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WO1997025076A1 - Desodorisation de compositions contenant des composes organiques soufres - Google Patents

Desodorisation de compositions contenant des composes organiques soufres Download PDF

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Publication number
WO1997025076A1
WO1997025076A1 PCT/US1997/000089 US9700089W WO9725076A1 WO 1997025076 A1 WO1997025076 A1 WO 1997025076A1 US 9700089 W US9700089 W US 9700089W WO 9725076 A1 WO9725076 A1 WO 9725076A1
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Prior art keywords
transition metal
metal compound
carrier
sulfur
composition
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PCT/US1997/000089
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English (en)
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WO1997025076A9 (fr
Inventor
Rasik Haridas Raythatha
Randy Eugene Fowler
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Isk Biosciences Corporation
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Publication date
Application filed by Isk Biosciences Corporation filed Critical Isk Biosciences Corporation
Priority to AU15254/97A priority Critical patent/AU1525497A/en
Publication of WO1997025076A1 publication Critical patent/WO1997025076A1/fr
Publication of WO1997025076A9 publication Critical patent/WO1997025076A9/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • A61L9/046—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating with the help of a non-organic compound
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions

Definitions

  • the present invention relates to a method for controlling the odor of sulfur-containing organic compounds, such as nematicides and other pesticides, more particularly, this invention relates to a method for controlling the odor of sulfur-containing organic compounds using a polyvalent transition metal compound.
  • Agricultural compositions often include active agents which are sulfur-containing organic compounds which frequently exhibit odor.
  • the odor results from by-products and other impurities, such as low molecular weight mercaptans which are formed in the course of manufacturing the compounds.
  • a number of approaches have been taken to controlling the odor of agricultural chemical formulations. Some of these approaches rely upon masking the odors with fragrances others have relied upon expensive methods, such as encapsulation. In general prior approaches have met with only limited success.
  • Japanese Patent No. 55/041846 to Furuya et al. discloses an adsorption process using activated charcoal impregnated with copper sulfate to remove the odorant, hydrogen sulfide, from a waste gas.
  • Czechoslovakia Patent No. 175003 to Brych et al. teaches impregnation of common sorbents, such as activated charcoal, with metal salts to give a sorbent which traps ammonia, hydrogen sulfide and potassium cyanate gases at high relative humidity (greater than 75%) .
  • Japanese Patent No. 52/108388 to Hamaguchi discloses the treatment of activated charcoal-sodium pellets with metal ions for gas treatment or deodorization.
  • Adsorption by an activated charcoal carrier impregnated with a metal ion is not always an effective approach to odor control because pesticides, such as Fosthiazate, bind to the activated charcoal so tenaciously that the Fosthiazate is not released and it is rendered nonfunctional as a pesticide.
  • transition metal compounds are useful in controlling and reducing the odor associated with sulfur-containing organic compounds. This finding is especially useful in controlling and reducing the odor of agricultural chemicals, such as pesticides. While the exact mechanism by which the transition metal compounds control the odor of the odoriferous components and by-products of the sulfur-containing organic compounds is not clear, the transition metal ions have been observed to complex with sulfur and it is believed that this complexation reaction may be functional in reducing odor in accordance with the present invention.
  • the transition metal ions may complex with the odoriferous components and by-products.
  • the transition metal ions may catalyze a reaction which decomposes the odoriferous components and by-products without affecting the stability of the sulfur-containing active agent. Furthermore, it is believed that the reaction is catalytic rather than adsorptive in nature because the odor control appears to endure indefinitely which suggests that the transition metal is not consumed in the reaction.
  • the transition metal compound is simply added to a formulation containing a sulfur-containing organic compound.
  • a transition metal compound can be added neat to a solution or dispersion of an agricultural chemical which exhibits an odor problem. It does not appear to matter whether the transition metal compound dissolves in the formulation or not. The transition metal compound has been observed to be capable of reducing odor if it dissolves in the formulation or if it simply resides as a sediment in the formulation.
  • the transition metal compound can also be dry mixed with a dry powder formulation and work effectively. While the transition metal compound can be used neat, it is preferred to adsorb or absorb or imbibe the transition metal compound onto an inert carrier. Where the formulation is a dry powder, a carrier containing the transition metal compound can be blended with the powder containing the active agent. In some cases, the active agent has been co-deposited on the carrier with the transition metal compound.
  • one manifestation of the present invention is for controlling the odor of odoriferous components and by-products of sulfur-containing organic compounds, such as nematicides and other pesticides, wherein a transition metal compound is added to the formulation containing the organic sulfur-containing compound.
  • compositions useful in controlling the odor of sulfur- containing compounds which comprises a transition metal compound on a carrier and a sulfur-containing organic compound.
