EP4110742A1 - Auxiliaires de traitement et leur utilisation dans un procédé d'obtention d'agrégats et/ou d'un matériau minéral de type poudre - Google Patents

Auxiliaires de traitement et leur utilisation dans un procédé d'obtention d'agrégats et/ou d'un matériau minéral de type poudre

Info

Publication number
EP4110742A1
EP4110742A1 EP21705970.8A EP21705970A EP4110742A1 EP 4110742 A1 EP4110742 A1 EP 4110742A1 EP 21705970 A EP21705970 A EP 21705970A EP 4110742 A1 EP4110742 A1 EP 4110742A1
Authority
EP
European Patent Office
Prior art keywords
salts
aggregates
processing aids
acid
glycol
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
Application number
EP21705970.8A
Other languages
German (de)
English (en)
Inventor
Arnd Eberhardt
Patrick JUILLAND
Luis Pegado
Emmanuel GALLUCCI
Lukas Frunz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP4110742A1 publication Critical patent/EP4110742A1/fr
Pending legal-status Critical Current

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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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/16—Waste materials; Refuse from building or ceramic industry
    • C04B18/167—Recycled materials, i.e. waste materials reused in the production of the same materials
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/023—Chemical treatment
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/026—Comminuting, e.g. by grinding or breaking; Defibrillating fibres other than asbestos
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/0013—Boron compounds
    • 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
    • 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
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/149—Iron-sulfates
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/003—Phosphorus-containing compounds
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/02—Alcohols; Phenols; Ethers
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/10—Carbohydrates or derivatives thereof
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/122—Hydroxy amines
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/128—Heterocyclic nitrogen compounds
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/20—Sulfonated aromatic compounds
    • 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
    • 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
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0051—Water-absorbing polymers, hydrophilic polymers
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/406—Surface-active agents, dispersants non-ionic
    • 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 the use of processing aids in a method for extracting aggregates and / or pulverulent mineral material from a starting material which contains hardened mineral binders and aggregates and which consists in particular of rubble or rubble.
  • demolition rubble or rubble material usually contain significant amounts of useful components, e.g. aggregates or binding agent components, which in principle can be completely recycled and reused for new structures.
  • useful components e.g. aggregates or binding agent components
  • the disposal of waste in certain regions and countries has become more and more expensive and difficult due to new laws in recent years.
  • the European Directive 2009/98 / CE stipulates the reuse of at least 70% by weight of the inert demolition waste by 2020.
  • EP 2 978724 describes a method for extracting aggregates and / or pulverulent mineral materials from demolition rubble or building rubble material.
  • the method comprises the steps of carbonation and comminution.
  • problems can arise which are related to the agglomeration of particles or the sticking of the material and thus the clogging of machines.
  • the material throughput can be slowed down in such a method and thus also the output of aggregated and / or pulverulent mineral material.
  • the aggregates and mineral powders obtained by such a process are not optimally adapted and can be further improved for use in hydraulically setting compositions.
  • the object of the present invention is to provide process aids for use in processes for extracting aggregates and / or powdery mineral materials from demolition rubble or building rubble material in order to increase the overall efficiency of these processes.
  • the object of the present invention is also to provide suitable processing aids for use in processes for the extraction of aggregates and / or powdered mineral materials from demolition rubble or building rubble material, which can improve the properties of the resulting materials, in particular in connection with their use in hydraulically setting compositions.
  • Another advantage is that the use of suitable processing aids enables the process moisture to be regulated.
  • a particular advantage is the avoidance or considerable reduction of undesired agglomerations of particles during a process according to the invention. This in particular prevents caking or peeling of particles.
  • a method for obtaining aggregates and / or pulverulent mineral material from a starting material comprising hardened mineral binder and aggregates comprises the following steps: , in particular essentially completely, carbonated and from the The surface of the aggregates is removed so that a powdery fragmentation product is formed; b) Separating the treated starting material at a predefined grain size limit in order to obtain treated aggregates with a grain size of at least the predefined grain size limit and / or in order to obtain pulverulent mineral material with a grain size below the predefined grain size limit.
  • the term “starting material” stands for any material that contains or consists of hardened mineral binders and aggregates.
  • the starting material consists of demolition rubble or construction rubble that comes from demolished structures or buildings.
  • the raw material can come from demolition work and / or from landfills.
  • other materials can be contained in the starting material, e.g. metals, plastics and / or wood.
  • the starting material preferably comprises or consists of hardened mortar and / or concrete.
  • the starting material to be treated comprises or consists of hardened mineral binder which is bound to the surface of the aggregate.
  • the hardened mineral binder at least partially encloses the aggregates and / or binds several individual units together.
  • the starting material is comminuted before the disintegration process or step a). This increases the surface area of the starting material, which in turn improves the disintegration process.
  • hardened mineral binder relates in particular to a mineral binder which has been hardened in a chemical hydration reaction in which hydrates have been formed.
  • the hardened mineral binder is preferably hardened for at least 2 days, preferably at least 7 days, in particular at least 28 or at least 60 days.
  • the hardened mineral binder comprises or consists of hardened hydraulic binder, for example hardened cementitious binder.
  • the hardened mineral binder can, however, also contain hardened latent hydraulic and / or pozzolanic binder substances or consist of these.
  • latently hydraulic and / or pozzolanic binders stands in particular for type II concrete admixtures with a latently hydraulic and / or pozzolanic character according to EN 206-1.
  • the latent hydraulic or pozzolanic binder comprises or consists of slag, fly ash, silica dust, activated clays and / or natural pozzolans.
  • the hardened mineral binder comprises or consists of 5-100% by weight, in particular 50-100% by weight, more preferably 65-100% by weight, of hardened hydraulic binder.
  • the hardened mineral binder comprises or consists of 5-95% by weight of hardened hydraulic binder and 95-5% by weight of hardened latent hydraulic and / or pozzolanic binder.
  • the hardened mineral binder can preferably contain or consist of 30-90% by weight hardened hydraulic binder and 70-10% by weight hardened latent hydraulic and / or pozzolanic binder.
  • Preferred hardened mineral binders comprise or consist of hardened cements of the type CEM I, II, III, IV or V according to the standard EN 197, in particular of the type CEM I or II. However, other types of cement may also be included.
