WO2013043626A1 - Particule de silice contenant du soufre - Google Patents

Particule de silice contenant du soufre Download PDF

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Publication number
WO2013043626A1
WO2013043626A1 PCT/US2012/055964 US2012055964W WO2013043626A1 WO 2013043626 A1 WO2013043626 A1 WO 2013043626A1 US 2012055964 W US2012055964 W US 2012055964W WO 2013043626 A1 WO2013043626 A1 WO 2013043626A1
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Prior art keywords
composition
compound
molar ratio
following
sulfur
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PCT/US2012/055964
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English (en)
Inventor
Nicholas S ERGANG
Ian Saratovsky
Hung-Ting Chen
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Nalco Company
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Priority claimed from US13/242,618 external-priority patent/US8377194B2/en
Application filed by Nalco Company filed Critical Nalco Company
Publication of WO2013043626A1 publication Critical patent/WO2013043626A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/42—Sulfides or polysulfides of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/20—Methods for preparing sulfides or polysulfides, in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/12—Carbamic acid or thiocarbamic acid; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates

Definitions

  • This invention disclosure pertains generally to a silica-containing composition, and more specifically to a silica-containing composition that includes a sulfur moiety.
  • the invention has particular relevance to silica-containing compositions that are dried on a hygroscopic solid and that further include a metal or metalloid cation and an optional organosilane moiety.
  • Silica-containing materials have ubiquitous applications. More specifically, a variety of manufacturing processes that produce either consumer or industrial products utilize silica- containing materials for various purposes. For example, silica-containing products can be utilized as fillers in coatings (e.g. paints) and polymer composites, catalysts supports, beer/wine/juice clarifiers. New and improved silica-containing products with increased performance and ease of use are desired by various industries. SUMMARY OF THE INVENTION
  • the present invention accordingly provides for a composition
  • a composition comprising a compound having the following formula (Si02) x (OH) y M z S a F*B: wherein M is at least one of the following metal or metalloid cations: boron, magnesium, aluminum, calcium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tin, platinum, gold, and bismuth; wherein S is a sulfur-based species selected from at least one of the following: sulfide salts, dithiocarbamates, polymer-based dithiocarbamates, and polys ulfide salts; wherein F optionally exists and said F is at least one of the following: a functionalized organosilane, a sulfur-containing organosilane, an amine-containing organosilane, and an alkyl-containing organosilane at a surface area coverage of about
  • the present invention also provides for a composition
  • a composition comprising a compound having a formula of: (Si0 2 )i5(OH) x -Cui S5-bCa(OH) 2 , where x is the surface concentration of hydroxyl species as determined by the moisture content and b is the relative amount of hydrated lime.
  • the present invention further provides for a product produced by filtering an aqueous- based material from a composition
  • a composition comprising a compound having the following formula (Si0 2 )x(OH) y M z S a F
  • M is selected from at least one of the following metal or metalloid cations: boron, magnesium, aluminum, calcium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tin, platinum, gold, and bismuth
  • S is a sulfur-based species selected from at least one of the following: sulfide salts, dithiocarbamates, polymer-based dithiocarbamates, and polysulfide salts
  • F optionally exists and said F is at least one of the following: a functionalized organosilane, a sulfur-containing organosilane, an amine-containing organosilane, and an alkyl-
  • the present invention also provides for a product produced from drying a composition at a temperature of about 100 °C to about 350 °C, wherein said composition comprises a compound containing the following formula (Si0 2 ) x (OH) y M z S a F*B: wherein M is selected from at least one of the following metal or metalloid cations: boron, magnesium, aluminum, calcium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tin, platinum, gold, and bismuth; wherein S is a sulfur -based species selected from at least one of the following: sulfide salts, dithiocarbamates, polymer-based dithiocarbamates, and polysulfide salts; wherein F optionally exists and said F is at least one of the following: a functionalized organosilane, a sulfur-containing organosilane, an amine-
  • the present invention also provides for a product produced by the addition of an aqueous- based composition to a hygroscopic solid such that the aqueous portion is adsorbed by the solid to form a hydrated product.
  • the composition comprises a compound containing the following formula (Si02) x (OH) y M z S a F B.
