EP4118058A1 - Method for producing a binder - Google Patents
Method for producing a binderInfo
- Publication number
- EP4118058A1 EP4118058A1 EP20839233.2A EP20839233A EP4118058A1 EP 4118058 A1 EP4118058 A1 EP 4118058A1 EP 20839233 A EP20839233 A EP 20839233A EP 4118058 A1 EP4118058 A1 EP 4118058A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- residue
- binder
- heating
- weight
- calcium
- 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
- 239000011230 binding agent Substances 0.000 title claims abstract description 112
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 60
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims description 60
- 238000010276 construction Methods 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 54
- 239000000047 product Substances 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 26
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 25
- 229910001424 calcium ion Inorganic materials 0.000 claims description 25
- 239000013067 intermediate product Substances 0.000 claims description 24
- 238000012545 processing Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000004570 mortar (masonry) Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 150000004645 aluminates Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000003651 drinking water Substances 0.000 claims description 6
- 235000020188 drinking water Nutrition 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- -1 calcium aluminates Chemical class 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011368 organic material Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 238000010891 electric arc Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 239000011505 plaster Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 31
- 229940024545 aluminum hydroxide Drugs 0.000 description 25
- 238000010304 firing Methods 0.000 description 17
- 239000002994 raw material Substances 0.000 description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 230000018109 developmental process Effects 0.000 description 8
- 150000004677 hydrates Chemical class 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- 229910021653 sulphate ion Inorganic materials 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000011411 calcium sulfoaluminate cement Substances 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- C04B7/24—Cements from oil shales, residues or waste other than slag
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- 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
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
- C02F11/08—Wet air oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/123—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using belt or band filters
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/13—Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
- C02F11/145—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances using calcium compounds
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- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
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- 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
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- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
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- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2611—Polyalkenes
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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- C04B28/06—Aluminous cements
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
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- C04B28/145—Calcium sulfate hemi-hydrate with a specific crystal form
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/145—Calcium sulfate hemi-hydrate with a specific crystal form
- C04B28/147—Calcium sulfate hemi-hydrate with a specific crystal form beta-hemihydrate
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/16—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing anhydrite, e.g. Keene's cement
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- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/40—Dehydrating; Forming, e.g. granulating
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- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/434—Preheating with addition of fuel, e.g. calcining
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- C04B7/00—Hydraulic cements
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- C04B7/44—Burning; Melting
- C04B7/4407—Treatment or selection of the fuel therefor, e.g. use of hazardous waste as secondary fuel ; Use of particular energy sources, e.g. waste hot gases from other processes
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- C04B7/52—Grinding ; After-treatment of ground cement
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- C04B7/522—After-treatment of ground cement
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
- F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
- F23G5/0273—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage using indirect heating
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/08—Rotary-drum furnaces, i.e. horizontal or slightly inclined externally heated
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
- F27B7/36—Arrangements of air or gas supply devices
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
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- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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- C04B2111/00646—Masonry mortars
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/60—Flooring materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F23G2201/20—Dewatering by mechanical means
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- 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
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- F27B2007/005—Rotary-drum furnaces, i.e. horizontal or slightly inclined for the treatment of slurries or wet materials
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- 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
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- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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
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- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/125—Fuels from renewable energy sources, e.g. waste or biomass
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to a binder, a method for producing a binder and the use of a binder.
- the invention also relates to a construction chemical product comprising such a binder.
- the construction industry has recorded steadily increasing incoming orders in recent years, driven by government investments, and occupies a considerable part of the manufacturing industry. With a view to complying with climate policy goals that have recently come into focus more and more, the construction industry is therefore increasingly required to pursue environmentally friendly and sustainable concepts. For this reason, the concept of sustainable building has been established for some time, which uses different approaches aims to carry out construction work while preserving the ecosystem and the environment.
- the object of the present invention to at least partially remedy the aforementioned disadvantages of known binders or construction chemical products.
- a method for producing a binder comprises the steps of processing a residue that has amorphous aluminum oxide-containing and / or aluminum hydroxide-containing components and heating the residue to produce a burned material, the heating of the residue taking place at a temperature of> 800 ° C.
