Method for producing metal oxide compositions and coated substrates

Abstract

The present invention generally relates to a process for making a metal oxide composition for use in removing contaminants from streams. A process of the present disclosure comprises contacting a metal salt with an aqueous solvent to form a metal salt mixture and reacting the metal salt mixture and a metal powder without the addition of heat. The present invention also relates to a process for making a coated metal oxide substrate.

Claims

1. A process for making a metal oxide composition for use in removing contaminants from fluid streams, the process comprising: a. contacting a metal salt with an aqueous solvent from about 5 seconds to about 10 minutes to form a metal salt mixture, wherein the ratio of solvent to metal salt is from about 20:1 to about 1:20 by weight and the amount of solvent is such that a slurry or solution is not formed; and, b. reacting a sufficient amount of the metal salt mixture and a metal powder for about 15 minutes to about 24 hours, at ambient conditions to initiate an oxidizing reaction between the metal powder and the metal salt mixture, wherein the ratio of metal powder to metal salt mixture is from about 7:1 to about 15:1, and wherein the oxidizing reaction substantially proceeds to form a metal oxide composition that is a free flowing, non-clumping powder comprising from at least 5% to more than 95% by weight metal oxide capable of removing contaminants from fluid streams.

2. The process of claim 1, wherein the metal salt is selected from the group consisting of metal chloride, carbonate, sulfate, acetate, nitrate, chelate, phosphate, oxide, and combinations thereof.

3. The process of claim 2 wherein the metal salt is selected from the group consisting of: copper chloride, copper chloride dihydrate, ferric chloride dihydrate, sodium chloride dehydrate, iron chloride, sodium chloride, nickel chloride, manganese chloride, magnesium chloride, copper sulfate, iron sulfate, zinc sulfate, nickel sulfate, manganese sulfate, magnesium sulfate, zinc phosphate, nickel phosphate, iron phosphate, aluminum phosphate, copper nitrate, nickel nitrate, manganese nitrate, zinc nitrate, magnesium phosphate, and combinations thereof.

4. The process of claim 1, wherein the aqueous solvent is selected from the group consisting of water and an alcohol/water mixture.

5. The process of claim 1, wherein the alcohol is selected from the group consisting of glycol and isopropanol.

6. The process of claim 1, wherein the metal salt and the aqueous solvent are contacted for from 5 seconds to 10 minutes.

7. The process of claim 1, wherein the metal powder is selected from the group 2A, 3B, 4B, 5B, 6B, 7B, 8, 1B, 2B, 3A, 4A, 5A metals, rare earth metals, metal oxides, and combinations thereof.

8. The process of claim 1, wherein the metal powder is selected from the group consisting of iron powder, zinc powder, tin powder, aluminum powder, antimony powder, magnesium powder, titanium powder, manganese powder, chromium powder, nickel powder, cobalt powder, platinum powder, metal oxides and combinations thereof.

9. The process of claim 1, wherein the metal powder further comprises at least one additive.

10. The process of claim 9, wherein the additive is selected from the group consisting of coconut coir, activated carbon, and combinations thereof.

11. The process of claim 1, wherein the metal salt mixture and the metal powder are reacted for from 15 minutes to 24 hours.

12. The process according to claim 1, wherein the resultant metal oxide composition is ready for use without further processing or drying.

13. A process for making a metal oxide composition for use in removing contaminants from streams, the process comprising: a. contacting a metal salt with an aqueous solvent for 5 seconds to 10 minutes to form a metal salt mixture, wherein the ratio of solvent to metal salt is from about 20:1 to about 1:20 by weight and the amount of solvent is such that a solution or slurry is not formed; and, b. reacting a sufficient amount of the metal salt mixture and a metal powder for 15 minutes to 24 hours at ambient conditions to initiate an oxidizing reaction between the metal powder and the metal salt mixture, wherein the ratio of metal powder to metal salt mixture is from about 7:1 to about 15:1, wherein the oxidizing reaction substantially proceeds to form a metal oxide composition that is a free flowing, non-clumping powder comprising from at least 5% to more than 95% by weight metal oxide, wherein the metal oxide composition reacts with contaminants in a stream, and wherein the contaminants are substantially removed from the stream.

14. The process of claim 13, wherein the stream is selected from the group consisting of gas stream or fluid stream.

15. A process for making a metal oxide composition for use in removing contaminants from fluid streams, the process comprising: a. contacting a metal salt with an aqueous solvent for 5 seconds to 10 minutes to form a metal salt mixture, wherein the ratio of solvent to metal salt is from about 20:1 to about 1:20 by weight and the amount of solvent is such that a solution or slurry is not formed; and, b. reacting a sufficient amount of the metal salt mixture and a metal powder for 15 minutes to 24 hours at ambient conditions to initiate an oxidizing reaction between the metal powder and the metal salt mixture, wherein the ratio of metal powder to metal salt mixture is from about 7:1 to about 15:1, wherein the oxidizing reaction substantially proceeds to form a metal oxide composition that is a free flowing, non-clumping powder comprising from at least 5% to more than 95% by weight metal oxide, wherein the metal oxide composition reacts with contaminants in a stream, and wherein the contaminants are substantially removed from the stream; and, c. placing the metal oxide composition in a reaction vessel; and, d. contacting the metal oxide composition with a contaminated stream, wherein the stream is a gas or fluid stream.

16. A process for making a metal oxide composition for use in removing contaminants from fluid streams, the process comprising: a. contacting a metal salt with an aqueous solvent for 5 seconds to 10 minutes to form a metal salt mixture, wherein the ratio of solvent to metal salt is from about 20:1 to about 1:20 by weight and the amount of solvent is such that a slurry or solution is not formed; and, b. reacting a sufficient amount of the metal salt mixture and a metal powder for 15 minutes to 24 hours at ambient conditions to initiate an oxidizing reaction between the metal powder and the metal salt mixture, wherein the ratio of metal powder to metal salt mixture is from about 7:1 to about 15:1, wherein the oxidizing reaction substantially proceeds to form a metal oxide composition that is a free flowing, non-clumping powder comprising from at least 5% to more than 95% by weight metal oxide; c. contacting the metal oxide composition with a stream; d. reacting the metal oxide composition with contaminants in the stream; and, e. removing the contaminants substantially from the stream.

