WO2007053252A1 - Procede de preparation de compositions de conservation de bois contenant du metal - Google Patents

Procede de preparation de compositions de conservation de bois contenant du metal Download PDF

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Publication number
WO2007053252A1
WO2007053252A1 PCT/US2006/037536 US2006037536W WO2007053252A1 WO 2007053252 A1 WO2007053252 A1 WO 2007053252A1 US 2006037536 W US2006037536 W US 2006037536W WO 2007053252 A1 WO2007053252 A1 WO 2007053252A1
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Prior art keywords
copper
amine
surfactant
metal
solution
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PCT/US2006/037536
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English (en)
Inventor
Joseph P. Guzzetta
Mark P. Pryzbylski
Jun Zhang
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Osmose, Inc.
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Publication date
Priority claimed from US11/367,443 external-priority patent/US20070207076A1/en
Application filed by Osmose, Inc. filed Critical Osmose, Inc.
Publication of WO2007053252A1 publication Critical patent/WO2007053252A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/14—Complexes with ammonia
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density

Definitions

  • the present invention relates to methods of preparing copper-containing aqueous solutions.
  • Wood preserving compositions are well known for preserving wood and other cellulose-based materials, such as paper, particleboard, textiles, rope, etc., against organisms responsible for the destruction of wood, namely fungus and insects.
  • Many conventional wood preserving compositions comprise copper amine complexes. Copper amine complexes have been used in the past because the copper when in such complexes become soluble in aqueous solutions.
  • the copper in such copper amine complexes is obtained from a variety of copper-containing materials, such as copper scrap, cuprous oxide, copper carbonate, copper hydroxide, a variety of cuprous and cupric salts, and copper-containing ores.
  • the amine in such copper amine complexes is normally obtained from an aqueous solution of ammonia and ammonium salts, such as ammonium carbonate, and ammonium sulfate.
  • U.S. Patent No. 4,622,248 describes forming copper amine complexes by dissolving copper oxide in ammonia in the presence of ammonium bicarbonate.
  • U.S. Patent No. 5,492,681 disclose processes to produce cupric oxide dissolving copper-containing materials with aqueous ammonia and an ammonium salt in the presence of oxygen to form a cupric amine compound. Upon heating, the cupric amine compounds decompose to cupric oxide, ammonia and water.
  • Copper amine complexes may also be produced by substituting an amine for ammonia to dissolve the copper-containing material. The reaction rate for forming such metal, in particular, copper amine complexes is not favorable and, therefore, the process is very time consuming, as shown in Table 1, which will be discussed in greater detail below.
  • the present invention provides methods for producing metal-containing solutions.
  • a metal or metal-containing material, amine, carbon dioxide and an oxidizing agent are provided, combined to produce an aqueous solution that promotes the dissolution of the metal.
  • the resulting metal amine solution can then be used to formulate a variety of metal-based wood preserving products.
  • the metal is copper metal.
  • the metal-containing material is cuprous oxide.
  • the present invention provides a method for dissolving copper or a copper- containing material comprising the steps of mixing copper or a copper-containing material, water, amine, carbon dioxide in an amount less than about 5% by weight, and an oxidant such that the aqueous solution contains between about 5 and about 12% dissolved copper within 5 hours.
  • the carbon dioxide is present in an amount less than about 4%, 3%, or 2%.
  • the methods of the present invention provide dissolution rates where the aqueous solution contains between 1 and 20%, 2 and 20%, 3 and 20%, 4 and 20% 5 and 20%, 6 and 20%, 7 and 20%, 8 and 20%, 9 and 20%, 10 and 20%, 11 and 20%, 12 and 20%, 13 and 20%, 14 and 20%, 15 and 20%, 16 and 20%, 17 and 20%, or 18 and 20% dissolved copper per hour.
  • the methods of the present invention provide dissolution rates where the aqueous solution contains about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% dissolved copper per hour.
  • the present invention also provides a method for dissolving copper or a copper-containing material comprising the steps of mixing the copper or a copper-containing material, water, amine, carbon dioxide, and an oxidant such that the aqueous solution contains between about 5 and about 12% dissolved copper within 5 hours.
  • the methods of the present invention provide dissolution rates where the aqueous solution contains between 1 and 20%, 2 and 20%, 3 and 20%, 4 and 20% 5 and 20%, 6 and 20%, 7 and 20%, 8 and 20%, 9 and 20%, 10 and 20%, 11 and 20%, 12 and 20%, 13 and 20%, 14 and 20%, 15 and 20%, 16 and 20%, 17 and 20%, or 18 and 20% dissolved copper per hour.
  • the methods of the present invention provide dissolution rates where the aqueous solution contains about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% dissolved copper per hour.