  • the composition comprises an inert carrier, a polyvalent transition metal compound and a sulfur-containing organic compound, such as a nematicide or other pesticide co-deposited on the carrier.
  • the composition is a liquid formulation containing a sulfur- containing organic compound in which a polyvalent transition metal compound is dissolved or dispersed in the formulation.
  • a container for a sulfur-containing organic compound which exhibits odor wherein the container includes a compartment therein for retaining a polyvalent transition metal compound separate from, but in deodorizing communication with the sulfur-containing organic compound such that the odor of the sulfur compound is reduced.
  • the compartment is typically porous. Examples of porous elements that can be used with the invention are filter bags, perforated cap inserts, tubes of semi-permeable films, etc.
  • Still another embodiment of the invention is a carrier which is useful in controlling the odor of chemicals such as organic sulfur-containing compounds wherein the carrier has adsorbed or absorbed therein a transition metal compound.
  • polyvalent transition metal compounds in association with sulfur-containing organic compounds, such as nematicides and other pesticides, as described herein, provides unexpectedly good levels of odor control ranging from 24 hours to over one year.
  • the polyvalent transition metal compounds provide enhanced stabilization of the active sulfur compounds in some cases. This stabilization has been observed using amounts less than is required for odor control .
  • all references to sulfur containing organic compounds mean not only the active chemical but also the odoriferous components present with the active chemical to which the odor is generally attributed.
  • the polyvalent transition metal compound is preferably selected from a group consisting of copper, nickel, iron, zinc compounds and combinations thereof.
  • the polyvalent transition metal compound is a salt, such as a sulfate, nitrate or chloride.
  • Representative examples of useful transition metal compounds include copper sulfate, nickel chloride, ferric chloride, zinc chloride, nickel sulfate, zinc sulfate, ferric sulfate and ferrous sulfate. More preferably, the salt is copper sulfate.
  • the transition metal compound can be associated with a sulfur-containing organic compound in various ways.
  • the polyvalent transition metal compound is deposited onto an inert carrier.
  • any of a wide variety of inert carriers can be used for this purpose.
  • useful carriers include clay granules, ground peanut hull, lava pumice stone, granulated gypsum, synthetic aluminum silicate, precipitated silica, activated charcoal, granular charcoal, powder kaolinite clays, granulated silica gel, powder silica, recycled paper granule, ground corncob, mullite, synthetic porous silicates, calcined clays, etc.
  • the inert carrier is selected from a group consisting of clay granules, ground peanut hull, lava pumice stone, granulated gypsum, synthetic aluminum silicate and precipitated silica.
  • the carrier preferably has an average particle size in the range of about 18 to 50 mesh and a liquid holding capacity of about 0.15 to 3.5 ml water per gram carrier.
  • a liquid holding capacity of about 0.15 to 3.5 ml water per gram carrier.
  • the transition metal compound will be deposited on the carrier in an amount of about 0.01 to 15 parts compound per 100 parts carrier.
  • the amount of the compound that can be added to the carrier will vary with the nature of the compound, the nature of the carrier and its particle size.
  • copper sulfate is used, the copper sulfate is added to the carrier in an amount ranging from 0.05 to 12% by weight of carrier.
  • the carrier can be impregnated with the transition metal compound using an aqueous imbibition technique.
  • the transition metal compound is typically dissolved in an amount of water equal to about 40 to 95% of the liquid holding capacity of the inert carrier.
  • the carrier is dried in a conventional manner.
  • One useful method for drying the carrier is to use a fluidized bed dryer.
  • the amount of the polyvalent transition metal compound blended with the active sulfur containing compound is a function of several factors including the nature of the formulation and the manner in which the transition metal compound is used with the formulation, e.g., whether it is admixed dry, dispersed in a liquid, adsorbed on a carrier, or containerized, as described herein in more detail.
  • the transition metal compound is added to the organic sulfur containing compound in an amount of about 0.02 to about 0.4 parts by weight per 100 parts by weight of the organic sulfur- containing compound (inclusive of its odoriferous contaminants or byproducts) .
  • polyvalent transition metal compounds should be effective in controlling the odor of substantially any sulfur-containing organic compound and be widely applicable in the field of agricultural chemicals. It is believed that the chemical entities responsible for the odor of these compositions react with the transition metal compound as previously discussed.
  • the sulfur-containing organic compound of the present invention is preferably selected from a group consisting of agricultural chemicals, such as pesticides.
  • agricultural chemicals include Fosthiazate, Chlormephos, Chlorpyrifos, methylene-bis- thiocyanate, Furadan and Thimate.
  • the sulfur-containing organic compound can be in a granular or dry powder form or dispersion form.
  • One of the advantages of the invention is that the addition of the odor control agent typically does not require a major change in the established formulation of the active agent.