17. A process for making a metal oxide composition, the process comprising: a. contacting a metal salt with an aqueous solvent for 5 seconds to 10 minutes to form a metal salt mixture, wherein the ratio of solvent to metal salt is from about 20:1 to about 1:20 by weight and the amount of solvent is such that a slurry or solution is not formed; and, b. reacting a sufficient amount of the metal salt mixture and a metal powder for 15 minutes to 24 hours at ambient conditions to initiate an oxidizing reaction between the metal powder and the metal salt mixture, wherein the ratio of metal powder to metal salt mixture is from about 7:1 to about 15:1, and wherein the oxidizing reaction substantially proceeds to form a metal oxide that is a free flowing, non-clumping powder composition comprising from at least 5% to more than 95% by weight metal oxide capable of use in removing contaminants from fluid streams, wherein the metal oxide composition comprises a mixture of metal compounds, the mixture comprising metal oxides, metal hydroxides, metal halides, elemental metal, and metal minerals.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1A depicts the formation of an iron oxide composition by treating 150 g of basic iron powder with a mixture of 20 g of water and 5 g of copper chloride dihydrate (CuCl.sub.2-2H.sub.2O) for 1 hour.

(2) FIG. 1B depicts that treating 150 g of basic iron powder with a mixture of 20 g of water and 5 g of sodium chloride (NaCl) for 1 hour, the sodium chloride did not oxidize the iron powder.

(3) FIG. 1C depicts that treating 150 g of basic iron powder with 20 g of water after 1 hour wherein the iron powder was not oxidized.

(4) FIG. 2A depicts the formation of an iron oxide composition by treating 150 g of basic iron powder with a mixture of 20 g of water and 5 g of CuCl.sub.2-2H.sub.2O for 6 hours.

(5) FIG. 2B depicts treating 150 g of basic iron powder with a mixture of 20 g of water and 5 g of NaCl for 6 hours whereby the iron powder did not oxidize.

(6) FIG. 2C depicts that treating 150 g of basic iron powder with 20 g of water after 6 hours whereby the iron powder did not oxidize.

(7) FIG. 3A depicts the formation of an iron oxide composition by treating 150 g of basic iron powder with a mixture of 20 g of water and 5 g of CuCl.sub.2-2H.sub.2O for 24 hours.

(8) FIG. 3B depicts that treating 150 g of basic iron powder with a mixture of 20 g of water and 5 g of NaCl for 24 hours whereby the iron powder did not oxidize.

(9) FIG. 3C depicts that treating 150 g of basic iron powder with 20 g of water whereby after 24 hours the iron powder did not oxidize.

(10) FIG. 4A depicts raw granular carbon.

(11) FIG. 4B depicts raw granular carbon coated with iron oxide as described in Example 1.

(12) FIG. 5A depicts granular vermiculite.

(13) FIG. 5B depicts granular vermiculite coated with iron oxide as described in Example 2.

(14) FIG. 6A depicts crushed rock.

(15) FIG. 6B depicts crushed rock coated with iron oxide as described in Example 3.

(16) FIG. 7A depicts polished rock.

(17) FIG. 7B depicts polished rock coated with iron oxide as described in Example 4.

(18) FIG. 8 depicts calcined clay coated with iron oxide as described in Example 5.

(19) FIG. 9 depicts the iron oxide coated calcined clay after reacting it with H.sub.2S as described in Example 5.

(20) FIG. 10 depicts the re-coated iron oxide calcined clay as described in Example 7.

(21) FIG. 11 depicts the iron oxide coated wood as described in Example 10.

(22) FIG. 12A depicts the zinc oxide coated lime as described in Example 11A.

(23) FIG. 12B depicts the iron oxide coated calcium chloride as described in Example 11B.

(24) FIG. 12C depicts the iron oxide coated lime as described in Example 110.

(25) FIG. 13A depicts the iron oxide/zinc oxide coated calcined clay described in Example 13A.

(26) FIG. 13B depicts the iron oxide/zinc oxide coated calcined clay described in Example 13B.

(27) FIG. 13C depicts the iron oxide/zinc oxide coated calcined clay described in Example 13C.

(28) FIG. 14 depicts the tin oxide/iron oxide coated calcined clay described in Example 13D.

DETAILED DESCRIPTION OF THE INVENTION

(29) The present invention relates to a process for making a metal oxide composition that is a substantially formed at dry ambient conditions within between about 15 minutes and about 24 hours. The composition is formed by reacting the metal salt mixture and basic metal powder together, with or without other additives, to form a free-flowing, non-clumping, powder. The present invention also relates to a process for making a tightly-adhered metal oxide composition formed from a metal/metal-oxide/additive, coating on a substrate having a metal oxide composition content of up to 75% by weight. The resultant coated metal oxide composition on a substrate may be used to remove contaminants, such as sulfur and heavy metal compounds, from fluids. Additionally, multiple coatings can be made of the same or different metal oxide compositions on substrates. The substrates can be optionally recoated with the metal oxide composition so that, in effect, the composition is re-coated and used again. This can reduce the quantity of product disposed of in a landfill thereby protecting the environment and reducing cost by substituting used material for new substrates.

(30) I. Metal Oxide Composition

(31) The process for making a metal oxide composition can be initiated by contacting an amount of a metal salt with an amount of an aqueous solvent to form a metal salt mixture or slurry. Any of a variety of metal salts may be used in the present invention. As used herein, a metal salt is a metal of any chloride, carbonate, sulfate, acetate, nitrate, chelate, phosphate, oxide, and combinations thereof. As mentioned a metal powder may also be mixed in. The metal ion of the metal salt may be any metal, however, it is preferred for the metal to have an equal or higher than electropotential as compared to the basic metal of the metal powder. The metal ion includes platinum, gold, silver, copper, cadmium, nickel, zinc, palladium, lead, chrome, iron, titanium, manganese, magnesium, tin, cobalt, or mixtures thereof. For example, the metal salt may be copper chloride, ferric chloride, sodium chloride, silver nitrate, copper sulfate, cobalt acetate, nickel-cobalt sulfate, zinc phosphate, iron phosphate and nickel phosphate. The aqueous solvent that is contacted with the metal salt may be selected from the group consisting of water, or a water/alcohol mixture. For example, the alcohol may be glycol or isopropanol.

