JPH06509052A - Inorganic perbromide compositions and methods of using them - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Inorganic Berbromide Compositions and Methods of Their Use Background of the Invention The present invention relates to a composition containing inorganic belbromide, and a hydrometallurgical method for recovering precious metals from the composition. and some of the compositions may be used for other purposes. Regarding.

Traditionally, precious metals such as gold and silver are leached from ores with alkaline cyanide solutions. It has been recovered by. Leaching with cyanide removes gold. , for example, by forming a gold cyanide complex Au(CN). Money leached by various techniques including zinc precipitation, carbon adsorption, ion exchange, etc. can be recovered from the solution used.

Cyanide leaching is widely practiced on a commercial scale, but it suffers from well-known disadvantages. suffer. For gold ores, leaching rates are slow, with contact times typically in the range of 24-27 hours. It is. Cyanide is toxic, so to prevent the release of hydrogen cyanide gas, Care must be taken to keep the cyanide solution on the alkaline side. all harsh environments that require careful monitoring and control of process purge flow Regulations must be followed. Used cyanide leach solution should be released into the environment. Disposal operations must be carried out before disposal.

Gold has also been commercially leached with aqua regia. In this case gold is also zinc metal It may be recovered by reduction or by raising the pH of the leaching solution. stomach.

However, this method is difficult because aqua regia is expensive, extremely corrosive, and contains toxic fumes. This makes it extremely unattractive. Besides, this method uses base metal quickly dissolves and gold only dissolves relatively slowly in aqueous solutions.

Thiourea has also been used as a leaching agent to dissolve gold from ores. Thio Urea, which is normally effective for this purpose, undergoes oxidative decomposition and is used to extract gold from ore. They tend to have higher consumption levels when extracted.

Halogens, halides or other halogens to recover precious metals from ores. Other processes using chemical-bearing compounds have been developed, e.g. Effer's U.S. Patent No. 267.723 roasts ore in a vat and roasts it. Add water to the ore and add liquid bromine to form a mixture, which is stirred, thereby A process is described for dissolving gold in the form of bromide in water. Filter to separate solids After release, the gold is precipitated from solution by oxalic acid or ferrous ions.

EPO Publication Specification 0 233 918 describes the methods used to recover gold from its sources. Alkaline concentrates are listed. This concentrate is Mate ion from about 1 to about 6% by weight, equi-valent velpromide bromate ions versus velpromide ions. and molecular bromine from 0.05 to about 0.8, [Bra] + [Has a promide ion concentration of 3 to 19% by weight over Br3-1, and has a pH of about 6.5 ~7.5. Example 1 is sodium perbromide 31.82% by weight, molecular bromine 2.1 4% by weight, sodium bromide 14.80% by weight, sodium bromate 3.94% by weight and an alkaline concentrate containing 47.30% by weight of water. . Example 3 of this specification is 1.4 g of concentrate and 0.8 g of 48% hydrobromic acid. It states that this concentrate can be made acidic by mixing it with Ru. The application further states that gold can be recovered from ore by diluting the acidified concentrate. It describes the production of a leaching solution for

US Pat. No. 2,283,198 to Fink et al. It is described that gold promotes dissolution in an aqueous bromine solution. This disclosure , chlorine or hypochlorite can be used as an intermediate oxidant as shown by the reaction below. It describes what can be done: 2 B r - + C12 = 2 CI - + B 　r　a or 28 r −+ CI O − + 2 H” = CI −+ B r t + Hz O Therefore, Fink et al. All gold is removed by leaching with a solvent created by adding free chlorine to the liquid. A process for extraction from ore was proposed. Alternatively, promid and a large excess of chloride A leaching agent is made by adding hypochlorite and mineral acid to a solution containing lido salt. to be accomplished. Fink et al. reported that gold can be extracted from solution using a method such as adding zinc or ferrous sulfate. Precipitation by any of the well known methods is described.

US Pat. No. 2,304,823 to Harrison et al. Gold is recovered from ore by dissolving it in a processing solution containing aluminum, water and nitric acid. It describes what to do. Then add mercury or zinc to recover precious metals from the solution. can do. The method uses refractory sulfur Applicable to treat difficult-to-dissolve materials such as hydrides, tellurides, etc. is said.

US Pat. No. 3,625,674 to Jacobs et al. AuI is produced by oxidation in an aqueous solution, which is decomposed by heating to produce metallic gold and Produces iodine vapor and recovers and circulates the iodine for further processing of the ore. It states: The AuI obtained from that process is also a gold thiomaleate. Suitable for forming other gold compounds for industrial use such as sodium are doing· Wison U.S. Pat. No. 3,709,681 describes how a fine precious metal source is solvents, dissolved iodine, bromine or chlorine, halide salts, preferably ice complex acids. It describes the process of treatment with a solution containing The precious metal part of the treatment solution is aluminum. It is recovered by leaching onto non-precious metal surfaces such as metal foil.

U.S. Pat. No. 3,957,505 to Hom1ck et al. Treatment with an aqueous solution of water-soluble iosite salts to produce a solution containing dissolved gold iodide salts. Describes the process to achieve this. Add solution to hydroxylamine, hydrazine, thio Precipitate the gold metal from solution by mixing with a reducing agent such as sodium sulfite, etc. Make me proud. Iodine from the spent aqueous solution makes the solution acidic and hydrogen peroxide, Adding oxidizing agents such as potassium manganate, sodium chromate, chlorine or bromine It is recovered by precipitating elemental iodine.

U.S. Pat. No. 4,557,759 to McGrew et al. A hydrometallurgical process for the hydrometallurgical recovery of gold from materials by leaching with a leaching agent containing The process is described. The leaching agent saturates the aqueous solution of iodine with iodine. built by. If sulfide is added to this reagent, iodine will be mixed with sulfide. The iodine element reacts and is converted to iodine.Next, elemental iodine is further added to this iodine-bearing solution. Add the desired total iodine concentration and iodine to iosite concentration to the solution to maximize leaching efficiency. are added until the ratio is achieved. The leaching agent then moves through the ore zone until all the gold is Circulate until dissolved. The gold is then recovered onto activated charcoal.

The excess ioside formed during the process is electrochemically removed in a special diaphragm cell. is reoxidized to iodine to regenerate the leaching agent. The desired iodine concentration in the leaching agent is between 1 and Approximately 20 grams/liter.

Co-pending Application No. 577.677 of the present applicant generates bromine in an aqueous solution. The process is described. Contains 0.5-8.8 mol/liter of promid ions An aqueous solution with a pH of ~6 is continuously passed through the electrolytic cell to generate bromine at the anode. Both zero-segmented and unsegmented tanks are disclosed. Conversion per passing of seed yarn The percentage ranges from 4 to 50%. The application claims that a bromine solution produced by electrolysis is Describe further process steps used as a leaching solution to recover gold from stone. Example 6 listed has an equivalent molecular weight of bromine of 0.68% and a promide ion of approximately 0.43% by weight. % and a leaching solution containing about 0.43% by weight of sodium ions. Ru. If a split tank is used, the cathode side should be used to recover gold from the leachate. Can be done. The leachate is preferably AuBr4-1.2x10-'~t,2xio- 3 mol/liter, promide ion 0.4-3.0 mol/liter, and sodium Contains approximately 0.4 to 3.0 moles/liter of um ions. The pH is preferably O~3. stomach.