  • the hardened hydraulic binder is hardened cement.
  • the latent hydraulic and / or pozzolanic binder is preferably hardened slag and / or fly ash.
  • a very preferred latent hydraulic binder is hardened slag.
  • the term "aggregate” includes any type of mortar and / or concrete aggregate.
  • the aggregates have a density of 2.2 - 3 kg / dm3.
  • the aggregates include in particular stone, gravel, sand or mixtures thereof.
  • the aggregates can, however, comprise or consist of light aggregates, in particular expanded clay or polystyrene, or heavy aggregates, such as barite, iron ore and the like.
  • the grain size of the aggregates is at least 0.125 mm or at least 0.250 mm.
  • the grain size of the aggregates is preferably a maximum of 125 mm or a maximum of 32 mm.
  • the grain size of the aggregates is 0.125-125 mm, in particular 0.125-32 mm, in particular 0.125-16 mm, for example 0.125-8 mm or 0.125-5 mm.
  • the grain size is determined by sieve analysis, especially in the case of sieves with square openings.
  • the grain size is expressed by the opening size of the test sieves, which the relevant grains or particles can just pass through.
  • carbonation is used here for the reaction of mineral binders, in particular hardened mineral binders, with CO2.
  • hardened cement of type CEM I is carbonated by reacting with CO2 from the ambient air.
  • Calcium carbonate in particular is formed in the process.
  • the progressive carbonation of mineral binders, especially hardened mineral binders, can be measured by a drop in the pH value.
  • the progressive carbonation of concrete can be detected by spraying the concrete surface with an ethanolic phenolphthalein solution. Colorless areas indicate carbonated concrete, purple areas indicate uncarbonated concrete.
  • carbonation in the present context means the incorporation of carbon dioxide into chemical compounds or the chemical reaction of carbon dioxide with the starting material.
  • carbonation stands for a reaction of the starting material with carbon dioxide.
  • hardened mineral binders e.g. mortar or concrete
  • carbonation stands for a process in which the carbonation is specifically strengthened or accelerated compared to the natural process. This can be achieved by providing excess carbon dioxide.
  • a hardened mineral binder in the form of hydraulic cement which essentially consists of calcium, silicate and aluminum hydrates, can react with carbon dioxide and form corresponding carbonates.
  • the microstructure of the hardened mineral binder or the binder matrix determines the rate of carbonation and the course of a Carbonation front from the exposed surface of the cementitious material to its core.
  • the method of the present invention aims at the complete disintegration of the hardened mineral binder by carbonation and additionally at the removal of the carbonation front, in particular by abrasion or shattering. This allows the newly exposed surface to carbonate again quickly.
  • the treatment is carried out continuously in an iterative process until a desired degree of removal (in particular an essentially complete removal) of the hardened mineral binder is achieved. This also removes the hardened mineral binder from the surface of the aggregate.
  • the hardened mineral binder is simultaneously and / or continuously carbonated and removed from the surface of the aggregates.
  • the progress of the carbonation can take place, for example, by measuring the CO2 partial pressure during a process according to the invention. If the CO2 partial pressure drops, carbonation takes place. If the CO 2 partial pressure does not decrease any further during the fragmentation process, it can be assumed that the carbonation is essentially complete.
  • the progress of the carbonation can also be determined, for example, by measuring the pH value of the mixture during the disintegration process. If the pH value falls during the fragmentation process, carbonation takes place. If the pH value does not drop any further during the disintegration process, it can be assumed that the carbonation is essentially complete. This is usually the case at a pH of 7-10, preferably 7-9.
  • a method according to the invention comprises a step a) consisting of treating the starting material in a disintegration process, in particular under abrasive conditions, the hardened mineral binder being carbonated and removed from the surface of the aggregates, so that a powdery disintegration product arises, the carbonation being continued until a pH of the mixture of 7-10, preferably 7-9, is reached.
  • the disintegration process or step a) is preferably carried out under abrasive conditions. These are conditions at which the starting material and move any decomposition products that may have formed in close contact with one another. This creates high shear forces and friction. Ultimately, these processes lead to an effective removal of hardened mineral binder and / or carbonated material from the surface of the aggregates by mechanical abrasion or shattering.
  • step a) the hardened mineral binder and / or carbonated material is removed from the surface of the aggregates by mechanical abrasion and / or abrasion.
  • the removal takes place in particular by mechanical force that acts on the starting material.
  • the mechanical force leads to high friction, impact and abrasion or abrasion of the starting material or the hardened mineral binder and / or the carbonated material.
  • the mechanical force and / or the abrasion can be caused by movement of the starting material.
  • the starting material is enclosed in a defined volume and subjected to movement. In particular, this induces high shear forces and abrasion or shattering.
  • the density of solid material, in particular of starting material and / or carbonated material, in the processing volume is preferably about 10-80% by volume, in particular 15-75% by volume, in particular 20-70% by volume, more preferably 30-65 % By volume or 40-60% by volume.
  • processing volume stands for the volume in which the mechano-chemical process is effectively carried out. In other words, the processing volume is defined as the space in which the material to be treated, in particular the starting material, is exposed to carbonation and / or abrasion and / or shattering.
  • the material to be processed in particular the starting material, fills the processing volume in accordance with the densities mentioned above, so that abrasive contacts occur between the particles when the material is moved.
  • An agitator, a mechanical mixer, a rotating drum, a crusher, an extruder, an ultrasonic treatment, a vibration, a liquid flow or combinations thereof can be used for stirring and / or for generating abrasive conditions.
  • the disintegration process thus consists of the combination of (i) a chemical process, ie carbonation, which decomposes the hardened mineral binder, and (ii) the removal of the decomposition or carbonation products from the surface of the aggregates.
  • the unreacted, hardened mineral binder present in the lower layers is gradually exposed and chemically converted in the carbonation process. This interaction between chemical and mechanical processes is particularly effective and leads to very clean units.
  • the disintegration products are in the form of fine-grained or powdery products with grain sizes ranging from nanometers to several micrometers.