- a binder according to the invention can then be used in particular in construction chemical products such as screeds, fillers, tile adhesives, leveling compounds, mortars, grouts or plasters or the like, which in turn can be used, for example, for laying natural stone, stone, tiles, slabs or the like.
- a binder can preferably be understood as a material which can be used as a hardening element in construction chemical products.
- binders according to the invention can independently harden or solidify, preferably as a result of chemical reactions with the mixing water, and after hardening remain solid and stable in space.
- the binder according to the invention can preferably be in the form of a hydraulic binder which, after hardening, remains solid and stable even under water.
- binders can be understood as meaning, for example: calcium aluminate cements and / or calcium sulfoaluminate cements and / or portland cements and / or hydrated lime and / or calcium oxide and / or calcium hydroxide and / or calcium sulfate.
- pozzolans, lime or similar substances that can act as binders.
- a residue is understood to mean, in particular, a residue that occurs in a process, for which no or only limited reuse is intended and which therefore has to be disposed of - sometimes in a complex and costly manner.
- processing can in particular be understood to mean a form of treatment that includes, for example, collecting, filtering, drying, comminuting or the like.
- An amorphous residue or an amorphous material can in particular be understood to mean a material which is present in a non-crystalline state at least in a proportion of 50% by weight.
- the material can in particular be X-ray amorphous to an extent of at least 50% by weight, i.e. that in particular at least 50% by weight of the material does not produce sharp reflections in X-ray diffraction experiments, but only broad diffuse maxima.
- the residual material containing aluminum oxide and / or aluminum hydroxide according to the invention can advantageously have an aluminum oxide or aluminum hydroxide content (the sum of the aluminum oxide and aluminum hydroxide) of at least 5% by weight, preferably of at least 30% by weight, in particular of at least 50% by weight, based on the dry content of the material or residue. It goes without saying that the material can essentially only be formed in the form of one of the two components.
- a fired material can in particular be understood to mean the material obtained in a thermal process, such as a firing process, which has a changed structure compared to its initial state, in particular a changed chemical structure, due to the energy supply during the firing process.
- a sintered material, a coked material, a pyrolysed material, a calcined or a roasted material or the like can also be understood as a burned material.
- a versatile binding agent can be produced in a simple and inexpensive manner, which at the same time makes a contribution to sustainable building, the contribution in this case in particular thereby it is delivered that natural resources are conserved by using residual or waste materials for the production of the binding agent, which otherwise would have to be disposed of in a complex and costly manner.
- a temperature above 800 ° C. is necessary for processing.
- the residue is at least partially, preferably completely, formed in the form of water treatment residues.
- the residue can at least partially, preferably completely in the form of Be formed drinking water treatment residues.
- Drinking water treatment residues in particular have a very high aluminum oxide and / or aluminum hydroxide content and are much less laborious to clean up than other residues, such as waste water treatment residues or similar residues, in particular because they are less polluted. Due to the different constituents of drinking water and wastewater, these (drinking water / wastewater) cannot be directly compared.
- the residual material can also preferably be designed in the manner of a sludge, for example in the form of a drinking water treatment sludge.
- the amorphous aluminum oxide-containing and / or aluminum hydroxide-containing residue has an X-ray amorphous proportion of more than 80% by weight, preferably of more than 85% by weight, in particular of has more than 90%.
- the amorphous residue advantageously has less than 20% by weight, preferably less than 15% by weight, in particular less than 10% by weight, crystalline proportions that can be detected by X-ray diffraction experiments.
- X-ray diffraction experiments to determine the amorphous portion of the residue can be carried out in accordance with DIN EN 13925-1, for example.
- the processing of the residue includes the removal of water, the removal of the water preferably via heating and / or a mechanical dewatering process or preferably via simple dumping of the residue he follows.
- the determination of the proportion of the relevant component for the production of a predetermined mixture can be carried out much more precisely and more simply because the exact water proportion does not have to be calculated out or is negligible.
- the processing of the residual material includes comminution, with the amorphous aluminum oxide-containing and / or aluminum hydroxide-containing residual material preferably having a particle size of less than 100 ⁇ m, particularly preferably a particle size of less than 50 ⁇ m, in particular to a particle size of less than 40 ⁇ m, is comminuted.