(32) Any method of mixing the metal salt and the solvent may be used so long as the two are thoroughly mixed and the metal salt is at least partially solubilized or disperses in the initial solvent. For example, a metal salt, such as copper chloride dihydrate, may be contacted with water, in any suitable vessel, at ambient conditions, and agitated to partially or fully dissolve the metal salt. Typically, the ratio of metal salt to solvent when making the metal salt mixture is from about 4:1 to about 1:4 by weight. Generally, the metal salt and solvent are contacted for from about 10 seconds to about 90 minutes mixed in a continuous process to form a solution or dispersion in the solvent.

(33) Once the metal salt mixture has been prepared, a sufficient amount of the metal salt mixture is reacted with a metal powder, in a zero valence or basic state, to initiate an oxidizing reaction between the metal powder and the metal salt mixture thereby forming a metal oxide composition. The amount of solvent in the metal oxide composition is limited so that the metal oxide composition does not become a slurry or solution, essentially, no free moisture is present. Rather, the resultant metal oxide composition is a free-flowing, or non-clumping powder that is ready for use without further processing or drying.

(34) As used herein, the metal powder may be any metal powder that is in a zero valence state, i.e. non-oxidized state. The metal used may come from a wide variety of sources, including semi-processed metal, scrap metal, reduced foundry dust, and byproducts of metal working facilities, all which reduce costs, waste, or disposal of materials. Suitable types of metals that may be used include one or more metals or metalloids selected from the group consisting of a group 1A element, a group 2A element, a group 1B element, a group 2B element, a group 3B element, a group 4B element, a group 5B element, a group 6B element, a group 7B element, a group 8B element, a group 3A element, a group 4A element, a group 5A element, a group 6A element, rare earth metals, metal oxides, and combinations thereof. Alternatively, the metal powder may be an alloy of the above metals. Suitable metal powders, for example, include iron powder, zinc powder, tin powder, nickel powder, aluminum powder, antimony powder, chrome, and combinations thereof. Typically, the metal powder has an average diameter of less than about 2 mm. Alternatively, the metal powder has an average diameter of less than about 1 mm.

(35) Any method of reacting the metal salt mixture and the metal powder may be used so long as the two are thoroughly mixed and an oxidizing reaction occurs between the metal salt mixture and the metal powder. When the solution is added it is preferred for a slurry or solution to not be formed. Throughout the oxidizing process, the metal powder heats and expands as it oxidizes to a partial or complete metal oxide powder, or composition. For example, the metal salt mixture may be reacted with a metal powder, such as iron powder, in a suitable vessel having an agitation device such that the metal salt mixture and metal powder are thoroughly mixed and an oxidation reaction is initiated. Typically, the reaction is conducted at ambient conditions and in a ratio of metal powder to metal salt mixture of from about 1:2 to about 50:1 by weight. Alternatively, the ratio of metal powder to metal salt mixture is about 15:1 by weight. Typically, the initiation of oxidation reaction between the metal salt mixture and the metal powder may take from about 5 minutes to about 1 hour and the metal oxide composition will be substantially dry at the end of the reaction from 30 minutes to 24 hours.

(36) Alternatively, the process for making a metal oxide composition includes contacting the metal powder, metal salt, and aqueous solvent concurrently in a suitable vessel having an agitation device such that the metal salt, metal powder, and aqueous solvent are thoroughly mixed and an oxidation reaction is initiated. The reaction is conducted at ambient conditions and in a ratio of metal powder to metal salt mixture of from about 1:2 to about 50:1 by weight and a ratio of metal salt to solvent from about 20:1 to 1:20. As described before, the aqueous solvent is used to at least partially solubilize, or disperse, the metal salt initiating an oxidation reaction between the metal salt mixture and the metal powder. Similarly, the amount of aqueous solvent is limited so that the metal oxide composition does not become a slurry or solution. Typically, the initiation of oxidation reaction between the metal salt mixture and the metal powder may take from about 5 minutes to about 1 hour and the metal oxide composition will be substantially dry at the end of the reaction from 30 minutes to 24 hours.

(37) The process for making a metal oxide composition of the present invention may also be adjusted to form a metal oxide composition that includes two or more metal oxides. One process may, for example, include reacting a metal salt mixture, such as a copper chloride and water mixture, with two or more distinct metal powders, such as zinc powder and iron powder, to form a metal oxide composition having two or more metals, such as an iron oxide/zinc oxide composition. In another alternative, the metal salt mixture, such as a copper chloride and water mixture, may be reacted with a first metal powder, such as iron powder, and then reacted with a second metal powder, such as a zinc powder, to form a metal oxide composition having two or more metals, such as an iron oxide/zinc oxide composition. In yet another alternative, the process may include contacting the metal salt mixture with a metal and a metal oxide powder or other non-reactive powders (not reactive to the metal salt) such that the resultant metal oxide composition include two or more metal oxides, basic metals, or incorporates other additives or combination. Such a process may, for example, include reacting a metal salt mixture, such as a copper chloride and water mixture, with a first metal powder, such as iron powder, and then reacting it with a metal oxide powder, such as iron oxide powder to form a metal oxide composition having a metal and a metal oxide mixture, such as an iron/iron oxide composition. Still another alternative, the basic metal powder, metal salt, and non-reactive powders and/or metal oxides are mixed together along with sufficient moisture to cause basic metal powder and metal salt to react and thereby incorporating the non-reactive powder and metal oxides into the final metal oxide composition. Non-reactive powders can be diatomaceous earth or clays (calcined or natural); or metals such as copper, molybdenum, titanium, gold, silver or alloys such as bronze, brass, stainless steels, etc.