  • the active agent can be co-deposited on a carrier with the transition metal compound.
  • the amount of the sulfur-containing organic compound deposited on the carrier will be a function of the EPA standards which regulate the application rate of the compound.
  • the sulfur-containing organic compound is dissolved in a solvent and the solution is sprayed upon or imbibed into the carrier.
  • any solvent in which the sulfur- containmg organic compound is soluble, which is easily removed by drying, and which does not attack the carrier should be suitable for this purpose.
  • a solvent useful for Fosthiazate is methylene chloride.
  • the concentration of the solution is easily adjusted for the liquid holding capacity of the carrier to provide a product having the desired amount of the active agent on the carrier which can be applied to crops or soil in a conventional manner.
  • the amounts of transition metal compound and sulfur-containing compound w ll be adjusted to provide the desired deodorizing effect.
  • the transition metal compound is effective in relatively small amounts. Higher amounts can be used, provided that the amount of transition metal compound does not destabilize the active compound too greatly.
  • the transition metal compound is present n an amount of about 0.02 to 0.4 parts of the transition metal compound per 100 parts of the organic sulfur-containing compound as previously stated.
  • the transition metal compound is usually added to the carrier in an amount of about -0.025 to 0.25 parts by weight based on 100 parts by dry weight of the carrier alone.
  • the composition is an admixture of a carrier containing a polyvalent transition metal compound and a dry powder formulation containing a sulfur-containing organic compound.
  • the transition metal compound is separately present on the carrier and mixed with the active compound in the amounts which have previously discussed.
  • the composition is a liquid formulation containing the sulfur-containing organic compound in which a polyvalent transition metal compound is dissolved or dispersed. It is desirable that a surfactant is added to the liquid formulation. The surfactant facilitates the blending of the formulation and the transition metal compound.
  • the transition metal compound is present in the liquid formulation in an amount ranging from about 0.2 to 14 parts by weight per 100 parts by weight of the organic sulfur containing compound.
  • Yet another embodiment of the present invention is a container for a liquid or powder formulation containing a sulfur-containing organic compound in which a compartment is provided for separately retaining a polyvalent transition metal compound. There must be vaporous communication between the compartment containing the transition metal compound and the formulation containing the sulfur compound.
  • the transition metal compound may be deposited onto a carrier in the same manner as described above or the compound may be used neat. The transition metal compound and carrier (optional) is then packaged in the compartment.
  • the amount of transition metal compound that is packaged into the porous container is in the range from about 0.03 to 0.2 per 100 parts by weight of the organic sulfur containing compound.
  • transition metal compound such as a porous bag which may be paper or a microporous film formed into a bag which is simply added to the formulation, alternatively the transition metal compound can be housed in a cap or lid and separated from the formulation by a porous membrane of paper or film.
  • a sponge member can be saturated with a solution of the transition metal compound, dried, and packaged with the formulation.
  • odor is rated on a scale of 0 to 10, with 0 being no odor and 10 being extremely strong odor.
  • An inert carrier 100 g granulated gypsum made by Agrisorbent Corporation (a division of Oil Dri Co.) with a maximum liquid holding capacity of 24 g of water/100 g of carrier, was impregnated with 0.2% by weight of copper sulfate pentahydrate supplied by Fisher Co., by dissolving 0.2 g of copper sulfate pentahydrate in 23 g of water and spraying this copper sulfate solution onto the carrier while gently mixing the granules. After all of the solution was added, the wet granules were mixed for 20 minutes using a device that tumbles granules with minimum shear force. The granules were then dried at 50°C in an oven for 8 hours.
  • This pre-treated carrier was then treated with 10% of the sulfur-containing organic compound active ingredient, Fosthiazate.
  • 10% of the sulfur-containing organic compound active ingredient, Fosthiazate For loading, 8.93 g of carrier was used. 1.07 g of Fosthiazate was dissolved in 25 ml of methylene chloride. The solution of Fosthiazate was sprayed onto the carrier. Excessive amounts of methylene chloride were removed by vacuum evaporation.
  • Example 2 The same carrier, polyvalent transition metal salt, active ingredient and method of preparing the carrier were used as in Example 1, except that the pre-treated carrier was loaded with Fosthiazate without using organic solvent. In this process Fosthiazate was sprayed directly on to carrier so there was no need to remove any solvent.
  • Example 1 The type of carrier, transition metal compound and the method of impregnation were similar to Example 1. However, the amount of transition metal compound was 0.05 g. Also, for final preparation 10.008 g of carrier impregnated with transition metal compound was used. In the process, 1.001 g of Fosthiazate was dissolved in 6 ml. of methylene chloride and added to the carrier. The rest of the process was similar to Example 1.
