CN110997102A - Porous composite blocks comprising guanylated media - Google Patents

Porous composite blocks comprising guanylated media Download PDF

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Publication number
CN110997102A
CN110997102A CN201880048957.XA CN201880048957A CN110997102A CN 110997102 A CN110997102 A CN 110997102A CN 201880048957 A CN201880048957 A CN 201880048957A CN 110997102 A CN110997102 A CN 110997102A
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porous composite
composite block
guanylated
particles
media particles
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安德鲁·J·哈彻
奥拉夫·C·莫伯格
曼吉里·T·克希尔萨加尔
乔治·W·格里斯格拉伯
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Shuwanuo Intellectual Property Co
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3M Innovative Properties Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1638—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being particulate
    • B01D39/1653—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being particulate of synthetic origin
    • B01D39/1661—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being particulate of synthetic origin sintered or bonded
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12—Special parameters characterising the filtering material
    • B01D2239/1241—Particle diameter

Abstract

The present invention relates to porous composite blocks comprising guanylated media particles for water filtration. The porous composite block comprises adsorbent media particles and a polymeric binder binding the adsorbent media particles together. The sorbent media particles comprise guanylated media particles.

Description

Porous composite blocks comprising guanylated media
Background
Clean drinking water is one of the basic needs of all people. However, for a number of reasons, in many parts of the world, there is no reliable supply of clean drinking water due to factors such as intermittent power outages, rapid urbanization resulting in limited water supply, and varying quality of water. Bacteria naturally grow in most aquatic systems and can pose problems for industrial and municipal applications that use water, such as cooling towers, heat exchangers, drinking water and wastewater applications, oil and gas exploration, and hydraulic fracturing operations.
Porous composite blocks comprising adsorbent materials 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 comprising 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.
Disclosure of Invention
In various embodiments, the present invention provides a porous composite block. The porous composite block comprises adsorbent media particles comprising guanylated media particles. The porous composite block also contains a polymeric binder that binds the sorbent media particles together.
In various embodiments, the present invention provides a porous composite block comprising adsorbent media particles. The sorbent media particles comprise guanylated siliceous media particles having a particle size of about 10 microns to about 50 microns and being about 10% to about 65% by weight of the porous composite block. The guanylated siliceous media particles comprise one or more guanidine-functionalized silicon atoms having the structure:
Figure BDA0002377045480000011
the sorbent media particles also include activated carbon particles having a particle size of from about 20 microns to about 200 microns and being from about 10% to about 50% by weight of the porous composite block. The porous composite block also comprises a non-fibrous polymeric binder binding the sorbent media particles together and being from about 35% to about 65% by weight of the porous composite block. The guanylated siliceous media particles and the activated carbon media particles are uniformly distributed in the porous composite block.
In various embodiments, the present invention provides a water filter comprising a porous composite block.
In various embodiments, the present invention provides a method of using a porous composite block. The method includes passing water through a porous composite block to provide water having an increased purity.
In various embodiments, the present invention provides a method of making a composite block. The method includes dispersing guanylated media particles (e.g., in binder particles and optionally with co-sorbent particles) to form a dispersed mixture comprising guanylated media particles. The method also includes sintering the dispersed mixture to form a porous composite block.
In various embodiments, the porous composite blocks and methods of using the same of the present invention have certain advantages over other porous composite blocks, at least some of which are unexpected. For example, in some embodiments, the porous composite blocks of the present invention can remove a greater amount of contaminants from water, such as microbial contaminants (e.g., cells or particles having genetic material and capable of replication), microbes (e.g., any cell or particle having genetic material suitable for detection analysis, such as bacteria, yeast, fungi, viruses, such as encapsulated or unencapsulated viruses, and bacterial endospores), other contaminants (e.g., heavy metals, chemical compounds, such as small molecules, etc.), or combinations thereof, wherein the comparative statement in the summary regarding bacteria removal is directed to a comparative test using a porous composite block that is substantially identical to an embodiment of the porous composite block of the present invention but lacks guanylated media particles, using water comprising the same bacteria at the same concentration of bacteria at the same flow rate and through the same amount of porous composite material.
In some embodiments, the porous composite blocks of the present invention can remove a greater amount of bacteria from water than porous composite blocks comprising silver. In some embodiments, the porous composite blocks of the present invention may be less expensive than porous composite blocks comprising silver, such as compared to silver-containing porous composite blocks capable of removing the same or less amount of bacteria from water. In some embodiments, the porous composite blocks of the present invention may comprise silver, and when used in combination with guanylated media particles, the silver may have an additive or synergistic effect on bacterial removal such that the amount of bacteria removed by the porous composite block comprising silver and guanylated media is equal to or greater than the total bacteria removed by the combination of the porous composite block comprising the same concentration of silver but no guanylated media and the porous composite block comprising the same concentration of guanylated media but no silver.
Many filtration additives do not maintain bacterial or non-bacterial removal capacity under the high temperature (e.g., 200 ℃ or greater, or 400 ℃ or greater) and high pressure conditions used to make porous composite blocks, such as carbon blocks. However, the guanylating medium remains little or no change in properties under the heating conditions used to prepare the porous composite block. Many filter additives interfere with the porous composite block filtration activity. However, guanylated media had little or no interference with the filtration activity of the porous composite block.
Drawings
The drawings are generally shown by way of example, and not by way of limitation, to the various embodiments discussed in this document.
Fig. 1 illustrates a water filtration system including a porous composite block according to various embodiments.
Figure 2 illustrates a reaction scheme for guanidine functionalization of silicates, according to various embodiments.
FIGS. 3A-3C show Scanning Electron Microscope (SEM) images of guanylated perlite.
Fig. 4 shows a manufactured carbon block with end caps according to various embodiments.
Detailed Description
Reference will now be made in detail to certain embodiments of the presently disclosed subject matter. While the presently disclosed subject matter will be described in conjunction with the recited claims, it will be understood that the exemplary subject matter is not intended to limit the claims to the disclosed subject matter.
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 only about 0.1% to about 5%, but also include individual values (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. Unless otherwise indicated, the expression "about X to Y" has the same meaning as "about X to about Y". Likewise, unless otherwise indicated, the expression "about X, Y or about Z" has the same meaning as "about X, about Y, or about Z".
In this document, the terms "a", "an" or "the" are used to include one or more than one unless the context clearly indicates otherwise. The term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. The expression "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". Also, 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 in the understanding of the document and should not be construed as limiting; information related to a section header may appear within or outside of that particular section.
In the methods described herein, various actions may be performed in any order, except when a time or sequence of operations is explicitly recited, without departing from the principles of the invention. Further, the acts specified may occur concurrently unless the express claim language implies that they occur separately. For example, the claimed act of performing X and the claimed act of performing Y may be performed simultaneously in a single operation, and the resulting process would fall within the literal scope of the claimed process.
As used herein, the term "about" can allow, for example, a degree of variability in the value or range, e.g., within 10%, within 5%, or within 1% of the stated value or limit of the range, and includes the exact stated value or range.
