicate composition to titanosilicate can be about 99:1, about 95:5, about 90:10, about 85:15, about 80:20, about 75:25, about 70:30, about 65:35, about 60:40, about 55:45, about 50:50, about 45:55, about 40:60, about 35:65, about 30:70, about 25:75, about 20:80, about 15:85, about 10:90, about 5:95, about 1:99, or any range including and / or between any two of the foregoing values. In any embodiment herein, the weight ratio can be from about 80:20 to about 20:80, from about 80:20 to about 50:50, from about 50:50 to about 20:80, or any range inclusive of and / or between any two of the foregoing values.

[0036] In some embodiments, the adsorbent material formulation of the present technology may further comprise an additional adsorbent. Suitable additional adsorbents may include titanosilicates, non-zeolitic molecular sieves, activated carbon, porous glass, clays, metal aluminates, metal phosphates, layered silicates, or combinations of two or more thereof.

[0037] In any embodiment disclosed herein, the adsorbent material formulations of the present invention, including silicate compositions, may exhibit an increase in lead (Pb) exchange capacity of more than 15% compared to conventional water filtrate materials based on titanosilicates. In any embodiment disclosed herein, the silicate compositions of the adsorbent material formulations may exhibit an increase in lead exchange capacity of from about 15% to about 150%. For example, in any embodiment disclosed herein, the lead exchange capacity can be about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 100%, about 105%, about 110%, about 115%, about 120%, about 125%, about 130%, about 135%, about 140%, about 145%, about 150%, or any range inclusive of and / or between any two of these values.

[0038] The adsorbent material of the present technology may further include an additional binder. The binder is used to bind individual zeolite matrices, form a shaped product, and reduce pressure drop during adsorption. The binder maintains the crush strength of the zeolite adsorbent used, and providing more binder in the molding process generally improves the crush strength of the finished product. In the present technology, the binder is used to form a granular structure in the zeolite. Illustrative binders include alumina, silicates, and clay minerals. Examples of clay minerals include kaolin clay, polygorskite-type minerals (i.e., attapulgite), and smectite-type clay minerals (e.g., montmorillonite or bentonite). For example, in any embodiment disclosed herein, the binder can include any clay mineral, such as kaolin clay, polygorskite-type minerals (i.e., attapulgite), and smectite-type clay minerals (e.g., montmorillonite or bentonite), or a combination of two or more thereof.

[0039] In any embodiment described herein, the binder can be kaolin clay. Kaolin clay particles naturally form in the form of stacked hexagonal platelets, and the presence of these stacked platelets has been confirmed using scanning electron microscopy (SEM). These platelets can be separated and formed into individual platelets by appropriate delamination and dispersion methods. When properly dispersed at high solids loadings, kaolin clay is used as a binder for zeolite particles for enhanced adsorption capacity as described herein. A typical high-solids kaolin clay slurry is prepared at a solids loading of about 60-70%.

[0040] In any embodiment herein, the binder may have a weight ratio of silicate composition to binder (weight ratio of silicate composition to binder) of about 90:10 to about 50:50, including about 80:20 to about 60:40. For example, in any embodiment herein, the weight ratio of silicate composition to binder may be about 90:10, about 85:15, about 80:20, about 75:25, about 70:30, about 65:35, about 60:40, about 55:45, about 50:50, or any range inclusive of and / or between any two of the foregoing values. In any embodiment herein, the weight ratio may be about 80:20 to about 60:40, or any range inclusive of and / or between any two of the foregoing values. In any embodiment herein, the weight ratio may be about 70:30.

[0041] In a related aspect, disclosed herein is a granular adsorptive material formulation comprising a silicate composition as described herein in any embodiment and a binder such as kaolin clay. For example, in any embodiment disclosed herein, the granular adsorptive material formulation may comprise a silicate composition comprising a crystalline phase that may comprise about 20% to about 60% by weight Y-zeolite, about 5% to about 95% by weight of a non-zeolitic matrix phase, and an interconnected porous scaffold having a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å, wherein the silicate composition comprises about 5% to about 20% sodium, calculated as atomic percent, and a binder such as kaolin clay. 2 / g~about 500m 2 The surface composition may have a surface area of ​​1 / g.

[0042] In any embodiment herein, the granular adsorptive material formulation may have a weight ratio of silicate composition to binder, such as kaolin clay, of about 90:10 to about 50:50, including about 80:20 to about 60:40. For example, in any embodiment herein, the weight ratio of silicate composition to binder may be about 90:10, about 85:15, about 80:20, about 75:25, about 70:30, about 65:35, about 60:40, about 55:45, about 50:50, or any range inclusive of and / or between any two of the foregoing values. In any embodiment herein, the weight ratio may be about 80:20 to about 60:40, or any range inclusive of and / or between any two of the foregoing values. In any embodiment herein, the weight ratio may be about 70:30.

[0043] In some embodiments, the granular adsorbent material formulation of the present technology may further include a pore-forming agent. The pore-forming agent may be added to a zeolite / binder mixture, such as a zeolite / kaolin clay mixture, during the granulation process to enhance the total pore volume of the final product. Suitable pore-forming agents include organic polymers, including, but not limited to, corn starch, starch derivatives, lignosulfonates, polyacrylamides, polyacrylic acids, polyvinyl alcohols, cellulose, cellulose derivatives, and the like. The amount of pore-forming agent that can be added is about 0.5% to about 5% by weight, or any range including and / or between any two of the foregoing values, such as about 0.5%, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, and 5% by weight.

[0044] In some embodiments, the granular adsorbent material formulation of the present technology may further comprise an additional adsorbent. Suitable additional adsorbents may include titanosilicates, non-zeolitic molecular sieves, activated carbon, porous glass, clays, metal aluminates, metal phosphates, layered silicates, or combinations of two or more thereof.

[0045] In any embodiment disclosed herein, the adsorbent material formulation including the silicate composition may exhibit an increase in cadmium (Cd) exchange capacity of more than 100% compared to conventional water filtrate materials based on titanosilicates. The adsorbent material may be in the form of granules or spray-dried beads. In any embodiment disclosed herein, the silicate composition of the adsorbent material formulation may exhibit an increase in cadmium exchange capacity of about 500% to about 500%. For example, in any embodiment disclosed herein, the cadmium exchange capacity can be about 50%, about 75%, about 100%, about 105%, about 110%, about 115%, about 120%, about 125%, about 130%, about 135%, about 140%, about 145%, about 150%, about 155%, about 160%, about 165%, about 170%, about 180%, about 190%, about 200%, about 250%, about 300%, about 350%, about 400%, about 450%, about 500%, or any range inclusive of and / or between any two of these values.

[0046] Method for producing an adsorbent material In another aspect, disclosed herein is a method for producing the adsorbent material described herein, the method comprising preforming precursor microspheres comprising a clay material, in situ crystallizing a zeolite in or on the preformed microspheres to provide a silicate composition as described herein in any embodiment comprising about 5% to about 95% crystalline phase, and drying the silicate composition to obtain the adsorbent material. In any embodiment herein, the silicate material obtained according to this method may comprise an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.1 cc / g for pores having a diameter of about 20 to 600 Å.

[0047] In some embodiments, the in situ crystallizing comprises combining the precursor microspheres with sodium silicate, sodium hydroxide, a zeolite initiator, and water to obtain an alkaline slurry, and heating the alkaline slurry at a temperature and for a time sufficient to crystallize at least about 15 wt% NaY-zeolite in the silicate composition. For example, in any of the embodiments described herein, the alkaline slurry can be heated for a time sufficient to crystallize about 20 wt% to about 60 wt% NaY-zeolite in the silicate composition.

