Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B1/00—Preliminary treatment of ores or scrap
  • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
  • C22B1/24—Binding; Briquetting ; Granulating
  • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B1/00—Preliminary treatment of ores or scrap
  • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
  • C22B1/24—Binding; Briquetting ; Granulating
  • C22B1/242—Binding; Briquetting ; Granulating with binders
  • C22B1/244—Binding; Briquetting ; Granulating with binders organic

Definitions

• Iron ore needs to be in the form of agglomerates of substantial size when it is charged into a blast furnace. If the available ore is in the form of particles that are too small for direct feed to the blast furnace it is necessary to convert them to a sinter or to pellets. With the increasing use of lower grade ores it has become necessary to grind the ore more finely and, for these fine particles, pelletisation is the only satisfactory method of production of feedstock for the furnaces.
• the pellets are made by adding binder to the fine particulate ore and stirring in the presence of a small amount of water (generally moisture in the ore) to form a moist mixture, and then pelletising the mixture, e.g., in a balling drum or disc pelletiser.
• the green pellets are then fired in a kiln through a temperature range that extends from an inlet temperature typically in the range 200-400°C up to a final temperature of e.g., 1200°C.
• Important properties of the pellets are the initial or wet strength, the dry strength (after drying the green pellets in an oven at 105°C) and the tendency of the pellets to spall (or burst) upon exposure to firing temperatures.
• the tendency for spalling can be defined by determining the minimum temperature at which spalling occurs or by observing the percentage of fines formed during a particular firing cycle.
• the moisture content of the mixture and the porosity of the pellets must be chosen carefully.
• a high "drop number" for the green pellets is desirable.
• the amount of binder should be as low as possible and, to ensure uniform properties, its flow properties must be such that it can easily be added uniformly in these low quantities.
• bentonite is the binder that is generally used.
• a disadvantage of the process in GB 1,324,838 is that it is necessary to introduce substantial amounts of water with the polymer and so the initial iron ore must be very dry (involving the use of drying energy) or the final pellets will be very wet (increasing the risk of spalling).
• a problem with bentonite and other binders is that the spalling temperature is low.
• the inlet temperature of the kiln has to be in the range 200 to 400°C to prevent spalling. Higher inlet temperatures would be economically desirable if spalling could still be avoided.
• a difficulty with powdered cellulosic binders such as carboxymethyl cellulose is that the irregular particle shape and size distribution is such that the powder does not flow freely. Instead the dry particles tend to clump together rather than flow over one another. As a result it is difficult to achieve uniform supply of the low dosages that are required.
• Another problem is that the amount of cellulosic binder that has to be used for adequate strength tends to be too high to be cost effective.
• Another problem with some cellulosic polymers is that they can reduce surface tension, and this appears to be undesirable in pellet formation.
• EP 0203855A2 (not published until after the priority date of this application) it is proposed to use a water soluble high molecular weight polymer in the form of a dry powder or, preferably, a water-in-oil emulsion that preferably contains both water-in-oil and oil-in-water surfactants.
• Non-ionic, anionic and cationic polymers are proposed.
• the use of the polymer in combination, with an inorganic salt, to increase strength, is also proposed.
• Rhone Poulenc AD10 which is said to be a non-ionic polyacrylamide having intrinsic viscosity (IV) 15.4dl/g and which we believe to be a coarse crushed gel product
• Percol 725 and Percol 726 both of which are made by the assignees of the present application.
• Percol 725 is a crushed gel copolymer having IV about 18 of 80% acrylamide and 20% by weight sodium acrylate
• Percol 726 is a bead copolymer of about 65% acrylamide and 35% by weight sodium acrylate and has IV about 17.
• Percol 726 is made by reverse phase polymerisation and a significant amount of the particles have a dry size above 450 ⁇ m and up to about 800 ⁇ m, and the crushed gel of Percol 725 also has a particle size of up to about 800 ⁇ m.
• the iron ore always has a very small particle size, and therefore a huge surface area.
• the binder must be introduced with the absolute minimum of water in order that the pellets can conveniently have a total moisture content of not more than about 15%.
• the duration and energy of mixing the binder with the iron ore particles must be as short as possible in order to maximise production and minimise capital costs.
• the amount of binder must be as low as possible in order to minimise cost and to avoid the risk of excess binder accentuating the stickiness problems noted in the article by R.L.Smythe.
• Bentonite has a very small particle size (typically below 10 ⁇ m) and adequate admixture of these very small particles with the particulate iron ore is achieved because the bentonite is used in a relatively large amount (typically 1%).