  • M is selected from at least one of the following metal or metalloid cations: boron, magnesium, aluminum, calcium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tin, platinum, gold, and bismuth;
  • S is a sulfur-based species selected from at least one of the following: sulfide salts, dithiocarbamates, polymer-based dithiocarbamates, and polysulfide salts;
  • F optionally exists and said F is at least one of the following: a functionalized organosilane, a sulfur-containing organosilane, an amine-containing organosilane, and an alkyl-containing organosilane at a surface area coverage of about 0.01 to about 100 %; wherein the molar ratio of y/x is equal to about 0.01 to about 0.5, the molar ratio of x z is equal to about
  • the present invention provides for a method of forming a silica-containing product/ composition
  • SCP silica-containing precursor
  • step e optionally reacting the dried product from step e with a functional group and optionally wherein the resultant functionalized dried product is at least one of the following: a functionalized metal oxide-doped or metal sulfide-doped silica- containing product; and g. adding the aqueous-based SCP to a hygroscopic solid such that the resulting product comprises a metal oxide-doped or metal sulfide-doped silica-containing product deposited on a hydrated alkaline earth oxide or lanthanide oxide substrate.
  • a functionalized metal oxide-doped or metal sulfide-doped silica- containing product optionally reacting the dried product from step e with a functional group and optionally wherein the resultant functionalized dried product is at least one of the following: a functionalized metal oxide-doped or metal sulfide-doped silica- containing product; and g. adding the aqueous-based SCP to
  • the present invention also provides for a method of forming a silica-containing product/composition comprising: a. providing a silica-containing precursor (SCP) contained in solution that has a pH greater than 7; b. adjusting the pH of the solution to less than or equal to about 7; c. optionally doping the SCP with one or more metal species, wherein said doping occurs when the solution has a pH less than or equal to a pH of about 7; d. adjusting the pH of the solution to greater than about 7; e. adding an effective amount of salt to the solution so that the conductivity of the solution is greater than or equal to about 4 mS, wherein said addition occurs prior to, simultaneous with, or after the pH adjustment in step 2d; f.
  • SCP silica-containing precursor
  • optionally filtering and drying the SCP optionally filtering and drying the SCP; g. optionally reacting the dried product from step f with a functional group and optionally wherein the resultant functionalized dried product is at least one of the following: a functionalized metal oxide-doped or metal sulfide-doped silica-containing product; and h. adding the aqueous-based SCP to a hygroscopic solid such that the resulting product comprises a metal oxide-doped or metal sulfide-doped silica-containing product deposited on a hydrated alkaline earth oxide or lanthanide oxide substrate.
  • the present invention provides a composition that contains a compound with a sulfur component, specifically a compound having a formula of (Si02)x(OH)yM z SaF «B: wherein M is selected from at least one of the following metal or metalloid cations: boron, magnesium, aluminum, calcium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tin, platinum, gold, and bismuth; wherein S is a sulfur-based species selected from at least one of the following: sulfide salts, dithiocarbamates, and polymer-based dithiocarbamates, polysulfide salts; wherein F optionally exists and said F is at least one of the following: a functionalized organosilane, a sulfur-containing organosilane, an amine-containing organosilane, and an alkyl-containing organosilane at a surface
  • hygroscopic solids e.g., anhydrous inorganic hygroscopic solids
  • examples of hygroscopic solids include, but are not limited to, alkali oxides, alkaline earth oxides, lanthanide oxides, the like, and combinations thereof.
  • Specific examples include calcium sulfate, magnesium sulfate, ammonium sulfate, alkali hydroxides, the like, and combinations thereof. It should be appreciated that one skilled in the art would recognize that the effective amount of solid needed to reach the desired dryness will vary dependent on the solid of choice.
  • the hygroscopic inorganic solid is at least one alkaline earth oxide or lanthanide oxide. Specific examples used herein are intended to encompass such variations.
  • the compound can be in various forms and proportions relative to the components of the compositions.
  • various products can contain the compounds encompassed by this invention.
  • the following compound embodiments can stand alone, be further modified by chemical and/or physical means, or integrated into other products (e.g., consumer or industrial products).
  • the invention also provides for a composition
  • a composition comprising a compound having a formula of: (Si0 2 )i 5(OH) y -Cui S5, where y is the surface concentration of hydroxyl species as determined by moisture content.
  • the invention also provides for a composition
  • a composition comprising a compound having a formula of: (Si0 2 )i5(OH) y -Cui S5-bCa(OH) 2 wherein y is a surface concentration of hydroxyl species as determined by the moisture content, and b is a relative amount of hydrated lime.