[0048] In any embodiment herein, the clay material is a clay material as described herein in any embodiment. For example, the clay material can include kaolin clay, metakaolin, or a mixture of any two or more thereof. In any embodiment herein, the clay material is a calcined clay material. For example, the clay material can include about 30% to about 60% by weight of metakaolin, based on the total weight of the clay material as described herein in any embodiment. In any embodiment herein, the clay material can include about 40% to about 70% by weight of kaolin clay, based on the total weight of the clay material. In any embodiment herein, the clay material can be substantially calcined by its characteristic exotherm.

[0049] In any embodiment herein, the precursor microspheres may further comprise chi-alumina, delta-alumina, theta-alumina, kappa-alumina, boehmite, or a mixture of two or more thereof. For example, in any embodiment herein, the precursor microspheres may comprise gamma-alumina, chi-alumina, and a mixture of one or more of delta-alumina, theta-alumina, kappa-alumina, and boehmite.

[0050] In any embodiment, the silicate composition as described herein may comprise about 5 wt.% to about 95 wt.% of an amorphous matrix phase, based on the total weight of the silicate composition. In any embodiment, the silicate composition as described herein may comprise about 20 wt.% to about 60 wt.% of a crystalline Y-zeolite phase. In any embodiment, the interconnected porous scaffold may comprise pores that are microporous, mesoporous, macroporous, or a mixture thereof. In any embodiment, the interconnected porous scaffold may have a mercury pore volume of about 0.01 cc / g to about 0.25 cc / g for pores having diameters of about 200 to 10,000 Å. In any embodiment, the silicate composition may have a mercury pore volume of about 200 m 2 / g~about 500m 2 / g. In any embodiment, the silicate composition as described herein has a surface composition comprising about 5% to about 20% sodium, calculated as atomic percent.

[0051] Alternatively, the silicate compositions can be prepared by the in situ procedures described in US Pat. Nos. 4,493,902 or 6,656,347, which are incorporated herein by reference.

[0052] Following in situ crystallization, the silicate composition can be reduced to a mean particle size distribution (D50) of about 50 microns or less and isolated or separated from the crystallization solution after contacting before drying. In any embodiment herein, the method can further include reducing the particle size of the silicate composition to a D50 of about 50 microns or less before drying. For example, the method can include reducing the mean particle size to about 50 microns or less, about 45 microns or less, about 40 microns or less, about 35 microns or less, about 30 microns or less, about 25 microns or less, about 20 microns or less, about 15 microns or less, about 10 microns or less, or any range including and / or between any two of the foregoing values.

[0053] In any embodiment herein, the method may further include separating the silicate composition from at least a majority of the alkaline slurry. Separation may be performed by commonly used methods such as filtration. In any embodiment herein, the silicate material may be washed or contacted with water or other suitable liquid to remove residual crystallization liquid.

[0054] In any embodiment herein, the method may further comprise forming the silicate composition into a porous silicate cake. In any embodiment herein, prior to drying, the method may further comprise grinding the porous silicate cake to obtain particles, filtering the particles, and forming a silicate cake slurry from the previously obtained particles. In any embodiment herein, filtering may comprise filtering the particles through about a 40 mesh screen to about a 170 mesh screen to obtain filtered particles. For example, filtration can include filtering particles using a screen having openings of about 40 mesh, about 45 mesh, about 50 mesh, about 55 mesh, about 60 mesh, about 65 mesh, about 70 mesh, about 75 mesh, 80 mesh, about 85 mesh, about 90 mesh, about 95 mesh, about 100 mesh, about 105 mesh, about 110 mesh, about 115 mesh, about 120 mesh, about 125 mesh, about 130 mesh, about 135 mesh, about 140 mesh, about 145 mesh, about 150 mesh, about 155 mesh, about 160 mesh, about 165 mesh, about 170 mesh, or any range between any two of these values. In some embodiments, the filtered particles can have an average particle size greater than about 40 to about 170 mesh (e.g., +40 mesh to +170 mesh). In some embodiments, the filtered particles can have an average particle size of about 40 mesh to less than about 170 mesh (e.g., -40 mesh to -170 mesh). In any embodiment herein, forming a silicate cake slurry can include mixing the filtered particles with water to obtain a silicate cake slurry. In any embodiment described herein, prior to drying, the method can include crushing the porous silicate cake to obtain particles, filtering the particles through a 170 mesh screen, and mixing the filtered particles with water to obtain a silicate cake slurry having a solids content of about 10% or less.

[0055] In any embodiment herein, the method may further include mixing the silicate cake slurry, as described herein in any embodiment, with an additional adsorbent slurry to obtain a formulation. For example, in any embodiment disclosed herein, the additional adsorbent slurry may be a titanosilicate slurry. The titanosilicate slurry may include about 5% to about 15% by weight of titanosilicate solids. For example, in any embodiment herein, the titanosilicate slurry may include about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15% by weight of titanosilicate solids.

[0056] In any embodiment herein, the formulation may include a weight ratio of silicate composition to additional sorbent (e.g., titanosilicate), calculated on a dry basis, of about 99:1 to about 1:99. For example, in any embodiment herein, the weight ratio of silicate composition to additional sorbent (calculated on a dry basis) may be about 99:1, about 95:5, about 90:10, about 85:15, about 80:20, about 75:25, about 70:30, about 65:35, about 60:40, about 55:45, about 50:50, about 45:55, about 40:60, about 35:65, about 30:70, about 25:75, about 20:80, about 15:85, about 10:90, about 5:95, about 1:99, or any range inclusive of and / or between any two of the foregoing values. In any embodiment herein, the weight ratio (calculated on a dry basis) can be from about 80:20 to about 20:80, from about 80:20 to about 50:50, from about 50:50 to about 20:80, or any range inclusive of and / or between any two of the foregoing values.

[0057] In any embodiment herein, the method may further include adding a binder to the silicate composition to prepare a granular sorbent formulation. For example, the granular sorbent formulation is prepared by drying (e.g., spray-drying) a silicate-based sorbent material. In some embodiments, kaolin clay is added to the silicate composition before drying, and the silicate composition and kaolin clay are dried together to better control the desired silicate sorbent / kaolin clay ratio in the final granulated product form. When kaolin clay is used as the binder, the binder comprises highly dispersed kaolin particles in a high solids slurry form (e.g., at least 60% solids or more). The dried silicate composition is granulated with a binder, such as a kaolin clay slurry, using granulation methods known to those skilled in the art to provide a granular sorbent formulation. The granular sorbent product can then be further screened to obtain a sorbent having a desired particle size range and then calcined to provide the final granular sorbent formulation product.

[0058] The binder (e.g., kaolin clay) may have a weight ratio of silicate composition to binder of about 90:10 to about 50:50, including about 80:20 to about 60:40. For example, in any embodiment herein, the weight ratio of silicate composition to binder may be about 90:10, about 85:15, about 80:20, about 75:25, about 70:30, about 65:35, about 60:40, about 55:45, about 50:50, or any range inclusive of and / or between any two of the foregoing values. In any embodiment herein, the weight ratio may be about 80:20 to about 60:40, or any range inclusive of and / or between any two of the foregoing values. In any embodiment herein, the weight ratio may be about 70:30. Sufficient water may be retained or added to the mixture to produce a moldable mixture that can be easily granulated or formed into a noodle structure in an extruder. The moisture content of the granular sorbent is in the range of about 15% to about 20% by weight, or any range inclusive of and / or between any two of these values.

[0059] In any embodiment herein, a pore-forming agent may be added to the silicate composition / binder mixture during the granulation process to enhance the total pore volume of the final product. Acceptable pore-forming agents include organic polymers, including corn starch, starch derivatives, lignosulfonates, polyacrylamides, polyacrylic acids, polyvinyl alcohols, cellulose, cellulose derivatives, and the like. The amount of pore-forming agent that may be added is about 0.5 to about 5 weight percent.

