EP4149900A1 - Verfahren und anlage zur aktivierung von tonen - Google Patents
Verfahren und anlage zur aktivierung von tonenInfo
- Publication number
- EP4149900A1 EP4149900A1 EP21729405.7A EP21729405A EP4149900A1 EP 4149900 A1 EP4149900 A1 EP 4149900A1 EP 21729405 A EP21729405 A EP 21729405A EP 4149900 A1 EP4149900 A1 EP 4149900A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- clay
- fraction
- gas
- activated
- fine
- 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.)
- Pending
Links
- 239000004927 clay Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000003213 activating effect Effects 0.000 title claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 77
- 239000007789 gas Substances 0.000 claims description 51
- 230000004913 activation Effects 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000004040 coloring Methods 0.000 abstract 1
- 239000002734 clay mineral Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000007725 thermal activation Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 239000010433 feldspar Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical group [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011513 prestressed concrete Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- -1 silt Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C04B7/12—Natural pozzuolanas; Natural pozzuolana cements; Artificial pozzuolanas or artificial pozzuolana cements other than those obtained from waste or combustion residues, e.g. burned clay; Treating inorganic materials to improve their pozzuolanic characteristics
Definitions
- the invention relates to a method and system for activating clays.
- thermally activated clays do not achieve the strength of concrete based on cement clinker, but the properties of activated clays as a building material are sufficient for a large number of construction projects that do not depend on the particular performance of the building material, as is the case with prestressed concrete bridges Is the case, or as is the case with extremely tall skyscrapers far beyond the 100 m limit.
- Clay minerals which are suitable for processing as building materials and which develop hydraulic properties through thermal treatment, can vary greatly in their chemical and mineralogical compositions and also in their physical properties.
- natural occurrences of these clay minerals usually contain various components with regard to the hydraulic properties of inert components such as quartz, feldspar, flint.
- Clay minerals of purely natural origin of various origins usually differ in terms of various properties such as particle size, density and moisture.
- clay minerals of various origins differ in the inorganic impurities they contain, such as iron, titanium and manganese.
- CONFIRMATION COPY These chemically bound metallic accompanying substances determine the color of the activated clay by changing their oxidation state during thermal treatment of the clay minerals.
- Iron impurities can be present as structural iron (part of the kaolinite structure or the structure of additional minerals) and as free iron in the form of oxides, hydroxides, carbonates and sulfides.
- the titanium and iron oxide content correlates with colorimetric parameters and the color saturation of red.
- Manganese turns brown when oxidized with the formation of manganese dioxide. It is known that the red color is caused by iron (III) compounds.
- the content of impurities such as iron and titanium in naturally occurring clay minerals leads to the undesired red coloration of the clay mineral activated by heat treatment during calcination under oxidizing conditions and subsequent cooling with atmospheric air.
- Clay is a naturally occurring material that consists mainly of clay mineral particles, is generally plastically deformable with sufficient water content and becomes brittle when dried or burned. Although clay usually contains layered silicates, it can contain other materials that give it plasticity and harden it when dried or fired. As associated phases, clay can contain materials that do not give it plasticity, e.g. B. quartz, calcite, dolomite, feldspar and organic substances.
- clay particles are considered to be particles ⁇ 2 pm (sometimes also ⁇ 4 pm [2]) and in colloid chemistry ⁇ 1 pm.
- clays are understood to mean the naturally occurring material that either mainly consists of clay mineral particles, i.e. more than 50% clay mineral particles, but also those made of clay mineral depository degradable materials that have less than 50% clay mineral particles to as little as 10% to 20% clay mineral particles.
- the rest consists of sand, silt, quartz, calcite, dolomite, feldspar and possibly also gravel.
- the large proportions of material that are not clay mineral particles are almost chemically inert, abrasive and cannot be activated thermally. The latter clays are thus similar to clay.
- the object of the invention is to provide a system and a method for the thermal activation of clays in which the undesired red coloration does not occur.
- a separation of a clay raw material into a coarse fraction and a fine fraction, subsequent preheating of the fine fraction in a preheater, and subsequent activation of the fine fraction in a fluidized bed and / or entrained flow reactor is provided.