  • the present invention also provides a method for dissolving copper or a copper-containing material comprising the steps of mixing the copper or a copper-containing material, water, an amine, and carbon dioxide, and introducing an oxidant to the solution at an air at flow rate of between about 0.5 and 100 standard cubic feet per hour (SCFH).
  • SCFH standard cubic feet per hour
  • the oxidant is introduced at an air flow rate of between 0.5 and 10, 0.5 and 20, 0.5 and 30, 0.5 and 40, 0.5 and 50, 1 and 5, 1 and 10, 1 and 20, 1 and 30, 1 and 40, 1 and 50, 2 and 10, 2 and 20, 2 and 30, 2 and 40, 2 and 50, 5 and 10, 5 and 20, 5 and 30, 5 and 40, 5 and 50, 10 and 20, 10 and 30, 10 and 40, 10 and 50, 10 and 60, 10 and 70, 10 and 80, 10 and 90, 10 and 100, 20 and 50, 20 and 60, 20 and 70, 20 and 80, 20 and 90, or 20 and 100.
  • the present invention also provides a method for dissolving copper or a copper-containing material comprising the steps of mixing the copper or a copper-containing material, water, amine, carbon dioxide, an oxidant and an and a quaternary ammonium compound in an amount sufficient to produce a rate at least 1.5-, 2-, 5-, or 10-fold of that rate observed in the absence of the quaternary ammonium compound, hi another embodiment, the surfactant is in a concentration sufficient to produce a metal-amine solution at a rate at least 50% greater than that observed in the absence of the surfactant.
  • the present invention also provides a method for dissolving copper comprising the steps of mixing the copper, water, between about 40 and about 50% monoethanolamine (by weight), carbon dioxide in an amount less than about 5% by weight, an oxidant and a quaternary ammonium compound such that the aqueous solution contains between about 5 and about 12% dissolved copper within 5 hours.
  • the methods of the present invention provide dissolution rates where the aqueous solution contains between 1 and 20%, 2 and 20%, 3 and 20%, 4 and 20% 5 and 20%, 6 and 20%, 7 and 20%, 8 and 20%, 9 and 20%, 10 and 20%, 11 and 20%, 12 and 20%, 13 and 20%, 14 and 20%, 15 and 20%, 16 and 20%, 17 and 20%, or 18 and 20% dissolved copper per hour, hi another embodiment, the methods of the present invention provide dissolution rates where the aqueous solution contains about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% dissolved copper per hour, hi one embodiment, the monoethanolamine is present in an amount between about 45 and 50%, between about 47 and 50% or between about 48 and 50%.
  • the present invention also provides a method for producing a metal amine solution, comprising the steps of: mixing a water-insoluble metal or metal-containing material, water, an amine, an oxidizing agent and a surfactant in a concentration sufficient to produce a metal-amine solution at a rate at least 1.5-, 2-, 5-, or 10-fold that observed in the absence of the quaternary ammonium compound, hi another embodiment, the surfactant is in a concentration sufficient to produce a metal-amine solution at a rate at least 50% greater than that observed in the absence of the surfactant.
  • the methods of the present invention may be used to dissolve a variety of metal-containing materials and metals, including copper, aluminum, iron, lead, tin, cadmium, nickel, chromium, and zinc, hi a preferred embodiment, the metal is copper.
  • the metal-containing material is a copper-containing material, hi a more preferred embodiment, the copper-containing material is cuprous oxide.
  • the methods of the present invention provide dissolution rates where the aqueous solution contains between about 5 and about 12% dissolved copper within 5 hours, hi a more preferred embodiment, the methods of the present invention provide dissolution rates where the aqueous solution contains between about 5 and about 12% dissolved copper within 3 hours.
  • the methods of the present invention provide dissolution rates where the aqueous solution contains between about 5 and about 12% dissolved copper within 1 hour
  • the methods of the present invention provide dissolution rates where the aqueous solution contains between 1 and 20%, 2 and 20%, 3 and 20%, 4 and 20% 5 and 20%, 6 and 20%, 7 and 20%, 8 and 20%, 9 and 20%, 10 and 20%, 11 and 20%, 12 and 20%, 13 and 20%, 14 and 20%, 15 and 20%, 16 and 20%, 17 and 20%, or 18 and 20% dissolved copper per hour
  • the methods of the present invention provide dissolution rates where the aqueous solution contains about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% dissolved copper per hour.
  • each of the methods of the present invention may also employ the use of a surfactant, hi one embodiment, the surfactant is a non-ionic surfactant. In another embodiment, the surfactant is an anionic surfactant. In yet another embodiment, the surfactant is a cationic surfactant. Preferably, the cationic surfactant is a quaternary ammonium compound. In a preferred embodiment, the cationic surfactant is a quaternary ammonium compound. In a preferred embodiment, the quaternary ammonium compound has the following structure:
  • R 1 , R 2 , R 3 , and R 4 are independently selected from alkyl or aryl groups and X " selected from chloride, bromide, iodide, carbonate, bicarbonate, borate, carboxylate, hydroxide, sulfate, acetate, laurate, or any other anionic group.
