AU678516B2 - Process for making steel and hydraulically active binders - Google Patents

Abstract

The process for making steel and hydraulically active binders uses slags rich in iron oxide, such as steel slag, as oxidizing agent for carbon in pig iron. The slag is reduced, yielding a type of blast furnace slag with improved hydraulic properties.

Description

OPI DATE 27/03/95 APPLN. ID 74527/94 AOJP DATE 18/05/95 PCT NUMBER PCT/AT94/00122 1III l1111iii 1111111111111 I11I11II II111 AU9474527 (51) Internationale Patentklasifikation 6 C21C 5136, C21B 3/06, C04B 5106, 71147 (11) Internationale Ver~5ffentlichungsnumnmer: WO 95/07365 Al (43) Internationales Vertiffentlicbungsdatum: 16, Malrz 1995 (16.03.95) (21) Internationales Aktenzeicben: PCT/AT94/00 122 (22) Internationales Anmeldedatum: 24. August 1994 (24.08,94) Prioritlltsdaten: A 1802/'93 A 1309/ 9 4 (81) Bestimmnungsstaaten: AU, BR, CA, CN, CZ HU, KR, N, RU, SK US, VN, eutropiiisches Patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE).

Verdffentlicht Mir inteemtionalem Rech.-rchenberidu.

Ifl: 7. September 1993 (07.09.93) 1. lull 1994 (01.07.94) (71) Ananelder Tair alle Bestimmungssraaren ausser US): 'HOLDERBANK" FINANCIERE GLARUS AG [CH/CH]; Hauptstrasse 44, CH-8750 Glarus (72) Erfinder; und Erfinder/Anmelder (nur fir US): EDLINGER, Alfred [AT/CR]; Chilemattweg 31, CH-5400 Baden (CH).

(74) Anwalt: HAFFNER, Thomas, Schottengasse 3a, A-1014 )Wien (AT).

(54) Title: PROCESS FOR MAKING STEEL AND HYDRAULICALLY ACTIVE BINDERS (54) Bezeichnung: VERFAHREN ZUM HERSTELLEN VON STAHL UND HYDRAULISCH AKT1YEN BJNDEMITIT7ELN (57) Abstract The process for making steel and hydraulically active binders uses slags rich in iron oxide, such as steel slag, as oxidizing agent for carbon in pig iron. The slag is reduced, yielding a type of blast furnace slag with improved hydraulic properties.

(57) Zusammenfassung Das Verfahren zum Herstellen von Stahl und hydraulisch aktiven Bindemittein verwendet eisenoxidreiche Schlacken wie z.B.

StabIschlacke als Oxidationsmittel fdr Kohlenstoff in Roheisen. Die Schiacke wird reduziert und es entsteht eine Art Hochofenschiacke mit verbesserten hydraulischen Eigenschaften.

1 Process for producing steel and hydraulically active binders The invention relates to a process for producing steel and hydraulically active binders, such as, blast furnace slag, clinker and the like.

When producing steel., steel slag is formed, which has a relatively high iron oxide content due to the refining process involved. Conventional steel slag contains MnO and FeO in amounts up to 33 by weight.

While blast furnace slag is remarkable by its favorable hydraulic properties and by a substantial2y lower iron oxide content, thus being more readily apt for utilization as a basic construction material, the disposal of slags from steelworks has become increasi'gly difficult, since steelworks slag in the incurring composition, without any metallurgical aftertreatment, cannot be readily used for construction purposes or the like. It has already been proposed to granulate steelworks slags along with blast furnace slags and use them as bottoming material in road construction. However, the relatively high CaO content of steelworks slag allows for the use of only limited amounts of steelworks slag also in that case.

In order to obtain a product of higher quality, the metallurgical processing of steelworks slag, as a rule, involves high energy consumption and, therefore, is not really economical.

Yet, slags having relatively high contents of iron oxide also incur in other metallurgical processes or combustion processes. In particular, it is known that Cu converter slags frequently have iron oxide contents of above 50 by weight, and slags from waste and garbage combustion plants that are characterized by relatively high iron oxide contents are also known.

