Compositions containing two or more different metals have found use in several areas. Sometimes the compositions themselves can act as catalysts; more often, they behave as catalyst precursors, being transformed into active catalysts by reduction to give alloys or thin films or by oxidation (calcination) to give mixed-metal oxides.

These oxides may behave as ceramics as well as catalysts. Often, these mixed-metal compositions are simple mixtures of single-metal compounds. Reduction or calcination of such mixtures can give non-homogeneous products because of incomplete mixing of the compounds, resulting in monometallic domains. When possible, it is advantageous to use as precursors unique compounds containing the desired metal ratio, because the metals will be intimately mixed, even at the molecular level.

Mixtures of metals have other uses, as well. For example, iron, zinc, and magnesium are found in agricultural nutrient formulations, whereas iron, zinc, chromium, cobalt, and calcium are found in animal and human dietary supplements.

Routinely, these sorts of formulations contain mixtures of compounds, each compound containing one of the desired metals. To reduce the amount of ancillary organic material in these formulations, it can be advantageous to provide two or more metals in a single compound, thereby increasing the percentage of metals vis-a-vis the organic ligands.

Iron chelates are a class of compounds that have found use in natural gas treating, photographic bleaching, fertilizers, and dietary supplements. Routinely, said iron chelates are used as ammonium or alkali metal salts. In such cases, the alkali metal or ammonium ion provides charge balance but otherwise imparts no useful properties to

the iron chelate. For example, sodium ferric ethylenediaminetetraacetate (NaFeEDTA) has been used for iron fortification in foods. The iron provided is beneficial, but the sodium is possibly hazardous to those people requiring a low-sodium diet. On the other hand, iron chelate complexes with calcium can potentially be used to provide the dietary benefits of both metals.

Because of its tetravalent nature, ethylenediamine-tetraacetic acid (EDTA) can conceivably combine with a divalent and a trivalent metal to form complexes of the general formula M (II) M' (III) EDTA (OH) xH2O. To our knowledge no such mixed- metal complexes of EDTA have been reported in the literature.

The calcium salt of the ferric chelate of a similar ligand, hydroxyethylethylenediaminetriacetate (HEDTA), was reported as an amorphous, red solid (without analytical data) by Schugar, et al. in J. Amer. Chem. Soc., 89,3712 (1967).

There is clearly a need for transition metal chelate, particularly iron chelate, complexes with calcium which can be used to provide the dietary benefits of both metals.

The present invention offers such transition metal chelate complexes with calcium and a process for their preparation.

In one aspect the present invention relates to mixed-metal chelates represented by the following general formula CaM (III) EDTA (OH) xH20 wherein M is a trivalent transition metal and x is 0,0.5,1,1.5,2,2.5,3,3.5,4,4.5,5, 5.5,6,6.5,7,7.5, or 8.

In another aspect the present invention relates to a process for preparing mixed- metal chelates of the general formula CaM (III) EDTA (OH) xH2O, wherein M is a transition metal and x is 0, 0.5,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5, or 8, said process comprising the steps of a) reacting calcium hydroxide or calcium oxide, ethylenediaminetetraacetic acid, and a transition metal-containing material in an aqueous medium, optionally in the presence of an oxidant to convert any transition metal present in a divalent form to its trivalent form; and b) separating the formed mixed-metal chelate by filtration or evaporation.

In the context of the present invention, the general formula CaM (III) EDTA (OH) *xH2O is an empirical formula and is intended to include structures of higher nuclearity, such as, for example, Ca2 [M (III) 2 (EDTA) z0] xH20. The amount of water of hydration,"x", is dependent both on M and the conditions of preparation.

For the purposes of this invention, the term transition metal includes the metals of the lanthanide series. The transition metal contemplated by the foregoing general formula may be any transition metal that can obtain a stable trivalent state, including, but not limited to, iron, manganese, cobalt, chromium, yttrium, and ruthenium. Iron is preferred.

The general reaction process comprehends the production of a mixed-metal chelate of the general formula CaM (III) EDTA (OH) xH2O, wherein M is a trivalent transition metal and x is as defined hereinbefore, by the steps of a) reacting calcium hydroxide or calcium oxide, ethylenediaminetetraacetic acid, and a transition metal- containing material in an aqueous medium, optionally in the presence of an oxidant to convert any transition metal present in a divalent form to its trivalent form; and b) removing water by evaporation.