Dadgar et al., J. Ph1s, Chem, 68, 106 (1964) and and Dadgar et al., J.

Inorganic Nucl, Chem, vol. 33, 4155 (1971) The equilibrium constant for ion pair formation co-exists with the reciprocal of the dielectric constant of the medium (organic solvent-water mixture). It has been reported that there is an increase in

Dubo　is　and Garnier, Bull　l.

Soc, Chim, Fr., 1715 (1965) in a methanol-water mixture. The production constant of (Brz+Br-=Brs) was calculated. These authors are A semi-empirical equation is derived that relates the formation constant of ON to the dielectric constant of the medium. Also, Nakaga Wa et al., J., Ph1s.

Chem, Vol. 61, 1007 (1957) also describes We investigated the formation of tripromide and found that the formation constant was just like that of the methanol-water mixture. showed that it increases with increasing concentration of acetic acid.

In addition to ore, there are a number of additional gold and silver sources that offer opportunities for economic recovery. Ru. In fact, some of these secondary sources have a relatively high content of metals to be recovered compared to ores. There are many things that are quite rich. Gold includes industrial waste and gold-plated electronic circuit boards. Copper, zinc from numerous scrap sources and in karat gold used in jewelry , silver or tin alloys. Silver emulsion, photographic, x-ray film from a number of industrial sources, from scrap sterling.

Is Bazi 1evsky's U.S. Patent No. 3,495°976 a plated substrate? gold by dissolving the gold in an aqueous solution of potassium iodide and free iodine. Describes the process of collection. For gold, add concentrated sulfuric acid and bring the resulting mixture to the boiling point. solution by near heating to distill out the molecular iodine and cause the precipitation of gold. recovered from.

Bahl et al., U.S. Pat. Six compositions describing compositions and methods for eroding layers include, for example, potassium bromide. By mixing aluminum (75g), elemental bromine (25g) and water (100ml). will be built. This solution recovers gold from ceramic substrates at essentially room temperature. It is effective for

Bahl et al., U.S. Pat. No. 4,375,984, discloses a method for eroding gold from a substrate. A process using an alkali metal bromide/bromine solution is described. With this disclosure For example, a dissolving solution contains potassium bromide (2 g), bromine (1 g) and water (2 g). 5 ml). The gold dissolved in the solution is , by precipitation with an alkali metal hydroxide or by driving a dissolving solution. It is recovered as metal gold either by being removed. alkali metal promi The bromine/bromine etchant solution can be regenerated by adding acid to it. Ru.

Kalocsai based on reexamination of U.S. Patent No. 4.6s4,404 B1 4,684,404 is a method for treating metallic gold with water or protic alcohol such as alcohol. Solvents, non-reducing cations such as sodium, potassium, ferrous or ammonium source of bromine, and molecular bromine, bromine water, or inorganic sources capable of liberating bromine into the reagent. Alternatively, note the dissolution in a reagent consisting of a free bromine source, such as an organobromine-containing compound. It is listed. The solution may be further diluted with hydrogen peroxide, sodium peroxide, or peroxide as needed. Potassium, sodium permanganate, potassium permanganate, potassium chromate Alternatively, it contains a strong oxidizing agent such as ferric sulfate.

Among the examples of reagents disclosed by Kalocsai are B r 21, Ov/v%, N a　B　r　1　w/　v% and Na0HO, 6w/v%, pH 7, 35 (Example 28).

No. 4,637,865 to Sergent et al. By contacting with an aqueous leaching solution containing a leaching agent consisting of a tontoin compound, It describes the process of extracting precious metals from source materials. The leaching solution is 1.3- Dibromo-5,5-dimethylhydantoin, l-bromo-3-chloro-5,5- Dimethylhydantoin, and 1,3-dichloro-5,5-dimethylhydantoin It is stated that it contains. Precious metals are precipitated from leaching solutions with low blue discoloration. by evaporation, ion exchange, treatment with activated carbon, solvent extraction or electric field sampling. It can be removed.

Simpson, U.S. Pat. No. 4,439,235, discloses that finely ground hydrocarbonaceous ore From stone, finely ground ore is contacted with an aqueous solution of hypochlorite, iron ions, and acid. It describes the process of removing valuable metals.

U.S. Pat. No. 4,319,923 to Fa 1 ange et al. is dissolved in a potassium iodide/iodine solution and an alkaline compound, preferably Precipitate metallic gold from solution by adding KOH to raise the pH to at least 12.5. Describes the process of recovering metals from solution by recovering gold by ing. Precipitate palladium using polyhydride. A similar process is performed by Ma cDonald, US Pat. No. 4,319.922.

Academic Press, New York.

Jolles, rBromine and its CompundsJ, 19 66. Page 173 shows that a mixture of sodium bromate and sodium bromide is used for the extraction of gold ore. describes that it has been used under the name "mining salt". Jol les contains 43% sodium bromate and bromide, although the proportions of each component vary. Sodium 57%, i.e. 2 moles of sodium bromide to 1 mole of sodium bromate It describes what is normal.

U.S. Pat. No. 3,222,276 to Belohlav et al. A process for producing aqueous bromine solutions from aqueous solutions of salts and mineral acids is described. That program According to the process, a concentrated aqueous solution of promide to bromate salt in a molar ratio of 5:1 is added to the mixing zone. There, the concentrated aqueous solution is mixed with mineral acid and the bromide/bromate solution is dissolved in concentrated bromine water. Convert to solution. This aqueous bromine mixture is delivered to a second mixing zone where the mixture is is diluted with a larger volume of water to produce a dilute stream of aqueous bromine, and this stream is further diluted with a larger volume of water. from mineral acids and promide/bromate salt solutions by diluting with a quantity of water to extremely dilute bromine water. The solution is produced in substantially quantitative yield. The process as described is a breeze. Useful for brominating pool water. The literature refers to precious metals as sources of precious metals. There is no mention of using bromine or bromide for recovery.

Prior art processes using molecular bromine have been effective in recovering gold from source materials. However, pure bromine is a corrosive fuming liquid that produces suffocating vapors and requires special handling. bromine must be dissolved in water to some extent, or alkali metal Although it can be incorporated into belpromide solutions, these aqueous materials exhibit significant bromine vapor pressure. However, their use also usually requires special handling. With another method can be used to acidify alkali metal bromates and generate molecular bromine. However, bromate itself is only a limited source of molecular bromine; Salts have high crystallization temperatures, which makes them inconvenient to use as leaching agents for precious metals. Ru. Promids and bromates, such as the "mining salts" described by Jolles, mixtures have found a role in the technology of precious metal recovery, but their known Solutions that have relatively high bromine vapor pressures to become as effective as did not become a source of molecular bromine.

In addition to being used in the recovery of precious metals from ores, inorganic bromine compositions are also used as disinfectants. has been used as.

As discussed above with respect to Be1ohlav U.S. Pat. No. 3,222,276. Among the particular uses of inorganic bromine compositions was the disinfection of swimming pools. bromine Due to the toxic nature of hume and the bromine evaporation of conventional aqueous bromine concentrates, Relatively high air pressure keeps pool water and other water circuits away from these concentrators. This causes inconvenience and trouble when processing at the site. Organobromine compounds also take Although they have been used in a wide variety of applications, they are typically more expensive than inorganic compositions. .