- the processing of the residual material takes place in such a way that a residual content of organic material remains as a fuel source in the amorphous aluminum oxide-containing and / or aluminum hydroxide-containing residual material.
- the organic material can function as fuel when it is subsequently heated and thus save energy and resources.
- An organic material is preferably understood here to mean a material which comprises carbon compounds and does not belong to one of the following types of compounds: anhydrous chalcogenides, carbonic acid, carbonates, carbides, cyanides, cyanates and thiocyanates.
- the processing of the residual material includes the removal of microorganisms, wherein the removal of the microorganisms can preferably include thermal treatment and / or drying.
- a calcium ion source is added to produce a material mixture before the residual material is heated.
- a source of calcium ions can in particular be understood to be a substance or mixture of substances which can release calcium ions.
- CaO, Ca (OH) 2 and CaCÜ 3 may be mentioned here as examples of calcium ion sources.
- the Ca (OH) 2 from residual and waste sources can advantageously be used here.
- a sulfate ion source can in particular be understood to be a substance or mixture of substances which can release sulfate ions.
- Calcium sulfate a-hemihydrate, calcium sulfate ß-hemihydrate, anhydrite, calcium sulfate dihydrate or mixtures thereof may be mentioned here by way of example as a source of sulfate ions.
- the CaSÜ 4 from residual and waste sources such as REA gypsum, can be used here.
- a sulfate ion source and subsequent addition of water can also be formed.
- Intermediate products containing hydrate phases can be formed in particular in the form of calcium aluminate hydrates and / or calcium sulfoaluminate hydrates or mixtures thereof.
- various binders or material mixtures can be produced before heating.
- a source of calcium ions and / or a source of sulfate ions can be added to produce the binder.
- the calcium ion source and / or the sulfate ion source can preferably be added before adding water to form advantageous hydrate phase intermediates, so that a mixture of:
- a sulphate ion source can also be prepared.
- the residue or the mixture of residue and / or a calcium ion source and / or a sulfate ion source can then be added to water to form an intermediate product containing hydrate phases.
- the resulting mixture can be blended and homogenized with one another using suitable processes.
- the resulting mixture can advantageously be given a reaction time of at least 30 minutes, preferably at least 12 hours, even more preferably at least 24 hours. In this way it can be ensured that a reaction equilibrium can develop that is free from crystalline Ca (OH) 2 or CaO.
- the intermediate products containing hydrate phases are additionally processed, the processing preferably including drying.
- the drying of the intermediate products containing the hydrate phase also saves energy in a downstream firing process and simplifies a subsequent comminution process of the intermediate products containing the hydrate phase.
- the processing of the hydrate phase-containing intermediate products includes comminution, the amorphous aluminum oxide-containing and / or aluminum hydroxide-containing residue preferably being comminuted to a particle size of less than 100 ⁇ m, particularly preferably to a particle size of less than 50 ⁇ m, in particular to a particle size of less than 40 ⁇ m will.
- a compression of the residual material and / or the material mixture and / or the hydrate phase-containing intermediate products can be provided to minimize the proportion of very fine material, the compression preferably being briquetting for the production of briquettes and / or pelleting for the production of pellets and / or can comprise granulating for the production of granules and / or pressing for the production of compacts.
- Such compression or compaction can in particular serve the purpose of introducing the residual material and / or the material mixture and / or the hydrate phase-containing intermediate products into a furnace in a simple and as complete manner as possible.
- Such a process can also be advantageous in order, for example, to ensure sufficient contact points for sintering or the like before a heating process.
- binders containing aluminate e.g. calcium aluminate cements
- aluminate e.g. calcium aluminate cements
- Conventional binders containing aluminate used in construction chemistry must be produced in an energy-intensive manner and are typically fired at firing temperatures of> 1400 ° C.
- Calcium sulfoaluminate-containing binders are usually fired at temperatures of> 1250 ° C.
- the necessary production temperature can be significantly reduced in the context of the invention compared to the prior art.
- binders containing aluminate preferably binders containing calcium aluminate or calcium sulfoaluminate
- binders containing calcium aluminate or calcium sulfoaluminate can be produced at temperatures well below the usual temperatures. These binders can then be used in construction chemical products.