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2 The invention aims at further processing steelworks slags and slags having relatively high iron oxide contents of the initially defined kind directly in a steelworks and to convert the same into more readily usable end products, namely hydraulically active binders. In order to solve this problem, the process according to the invention consists in that pig iron is refined by adding slags containing iron oxides in amounts exceeding 5 by weight, such as, steel slags, Cu converter slags after reaction with a lead bath or oxidized slags from waste combustion plants. In this process, the high iron oxide content of the liquid slags, such as, e.g.,of the steel slag, thus is utilized to refine molten pig iron having relatively high carbon and silicon contents. In doing so, iron oxide basically reacts with carbon or iron carbide to form iror and carbon monoxide, whereas the iron oxide of the slag reacts with the silicon of the pig iron bath to form iron and SiO2. These reactions partially are exothermic so as to provide for a high degree of economy. Due to the iron oxide content in the steel slag being reduced, an analysis deviating from the original slag analysis is obtained, resulting in substantially more favorable hydraulic properties. The iron oxide content is utilized to oxidize the pig iron bath, and, for iiistance, in the case of steel slags reduction of the iron oxide content to below one third of the original value may be achieved, the volume portions of the other components of the original steel slag thus increasing in respect of their portions in the overall slag. Hence results a new slag analysis no longer corresponding to the original steel slag analysis. The new slag analysis is characterized by a substantially more favorable hydraulic module and a relatively high content of alite. Even though the thus obtained slag end product, which may be denoted as cement clinker, does not conform to standardized Portland cement clinker, a highestquality alite cement clinker is obtained which is suitable as an extremely favorable base for mixing with other hydraulic or latent hydraulic substances. The cement clinker to be obtained 3 in this manner is suitable, in particular, for mixing with puzzolanes, wherein a particularly high 28-day strength could be attained.

Analogous considerations as have been made in respect of steel slag also apply to Cu converter slag and other slags, wherein, in case of Cu converter slags, care has, of course, to be taken that copper will not get into the steel bath, being detrimental to steel. Consequently, copper must at first be separated above a lead bath, the copper being eliminated from the slag prior to the iron bath. The lead itself subsequently is reduced in an iron bath reaction, wherein iron and lead can be drawn off separately in a simple manner, beause iron and lead together do not enter into solution. Below the iron or steel bath a sea of lead is formed, steel and lead being capable of being drawn off separately in such cases.

Due to the possibility, beside the simultaneous recovery or recuperation of metal fractions, of converting the remaining slag into a superior product to be reused, a substantial economic advantage is achieved, slags being disposable for which no suitable application has existed so far. In order to enable the desired oxidation of the carbon content within the pig iron bath and hence the refining to steel, it is advantageously proceeded in a manner that the iron oxide content of the slag is chosen to exceed 8 by weight, preferably 10 by weight.

For the initially mentioned basic reactions as they occur in the pig iron bath, the observance of relatively high temperatures is essential. Despite the at least partially exothermic reactions, the temperature required may drop on account of thermal losses, the lost heat being reintroducible via bath electrodes in a particularly simple manner. Due to its chemical composition, the molten bath may be used as an electric resistance in a particularly simple manner, the pig iron bath being usable as the counter electrode. In order to 4 be able to carry out the process according to the invention in a particularly economic manner and, above all, to terminate the desired reactions within acceptable periods of time, it is required in any case to use the liquid steel slag at temperatures of above 1550 0 C, in particular 1600'C, and molten pig iron at temperatures ranging from 1450 to 1550 0 C, wherein it is advantageously proceeded in a manner that the liquid phases together are maintained at temperatures of above 1550C, in particular 1660 0 C to 1800 0 C, for 3 to 8 hours, in particular about 6 hours. The upper limit of 1800 0 C is chosen in consideration of the upper limit of the stability of alite.

The pig iron used as a reducing agent must be overheated to at least 1350 0 C in order to render the formation of alite feasible at all. According to a preferred process control it is provided to use the liquid steel slag at temperatures exceeding 1550 0 C in order to ensure the optimum phase formation for any further use of the slag.

