NZ726038B2 - Micronutrient supplement made from copper metal - Google Patents

Abstract

micronutrient supplement which is made by reacting together copper metal and hydrochloric acid under oxidizing conditions.

Description

_ 1 _ MICRONUTRIENT MENT MADE FROM COPPER METAL BACKGROUND The present invention relates generally to micronutrient supplements for food or animal feeds that enhance the survivability, growth, health and/or reproductivity of humans and other animals. More speci?cally, the present invention is directed to method of producing a basic salt of an essential metal, which provides high bioavailability of the essential metal to humans and other s. In ular the t application provides a method of producing micronutrients in the form of basic metal salts that uses copper metal as a starting material.

Nutrients include vitamins and some elements usually in the form of minerals or metal salts; most notably the elements include calcium, phosphorus, potassium, iron, zinc, , magnesium, manganese and iodine. utrients are generally ed in small amounts, i.e., less than 1 gm/day, and many essential elements have catalytic functions. While the micronutrients are often t in minute amounts, their bioavailability is essential for survival, growth, health and reproduction. Micronutrients are important for children and other young animals, particularly during their early development years when they are rapidly growing. Furthermore, many new animal breeds require additional amounts of micronutrients as their ies to grow at a faster rate while consuming less feed has improved. This intensive growth imposes greater metabolic stresses, causing increased susceptibility to vitamin de?ciencies. It is well recognized that the needed micronutrients are o?en not found or not found in suf?cient quantities in their food or feed sources, whether these sources are naturally occurring or commercially prepared. Consequently, virtually all industrial food and feed ations are fortified with vitamins and minerals. The cost to commercial livestock producers for ing micronutrients to their livestock herds can be staggering.

While human and animals' needs for additional nutrients have been well documented, the availability of the micronutrients has not always met their needs. It is not suf?cient to simply se amounts of the micronutrients in the food or feed sources. This method is ineffective, wasteful and unsafe. Many of the micronutrients are not readily absorbed; the added amounts of vitamins and minerals are simply ed t being absorbed. Excess loading ofvitamins and minerals is unsafe, and in certain circumstances, excess loading can be toxic, causing severe acute and chronic harm and can even be fatal. Thus, there is a need to provide an inexpensive, readily absorbed micronutrient to decrease costs, reduce waste and to help establish a more precise control of the nutritional requirement for humans and animals.

There is a need to provide a micronutrient supplement that is readily bioavailable, storage stable and compatible with a wide variety of different vitamins. The micronutrient supplement must also be cost-ef?cient to produce and provide a food source for humans and animals that will increase their survivability, growth, health and/or uctivity.

Micronutrients are commonly produced and available in the form of salts, oxides and complexes. Oxides are relatively inexpensive; however, they are not as ively ed as salts and chelated forms of micronutrients. xes and particularly well-de?ned chelated micronutrients are relatively ive; however, they are more easily absorbed and have good bioavailability. _ 3 _ Examples ofvarious micronutrients can be found in U.S. Patent Nos. 4,021,569, 3,941,818, 243 all to Abdel-Monem, U.S. Patent No. 4,103,003 to Ashmead, 4,546,195 to Helbig et a1., U.S. Patent Nos. 4,900,561, 4,948594 both to Abdel-Monem et a1. U.S. Patent No. 5,061,815 to Leu, U.S. Patent No. 5,278,329 to Anderson, U.S. Patent No. 5,698,724 to Anderson et al. 379 to Wheelwright et a1.

U.S. Patent No. 563 to Hopf and U.S. Patent Application Publication No. 2010/0222219 to Lohmann et a1.

At least one of the present inventors is a co-inventor of U.S. Patent Nos. 043, 5,451,414 and 6,265,438, and U.S. Patent Application Publication No. 2013/0064963. These s and published patent application disclose micronutrients that are basic metal salt of the formula M(OH)yX(2-y),=’i, and its hydrate forms, where M is metal cation, X is an anion or anionic group, and i is 1-3 depending on the valence of The micronutrients disclosed in U.S. Patent Nos. 5,534,043, 5,451,414 and 6,265,438 were originally developed from a process that used spend etchant solutions as a source of the metal cations and a crystallization process to produce a basic metal salt having a particle size of about 30 to 300 microns.