  • the grain size of the pulverulent comminution product is in the range of 0-0.250 mm or 0-0.125 mm. This fact has several advantages. Firstly, this facilitates the separation of the decay products from the purified aggregates. Secondly, this means that the fine-grained comminution products can be used, for example, as a filler for various industrial applications or as a raw material for cement-like materials without the need for further mechanical treatment such as grinding.
  • This method which can be viewed as a combined chemical-mechanical process, includes a high efficiency both for the rate of disintegration and for the separation of clean aggregates and dissolved, hardened mineral binders.
  • the treatment of the starting material takes place in the presence of water.
  • the water can be present, for example, in the form of a gas and / or a liquid.
  • the treatment of the starting material preferably takes place in a liquid, in particular in an aqueous liquid, preferably in water. This means that the starting material is at least partially, in particular completely, immersed in the liquid.
  • Humid conditions are understood to mean, in particular, a relative humidity of 40-100%.
  • the carbonation takes place in particular by treating the starting material with carbon dioxide.
  • the carbon dioxide can be a product or a by-product of any industrial process.
  • Substantially pure carbon dioxide is preferably used.
  • the purity of the carbon dioxide is preferably> 1% by weight, e.g.> 8% by weight, preferably> 50% by weight, in particular> 95% by weight, in particular> 99% by weight. In terms of treatment efficiency, essentially pure carbon dioxide is the most beneficial.
  • mixtures of carbon dioxide with other substances such as water vapor, nitrogen and the like, e.g. air, can also be used.
  • Such mixtures comprise in particular CO 2 in an amount> 1% by weight, for example> 8% by weight, preferably> 10% by weight, particularly preferably> 50% by weight, in particular> 95% by weight, in particular> 99% by weight.
  • the C02 concentration used is in particular above the C02 concentration of normal air.
  • exhaust gases from an industrial process and / or a mixture of carbon dioxide with other substances can be used for carbonation. It is advantageous that the exhaust gas or the mixture contains about 5 to 25% by weight of CO 2, preferably 8 to 20% by weight of CO 2 or 10 to 15% by weight of CO 2.
  • the carbon dioxide can be added in gaseous, solid or liquid form.
  • the carbon dioxide used can also be obtained from an in-situ decomposition of organic or inorganic substances, in particular carbonates, or from the oxidation of carbon monoxide.
  • Suitable carbonates are, for example, carbonate salts, alkene carbonates and the like.
  • the starting material is particularly preferably carbonated in a liquid, with carbon dioxide being added to the liquid in gaseous form.
  • the Liquid is in particular an aqueous liquid, preferably water. This causes the carbon dioxide to dissolve in the aqueous liquid or in water.
  • the proportion of the solid material, in particular the starting material and / or the carbonated material, in the liquid, which is in particular water, is preferably about 10-80% by volume, in particular 15-75% by volume, in particular 20-70% by volume %, more preferably 30-65% by volume or 40-60% by volume. If the starting material is subjected to a mechanical force under such conditions, effective abrasion or disintegration of the hardened mineral binder and / or the carbonated material is induced. In other words, such concentrations lead to highly abrasive conditions.
  • the mechanical force or abrasion is generally much less effective and removal of the hardened mineral binder and / or carbonated material from the surface of the aggregates becomes difficult or even difficult not possible. This is particularly due to the fact that under these conditions the solid in the liquid is deposited quite far away from the surface of the aggregates. As a result, there is usually hardly any mechanical contact between the solid particles.
  • the carbon dioxide is added to the liquid in gaseous form, so that bubbles form.
  • the bubbles help to remove the carbonation or decay products from the surface of the aggregates.
  • the treatment of the starting material with carbon dioxide is advantageously carried out at atmospheric pressure. However, lower or higher pressures are also possible.
  • the amount of carbon dioxide required for the treatment depends on the proportion of hardened binder in the starting material. The more hardened binder, the more carbon dioxide is required.
  • the treatment takes place at a temperature between -10-100.degree. C., in particular between -5-75.degree. C. or 5-40.degree.
  • the treatment can take place, for example, under humid conditions above 100 ° C.
  • the treatment of the starting material is carried out for as long as new fragmentation or carbonation products are created. This means in particular that the treatment is carried out for as long as significant or measurable quantities of new fragmentation or carbonation products are formed.
  • step a) the treatment in step a) is carried out until an amount of hardened mineral binder and carbonated hardened mineral binder bound to the aggregate is 0.0001-50% by weight, in particular 0.001-25% by weight, in particular 0.001-10% by weight .-%, preferably 0.01-1% by weight, based on the total weight of the additives.
  • the treatment in step a) is carried out until a porosity of the recovered treated aggregates measured in accordance with standard EN 1097-6 is ⁇ 10% by volume, in particular ⁇ 5% by volume, in particular ⁇ 2% by volume, is preferably 0.1-3% by volume or 1-3% by volume.
  • the powdered mineral material and the treated aggregates are separated at a characteristic grain size limit.
  • the separating grain size is preferably between 0.06-1 mm, in particular 0.1-0.5 mm, preferably 0.125 mm or 0.250 mm. This means that particles below the limit grain size are collected as pulverulent mineral material, while particles with a size above the limit grain size are collected as aggregates.
  • the powdery mineral material comprises or consists of the powdery disintegration product.
  • the pulverulent mineral material can comprise small aggregates with a grain size below the limiting grain size and / or untreated hardened mineral binder with a grain size below the limiting grain size.
  • the pulverulent mineral material is separated from the treated aggregates in particular by filtration, sieving, sedimentation, density separation and / or centrifugation.
  • the treatment can be carried out in a batch process or in a continuous process.
  • the starting material can be immersed, for example, in an aqueous liquid, for example water, in a reaction vessel, for example with a concentration of 0.5-5 kg of starting material per liter of liquid, and treated with carbon dioxide with stirring or abrasive conditions.
  • the carbon dioxide can, for example be introduced into the reaction vessel through an inlet which allows the carbon dioxide to be introduced directly into the aqueous liquid in gaseous form.
  • the gaseous carbon dioxide is dissolved in water and reacts with the hardened binder under stirring and grinding conditions in order to produce the disintegration product or the pulverulent mineral material.
  • the reaction vessel is preferably stirred and / or comprises a mechanical stirrer for stirring the reaction mixture and for generating abrasive conditions.
