Chemical process for the manufacture of magnesium bicarbonate from impure reagent including magnesium hydroxide and calcium carbonate

Abstract

A process for the chemical conversion of contaminated magnesium hydroxide to high purity solutions of magnesium bicarbonate include steps of providing an impure reagent including at least 40% and less than 95% by total weight of total metals of magnesium in a form of solid magnesium hydroxide and at least 10% by weight of total metals of calcium carbonate, combining the impure reagent containing the solid magnesium hydroxide with carbonic acid in water, thereby generating magnesium bicarbonate and water and then filtering out solid calcium carbonate leaving a solution of magnesium bicarbonate in water having a by weight ratio of Mg/(Mg+Ca) in the solution of greater than 95%. Heating and/or drying the magnesium bicarbonate solution produces correspondingly high purity magnesium carbonate.

Claims

1. A process for the chemical conversion of magnesium hydroxide to magnesium bicarbonate comprising: providing an impure reagent including at least 40% and less than 95% by total weight of total metals in the impure reagent comprising magnesium in a form of solid magnesium hydroxide and at least 10% by weight of the total metals in the impure reagent comprising calcium carbonate, combining the impure reagent containing the solid magnesium hydroxide and calcium carbonate with carbonic acid in water, thereby generating magnesium bicarbonate and water and then filtering out solid calcium carbonate leaving a solution of magnesium bicarbonate in water having a weight ratio of Mg/(Mg+Ca) in the solution of greater than 98%.

2. The process of claim 1 wherein the magnesium hydroxide is first formed in the impure reagent by reaction of magnesium carbonate with an inorganic hydroxide.

3. The method of claim 2 wherein the inorganic hydroxide is selected from the group consisting of ammonium hydroxide, lithium hydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide.

4. The process of claim 1 wherein the solid magnesium hydroxide comprises tailings from a mining operation.

5. The process of claim 1 wherein the solid magnesium hydroxide is first washed with water to remove contaminants to form the impure reagent and the solution of magnesium bicarbonate in water has a weight ratio of Mg/(Mg+Ca) in the solution of greater than 99%.

6. The process of claim 1 wherein the solid magnesium hydroxide comprises tailings from a mining operation mixed with less than 40% by weight calcium carbonate.

7. The process of claim 1, wherein the conversion is determined by a reaction formula of:
Mg(OH).sub.2(s)+2H.sub.2CO.sub.3(solution+xR.sub.y.fwdarw.Mg(HCO.sub.3).sub.2(solution)+2H.sub.2O(liq)+xR.sub.y, wherein x is approximately and proportionally between 0 and 1.0 and R.sub.y is extraneous solid, inorganic material present with the Mg(OH).sub.2.

8. The process of claim 2, wherein the conversion of magnesium carbonate to magnesium bicarbonate is determined by a reaction formula of:
MgCO.sub.3+A.sub.x(OH).sub.z.fwdarw.Mg(HCO.sub.3).sub.2+H.sub.2O wherein A is a cation selected from the group consisting of NH.sub.4.sup.+, Li.sup.+, K.sup.+, Na.sup.+ and Ca.sup.+2, and z is a number selected from the group consisting of 1 and 2 sufficient to electronically balance the cation.

9. The process of claim 1 wherein the carbonic acid is formed by the reaction mechanism of:
CO.sub.2(g)+H.sub.2O(liq).fwdarw.H.sub.2CO.sub.3(solution).

10. The process of claim 8 wherein the solid magnesium hydroxide comprises tailings from a mining operation mixed with less than 40% by weight calcium carbonate.

11. The process of claim 10 wherein the solid magnesium hydroxide is first washed with water to remove contaminants.

12. The process of claim 1 wherein the conversion of magnesium hydroxide to magnesium bicarbonate is performed as a batch process, with all magnesium from all initial magnesium compounds present in each sequential step of the process.

13. The process of claim 12 wherein the conversion of magnesium hydroxide to magnesium bicarbonate is performed as a batch process, with all magnesium from all initial magnesium compounds present in each sequential step of the process.

14. The method of claim 1 wherein at least 95% by weight of all metals in the impure reagent consist of magnesium and calcium.

15. The method of claim 5 wherein at least 95% by weight of all metals in the impure reagent consist of magnesium and calcium.