- a thermal treatment of the fine material fraction takes place in the fluidized bed and / or entrained flow reactor.
- the still hot fine material fraction is combined with the separated and cold coarse material fraction and the combined clay fractions are discharged from the reactor.
- a system having at least one fluidized bed and / or entrained flow reactor and at least one cyclone heat exchanger, the cyclone heat exchanger following the fluidized bed and / or entrained flow reactor in the gas flow direction, and with a feed device for clay to be activated at the upper end of the cyclone heat. exchanger is arranged.
- the system is characterized in that a sifter is in flow connection with a coarse material discharge opening of the sifter in the material flow direction upstream with a gas feed device for the fluidized bed and / or entrained flow reactor, and the sifter with a Fine material discharge opening of the classifier is in flow connection upstream in the material flow direction with the feed device for clay to be activated.
- This system enables the clay to be treated in accordance with the aforementioned method.
- the invention is based on the surprising finding that the red coloration of clays when activated by oxidation of the iron contained in the clay mineral to iron (III) in conjunction with other chemically bonded metallic components occurs exclusively in the fine-grained components of natural clays.
- the coarse-grained components of the natural clays show no tendency to turn red.
- the invention is based on the knowledge that the fine components of the clay can be activated by thermal treatment. If this is carried out under chemically strongly reductive conditions, iron (III) is not formed in the clay, but iron (II), which appears chemically bonded in clay minerals rather greenish to colorless.
- the clay fraction activated under chemically reducing conditions therefore has a gray to anthracite color in conjunction with all accompanying substances.
- the fine fraction of natural clays activated by thermal treatment initially remains very sensitive to oxidation in atmospheric air.
- the fine, thermally activated clay fraction is quenched from a temperature of 600 ° C to 1000 ° C at the end of a reactor for thermal activation to a temperature well below 600 ° C.
- This thermal quenching must not take place with atmospheric air, otherwise the undesired iron (III) would be formed.
- the quenching must be chemically neutral.
- the coarse fraction separated from the natural clay in the first process step is suitable for this purpose. This coarse fraction is almost chemically inert and can absorb a large amount of heat without oxidizing itself.
- the invention is based on a separation of clay minerals into a fine fraction, which is thermally activated, and a coarse fraction, which is not heated as an inert material.
- the surprising effect is that it is separated into a coarse fraction and in a fine material fraction leads to a clay-depleted and inert coarse material fraction and to a clay-enriched fine material fraction.
- the activated fine material is quenched with the previously separated coarse fraction, the coarse material fraction being significantly colder. In the quenched state, the chemically bound iron (II) is protected from oxidation.
- the clay mineral treated in this way has a gray to anthracite tint.
- the activated gray to anthracite-colored mineral is discharged from the reactor.
- the material flow outlet of the cyclone heat exchanger at the lower end is in flow connection with a gas feed device for the entrained flow reactor, at which point the activated clay combines with the coarse material from the coarse material discharge opening of the classifier.
- the gas feed device can be in the form of a cyclone, from which the carrier gas escapes through a dip tube and the solid suspended in the carrier gas emerges as dust from a cone that is usually pointing downwards.
- the temperature has an influence on the activated product not only during activation, but also after activation. Tests have shown that combining the thermally activated fine material fraction in a temperature window of 600 ° C to 1000 ° C with the coarse material fraction of the raw material leads to a final temperature of 350 ° C to 600 ° C. A temperature control that leads to a final temperature of below 500 ° C. is preferred.
- the fine material fraction of the activated clay quenched in this way shows itself to be insensitive to discoloration due to oxidation in atmospheric air with natural air humidity at these temperatures.
- the separation of the natural clay into a fine material fraction and a coarse material fraction and the exclusive thermal activation of the separated fine material fraction and subsequent quenching with the previously separated coarse material fraction has several advantages.
- the activated Quench the fine fraction under chemically inert conditions, which stabilizes the activated clay component against red discolouration.
- the thermal activation only a fraction of the heat is required, which saves fuel and resources.