  • the compound comprises about 3 % to about 15 % by weight in an aqueous-based slurry.
  • the compound comprises about 15% to about 40% by weight in a wet cake form.
  • the compound comprises about 40% to about 99% by weight in a powder form. In embodiments, the compound comprises about 60% to about 99% by weight in a powder form.
  • the compound has a particle size of about 5 to about 200 um containing aggregated nanoparticles ranging from about 3 to about 500nm. In embodiments, the compound has a particle size of about 5 to about 500 um containing aggregated nanoparticles ranging from about 3 to about 500 ran.
  • the compound has a surface area of about 30 m /g to about 800 m 2 /g. In embodiments, the compound has a surface area of about 2 m 2 /g to about 200 m 2 /g.
  • the compound has a pore volume of about 0.3 cc/g to about 2.0 cc/g. In embodiments, the compound has a pore volume of about 0.01 cc/g to about 1.0 cc/g.
  • a product is produced by filtering an aqueous-based material from a composition comprising a compound having the following formula (Si02)x(OH)yM z S a F wherein M is selected from at least one of the following: boron, magnesium, aluminum, calcium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tin, platinum, gold, and bismuth; wherein S is a sulfur-based species selected from at least one of the following: sulfide salts, dithiocarbamates, polymer-based dithiocarbamates, and polysulfide salts; wherein F optionally exists and said F is at least one of the following: a functionalized organosilane, a sulfur-containing organosilane, an amine- containing organosilane, and an alkyl-containing organosilane at a surface area coverage of about 0.
  • M
  • the product is produced from drying a composition at a temperature of about 100 °C to about 350 °C, wherein said composition comprises a compound having the following formula (Si0 2 ) x (OH) y M z S a F: wherein M is at least one of the following metal or metalloid cations: boron, magnesium, aluminum, calcium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tin, platinum, gold, and bismuth; wherein S is a sulfur-based species selected from at least one of the following: sulfide salts, dithiocarbamates, polymer-based dithiocarbamates, and polysulfide salts; wherein F optionally exists and said F is at least one of the following: a functionalized organosilane, a sulfur-containing organosilane, an amine-containing organosilane, and an al
  • the product is produced by the addition of an aqueous-based composition to a hygroscopic solid such that the aqueous portion is adsorbed by the solid to form a hydrated product, wherein said composition comprises a compound containing the following formula (Si0 2 ) x (OH)yM z S a F-B.
  • M is selected from at least one of the following metal or metalloid cations: boron, magnesium, aluminum, calcium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tin, platinum, gold, and bismuth.
  • S is a sulfur-based species selected from at least one of the following: sulfide salts, dithiocarbamates, polymer -based dithiocarbamates, and polysulfide saltsand F optionally exists and comprises at least one of the following: a functionalized organosilane, a sulfur- containing organosilane, an amine-containing organosilane, and an alkyl-containing organosilane at a surface area coverage of about 0.01 to about 100 %; wherein the molar ratio of y/x is equal to about 0.01 to about 0.5, the molar ratio of x/z is equal to about 0.5 to about 300 or from about 0.5 to about 100, and the molar ratio of a/z is about 0.5 to about 5; and wherein B comprises a hygroscopic solid at a water to solid molar ratio of about 0. 1 to about 6 and is at least one alkaline earth oxide or lanthanide oxide.
  • the compounds can be made in various
  • silica-containing products encompassed by this invention can be made by the following methods.
  • One methodology involves starting from an acidic starting point.
  • the method comprises forming a silica-containing product comprising the steps of: a. providing a silica-containing precursor (SCP) contained in solution that has a pH less than or equal to a pH of 7; b. optionally doping the SCP with one or more metal species, wherein said doping occurs when the solution has a pH less than or equal to a pH of 7; c. adjusting the pH of the solution to greater than 7; d. adding an effective amount of salt to the solution so that the conductivity of the solution is greater than or equal to 4 mS, wherein said addition occurs prior to, simultaneous with, or after the pH adjustment in step lc; e. optionally filtering and drying the SCP; f.
