CA2227470A1 - Method and apparatus for producing cement clinker - Google Patents
Method and apparatus for producing cement clinker Download PDFInfo
- Publication number
- CA2227470A1 CA2227470A1 CA002227470A CA2227470A CA2227470A1 CA 2227470 A1 CA2227470 A1 CA 2227470A1 CA 002227470 A CA002227470 A CA 002227470A CA 2227470 A CA2227470 A CA 2227470A CA 2227470 A1 CA2227470 A1 CA 2227470A1
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- Canada
- Prior art keywords
- cement clinker
- fuel
- cooling
- reactor
- steam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000004568 cement Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 41
- 239000000446 fuel Substances 0.000 claims abstract description 37
- 239000012071 phase Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 15
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 238000002309 gasification Methods 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002737 fuel gas Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 239000000395 magnesium oxide Substances 0.000 description 9
- 235000012245 magnesium oxide Nutrition 0.000 description 9
- 239000011398 Portland cement Substances 0.000 description 5
- 235000012241 calcium silicate Nutrition 0.000 description 5
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 5
- 229910052918 calcium silicate Inorganic materials 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical class [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- GSSXLFACIJSBOM-UHFFFAOYSA-N 2h-pyran-2-ol Chemical compound OC1OC=CC=C1 GSSXLFACIJSBOM-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
- F27B7/38—Arrangements of cooling devices
- F27B7/383—Cooling devices for the charge
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/02—Portland cement
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/47—Cooling ; Waste heat management
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D15/00—Handling or treating discharged material; Supports or receiving chambers therefor
- F27D15/02—Cooling
- F27D15/0206—Cooling with means to convey the charge
- F27D15/0213—Cooling with means to convey the charge comprising a cooling grate
- F27D2015/024—Multiple grates
Abstract
The invention is related to a method and an apparatus for producing cement clinker, in which the cement clinker is first of all burnt in a burning zone and then cooled in a cooling zone, wherein the cooling takes place at least partially by the delivery of fuel and steam, characterised in that in a first cooling phase the delivered fuel is mixed with the cement clinker and initially pyrolysed and the resulting pyrolysis products have a strong endothermic reaction with the steam, so that the cement clinker is quenched in such a way that at least 95 %, preferably all, of the liquid phase contained therein is transformed into glass.
Description
W O 97/16390 PCT~B96/OU3S6 Method and aPparatus for producinq cement clinker i The invention relates to a method and to apparatus for producing cement clinker according to the preamble to claim 1 and the generic concept of claim 10.
So-called Portland Cement Clinker consists essentially of alite ~C3S~ and belite (C2S~ f tricalGium aluminate (C3A) and tetracalcium aluminate ferrite (C4AF).
Further constituents are in particular free magnesium oxide as well as alkalis.
The cooling of the cement clinker influences its structure, the mineralogical composition and the properties of the cement produced therefrom. The rate of cooling of the clinker has an influence in particular on the ratio between the crystalline phase content and the glass phase content in the clinker.
With slow cooling, crystal formation takes place for almost all clinker components, whilst rapid cooling impedes the crystal formation and allows the called liguid phase (2,95 Al203 + 2,2 Fe2+MgO + alkalis) to solidify in glass form. The proportion of liquid phase in clinkers from rotary kilns is approximately 20 to 28 %.
The rapid cooling of the clinker increases in particular the sulphate resistance of the cement to sulphates (magnesium, sodium, potassium, etc.) Free alcalis and MgO cristals (periclase) entering in the glass formation. This may be explained by the fact that the C3A content which is responsible of the capacity of cement to sulfates resistance, becomes part of the glass and also free alcalis and MgO (periclase), due to W O 97/16390 PCT~9'1~_956 -rapid cooling of the clinker and therefore will be resistant to attack by sulfates. As free alkali disappear, free alkali will not anymore attack the silica in aggregates.
A cement clinker which essentially consists only of alite, belite and glass, i.e. in which C3A and C4AF are bonded in the glassS could be designa~ed as ~lass Portland Cement. It is distinguished in particular by a special capacity for resistance to environmental influences without restriction of its strength.
Although the so-called Glass Portland Cement has already been produced in the laboratory, no method has hitherto been known which permits commercial production thereof.
The necessary rate of cooling cannot be achieved with the clinker cooling processes which are known in the art, particularly with the aid of so-called grate coolers.
A method of producing active belite cement is known from DD-A-206 422. In this case the belite clinker from the rotary kiln is delivered to a first cooling stage into which brown coal dust and low-temperature exit gas contains in particular carbon dioxide and steam. This leads to gasification of the supplied fuel with steam or with carbon dioxide, these gasification reactions extracting the necessary reaction enthalpy from the cement clinker.
WO 97/16390 PCT~96,'~9S6 -The object of the invention is to provide a method and , apparatus for industrial production of Glass Portland Cement.
This object is achieved by the characterising features of claims 1 and 10. According to the invention the fuel delivered in the first cooling phase is i~e~ with the cement clinker and initial.l.y pyrol.ysed~ The res~ g pyrolysis products have a strong endothermic reaction with the steam, so that the cement clinker is quenched in such a way that at least 95 ~, preferably all, of the liquid phase contained therein is transformed into glass.