- the processing time of the construction chemical products depends on the firing temperature during the production of the binders used. In the course of the invention, it was therefore necessary to find an optimal firing temperature which, on the one hand, should be as low as possible for environmental reasons and, on the other hand, high enough to be able to produce binders which enable practicable processing times when used in construction chemical products.
- the process steps provided according to the invention can be used to achieve a particularly advantageous compromise between a practical processing time when used in a construction chemical product and energy-saving production, especially at a temperature between 800 ° C and 1700 ° C.
- the heating of the residue and / or the material mixture and / or the hydrate phase-containing intermediates should be at a temperature of> 800 ° C, preferably at a temperature between 900 ° C and 1150 ° C, particularly preferably at a temperature between 950 ° C and 1050 ° C, in particular at a temperature of 980 ° C.
- the heating can advantageously take place in a rotary tube furnace and / or in a melting furnace and / or in an electric arc furnace and / or in a tub shaft furnace and / or in a fluidized bed calciner or the like.
- a final preparation of the fired material can be provided, wherein the preparation can include comminution, the binder preferably to a particle size of less than 100 ⁇ m, particularly preferably to a particle size of less than 50 ⁇ m, in particular to a particle size of less than 40 ⁇ m.
- preparation of the fired material can also advantageously include the addition of additives such as grinding aids, aging inhibitors and / or anti-dust agents.
- the invention also relates to a binder, in particular produced using a method described above.
- the binding agent in question has aluminates and / or calcium aluminates and / or calcium sulfoaluminates.
- the binder thus has the same advantages as have already been described in detail with regard to the method according to the invention.
- the possible resulting fired binders can then, depending on the raw material used, include the mineral phases CA and / or CA 2 and / or CA 3 and / or C 12 A 7 and / or CSA, in particular Ye'elimit, in various proportions.
- a particular advantage of the present invention is that the ratio of the resulting main mineral phases within the resulting binder is simple and flexible due to the mixing ratio of the three main components
- the invention can advantageously provide that the Al 2 O 3 from the processed aluminum oxide-containing and / or aluminum-hydroxide-containing residue in a proportion of more than 50 mol%, preferably in a proportion of more than 55 mol%, in particular in a proportion of more than 65 mol% based on the total mass of the binder.
- the invention also relates to the use of a binder described above for the production of a construction chemical product, preferably a screed, a filler, a tile adhesive, a leveling compound, a mortar, a joint mortar or a plaster.
- a binder described above for the production of a construction chemical product, preferably a screed, a filler, a tile adhesive, a leveling compound, a mortar, a joint mortar or a plaster.
- a construction chemical product can preferably be understood as a dry mixture of various functional substances made up of binders, fillers and functional additives in order to obtain a product which can fulfill construction chemical tasks tailored to construction sites.
- Examples include a screed, a filler, a tile adhesive, a leveling compound and / or a mortar for laying natural stone, stone, tiles or slabs.
- the chemical building products that can be produced with the aid of the binding agents in question can be suitable not only for laying natural stone, stone, tiles or slabs but also for laying other supporting materials such as mats, wooden floors, parquet, carpet, laminate and the like.
- the screed in question can also be designed as a flowing or dry screed.
- the mortar in question can also be designed as a joint mortar or thin-bed mortar.
- the filler can be designed, for example, in the form of a floor, wall or ceiling filler, whereas the tile adhesive can also be designed as a floor or wall tile adhesive.
- the invention also relates to a construction chemical product comprising an above-described binder, the binder in the construction chemical product in a proportion of 0.1% by weight to 80% by weight, preferably in a proportion of 1% by weight. % - 50% by weight, particularly preferably in a proportion of 5% by weight to 30% by weight, the construction chemical product additionally comprising fillers and / or additives.
- fillers for example, sands, chalk and light fillers or the like can be understood as fillers.
- Additives can be understood to mean, for example, flow agents and / or thickeners and / or dyes and / or color pigments and / or defoamers and / or stabilizers and / or hardening retarders and / or plastic fibers or the like.
- the construction chemical product can in particular be designed in such a way that the amount of heat given off by the mixture of water and construction chemical product after it has been mixed with water has an absolute maximum over time absolute maximum is preferably more than 20 minutes, particularly preferably more than 45 minutes, in particular more than 60 minutes.