In a straightforward reaction, a water-soluble salt of the trivalent transition metal is reacted with calcium hydroxide and EDTA according to the following equation: 2MX3 + 5Ca (OH) 2 + 2H4EDTA-2CaMEDTA (OH) + 3CaX2 + 8I-I20 (1) wherein M is a transition metal, X is an inorganic or organic anion and H4EDTA is used to distinguish the free acid from the tetraanion. When the calcium salt of X-is soluble (for example, X-is Cl-, N03-, CH3COO-), the bimetallic complex can, in principle, be separated by precipitation or crystallization. When the complex is crystallized from aqueous solution, water may be included in the crystals, either bound directly to one or both of the metals or held in by lattice forces. The amount of water of crystallization will be dependent on solution pH, temperature, and the metals, among other things.

Sometimes water can be driven off at high temperature or under vacuum, providing other stoichiometric hydrates or anhydrous materials.

Many transition metals (for example, Fe, Co, Mn, Ru, etc.) form stable divalent ions as well as trivalent ones. With the addition of an oxidant, the divalent salts of these metals can also be reacted with calcium hydroxide and EDTA to give the same type of bimetallic product: MX2 + 2Ca (OH) 2+ H4EDTA +'/2H202-j CaMEDTA (OH) + CaX2 + 4H2O (2) Because of its powerful chelating ability for many transition metal ions, aqueous slurries of EDTA are often able to dissolve metal oxides. For example, partially ammoniated slurries of EDTA are commonly reacted with Fe304 to form ferric EDTA solutions used in the photographic industry. Metal oxides can likewise be used to prepare CaMEDTA (OH) solutions according to the following reactions: MO + Ca (OH) 2 + H4EDTA +'/zH202- CaMEDTA (OH) + 3H20 (3)

M203 + 2Ca (OH) 2 +2H4EDTA-2CaMEDTA (OH) + 5H20 (4) M304 +3Ca (OH) 2 + 3H4EDTA + l/2H202) 3CaMEDTA (OH) + 8 H20 (5) wherein M is a transition metal.

Oxidants other than hydrogen peroxide may be employed. A potential advantage to the metal-oxide route is that there is no concomitant formation of calcium salt by-products.

The elemental transition metal may also be used. EDTA will chelate the metal and oxidize it to the divalent state; another oxidant can complete the oxidation to the trivalent state: M + Ca (OH) 2 + H4EDTA +/2H20z- CaMEDTA (OH) + H2 + 2H20 (6) Inasmuch as calcium oxide is converted to calcium hydroxide in aqueous medium, the oxide may replace the hydroxide as the calcium source. The transition metal may be any one that can obtain a stable trivalent state, including, but not limited to, iron, manganese, cobalt, chromium, yttrium, and ruthenium. The transition metal- containing material may be the elemental metal, a salt, an oxide, or a hydroxide. For example, iron may be introduced as iron metal, ferric chloride, ferric nitrate, ferric acetate, ferric citrate, ferrous sulfate, ferrous perchlorate, ferrous oxide, ferric oxide, ferrosoferric oxide, or ferric hydroxide.

Preferably, the transition metal-containing material will be an oxide or hydroxide. As can be seen from an inspection of Equations 1-5, above, the use of a metal salt requires an excess of calcium hydroxide, relative to the transition metal, in order to bind the anions of the salt, resulting in a calcium salt by-product which must be separated from the desired calcium/transition metal/EDTA compound. Use of the

elemental transition metal also obviates the need for excess calcium hydroxide, but results in the generation of flammable hydrogen gas.

The molar ratio of EDTA to transition metal can be from 0.75 to 1.25, but preferably from 0.9 to 1.1, and more preferably from 0.99 to 1.01. An excess of EDTA or transition metal will result in unreacted material which must be separated from the desired product. The optimum molar ratio of calcium hydroxide (or oxide) to transition metal is dependent on the transition metal-containing reactant. If said reactant is a salt of a trivalent transition metal, the calcium hydroxide: transition metal ratio can be from 2.0 to 3.0, preferably 2.3 to 2.7, and more preferably from 2.45 to 2.55. If said reactant is a salt of a divalent transition metal, the calcium hydroxide: transition metal ratio can be from 1.0 to 3.0, preferably 1.5 to 2.5, more preferably 1.9 to 2.1. If said reactant is an elemental metal, oxide or hydroxide, the calcium hydroxide: transition metal ratio can be from 0.5 to 1.5, preferably from 0.7 to 1.3, more preferably from 0.9 to 1.1.