U.8. Patent Application Publication No. 2013/0064963 bes micronutrients in the form of basic metal salts that have more versatility than similar micronutrients and which have a high degree of bioavailability and which are produced by reacting a metal oxide, or metal hydroxide, or metal carbonate of an essential mineral and an acid to form a slurry with a ible binder and forming agglomerated particles by spray drying or other means of agglomeration. _ 4 _ The present application provides a method of producing micronutrients in the form of basic metal salts that uses copper metal as a ng material.

Prior to the present invention at least one co-inventor of the present invention were interested in ?nding better ways to make essential trace minerals to be used as nutritional supplements. They discovered that a compound’s chemical structure would dictate its reactivity (rate of undergoing ali'biochemical reactions), so they initially tumed their attention to the development of a manufacturing process that would consistently produce a particular crystalline structure. Eventually they developed and re?ned a process to e a unique lline compound that is a combination of the minerals ataeamite and clinoatacamite.

Later us animal g trials were conducted and it was unexpectedly discovered that the tested essential trace ls demonstrated signi?cant advantages over traditional copper compounds used in ion. US. Patent No. 5,451,414 (cited above) is directed to the discovered improved way to supply copper, a critically important mineral, into animal and human diets, and a crystallization s that was developed to make a consistent polymorph of the product at all times. That original crystallization process ed on having solutions of dissolved copper as feedstocks to feed a crystallizer.

Patent Application Publication No. 201310064963 (cited above) describes a different production process that uses copper oxide and either hydrochloric acid or cupric chloride solution as feedstocks to produce essential trace minerals. The primary advantage of the alternate approach was that it allowed the tion of a much smaller crystal particle size range which was agglomerated to improve handling properties and reduce dustiness when the product is used. _ 5 _ The present invention is in part the outcome of research directed at determining whether it was possible to start with elemental copper and produce the desired polymorph of crystal structure directly, without first completely ving the metal to make a on to feed into a crystallizer. The present inventors were unable to ?nd evidence that such a process was possible. Unexpectedly the present inventors were able to ?nd ions under which the desired reacuon proceeded, and could be controlled to yield the desired product, tribasic copper chloride, with good ef?ciency.

Qaimkhani et al. A New Methodfor the Preparation ofCopper Oxyclzloride (A Fungicide), (J. Chem. Soc. Pak, Vol. 30, No. 3, 2008) discloses several methods by which a compound generally identi?ed as copper oxychloride can be made, and in particular compares three s that use copper wire as a reactant. In Method II ani et al. s reacting copper wire with hloric acid to form a dark green solution of cupric chloride (CuClz). In a second on the cupric chloride is neutralized with sodium ide to form what is described as copper oxychloride and sodium chloride (NaCl). The need for two separate reactions in Method 11 is because copper will react with chloride (from the NaCl solution) to form cuprous chloride (CuCl) which forms an ble coating that prevents the copper from further reaction as noted by Qaimkhani et The present invention provides a process for producing tribasic copper de (Cu2(OH)3C1) by reacting copper metal with hydrochloric acid or cupric chloride under conditions that allow a single overall reaction to proceed without forming unwanted salts, e.g. sodium chloride. The resulting tribasic copper chloride is of a purity that allows its used as a micronutrient. The overall process uses less expensive raw materials and results in lower environmental impact than prior known processes.

BRIEF SUMMARY According to various features, characteristics and embodiments of the present invention which will become apparent as the description f proceeds, the present invention provides a method of making a micronutrient supplement basic copper de (Cu2(OH)3Cl) from copper metal which comprises reacting together: copper metal; one of: i) hydrochloric acid or ii) cupric chloride; and an oxidizing agent to form ic copper chloride.