  • the pulverulent mineral material is then separated off from the treated aggregates, in particular by filtration.
  • the pulverulent mineral material and / or the aggregates obtained are dried after separation. This is particularly useful if the treatment was carried out under wet conditions or in a liquid.
  • the powdery mineral material can also be collected as a stable suspension and used in this form. This also does not require any additional energy and enables water consumption to be reduced.
  • this liquid phase can be reused / recycled for a further treatment according to the present invention.
  • the present invention relates to the use of processing aids in a method for obtaining aggregates and / or pulverulent mineral material from a starting material which comprises hardened mineral binders and aggregates, the method comprising the following steps: a) Treatment of the starting material in a smashing process, in particular under abrasive conditions, the hardened mineral binder at least is partially, in particular essentially completely, carbonated and removed from the surface of the aggregates, so that a pulverulent fragmentation product is created, b) separation of the treated starting material at a predefined grain size limit in order to obtain treated aggregates with a grain size of at least the predefined grain size limit and / or to extract pulverulent mineral material with a grain size below the predefined limit grain size.
  • Processing aids which can be used in the context of the present invention are selected from the group consisting of polycarboxylate ethers and / or esters (PCE), glycols, organic amines, in particular alkanolamines, ammonium salts of organic amines with carboxylic acids, surfactants, in particular non-ionic surfactants , Gemini surfactants, calcium stearate, alkoxylated phosphonic or phosphoric acid esters, 1,3-propanediol, carboxylic acids, sulphonated amino alcohols, boric acid, salts of boric acid, borax, salts of phosphoric acid, gluconate, iron sulphate, tin sulphate, antimony salts, alkali metal salts, earth salts Glycerine, melamine, melamine sulphonates, water-absorbing agents in the form of a superabsorbent polymer or in the form of a layered silicate, anti-caking agents, sugar, sugar
  • organic amines in particular alkanolamines
  • the processing aid accordingly comprises alkanolamines or consists essentially of these.
  • Suitable organic amines are known per se to the person skilled in the art, for example from US 2009/0292041.
  • Alkanolamines are especially preferred in the context of the present invention.
  • Suitable alkanolamines are particularly preferably selected from the group comprising monoethanolamine, diethanolamine, triethanolamine (TEA), diethanol isopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), isopropanolamine, diisopropanolamine, triisopropanolamine (TI PA), N-methyldiisopropanolamine (MDI PA), N-methyldiisopropanolamine (MDI PA), N-methyldiisopropanolamine (MDI PA) (MDEA), tetrahydroxyethylethylenediamine (THEED) and tetrahydroxyisopropylethylenediamine (THIPD) and mixtures of two or more of these alkanolamines. It is also possible to use salts of these alkanolamines.
  • Suitable organic amines can also be amines of the general formula
  • R e represents a linear, branched or cyclic alkyl group with 1-6 carbon atoms
  • organic amines which can be used in the context of the present invention are ethylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine, isophoronediamine, polyamino alcohols such as aminoethylethanolamine, tetra (hydroxyethyl) ethylenediamine, polyaminocarboxylates such as iminodisuccinic acid, ethylenediaminosuccinic acid, ethylenediaminosuccinic acid, ethylenediamine.
  • glycols and / or glycerol are used as processing aids.
  • the processing aid accordingly comprises glycols and / or glycerol or consists essentially of these.
  • suitable glycols are monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol, in particular with 6 or more ethylene units, e.g. PEG 200, neopentyl glycol, hexylene glycol, propylene glycol, dipropylene glycol and polypropylene glycol. It is also possible to use mixtures of two or more different glycols and of at least one glycol and glycerine.
  • the glycerine is what is known as bio-glycerine, which can be produced from a renewable raw material.
  • mixtures of glycols and alkanolamines as processing aids. These can be added separately from one another to a process according to the invention. But it is also possible to produce premixes and use them. The use of such premixes can be helpful in avoiding dosing errors.
  • lignosulphonate is used as the processing aid.
  • the processing aid accordingly comprises lignosulphonate or consists essentially of this.
  • lignosulphonate here stands for a salt that is composed of ligninsulphonate anions and suitable cations and in particular includes the substances Sodium lignosulphonate (CAS no. 8061-51-6), magnesium ligninsulphonate (CAS no. 8061- 54-9), calcium lignosulphonate (CAS no. 8061-52-7). The cation does not play a role in the effectiveness in the present invention.
  • Ligninsulphonates are made from lignin, which in turn arises in plants, especially woody plants.
  • Lignin is a three-dimensional, amorphous polymer which, unlike most other biopolymers, does not have regularly ordered or repeated units. For this reason, no defined lignin structure can be given, although various models for an "average" structure have been proposed. The inconsistency of lignin between plants of different taxa, as well as between the different tissues, cells and cell wall layers of each species, is well known to those skilled in the art.
  • Lignosulphonates are produced as by-products of pulp production under the influence of sulphurous acid, which causes sulphonation and a certain degree of demethylation of the lignins. Like lignins, they are diverse in structure and composition. They are soluble in water over the entire pH range, but insoluble in ethanol, acetone and other common organic solvents
  • Lignosulphonates are only slightly surface-active. They have little tendency to reduce the interfacial tension between liquids and are not suitable for reducing the surface tension of water or for micelle formation. They can act as dispersants through adsorption / desorption and charge formation on substrates. However, their surface activity can be increased by incorporating long-chain alkylamines into the lignin structure.
  • lignosulphonates are familiar to the person skilled in the art.
  • calcium lignosulphonates are precipitated by adding an excess of lime to spent sulphite leachate.
  • Lignosulphonates can also be isolated by forming insoluble quaternary ammonium salts with long chain amines.
  • ultrafiltration and ion exchange chromatography can be used to purify lignosulphonates.
  • Lignosulphonate series which can be used according to the invention are commercially available under various trade names, such as Ameri-Bond, Borresperse (Borregaard), Dynasperse, Kelig, Lignosol, Marasperse, Norlig (Daishowa Chemicals), Lignosite (Georgia Pacific), Reax (MEAD Westvaco), Wafolin, Wafex, Wargotan, Wanin, Wargonin (Holmens), Vanillex (Nippon Paper), Vanisperse, Vanicell, Ultrazine , Ufoxane (Borregaard), Serla-Bondex, Serla-Con, Serla-Pon, Serla-Sol (Serlachius), Collex, Zewa (Wadhof-Holmes), Raylig (ITT Rayonier).
