CA2215409A1 - Reuse of metallurgical fines - Google Patents

Abstract

Waste material containing heavy metals are mixed with oily mill scale or with reduced iron or fines and with a fine grained carrier material having a low density until a crumbly mixed product results, of which a fine fraction of between 0 and 6 mm in grain size is sievable for injection into a metallurgical furnace. Water may be added to the mixed product using wet carbon-containing slurries. Lime-containing dusts may be added.

Description

W 096/31630 PCT/~9G/00821 R~US~ OF METALLURGICAL FINES

The invention relates to a method of use of a wide range of metal Cont~inin~ m~t~ lc which are otherwise used with ~liffi~lllty or just dumped as waste.

One suitable rnaterial is iron ore fine dust. This is difficult to dispose of. During pelletising fine ores having a grain diameter of under about 0.2 rnm are wetted and mixed with binders, e.g. bentonite, to form lu~s. The pellets are subjected to flame hardening or sintering because this is the only way in which such fines can only be used in a subsequent m~t~ lrgical process. This is similar to the l.le~ ion of fines by direct reduction. known as the names of COREX ~ MIDREX ~ or HYL~. For example in the case of the MIDREX~ process the fine ore is acted upon by reduction gases in fllli(1iced bed reactors at te~ c.~Lul~s between 500 and 800~C. The reduction gases contain H2 and CO and also CO2, H2O~ CH4 and N2 . Ple~ ion takes place in a series of fllli~liced bed reactors~ connected in series, in which the degree of reduction increases from reactor to reactor to reach values of mt-t~llic~tion of between 92 and 94% at the exit of the last fluidised bed reactor. The fines reduced in this manner are then hot briquetted in order to obtain the lump form which is necessary for the subsequent metallurgical process. Both during such sintering and during ~,lc~al~ion of the fines. ferrous dusts accumulate~ which are very fine and extremelv reactive. The CA 0221~409 1997-09-29 dusts also contain proportions of non-converted carbon. Such fines cannot be blown or injected into a metallurgical furnace because they have too high a density.

Other heavy metal cu~ ;i.;,.g dusts or slurries are produced as by-products in the m~ntlf~ctnre and processing of high quality steels. By high quality steel is meant a grade of steel which is intP.nclecl generally for heat tre~tm~nt such as hardening and te~ering. High quality steel has a higher purity than quality or basic steel (cf.
Brockhaus. NaturwissPn~.h~ften und Technik (Natural Science and Technology), special edition 1989, volume l, key word). Such steels are produced in electric arc furnaces from steel scrap and alloying conctit~l.o.nt~ The dust contained i~ the smplting gases is very finely divided and has a high specific weight more than 4 grams per cubic cPntimP.tre. The dust is separated in the electric filters installed beyond the electric furnace. It is also usual to wash out the dust from the .cmelting gases using water to produce a heavy metal co-~ g slurry. The scrap charge usually contains zinc which evaporates at the high temperatures in the mPt~llnrgical vessel and is deposited in the flue gas. These dusts (loaded with the heavy metal zinc) from dry dust extraction or slurries in the case of wet dust extraction can only be deposited at special dumps or must be subjected to expensive separation measures.

For the separation ~ ~aLiOn process of this kind of Zn-loaded dusts or slurries it is of great economic advantage if the Zn content is enriched to over ~5% e.g. 40% or more bv recycling.

W 096131630 PCT/GB~"~CQ~1 High quality steel may be treated in a rolling mill. In this case an extremely heavy rolling mill scale slurry results~ which besides the metallic components also contains ul;Lies in lump form from metal parts, orgar~ic material or plastics. Larger pieces of metaL such as screws. and cle~ning rags, cigarette ends and working gloves, yoghurt cartons and plastic bags can also be dumped by mtidy workmen in the rolling mi'il scale slurry.