• a binder that is substantially coarser and/or present in a substantially smaller amount would tend to give less satisfactory results, due to non-uniform mixing of the binder with the relatively large volume of very fine particulate iron ore.
• mineral ore pellets are made by adding binder comprising organic polymer to particulate mineral ore having substantially all particles below 250 ⁇ m and stirring in the presence of about 5 to about 15% by weight water (based on total mixture) to form a substantially homogeneous moist mixture and pelletising the moist mixture.
• EP225171 (not published at the priority date of this application) there is claimed a process in which iron ore pellets are made by adding binder comprising organic polymer to particulate iron ore having substantially all particles below 250 ⁇ m and stirring in the presence of 5 to 15% by weight (based on total mix) to form a substantially homogeneous moist mixture and pelletising the moist mixture, and the process is characterised in that the binder comprises up to 0.2% by weight, based on total mix, of a water soluble synthetic polymer that has intrinsic viscosity 3 to 16dl/g and that is an anionic polymer of one or more water soluble ethylenically unsaturated monomers comprising an anionic monomer and that is added to the iron ore as a dry, free flowing, powder having substantially all particles above 20 ⁇ m and below 300 ⁇ m.
• pellets are made from mineral ore by adding binder comprising organic polymer to acidic particulate mineral ore having substantially all particles below 250 ⁇ m and stirring in the presence of 5 to 15% by weight water (based on total mix) to form a substantially homogeneous moist mixture and pelletising the moist mixture, and in this process the binder comprises about 0.02% to about 0.5% by weight, based on total mix, of water soluble polymer that is cationic.
• the pH of the resultant water may depend upon the amount of ore that is used but at higher amounts of ore, typically 30 to 40% solids, the pH becomes substantially independent of the amount of ore. It is this pH, that is substantially independent of ore concentration, which is intended herein when reference is made to the ore giving a specified pH.
• Normal ores give a pH of above 8.1, typically 8.2 to 8.4 or higher.
• the invention is of particular value when the ore is acidic and thus gives a pH in this test of below 7, and often below 6.
• the mineral can be any acidic ore, e.g., a zinc ore, but is preferably an iron ore, normally a haematite, magnetite or tachonite.
• the ore may be naturally acidic or may have been rendered acidic by some treatment prior to blending with the binder. For instance the ore may have been washed with acid to remove acid soluble components, typically to produce a pH of from 5 to 6 if manganese is being washed out of the ore.
• the ore may have acquired an acidic pH during other processing treatments.
• the ore may be dried under conditions that result in the dry ore giving the specified relatively low pH in water. This may be because, for instance, the drying is conducted using hot gases that contain sulphur or other impurities that cause acidification of the ore during drying or may be due to chemical changes in the surface properties of the ore that are caused by dehydration.
• a preferred process of the invention comprises forming acidic particulate ore from the mineral ore (that can be of low grade) by a process comprising washing or leaching the mineral ore in acid, and thereafter using the resultant, enriched, acidic particulate ore for pelletising. It has not previously been practicable to use acid washed or acid leached ores for pelletising.
• the ore that is acid washed or leached is normally an iron ore.
• the soluble cationic polymer is formed by the polymerisation of cationic ethylenically unsaturated monomer, optionally with other ethylenically unsaturated monomers.
• the monomer or monomer blend will normally be water soluble.
• One suitable class of cationic monomers are the dialkylaminoalkyl (meth) acrylates, especially dimethylaminoethyl (meth) acrylate (DMAEA or DMAEMA).
• Another suitable class are the dialkylaminoalkyl (meth) acrylamides.
• a suitable material is dimethylaminopropyl (meth) acrylamide. All such monomers are generally present in the form of acid addition or quaternary ammonium salts.
• a suitable monomer is methacrylamido propyl trimethyl ammonium chloride (MAPTAC).
• suitable cationic monomers include diallyl dialkyl quaternary monomers, especially diallyl dimethyl ammonium chloride (DADMAC).
• DMDMAC diallyl dimethyl ammonium chloride
• Preferred cationic polymers are polymers having recurring quaternary ammonium groups. Blends of cationic polymers (e.g., a blend of synthetic cationic with natural or modified natural cationic polymer) can be used.
• the polymers can be copolymerised with non-ionic monomers, generally (meth) acrylamide (ACM).
• suitable cationic polymers are polyethylene imines and epichlorhydrin polyamine reaction products made in bead form.