16. A process for the chemical conversion of magnesium hydroxide to magnesium bicarbonate comprising: providing an impure reagent including at least 35% and less than 95% by total weight metals in the impure reagent of magnesium in a form of solid magnesium hydroxide, and at least 3% of calcium carbonate, combining the impure reagent containing the solid magnesium hydroxide and calcium carbonate with carbonic acid in water, thereby generating magnesium bicarbonate and water and then filtering out solid calcium carbonate leaving a solution of magnesium bicarbonate in water having a weight ratio of Mg/(Mg+Ca) in the solution of greater than 95%.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows a schematic of a system for performing elements of the present invention in a continuous process.

(2) FIG. 2 shows a Parr Bomb apparatus that may be used for a batch process in the practice of the present technology.

DETAILED DESCRIPTION OF THE INVENTION

(3) Contaminated batches of magnesium hydroxide (in the presence of calcium carbonate as a major (at least 10% by total weight of magnesium hydroxide and calcium carbonate) is converted to magnesium bicarbonate in a process including: providing a reagent including solid magnesium hydroxide, combining the solid magnesium hydroxide with carbonic acid in water, and thereby generating magnesium bicarbonate and water. The magnesium hydroxide (in the contaminated mixture with calcium carbonate) may be first formed by reaction of magnesium carbonate with an inorganic hydroxide. The inorganic hydroxide may, for example, be selected from the group consisting of ammonium hydroxide, lithium hydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide. The limitation on purity is not absolute with respect to the presence of calcium carbonate, but to a relatively minor degree, the amount of impurity will impact the ultimate purity of the final magnesium-containing products. For example, using tailing sources with approximately 40% calcium carbonate to 60% by weight magnesium hydroxide, products (magnesium-bicarbonate) can be formed with >95%, greater than 98%, greater than 99% and even levels greater than 99.5% (actually measured at 99.85% magnesium/(magnesium+calcium)) in the final magnesium carbonate product.

(4) Because of a determined significant rate of reaction differentiation between the rate of the magnesium hydroxide reaction with carbonic acid and the rate of the calcium carbonate reaction with carbonic acid, the calcium carbonate can be filtered or otherwise collected out of the formed magnesium bicarbonate solution and solution compositions with over 95% by weight magnesium/(magnesium+calcium) can be formed. These solutions may be heated or dried to provide similarly pure carbonate solids (e.g., with over 95% by weight magnesium/(magnesium+calcium).

(5) The faster the calcium bicarbonate is filtered out of the solution of magnesium bicarbonate, the higher the purity of the magnesium bicarbonate in the remaining solution as less calcium bicarbonate will have been formed. The differential of the rate of reaction is so significant that the filtration may be done seconds (e.g., 10-90 seconds) after mixing of the reagent with the carbonic acid to obtain highest purity levels, or minutes (e.g., 1-10 minutes, even with heating) to obtain high levels of purity (e.g., >95%) of the magnesium bicarbonate in solution as compared to its proportionality with respect to calcium bicarbonate in solution.

(6) An included process, with additional preparation of reactants and further conversion of the intermediate magnesium-bicarbonate products includes a process by which magnesium can be extracted from mixtures of magnesium hydroxide and calcium carbonate materials using carbonic acid produced from carbon dioxide and water. Carbonic acid reacts with magnesium hydroxide to form magnesium bicarbonate. This reaction takes place spontaneously at ambient temperature and pressure preferentially over the reaction of carbonic acid with calcium carbonate. Magnesium bicarbonate is soluble in water up to just over one percent by weight at standard temperature and pressure. The magnesium bicarbonate solution is transferred to a second vessel, where it can be heated. At temperatures of 150° F. to the boiling point of water, the bicarbonate decomposes, giving up a molecule of carbon dioxide, to form magnesium carbonate, which being water insoluble, precipitates readily. The depleted water can then be recycled to the front of the process to remove impurities, or discarded. The precipitated magnesium carbonate can be filtered, centrifuged or gravity separated from the water and dried or maintained in a slurry as the need dictates. The carbon dioxide gas can be collected, compressed, dewatered, and returned to the front end of the process.

(7) The governing chemical reactions for the process are:

(8) ##STR00001##

(9) Additionally, and very importantly, the magnesium bicarbonate solution (Mg(HCO.sub.3).sub.2(sln)) can be dried, heated or heated and dried to precipitate out or deposit magnesium carbonate with the level of purity of Mg/Ca in the solution. This is a high value, food grade product with significant commercial value. Additionally, the calcium carbonate residue filtered or deposited or otherwise collected in the conversion of the magnesium hydroxide to magnesium bicarbonate is also of commercial quality, and its percentage of purity with respect to magnesium content can be even higher than the Mg/Ca purity in the primary product.