Again, the most preferable ratio results in the least unreacted staring material.

When the transition metal-containing material contains the transition metal in a lower-valent state than trivalent (for example, cobaltous chloride or iron metal), the resulting product can be converted to the desired trivalent complex by contacting the mixture with an oxidizing agent. The oxidizing agent need only be a more powerful oxidant than the trivalent transition metal. A practitioner skilled in the art will be able to determine if an oxidant has the desired oxidizing strength from tables of thermodynamic data. Useful oxidants include, but are not limited to, persulfates (for example, ammonium persulfate or sodium persulfate); periodates (for example, potassium periodate); permanganates (for example, potassium permanganate); hypochlorites (for example, sodium hypochlorite); hydrogen peroxide; and oxygen.

Hydrogen peroxide and oxygen are especially preferred, due both to low cost and to the fact that neither introduces counterions to complicate the reaction mixture.

In some cases, the desired calcium/transition metal/EDTA compound will have low solubility in water. In such cases, it is only necessary to filter the reaction mixture to obtain the product. If the product is more soluble in water, it can still be removed by crystallization, either by evaporating the water or by adding a co-solvent in which the product is less soluble. In cases where there are no other calcium salts present (that is, the transition metal-containing reactant was the element or an oxide or hydroxide), the product can be obtained by spray-drying or otherwise removing all the water.

The amount of water of crystallization in the calcium/transition metal/EDTA compound will vary depending on the transition metal, the pH, and the nuclearity of the complex. The water of crystallization can be removed to a desired degree by heating the compound and/or placing it under a vacuum. Such processes are well-known in the art.

The mixed-metal chelates of the present invention are useful as catalyst precursors and dietary supplements.

The invention will be further clarified by a consideration of the following examples, which are intended to be exemplary of the present invention and should not be construed to limit its scope in any way.

Example 1 A two-liter beaker was charged with ethylenediaminetetraacetic acid (H4EDTA, 146 g, 0.500 mole); Ca (OH) 2 (92.6 g, 1.25 mole); and water (1400 g). The resulting mixture was stirred vigorously; and a solution of Fe (N03) 3 (11. 1 percent Fe by weight) was added quickly (251.5 g, 0.500 mole Fe) to the slurry, immediately giving a dark red solution. The solution was stirred for ten minutes at 45°C and filtered through a 1.2 nylon filter. The filtrate was allowed to evaporate at 70°C for three days, after which large, red crystals of CaFeEDTA (OH)-6. 5H2O were removed (82.1 g, 0.158

mole, 31.7 percent yield). The composition was determined by elemental analysis.

Calc. (Found) for CaFeEDTA (OH) @6. 5H2O : C 23.18 percent (23.01 percent); H 5.06 percent (5.27 percent); N 5.41 percent (5.41 percent); Fe 10.78 percent (10.58 percent); Ca 7.73 percent (7.71 percent).

Example 2 A one-liter beaker was charged with H4EDTA (73 g, 0.25 mole); Ca (OH) 2 (46.3 g, 0.625 mole); and water (700 g). The mixture was stirred vigorously; and to it was added at once a solution of FeCl3@6H2O (67. 6 g, 0.250 mole) in water (120 g). The resulting brown slurry was heated to 90°C, producing a dark, red-brown solution. Trace insolubles were filtered out, and the filtrate was allowed to evaporate at 65°C overnight.

The product was removed from the mixture by filtration as small, red crystals (12.1 g, 0.023 mole, 9.3 percent).

Example 3 A two-liter, five-necked, round-bottomed flask fitted with a pH probe, a thermometer, and a mechanical stirrer was charged with H4EDTA (379 g., 1.330 mole); Ca (OH) 2 (48.2 g, 0.650 mole); commercial Fe304 (69 percent Fe by weight, 100 g, 1.24 mole Fe); and water (1200 g). The slurry was stirred vigorously and heated to 93°C over one hour, during which time the slurry changed color from black to green. The mixture was cooled to 56°C over fifty minutes; and Ca (OH) 2 was added to bring the pH up to 5.4 (24 g, 0.324 mole). During the addition, the green slurry became a deep red solution and then a red slurry. The slurry was sparged with air for three hours, and then more Ca (OH) 2 was added to bring the pH up to 5.9 (17.7 g, 0.239 mole). The crimson, crystalline product was removed by filtration and air-dried to give 508 g (0.980 mole, 80.8 percent yield (based on Ca)). The microcrystalline product was shown to be the same as the product in Example 1 by elemental analysis. Found: C 23.03 percent; H 5.28 percent; N 5.46 percent; Fe 10.68 percent; Ca 7.69 percent.

