KR19990022152A - How to recover iron from iron rich materials - Google Patents

Abstract

Iron-rich material waste, such as electric arc dust, is formed into briquettes or other solid forms by organic binders. This form can then be used in the steelmaking process and heavy metals in the waste can be recovered.

Description

How to recover iron from iron rich materials

The present invention relates to a method for recovering metals from metallurgical waste, in particular from waste formed in the steel manufacturing process.

Known Technology

In the steelmaking process, wastes containing oxidized iron and other oxidized metals are formed. These are dusty substances in the gaseous waste stream. These wastes are difficult to treat because of the fine particle size of the dust, and when the waste is reintroduced into the reduction furnace for withdrawal, it again forms part of the waste gas stream. Thus, these fine particle size materials are essentially useless even though they have a significant metal content.

There is a method of storing and stabilizing dust in piles near the forced tank plant, but this is unacceptable due to stricter environmental regulations and the limited space available due to the ground. Dust can be recycled and stabilized with ceramic or bildyl materials but is not cost effective. However, these methods do not develop the value of residual iron and other metals in the waste.

Dust of common interest is dust from electric arcs, EAF dust. Electrical arc furnaces melt scrap metal through the use of high voltage currents. Scrap metals come from a variety of sources, including: scrapped steel, cut sheet steel, scrap structural steel and automotive scrap. Scrap metals are added to the electric arc without separating nonferrous metals such as lead, zinc and cadmium. During operation of the electric arc these non-ferrous metals are evaporated from the scrap, condensed into dust from the waste gas stream and deposited in bag houses. In addition to these metals, waste gas streams deposit a significant amount of recoverable iron in the baghouse. Thus, iron and heavy metals, usually in oxidized form, are combined with amorphous EAF dust having a particle size of less than 20 microns. These EAF dusts are classified as hazardous wastes by EPA because of their lead and cadmium content. As such, considerable steps must be taken to protect the environment from heavy metal contamination and to meet EPA regulations. All metals in EAF dust are valuable and can be recycled if an effective separation and reduction method of dust components can be achieved. In addition, EAF dust can be non-toxic if residual heavy metals can be removed from the dust.

Several processes have been applied to address this problem, but vary in their success. Although these processes have been successful in removing heavy metals, they are inadequate for withdrawal and leave valuable iron oxide particulate content.

The most common method is fuming. This method uses the boiling point difference of heavy metals for separation. The dust is heated to a temperature above the boiling point of the metal to be separated, causing the metal to evaporate. The evaporated metal is removed from the gas as dust and condensed in the collector for further treatment. The boiling point of these residual metals is significantly lower than the boiling point of iron, the largest single component of dust. The dust remaining after the lead, zinc and cadmium segregation consists mainly of iron in the form of iron oxides. When in dust form, these materials are left as waste because they cannot be successfully processed with iron. Another problem with fuming is that it is energy intensive and generates a significant amount of waste.

Another process used for EAF treatment is electrowinning. This process combines the exudation and precipitation processes with electrolytic deposition. EAF dust first dissolves in the electrolyte to stabilize lead, zinc and cadmium. The solution is filtered and precipitated with zinc powder to capture lead and cadmium. The resulting zinc solution is passed through an electrochemical recovery cell to recover zinc. This process recovers zinc well but the exudation process does not dissolve iron oxide and zinc ferrite, leaving it as a waste that must be dried. This dried material is in the form of fine or low value dust.

In addition, EAF dust is treated by mixing with silicate materials such as silica sand, clay or cullets and heated in a furnace to form a glassy ceramic product. These ceramics are useful as abrasives and EAF dust is harmless, but valuable metals contained in the dust are not recovered. These metals are processed through expensive smelting techniques and converted into relatively inexpensive materials, making them harmless.

1 is a flowchart showing an embodiment of the present invention.

It is therefore an object of the present invention to provide a method for treating iron and heavy metal-containing dust which recovers iron and heavy metals as useful products.