Aqueous bromine compositions are used in a variety of applications, particularly in the recovery of gold from ore in remote mines. These compositions are susceptible to freezing when transported and handled for use. This will cause difficulties. Some bromine compositions do not undergo freeze/thaw cycles. The lack of stability and susceptibility to freezing can also complicate packaging and transportation. Ru. Many of the mines are located in areas with harsh climatic conditions. Moreover, many of the known compositions has a rather high freezing point, so freezing is a problem even at relatively mild environmental temperatures. It becomes a problem.

Lu standing 11 Among some objects of the invention, mention may therefore be made of: gold and silver Provide an improved method for the hydrometallurgy recovery of ores or other such sources; in particular , without the need to handle liquid bromine or solutions with significant bromine vapor pressure. Nidia provides such a method of providing a substantial source of bromine for dissolving metals. This method avoids the use of gold oxides; provides such a method that can be used to recover from types of ores. produce a leachate from which gold or silver can be easily recovered; We provide such a method to accomplish this.

A further object of the invention is a method useful for leaching metals and silver from sources, including: and provide an effective composition. Such compositions containing a substantial source of molecular bromine provide such a composition that does not exhibit high bromine vapor pressure; low thermal power; exhibits a chemical crystallization temperature so that it remains stable during storage or transportation even in harsh climatic conditions. Provision of such compositions that do not freeze: This composition exhibits a high degree of freeze/thaw stability. to provide a composition that can be used directly or without dilution with water; Provided are such compositions that do not require pre-acid activation.

A further object of the invention is to provide a disinfectant, particularly for swimming pool water and water, which is useful as a disinfectant. An object of the present invention is to provide a composition for exterminating microorganisms in ring tower water.

Accordingly, the present invention provides, briefly, that the formulation contains at least 251% bromine and hydrobromic acid. and about 4 to about 15% by weight of the metal promid. do. Select the metal promide from LiBr, NaBr, KBr and CaBr* . The composition has at least about a percentage weight percentage of excess promid ion. Contains an excess of promide ions greater than 5% bromine and not greater than about 1.0 It has a pH.

The invention further provides that the composition contains about 10 to about 40% by weight of bromine and about 4 to about 20% of metal promid. , 5% to about 24% by weight hydrobromic acid, and a polar organic solvent (i.e. alcohol or acid). ) at least about 10% by weight. Metal promide is lithium bromide Select from among silica, sodium bromide, potassium bromide, and calcium bromide.

The invention is also directed to a method of recovering precious metals such as silver or gold from their sources. . The method is to dilute concentrates of the above types with water for leaching. preparing a solution and contacting said source with a leaching solution, thereby leaching a leaching solution containing precious metals. Involves producing exudate.

The composition of the invention may also be used in a method for combating microorganisms in a body or stream of water. can be done. Bromine from concentrates of the type specified above can be directly Either after dilution or after dilution, the presence of nucleic acids in a body of water or stream or the growth of microorganisms in the stream. Introduce it in an amount that suppresses proliferation.

A day of Figure 1 shows the dissolution for testing the solubility of gold in the diluted concentrate of Example 5. Figure 2 is a plot of the concentration of gold versus bromine; Plot of amount of dissolved gold versus time for the simulated patch kinetics test. be; Figure 3 is for the rotating disk kinetics test of the dissolution of gold into the concentrate of Example 6. is a plot of total dissolved versus time; Figure 4 shows simulated patch kinetics of gold dissolution into concentrates for Example 6. Figure 2 is a plot of amount of dissolved gold versus time for the test.

Figure 5 shows the total remaining cooling tower water through the cooling tower water treatment test of Example 8. is a plot of distillate oxidant (TRO) content versus time; Figure 6 is a plot of bacterial density in cooling tower water versus time during the test of Example 8. be. This plot is superimposed on the plot of FIG.

H of t According to the invention, an inorganic belpromide can be used advantageously in various applications. discovered a deconcentrate. Some uses like recovering gold from ore The method requires that these concentrates be diluted with water and used in carrying out the method. A working aqueous solution can be provided. swimming pool or cooling tower In other applications, such as water treatment, the concentrate may be metered to the area of water being treated. The concentrate contains a significant percent of the molecular bromine. It is common, but not significant, to be acidic, with a pH of zero or less. exhibits a low vapor pressure, which makes the concentrate easy to handle and eliminates molecular odors. avoids the risks that would be incurred if the element were used in comparable applications.

Many compositions of the invention are suitable for transportation, storage and/or use in harsh climatic conditions. advantageously adapted for

A variety of these concentrates exhibit favorable freeze/thaw stability and their Some of them exhibit exceptionally low thermodynamic crystallization temperatures.

The composition of the invention comprises a metal promide, a hydrohalic acid, a molecular bromine, and a protic It is common to mix from a solvent. The protic solvent is water, alcohol or organic acid. or a mixture thereof, one composition of the invention includes molecular bromine compounds. molar concentration of velpromide ion, molar concentration of hypobromite ion, and Equivalent molecular bromine, defined in moles as the sum of the molar concentrations of bromate ions According to the invention, the equivalent molecular bromine content is preferably 0 to 40% by weight, or 25% or less. Concentrates containing more than It has been found to exhibit stability and an exceptionally low thermodynamic crystallization temperature. molecule bromine cone Advantageously, the centrate is about 30 to about 35% by weight.

Each of the compositions combines a halide ion source and molecular bromine with an excess of bromide ions. Prepare by mixing in the following proportions. Halide sources include metal halide salts and It usually contains both hydrogen halides. The halide ion is preferably bromide. and the molar ratio of promid ion to molecular bromine in the formulation is from about 12=1 to about 2.0:1. in solution, most preferably from about 1.4:1 to about 1.8+l. is combined with a promid ion according to the following formula to form belpromide or mixed belhalai. form a doion. Br-+Brz=Brs-(1) Or CI-+Brz=CIBra-(2) Promidoid used when blending the composition (and other halide ions), complementary countercations, and molecular bromine fractions. By adjusting the range of Can be produced at extremely low I)Hl, i.e. both zero or below. I discovered that.

Among the metal bromides that can be incorporated into the compositions of the invention, sodium bromide, odor Alkali metal salts such as potassium chloride, and lithium bromide, as well as calcium bromide There are alkaline earth metal salts such as Halogenated water used in preparing the composition Elements include HCI, Hl and HBr, with the latter being preferred.

The concentrate of the invention may further contain alcohol or a low molecular weight organic acid, if necessary. have Alcohols and low molecular weight organic acids have lower dielectric constants than water. Up Since the equilibrium constant for the reaction described above increases with the reciprocal of the dielectric constant, Incorporation into the product also helps maintain low bromine vapor pressure at high molecular bromine concentrations. Become. Useful organic acids include propionic acid, succinic acid, adipic acid, and the like. Yes Useful alcohols include methanol, butanol, etc.

Compositions containing alcohol and bromine may, under certain explosive circumstances, It is known that the reaction between bromine and bromine can result in instability. This is it It is usually preferred to use organic solvents other than alcohols. However, Bowm an etc. rAPoten-tial Hazard in Preparing Bromine-Methanol 5 olu-tions J, J, Elec trochem.

As explained in Soc, Volume 137, Issue 4 (April 1990), 1309-11. In addition, the Bra/alcohol composition is stable if the alcohol content is sufficiently low. can be used safely.