The copper metal can comprise stock copper or scrap or recyclable copper, The oxidizing agent can comprise an oxygen containing gas or oxygen which can be injected into the reaction mixture to prevent the copper metal from settling during the reaction.

The copper metal and one of hydrochloric acid and cupric chloride and oxidizing agent are reacted at a temperature of about 180°F and stirred during the reaction.

The formed tribasic copper chloride ses a slurry which can be spray dried or agglomerated by other means.

DETAILED DESCRIPTION OF THE DRAWINGS AND THE PRESENTLY PREFERRED EMBODIMENTS _ 7 _ The present invention is directed to micronutrient supplements and methods of preparing the micronutrient supplements. The micronutrient supplements of the t invention can be administered directly to humans or animals as a solid, a suspension or an admixture containing other nutrients such as vitamins, minerals, and food or animal feeds to enhance the survivability, growth, health and/or reproductivity of humans and animals.

The basic salt in the micronutrient supplement includes a divalent cation of an essential metal, a phannaceutically acceptable anion, and a hydr0xyl moiety. The utrient ment of the present invention provides good bioavailability of the essential metal in that it is y absorbed or taken up in a biologically-effective amount. The micronutrient can be combined with other nutrients, ularly vitamins, to provide a premixed supplement. The premixed supplement that includes the basic salt according to the present invention can be stored for extended periods of time t signi?cant decrease in the bioactivity of the included vitamin(s).

An essential metal is de?ned for the purposes of this invention as a pharmaceutically acceptable metal whose uptake by humans or other animals in a biologically effective amount increases their survivability, , health and/or reproductivity. The mode of action of the essential metal is not critical for the present invention. For example, the ial metal can act as a co-factor or a catalyst in a metalloenzyme or metalloprotein; it can be absorbed by a variety of tissues.

Alternatively, the essential metal or a metabolite thereof can inhibit growth of bacteria or other pathogens detrimental to the survivability, growth, health and/or reproductivity of the animal.

According to the t invention the basic metal salt, tribasic copper chloride (Cu2(OH)3Cl), includes a divalent copper cation, a hydroxyl group and a monovalent _ 8 _ chlorine anion. In the tructure that makes up the basic salt, the copper cation includes a hydroxyl group in its coordination sphere.

The chlorine anion of the basic metal salt is a pharrnaceutically acceptable anion. Pharmaceutically acceptable anions are well known in the art. See, for example, S. M. Berge et al. J. Pharmaceutical Sciences, 66: 1-19, 1977 for a listing of phannaceutically acceptable anions, which is incorporated herein by reference.

The chlorine anion that is used in the present invention imparts signi?cant biological effects in its own right. In general specific examples of biologically icant anions include, but are not limited to: , chloride, and phosphate (phosphorus).

These biologically signi?cant anions can also be considered as micronutrients, with chlorine anion being particularly useful for purposes of the present invention. Thus, it is within the scope of the present invention to provide basic salts of essential elements that may not necessarily be considered metals such as chloride.

Basic metal salts that are used as micronutrients are generally water insoluble, but their solubility can depend upon pH. Typically, the basic metal salts have some solubility at a low pH, i.e., pH less than about 2.0 to about 0.1. In addition, certain basic metal salts dissolve in water at a high pH, lly at a pH greater than about 7.5 or 8 to about 1 l.

The basic reaction for producing the micronutrients according to the present ion involves ng copper metal with hydrochloric acid or cupric chloride z) under oxidizing conditions.

The copper metal can be any type of stock copper or scrap or recyclable copper such as, but not limited to, copper rod mill scale, wire chop, copper filings, copper millings, etc. The copper ed as a powder, in granular form or chopped pieces (e.g. _ 9 _ chopped wire), or any form, it being noted that increasing the surface area of the copper such as by reducing the particle size, will se the reaction rate.

In laboratory bench scale g, the necessary oxygen was supplied by adding hydrogen peroxide to the reaction mixture. In larger scale testing and commercial applications oxygen can be ed by injecting oxygen into the reaction mixture. Any suitable conventional oxygen injection system can be used. A particularly suitable Oxygen or system developed during the course of the t invention referred to as a pipeline oxidizer is described below in reference to the working examples.