Due to the reduction of the iron bath, the iron oxide content of the slag, for instance, is lowered to about 5 by weight, the process advantageously being conducted in a manner that the slag is converted into a sinter phase consisting of 15 to by weight of nolten phase (aluminates, ferrites) and clinker phase (minerals, alite, belite).

The required overheating, which partially results from the exothermic reactions of the slag with the pig iron bath, may be effected by external heating, advantageously by proceeding in a manner that an electrically heatable tilting converter is employed as the mixing vessel. Another way of ensuring the appropriate temperature in addition to a relatively high iron oxide content in the slag consists in maintaining the slag at overheating temperature by blowing in or up oxygen. In particular, if the slag is to be maintained at overheating temperature by blowing up oxygen, it is advantageously proceeded in a manner that the slag bath height for the reaction with pig iron is chosen to be between 2 and 8 cm, 5 preferably 2 to 6 cm, whereby it is ensured that merely the slag, but not the iron bath located therebelow is refined by means of oxygen.

The sinter phase floats on the iron bath, reduced iron droplets sedimenting into the iron bath from the slag or sinter phase. Since there is a high resistance to sedimentation in the sinter phase, it is again advantageous, as already pointed out above, to limit the thickness of the slag or sinter phase to 2 to 6 cm, metallic iron being removable from the slag almost completely at residence times ranging between 3 and 8 hours.

Another way of adjusting the desired slag parameters consists in that basic poor ores are added to the slags in order to increase their iron oxide contents to above 8 by weight.

Preferably, also CaC03, A1 2 0 3 and/or Si02 are used as additives. In particular, when using such further additives, the waste heat from the process, both the sensible and the chemical heat, may be applied for preheating these substances.

In addition to recovering copper by means of the lead bath, it is, of course, also feasible to recover zinc advantageously by proceeding in a manner that, when using Cu converter slags, lead is drawn off below the steel bath and Zn is condensed from the gas phase.

To supplement the lost heat, it is advantageously proceeded in a manner that an electrically heatable tilting converter is used as a mixing vessel.

The iron oxide content of the slag is reduced as a function of the volume ratio of slag to pig iron, wherein, naturally, only balance reactions are brought about such that the complete reaction of the iron oxide content is not readily feasible. A particularly economic and efficient mode of operation results 6 if molten pig iron is added to the liquid slag phase in amounts by weight ranging from 1 to 2 to 1 to 3.

The sintered cement clinker can be processed further according to conventional technology. Advantageously, the reduced slag is supplied to a clinker coo.ing and granulating means, the clinker being cooled by air according to the direct method in a particularly simple manner.

Also the refined molten pig iron already largely conforming to a steel composition subsequently may be further processed according to known steel aftertreatment procedures.

In the following, the invention will be explained in more detail by way of exemplary embodiments.

Example i: parts by weight of molten pig iron were added to a portion of steel slag, the two phases together having been maintained at 1660 0 C for 6 hours. During the reaction, 35 g carbon monoxide, corresponding to 28 standard liters, formed per kg steel slag melt. The steel slag had the following analysis: SiO 2 8 A1 2 0 3 7 CaO MgO MnO FeC 30.5 TiO2 1 The pig iron had the following analysis: Si 4 C Fe 91

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7 After six hours of reaction, the slag analysis and the steel analysis had changed in the following manner: Slag analysis SiO 2 13 A1 2 0 3 8.9 CaO MgO 6.4 MnO FeO 10.5 TiO 2 1.3 Steel analysis Si 0 C 2 Fe 97 When assessing the slag, which was used as a cement clinker, a conventional cement-technological assessment was made, yielding the following values. For comparison, the Table below also indicates the typical ranges for Portland clinker.

Criterion Value Typical Range (Portland clinker) Hydraulic module 1.85 1.7 2.3 Silicate module 0.67 1.8 3.2 Silicic acid module 1.46 2.5 Alumina module 0.85 1,5 Lime standard 1,12 0.8 0.95 Alite content (C3S) 70.7 In total, a highest-quality alite cement clinker was obtained.