  • SCP silica-containing precursor
  • step f optionally reacting the dried product from step e with a functional group and optionally wherein the resultant functionalized dried product is at least one of the following: a functionalized metal oxide-doped or metal sulfide-doped silica-containing product; and g. adding the aqueous-based SCP to a hygroscopic solid such that the resulting product comprises a metal oxide-doped or metal sulfide-doped silica-containing product deposited on a hydrated alkaline earth oxide or lanthanide oxide substrate.
  • the functional group in step f is an organosilane.
  • the silicon-containing precursor is selected from at least one of the following: silicic acid, colloidal silica, tetraethylorthosilicate, and dispersed fumed silica.
  • the pH range of the SCP in step 1(a) is from about 3 to about 4.
  • the pH of the SCP is adjusted to greater than 7 by mixing/ interacting the molecules of said SCP with an alkaline solution at a shear rate of 6 to 23 m/s based on tip speed.
  • the method further comprises adjusting the pH of the SCP to greater than about 7 by mixing said SCP with an alkaline solution via a mixing chamber.
  • a mixing chamber is described in U.S. Patent No.
  • the mixing chamber comprises a first conduit having one or more inlets and outlets; a second conduit having one or more inlets and outlets, wherein said first conduit secures to said second conduit and traverses said second conduit; a mixing chamber that has one or more inlets and outlets, wherein said second conduit secures to said mixing chamber and wherein said outlets of said first conduit and said outlets of said second conduit are in communication with said mixing chamber; and an adaptor that is in communication with said outlet of said mixing chamber and is secured to said mixing chamber.
  • the mixing chamber can then be attached or in communication with a receptacle that holds/processes through (e.g. a conduit) a mixed product.
  • said mixing chamber can then be attached or in communication with a receptacle that holds/processes a mixed product resulting from said pH adjustment of said SCP.
  • Ultra Turax Model Number UTI-25 (available from IKA® Works, Inc. in Wilmington, NC), a mixing device, can be utilized.
  • any suitable reactor or mixing device/ chamber may be utilized in the method of the invention.
  • the method further comprises adjusting the pH of the SCP to greater than about 7 by combining said SCP with an alkaline solution with mixing yielding a Reynolds Number greater than or equal to 2,000 to form the silica- containing product.
  • the method further comprises adjusting the pH of the SCP to greater than about 7 by combining said SCP with an alkaline solution under transitional flow conditions (i.e., Reynolds Numbers between 2,000 and 4,000) to form the silica-containing product.
  • transitional flow conditions i.e., Reynolds Numbers between 2,000 and 4,000
  • the method further comprises adjusting the pH of the SCP to greater than about 7 by combining said SCP with an alkaline solution under turbulent flow conditions (i.e., Reynolds Numbers greater than or equal to 4,000) to form the silica-containing product.
  • turbulent flow conditions i.e., Reynolds Numbers greater than or equal to 4,000
  • the pH of the SCP is adjusted to a pH range of about 7 to about 11 with the use of a chemistry selected from at least one of the following: ammonium hydroxide, ammonium carbonate, mineral bases such as but not limited to sodium hydroxide and/or potassium hydroxide, organic bases such as but not limited to trimethylammonium hydroxide, alkaline silicates, sulfide salts such as but not limited to sodium sulfide, and polysulfide containing salts such as but not limited to calcium polysulfide and/ or sodium polysulfide.
  • a chemistry selected from at least one of the following: ammonium hydroxide, ammonium carbonate, mineral bases such as but not limited to sodium hydroxide and/or potassium hydroxide, organic bases such as but not limited to trimethylammonium hydroxide, alkaline silicates, sulfide salts such as but not limited to sodium sulfide, and polysulfide containing salts such as but not limited to calcium
  • the resulting slurry from step d is filtered and dried such that the solid concentration of said dried and filtered product is increased from about 5 wt% to about 99 wt%.
  • the dried product from step e is surface treated with an organosilane via controlled hydrolysis and condensation of the silane to the silica surface in at least one of the processes: an organic solvent, supercritical solvent, or solvent-free process.
  • the aqueous-based SCP is added to a hygroscopic inorganic solid in a fluidized bed mixer such that the water is adsorbed uniformly by the solid to form a hydrated powder containing the SCP.
  • Another methodology involves starting from an alkaline starting point.