Bowman et al. reported that methanol/Br, a composition with an alcohol content of Essentially non-reactive if less than 10% by volume based on Cole+Brz is reported.

The composition of the invention containing hypobromous acid and an organic protic solvent is formulated from the following: Usually: Br2 10~40% by weight Metal promid 4-30% by weight HBr 5-24% by weight Organic solvent 10-40% by weight Water is optionally present as a co-solvent. A suitable composition is formulated from the following: : Br, 20-35% by weight Metal promid 8-16% by weight HBr 10-20% by weight Organic solvent 15-30% by weight These compositions contain 25% bromine and greater than about 40 mm Hg at 20°C. bromine vapor partial pressure of less than about 50 mm Hg at 34% bromine and 20°C The thermodynamic crystallization temperature, which exhibits a modest bromine vapor pressure, is The temperature ranges from about -30°C to about -50°C at 34% Brz, and the solvent is an organic solvent. range from about -55°C to about -68°C for compositions containing media.

The pH is less than 1.0 and usually less than 0.20. A preferred composition has a pH <Has O.

Bra concentration, regardless of whether the solvent contains water, organic acids, or mixtures thereof. is particularly preferably higher than 25%. Such compositions are formulated from the following: Br: 225% by weight HBr 4-20% by weight Metal promid 4-15% by weight [Br-]/[Br2] 1.2: 2. O (molar ratio) protic solvent remainder the law of nature The pH is O. More preferably, such compositions are formulated from: Br2 25-35% by weight HBr 10-20% by weight Metal promid 10-15% by weight [Br-]/[Br,] 1.4: 1.8 (molar ratio) Protic solvent rest Again, the pH is O. Such formulations have a Br2 of 230%, optionally from 32 to 36%, and a molar excess of the bromide of more than 30%. It can be.

Similar compositions using HCI in place of HCI are more preferably formulated from the following: Katsu has pH<O: Br2 ≧25% by weight HCI 24% by weight Metal promid 10-15% by weight [H20] / [N a B r ≧ 4.0 (weight ratio) N a B r 3 In the composition, the sodium ion content of the formulation ranges from about 1 to about 3% by weight; It is particularly preferred that the molar ratio of Na'' to equivalent Br is not greater than about 0.8.

This relatively small proportion of Na results in a relatively low thermodynamic crystallization temperature. It has been found that this results in excellent freeze/thaw stability of the concentrate. Frozen The preferred formulation for crystallization/melting stable NaBr5 concentrate is as follows: : NaBr 5-15% HBr 15-30% Br2 25-35% H2O remaining.

Particularly suitable low Na' compositions include: NaBr 5-10% HBr 17-27% Br2 30-35% H2O remaining.

Calcium bromide compositions exhibit exceptionally low vapor pressures at high equilibrium molecular bromine concentrations . This is because the ionic strength of calcium bromide is greater than that of alkali metal bromide. This is thought to be due to this. The increase in ionic strength is related to the following reactions. tends to increase the equilibrium constant: Br-+Brz=Brs-(1) Or CI-+Brt=CIBrz-(2) Ca(Brs)s concentrate was prepared at 20°C with an equilibrium molecular bromine concentration of 25%. exhibiting a bromine vapor partial pressure of less than about 40 mm Hg at equilibrium molecular bromine of 34% and has a bromine vapor partial pressure of less than about 50 mm Hg at such temperatures. Canada In addition, calcium perbromide compositions have particularly low thermodynamic crystallization temperatures (TCTs), e.g. in the range of about -50°C to about -60°C when water is the only solvent, and when the solvent is an organic solvent. Such TCTs may also yield crystallization temperatures below about -60°C when containing a medium. Additionally, the ionic strength of these formulations is greater than that of alkali metal belpromides. This is thought to be due to the following. Calcium perbromide composition is formulated from the following: Preferably and with pH<O.

B　r　z　≧25% by weight Ca　B　　　　2　25% by weight HBr 210% by weight [Br-]/, [Brz] 1.4: 1.8 (molar ratio) the above electrical outlet Torate converts promide or other halide salts and hydrogen halides into protic Prepared by adding solvent and then liquid bromine to acidic promid salt solution is preferable. This order allows the process to react with liquid bromine while adding bromine. By making the mid ion exist in excess, velpromide or XBrz-ion (X is halides). Saturated or nearly saturated Remix solutions were prepared for both promid salts and hydrogen halides, and these The premix solution is added to water to produce a precursor solution, and liquid bromine is added to this. It is advantageous to be able to From this, for example, a solution containing an organic protic solvent is , can be prepared by mixing: 10-40% by weight organic solvent medium 8-45% by weight 46% by weight NaBr solution: 10-50% by weight 48% by weight HB r solution 10-40% by weight liquid bromine; Or 10-40% by weight organic solvent 8-40% by weight 52% by weight CaBr solution; 10-50% by weight 48% by weight H Br solution 10-40% by weight liquid bromine: Or 10-40% by weight organic solvent 10-50 wt% 38 wt% KBr solution; 10-50 wt% 48 wt% HB r solution 10-4o wt% liquid bromine; Or 10-40% by weight organic solvent 7-35 wt% 54 wt% LiBr solution; 10-50 wt% 48 wt% HB r solution 10-40% by weight liquid bromine; When water is the only solvent, NaBra Concentrate can be mixed with: Preferably prepared from: 6-40% by weight water 9-35% by weight 46% by weight NaBr solution: 10-50% by weight 48% by weight HB r solution ≧25% by weight liquid bromine: Concentrates are preferably prepared as described above, but also contain bromates. Salts and bromide salts may be provided by acidifying alkaline solutions.

Such alkaline concentrates are described, for example, in U.S. Patent Application No. 401,03 It can be prepared by the method generally described in No. 6. Making it acidic , convert the bromate to bromine according to the following reaction: B r Os−+ 58 r~+6H” -3Br, +3H* O(3) Acidic to a pH close to zero Then, the above equation is quantitatively pushed to the right. By equation (1), Br and Br- The reaction further promotes the conversion of bromates.

The composition of the invention further includes a hydrogen perbromide concentrate formulated from: Br, 215% by weight HBr 15-40% by weight Organic solvent 40-60% by weight When water is the only solvent, the composition preferably contains: Br2 225% by weight HBr 30-40% by weight These HBr5 compositions are approximately 40 mm at a bromine concentration of 25% and a temperature of 20°C. Indicates a bromine vapor partial pressure smaller than Hg.

The composition of the concentrate of the invention as previously contemplated consists of a formulation, i.e. from which concentrates are used in forming the concentrates. It should be noted that this is a list of things that form in relative proportions. these The formulations of Br.

and balancing the conversion of Br- to B r s-. In addition, in Br. Some reacts with water to form hypobromite, which in turn becomes limited. dissociates to a certain extent.

The exact equilibrium composition of each formulation can be calculated based on known equilibrium constants. can. Applicant's invention encompasses such balanced but produced compositions. . However, for purposes of clarity and brevity, concentrates are and by their formulation from water, promid salt, hydrogen halide and liquid bromine. Set.