The 28-day strength according to DIN 1164 was 62 N/mm 2 which may be classified as extremely high. However, this is no standard Portland cement clinker, yet continued reduction of the iron oxide and slight addition of additives, such as, for instance, clays, for increasing the Si0 2 and A1203 contents are -LL I~ I 8 feasible if Portland cement clinker according to standards is desired.

Example 2: To react the steel slag already indicated in Example 1 to a target slag which might be denoted as blast furnace slag having the following composition: TarQet Slag SiO 2 36.5 A1 2 0 3 CaO 48 MgO MnO FeO 0 TiO 2 the original steel slag is reduced to the target slag. 733 g pig iron are required per kg steel slag with 950 g steel being formed and 60 g CO, or 48 standard liter CO, being released.

In addition, 225 g quartz sand were admixed to produce the above-mentioned target slag. The pig iron and steel compositions are indicated in the Table below: Pig Iron Steel Si 4 0 C 5 Fe 91 98 The melting temperature was approximately 1600°C, a redox time of approximately 4.5 hours having been observed. The blast furnace slag formed is excellently usable as a hydraulically active binder. The relevant characteristic data have been determined to be as follows: Hydraulic index (wedge) 92 (very good) Puzzolanity (ASTM C 618) 118 (excellent) y 9 Example 3: Using Cu slag from a converter, a starting slag having the following chemical analysis was used: Main component SiO2 A1203 Fe203 CaO MgO Portion Secondary component Portion 28 S03 6 K20 0.13 53 Na20 0.64 8 Ti02 0.36 2 Cr203 1.4 Mn203 0.35 P205 0.27 C1 F 1 Nonferrous Metal Portion (ppm) 11'000 6'800 3'760 Due to the high copper content of the slag, copper was removed from the slag prior to the iron bath by previously arranging a lead bath. As a result, lead was reduced, wherein iron and lead together do not enter into solution such that a lead sea formed below the iron or steel bath. Steel and lead could be drawn off separately.

The relatively high portion of zinc in the slag was reduced above the iron bath and condensed in the vapor phase.

The remaining heavy metal concentration was within the range of cement clinker raw material. After reduction of the slag by aid of the carbon dissolved in the iron bath, the following slag analysis was obtained: 10 Component Portion Si02 A1203 13 Fe203 Ca0 17 MgO 4 The slag was cooled in the water bath and exhj'.I,:f excellent puzzolanic properties. Simultaneously with the wecovery of the metal fraction zinc from the gas phase by in. sation and with the recovery of copper as well as recovery of the lead bath, a hydraulically active material was obtained, which exhibited a high final strength, a low hydration heat and a high chemical resistance on grounds of its favorable puzzolanic properties.

Example 4: Copper was extracted from liquid oxidized waste slag by means of the redox reaction described in Example 3 at a period of reaction of 3.5 hours and a melting temperature of 1500 0

C.

The starting slag had the following analysis: Component .Portion Nonferrous Metals Portion SiO2 42 Cu 1.2 A1203 8 Pb 0.25 Fe203 28 Zn 0.3 CaO 11 Sn 0.1 MgO 2 Ni 0.1 1 3 Ti02 1 P205 0.1 WUII~LIMI~.~---a~ 3BPllj~L~q/ld~ P 11 At a copper activity in the lead bath of 30 to 40 and a slag layer height of 3.5 cm, the equilibrium concentration of copper in the slag amounted to 200 ppm.

From the decoppered liquid slag, the remaining heavy metals lead, zinc, tin, nickel and iron were subsequently reduced and separated.

Separation of the two metal phases iron/lead assured the recovery of hiqh-grade pig iron practically free of copper and having the following analytical data: Nonferrous Metal Portion Ni 0.34 Sn 0,13 Cu 0.07 Cooling, granulating and grinding of the liquid slag enriched with heavy metals yielded the slag product "puzzolane" having the following analysis: (om e-%on an Prnrt-in (%1 Si0 2 A1203 Fe203 CaO MgO TiO2 P205 59 12 16 0.2 On account of the relatively high A1203 content, the puzzolane cement has a high early strength. Its wedge index is about 95 I o-arr, 12 On the whole, optimized blast furnace slags may be produced by the addition of Si02 and, if required, A1203 carriers, such as clays, quartz sand and bauxite, the melt viscosity being considerably lowered at the same time. When reducing such melts, steel droplets are more easily eliminated by sedimentation such that the free iron content in the hydraulic binder can be substantially lowered.