  • Example 1 The type of carrier, transition metal compound and method of impregnation were similar to Example 1. However, the amount of transition metal compound was 0.05 g. Also, for final preparation 10.053 g of carrier impregnated with transition metal compound was used. In the process, 1.028 g Chlormephos was dissolved in 66.87 g of acetone and added to the carrier. The rest of the process was similar to Example 1.
  • Example 2 The type of transition metal compound, active ingredient and method of impregnating the carrier were similar to Example 1.
  • the carrier was ground peanut-hull.
  • the peanut-hull was ground to the size fraction between 18 to 30 mesh.
  • the ground peanut-hull was dried overnight in an oven at 50°C.
  • 0.026 g of transition metal compound was dissolved in 25.118 g of water and sprayed on to 12.48 g of the ground peanut-hull.
  • the material was then dried overnight at 50°C to remove excessive moisture.
  • the impregnation with Fosthiazate was carried out by dissolving 0.999 g of Fosthiazate in 6 ml. of methylene chloride. This solution was then added to 9.001 g of ground peanut-hull containing transition metal compound.
  • the rest of the process was similar to Example 1.
  • Example 1 The type of transition metal compound, active ingredient and method of impregnating the carrier were similar to Example 1.
  • the carrier was ground lava pumice stone from Guatemala.
  • the carrier was in the size range of 12 to 35 mesh.
  • the carrier was dried overnight at 50°C.
  • 0.078 g of transition metal compound was dissolved in 44.6 g of water, sprayed on to 100.2 g of the ground lava pumice stone, and dried overnight at 50°C.
  • Fosthiazate impregnation the method and process were similar to Example 1.
  • Example 1 The type of transition metal compound, active ingredient and method of impregnating the carrier were similar to Example 1.
  • the carrier was Synthetic Silica BXR 493 supplied by PPG Industries, Inc.
  • the carrier was in the size range of 35 to 120 mesh.
  • the carrier was dried overnight at 50"C.
  • 0.008 g of transition metal compound was dissolved in 102.3 g of water, sprayed on to 30.02 g of the carrier, and dried overnight at 50'C.
  • Fosthiazate impregnation the method and process were similar to Example 1.
  • Example 9 The type of transition metal compound, active ingredient and method of impregnating the carrier were similar to Example 1.
  • the carrier was Agsorb CN, manufactured by Agrisorbents (Group of Oil Dri) .
  • the carrier was in the size range of 24 to 48 mesh.
  • the carrier was dried overnight at 50"C.
  • the amount of carrier used ranged from 100.000 g to 99.755 g.
  • Various amounts of transition metal compound ranging from 0.000 g to 0.258 g was dissolved in 0 g to 20.003 g of water and sprayed on to the carrier.
  • Fosthiazate impregnation the method and process were similar to Example 1.
  • a liquid formulation was prepared by dissolving 0.15 g copper sulfate in 161.67 g of water. To increase wetting and dispersing of the organic sulfur compound, 9.0 g of a surfactant was added to the liquid formulation. The organic sulfur compound, Methylene-bis-thiocyanate, was added to the formulation in an amount of 45.62 g. In addition, 45.62 g of another non-sulfurous active ingredient, Chlorothalonil, was also added to the formulation. This formulation was ground using a ball mill and its viscosity was adjusted. The resulting suspension concentrate had an odor rating of 3 compared to an odor rating of 10 for similar formulations prepared without copper sulfate.
  • a carrier 10 g activated charcoal, was impregnated with a polyvalent transition metal compound, 10% by weight of carrier CuS0 4 .
  • the pre-treated carrier was then packaged into a small filter bag in an amount of 0.3 g. This bag was then left in a container containing 10 g of a Fosthiazate formulation.
  • Three observers were asked to rate severity of the odor on the scale of 0 to 10 where 0 indicates total odor control and 10 means no odor control. Use of the deodorizer gave odor control of 3 or less.
  • the type of polyvalent transition metal compound, active ingredient and method of impregnating the carrier were similar to Example 10.
  • the carrier was Kurry charcoal from Japan.
  • the carrier was dried overnight at 50°C before using.
  • 163.7 g of copper sulfate was dissolved in 950 g of water and sprayed on to 1200.2 g of dried Kurry charcoal.
  • the resulting material was once again dried overnight at 50°C.
  • 0.1 g, 0.2 g and 0.3 g of the resulting material was packaged in small micro-porous filter bags. These bags were then placed in containers containing 10 g of Fosthiazate 10G formulation.
  • the odor was rated at regular intervals after storage at ambient condition and at 45°C. Table I below shows that the copper sulfate impregnated Kurry charcoal produced a significant reduction in the odor. The results are based on an average of three observations.
  • the type of polyvalent transition metal compound, active ingredient and method of impregnating the carrier were similar to Example 10.
