WO2019023002A2

WO2019023002A2 - Porous composite blocks including guanylated media

Info

Publication number: WO2019023002A2
Application number: PCT/US2018/042492
Authority: WO
Inventors: Andrew J. HATCH; Olaf C. Moberg; Manjiri T. Kshirsagar; George W. Griesgraber
Original assignee: 3M Innovative Properties Company
Priority date: 2017-07-24
Filing date: 2018-07-17
Publication date: 2019-01-31
Also published as: BR112020001525A2; CN110997102A; WO2019023002A3

Abstract

The present invention relates to porous composite blocks including guanylated media particles for water filtration. A porous composite block includes sorbent media particles and a polymeric binder that bonds the sorbent media particles together. The sorbent media particles include guanylated media particles.

Description

POROUS COMPOSITE BLOCKS INCLUDING GUANYLATED MEDIA

BACKGROUND

[0001] Clean drinking water is one of the basic needs for all humans. Yet, due to numerous reasons, in many places in the world there is not an assured supply of clean drinking due to factors such as intermittent electricity cuts, rapid urbanization leading to limited water supply, and varying quality of water. Bacteria occur naturally in most aquatic systems and can cause problems in industrial and municipal applications using water such as cooling towers, heat exchangers, potable and wastewater applications, oil and gas exploration, and hydraulic fracturing operations.

[0002] Porous composite blocks including sorbent material are useful as filtration media in the treatment of liquid feed streams such as in water treatment applications. For example, one type of porous composite block is a carbon block filter, which includes activated carbon particles bound together by a polymeric binder material. However, current porous composite blocks have limited ability to eliminate bacteria during filtration of water.

SUMMARY OF THE INVENTION

[0003] In various embodiments, the present invention provides a porous composite block. The porous composite block includes sorbent media particles that include guanylated media particles. The porous composite block also includes a polymeric binder that bonds the sorbent media particles together.

[0004] In various embodiments, the present invention provides a porous composite block including sorbent media particles. The sorbent media particles include guanylated siliceous media particles having a particle size of about 10 microns to about 50 microns and that are about 10 wt% to about 65 wt% of the porous composite block. The guanylated siliceous media particles include one or more guanidine-functionalized silicon atoms having the structure:

The sorbent media particles also include activated carbon particles having a particle size of about 20 microns to about 200 microns and that are about 10 wt% to about 50 wt% of the porous composite block. The porous composite block also includes a non-fibrous polymeric binder that bonds the sorbent media particles together and that is about 35 wt% to about 65 wt% of the porous composite block. The guanylated siliceous media particles and the activated carbon media particles are homogeneously distributed in the porous composite block.

[0005] In various embodiments, the present invention provides a water filter including the porous composite block.

[0006] In various embodiments, the present invention provides a method of using the porous composite block. The method includes passing water through the porous composite block to provide water having enhanced purity.

[0007] In various embodiments, the present invention provides a method of making the composite block. The method includes dispersing the guanylated media particles (e.g., in binder particles and optionally with secondary sorbent particles) to form a dispersed mixture including the guanylated media particles. The method also includes sintering the dispersed mixture to form the porous composite block.

[0008] In various embodiments, the porous composite block of the present invention and methods of using the same have certain advantages as compared to other porous composite blocks, at least some of which are unexpected. For example, in some embodiments, the porous composite block of the present invention can remove a greater amount of contaminants from water, such as microbial contaminants (e.g., a cell or particle having genetic material and is capable of replicating), microorganisms (e.g., any cell or particle having genetic material suitable for analysis of detection, such as bacteria, yeasts, fungus, viruses such as enveloped or non-enveloped viruses, and bacterial endospores), other contaminants (e.g., heavy metals, chemical compounds such as small molecules, and the like), or a combination thereof, wherein comparative statements in the Summary regarding bacterial removal are with respect to comparative testing using a porous composite block that is substantially identical to the embodiment of the inventive porous composite block but lacking the guanylated media particles, using water including the same bacteria at the same bacterial concentration at the same flowrate and through the same amount of porous composite material.

[0009] In some embodiments, the porous composite block of the present invention can remove a greater amount of bacteria from water than a porous composite block including silver. In some embodiments, the porous composite block of the present invention can be less expensive than a porous composite block including silver, such as compared to a silver- containing porous composite block that can remove the same or less amount of bacteria from water. In some embodiments, the porous composite block of the present invention can include silver, and the silver can have an additive or synergistic effect on bacteria removal when used in combination with the guanylated media particles, such that a porous composite block including silver and guanylated media removes an amount of bacteria equal to or greater than the total bacteria removed by a combination of a porous composite block including the same concentration of silver but free of the guanylated media and a porous composite block including the same concentration of guanylated media but free of the silver.

[0010] Many filtration additives cannot retain bacterial or non-bacterial removal abilities under the high temperature (e.g., 200 °C or more, or 400 °C or more) and high-pressure conditions used to prepare porous composite blocks, such as carbon blocks. However, the guanylated media survive the heating conditions used to make the porous composite block with little to no change in performance. Many filtration additives interfere with porous composite block filtration activity. However, the guanylated media causes little to no interference to filtration activity of the porous composite block.

BRIEF DESCRIPTION OF THE FIGURES

[0011] The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments of the present invention.

[0012] FIG. 1 illustrates a water filtration system including a porous composite block, in accordance with various embodiments.

[0013] FIG. 2 illustrates a reaction scheme for guanidine functionalization of a silicate, in accordance with various embodiments.

[0014] FIGS. 3A-3C illustrate scanning electron microscope (SEM) images of guanylated perlite.

[0015] FIG. 4 illustrates prepared carbon blocks with end caps, in accordance with various embodiments.

DETAILED DESCRIPTION OF THE INVENTION

[0016] Reference will now be made in detail to certain embodiments of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0017] Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement "about X to Y" has the same meaning as "about X to about Y," unless indicated otherwise. Likewise, the statement "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z," unless indicated otherwise.

[0018] In this document, the terms "a," "an," or "the" are used to include one or more than one unless the context clearly dictates otherwise. The term "or" is used to refer to a nonexclusive "or" unless otherwise indicated. The statement "at least one of A and B" or "at least one of A or B" has the same meaning as "A, B, or A and B." In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section.

[0019] In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0020] The term "about" as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.

[0021] The term "substantially" as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999%) or more, or 100%. The term "substantially free of as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that the composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less. The term "substantially free of can mean having a trivial amount of, such that a composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.

[0022] The term "organic group" as used herein refers to any carbon-containing functional group. Examples can include an oxygen-containing group such as an alkoxy group, aryloxy group, aralkyloxy group, oxo(carbonyl) group; a carboxyl group including a carboxylic acid, carboxylate, and a carboxylate ester; a sulfur-containing group such as an alkyl and aryl sulfide group; and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(0)N(R)₂, CN, CF₃, OCF₃, R, C(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SOzR, S0₂N(R)₂, S0₃R, C(0)R, C(0)C(0)R, C(0)CH₂C(0)R, C(S)R, C(0)OR, OC(0)R, C(0)N(R)₂, OC(0)N(R)₂, C(S)N(R)₂, (CH₂)o- ₂N(R)C(0)R, (CH₂)o-₂N(R)N(R)₂, N(R)N(R)C(0)R, N(R)N(R)C(0)OR, N(R)N(R)CON(R)₂, N(R)S0₂R, N(R)S0₂N(R)₂, N(R)C(0)OR, N(R)C(0)R, N(R)C(S)R, N(R)C(0)N(R)₂, N(R)C(S)N(R)₂, N(COR)COR, N(OR)R, C(=NH)N(R)₂, C(0)N(OR)R, C(=NOR)R, and substituted or unsubstituted (Ci-Cioo)hydrocarbyl, wherein R can be hydrogen (in examples that include other carbon atoms) or a carbon-based moiety, and wherein the carbon-based moiety can be substituted or unsubstituted.