Diluting the invention's concentrate to produce a leaching solution to recover precious metals 401.03 et al. Use as described. i.e. by diluting the above type of concentrate. from about 0.01 to about 1% by weight, preferably from about 0.02 to about 0.5% by weight of molecular bromine. %, from about 0.005 to about 10% by weight of promid ion, preferably from about 0.01 to about 1 % by weight, and from about 0.005 to about 15% by weight of total halide ions, preferably about 0.005 to about 15% by weight. The leaching solution contains 0.01 to about 1.5% by weight. However, e.g. electronic circuit board or even more concentrated in certain applications, such as recovering metallic gold from jewelry scrap. A leaching solution may also be used. Such a solution is made from the above concentrate with water in moderation. It can be prepared by diluting it to concentrated metal gold or There are some cases where it may be used directly to dissolve silver.

Gold and silver are extracted from their sources, such as finely ground whole ore, by adding bromine leaching water to the source material. Collect by contacting the solution. In the case of gold, the oxidation and complexation of gold is expressed by the following formula: Therefore, it is thought to proceed: Or H+ The relative proportions of ore (or other source material) and leaching agent will vary depending on the nature of the ore. The output slurry contains about 1 to about 100 pounds (0.5 to 45 kg) of activator per ton of source. In this case, the activator preferably contains a promid in the leaching solution, Defined as the sum of the amounts of velpromide, metal hypobromite, hypobromite, and molecular bromine. .

If the source material is a poorly soluble ore, remove sulfides and carbonaceous materials. It may be necessary to pre-treat the ore for This can be done by methods known at the time, such as pressure oxidation. Roasting is , for leaching according to the invention, which can be a sufficient pretreatment if carried out at a temperature of 500 to 750°C. The compositions and methods also include high grade non-refractory ores, low grade soluble ores, Hard to understand and oxide ores, electronic parts scrap, jewelry scrap and the like advantageous for recovering gold from low grade refractory and oxide ores. Can be used. The compositions and methods include obtaining silver from a variety of sources including photographic film. It can be used for recovery.

The slurry in the ore leaching solution is stirred to move the precious metals from the ore particles into the aqueous phase. It is preferable to encourage the In this way, gold or silver is complexed with promid ions. to produce a leachate containing it. Leaching can be carried out at ambient temperature. from ore It is preferred to maintain contact for a period of 2 to 6 hours to achieve maximum transfer of gold or silver. Delicious.

After completing the treatment with the precious metal source leaching solution, the leachate is removed from the leached ore. , by filtration, etc. Wash the filtrate (leachate) with an aqueous cleaning medium and use Combine the washed solution with the filtrate and then add the combined filtrate and wash solution to the precious metal. Process to recover the genus. Particularly in the case of silver, the filter cake is mixed with 2-4 molar H It is advantageous to process with CI. Cleaning the filter cake in this way can be effective in removing further silver from the cake in the form of AgC1a- Ru. A solution of 4M HCI is particularly suitable.

Gold from combined filtrate and washing solution, zinc or aluminum precipitation, ion exchange , carbon adsorption, or by conventional means such as electrowinning. . The inventive leaching solution can be used to recover silver in a similar manner.

When disinfecting areas of water such as swimming pools and cooling tower basins. can be added to the concentrated water body in a variety of different ways. Conse Advantageously, the concentrate is metered into the circulating stream of water.

For example, in the case of a cooling tower, the concentrate is It is best to meter the water into the stream of water that is circulated between the heat exchanger and the heat exchanger. In the case of swimming pools, the water flow is withdrawn from the pool continuously or intermittently. Circulate through the brominator and add concentrate to the brominator.

If desired, the concentrate can be diluted with water and then added to the water area to be treated. good.

For swimming pool treatment, the concentrate is sufficient to kill bacteria in the circulating water. It should be added in proportion. This is also done for cooling tower water. good. However, cooling tower water can only inhibit the growth of microorganisms. It is advantageous to treat with a bromine concentrate that is only non-killing. this method results in savings in bromine consumption, cooling tower parts, piping and cooling Minimize corrosion to heat exchangers using water. The concentrate is using a positive displacement pump, e.g. a diaphragm pump, in the ring tower basin. It is preferable to measure and add. Hydraulic pumps are self-priming and have a backflow siphon effect. This is the most suitable because it does not cause any damage. Total residual oxidant (TRO) level approximately 0 2 to about 2 ppm, preferably about 0.2 to about 0.7 ppm (measured as CI*). By supplying at a rate that maintains Minimize corrosion of vibrators, pumps and other cooling tower system components can be done.

The following illustrates the invention.

Kaiyu The precursor was prepared by adding 48% HBr solution and 46% NaBr solution to water. A surfactant composition was prepared. Add liquid bromine to this precursor solution to obtain 34% An acidic concentrate containing % equivalent molecular bromine was prepared. Listed in Table 1 A satisfactory solution is prepared from proportions of water, HBr solution, NaBr solution and liquid bromine. It was done.

Composition HzO (g) 48% HBr (g) 46% NaBr (g) Br s (g) pH2526103034<0 26 16 20 30 34 <0 276 30 30 34<0 28 36 10 20 34 <0 29 24 20 20 34 <0 30 14 30 20 34 <0 32 36 20 10 34 <0 33 26 30 10 34 <0 These solutions were clear and stable. No phase separation occurs when left alone It was.

carp delivery Using the method generally described in Example 1, water, a 46 wt.% NaBr solution and a 37 wt. An acidic concentrate containing molecular bromine equivalent to 34% by weight from a %HCl2 solution A sheet was prepared. Satisfactory compositions were prepared from the proportions listed in Table 2.

Table 1 Composition 8.0 (g) 37% HCII (g) 46% NaBr (g) B rz (g) 14 16 20 30 3L Takumi 1 Using the method generally described in Example 1, water, 48% by weight HBr solution, 52% by weight An acidic solution containing 34% by weight equivalent molecular bromine from CaBra solution and liquid bromine. The centrate was prepared. A satisfactory composition was prepared from the proportions listed in Table 3. It was done.

table no Composition H2O (g) 48%) IBr (g) 46% NaBr (g) e rg (g) pH3726103034<0 38 16 20 30 34 <0 3j 6 30 30 34 <0 40 36 1 [120340,6 41242020340,2 4214302034<0 44 36 20 10 34 0.745 26 30 10 34 0.4 CaBrz, Bra, methanol, HBr or HCI and optionally Additional compositions were prepared from water as follows. From the percentages listed in Table 4, it is satisfactory. A composition was prepared.

Tile A Carp A From water or organic solvent, 46% by weight NaBr solution, 48% HBr solution and liquid bromine , an acidic concentrate was prepared. NaBr solution and HBr in water or organic solvent solution and liquid bromine was added to the precursor mixture at a moderate rate. B During the addition of rx, the mixture was stirred at a steady but steady rate. four Different concentrates were prepared. Each of these is a stable and clear liquid. Ta. The vapor partial pressure was measured 24 hours after the concentrate was formulated. these The concentrate composition, bromine vapor partial pressure and thermodynamic crystallization temperature are listed in Table 5. do.