The term "substantially" as used herein refers to a majority or majority, such as 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%. As used herein, the term "substantially free" can mean no or negligible amount such that the amount of material present does not affect the material properties of a composition comprising the material, such that the composition contains from about 0 wt% to about 5 wt% of the material, or from 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 wt%, 3.5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.5 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.01 wt%, or about 0.001 wt% or less. The term "substantially free" can be intended to have an insignificant amount of material such that the composition contains from about 0 wt% to about 5 wt% of the material, or from 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 wt%, 3.5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.5 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.01 wt%, or about 0.001 wt% or less, or about 0 wt%.
As used herein, the term "organic group" refers to any carbon-containing functional group. Examples may include oxygen-containing groups such as alkoxy groups, aryloxy groups, aralkyloxy groups, oxo (carbonyl) groups; carboxyl groups including carboxylic acids, carboxylic acid salts, and carboxylic acid esters; sulfur-containing groups such as alkyl and aryl sulfide groups; and other heteroatom-containing groups. Non-limiting exemplary packages of organic groupsIncluding OR, OOR, OC (O) N (R)2、CN、CF3、OCF3R, C (O), methylenedioxy, ethylenedioxy, N (R)2、SR、SOR、SO2R、SO2N(R)2、SO3R、C(O)R、C(O)C(O)R、C(O)CH2C(O)R、C(S)R、C(O)OR、OC(O)R、C(O)N(R)2、OC(O)N(R)2、C(S)N(R)2、(CH2)0-2N(R)C(O)R、(CH2)0-2N(R)N(R)2、N(R)N(R)C(O)R、N(R)N(R)C(O)OR、N(R)N(R)CON(R)2、N(R)SO2R、N(R)SO2N(R)2、N(R)C(O)OR、N(R)C(O)R、N(R)C(S)R、N(R)C(O)N(R)2、N(R)C(S)N(R)2、N(COR)COR、N(OR)R、C(＝NH)N(R)2C (o) n (or) R, C (═ NOR) R, and substituted or unsubstituted (C)1-C100) A hydrocarbyl group, wherein R can be hydrogen (in examples including other carbon atoms) or a carbyl moiety, and wherein the carbyl moiety can be substituted or unsubstituted.
As used herein, the term "substituted" as defined herein in connection with a molecule or organic group refers to a state wherein one or more hydrogen atoms contained therein are replaced with one or more non-hydrogen atoms. As used herein, the term "functional group" or "substituent" refers to a group that can be or be substituted onto a molecule or organic group. Examples of substituents or functional groups include, but are not limited to, halogens (e.g., F, Cl, Br, and I); oxygen atoms in the group, such as hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo (carbonyl) groups, including carboxylic acid, carboxylate salt, and carboxylic acid ester carboxyl groups; having sulfur atoms in the group, such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; having nitrogen atoms in the group, such as amines, hydroxylamines, 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, Cl, Br, I, OR, OC (O) N (R)2、CN、NO、NO2、ONO2(iii) AzideBasic, CF3、OCF3R, O (oxo), S (thiocarbonyl), C (O), S (O), methylenedioxy, ethylenedioxy, N (R)2、SR、SOR、SO2R、SO2N(R)2、SO3R、C(O)R、C(O)C(O)R、C(O)CH2C(O)R、C(S)R、C(O)OR、OC(O)R、C(O)N(R)2、OC(O)N(R)2、C(S)N(R)2、(CH2)0-2N(R)C(O)R、(CH2)0-2N(R)N(R)2、N(R)N(R)C(O)R、N(R)N(R)C(O)OR、N(R)N(R)CON(R)2、N(R)SO2R、N(R)SO2N(R)2、N(R)C(O)OR、N(R)C(O)R、N(R)C(S)R、N(R)C(O)N(R)2、N(R)C(S)N(R)2、N(COR)COR、N(OR)R、C(＝NH)N(R)2C (o) n (or) R and C (═ NOR) R, where R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (C)1-C100) Hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or to an adjacent nitrogen atom may form a heterocyclic group together with one or more nitrogen atoms.
As used herein, the term "hydrocarbon" or "hydrocarbyl group" refers to a molecule or functional group that comprises carbon and hydrogen atoms. The term may also refer to molecules or functional groups that typically contain both carbon and hydrogen atoms, but in which all hydrogen atoms are replaced by other functional groups. The term "hydrocarbyl" refers to a functional group derived from a straight, branched, or cyclic hydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof. The hydrocarbyl group may be shown as (C)a-Cb) Hydrocarbyl, wherein a and b are integers, and means having any number a to b of carbon atoms. For example, (C)1-C4) Hydrocarbyl means that the hydrocarbyl group can be methyl (C)1) Ethyl (C)2) Propyl group (C)3) Or butyl (C)4) And (C)0-Cb) Hydrocarbyl means that in certain embodiments there are no hydrocarbyl groups. The alkylene group is a diradical hydrocarbon, for example a hydrocarbon bonded at two positions.
As used herein, the term "polymer" refers to a molecule having at least one repeating unit, and may include copolymers.
In various embodiments, the salt having a positively charged counterion can comprise any suitable positively charged counterion. For example, the counterion can be ammonium (NH)4 +) Or alkali metals such as sodium (Na)+) Potassium (K)+) Or lithium (Li)+). In some embodiments, the counterion may have a positive charge greater than +1, and in some embodiments, the counterion may be complexed with multiple ionizing groups, such as Zn2+、Al3+Or alkaline earth metals such as Ca2+Or Mg2+。
In various embodiments, the salt having a negatively charged counterion can comprise any suitable negatively charged counterion. For example, the counter ion may be a halide ion, such as fluoride, chloride, iodide, or bromide. In other examples, the counter ion can be a nitrate, hydrogen sulfate, dihydrogen phosphate, hydrogen carbonate, nitrite, perchlorate, iodate, chlorate, bromate, chlorite, hypochlorite, hypobromite, cyanide, amide, cyanate, hydroxide, permanganate. The counterion can be the conjugate base of any carboxylic acid, such as acetate or formate. In some embodiments, the counter ion may have a negative charge greater than-1, and in some embodiments, the counter ion may be complexed with multiple ionizing groups, such as oxides, sulfides, nitrides, arsenates, phosphates, arsenites, hydrogenphosphates, sulfates, thiosulfates, sulfites, carbonates, chromates, dichromates, peroxides, or oxalates.
Porous composite block:
the present invention provides a porous composite block comprising adsorbent media particles and a polymeric binder binding the adsorbent media particles together. The sorbent media particles comprise guanylated media particles. The porous composite block may be monolithic. The pores of the block may include spaces formed between the sorbent media particles and particles of the binder particles when sintered together to soften the polymeric binder and adhere the sorbent media particles to one another to form the porous composite block. The bores of the block include through-holes that are fluidly connected to each other in a tortuous or direct path and from one side of the block to the other (e.g., to about the opposite side). The through-holes allow the porous composite block to be used as a filter, such as for aqueous fluids. When the porous composite block is used as a water filter, the guanidine groups can provide for removal of: microbial contaminants (e.g., cells or particles having genetic material and capable of replication), microorganisms (e.g., any cells or particles having genetic material suitable for analysis or detection, such as bacteria, yeast, fungi, viruses such as encapsulated or unencapsulated viruses, and bacterial endospores), or combinations 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.