[0023] The term "substituted" as used herein in conjunction with a molecule or an organic group as defined herein refers to the state in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms. The term "functional group" or "substituent" as used herein refers to a group that can be or is substituted onto a molecule or onto an organic group. Examples of substituents or functional groups include, but are not limited to, a halogen (e.g., F, CI, Br, and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents that can be bonded to a substituted carbon (or other) atom include F, CI, Br, I, OR, OC(0)N(R)₂, CN, NO, N0₂, ON0₂, azido, CF₃, OCF₃, R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SOzR, S0₂N(R)₂, S0₃R, C(0)R, C(0)C(0)R, C(0)CH₂C(0)R, C(S)R, C(0)OR, OC(0)R, C(0)N(R)₂, OC(0)N(R)₂, C(S)N(R)₂, (CH₂)o-₂N(R)C(0)R, (CH₂)o-₂N(R)N(R)₂, N(R)N(R)C(0)R, N(R)N(R)C(0)OR, N(R)N(R)CON(R)₂, N(R)S0₂R, N(R)S0₂N(R)₂, N(R)C(0)OR, N(R)C(0)R, N(R)C(S)R, N(R)C(0)N(R)₂, N(R)C(S)N(R)₂, N(COR)COR, N(OR)R,

C(0)N(OR)R, and C(=NOR)R, wherein R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (Ci-Cioo)hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or to adjacent nitrogen atoms can together with the nitrogen atom or atoms form a heterocyclyl.

[0024] The term "hydrocarbon" or "hydrocarbyl" as used herein refers to a molecule or functional group that includes carbon and hydrogen atoms. The term can also refer to a molecule or functional group that normally includes both carbon and hydrogen atoms but wherein all the hydrogen atoms are substituted with other functional groups. The term "hydrocarbyl" refers to a functional group derived from a straight chain, branched, or cyclic hydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof. Hydrocarbyl groups can be shown as (Ca-Cb)hydrocarbyl, wherein a and b are integers and mean having any of a to b number of carbon atoms. For example, (Ci-C4)hydrocarbyl means the hydrocarbyl group can be methyl (Ci), ethyl (C₂), propyl (C₃), or butyl (C₄), and (Co-Cb)hydrocarbyl means in certain embodiments there is no hydrocarbyl group. A hydrocarbylene group is a diradical hydrocarbon, e.g., a hydrocarbon that is bonded at two locations.

[0025] As used herein, the term "polymer" refers to a molecule having at least one repeating unit and can include copolymers.

[0026] In various embodiments, salts having a positively charged counterion can include any suitable positively charged counterion. For example, the counterion can be ammonium ( Η₄ ⁺), or an alkali metal such as sodium (Na⁺), potassium (K⁺), or lithium (Li⁺). In some embodiments, the counterion can have a positive charge greater than +1, which can in some embodiments complex to multiple ionized groups, such as Zn²⁺, Al³⁺, or alkaline earth metals such as Ca²⁺ or Mg²⁺.

[0027] In various embodiments, salts having a negatively charged counterion can include any suitable negatively charged counterion. For example, the counterion can be a halide, such as fluoride, chloride, iodide, or bromide. In other examples, the counterion can be nitrate, hydrogen sulfate, dihydrogen phosphate, bicarbonate, nitrite, perchlorate, iodate, chlorate, bromate, chlorite, hypochlorite, hypobromite, cyanide, amide, cyanate, hydroxide, permanganate. The counterion can be a conjugate base of any carboxylic acid, such as acetate or formate. In some embodiments, a counterion can have a negative charge greater than -1, which can in some embodiments complex to multiple ionized groups, such as oxide, sulfide, nitride, arsenate, phosphate, arsenite, hydrogen phosphate, sulfate, thiosulfate, sulfite, carbonate, chromate, dichromate, peroxide, or oxalate.

Porous composite block.

[0028] The present invention provides a porous composite block that includes sorbent media particles and a polymeric binder that bonds the sorbent media particles together. The sorbent media particles include guanylated media particles. The porous composite block can be monolithic. The pores of the block can include spaces formed between particles of the sorbent media particles and binder particles when sintered together to soften the polymeric binder and stick the sorbent media particles to one another to form the porous composite block. The pores of the block include through-pores that fluidly connect to one another and from one side of the block to another side (e.g., to an approximately opposite side) in a tortuous or direct path. The through-pores allow the porous composite block to function as a filter, such as for aqueous fluids. When the porous composite block is used as a water filter, the guanidine groups can provide removal of microbial contaminants (e.g., a cell or particle having genetic material and that is capable of replicating), microorganisms (e.g., any cell or particle having genetic material suitable for analysis or detection, such as bacteria, yeasts, fungus, viruses such as enveloped or non-enveloped viruses, and bacterial endospores), other contaminants (e.g., heavy metals, chemical compounds such as small molecules, and the like), or a combination thereof. In various embodiments, when used as a filter for aqueous fluids the composite block can remove microbial contaminants and other non-microbial contaminants, preferably bacteria and viruses, and most preferably bacteria.

[0029] The porous composite block can be non-fibrous, such that the porous composite block is substantially free of fibers (e.g., fibrous binders or fillers, such as cellulose fibers). The polymeric binder used in the porous composite block can be a non-fibrous binder, wherein the binder can have any suitable form prior to sintering but has a non-fibrous form after formation into the porous composite block. For example, prior to sintering to form the porous composite block, the binder can be in any suitable form, such as particles, extruded pellets, or fibers. After formation of the porous composite block the binder can be non-fibrous, such as particulate, agglomerated, or a combination thereof. In other embodiments, the porous composite block can include fibers such as fibrous binders or fillers (e.g., glass fibers).

[0030] The sorbent media particles can be any suitable proportion of the porous composite block, such that the porous composite block can be used as descried herein. For example, the sorbent media particles can be about 10 wt% to about 90 wt% of the porous composite block, about 35 wt% to about 65 wt%, about 40 wt% to about 60 wt%, or about 10 wt% or less, or less than, equal to, or greater than about 15 wt%, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 wt%, or about 90 wt% or more of the porous composite block.

[0031] The porous composite block can have any suitable pore size and porosity such that the block has a desired pressure drop across the filtration area and to remove materials from liquids passing therethrough. For example, the porous composite block can have a pore size sufficient to remove materials from water passing therethrough having a largest dimension of 10 microns or more, 1 micron or more, or less than, equal to, or greater than 10 microns, 8, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05 microns, or about 0.01 microns or less.

[0032] The porous composite block can have a pore size and porosity such that it can filter water at a flow rate of 0.1 L/min to about 1000 L/min, or about 1 L/min to about 100 L/min, or about 0.1 L/min or less, or less than, equal to, or greater than about 0.5 L/min, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 30, 40, 50, 60, 70, 80, 90 L/min, or about 100 L/min or more. The pressure drop can be 1 kPa to about 1,000 kPa, or about 20 kPa to about 200 kPa, or about 1 kPa or less, or less than, equal to, or greater than about 10 kPa, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 300, 400, 500, 600, 800 kPa, or about 1000 kPa or more. The flow rate and pressure drop can depend on the pressure of the water applied and on the amount of fouling of the block (e.g., by minerals and particulates), and can depend on the pressure of the water.