Example 4 A 500-ml, three-neck flask, fitted with an overhead mechanical stirrer and thermometer was charged with H4EDTA (58. 5 g, 0.200 mole); Ca (OH) 2 (14.8 g, 0.200 mole); and water (350 ml). Vigorous stirring was begun; and Fe powder (11.2 g, 0.200 mole) was added. The resulting mixture was heated to 80°C to initiate reaction, and then stirred, open to the atmosphere, for four days. The resulting dark red solution displayed a small amount of residual ferrous ion, so 30 percent aqueous H202 was added (0.1 g, 1 mmole). Filtration of the mixture gave CaFeEDTA (OH) @6. 5H2O as fine, red-orange crystals (31.5 g). Evaporation of the filtrate at 65°C for one day resulted in the precipitation of another 17.5 g as large, red crystals. Total yield 49 g (0.0945 mole, 47 percent).

Example 5 A 2.0046-gram sample of the product from Example 3 (3.868 millimoles) was placed in a Petri dish and set in an oven at 115°C for three days. The resulting tan powder was shown to be CaFeEDTA (OH) by elemental analysis. Calc. (Found): C 29.94 percent (29.90 percent); H 3.27 percent (3.32 percent); N 6.98 percent (7.01 percent); Fe 13.92 percent (14.19 percent); Ca 9.99 percent (10.02 percent). The yield was 1. 5307 g (3.816 mmoles).

Example 6 A one-liter beaker was charged with H4EDTA (73.1 g, 0.250 mole); Ca (OH) 2 (37.0 g, 0.500 mole); and water (400 g). The mixture was stirred rapidly, and to the resulting slurry was added a solution of Co (NO3) 2*6H2O (72.7 g, 0.250 mole) in water (300 g). The resulting mixture was warmed gently to give a purple solution. To this was added dropwise 30 percent aqueous H202 (14.2 g, 0.12 5 mole), causing a mild exotherm and darkening of the solution. The solution was stirred for one hour and then

filtered to remove a small amount of brown, insoluble material. The solution was allowed to evaporate at 65°C for four days, after which purple crystals of CaCoEDTA (OH) @5. 5H2O. (36.5 g, 0.072 mole). The composition was determined by elemental analysis. Calc. (Found) for CaCoEDTA (OH)-5. 5H2O : C 23.86 percent (24.53 percent); H 4.81 percent (5.00 percent); N 5.57 percent (5.86 percent); Ca 7.96 percent (8.63 percent); Co 11.71 percent (11.62 percent).

Example 7 A 1.0982-g sample of CaCoEDTA (OH) o5. 5H2O (2.182 mmoles) was placed in a Petri dish and heated at 105°C for three hours, giving 0.8299 g of CaCoEDTA (OH) (2.053 mmoles) as a pink powder.

Example 8 A one-liter beaker was charged with H4EDTA (73.1 g, 0.250 mole); Ca (OH) 2 (46.3 g, 0.625 mole); and water (450 g). The mixture was stirred rapidly, and to the resulting slurry was added a solution of CrCl3-6H2O (66. 6 g, 0.250 mole) in water (250 g). The initially green mixture quickly became a blue-violet slurry, which was stirred another half-hour. The product, CaCrEDTA (OH)-7H,, O was removed by filtration, washed with water (500 g), and air-dried at 40C, giving 92.9 g. Elemental analyses show that the product contained a by-product wherein some of the calcium had been replaced with chromium Calc. for CaCrEDTA (OH)-7H,, O : C 22.95 percent; H 5.20 percent, N 5. 35 percent; Ca 7.66 percent; Cr 9.93 percent. Calc. for CaCr,,, EDTA (OH)'7H20 : C 22.87 percent; H 5.18 percent; N 5.33 percent; Ca 6.49 percent, Cr 11.39 percent. Found: C 22.50 percent; H 5.34 percent; N 5.23 percent; Ca 6.55 percent; Cr 11.63 percent.