All metal dusts and slurries arising during the production of basic, quality and high quality steel are finely divided (fine granulometry in the grain size range of a few microns up to 1 mm) and contain alloying metals. These alloying metals include chiefly chromillm, cobalt nickel, lead, m~nganese7 t-mg.ct~n~ ;.. , v~n~ m, zinc and molybdenu~ which are added to the individual grades of steel in differing amounts according to pre-set recipes and together with the iron, are responsible for the heaviness of the dusts and slurries. Although these dusts and slurries contain valuable sllbst~nces it has not been possible to reclaim and re-use these substances to a s~ticfactQry extent because of their inherent fineness and heaviness. In many cases the dusts c~..l~;..;..~ valuable substances are dumped but this is bad for en~ o.... ~-.l~l protection and wasteful.

~ It is one object of this invention to provide a method of recovering the valuable components of a wide variety of waste materials and introducing them in a particularly convenient way into a metallurgical vessel for re-use.

CA 0221~409 1997-09-29 W 096/31630 PCT/~b9C1'~.~21 According to the invention in one aspect there is provided a method of treating a waste f material cont~ining heavy metals. the method comprising mixing the waste material and a relatively less dense particulate material cont~ining metal oxide material and water so as to cause an exothermic reaction and thereby for_ relatively dry agglomerates;
sieving the agglomerates to isolate those having a size in the range of from about Omm to about 6mm; and pneum~ti~lly injecting the isolated agglomerates into a m~t~lhlrgical vessel Co,.l~;..i"g molten metal and under a reducing atmosphere.

The oxide material may be burnt lime or directly reduced iron. Most preferably the agglomerates are injected with carbon (which is required for other purposes in the m~t~ lrgical vessel such as a reduction reaction). The carbon may be provided from a variety of sources and may already be in the waste material.

Where fines having little or no carbon are used, a carbon-bearing carrier material may be used. Suitable materials are coke consisting of coal or lignite or brown coaL or petroleum coke because these cokes, owing to their surface structure and porosity, are particularly suitable to carry the fines on to their surface. However, finely divided or dust form fractions of coal or lignite are also suitable as carrier material, just as are finely divided lightweight fractions from the shredding of plastics. The latter have a tendency to form aggregates similar to flakes and are not injectable in this form.

One criterion for the selection of suitable carrier material is the foaming of the slag. 5 Consequently~ for injection into electric arc furnaces or cupola-type furnaces. carbon-cont~ining carrier materials which exhibit a low proportion of volatile constituents are ~ler~lled. These include lignite coke, anthracite, petrole1lm coke and coke breeze.
For injection into a blast furnace. carbon-co"l~;"illg carrier m~tP.ri~ls having volatile c~ n~titllent~ are best. The amount of volatiles in the total carbon content of the carrier materials should be greater than 8%. T i~nites as well as other low coalified types of coal, wood chippings, plastics chips, or the like can also be used.

For the promotion of the foaming of the slag, the product should have a carbon content between 20 and 40 percent by weight. The carrier materials may be selected and determined by means of pre-analysis.

For the sake of complet~-nec~, it should be est~blish~d that the mixed, reaction and combined products still exhibit amounts of Fe, FeO, Fe203 CaO and CaC03, and the residual hllmi-lity is between S and 15 percent by weight.

The illve~lioll also makes use of the reactivity of the fines. According to the degree of m~-t~ tion~ the fines react with water to form iron oxide, rele~cing heat. When mixing a slurry with the fines iron oxide forms. The heat released during the exothermic reaction causes part of the moisture to evaporate and allows the agglomerates to become crumbly.

For injection the agglomerates must have a density of about 1,2 to about 4 grams per cubic centim~tre. The delivery cross-sections of standard injection devices in the order of between l/2 (about 1 2mm) and 2 inches (about 50mm) made it necessary to sieve the CA 0221~409 1997-09-29 W 096/31630 PCT/~b~"~C-21 products to grain sizes of below about 6 mrn in diameter. Standard injection ~1 ~S~ S
are about 4 to 5 bars for electric arc furnaces and about ~ to 6 bars for blast filrn~c~5 Mixing of dry carrier material and the fines may be carried out both directly and indirectly and in any sequence of steps. For example~ fines and carrier material are first mixed together and then if applicable with water or with a moist carbon-co~ lg slurry; or carbon-cont~ining slurry and carrier material are mixed together first and then mixed with the fines. It is possible to mix fines. carrier material and carbon-cont~ining slurry at the same time.