(38) As described above, the resultant metal oxide composition is a free-flowing powder and non-clumping powder, that is ready for use without further processing or drying. The resultant metal oxide composition may be used as is to remove contaminants from fluids. Conversely, the metal oxide composition may be coated onto a carrier or substrate. It should be noted that the density of the resulting metal oxide composition is similar to the density of commercially available pigments indicating a high surface area is created.

(39) II. Coated Metal Oxide Substrate

(40) The present invention is also directed to a process for making a tightly-adhered metal oxide composition coated substrate, wherein the metal oxide substrate composition comprises up to about 75% by final weight. Generally, the process for making a coated metal oxide substrate includes contacting a metal salt and an aqueous solvent to form a metal salt mixture, reacting a sufficient amount of the metal salt mixture with a metal powder to initiate the oxidation of the metal powder, contacting the metal powder and metal salt mixture, i.e. the oxidizing metal composition, with a substrate, and adding a sufficient amount of a second moistening agent to the metal oxide composition and substrate mixture to evenly, or uniformly, coat the oxidizing metal oxide composition mixture onto the substrate. Most any substrate can be coated with the metal oxide composition can be used in the present invention. Even water or liquid sensitive substrates that would normally degrade or dissolve when exposed to an aqueous solution and/or heat or substrates that are initially soft or easily crushed may be used. It is believed, that as the metal oxide continues to oxidize around the wetted substrate, a tight bond or matrix is formed between the metal oxide particles and the substrate. As such, as the metal oxide coating increases the hardness of the substrate or its resistance to crushing. Suitable substrates include, but are not limited to, desiccation products, natural products, and synthetic products. Desiccation products include calcium chloride, calcium oxide, silica gel, silica-based beads, activated alumina, alumina-gel balls, activated bauxite, molecular sieves, raw or calcined natural zeolites, synthetic zeolites, and combinations thereof. Suitable natural products include raw or activated carbon, partially or fully calcined vermiculite, rock, raw or calcined clay, wood, coconut shell chip or coir, coal, raw or bloated shale, raw or calcined diatomaceous earth, and lime. Alternatively, the substrate may be an inert carrier material such as a calcined montmorillonite. The solvent may be the same solvent used to make the metal salt mixture or it may be different. Typically, for a water-sensitive substrate the moistening agent is an alcohol or similar non-aqueous liquid.

(41) Any method of reacting the metal powder, metal salt mixture, moistening agent, and the substrate may be used so long as the moistening agent at least partially wets the surface of the substrate and the metal powder continues to oxidize forming a tight bond or matrix with the substrate as the metal oxide mixture continues oxidation. For example, the metal powder and metal salt mixture may be reacted with the substrate and a moistening agent in a suitable vessel having an agitation device, at ambient conditions, and in a ratio of metal powder to metal salt mixture of from about 1:2 to about 50:1 by weight and a ratio of metal salt to solvent from about 20:1 to 1:20, and a metal powder, metal salt, and solvent composition ratio of about 1:20 to 20:1. The metal powder to substrate ratio is less than 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1 or less depending upon the substrate. Typically, the metal powder, metal salt mixture, substrate, and second solvent are mixed or agitated for from about 5 minutes to about 6 hours. The coated metal oxide composition on the substrate is then allowed to oxidize at ambient conditions for from about 15 minutes to about 24 hours prior to use.

(42) Alternatively, the process for making a coated metal oxide substrate includes mixing a metal salt, metal powder, and any other additives with a substrate concurrently and then adding the solvent while mixing at ambient conditions to form a coated metal oxide composition on a substrate. The ratio of metal powder to metal salt mixture of from about 1:2 to about 50:1 by weight a ratio of metal salt to solvent from about 20:1 to 1:20, with the metal oxide composition being about 5 to 75% by weight on the final product. Typically, the metal salt, solvent, metal powder, additives and a substrate are reacted for from about 5 minutes to about 16 hours. The coated metal oxide substrate is then allowed to further oxidize at ambient conditions for from about 8 hours to about 24 hours prior to use or packaging.

(43) In another alternative, the process for making a coated metal oxide composition on a substrate of the present invention may be used to regenerate or re-coat a metal oxide substrate that already has a metal oxide coating or has been spent, i.e. the metal oxide coating is depleted. This simply involves the above process but the substrate has spent metal oxide coated on its surface. The same mixture or different mixtures may be used on the substrate with the recoated or spent metal oxide coating. This allows multiple metal oxide coatings and the continued use of the substrate reducing the cost of purchasing new coated metal oxide substrates and reducing the cost of disposing of the spent substrate thereby limiting the environment impact. It is also anticipated that sufficient metal or metal oxide content can be achieved on the new or used substrate making the final product attractive to recycle operations such as fertilizer blending operations or metal recovery.

(44) Examples of the resultant tightly-adhered metal oxide composition coated substrate of the present invention include an iron oxide coated raw carbon, an iron oxide coated vermiculite, an iron oxide coated crushed rock, an iron oxide coated polished rock, an iron oxide coated calcined clay, a red iron oxide/iron oxide coated calcined clay, a black iron oxide/iron oxide coated calcined clay, an iron oxide coated wood saw dust, a zinc oxide coated lime, an iron oxide coated lime, an iron oxide coated calcium chloride, an iron oxide coated silica gel, an iron oxide/zinc oxide coated calcined clay, among others.

(45) The resultant coated metal oxide substrate includes from about 5% to about 75% by weight metal oxide composition and from about 25% to about 95% by weight substrate. For example, an iron oxide coated calcinated montmorillonite substrate coated by the process of the present invention includes about 35% by weight iron oxide and 65% by weight calcinated montmorillonite. Alternatively, the coated metal oxide composition on a substrate of the present invention may be coated one or more additional times to produce a coated metal oxide composition on a substrate that includes more than 75% by weight metal oxide composition, such as about 80%, 85%, 90%, 95% or more. Importantly, the substrate is coated. This essentially means that the substrate is completely covered with the metal oxide composition and that the composition is held in contact with the substrate, such that it does not readily separate from the substrate due to contact with a fluid stream. Further, the coatings can be found in the pores on the substrate. Practically speaking, coating means forming a nearly continuous layer around a substrate, with the coating held in contact with the substrate regardless of conditions. Furthermore, the coating is not readily removed upon contact with a fluid flowing in a reactor vessel. For example: The flow rate of fluids through a column, are calculated by open bed (rising velocity of fluids in a column without material) of the following fluids:

(46) TABLE-US-00001 Open Bed Rising Fluid Velocity in Inches Per Minute Fluid as Liquids 10 C. or 50 F. 38 C. or 100 F. Water 3.0 5.5 Gasoline 4.3 7.5 Butane 12 14 Propane 17 19
Under these flow rates the metal oxide composition is not removed.