• homopolymers and other polymers having a very high cationic content can be of relatively low molecular weight, for instance having intrinsic viscosity below 5 dl/g, often in the range 0.4 to 2 dl/g.
• ethylenically unsaturated monomers at least 70 weight percent, and preferably at least 90 weight percent, of the monomers should be cationic, and preferably the polymer is substantially a homopolymer.
• polymers have medium to high molecular weight and medium cationic content.
• the IV may be from about 3 to about 20 dl/g or higher, generally 3 to 12 dl/g, preferably from 5 to 9 dl/g.
• Such polymers are best made by copolymerisation of about 20 to about 75, preferably about 25 to about 60, weight percent cationic monomer with a non-ionic monomer such as acrylamide. Best results are generally obtained with about 35 to about 55 weight percent cationic monomer, with the balance non-ionic.
• the cationic polymer can be added in other forms.
• it can be added in the form of particles that are within the size ranges discussed above for beads but which have been made by comminution of gel in air or, preferably, in an organic liquid for instance as described in EP 169674. It may be necessary to sieve the particles to give the desired particle range and to exclude oversize particles.
• polystyrene resin instead of being a synthetic polymer, it can be a naturally occurring polymer (or a modified natural polymer) such as Chitosan or cationic starch, but this usually less satisfactory than the use of synthetic polymers.
• the polymer can initially be provided in any suitable physical form.
• the aqueous polymer solution may be sprayed on to the ore prior to pelleting.
• the solution can be made from polymer in the form of a concentrated solution, a polymer-in-oil dispersion or powder.
• the polymer-in-oil dispersion of the polymer can be added direct to the ore.
• the polymer particles in any such dispersion can be dry or can be swollen gel particles.
• the polymer is added in the form of dry, free flowing powder having substantially all particles below about 300 ⁇ m, usually in the range about 20 to about 300 ⁇ m.
• the particles can be comminuted gel, especially if the comminuted gel particles had been formed or treated in known manner so as to promote their flow, but preferably the particles are beads, for instance as made by reverse phase bead polymerisation.
• Reverse phase bead polymerisation is a well known process.
• an aqueous solution of the chosen monomer or monomer blend is dispersed in water immiscible liquid, generally in the absence of an emulsifying agent but often in the presence of an amphipathic polymeric stabiliser, the polymerisation is induced in conventional manner to provide a suspension of gel particles in the non-aqueous liquid, the suspension is then dried by azeotropic distillation and the particles are separated from the non-aqueous liquid in conventional manner.
• the desired particle size range is controlled in known manner, for instance by the choice of stabiliser, emulsifying agent (if present) and, especially, the degree of agitation during the formation of the initial suspension of aqueous monomer particles in the water immiscible liquid.
• the beads are substantially spherical.
• Some reverse phase polymerisation methods involve the use of relatively large amounts of emulsifiers or other materials that depress surface tension. It is particularly desirable in the invention to make the polymer particles in the substantial absence of any such material. In particular, it is desirable that the entire binder (and also the polymer component of the binder) should have substantially no depressant effect on surface tension. Thus if binder is dissolved with water at 20°C at 0.075% by weight concentration the surface tension of the solution should be above 65, and preferably above 70 dynes/cm. Thus it is preferred to avoid the use of amounts of surfactant that would depress surface tension significantly and reliance should be placed instead on agitation or stabiliser, in known manner, to control bead size.
• the powdered binder that is added to the ore includes additional monomeric compound that is usually an inorganic or organic electrolyte but can be a non-electrolyte.
• the compound is normally water soluble and inorganic and so is preferably a water soluble salt of an acid.
• salts of strong acids e.g., sodium chloride, sulphate or nitrate
• the strong acid salts may generate corrosive acids during smelting or firing.
• organic molecules such as urea, inorganic water soluble salts of carboxylic, dicarboxylic and tricarboxylic acids such as sodium acetate, sodium citrate, sodium oxalate, sodium tartrate, sodium benzoate and sodium stearate, other sodium salts of weak acids such as sodium bicarbonate and sodium carbonate, other miscellaneous sodium salts such as sodium silicate or phosphate, the corresponding ammonium, potassium, calcium or magnesium salts of the preceding salts and calcium oxide.
• Sodium carbonate, bicarbonate or silicate are generally preferred as they give the best anti-spalling and dry strength results.
• beads made by reverse phase bead polymerisation are those that they can readily be added in very uniform and very small amounts to the ore that is to be pelleted, because of the substantially spherical shape of the beads.
• the binder is to be a blend of the polymer with other material such as any of the compounds discussed above then this other material should also be added in a form that is easily flowable on to the ore.
