CA2912945C - Method for producing a cement clinker substitute - Google Patents
Method for producing a cement clinker substitute Download PDFInfo
- Publication number
- CA2912945C CA2912945C CA2912945A CA2912945A CA2912945C CA 2912945 C CA2912945 C CA 2912945C CA 2912945 A CA2912945 A CA 2912945A CA 2912945 A CA2912945 A CA 2912945A CA 2912945 C CA2912945 C CA 2912945C
- Authority
- CA
- Canada
- Prior art keywords
- flux
- starting material
- alkaline earth
- cement clinker
- heat treatment
- 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.)
- Expired - Fee Related
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- 239000004568 cement Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000007858 starting material Substances 0.000 claims abstract description 24
- 239000010457 zeolite Substances 0.000 claims abstract description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 230000004907 flux Effects 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 10
- -1 alkaline earth metal sulfates Chemical class 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 150000003839 salts Chemical group 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 3
- 239000002734 clay mineral Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000001339 alkali metal compounds Chemical group 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 12
- 229910001508 alkali metal halide Inorganic materials 0.000 claims 1
- 150000008045 alkali metal halides Chemical class 0.000 claims 1
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 1
- 239000004927 clay Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 238000012545 processing Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004567 concrete Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 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
- C04B7/13—Mixtures thereof with inorganic cementitious materials, e.g. Portland cements
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/10—Clay
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/10—Clay
- C04B14/106—Kaolin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/18—Carbon capture and storage [CCS]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Civil Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the production of a cement clinker substitute, in which a) a starting material in the form of natural and/or synthetic, zeolite-containing puzzolan and/or clay is provided, and b) said starting material is thermally treated to produce the cement clinker substitute in a temperature range of between 500 - 1200°C, characterized in that c) prior to and/or during the thermal treatment of the starting material, at least one liquid agent, which reduces the inner surface of the cement clinker substitute, is added.
Description
METHOD FOR PRODUCING A CEMENT CLINKER SUBSTITUTE
The invention relates to a method for producing a cement clinker substitute with a starting material in the form of natural and/or synthetic, zeolite-containing pozzolan and/or clays.
Cement is used as a binder in the production of concrete and mortar and consists essentially of cement clinker which causes high CO2 emissions in its production. Against the background of CO2 saving, cement clinker substitutes are more and more often being admixed to the cement, and for their part emit little or no physical CO2 in the course of a heat treatment, and also have a lower energy requirement relative to cement clinker, by virtue of the lower temperature level needed for their activation, so producing a reduction in CO2 output. Particularly suitable in this regard are naturally occurring clays or zeolite-containing pozzolans, which, through a targeted heat treatment, can be converted into substances having pozzolanic properties and can be used in particular as a cement clinker substitute.
A drawback of cement clinker substitutes produced in such a way, however, is a significantly increased water demand (w/c index) when employed technically in the building material, resulting in particular in a deterioration as well in the early strength and in the processability of the fresh concrete. As the water demand goes up, a less favorable development of strength is observed.
The object on which the invention was based was therefore that of achieving a significant lowering of the water demand of the cement clinker substitute, placing it preferably within the order of magnitude of a pure OPC cement, and thereby allowing an increase in the strength, especially the early strength.
The invention relates to a method for producing a cement clinker substitute with a starting material in the form of natural and/or synthetic, zeolite-containing pozzolan and/or clays.
Cement is used as a binder in the production of concrete and mortar and consists essentially of cement clinker which causes high CO2 emissions in its production. Against the background of CO2 saving, cement clinker substitutes are more and more often being admixed to the cement, and for their part emit little or no physical CO2 in the course of a heat treatment, and also have a lower energy requirement relative to cement clinker, by virtue of the lower temperature level needed for their activation, so producing a reduction in CO2 output. Particularly suitable in this regard are naturally occurring clays or zeolite-containing pozzolans, which, through a targeted heat treatment, can be converted into substances having pozzolanic properties and can be used in particular as a cement clinker substitute.
A drawback of cement clinker substitutes produced in such a way, however, is a significantly increased water demand (w/c index) when employed technically in the building material, resulting in particular in a deterioration as well in the early strength and in the processability of the fresh concrete. As the water demand goes up, a less favorable development of strength is observed.
The object on which the invention was based was therefore that of achieving a significant lowering of the water demand of the cement clinker substitute, placing it preferably within the order of magnitude of a pure OPC cement, and thereby allowing an increase in the strength, especially the early strength.