The gaseous pyrolysis poducts resulting from the pyrolysis react directly with the steam. As a result the cement clinker can be quenched from its burning temperature of the order of magnitude of 1.450 ~C in a few seconds. This rapid cooling process effects the transformation of the liquid clinker constituents C3A
and C4AF into glass including free alcalis and MgO
(periclase).
The further cooling takes place through the generally known gasification of the fuel with steam, which also proceeds endothermically, but this takes place significantly more slowly by comparison with the reaction of the gaseous pyrolysis products with steam.
Further embodiments and advantages of the invention are the subject matter of the subordinate claims and are explained in greater detail with reference to the ~ description and the drawings, in which:
WO 97/16390 PCT~B~5/~09S6 -Fig.1 shows a schematic representation of apparatus according to the invention and Fig.2 shows a sectional representation along the line II-II of Fig.1.
The apparatus according to the invention for producing cement cl~nker is described first of all with reference to Fig. 1 and 2. It consists essentially of a rotary kiln 21 ~or burning the cement clinker, a first cooling stage constructed as a reactor 23 and a second cooling stage constructed for example as a grate cooler 22.
In the illustrated embodiment the reactor 23 is constructed as a part of the rotary kiln 21 with enlarged diameter and is disposed at the outlet end of the kiln. The rotary kiln 21 has at its outlet end a kiln hood 2la which together with a connecting arrangement 24 constitutes the transition from the kiln 21 to the grate cooler 22.
The kiln hood 21a as well as the connecting arrangement 24 are constructed in the conventional manner. A crusher, preferably a roll crusher 25, which is advantageously cooled from the inside by demineralised water, is disposed in the connecting arrangement 24. Here the cl;nke~ is ~ ;nuted for example to a particle size of 25 mm before it passes to a rotary vane gate 26 which delivers the clinker to the grate cooler 22. The rotary vane gate 26 is preferably also cooled from the inside with demineralised water.
In the grate cooler 22 the cement cl ;nk~ which has already been precooled in the reactor 23 is further cooled by means of air. The cooling air heated thereby W O 97/16390 PCT~B96/00956 is used in the apparatus as air for combustion in the usual way as secondary air 27 or as tertiary air 28.
A pressure-measuring device 29 is provided in the connecting arrangement 24 shortly before the rotary vane gate 26, and by way of a control device 30 this pressure-measuring device controls the speed of the first ~wo fans 31a ~nd 31b of the cooler 22 in sllch a way that no pressure builds up in the region of the pressure-measuring device 29.
The secondary air 27 generated by the grate cooler 22 is introduced into the rotary kiln 21 in the region of the kiln hood 21a by way of a secondary air line 31.
The secondary air line 31 is of double-walled construction and is cooled with demineralised water. In the middle of the secondary air line 31 there is provided an additional burner 32 for any fuel.
The reactor illustrated in this embodiment is approximately three times greater in diameter than the rotary kiln 21, and the width of the reactor corresponds to approximately 1/5 of its diameter.
In the illustrated embodiment the rotary kiln 21 is supported in the region of the reactor 23 by way of two supporting tyre-rollers stands 36, 37 which are each disposed respectively shortly before and shortly after the reactor. A further supporting tyre-roller stand could be provided if necessary in the region of kiln outlet. With the two supporting roller stands provided before and after the reactor 23 the additional weight due to the reactor 23 can best be distributed. Each supporting roller stand consists of two supporting CA 02227470 l998-0l-2l WO 97/16390 PCT~B~G/~_956 -rollers. In Fig. 1 supporting rollers 36a, 37a of the supporting roller stands 36, 37 can be seen.
The reactor 23 also has an arrangement constructed as a screw conveyor 33 for delivery of a fuel, in particular a carbonaceous fuel. The screw conveyor is again of double-walled construction and is cooled with demineralised water~ The feed point fo~ the fuel lies in the inlet region of the Xot bulk material into the reactor 23.
The saturated steam required in the reactor 23 is obtained completely or partially from the cooling water from the various apparatus parts described above.
Furthermore, the reactor 23 has an arrangement 34 for blowing steam into the cement clinker which is mixed with the fuel. This arrangement is disposed parallel to the walls delimiting the reactor 23 and is constructed in the form of a plate, the edges of which are chamfered in order to provide the least possible resistance for the clinker coming into the reactor. The steam will preferably stream out in the region of the base of the reactor 23.
At the lower end of the reactor 23 a closable opening 23a is also provided in order to transport the clinker located in the reactor to the cooler outlet by way of a conveying arrangement 35, represented by broken lines, when a longer kiln stop is necessary.
In the production of cement clinker with the aid of the apparatus described above the cement clinker is first of all burnt in the rotary kiln 21 in a burning zone and then passes into the reactor 23. The fuel which is W O 97/16390 PCT~96/~C956 also delivered there, particularly carbonaceous fuel with a pyrolysable component, is mixed with the cement clinker in a first cooling phase and pyrolysed. The resulting pyrolysis products, such as in particular tar, light hydrocarbons with some C02 and C0, have a strong endothermic reaction with the steam which is also delivered. A particularly rapid reaction takes place between the gaseotls pyrolysis products and steam~
so that the cement clinker is quenched in such a way that at least 95 ~, preferably all, of the liquid phase contained therein is transformed into glass.