The porous composite block may be non-fibrous such that the porous composite block is substantially free of fibers (e.g., a fibrous binder or filler, such as cellulose fibers). The polymeric binder used in the porous composite block may be a non-fibrous binder, wherein the binder may have any suitable form prior to sintering, but has a non-fibrous form after being formed into the porous composite block. For example, the binder may be in any suitable form, such as particles, extruded pellets, or fibers, prior to sintering to form the porous composite block. After forming the porous composite block, the binder may be non-fibrous, such as particulate, agglomerated, or a combination thereof. In other embodiments, the porous composite block may include fibers, such as a fibrous binder or filler (e.g., glass fibers).
The sorbent media particles 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 sorbent media particles can be about 10 wt.% to about 90 wt.%, about 35 wt.% to about 65 wt.%, about 40 wt.% to about 60 wt.%, or about 10 wt.% or less of the porous composite block, or less than, equal to, or greater than about 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, or about 90 wt.% or more of the porous composite block.
The porous composite block may have any suitable pore size and porosity such that the block has a desired pressure drop throughout the filtration zone and removes material from the liquid passing therethrough. For example, the porous composite block can have a pore size sufficient to remove material from water passing therethrough that has a largest dimension of 10 microns or greater, 1 micron or greater, or less than, equal to, or greater than 10 microns, 8 microns, 6 microns, 5 microns, 4 microns, 3 microns, 2 microns, 1 micron, 0.5 microns, 0.1 microns, 0.05 microns, or about 0.01 microns or less.
The porous composite block may have a pore size and porosity such that it can filter water at the following flow rates: 0.1L/min to about 1000L/min, or about 1L/min to about 100L/min, or about 0.1L/min or less, or less than, equal to, or greater than about 0.5L/min, 1L/min, 1.5L/min, 2L/min, 2.5L/min, 3L/min, 3.5L/min, 4L/min, 4.5L/min, 5L/min, 6L/min, 7L/min, 8L/min, 9L/min, 10L/min, 12L/min, 14L/min, 16L/min, 18L/min, 20L/min, 30L/min, 40L/min, 50L/min, 60L/min, 70L/min, 80L/min, 90L/min, or about 100L/min or more. The pressure drop may be from 1kPa to about 1000kPa, or from about 20kPa to about 200kPa, or about 1kPa or less, or less than, equal to, or greater than about 10kPa, 20kPa, 30kPa, 40kPa, 50kPa, 60kPa, 70kPa, 80kPa, 90kPa, 100kPa, 125kPa, 150kPa, 175kPa, 200kPa, 225kPa, 250kPa, 300kPa, 400kPa, 500kPa, 600kPa, 800kPa, or about 1000kPa or more. The flow rate and pressure drop may depend on the pressure of the applied water and the amount of fouling of the cake (e.g., by minerals and particulates), and may depend on the pressure of the water.
In various embodiments, the porous composite block can have a bacteria removal capacity, wherein the log reduction value of water passing through the porous composite block (i.e., the log of Colony Forming Units (CFU)/mL in the pre-filtered sample minus the log of CFU/mL in the filtrate sample) is from about 50% to about 100%, or from 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 of the log of CFU/mL of escherichia coli of the pre-filtered sample. The porous composite block can produce a log reduction in water with a prefiltered bacterial concentration of 4.3log CFU/mL (e.g., e.coli) as follows: 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.
Oregoside mediator particles：
The porous composite block includes guanylated media particles immobilized within the porous composite. The guanylated media particles may comprise guanidine groups attached directly to atoms of the media particles via siloxane bonds or comprise alkylene linking groups. In some examples, guanylated media particles can be prepared by treating media particles containing-OH or alkoxide groups with an aminohydrocarbylalkoxysilane (e.g., a monoalkoxysilane, dialkoxysilane, or trialkoxysilane, such as a monoalkoxydialkylsilane or dialkoxymonoalkylsilane) to form-O-Si bonds. Guanylated media particles can be uniformly distributed throughout the composite block to allow exposure of water even to guanidine groups during filtration.
The guanylated media particles can be guanylated siliceous media particles comprising guanidine groups attached to the silicon atoms of the siliceous media particles via siloxane bonds or comprising alkylene linking groups. In some examples, guanylated siliceous media particles can be prepared by treating siliceous media particles comprising Si-OH or silanol groups with an aminohydrocarbyl trialkoxysilane to form Si-O-Si bonds.
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%, or about 10 wt% to about 65 wt%, about 15 wt% to about 60 wt%, or about 0.001 wt% or less of the porous composite block, or less than, equal to, or greater than about 0.01 wt%, 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 82 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 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%, 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 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 92 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt% of the sorbent particles, 98 wt%, 99 wt%, 99.9 wt%, 99.99 wt%, or about 99.999 wt% or more.
The guanylated media particles can have any suitable particle size (e.g., largest dimension, such as weight average or number average) such that the desired pore size and porosity are present in the porous composite block. The guanylated medium particles may have the following particle size: from about 10nm to about 1mm, from about 10 microns to about 50 microns, from about 20 microns to about 40 microns, or about 10nm or less, or less than, equal to, or greater than about 20nm, 30nm, 40nm, 50nm, 75nm, 100nm, 125nm, 150nm, 175nm, 200nm, 250nm, 300nm, 400nm, 500nm, 750nm, 1 micron, 2 microns, 3 microns, 4 microns, 5 microns, 6 microns, 8 microns, 10 microns, 15 microns, 20 microns, 30 microns, 40 microns, or about 50 microns or more. The guanylated medium particles may be a powder. The individual particles may independently have the approximate shape of a sphere, a flake, a chip, a polygon, or a combination thereof.
Guanylated media particles include media particles comprising-OH bonds that have been guanylated. The media particles can comprise any suitable material, compound, or combination thereof, such as comprising a metal, a nonmetal, a metalloid, or a combination thereof. The guanylated-OH bond may be a C-OH bond or a Si-OH bond. Guanylated media particles can include media particles that include an ornithiated metal-OH bond, 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 comprise metal silicates, such as silicates of magnesium, calcium, zinc, aluminum, iron, titanium, or combinations thereof. The metal silicate may be an amorphous metal silicate. The metal silicate may be in at least partially molten form. The metal silicate may be an amorphous, spheroidized metal silicate, such as amorphous, spheroidized magnesium silicate.
The guanylated media particles can be guanylated siliceous media particles comprising guanylated Si-OH atoms, where the Si atoms in the siliceous media can be any suitable atomic percent of the siliceous media. The siliceous media particles can comprise metal silicates, diatomaceous earth, surface-modified diatomaceous earth, gamma-FeO (OH) (e.g., lepidocrocite), metal carbonates (e.g., calcium carbonate), metal phosphates (e.g., hydroxyapatite), silica (e.g., SiO)2Such as a network comprising Si-O-Si bonds and Si-OH or Si ═ O end groups), perlite, or combinations thereof.