(10) The present invention includes a process in which magnesium hydroxide is converted to magnesium bicarbonate in a process including:

(11) providing a reagent including solid magnesium hydroxide, combining the solid magnesium hydroxide with carbonic acid in water, and thereby generating magnesium bicarbonate and water. The magnesium hydroxide may be first formed by reaction of magnesium carbonate with an inorganic hydroxide. The inorganic hydroxide may, for example, selected from the group consisting of ammonium hydroxide, lithium hydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide.

(12) The present invention further includes a process for the chemical conversion of magnesium hydroxide to magnesium bicarbonate by:

(13) providing a reagent including solid magnesium hydroxide, combining the solid magnesium hydroxide with carbonic acid in water, thereby generating magnesium bicarbonate and water. The magnesium hydroxide at this stage of the process should constitute greater than 30%, greater than 50% and even greater than 70% by weight of total solids in a reaction mix. The percentage of magnesium hydroxide in some naturally occurring sites and tailings from mining operations can be found in ranges from 50% by weight to 90% by weight and more, especially after the tailings have been washed with water and drained. In mining sites, typical contaminants include carbonates, such as calcium carbonate, which tends to be neutral throughout the entire process when present. When the magnesium bicarbonate is formed (in solution), the calcium carbonate is easily separated by settling or filtering from the bicarbonate solution.

(14) In this process, the magnesium hydroxide may be first formed by reaction of magnesium carbonate with an inorganic hydroxide. In this type of method, the inorganic hydroxide is preferably selected from the group consisting of ammonium hydroxide, lithium hydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide. As suggested earlier, the solid magnesium hydroxide may be provide at least in part from tailings from a mining operation. In that type of raw sourcing of the magnesium hydroxide, the solid magnesium hydroxide is first washed with water to remove contaminants. The solid magnesium hydroxide may include tailings from a mining operation naturally occurring with less than 40% by total weight of solids as calcium carbonate.

(15) The conversion may be determined by a reaction formula of:
Mg(OH).sub.2(s)+2H.sub.2CO.sub.3(sln)+xR.sub.y.fwdarw.Mg(HCO.sub.3).sub.2(sln)+2H.sub.2O(liq)+xR.sub.y,

(16) wherein x is approximately and proportionally between 0 and 1.0 and R.sub.y is extraneous solid, inorganic material present with the Mg(OH).sub.2.

(17) In the above sequence of reaction steps, the process of conversion of magnesium oxide to magnesium hydroxide may be determined by a reaction formula of:
MgCO.sub.3+A.sub.x(OH).sub.z.fwdarw.Mg(HCO.sub.3).sub.2+H.sub.2O

(18) wherein A is an cation selected from the group consisting of NH.sub.4.sup.+, Li.sup.+, K.sup.+, Na.sup.+ and Ca.sup.+2, and z is a number selected from the group consisting of 1 and 2 sufficient to electronically balance the cation.

(19) It is economically and environmentally desirable in the process to have the carbonic acid formed by the reaction mechanism of:
CO.sub.2(g)+H.sub.2O(liq).fwdarw.H.sub.2CO.sub.3(sln).

(20) This then becomes in part a carbon-fixing process, and as the carbon dioxide is bound, is environmentally desirable.

(21) In the process, not only is it not necessary to convert materials to magnesium oxide, but also no magnesium oxide is formed during the process. Therefore, no magnesium compounds are calcined during the conversion and no magnesium oxide is formed during the conversion process. As described in greater detail herein the conversion may be performed as a continuous or a batch process, with all magnesium from all initial magnesium compounds are present in each sequential step of the process.

(22) Alternative reaction schemes that are known for magnesium compounds include:
MgO.sub.2(s)+H.sub.2CO.sub.3(sln).fwdarw.Mg(CO.sub.3)(sln)+H.sub.2O(liq), and
MgO.sub.2(s)+H.sub.2CO.sub.3(sln)+xR.sub.y.fwdarw.Mg(HCO.sub.3)(sln)+H.sub.2O(liq)+xR.sub.y

(23) wherein x is approximately and proportionally between 0 and 1.0 and xR.sub.y is extraneous (generally inorganic) material present with the MgO.sub.2(s),

(24) The conversion process can be performed with contaminated magnesium oxide up to levels where the contaminant can be physically separated (by differential solubility during precipitation or leaching with differential solvents). The purer the starting magnesium oxide, the likely the purer that any product will be. Many tailings are internally highly pure, but can have surface contaminants, as residues from mining processes or accrued contaminants from sand, salt, air-borne materials and organic materials carried by or deposited by organisms.