- the thermally activatable fine material fraction is significantly less abrasive than the coarse material fraction.
- the coarse fraction includes quartz, feldspar and flint.
- FIG. 1 shows a sketch of a system according to the invention for activating clays
- FIG. 1 shows a sketch of a system according to the invention for activating clays.
- Moist raw material runs through the system in the sketch from a feed hopper 10 at the top left in the sketch to the finished, activated product, which leaves the system shown here via a conveying device 240 at the bottom right in the sketch.
- Fresh air enters the system via a separator cyclone 230 in the sketch at the bottom right and leaves the system as exhaust air in this sketch via a compressor 180 at the top right in this sketch.
- the raw material is fed from the feed hopper 10 via a conveyor device 20 to a regulated conveyor device 30, where it is combined with raw material that is in the sifter circulation.
- a sifter 40 here a vertical sifter, in which the raw material rolls over cascades of stairs, deagglomerated and freed from the fine material fraction by sifting gas entering the sifter 40 from the left in this sketch.
- the coarse fraction and the fine fraction separate.
- the coarse material of the classifier 40 falls from the classifier 40 onto a regulated conveying device 50 and is conveyed by this conveying device 50 to the left in this sketch.
- the coarse material falls into a regulated material switch 60.
- a first part of the coarse material is transported through the material switch 60 to a further conveyor device 70 to a bucket elevator 80, which throws the circulating material back onto the conveyor device 30 described above where the sifting material in circulation is combined with the raw material.
- a second part of the coarse material from the sifter 40 is transported as inert material to the right in this sketch via a conveying device 90, where it combines with the activated fine material of the raw material.
- a processing device 92 for example in the form of a sieving device 92 or a grinding device, can be arranged, which can be reached via the bucket elevator 91 in order to sift out the coarser components of the natural clays and also to the relative proportions of the activated clay and the inert material in the end product.
- an optional soaking device 93 can be present which moisten the coarse material before combining with the activated clay in order to increase the heat absorption capacity of the coarse material.
- the coarse material has a temperature of atmospheric temperature up to a maximum of below 150 ° C. due to the temperature of the separator gas in the separator 40.
- the route of the fine material from the raw material out of the sifter 40 leads into the gas line 160 into which it is carried by the sifting gas.
- the fine material is separated from the classifying gas in a dust separator 170.
- the classifying gas leaves the system to the top right via the compressor 180 as exhaust air, as was already described at the beginning.
- Below the dust separator 170 there is a conveying device 190 which conveys the fine material fraction into a feeding device 200. From the feed device 200, the fine material falls into the uppermost gas supply line to the uppermost heat exchanger cyclone 123 of the heat exchanger 120 shown here with three cyclones. It is also possible to use this system with a different number of cyclones in the heat to operate the exchanger strand.
- the fine material fraction Suspended in the gas of the gas supply line to cyclone 123, the fine material fraction is heated in the warm gas of heat exchanger 120. In the uppermost heat exchanger cyclone 123, the fine material fraction is fed into the gas inlet to the penultimate cyclone 122, where the heating and subsequent separation are repeated. At the exit of the penultimate cyclone 122, the preheated fines fraction falls into the lower area of an entrained flow reactor shown here, which is constructed similarly to a calciner of a plant for the production of cement clinker. A fluidized bed reactor can also be located at this point.
- the fine material fraction of the clay is thermally activated to a hydraulic binder that sets when mixed with water.
- the fuel from the entrained flow reactor burns out.
- the free oxygen concentration in the entrained flow reactor should not rise above 4%.
- the flame of the burner in entrained flow reactor 110 is therefore operated in a strongly reductive manner, which can take place through a substoichiometric oxygen supply or a superstoichiometric fuel supply.
- the descending branch of the entrained flow reactor 110 is followed by the heat exchanger 120.
- the thermally activated fines fraction of the clay suspended in the hot gas is separated by the lowest cyclone 121 of the heat exchanger 120 and has a temperature between 600 ° C and 1000 ° C at this point.
- the hot gas flows in the heat exchanger 120 towards the fresh fine material.