  • the quaternary ammonium compound is n-alkydimethyl benzyl ammonium chloride, alkyldimethylbenzylammonium chloride, alkyldimethylbenzylammonium carbonate/bicarbonate, dimethyldidecylammonium chloride, didecyl dimethyl ammonium chloride, or dimethyldidecylammonium carbonate/bicarbonate.
  • the quaternary ammonium compound is (C 12 -C 18 ) dimethylbenzylammonium chloride or Q-5097.
  • the surfactant is a low-foaming surfactant.
  • the low foaming surfactant is a quaternary ammonium compound.
  • the low foaming surfactant is Bardac LF, Triton X-IOO, Triton X-45, an ethoxylated octylphenol, or benzyltrimethylammonium chloride (BTMAC).
  • the reactions of the present invention may be run with a low-foaming surfactant and a defoaming agent.
  • a surfactant is present in an amount between about
  • a surfactant is present in an amount between about 0.050 and 0.250%, 0.100 and 0.250%, 0.125 and 0.250%, 0.150 and 0.250%, 0.175 and 0.250%, and 0.200 and 0.250% by weight. More preferably, a surfactant is present in an amount between about 0.125 and 0.250% by weight. Most preferably, a surfactant is present in an amount between about 0.125 and 0.150% by weight.
  • Each of the methods of the present invention may also be practiced by introducing the oxidant to the solution at a flow rate of between about 0.5 and about 100 standard cubic feet per hour (SCFH). In one embodiment, the oxidant flow rate is between about 0.5 and 5 SCFH. In another embodiment, the oxidant flow rate is between about 0.5 and about 10 SCFH.
  • SCFH standard cubic feet per hour
  • the oxidant is introduced at an air flow rate of between 0.5 and 10, 0.5 and 20, 0.5 and 30, 0.5 and 40, 0.5 and 50, 1 and 5, 1 and 10, 1 and 20, 1 and 30, 1 and 40, 1 and 50, 2 and 10, 2 and 20, 2 and 30, 2 and 40, 2 and 50, 5 and 10, 5 and 20, 5 and 30, 5 and 40, 5 and 50, 10 and 20, 10 and 30, 10 and 40, 10 and 50, 10 and 60, 10 and 70, 10 and 80, 10 and 90, 10 and 100, 20 and 50, 20 and 60, 20 and 70, 20 and 80, 20 and 90, or 20 and 100 SCFH.
  • the metal or a metal-containing material, water, amine and the oxidant are mixed in a single reaction chamber.
  • the single reaction chamber is columnar.
  • the water, amine and the oxidant are mixed in a first reaction chamber and the resulting solution is circulated through copper or a copper-containing material in a second reaction chamber.
  • carbon dioxide is introduced either in the form of air or as carbon dioxide gas into the solution in the first reaction chamber.
  • carbon dioxide is introduced either in the form of air or as carbon dioxide gas into the solution and copper or copper- containing material in the second reaction chamber.
  • the methods of the present invention may be practiced by adding the carbon dioxide to the solution, either in the first or second reaction chamber, after addition of the copper.
  • the amine is selected from the group consisting of any compound that has the following chemical structure:
  • Rl, R2, R3, R4, R5, R6 is independently selected from the group consisting of H,-CH3,-
  • the amine is monoethanolamine, diethanolamine, ethylamine, diethylamine, dimethylethylamine, dimethylethanolamine, or mixtures thereof. In the most preferred embodiment, the amine is monoethanolamine. [0023] In the methods of the present invention, the solution contains between about
  • the solution contains between about 30 and about 50% amine. More preferably, the solution contains between about 40 and about 50% amine. In one embodiment, the monoethanolamine is present in an amount between about 45 and 50%, between about 47 and 50% or between about 48 and 50%.
  • the oxidizing agent is oxygen, air, ozone, or hydrogen peroxide.
  • each of the methods of the present invention may also be practiced by adding a defoaming agent to the solution, hi one embodiment, the defoaming agent is a silicon polymer. In another embodiment, the silicon polymer is polyoxylalkylene silicon.
  • Each of the methods of the present invention may also be practiced by heating the solution to between about 30 and about 100°C.
  • the temperature is maintained between about 50° and about 100° C. More preferably, the temperature is maintained between about 50° and about 70° C. Most preferably, the temperature is about 70° C.
  • each of the methods of the present invention may also be practiced by adding an acid to the solution, hi a preferred embodiment, the acid is carbon dioxide.
  • the acid or the carbon dioxide are present in the solution in an amount less than about 5% acid by weight.