The present invention overcomes or greatly reduces the problems of the known art. Methods of forming solid products in the form of briquettes, pellets or other solids are provided. The resulting product consists of materials that are bound together in solid form, such as iron enrichment (EAF dust), carbon sources (coke ash, coal particulates) or briquettes, to prevent decomposition into dust or smaller pieces. Such briquettes provide a source of iron and carbon for iron reduction in the steel manufacturing process. In addition, heavy metals in the iron-rich material are also included in the briquettes and can be separated and recovered by evaporation or purging during the iron reduction process. This fusing process is unique in that the feedstock uses a technique for extruding into a convenient shape and is formed into a stable solid and utilizes the reaction product of particulate carbon and an organic binder. The binder reaction product retains the dust formed until zinc, lead and cadmium evaporate and iron oxide is reduced to elemental iron. This method allows all materials contained in EAF dust to be recycled in one process. Fuel for this process is waste coke ash, waste coal particulates, electric arc or natural gas, depending on cost.

Thus, the method of the present invention recovers iron and heavy metals from the iron rich material powder. Powders that previously could not recover valuable iron can now be produced in forms that can be used to make steel. Not only iron is recovered but also heavy metals. Known attempts to make carbonaceous materials, such as coke, coal particulates, or reversible materials, into solid forms such as briquettes, have not been properly combined with the product and are unstable and decompose or decompose into small particulates during storage and handling prior to use. It was not successful. However, the present invention not only allows the carbon and iron-containing materials to be formed into solid forms that are strong and durable enough for handling and storage, but also combines the forms sufficiently to prevent premature dissolution of the form in the iron reduction process so that they are dusty. To be transported in the waste gas.

The process of manufacturing the form from fine iron-rich materials includes:

(a) the iron rich material and carbon source are mixed to form an iron rich / carbon mixture, the powder material free of oil and moisture;

(b) dissolving styrene or acrylonitrile polymer resin in a hygroscopic solvent to form a dissolved resin or conditioner;

(c) combining dissolved resin, iron rich / carbon mixture, calcium carbonate and alumino-silicate binder;

(d) emulsify the polyvinyl homopolymer in water and add the emulsion to the combination of step (c) and homogenize;

(e) compacting the mixture of step (d) into a form.

The term fine iron-rich material means a powdered or small particle sized material containing iron, iron oxides or other iron compounds. Powdered materials may include other metals, including heavy metals in the form of metal oxides, and other minerals found in waste from ore and mineral extraction.

Suitable iron rich materials are electric arc dust (EAF dust) deposited from waste gas streams from the electric arc used for steel production. Other suitable iron enriched materials include by-products of forced baths such as mill scale, precipitated iron oxides, and dust (so-called sludge) collected in the filter bag house into oxygen.

Iron-rich materials are free of moisture, ie up to 2% by weight of moisture and non-minerals such as oil. This can be achieved by a suitable cleaning and drying method by the method detailed in the Examples.

The powder material is first mixed with the carbon source. At this moment, the iron-rich material and carbon source can be secondaryly reacted with an inorganic acid such as hydrochloric acid. The carbon source is a source such as metallurgical grade coke. The carbon source is in particulate form which allows the formation of the solid form described below. In addition, the carbon source should not contain impurities that interfere with the formation of the shape or with subsequent iron reduction processes in which the shape is used. The carbon source is usually a fine powder material.

The powdered material and the carbon source are mixed so that the carbon source is 15 to 35% by weight, in particular 25% by weight. This mixture is subsequently reacted with hydrochloric acid. The mixture is reacted with 1 to 4% by weight, in particular 2% by weight of hydrochloric acid.

After reaction with hydrochloric acid, the iron rich / carbon mixture is combined with a binder to form one or more shapes. The reacted mixture is mixed with calcium carbonate, alumino-silicate binder, organic binder and polyvinyl alcohol. This is done by mixing the reacted mixture with calcium carbonate and alumino-silicate materials. Calcium carbonate acts as a flux for removing impurities during the reduction of the hardener and iron. Aluminosilicates also function as shaped hardeners and fluxes. Alumino-silicate materials are materials used for shaping such as kaolin clay, kaolin, alumina and silica mixtures, and dolomite lime clay.

The organic binder is mixed with calcium carbonate and alumino-silicates. Such binders are the binders described in US patent application Ser. No. 08 / 184,099 (1994, 1, 21). Such binders are prepared by dissolving styrene or acrylonitrile polymer resin in a hygroscopic solvent such as methylethylketone.

An emulsion prepared by emulsifying the polyvinyl polymer in water is added to the mixture together with the styrene polymer binder. Homogenize the result. The polyvinyl polymer is polyvinyl alcohol or polyvinyl acetate.