- 2 -In accordance with the invention, this object is achieved by means of a method for producing a cement clinker substitute by providing a starting material in the form of natural clays, alone or with or else natural or synthetic, zeolite-containing pozzolan alone, and heat-treating it as a starting material for producing the cement clinker substitute in a temperature range of 500-1200 C. Here, before and/or during the heat treatment of the starting material, at least one flux is added which reduces the specific surface area of the cement clinker substitute during the actual heat treatment. In particular, as a result of the flux, open pores in the clinker substitute that are unfavorable with regard to water demand become calcined clay, and partial to complete melting causes collapse of the framework structures of the zeolite minerals.
Another effect of the flux is to lower the melting point, thereby promoting melt formation during the heat treatment, especially in rotary kilns or entrained flow reactors. This leads to earlier and/or better melting of the clay-containing and/or zeolite-containing particles, and so the evaporated water of crystallization can escape from the plastified microstructure more quickly or more completely, open-pore bubble structures collapse as a result of the increased melt proportion, and hence the formation of permanent cavities is suppressed.
As a result of the addition of the flux, the water demand of the cement clinker substitute can be lowered by 6.5% or more. As a measurement variable for assessing the effect of the flux on the processing capacity, the water/cement index is employed. It is determined on the basis of ASTM C1437-07 and C230. The quantity determined in this case is the amount of water required to achieve a slump of 110%. In the text below, this variable is referred to as w/c index.
Another effect of the flux is to lower the melting point, thereby promoting melt formation during the heat treatment, especially in rotary kilns or entrained flow reactors. This leads to earlier and/or better melting of the clay-containing and/or zeolite-containing particles, and so the evaporated water of crystallization can escape from the plastified microstructure more quickly or more completely, open-pore bubble structures collapse as a result of the increased melt proportion, and hence the formation of permanent cavities is suppressed.
As a result of the addition of the flux, the water demand of the cement clinker substitute can be lowered by 6.5% or more. As a measurement variable for assessing the effect of the flux on the processing capacity, the water/cement index is employed. It is determined on the basis of ASTM C1437-07 and C230. The quantity determined in this case is the amount of water required to achieve a slump of 110%. In the text below, this variable is referred to as w/c index.
- 3 -Further embodiments of the invention are described herein.
According to one preferred embodiment of the invention, the at least one flux is selected from the group of the alkali metal compounds or from the group of the alkaline earth metal compounds and/or from mixtures of these compounds. The at least one flux here may be selected more particularly from the group of the alkali metal oxides and/or alkaline earth metal oxides or alkali alkaline metal-alkaline earth metal halides or alkali metal hydroxides and/or alkaline earth metal hydroxides or alkali metal sulfates and/or alkaline earth metal sulfates or alkali metal carbonates and/or alkaline earth metal carbonates, or an oxide from the group of the transition metals (e.g., Fe0, Fe2O3), and/or from mixtures of these groups.
The at least one flux may further comprise salts of aluminum, iron, or zinc, or salts of organic acids (especially carboxylic acids), and/or mixtures thereof. Furthermore, the at least one flux may be at least one chloridic compound with a proportion of 0.1 to 0.52 wt%, preferably 0.2 to 0.4 wt%, more particularly 0.25 to 0.35 wt%, relative to the raw material applied.
The addition in solution form in particular ensures that with the low volume proportions of the solid in the atmosphere of the kiln/reactor, an effect is obtained on the clay particles or zeolites themselves. In the case of dry addition, this effect may be achieved by intensive mixing or joint milling or by electrochemical modifications to the particle surfaces.
The heat treatment may take place in particular in an entrained flow reactor or in a kiln, more particularly a rotary kiln, or in a fluidized bed. It is possible here to employ temperatures preferably of 650 to 1000 C and most preferably of 830 to 950 C.
Starting material contemplated includes, in particular, clay mineral-containing substances and/or zeolite-containing
According to one preferred embodiment of the invention, the at least one flux is selected from the group of the alkali metal compounds or from the group of the alkaline earth metal compounds and/or from mixtures of these compounds. The at least one flux here may be selected more particularly from the group of the alkali metal oxides and/or alkaline earth metal oxides or alkali alkaline metal-alkaline earth metal halides or alkali metal hydroxides and/or alkaline earth metal hydroxides or alkali metal sulfates and/or alkaline earth metal sulfates or alkali metal carbonates and/or alkaline earth metal carbonates, or an oxide from the group of the transition metals (e.g., Fe0, Fe2O3), and/or from mixtures of these groups.