~valuations injecting agglo",t;l~es consisting of fines, oil-col~ ;llg rolling mill scale slurry, fine coal, petroleum coke or electric furnace filter dust and quick lime or caustic lime into an electric arc furnace have revealed that finer grain fractions of the sieved combined product of below 4 mm in grain size produced a better conversion of the injection product in the molten metal than a grain fraction of under 6 mm in .~i~",~
which is attributed to the larger overall surface area of the smaller grain fraction.

The crumbly agglomerate is readily storable. As soon as it has reacted~ it becomes inert and is suitable for pneumatic conveying. It is possible to inject product into the blast furnace~ electric arc furnace~ converter or cupola-type furnace and even into rotary cement kilns~ (although in this respect it is no longer a metallurgical process in the narrower sense). In principle, it is possible to use slurry of any kind~ that is also metal-cont~ining and mineral-cont~ining slurries but in this respect it must be considered whether, when using metal-cont~ining slurries the alloy arising in the CA 022 1.?409 1997 - 09 - 29 WO 96/31630 PCTI~,.~G;~

metallurgical process still conforrns to the required recipe and whether~ when usmg mineral-co~ illillg slurries the amount of slag resulting does not have a negative effect on the profitability of the steelm~kin~ process. In the simplest case it is therefore also possible to treat the fines with coal slurry~ of the type from washing coal. However such coal slurry has only a low calorific value (because it exhibits a high L)lol~olLion of sterile rnine waste material which only increases the amount of slag of the m~t~ rgical process! but co~ ibules nothing to the foaming of the slag).

Preferably energy-rich slurries are used. such as result. from oil-cont~ining rolling m;ll scale slurry? Fuller's earth or slurries which contain lignite dust or coke dust from coal or lignite or waste m~teri~l slurries from petro~,h~,mictry. Such slurries at the same time reduce the energy required in the subsequent m~t~ rgical process~ because they provide part of the carbon requirement. Although rolling mill scale slurry in particular is regularly interspersed with foreign bodies, as is well known~ such impurities play no role in the present invention~ because the foreign bodies separate from the slurries during tre~tm~,nt of the fines and after the thorough mixing of the components are removed by sieving. This applies also to the lumps or aggregates ~vhich rnay .
occaslonally anse dunng mlxmg.

It is also suitable to use slurries which result from wet dust-extraction of ore reduction plants. The dusts from dry dust-extraction are suitable for a~lmixing to the fines insofar as they do not already themselves form these fines. Also suitable are slurries which result from the wet dust-extraction of blast furnaces~ cupola-type furnaces. electric arc CA 0221~409 1997-09-29 W 096/31630 PCT/GB~G~?-l furnaces, converters. sintering plants and surface tre~tment plants for the grin~ling/and polishing of metals. The corresponding dust from dry dust-extraction may be ~tlmixe to the fines insofar as they do not already themselves form these fines.

In a variation, the additive may include sufficient lime for the lime requirement of the furnace by the addition of substances which exhibit free quicklime, CaO. So according to the invention the amount of slurry necessary to form the reaction product is increased beyond the actual requirement and fly ash is added to the reaction product in addition. The free qllicklime of the fly ash reacts with the residual moisture of the slurry to form calcium hydroxide Ca(OH)2, by which heat is also liberated. The limestone favours the subsequent mP.t~llllrgical process and the liberated heat makes the combined product crumbly.

Preferred is fly ash from the flue gas in the electric filter behind the power station boiler when burning low sulphur fossil fuels. and this includes prim~rily lignite from the Rhine. However, that fly ash which accllmlll~tes during the tre~tmPnt of fuels according to the dry additive process is also suitable if limestone has been added to the fuel to bind the sulphur before combustion. These so-called DAP ashes are usable.

The use of dust or sand from blast furnace top gas is also possible: this accum~ tec when the gas is cleaned from the blast fumace flue. Both stiU contain the residue of non-converted carbon and limestone as well as amounts of iron and iron oxide.