For the embodiment of the invention in which copper metal is reacted with hydrochloric acid under oxidizing conditions the overall reaction for producing tribasic copper chloride is: 2Cu + 02 + H20 + HCl—> )3Cl The present inventors theorize that the overall general reaction proceeds as Copper dissolves forming cupric chloride: Cu + 2HC1 + '/2 Oz —> CuCl2 + H20 (i) Cupric chloride dissolves more Cu forming cuprous chloride: (TuCl2 + Cu —> 2CuCl (ii) Cuprous chloride is oxidized to form tribasic copper chloride and cupric chloride returns to ve more copper in step (ii): l2CuCl + 302 + 6H20 —> 4CuC12 + 4Cu2(OH)3Cl (iii) This reaction can be carried out in a reactor in which the copper metal is added to a mixture of hydrochloric acid and water. Oxygen is added/injected into the reaction mixture and continuously added/injeCIed throughout the reaction. _ 10 _ The reaction mixture is heated to and maintained at a temperature of about 180°F. To prevent metal copper from settling to the bottom of the reaction mixture a mixer of any conventional type that can inhibit material from settling in the bottom of the reactor and/or an oxygen injector that can mix/?ush copper metal from the reactor bottom as discussed herein is provided and operated during the on.

For the embodiment of the invention in which copper metal is reacted with cupric chloride under oxidizing conditions the overall reaction for producing tribasic copper chloride is: 3Cu + CuClz + 1.502 +3H2O —> H)3Cl The reaction can be carried out in a reactor in which the copper metal is added to a mixture of the cupric chloride and water. As in the reaction above, oxygen is added/injected into the reaction mixture and continuously added/injected throughout the reaction.

The reaction mixture is heated to and maintained at a temperature of about 180°F and a mixer of any conventional type that can inhibit material from ng in the bottom of the reactor and/or an oxygen injector that can mix/?ush copper metal that might otherwise settle in the bottom of the reactor as discussed herein is provided and operated during the reaction.

Either of the reactions can be conducted in a batch mode. semi-batch mode or in a uous manner.

Each on produces a solid slurry of tribasic copper de ls which can be spray dried or processed in any manner to recover the tribasic copper chloride crystals. According to one embodiment a digestible binder can be added to the solids slurry and the resulting slurry can be agglomerated by spray drying or other means of _ 11 _ agglomeration to form agglomerates of the micronutrient crystals as taught in US. Patent Application ation No. 2013/0064963.

The micronutrient supplements of the present invention can be admixed with other nutrients. Nutrients include both micro- and macronutrients. Examples of micronutrients include vitamins and minerals. Examples of vitamins useful for the present ion include: vitamin A, vitamin D3 vitamin E (tocopherol), vitamin K (menadione), vitamin B12 (cyanocobalamin), vitamin 136 vitamin B1 vitamin C (ascorbic , , acid), niacin, ribo?avin, thiamine mononitrate, folic acid, calcium pentothenate, xine, choline chloride, biotin, known pharmaceutically acceptable derivatives of these ns and mixtures thereof. Examples of minerals or metal salts useful for the present invention include copper sulfate, iron sulfate, zinc oxide, manganese, iron, iodine, selenium, amino acid complexes of the trace metals and mixtures thereof. The macronutrients that can be used in the present invention include any of the common feed ingredients such as, for example, grain, seeds, grasses, meat meal, fish meal, fats and oils.

Features and teristics of the present invention will be exempli?ed by the following examples which are provided as a non-limiting example for rative purposes only.

The following Examples include laboratory bench trials and pilot scale trials.

The laboratory bench trials were conducted in glass beakers on heated, magnetic stir plates or in some cases top mounted mixers were employed. In all cases the chemistry and s were similar in that copper was added to a mixture of HCl and water, at or near stoichiometric ratios to produce basic copper de. The mixtures were mixed and heated to about 180°F. For all the laboratory trials 30% hydrogen peroxide was used as the oxygen . The en peroxide was added _ 12 _ incrementally throughout the trials as needed to convert Cu‘ to Cu") The target recipe for the mixtures were designed to yield 50% by weight solids slurrics of ic copper chloride crystals which was determined to be suitable for spray drying.