  • trade names such as Ameri-Bond, Borresperse (Borregaard), Dynasperse, Kelig, Lignosol, Mar
  • ligninsulphonates can of course also be used, and the ligninsulphonates can also be present in both liquid and solid form.
  • the term “soot” is understood to mean a form of carbon that forms in the event of incomplete combustion or thermal splitting of vaporous carbon-containing substances.
  • the ligning sulphonate can be present as a pourable composition, for example as a powder, or as a liquid composition, for example as an aqueous composition.
  • the amount of lignosulphonate is 0.001-2.5% by weight, in particular between 0.005 and 1.0% by weight, preferably between 0.01 and 0.5% by weight, based in each case on the total mass of the demolition rubble or the rubble materials.
  • the processing aid accordingly comprises at least one PCE or consists essentially of this.
  • each R u is independently hydrogen or a methyl group
  • each R v is independently hydrogen or COOM
  • M is independently H, an alkali metal, or an alkaline earth metal
  • m 0, 1, 2 or 3
  • p 0 or 1
  • Ri is a hydrogen atom or an alkyl group having 1-4 carbon atoms and M is a hydrogen atom, an alkali metal, or an alkaline earth metal
  • m 0, 1, 2 or 3
  • p 0
  • n 10-250, more preferably 30-200, particularly preferably 35-200, in particular 40-110.
  • the PCE comprises recurring units A of the general structure (I) and recurring units B of the general structure (II), the molar ratios of A to B in the range from 20:80-80:20, more preferably 30:70 - 80:20, in particular 35:65 - 75:25.
  • a PCE preferably has an average molar mass M w in the range from 1 ⁇ 00-100 ⁇ 00, particularly preferably 1,500–500 ⁇ 00, very particularly preferably 2 ⁇ 00–100 ⁇ 00, in particular 300–75 ⁇ 00 or 3 ⁇ 00–50 ⁇ 00 g / mol.
  • the molar mass M w is in the present case determined by gel permeation chromatography (GPC) with polyethylene glycol (PEG) as the standard. This technique is known per se to the person skilled in the art.
  • PCEs according to the invention can be random or non-random copolymers.
  • Non-random copolymers are in particular alternating copolymers or block or gradient copolymers or mixtures thereof.
  • PCE according to the invention which are random copolymers, can be produced by free radical polymerization of mixtures comprising at least one olefinically unsaturated carboxylic acid monomer of the general structure (la) as well as at least one olefinically unsaturated monomer of the general structure (lla) are prepared, where R u , R v , m, p, and R 1 have the meanings given above and the serpentine bond stands for both cis and trans double bond isomers or a mixture thereof.
  • PCEs according to the invention which are non-random copolymers, in particular block or gradient copolymers, can preferably be produced by living free radical polymerization.
  • Living free radical polymerization techniques include nitroxide-mediated polymerization (NMP), the Atom Transfer Radical Polymerization (ATRP) or Reversible Addition Fragmentation Chain Transfer Polymerization (RAFT).
  • NMP nitroxide-mediated polymerization
  • ATRP Atom Transfer Radical Polymerization
  • RAFT Reversible Addition Fragmentation Chain Transfer Polymerization
  • Living free radical polymerization essentially takes place in the absence of irreversible transfer or termination reactions. The number of active chain ends is low and remains essentially constant during the polymerization. This is achieved, for example, in RAFT polymerization through the use of a RAFT agent and only a small amount of initiator. This enables a substantially simultaneous and sustained growth of the chains during the entire polymerization process.
  • non-random copolymers of the present invention can be prepared by means of RAFT polymerization.
  • Advantageous RAFT agents are dithioesters, dithiocarbamate, trithiocarbonate or xanthate.
  • Advantageous initiators are azobisisobutyronitrile (AIBN), a, a'-azodiisobutyramidine dihydrochloride (AAPH) or azo-bis-isobutyramidine (AIBA).
  • the free-radical polymerization is carried out as a solution polymerization, in particular in a solvent containing water. It is very particularly preferred to carry out the polymerization in pure water. It is preferred to use the free-radical polymerization for the preparation of PCE according to the invention up to a conversion of at least 75%, preferably at least 80%, more preferably at least 90%, very particularly preferably at least 95%, in particular at least 98% or more, based in each case on the total amount of substance of the monomers present to drive.
  • PCEs according to the invention can also be produced by a polymer-analogous reaction.
  • PCEs according to the invention can be prepared by esterifying a homo- or copolymer comprising repeating units of the general structure (I) with polyalkylene glycols of the general structure (III)
  • PCEs according to the invention can contain one or more further monomers M.
  • These further monomers M can be selected from styrene, ethylene, propylene, butylene, butadiene, isoprene, vinyl acetate, vinyl chloride, acrylonitrile, N-vinylpyrrolidone and / or hydroxyalkyl (meth) acrylates.
  • the molar proportion of the one or more further monomers M is equal to or less than 66 mol%, preferably equal to or less than 50 mol%, more preferably equal to or less than 25 mol%, particularly preferably equal to or less than 10 mol% %, in particular equal to or less than 5 mol%, in each case based on all monomers making up the PCE.
  • the PCE is essentially free of further monomer units M. Accordingly, a PCE according to the invention consists of at least 34 mol%, preferably at least 50 mol%, more preferably at least 75 mol%, particularly preferably at least 90 mol%, in particular 100 mol% from the repeating units A and B.
  • the PCE of the present invention accordingly consists of
  • each R u independently represents hydrogen or a methyl group
  • each R v is independently hydrogen or COOM
  • M is independently H, an alkali metal, or an alkaline earth metal
  • m 0, 1, 2 or 3
  • p 0 or 1
  • the repeating units A and B in the PCE have a molar ratio of A: B in the range 10:90-90:10.