(47) The resultant coated metal oxide composition on a substrate has several uses. One use for the coated substrate is for sulfur removal, particularly H.sub.2S removal from fluids, such as natural gas. Typically, in this case a vessel is packed with the coated substrate and as the sulfur rich natural gas passes through the vessel the gas reacts with the oxide coating removing the sulfur from the natural gas and producing a sulfur free gas. Alternatively, the coated metal oxide substrate may be used for the reduction of NO.sub.x, SO.sub.x, CO.sub.x, halogenated hydrocarbons, treatment of radioactive wastes, heavy metal removal or reduction, and catalytic reactions of hydrocarbons.

(48) The following examples are simply intended to further illustrate and explain the present invention. The invention, therefore, should not be limited to any of the details in these examples.

EXAMPLES

Example 1

Metal Oxide Coated Raw Carbon

(49) The following experiment was conducted to form an iron oxide coated granular raw carbon by the process of the present invention.

(50) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 75 g of commercial iron powder, mixed, and allowed to start oxidizing for about 15 minutes. 30 g of granular raw carbon (0.35 g/cc) were then added to the powder and mixed. 19 g of additional water were then added and mixed to bond the oxidizing powder to the carbon. The finished product was dried for 8 hours without additional processing.

(51) The iron oxide coated carbon included 38% by weight iron or about 55% as iron oxide Fe.sub.2O.sub.3. The density of the iron oxide was 0.53 g/cc. The finished iron oxide coated carbon was hard and not easily broken or crushed as compared to the starting raw granular carbon.

Example 2

Metal Oxide Mixture on Granular Vermiculite

(52) The following experiment was conducted to form an iron oxide coated granular vermiculite by the process of the present invention.

(53) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 75 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 30 g of granular vermiculite (0.11 g/cc) were then added to the powder and mixed. 14 g of additional water were then added and mixed to affix the oxidized powder to the vermiculite. The finished product was dried for 8 hours without additional processing.

(54) The iron oxide vermiculite included 59% by weight iron or about 84% as iron oxide Fe.sub.2O.sub.3. The density of the iron oxide was 0.23 g/cc. The finished iron oxide coated vermiculite was hard and not easily broken or crushed as compared to the starting raw granular vermiculite.

Example 3

Metal Oxide Mixture on Crushed Rock

(55) The following experiment was conducted to form an iron oxide coated crushed rock by the process of the present invention.

(56) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 75 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 250 g of crushed rock were then added to the powder and mixed. 9 g of additional water were then added and mixed to affix the oxidized powder to the rock. The finished product was dried for 12 hours and was ready for use without additional processing.

(57) The iron oxide crushed rock included 22% by weight iron or about 31% as iron oxide Fe.sub.2O.sub.3.

Example 4

Metal Oxide on Polished Rock

(58) The following experiment was conducted to form an iron oxide coated polished rock by the process of the present invention.

(59) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 75 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 250 g of polished rock were then added to the powder and mixed. 9 g of additional water were then added and mixed to affix the oxidized powder to the rock. The finished product was dried for 12 hours and was ready for use without additional processing.

(60) The iron oxide polished rock included 22% by weight iron or about 31% as iron oxide Fe.sub.2O.sub.3.

Example 5

Metal Oxide on Calcined Clay

(61) An iron oxide coated calcined clay was tested for its ability to remove hydrogen sulfide from contaminated air.

(62) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 75 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 100 g of calcined clay were then added to the powder and mixed. 50 g of additional water were then added and mixed to affix the oxidizing powder to the clay. The finished product was dried for 8 hours and was ready for use without additional processing.

(63) The iron oxide coated calcined clay included 59% by weight iron or about 84% as iron oxide Fe.sub.2O.sub.3. The density of the iron oxide was 0.67 g/cc.

Example 6

H2S Removal Test

(64) A 1-inch tube that was 30 inches long was filled with 185 g of the iron oxide coated calcined clay formed according to Example 5. Air with variable amounts of H.sub.2S was passed through the tube, from top to bottom, at a flow rate of 1 to 1.25 liters per minute (about 14 to 18 seconds total contact time).

(65) The table below shows the removal of H.sub.2S during a total time of 54 hours. The amount of H.sub.2S in the inlet and outlet air was measured using gastec stain tubes.

(66) TABLE-US-00002 Time Inlet H.sub.2S Outlet Wave Front (1) 1 Hour 30 ppm 0 ppm 2 inches 2 Hours 60 ppm 0 ppm 2 inches 3 Hours 700 ppm 0 ppm 3 inches 5 Hours 200 ppm 0 ppm 2 inches 6 Hours 200 ppm 0 ppm 2 inches 7 Hours 250 ppm 0 ppm 2 inches 8 Hours 1400 ppm 0 ppm 5 inches 10 Hours 400 ppm 0 ppm 3 inches 12 Hours 1400 ppm 0 ppm 5 inches 18 Hours 4500 ppm 0 ppm 10 inches 22 Hours 500 ppm 0 ppm 7 inches 24 Hours 3500 ppm 0 ppm 10 inches 27 Hours 3750 ppm 0 ppm 10 inches 30 Hours 1500 ppm 0 ppm 8 inches 31 Hours 700 ppm 0 ppm 5 inches 32 Hours 800 ppm 0 ppm 6 inches 34 Hours 800 ppm 0 ppm 6 inches 40 Hours 400 ppm 0 ppm 5 inches 43 Hours 200 ppm 0 ppm 4 inches 44 Hours 500 ppm 0 ppm 6 inches 45 Hours 200 ppm 0 ppm 5 inches 46 Hours 12000 ppm 0 ppm 20 inches 48 Hours 12000 ppm 0 ppm 21 inches 51 Hours 1400 ppm 0 ppm 12 inches 52 Hours 200 ppm 0 ppm 6 inches 53 Hours 500 ppm 0 ppm 7 inches 54 Hours 500 ppm 0 ppm 7 inches
As the H.sub.2S reacted with the red iron oxide, it turned the iron oxide black, which illustrated the distance the H.sub.2S penetrated down the column. As the amount of H.sub.2S on the inlet increased, the distance the H.sub.2S penetrated the column increased. As the amount of H.sub.2S decreased, the distance the H.sub.2S penetrated the column was reduced as noted by the change in color of the media as it returned from black to red. Also, note that after 54 hours the H.sub.2S continued to be removed.