  • the method comprises forming a silica-containing product comprising the steps of: a. providing a silica-containing precursor (SCP) contained in solution that has a pH greater than about 7; b. adjusting the pH of the solution to less than or equal to about 7; c. optionally doping the SCP with one or more metal species, wherein said doping occurs when the solution has a pH less than or equal to a pH of about 7; d. adjusting the pH of the solution to greater than about 7; e. adding an effective amount of salt to the solution so that the conductivity of the solution is greater than or equal to about 4 mS, wherein said addition occurs prior to, simultaneous with, or after the pH adjustment in step 2d; f.
  • SCP silica-containing precursor
  • optionally filtering and drying the SCP optionally filtering and drying the SCP; g. optionally reacting the dried product from step f with a functional group and optionally wherein the resultant functionalized dried product is at least one of the following: functionalized metal oxide-doped or metal sulfide-doped silica-containing product; adding the aqueous-based SCP to a hygroscopic solid such that the resulting product comprises a metal oxide-doped or metal sulfide-doped silica-containing product deposited on a hydrated alkaline earth oxide or lanthanide oxide substrate.
  • the functional group in step g is an organosilane.
  • the silicon-containing precursor is selected from at least one of the following: silicic acid, colloidal silica, alkaline silicates, tetraethylortho silicate, and dispersed fumed silica.
  • the pH of the silicon-containing precursor is adjusted through the use of at least one of the following: carbonic acid, an organic acid(s) such as but not limited to acetic acid, a mineral acid(s) such as but not limited to sulfuric acid and/or hydrochloric acid such that the pH is decreased to a range of from to about 2 to about 7.
  • the pH range of the SCP is adjusted to a range of about 3 to about 4 with acetic acid.
  • the pH of the SCP is adjusted to a pH range of about 7 to about 11 with the use of a chemistry selected from at least one of the following: ammonium hydroxide, ammonium carbonate, mineral bases, organic bases, alkaline salts, sulfide salts, alkaline silicates, and polysulfide containing salts.
  • a chemistry selected from at least one of the following: ammonium hydroxide, ammonium carbonate, mineral bases, organic bases, alkaline salts, sulfide salts, alkaline silicates, and polysulfide containing salts.
  • the resulting slurry from step e is filtered and dried such that the solid concentration of said dried and filtered product is increased from about 5 wt% to about 99 wt%.
  • the dried product from step f is surface treated with an organosilane via controlled hydrolysis and condensation of the silane to the surface of the SCP in at least one of the following: an organic solvent, supercritical solvent, or solvent-free process.
  • the pH of the SCP is adjusted to greater than about 7 by mixing said SCP with an alkaline solution at a shear rate of about 6 to about 23 m/s based on tip speed.
  • the method further comprises adjusting the pH of the SCP to greater than about 7 by mixing said SCP with an alkaline solution via a mixing chamber.
  • a mixing chamber is described in U. S. Patent No. 7,550,060, "Method and Arrangement for Feeding Chemicals into a Process Stream". This patent is herein incorporated by reference.
  • the mixing chamber comprises a first conduit having one or more inlets and outlets; a second conduit having one or more inlets and outlets, wherein said first conduit secures to said second conduit and traverses said second conduit; a mixing chamber that has one or more inlets and outlets, wherein said second conduit secures to said mixing chamber and wherein said outlets of said first conduit and said outlets of said second conduit are in communication with said mixing chamber; and an adaptor that is in communication with said outlet of said mixing chamber and is secured to said mixing chamber.
  • the mixing chamber can then be attached or in communication with a receptacle that holds/processes through (e.g. a conduit) a mixed product.
  • said mixing chamber can then be attached or in communication with a receptacle that holds/processes a mixed product resulting from said pH adjustment of said SCP.
  • Ultra Turax Model Number UTI-25 (available from IKA® Works, Inc. in Wilmington, NC), a mixing device, can be utilized. It is envisioned that any suitable reactor or mixing device/chamber may be utilized in the method of the invention.
  • the method further comprises adjusting the pH of the SCP to greater than about 7 by combining said SCP with an alkaline solution with mixing yielding a Reynolds Number greater than or equal to 2,000, to form the silica-containing product.
  • the method further comprises adjusting the pH of the SCP to greater than about 7 by combining said SCP with an alkaline solution under transitional flow conditions (i.e., Reynolds Numbers between 2,000 and 4,000) to form the silica-containg product.
  • the method further comprises adjusting the pH of the SCP to greater than about 7 by combining said SCP with an alkaline solution under turbulent flow conditions (i.e., Reynolds Numbers greater than or equal to 4,000) to form the silica-containing product.