The homogenized mixture with polyvinyl acetate or polyvinyl alcohol is formed into a solid shape by a suitable method such as extrusion, molding or compression. In general, the extrusion or molding pressure is 15,000 to 45,000 psi, in particular 30,000 psi, to produce a dense and resistant to grinding and abrasion.

Example 1

This example illustrates the treatment of powdered iron rich material (IRM) feedstock and maximizes the production of high quality iron. With reference to FIG. 1, the IRM is first cleaned with a surfactant to produce an emollient containing oil and other contaminants found in the IRM. IRM evaporates the emollient and may be dried in a rotary kiln to reduce the total moisture content to less than 2% by weight, although up to 6% by weight of water may be used depending on the composition being processed.

The washed IRM is weighed and placed in a mixer with about 25% by weight metallurgical coke and reacted with about 2% by weight hydrochloric acid. IRM, coke and hydrochloric acid are then mixed for about 5 minutes.

After mixing, about 5% by weight calcium carbonate and 2.5% by weight kaolinite (Al ₂ O ₃ + SiO ₂ ) are added to the acid treated IRM and coke and mixed for 5 minutes. Calcium carbonate and kaolin act as hardeners in the IRM mixture and as flux when the material is reduced to metal.

After mixing, 3% by weight of organic binder material is added to the batch mixer and mixed for 5 minutes. The binder is styrene polymer resin (10% by weight) dissolved in a hygroscopic solvent such as methylethylketone. Since the binder contains a hygroscopic solvent, the water generated in the previous reaction is discharged into the solvent.

After mixing about 4% by weight polyvinyl alcohol homopolymer is added to the mixture and mixed for 10 minutes. The material is then transferred to a machine such as a briquette press under high injection pressure to form a rigid shape that is easily handled.

The formed shape or other solid shape is subsequently heated to 250-400 ° F. to cure. The hardening process reduces the water content of briquettes to less than 2% by weight. After hardening, briquettes are introduced into the electric arc to reduce the oxides. Reduction of the iron oxide is done with minimal power due to the fact that briquettes are kept under the slag layer by the binder until a reduction reaction occurs between the coke and the oxidized iron. Other materials added to briquettes or other solid forms act as a flux to transport impurities into the slag layer on the liquid metal bath.

Acrylonitrile polymers may be used instead of styrene polymers. Suitable homopolymers are 32-024 homopolymer PVA emulsions from National Starch and Adhesive. Acrylonitrile polymers are maintained in fluid state for a long time by methyl ethyl ketone. Acrylonitrile is available from Polymerland and industrial methyl ethyl ketone is available from Dice Chemical Co. and Thatcher Chemical Co. 90% by weight methylethylketone and 10% by weight acrylonitrile polymer are suitable but these amounts are variable.

Examples II to V

These examples illustrate the treatment of powdered iron rich material (IRM) feedstock and maximize the production of high quality iron. The IRE is first cleaned with a surfactant to produce an emollient containing oils and other contaminants found in IRM. IRE is dried in a rotary kiln to evaporate the emollient and reduce the total moisture content.

The washed IRM is weighed and placed in a mixer with the particulate carbon source and reacted with about 2% by weight hydrochloric acid. IRM, particulate carbon source and hydrochloric acid are then mixed for about 5 minutes.

After mixing, about 5% by weight calcium carbonate and 2.5% by weight kaolinite (Al ₂ O ₃ + SiO ₂ ) are added to the acid-treated IRM and particulate carbon and mixed for 5 minutes.

After mixing, 3% by weight of organic binder material is added to the batch mixer and mixed for 5 minutes. The binder is an acrylonitrile polymer and is maintained in fluid state for a long time by methyl ethyl ketone.

After mixing about 4% by weight polyvinyl alcohol homopolymer is added to the mixture and mixed for 10 minutes. The material is then transferred to a machine such as a briquette press under high injection pressure to form a rigid shape that is easily handled.

The shape or other solid shape formed is then cured by heating to 250 to 400 ° F. The hardening process reduces the water content of briquettes to less than 2% by weight. After hardening, briquettes are introduced into the electric arc to reduce the oxides. Starting materials and iron and slag products as a result of the reduction are analyzed. The test results are summarized below.