• the compound is incorporated in the beads.
• a salt of a weak acid can be present in the aqueous monomer during polymerisation.
• the compound can be added separately to the ore or it can be preblended with the polymer beads, but in either instance the compound itself is preferably put into a free flowable, generally bead, form, by known techniques.
• the optimum amount of added salt or other compound can be found by experimentation. For many purposes it is in the range 0 to about 60% by weight based on the binder (below 0.1% and usually below 0.02% based on ore). In some instances amounts of from about 10 to about 30% based on soluble polymer are the most cost effective but usually greater amounts, for instance 30 to about 100% or even 150%, preferably 50 to 90%, based on soluble polymer are preferred.
• the soluble polymer in bead or other form
• cross linked polymers have proved, by themselves, to be unsatisfactory we find valuable results are achieved if a cross linked, swellable, particulate organic polymer is included with the soluble polymer.
• the cross linked polymer must have a small particle size, below 100 ⁇ m and often below 50 ⁇ m. The size can be as small as is commercially available, e.g., down to 10 ⁇ m or 1 ⁇ m.
• the particles are normally introduced as dry powder and preferably this powder is in the form of bead fines separated during the production of coarser particulate swellable polymer as produced by bead polymerisation.
• the inclusion of the cross linked polymer particles can give surprisingly improved dry strength and drop number values and so a blend of soluble particles and cross linked particles can give an excellent combination of dry strength, wet strength and spalling properties. Also the pellets tend to have improved surface appearance, such as smoothness.
• the cross linked polymer may be non-ionic (e.g., polyacrylamide), but when the soluble polymer is ionic it is preferably of the same ionic type as the soluble polymer and so may be formed from the same monomers as are discussed below for the preparation of the soluble polymer. Preferably 20 to 100% by weight, most preferably 60 to 100% by weight, are ionic. The use of homopolymer, e.g., cross linked sodium polyacrylate, is very satisfactory. Cross linking may be by any of the conventional cross linking agents used in the production of swellable or absorbent polymers.
• cross linking agent may be by an ionic cross linking agent but is preferably covalent, e.g., methylene bis acrylamide or other polyethylenically unsaturated monomer.
• the amount of cross linking agent is generally in the range 20 to 1,000 ppm, preferably 50 to 500 ppm, and must be such that the particles are insoluble but highly swellable in water, e.g., having a gel capacity in water above 50, and preferably above 200, grams per gram.
• the amount of cross linked polymer particles may be relatively low, e.g., 10 to 30% based on soluble polymer, but generally greater amounts, e.g., up to 300% or even 600% based on soluble polymer are preferred. Amounts of 0 to 80% often 20 to 50%, based on total binder are suitable. Particularly preferred binders consist essentially of 1 part by weight soluble polymer, 0.3 to 1.5 parts by weight sodium carbonate or other added salt or simple compound, and 0.3 to 5 parts by weight cross linked anionic homopolymer or copolymer, with proportions of about 1:1:1 often being convenient.
• substantially all the particles of the soluble polymer must be below about 300 ⁇ m for good results, presumably since otherwise the particle size is too large to establish adequate contact with the very large number of very small iron ore particles.
• substantially all the polymer particles are below about 200 and preferably below about 150 microns. Although it might be expected to be necessary to have exceedingly small polymer particle size, similar to bentonite, this is unnecessary and it is satisfactory for most or all of the particles to be above 20 microns. Best results are often achieved when substantially all the polymer particles are in the range 20 to 100 microns but a satisfactory fraction is 100% below about 200 ⁇ m and at least 50% below about 100 ⁇ m.
• the amount is usually below about 0.2% and generally it is below about 0.1% (by weight based on the total mix). It is often preferred for the amount to be below 0.05% by weight, but amounts below 0.01% are usually inadequate except when the soluble polymer is used with significant (e.g., at least 20% by weight) other binder components. the amount of soluble polymer may then sometimes be reduced, e.g., to 0.005%.
• the particle size of the ore is generally less than 250 microns, usually 90% or 80% by weight of the particles being less than 50 microns.
• the ore is preferably an iron ore such as magnetite, haemetite or taconite, but can be any other mineral ore that needs to be put into the form of pellets, for instance a zinc ore. Satisfactory results can be obtained even if the ore is contaminated with clay.
• the ore Before adding binder in the form of dry polymer, the ore usually already has the desired final moisture content of 5 to 15%, preferably 8 to 10%, by weight based on the weight of iron ore. This moisture content is the moisture as measured by heating up to 105°C. However if the ore is too dry then water may be added to it, e.g., before or after the addition of polymer binder (or the binder may be predissolved).