The at least one flux may further comprise salts of aluminum, iron, or zinc, or salts of organic acids (especially carboxylic acids), and/or mixtures thereof. Furthermore, the at least one flux may be at least one chloridic compound with a proportion of 0.1 to 0.52 wt%, preferably 0.2 to 0.4 wt%, more particularly 0.25 to 0.35 wt%, relative to the raw material applied.
The addition in solution form in particular ensures that with the low volume proportions of the solid in the atmosphere of the kiln/reactor, an effect is obtained on the clay particles or zeolites themselves. In the case of dry addition, this effect may be achieved by intensive mixing or joint milling or by electrochemical modifications to the particle surfaces.
The heat treatment may take place in particular in an entrained flow reactor or in a kiln, more particularly a rotary kiln, or in a fluidized bed. It is possible here to employ temperatures preferably of 650 to 1000 C and most preferably of 830 to 950 C.
Starting material contemplated includes, in particular, clay mineral-containing substances and/or zeolite-containing
- 4 -substances, such as kaolin or zeolitized natural pozzolans, for example. The proportion of the flux is preferably 0.1 to 5 wt%, preferably 1 to 2.5 wt%, and more particularly 1.2 to 1.8 wt%.
The at least one flux is mixed with the starting material preferably before the heat treatment. It is also possible for the at least one flux to be added together with a liquid or in dry form to the starting material. It is conceivable, furthermore, for a mixture of starting material and the at least one flux to be electrostatically charged before the heat treatment, causing the flux to accumulate on surfaces and promoting the reduction in the specific surface area of the cement clinker substitute. It is further conceivable for a flocculant to be added to the mixture of starting material and the at least one flux before the heat treatment. As a result of such a flocculant, a higher internal surface area is generated in the agglomerates, and in turn brings about greater bonding between the flux and the clay-containing or zeolite-containing material to be calcined, and also provides a more intense interaction between flux and the material to be calcined.
The open pore structure of untreated clays and of zeolite-containing pozzolans, in particular, is unbeneficial to the water demand and hence to the processing properties of untreated raw materials. As a result of the addition of the flux, the usually porous grains of the starting material in the heat operation become sealed at the surface, and so, in the course of subsequent processing, initially to give the binder and then in the concrete, less water is taken up and absorbed on the internal surface area. As a result of the addition of the flux, the cement clinker substitute produced is found to have significantly better processing qualities. In particular, for the same or similar addition of water, the processability approaches that of the conventional OPC cement. Moreover, the early strength is increased as a result of dispensing with
The at least one flux is mixed with the starting material preferably before the heat treatment. It is also possible for the at least one flux to be added together with a liquid or in dry form to the starting material. It is conceivable, furthermore, for a mixture of starting material and the at least one flux to be electrostatically charged before the heat treatment, causing the flux to accumulate on surfaces and promoting the reduction in the specific surface area of the cement clinker substitute. It is further conceivable for a flocculant to be added to the mixture of starting material and the at least one flux before the heat treatment. As a result of such a flocculant, a higher internal surface area is generated in the agglomerates, and in turn brings about greater bonding between the flux and the clay-containing or zeolite-containing material to be calcined, and also provides a more intense interaction between flux and the material to be calcined.
The open pore structure of untreated clays and of zeolite-containing pozzolans, in particular, is unbeneficial to the water demand and hence to the processing properties of untreated raw materials. As a result of the addition of the flux, the usually porous grains of the starting material in the heat operation become sealed at the surface, and so, in the course of subsequent processing, initially to give the binder and then in the concrete, less water is taken up and absorbed on the internal surface area. As a result of the addition of the flux, the cement clinker substitute produced is found to have significantly better processing qualities. In particular, for the same or similar addition of water, the processability approaches that of the conventional OPC cement. Moreover, the early strength is increased as a result of dispensing with
- 5 -diluting "water and/or plasticizer". The addition of the flux can also be used, however, to correct the water demand of zeolite-containing pozzolans. Without the heat treatment, these pozzolans absorb water in the open framework structures, and so reduce the processing capacity. Through the addition of the flux before and/or during a heat treatment of the cement clinker substitute, the water demand of these substances is also reduced by partial melting of the zeolites.