[0060] In any embodiment of the present invention, after drying, the method can further include granulating the silicate composition with a binder such as kaolin clay using a granulation method known to those skilled in the art. For example, a well-dispersed kaolin slurry is added to the dried silicate composition until a granular structure is formed using conventional granulation equipment, including but not limited to a paddle mixer, pan granulator, drum granulator, compactor, and extruder. After mixing with the binder, the mixed mixture can be formed into a suitable molded product, which can be formed into any conventional shape, such as beads, pellets, noodles, and tablets.

[0061] In any embodiment herein, screening is used to obtain a granular sorbent formulation having a desired particle size, which may range from about 10 mesh to about 80 mesh, or any range including and / or between any two of these values. In some embodiments, the granular sorbent formulation may have a particle size of about 10 mesh, about 15 mesh, about 20 mesh, about 25 mesh, about 30 mesh, about 35 mesh, about 40 mesh, about 45 mesh, about 50 mesh, about 55 mesh, about 60 mesh, about 65 mesh, about 70 mesh, about 75 mesh, and about 80 mesh.

[0062] Once the desired shape and size is obtained, the granular sorbent formulation may be calcined, preferably at about 600° C. for about 1 to about 2 hours.

[0063] In any embodiment herein, drying may include spray drying to obtain the adsorbent material.

[0064] treatment method Without being bound by theory, it is believed that the sorbent material may demonstrate improved removal of metal contaminants from liquids, particularly from water during water treatment. Metal contaminants disclosed in any embodiment herein may include, but are not limited to, lead (Pb), zinc (Zn), chromium (Cr), cadmium (Cd), copper (Cu), manganese (Mn), iron (Fe), and the like. As used herein, water treatment refers to a process for improving water quality by removing contaminants or other undesirable components for a specific end use. Such end uses may include water treatment for industrial, recreational, environmental, domestic, or drinking purposes. In any embodiment, the treatment method described herein may be performed as part of a conventional water treatment process or may be used alone for water treatment.

[0065] In yet another aspect, the present technology provides a method for treating a liquid containing metal contaminants, comprising contacting the liquid with an adsorbent material and / or adsorbent material formulation as described herein in any embodiment to obtain a treated liquid, wherein the contacting removes the metal contaminants from the liquid. In any embodiment disclosed herein, the liquid may be water. In any embodiment disclosed herein, the metal contaminants may include, but are not limited to, lead, zinc, chromium, cadmium, copper, manganese, iron, or a mixture of two or more thereof. For example, in any embodiment disclosed herein, the metal contaminant may be lead. In another embodiment disclosed herein, the metal contaminant may be cadmium.

[0066] In any embodiment disclosed herein, the method can be a water treatment method. For example, in any embodiment disclosed herein, the method can be a water treatment method, including, but not limited to, portable water purification, water supply treatment, wastewater treatment, waterworks treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof. Additionally or alternatively, in some embodiments, the method can be combined with a conventional water treatment method, including portable water purification, water supply treatment, wastewater treatment, waterworks treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof.

[0067] In a further aspect, the present technology provides a method for treating water, comprising contacting the water with an adsorbent material and / or adsorbent material formulation as described herein in any embodiment, wherein the contacting removes metal contaminants from the water. In any embodiment disclosed herein, the metal contaminants may include, but are not limited to, lead, zinc, chromium, cadmium, copper, manganese, iron, or a mixture of two or more thereof. For example, in any embodiment disclosed herein, the metal contaminant may be lead. In another embodiment disclosed herein, the metal contaminant may be cadmium.

[0068] In any embodiment disclosed herein, the method can be a water treatment method. For example, in any embodiment disclosed herein, the method can be a water treatment method, including, but not limited to, portable water purification, water supply treatment, wastewater treatment, waterworks treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof. Additionally or alternatively, in some embodiments, the method can be combined with a conventional water treatment method, including portable water purification, water supply treatment, wastewater treatment, waterworks treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof.

[0069] In another aspect, the present technology provides a method for removing metal contaminants from water, as described herein in any embodiment, comprising contacting the water with an adsorbent material and / or adsorbent material formulation as described herein, wherein the contacting removes the metal contaminants from the water. In any embodiment disclosed herein, the metal contaminants may include, but are not limited to, lead, zinc, chromium, cadmium, copper, manganese, iron, or a mixture of two or more thereof. For example, in any embodiment disclosed herein, the metal contaminant may be lead. In another embodiment disclosed herein, the metal contaminant may be cadmium.

[0070] In any embodiment disclosed herein, the method can be a water treatment method. For example, in any embodiment disclosed herein, the method can be a water treatment method, including, but not limited to, portable water purification, water supply treatment, wastewater treatment, waterworks treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof. Additionally or alternatively, in some embodiments, the method can be combined with a conventional water treatment method, including portable water purification, water supply treatment, wastewater treatment, waterworks treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof.

[0071] The invention thus generally described will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the invention. [Example]

[0072] Example 1: Preparation of Silicate Compositions. Silicate compositions were prepared according to the manufacturing methods described herein in any embodiment. A microsphere precursor comprising a clay material was subjected to an in situ crystallization procedure to prepare silicate compositions according to conventional procedures. The resulting silicate composition was reduced to a particle size of 50 microns or less, filtered, and the solids formed into a porous silicate cake. The porous silicate cake was crushed and filtered through a 170 mesh screen. Particles corresponding to -170 mesh (1A) and +170 mesh (1B) were used to prepare a 10% solids slurry, which was spray-dried to obtain the final adsorbent material. Samples were analyzed, and the properties of the prepared silicate compositions are summarized in Table 1 below. HgPV provides the mercury pore volume in cc / g, and TSA provides the mercury pore volume in m 2 / g and MSA is m 2 / g provides the matrix surface area. [Table 1]

[0073] X-ray photoelectron spectroscopy was performed to determine the elemental composition of the surface of the silicate composition, as shown in the table below. [Table 2] As shown in the table above, the silicate composition exhibits a sodium (Na) surface concentration of 9.8%, calculated as atomic percent, while only 0.4% potassium (K) was observed on the surface of the silicate composition.

[0074] Example 2: Preparation of Adsorbent Material Blends. Adsorbent material blends containing weight ratios of titanosilicate (ATS) to silicate composition of 80:20 (Example 2A) and 50:50 (Example 2B), respectively, were prepared according to the methods described herein. A porous silicate cake was formed according to Example 1 and mixed in water at approximately 12% solids, resulting in a -170 mesh size fraction at 9-10% solids of the silicate composition. The resulting -170 mesh silicate slurry containing 9-10% solids was blended with an ATS slurry containing 8.7-10% solids. The blend was spray-dried to yield microspheres of the final adsorbent material.

[0075] Example 3: Electron microscopy images and X-ray powder diffraction (XRD) scans of adsorbent materials. The interconnected porous scaffolds for adsorbent materials containing only the silicate composition prepared in Example 1A (-170 mesh) and the 50:50 and 80:20 (ATS:silicate composition) blends prepared in Example 2 were observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). As shown in Figure 1A, a cut / mount / polished (CMP) cross-sectional SEM image of the adsorbent material of Example 1 showed that the crystallized Y-zeolite phase and interconnected porous scaffolds were readily observed. Figures 1B and 1C show CMP cross-sectional views of the 50:50 and 80:20 blends of Example 2, showing that the crystallized Y-zeolite and interconnected porous scaffolds are maintained throughout the blended materials. As shown in Figures 2A-2C, TEM images show the pores observed in the adsorbent materials of Examples 1 and 2, which contain crystallized Y-zeolite throughout the porous network and amorphous matrix phase.