The process according to the invention may be realized in a steelworks in a simple manner. On the assumption of about of slag incurring per hour, a converter having an activ weight of about 125 t, or an active volume of 35 m 3 would have to be employed in order to be able to mix 90 t, or aout m 3 of steel slag each with approximately 34 t (approximately 5 m 3 of pig iron. The clinker pbase is drawn off separately from steel and is tapped into a mixing vessel to be completed there. In that mixing vessel, processing to Portland cement clinker may be effected, for instance, by the addition of additives, such as, for instance, clays, and further reduction. Yet, such a mixing vessel, in the first pl&ce, also may serve to balance out slag fluctuations.

The clinker cooling and granulating means may be cooled by air in the direct method. In such cases, air at temperatures of 20 0 C is heated to about 1100 0 C, the clinker being cooled from approximately 1600 0 C to 250 0

C.

The amount of CO formed constitutes a further source of energy. CO incurs at temperatures of about 1600'C, thus also containing sensible heat in addition to the latent chemical thermal ener-Ty. If a thermal loss of 30 at the most is taken into account with a suitably well insulated metallurgical vessel, this means that the process according to the invention might be operated exothermally for the production of steel and clinker, provided the combustible gases formed could be utilized t, the optimum degree.

13 The process according to the invention renders feasible in a particularly simple manner the conversion of a hardly reusable steel slag to ore cement clinker under simultaneous refining.

The process according to the invention, furthermore, enables the utilization of heat amounts not readily applicable in conventional processes and, in this way, also the decrease of emissions of gases, in particular, C02.

Within the scope of the process according to the invention, the decisive reactions each occur on the interfaces of the melts, the process being realizable in a sintering furnace.

The carbon monoxide evoluting from the interface reduces dissolved iron oxide in the slag bath layer, the C02 portion of the reducing gas in the slag layer naturally increasing.

From a volume portion of about 15 by vol. of C02, the gas looses its reducing effect, wherein, however, further energetic use remains possible at least partially, since such gases may be burnt by ventilation or oxygen or air-oxygen mixtures above the slag layer. Heat transfer to the slag and iron phases in that case occurs practically exclusively through radiation procedures.

As already mentioned, the waste heat developing may be used for preheating additives, the sinter phase floating on the surface being withdrawable separately. The temperature control according to the invention is adjusted to the stability range of alite, from which the initially demanded overheating results. The alite sinter formed may be frozen to alite clinker by conventional clinker cooling technique, the main target in that context having to be the minimization of the content of free lime.

Optionally desired introduction of carbon for controlling the melting temperature of pig iron and the reduction potential may be effected by saturation with carbon in the bath, for instance, by means of immersed lances or the like. Carbon introduction may be effected on several points in counterflow 14 or in co-current flow. In doing so, the iron bath not only functions as a reductant carrier, but also acts as a conveying medium for the slag and sinter phases, particularly simple furnace constructions being applicable.

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Claims (20)

1. A process for producing steel and hydraulically active binders from slag, characterized in that pig iron is refined by adding slags containing at least 5% by weight iron oxide.

2. A process according to claim 1, wherein the slags comprise steel slags, copper converter slags after reaction with a lead bath, oxidised slags from waste combustion plants, or combinations thereof. 10 3. A process according to claim 1 or claim 2, characterized in that the iron oxide content of the slag is e greater than 8% by weight.

4. A process according to claim 3, characterized in that the iron oxide content of the slag is greater than by weight.

5. A process according to any one of claims 1 to 4, characterized in that the slag comprises a liquid slag at temperatures of above 1550"C, and the pig iron is added to the process in molten form at temperatures ranging from 20 1450 0 C to 1550 0 C.