The pilot scale trials were conducted in cone bottom, ?berglass mix tanks equipped with live steam injection for temperature control. The recipes used in the pilot trials were similar to those used in the laboratory bench trials however gaseous oxygen was utilized as the oxygen source rather than hydrogen peroxide. The 02 gas is more ef?cient both from a cost and processing standpoint. The oxidation was lished through a ine oxidizer." This set up consisted of a pump which draws from the top of the tank (to avoid inclusion of large copper pieces) and pumps through 100’ coil and then back into the bottom of the tank. Oxygen is injected inline just before the coil. Static mixers were provided at the ing and end of the coil to provide intimate mixing of the oxygen with the liquid stream. The concept is to provide good contact and residence time under re to yield high oxidation efficiencies. The discharge of the pipeline oxidizer entering the bottom of the cone provided two functions: 1) Mixing/ ?ushing action to any copper pieces that may have settled to the bottom of the cone to prevent ng; and 2) Providing a Cu" rich solution to any settled copper in the bottom of the reactor to continue to drive the reaction. Also any unreacted oxygen gas has a second chance to oxidize Cu' inside the mix tank increasing oxidation efficiency.

Example 1 In this Example basic copper chloride was produced by ng ?ne copper metal powder with hydrochloric acid and hydrogen peroxide according to the following reaction. _ 13 _ 2C1] + IICl 4' 211202 = CU2(OII)3C1 "l' 1120 The reactants are added at or near their stoichiometry amounts. HCl was added at a slight excess to assist in driving the reaction. 61 ml of water was ?rst added to a 250 ml beaker followed by 46 ml of 32% HCl. While mixing, 53.57 g/l of copper powder was added to the beaker. The temperature of the beaker was maintained at or near 180°F. Throughout the trial 30% hydrogen peroxide was added incrementally to convert Cu+ as it formed to Cu". The reaction was d to proceed for a total of 24 hours. During the reaction time the mixture transitioned from clear to dark brown (cuprous chloride) solution to dark brown solution with white crystals of cuprous chloride, and then y to a thick slurry ofbright green crystals (tribasic copper chloride). At the end of the 24 hour period there was no visible copper present. A sample of the slurry was dried and ed by XRAY Diffraction to determine crystal ure.

The results showed that the material was 99.1% basic copper chloride (de?ned as atacamite and clinoatacamite) and .1 % cuprous chloride. The solids t of the slurry was about 50% solids. which was determined to be suitable for purposes of spray .

Example 2 The process and recipe for this Example were exactly the same as in Example I r the copper source was a bare bright, copper wire chop. The copper was of a size and density that would not allow it to be evenly dispersed through the solution as was the copper powder in Example 1. The copper remained in the bottom 1/3 of the beaker and was being moved around by the mixing action. During the trial the same transitions were observed throughout the trial as were in Example 1 however at a much slower rate.

After 24 hours it was visually estimated that about 50% of the copper had been converted _ 14 _ to basic copper chloride. After about 32 hours of reaction time the contents of the beaker had turned to the typical green color of basic copper chloride however there was still unreacted copper metal still Visible on the bottom of the beaker. Analysis showed a 70% conversion of the copper into basic copper de.

Example 3 In this Example basic copper chloride was produced from copper rod mill scale — a uct from copper rod manufacturing. The copper rod mill scale was granular and included about 50 wt.% copper with a balance of cuprous oxide and eupric oxide.

The copper assay on the material used was about 87.46 wt.% .