Table 5 4.A. Water (wt%) 610 Methanol (wt%) +526 48%) IBr (weight%) 25 30 36Brz (weight%) 34 3 4 34 34 Br by soaking, (%) 33.6 34.6 35.1 34 ．． 5 Density (g/ml) 1.67 +, 56 1.92 1.72 Steam partial pressure ( mmHg/20℃) 22.5 39.5 48.5 39.5 Crystallization temperature (℃ ) -55<X<-68X<-68-50-30pHX<0 0.11 X<O X<0 Tests were conducted on the solubility of gold in these concentrates. that For each concentrate, soak the concentrate in water before testing solubility. Solubility at five different equivalent molecular bromine concentrations by diluting with was tested. These concentrations are 2. OOg/β, 1. OOg/I2.0.40g/β, 0.20g/I2 and O,L og/β. The amount of gold added to the concentrate varies depending on the bromine content. Ta. After stirring each specimen of gold in the diluted concentrate for 24 hours, The solution was filtered using a 0.45μ membrane. Gold analysis by Thermo Jarr ICP using ell Ash Atomscan 25: Therefore, Ta. Figure 1 shows the solubility of gold.

Additionally, to determine the activity of each concentrate in this example for dissolving gold, Pseudo-batch kinetic studies were also performed. This experiment was conducted using Corning It was performed using a stir plate and sealed glass bottles. In each test operation, A test specimen of powdered gold (99.99% purity) that passed through a 325 mesh was In a test sample of concentrate diluted to an equivalent concentration of molecular bromine, 0.6 g/l was introduced at a concentration of of a batch of kinetic tests by adding deionized water. The total capacity was 500 mβ. The resulting mixture was stirred at room temperature.

After 0.05 hours, 0.5 hours, 1 hour, 2 hours, 4 hours and 24 hours, respectively. A sample of 20 mI2 was extracted. The batch volume should be equivalent to the sample taken. The amount was kept constant throughout the test by adding deionized water. kinetics test The results are shown in Figure 2.

ox j The four concentrates of Example 4 were prepared from a difficult-to-dissolve gold concentrate sample. The conditions and results of these tests tested as reagents for gold recovery are shown in Tables 6-9. Shown below.

■ Sample size of difficult-to-mix concentrate: So, oo g Flame analysis (fired product) +17.3 oz/l Au feed preparation: 100 mesh passing; Roasted at 700℃ Conditions = 22°C; pH = 5; Solids content 20.0%; Mixed for 4 hours; ORP = 930 mv Developing agent: Compound No. 1 1.0g 11 Rinu Dissolved Au 93.91% Roasted 1- 6. Concentrates that are difficult to prepare Sample size: ■Potted food 50.00g Flame analysis (■ pottery): 17.3 oz/l Au feed preparation: 100 mesh past; Roasted at 700℃ Conditions: 22°C, pl (=5; solid content 20.0%; mixing for 4 hours; 0RP=93 0 Leaching agent: Blend No. 2 1.0g 11risu 2-door liquid 650m I2. 44.62 m g/I2 A u (29,00 mg) Residue 44.4 g 1.19 oz/t A u (1,96 mg) Dissolved Au 93.67% Nisumi 7 Difficult to prepare concentrate' Sample size: ■Potted food 50.00g Flame analysis (grilled food): 17.3 oz/l Au feed preparation: ioo mesh past; Roasted at 700℃ Conditions: 22°C; pH = 5; solids content 20.0%; mixing for 4 hours; ORP = 930mv Leaching agent: Formulation No. 3], Og 1 summer dish Dissolved Au 94.81% Table of contents Flame analysis (smoking): 17.3 oz/l Au feed preparation = 10 lome past; Roasted at 700℃ Conditions = 22°C, pl (=5; solid content 20.0%; mixing for 4 hours; ORP = 9 30mv Leaching agent: Blend No. 4 1.0g 11 dishes Dissolved Au 96.7% salmon mutual Using the method generally described in Example 1, having the formulation No. 4 of Table 4 (Example 4) A concentrate was prepared. Efficacy of this composition for the recovery of gold from ores using the spinning disk technique and also using a pseudo-batch as generally described in Example 4. It was tested using the same technique.

The rotating disk test was performed using a pine instrument (Pi) with gold disk electrodes. A model AFASR rotation apparatus was used. fruit The parameters of the experiment were as follows.

Temperature = 25℃ Rotation speed = 500rpm Sample volume = 200mI2 Electrode area = 0.203crf Velpromide concentration = 5g/β pH=3.2 In the rotating disk experiment, a gold disk electrode is introduced into a solution while rotating. So I started. Sample the solution at 5 minute intervals to record gold analysis, pH and temperature. I took out the fee.

In pseudo-batch kinetic experiments, 0.16 hours, 0.33 hours, 0.5 hours, Samples were removed after 1 hour, 2 hours, 4 hours, 8 hours and 24 hours.

In both experiments, deionized water was used to compensate for sample removal and maintain a constant volume. was added. All analyzes were performed using Thermal Jarrell Ash At TCP (Inductively Coupled) using omscan 25 This was done using a Plasma Spectrophotometer.

The results of the pseudo-batch kinetic study are shown in Figure 3 and the results of the rotating disk study are shown in Figure 4.

salmon yu Compositions having the formulations shown in Table 10 were prepared. For each of these compositions, the odor The elementary vapor partial pressure and initial crystallization temperature were measured. These data are also listed in Table 10. Record.

A" 28. + 0 43.7 28.1 - 79.5 C9,559,692 1,159,7-1542,0D''-24,648,726,7-74,5 E 15.8 16.0 35.0 33.2 +13 -F 8.3 26. 8 24.1 40.8 -3528.0G 7.2 23. + 34.7 3 5.1-242. OH7,423,932,536,3-240,OK 10 ．． 3 19.2 28.2 42.4 -637. OL 13.6 13.4 30.1 42.9-547.5M 4.88'29. + 23.8 42. 2-24. ON 3.75 22.4 4+, 4 32.4 - 53.0 0 4.3 25.7 32.8 37.2 - 29.0 [shares] 1 At the beginning Temperature at which crystals appeared ('C)2 Vapor partial pressure of bromine (mmHg) *A = N a B r 1.　D　=　HB　r　.

NaBr/HBr ratio, Brz content and The bromine vapor partial pressures are listed in Table 11. NaBr/Her Dr-/era Br* Composition Weight ratio Molar ratio Weight ratio Weight% Sole% Vp"F O, 3 + 0.24 1.4 24.1 5.3 28G O, 3+ 0.25 0.8 34.7 8.6 42HO, 3+ 0.25 0.9 32.5 7.9 40M O, 170,131,423,85,124N　O,170,130,641,4+ 0.9 530 0.17 0. +3 0.9 32.8 7.8 29@Br Steam partial pressure of z (mmHg) Formulations G and H were prepared by adding bromine to Formula F. Formulation F ~H each have a NaBr/HBr weight ratio of 0,31, but bromine-containing The rates are different. of bromine at a bromine content of 32.1%, Br-/Br, and a weight ratio of 0.9. It will be noted that the vapor partial pressure is 40 mm Hg. As a comparison, only Compositions M, N and 0 with a N a B r / H B r weight ratio of 0,17 are , for comparable Br-/Br2 ratio and Brz content combinations. , appear to exhibit lower vapor pressure. Therefore, the preferred range of compositions of the present invention is , less than 0.25, preferably less than about 0.2 N a B r / H Br ratio of at least about 10 and a Br-/Brt ratio of at least about 30% by weight with a bromine content of

Each composition in Table IO was tested for gold recovery from ore concentrates and Each was found to be effective for this purpose.

Takumi 1 Acidic bromine concentrates having the compositions listed in Table 12 were prepared. Brs minute Measurements of pressure and other parameters were made. These are also listed in Table 12. child The compositions in the table are useful for precious metal recovery and industrial water treatment.