Example II

Particulate carbon in this example is coke material (10400 BTU) and IRM is a mixture of iron scale precipitates in the mill scale and oxygen furnace (Gulf States, Gadston, Alabama) of steel mills (Nucor, Plymoth, Utah). Weight percent analysis of the starting materials, briquettes produced, and reduction products is shown in Table 1. Of the briquettes introduced in the reduction process, about 88% are iron products and 21% are slags (the sum of these values is not exactly 100% due to measurement errors).

Basic iron test Starting material for briquetting briquet Reduction product Coke ash NUCOR Millscale Iron oxides from GULF STATES iron Slag Sample number 1 / 8-15-1 2 / 8-15-1 3 / 8-15-1 4 / 8-15-1 5 / 8-15-1 6 / 8-15-1 carbon 63.3 0.41 6.59 18.2 3.27 0.82 sulfur 0.54 0.03 0.12 0.22 0.12 0.46 iron 73.4 51.1 45.5 83.6 6.88 manganese 0.54 0.26 0.316 0.131 0.843 sign 0.01 0.01 0.01 0.005 0.018 silicon 0.32 0.84 1.15 0.35 12 Copper 0.206 0.061 0.088 0.194 0.028 nickel 0.063 0.029 0.032 0.101 0.01 chrome 0.063 0.03 0.046 0.094 0.039 molybdenum 0.005 0.015 0.005 0.004 0.003

Remark 0.026 0.07 0.017 0.03 0.001 zinc 0.008 0.426 0.143 0.008 0.001 boron 0.01 0.01 0.01 0.03 0.01 titanium 0.002 0.022 0.025 0.002 0.167 arsenic 0.001 0.001 0.001 0.001 0.001

Example III

In this example, the particulate carbon is coke material (10400 BTU) and the IRM is a mixture of mill scale of the steel mill and sludge (both Geneva, Utah) from the filter of the oxygen furnace (Q-BOP). Weight percent analysis of the starting materials, briquettes produced, and reduction products are shown in Tables 2 and 3. Results for slag accumulating three tests in tests 1 to 3 and the percentages of iron product and slag in briquettes introduced in the reduction process are shown in Table 4 (the sum of these values is not exactly 100% due to measurement error). .

Basic iron test Starting material for briquetting briquet Reduction product GENEVA Millscale GENEVA sludge Test 1 iron Test 2 iron Test 3 iron Test 1-3 Slag Sample / Test Number 11 / 8-16-2 12 / 8-16-2 13 / 8-16-2 14 / 8-16-2 15 / 8-16-3 16 / 8-17-4 17 / 8-17-4 carbon 2.28 19.4 7.35 1.85 2.21 1.61 0.15 sulfur 0.07 0.28 0.09 0.08 0.06 0.07 0.28 iron 69.3 41.5 57.5 93.2 96 97 1.22 manganese 0.596 0.083 0.475 0.3 0.024 0.081 0.94

sign 0.01 0.084 0.007 0.007 0.008 0.005 0.011 silicon 0.01 0.014 8 0.06 0.01 0.21 0.01 Copper 0.087 0.01 0.007 0.063 0.009 0.031 0.003 nickel 0.032 0.001 0.008 0.069 0.011 0.022 0.003 chrome 0.042 0.01 0.01 0.89 0.021 0.0119 0.002 molybdenum 0.003 0.01 0.01 0.014 0.012 0.157 0.01 Remark 0.003 0.034 0.007 0.004 0.001 0.001 0.29 zinc 0.015 0.35 0.036 0.013 0.005 0.007 0.005 boron 0.01 0.25 0.26 0.01 0.01 0.01 1.45 titanium 0.003 0.034 0.007 0.004 0.001 0.001 0.29 arsenic 0.003 0.003 0.003 0.03 0.003 0.003 0.003 aluminum 18.4 magnesium 6.64 lead 3.77 cadmium 0.01

Basic iron test Starting material for briquetting briquet Reduction product GENEVA Millscale GENEVA sludge Test 1 iron Test 2 iron Test 3 iron Test 1-3 Slag Sample / Test Number 11 / 8-16-2 12 / 8-16-2 13 / 8-16-2 18 / 8-17-5 19 / 8-17-5 20 / 8-21-6 21 / 8-21-6 carbon 2.28 19.4 7.35 2.34 0.16 2.39 0.26 sulfur 0.07 0.28 0.09 0.06 0.37 0.07 0.33 iron 69.3 41.5 57.5 86.1 1.5 89.6 0.75 manganese 0.596 0.083 0.475 0.446 1.2 0.175 0.678 sign 0.01 0.084 0.007 0.09 0.017 0.01 0.003 silicon 0.01 0.014 8 0.05 0.01 0.193 23.5 Copper 0.087 0.01 0.007 0.04 0.002 0.036 0.014 nickel 0.032 0.001 0.008 0.043 0.003 0.027 0.001 chrome 0.042 0.01 0.01 0.064 0.01 0.029 0.001 molybdenum 0.003 0.01 0.01 0.003 0.003 0.01 0.01