Example 7

Recoated Metal Oxide on Calcined Clay from Example 5

(67) The following experiment was conducted to recoat the spent iron oxide coated calcinated clay from Example 5 by the process of the present invention.

(68) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 75 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 120 g of used iron oxide coated calcined clay from Example 5 were then added to the powder and mixed. 27 g of additional water were then added and mixed to affix the oxidized powder to the calcined clay. The finished product was dried for 8 hours and was ready for use without additional processing.

(69) The iron oxide recoated calcined clay included 60% by weight iron or about 85% as iron oxide Fe.sub.2O.sub.3 (not including previously coated iron oxide mixture). The density of the iron oxide was 0.8 g/cc.

Example 8

Iron Oxide/Red Iron Oxide on Calcined Clay

(70) The following experiment was conducted to form an iron oxide/red iron oxide coated calcined clay by using a metal powder, iron powder, and a metal oxide powder, red iron oxide powder.

(71) 2 g of copper chloride dihydrate were added to 4 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 40 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 40 g of red iron oxide powder were then added to the iron powder and mixed. 100 g calcined clay were then added to the commercial iron and red iron powder mixture and mixed. 33 g of additional water were then added and mixed to affix the oxidized powders to the clay. The finished product was dried for 84 hours and was ready for use without additional processing.

Example 9

Iron Oxide/Black Iron Oxide on Calcined clay

(72) The following experiment was conducted to form an iron oxide/black iron oxide coated calcined clay by using a metal powder, iron powder, and a metal oxide powder, black iron oxide powder.

(73) 2 g of copper chloride dihydrate were added to 4 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 40 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 40 g of black iron oxide powder were then added to the commercial iron powder and mixed. 100. g of calcined clay were then added to the commercial iron and black iron oxide powder mixture and mixed. 33 g of additional water were then added and mixed to affix the oxidized powders to the clay. The finished product was dried for 84 hours and was ready for use without additional processing.

Example 10

Metal Oxide on Wood Saw Dust

(74) The following experiment was conducted to form an iron oxide coated wood sawdust by the process of the present invention.

(75) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 75 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 20 g of wood saw dust were then added to the powder and mixed. 20 g of additional water were then added and mixed to affix the oxidized powder to the wood sawdust. The finished product was dried for 12 hours and was ready to break into smaller pieces for use without additional processing. The iron oxide coated wood included 63% by weight iron or about 90% as iron oxide Fe.sub.2O.sub.3. The density of the iron oxide was 1.3 g/cc.

Example 11A

Zinc on Pelletized Lime

(76) The following experiment was conducted to form a zinc oxide coated pelletized lime by the process of the present invention.

(77) 2 g of copper chloride dihydrate were added to 3 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 70 g of commercial zinc powder and mixed. The powder was then immediately added to 150 g of lime and mixed. 15 g of isopropanol were then added to the lime and powder mixture, mixed, and allowed to air-dry for 30 minutes. The iron oxide coated lime included 31% by weight zinc or about 38% as zinc oxide, ZnO.

Example 11B

Iron on Pelletized Lime

(78) The following experiment was conducted to form an iron oxide coated pelletized lime by the process of the present invention.

(79) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 70 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 150 g pelletized lime were then added to the powder and mixed. 15 g of isopropanol were then added to the powder and lime mixture and mixed to affix the oxidized powder to the lime. The finished product was dried for 3 hours and was ready for use without additional processing. The iron oxide coated lime included 31% by weight iron or about 44% as iron oxide Fe.sub.2O.sub.3.

Example 11C

Iron on Pelletized Calcium Chloride

(80) The following experiment was conducted to form an iron oxide coated pelletized calcium chloride by the process of the present invention.

(81) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 70 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 120 g of pelletized calcium were then added to the powder and mixed. 10 g of isopropanol were then added to the powder and calcium mixture and mixed to affix the oxidizing powder to the calcium in a partially opened container or bag. (NoteIf pelletized calcium chloride was exposed to humid air or moisture for a few minutes, it would liquefy). The finished product was dried for 6 hours and was ready for use without additional processing.

Example 12A

Iron Oxide on Silica Gel

(82) The following experiment was conducted to form an iron oxide coated silica gel by the process of the present invention.

(83) 3 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 75 g of commercial iron powder, mixed, and allowed to oxidize for about 15 minutes. 150 g of silica gel were then added to the powder and mixed. 9 g of additional water were then added to the powder and gel mixture and mixed to affix the oxidized powder to the gel. The finished product was dried for 8 hours and was ready for use without additional processing.

Example 12B

Zinc Oxide on Silica Gel

(84) The following experiment was conducted to form a zinc oxide coated silica gel by the process of the present invention.

(85) 1 g copper chloride dihydrate was added to 3 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 75 g of commercial zinc powder and mixed. 150 g silica gel were added to the powder and mixed. 9 g of additional water were then added to the powder and gel mixture and mixed to bond the oxidized powder to the gel. The finished product was dried for 1 hour and was ready for use without additional processing.

Example 13A

Iron Oxide/Zinc Oxide on Calcined Clay

(86) The following experiment was conducted to form an iron oxide/zinc oxide coated calcined clay by the process of the present invention. The iron powder and zinc powder were contacted with the copper chloride dihydrate and water mixture concurrently.