[0076] XRD scans of the silicate composition according to Example 1A, the 80:20 blend of ATS / silicate composition according to Example 2A, and ATS alone were obtained. As shown in Figure 3, the XRD scan of the silicate composition (Example 1A) crystalline phase through the typical faujasite peak. The XRD scan of the 80:20 ATS / silicate composition blend (Example 2A) shows the presence of both amorphous and crystalline phases (Figure 3), and the XRD scan of ATS only shows the amorphous structure of the ATS material.

[0077] Example 4: Determination of lead exchange capacity of ATS and silicate compositions. The sorbent materials from Examples 1 and 2 were evaluated for lead exchange capacity. A comparative sample was treated with ATS only. A 0.20 g portion of the sorbent material from Examples 1 and 2 and the comparative ATS material were each stirred in 100 mL of a 1000 mg / L aqueous lead nitrate solution for 1 hour with stirring. The solutions containing the sorbent material or ATS were then filtered and analyzed for lead content by inductively coupled plasma optical emission spectroscopy (ICP-OES). The following table summarizes the analysis. [Table 3]

[0078] As shown in the table above, the adsorbent materials containing silicate compositions 1A, 2A, and 2B according to the present technology, respectively, exhibited higher lead (Pb) exchange capacities than the comparative ATS adsorbent. In particular, Examples 1A, 2A, and 2B exhibited Pb exchange percentages of 34.9%, 25.3%, and 29.9%, respectively. In contrast, ATS exhibited a Pb exchange percentage of 22.3%.

[0079] Example 5: Preparation of a granular sorbent blend. 210 grams of silicate product prepared according to Example 1 with a -80 mesh size was blended with 90 grams of a commercially available kaolin product (ASP® 602). The kaolin was prepared as highly dispersed kaolin particles in a high solids slurry form (60% solids) and then blended with the silicate product at a blend ratio of 70% silicate / 30% kaolin clay (w / w dry basis). This blend was spray dried in a laboratory spray dryer to provide a spray-dried product.

[0080] Granulation used a variable speed laboratory pin mixer and pins fitted with a 1 L capacity.

[0081] 300 grams of the spray-dried product was added to the container of a laboratory pin mixer, and the laboratory pin mixer was turned on. While mixing, a previously prepared 60% solids kaolin slurry was slowly added to the spray-dried product. Once a sufficient amount of kaolin slurry was added, granules formed in the mixing chamber. The mixer speed was adjusted during the granulation process to control granule size. The amount of slurry was recorded as 120 grams. After granules were formed, the resulting granular adsorbent blend was removed from the container. The moisture content was measured using a CEM microwave moisture meter, and the moisture content of the granular adsorbent blend was 17.0%. The granular adsorbent blend was screened using screens with different mesh sizes. The final granulated product was a 50% silicate / 50% kaolin clay (w / w on a dry basis), and screening provided granulated products with mesh sizes of 6, 10, 20, 40, and 80.

[0082] Example 6: Determination of Cadmium Exchange Capacity of ATS and Silicate Sorbents. Note: The sorbent used for cadmium exchange capacity was a 100% silicate material in spray-dried form with a particle size of -80 mesh. To determine cadmium exchange capacity, the test was repeated twice on comparative samples of ATS and silicate sorbents (Tests A and B). A 0.20 g portion of the sorbent material from Example 1 and the comparative ATS material were each stirred in 100 mL of a 1000 mg / L aqueous cadmium nitrate solution for 1 hour with stirring. The solutions containing the silicate sorbent or ATS were then filtered and analyzed for cadmium content by inductively coupled plasma optical emission spectroscopy (ICP-OES). The following table summarizes the analysis. [Table 4]

[0083] As shown in the table above, the silicate adsorbent material of the present invention exhibited a higher cadmium (Cd) exchange capacity than the comparative ATS adsorbent. In particular, the silicate adsorbent exhibited a Cd exchange percentage of 17.83-18.12%, with an average of 17.98% for two replicate tests. In contrast, the ATS Comp exhibited a Cd exchange percentage of 9.53-9.67%, with an average of 9.60% for two replicate tests.

[0084] Thus, the adsorbent material of the present technology exhibits high porosity, high surface area, and a unique interconnected pore network (i.e., a porous scaffold), and improved removal of lead and cadmium from water.

