This disclosure describes a family of micronutrient supplements and a method for their use to enhance the survivability, growth, health and/or reproductivity of humans and animals. More specifically, this disclosure is directed to a variety of metal ammine chloride micronutrient supplements that provide a high bioavailability of an essential metal to humans and animals, and to a method of enhancing their growth by administering the micronutrient supplement in a variety of ways, including, but not limited to foods and animal feeds.
Micronutrients include vitamins and some elements usually in the form of minerals or metal salts; most notably the elements include calcium, phosphorus, potassium, iron, zinc, copper, magnesium, manganese and iodine. Micronutrients are generally consumed in small amounts, i.e., less than 1 gm/day, and are usually absorbed unchanged. Many essential elements have catalytic functions. While the micronutrients are often present 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 abilities to grow at a faster rate while consuming less feed has improved. This intensive growth imposes greater metabolic stresses, thereby causing increased susceptibility to vitamin deficiencies. It is well recognized that the needed micronutrients are often not found or not found in sufficient quantities in their food or feed sources, whether these sources are naturally occurring or commercially prepared. Consequently, virtually all industrial food and feed formulations are fortified with vitamins and minerals. The cost to commercial livestock producers for supplying micronutrients to their livestock herds can be staggering.
While human and animal requirements for additional nutrients have been well documented, the availability of the micronutrients has not always met their needs. It
A representative example of a procedure for preparing copper diammine chloride (“CDC”) and/or ammonium ammine copper chloride (“AACC”) is depicted in
As the pH is raised to between about 4.5 and 5.0, the equilibrium for ammonium ion (NH4+) is shifted toward free ammonia (NH3) and a green precipitant forms that is thought to be copper diammine chloride as illustrated in Equation 3 below.
CuCl2+2NH4OH→Cu(NH3)2Cl2↓+2H2O Equation 3
As the pH is increased higher to between about 5.0 and about 5.5, more free ammonia becomes available and the green colored copper diammine chloride salt transitions to a robin-egg blue colored salt believed to be insoluble ammonium ammine copper chloride. The chemical reaction is conjectured to be that of Equation 4:
Cu(NH3)2Cl2+NH4Cl→NH4Cl.Cu(NH3)2Cl2↓ Equation 4
is not sufficient to simply increase amounts of the micronutrients in the food or feed sources. This method can be ineffective, wasteful and unsafe. Many of the micronutrients are not readily absorbed so that the added amounts of vitamins and minerals are simply excreted. Excess loading of vitamins and minerals can be unsafe and in certain circumstances can be toxic, thereby causing severe acute or chronic harm or even death. Thus, there is a need to provide an inexpensive, readily absorbed micronutrient to decrease costs, reduce waste and help establish a more precise control of the nutritional requirement for humans and animals.
It has been well established that different levels of a variety of metals are necessary micronutrients for humans and animals. For example, Batal and coworkers determined the minimum bioavailable zinc required for chicks at 1 to 3 weeks of age to be about 22.4 mg of zinc per kg of feed. (2001 Poultry Science 80:87-90). The tests were performed using a zinc deficient soy concentrate diet supplemented with either zinc sulfate heptahydrate or tetrabasic zinc chloride (“TBZC”). The bioavailability of the zinc from TBZC was essentially the same as that from zinc sulfate heptahydrate.
Like other micronutrients, not all zinc-containing compounds are efficient dietary sources of zinc. Results from experiments conducted by Cao and his coworkers (2000 J. Appl. Poultry Res. 9:513-517) showed that only about 49% of the zinc contained in feed-grade zinc oxide was bioavailable to Avian broiler chicks compared to the zinc contained in reagent-grade zinc sulfate heptahydrate. Their tests also showed that basic zinc sulfate and tetrabasic zinc chloride (Zn5Cl2(OH)8) have zinc bioavailability values of 101% and 107%, respectively, relative to the zinc contained in reagent-grade zinc sulfate heptahydrate.
Thus, there is a continuing need to provide micronutrient supplements that are readily bioavailable, storage stable and compatible with a wide variety of different vitamins. The micronutrient supplements should also be cost-efficient to produce and provide a food source for humans and animals that will increase their survivability, growth, health and/or reproductivity.