Remark 0.003 0.034 0.007 0.058 0.251 0.03 0.01 zinc 0.015 0.35 0.036 0.014 0.002 0.006 0.005 boron 0.01 0.25 0.26 0.01 1.56 0.01 1.53 titanium 0.003 0.034 0.007 0.058 0.251 0.046 0.357 arsenic 0.003 0.003 0.003 0.003 0.003 0.005 0.0058

Reduction product Reduction test iron Slag One 96.594 4.667 2 98.385 3 99.2199 4 89.379 5.342 5 92.637 27.4548

Example IV

In this example, the particulate carbon is coke material (10400 BTU) and the IRM is a mixture of iron ore at Geneva near Cedar City, Utah and sludge from a filter at Q-BOP (Geneva Steel, Geneva, Utah). to be. The weight percentages for starting materials, briquettes produced, and the reduction products of the five briquette reduction tests are shown in Table 5. Of the briquettes introduced in the reduction process, 88.9% are iron products and 22.1% are slag for Test 1 (the sum of these values is not exactly 100% due to measurement errors). This data is not obtained in test 2.

Basic iron test Starting material for briquetting briquet Reduction product RED SEA Sludge CEDAR Ore Test 1 iron Slag for test 2 Test 2 iron Slag for test 2 Sample number 24 / 8-21-8 25 / 8-21-8 26 / 8-21-8 22 / 8-21-7 23 / 8-21-7 27 / 8-21-8 28 / 8-21-8 carbon 0.82 0.24 21.6 2.29 0.86 2.69 10.7 sulfur 0.1 0.06 0.19 0.05 0.47 0.01 1.5 iron 46.1 46.4 33.9 86 2.25 40.5 2.93 manganese 0.319 0.058 0.113 0.2 0.897 0.084 0.013 sign 0.012 0.06 0.033 0.008 0.013 0.03 0.01 silicon 1.96 3.11 6.5 0.229 15.7 0.515 3.6 Copper 0.052 0.001 0.015 0.024 0.002 0.017 0.006 nickel 0.011 0.028 0.014 0.025 0.001 0.025 0.004 chrome 0.03 0.006 0.001 0.033 0.01 0.03 0.005 molybdenum 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Remark 0.02 0.02 0.01 0.03 0.01 0.01 0.01 zinc 0.386 0.012 0.142 0.006 0.005 0.005 0.005 boron 0.01 0.01 0.01 0.01 1.67 0.05 0.06 titanium 0.02 0.005 0.018 0.033 0.228 0.046 0.021 arsenic 0.005 0.005 0.005 0.005 0.005 0.005 0.005

Example V

In this example, the particulate carbon is coke material (10400 BTU) and the IRM is iron oxide dust derived as a by-product of photo film production. Analysis of the various batches of starting materials and accumulation results of iron reduction products (% by weight) are shown in Table 6.

Basic iron test Starting iron material for briquette formation Iron Product KMFE203 KMFE203 Dust 0 KMFE203 dust KMFE203 dust KMFE203 dust Test number 29.00 30.00 29.00 30.00 31.00 carbon 0.030 0.030 0.030 0.030 3.020 sulfur 0.020 0.025 0.020 0.025 0.022 iron 60.500 63.600 60.500 63.600 88.200 manganese 2.270 2.280 2.270 2.280 0.200 sign 0.003 0.003 0.003 0.003 0.032 silicon 0.570 0.610 0.570 0.610 0.330 Copper 0.001 0.001 0.001 0.001 0.514 nickel 0.007 0.006 0.007 0.006 0.114 chrome 0.048 0.047 0.048 0.047 0.275 molybdenum 0.010 0.010 0.010 0.010 0.090 Remark 0.010 0.020 0.010 0.020 0.030 zinc 0.067 0.068 0.067 0.068 0.013 titanium 0.027 0.030 0.027 0.030 0.015

Example VI

In this example, the particulate carbon is coal fines and the IRM is the same as in Example III. The analysis (% by weight) of iron and slag reduction products is shown in Table 7.