  • PCEs of the present invention can be in the form of a solid, in particular a powder. However, PCEs of the present invention can also be in liquid form. Suitable liquid forms are melts of the PCE according to the invention, or aqueous compositions, such as aqueous solutions or aqueous dispersions of the PCE.
  • Aqueous compositions are produced by adding water during the production of the PCE or by subsequently mixing the PCE with water.
  • the proportion of PCE is typically 10 to 90% by weight, in particular 25 to 50% by weight, based on the weight of the aqueous composition.
  • a dispersion or a solution is created.
  • a solution is preferred.
  • the aqueous composition can contain further components.
  • solvents or additives as they are common in concrete technology, in particular surface-active substances, stabilizers against heat and light, dyes, defoamers, accelerators, retarders, corrosion inhibitors, air entrainment.
  • a PCE is used.
  • PCEs are used in a method according to the invention which is carried out in a liquid, in particular in water. Without the addition of PCE in such a process, a thickening of the suspension is often observed during the disintegration and carbonation. Through the Using PCE in such a procedure can prevent or significantly reduce this thickening.
  • a PCE is used in combination with at least one further processing aid.
  • Particularly preferred further processing aids are glycols, organic amines, in particular alkanolamines, ammonium salts of organic amines with carboxylic acids, surfactants, in particular nonionic surfactants, gemini surfactants, calcium stearate, alkoxylated phosphonic or phosphoric acid esters, 1,3-propanediol, carboxylic acids, sulphonated amino alcohols , Boric acid, salts of boric acid, borax, salts of phosphoric acid, sorbitol, saccharides, gluconate, iron sulphate, tin sulphate, antimony salts, alkali salts, alkaline earth salts, lignin sulphonate, glycerine,
  • Glycols organic amines, in particular alkanolamines and lignosulphonates are as defined above.
  • the carboxylic acid is preferably selected from formic acid, acetic acid, propionic acid, lactic acid, citric acid or tartaric acid.
  • the alkali metal or alkaline earth metal salt is preferably selected from alkali metal or alkaline earth metal halide, alkali metal or alkaline earth metal hydroxide, alkali metal or alkaline earth metal nitrate, alkali metal or alkaline earth metal nitrite and alkali metal or alkaline earth metal thiocyanate.
  • alkali and alkaline earth halides are alkali and alkaline earth chlorides, alkali and alkaline earth fluorides, alkali and alkaline earth bromides and alkali and alkaline earth iodides.
  • suitable alkali and alkaline earth metals for these salts are Li, Na, K, Mg and Ca. Concrete examples are calcium chloride, sodium chloride, sodium thiocyanate and sodium carbonate.
  • the saccharides or carbohydrates can be polysaccharides and oligosaccharides or sugars.
  • An example of a gluconate is sodium gluconate.
  • the at least one processing aid is added to an aqueous PCE composition as described above.
  • An aqueous composition is therefore used which contains at least one PCE and the one or more further processing aids.
  • the dosage is preferably such that the at least one PCE is present at 0.001-2.5% by weight, in particular between 0.005 and 1.0% by weight, preferably between 0.01 and 0.5% by weight, based on the rubble or rubble used .
  • the at least one PCE is used in the form of a composition with at least one additive, for example a grinding additive, a concrete additive and / or a mortar additive.
  • the at least one additive is in particular selected from the group consisting of plasticizers which are not PCE, grinding aids, chromium reducers, defoamers, dyes, pigments, preservatives, retarders, accelerators, air entrainers, shrinkage reducers, corrosion inhibitors or mixtures thereof.
  • Such a composition contains or preferably consists of: a) 5-99% by weight, preferably 5-50, more preferably 5-30% by weight, PCE; b) 1-80% by weight, preferably 5-60% by weight, more preferably 5-30% by weight, of at least one further processing aid; c) 0-90% by weight, in particular 1-20% by weight, of at least one further additive; d) 0-90% by weight, in particular 10-60% by weight, of water, based in each case on the total weight of the composition.
  • the polyalkylene glycol preferably has a molecular weight Mw of T000-50-00 g / mol, preferably 4-00 to 600 g / mol.
  • the polyalkylene glycol is a polyethylene glycol (PEG), methoxypolyethylene glycol (MPEG) or a polypropylene glycol (PPG). Polyethylene glycol (PEG) or methoxypolyethylene glycol (MPEG) is particularly preferred.
  • Such mixtures are particularly suitable for extending the processing time of hydraulically setting compositions and improving the flow behavior.
  • at least one surfactant is used as the processing aid.
  • the processing aid accordingly comprises at least one surfactant or consists essentially of this.
  • Surfactants are well known per se to the person skilled in the art and are summarized, for example, in “Surfactants and Polymers in Aqueous Solutions” (Wiley-VCH, K. Holmberg et al, 2nd Edition, 2007).
  • Surfactants can be nonionic surfactants, cationic surfactants, anionic surfactants or zwitterionic surfactants. It can be particularly advantageous to use non-ionic surfactants, since these have a low tendency to be absorbed by cement phases. Such non-ionic surfactants with a low tendency to absorb on cement phases are particularly preferred in certain applications. However, it is also possible to use cationic, anionic or zwitterionic surfactants.
  • Suitable surfactants in the context of the present invention are, for example, lipids such as cholates, glycocholates, fatty acid salts, glycerides, glycolipids and phospholipids. These can come from natural sources or be synthetically produced. Nonionic lipids are preferred in certain embodiments.
  • Suitable anionic surfactants are in particular alkyl ether carboxylates, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl phosphates, alkyl ether phosphonates and alkyl benzene sulfonates.
  • Suitable non-ionic surfactants are in particular fatty acid alkoxylates, alkoxylated alcohols, in particular fatty acid alcohol alkoxylates and alkoxylates of glycerol and pentaerythritol, alkylphenol alkoxylates, alkoxylated polysaccharides, alkoxylated polycondensates, fatty acid amide alkoxylates, fatty acid amide alkoxylates with a glycerol or pentyl amine, alkoxylated fatty acid alkoxylates, sorbitol alkoxylates with a methanol, sorbitol, sorbitol, alkoxylate, alkoxylate, sorbitol ester of methanol, sorbitol, sorbitol, alkoxylate, sorbitol, alkoxylate from methanol, especially sorbitol Alkyl radical consisting of 6-20 carbon atoms, alkyl glycoside
  • Suitable cationic surfactants contain in particular ammonium groups or quaternary nitrogen atoms and also have at least one long-chain Alkyl radical.