  • the acid is added to the solution prior to addition of the metal or metal-containing material, hi another embodiment, the acid is added to the solution after addition of the metal or metal-containing material.
  • Each of the methods of the present invention may also be practiced by initially adjusting the pH of the solution to between about 9 and 12.
  • the pH is initially adjusted to between about 10.5 and about 11.5.
  • the pH of the solution is maintained between about 10 and 12 by the addition of carbon dioxide, hi a preferred embodiment, the pH of the reaction is maintained at about 10.5 and about 11.5. hi a more preferred embodiment, the pH of the reaction is maintained about pH 11.
  • Each of the methods of the present invention may also be practiced by adding an anti-foaming agent, stirring the solution, circulating the solution or conducting the methods of the present invention at pressure greater than 1 atmosphere.
  • Figure 1 depicts(a) the effect of a 1% heel on copper metal dissolution rate and (b) the comparative dissolution rates of copper metal and cuprous oxide.
  • Figure 2 depicts the effect of a 1% heel on copper metal dissolution rate.
  • Figure 3 depicts the effect of a surfactant and antifoam agent on the dissolution rate of cuprous oxide.
  • Figure 4 depicts the effect of an air sparge on the dissolution rate of cuprous oxide.
  • Figure 5 depicts the effect of an air sparge in the presence of a surfactant on the dissolution rate of cuprous oxide.
  • Figure 6 depicts the effect of an air sparge in the presence of a surfactant and antifoam agent on the dissolution rate of cuprous oxide.
  • Figure 7 depicts the effect of copper loading on the dissolution rate of copper metal.
  • Figure 8 depicts the effect of air flow on the dissolution rate of copper metal.
  • Figure 9 depicts the effect of reaction temperature on the dissolution rate of copper metal.
  • Figure 10 depicts the effect of liquid flow rate on the dissolution rate of copper metal.
  • Figure 11 depicts the effect of heel on the dissolution rate of copper metal.
  • Figure 12 depicts the effect of pH on the dissolution rate of copper metal.
  • Figure 13 depicts the effect of copper source on the dissolution rate of copper metal.
  • Figure 14 depicts the effect of surfactant on the dissolution rate of copper metal.
  • Figure 15 depicts the effect of air flow on the dissolution rate of copper metal.
  • Figure 16 depicts the effect of pressure on the dissolution rate of copper metal.
  • Figure 17 depicts the density profile of a copper-containing solution.
  • the present invention provides a method for the production of a copper amine solution is provided that efficiently produces the solution at an expedited rate.
  • the copper amine solution is obtained from dissolving either copper or a copper-containing compound that is normally insoluble in water.
  • Any copper-containing material can be used in this process that provides copper amine of the desired purity.
  • pure metallic copper is used.
  • Impure forms of copper, such as #1 and #2 scrap copper metal, and cuprous oxide can also be used.
  • #1 Scrap copper metal typically contains approximately 99% copper, and #2 scrap metal typically contains approximately 97% copper, but this can vary somewhat among suppliers.
  • #1 Scrap metal is often recycled copper wire that has been stripped of its insulation, and chopped into particles.
  • Scrap metal can include any number of inorganic impurities, including but not limited to aluminum, iron, lead, tin, cadmium, nickel, chromium, and zinc. Scrap metal also sometimes includes organic impurities such as cutting grease.
  • the preferred copper source for this process is cuprous oxide.
  • cuprous oxide is preferred because it greatly enhances the reaction rate of the copper with amine.
  • cuprous oxide has a large surface area and has a higher oxidation state than copper metal.
  • the use of cuprous oxide as the copper source increases the reaction rate by several fold over that of copper metal, in the form of chopped copper wire, as illustrated in Figure 1.
  • Copper metal and copper compounds are normally insoluble in water but can be solubilized in the presence of an amine containing compound with an oxidizing agent (the solution used in Table 1).
  • an amine containing compound with an oxidizing agent
  • the preferred amine containing compound is monoethanolamine
  • other amines that can also be used are diethanolamine, ethylamine, diethylamine, dimethylethylamine, dimethylethanolamine, and include any amine that has the following chemical structure:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently H-, methyl, ethyl, or hydroxy ethyl.
  • Carbon dioxide may be added prior to or after the addition of the copper metal or copper compound to the composition to adjust the pH of the mixture to about 11.0.
  • the preferred addition order is prior to the addition of the copper source. The process can be run without the addition of carbon dioxide; however, the dissolution rate of the copper source is reduced significantly.
  • Any source of oxygen can be used to oxidize copper in this process, as demonstrated in Table I and Charts 1 and 2, pure oxygen, however, is preferred. Air, ozone, and hydrogen peroxide are also suitable sources of oxygen for use in this process providing standard safety precautions are taken for using oxidizing agents in the presence of organic compounds.
  • Process operating pressures can vary from 0 to 100 PSI with the preferred pressure being between 40 to 55 PSI.
