Not Applicable.
Not Applicable.
Not Applicable.
1. Field of the Invention
The present invention relates to a process for the dissolution of copper metal. More particularly, the invention relates to a process for producing a copper-containing aqueous solution by dissolving copper in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (monoethanolammonium)2 carbonate (HMEA)2CO3.
2. Description of the Prior Art
It is known to employ copper-containing aqueous solutions as biocidal fluids, for example, for the pressure treatment of lumber and for water purification. Examples of such fluids and uses thereof may be found, for example, in U.S. Pat. Nos. 4,929,454 and 6,294,071. The copper-containing solutions may be formulated, for example, by dissolving copper in aqueous solutions containing alkyl amines or alkyl hydroxy amines, such as 2-hydroxyethylamine.
Alternatively, copper-containing solutions may be produced by reacting copper oxide with chromic acid and arsenous acid to produce a solution of the copper with chrome and arsenic. The solution is subsequently diluted with water and the resulting aqueous solution may be injected into wood under pressure.
This chromated copper arsenate (“CCA”) is the primary additive used in the treatment of wood against termite and other biological infestation. Although the CCA is very effective, it has come under increased pressure because of the environmental concerns associated with chromium and arsenic.
A new generation of pesticide is now emerging that appears to be efficacious, and which relies on the use of copper (in larger quantities than in the CCA) in combination with other pesticidal components, such as quaternary amines, nitrosoamines, and triazoles. The copper is typically applied as a solution of the monoethanolamine complex of copper carbonate or borate. The commercial form of the copper concentrate usually contains about 100 to 130 g/l copper which is diluted with water prior to injection into the wood.
The copper complex is typically produced commercially by the dissolution of basic copper carbonate in a solution of monoethanolamine (MEA), followed by further carbonation or addition of boric acid. The reactions can be approximately represented by the following equations:
CuCO3Cu(OH)2+7MEA→Cu(MEA)3.5CO3+Cu(MEA)3.5(OH)2
Cu(MEA)3.5(OH)2+CO2(or Boric acid)→Cu(MEA)3.5CO3+H2O
The production of the copper carbonate precursor has its own production and raw material costs, and a brine waste is generated which gives rise to environmental concerns. A more efficient process might be to produce the complex without the aid of an isolated precursor. It is known from the prior art that ammonia and carbon dioxide in water can be used to dissolve copper metal with oxygen from air as the oxidant. This is represented by the following equation:
Cu+2NH3+(NH4)2CO3+1/2O2→Cu(NH3)4CO3+H2O
The reaction proceeds well and has been the basis for copper dissolution in several commercial facilities. However, if the ammonia is not initially carbonated, the kinetics are very poor which makes the process unattractive from a commercial standpoint.
A need exists for a more efficient process for producing copper-containing aqueous solutions, suitable for use in the wood-treatment industry. The present invention seeks to fill that need.
It has been discovered, according to the present invention, that it is possible to efficiently produce copper-containing solutions directly without initially producing or isolating a precursor such as copper carbonate. The present invention accordingly provides a process for producing a copper-containing aqueous solution, wherein a copper mass is dissolved in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (monoethanolammonium)2 carbonate (HMEA)2CO3, the leach liquor being produced by partially carbonating the monoethanolamine. According to the process, copper-containing solution may be produced in 48 hours or less, usually within about 8-12 hours or less, and more usually within about 8 hours or less.
The present invention will now be described in more detail with reference to the accompanying drawings, in which:
Referring to
The term “copper” as used herein means copper metal, including scrap copper, such as for example copper wire, copper clippings, copper tubing, copper cabling and/or copper plate, compounds of copper, such as copper oxide, and/or mixtures of copper metal and copper compounds.