In this first cooling phase the cement clinker is quenched from the burning temperature of the order of magnitude of 1.450 ~C to approximately 1.250 ~C, the rate of cooling in the first cooling phase being between 600 K/min and 6.000 K/min.
In the reaction between pyrolysis products and steam, gases such as CH4, H2, C0, C02 to C4 hydrocarbons are produced.
In a second cooling phase, which also takes place in the reactor 23, the principal occurrence is a gasification of the delivered fuel as well as the pyrolysis products still present with steam. This gasification reaction again proceeds endothermically and extracts the necessary reaction enthalpy from the cement clinker. In the gasification the following reactions occur in particular:
C + H20 ___~ H2 + CO
CO + H20 ___~ H2 + co2 C + C02 ---> 2C0 W O 97/16390 PcT/l~5c~9s6 -Thus in the method according to the invention for producing cement clinker the clinker is first of all quenched in a first cooling phase from approximately 1.450 ~C to 1.250 ~C within a few seconds. in the second cooling phase the further cooling of the cement clinker takes place principally through endothermic gasififac,tion. In the third cooling phase the Gement clinker which has been cooled to approximately 1.000 to 1.100 ~C is fed to the grate cooler.
The quantity of coal or the ratio between coal and liquid or gaseous fuel introduced in the reactor to produce through pyrolysis enough rapid gasifed products, is completely independent of the fuel needed for precalcining at preheater outlet (before kiln-inlet). The air nec~ary for the combustion process is introduced into the rotary kiln by way of the secondary air line 31. The temperature of the secondary air is approximately 750 ~C. The additional burner 32 in the middle of the secondary air line 31 is used in particular when starting the rotary kiln and can also be used when the fuel gas produced in the reactor 23 is not sufficient for sintering the raw meal to clinker in the sintering zone.
In order to achieve the fullest possible transformation of the liquid phase into glass, a thorough ~;~;ng of the fuel with the cement clinker and the most uniform possible blowing in of steam is necessary. The arrangement 34 for introducing the steam is normally provided so as to be stationary. However, it can also be disposed so as to be movable to and from in the direction of the rotational movement of the rotary WO 97/16390 PCT~B96i'~356 -kiln/reactor arrangement, in order to reach the most effective location for the chemical reactions.
Liquid and/or gaseous fuels react in the first cooling phase significantly more quickly than solid carbonaceous fuel, since the latter must first be broken up by pyrolysis. Therefore in order to set a sufficient rate of coolingr additiona] fuel ln li~id and/or gaseous form can be introduced into the reactor 23. Arangements similar to those used for blowing in the steam are particularly suitable for this. The rate of cooling in the first cooling phase can be set between 600 K/min and 6.000 K/min.
The inte~ ;~;ng of the delivered fuel with the cement clinker takes place particularly reliably in the reactor according to the invention. Since the reactor moves with the rotary kiln, the introduced cement clinker is constantly moving. In an advantageous embodiment the reactor can be provided internally with ceramic lifters for lifting the cement clinker. This effects an even more intensive inteL ;~;ng and moreover the lifting and dropping of the cement clinker leads to ~ ;nution thereof, so that a homogenisation of the size of the cement clinker lumps takes place. This in turn ensures a uniform cooling of the cement clinker.
When the rotary kiln/reactor arrangement is being started, the additional burner 32 located in the secondary air line 31 is used. If the fuel/hydrogen ratio has adjusted to the gasification capacity of the reactor 23 the combustion process can be operated J independently of the additional burner 32, in which case the fuel consumed, the regulation of the flame and W O 97/16390 PCT~BS'~ 9S6 -the quantitiy of fuel deliverd to the rotary kiln is independent of the fuel needed for precalcining.
With the aid of the reactor 23 described above the hot bulk material passes into the cooler having already been precooled, so that the entire quantity of air to be used in the cooler can be used as secondary air for the kiln and tertiary air for precalcining~ The quantity of air used by the cooler 22 is sufficient and there is no excess quantity of air and then no heat must be given off into the atmosphere. In this way between 75 and 100 kcal/kg of energy can be saved.
Furthermore, it is possible to dispense with filters and cleaning arrangements for the quantities of air which would otherwise be given off into the atmosphere.
The gas (C0 + H2) produced in the reactor meets the secondary air with a temperature of 1.000 ~C, whilst the secondary and tertiary air is at 750 ~C
approximately. Therefore the temperature of the flame can easily reach temperatures between 2.300 and 2.500 ~C. The burning process can be controlled ~much more easily due to this high temperature of the flame.
Also the coating of the clinker which is necessary for the protection of the lining of the burning zone can be controlled much more simply.