  • Operating temperatures can vary from 25°C to 95°C with the preferred range being 60°C to 75°C.
  • the leach rate of the metals can be enhanced dramatically by the addition into the solution of a small amount of a quaternary ammonium compound such as diethyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, and further enhanced by the further combination with a surfactant compound such as a defoamer, emulsifying agent, foaming agent, and/or silicone polymers.
  • a surfactant compound can be a non-ionic, a cationic or an anionic surfactant.
  • the surfactant is a cationic compound.
  • the quaternary ammonium compound has the following structure:
  • R 1 , R 2 , R 3 , and R 4 are independently selected from alkyl or aryl groups and X " selected from chloride, bromide, iodide, carbonate, bicarbonate, borate, carboxylate, hydroxide, sulfate, acetate, laurate, or any other anionic group.
  • Preferred quaternary ammonium compounds include alkyldimethylbenzylammonium chloride, alkyldimethylbenzylammonium carbonate/bicarbonate, dimethyldidecylammonium chloride, and dimethyldidecylammonium carbonate/bicarbonate.
  • the quaternary ammonium compound is (Ci 2 -C 18 ) dimethylbenzylammonium chloride.
  • Preferred aqueous amine solutions of the present invention comprise a quaternary ammonium compound, such as n-alkyldimethyl benzyl ammonium chloride and didecyl dimethyl ammonium chloride, in combination with a defoamer, such as fluoroalkyl phosphate esters, amine oxides and silicone-containing compounds, such as silicone polymers.
  • a defoamer such as fluoroalkyl phosphate esters, amine oxides and silicone-containing compounds, such as silicone polymers.
  • the preferred defoamers include perfluoroalkylethyl phosphate ester, lauryl dimethyl amine oxide, and dimethicone. Concentrations of the quaternary ammonium compound vary from 0.01- 10% with 0.25% - 1.0% being the preferred range. Concentrations of silicon polymer can vary from 0.1% - 10% with the preferred range being 0.1% - 1.0%.
  • the resulting copper amine solution can be mixed with a variety of biocides such as fungicides and insecticides to produce a formulation suitable for the preservation of wood and other cellulose-base materials.
  • biocides such as fungicides and insecticides
  • Typical biocides that can be used for this formulation are fungicides such as azoles, quaternary ammonium compounds, and various other conventional insecticides.
  • Another embodiment of the present invention is a method for preserving and/or waterproofing a wood substrate by contacting a wood substrate with the composition of the present invention.
  • the composition may be applied by any wood treating method known to one of ordinary skill in the art including, but not limited to, brushing, dipping, soaking, vacuum impregnation (e.g. double vacuum technique), and pressure treatment using various cycles.
  • a copper amine solution was prepared by combining 530 grams water, 319 grams 99% MEA, 30 grams carbon dioxide, 5 grams N-alkyldimethyl benzyl ammonium chloride, 1 gram fluoroalkyl phosphate ester, and 116 grams cuprous oxide. The mixture was agitated and air was introduced at a rate of 2 SCFH until the concentration of dissolved copper in the solution reached 9.3%. The cuprous oxide mixture was maintained at a temperature of 25 °C throughout the course of the reaction.
  • Example 2 Preparation of a Copper Amine Solution from Cuprous Oxide
  • a solution of copper amine applicable for wood preservation was prepared by charging a reactor with 162 grams monoethanolamine and 270 grams water. The pH of the resulting solution was then adjusted to pH 10.95 with carbon dioxide. An initial charge of 2.5 grams alkyldimethyl benzylammonium chloride was added, followed immediately by the addition of 0.05 grams of a fluoro phosphate ester. After mixing, 61 grams cuprous oxide were added to the reactor. The reactor was sealed and pressurized to 65 PSI with air. The reactor was heated to 40 0 C and continuously stirred. After the dissolved copper in the solution reached 9.2 %, the solution was removed from the reactor and filtered. An additional charge of alkyl ammonium chloride was added to the solution.
  • Example 4 Preparation of a Copper Amine Solution from Cuprous Oxide [0063] The reactor was charged with 320 grams diethanolamine, 529 grams water, and 6 grams of an N- polymer. The pH of the resulting mixture was adjusted from about pH 13.5 to pH 11.0 by the addition of 20 grams carbon dioxide. 120 grams cuprous oxide were then added to the reactor which was sealed and pressurized to 65 PSI by the injection of oxygen. The temperature of the reactor was maintained at 40 0 C and the oxygen injection continued until the dissolved copper content of the solution reached 9.3%.