  • the carrier was calcined Kaolinite, Alphatex supplied by ECC America. The carrier was dried overnight at 50°C before using. 10 g of copper sulfate was dissolved in 45 g of water and sprayed on to 90 g of dried Alphatex. The resulting material was once again dried overnight at 50°C. 0.1 g, 0.2 g and 0.3 g of the resulting material was packaged in small micro-porous filter bags. These bags were placed in containers containing 10 g of Fosthiazate 10G formulation. The odor was rated at regular intervals after storage at ambient and at 45°C. Table II below shows that the copper sulfate impregnated Alphatex produced a significant reduction in the odor. The results are based on an average of three observations. TABLE II
  • the type of polyvalent transition metal compound, active ingredient and method of impregnating the carrier were similar to Example 10.
  • the carrier was precipitated silica.
  • the silica was precipitated by acidification of sodium silicate with sulfuric acid.
  • the precipitated silica was washed thoroughly to remove adsorbed salt and dried in oven at 50°C.
  • the material was ground an particles below 100 mesh were collected.
  • 0.026 g of copper sulfate was dissolved in 6.013 g of water and sprayed on to 12.493 g of dried precipitated silica. The resulting material was then dried at 50°C for 24 hours to remove excess water.
  • the type of polyvalent transition metal compound, active ingredient and method of impregnating the carrier were similar to Example 10.
  • the carrier was dried Kurry charcoal.
  • the amount of copper sulfate was in the range of 0.2 to 12% by weight of carrier.
  • the amount of copper sulfate was varied as follows: 1) 163.7 g of copper sulfate was dissolved in 950 g of water and sprayed on to 1200.2 g of Kurry charcoal granules. The resulting material was dried overnight at 50 ⁇ . The resulting material had a copper sulfate loading of 11.95%; 2) for medium loading material, 18.05 g of copper sulfate was dissolved in 144.1 g of water and sprayed on to 182.02 g of Kurry charcoal.
  • the resulting material was dried overnight at 50°C.
  • the resulting material had a copper sulfate loading of 9.0%; 3) for lower loading material, 3.6 g of copper sulfate was dissolved in 960 g of water and sprayed on to 1200 g of Kurry charcoal.
  • the resulting material was dried overnight at 50°C.
  • the resulting material had a copper sulfate loading of 0.3%.
  • 0.2 g of each of the resulting materials was packaged in micro-porous filter bags and placed with 20 g of Fosthiazate granules. The odor was rated after 24 hour day and one week. Table IV below shows that the loading percent of copper sulfate on to a carrier does not have a significant effect on the reduction in odor.
  • the type of active ingredient and method of impregnating the carrier were similar to Example 10.
  • the carrier was precipitated silica and the transition metal compounds were nickel chloride hexahydrate and ferric (III) chloride hexahydrate.
  • 0.115 g of nickel chloride hexahydrate was dissolved in 9.6 g of water and sprayed on to 15 g of silica.
  • the resulting material was dried at 50°C for 24 hours.
  • 0.128 g of ferric (III) chloride hexahydrate was dissolved in 9.6 g of water and sprayed on to 15 g. of silica.
  • the resulting material was dried at 50°C for 24 hours.
  • the type of active ingredient and method of impregnating the carrier were similar to Example 10.
  • the carriers for this study were precipitated silica and Kurry charcoal and the transition metal compounds were copper sulfate and nickel chloride. Both carriers were dried at 50°C for 24 hours before transition metal compound impregnation. 0.121 g. of copper sulfate pentahydrate was dissolved in 9.6 g of water and sprayed on to 15 g of dry silica. The resulting material was dried at 50°C for 24 hours. 0.115 g of nickel chloride hexahydrate was dissolved in 9.6 g of water and sprayed on to 15 g of dry silica. The resulting material was dried at 50°C for 24 hours.
  • the carrier was Agsorb S2100CN supplied by Agrisorbents (Oil Dri) Europe.
  • the carrier was in the size range of 24 to 48 mesh.
  • the carrier was dried overnight at 50°C.
  • the transition metal compound is copper sulfate. 0.008 g of copper sulfate was dissolved in 7.2 g of water and sprayed on to 30.0 g of Agsorb S2100CN. The resulting material was dried overnight at 50°C.
  • Fosthiazate impregnation method and process were similar to Example 1.
  • the odor was rated after one week and one month of storage at 22°C and at 45°C. Table VII below shows that the copper sulfate on this carrier produced a significant reduction in odor. The results are based on an average of three observations.
  • the carrier was Biofix E2 supplied by ECC International.
  • the carrier was in the size range of 24 to 48 mesh.
  • the carrier was dried overnight at 50°C.