Since the cement clinker in the reactor 23 is quenched by 200 to 250 ~C within a few seconds only alite and belite crystallise. The only other constituent present is glass in which in particular C3A, C4AF, alkalis and magnesium oxide are bonded. Such a cement clinker could be designated as Glass Portland Cement.
WO 97/16390 PcT/l~5G/~-956 The fuel ashes used in the gasification reaction do not ~ have to be taken into account in the composition of the raw material. These ahses form a filler in the clinker.
Pit coal and brown coal with high proportions of ash as well as coals with high volatile components can therefore be used. The fuel supplied to the reactor 23 does not have to be either dried or crushed and can be~
delivered i~ the fo~m of 5 to 10 mm particles~
Due to the rapid quenching the calcium sulphates will not decompose and pass in the clinker as CaS04 (anhydrite).
This can have a result of reducing sulphur circulation problem in rotary kilns and substantially simplify the sulphur problem leading to the possibility of using fuels with higher sulphur content.
So-called Portland Cement Clinker consists essentially of alite ~C3S~ and belite (C2S~ f tricalGium aluminate (C3A) and tetracalcium aluminate ferrite (C4AF).
Further constituents are in particular free magnesium oxide as well as alkalis.
The cooling of the cement clinker influences its structure, the mineralogical composition and the properties of the cement produced therefrom. The rate of cooling of the clinker has an influence in particular on the ratio between the crystalline phase content and the glass phase content in the clinker.
With slow cooling, crystal formation takes place for almost all clinker components, whilst rapid cooling impedes the crystal formation and allows the called liguid phase (2,95 Al203 + 2,2 Fe2+MgO + alkalis) to solidify in glass form. The proportion of liquid phase in clinkers from rotary kilns is approximately 20 to 28 %.
The rapid cooling of the clinker increases in particular the sulphate resistance of the cement to sulphates (magnesium, sodium, potassium, etc.) Free alcalis and MgO cristals (periclase) entering in the glass formation. This may be explained by the fact that the C3A content which is responsible of the capacity of cement to sulfates resistance, becomes part of the glass and also free alcalis and MgO (periclase), due to W O 97/16390 PCT~9'1~_956 -rapid cooling of the clinker and therefore will be resistant to attack by sulfates. As free alkali disappear, free alkali will not anymore attack the silica in aggregates.
A cement clinker which essentially consists only of alite, belite and glass, i.e. in which C3A and C4AF are bonded in the glassS could be designa~ed as ~lass Portland Cement. It is distinguished in particular by a special capacity for resistance to environmental influences without restriction of its strength.
Although the so-called Glass Portland Cement has already been produced in the laboratory, no method has hitherto been known which permits commercial production thereof.
The necessary rate of cooling cannot be achieved with the clinker cooling processes which are known in the art, particularly with the aid of so-called grate coolers.
A method of producing active belite cement is known from DD-A-206 422. In this case the belite clinker from the rotary kiln is delivered to a first cooling stage into which brown coal dust and low-temperature exit gas contains in particular carbon dioxide and steam. This leads to gasification of the supplied fuel with steam or with carbon dioxide, these gasification reactions extracting the necessary reaction enthalpy from the cement clinker.
WO 97/16390 PCT~96,'~9S6 -The object of the invention is to provide a method and , apparatus for industrial production of Glass Portland Cement.
This object is achieved by the characterising features of claims 1 and 10. According to the invention the fuel delivered in the first cooling phase is i~e~ with the cement clinker and initial.l.y pyrol.ysed~ The res~ g pyrolysis products have a strong endothermic reaction with the steam, so that the cement clinker is quenched in such a way that at least 95 ~, preferably all, of the liquid phase contained therein is transformed into glass.
The gaseous pyrolysis poducts resulting from the pyrolysis react directly with the steam. As a result the cement clinker can be quenched from its burning temperature of the order of magnitude of 1.450 ~C in a few seconds. This rapid cooling process effects the transformation of the liquid clinker constituents C3A
and C4AF into glass including free alcalis and MgO
(periclase).
The further cooling takes place through the generally known gasification of the fuel with steam, which also proceeds endothermically, but this takes place significantly more slowly by comparison with the reaction of the gaseous pyrolysis products with steam.
Further embodiments and advantages of the invention are the subject matter of the subordinate claims and are explained in greater detail with reference to the ~ description and the drawings, in which:
WO 97/16390 PCT~B~5/~09S6 -Fig.1 shows a schematic representation of apparatus according to the invention and Fig.2 shows a sectional representation along the line II-II of Fig.1.
The apparatus according to the invention for producing cement cl~nker is described first of all with reference to Fig. 1 and 2. It consists essentially of a rotary kiln 21 ~or burning the cement clinker, a first cooling stage constructed as a reactor 23 and a second cooling stage constructed for example as a grate cooler 22.
In the illustrated embodiment the reactor 23 is constructed as a part of the rotary kiln 21 with enlarged diameter and is disposed at the outlet end of the kiln. The rotary kiln 21 has at its outlet end a kiln hood 2la which together with a connecting arrangement 24 constitutes the transition from the kiln 21 to the grate cooler 22.