The metal silicate may include particles of amorphous metal silicate, such as amorphous, spheroidized magnesium silicate, amorphous aluminum spherical silicate, or combinations thereof. The metal silicate in amorphous and at least partially molten particulate form can be prepared by: the feed particles (e.g., having an irregular shape or any suitable shape) are melted or softened under controlled conditions to produce generally ellipsoidal or spherical particles (i.e., particles having enlarged two-dimensional images that are generally rounded and free of sharp or pointed edges, including true or substantially circular and ellipsoidal shapes and any other rounded or curved shapes). Such methods include atomization, fire polishing, direct melting, flame melting, and the like. Flame melting can form at least partially melted, substantially glassy particles by direct melting or fire polishing of solid feed particles.
Diatomaceous earth is a natural silica material produced from residues of diatoms, a marine inhabitant microorganism. It is available from natural sources and is also commercially available. The diatomaceous earth particles may comprise small, open silica networks in the form of symmetric cubes, cylinders, spheres, plates, rectangular boxes, and the like. The pore structure in these particles may be substantially uniform. Diatomaceous earth may be used as raw mined material or as purified and optionally milled particles. The diatomaceous earth may be in the form of milled particles. The diatomaceous earth may optionally be heat treated to remove organic residues prior to use.
The surface-modified diatomaceous earth may comprise, on at least a portion of its surface, diatomaceous earth bearing a surface treatment comprising titanium dioxide, iron oxide, gold, platinum, or a combination thereof. The surface treatment agent may include fme-nanoscale gold, fme-nanoscale platinum, a metal oxide (e.g., at least one of titanium dioxide and iron oxide), or a combination thereof.
The metal particles may comprise perlite. Perlite is a naturally occurring amorphous volcanic glass that can contain about 70-75% silica and about 12-15% alumina, 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 heating, it forms a lightweight aggregate. The guanylated media particles can be guanylated perlite particles.
The guanylated media particles can have any suitable concentration of guanidine groups on their surfaces such that the porous composite block has a desired amount of bacterial or non-bacterial removal activity. For example, guanylated media particles may have the following surface nitrogen concentrations as measured by X-ray photoelectron spectroscopy (XPS): about 2 atomic% to about 20 atomic%, 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 atomic%, 5 atomic%, 6 atomic%, 7 atomic%, 8 atomic%, 9 atomic%, 10 atomic%, 11 atomic%, 12 atomic%, 13 atomic%, 14 atomic%, 15 atomic%, 16 atomic%, 17 atomic%, 18 atomic%, 19 atomic%, or about 20 atomic% or greater.
Guanylated media particles comprise one or more guanidine-functionalized silicon atoms. The guanylated media particles comprise one or more guanidine-functionalized silicon atoms having the following structure:
Figure BDA0002377045480000111
the guanidine moiety can comprise any suitable counterion, such as a sulfate (e.g., multiple guanidine groups can share a single anion with multiple negative charges). The variables L are independently selected from the group consisting of a bond and substituted or unsubstituted (C)1-C20) Alkylene radicals, e.g. (C)1-C10) Alkylene, (C)2-C5) Alkylene or propylene (i.e. -CH)2-CH2-CH2-). The linking group L may be substituted with one or more other guanidine groups, either directly or via another L linking group. One of the remaining bonds on the silicon atom is directly connected to an atom of the medium (e.g., a silicon atom, a metal atom, or another atom that contains an-OH bond prior to guanylation). The other two remaining bonds on the silicon atom may be independently selected to be atoms bonded to the medium (e.g., there may be more than one bond from the silicon atom to the medium), to alkoxy groups, hydroxyl groups, to another guanidine or amine group directly or via an alkylene linker, to-O-Si bonds or-alkyl-O-Si bonds (where the attached silicon atom may be functionalized in the same manner as the silicon atom shown in the structure of the guanidine-functionalized silicon atom), or combinations thereof. In some embodiments, both remaining Si bonds may be bonded to a single oxygen atom to form a Si ═ O bond.
The functionalized silicon atoms may be attached to the 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 may be attached to the 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 following structure:
Figure BDA0002377045480000121
atomic SiMediumBefore being guanidine-functionalized with a compound having the structureMedium-silicon atoms of the OH groups present in the siliceous media particles:
Figure BDA0002377045480000122
variable R1Independently at each occurrence is (C)1-C20) Hydrocarbyl radical, (C)1-C10) Alkyl, (C)1-C3) Alkyl or methyl. The variable n may be 1 to 3, such as 1,2 or 3. When R is1In the case of methyl, the guanylating compound used to form the guanylated mediator particles may be, for example, guanylpropyl trimethoxysilane.
The guanylating compound used to form the guanylated media particles may be any suitable guanylating compound such as including amines which may subsequently be converted to guanidine groups (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) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyl-trimethoxysilane, N-3[ (amino (polypropoxy) ] aminopropyltrimethoxysilane, N-3- (meth) acrylic acid, N-methyl-3-aminohexyl) aminopropyltrimethoxysilane, N-methyl-3-aminoundecyl-trimethoxysilane, N-3[ (amino (polypropoxy) ] aminopropyltrimethoxysilane, N-methyl-3, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, aminopropylsilanetriol, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, (3-trimethoxysilylpropyl) diethylene-triamine, or a combination thereof.
Auxiliary adsorbent particles：
In addition to the guanylated media particles, the porous composite block may also contain auxiliary adsorbent particles. The co-sorbent particles can be any suitable sorbent particles other than guanylated media particles, such as particles that absorb or adsorb one or more materials (e.g., particles, organic compounds, microorganisms (such as bacteria, viruses), heavy metals, etc.) from water passing through the particles. The co-sorbent particles may be non-guanylated particles. The auxiliary adsorbent particles may comprise 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 perlite; activated alumina or other active metal oxides or other inorganics; ion exchange resins (e.g., crushed or otherwise); carbon fibers; a chelating agent; a cyclodextrin; polymers other than ultra-high molecular weight polyethylene, such as adhesives or halogenated resins (e.g., having antimicrobial functionality); or a combination thereof. The porous composite block may be a porous carbon block comprising guanylated media particles formed by sintering a mixture of activated carbon particles and guanylated media particles.
The supplemental sorbent particles can be about 0 wt% to about 89.999 wt%, about 0 wt% to about 50 wt%, about 0 wt% to about 45 wt%, or about 0 wt% of the porous composite block, or less than, equal to, or greater than about 0.001 wt%, 0.01 wt%, 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 82 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 89.9 wt%, 89.99 wt%, or about 89.999 wt% or more of the porous composite block. The auxiliary sorbent particles can be about 0 wt% to about 99.999 wt%, 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 wt%, 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, or about 80 wt% or more of the total sorbent media particles.
The auxiliary adsorbent particles can have any suitable particle size (e.g., largest dimension, such as weight average or number average) such that the desired pore size and porosity are present in the porous composite block. The auxiliary adsorbent can have any suitable particle size, such as from about 10nm to about 1mm, from about 20 microns to about 200 microns, or about 10nm or less, or less than, equal to, or greater than about 20nm, 30nm, 40nm, 50nm, 75nm, 100nm, 125nm, 150nm, 175nm, 200nm, 250nm, 300nm, 400nm, 500nm, 750nm, 1 micron, 2 microns, 3 microns, 4 microns, 5 microns, 6 microns, 8 microns, 10 microns, 15 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 80 microns, 100 microns, 125 microns, 150 microns, 175 microns, or about 200 microns or more.