  • the sulfur-based species of the present invention may be selected from a representative list but not intended to be a limiting list of at least one of the following: sulfide salts, dithiocarbamates, polymer-based dithiocarbamates, and polysulfide salts.
  • Sulfide salts maybe but not limited to sodium sulfide, potassium sulfide, and/or metal sulfides such as copper sulfide.
  • Dithiocarbamates may be but not limited to dimethyldithiocarbamate (DMDTC) or diethyldithiocarbamate (DEDTC).
  • DMDTC dimethyldithiocarbamate
  • DEDTC diethyldithiocarbamate
  • Polymer-based dithiocarbamates contain organic polymers containing the functional group R n CS 2 .
  • R is an alkyl group which is linear or branched.
  • R is an alkyl group which is linear or branched.
  • An example of a commercially available polymer-based dithiocarbamate is described in U.S. Patent Nos. 5, 164.095 and U.S. Patent Nos. 5 ,346,627. which are herein incorporated by reference.
  • Polysulfides that can be used in the present invention include, but are not limited to, sodium polysulfide and calcium polysulfide.
  • Organosilanes that can be used in the current invention are well known in the art and may be represented generally by R( 4 - a )-SiX a , wherein a may be from 1 to 3.
  • the organo-functional group, R- may be any aliphatic or alkene containing functionalized group such as propyl, butyl, 3-chloropropyl, amine, thiol, and combinations thereof.
  • X is representative of a hydrolysable alkoxy group, typically methoxy or ethoxy. Some examples are 3-thiopropyl and mercaptopropyl silanes.
  • salt is added to increase the conductivity of the reaction solution to 4mS.
  • the salts include, but are not limited to, alkali and alkaline halides, sulfates, phosphates, and nitrates such as sodium sulfite, potassium chloride, sodium chloride, sodium nitrate, calcium sulfate, and potassium phosphate.
  • alkali and alkaline halides, sulfates, phosphates, and nitrates such as sodium sulfite, potassium chloride, sodium chloride, sodium nitrate, calcium sulfate, and potassium phosphate.
  • the effective amount of salt added to reach the desired conductivity will vary dependent on the salt of choice.
  • Thiols and amines are represented generally by the class of organic and inorganic compounds containing the amine or thiol group having the general formula B-(SH) or— B- (NH2), wherein B is a linear or branched group consisting of carbon atoms such as -(CH2) n -, wherein n is from 1 to 15, in particular where n is 1 to 6, and most preferred where n is 3.
  • B is a linear or branched group consisting of carbon atoms such as -(CH2) n -, wherein n is from 1 to 15, in particular where n is 1 to 6, and most preferred where n is 3.
  • a solution containing 16.4 g of a 25 wt% ammonia solution and 5.84 g ammonium carbonate was prepared in 24.6 g DI water. The solution was added to the reaction flask quickly whereupon the viscosity of the solution increased significantly. The mixture was stirred for 30 minutes, then any remaining silicic acid was fed at 20 ml/min. Upon completion of the silicic acid feed, the heating was turned off and the solution was allowed to cool.
  • the silica slurry was filtered and freeze-dried at 150 °C to produce a dry powder.
  • Nitrogen sorption analysis of the powder was performed on an Autosorb- lC unit from Quantachrome.
  • the sample was degassed at 300 °C for 2 h, then characterized by a multi-point BET (Brunauer, Emmett, and Teller a surface area test) surface area, total pore volume, and BJH (Barrett- Joyner-Halenda) adsorption pore size distribution.
  • Physical data indicated a surface area of 354 square meters per gram, a pore volume of 1.19 cc/g, and a pore diameter of 13.5 nm.
  • a solution containing 17.3 g sodium sulfide and 1 1.8 g of a 25 wt% ammonia was prepared in 200 g DI water.
  • the solution was quickly added to the reaction flask after 3 h of silicic acid feed where the viscosity of the solution increased significantly.
  • the mixture was stirred for 30 minutes, then any remaining silicic acid was fed at 16 ml/min. Upon completion of the silicic acid feed, the heating was turned off and the solution was allowed to cool.
  • the CuS-doped silica slurry was filtered and dried at 105 °C to produce a dry powder.