  • the reactor was charged with 322 grams MEA, 530 grams water, 4.8 grams alkyldimethyl benzylammonium chloride and 1.1 grams of a silicone compound. 120 grams cuprous oxide was then added to the reactor. The solution was sparged with air and the temperature maintained at 70 0 C until the dissolved copper content of the solution reached 9.3%. Upon dissolution of all the cuprous oxide, carbon dioxide was then sparged into the mixture to reduce the pH from 12.5 to 10. The resulting solution was then mixed with 90 grams alkyldimethyl benzylammonium chloride to form a composition, which is suitable for the preservation of wood and other cellulose materials.
  • a copper amine solution was prepared by adding 190 grams monoethanolamine, 320 grams water, 3.1 grams didethyldimethylammonium chloride and 0.8 grams of a silicone compound to the reactor. The composition was agitated until thoroughly mixed and then carbon dioxide sparged into the solution until the pH was reduced from pH 13.7 to pH 11. Once the pH stabilized was at pH 11, 73 grams cuprous oxide were added to the solution and then agitated to form a uniform slurry of cuprous oxide. The reactor was then pressurized to 20 PSI by the injection of oxygen into the slurry. The temperature of the reaction was maintained at 4O 0 C until the dissolved copper content of the solution reached 9.2%. The solution was filtered to remove, any undissolved solids and the resulting solution was then mixed with 2.1 grams cyproconazole and 49.9 grams boric acid to form a product suitable for the preservation of wood and other cellulose-based products.
  • Example 7 Preparation of a Copper Amine Solution from Copper Metal [0066] A glass kettle reactor was charged with 542 grams water and 323 grams MEA.
  • a composition containing copper amine was prepared by the addition 317 grams water, 192 grams MEA, 3 grams diethyldimethylammonium chloride, 0.9 grams of an amine oxide, 19 grams carbon dioxide, and 68 grams finely chopped copper wire.
  • the reactor was sealed and oxygen sparged into the reactor at a rate of 4 SCFH.
  • the reactor pressure was maintained at 55 PSI and the temperature maintained at 70 0 C until the copper concentration reached 9.2%.
  • the solution was then filtered to remove any undissolved solids and the solution was mixed with 0.09 grams cyproconazole to produce a concentrate suitable for the preservation of wood and other cellulose based materials.
  • the reactor in each of exemplified Runs was filled to 90% capacity with an aqueous MEA solution containing a surfactant (active) and antifoam (active).
  • the antifoam used was Foamtrol WP-55, supplied by Ultra Additives, which was diluted to a 10% active solution prior to use.
  • the pH of this solution was then measured and adjusted down to pH 11 by sparging carbon dioxide through the solution.
  • the solution was then heated to 50°C prior to initiating the reaction.
  • the air flow was set at 2 SCFH and the liquid flow rate was 600 ml/min at the beginning of each Run.
  • an MEA: copper oxide ratio of 2.75 ⁇ 0.25 was targeted. Accordingly, the final copper amine solution would contain about 10% copper.
  • a typical material balance is shown below in Table V.
  • Example 10 Effect of Adding a Low-Foam Quaternary Ammonium Compound on Dissolution of Copper Metal in an Aqueous Amine Solution
  • Run 11 used Bardac LF as the surfactant. This is a low foam 50% active Q-
  • Run 11 was repeated as Run 12, but using higher copper levels. The results were comparable to Run 5, which used Q-5097 as the surfactant. Foaming was not seen during the first 6 hours, but occurred thereafter. No accumulation of foam was observed in the reactor, however. Because the addition of more copper to the system had a positive effect on the rate, the copper column was replenished to a level 7-8x the required amount following each run after Run 12. A new phenomenon that occurred during these two runs was a large accumulation of solid residue on the walls of the glass reactor above the operating liquid surface. ICP analysis showed that these were over 77% copper with small amounts (-200 ppm) of iron and aluminum.
  • Run 14 the reaction was completed in less than 4 hours. This reaction was run at 7O 0 C, with 4 SCFH airflow and continuous pH adjustment. This run reached 10% copper in 3.25 hours. The dissolution rate was within the first hour was measured at 6.6%/hour. This corresponds to nearly complete oxygen consumption.
  • the foam levels in this run were similar to Run 13. Substantial amounts of foam were returned by the overhead vent, but the accumulation was only 1 - 2 inches.
  • Example 13 Effect of Liquid Flow Rate on Dissolution of Copper Metal in an Aqueous Amine Solution
  • Run 18 the reactor and column were not cleaned prior to start-up. Run 18 started with a 0.43% heel. This was done for two reasons: 1) to see the effect on the rate by essentially starting with a "heel” and also to see if the solids deposited on the walls of the reactor during Run 17 would dissolve. The presence of the heel did have a positive effect on the rate as the system reached 10% copper in under 6 hours. The observed rate was near maximal from the start of the reaction and remained high for the first 2 hours. Throughout the run, foam was again seen in the vapor outlet with very little accumulation in the reactor. During the carbon dioxide addition, it appeared as if about 15-20% of the material on the reactor walls dissolved. Following the reaction, the amount of solids on the walls was about the same as the previous run, so there was no additional accumulation.