• the binder can be blended with the ore in the same manner as bentonite is blended, preferably by scattering the polymer particles on to the ore as it is carried towards a mixer, for instance a paddle mixer provided with stators. It may be mixed for the same duration as when bentonite is used, for instance 2 to 20, generally about 10, minutes.
• the damp blend of ore and polymer is converted to pellets in conventional manner, for instance by balling in conventional manner. This may be effected using a rotating tilting disc but generally is conducted in a balling drum.
• the size of the pellets is generally from 5 to 16 mm, preferably 8 to 12 mm.
• the resultant green pellets Before the resultant green pellets can be utilised for the production of metal they need to be fired, generally at a temperature up to above 1000°C, for instance up to 1200°C. For this purpose they can be introduced into a kiln or other firing apparatus and fired in conventional manner. It is desirable to be able to introduce them into this furnace at the highest possible inlet temperature with the minimum risk of spalling.
• the inlet temperature at which spalling becomes significant can be referred to as the spalling temperature and a particular advantage of the invention is that it is possible to make pellets having a spalling temperature higher than can conveniently be obtained by the use of bentonite and other known binders.
• the invention also includes a process in which organic polymer is added to conventional particulate iron or other ore having substantially all particles below 250 ⁇ m and stirring in the presence of 5 to 15% by weight water (based on total mix) to form a substantially homogeneous moist mixture and pelletising the moist mixture, the process being characterised in that the binder comprises up to 0.2% by weight, based on total mix, of water soluble synthetic polymer that has intrinsic viscosity above about 17dl/g and that is an anionic polymer of one or more water soluble ethylenically unsaturated monomers comprising an anionic monomer and the binder also comprises about 10 to about 150%, based on total binder, of added salt or other monomeric compound as discussed above.
• the high IV anionic monomers cannot be used alone, adequate results are obtainable when blended with such salt or other monomeric compound, for instance in proportions by weight 2:1 to 1:2.
• the very high molecular weight polymer is introduced in the form of fine powder which can be beads or crushed gel.
• the particle sizes and other characterisitcs of the anionic polymer, suitable inorganic materials and cross linked polymes and other additives may all be as described above for the cationic binders.
• the binder comprises about 0.005% to 0.5% by weight, based on total mix, of a water soluble synthetic polymer that is added to the ore as dry, free flowing, beads that are substantially all above 20 ⁇ m and below 300 ⁇ m and that are made by reverse phase bead polymerisation from water soluble ethylenically unsaturated monomer or monomer blend.
• the polymer of the beads preferably is not anionic polymer of intrinsic viscosity 3 to 16. Thus it may be anionic below 3 and preferably below 2, anionic above 16 and preferably above 17, nonionic or cationic.
• the bead polymer may be mixed with other polymer particles and/or add salts, for instance as described above.
• binders were each scattered on to acidic moist particulate haematite iron ore at an appropriate dosage.
• the moisture content was 8.3%.
• the blend was then converted to pellets in a balling drum, the pellets having a size typically of about 5-16mm.
• the following synthetic cationic polymeric binders were used. They were made by reverse phase polymerisation to a bead size below 200 ⁇ m and the beads were dried and separated.
• Polymer A copolymer of 40% methyl chloride quaternised dimethylaminoethyl acrylate (MeCl.q DMAEA) 60% acrylamide (ACM) IV ⁇ 7-8 dlg ⁇ 1
• Polymer E copolymer of 80% MeCl q DMAEA with 20% ACM IV ⁇ 8-9 dlg ⁇ 1
• a gel polymer of 60% acrylamide 40% sodium acrylate having intrinsic viscosity 23.9dl/g was dried and comminuted in conventional manner to a particle size of around 100 ⁇ m and is blended with an equal amount by weight of sodium carbonate particles.
• This binder was blended with iron ore giving a conventional alkaline pH, at a dosage of 0.04%.
• the spalling properties of the anionic synthetic polymer binder system at 1,000°C were excellent relative to the other systems and the other properties were satisfactory, although the moisture content was slightly higher than with the other systems.

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• 1988
  • 1988-03-21 EP EP88302455A patent/EP0288150B1/de not_active Expired - Lifetime
  • 1988-03-23 CA CA000562249A patent/CA1319016C/en not_active Expired - Lifetime
  • 1988-03-24 AU AU13705/88A patent/AU613351B2/en not_active Expired

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