  • the transition metal compound is copper sulfate. 0.008 g of copper sulfate was dissolved in 9.2 g of water and sprayed on to 30.022 g of Biofix E2. The resulting material was dried overnight at 50°C.
  • Fosthiazate impregnation method and process were similar to Example 1.
  • the odor was rated after one week and one month of storage at 22"C and at 45°C.
  • Table VIII shows that the copper sulfate on this carrier produced a significant reduction in odor. The results are based on an average of three observations. TABLE VIII
  • the carrier was Illite clay granules supplied by Kentish Mineral.
  • the carrier was in the size range of 18/40 mesh.
  • the carrier was dried overnight at 50 * C.
  • the transition metal compound is copper sulfate. 0.008 g of copper sulfate was dissolved in 8.5 g of water and sprayed on to 30.004 g of Illite clay granules. The resulting material was dried overnight at 50°C.
  • Fosthiazate impregnation method and process were similar to Example 1.
  • the odor was rated after one week and one month of storage at 22°C and at 45°C. Table IX below shows that the copper sulfate on this carrier produced a significant reduction in odor. The results are based on an average of three observations.
  • the carrier was Biodac (recycled paper) granules supplied by Edward Lowe Industry.
  • the carrier was in the size range of 16/30 mesh.
  • the carrier was dried overnight at 50°C.
  • the transition metal compound is copper sulfate. 0.008 g of copper sulfate was dissolved in 13.6 g of water and sprayed on to 30.004 g of Biodac granules. The resulting material was dried overnight at 50"C.
  • Fosthiazate impregnation method and process were similar to Example 1.
  • the odor was rated after one week and one month of storage at 22°C and at 45°C. Table X below shows that the copper sulfate on this carrier produced a significant reduction in odor. The results are based on an average of three observations.
  • the impregnated carriers were evaluated as to their odor compared with a 10 g Agsorb CN carrier impregnated with only Fosthiazate, no CuS0ray.
  • Table XI shows that the odor rating of the carriers with CuS0 4 is substantially less than that of the carrier without CuSO,, .
  • Two groups of four carriers were impregnated with Fosthiazate and stored for 6 months at 22°C and 45°C to evaluate the odor.
  • the four carriers were: 1) Mexican pumice stone, 2) Mexican pumice stone impregnated with 0.05% CuS0 4 , 3) Guatemalan pumice stone, 4) Guatemalan pumice stone impregnated with 0.05% CuS0 4 .
  • Table XII shows that the odor rating of the carriers that were impregnated with CuS0 4 were substantially less than the carriers without CuS0 4 , especially at the storage temperature of 45°C.
  • the control was no odor eliminator.
  • the odor eliminators were charcoal, 0.3 g charcoal impregnated with copper and 0.3 g clay impregnated with copper.
  • the deodorizers were packaged into micro-porous filter bags placed directly over 20.0 g of Fosthiazate granules contained within a container and stored for 14 days at room temperature and at 45°C and for 439 days at room temperature and at 45°C.
  • the odor control of each type of deodorizer was evaluated. Table XVI below shows that the charcoal impregnated with copper gave the best odor control.
  • odor eliminators were charcoal, charcoal impregnated with copper and clay impregnated with copper.
  • the odor eliminators were charcoal, charcoal impregnated with copper and clay impregnated with copper.
  • 0.1 g of each deodorizer was packaged into a micro-filter bags placed directly over 20.0 g of Fosthiazate granules contained within a container and stored at room temperature for various days.
  • the odor control of each deodorizer was evaluated. Table XVII below shows that the activated charcoal impregnated with copper gave the best odor control .
  • Clay impregnated with copper was less effective at controlling odor.
  • Activated charcoal was only partially effective in controlling odor over a 120 day period.
  • odor eliminators were charcoal, charcoal impregnated with copper and clay impregnated with copper. 0.1 g of each deodorizer was packaged into micro-porous filter bags and placed directly over 20.0 g of Fosthiazate granules contained within a container and stored at 45°C for various days. Table XIX below shows that the charcoal impregnated with copper gave the best odor control.
  • the polyvalent transition metal compounds In addition to the odor control, the polyvalent transition metal compounds also enhance the stability of the sulfur-containing organic compounds impregnated into a polyvalent transition metal compound treated carrier. Several tests which follow were completed to support this finding.
  • Fosthiazate impregnated carriers Two Fosthiazate impregnated carriers were prepared.
  • Table XXIV below shows the results of the study that evaluated the stability of Fosthiazate. The stability of Fosthiazate is significantly enhanced when a carrier is pre-treated with a polyvalent transition metal compound.
  • Fosthiazate impregnated carriers were prepared and stored at 22°C for 0 to 180 days to evaluate the percent of Fosthiazate remaining in the carriers.
  • the first carrier was Mexican pumice stone .