The kiln hood 21a as well as the connecting arrangement 24 are constructed in the conventional manner. A crusher, preferably a roll crusher 25, which is advantageously cooled from the inside by demineralised water, is disposed in the connecting arrangement 24. Here the cl;nke~ is ~ ;nuted for example to a particle size of 25 mm before it passes to a rotary vane gate 26 which delivers the clinker to the grate cooler 22. The rotary vane gate 26 is preferably also cooled from the inside with demineralised water.
In the grate cooler 22 the cement cl ;nk~ which has already been precooled in the reactor 23 is further cooled by means of air. The cooling air heated thereby W O 97/16390 PCT~B96/00956 is used in the apparatus as air for combustion in the usual way as secondary air 27 or as tertiary air 28.
A pressure-measuring device 29 is provided in the connecting arrangement 24 shortly before the rotary vane gate 26, and by way of a control device 30 this pressure-measuring device controls the speed of the first ~wo fans 31a ~nd 31b of the cooler 22 in sllch a way that no pressure builds up in the region of the pressure-measuring device 29.
The secondary air 27 generated by the grate cooler 22 is introduced into the rotary kiln 21 in the region of the kiln hood 21a by way of a secondary air line 31.
The secondary air line 31 is of double-walled construction and is cooled with demineralised water. In the middle of the secondary air line 31 there is provided an additional burner 32 for any fuel.
The reactor illustrated in this embodiment is approximately three times greater in diameter than the rotary kiln 21, and the width of the reactor corresponds to approximately 1/5 of its diameter.
In the illustrated embodiment the rotary kiln 21 is supported in the region of the reactor 23 by way of two supporting tyre-rollers stands 36, 37 which are each disposed respectively shortly before and shortly after the reactor. A further supporting tyre-roller stand could be provided if necessary in the region of kiln outlet. With the two supporting roller stands provided before and after the reactor 23 the additional weight due to the reactor 23 can best be distributed. Each supporting roller stand consists of two supporting CA 02227470 l998-0l-2l WO 97/16390 PCT~B~G/~_956 -rollers. In Fig. 1 supporting rollers 36a, 37a of the supporting roller stands 36, 37 can be seen.
The reactor 23 also has an arrangement constructed as a screw conveyor 33 for delivery of a fuel, in particular a carbonaceous fuel. The screw conveyor is again of double-walled construction and is cooled with demineralised water~ The feed point fo~ the fuel lies in the inlet region of the Xot bulk material into the reactor 23.
The saturated steam required in the reactor 23 is obtained completely or partially from the cooling water from the various apparatus parts described above.
Furthermore, the reactor 23 has an arrangement 34 for blowing steam into the cement clinker which is mixed with the fuel. This arrangement is disposed parallel to the walls delimiting the reactor 23 and is constructed in the form of a plate, the edges of which are chamfered in order to provide the least possible resistance for the clinker coming into the reactor. The steam will preferably stream out in the region of the base of the reactor 23.
At the lower end of the reactor 23 a closable opening 23a is also provided in order to transport the clinker located in the reactor to the cooler outlet by way of a conveying arrangement 35, represented by broken lines, when a longer kiln stop is necessary.
In the production of cement clinker with the aid of the apparatus described above the cement clinker is first of all burnt in the rotary kiln 21 in a burning zone and then passes into the reactor 23. The fuel which is W O 97/16390 PCT~96/~C956 also delivered there, particularly carbonaceous fuel with a pyrolysable component, is mixed with the cement clinker in a first cooling phase and pyrolysed. The resulting pyrolysis products, such as in particular tar, light hydrocarbons with some C02 and C0, have a strong endothermic reaction with the steam which is also delivered. A particularly rapid reaction takes place between the gaseotls pyrolysis products and steam~
so that the cement clinker is quenched in such a way that at least 95 ~, preferably all, of the liquid phase contained therein is transformed into glass.
In this first cooling phase the cement clinker is quenched from the burning temperature of the order of magnitude of 1.450 ~C to approximately 1.250 ~C, the rate of cooling in the first cooling phase being between 600 K/min and 6.000 K/min.
In the reaction between pyrolysis products and steam, gases such as CH4, H2, C0, C02 to C4 hydrocarbons are produced.
In a second cooling phase, which also takes place in the reactor 23, the principal occurrence is a gasification of the delivered fuel as well as the pyrolysis products still present with steam. This gasification reaction again proceeds endothermically and extracts the necessary reaction enthalpy from the cement clinker. In the gasification the following reactions occur in particular:
C + H20 ___~ H2 + CO
CO + H20 ___~ H2 + co2 C + C02 ---> 2C0 W O 97/16390 PcT/l~5c~9s6 -Thus in the method according to the invention for producing cement clinker the clinker is first of all quenched in a first cooling phase from approximately 1.450 ~C to 1.250 ~C within a few seconds. in the second cooling phase the further cooling of the cement clinker takes place principally through endothermic gasififac,tion. In the third cooling phase the Gement clinker which has been cooled to approximately 1.000 to 1.100 ~C is fed to the grate cooler.