6. A process according to claim 5, characterized in that the liquid slag is at' a temperature of above 1600 0 C.

7. A process according to claim 5 or claim 6, characterized in that molten pig iron is added to the liquid slag phase in amounts by weight ranging from 1:2 to 1:3.

8. A process according to any one of claims 5 to 7 characterized in that the liquid phases together are I- staffuanlkoepf74627.94 19.3.97 i 16 maintained at temperatures of above 1550 0 C for 3 to 8 hours.

9. A process according to claim 8, characterized in that the liquid phases together are maintained at temperatures of between 1660 0 C and 1800 0 C. A process according to claim 9, characterized in that the liquid phases are maintained at temperatures of between 1660 0 C and 1800 0 C for about 6 hours.

11. A process according to any one of claims 1 to characterized in that the slag added to the pig iron o comprises a copper converter slag, lead is drawn off below e the steel bath and zinc is condensed from the gas phase.

12. A process according to one of claims 1 to 11, characterized in that an electrically heatable tilting converter is employed as the mixing vessel.

13. A process according to any one of claims 1 to 12, :0 characterized in that the slags are maintained at overheating temperature by blowing in or up oxygen.

14. A process according to any one of clams 1 to 13, 20 characterized in that basic poor ores are added to the slags to increase their iron oxide contents to above 8 by weight. A process according to any one of claims 1 to 14, characterized in that the slag bath height for the reaction with pig iron is chosen to be between 2 and 8 cm.

16. A process according to claim 15, characterized in that the slag bath for the reaction with pig iron is between 2 and 6 cm in height. staWuan*keep/74527.94 19.397 17

17. A process according to any one of claims 1 to 17, characterized in that CaCO 3 A1 2 03, and/or SiO 2 are used as additives.

18. A process according to any one of claims 1 to 17, characterized in that the slag is converted into a sinter phase consisting of 15 to 25% by weight of molten phase (aluminates, ferrites) and clinker phase (minerals, alite, belite).

19. A process according to claim 18, characterized in that the sinter phase is supplied to a clinker cooling and granulating means. C

20. A process according to claim 18, characterized in i: that a reduced slag product of the pig iron refining process is supplied to a clinker cooling and granulating 15 means.

21. A process according to claim 19 or claim characterized in that the clinker is cooled by air in the direct method.

22. A process for producing steel and hydraulically 20 active binders from slag substantially as herein described with reference to the examples. DATED THIS 19TH DAY OF MARCH 1997. "HOLDERBANK" FINANCIERE GLARUS AG By its Patent Attorneys: GRIFFITH HACK Fellows Institute of Patent Attorneys of Australia tafWuan/keep/74527.94 19.3.97 s I a Abstract: Process for producing steel and hydraulically active binders The process for producing steel and hydraulically active binders uses iron-oxide-rich slags, such as,e.g., steel slags as oxidants for carbon in pig iron. The slag is reduced, thus forming kind of a blast furnace slag having improved hydraulic properties. INTERNATIONAL SEARCHI REPORT Inter. on/l Application No PCT/AT 94/00122 A. CLASSIFICATION OF SUBJECT MATTER IPC 6 C21C5/36 C21B3/06 C04B5/06 C0487/147 According to International Patent Classification (IPC) or toboth natonal classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) IPC 6 C21C C21B C04B Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted durng the intemaUtnal search (name of data base and, where practical, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category' Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. A STAHL UND EISEN., vol.104, no.16, 13 August 1984, DUSSELDORF DE pages 774 778 PIRET ET AL. 'Verwertung von LD-Schlacke zur Erzeugung von Portlandzementklinker und Roheisen' A LU,A,71 715 (CENTRE DE RECHERCHE METALLURGIQUES) 31 December 1976 A DE,A,26 11 889 (FINK) 22 September 1977 A US,A,4 102 675 (MIYASHITA ET AL.) 25 July 1978 A US,A,4 009 024 (MILLER) 22 February 1977 Further documents are listed in the continuation of box C. Patent family members arc li.ted in annex. *Special categories of cited documents: -T later document published after the international filing date or' iority date and not m conflict with the s.iplicaton but document defining the general state of the art which is not .te to understand the pcrinple or theory uneriying ute considered to be of particular relevance invention earlier document but published on or after the international "X document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step when the document is taken alone which is cited to establish the publication date of another "Y document of particular relevance; the claimed invention citation or other special r-on (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report 28 October 1994 1 -il. Name and mailing address of the ISA Authonzed officer European Patent Office, P.B. 5818 Patentlaan 2 NL 2280 H V oiiwijk Tel. (+31-70) 34 Tx 31 651 epon, Oberwalleney, R Fac (+31-70)