  • the second carrier was Mexican pumice stone impregnated with 0.05% by weight carrier CuS0 4 .
  • the third carrier was Guatemalan pumice stone.
  • the fourth carrier was Guatemalan pumice stone impregnated with 0.05% by weight carrier CuS0 4 .
  • Table XXV shows that only a minute percent of Fosthiazate is lost during the 180 days of storage.
  • An Agsorb CN carrier was impregnated with 0.05% nickel ion.
  • Two peanutshell carriers were impregnated with 0.025% copper ion and 0.025% nickel ion, respectively.
  • a pumice stone carrier was not impregnated with a metal ion. All the carriers were impregnated with Fosthiazate and stored at 22"C for up to 150 days to evaluate the effect of carriers and metal ions on the stability of Fosthiazate.
  • Table XXVIII shows that peanutshell carrier impregnated with nickel ion stabilized the Fosthiazate the best after 150 days of storage.
  • a porous container filled with a charcoal carrier impregnated with 0.15% CuS0 4 was placed within a container containing Fosthiazate 10G to evaluate the effect of the Cu/Charcoal deodorizer on the stability of the Fosthiazate.
  • the container was stored for 1 month at room temperature.
  • Table XXXI below shows that the stability was unaffected by the Cu/Charcoal deodorizer.
  • composition of the present invention is useful with any composition that contains a sulfur-containing organic compound. While specific examples of sulfur-containing organic compounds were illustrated above, those in the art will appreciate that other materials containing sulfur- containing organic compounds can be substituted for those shown above.

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  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne un procédé et une composition de régulation et de réduction de l'odeur des composants et/ou sous-produits odoriférants de formulations incluant des composés organiques contenant du soufre. On utilise pour cela un composé d'un métal de transition. Le composé de métal de transition polyvalent se présente de préférence sur un support.
PCT/US1997/000089 1996-01-11 1997-01-03 Desodorisation de compositions contenant des composes organiques soufres WO1997025076A1 (fr)

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AU15254/97A AU1525497A (en) 1996-01-11 1997-01-03 Odor control for compositions containing organic sulfur compounds

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US989896P 1996-01-11 1996-01-11
US60/009,898 1996-01-11
US60466596A 1996-02-21 1996-02-21
US08/604,665 1996-02-21

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Cited By (17)

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Publication number Priority date Publication date Assignee Title
WO2005039655A1 (fr) * 2003-10-16 2005-05-06 Kimberly-Clark Worldwide, Inc. Procede de reduction d'odeur au moyen de particules de silice modifiees par un metal
EP1667738A1 (fr) * 2003-10-16 2006-06-14 Kimberly-Clark Worldwide, Inc. Article pour combattre les odeurs comprenant un dispositif d'indication visuelle indiquant l'absorption des odeurs
US7141518B2 (en) 2003-10-16 2006-11-28 Kimberly-Clark Worldwide, Inc. Durable charged particle coatings and materials
US7338516B2 (en) 2004-12-23 2008-03-04 Kimberly-Clark Worldwide, Inc. Method for applying an exothermic coating to a substrate
US7488520B2 (en) 2003-10-16 2009-02-10 Kimberly-Clark Worldwide, Inc. High surface area material blends for odor reduction, articles utilizing such blends and methods of using same
US7582308B2 (en) 2002-12-23 2009-09-01 Kimberly-Clark Worldwide, Inc. Odor control composition
US7582485B2 (en) 2003-10-16 2009-09-01 Kimberly-Clark Worldride, Inc. Method and device for detecting ammonia odors and helicobacter pylori urease infection
US7666410B2 (en) 2002-12-20 2010-02-23 Kimberly-Clark Worldwide, Inc. Delivery system for functional compounds
US7678367B2 (en) 2003-10-16 2010-03-16 Kimberly-Clark Worldwide, Inc. Method for reducing odor using metal-modified particles
US7754197B2 (en) 2003-10-16 2010-07-13 Kimberly-Clark Worldwide, Inc. Method for reducing odor using coordinated polydentate compounds
US7763061B2 (en) 2004-12-23 2010-07-27 Kimberly-Clark Worldwide, Inc. Thermal coverings
US7794737B2 (en) 2003-10-16 2010-09-14 Kimberly-Clark Worldwide, Inc. Odor absorbing extrudates