As fluxes, from the group of the alkali metal salts, the following substances are contemplated in particular:
KC1, K2S 0 4 f K2S , K2C0 3 , KF, KNO3, K2CO3 , K3 PO4 , K2B0 3 , K20, etc., or NaCi, Na2SO4, Na2S03, NaF, NaNO3, Na2CO3, Na3PO4, Na2B03, Na2O.
Examples contemplated from the group of the alkaline earth metal compounds include CaF2, CaCl2, CaSO4, CaS, CaCO3, CaF2, Ca(NO3)2, CaCO3, Ca3(PO4)2, CaB03, CaO, etc., or MgF2, MgCl2, MgSO4, MgS, MgCO3, MgF2, Mg(NO3)2, MgCO3, Mg3(PO4)2, MgB 3, MgO.
In the experiments of which the invention was based, sodium carbonate (Na2CO3) gave the best values for a lower w/c index.
Example 1 In this example, the starting material selected was kaolin, and 1% Na2CO3 was added as flux.
Following the heat treatment, about 70% of CEM I and about 30%
of meta-kaolin with flux adhering were mixed for the w/c index determination. The w/c index of the meta-kaolin-comprising cement with flux adhering resulted in a reduction, as a consequence of the addition of flux, by 4.7%, in comparison to a cement comprising meta-kaolin which had undergone flux-free treatment (w/c index = 0.618).
As fluxes, from the group of the alkali metal salts, the following substances are contemplated in particular:
KC1, K2S 0 4 f K2S , K2C0 3 , KF, KNO3, K2CO3 , K3 PO4 , K2B0 3 , K20, etc., or NaCi, Na2SO4, Na2S03, NaF, NaNO3, Na2CO3, Na3PO4, Na2B03, Na2O.
Examples contemplated from the group of the alkaline earth metal compounds include CaF2, CaCl2, CaSO4, CaS, CaCO3, CaF2, Ca(NO3)2, CaCO3, Ca3(PO4)2, CaB03, CaO, etc., or MgF2, MgCl2, MgSO4, MgS, MgCO3, MgF2, Mg(NO3)2, MgCO3, Mg3(PO4)2, MgB 3, MgO.
In the experiments of which the invention was based, sodium carbonate (Na2CO3) gave the best values for a lower w/c index.
Example 1 In this example, the starting material selected was kaolin, and 1% Na2CO3 was added as flux.
Following the heat treatment, about 70% of CEM I and about 30%
of meta-kaolin with flux adhering were mixed for the w/c index determination. The w/c index of the meta-kaolin-comprising cement with flux adhering resulted in a reduction, as a consequence of the addition of flux, by 4.7%, in comparison to a cement comprising meta-kaolin which had undergone flux-free treatment (w/c index = 0.618).
- 6 -Example 2 With a higher addition of Na2CO3, of 1.75%, it was possible to lower the w/c index to 0.58. Starting from the w/c value of 0.618 for a cement comprising meta-kaolin which had undergone flux-free treatment, this corresponds to an improvement of 6.1%.
Example 3 In the case of even higher addition of Na2CO3 (2.5%), an improvement in the w/c index of 6.5% was found, in comparison to a flux-free kaolin treatment.
Example 4 When sodium chloride is used as a flux, the w/c index, for a 1%
addition, is situated within the same order of magnitude as for the addition of 1% of Na2CO3, namely at 0.586.
The use of the flux significantly improves the processing properties of the starting material in the form of natural and/or synthetic, zeolite-containing pozzolans and/or clays. The reason for this lies in particular in the melting point-lowering effect of the flux, and so the particle surface softens even at relatively low temperatures.
As elucidated above, a reduced water demand in the processing of the cement may contribute to an increase in the early strength and hence, for example, to earlier deshuttering. This can be controlled or influenced deliberately through the use of fluxes in the production of cement clinker substitutes. In addition, the use of fluxes allows energy-optimized production of certain cement clinker substitutes, by virtue of the possibility of treating the materials for achieving the desired properties of the cement clinker substitute at a lower temperature level.
Example 3 In the case of even higher addition of Na2CO3 (2.5%), an improvement in the w/c index of 6.5% was found, in comparison to a flux-free kaolin treatment.
Example 4 When sodium chloride is used as a flux, the w/c index, for a 1%
addition, is situated within the same order of magnitude as for the addition of 1% of Na2CO3, namely at 0.586.