The quantity of coal or the ratio between coal and liquid or gaseous fuel introduced in the reactor to produce through pyrolysis enough rapid gasifed products, is completely independent of the fuel needed for precalcining at preheater outlet (before kiln-inlet). The air nec~ary for the combustion process is introduced into the rotary kiln by way of the secondary air line 31. The temperature of the secondary air is approximately 750 ~C. The additional burner 32 in the middle of the secondary air line 31 is used in particular when starting the rotary kiln and can also be used when the fuel gas produced in the reactor 23 is not sufficient for sintering the raw meal to clinker in the sintering zone.
In order to achieve the fullest possible transformation of the liquid phase into glass, a thorough ~;~;ng of the fuel with the cement clinker and the most uniform possible blowing in of steam is necessary. The arrangement 34 for introducing the steam is normally provided so as to be stationary. However, it can also be disposed so as to be movable to and from in the direction of the rotational movement of the rotary WO 97/16390 PCT~B96i'~356 -kiln/reactor arrangement, in order to reach the most effective location for the chemical reactions.
Liquid and/or gaseous fuels react in the first cooling phase significantly more quickly than solid carbonaceous fuel, since the latter must first be broken up by pyrolysis. Therefore in order to set a sufficient rate of coolingr additiona] fuel ln li~id and/or gaseous form can be introduced into the reactor 23. Arangements similar to those used for blowing in the steam are particularly suitable for this. The rate of cooling in the first cooling phase can be set between 600 K/min and 6.000 K/min.
The inte~ ;~;ng of the delivered fuel with the cement clinker takes place particularly reliably in the reactor according to the invention. Since the reactor moves with the rotary kiln, the introduced cement clinker is constantly moving. In an advantageous embodiment the reactor can be provided internally with ceramic lifters for lifting the cement clinker. This effects an even more intensive inteL ;~;ng and moreover the lifting and dropping of the cement clinker leads to ~ ;nution thereof, so that a homogenisation of the size of the cement clinker lumps takes place. This in turn ensures a uniform cooling of the cement clinker.
When the rotary kiln/reactor arrangement is being started, the additional burner 32 located in the secondary air line 31 is used. If the fuel/hydrogen ratio has adjusted to the gasification capacity of the reactor 23 the combustion process can be operated J independently of the additional burner 32, in which case the fuel consumed, the regulation of the flame and W O 97/16390 PCT~BS'~ 9S6 -the quantitiy of fuel deliverd to the rotary kiln is independent of the fuel needed for precalcining.
With the aid of the reactor 23 described above the hot bulk material passes into the cooler having already been precooled, so that the entire quantity of air to be used in the cooler can be used as secondary air for the kiln and tertiary air for precalcining~ The quantity of air used by the cooler 22 is sufficient and there is no excess quantity of air and then no heat must be given off into the atmosphere. In this way between 75 and 100 kcal/kg of energy can be saved.
Furthermore, it is possible to dispense with filters and cleaning arrangements for the quantities of air which would otherwise be given off into the atmosphere.
The gas (C0 + H2) produced in the reactor meets the secondary air with a temperature of 1.000 ~C, whilst the secondary and tertiary air is at 750 ~C
approximately. Therefore the temperature of the flame can easily reach temperatures between 2.300 and 2.500 ~C. The burning process can be controlled ~much more easily due to this high temperature of the flame.
Also the coating of the clinker which is necessary for the protection of the lining of the burning zone can be controlled much more simply.
Since the cement clinker in the reactor 23 is quenched by 200 to 250 ~C within a few seconds only alite and belite crystallise. The only other constituent present is glass in which in particular C3A, C4AF, alkalis and magnesium oxide are bonded. Such a cement clinker could be designated as Glass Portland Cement.
WO 97/16390 PcT/l~5G/~-956 The fuel ashes used in the gasification reaction do not ~ have to be taken into account in the composition of the raw material. These ahses form a filler in the clinker.
Pit coal and brown coal with high proportions of ash as well as coals with high volatile components can therefore be used. The fuel supplied to the reactor 23 does not have to be either dried or crushed and can be~
delivered i~ the fo~m of 5 to 10 mm particles~
Due to the rapid quenching the calcium sulphates will not decompose and pass in the clinker as CaS04 (anhydrite).
This can have a result of reducing sulphur circulation problem in rotary kilns and substantially simplify the sulphur problem leading to the possibility of using fuels with higher sulphur content.
Claims (14)
1. Method of producing cement clinker, in which the cement clinker is first of all burnt in a burning zone and then cooled in a cooling zone, wherein the cooling takes place at least partially by the delivery of fuel and steam, characterised in that in a first cooling phase the delivered fuel is mixed with the cement clinker and initially pyrolysed and the resulting pyrolysis products have a strong endothermic reaction with the steam, so that the cement clinker is quenched in such a way that at least 95 %, preferably all, of the liquid phase contained therein is transformed into glass.
2. Method as claimed in claim 1, characterised in that carbonaceous fuel with a pyrolysable component is delivered as fuel.
3. Method as claimed in claim 1, characterised in that liquid and/or gaseous fuel is added for setting the rate of cooling in the first cooling phase.