- FIG. 1 shows a schematic representation of a phase diagram by way of example
- FIG. 2a shows a schematic representation of the individual steps of a method according to the invention for producing a binder according to a first exemplary embodiment
- FIG. 2b shows a schematic representation of the individual steps of a method according to the invention for producing a binder according to a second exemplary embodiment
- FIG. 2c shows a schematic representation of the individual steps of a method according to the invention for producing a binder according to a third exemplary embodiment
- FIG. 3 shows a schematic representation of various thermal calorimetric measurements a to f.
- FIG. 1 shows a schematic representation of a phase diagram of exemplary phases of a calcium aluminate cement.
- the raw materials used must be brought to temperatures close to the necessary solid / liquid phase transition, which, as can be seen in FIG. 1, are generally at least> 1700 K (> 1430 ° C).
- the necessary ones Production temperature for the production of binders containing aluminate can be significantly reduced.
- responsible for this is in particular the upstream formation of hydrates, which markedly lower the necessary firing temperature for producing the binder according to the invention in contrast to known firing temperatures.
- FIG. 2a shows a schematic representation of the individual steps of a method according to the invention for producing a binder according to a first exemplary embodiment.
- the method according to the invention according to the first exemplary embodiment can in particular be referred to as the calcium aluminate route and comprises the steps of processing 20 an amorphous aluminum oxide-containing and / or aluminum hydroxide-containing residue, adding 22 a calcium ion source and adding 26 water to form an intermediate product containing hydrate phases. Furthermore, the method according to the first exemplary embodiment comprises processing 28 of the intermediate product containing the hydrate phase and heating 30 of the material to produce a fired material, the material initially being heated at> 800.degree.
- the heated material is then processed 32 to obtain binding agents, before the binding agent is used 34 to produce a construction chemical product and 36 the construction chemical product is used as screed, filler, tile adhesive, leveling compound or mortar can.
- FIG. 2b shows a schematic representation of the individual steps of a method according to the invention for producing a binder according to a second exemplary embodiment.
- the method according to the second exemplary embodiment differs from the method according to the first exemplary embodiment only in that, in addition to adding 22 a calcium ion source, before adding 26 water to form an intermediate product containing hydrate phases, a sulfate ion source is also added.
- 2c shows a schematic representation of the individual steps of a method according to the invention for producing a binder according to a third exemplary embodiment.
- the method according to the invention according to the third exemplary embodiment runs without the addition of water and, in contrast to the exemplary embodiments according to FIGS Manufacture of a fired material, whereby the heating of the submitted material takes place at> 800 ° C.
- FIG. 3 shows a schematic representation of various thermal calorimetric measurements a) to f).
- the measurements of the heat development provide indirect information about the setting behavior of the respective binder-containing construction chemical product.
- a rapid and strong development of heat (here measured in the form of the voltage in mV) corresponds to a rapid setting of the construction chemical product containing the binder.
- the construction chemical products were measured by thermal calorimetry for 2 hours after the addition of water.
- the construction chemical products which contain binders, which were fired at a firing temperature of 800 ° C (b, e), show a rapid but controllable development of heat. After about 5 to 10 minutes, a sharp peak can be seen here, which then flattens off sharply.
- the absolute maximum of the heat development which is an easily determinable yet meaningful parameter for determining the processing time of a construction chemical product, is above 60 minutes for both construction chemical products with binders with a firing temperature of 980 ° C (c, f).
- a calcium ion source and / or optionally an additional sulfate ion source is added.
- the optional addition of the calcium ion source and / or the sulfate ion source is preferably carried out before the optional addition of water, which can advantageously be added to form intermediate products containing hydrate phases, so that a mixture of:
- the possible resulting binders after the process steps provided according to the invention have been carried out, have inter alia the mineral phases CA and / or CA 2 and / or CA 3 and / or C 12 A 7 and / or CSA in various concentrations, depending on the raw material used.
- a particular advantage of the present invention is that the main mineral phases of the resulting binder can be adjusted easily and flexibly through the mixing ratio of the three components 1, 2 and 3.
- the specified ratios are to be understood as molar ratios, based on the Aluminum content in the processed amorphous residual material containing aluminum oxide and / or aluminum hydroxide (1), on the calcium content in the calcium ion source (2) and on the sulphate content in the sulphate ion source (3).