During the ~ ~a~ion of heavy, metal-co"l~;";"g dusts, (and besides those already mentioned this also includes those which result during the grinding of steels), in the first step of the method, by means of mLxing with finely-divided quicklim~ or dolomite the fluidity of the slag is increased in the subsequent m~t~ rgical process. The l,le~ ion of heavy, metal-cont~ining slurries also includes~ besides those already mentioned? grinding slurries for use in the first step of the method. ~y means of the cr~ d use of finely divided fly ash the usually impenetrable slurries are dried at first and thereby made easy to handle. The amount of qllir~lim~ in the fly ash or slag from the ladle furnace assists drying since the free qnicl-lime reacts exothermally with the moisture of the slurry and a considerable part of the moisture inherent in the slurry evaporates thereby; the lime addition which is advantageous for the subsequent mt-t~llnrgical process remains unaffected.

Another waste m~t~ri~l useful in the present invention is made up of di~t;l~;llL forms of ~11"";";l-lll The addition of ~ iS known to be useful in deoxidation and in the fiuxing of slag. Certain forms of ;~ ,;";1"" can attack the lining of a m~t~ rgical vessel, and others are costly. According to this invention waste alll.,,;,,i,l,,, oxide or ;~11"",;";"", metal, e.g. oilywet grinclingc, can be inc~ e~l Such ~ l;lllll m ay also be present in the flyash Where ~1"",;.,;"", is present and the agglomerate has other suitable ingredients, e.g. a high content of iron~ the agglomerates are useful in the cement industry.

W 096131630 PCT/~r~C~21 By means of the sieving in the second stage, a ulliro~ granulation band of under 6 mm in ~ mPter is obtained. At the same time foreign bodies are retained, having been exposed in the first step by the so-called "rolling up" more particularly of the rolling mill scale slurry. These foreign bodies and larger lumps may be ground up if applicable and can be inserted into the method cycle again at a suitable point.

In the third step of the method the sieved off fine fraction co~ ;llg carbon-cont~ining dusts and lime-stone-cont~ining agglomerates is mixed thoroughly with these. This final step contributes substantially lowering the density until they become blowable or injectable under air or other gas ~leS~

In the case of the added carbon-co. ,1 ~ ;. .;. .g dusts the use of lignite coke dust, petroleum coke or anthracite or dusts from slightly or low volatile coal or l~~ s thereof is ~rcr~ d, wherein their respective grain size is below 1 mm in ~i~mPtçr. The addition of carbon is known to promote the foaming of slag in the subsequent metallurgical process. Where the waste material has an organic fraction! e.g. an oiL as in the case of metal-ca,-l;1;..;..g slurries from surface m~c~,hining, such as~ e.g. grin~ling slurries. or in the case of rolling mill scale slurries less carbon dust will be required than for slurries which do not bring with them per se this kind of organic a~l.";~ill"~s~ e.g. with slurries from the wet cleaning of gas from molten metals.

W 096/31630 PcTl~b~ Q?

The addition of carbon-co"li.;";,.~ dusts alone may not be enough to lower the density to the point where the product can be injected pne -m~ti~.~lly. Instead a carrier material in which the mixture consisting of metal-co"l~;";,.g dust~ calcium and carbon can be added may be present in order to reduce its density further. T im~stone-co..l~
agglomerates in sphere form. as they result from the ~ ion of the boiler feed water from steam power stations~ which operate with steam turbines have proved suitable for this purpose. These agglomerates are smalL light, stable spheres of an average diameter of 1 to 2 mr4 which are extremely resistant to compression and abrasion; the grain size ranges from 0.5 to 6 mm. These spheres result from the removal of calcium and iron from the boiler feed water suitable for the steam-driven turbines. In the centre of the spheres there is a tiny quartz grain on which the lime extracted from the boiler feed water and the iron in crystalline form have acc~lm~ te-l The colour of these spheres is beige, they have a smooth surface and exhibit a high co..4,les~ive strength. Normally they are disposed of on the dump.

In the case of the present invention the spheres are suitable preferably as carrier for the mix consisting of heavy metal particles, lime and carbon. Bonding to the carrier is ensured by electrostatic forces as well as the moisture from the water ~ al~Lion.
Their content of silicon~ lime and iron are helpful for the subsequent metallurgical process.