[0085] Item 1. An adsorbent material comprising a silicate composition, wherein the silicate composition comprises about 5% by weight to about 95% by weight of a crystalline phase; The silicate composition comprises an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having diameters of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having diameters of about 20 to 600 Å, an adsorbent material. Item 2. The adsorption material of Item 1, wherein the crystalline phase comprises a zeolite. Item 3. The adsorbent material of items 1 or 2, wherein the crystalline phase comprises a zeolite selected from zeolite X, Y-zeolite, ZSM-5, beta zeolite, ZSM-11, ZSM-14, ZSM-17, ZSM-18, ZSM-20, ZSM-31, ZSM-34, ZSM-41, ZSM-46, mordenite, chabazite, or a mixture of two or more thereof. Item 4. The adsorption material according to any one of Items 1 to 3, wherein the crystalline phase comprises Y-zeolite. Item 5. The adsorption material according to any one of Items 1 to 4, wherein the silicate composition comprises about 20% to about 60% by weight of a crystalline phase. Item 6. The adsorption material according to any one of Items 1 to 5, wherein the silicate composition further comprises about 5 wt. % to about 95 wt. % of a non-zeolitic matrix phase, based on the total weight of the silicate composition. Item 7. The adsorption material of any one of items 1 to 6, wherein the interconnected porous scaffold comprises pores that are microporous, mesoporous, macroporous, or a mixture thereof. Item 8. The adsorption material according to any one of items 1 to 7, wherein the interconnected porous scaffold has a mercury pore volume of about 0.01 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å. Item 9. The adsorption material of item 8, wherein the mercury pore volume is about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å. Item 10. Silicate composition is about 200m 2 / g~about 500m 2 Item 10. The adsorption material according to any one of items 1 to 9, having a surface area of ​​1 / g. Item 11. The adsorbent material of any one of items 1 to 10, wherein the silicate composition has a surface composition comprising about 5% to about 20% sodium, calculated as atomic percent. Item 12. The adsorbent material of item 11, wherein the surface composition comprises about 7% to about 12% sodium, calculated as atomic percent. Item 13. The adsorbent material of item 12, wherein the surface composition comprises about 9% to about 11% sodium, calculated as atomic percent. Item 14. The adsorption material according to any one of Items 1 to 13, wherein the silicate composition has a particle size of about 40 microns to about 150 microns. Item 15. The adsorption material according to any one of Items 1 to 14, wherein the silicate composition has an average particle size distribution of about 10 microns to about 60 microns. Item 16. The adsorbent material of item 15, wherein the average particle size distribution is about 45 microns to about 55 microns. Item 17. The adsorbent material of paragraphs 15 or 16, wherein the mean particle size distribution is measured by a Microtrac S3500 particle size analyzer. Item 18. The adsorption material of any one of items 1 to 17, wherein the crystalline phase comprising Y-zeolite is a clay zeolite crystallization process residue. Item 19. The adsorbent material of Item 18, wherein the clay is calcined clay. Item 20. The adsorbent material of item 18 or 19, wherein the clay comprises metakaolin, kaolin clay, or a mixture of any two or more thereof. Item 21. The adsorption material according to any one of Items 18 to 20, wherein the clay comprises about 30% by weight to about 60% by weight of metakaolin and about 40% by weight to about 70% by weight of kaolin clay that has substantially undergone its characteristic exotherm. Item 22. The silicate composition, a crystalline phase comprising about 20% by weight to about 60% by weight of Y-zeolite; about 5 wt. % to about 95 wt. % of a non-zeolitic matrix phase; an interconnected porous scaffold having a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å; The silicate composition contains about 5% to about 20% sodium, calculated as atomic percent, and about 200m 2 / g~about 500m 2 Item 22. The adsorption material according to any one of items 1 to 21, comprising a surface composition having a surface area of ​​0.15 to 0.25g. Item 23. The adsorbent material of any one of items 1 to 22, further comprising an additional adsorbent. Item 24. The adsorbent material of item 23, wherein the additional adsorbent comprises a titanosilicate, a non-zeolitic molecular sieve, activated carbon, porous glass, clay, a metal aluminate, a metal phosphate, a layered silicate, or a combination of two or more thereof. Item 25. The adsorbent material of items 23 or 24, wherein the additional adsorbent comprises a titanosilicate. Item 26. The adsorbent material of any one of items 23 to 25, wherein the adsorbent material comprises a weight ratio of silicate composition to additional adsorbent of about 99:1 to about 1:99. Item 27. The adsorbent material of item 26, wherein the weight ratio of the silicate composition to the additional adsorbent is from about 50:50 to about 20:80. Item 28. The adsorption material according to any one of Items 1 to 22, further comprising a binder. Item 29. The adsorbent material of item 28, wherein the binder comprises alumina, silicate, and clay minerals, or a combination of two or more. Item 30. The adsorbent material of item 28, wherein the binder comprises kaolin clay. Item 31. The adsorption material according to any one of Items 28 to 30, further comprising a pore-forming agent. Item 32. The adsorbent material of item 31, wherein the pore-forming agent comprises an organic polymer, corn starch, a starch derivative, a lignosulfonate, a polyacrylamide, a polyacrylic acid, a polyvinyl alcohol, cellulose, a cellulose derivative, or a combination of two or more thereof. Item 33. The adsorbent material of any one of items 28 to 33, wherein the binder has a weight ratio of silicate composition to binder of about 90:10 to about 50:50. Item 34. The adsorbent material of item 33, wherein the binder has a weight ratio of silicate composition to binder of about 80:20 to about 60:40. Item 35. The adsorption material according to any one of Items 28 to 34, wherein the adsorption material is a granular adsorption material. Item 36. The adsorption material of Item 35, wherein the granular adsorption material has a mesh size of about 10 mesh to about 80 mesh. Item 37. An adsorbent material formulation comprising a silicate composition and a titanosilicate, wherein the silicate composition is comprising about 5% by weight to about 95% by weight of a crystalline phase; An adsorbent material formulation comprising an interconnected porous scaffold, wherein the silicate composition has a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å. Item 38. The adsorbent material formulation of item 37, wherein the crystalline phase comprises a zeolite. Item 39. The adhesive formulation of paragraphs 37 or 38, wherein the crystalline phase comprises a zeolite selected from zeolite X, Y-zeolite, ZSM-5, beta zeolite, ZSM-11, ZSM-14, ZSM-17, ZSM-18, ZSM-20, ZSM-31, ZSM-34, ZSM-41, ZSM-46, mordenite, chabazite, or a mixture of two or more thereof. Item 40. The adsorbent material formulation of any one of items 37 to 39, wherein the crystalline phase comprises Y-zeolite. Item 41. The adsorbent material formulation of any one of items 37 to 40, wherein the silicate composition formulation comprises about 20% to about 60% by weight of a crystalline phase. Item 42. The adsorbent material formulation of any one of items 37 to 41, wherein the silicate composition formulation further comprises about 5 wt.% to about 95 wt.% of a non-zeolitic matrix phase, based on the total weight of the silicate composition. Item 43. The adsorbent material formulation of any one of items 37 to 42, wherein the interconnected porous scaffold comprises pores that are microporous, mesoporous, macroporous, or a mixture thereof. Item 44. The silicate composition is about 200 m 2 / g~about 500m 2 44. The adsorbent material formulation of any one of paragraphs 37 to 43, having a surface area of ​​1 / g. Item 45. The adsorbent material formulation of any one of items 37 to 44, wherein the silicate composition has a surface composition comprising about 5% to about 20% sodium, calculated as atomic percent. Item 46. The adsorbent material formulation of any one of items 37 to 45, wherein the silicate composition has an average particle size distribution of about 10 microns to about 60 microns. Item 47. The adsorbent material formulation of any one of paragraphs 37 to 46, wherein the crystalline phase comprising Y-zeolite is a clay zeolite crystallization process residue. Item 48. The silicate composition, a crystalline phase comprising about 20% by weight to about 60% by weight of Y-zeolite; about 5 wt. % to about 95 wt. % of a non-zeolitic matrix phase; an interconnected porous scaffold having a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å; The silicate composition contains about 5% to about 20% sodium, calculated as atomic percent, and about 200m 2 / g~about 500m 2 48. The adsorbent material formulation of any one of claims 37 to 47, comprising a surface composition having a surface area of ​​1 / g. Item 49. The adsorbent material formulation of any one of items 37-48, wherein the adsorbent material comprises a weight ratio of silicate composition to titanosilicate of about 99:1 to about 1:99. Item 50. A silicate composition and a binder, The silicate composition comprises: comprising about 5% by weight to about 95% by weight of a crystalline phase; the silicate composition comprises an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å; An adsorbent material formulation, wherein the adsorbent material formulation is a granular adsorbent material formulation. Item 51. The adsorbent material formulation of item 50, wherein the crystalline phase comprises a zeolite. Item 52. The adsorbent material formulation of paragraphs 50 or 51, wherein the crystalline phase comprises a zeolite selected from zeolite X, Y-zeolite, ZSM-5, beta zeolite, ZSM-11, ZSM-14, ZSM-17, ZSM-18, ZSM-20, ZSM-31, ZSM-34, ZSM-41, ZSM-46, mordenite, chabazite, or a mixture of two or more thereof. Item 53. The adsorbent material formulation of any one of items 50 to 52, wherein the crystalline phase comprises Y-zeolite. Item 54. The adsorbent material formulation of any one of items 50 to 53, wherein the silicate composition comprises about 20% to about 60% by weight of a crystalline phase. Item 55. The adsorbent material formulation of any one of items 50 to 54, wherein the silicate composition formulation further comprises about 5 wt.% to about 95 wt.