340-3i)16 Form PCT/ISA/210 (second shtet) (July 199% page 1 of 2 INTERNATIONAL SEAR~CH REIPORT niAlcao N PCT/AT 94/0122 C.(Continuation) DOCUMENTS CONSIDERED TO BE RELEVANT Category 'Citation of document, with indication, where approPriate, of the relevant passages Relevant to chaum. No. A GB,A,2 199 025 (DIDIER) 29 June 1988 PorM PCTISA1210 (continuation of tftnd cheat) (July 1992) page 2 of 2 INTERNATIONAL SEARCH REPORT N *ntonutc~non atrn (mtimcrbrr PT/AT 94/00122 Patent document Publication Patent family I Publiczan cited in search report date member(s) Idate LU-A-71715 31-12-76 BE-A- 837459 03-05-76 DE-A-26 11889 22-09-77 NONE US-A-4102675 25-07-78 JP-A- 51121030 22-10-76 JP-B- 55023781 25-06-80 CA-A- 1075471 15-04-80 DE-A- 2616784 28-10-76 FR-A,B 2307875 12-11-76 US-A-4009024 22-02-77 NONE GB-A-2199025 29-06-88 OE-A- 3644518 14-07-88 FR-A- 2609019 01-07-88 F~orm PCf/ISA/210 (patent family annex) (July 1992) I NTIRNAri ONA hJ3R RECHERCHEU1RI CU-T IlntirolooI~ Akknuelvhe PCT/AT 94/00122 A. KLASSW[IZIERUNG DES ANMELDUNGSGEGENSTANDES IPK 6 C2lC5/36 C21B3/06 C04B5/06 C04B7/147 Nach der Intcrnaflonalen Patentklamsfikaton (IPIC) oder nach dcr nationalen Klassifikation und der IPK B. RECHERCH-IERTE GEBIETE Recherchiener Mindestprfifstoff (Klamikationstcm und Klam',ieatiorisymbole) IPK 6 C21C C21B C04B Recherrhierte aber nicht zum Mindesipsifitoff geh6rende Verofentlichungen, soweit thesc unter die recherchuerten Gebiete fallen W~lbrend der intemaanonalen Recherche konsulierte clektronische Datenbank (Name der Datenbank und cyti. verwendlete Suchbegiffe) C. ALS WESENTLICH ANGESEHENE UNTERLAGEN K.Ategonec Bezechnung der Ver~ffentlichung, soweit erforderlich unter Angabe der in Ectracht koinmenden Tile Mr.i Antpruch Nr. A STAHL UND EISEN., Bd.104, Nr.16, 13. August 1984, DUSSELDORF DE Seiten 774 778 PIRET ET AL. 'Verwertung von L-Schiacke zur Erzeugung von Portlandzementklinker und Roheisen' A LU,A,71 715 (CENTRE DE RECHERCHE METALLURGIQUES) 31. Dezember 1976 A DE,A,26 11 889 (FINK) 22. September 1977 A US,A,4 102 675 (MIYASHITA ET AL.) 25. Juli 1978 A US,A,4 009 024 (MILLER) 22. Februar 1977 MY Weitce ~Verdffentlchungen sind der Fortsetung von Feld C zu r7 Siehe Anhang Patentifamii *Besondeme Kategoricn von angegebenen Ver6ffentlichtngen 'T Sptre Ver~tentiehung, die nach dern intrnationalen Anineldedau A' Vr~fentichng, ie en llp eine Stmd er echnk drincM 91oder e Priontclaatumn ver~ffentlicht worden ist und it der ab erffnichungs ie dens bctallm Srnd dcer Thi k ein Anmeldung nicht kollidlert, sondern nur zuinVertindnis des der abernjct al beondes bdeutam nz hn ~Erfindung zugrundellegenden Prinzips otter