  • Nitrogen sorption analysis of the powder was performed on an Autosorb- lC unit from Quantachrome. The sample was degassed at 105 °C for 4 h, then characterized by a multi-point BET surface area, total pore volume, and BJH adsorption pore size distribution. Nitrogen sorption analysis indicated a surface area of 321 square meters per gram, a pore volume of 1.46 cc/g, and a pore diameter of 18.2 nm.
  • the CuS-doped silica slurry was filtered and flash-dried at 565 °F to produce a dry powder.
  • Nitrogen sorption analysis of the powder was performed on an Autosorb- lC unit from Quantachrome. The sample was degassed at 105 °C for 4 h, then characterized by a multi-point BET surface area, total pore volume, and BJH adsorption pore size distribution. Nitrogen sorption analysis indicated a surface area of 227 square meters per gram, a pore volume of 0.45 cc/ g, and a pore diameter of 7.9 nm.
  • three solutions are prepared: A) 2 kg Nalco N8691 silica sol, B) 53.2 g ferric sulfate and 60 g glacial acetic acid dissolved in 887 g DI water, and C) 184 g calcium polysulfide solution and 150 g 25 wt% ammonia dissolved in 2667 g DI water.
  • Solution B is added to solution A, followed by subsequent addition of solution C at a high shear rate. The mixture is stirred for 1-2 minutes before filtration. The iron sulfide-doped silica slurry is then filtered and flash-dried at 565 °F to produce a dry powder.
  • Quantachrome The sample was degassed at 150 °C for 6 h, then characterized by a multi-point BET surface area, total pore volume, and BJH adsorption pore size distribution. Nitrogen sorption analysis indicated a surface area of 227 square meters per gram, a pore volume of 0.45 cc/g, and a pore diameter of 7.9 nm. TGA analysis of the powder indicated 2.3 wt% mass loss due to moisture.
  • three solutions were prepared: A) 100 g Nalco N8691 silica sol, B) 3.32 g copper sulfate and 3 g glacial acetic acid dissolved in 55. 1 g DI water, and C) 9.2 g calcium polys ulfide solution and 7.5 g 25 wt% ammonia dissolved in 145.2 g DI water.
  • Solution B was added to solution A, followed by subsequent addition of solution C at a high shear rate. After mixing, 300 g of DI water was added at a high shear rate. The mixture was stirred for 1-2 minutes. 38.6 g of aqueous slurry was sprayed onto 56.1 g of CaO with a spray bottle while stirring in a round bottom flask.
  • Nitrogen sorption analysis of the powder was performed on an Autosorb- lC unit from Quantachrome. The sample was degassed at 150 °C for 6 h, then characterized by a multi-point BET surface area, total pore volume, and BJH adsorption pore size distribution. Nitrogen sorption analysis indicated a surface area of 227 square meters per gram, a pore volume of 0.45 cc/g, and a pore diameter of 7.9 nm. TGA analysis of the powder indicated 8.7 wt% mass loss due to moisture.
  • Example 7 In this example, three solutions were prepared: A) 25 g Nalco N8691 silica sol, B) 12.45 g copper sulfate and 3 g glacial acetic acid dissolved in 200 g DI water, and C) 39.5 g calcium polysulfide solution and 7.5 g 25 wt% ammonia dissolved in 200 g DI water. Solution B was added to solution A, followed by subsequent addition of solution C at a high shear rate. After mixing, 425 g of DI water was added at a high shear rate. The mixture was stirred for 1-2 minutes. 37.6 g of aqueous slurry was sprayed onto 56.1 g of CaO with a spray bottle while stirring in a round bottom flask.
  • Nitrogen sorption analysis of the powder was performed on an Autosorb- lC unit from Quantachrome. The sample was degassed at 150 °C for 6 h, then characterized by a multi-point BET surface area, total pore volume, and BJH adsorption pore size distribution. Nitrogen sorption analysis indicated a surface area of 20.4 square meters per gram, a pore volume of 0. 18 cc/g, and a pore diameter of 34.7 nm. TGA analysis of the powder indicated 3.8 wt% mass loss due to moisture.
  • three solutions are prepared: A) 500 g Nalco N8691 silica sol, B) 16.6 g copper sulfate and 15 g glacial acetic acid dissolved in 218 g DI water, and C) 46 g calcium polysulfide solution and 37.5 g 25 wt% ammonia dissolved in 667 g DI water.