- Binder mixture 1 (CA mixture):
- Binder mixture 2 (C ⁇ 2 mixture):
- Binder mixture 3 (Ci2A7 mixture):
- Binder mix 4 (CSA mix):
- Binder mixture 5 pure aluminate-containing binder:
- binders according to the invention can here in particular by a method according to the invention via the initial charge of components (1) or mixtures of components 1, 2 and 3, the optional addition of water to these components or mixtures to form hydrates, the processing of these hydrates, as well as heating the processed hydrates to a temperature of> 800 ° C.
- the binders according to the invention can also be produced without the addition of water to form intermediate products containing hydrate phases.
- the versatile, different binders according to the invention that can be produced using the mixtures listed in the exemplary embodiments are not only versatile and can be produced simply and inexpensively, but also make a contribution to sustainable construction at the same time, which is provided in particular by conserving resources for producing the hydraulic binders by using residual or waste materials to produce the binding agent, which otherwise would have to be disposed of in a complex and costly manner.
- Raw material base internally referred to as “CA”, manufactured at 180 ° C b construction chemical product, containing 20% by weight of a binding agent
- Raw material base internally referred to as “CA”, manufactured at 800 ° C c construction chemical product, containing 20% by weight of a binding agent
- Raw material base internally referred to as "CA”, manufactured at 980 ° C d construction chemical product, containing 20% by weight of a binder
- Raw material base internally referred to as "CA2”, manufactured at 180 ° C e construction chemical product, containing 20% by weight of a binding agent
- Raw material base internally referred to as “CA2”, manufactured at 800 ° C for a construction chemical product, containing 20% by weight of a binding agent
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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GB1908383.1A GB2586951B (en) | 2019-06-12 | 2019-06-12 | A method and apparatus for processing water treatment residuals |
GB2003674.5A GB2592985A (en) | 2019-06-12 | 2020-03-13 | A method for the manufacture of hydraulic binders from water treatment residuals |
PCT/EP2020/085745 WO2021180351A1 (en) | 2019-06-12 | 2020-12-11 | Method for producing a binder |
Publications (1)
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EP4118058A1 true EP4118058A1 (en) | 2023-01-18 |
Family
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Family Applications (4)
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EP20732860.0A Pending EP3983357A1 (en) | 2019-06-12 | 2020-06-12 | Use of a calcium aluminate-containing hydraulic binder for producing a building material |
EP20732866.7A Pending EP3983359A1 (en) | 2019-06-12 | 2020-06-12 | A method for the manufacture of hydraulic binders from water treatment residuals |
EP20732865.9A Pending EP3983358A1 (en) | 2019-06-12 | 2020-06-12 | A method and apparatus for processing water treatment residuals |
EP20839233.2A Pending EP4118058A1 (en) | 2019-06-12 | 2020-12-11 | Method for producing a binder |
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EP20732860.0A Pending EP3983357A1 (en) | 2019-06-12 | 2020-06-12 | Use of a calcium aluminate-containing hydraulic binder for producing a building material |
EP20732866.7A Pending EP3983359A1 (en) | 2019-06-12 | 2020-06-12 | A method for the manufacture of hydraulic binders from water treatment residuals |
EP20732865.9A Pending EP3983358A1 (en) | 2019-06-12 | 2020-06-12 | A method and apparatus for processing water treatment residuals |
Country Status (12)
Country | Link |
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US (4) | US20220242788A1 (en) |
EP (4) | EP3983357A1 (en) |
JP (4) | JP2022539963A (en) |
KR (4) | KR20220022485A (en) |
CN (4) | CN113939486A (en) |
AU (4) | AU2020290768A1 (en) |
BR (4) | BR112021024412A2 (en) |
CA (4) | CA3141396A1 (en) |
GB (2) | GB2586951B (en) |
MX (4) | MX2021014670A (en) |
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WO (5) | WO2020249736A1 (en) |
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KR102178176B1 (en) * | 2019-12-09 | 2020-11-12 | 김경철 | User terminal, video call apparatus, video call sysyem and method of controlling thereof |
CN111453970A (en) * | 2020-05-25 | 2020-07-28 | 中建水务环保有限公司 | Sludge atomization molding device |
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