"Clothing" once Organic solvent---monoacetic acid propionic acid 820% by weight (48%) from IBr) 33.8 19.3 19.348% HBr weight% 65.0 37.0 3 7.0 organic solvent weight%---28,028,0Brz weight% (experimental value) 3 6.5 36.8 36.6p H<0<O<0 Brx partial pressure (mmHg/20℃’) 39.8 20.0 17.0 Density (g/ rnJ2) 1.87 1.64 1.60 Crystallization temperature (℃) -45<-50 -42 Takumi Yu Cooling tower water can be added to a concentrator comparable to that in column 1 of Table 12 (Example 8). Processed at Diaphragm pump (Liquid Metronics) Metro-nics), Model A15l-927) and No. 15 Vuitton ( Transfer the concentrate to the cooling tower bay thread using a Viton tube. I sent it inside. Two methods were used to determine the most effective delivery of product. . The first method is to simply submerge the tube into the water from the end of the tube connected to the discharge side of the pump. It drips the product. The feeding rate is 1 minute to pump into the graduated cylinder. Calculated by measuring the volume delivered. The last foot of tubing ( 0.3 m) is approximately 1.5 ft (0.46 m) above the surface of the water. was placed horizontally. In the second method, the end of the drain tube is placed above the surface of the water. I put it down. The feed rate was measured as in the first method, except that this For instructions, use the pump straw to prevent backflow due to siphon action. The pump width was made wider and the frequency of pump operation was increased. Pump works properly The only indication of whether or not it is is the brown color in the water when the pump is turned on. The question was whether cloudiness existed.

Total residual oxidant (TRO) sampling points are located before the water is sent to the tower. This was almost a turning point for water. TPO is Hach CA-17 salt Measured using an elementary analyzer. This analyzer uses the DPD colorimetric method, which allows for separation. The analyzer compares the optical absorbance of the raw water with the optical absorbance of water containing the DPD reagent. Ru. The difference is used to calculate TRO(1)1)m) as Cβ2. Ru. The optical wavelength used in this method was 510 nm. Cβ-17 chlorine analyzer is LED display with two decimal places for recording real-time data, and Has a chart recorder to obtain data throughout the night. This analyzer can be held by hand. Accuracy was checked using a DPD colorimeter (hue wheel).

To measure the microbial density of water in cooling towers, selecticult (Se lecticult)-TTC (Scott Laboratories, Inc.) tt Laboratories, Inc.) dip slide (dipsl ide) was used. Sample collection points were in and above the basin of the cooling tower. , and the usual place for the driver to analyze the water. dip slide underwater for approximately 1 second and then incubated for 2-3 days at room temperature before reading the slides. Incubated.

Table 13 lists all of the cooling tower data generated during testing. from water Cooled samples were analyzed for calcium concentration, residual chlorine, and pH. exam week All readings showed no significant change in concentration or content.

“old” – and Test date Calcium Alkalinity Conductivity Sulphate Chlorine pH 1st day 50ppm 20ppm 240mV 1100pp 0. lppm T, T2 2nd day 60ppm 40ppm 240mV 1100pp O, lppm T , 53rd day -2ppm- 4th day 50ppm 18ppm 240mV 50ppm 0.4ppm 7 ．． Day 55 50ppm 18ppm 240mV 50ppm O, 3ppm Table 14 lists the data generated on the second day of the test. This data has , time, temperature, TRO, CN-1767 supply flow rate (capacity), supply method, pump Includes setting and microbial density. The initial microbial density is approximately 10' microorganisms/mA. It was. At 9:45 a.m., drop the product into water at a speed of approximately 2.0 m 127 minutes. As a result, we have begun supplying concentrates. Pump stroke size is set to its lowest setting, and the frequency is set to 25 strokes per minute (spm) (approximately). Set. TPO is recorded every hour, and at 14:45, TRO is Cβ. and stabilized at 0.27ppm while maintaining the minimum stroke setting. By changing the frequency of pump operation to 35 spm, the feed flow rate was reduced to approximately 4.0 m increased to β/min. Over the next 15 hours, the average TRO is 0.44 ppm as Cβ2. It was.

Todoroki 11 1990116 Feel - Ichita 9:4545 tons (7.2℃) -2.0 drops Maximum 11zo 25 100. E◆05 Ill-450,112,0 dripping maximum 11zo 25+1; 45 G, 22 2.0 Dripping Minimum/25+2:45 0.24 2.0 Dripping Maximum IJzu2513: 45 G, 211 2.0 Dripping maximum 11 zo 25 1. O[lE+0414・4 560 pieces (15.6℃) 0.27 2.0 Dripping 11th 2514:55 - 4.0 Dripping Minimum Ha 515: 45 G, 33 4.0 Dripping Minimum Ha 51 6:45 0.40 4.11 Dripping Minimum 5 + 7:45 50 pieces (1G, 0 °C) 0.40 4.0 Dripping most/1zo 3518:45 fl, 40 4.0 Dripping Minimum 519:45 G, 43 4.11 Dripping Minimum 520:45 0.44 4.0 Drop Maximum 71%/3521:45 0.36 4.0 Drop Lower minimum 522:45 0.36 4.0 Dripping minimum 523:45 Q, S9 4. Q Dripping most/1zo 3524:45 0.44 4.0 Dripping most IX/35-... Not measured At 7:45 on the third day, TRO was 0.53 ppm as C℃□, and microbial The material density was less than 103 pieces/m12. Supply method is to soak the tube I changed the method to The pump was set at minimum stroke and frequency of 25 spm. T RO is cI2. 0.16ppm, and the pump was set at 1:50 p.m. The frequency was increased to 17 strokes/30 spm. At 3:45 p.m., TRO 0.35 ppm, which was higher than expected. Reduce the settings to 18 strokes/25 spm per minute, which is 2.0 mA per minute. It was. These data are shown in Table 15. For the 0th 15 hours, the average TRO is cn. It was 0.44 ppm.

Δ1 mutual 1990117 field data Time Temperature TPO supply flow rate Supply method Pump settings Cell count tcb> (s 1 minute) Stotoku Nori (Ki 2/number of times (individual attack missing/argument) ■・45 0.44 4.0 Dripping minimum/352・45 0.44 4.0 Dripping minimum/353. 45 0.42 4.0 Dripping Min/K54: 45G, 64 4.0 Dripping Min/355・45 0,52 4.0 Dripping Min/356:45 (1,5 14.0 drops Minimum/357.45 KoS"Ffl, 7'C) 0.53 4. 0 Dripping Minimum/358:15 0.53 4.0 Dripping Minimum/35 <1. oOE◆03B: 2G -2,0 immersion minimum/25 8.45 0.48 2.0 Immersion minimum/259:45 0j5 2.11 Immersion minimum/2510・45 0.26 2.0 Immersion minimum/251b4s O, 212,0 immersion minimum/2512:4S O, 192,0 immersion minimum/25 +3:4s 11.18 2.0 immersion minimum /2513・50 to 18730 change +4:4s 59 bottom (150℃) 0.26N, ^, immersion l♂/30+5 ・45 0.35 N, ^, immersion 1873G+5=50 Changed to 18725 ! 6+45 0.33 2.0 Soaking 111/2517:45 50 pieces (10 ,0℃) 0.34 1.0 Immersion 187251+145 0.32 2.0 Soaking 18/25+9:45 (l!6 2.0 Soaking 1872520・4 5 0, 37 2.0 immersion 1872521:45 G, 44 2.0 immersion 18/2522.45 G, 48 2.0? ! Pickled 18/2523:45 11.52 2.0 immersion +1172524:45 0.53 2.0 immersion 18725N, A, = Not obtained - No wealth measurement At 7:45 on the fourth day, TRO was 0.51 ppm as CI2z, The microbial density was less than 10'/mA. 0.30ppm as Cε2 To obtain a TRO of , pump settings to 18 strokes/frequency 20 spm, or It was reduced to 1.0 mj2/min. TRO is cI2. As o, osppm decreases. Ta.