% of a non-zeolitic matrix phase, based on the total weight of the silicate composition. Item 56. The adsorbent material formulation of any one of items 50 to 55, wherein the interconnected porous scaffold comprises pores that are microporous, mesoporous, macroporous, or a mixture thereof. Item 57. The silicate composition is about 200 m 2 / g~about 500m 2 57. The adsorbent material formulation of any one of paragraphs 50 to 56, having a surface area of ​​1 / g. Item 58. The adsorbent material formulation of any one of items 50 to 57, wherein the silicate composition has a surface composition comprising about 5% to about 20% sodium, calculated as atomic percent. Item 59. The adsorbent material formulation of any one of items 50 to 58, wherein the silicate composition has an average particle size distribution of about 10 microns to about 60 microns. Item 60. The adsorbent material formulation of any one of paragraphs 50 to 59, wherein the crystalline phase comprising Y-zeolite is a clay zeolite crystallization process residue. Item 61. The silicate composition, a crystalline phase comprising about 20% by weight to about 60% by weight of Y-zeolite; about 5 wt. % to about 95 wt. % of a non-zeolitic matrix phase; an interconnected porous scaffold having a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å; The silicate composition contains about 5% to about 20% sodium, calculated as atomic percent, and about 200m 2 / g~about 500m 2 61. The adsorbent material formulation of any one of paragraphs 50 to 60, comprising: a surface composition having a surface area of ​​0.15 to 0.25 g; Item 62. The adsorbent material of any one of items 50 to 61, wherein the binder comprises alumina, silicate, and clay minerals, or a combination of two or more thereof. Item 63. The adsorbent material of item 62, wherein the binder comprises kaolin clay. Item 64. The adsorption material according to any one of Items 50 to 63, further comprising a pore-forming agent. Clause 65. The adsorbent material of clause 64, wherein the pore-forming agent comprises an organic polymer, corn starch, a starch derivative, a lignosulfonate, a polyacrylamide, a polyacrylic acid, a polyvinyl alcohol, cellulose, a cellulose derivative, or a combination of two or more thereof. Item 66. The adsorbent material of any one of items 50 to 65, wherein the binder has a weight ratio of silicate composition to binder of about 90:10 to about 50:50. Item 67. The adsorbent material of item 66, wherein the binder has a weight ratio of silicate composition to binder of about 80:20 to about 60:40. Item 68. The adsorption material according to any one of Items 50 to 67, wherein the granular adsorption material has a mesh size of about 10 mesh to about 80 mesh. Item 69. The adsorbent material of any one of items 1 to 36 or the adsorbent material formulation of any one of items 37 to 68, wherein the adsorbent material has a percent increase in lead exchange capacity in water of about 15% to about 150% compared to titanosilicate-based adsorbent materials. Item 70. The adsorbent material according to any one of items 1 to 36 or the adsorbent material formulation according to any one of items 37 to 68, wherein the adsorbent material has an increased cadmium exchange capacity in water of about 50% to about 500% compared to a titanosilicate-based adsorbent material. Item 71. A method for treating a liquid containing metal contaminants, comprising: contacting a liquid with the adsorbent material according to any one of paragraphs 1 to 36 and / or the adsorbent material formulation according to any one of paragraphs 37 to 68 to obtain a treated liquid; The method wherein the treated liquid contains a lower concentration of metal contaminants compared to the liquid. Item 72. The method of item 72, wherein the liquid is water. Item 73. The method of paragraphs 71 or 72, wherein the metal contaminants include lead, zinc, chromium, cadmium, copper, manganese, iron, or a mixture of any two or more thereof. Item 74. The method according to any one of Items 71 to 73, wherein the metal contaminant is lead. Item 75. The method according to any one of Items 71 to 73, wherein the metal contaminant is cadmium. Clause 76. The method of any one of clauses 71 to 75, wherein the method is a water treatment method selected from portable water purification, water supply treatment, wastewater treatment, water supply treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof. Clause 77. The method of any one of clauses 71-75, wherein the method is combined with a conventional water treatment method, including portable water purification, water supply treatment, wastewater treatment, water supply treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof. Item 78. A method for treating water, comprising: Item 36. The adsorbent material according to any one of items 1 to 36 and / or the adsorbent material formulation according to any one of items 37 to 68, comprising contacting water with The method wherein the contacting removes metal contaminants from the water. Item 79. The method of item 78, wherein the metal contaminants include lead, zinc, chromium, cadmium, copper, manganese, iron, or a mixture of any two or more thereof. Item 80. The method of paragraphs 78 or 79, wherein the metal contaminant is lead. Item 81. The method of items 78 or 79, wherein the metal contaminant is cadmium. Clause 82. The method of any one of clauses 78 to 81, wherein the method is a water treatment method selected from portable water purification, water supply treatment, wastewater treatment, water supply treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof. Clause 83. The method of any one of clauses 78-81, wherein the method is combined with a conventional water treatment method, including portable water purification, water supply treatment, wastewater treatment, water supply treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof. Item 84. A method for removing metal contaminants from water, comprising: contacting water with an adsorbent material comprising a silicate composition; contacting the water removes metal contaminants from the water; The silicate composition comprises: comprising about 5% by weight to about 95% by weight of a crystalline phase; The method, wherein the silicate composition comprises an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having diameters of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having diameters of about 20 to 600 Å. Item 85. The method of item 84, wherein the crystalline phase comprises Y-zeolite. Item 86. The method of any one of items 84 or 85, wherein the silicate composition comprises about 20% to about 60% by weight of a crystalline phase. Item 87. The method of any one of Items 84 to 86, wherein the silicate composition further comprises about 5 wt% to about 95 wt% of an amorphous matrix phase, based on the total weight of the silicate composition. Clause 88. The method of any one of clauses 84 to 87, wherein the interconnected porous scaffold comprises pores that are microporous, mesoporous, macroporous, or a mixture thereof. Clause 89. The method of any one of clauses 84 to 88, wherein the interconnected porous scaffold has a mercury pore volume of about 0.01 cc / g to about 0.25 cc / g for pores having diameters of about 200 to 10,000 Å. Item 90. The silicate composition is about 200 m 2 / g~about 500m 2 Item 89. The method according to any one of items 84 to 89, having a surface area of ​​ / g. Item 91. The method of any one of items 84 to 90, wherein the silicate composition has a surface composition comprising about 5% to about 20% sodium, calculated as atomic percent. Item 92. The method according to any one of Items 84 to 91, wherein the silicate composition has an average particle size of about 40 microns to about 150 microns. Item 93. The method of any one of Items 84 to 92, wherein the silicate composition has an average particle size distribution of about 10 microns to about 60 microns. Item 94. The silicate composition, a crystalline phase comprising about 20% by weight to about 60% by weight of Y-zeolite; about 5 wt% to about 95 wt% of an amorphous matrix phase; an interconnected porous scaffold having a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å; The silicate composition contains about 5% to about 20% sodium, calculated as atomic percent, and about 200m 2 / g~about 500m 2 Item 94. The method according to any one of items 84 to 93, comprising a surface composition having a surface area of ​​0.1g / g. Item 95. The method of any one of items 84-94, further comprising an additional adsorbent. Clause 96. The method of clause 95, wherein the additional adsorbent comprises a titanosilicate, a non-zeolitic molecular sieve, activated carbon, porous glass, clay, a metal aluminate, a metal phosphate, or a combination of two or more thereof. Item 97. The method of items 95 or 96, wherein the additional adsorbent comprises a titanosilicate. Item 98. The method of any one of items 95-97, wherein the adsorbent material comprises a weight ratio of silicate composition to additional adsorbent of about 99:1 to about 1:99. Item 99. The method of item 98, wherein the weight ratio of the silicate composition to the additional adsorbent is from about 50:50 to about 20:80. Item 100. The method of any one of items 84 to 94, wherein the adsorbent material further comprises a binder. Item 101. The method of item 100, wherein the binder comprises alumina, silicates, and clay minerals, or a combination of two or more. Item 102. The method of item 100, wherein the binder comprises kaolin clay. Item 103. The method of any one of items 100 to 102, wherein the adsorbent material further comprises a pore-forming agent. Clause 104. The method of clause 103, wherein the pore-forming agent comprises an organic polymer, corn starch, a starch derivative, a lignosulfonate, a polyacrylamide, a polyacrylic acid, a polyvinyl alcohol, a cellulose, a cellulose derivative, or a combination of two or more thereof. Item 105. The method of any one of items 100 to 104, wherein the binder has a weight ratio of silicate composition to binder of about 90:10 to about 50:50. Item 106. The method of item 105, wherein the binder has a weight ratio of silicate composition to binder of about 80:20 to about 60:40. Item 107. The method of any one of Items 100 to 106, wherein the adsorbent material is a granular adsorbent material. Item 108. The method of item 107, wherein the granular adsorptive material has a mesh size of about 10 mesh to about 80 mesh. Clause 109. The method of any one of clauses 84-108, wherein the method is a water treatment method selected from portable water purification, water supply treatment, wastewater treatment, water supply treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof. Clause 110. The method of any one of clauses 84-108, wherein the method is combined with a conventional water treatment method, including portable water purification, water supply treatment, wastewater treatment, water supply treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof.