  • Example 15 Effect of Quaternary Ammonium Compounds and Maintaining Constant pH on Dissolution of Copper Metal in an Aqueous Amine Solution
  • Run 19 was run with no surfactant. pH was monitored and continuously adjusted to about pH 11. The profile of this run was well short of Run 8 which was operated under identical conditions, except with the addition of 0.125% quaternary ammonium compound. This demonstrates that although constant pH is a large factor in the rate, some surfactant is still necessary to maximize the rate. Without surfactant, Run 19 exhibited no foaming. After running overnight, there was again a film on the walls which was not present after 7 hours.
  • Run 20 was run with a reduced amount of surfactant to improve the dissolution rate (compared to Run 19) while maintaining the foam level at a minimum. To enhance the dissolution rate, "heel" was again present. The pH was also adjusted throughout the run. Run 20 started at a moderate rate, but did not reach its maximum rate until about 2 hours. Although the overall reaction was fast, reaching 10% Copper in 5 hours, it appears that more surfactant may be necessary to maximize the initial rate.
  • shredded copper comes in all shapes and sizes, from very fine wire (-1/32") to large tubing ( ⁇ 1") and all sizes in between. Pieces can be straight, bent, flattened or bundled, depending on the copper source and how each particular piece went through the shredder. For the next few runs, a comparison was made between the dissolution rates observed between shredded copper and copper chops.
  • Shredded copper was used for Run 22. Since the shredded copper is inconsistent in shape and size, it does not pack the column as well as the chops, hi packing the entire column, only 2.1 times the required amount of copper was charged. This is much less than the 7-8x copper loading that may be achieved using copper chops. Run 22 was run at 5O 0 C, 2 SCFH airflow and a single pH adjustment prior to the start of the run. Run 22 started very slowly, but had a good rate in the 3-5 hour range, eventually reaching 10% copper after about 15 hours. After several hours, foam was seen in the vapor outlet, but there was no accumulation in the reactor.
  • Run 23 the column was emptied of the shredded copper and charged with an identical amount (2.Ix) of copper chops. Run 23 was run using the same conditions as Run 22. This run was much slower and did not reach 10% copper until 22 hours. This is most likely due to differences in surface area. Even though there were large pieces of tubing in the shredded copper, the overall surface area may have been greater because of the bundles of fine wire. Foaming was about the same as in Run 22. Samples of the final solutions and of the solids from each of these runs were submitted for metals analysis.
  • Run 24 was run with 1.6 times the required amount of shredded copper. Run
  • Example 17 Effect of Surfactant on Dissolution Rates in an Aqueous Amine Solution
  • Run 21 used Triton X-100 (Union Carbide/Dow), a common nonionic surfactant, as the surfactant.
  • Triton X-100 is an ethoxylated octylphenol, which is much different than the quaternary ammonium structures of Q-5097 and Bardac LF.
  • Run 25 used benzyltrimethylammonium chloride (BTMAC), which is a quaternary ammonium compound with a structure similar to Q-5097, except the C 12 -C 18 group is replaced by a third methyl group.
  • BTMAC benzyltrimethylammonium chloride
  • Run 26 used Triton X-45 (Union Carbide/Dow), another nonionic surfactant with fewer ethylene oxide units in its structure than Triton X-100.
  • Run 27 used Q-5097 under identical operating conditions as the previous runs. In the results shown above, the fastest rates were observed under the conditions of Run 27, using Q-5097. Run 27 outperformed Run 5, which used 0.250% Q-5097.
  • the copper dissolution rate may be optimized by initially adding 25 - 3O g carbon dioxide (-1.5% by weight of the MEA/water charge) followed by continuous adjustment of the pH as the run progresses.
  • Example 19 Effect of Various Surfactants on Dissolution Rates in an Aqueous Amine Solution
  • Bardac LF was used as the surfactant in Run 30. This run reached 7% copper in the first hour and 10% copper in 2.67 hours. As the reaction progressed, foaming occurred out the vapor outlet; however, the foam level in the reactor was insignificant after 3 hours and was only 1 — 2 inches after 5 hours. It is expected that one or two additions of antifoam during the run would cause the foam to subside completely.
  • Example 20 Solid Deposits Produced During Dissolution Reactions
  • Example 23 Effect of Adding Air and Carbon Dioxide Gas Simultaneously to The Reaction Column
  • the copper dissolution process was run at a temperature of 70°C.
  • the surfactant used was Bardac LF, and the antifoam used was a 10% solution of Foamtrol WP- 55.
  • Fresh scrap copper (#1 chops) was loaded into the column in an amount 7.3 times the theoretical amount of copper necessary.
  • Carbon dioxide was added at a flow rate of 5.5 SCFH.