Activated carbon (also known as activated charcoal) is a form of carbon that is processed to have small, low volume pores, which increases the surface area available for adsorption. The activated carbon may be formed from any suitable carbonaceous material (e.g., nut shells, coconut shells, peat, wood, coconut shells, lignite, coal, petroleum pitch, etc.), such as via exposure to high temperatures to cause pyrolysis. The activated carbon may comprise standard activated carbon without chemical impregnation or other chemical activation. In some embodiments, the activated carbon may comprise silver impregnated activated carbon (e.g., elemental silver or 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 combinations thereof. Prior to carbonization, the activated carbon may be impregnated via treatment with an impregnating material. In some embodiments, the auxiliary sorbent particles comprise activated carbon, silver-impregnated activated carbon, or a combination thereof. The silver-impregnated activated carbon may form any suitable proportion of the co-sorbent, such as from about 0 wt% to about 100 wt%, or from about 30 wt% to about 100 wt%, from 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 wt%, 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 92 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, 99.9 wt%, 99.99 wt%, or about 99.999 wt% or more of the porous composite block. In some embodiments, the supplemental sorbent particles can be substantially free of any one or more of the impregnated carbons described herein, such as substantially free of sulfur-impregnated activated carbon (e.g., a sulfur salt), or substantially free of silver-impregnated activated carbon (e.g., a silver salt).
Polymer adhesive：
The porous composite block comprises a polymeric binder that binds the sorbent particles to one another. The mixture of polymeric binder particles and sorbent media particles may be heated to soften the polymeric binder particles and adhere the sorbent media particles thereto to form a porous composite mass. The polymeric binder may promote cohesion of the aggregates or particles, and may comprise a polymeric material, such as a thermoplastic material capable of softening and becoming tacky at elevated temperatures and hardening upon cooling.
The polymeric binder may be uniformly 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%, about 35 wt% to about 65 wt%, about 40 wt% to about 60 wt%, or about 10 wt% or less of the porous composite block, or less than, equal to, or greater than about 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 82 wt%, 84 wt%, 86 wt%, 88 wt%, or about 90 wt% or more.
The polymeric binder can be any suitable polymeric binder. The polymeric binder may comprise a polyethylene polymer or copolymer, a polypropylene polymer or copolymer, a polyamide, a fluoropolymer, a polyvinyl ionomer, an acrylic or methacrylic acid polymer or copolymer, an acrylate or methacrylate polymer or copolymer, or a combination thereof. The polymeric binder may comprise ultra-high molecular weight polyethylene (UHMWPE).
Examples of suitable binders that may be included in the porous composite block include, but are not limited to, end-capped polyacetals such as poly (oxymethylene) or polyoxymethylene, poly (trichloroacetaldehyde), 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), perfluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, poly (chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene copolymer, poly (vinylidene fluoride), poly (vinyl fluoride), and the like; polyamides such as poly (6-aminocaproic acid) or poly (caprolactam), poly (hexamethylene adipamide), poly (hexamethylene sebacamide), poly (11-aminoundecylenic acid), and the like; polyaramids such as poly (imino-1, 3-phenyliminophthalide) or poly (m-phenylene isophthalamide) and the like; parylene, such as parylene, poly (chloro-p-xylene), and the like; polyaryl ethers such as poly (oxy-2, 6-dimethyl-1, 4-phenylene) or poly (p-phenylene oxide) and the like; polyarylsulfones such as poly (oxy-1, 4-phenylene sulfonyl-1, 4-phenylene oxy-1, 4-phenylene-isopropylidene-1, 4-phenylene), poly (sulfonyl-1, 4-phenylene oxy-1, 4-phenylene sulfonyl-4, 4' -biphenyl), and the like; polycarbonates such as poly (bisphenol a) or poly (carbonyldioxy-1, 4-phenyleneisopropylene-1, 4-phenylene), and the like; polyesters such as poly (ethylene terephthalate), poly (tetramethylene terephthalate), poly (cyclohexene-1, 4-dimethyl terephthalate), or poly (oxymethylene-1, 4-cyclohexylene-oxy terephthalate), and the like; polyarylate sulfides such as poly (p-phenylene sulfide) or poly (thio-1, 4-phenylene), and the like; polyimides such as poly (pyromellitic dianhydride-1, 4-phenylene), and the like; polyolefins such as polyethylene, polypropylene, poly (1-butene), poly (2-butene), poly (1-pentene), poly (2-pentene), poly (3-methyl-1-pentene), poly (4-methyl-1-pentene), and the like; vinyl polymers such as poly (vinyl acetate), poly (vinylidene chloride), poly (vinyl chloride), and the like; diene polymers such as 1, 2-poly-1, 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 combinations thereof.
Other Components：
The porous composite block may or may not include ion exchange resins (e.g., powdered particles thereof), fillers, binders, pigments, dyes, titanium silicates, titanium oxides, elemental metals, metal ions, metal oxides, elemental silver, silver ions, silver oxides, salts, hydroxide salts, zinc salts, sodium salts, potassium salts, silver salts, or combinations thereof. Titanium silicates and titanium oxides can remove heavy metals.
Water filter：
In various embodiments, the present invention provides a water filter or a water filtration system including the water filter. The water filter can be any type of water filter including embodiments of the porous composite blocks described herein. The water filter may be considered to be simply a porous composite block, or may be a porous composite block having one or more components thereon, such as a top cover.
Fig. 1 shows an example of a porous composite block for use as a water filter 102 in a water filtration system 100. The water filtration system 100 includes a housing 130 having an inlet 140 fluidly connected to an outlet 150. The water filter 102 according to the present invention is sealed with the top cover 122 and positioned within the housing 130 such that any water (not shown) entering the housing 130 through the inlet 140 passes through the water filter 102 into the conduit 180 and then to and from the outlet 150. The O-ring 140 forms a water-tight seal between the outlet 150 of the top cover 122 and the outlet tube 145.
As shown, the housing 130 includes a head portion 190 and a body portion 192. The head portion 190 includes an inlet 140 and an outlet 150. The head portion 190 and the body portion 192 are capable of mechanically engaging each other (as indicated by threads 194) to form a watertight seal. In such embodiments, the head portion and the body portion may be mechanically engageable (e.g., bayonet mount or screw thread) by movement (including relative twisting of the head portion and the body portion).
Method of using a water filter：
Various embodiments of the present invention provide a method of using a water filter comprising a porous composite block, such as any of the porous composite blocks described herein. The method includes passing water through a porous composite block to provide water having an increased purity. Passing water through the porous composite block may include pressurizing the water, using gravity to pass the water through the porous composite block, or a combination thereof.