[0086] While certain embodiments have been shown and described, it is to be understood that changes and modifications can be made therein by those skilled in the art without departing from the technology in its broader aspects, as defined in the following claims.

[0087] The illustrative embodiments described herein may suitably be practiced in the absence of any element or elements, or any limitation or limitations, not specifically disclosed herein. Thus, for example, terms such as "comprising," "including," and "containing" should be read expansively and not limitingly. Furthermore, the terms and expressions used herein are used as terms of description rather than limitation, and there is no intention to use such terms and expressions to exclude any equivalents of the shown and described functionality or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Furthermore, the phrase "consisting essentially of" will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of" excludes any elements not specified.

[0088] The present disclosure should not be limited with respect to the specific embodiments described in this application. It will be apparent to those skilled in the art that many modifications and variations can be made without departing from its spirit and scope. Functionally equivalent methods and compositions within the scope of the present disclosure, in addition to those recited herein, will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that the present disclosure is not limited to particular methods, reagents, compounds, or compositions, which may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0089] In addition, when features or aspects of the disclosure are described in terms of a Markush group, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual element or subgroup of elements of the Markush group.

[0090] As will be understood by those skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein encompass any and all possible subranges and combinations of these subranges. The listed ranges are fully descriptive, and it is easily recognizable that the same range can be divided into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be easily divided into a lower third, a middle third, and an upper third. Also, as will be understood by those skilled in the art, all terms such as "maximum," "at least," "greater than," "less than," etc., are inclusive of the recited numbers and refer to ranges that can be subsequently divided into subranges, as discussed above. Finally, as will be understood by those skilled in the art, a range includes each individual element.

[0091] All publications, patent applications, issued patents, and other documents referred to herein are incorporated by reference herein as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in the text incorporated by reference are excluded to the extent they conflict with definitions in the present disclosure.

[0092] Other embodiments are set forth in the following claims. Some embodiments are given below. Item 1 1. An adsorbent material comprising a silicate composition, the silicate composition comprising about 5% to about 95% by weight of a crystalline phase; The silicate composition is an adsorbent material comprising an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å. Section 2 Item 1. The adsorbent material of item 1, wherein the crystalline phase comprises a zeolite comprising zeolite X, Y-zeolite, ZSM-5, beta zeolite, ZSM-11, ZSM-14, ZSM-17, ZSM-18, ZSM-20, ZSM-31, ZSM-34, ZSM-41, ZSM-46, mordenite, chabazite, or a mixture of two or more thereof. Section 3 Item 3. The adsorption material according to item 1 or 2, wherein the silicate composition contains about 20% by weight to about 60% by weight of the crystalline phase. Section 4 Item 4. The adsorption material according to any one of items 1 to 3, wherein the silicate composition further comprises about 5 wt% to about 95 wt% of a non-zeolitic matrix phase, based on the total weight of the silicate composition. Section 5 Item 5. The adsorption material according to any one of items 1 to 4, wherein the interconnected porous scaffold comprises pores that are microporous, mesoporous, macroporous, or a mixture thereof. Section 6 Item 6. The adsorption material according to any one of items 1 to 5, wherein the interconnected porous scaffold has a mercury pore volume of about 0.01 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å. Section 7 The silicate composition is about 200 ml 2 / g~about 500m 2 Item 7. The adsorption material according to any one of Items 1 to 6, having a surface area of ​​1 / g. Section 8 Item 8. The adsorbent material of any one of items 1 to 7, wherein the silicate composition has a surface composition comprising about 5% to about 20% sodium, calculated as atomic percent. Section 9 Item 9. The adsorption material according to any one of items 1 to 8, wherein the silicate composition has a particle size of about 40 microns to about 150 microns. Item 10 Item 10. The adsorption material according to any one of items 1 to 9, wherein the crystalline phase comprising Y-zeolite is a clay zeolite crystallization process residue. Section 11 Item 11. The adsorbent material of item 10, wherein the clay comprises metakaolin, kaolin clay, or a mixture of any two or more thereof. Item 12 Item 10 or 11, wherein the clay comprises about 30% by weight to about 60% by weight of metakaolin and about 40% by weight to about 70% by weight of kaolin clay that has substantially undergone its characteristic exotherm. Section 13 The silicate composition the crystalline phase comprising about 20% by weight to about 60% by weight of Y-zeolite; about 5% to about 95% by weight of the non-zeolitic matrix phase; the interconnected porous scaffold having a total mercury pore volume of about 0.10 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å; The silicate composition comprises about 5% to about 20% sodium, calculated as atomic percent, and about 200m 2 / g~about 500m 2 Item 13. The adsorption material according to any one of items 1 to 12, comprising a surface composition having a surface area of ​​0.15 to 0.25g. Item 14 Item 14. The adsorbent material according to any one of items 1 to 13, further comprising an additional adsorbent comprising a titanosilicate, a non-zeolite molecular sieve, activated carbon, porous glass, clay, a metal aluminate, a metal phosphate, a layered silicate, or a combination of two or more thereof. Item 15 Item 15. The adsorbent material of item 14, wherein the additional adsorbent comprises a titanosilicate. Item 16 Item 16. The adsorbent material of item 14 or 15, wherein the adsorbent material comprises a weight ratio of the silicate composition to the additional adsorbent of about 99:1 to about 1:99. Item 17 Item 14. The adsorbent material of any one of items 1 to 13, further comprising a binder comprising alumina, silicate, and clay minerals, or a combination of two or more thereof. Section 18 Item 18. The adsorbent material of item 17, wherein the binder comprises kaolin clay. Section 19 Item 19. The adsorbent material of item 17 or 18, further comprising a pore-forming agent comprising an organic polymer, corn starch, a starch derivative, a lignosulfonate, a polyacrylamide, a polyacrylic acid, a polyvinyl alcohol, a cellulose, a cellulose derivative, or a combination of two or more thereof. Section 20 20. The adsorptive material of any one of items 17 to 19, wherein the binder has a weight ratio of the silicate composition to the binder of about 90:10 to about 50:50. Section 21 Item 21. The adsorption material according to any one of Items 17 to 20, wherein the adsorption material is a granular adsorption material. Section 22 Item 22. The adsorptive material according to Item 21, wherein the granular adsorptive material has a mesh size of about 10 mesh to about 80 mesh. Section 23 silicate compositions and titanosilicates, The silicate composition comprising about 5% by weight to about 95% by weight of a crystalline phase; 1. An adsorbent material formulation, wherein the silicate composition comprises an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å. Section 24 1. An adsorbent material formulation comprising a silicate composition and a binder, The silicate composition comprising about 5% by weight to about 95% by weight of a crystalline phase; the silicate composition comprises an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å; An adsorbent material formulation, wherein said adsorbent material formulation is a granular adsorbent material formulation. Section 25 Item 25. The adsorbent material of item 24, wherein the binder comprises alumina, silicate, and clay minerals, or a combination of two or more. Section 26 26. The adsorptive material of claim 25, wherein the binder comprises kaolin clay. Section 27 Item 27. The adsorbent material of any one of items 24 to 26, further comprising a pore-forming agent comprising an organic polymer, corn starch, a starch derivative, a lignosulfonate, a polyacrylamide, a polyacrylic acid, a polyvinyl alcohol, a cellulose, a cellulose derivative, or a combination of two or more thereof. Section 28 Item 28. The adsorptive material according to any one of Items 24 to 27, wherein the granular adsorptive material has a mesh size of about 10 mesh to about 80 mesh. Section 29 The adsorbent material of any one of paragraphs 1 to 22 or the adsorbent material formulation of any one of paragraphs 23 to 28, wherein the adsorbent material has an increased lead exchange capacity in water of about 15% to about 150% compared to titanosilicate-based adsorbent materials. Section 30 The adsorbent material according to any one of paragraphs 1 to 22 or the adsorbent material formulation according to any one of paragraphs 23 to 28, wherein the adsorbent material has an increased cadmium exchange capacity in water of about 50% to about 500% compared to a titanosilicate-based adsorbent material. Section 31 1. A method for treating a liquid containing metal contaminants, comprising: contacting the liquid with the adsorbent material according to any one of claims 1 to 22 and / or the adsorbent material formulation according to any one of claims 23 to 28 to obtain a treated liquid; The method wherein the treated liquid contains a lower concentration of metal contaminants compared to the liquid. Section 32 1. A method for treating water, comprising: Contacting the water with the adsorbent material according to any one of items 1 to 22 and / or the adsorbent material blend according to any one of items 23 to 28, The method, wherein said contacting removes metal contaminants from said water. Item 33 1. A method for removing metal contaminants from water, comprising: contacting the water with an adsorbent material comprising a silicate composition; contacting the water removes the metal contaminants from the water; The silicate composition comprising about 5% by weight to about 95% by weight of a crystalline phase; The method of claim 1, wherein the silicate composition comprises an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å. Section 34 34. The method of claim 33, wherein the adsorbent material further comprises an additional adsorbent comprising titanosilicate, non-zeolitic molecular sieve, activated carbon, porous glass, clay, metal aluminate, metal phosphate, or a combination of two or more thereof. Section 35 35. The method of claim 34, wherein the additional adsorbent comprises a titanosilicate. Section 36 35. The method of claim 34, wherein the adsorbent material further comprises a binder comprising alumina, silicates, and clay minerals, or a combination of two or more. Section 37 37. The method of claim 36, wherein the binder comprises kaolin clay. Section 38 Item 38. The method according to any one of items 31 to 37, wherein the metal contaminants include lead, zinc, chromium, cadmium, copper, manganese, iron, or a mixture of any two or more thereof. Section 39 Item 39. The method of any one of items 31 to 38, wherein the method is a water treatment method selected from portable water purification, water supply treatment, wastewater treatment, waterworks treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof. Section 40 40. The method of any one of paragraphs 31 to 39, wherein the method is combined with a conventional water treatment method, including portable water purification, water supply treatment, wastewater treatment, water supply treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof.