[0033] In various embodiments, the porous composite block can have bacterial removal capabilities wherein a log reduction value of water passed through the porous composite block (i.e., log of colony-forming units (CFUs)/mL in pre-filtration sample minus log of CFUs/mL in filtrate sample) is about 50% to about 100% of the log CFU/mL of E. coli of the pre-filtration sample, or about 80% to about 100%, or about 50% or less, or less than, equal to, or greater than about 55%, 60, 65, 70, 75, 80, 85, 90, 92, 94, 95, 96, 97, 98, 99, 99.9, 99.99%, or about 99.999%) or more. The porous composite block can produce a log reduction value of water having a pre-filtration bacterial concentration of 4.3 log CFU/mL (e.g., of E. coli) of about 2.2 to about 4.3, or about 2.2 or less, or less than, equal to, or greater than about 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.1, 4.2, or about 4.3.

Guanylated media particles.

[0034] The porous composite block includes guanylated media particles that are immobilized within the porous composite. The guanylated media particles can include a guanidine group attached via a siloxane bond to an atom of the media particles directly or including a hydrocarbylene linker group. In some examples, the guanylated media particles can be prepared by treatment of media particles including -OH or alkoxide groups with an aminohydrocarbylalkoxysilane (e.g., a mono-, di-, or trialkoxysilane, such as a monoalkoxydialkoylsilane or a dialkoxymonoalkylsilane) to form an -O-Si bond. The guanylated media particles can be homogeneously distributed throughout the composite block to allow even exposure of water to the guanidine groups during filtration.

[0035] The guanylated media particles can be guanylated siliceous media particles including a guanidine group attached via a siloxane bond to a silicon atom of the siliceous media particles directly or including a hydrocarbylene linker group. In some examples, the guanylated siliceous media particles can be prepared by treatment of siliceous media particles including Si-OH or silicon alkoxide groups with an aminohydrocarbyltrialkoxysilane to form an Si-O-Si bond.

[0036] The guanylated media particles can be any suitable proportion of the porous composite block, such that the porous composite block can be used as described herein. The guanylated media particles can be about 0.001 wt% to about 90 wt% of the porous composite block, or about 10 wt% to about 65 wt%, about 15 wt% to about 60 wt%, or about 0.001 wt% or less, or less than, equal to, or greater than about 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 85, 86, 87, 88, or about 90 wt% of the porous composite block. The guanylated media particles can be any suitable proportion of the total amount of media particles in the porous composite block, such as about 0.001 wt% to about 100 wt% of the sorbent media particles, about 20 wt% to about 100 wt%, about 25 wt% to about 100 wt%, or about 0.001 wt% or less, or about 0.01 wt%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 92, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more.

[0037] The guanylated media particles can have any suitable particle size (e.g., largest dimension, such as weight or number average) such that a desired pore size and porosity is present in the porous composite block. The guanylated media particles can have a particle size of about 10 nm to about 1 mm, about 10 microns to about 50 microns, about 20 microns to about 40 microns, or about 10 nm or less, or less than, equal to, or greater than about 20 nm, 30, 40, 50, 75, 100, 125, 150, 175, 200, 250, 300, 400, 500, 750 nm, 1 micron, 2, 3, 4, 5, 6, 8, 10, 15, 20, 30, 40, or about 50 microns or more. The guanylated media particles can be a powder. The individual particles can independently have the approximate shape of a sphere, a flake, a chip, a polygon, or a combination thereof. [0038] The guanylated media particles include media particles that include -OH bonds that have been guanylated. The media particles can including any suitable material, compound, or combination thereof, such as including a metal, non-metal, metalloid, or combination thereof. The -OH bonds that are guanylated can be C-OH bonds or Si-OH bonds. The guanylated media particles can include media particles including metal-OH bonds that are guanylated, such as magnesium-OH (e.g., the media includes magnesium oxide), calcium-OH (e.g., the media includes calcium oxide), zinc-OH (e.g., the media includes zinc oxide), aluminum-OH (e.g., the media includes aluminum oxide), iron-OH (e.g., the media includes iron oxide), titanium-OH (e.g., the media includes titanium oxide), or a combination thereof. The guanylated media particles can include a metal silicate, such as a silicate of magnesium, calcium, zinc, aluminum, iron, titanium, or a combination thereof. The metal silicate can be an amorphous metal silicate. The metal silicate can be in at least partially fused form. The metal silicate can be an amorphous, spheroidized metal silicate, such as amorphous, spheroidized magnesium silicate.

[0039] The guanylated media particles can be guanylated siliceous media particles including Si-OH atoms that are guanylated, wherein the Si atoms in the siliceous media can be any suitable atomic% of the siliceous media. The siliceous media particles can include a metal silicate, diatomaceous earth, surface-modified diatomaceous earth, gamma-FeO(OH) (e.g., lepidocrocite), a metal carbonate (e.g., calcium carbonate), a metal phosphate (e.g., hydroxyapatite), silica (e.g., S1O2, such as including a network of Si-O-Si linkages and Si-OH or Si=0 terminal groups), perlite, or a combination thereof.

[0040] Metal silicates can include particles of amorphous metal silicates, such as amorphous, spheroidized magnesium silicate, amorphous, spherical aluminum silicate, or a combination thereof. Amorphous and at least partially fused particulate forms of metal silicates can be prepared by melting or softening feed particles (e.g., having irregular shapes, or any suitable shapes) under controlled conditions to make generally ellipsoidal or spheroidal particles (that is, particles having magnified two-dimensional images that are generally rounded and free of sharp comers or edges, including truly or substantially circular and elliptical shapes and any other rounded or curved shapes). Such methods include atomization, fire polishing, direct fusion, flame fusion, and the like. Flame fusion can form at least partially fused, substantially glassy particles by direct fusion or fire polishing of solid feed particles.

[0041] Diatomaceous earth is a natural siliceous material produced from the remnants of diatoms, a class of ocean-dwelling microorganisms. It can be obtained from natural sources and is also commercially available. Diatomaceous earth particles can include small, open networks of silica in the form of symmetrical cubes, cylinders, spheres, plates, rectangular boxes, and the like. The pore structures in these particles can be substantially uniform. Diatomaceous earth can be used as a raw mined material or as purified and optionally milled particles. The diatomaceous earth can be in the form of milled particles. The diatomaceous earth can optionally be heat treated prior to use to remove organic residues.

[0042] Surface-modified diatomaceous earth can include diatomaceous earth bearing, on at least a portion of its surface, a surface treatment including titanium dioxide, ferric oxide, gold, platinum, or a combination thereof. Surface treatments can include fine-nanoscale gold, fine-nanoscale platinum, a metal oxide (e.g., at least one of titanium dioxide and ferric oxide), or a combination thereof.

[0043] The media particles can include perlite. Perlite is a naturally-forming amorphous volcanic glass, that can contain about 70-75% silicon dioxide and about 12-15% aluminum oxide, as well as smaller amounts of other metal oxides, including sodium oxide, potassium oxide, iron oxide, magnesium oxide, and calcium oxide. When perlite is expanded by heat it forms a lightweight aggregate. The guanylated media particles can be guanylated perlite particles.

[0044] The guanylated media particles can have any suitable concentration of guanidine groups on their surfaces such that the porous composite block has the desired amount of bacterial removal activity or non-bacterial removal activity. For example, the guanylated media particles can have a surface nitrogen concentration, as measured by X-ray photoelectron spectroscopy (XPS), of about 2 atomic% to about 20 atomic%, or about 6 atomic% to about 10 atomic%, about 7 atomic% to about 9 atomic%, about 7.5 atomic% to about 8.5 atomic% or about 2 atomic% or less, or less than, equal to, or greater than about 3 atomic%, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 atomic%, or about 20 atomic% or more.