The use of the flux significantly improves the processing properties of the starting material in the form of natural and/or synthetic, zeolite-containing pozzolans and/or clays. The reason for this lies in particular in the melting point-lowering effect of the flux, and so the particle surface softens even at relatively low temperatures.
As elucidated above, a reduced water demand in the processing of the cement may contribute to an increase in the early strength and hence, for example, to earlier deshuttering. This can be controlled or influenced deliberately through the use of fluxes in the production of cement clinker substitutes. In addition, the use of fluxes allows energy-optimized production of certain cement clinker substitutes, by virtue of the possibility of treating the materials for achieving the desired properties of the cement clinker substitute at a lower temperature level.
Claims (13)
1. A method for producing a cement clinker substitute by a. providing a starting material in the form of natural or synthetic zeolite-containing pozzolan or clays, and b. heat-treating the starting material for producing the cement clinker substitute in a temperature range of 650-1000°C, wherein the heat treatment takes place in an entrained flow reactor, in a kiln, or in a fluidized bed;
and wherein before or during the heat treatment of the starting material, at least one flux is added which reduces the internal surface area of the cement clinker substitute.
and wherein before or during the heat treatment of the starting material, at least one flux is added which reduces the internal surface area of the cement clinker substitute.
2. The method as claimed in claim 1, wherein the at least one flux is selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, and mixtures thereof.
3. The method as claimed in claim 1 or 2, wherein the at least one flux is selected from the group consisting of alkali metal oxides, alkaline earth metal oxides, alkali metal halides, alkaline earth metal halides, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal sulfates, alkaline earth metal sulfates, alkali metal carbonates, alkaline earth metal carbonates, transition metal oxides, and mixtures thereof.
4. The method as claimed in claim 1, wherein the at least one flux is selected from the group consisting of salts of aluminum, salts of iron, salts of zinc, salts of organic acids, and mixtures thereof.
5. The method as claimed in claim 1, wherein the starting material comprises a clay mineral-containing substance.
6. The method as claimed in claim 1, wherein the starting material comprises a zeolite-containing natural or synthetic pozzolan.
7. The method as claimed in claim 5, wherein kaolin is used as the clay mineral-containing substance.
8. The method as claimed in claim 1, wherein the flux is used with a proportion of 0.1-5 wt%.
9. The method as claimed in claim 1, wherein a chloridic compound with a proportion of 0.1-0.52 wt% is used as the at least one flux.
10. The method as claimed in claim 1, wherein the at least one flux is mixed with the starting material before the heat treatment.
11. The method as claimed in claim 1, wherein the at least one flux is added together with a liquid or in dry form to the starting material.
12. The method as claimed in claim 1, wherein a mixture of the starting material and the at least one flux is electrostatically charged before the heat treatment.
13. The method as claimed in claim 1, wherein a flocculant is added to a mixture of the starting material and the at least one flux before the heat treatment.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102013105301.7A DE102013105301A1 (en) | 2013-05-23 | 2013-05-23 | Process for the preparation of a binder substitute |
| DE102013105301.7 | 2013-05-23 | ||
| PCT/EP2014/001284 WO2014187537A1 (en) | 2013-05-23 | 2014-05-13 | Method for producing a cement clinker substitute |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2912945A1 CA2912945A1 (en) | 2014-11-27 |
| CA2912945C true CA2912945C (en) | 2020-03-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2912945A Expired - Fee Related CA2912945C (en) | 2013-05-23 | 2014-05-13 | Method for producing a cement clinker substitute |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2999673B1 (en) |
| CN (1) | CN105324346B (en) |
| BR (1) | BR112015029128A2 (en) |
| CA (1) | CA2912945C (en) |
| DE (1) | DE102013105301A1 (en) |