Method for preparing porous composite block：
Various embodiments of the present invention provide a method of making a porous composite block, such as any of the porous composite blocks described herein. The method may include dispersing guanylated media particles with particles of a polymeric binder and optionally with auxiliary adsorbent particles to form a dispersed mixture comprising guanylated media particles uniformly dispersed therein. The method may further include sintering the dispersed mixture to form a porous composite block, including heating the dispersed mixture, and optionally including applying pressure to the dispersed mixture. The heating can be performed at any suitable temperature, and can include sintering the dispersed mixture, such as at about 100 ℃ to about 1000 ℃, about 200 ℃ to about 1000 ℃, such as about 200 ℃ to about 500 ℃, or about 100 ℃ or less, or less than, equal to, or greater than 105 ℃, 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 ℃ or more. Dispersing the guanylated medium particles may include sieving or screening the particles prior to or during mixing with the other components to break up agglomerates of guanylated material and produce a more uniform particle size.
Examples
Various embodiments of the present invention may be better understood by reference to the following examples, which are provided by way of illustration. The present invention is not limited to the examples given herein.
Materials:
the materials used in the examples are shown in table 1. Unless otherwise indicated, all chemicals were purchased from Sigma Aldrich (Sigma Aldrich)/fisher Scientific (Fischer Scientific).
Table 1: a material.
Figure BDA0002377045480000181
Example 1: preparation of guanylated perlite
A3-L flask equipped with an overhead L mechanical stirrer was charged with 3-aminopropyltrimethoxysilane (44.8g, 250mmol) and anhydrous methanol (200 mL). The reaction mixture was then treated with O-methylisourea hemisulfate (30.8g, 250mmol) and the reaction mixture was stirred under a nitrogen atmosphere overnight. The reaction mixture was diluted with 1.2L of methanol and perlite particles (249g) were added to the flask followed by H2O (4.5mL, 250 mmol). The mixture was stirred rapidly for two days to facilitate the reaction between guanylated trimethoxysilane and the particles. The resulting guanidine-functionalized perlite particles were isolated by filtration and rinsed with 500mL of methanol. The particles were returned to the flask and treated with 1L of deionized water. After stirring for 45 minutes, the particles were isolated by filtration and washed with an additional 500mL of deionized water.The particles were again returned to the flask and treated with 1L of deionized water. After stirring for 3 days, the particles were isolated by filtration and washed with an additional 500mL of deionized water. The particles were then dried under vacuum at 65 ℃ to give 249g of functionalized particles as a grey powder. As shown in table 2 below, the nitrogen content was 8.1 ± 0.3 atomic percent as measured by electron spectroscopy for chemical analysis (ECSA). A reaction scheme showing perlite functionalization is shown in fig. 2. Fig. 3A-3C show SEM images of guanylated perlite.
Table 2: XPS surface concentration (atomic%)。
Region(s) C N O F Na Al Si S K Ca Fe
Region A 17 8.1 50 0.1 0.8 2.3 19 1.1 0.7 0.07 0.13
Region B 16 7.9 51 0.4 0.7 2.3 19 1.0 1.1 0.08 0.08
Region C 17 8.4 51 0.3 0.8 2.1 19 1.1 0.9 0.12 0.02
Region D 16 7.6 52 0.3 0.8 2.1 19 1.1 0.8 0.06 0.05
Region E 17 8.0 51 0.5 0.7 2.3 19 1.1 0.8 0.06 0.08
Region F 16 8.4 51 0.5 0.6 2.0 19 1.1 0.7 0.05 0.10
Mean value of 16.5 8.1 51.0 0.34 0.74 2.2 19.2 1.08 0.81 0.07 0.08
Standard deviation of 0.40 0.30 0.38 0.15 0.09 0.13 0.18 0.03 0.14 0.03 0.04
Examples 2 to 5: carbon bits comprising guanylated perlite。
The tablets were prepared by dry mixing the ingredients, loading the mixture into a mold and holding at 204 ℃ for one hour to sinter the carbon blocks. The compositions shown in table 3 were used to prepare the tablets.
Table 3: small block formula (weight percent)
Figure BDA0002377045480000191
Figure 4 shows photographs of the carbon blocks of examples 2-5, including the end caps and ready for testing.
Example 6: bacterial removal of guanylated perlite pieces of examples 2-5。
The blocks of examples 2-5 were tested using the following procedure.
Streaked cultures of E.coli (ATCC 11229) on TSA were incubated overnight at 37 ℃. Isolated colonies were removed from the plate and inoculated into 10mL of TSB using a standard microbiology loop, and the incubator was shaken at 37 ℃ (from New Brunswick Scientific
Figure BDA0002377045480000201
44) Incubated for 20-22 hours. Cultured in a shaking incubator for up to hours. Will contain about 2-3X 109CFU/mL overnight cultures were serially diluted in Butterfield buffer to obtain a solution with approximately 1X 106CFU/mL inoculum.
Test samples were prepared as follows: by 106A1: 100 dilution of CFU/mL inoculum was inoculated with 200mL deionized water (MilliQ gradient System, Millipore, Ma.) to yield a concentrate containing about 104CFU/mL (about 4Log CFU/mL) of water test samples.
10 using a Walchem class E metering pump4The CFU/mL E.coli mixture was delivered to the filter block. Initially, the pump head and air tubing were purged with DI water. The pump head is purged by opening a purge valve on the pump head and running the pump at high flow. Tubing at the pump head outlet purges air by running the pump at high flow, while raising the tubing and allowing air bubbles to rise and exit the system. The pump tubing was then connected to the camel bak QSM cartridge containing the carbon block. The pump was run at high flow to wet the carbon block and purge the air cartridge. The outlet of the cartridge was connected to a filtrate collector via PVC tubing. The pump stroke length is then set to its minimum level (about 20%) and the stroke frequency is adjusted to provide a flow rate through the cartridge of 20 mL/min. Then will containThe prefiltered solution with E.coli was introduced into the pump inlet.
The pre-filtered solution was pumped through the block holder containing the carbon block using a metering pump with 1/8 "wall thickness PVC tubing (VWR catalog No. 60985-. The spiked water was pumped through the sintered cake matrix at a flow rate of 20 mL/min. The filtrate was collected in a 250mL sterile glass bottle. The first 100mL of filtrate was collected and discarded. The second 100mL of filtrate was collected for further processing.
A second 100mL volume of the filtrate, 10mL, was added to a 100mL flip-top bottle containing Butterfield buffer to obtain a 1:10 dilution. The bottle was capped and mixed manually by shaking for 10 seconds. Remove the 10mL volume and add this volume to another flip-top bottle to obtain a 1:100 dilution. Similarly, the filtrate was further diluted to 1:1000 and 1: 10000. These 100mL diluted filtrates were vacuum filtered through a 0.45 micron filter. Filtration was started from highest dilution to lowest dilution using standard vacuum filtration equipment. For each block, a new holder is used. Between the various samples, the filtration apparatus was rinsed with 500mL of deionized water.
The filters were removed from the apparatus with a sterile tweezer plate and placed on an Endo agar plate with the mesh side up. The plates were incubated at 37 ℃ for 18-20 hours. Colony counts were obtained from the plates by manual counting. The prefiltered sample was also diluted and filtered by the procedure described above. CFU/mL colony counts were converted to log CFU/mL values.
By using the following formula: LRV ═ (log CFU/mL in pre-filtered samples) - (log CFU/mL in filtrate samples), Log Reduction Values (LRV) were calculated based on counts from plated filtrates and pre-filtered samples. The results of the tests are shown in table 4.