Claims

1. An adsorbent material for removing Pb and / or Cd from water, the adsorbent material comprising a silicate composition, the silicate composition comprising a crystalline phase; the silicate composition comprises an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å, a total mercury pore volume of about 0.01 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å, and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å; The silicate composition comprises, based on the total weight of the silicate composition: the crystalline phase comprising about 20% to about 60% by weight of Y-zeolite; about 40% to about 80% by weight of a non-zeolitic matrix phase Including, the silicate composition has a surface composition comprising about 5% to about 20% sodium, calculated as atomic percent, and a surface area of ​​about 200 m 2 / g to about 500 m 2 / g; The adsorbent material, wherein the composition further comprises an adsorbent comprising a titanosilicate.

2. The adsorptive material of claim 1 , wherein the interconnected porous scaffold comprises pores that are microporous, mesoporous, macroporous, or a mixture thereof.

3. 10. The adsorptive material of claim 1, wherein said silicate composition has a particle size of from about 40 microns to about 150 microns.

4. 10. The adsorptive material of claim 1, wherein said crystalline phase comprising Y-zeolite is a clay zeolite crystallization process residue.

5. 5. The adsorptive material of claim 4, wherein the clay comprises metakaolin, kaolin clay, or a mixture of any two or more thereof.

6. 6. The adsorptive material of claim 5, wherein the clay comprises about 30% to about 60% by weight metakaolin and about 40% to about 70% by weight kaolin clay that has substantially undergone its characteristic exotherm.

7. The adsorbent material of claim 1, further comprising an additional adsorbent comprising a non-zeolitic molecular sieve, activated carbon, porous glass, clay, metal aluminate, metal phosphate, layered silicate, or a combination of two or more thereof.

8. 8. The adsorbent material of claim 7, wherein said adsorbent material comprises a weight ratio of said silicate composition to said additional adsorbent of from about 99:1 to about 1:

99.

9. 10. The adsorptive material of claim 1, further comprising a binder comprising alumina, silicates, and clay minerals, or a combination of two or more.

10. 10. The adsorptive material of claim 9, wherein the binder comprises kaolin clay.

11. 10. The adsorptive material of claim 9, further comprising a pore former comprising an organic polymer, corn starch, a starch derivative, a lignosulfonate, a polyacrylamide, a polyacrylic acid, a polyvinyl alcohol, a cellulose, a cellulose derivative, or a combination of two or more.

12. 10. The adsorptive material of claim 9, wherein the binder has a weight ratio of said silicate composition to said binder of about 90:10 to about 50:

50.

13. The adsorptive material of claim 9 , wherein the adsorptive material is a granular adsorptive material.

14. 14. The adsorptive material of claim 13, wherein said granular adsorptive material has a mesh size of from about 10 mesh to about 80 mesh.

15. A method for treating water containing Pb and / or Cd metal contaminants, comprising: contacting the water with the adsorbent material of claim 1 to obtain treated water; The method wherein the treated water contains lower concentrations of Pb and / or Cd metal contaminants compared to the water.

16. A method for treating water containing Pb and / or Cd contaminants, comprising: contacting the water with the adsorbent material of claim 1; The method, wherein said contacting removes Pb and / or Cd metal contaminants from said water.

17. A method for removing Pb and / or Cd metal contaminants from water containing Pb and / or Cd contaminants, comprising: contacting the water with an adsorbent material comprising a silicate composition; contacting the water removes the metal contaminants from the water; The silicate composition Contains a crystalline phase, the silicate composition comprises an interconnected porous scaffold having a total mercury (Hg) pore volume of about 0.005 cc / g to about 0.25 cc / g for pores having a diameter of about 20 to 10,000 Å, a total mercury pore volume of about 0.01 cc / g to about 0.25 cc / g for pores having a diameter of about 200 to 10,000 Å, and a total nitrogen (N) pore volume of about 0.02 cc / g to about 0.10 cc / g for pores having a diameter of about 20 to 600 Å; The silicate composition comprises, based on the total weight of the silicate composition: the crystalline phase comprising about 20% to about 60% by weight of Y-zeolite; about 40% to about 80% by weight of a non-zeolitic matrix phase Including, the silicate composition has a surface composition comprising about 5% to about 20% sodium, calculated as atomic percent, and a surface area of ​​about 200 m 2 / g to about 500 m 2 / g; The method, wherein the adsorbent material further comprises an adsorbent comprising a titanosilicate.

18. 20. The method of claim 17, wherein the adsorbent material further comprises a binder comprising alumina, silicates, and clay minerals, or a combination of two or more.

19. 20. The method of claim 18, wherein the binder comprises kaolin clay.

20. 20. The method of claim 17, wherein the method is a water treatment method selected from portable water purification, water supply treatment, wastewater treatment, water supply treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof.

21. 18. The method of claim 17, wherein the method is combined with a conventional water treatment method, including portable water purification, water supply treatment, wastewater treatment, water supply treatment, irrigation water treatment, water filtration, drinking water production, recreational water treatment, process water treatment, or a combination thereof.

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