[0045] The guanylated media particles include one or more guanidine-functionalized silicon atoms. The guanylated media particles include one or more guanidine-functionalized silicon atoms having the structure:

The guanidine moiety can include any suitable counterion, such as sulfate (e.g., multiple guanidine groups can share a single anion having multiple negative charges). The variable L is independently chosen from a bond and a substituted or unsubstituted (Ci-C2o)hydrocarbylene, such as a (Ci-Cio)alkylene, a (C2-Cs)alkylene, or propylene (i.e., -CH2-CH2-CH2-). Linker L can be substituted with one or more other guanidine groups, either directly or via another L linker. One of the remaining bonds on the silicon atom is directly connected to an atom of the media (e.g., a silicon atom, a metal atom, or another atom that included an -OH bond prior to guanylation). The other two remaining bonds on the silicon atoms can be independently selected to be a bond to an atom of the media (e.g., there can be more than one bond from the silicon atom to the media), to an alkoxy group, a hydroxy group, to another guanidine or amine group directly or via a hydrocarbylene linker, to an -O-Si bond or -hydrocarbyl-O-Si bond wherein the appended silicon atom can be functionalized the same way as the silicon atom shown in the structure of the guanidine-functionalized silicon atom, or a combination thereof. In some embodiments, both remaining Si bonds can be to a single oxygen atom to form an Si=0 bond.

[0046] The functionalized silicon atoms can be attached to a media particle via atoms in the media particle that were present in the media particle as -OH bonded atoms prior to guanylation. For example, the functionalized silicon atoms can be attached to a siliceous media particle via silicon atoms in the media particle that were present in the siliceous media particle prior to guanylation. The one or more guanidine-functionalized silicon atoms can have the structure:

The atom Si^media is a silicon atom that was present in the siliceous media particle as an Si OH group prior to guanidine functionalization with a compound having the structure:

The variable R¹ at each occurrence is independently (Ci-C2o)hydrocarbyl, (Ci-Cio)alkyl, (Ci- C₃)alkyl, or methyl. The variable n can be 1 to 3, such as 1, 2, or 3. When R¹ is methyl, the guanylating compound used to form the guanylated media particles can be, for example, guanidinylpropyltrimethoxysilane. [0047] The guanylating compound used to form the guanylated media particles can be any suitable guanylating compound, such as including an amine that can be subsequently transformed into a guanidine group (e.g., via treatment with an O-methylisourea salt, such as O-methylisourea hemisulfate), such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3- aminopropyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(6- aminohexyl)aminopropyltrimethoxy silane, N-(2-aminoethyl)- 11 -aminoundecyl- trimethoxysilane, N-3 [(amino(polypropylenoxy)]aminopropyltrimethoxysilane, 3- aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, aminopropylsilanetriol, 3 -aminopropyltriethoxy silane, 3-aminopropyltrimethoxysilane, (3- trimethoxysilylpropyl)diethylene-triamine, or a combination thereof.

Secondary sorbent particles.

[0048] The porous composite block can include secondary sorbent particles in addition to the guanylated media particles. The secondary sorbent particles can be any suitable sorbent particles that are different than the guanylated media particles, such as particles that absorb or adsorb one or more materials (e.g., particulates, organic compounds, microorganisms such as bacteria, viruses, heavy metals, and the like) from water passing by the particle. The secondary sorbent particles can be non-guanylated particles. The secondary sorbent particles can include activated carbon; anthracite coal; sand; oxides of iron, aluminum, titanium, or other metals; hydroxides of iron, aluminum, titanium, or other metals; silicates of iron, aluminum, titanium, or other metals, such as non-guanylated diatomaceous earth or pearlite; activated alumina or other activated metal oxides or other inorganics; ion exchange resin (e.g., crushed or otherwise); carbon fibers; chelating agents; cyclodextrins; polymers other than ultra high molecular weight polyethylene, such as binders or halogenated resins (e.g., having antimicrobial functionality); or a combination thereof. The porous composite block can be a porous carbon block including the guanylated media particles, formed by sintering a mixture of activated carbon particles and guanylated media particles.

[0049] The secondary sorbent particles can be about 0 wt% to about 89.999 wt% of the porous composite block, about 0 wt% to about 50 wt%, about 0 wt% to about 45 wt%, or about 0 wt%, or less than, equal to, or greater than about 0.001 wt%, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 85, 86, 87, 88, 89, 89.9, 89.99, or about 89.999 wt% or more of the porous composite block. The secondary sorbent particles can be about 0 wt% to about 99.999 wt% of the total sorbent media particles, or about 0 wt% to about 80 wt%, about 0 wt% to about 75 wt%, or about 0 wt%, or less than, equal to, or greater than about 0.001 wt%, 0.01, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or about 80 wt% or more.

[0050] The secondary sorbent particles can have any suitable particle size (e.g., largest dimension, such as weight or number average) such that a desired pore size and porosity is present in the porous composite block. The secondary sorbent particles can have any suitable particle size, such as about 10 nm to about 1 mm, about 20 microns to about 200 microns, or about 10 nm or less, or less than, equal to, or greater than about 20 nm, 30, 40, 50, 75, 100, 125, 150, 175, 200, 250, 300, 400, 500, 750 nm, 1 micron, 2, 3, 4, 5, 6, 8, 10, 15, 20, 30, 40, 50, 60, 80, 100, 125, 150, 175, or about 200 microns or more.

[0051] Activated carbon, also called activated charcoal, is a form of carbon processed to have small low-volume pores that increase the surface area available for sorption. Activated carbon can be formed from any suitable carbonaceous material (e.g., nutshells, coconut husk, peat, wood, coir, lignite, coal, petroleum pitch, and the like), such as via exposure to high temperatures to cause pyrolysis. The activated carbon can include standard activated carbon that is free of chemical-impregnation or other chemical activation. In some embodiments, the activated carbon can include silver-impregnated activated carbon (e.g., elemental silver, or a silver salt), hydroxide-impregnated activated carbon (e.g., hydroxide salt, such as sodium hydroxide, calcium hydroxide, or potassium hydroxide), metal-impregnated activated carbon, metal oxide-impregnated activated carbon, metal ion-impregnated activated carbon (e.g., copper sulfate, copper chloride, zinc chloride), salt-impregnated activated carbon (e.g., zinc salt, potassium salt, sodium salt, silver salt, sulfur salt), or a combination thereof. The activated carbon can be impregnated via treatment with the impregnating material prior to carbonization. In some embodiments, the secondary sorbent particles include activated carbon, silver- impregnated activated carbon, or a combination thereof. Silver-impregnated activated carbon can form any suitable proportion of the secondary sorbent, such as about 0 wt% to about 100 wt%, or about 30 wt% to about 100 wt%, or about 0 wt%, or less than, equal to, or greater than about 0.001 wt%, 0.01, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 92, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more. In some embodiments, the secondary sorbent particles can be substantially free of any one or more impregnated carbons described herein, such as substantially free of sulfur-impregnated activated carbon (e.g., sulfur salts), or substantially free of silver-impregnated activated carbon (e.g., silver salts). Polymeric binder.

[0052] The porous composite block includes a polymeric binder that bonds the sorbent particles to one another. A mixture of polymeric binder particles and the sorbent media particles can be heated to soften the polymeric binder particles stick the sorbent media particles thereto to form the porous composite block. The polymeric binder can promote cohesion of aggregates or particles, and can include polymeric materials, such as thermoplastic materials that are capable of softening and becoming tacky at elevated temperatures and hardening when cooled.