(25) The process can be operated at ambient temperatures and pressures or the reaction vessel can be pressurized to increase the solubility of magnesium bicarbonate in solution, increasing the production rate. Operating at ambient pressure has been shown to produce better separation of the magnesium and calcium species.

(26) A laboratory scale version of the process is represented in the FIG. 1 in its simplest embodiment. Magnesium rich tailings are ground preferably into particles with a mean diameter of less than 45 microns. Larger particles sizes will work, but the reaction time is increased, and the yield is reduced. Distilled water or deionized water is added to the reaction vessel. Carbon dioxide is introduced to the system from a high concentration source. Ambient air would work, but the concentration of carbon dioxide would increase the reaction times to the point the process would not be economical. The reaction is allowed to proceed with the carbon dioxide flow rate being measured at the inlet and outlet of the reaction vessel. At the beginning of the reaction, most of the carbon dioxide will be consumed by the magnesium hydroxide, which results in the flow rate of carbon dioxide at the outlet being a fraction of the flow rate introduced. Once a substantial portion of the magnesium tailings have been consumed (i.e. converted to magnesium bicarbonate) the outlet carbon dioxide flow rate will increase and approach the magnitude of the inlet flow rate. When the outlet flow rate reaches a predetermined percentage of the inlet, determined experimentally, more distilled water is introduced to the system to dilute the now saturated solution in the reactor, enabling additional reaction between the carbon dioxide and magnesium hydroxide to occur. The conductivity of the solution is measured to confirm that the produced solution is at or near saturation with magnesium bicarbonate. The pH is also measured to determine the reaction products relative to the carbonate equilibrium curve. Once the conductivity drops to a predetermined value, the feed water is cut off and the reactor is again allowed to react until the solution reaches saturation again, and the cycle is repeated until no additional magnesium can be extracted from the tailings. In the laboratory embodiment, the highly enriched magnesium bicarbonate solution is heated to facilitate the precipitation of magnesium carbonate, releasing carbon dioxide to the atmosphere. (In a commercial scale unit, the carbon dioxide would be collected, cleaned, compressed, and reused).

(27) The reaction produces a bright white powder, as shown in the photograph below. The magnesium carbonate shown, produced from process tailings, was analyzed using ion chromatography and was >99.85% pure magnesium relative to calcium content. Magnesium carbonate exists in several forms, including anhydrous and di-, tri-, and pentahydrates known as magnesite (MgCO.sub.3), barringtonite (MgCO.sub.3.2H.sub.2O), nesquehonite (MgCO.sub.3.3H.sub.2O), and lansfordite (MgCO.sub.3.5H.sub.2O), respectively. When heated all forms of magnesium carbonate decompose, giving up the water of hydration and ultimately decomposing into magnesium oxide (MgO) and carbon dioxide (CO.sub.2) at approximately 350° C. (662° F.).

(28) Magnesium carbonate is used in flooring, fireproofing, cosmetics, dusting powder, and toothpaste. The magnesium carbonate produced by the invention has proven to far exceed the USP requirements for pharmaceutical grade. It could then be used as an antacid and as an anticaking agent in table salt.

(29) Some materials, especially in tailings near ocean water can be cleaned (at least have surface film disrupted and removed) by a simple room temperature water wash. Other materials, such as algae may have to be physically washed under pressure and even separated with flocculation (as with aluminum sulfate) or centrifuged to distinguish solids of different densities. Washes with surfactants or additional solvents specific to the impurities may also be used. Alcohols, and other solvents with too great an activity for magnesium oxide and/or magnesium carbonate may be used.

(30) Particle size is of some functional importance, as extremely large size materials will only slowly be converted and that with primarily surface reactions. Therefor, it may be desirable or essential to crush and pulverize larger particles into powder form (e.g., X-Y microns, millimeters) to facilitate the provision of reactive surfaces of the solid magnesium oxide to convert it to magnesium carbonate (in its targeted composition or state).