In other aspects the invention provides;

W O96/31630 PcTlGB9rl~~Q2 - a pnellm~tir~lly injectable feed material for use as an additive to the molten metal in an electric arc fur~ace, the m~trri~l comprising the reaction product of a waste particulate material co~ ;"i"g heavy metal elements and oily mill scale, the material being in the form of agglomerates having a particle size from about Omm to about 6mm;

- a pnenm~ir~lly injectable feed material for use as an additive to the molten metal in an electric arc furnace. the material comprising the reaction product of a waste particulate material co"l ~ g heavy metal elçmrnt~ and directly reduced iron fines, the feed material being in the form of agglomerates having a particle size from about Omm to about 6mm;

- either of these feed materials, and including a source of carbon in particulate form: and - either of these feed materials and in which burnt lime was present and particip~tecl in the reaction In order that the invention may be well understood it will now be discussed by way of çx~mple only and with reference to the accompanving dia~rammatic drawings in which:

W 096/31630 PCT/GB9''~ Y?-Figure 1 shows sch~m~tic~lly one process of the invention. and sl Figure 2 is graphs showing exotherrnic reactions.

As shown in Figure 1, a high quality steel slab 2 is rolled into a sheet 3 at a rolling mill.
Water S under ~es~ is added to the rolling process via a nozle 4. The rolling mill scale 6 is collected as rolling mill scale slurry 7 in a trough 8 undemeath the rolling rnill stand 1.

Separately coal 10 is burned in a power station boiler 9. The hot flue gas 11 arising is passed over heat exeh~nger surfaces 12 in which boiler feed water 13 circulates and which is converted into steam 14 on the heat çxch~nger surface 12. The flue gas 11 leaves the boiler via an electric filter 33, where the finely divided fly ash 15 which is carried along and separated from the flue gas before it can be dischalged through the chimney 16 into the atmosphere.

The rolling mill scale slurry 7 and separated fly ash 15 are fed to a first rnixer 17~
wherein the rolling mill scale slurry 7 and the fly ash 15 are intim~tçly mixed. During mixing with the fly ash 15 the moist rolling mill scale slurry 7 dries out to form an agglomerate product having a crumbly con~ictl~nCy. The reaction is exotherrnic and the water evaporates. The first mix 1~ leaving the mixer 17 has a temperature above ~mhiçnt and passed through a sieve 19. where a fine fraction ~0 is sieved off. The CA 0221~409 1997-09-29 W O96/31630 PCT/~ r-~~~21 oversize 21 from the sieve 19 contains the foreign bodies and i"~ iLies present previously in the rolling mill scale slurry 7; these are discarded. The fine fraction 20 having a grain size range of under 1 mm flows to a second mixer 22 where it is mixed with lignite coke dust 23 and lime-c~"l;.;"i"g spherical agglomerates whose average grain size is between O.S and 2 mm.

The spheres 24 have been derived from a filter 25 where the boiler feed water 13 of the power station boiler 9 is prepared for passage to the turbines. After the water vapour 14 has been stress relieved in the steam turbine 34, it flows through a condenser 26, where it condenses again to form boiler feed water 13. The con-l~n~ed boiler feed water 13 is forced by feed water pump through a filter 25. Quartz grains 28 are added to the filter 25, where the lime contained in the boiler feed water 13 and the iron acc~lml-l~te in order to form the spheres 24. Losses of boiler feed water 13 are compensated for by fresh water introduced via the pipe 29.

The agglomerated product 30, consisting of finely divided metals, lime and carbon~
which leaves the second mixer 22 has a dry, powder-like con~ict~ncy with grain sizes between 1 and 6 mm and average specific weight of 2g/cm3 and is injected by blower 32 into a blast furnace 33.

In an evaluation to confirrn that direct reduced iron could be used~ differing amounts of water were added one after the other to a quantity of 1 kg. of ultra-fine sponge iron and then stirred. The reaction of the iron oxide with the water was measured by the temperature increase observed in the process. The measured values are recorded in the Tables I to III and illustrated in the corresponding graphs of Figure 2.

Initial Material: 1 kg ultra-fine sponge iron in a beaker at 20~C.

Addition of 5 per cent by weight of water corresponding to 50 grams.