der ibr zugrsmdel1egcndc7 Altercs Dokcument, clas jedoch at am oder nach demn internationalen Theonec angegeben it Anincldedatum veroffentfieht worden ist W Verdfentliehung von besonderer BEdeutxmg; die beanspruchte Erfindun W Ver~ffentlichung, die gecsgnet ist, cinen Priorititsanspruch zweifclhaft er- kann allein aufgnind dicier Vcr6ffentlichung nicht als neu oder auf seheincn zu lassam, oder durch die dlas Verdflentlichungadatum ciner erfindenscher Titigkceit beruhatti betrachtet werden anderen urn Rechcrchenbencht genannten Ver~fentlichung becgt werden 'Y Verdffentlichung Yon besonderer Bedeutaang die ram~pruchte: Erfindun soll oder die axis cinem andere besonderen Grund angegeben it (Wi kann nieht ala auf erfinilerischer Titigkrt banzeid betraclflet geruhlrt) werdien, wenn die Verdfentlichung nut ciner oder mebrern anderen Ver~ffentlichung, die sich aur dine mflndihe Offenbarwig, Verdifentlichungen dWcser Kategonec in Verbindimggebracht wird und cine Benutzimg, cine Ausstellung oder andere Maflnahimen bezieht diese Verbindlung ftir cinen Fadsmann naheliegend it Verdifentlichung, die vor dern snntationalen Anincidedlatum, aber naeh e etihndeMtlc eile aeeaif s demn beanspructiten PriciritAtsdatumn verbfecnthcht warden istW rfenhugdeMticdrslnPanfmicit Datum des Abschiusses der inteinationalen Recherche Absendledaturn des meternationalen Recherchenbesebta 28. Oktober 1994 11. T J Name und Postanschrift der Internationale Recherchenbehnrde Bevollrnichtigter Bedienateter Europiisches Patentamet, P.B. 5818 Patentlaan 2 NL 2280 I-V Rijswijk Tel. (+31.70) 340-2040, Tx. 31 651 epo nlbrwl1eny, Faxc (±31.70) 340-3016 b ra lny R Fonnblatt PCI'/ISA/310 (Baut 2) (Jull 1992) Seite 1 von 2 NTJ3RNATIONALEJR 1JG lGJN)3~ICI Inter. .,nAla Aktaxeicben IPCT/AT 94/00122 C.(Fortsetztmg) ALS WESENTLICH ANGESEHENE UNTERLAGEN Kategonc' Bezeichnung der Vcrdffentlichung. soweit erforderlich tunter Angabc der in Betracht kommenden Teilc Betr. Anqxrtlch Nr. A GB,A,2 199 025 (DIDIER) 29. Juni 1988 Formblatt PCT/ISA/210 (Fortsattung van Blatt 2) (lull 1992) Seite 2 von 2 I NT1IRNATI ONALIR RUCURC I PN1JW RICFT Ar~bn a Wrtt~n~hu~n iiPCT/AT 94/00122 I m Recherchenberih Datum dor M[ited(or) der Datum der angcrtlhrtcs Patcntdoku n Verbffcndichun Putentfaznilie Ver~ffentlichung LU-A-71715 31-12-76 BE-A- 837459 03-05-76 !JE-A-2611889 22-09-77 KEINE US-A-4102675 25-07-78 t JP-A- 51121030 22-10-76 JP-B- 55023781 25-06-80 CA-A- 1075471 15-04-80 DE-A- 2616784 28-10-76 FR-A,B 2307875 12-11-76 US-A-4009024 22-02-77 KEINE GB-A-2199025 29-06-88 DE-A- 3644518 14-07-88 FR-A- 2609019 01-07-88 Fonnblatt PCI'/1SA4310 (Anhifli Patentftamige)(Jull 1992)