[0053] The polymeric binder can be homogeneously distributed in the porous composite block. The polymeric binder can be any suitable proportion of the porous composite block, such that the porous composite block can be used as described herein. For example, the polymeric binder can be about 10 wt% to about 90 wt% of the porous composite block, about 35 wt% to about 65 wt%, about 40 wt% to about 60 wt% of the porous composite block, or about 10 wt% or less, or less than, equal to, or greater than about 15 wt%, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, or about 90 wt% or more.

[0054] The polymeric binder can be any suitable polymeric binder. The polymeric binder can include a polyethylene polymer or copolymer, a polypropylene polymer or copolymer, a polyamide, a fluoropolymer, a polyethylene-based ion-containing polymer, an acrylic acid or methacrylic acid polymer or copolymer, an acrylic acid ester or methacrylic acid ester polymer or copolymer, or a combination thereof. The polymeric binder can include ultra high molecular weight polyethylene (UFIMWPE).

[0055] Examples of suitable binders that can be included in the porous composite block include, but are not limited to, end-capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, poly(trichloroacetaidehyde), poly(n-valeraldehyde), poly(acetaldehyde), poly(propionaldehyde), and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate), poly(methyl methacrylate), and the like; fluorocarbon polymers, such as poly(tetrafluoroethylene), perfluorinated ethylene-propylene copolymers, ethylene-tetrafluoroethylene copolymers, poly(chlorotrifluoroethylene), ethylene- chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the like; polyamides, such as poly(6-aminocaproic acid) or poly(caprolactam), poly(hexam ethylene adipamide), poly(hexam ethylene sebacamide), poly(l 1-aminoundecanoic acid), and the like; polyaramides, such as poly(imino-l,3-phenyleneiminoisophthaloyl) or poly(m-phenylene isophthalamide), and the like; parylenes, such as poly-p-xylylene, poly(chloro-p-xylylene), and the like; polyaryl ethers, such as poly(oxy-2,6-dimethyl-l,4- phenylene) or poly(p-phenylene oxide), and the like; polyaryl sulfones, such as poly(oxy-l,4- phenylenesulfonyl- 1 ,4-phenyleneoxy- 1 ,4-phenylene-isopropylidene- 1 ,4-phenylene), poly- (sulfonyl-l,4-phenyleneoxy-l,4-phenylenesulfonyl-4,4'-biphenylene), and the like; polycarbonates, such as poly(bisphenol A) or poly(carbonyldioxy-l,4- phenyleneisopropylidene-l,4-phenylene), and the like; polyesters, such as poly(ethylene terephthalate), poly(tetramethylene terephthalate), poly(cyclohexylene-l,4-dimethylene terephthalate) or poly(oxymethylene-l,4-cyclohexylenemethyleneoxyterephthaloyl), and the like; polyaryl sulfides, such as poly(p-phenylene sulfide) or poly(thio-l,4-phenylene), and the like; polyimides, such as poly(pyromellitimido-l,4-phenylene), and the like; poly olefins, such as polyethylene, polypropylene, poly(l-butene), poly(2-butene), poly(l-pentene), poly(2- pentene), poly(3 -methyl- 1-pentene), poly(4-methyl-l-pentene), and the like; vinyl polymers, such as poly(vinyl acetate), poly(vinylidene chloride), poly(vinyl chloride), and the like; diene polymers, such as l,2-poly-l,3-butadiene, 1,4-poly- 1,3 -butadiene, polyisoprene, polychloroprene, and the like; polystyrenes; copolymers of the foregoing, such as acrylonitrile- butadiene-styrene (ABS) copolymers, and the like; and the like; and a combination thereof.

Other components.

[0056] The porous composite block can include or be free of an ion-exchange resin

(e.g., pulverized particles thereof), a filler, an adhesive, a pigment, a dye, titanium silicate, titanium oxide, an elemental metal, a metal ion, a metal oxide, elemental silver, a silver ion, a silver oxide, a salt, a hydroxide salt, a zinc salt, a sodium salt, a potassium salt, a silver salt, or a combination thereof. Titanium silicate and titanium oxide can remove heavy metals.

Water filter.

[0057] In various embodiments, the present invention provides a water filter or a water filtration system including the same. The water filter can be any type of water filter that includes an embodiment of the porous composite block described herein. The water filter can be considered to be only the porous composite block, or can be the porous composite block having one or more components thereon such as a cap.

[0058] FIG. 1 illustrates an example of a porous composite block used as a water filter

102 in water filtration system 100. Water filtration system 100 includes housing 130 having inlet port 140 fluidly connected to outlet port 150. Water filter 102 according to the present disclosure is sealed with cap 122 and positioned within the housing 130 such that any water (not shown) entering housing 130 through inlet port 140 passes through water filter 102 into conduit 180 before reaching outlet port 150 and issuing therefrom. O-rings 140 form a watertight seal between outlet port 150 and outlet port tube 145 of cap 122.

[0059] As shown housing 130 includes head portion 190 and body portion 192. Head portion 190 includes inlet port 140 and outlet port 150. Head portion 190 and body portion 192 are mechanically engageable (shown as screw threads 194) with one another to form a watertight seal. In such embodiments, the head portion and the body portion may be mechanically engageable by a motion including relative twisting of the head portion and the body portion (e.g., a bayonet mount or a screw thread).

Method using a water filter.

[0060] Various embodiments of the present invention provide a method of using a water filter including a porous composite block, such as any porous composite block described herein. The method includes passing water through the porous composite block to provide water having enhanced purity. The passing of the water through the porous composite block can include pressurizing the water, using gravity to bring the water through the porous composite block, or a combination thereof.

Method of making a porous composite block.

[0061] Various embodiments of the present invention provide a method of making a porous composite block, such as any porous composite block described herein. The method can include dispersing the guanylated media particles with particles of the polymeric binder, and optionally with secondary sorbent particles, to form a dispersed mixture including the guanylated media particles homogeneously dispersed therein. The method can also include sintering the dispersed mixture to form the porous composite block, including heating the dispersed mixture and optionally including applying pressure to the dispersed mixture. Heating can be performed at any suitable temperature, and can include sintering the dispersed mixture, such as at about 100 °C to about 1000 °C, about 200 °C to about 1000 °C, such as about 200 °C to about 500 °C, or about 100 °C or less, or less than, equal to, or greater than 105 °C, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 202, 204, 206, 208, 210, 212, 214, 216, 218, 220, 225, 230, 235, 240, 245, 250, 260, 270, 280, 290, 300, 320, 340, 360, 380, 400, 450, 500, 600, 700, 800, 900, or about 1000 °C or more. Dispersing the guanylated media particles can include sieving or screening the particles prior to or during mixing with other components to break up agglomerates of guanylated material and produce a more uniform particle size. Examples

[0062] Various embodiments of the present invention can be better understood by reference to the following Examples which are offered by way of illustration. The present invention is not limited to the Examples given herein.

Materials.

[0063] The materials used in the Examples are shown in Table 1. All chemicals were purchased from Sigma Aldrich/Fischer Scientific unless otherwise noted.

[0064] Table 1. Materials.

Example 1. Preparation of guanylated perlite.