The present disclosure relates to micronutrient food or feed supplements, and the manufacture and use thereof. Various aspects of the disclosure are novel, nonobvious, and provide various advantages. While the actual nature of the disclosure provided herein can only be determined with reference to the claims appended hereto, certain forms and features, which are characteristic of the preferred embodiments disclosed herein, are described briefly as follows.
Thus, there is provided in the present disclosure a micronutrient food or feed supplement comprising an ammine chloride salt provided in a form suitable for consumption by animals and having the formula (NH4Cl)x.M(NH3)yClz where M represents an essential metal, x is zero or greater, y is greater than zero, and z is at least 2. A variety of essential metals, including, but not limited to Zn, Cu, Mg, Mn, Ca, Fe, Co and Cr are readily absorbed by animals when the metal is formulated as ammine chloride salt. Specific embodiments of the preferred metal ammine chloride salt include, but are not limited to, a zinc diammine chloride micronutrient supplement of the formula Zn(NH3)2Cl2, a copper diammine chloride micronutrient supplement of the formula Cu(NH3)2Cl2, and related double salts such as ammonium amine copper chloride, NH4Cl.Cu(NH3)2Cl2, otherwise written as (NH4Cu(NH3)2Cl3)0.3333 by crystallographers.
The present disclosure also provides a method of enhancing the growth of humans and other animals by providing a micronutrient comprising at least one ammine salt of an essential metal having the formula (NH4Cl)x.M(NH3)yClz where M is a cation of the essential metal, x is zero or greater, y is greater than zero and z is at least 2. Preferred essential metals include, but are not limited to Zn, Cu, Mg, Mn, Ca, Fe, Co and Cr. The micronutrient supplement can be administered directly or it can be admixed with vitamins and other micronutrients to provide a supplemental premix that may be administered to humans or animals. Alternatively, the supplemental premix can be combined with a food or animal feed. When the micronutrient supplement is provided to humans or other animals in a physiologically effective amount, their survivability, growth rate, health and/or reproductivity increases.
The present disclosure further provides a method for preparing a copper ammine chloride salt by first selecting a solution containing a copper salt, an ammonium salt and a chloride salt and additionally having a hydrogen ion concentration reflected by the solution's pH. The solutions selected can be acidic or basic. The solution's pH is adjusted by the addition of acid or base to provide a pH value of from about 4.5 to about 6.5 and to form a slurry. The slurry contains a copper ammine chloride salt which can be isolated from the slurry by a variety of conventional means including, but not limited to, filtration or centrifugation.
Generally, this disclosure provides a micronutrient supplement that comprises an ammine chloride that contains a divalent or trivalent cation of an essential metal. The micronutrient supplements according to the current disclosure can be administered directly to humans or animals in a variety of forms including, but not limited to, as a solid, a suspension or an admixture containing other nutrients such as vitamins, minerals, and food or animal feeds. The micronutrients are administered to enhance the survivability, growth, health and/or reproductivity of humans and animals.
The micronutrient supplement of the present disclosure provides good bioavailability of the essential metal in that it is readily absorbed or taken up in a biologically-effective amount. The micronutrient can be combined with other nutrients or vitamins, to provide a premixed supplement.
An essential metal is defined for the purposes of this disclosure as a metal whose uptake by humans or other animals in a biologically effective amount increases their survivability, growth, health and/or reproductivity. The mode of action of the essential metal is not critical for the present disclosure. For example, the essential metal can act as a co-factor or a catalyst in a metalloenzyme or metalloprotein; it can be adsorbed 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.
Preferred metal amine chloride salts have the formula (NH4Cl)x·M(NH3)yClz, where M is a divalent or trivalent metal, x is zero or larger, y is selected to be a real number greater than zero, and z is generally at least 2. The subscripts x, y and z can be selected as non-integers in certain embodiments. Preferred essential metals include, but are not limited to zinc, copper, magnesium, manganese, calcium, iron, cobalt and chromium.
In one embodiment of the present disclosure, the essential metal is a divalent metal cation, M, preferably selected from the group of divalent metal cations that includes zinc, copper, magnesium, manganese, calcium, iron, and cobalt; x is zero or larger, y is selected to be a real number greater that zero; and z is generally at least 2. In certain embodiments, x, y and z can be selected as non-integers.