The term “copper mass” as used herein refers to copper metal in a form which, when present in the chamber, is permeable to the leach liquor and which presents high surface area for contact with the leach liquor to thereby expedite dissolution of the copper. The copper mass may be present for example as a three-dimensional open permeable network, such as a bale of scrap copper comprised of copper wire, copper tubing, copper cabling, copper plates, providing voids between the copper pieces to allow free flow and maximum contact of the leach liquor with the copper. A bale may have a volume of for example about 25-100 cubic feet. Alternatively, the copper mass may be present in the chamber as smaller irregular shaped pieces resembling “popcorn” (“blister shot”) having an average dimension of about 1-3″, which allow for good permeation of the leach liquor between and around the copper pieces to expedite dissolution thereof. The ratio of copper surface area to volume of leach liquor for this process (versus a standard agitated reactor) may reach about 200:1, more usually 10-20:1, for example about 15:1.
According to the process, the copper mass is dissolved in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (HMEA)2CO3. Typically, for a 1 liter chamber, the air flow SCFH ranges from about 2-20, for example 3-10. The air flow SCFH will increase as the volume of the chamber increases. For example, for a chamber having volume in the region of 11,500 gallons, the SCFH will be in the range of 12,000 to 24,000.
The leach liquor is produced by partially carbonating the monoethanolamine and may be generated externally of the dissolver or in situ in the chamber through addition of for example carbon dioxide to the monoethanolamine/water solution by sparging or bubbling into the chamber. Usually, the leach liquor is produced externally of the chamber and introduced into the chamber into contact with the copper as required, or re-circulated as necessary.
The equation that represents the overall reaction is as follows:
Cu+3.5MEA+(1-x)CO2+0.5O2+xH2O →Cu(MEA)3.5(CO3)(1-x)(OH)2x
The equation that represents the in situ or external partial carbonation of the monoethanolamine is as follows:
3.5MEA+CO2+H2O→1.5MEA+(HMEA)2CO3.
The term “:partially carbonating” as used herein means that the amount of carbon dioxide introduced during the process is controlled such that partial carbonation occurs to form (HMEA)2CO3. Preferably, the carbon dioxide is present in an amount of about 30% or less by weight, more preferably, for example from about 0.5-5% by weight.
The MEA is usually present in an amount of about 30-45 wt %, more usually 32-40 wt %. A typical finished aqueous leach solution comprises about 36-40 wt % MEA and about 8-12% by weight carbon dioxide.
The monoethanolamine complex of copper carbonate solutions are typically prepared by dissolving the copper mass in a monoethanolamine/CO2/H2O solution. The dissolution may be carried out in a batch dissolver (see FIG. 1), or may be performed as a continuous process in towers packed with copper (see FIG. 4). Typically, the copper and MEA/CO2/H2O solution are charged into the dissolver, and the circulation pump, air-flow and temperature controller are actuated. Examples of conditions are given in Table 3 below.
The present inventors have discovered that it is not necessary to utilize precursors, such as copper carbonate which is expensive. The dissolution of the copper metal may be achieved in the presence of MEA, (HMEA)2CO3 and an oxidant at elevated temperature, without the need for the addition of ammonium compounds such as ammonium hydroxide, fungicidal anions, polyamines, carboxylic acids, alkali metal hydroxides such as sodium hydroxide, and/or alcohol-based solvents.
The dissolution of the copper metal is performed in the presence of an oxidant. Typically the oxidant is an air and/or oxygen, most usually air sparging.
While not essential, the leach solution may be re-circulated in the reactor to benefit mass transfer and reaction rate. If re-circulation is performed, typically the re-circulation is carried out at a constant rate, and may be, for example, a constant rate of about 2 to 10% by volume of the leach solution volume per minute.
The process may be carried out at atmospheric pressure and at a temperature of 25-100° C., for example 40-80° C., more usually 45-65° C. Typically, the temperature is maintained at 45-55° C.
The pH is typically maintained in the basic region, i.e. greater than 7, for example 8-13, usually greater than 9.0 and less than 12.5, more usually from about 9.5-12.5. The pH is usually maintained by addition of carbon dioxide as acid to lower pH, or as MEA as base to raise pH.
The reaction proceeds slowly where there is a small surface area of copper available to contact the leach solution. For example, if the contact area of the copper metal to leach solution is doubled, the rate of the process doubles assuming adequate air-distribution.