[0065] A 3-L flask equipped with an overhead mechanical stirrer was charged with 3- aminopropyltrimethoxysilane (44.8 g, 250 mmol) and anhydrous methanol (200 mL). The reaction mixture was then treated with of O-methylisourea hemisulfate (30.8 g, 250 mmol) and the reaction mixture was stirred under an atmosphere of nitrogen overnight. The reaction mixture was diluted with 1.2 L of methanol and perlite particles (249 g) were added to the flask followed by the addition of H2O (4.5 mL, 250 mmol). The mixture was stirred rapidly for two days to facilitate reaction between the guanylated trimethoxysilane and the particles. The resulting guanidine-functionalized perlite particles were isolated by filtration and rinsed with 500 mL of methanol. The particles were returned to the flask and treated with 1 L of deionized water. After stirring for 45 min, the particles were isolated by filtration and washed with an additional 500 mL of deionized water. The particles were again returned to the flask and treated with 1 L of deionized water. After stirring for 3 days, the particles were isolated by filtration and washed with an additional 500 mL of deionized water. The particles were then dried under vacuum at 65 °C to give 249 g of functionalized particles as a grey powder. The atomic percent nitrogen content was 8.1 ± 0.3% as measured by electron spectroscopy for chemical analysis (ECS A), as shown in Table 2 below. A reaction scheme illustrating the functionalization of the perlite is shown in FIG. 2. FIGS. 3A-3C illustrates SEM images of the guanylated perlite.

[0066] Table 2. XPS surface concentrations (Atomic

Examples 2-5. Carbon miniblocks including guanylated perlite.

[0067] The miniblocks were made by dry blending the ingredients, charging the mixture into molds and holding at 204°C for one hour to sinter the carbon blocks. The miniblocks were made using the compositions shown in Table 3. [0068] Table 3. Miniblock formulations (wt%).

[0069] FIG. 4 shows a photograph of the carbon blocks of Examples 2-5 including end caps and ready for testing.

Example 6. Bacterial removal by guanylated perlite blocks of Examples 2-5.

[0070] The blocks of Examples 2-5 were tested using the following procedure.

[0071] A streaked culture of E coli (ATCC 11229) on a TSA was incubated overnight at 37°C. From the plate an isolated colony was removed and inoculated into 10 mL of TSB using a standard microbiology loop and incubated in a shaking incubator (Innova® 44 from New Brunswick Scientific) at 37°C for 20-22 hrs. The overnight culture that contained ~ 2-3 x 10⁹ CFU/mL was serially diluted in Butterfield's Buffer to obtain an inoculum with approximately 1 X 10⁶ CFU/mL.

[0072] A test sample was prepared by inoculating 200 mL deionized of water (MilliQ

Gradient system, Millipore, Ma) a 1 : 100 dilution of the 10⁶ CFU/mL inoculum resulting in water test sample containing approximately 10⁴ CFU/mL (~ 4 Log CFUs/mL).

[0073] A Walchem E-Class Metering Pump was used to deliver the 10⁴ CFU/mL E coli mixture to the filter block. Initially, DI water was used to purge the pump head and tubing of air. The pump head was purged by opening the purge valve on the pump head and running the pump at high flow. The tubing at the outlet of the pump head was purged of air by running the pump at high flow while elevating the tubing and allowing the air bubbles to rise and leave the system. The pump tubing was then connected to a CamelBak QSM filter cartridge containing a carbon block. The pump was run at high flow to wet out the carbon block and purge the cartridge of air. The outlet of the cartridge was connected via PVC tubing to a filtrate collector. The stroke length for the pump was then set to its lowest level (-20%) and the stroke frequency was adjusted to provide 20 mL/min of flow through the filter cartridge. Then the E coli containing pre-filtration solution was introduced to the pump inlet.

[0074] A pre-filtration solution was pumped through the block holder containing the carbon block using a metering pump using 1/8" wall thick PVC tubing (VWR catalog # 60985- 522). The spiked water was pumped through the sintered block matrix at a flow rate of -20 mL/minute. Filtrates were collected in 250 mL sterile glass bottles. The first 100 ml filtrate was collected and discarded. The second 100 mL filtrate was collected for further processing.

[0075] A 10 mL volume of the second 100 mL filtrate was added to a 100 mL containing Butterfi eld's Buffer flip-top bottle to obtain a 1 : 10 dilution. The bottle was capped and mixed manually by shaking for 10 seconds. A 10 mL volume was removed and added to another flip-top bottle to obtain a 1 : 100. Similarly the filtrate was further diluted to 1 : 1000 and 1 : 10000. These 100 mL diluted filtrates were vacuum filtered thru 0.45 micron filters. Filtration was done starting with the highest dilution to the lowest dilution using a standard vacuum filtration apparatus. For each block a new holder was used. Between various samples the filtration device was rinsed with filtered with 500 mL deionized water.

[0076] The filters were removed from the apparatus with sterile forceps plates and placed on Endo Agar plates, grid side up. The plates were incubated at 37 °C for 18-20 hours. Colony counts were obtained from plates by manual counting. Pre-filtration samples were also diluted and filtered as the procedure above. The CFU/mL colony counts were converted to Log CFU/mL values.

[0077] Log Reduction Values (LRV) were calculated based on counts obtained from the plated filtrate and pre-filtration samples by using the formula: LRV = (Log of CFUs/mL in pre-filtration sample) - (Log of CFUs/mL in filtrate sample). Results of the testing are shown in Table 4.

[0078] Table 4. Bacterial removal results.

[0079] The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present invention. Thus, it should be understood that although the present invention has been specifically disclosed by specific embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present invention.

Exemplary Embodiments.

[0080] The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance:

[0081] Embodiment 1 provides a porous composite block comprising:

sorbent media particles comprising guanylated media particles; and

a polymeric binder that bonds the sorbent media particles together.

[0082] Embodiment 2 provides the porous composite block of Embodiment 1, wherein the porous composite block is a non-fibrous porous composite block.

[0083] Embodiment 3 provides the porous composite block of any one of Embodiments

1-2, wherein the polymeric binder is a non-fibrous polymeric binder.

[0084] Embodiment 4 provides the porous composite block of any one of Embodiments

1-3, wherein the porous composite block is free of fibrous binders.

[0085] Embodiment 5 provides the porous composite block of any one of Embodiments

1-4, wherein the sorbent media particles are about 10 wt% to about 90 wt% of the porous composite block.

[0086] Embodiment 6 provides the porous composite block of any one of Embodiments

1-5, wherein the sorbent media particles are about 35 wt% to about 65 wt% of the porous composite block.

[0087] Embodiment 7 provides the porous composite block of any one of Embodiments

1-6, wherein the guanylated media particles are homogeneously distributed throughout the composite block.

[0088] Embodiment 8 provides the porous composite block of any one of Embodiments

1-7, wherein the guanylated media particles are about 0.001 wt% to about 90 wt% of the porous composite block. [0089] Embodiment 9 provides the porous composite block of any one of Embodiments

1-8, wherein the guanylated media particles are about 10 wt% to about 65 wt% of the porous composite block.

[0090] Embodiment 10 provides the porous composite block of any one of

Embodiments 1-9, wherein the guanylated media particles are about 0.001 wt% to about 100 wt% of the sorbent media particles.

[0091] Embodiment 11 provides the porous composite block of any one of

Embodiments 1-10, wherein the guanylated media particles are about 20 wt% to about 100 wt% of the sorbent media particles.

[0092] Embodiment 12 provides the porous composite block of any one of

Embodiments 1-11, wherein the guanylated media particles have a particle size of about 10 nm to about 1 mm.

[0093] Embodiment 13 provides the porous composite block of any one of

Embodiments 1-12, wherein the guanylated media particles have a particle size of about 10 microns to about 50 microns.