- the freshly thermally activated clay fraction leaves the heat exchanger via the solids line of the lowermost cyclone 121 and combines there with the inert, cold coarse material of the clay which was separated in the classifier 40.
- water can be added to the cold coarse material fraction before it is combined with the hot, activated clay fraction.
- the combined clay fractions flow into the gas feed line of the separation cyclone 230 where these fractions flow against fresh atmospheric air.
- the fractions cooled to approx. 80 ° C. to 120 ° C. leave the system via the solids line of the separating cyclone 230 via the conveying device 240 as a finished product.
- the fresh air entering the system flows conveyed through a compressor 210 to a gas line 220 and as a gas feed line to the separating cyclone 100, the fresh air taking up the clay fractions quenched and combined in the gas space.
- the fish air that gets there serves as combustion air for a burner in entrained flow reactor 110 and as carrier air.
- Another portion of the fresh air flows to a T-junction with the gas discharge line 130, which guides the warm heat exchanger exhaust gas from the heat exchanger 120 to a hot gas generator 140.
- the combined gas fractions are heated in the hot gas generator 140 and, after the hot gas generator 140, a gas line 150 leads the heated gas as sifting and drying gas to the sifter 40, where all gas and material cycles and / or flows are now closed.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102020112894.0A DE102020112894A1 (de) | 2020-05-13 | 2020-05-13 | Verfahren und Anlage zur Aktivierung von Tonen |
PCT/EP2021/000065 WO2021228430A1 (de) | 2020-05-13 | 2021-05-11 | Verfahren und anlage zur aktivierung von tonen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4149900A1 true EP4149900A1 (de) | 2023-03-22 |
Family
ID=76250268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21729405.7A Pending EP4149900A1 (de) | 2020-05-13 | 2021-05-11 | Verfahren und anlage zur aktivierung von tonen |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP4149900A1 (de) |
CN (1) | CN115916722A (de) |
DE (1) | DE102020112894A1 (de) |
WO (1) | WO2021228430A1 (de) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2223854C2 (ru) * | 2001-08-28 | 2004-02-20 | Шлегель Игорь Феликсович | Способ подготовки глинистого сырья и устройство для его осуществления |
WO2007099415A1 (en) * | 2006-02-28 | 2007-09-07 | Flsmidth A/S | Method and plant for drying and comminution of moist, mineral raw materials |
US20120160135A1 (en) | 2010-12-13 | 2012-06-28 | Flsmidth A/S | Process for the Manufacture of Synthetic Pozzolan |
DE102011014498B4 (de) | 2011-03-18 | 2013-04-25 | Outotec Oyj | Verfahren zur Herstellung eines Klinkerersatzstoffes, Klinkerersatzstoff, Verwendung des Klinkerersatzstoffs, Zementklinker, Zement, Mörtel oder Beton, Verfahren zur Herstellung des Zementklinkers oder eines Baustoffs und Bauwerk |
DE102014116373A1 (de) | 2014-11-10 | 2016-05-12 | Thyssenkrupp Ag | Verfahren zur Wärmebehandlung von natürlichen Tonen und/oder Zeolithen |
DE102016005285B3 (de) * | 2016-04-30 | 2017-08-10 | Khd Humboldt Wedag Gmbh | Verfahren und Anlage zur Aktivierung von Tonen als Zusatzstoff für Beton |
CN109776002B (zh) * | 2019-03-06 | 2024-01-19 | 中国中材国际工程股份有限公司 | 一种适宜粘土矿尾矿的悬浮煅烧活化系统及方法 |
-
2020
- 2020-05-13 DE DE102020112894.0A patent/DE102020112894A1/de active Pending
-
2021
- 2021-05-11 EP EP21729405.7A patent/EP4149900A1/de active Pending
- 2021-05-11 WO PCT/EP2021/000065 patent/WO2021228430A1/de unknown
- 2021-05-11 CN CN202180049732.8A patent/CN115916722A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
CN115916722A (zh) | 2023-04-04 |
DE102020112894A1 (de) | 2021-11-18 |
WO2021228430A1 (de) | 2021-11-18 |
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