It has been found that an aerated packed tower containing copper metal and circulating leach liquor is the most preferred method for commercial purposes. The advantage of using a packed tower is that it maintains a relatively high surface area to solution volume of copper metal.
According to another embodiment of the present invention, it is possible to utilize a reactor that contains a bed of copper and can be rotated while being heated and aerated.
Dissolving studies were conducted either batch-wise or continuously.
The leach solutions are typically re-circulated in the reactor. Most typically, the re-circulation is carried out at a constant rate of about 2-10% by volume.
The solution concentration of copper (g/l) as a function of dissolution time is shown in Table 2:
In experiments 1 and 2 reported above, average copper dissolution rates of about 17 g/l-hr were achieved over the course of the experiments. At those rates, the process is viable commercially.
Examples of the process according to the present invention will now be described.
Batch Preparation of Monoethanolamine Complex of Copper Carbonate
Monoethanolamine complex of copper carbonate solutions were prepared by dissolving a copper metal mass in monoethanolamine/CO2/H2O solution in the batch dissolver in the presence of air sparging and at an elevated temperature.
Three experiments were conducted using the batch dissolver shown in FIG. 1. In each experiment, about 1200 g copper and 1 liter MEA-CO2—H2O solution were charged into the dissolver. The circulation pump, airflow and temperature controller were then started. The experimental conditions are given in Table 3.
1weight ratio
When temperature reached the target temperature, the first sample of each batch was taken for analysis, and the timer was started. Complete results of these three dissolving batches are shown below, and are presented in
A continuous dissolver assembly (see
A leach solution using 2% (also one data point for 1% carbonation) carbonation is reported in Table 8 and shown in FIG. 8.
Production Scale Batch Preparation of Monoethanolamine Complex of Copper Carbonate
Commercial quantities of monoethanolamine complex of copper carbonate solutions have been prepared by dissolving a copper metal mass in monoethanolamine/CO2/H2O solution in an 11,500 gal vessel in the presence of air sparging at an elevated temperature.
Whereas the laboratory scale vessel is glass, the production scale vessel is constructed of a suitable, corrosion resistant material.
Whereas the laboratory vessel is depicted with a heating mantle, there is a heat exchanger in the recirculation loop in the production equipment that has both heating and cooling capability. Normally, only cooling is required as the simultaneous absorption of CO2 and dissolution of copper metal are both exothermic events.
While the leachate solution can be prepared in situ or external to the dissolving vessel, it has normally been prepared in situ. In the preparation of the leachate, the initial amount of CO2 has been varied to demonstrate the threshold value from which a sustained reaction can be initiated. The quantity of air introduced below the perforated false bottom has been varied to demonstrate the overall and peak dissolution rates. Peak dissolution rates and overall dissolution rates are obviously dependent upon the reaction temperature, the initial and final wt % CO2. It should be noted that the conditions examined herein are constrained only by the combination of an upper temperature, the area of the heat exchanger, the temperature and flow rate of the cooling tower water for the existing facility. Obviously, faster conversion rates could be attained given additional heat removal capacity so as to maintain the desired temperature. The rate of recirculation through the heat exchanger has been constant at {fraction (1/30)}th of the active volume of the vessel. The pH range is somewhat pre-determined by the amount of MEA present, the amount of initial CO2 present, the final amount of CO2 added, and the degree of conversion from copper metal to complexed copper. The specific gravity has remained relatively constant.
Numerous batches have been produced reflecting a range of operating parameters:
Specific batches offered for reference:
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
This application is a continuation in part of application Ser. No. 10/074,251 filed on Feb. 14, 2002, now U.S. Pat. No. 6,646,147 B2, the entire application of which is incoporated herein by reference for all purposes.
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Number | Date | Country | |
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20040191143 A1 | Sep 2004 | US |
Number | Date | Country | |
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Parent | 10074251 | Feb 2002 | US |
Child | 10704155 | US |