In an alternative embodiment of the present disclosure, the essential metal is a trivalent metal cation, M, selected from the group of trivalent metal cations that includes chromium, iron and cobalt; x is zero or larger, y is selected to be a real number greater than zero; and z is generally 3 or higher. In certain embodiments, x, y and z can be selected as non-integers.
Within a homologous series of ammine chloride compounds of metal M, the values of x, y and z may be dependent on the experimental conditions used to prepare the salt. For example, x, y or z may be dependent upon the pH at which the salt is prepared. Alternatively, x, y or z may be dependent upon the ammonia, ammonium or chloride concentration in the reaction medium. Accordingly, a variety of ammine chloride salts can be prepared for a homologous series of compounds having the same cationic essential metal. It is understood that varying the values for x, y and z influences the solubility, bioavailability, nutritional value and enhanced vitamin stability of the micronutrient supplement.
A representative example of a laboratory bench-scale procedure for preparing zinc diammine chloride (“ZDC”) is depicted in
The first step of the method depicted in
ZnO+2NH4Cl→Zn(NH3)2Cl2+H2O Equation 1
The hot ammonium chloride extraction method is not selective for zinc. Impurities such as lead, copper and cadmium are also dissolved by the leach solution. When present in the zinc bearing raw material, these impurities are generally displaced from the leach solution by the addition of metallic zinc. This “cementation” technology is an oxidation-reduction reaction where the added metal (e.g., zinc) goes into solution and the dissolved metal (e.g., lead) comes out of solution in metallic form. An example of the cementation reaction is as follows:
PbCl2+Zno→Pbo+ZnCl2 Equation 2
The method shown in
Further background related to the ammonium chloride extraction of zinc can be found in U.S. Pat. Nos. 3,849,121, 5,208,004, 5,810,946, 6,423,281 and 6,517,789. Additional references to the preparation of ZDC can be found in U.S. Pat. Nos. 6,454,828 and 4,865,831.
The CDC and/or AACC salt can similarly be prepared from tribasic copper chloride by a similar pH adjustment as illustrated in Equation 5 and as described in Example IV below.
Cu2(OH)3Cl+3NH4Cl+NH4OH→2Cu(NH3)2Cl2↓+4H2O Equation 5
As illustrated in
For the purpose of promoting further understanding and appreciation of the present disclosure and its advantages, the following examples are provided. It will be understood, however, that these examples are illustrative and not limiting in any fashion.
The raw material for this example was zinc oxide “baghouse dust” from a brass mill. The dust contained about 34% zinc and the impurities included lead (1.4%), copper (3,400 mg/kg) and cadmium (190 mg/kg). ZDC was made from this material by the in situ purification/hot ammonium chloride zinc extraction procedure described above.
(a) The effectiveness of the in-situ purification/hot extraction method was evaluated by comparing performance at hot vs. cold temperatures. For this experiment, 25 grams of baghouse dust and 8 grams of metallic zinc were added to 200 ml of stock ammonium chloride solution (300 g/L). After mixing for about an hour at room temperature, a sample of the supernatant was collected and filtered.
The reactor was then operated at a temperature of about 175° F. for 1.5 hours, after which a sample of the supernatant was collected and filtered. The analyses of the filtered samples from the two temperature conditions clearly showed that the extraction and cementation reactions are very effective when operated at hot temperatures, but less effective at temperatures approaching room temperatures:
(b) Additional tests were conducted to further assess the effectiveness of various methods for producing a clean ZDC product. Three different samples of ZDC salts were analyzed for purity by dissolving them with hydrochloric acid in deionized water. The first sample of ZDC was prepared without the in situ purification feature and was not washed after filtration. The second sample was the same as the first, but had been washed after filtration. The third sample was prepared using the in situ purification technique, but was not washed after filtration. The results summarized in TABLE I showed that a clean ZDC salt could be prepared by the in situ purification technique used alone or in combination with washing the salt after filtration:
The starting material used for this example was crude zinc oxide generated from thermal treatment of electric arc furnace dust. Impurities included lead (1.2%). The extraction liquor used was ammonium chloride brine generated as a byproduct from a manufacturing process for making tribasic copper chloride from spent circuit board etchants. The metallic zinc used for the cementation purification reaction was waste zinc shot material. All of the key components for this example thus came from low-grade byproducts or waste materials.