Figure 5 shows the hourly TRO and daily bacterial density; at the beginning of the study, the cell density was negligible. The number of organisms was 105/m I2. TPO cn, 0.28 and 0.5 When increased to 3 ppm, the cell density is less than 10' microorganisms/mβ, respectively. and decreased to a value smaller than 103 pieces/m12. TPO by remaining exam When Cβ is reduced to 0.10 ppm, the cell density is 103 microorganisms/ m remained smaller than I2. Dip slide for measuring cell density The method will not identify cell densities smaller than 10' microorganisms/m12.

Figure 6 compares TPO with respect to feeding style. Two types of supplies used The styles are expressed as “dropping” and “soaking” as mentioned above, and TPO is Cβ2. 2.0 ppm until the same level is reached at 0.28 ppm. A feed flow rate of 127 m was used. Then increase the supply flow rate to 4.0 mI2/min. , TPO was at the same level as Cβ2 at around 0.53 ppm. After that, The feed style was changed to "immersion" style and the feed flow rate was 2.0 mβ/min. product However, the 5-gallon water bowl was apparently TP due to backflow due to siphon action. O dropped to 0.16 ppm as Cl22. Adjust pump settings to minimum stroke/frequency. The frequency was changed from 25 spm to 18 strokes/30 spm, which caused the siphon effect. This suppressed the backflow caused by the heat exchanger and increased TPO to approximately 0.50 ppm at 0°C. same child Using the feed style, reduce the feed flow to 1.0 m (17 min, TRO cg, and reduced to approximately 0.28 ppm as Cl22 at the beginning of the experimental day. It dropped to 10ppm.

There are currently three types of plastics that can be used to construct the delivery tube: standard PVC, polypropylene and XL-polyethylene were tested. concentrate PvC surfaces in full contact with did not show any signs of incompatibility, but However, certain problems arise when two coupons (plate-like specimens) are brought into contact with each other. was recognized. Polypropylene and XL-polyethylene coupons have similar characteristics showed that. Both types of plastic absorb the bromine color into the coupon and the plastic still maintained its integrity and potential. From the XL-polyethylene coupon The odor of bromine was very noticeable, but not from polypropylene or PVC coupons. This odor was not noticeable. Store these coupons at room temperature for 3-4 months. immersed in centrate.

At the end of the test, the pump was inspected. The PVC head had streaks inside, but the Teflon head Ron's diaphragm was not damaged at all. Pump inlet & outflow valve will not be damaged However, it stopped working. Vuitton tubing with pumps provides excellent compatibility showed that.

From the foregoing description, it can be seen that several objects of the invention are achieved and other advantageous results obtained. You can see that.

Various changes may be made to the products and methods described above without departing from the scope of the invention. All matters contained in the above description are to be construed as illustrative and non-limiting. It is not intended that it be interpreted in any other way.

h Note table flat 6-509052 (1B) Continuation of front page (72) Inventor: Fabstricki, Nikolai Ei.

Indiana, USA 47906.

West Laugh Eyet, B-O Box 2200. Highway 52 Northwest (no street address) (72) Inventor: Macuri, Julie A.

Indiana, USA 47906.

West Laugh Eyet, B-O Box 2200. Highway 52 Northwest (no street address) (72) Inventor Sanders, Blend M.

Indiana, USA 47906.

West Rough Eyet, B-O Box 2200, Highway 52 Northwest (no street address) (72) Inventor Hauers, Jonathan N.

Indiana, USA 47906.

West Laugh Eyet, P-O Box 2200. Highway 52 Northwest (no street address) (72) Inventor Rickens, L., Jane United States of America 47906 In Deanna.

West Laugh Eyet, P-O Box 2200. Highway 52 Northwest (no street address) (72) Inventor Borden, Dennis M.

Indiana, USA 47906.

West Laugh Eyet, P-O Box 2200. Highway 52 Northwest (no street address)

Claims (13)

[Claims] 1. The formulation is at least about 25% by weight bromine, about 4% to about 30% by weight hydrobromic acid, and The group consisting of lithium bromide, sodium bromide, potassium bromide and calcium bromide from about 4 to about 15% by weight of a metal bromide selected from the group consisting of at least about 30% bromine; A composition comprising a molar excess of bromide ions greater than about 1.0 A composition having a low pH. 2. The formulation includes at least about 30% by weight bromine and about 10 to about 20% by weight hydrobromic acid. , and about 10 to about 15% by weight of the metal bromide. 3. The composition of claim 1, wherein said metal bromide consists essentially of sodium bromide. 4. A claim in which the molar ratio of sodium ions to equivalent molecular bromine is not greater than about 0.8. Composition of 3. 5. Claim 1 wherein the formulation has a bromide ion to bromine molar ratio of about 1.2 to about 2.0. Composition of. 6. The composition is about 10 to about 40% by weight of bromine, lithium bromide, sodium bromide, and carbon bromide. 4 to about 20% by weight of a metal bromide selected from the group consisting of calcium bromide and calcium bromide; from about 5% to about 24% by weight of hydrobromic acid, and at least about 24% by weight of an alcohol or lower organic acid. A composition containing 10% by weight. 7. The formulation is selected from the group consisting of complex acids, propionic acid, succinic acid and adivic acid. 7. The composition of claim 6, comprising from about 10 to about 40% by weight of hydrochloric acid. 8. Methanol, ethanol, n-propanol, isopropanol, n-butanol Alcohol selected from the group consisting of alcohol, iso-butanol and t-butanol 7. The composition of claim 6 comprising from 10 to about 40% by weight. 9. The formulation contains at least about 25% by weight bromine, at least about 4% by weight hydrochloric acid, and about 10 to about 15% by weight of sodium bromide and at least about 30% bromine. A composition comprising a molar excess of halide ions exceeding the weight ratio of water to NaBr. is not less than about 4.0 and not greater than about 1.0. 10. Contains at least about 25% by weight bromine and at least about 10% by weight hydrobromic acid , and at least about 5% by weight of calcium bromide and at least about 30% bromine. A composition comprising a molar excess of bromide ions greater than about 1.0 Compositions with no pH. 11. The formulation contains at least about 15% by weight bromine, about 15% to about 40% by weight HBr, and A composition comprising from about 40 to about 60% by weight of an alcohol or lower organic acid. 12. The formulation includes water, at least about 25% bromine, and about 30 to about 40% HBr by weight. Composition containing %. 13. A method for recovering precious metals from their sources, comprising: the concentrate of claim 1; A leaching solution is prepared by diluting the leaching solution with water, and the source is contacted with the leaching solution. and thereby producing a leachate containing said precious metal.