Time (minutes) Tempe.~lure (~C) ~ 20 The results are also shown in Figure 1 from which it can be seen that the temperature rises by 4~C in the course of 6 mimltes and remains constant therea~er.

II Another 50 grams of water is added to the mix from I and both are stirred by hand for 4 minlltes Time (Minutes) Temperature (~C) 0 ~5 ~ 2 26 W 096/31630 PCT/~b-''O~Q21 6 27.5 lg 32 The results are also shown in the graph. The temperature rises by another 7~C
in the course of 16 misllltes and ~ S constant thereafter.

III Another 50 gra_s of water is added to the mix from ~1 and both stirred by hand for 3 minlltes. The temperature was measured.

Time (Minutes) TemPerature (~C) 2 32.5 6 33.5 2 34.5 35.5 22 35.5 24 35.5 Results are also shown in the graph. The temperature rises slowly by a further 3.5~C in the course of 18 minlltes and remains constant thereafter.

As can be seen therefrom, the most violent reaction starts in mixing phase II and fades gradually in mixing phase III.

Claims (22)

1. A method of treating a waste material containing heavy metal metals, the method comprising mixing the waste material and a relatively less dense particulate material containing oxide metal and water so as to cause an exothermic reaction and thereby form relatively dry agglomerates; sieving the agglomerates to isolate those having a size in the range of from about 0 mm to about 6mm; and pneumatically injecting the isolated agglomerates into a metallurgical vessel containing molten metal and under a reducing atmosphere.

2. A method according to Claim 1, wherein the oxide material is burnt lime.

3. A method according to Claim 1, wherein the oxide material is directly reduced iron.

4. A method according to Claim 1, 2 or 3, wherein the waste material is a dust obtained from an electric arc furnace.

5. A method according to any of Claims 1, 2 or 3, wherein a source of aluminium is present.

6. A method for preparing fines for use in a subsequent metallurgical process, the fines being from at least partly reduced iron ore in dust form, comprising mixing the fines with a fine-grained carrier material having a low density to produce crumbly product results and sieving the product to provide material between 0 and 6 mm grain size suitable for injection in the metallurgical process.

7. A method according to Claim 6, wherein the carrier material used is a carbon-containing material.

8. A method according to Claim 6 or 7, wherein sufficient water is added to improve the adhesion between the fines and the carrier material.

9. A method according to Claim 6, 7 or 8, wherein by adding a slurry of water and carbon to the mixed product and mixing thoroughly.

10. A method according to Claim 9, wherein an excess of slurry is used together with a substance in dust form to finely divided form, containing free quick lime.

11. A method according to Claim 9 or 10, wherein the slurry is an oil-containing rolling mill scale slurry or one from the machining of steel or metals suitable for alloying steel by means of oil-containing cutting fluids.

12. A method according to Claim 9. wherein the slurry is from treating blast furnace gas with water.

13. A method according to Claim 10, wherein the slurry contains fly ash from the combustion of fossil fuels which contain calcium.

14. A method according to Claim 13, wherein the slurry contains fly ash which result from the cleaning of flue gases by means of limestone or calcium hydroxide at a power station boiler.

15. A method according to Claim 14, wherein the slurry contains blast furnace flue dust.

16. A method according to one of Claims 9 to 15, wherein an injectable fine fraction is sieved off from the reaction or combined product and an oversize comminuted for reprocessing.

17. A pneumatically injectable feed material for use as an additive to the molten metal in an electric arc furnace, the material comprising the reaction product of a waste particulate material containing heavy metal elements and oily mill scale, the material being in the form of agglomerates having a particle size from about 0mm to about 6mm.

18. A pneumatic injectable feed material for use as an additive to the molten metal in an electric arc furnace, the material comprising the reaction product of a waste particulate material containing heavy metal elements and directly reduced iron fines. the feed material being in the form of agglomerates having a particle size from about 0mm to about 6mm.

19. A feed material according to Claim 17 or 18, including a source of carbon in particulate form.

20. A feed material according to Claim 19, wherein the content of carbon source is sufficient to reduce the content of iron oxide in the feed material.

21. A feed material according to any of Claims 17 to 20, wherein burnt limes was present and participated in the reaction.

22. A feed material according to any of Claim 17 to 21, also containing aluminium