Basic iron test Slag product from coal Iron products from coal Sample / test number 33 / 9-21-37 34 / 9-21-37 carbon 3.29 2.74 sulfur 0.02 1.05 iron 14.03 89.10 manganese 0.22 0.55 sign 0.02 0.01 silicon 7.38 1.65 Copper 0.00 0.45 nickel 0.01 0.06 chrome 0.03 0.12 molybdenum 0.01 0.01 Remark 0.01 0.04 zinc 0.01 0.01 titanium 0.07 0.05

theory

The present invention is believed to polymerize the carbon particles contained in the carbon source to a new long chain polymer compound to form a structurally excellent strength form. Carbon oxides are known to hydrolyze in water. This reaction results in the presence of free carboxyl ions in the compound.

The introduction of doped methylethylketone is believed to attach the styrene polymer to free carbon ions by exchanging water absorbed in the solvent with the polymer.

In the next step polyvinylacetate is introduced. The presence of methyl ethyl ketone is removed and acts as a catalyst to allow acrylonitrile or styrene to react with polyvinylacetate.

Compressed forms such as briquettes, pellets or extruded solid pieces are structurally stable and do not disintegrate into particulates during storage and handling.

Claims (18)

(a) the iron rich material and carbon source are mixed to form an iron rich / carbon mixture, the powder material free of oil and moisture; (b) dissolving styrene or acrylonitrile polymer in a hygroscopic solvent; (c) combining dissolved styrene or acrylonitrile polymer, iron rich / carbon mixture, calcium carbonate, and alumino-silicate binder; (d) emulsify the polyvinyl polymer in water and add the emulsion to the combination of step (c) and homogenize; (e) compressing the mixture of step (d) into a form, wherein the form is prepared from a fine iron-rich material. The method of claim 1 wherein the polyvinyl polymer is polyvinyl alcohol. The method of claim 1 wherein the polyvinyl polymer is polyvinyl acetate. The process of claim 1, wherein hydrochloric acid is added in the mixing step (a) of the iron-rich material and the carbon source. The method of claim 1, wherein the mixture of step (e) is compressed into form in a briquette press. 2. Process according to claim 1, characterized in that the mixture of step (e) is compressed into form via extrusion. 2. The method of claim 1, further comprising heating the form to remove moisture from the form. The method of claim 1 further comprising introducing into the reaction environment for the reduction of iron in form. The method of claim 1, wherein the iron-rich material comprises heavy metals and a form is introduced into the furnace for evaporation of heavy metals and reduction of iron. The method of claim 1, wherein the ion-rich material is mixed with the surface active agent prior to step (a) to disintegrate the non-inorganic material of the powder to form a softener composed of the surface active agent and the non-inorganic material, and the powder material is dried to evaporate the softener to moisture content. Characterized in that for reducing. The method of claim 1 wherein the form is compressed to a pressure of 30,00 psi. The method of claim 1 wherein the hygroscopic solvent comprises methyl ethyl ketone. A method of forming a form from a fine iron-rich material comprising polymerizing styrene or acrylonitrile in the presence of a composition comprising a carbon source and an iron rich material and forming the composition under high compression pressure. Form from a fine iron-rich material comprising applying polyvinyl acetate to a composition comprising an iron-rich material bound by a reaction product of a styrene or acrylonitrile polymer and a carbon source and forming the composition under high compression pressure. How to form. Combining and mixing iron rich materials, carbon sources, conditioners and homopolymers; Compacting the resulting mixture into a form comprising fine iron-rich material. (a) the iron rich material and carbon source are mixed to form an iron rich / carbon mixture, the powder material free of oil and moisture; (b) dissolving the acrylonitrile polymer in a hygroscopic solvent; (c) combining dissolved acrylonitrile polymer, iron rich / carbon mixture, calcium carbonate, and alumino-silicate binder; (d) emulsify the polyvinyl polymer in water and add the emulsion to the combination of step (c) and homogenize; (e) compressing the mixture of step (d) into a form, wherein the form is prepared from a fine iron-rich material. A form comprising a carbon source and an iron rich substance having molecular carbon attachment sites bound by long chain polymers. 18. The form according to claim 17, wherein the long chain polymer comprises a compound of styrene or acrylonitrile.