[0094] Embodiment 14 provides the porous composite block of any one of

Embodiments 1-13, wherein the guanylated media particles have a shape of a sphere, a flake, a chip, a polygon, or a combination thereof.

[0095] Embodiment 15 provides the porous composite block of any one of

Embodiments 1-14, wherein the media particles that are guanylated comprise media particles comprising silicon atoms.

[0096] Embodiment 16 provides the porous composite block of any one of

Embodiments 1-15, wherein the guanylated media particles comprise media particles comprising -OH bonds that are guanylated.

[0097] Embodiment 17 provides the porous composite block of Embodiment 16, wherein the -OH bonds that are guanylated are C-OH, Si-OH, or a combination hereof.

[0098] Embodiment 18 provides the porous composite block of any one of

Embodiments 1-17, wherein the guanylated media particles comprise media particles comprising metal-OH bonds that are guanylated.

[0099] Embodiment 19 provides the porous composite block of any one of

Embodiments 1-18, wherein the guanylated metal-OH bonds are magnesium-OH, calcium-OH, zinc-OH, aluminum-OH, iron-OH, titanium-OH, or a combination thereof. [00100] Embodiment 20 provides the porous composite block of any one of

Embodiments 1-19, wherein the media particles that are guanylated comprise media particles comprising a metal silicate.

[00101] Embodiment 21 provides the porous composite block of Embodiment 20, wherein the metal silicate comprises a silicate of magnesium, calcium, zinc, aluminum, iron, titanium, or a combination thereof.

[00102] Embodiment 22 provides the porous composite block of any one of

Embodiments 1-21, wherein the media particles that are guanylated comprise media particles comprising silica.

[00103] Embodiment 23 provides the porous composite block of any one of

Embodiments 1-22, wherein the media particles that are guanylated comprise a metal silicate, diatomaceous earth, surface-modified diatomaceous earth, gamma-FeO(OH), a metal carbonate, a metal phosphate, silica, perlite, or a combination thereof.

[00104] Embodiment 24 provides the porous composite block of any one of

Embodiments 1-23, wherein the media particles that are guanylated comprise perlite.

[00105] Embodiment 25 provides the porous composite block of any one of

Embodiments 1-24, wherein the guanylated media particles are guanylated perlite particles.

[00106] Embodiment 26 provides the porous composite block of any one of

Embodiments 1-25, wherein the guanylated media particles have a surface nitrogen concentration, as measured by X-ray photoelectron spectroscopy, of about 2 atomic% to about 20 atomic%.

[00107] Embodiment 27 provides the porous composite block of any one of

Embodiments 1-26, wherein the guanylated media particles have a surface nitrogen concentration, as measured by X-ray photoelectron spectroscopy, of about 6 atomic% to about 10 atomic%.

[00108] Embodiment 28 provides the porous composite block of any one of

Embodiments 1-27, wherein the guanylated media particles comprise one or more guanidine- functionalized silicon atoms.

[00109] Embodiment 29 provides the porous composite block of any one of

Embodiments 1-28, wherein the guanylated media particles comprise one or more guanidine- functionalized silicon atoms having the structure:

wherein L is independently chosen from a bond and a substituted or unsubstituted (Ci- C2o)hydrocarbylene.

[00110] Embodiment 30 provides the porous composite block of Embodiment 29, wherein L is a (Ci-Cio)alkylene.

[00111] Embodiment 31 provides the porous composite block of any one of

Embodiments 29-30, wherein L is a (C2-Cs)alkylene.

[00112] Embodiment 32 provides the porous composite block of any one of

Embodiments 29-31, wherein L is propylene.

[00113] Embodiment 33 provides the porous composite block of any one of

Embodiments 29-32, wherein the guanylated media particles comprise siliceous guanylated media particles comprising one or more guanidine-functionalized silicon atoms having the structure:

wherein Si^media is a silicon atom that was present in the siliceous media particle as an

Si ^a-OH group prior to guanidine functionalization with a compound having the structure:

wherein at each occurrence R¹ is independently (Ci-C2o)hydrocarbyl, and wherein n is

1 to 3.

[00114] Embodiment 34 provides the porous composite block of Embodiment 33, wherein Ri is independently (Ci-Cio)alkyl.

[00115] Embodiment 35 provides the porous composite block of any one of

Embodiments 33-34, wherein Ri is independently (Ci-C3)alkyl. [00116] Embodiment 36 provides the porous composite block of any one of

Embodiments 33-35, wherein Ri is methyl, wherein the guanylating compound is guanidinylpropyltrimethoxysilane.

[00117] Embodiment 37 provides the porous composite block of any one of

Embodiments 1-36, wherein the sorbent media particles comprise secondary sorbent particles.

[00118] Embodiment 38 provides the porous composite block of Embodiment 37, wherein the secondary sorbent particles are non-guanylated particles.

[00119] Embodiment 39 provides the porous composite block of any one of

Embodiments 37-38, wherein the secondary sorbent particles are about 0 wt% to about 89.999 wt% of the porous composite block.

[00120] Embodiment 40 provides the porous composite block of any one of

Embodiments 37-39, wherein the secondary sorbent particles are about 0 wt% to about 50 wt% of the porous composite block.

[00121] Embodiment 41 provides the porous composite block of any one of

Embodiments 37-40, wherein the secondary sorbent particles are about 0 wt% to about 99.999 wt% of the sorbent media particles.

[00122] Embodiment 42 provides the porous composite block of any one of

Embodiments 37-41, wherein the secondary sorbent particles are about 0 wt% to about 80 wt% of the sorbent media particles.

[00123] Embodiment 43 provides the porous composite block of any one of

Embodiments 37-42, wherein the secondary sorbent particles have a particle size of about 10 nm to about 1 mm.

[00124] Embodiment 44 provides the porous composite block of any one of

Embodiments 37-43, wherein the secondary sorbent particles have a particle size of about 20 microns to about 200 microns.

[00125] Embodiment 45 provides the porous composite block of any one of

Embodiments 37-44, wherein the secondary sorbent particles comprise activated carbon, anthracite coal, sand, a metal oxide, a metal hydroxide, a metal silicate, an activated metal oxide, an ion exchange resin, carbon fibers, a chelating agent, a cyclodextrin, a polymer, or a combination thereof.

[00126] Embodiment 46 provides the porous composite block of any one of

Embodiments 37-45, wherein the secondary sorbent particles comprise activated carbon, silver-impregnated activated carbon, hydroxide-impregnated activated carbon, metal- impregnated activated carbon, metal oxide-impregnated activated carbon, metal ion- impregnated activated carbon, salt-impregnated activated carbon, or a combination thereof.

[00127] Embodiment 47 provides the porous composite block of any one of

Embodiments 37-46, wherein the secondary sorbent particles comprise activated carbon, silver-impregnated activated carbon, or a combination thereof.

[00128] Embodiment 48 provides the porous composite block of any one of

Embodiments 37-47, wherein the secondary sorbent particles comprise activated carbon and silver-impregnated activated carbon.

[00129] Embodiment 49 provides the porous composite block of any one of

Embodiments 37-48, wherein the secondary sorbent particles are activated carbon.

[00130] Embodiment 50 provides the porous composite block of any one of

Embodiments 37-49, wherein the porous composite block is a porous carbon block comprising the guanylated media particles.

[00131] Embodiment 51 provides the porous composite block of any one of

Embodiments 1-50, wherein the polymeric binder is about 10 wt% to about 90 wt% of the porous composite block.