(87) 2.5 g copper chloride dihydrate were added to 5 g water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then mixed into a mixture of 35 g of commercial zinc powder and 35 g of commercial iron powder. 100 g of calcined clay were then added to the powder mixture and mixed. 20 g of additional water were then added to the powder and clay mixture and mixed to affix the oxidized powders to the clay. The finished product was dried for 1 hour and was ready for use without additional processing.

(88) The zinc acted as galvanizing where little red iron oxide could be seen when the basic zinc and iron were mixed, then oxidized. The product is a mixture of basic iron powder and zinc oxide coating on the substrate.

Example 13B

Iron Oxide/Zinc Oxide on Calcined Clay

(89) The following experiment was conducted to form an iron oxide/zinc oxide coated calcined clay by the process of the present invention. The iron powder was first contacted with the copper chloride dihydrate and water mixture and then contacted with the zinc powder.

(90) 2.5 g of copper chloride dihydrate were added to 5 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 35 g of commercial iron powder, mixed and allowed to oxidize for 15 minutes. 35 g commercial zinc powder were then added to the iron powder and mixed. 100 g of calcined clay were then added to the iron and zinc powder mixture and mixed. 20 g of additional water were added to the iron powder, zinc powder, and clay mixture and mixed to affix the oxidized powders to the gel. The finished product was dried for 3 hours and was ready for use without additional processing.

(91) Some iron oxides could be seen when the basic iron was allowed to partially oxidize first. This product was a mixture of basic iron and iron oxides with zinc oxide coating on the substrate.

Example 13C

Iron Oxide/Zinc Oxide on Calcined Clay

(92) The following experiment was conducted to form an iron oxide/zinc oxide coated calcined clay by the process of the present invention. The iron powder was first contacted with the copper chloride dihydrate and water mixture and then contacted with the calcined clay. The iron oxide coated calcined clay was then contacted with the zinc powder.

(93) 2.5 g of copper chloride dihydrate were added to 5 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added to 35 g of commercial iron powder, mixed and allowed to oxidize for 15 minutes. 100 g of calcined clay were then added to the powder and mixed. 20 g of additional water were then added to the powder and clay mixture and mixed to affix the oxidized powder to the clay and let sit for 15 minutes. 35 g of commercial zinc powder was then added to the iron oxide coated clay and mixed. The finished product was dried for 3 hours and was ready for use without additional processing.

(94) The basic iron oxidation was nearly complete and then basic zinc was applied and oxidized. This product was mostly iron oxide with possibly some basic iron with zinc oxide on the substrate.

(95) As can be seen from the above example, the degree of oxidation of one or more metal powders in a basic metal mixture, was controlled to achieve varying degrees of metal oxidation, especially where one or more of the metals was catholically protective to one or more of the other basic metals present in the mixture.

Example 13D

Iron Oxide/Tin Oxide on Calcined Clay

(96) The following experiment was conducted to form an iron oxide/tin oxide coated calcined clay by the process of the present invention. The iron powder and tin powder were contacted with the copper chloride dihydrate and water mixture concurrently.

(97) 4 g of copper chloride dihydrate were added to 6 g of water to solubilize or partially dissolve the copper chloride dihydrate at ambient conditions. The metal salt mixture was then added and mixed with a powder mixture of 35 g of commercial tin powder and 35 g commercial iron powder and allowed to oxidize for about 15 minutes. 100 g of calcined clay were then added to the powder mixture and mixed. 20 g of additional water were then added to the powder and clay mixture and mixed to affix the oxidized powders to the clay. The finished product was dried for 8 hours and was ready for use without additional processing.

(98) The products produced according to the above examples were analyzed on the substrate to determine the composition make-up.

(99) The phases constitute the majority components in the sample analyzed and possible secondary/trace phases likely in 2 to 5% by weight ranges.

Example 14

Best Matches from ICDD/ICSD Data Bases

(100) Metal oxide compositions were produced from basic iron powder alone and in combination with added iron oxides, alone and on a substrate such as natural zeolite. Where a substrate was used, the coating was abraded to remove the metal oxide composition from the surface of the particles before analyzing. The compositions were mixed and allowed to oxidize for 24 hours before packaging for analysis.

(101) An x-ray diffraction test was conducted by Evans Analytical Group using standard protocols.