(31) FIG. 1 shows a schematic of a system for performing elements of the present invention in a continuous process. In the process, even though continuous flow occurs over periods of time, it is preferred that the process be halted periodically to remove the tailings in the flow stream. This can be done periodically in a steady replenishment/replacement of the tailings, but this can be awkward. It is simpler to stop the flow, empty the tailings chamber, replenish with new tailings and being the flow again, with the carbon dioxide forming the carbonic acid in the flow stream. Because the relative rates of reaction between the magnesium oxide and calcium carbonate are so great, the high levels of purity are still obtained.

(32) FIG. 2 shows a Parr Bomb apparatus made by Parr Instrument Company that may be used for a batch process in the practice of the present technology.

(33) Several variations in the full-scale process can be implemented without changing fundamental sequence of events that generate the product: 1. Initial de-clumping and sizing 2. Final sizing to increase reactive surface area 3. Reaction with carbon dioxide to form magnesium bicarbonate 4. Removal of non-reacted solids 5. Heating to release carbon dioxide to form magnesium carbonate 6. Precipitation 7. Solids separation and 8. Drying

(34) As shown in the table, the process has demonstrated consistent efficacy in extracting magnesium from the tailings and forming high-grade magnesium carbonate, with magnesium concentration relative to calcium as high as 99.84%. It is believed, although not yet demonstrated, that reprocessing the magnesium carbonate through the reaction will refine the product. However, since a single pass through the process has produced pharmaceutical grade material, further refining has not been attempted.

(35) TABLE-US-00001 Representative Analytical Results Magnesium Rich Tailings from Moss Landing, California Na K Mg Ca Mg/(Mg + Ca) Sample Name mg/l mg/l mg/l mg/l % Tailings Feed Clay 324 n.a. 232,837 169,166 57.92 Tailings Feed 1682 n.a. 205,186 165,038 55.42 Sandy Run 8 Product 830 n.a. 211,000 2,910 98.64 Run 9 Product 900 n.a. 248,000 3,390 98.65 Sample Clay 470 n.a. 311,000 39,200 88.81 Product Run 12 Product 580 1,160 243,000 12,800 95.00 Run 13 Product 240 240 236,000 2,190 99.08 Run 6 Product 502 n.a. 247,775 5,929 97.66 Run 7 Product 374 n.a. 245,892 18,291 93.08 Run 3 Product 255 n.a. 211,365 345 99.84 crystals Run 3 Product 507 n.a. 212,320 350 99.84 surface crystals (duplicate injection)

(36) The invention was developed specifically to convert the process tailings deposited in the impoundment at manufacturing sites, such as the Moss Landing site in California. Although the tailings are not hazardous, either from a regulatory or physical/chemical perspective, the 36 acres covered by the material cannot be repurposed or used in any way until the 1.1 million cubic yards of material are removed. The invention has the potential to convert the material into approximately one billion pounds of salable, high-grade magnesium carbonate, representing a significant increase in the value of the tailings and eventually a significant increase in the value of the land.

(37) Once developed, it became clear that other similar sites exist within the United States. These sites could be remediated using the same process, increasing the value to the stakeholders, while providing a “greenfield” level of conversion to the land itself.

(38) The initial experiments with carbonic acid were conducted with commercial beverage grade carbonic acid solution packaged at approximately 50 psig, also known as club soda. The first experiment, done with club soda, produced a product that was 95.97% magnesium carbonate. Given this result, a more quantitative approach was done using a Parr Bomb apparatus, pictured in FIG. 2. A Parr Bomb is a lab scale reaction vessel that can operate at pressures up to 3,000 psig. As shown in FIG. 1, a 100 ml chamber made of Teflon is enclosed inside a stainless-steel pressure unit. The reactants are placed inside the Teflon container and sealed to contain the reactants and the products of the reaction. For each sample, a carefully measured mass of either Clay like or Sandy like tailings were placed in the chamber, with a measured mass of dry ice (solid carbon dioxide).

(39) The Parr bomb was quickly assembled and sealed against the pressure of reaction and placed in a 110° C. oven. After 12 hours, each Parr Bomb was disassembled, the contents were centrifuged, and the liquid was decanted into sample containers. Each sample was desiccated and weighed to determine yield and then two of the samples were analyzed using IC. One of the two samples analyzed produced magnesium carbonate that was 99.11% purity (Mg mass/(Ca+Mg mass)).