  • Air was added at a flow rate of 8.0 SCFH.
  • the reaction achieved an 11.61% copper concentration in 3.50 hours.
  • the results are shown in Table VIII.
  • the copper dissolution rate achieved a maximum rate of 8.8% copper/hour, 1.08 hours into the reaction.
  • the amount of carbon dioxide added to the reaction was about 4.7%.

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Abstract

L'invention concerne un procédé destiné à produire des solutions d'amine contenant du métal par mise en réaction d'un métal ou d'un composé contenant du métal, plus particulièrement du cuivre ou un composé contenant du cuivre, avec un amine, du dioxyde de carbone et un agent oxydant. La solution d'amine métallique obtenue peut ensuite être utilisée afin de formuler une variété de produits de conservation de bois à base de métal.
PCT/US2006/037536 2005-11-01 2006-09-26 Procede de preparation de compositions de conservation de bois contenant du metal WO2007053252A1 (fr)

Applications Claiming Priority (4)

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US73192905P 2005-11-01 2005-11-01
US60/731,929 2005-11-01
US11/367,443 2006-03-03
US11/367,443 US20070207076A1 (en) 2006-03-06 2006-03-06 Method of preparing metal-containing wood preserving compositions

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2481526A (en) * 2010-06-21 2011-12-28 Arch Timber Protection Ltd Wood preservative compositions useful for treating copper-tolerant fungi
US9603358B2 (en) 2011-11-04 2017-03-28 Arch Timber Protection Limited Additives for use in wood preservation
WO2019046245A1 (fr) * 2017-09-01 2019-03-07 Koppers Performance Chemicals Inc. Procédé de préparation de compositions de préservation du bois contenant du cuivre
US11173626B2 (en) * 2016-08-03 2021-11-16 Koppers Performance Chemicals Inc. Stable wood preservative formulations
US11312038B2 (en) 2014-05-02 2022-04-26 Arch Wood Protection, Inc. Wood preservative composition
WO2024147001A1 (fr) * 2023-01-06 2024-07-11 Micronclean Limited Formulation désinfectante

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6541038B1 (en) * 1997-11-26 2003-04-01 Sds Biotech K.K. Method for treating wood with a metal-containing treating agent and wood treated thereby
WO2003069025A2 (fr) * 2002-02-14 2003-08-21 Phibrotech, Inc. Procede de dissolution de cuivre
WO2005051961A1 (fr) * 2003-11-19 2005-06-09 Arch Chemicals, Inc. Procedes permettant de produire des solutions d'ethanolamine de cuivre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6541038B1 (en) * 1997-11-26 2003-04-01 Sds Biotech K.K. Method for treating wood with a metal-containing treating agent and wood treated thereby
WO2003069025A2 (fr) * 2002-02-14 2003-08-21 Phibrotech, Inc. Procede de dissolution de cuivre
WO2005051961A1 (fr) * 2003-11-19 2005-06-09 Arch Chemicals, Inc. Procedes permettant de produire des solutions d'ethanolamine de cuivre

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2481526A (en) * 2010-06-21 2011-12-28 Arch Timber Protection Ltd Wood preservative compositions useful for treating copper-tolerant fungi
AU2011268757B2 (en) * 2010-06-21 2014-07-10 Arch Timber Protection Limited Wood preservative compositions useful for treating copper-tolerant fungi
US9023483B2 (en) 2010-06-21 2015-05-05 Arch Timber Protection Limited Wood preservative compositions useful for treating copper-tolerant fungi
AU2011268757C1 (en) * 2010-06-21 2016-11-10 Arch Timber Protection Limited Wood preservative compositions useful for treating copper-tolerant fungi
GB2481526B (en) * 2010-06-21 2018-02-14 Arch Timber Prot Limited Wood preservative compositions useful for treating copper-tolerant fungi
US9603358B2 (en) 2011-11-04 2017-03-28 Arch Timber Protection Limited Additives for use in wood preservation
US9961895B2 (en) 2011-11-04 2018-05-08 Arch Timber Protection Limited Additives for use in wood preservation
US11312038B2 (en) 2014-05-02 2022-04-26 Arch Wood Protection, Inc. Wood preservative composition
US11173626B2 (en) * 2016-08-03 2021-11-16 Koppers Performance Chemicals Inc. Stable wood preservative formulations
WO2019046245A1 (fr) * 2017-09-01 2019-03-07 Koppers Performance Chemicals Inc. Procédé de préparation de compositions de préservation du bois contenant du cuivre
US11102980B2 (en) 2017-09-01 2021-08-31 Koppers Performance Chemicals Inc. Method of preparing copper-containing wood preserving compositions
WO2024147001A1 (fr) * 2023-01-06 2024-07-11 Micronclean Limited Formulation désinfectante

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