In this Example 70 ml of water was ?rst added to a 250 ml beaker followed by 45.1 ml of 32% HCl. While mixing, 68.05 gr’l of copper rod mill scale was added to the beaker. The temperature of the beaker was maintained at or near 180°F. Throughout the trial 30% hydrogen peroxide was added entally to convert Cu‘ as it formed to Cu". The reaction was allowed to d for a total of 24 hours. During the reaction time the mixture transitioned from clear to dark brown (cuprous chloride) solution to dark brown solution with white crystals of cuprous chloride, and then ?nally a thick slurry of bright green crystals (basic copper chloride) At the end of the 24 hour period there was no visible copper present. A sample of the slurry was dried and analyzed by XRAY Diffraction to determine crystal structure. The results showed that the material was 95.7% basic copper chloride (de?ned as atacamite and tacamite) and 4.3% cuprous oxide.

Example 4 _ 15 _ In this e a pilot scale trial was performed to convert copper chop to basic copper chloride using cupric chloride in place of HCl. The basic copper chloride was produced by reacting cupric chloride with copper metal by the following reaction: 3C1] + CUClg + 1.5 02 +3H20= 2CU2(OH)3C1 This pilot trial was performed in a 5000 , cone bottom ?berglass mix tank equipped with a pipeline oxidizer as described above. The recipe was ed to yield about 1 1,000 lbs of basic copper chloride assuming a 100% completion of reaction.

The cupric chloride used in this trial contained 188 g/l of Cu and 1.34N free hydrochloric acid. 844 gallon of this solution was transferred to the mix tank along with 715 gallon of water. While mixing, 5229 lbs of copper wire chop was added incrementally over 12 hours at a rate of 1]01b/’15min. After the ?rst addition of copper, the pump was started to send ?ow through the pipeline Oxidizer. Oxygen injection into the pipeline was also d at this time. Progress was monitored by measuring total copper and density of the e. The reaction rate slowed ically after 24 hours and a?er 48 hours seemed to have almost completely stalled. After 48 hours of reaction a total of 77.4% of the copper had been converted to basic copper chloride.

The basic metal salts of this invention can be used to enhance the survivability, growth rate, health and/or reproductivity in humans and other animals. While not to be bound by any theory, it is thought that the basic metal salts are more y absorbed and/or exhibit an increased bioavailability over minerals, inorganic metal salts or other nutrients containing the corresponding essential metals. It has been determined the preferred embodiments of the basic metal salts of this invention signi?cantly reduce the growth of bacteria, thus ting the usc of preferred forms of this invcntion can _ 16 _ effectively enhance the growth and health of humans and other animals. Furthermore, the preferred basic metal salts of this invention demonstrate an enhanced ef?cacy against certain bacteria, thereby allowing for the use of smaller amounts and/or lower concentrations of the essential metals to provide substantially equal or equal potent effects on animals. gh the present invention has been described with reference to particular means, materials and embodiments, from the foregoing description, one d in the art can easily ain the essential teristics of the present invention and various changes and modifications can be made to adapt the various uses and characteristics without departing from the spirit and scope of the present invention as described above and set forth in the ed claims.

WHAT I / WE

Claims (5)

CLAIM IS:-

1. A method of making a micronutrient supplement from elemental copper metal which consists of ng together: i) elemental copper metal; ii) hydrochloric acid ; and iii) an oxidizing agent to form tribasic copper chloride, wherein the oxidizing agent is oxygen gas (02) or hydrogen peroxide (lfaO2), according to one of the following equations: a) 2 Cu+ HCl + 2H2O2 ---> Cu2(OH)3Cl + H2O b) 2 Cu+ 02 + H2O + HCl---> Cu2(OH)JCI.

2. A method of making a micronutrient supplement according to claim 1, wherein copper metal, hydrochloric acid and the oxidizing agent are reacted together to form tribasic copper chloride.

3. A method of making a micronutrient supplement according to claim 1, wherein copper metal and the oxidizing agent are reacted together to form tribasic copper chloride.

4. A method of making a micronutrient supplement according to claim 1, wherein the copper metal and hydrochloric acid form a reaction e and the oxygen gas (02) is injected into the reaction mixture.

5. A method of making a micronutrient supplement ing to claim 4, n oxygen gas (02) inhibits the copper metal from ng during the reaction.