(102) TABLE-US-00003 Sample Primary Phases Possible Secondary/Trace phases 1B FeO(OH)Lepidocrocite Fe.sub.8(O,OH).sub.16Cl.sub.1.3Akaganeite-M Iron Oxide Hydroxide Monoclinic I2/m Orthorhombic Bbmm FeO(OH)Goethite Fe.sub.3O.sub.4Magnetite Orthorhombic Pbnm Cubic Fd3m Fe(OH,Cl).sub.2.55Iron Chloride This sample is oxidized iron powder HydroxideGreen Rust using the following formula: Rhombohedral R 50 grams iron powder FeIron 1 gram copper chloride Cubic Im3m 1 gram water 2A Fe.sub.3O.sub.4Magnetite FeO(OH)Lepidocrocite Cubic Fd3m Iron Oxide Hydroxide FeO(OH)Goethite Orthorhombic Bbmm Orthorhombic Pbnm Fe.sub.8(O,OH).sub.16Cl.sub.1.3Akaganeite-M This sample is oxidized iron powder Monoclinic I2/m using the following formula: Fe(OH,Cl).sub.2.55Iron Chloride 25 grams iron powder HydroxideGreen Rust 1 gram copper chloride Rhombohedral R 1 gram water FeIron 100 grams of granular zeolite Cubic Im3m 10 grams of water Note: metal oxide coating removed before analysis. 3B FeO(OH)Goethite Fe(OH,Cl).sub.2.55Iron Chloride Orthorhombic Pbnm HydroxideGreen Rust (Fe,Ni)Taenite Rhombohedral R Cubic Fm3m FeIron This sample is oxidized iron powder Cubic Im3m using the following formula: Ca(SO.sub.4)(H.sub.2O).sub.2Gypsum 50 grams iron and nickel powder Monoclinic C2/c 1 gram copper sulfate Fe.sub.3O.sub.4Magnetite 1 gram water Cubic Fd3m 4A Fe.sub.3O.sub.4Magnetite FeO(OH)Lepidocrocite Cubic Fd3m Iron Oxide Hydroxide FeO(OH)Goethite Orthorhombic Bbmm Orthorhombic Pbnm Fe(OH,Cl).sub.2.55Iron Chloride This sample is oxidized iron powder HydroxideGreen Rust using the following formula: Rhombohedral R 25 grams iron powder FeIron 1 gram copper sulfate Cubic Im3m 1 gram water PDF# 00-006-0696 100 grams of granular zeolite 10 grams of water Note: metal oxide coating removed before analysis. 4B Fe.sub.3O.sub.4Magnetite FeO(OH)Lepidocrocite Cubic Fd3m Iron Oxide Hydroxide This sample is oxidized iron powder Orthorhombic Bbmm and synthetic iron oxide mix using the FeO(OH)Goethite following formula: Orthorhombic Pbnm 12.5 grams iron powder Fe(OH,Cl).sub.2.55Iron Chloride 12.5 grams synthetic magnetite HydroxideGreen Rust 1 gram copper chloride Rhombohedral R 1 gram water Fe.sub.8(O,OH).sub.16Cl.sub.1.3Akaganeite-M 100 grams of granular zeolite Monoclinic I2/m 10 grams of water FeIron Note: metal oxide coating removed Cubic Im3m before analysis. 5A Fe.sub.3O.sub.4Magnetite FeO(OH)Lepidocrocite Cubic Fd3m Iron Oxide Hydroxide FeO(OH)Goethite Orthorhombic Bbmm Orthorhombic Pbnm Fe.sub.8(O,OH).sub.16Cl.sub.1.3Akaganeite-M This sample is oxidized iron powder Monoclinic I2/m and natural iron oxide mix using the Fe(OH,Cl).sub.2.55Iron Chloride following formula: HydroxideGreen Rust 12.5 grams iron powder Rhombohedral R 12.5 grams natural magnetite FeIron 1 gram copper chloride Cubic Im3m 1 gram water 100 grams of granular zeolite 10 grams of water Note: metal oxide coating removed before analysis. 5B Fe.sub.3O.sub.4Magnetite FeO(OH)Goethite Cubic Fd3m Orthorhombic Pbnm FeO(OH)Lepidocrocite FeIron Iron Oxide Hydroxide Cubic Im3m Orthorhombic Bbmm Fe.sub.8(O,OH).sub.16Cl.sub.1.3Akaganeite-M Monoclinic I2/m Fe(OH,Cl).sub.2.55Iron Chloride HydroxideGreen Rust Rhombohedral R This sample is oxidized iron powder and iron oxide mix using the following formula: 12.5 grams iron powder 10 grams synthetic magnetite 10 grams natural magnetite 1 gram copper chloride 1 gram water 100 grams of granular zeolite 10 grams of water Note: metal oxide coating removed before analysis. 6 Fe.sub.3O.sub.4Magnetite Fe(OH,Cl).sub.2.55Iron Chloride Cubic Fd3m HydroxideGreen Rust FeO(OH)Goethite Rhombohedral R Orthorhombic Pbnm Ca(SO.sub.4)(H.sub.2O).sub.2Gypsum This sample is oxidized iron powder Monoclinic C2/c and iron oxide mix using the following Possible: formula: Fe.sub.2Si.sub.2O.sub.5(OH).sub.4 12.5 grams iron powder 2H.sub.2OHisingerite 10 grams synthetic magnetite Monoclinic P 10 grams natural magnetite 1 gram copper sulfate 1 gram water 100 grams of granular zeolite 10 grams of water Note: metal oxide coating removed before analysis. 7A Fe.sub.3O.sub.4Magnetite FeO(OH)Goethite Cubic Fd3m Orthorhombic Pbnm This sample is oxidized iron powder Ca(SO.sub.4)(H.sub.2O).sub.2Gypsum and iron oxide mix using the Monoclinic C2/c following formula: Fe(OH,Cl).sub.2.55Iron Chloride 12.5 grams iron powder HydroxideGreen Rust 12.5 grams metal phosphate Rhombohedral R 1 gram copper chloride Possible Trace: 1 gram water CaAl.sub.2Si.sub.2O.sub.8 4H.sub.2OGismondine 100 grams of granular zeolite Monoclinic P21/c 10 grams of water HeulanditeCaKAlSiO H2O Note: metal oxide coating removed Monoclinic C2/m before analysis. 8 FeO(OH)Lepidocrocite Fe.sub.8(O,OH).sub.16Cl.sub.1.3Akaganeite-M Iron Oxide Hydroxide Monoclinic I2/m Orthorhombic Bbmm Fe.sub.3O.sub.4Magnetite FeO(OH)Goethite Cubic Fd3m Orthorhombic Pbnm Fe(OH,Cl).sub.2.55Iron Chloride HydroxideGreen Rust Rhombohedral R This sample is oxidized iron powder and iron oxide mix using the following formula: 12.5 grams iron powder 12.5 grams metal phosphate 100 grams of granular zeolite 10 grams of water Note: metal oxide coating removed before analysis.
The table above lists the compounds identified with highest figure of merit from the ICDD/ICSD data bases. Although the basic phases are similar for the set of samples, the relative amounts of the phases differ significantly for the individual samples. In order to emphasize this, the table above is separated into two columns. The first column lists the primary phase, and the second column lists secondary and trace phases. Typically, primary phases are responsible for >70% of the total diffraction intensity.
Note that, given the complexity of the XRD patterns, it is possible that some trace phases were not identified. Also, in many cases, the (OH) and Clare substitutable into the matrix, and without elemental analysis verifying the presence of Cl, the actual formulas may have (OH) groups present instead of Cl.
Note that the NMR readings are excluded.

(103) The invention illustratively disclosed herein suitably may be practiced in the absence of any element, which is not specifically disclosed herein. It is apparent to those skilled in the art, however, that many changes, variations, modifications, other uses, and applications to the method are possible, and also changes, variations, modifications, other uses, and applications which do not depart from the spirit and scope of the invention are deemed to be covered by the invention, which is limited only by the claims which follow.