Table 4: bacteria removal results。
Block, description Logarithmic CFU in prefiltered samples LRV
Example 2, carbon control 4.34 1.34
Example 3, 60 wt% silver-carbon 4.34 0.42
Example 4, 35 wt% silver-carbon +15 wt% guanylated perlite 4.34 3.19
Example 5, 60 wt% guanylated perlite 4.34 4.34
Although the terms and expressions which 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, it being recognized that various modifications are possible within the scope of the embodiments of the invention. Thus, it should be understood that although the present invention has been specifically disclosed by particular embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of embodiments of this invention.
Exemplary embodiments：
The present invention provides the following exemplary embodiments, the numbering of which should not be construed as specifying the degree of importance:
embodiment 1 provides a porous composite block comprising:
sorbent media particles comprising guanylated media particles; and
a polymeric binder binding the sorbent media particles together.
Embodiment 2 provides the porous composite block of embodiment 1, wherein the porous composite block is a non-fibrous porous composite block.
Embodiment 3 provides the porous composite block of any one of embodiments 1-2, wherein the polymeric binder is a non-fibrous polymeric binder.
Embodiment 4 provides the porous composite block of any one of embodiments 1-3, wherein the porous composite block is free of fibrous binder.
Embodiment 5 provides the porous composite block of any one of embodiments 1-4, wherein the sorbent media particles are from about 10% to about 90% by weight of the porous composite block.
Embodiment 6 provides the porous composite block of any one of embodiments 1-5, wherein the sorbent media particles are about 35% to about 65% by weight of the porous composite block.
Embodiment 7 provides the porous composite block of any one of embodiments 1-6, wherein the guanylated media particles are uniformly distributed throughout the composite block.
Embodiment 8 provides the porous composite block of any one of embodiments 1-7 wherein the guanylated media particles are about 0.001% to about 90% by weight of the porous composite block.
Embodiment 9 provides the porous composite block of any one of embodiments 1-8 wherein the guanylated media particles are about 10 weight percent to about 65 weight percent of the porous composite block.
Embodiment 10 provides the porous composite block of any of embodiments 1-9 wherein the guanylated media particles are about 0.001% to about 100% by weight of the sorbent media particles.
Embodiment 11 provides the porous composite block of any one of embodiments 1-10 wherein the guanylated media particles are about 20% to about 100% by weight of the adsorbent media particles.
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 10nm to about 1 mm.
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.
Embodiment 14 provides the porous composite block of any one of embodiments 1-13, wherein the guanylated media particles have a shape of spheres, flakes, chips, polygons, or a combination thereof.
Embodiment 15 provides the porous composite block of any one of embodiments 1-14, wherein the guanylated media particle comprises a media particle comprising silicon atoms.
Embodiment 16 provides the porous composite block of any one of embodiments 1-15, wherein the guanylated media particles comprise media particles comprising guanylated-OH bonds.
Embodiment 17 provides the porous composite block of embodiment 16, wherein the-OH bond that is guanylated is C-OH, Si-OH, or a combination thereof.
Embodiment 18 provides the porous composite block of any one of embodiments 1-17, wherein the guanylated media particles comprise media particles comprising guanylated metal-OH bonds.
Embodiment 19 provides the porous composite block of any one of embodiments 1-18, wherein the guanylated metal-OH bond is magnesium-OH, calcium-OH, zinc-OH, aluminum-OH, iron-OH, titanium-OH, or a combination thereof.
Embodiment 20 provides the porous composite block of any one of embodiments 1-19, wherein the guanylated media particles comprise media particles comprising a metal silicate.
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.
Embodiment 22 provides the porous composite block of any one of embodiments 1-21, wherein the guanylated media particles comprise media particles comprising silica.
Embodiment 23 provides the porous composite block of any one of embodiments 1-22, wherein the guanylated media particles comprise metal silicates, diatomaceous earth, surface-modified diatomaceous earth, gamma-feo (oh), metal carbonates, metal phosphates, silica, perlite, or a combination thereof.
Embodiment 24 provides the porous composite block of any one of embodiments 1-23, wherein the guanylated media particles comprise perlite.
Embodiment 25 provides the porous composite block of any one of embodiments 1-24, wherein the guanylated media particles are guanylated perlite particles.
Embodiment 26 provides the porous composite block of any one of embodiments 1-25, wherein the guanylated media particles have a surface nitrogen concentration of about 2 atomic% to about 20 atomic% as measured by X-ray photoelectron spectroscopy.
Embodiment 27 provides the porous composite block of any one of embodiments 1-26, wherein the guanylated media particles have a surface nitrogen concentration of about 6 atomic% to about 10 atomic% as measured by X-ray photoelectron spectroscopy.
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.
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 following structure:
Figure BDA0002377045480000241
wherein L is independently selected from the group consisting of a bond and substituted or unsubstituted (C)1-C20) Alkylene groups.
Embodiment 30 provides the porous composite block of embodiment 29, wherein L is (C)1-C10) An alkylene group.
Embodiment 31 provides the porous composite block of any one of embodiments 29-30, wherein L is (C)2-C5) An alkylene group.
Embodiment 32 provides the porous composite block of any one of embodiments 29-31, wherein L is propylene.
Embodiment 33 provides the porous composite block of any one of embodiments 29-32, wherein the guanylating media particles comprise siliceous guanylating media particles comprising one or more guanidine-functionalized silicon atoms having the structure:
Figure BDA0002377045480000242
wherein Si isMediumBefore being guanidine-functionalized with a compound having the structureMedium-silicon atoms of OH groups present in the siliceous media particles:
Figure BDA0002377045480000243
wherein at each occurrence, R1Independently is (C)1-C20) And wherein n is 1 to 3.
Embodiment 34 provides the porous composite block of embodiment 33, wherein R1Independently is (C)1-C10) An alkyl group.
Embodiment 35 provides the porous composite block of any one of embodiments 33-34, wherein R1Independently is (C)1-C3) Alkane (I) and its preparation methodAnd (4) a base.
Embodiment 36 provides the porous composite block of any one of embodiments 33-35, wherein R1Is methyl, wherein the guanylated compound is guanidyl propyl trimethoxy silane.
Embodiment 37 provides the porous composite block of any one of embodiments 1-36, wherein the sorbent media particles comprise supplemental sorbent particles.
Embodiment 38 provides the porous composite block of embodiment 37, wherein the supplemental sorbent particles are non-guanylated particles.
Embodiment 39 provides the porous composite block of any one of embodiments 37-38, wherein the auxiliary adsorbent particles are about 0 wt% to about 89.999 wt% of the porous composite block.
Embodiment 40 provides the porous composite block of any one of embodiments 37-39, wherein the auxiliary adsorbent particles are about 0 wt% to about 50 wt% of the porous composite block.
Embodiment 41 provides the porous composite block of any one of embodiments 37-40, wherein the auxiliary adsorbent particles are about 0 wt% to about 99.999 wt% of the adsorbent media particles.
Embodiment 42 provides the porous composite block of any one of embodiments 37-41, wherein the auxiliary adsorbent particles are about 0 wt% to about 80 wt% of the adsorbent media particles.