[00132] Embodiment 52 provides the porous composite block of any one of

Embodiments 1-51, wherein the polymeric binder is about 35 wt% to about 65 wt% of the porous composite block.

[00133] Embodiment 53 provides the porous composite block of any one of

Embodiments 1-52, wherein the polymeric binder comprises a polyethylene polymer or copolymer, a polypropylene polymer or copolymer, a polyamide, a fluoropolymer, a polyethylene-based ion-containing polymer, an acrylic acid or methacrylic acid polymer or copolymer, an acrylic acid ester or methacrylic acid ester polymer or copolymer, or a combination thereof.

[00134] Embodiment 54 provides the porous composite block of any one of

Embodiments 1-53, wherein the polymeric binder comprises ultra high molecular weight polyethylene.

[00135] Embodiment 55 provides the porous composite block of any one of

Embodiments 1-54, wherein the porous composite block further comprises an ion-exchange resin.

[00136] Embodiment 56 provides the porous composite block of any one of

Embodiments 1-55, wherein the porous composite block further comprises titanium silicate, titanium oxide, or a combination thereof. [00137] Embodiment 57 provides the porous composite block of any one of

Embodiments 1-56, wherein the porous composite block is substantially free of sulfur- impregnated activated carbon.

[00138] Embodiment 58 provides the porous composite block of any one of

Embodiments 1-57, wherein the porous composite block further comprises an elemental metal, a metal ion, a metal oxide, elemental silver, a silver ion, a silver oxide, a salt, a hydroxide salt, a zinc salt, a sodium salt, a potassium salt, a silver salt, or a combination thereof

[00139] Embodiment 59 provides the porous composite block of any one of

Embodiments 1-58, wherein the porous composite block has a pore size sufficient to remove materials from water passing therethrough having a largest dimension of 10 microns or more.

[00140] Embodiment 60 provides the porous composite block of any one of

Embodiments 1-59, wherein the porous composite block has a pore size sufficient to remove materials from water passing therethrough having a largest dimension of 1 micron or more.

[00141] Embodiment 61 provides the porous composite block of any one of

Embodiments 1-60, wherein the porous composite block is sufficient such that a log reduction value of water passed through the porous composite block is about 50% to about 100% of the log CFU/mL of E. coli of the water prior to passage through the porous composite block.

[00142] Embodiment 62 provides the porous composite block of any one of

Embodiments 1-61, wherein the porous composite block is sufficient such that a log reduction value of 4.3 log CFU/mL water passed through the porous composite block is about 2.2 to about 4.3.

[00143] Embodiment 63 provides a porous composite block comprising:

sorbent media particles comprising

guanylated siliceous media particles having a particle size of about 10 microns to about 50 microns and that are about 10 wt% to about 65 wt% of the porous composite block, wherein the guanylated siliceous media particles comprise one or more guanidine- functionalized silicon atoms having the structure:

activated carbon particles having a particle size of about 20 microns to about 200 microns and that are about 10 wt% to about 50 wt% of the porous composite block; and a non-fibrous polymeric binder that bonds the sorbent media particles together and that is about 35 wt% to about 65 wt% of the porous composite block;

wherein the guanylated siliceous media particles and the activated carbon media particles are homogeneously distributed in the porous composite block.

[00144] Embodiment 64 provides a water filter comprising the composite porous block of any one of Embodiments 1-63.

[00145] Embodiment 65 provides a method of using the water filter of Embodiment 64, the method comprising:

passing water through the porous composite block to provide water having enhanced purity.

[00146] Embodiment 66 provides the method of Embodiment 65, wherein the passing of the water through the porous composite block comprises pressurizing the water, using gravity to bring the water through the porous composite block, or a combination thereof.

[00147] Embodiment 67 provides a method of making the porous composite block of any one of Embodiments 1-63, the method comprising:

dispersing the guanylated media particles with polymeric binder particles to form a dispersed mixture comprising the guanylated media particles homogeneously dispersed therein; and

sintering the dispersed mixture to form the porous composite block.

[00148] Embodiment 68 provides the method of Embodiment 67, wherein the dispersing comprises sieving or screening the guanylated media particles prior to mixing with the polymeric binder particles.

[00149] Embodiment 69 provides the method of any one of Embodiments 67-68, wherein the sintering comprises heating to about 100 °C to about 1000 °C.

[00150] Embodiment 70 provides the porous composite block, water filter, or method of any one or any combination of Embodiments 1-69 optionally configured such that all elements or options recited are available to use or select from.

Claims

CLAIMS What is claimed is:

1. A porous composite block comprising:

sorbent media particles comprising guanylated media particles; and

a polymeric binder that bonds the sorbent media particles together.

2. The porous composite block of claim 1, wherein the porous composite block is a non- fibrous porous composite block.

3. The porous composite block of claim 1, wherein the sorbent media particles are about 10 wt% to about 90 wt% of the porous composite block.

4. The porous composite block of claim 1, wherein the guanylated media particles are about 0.001 wt% to about 90 wt% of the porous composite block.

5. The porous composite block of claim 1, wherein the guanylated media particles have a particle size of about 10 nm to about 1 mm.

6. The porous composite block of claim 1, wherein the guanylated media particles comprise media particles comprising -OH bonds that are guanylated.

7. The porous composite block of claim 1, wherein the guanylated media particles are guanylated siliceous media particles.

8. The porous composite block of claim 1, wherein the guanylated media particles comprise one or more guanidine-functionalized silicon atoms having the structure:

9. The porous composite block of claim 8, wherein the guanylated media particles comprise siliceous guanylated media particles comprising one or more guanidine- functionalized silicon atoms having the structure:

wherein Si^media is a silicon atom that was present in the siliceous media particle as an -OH group prior to guanidine functionalization with a compound having the structure:

1 to 3.

10. The porous composite block of claim 1, wherein the sorbent media particles comprise secondary sorbent particles.

11. The porous composite block of claim 10, wherein the secondary sorbent particles comprise activated carbon, anthracite coal, sand, a metal oxide, a metal hydroxide, a metal silicate, an activated metal oxide, an ion exchange resin, carbon fibers, a chelating agent, a cyclodextrin, a polymer, or a combination thereof.

12. The porous composite block of claim 10, wherein the secondary sorbent particles comprise activated carbon, silver-impregnated activated carbon, hydroxide-impregnated activated carbon, metal-impregnated activated carbon, metal oxide-impregnated activated carbon, metal ion-impregnated activated carbon, salt-impregnated activated carbon, or a combination thereof.

13. The porous composite block of claim 1, wherein the polymeric binder is about 10 wt% to about 90 wt% of the porous composite block.

14. The porous composite block of claim 1, wherein the polymeric binder comprises a polyethylene polymer or copolymer, a polypropylene polymer or copolymer, a polyamide, a fluoropolymer, a polyethylene-based ion-containing polymer, an acrylic acid or methacrylic acid polymer or copolymer, an acrylic acid ester or methacrylic acid ester polymer or copolymer, or a combination thereof.

15. The porous composite block of claim 1, wherein the polymeric binder comprises ultra high molecular weight polyethylene.

16. A porous composite block comprising:

sorbent media particles comprising

17. A water filter comprising the composite porous block of claim 1.

18. A method of using the water filter of claim 17, the method comprising:

19. A method of making the porous composite block of claim 1, the method comprising: dispersing the guanylated media particles with polymeric binder particles to form a dispersed mixture comprising the guanylated media particles homogeneously dispersed therein; and

sintering the dispersed mixture to form the porous composite block.

20. The method of claim 19, wherein the sintering is performed at about 100 °C to about 1000 °C.