  • Examples of cationic surfactants are betaines, amidobetaines, imidazolines and amine N-oxides.
  • At least one surfactant is used in combination with at least one further processing aid, in particular at least one PCE, a lignin sulphonate, an alkanolamine, an alkali salt, an alkaline earth salt, or a water-absorbing agent.
  • at least one further processing aid in particular at least one PCE, a lignin sulphonate, an alkanolamine, an alkali salt, an alkaline earth salt, or a water-absorbing agent.
  • non-ionic surfactants are compounds of the general formula (IV)
  • R ' is an a'-valent, linear or branched, saturated, mono- or polyunsaturated aliphatic, cycloaliphatic or aromatic hydrocarbon radical with 3 to 38 carbon atoms, preferably with 5 to 17 carbon atoms, the hydrocarbon chain with a' polyoxyalkylene radicals A 'being linear Hydrocarbon chains are preferably terminally substituted (i.e.
  • alkoxylated polycondensates are in particular polycondensation products which are obtained from a condensation of the following compounds A, B and at least one aldehyde of the general formula C.
  • A1O and A2O independently represent an alkylene oxide group with 2-4 carbon atoms, p and q independently represent a number between 1 to 300,
  • X represents a hydrogen atom, an alkyl group with 1-10 carbon atoms or an acyl group with 2-24 carbon atoms,
  • R2 represents an alkyl group with 4 - 24 carbon atoms or an alkenyl group with 4 - 24 carbon atoms
  • Yi is a phosphonate or a phosphate group
  • R3 represents a hydrogen atom, a carboxyl group, an alkyl group with 1-10 carbon atoms, an alkenyl group with 2-10 carbon atoms, a phenyl group, a naphthyl group, or a heterocycle, and r is a number between 1-100.
  • non-ionic surfactants can also reduce the shrinkage of hydraulic compositions.
  • at least one gemini surfactant is used as the processing aid.
  • the processing aid accordingly comprises a gemini surfactant or consists essentially of this.
  • Gemini surfactants contain two hydrophilic headgroups and two hydrophobic tails that are separated by a spacer on or near the headgroups. When both hydrophobic tails are the same and the hydrophilic groups are identical, one speaks of gemini surfactants with a symmetrical structure. The substituents in Gemini surfactants are largely responsible for the behavior of these compounds in solution and their possible applications. In particular, gemini surfactants can contain quaternary nitrogen atoms, which as a rule are in acyclic forms. However, there are also Gemini surfactants that contain nitrogen in both saturated and unsaturated rings. The spacer can be either rigid or flexible, with a tendency towards hydrophobicity or hydrophilicity. The special properties of Gemini surfactants can be influenced by optimizing the hydrohilic-lipophilic balance (HLB value). This can be done, for example, by introducing balanced polar or hydrophobic groups in both head groups, tails or spacers.
  • HLB value hydrohilic-lipophilic balance
  • gemini surfactants are structures of the following formulas where L is a hydrogen atom or a sulphonic acid group.
  • Examples of preferred Gemini surfactants in the present case are, in particular, alkoxylated acetyl diols or Gemini surfactants, as described in EP0884298.
  • at least one alkoxylated phosphonic or phosphoric ester is used as the processing aid.
  • the processing aid accordingly comprises at least one alkoxylated phosphonic acid or phosphoric acid ester or consists essentially of this.
  • alkoxylated phosphonic or phosphoric acid esters are particularly advantageous if pulverulent mineral materials are to be used in hydraulic compositions containing fly ash by a process according to the invention.
  • Such alkoxylated phosphonic or phosphoric acid esters are also advantageous in applications for ash improvement technology.
  • Suitable alkoxylated phosphonic or phosphoric acid esters are structures of the general formula (V) where R ° represents a hydrogen atom, an alkyl group with 1-5 carbon atoms, an alkenyl group with 2-5 carbon atoms or a (meth) acryloyl group,
  • C 1 0 represents an alkylene oxide group having 2-4 carbon atoms
  • k represents a number between 2-150
  • I represents a number between 1-3
  • M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group or an organic ammonium group.
  • an alkoxylated phosphonic acid or phosphoric acid ester of the general structure (V) with a polyalkylene glycol, a PCE as described above or a lignosulphonate as described above.
  • the processing aid accordingly comprises at least one water-absorbing agent or consists essentially of this.
  • the water-absorbing agent according to the present invention is in particular a water-absorbing agent in the form of a superabsorbent polymer or in the form of a sheet silicate, sheet silicates in the form of vermiculite being particularly preferred.
  • superabsorbent polymers means polymers that can absorb large amounts of water. When superabsorbent polymers come into contact with water, the water molecules diffuse into the cavities of the polymer network and hydrate the polymer chains. This allows the polymer to swell and form a polymer gel or to dissolve slowly.
  • This step is reversible so that the superabsorbent polymers can be regenerated to their solid state by removing the water.
  • the property of water absorption is denoted by the swelling ratio, by which the ratio of the weight of a swollen superabsorbent polymer to its weight in the dried state is meant.
  • the swelling ratio is influenced by the degree of branching of the superabsorbent polymer, any crosslinking that may be present, the chemical structure of the monomers that form the superabsorbent polymer network, and external factors such as the pH, the ion concentration of the solution and the temperature. Because of their ability to interact with water, superabsorbent polymers are also known as hydrogels.
  • superabsorbent polymers which can be used in the context of the present invention include, inter alia, natural polymers such as starch, cellulose such as cellulose ether, chitosan or collagen, alginates, synthetic polymers such as poly (hydroxyethyl methacrylate), poly (ethylene glycol) or poly (ethylene oxide) or ionic synthetic polymers such as polyacrylic acid (PAA), polymethacrylic acid (PMAA), polyacrylamides (PAM), polylactic acid (PLA), polyethyleneimine, polyvinyl alcohol (PVA) or polyvinylpyrrolidone.