The concentration of ammonium chloride in the brine was adjusted to about 275 g/L. Crude zinc oxide was added to the brine to produce a zinc loading of about 80 g/L. The slurry was mixed and heated to between 165° F. and 175° F. for at least 30 minutes. While heating, 8 g/L of metallic zinc shot was added to remove metal impurities via the in situ purification method. The hot slurry was then filtered using a pre-heated Buchner funnel. Preheating the filter apparatus enabled the pregnant liquor to remain hot during filtration to keep the ZDC in solution. The hot filtrate was collected in an Erlenmeyer filter flask and then cooled to room temperature. The white ZDC salt precipitated from solution as the pregnant liquor cooled. The cooled slurry was then filtered to harvest the ZDC salt. Near the end of the filtration, a small amount of deionized water was added to rinse dissolved components and soluble impurities off the ZDC salt. The washed ZDC solids were then dried at about 220° F. Finishing operations included crushing and size classification of the ZDC product. The assay of the finished product was 38.8% zinc, as expected for ZDC. Impurities from the raw feed stock were either absent or present in trace amounts.
An experiment was conducted to compare the bioavailability of zinc from zinc diammine chloride (ZDC or Zn(NH3)2Cl2) with that of reagent grade zinc sulfate heptahydrate (ZSH or ZnSO4.7H2O). A zinc-free basal corn-soybean diet was formulated. The zinc sources were added to the basal diet at doses of 4 mg Zn per kg and 8 mg Zn per kg. The basal and experimental diets were mixed using a horizontal mixer for basal diet and a Hobart mixer for individual treatments. All diets were fed as a mash feed. Eighty male avian broiler chicks were used in the 20-day experiment. The test birds were randomly divided into 20 pens of 4 birds each. The birds were housed in thermostatically controlled, stainless steel battery cages with raised wire flooring in an environmentally controlled facility. Environmental conditions for the birds (i.e., floor space, temperature, lighting, feeder and water space) were similar for all test groups. The chicks were pretested for the first three days after hatching; and then they were switched to the basal diet until the start of the study at day eight. Water that had been deionized and distilled and feed was available for ad libitum consumption.
All feed added to the pens was recorded. Feed was weighed back at the conclusion of the trial and the feed intake was calculated. The ratio of weight gain to feed consumed was calculated for the period using the average weight gain of birds per treatment divided by the average feed consumption for the treatment throughout the test period. The results from the experiment are summarized in TABLE 2.
Compared to the control, the addition of 4 and 8 mg Zn from ZDC per kg feed improved overall weight gain by about 37% and 75%, respectively. The addition of 4 and 8 mg Zn from ZDC also improved the weight gain per unit of feed by about 24% and 28%, respectively. The test results for the ZDC treatments were better than those observed from the lab grade ZSH treatments. Assuming a zinc availability of 100% for reagent-grade zinc sulfate, the relative bioavailability of zinc from zinc diammine chloride was 110%. Thus the overall conclusion from the experiment was that zinc diammine chloride was an excellent source of bioavailable zinc.
The starting material used for this example was mother liquor remaining after the production of tribasic copper chloride (TBCC) from spent circuit board chemical etchants. The particular sample of mother liquor was slightly acidic, contained several hundred grams per liter of ammonium chloride and about 12 g/L of dissolved copper. The series of tests were conducted at room temperature. A 400 mL sample was titrated with NH4OH solution having a specific gravity of 0.93 and containing about 16% NH3 by weight. The pH and soluble copper concentrations were measured after each increment of NH4OH solution added. The results are illustrated in
The titration curve shown in
The present disclosure contemplates modifications as would occur to those skilled in the art. It is also contemplated that processes embodied in the present disclosure can be altered, rearranged, substituted, deleted, duplicated, combined, or added to other processes as would occur to those skilled in the art without departing from the spirit of the present disclosure. In addition, the various stages, steps, procedures, techniques, phases, and operations within these processes can be altered, rearranged, substituted, deleted, duplicated, or combined as would occur to those skilled in the art. All publications, patents, and patent applications cited in this specification are herein incorporated by reference as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference and set forth in its entirety herein.
Further, any theory of operation, proof, or finding stated herein is meant to further enhance understanding of the present disclosure and is not intended to make the scope of the present disclosure dependent upon such theory, proof, or finding.