4. Method as claimed in claim 1, characterised in that the rate of cooling in the first cooling phase is between 600 K/min and 6.000 K/min.
5. Method as claimed in claim 1, characterised in that the cement clinker is cooled by approximately 200 K
in the first cooling phase.
in the first cooling phase.
6. Method as claimed in claim 1, characterised in that the cement clinker is quenched in the first cooling phase from the burning temperature of the order of magnitude of 1.450 °C to 1.250 °C.
7. Method as claimed in claim 1, characterised in that during mixing of the fuel with the cement clinker a comminution of the cement clinker takes place simultaneously.
8. Method as claimed in claim 1, characterised in that in a second cooling phase a gasification of the delivered fuel with steam takes place, the gasification reaction extracting the necessary reaction enthalpy from the cement clinker.
9. Method as claimed in claim 8, characterised in that the fuel gases produced in the gasification reaction are used in the burning of the cement clinker in the burning zone.
10. Apparatus for producing cement clinker according to the method as claimed in one of claims 1 to 9, with a) a rotary kiln (21) for burning the cement clinker, b) a cooler (22) for cooling the burnt cement clinker, c) an arrangement (33) for delivering a fuel, d) an arrangement (34) for blowing in steam, characterised in that e) a reactor (23) is provided which has the arrangement (33) for delivery of the fuel and the arrangement (34) for blowing in of the steam, and f) the reactor (23) is constructed as part of the rotary kiln and rotates therewith.
11. Apparatus as claimed in claim 10, characterised in that the reactor is constructed as a part of the rotary kiln (21) with enlarged diameter.
12. Apparatus as claimed in claim 10, characterised in that the reactor (23) is disposed substantially immediately before the discharge end of the rotary kiln (21).
13. Apparatus as claimed in claim 10, characterised in that the rotary kiln (21) is supported immediately before and behind the reactor (23).
14. Apparatus as claimed in claim 10, characterised in that the reactor is provided with a further arrangement for introducing liquid and/or gaseous fuel.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95117163.6 | 1995-10-31 | ||
EP95117163A EP0716052B1 (en) | 1994-12-07 | 1995-10-31 | Bulk material production plant comprising a special type of cooler unit |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2227470A1 true CA2227470A1 (en) | 1997-05-09 |
Family
ID=8219767
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002227470A Abandoned CA2227470A1 (en) | 1995-10-31 | 1996-07-29 | Method and apparatus for producing cement clinker |
Country Status (19)
Country | Link |
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US (1) | US5972104A (en) |
EP (1) | EP0858436B1 (en) |
JP (1) | JPH11500706A (en) |
CN (1) | CN1200714A (en) |
AT (1) | ATE186714T1 (en) |
AU (1) | AU6835496A (en) |
BR (1) | BR9611399A (en) |
CA (1) | CA2227470A1 (en) |
CZ (1) | CZ287081B6 (en) |
DE (1) | DE69605209T2 (en) |
ES (1) | ES2140889T3 (en) |
GR (1) | GR3032400T3 (en) |
IL (1) | IL123548A0 (en) |
NO (1) | NO981889L (en) |
PL (1) | PL328166A1 (en) |
PT (1) | PT858436E (en) |
RU (1) | RU2133234C1 (en) |
TR (1) | TR199800709T2 (en) |
WO (1) | WO1997016390A1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6050813A (en) * | 1997-12-02 | 2000-04-18 | Cement Petcoptimizer Company | Control of cement clinker production by analysis of sulfur in the end product |
US6383283B1 (en) | 1997-12-02 | 2002-05-07 | Cement Petcoptimizer Company | Control of cement clinker production by analysis of sulfur in the end product |
US6183244B1 (en) | 1999-04-14 | 2001-02-06 | Cement Petcoptimizer Company | Control of cement clinker production in a wet process rotary kiln by analysis of sulfur in the end product |
DE10003283A1 (en) * | 2000-01-26 | 2001-08-02 | Krupp Polysius Ag | Process and plant for the heat treatment of fine-grained material |
DE102007015089A1 (en) * | 2007-03-29 | 2008-10-02 | Khd Humboldt Wedag Gmbh | Process for drying wet biomass |
US8500902B2 (en) * | 2009-09-04 | 2013-08-06 | Srinivas Kilambi | Methods of making cementitious compositions and products made thereby |
DE102009041089C5 (en) * | 2009-09-10 | 2013-06-27 | Khd Humboldt Wedag Gmbh | Process and plant for the production of cement with reduced CO2 emission |