Embodiment 43 provides the porous composite block of any one of embodiments 37-42, wherein the auxiliary adsorbent particles have a particle size of about 10nm to about 1 mm.
Embodiment 44 provides the porous composite block of any one of embodiments 37-43, wherein the auxiliary adsorbent particles have a particle size of about 20 microns to about 200 microns.
Embodiment 45 provides the porous composite block of any one of embodiments 37-44, wherein the auxiliary sorbent particles comprise activated carbon, anthracite coal, sand, metal oxides, metal hydroxides, metal silicates, active metal oxides, ion exchange resins, carbon fibers, chelating agents, cyclodextrins, polymers, or combinations thereof.
Embodiment 46 provides the porous composite block of any one of embodiments 37-45, wherein the auxiliary adsorbent particles comprise activated carbon, silver-impregnated activated carbon, hydroxide-impregnated activated carbon, metal oxide-impregnated activated carbon, metal ion-impregnated activated carbon, salt-impregnated activated carbon, or a combination thereof.
Embodiment 47 provides the porous composite block of any one of embodiments 37-46, wherein the auxiliary adsorbent particles comprise activated carbon, silver-impregnated activated carbon, or a combination thereof.
Embodiment 48 provides the porous composite block of any one of embodiments 37-47, wherein the auxiliary adsorbent particles comprise activated carbon or silver-impregnated activated carbon.
Embodiment 49 provides the porous composite block of any one of embodiments 37-48, wherein the auxiliary adsorbent particles are activated carbon.
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 guanylated media particles.
Embodiment 51 provides the porous composite block of any one of embodiments 1-50, wherein the polymeric binder is about 10% to about 90% by weight of the porous composite block.
Embodiment 52 provides the porous composite block of any one of embodiments 1-51, wherein the polymeric binder is about 35% to about 65% by weight of the porous composite block.
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 polyvinyl ionomer, an acrylic or methacrylic acid polymer or copolymer, an acrylate or methacrylate ester polymer or copolymer, or a combination thereof.
Embodiment 54 provides the porous composite block of any one of embodiments 1-53, wherein the polymeric binder comprises ultra high molecular weight polyethylene.
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.
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.
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.
Embodiment 58 provides the porous composite block of any one of embodiments 1-57, wherein the porous composite block further comprises elemental metal, metal ions, metal oxides, elemental silver, silver ions, silver oxide, salts, hydroxide salts, zinc salts, sodium salts, potassium salts, silver salts, or combinations thereof.
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 material from water passing therethrough, the material having a largest dimension of 10 microns or greater.
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 material from water passing therethrough, the material having a largest dimension of 1 micron or greater.
Embodiment 61 provides the porous composite block of any one of embodiments 1-60, wherein the porous composite block is sufficient such that the log reduction value of water passing through the porous composite block is from about 50% to about 100% of the log CFU/mL of e.
Embodiment 62 provides the porous composite block of any one of embodiments 1-61, wherein the porous composite block is sufficient such that the 4.3log CFU/mL water log reduction through the porous composite block is from about 2.2 to about 4.3.
Embodiment 63 provides a porous composite block comprising:
adsorbent media particles comprising
A guanylated siliceous media particle having a particle size of from about 10 microns to about 50 microns and being from about 10% to about 65% by weight of the porous composite block, wherein the guanylated siliceous media particle comprises one or more guanidine-functionalized silicon atoms having the structure:
Figure BDA0002377045480000271
activated carbon particles having a particle size of about 20 microns to about 200 microns and being about 10 wt% to about 50 wt% of the porous composite block; and
a non-fibrous polymeric binder binding the sorbent media particles together and being about 35% to about 65% by weight of the porous composite block;
wherein the guanylated siliceous media particles and the activated carbon media particles are uniformly distributed in the porous composite block.
Embodiment 64 provides a water filter comprising the composite porous block of any one of embodiments 1-63.
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 an increased purity.
Embodiment 66 provides the method of embodiment 65, wherein passing the water through the porous composite block comprises pressurizing the water, using gravity to pass the water through the porous composite block, or a combination thereof.
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 and polymeric binder particles to form a dispersed mixture comprising the guanylated media particles uniformly dispersed therein; and
sintering the dispersed mixture to form the porous composite block.
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.
Embodiment 69 provides the method of any one of embodiments 67-68, wherein the sintering comprises heating to about 100 ℃ to about 1000 ℃.
Embodiment 70 provides a porous composite block, water filter, or method according to any one or any combination of embodiments 1-69, optionally configured such that all elements or options listed are available for use or selection.

Claims (20)

1. A porous composite block, comprising:
sorbent media particles comprising guanylated media particles; and
a polymeric binder binding 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 from about 10% to about 90% by weight of the porous composite block.
4. The porous composite block of claim 1 wherein the guanylated media particles are about 0.001% to about 90% by weight of the porous composite block.
5. The porous composite block of claim 1 wherein the guanylated media particles have a particle size of about 10nm to about 1 mm.
6. The porous composite block of claim 1, wherein the guanylated media particles comprise media particles comprising guanylated-OH bonds.
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 following structure:
Figure FDA0002377045470000011
wherein L is independently selected from the group consisting of a bond and substituted or unsubstituted (C)1-C20) Alkylene groups.
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 following structure:
Figure FDA0002377045470000021
wherein Si isMediumBefore being guanidine-functionalized with a compound having the structureMedium-silicon atoms of OH groups present in the siliceous media particles:
Figure FDA0002377045470000022
wherein at each occurrence, R1Independently is (C)1-C20) And wherein n is 1 to 3.
10. The porous composite block of claim 1 wherein said sorbent media particles comprise auxiliary sorbent particles.
11. The porous composite block of claim 10, wherein the auxiliary sorbent particles comprise activated carbon, anthracite coal, sand, metal oxides, metal hydroxides, metal silicates, active metal oxides, ion exchange resins, carbon fibers, chelating agents, cyclodextrins, polymers, or combinations thereof.
12. The porous composite block of claim 10, wherein the auxiliary sorbent particles comprise activated carbon, silver-impregnated activated carbon, hydroxide-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% to about 90% by weight 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 or methacrylic acid polymer or copolymer, an acrylate or methacrylate 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:
adsorbent media particles comprising
A guanylated siliceous media particle having a particle size of from about 10 microns to about 50 microns and being from about 10% to about 65% by weight of the porous composite block, wherein the guanylated siliceous media particle comprises one or more guanidine-functionalized silicon atoms having the structure:
Figure FDA0002377045470000031
and
activated carbon particles having a particle size of about 20 microns to about 200 microns and being about 10 wt% to about 50 wt% of the porous composite block; and
a non-fibrous polymeric binder binding the sorbent media particles together and being about 35% to about 65% by weight of the porous composite block;
wherein the guanylated siliceous media particles and the activated carbon media particles are uniformly distributed in the porous composite block.
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:
passing water through the porous composite block to provide water having an increased purity.
19. A method of making the porous composite block of claim 1, the method comprising:
dispersing the guanylated media particles and polymeric binder particles to form a dispersed mixture comprising the guanylated media particles uniformly 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 ℃ to about 1000 ℃.
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