  • Solution B was added to solution A, followed by subsequent addition of solution C at a high shear rate. After mixing, 1.5 kg of DI water was added at a high shear rate. The mixture was stirred for 1-2 minutes. 2.3 kg of aqueous slurry was sprayed onto 3.5 kg of CaO in a Littleford-Day plow mixer.
  • composition of matter claims include various combinations of sorbent components and associated compositions, such molar ratios of constituent particles.
  • the claimed compositions include combinations of the dependent claims.
  • a range or equivalent thereof of a particular component shall include the individual component(s) within the range or ranges within the range.
  • the method of use claims include various combinations of the sorbent components and associated compositions, such molar ratios of constituent particles.
  • the claimed methods of use include combinations of the dependent claims.
  • a range or equivalent thereof of a particular component shall include the individual component(s) within the range or ranges within the range.
  • the method of manufacture claims include various combinations of the sorbent components and associated compositions, such pH control.
  • the claimed methods of use include combinations of the dependent claims.
  • a range or equivalent thereof of a particular component shall include the individual component(s) within the range or ranges within the range.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne une composition contenant de la silice. La composition comporte un composé ayant la formule suivante : (SiO2)x(OH)yMzSaFB, dans laquelle M est au moins l'un des cations métalliques ou métalloïdes suivants : bore, magnésium, aluminium, calcium, titane, vanadium, manganèse, fer, cobalt, nickel, cuivre, zinc, zirconium, molybdène, palladium, argent, cadmium, étain, platine, or et bismuth ; S est une espèce à base de soufre choisie parmi au moins l'un des suivants : sels sulfure, dithiocarbamates, dithiocarbamates à base de polymère et sels polysulfure ; F existe éventuellement et ledit F est au moins l'un parmi les suivants : un organosilane fonctionnalisé, un organosilane contenant du soufre, un organosilane contenant une amine et un organosilane contenant un alkyle à une couverture d'aire de surface d'environ 0,01 à environ 100 ; le rapport molaire de y/x est égal à environ 0,01 à environ 0,5, le rapport molaire de x/z est égal à environ 0,5 à environ 300 ou d'environ 0,5 à environ 100 et le rapport molaire de a/z est d'environ 0,5 à environ 5 ; B est un solide hygroscopique à un rapport molaire eau à solide de 0,1 à 6 et de préférence comporte au moins un oxyde d'alcalino-terreux ou un oxyde de lanthanide.
PCT/US2012/055964 2011-09-23 2012-09-19 Particule de silice contenant du soufre WO2013043626A1 (fr)

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US13/242,618 US8377194B2 (en) 2010-04-08 2011-09-23 Sulfur containing silica particle

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4474896A (en) * 1983-03-31 1984-10-02 Union Carbide Corporation Adsorbent compositions
US20050170109A1 (en) * 2004-01-30 2005-08-04 Tienteh Chen Surface modification of silica in an aqueous environment
US20060078696A1 (en) * 2004-10-13 2006-04-13 Ilford Imaging Switzerland Gmbh Recording sheet for ink jet printing
US20070259169A1 (en) * 2006-05-03 2007-11-08 United States Of America As Represented By The Administrator Of The National Aeronautics And Spac Aerogel / Polymer Composite Materials
US20090038512A1 (en) * 2007-08-08 2009-02-12 Ppg Industries Ohio, Inc. Crystalline colloidal arrays with inorganic sol-gel matrix
US20110251058A1 (en) * 2010-04-08 2011-10-13 Keiser Bruce A Sulfur containing silica particle

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4474896A (en) * 1983-03-31 1984-10-02 Union Carbide Corporation Adsorbent compositions
US20050170109A1 (en) * 2004-01-30 2005-08-04 Tienteh Chen Surface modification of silica in an aqueous environment
US20060078696A1 (en) * 2004-10-13 2006-04-13 Ilford Imaging Switzerland Gmbh Recording sheet for ink jet printing
US20070259169A1 (en) * 2006-05-03 2007-11-08 United States Of America As Represented By The Administrator Of The National Aeronautics And Spac Aerogel / Polymer Composite Materials
US20090038512A1 (en) * 2007-08-08 2009-02-12 Ppg Industries Ohio, Inc. Crystalline colloidal arrays with inorganic sol-gel matrix
US20110251058A1 (en) * 2010-04-08 2011-10-13 Keiser Bruce A Sulfur containing silica particle

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