US7879350B2 (en) 2003-10-16 2011-02-01 Kimberly-Clark Worldwide, Inc. Method for reducing odor using colloidal nanoparticles
US8221328B2 (en) 2003-10-16 2012-07-17 Kimberly-Clark Worldwide, Inc. Visual indicating device for bad breath
WO2012057362A3 (fr) * 2010-10-26 2012-08-30 Ishihara Sangyo Kaisha, Ltd. Composition stable granulaire pour l'agriculture
US8409618B2 (en) 2002-12-20 2013-04-02 Kimberly-Clark Worldwide, Inc. Odor-reducing quinone compounds
KR101966060B1 (ko) * 2018-10-18 2019-04-05 주황윤 제강분진 재활용 부산물인 철함유 슬러지로부터 황산철분말을 수득하는 방법

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US5458848A (en) * 1993-04-30 1995-10-17 L'oreal Method of deodorizing a formulation containing at least one compound bearing a thiol group and deodorized formulation thus obtained

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US4494481A (en) * 1982-11-12 1985-01-22 The Procter & Gamble Company Animal litter composition
US5346068A (en) * 1991-04-02 1994-09-13 Rhone-Poulenc Inc. Containerization system
US5458848A (en) * 1993-04-30 1995-10-17 L'oreal Method of deodorizing a formulation containing at least one compound bearing a thiol group and deodorized formulation thus obtained

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8409618B2 (en) 2002-12-20 2013-04-02 Kimberly-Clark Worldwide, Inc. Odor-reducing quinone compounds
US7666410B2 (en) 2002-12-20 2010-02-23 Kimberly-Clark Worldwide, Inc. Delivery system for functional compounds
US7582308B2 (en) 2002-12-23 2009-09-01 Kimberly-Clark Worldwide, Inc. Odor control composition
US7794737B2 (en) 2003-10-16 2010-09-14 Kimberly-Clark Worldwide, Inc. Odor absorbing extrudates
US7879350B2 (en) 2003-10-16 2011-02-01 Kimberly-Clark Worldwide, Inc. Method for reducing odor using colloidal nanoparticles
US7488520B2 (en) 2003-10-16 2009-02-10 Kimberly-Clark Worldwide, Inc. High surface area material blends for odor reduction, articles utilizing such blends and methods of using same
US8702618B2 (en) 2003-10-16 2014-04-22 Kimberly-Clark Worldwide, Inc. Visual indicating device for bad breath
US7582485B2 (en) 2003-10-16 2009-09-01 Kimberly-Clark Worldride, Inc. Method and device for detecting ammonia odors and helicobacter pylori urease infection
US7141518B2 (en) 2003-10-16 2006-11-28 Kimberly-Clark Worldwide, Inc. Durable charged particle coatings and materials
US7678367B2 (en) 2003-10-16 2010-03-16 Kimberly-Clark Worldwide, Inc. Method for reducing odor using metal-modified particles
US7754197B2 (en) 2003-10-16 2010-07-13 Kimberly-Clark Worldwide, Inc. Method for reducing odor using coordinated polydentate compounds
EP1667738A1 (fr) * 2003-10-16 2006-06-14 Kimberly-Clark Worldwide, Inc. Article pour combattre les odeurs comprenant un dispositif d'indication visuelle indiquant l'absorption des odeurs
WO2005039655A1 (fr) * 2003-10-16 2005-05-06 Kimberly-Clark Worldwide, Inc. Procede de reduction d'odeur au moyen de particules de silice modifiees par un metal
US7837663B2 (en) 2003-10-16 2010-11-23 Kimberly-Clark Worldwide, Inc. Odor controlling article including a visual indicating device for monitoring odor absorption
US7438875B2 (en) 2003-10-16 2008-10-21 Kimberly-Clark Worldwide, Inc. Method for reducing odor using metal-modified silica particles
US8168563B2 (en) 2003-10-16 2012-05-01 Kimberly-Clark Worldwide, Inc. Metal-modified silica particles for reducing odor
US8211369B2 (en) 2003-10-16 2012-07-03 Kimberly-Clark Worldwide, Inc. High surface area material blends for odor reduction, articles utilizing such blends and methods of using same
US8221328B2 (en) 2003-10-16 2012-07-17 Kimberly-Clark Worldwide, Inc. Visual indicating device for bad breath
US7763061B2 (en) 2004-12-23 2010-07-27 Kimberly-Clark Worldwide, Inc. Thermal coverings
US7338516B2 (en) 2004-12-23 2008-03-04 Kimberly-Clark Worldwide, Inc. Method for applying an exothermic coating to a substrate
WO2012057362A3 (fr) * 2010-10-26 2012-08-30 Ishihara Sangyo Kaisha, Ltd. Composition stable granulaire pour l'agriculture
CN103188931A (zh) * 2010-10-26 2013-07-03 石原产业株式会社 稳定的粒状农药组合物
CN103188931B (zh) * 2010-10-26 2014-06-11 石原产业株式会社 稳定的粒状农药组合物
KR101966060B1 (ko) * 2018-10-18 2019-04-05 주황윤 제강분진 재활용 부산물인 철함유 슬러지로부터 황산철분말을 수득하는 방법

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