EP2390608A1 (en) * | 2010-05-25 | 2011-11-30 | Messer France S.A.S. | Method and device for cooling |
FI126564B (en) * | 2011-02-28 | 2017-02-15 | Andritz Oy | Method and apparatus for burning lime slurry |
AT517813A1 (en) * | 2015-09-08 | 2017-04-15 | Holcim Technology Ltd | Method and apparatus for reducing the NOx emissions of a rotary kiln |
CN109504409B (en) * | 2018-11-02 | 2024-01-02 | 北京鸿机装备科技有限公司 | Rotary bed pyrolysis device and method for carrying out oil sludge pyrolysis by adopting same |
CN109401766B (en) * | 2018-11-02 | 2024-01-02 | 湖北亚首生物质新能源科技有限公司 | Rotary bed pyrolysis device and method for carrying out oil sludge pyrolysis by adopting same |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US21633A (en) * | 1858-09-28 | Improved embroidery and sewing stand | ||
DE641122C (en) * | 1933-04-25 | 1937-01-20 | Ciments Francais Et Des Portla | Process and device for the production of colorless (white) cements |
US2130626A (en) * | 1937-09-20 | 1938-09-20 | California Portland Cement Co | Process for quenching portland cement clinker |
DE2412695C3 (en) * | 1974-03-16 | 1980-11-06 | Kloeckner-Humboldt-Deutz Ag, 5000 Koeln | Method and device for cooling hot bulk material |
US4101337A (en) * | 1974-10-03 | 1978-07-18 | F. L. Smidth & Co. | Cement manufacture |
GB1434339A (en) * | 1974-10-03 | 1976-05-05 | Smidth & Co As F L | Coolers for cooling granular or pulverous material |
US4174974A (en) * | 1978-04-14 | 1979-11-20 | Standard Oil Company (Indiana) | Process for converting coal ash slag into portland cement |
DE3120683C2 (en) * | 1981-05-23 | 1985-04-11 | BKMI Industrieanlagen GmbH, 8000 München | Device for cooling burnt white cement clinker |
DD206422A1 (en) * | 1982-03-04 | 1984-01-25 | Jochen Stark | PROCESS FOR COOLING HOT SHOE GRIPPERS |
DE3522839A1 (en) * | 1985-06-26 | 1987-01-02 | Valenciana Cemento | METHOD AND DEVICE FOR COOLING AND FURTHER TREATING HOT WHITE CEMENT CLINKER |
DK169177B1 (en) * | 1991-11-27 | 1994-09-05 | Smidth & Co As F L | Process for making cement |
DE4414292A1 (en) * | 1994-04-23 | 1995-10-26 | Krupp Foerdertechnik Gmbh | Process and plant for cooling white cement clinker |
-
1996
- 1996-07-29 CN CN96197910A patent/CN1200714A/en active Pending
- 1996-07-29 PT PT96928656T patent/PT858436E/en unknown
- 1996-07-29 PL PL96328166A patent/PL328166A1/en unknown
- 1996-07-29 IL IL12354896A patent/IL123548A0/en unknown
- 1996-07-29 BR BR9611399A patent/BR9611399A/en not_active Application Discontinuation
- 1996-07-29 TR TR1998/00709T patent/TR199800709T2/en unknown
- 1996-07-29 EP EP96928656A patent/EP0858436B1/en not_active Expired - Lifetime
- 1996-07-29 CA CA002227470A patent/CA2227470A1/en not_active Abandoned
- 1996-07-29 US US08/983,246 patent/US5972104A/en not_active Expired - Fee Related
- 1996-07-29 AU AU68354/96A patent/AU6835496A/en not_active Abandoned
- 1996-07-29 ES ES96928656T patent/ES2140889T3/en not_active Expired - Lifetime
- 1996-07-29 RU RU98101130A patent/RU2133234C1/en active
- 1996-07-29 CZ CZ19981305A patent/CZ287081B6/en not_active IP Right Cessation
- 1996-07-29 JP JP9517179A patent/JPH11500706A/en active Pending
- 1996-07-29 WO PCT/IB1996/000956 patent/WO1997016390A1/en active IP Right Grant
- 1996-07-29 DE DE69605209T patent/DE69605209T2/en not_active Expired - Fee Related
- 1996-07-29 AT AT96928656T patent/ATE186714T1/en not_active IP Right Cessation
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1998
- 1998-04-27 NO NO981889A patent/NO981889L/en not_active Application Discontinuation
-
2000
- 2000-01-17 GR GR20000400094T patent/GR3032400T3/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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GR3032400T3 (en) | 2000-05-31 |
WO1997016390A1 (en) | 1997-05-09 |
CZ287081B6 (en) | 2000-08-16 |
NO981889D0 (en) | 1998-04-27 |
ATE186714T1 (en) | 1999-12-15 |
US5972104A (en) | 1999-10-26 |
EP0858436B1 (en) | 1999-11-17 |
CZ130598A3 (en) | 1998-11-11 |
TR199800709T2 (en) | 1998-07-21 |
PT858436E (en) | 2000-04-28 |
PL328166A1 (en) | 1999-01-18 |
AU6835496A (en) | 1997-05-22 |
ES2140889T3 (en) | 2000-03-01 |
NO981889L (en) | 1998-04-27 |
IL123548A0 (en) | 1998-10-30 |
DE69605209T2 (en) | 2000-05-11 |
CN1200714A (en) | 1998-12-02 |
EP0858436A1 (en) | 1998-08-19 |
MX9803499A (en) | 1998-09-30 |
BR9611399A (en) | 1999-07-13 |
DE69605209D1 (en) | 1999-12-23 |
JPH11500706A (en) | 1999-01-19 |
RU2133234C1 (en) | 1999-07-20 |
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