| RU (1) | RU2672271C2 (en) |
| WO (1) | WO2014187537A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3224219B1 (en) * | 2014-11-24 | 2020-06-17 | HeidelbergCement AG | Clinker replacement material made of aluminium silicate and dolomite |
| DE102015118391A1 (en) * | 2015-10-28 | 2017-05-04 | Thyssenkrupp Ag | Process for the preparation of a cement clinker substitute consisting primarily of calcined clay |
| CN108640558B (en) * | 2018-04-04 | 2019-10-01 | 乐清市华尊电气有限公司 | A kind of enhancing concrete admixture and preparation method thereof |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU41899A1 (en) * | 1934-03-01 | 1935-02-28 | А.П. Глинский | The method of burning in dying substances and hydraulic additives in suspension |
| US2307239A (en) * | 1939-09-26 | 1943-01-05 | Edgar Brothers Company | Modified clay |
| SU90807A1 (en) * | 1950-09-09 | 1950-11-30 | П.Д. Требуков | The method of obtaining in the living substance of the type of cement |
| SU92580A1 (en) * | 1951-01-29 | 1951-11-30 | В.Р. Фирфаров | The method of obtaining from clay-gypsum (drywall) high-strength concrete construction material |
| AU469769B2 (en) * | 1973-11-19 | 1976-02-26 | Warman International Limited | Process forthe separation of tungsten and molybdenum |
| DE2722564A1 (en) * | 1977-05-18 | 1978-11-30 | Giulini Chemie | Zeolite A prodn. from meta:kaolin and sodium hydroxide - by mixing to aq. slurry and heating, for short reaction time |
| FR2566388B1 (en) * | 1984-06-25 | 1986-11-14 | Champagnole Ciments | IMPROVEMENTS IN THE MANUFACTURE OF HYDRAULIC BINDERS AND PRODUCTS THUS OBTAINED |
| US5183506A (en) * | 1987-08-19 | 1993-02-02 | Zhang Zhong M | Modified flux composition for cement |
| FR2694552B1 (en) * | 1992-08-05 | 1994-10-28 | Vicat | Hydraulic binders with rapid setting and hardening, their preparation and their use for the preparation of mortars and concretes. |
| UA10527C2 (en) * | 1993-03-31 | 1997-12-25 | Тетяна Іванівна Спінжар | binding agent |
| NL9401366A (en) * | 1994-08-24 | 1996-04-01 | Brp De Bilt Bv | Process for the preparation of a pozzolanic material from paper residue and process for the production of cement therefrom. |
| US6409819B1 (en) * | 1998-06-30 | 2002-06-25 | International Mineral Technology Ag | Alkali activated supersulphated binder |
| US6136086A (en) * | 1998-11-19 | 2000-10-24 | Englehard Corporation | Low sheen opacifying pigments and manufacture thereof by calcination of kaolin clay |
| CN1115309C (en) * | 2000-05-31 | 2003-07-23 | 蒋兆广 | Flyash treating method |
| RU2275505C1 (en) * | 2004-11-05 | 2006-04-27 | Акционерная компания "АЛРОСА" (Закрытое акционерное общество) | Solidifying clinker-free stowing mix |
| DE102010009373A1 (en) * | 2010-02-25 | 2011-08-25 | SRZ Schutzrechte Verwaltungs-GmbH, 90571 | Composition of a shaped body for use as an insulating board, method for its production and insulation board |
| WO2012129476A1 (en) * | 2011-03-24 | 2012-09-27 | Board Of Regents Of The University Of Texas System | Encapsulated zinc compounds and methods for preparing and using same |
| BR112014003590A2 (en) * | 2011-08-18 | 2017-03-14 | Heidelbergcement Ag | process for ternesite preparation |
| CN102515579B (en) * | 2011-12-08 | 2013-11-13 | 湖南科技大学 | Method for preparing geological polymeric material by using low-grade kaolin |
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- 2013-05-23 DE DE102013105301.7A patent/DE102013105301A1/en not_active Ceased
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- 2014-05-13 BR BR112015029128A patent/BR112015029128A2/en active Search and Examination
- 2014-05-13 RU RU2015152260A patent/RU2672271C2/en active
- 2014-05-13 EP EP14725009.6A patent/EP2999673B1/en active Active
- 2014-05-13 CA CA2912945A patent/CA2912945C/en not_active Expired - Fee Related
- 2014-05-13 CN CN201480035613.7A patent/CN105324346B/en not_active Expired - Fee Related
- 2014-05-13 WO PCT/EP2014/001284 patent/WO2014187537A1/en active Application Filing
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| RU2672271C2 (en) | 2018-11-13 |
| CA2912945A1 (en) | 2014-11-27 |
| RU2015152260A (en) | 2017-06-28 |
| EP2999673B1 (en) | 2020-11-11 |
| EP2999673A1 (en) | 2016-03-30 |
| BR112015029128A2 (en) | 2017-07-25 |
| CN105324346A (en) | 2016-02-10 |
| WO2014187537A1 (en) | 2014-11-27 |
| CN105324346B (en) | 2018-09-25 |
| DE102013105301A1 (en) | 2014-11-27 |
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