  • natural polymers such as starch, cellulose such as cellulose ether, chitosan or collagen, alginates
  • synthetic polymers such as poly (hydroxyethyl methacrylate), poly (ethylene glycol) or poly (ethylene oxide) or ionic synthetic polymers such as polyacrylic acid (PAA), polymethacrylic acid (PMAA), polyacrylamides (PAM), polylactic acid (PLA), polyethylene
  • Superabsorbent polymers made from ionic monomers normally absorb more water than those made from neutral monomers, which is due to the electrostatic repulsion between the individual polymer chains.
  • the degree of crosslinking corresponds to the number of chemical compounds. The higher the degree of crosslinking and the higher the proportion of crosslinking agents, the shorter the distance between two crosslinking points, which leads to a reduction in the degree of swelling.
  • the degree of swelling also depends on external factors such as pH and temperature.
  • Superabsorbent polymers that are formed from acidic monomers such as acrylic acid or methacrylic acid can be deprotonated at pH values above 7, so that negative charges are generated in the polymer chains. The associated electrostatic repulsion leads to a higher degree of swelling in alkaline media.
  • Superabsorbent polymers which are particularly suitable in the context of the present invention are ionic Superabsorbent polymers, in particular those which are based on polyacrylamide modified with acrylic acid and can be of both a linear and a crosslinked structure.
  • a second class of water-absorbing agents which can be used with particular advantages in the context of the process according to the invention are sheet silicates, in particular in the form of vermiculite.
  • the term "vermiculite” denotes a layered silicate which is present in the monoclinic crystal system with the general chemical composition Mg 0j (Mg, Fe, Al) 6 (SiAl) 8 0 2 o (OH) 4 8 H 2 0.
  • Vermiculite develops leafy, scaly or massive aggregates that are either colorless or gray-white, yellow-brown, gray-green or green due to foreign admixtures.
  • the amount of the water-absorbing agent which leads to particularly favorable results in the process according to the invention depends essentially on the water absorption capacity of the material used.
  • Superabsorbent polymers generally have a greater water absorption than sheet silicates, so that a small amount of a superabsorbent polymer is sufficient to achieve an effect comparable to a certain amount of sheet silicate.
  • the superabsorbent polymer can expediently in the context of the method according to the invention in an amount of 0.04 to 2.5 wt.%, Preferably 0.08 to 1.0 wt.%, And most preferably 0.1 to 0.5 wt , be admitted.
  • sheet silicates amounts in the range from 2 to 30% by weight, preferably in the range from 4 to 15% by weight, and most preferably in the range from 6 to 10% by weight, are sensible.
  • the water-absorbing agents are particularly suitable for regulating the process moisture in a method according to the invention. This means that the moisture generated in the chemical process can be consumed. This also allows excess water to be removed, which is present, for example, when using moist or wet starting material. This is particularly desirable when the method according to the invention is to be carried out in a narrow humidity range.
  • the processing aid accordingly comprises at least one carboxylic acid or consists essentially of this.
  • the carboxylic acid is preferably selected from formic acid, acetic acid, propionic acid, glycolic acid, lactic acid, malic acid, citric acid, isocitric acid, tartaric acid, oxalic acid, tartronic acid, mandelic acid, salicylic acid, fatty acids with 6-20 carbon atoms, in particular stearic acid, or their salts.
  • stearic acid or its salts are used as the processing aid.
  • the processing aid accordingly comprises stearic acid and / or its salts or consists essentially of these.
  • stearic acid and / or its salts in particular calcium stearate, as a processing aid leads to a hydrophobization of the surface of the resulting additives and / or pulverulent mineral materials.
  • alkali and / or alkaline earth salts are used as processing aids.
  • the processing aid accordingly comprises alkali and / or alkaline earth salts or consists essentially of these.
  • the alkali or alkaline earth metal salt is preferably selected from alkali metal or alkaline earth metal halide, alkali metal or alkaline earth metal hydroxide, alkali metal or alkaline earth metal nitrate, alkali or alkaline earth metal nitrite, alkali metal or alkaline earth metal thiocyanate, alkali metal or alkaline earth metal carbonate, alkali metal or alkaline earth metal hydrogen carbonate, alkali metal or alkaline earth metal sulfate - Or alkaline earth thiosulphate, alkali or alkaline earth silicate, alkali or alkaline earth aluminate.
  • alkali and alkaline earth halides are alkali and alkaline earth chlorides, alkali and alkaline earth fluorides, alkali and alkaline earth bromides and alkali and alkaline earth iodides.
  • suitable alkali and alkaline earth metals for these salts are Li, Na, K, Mg and Ca.
  • anti-caking agents are used as processing aids.
  • the processing aid accordingly comprises anti-caking agents or consists essentially of these.
  • Anti-caking agents which can be used within the scope of the present invention are selected from the group consisting of tricalcium phosphate, cellulose, magnesium stearate, sodium hydrogen carbonate, sodium hexacyanoferrate, potassium hexacyanoferrate, calcium hexacyanoferrate, calcium phosphate, sodium silicate, silicon dioxide, in particular fumed silica, sodium silicate, magnesium silicate , Calcium aluminosilicate, bentonite, aluminum silicate, stearic acid, polydimethylsiloxane, sodium laurate.
  • sugar, sugar acids or sugar alcohols are used as processing aids.
  • the processing aid accordingly comprises sugar, sugar acids or sugar alcohols or consists essentially of these.
  • a “sugar” in the context of the present invention is a carbohydrate with an aldehyde group.
  • the sugar belongs to Group of monosaccharides or disaccharides.
  • sugars include glyceraldehyde, threose, erythrose, xylose, lyxose, ribose, arabinose, allose, altrose, glucose, mannose, gulose, idose, galactose, tallose, fructose, sorbose, lactose, maltose, sucrose, lactulose, trehalose, Cellobiose, Chitobiose, Isomaltose, Palatinose, Mannobiose, Raffinose and Xylobiose.
  • a "sugar acid” in connection with the present invention is a monosaccharide having a carboxyl group. It can belong to any of the classes of aldonic acids, uronic acids, uronic acids or aldaric acids. It is preferably an aldonic acid.
  • sugar acids useful in connection with the present invention include glyceric acid, xylonic acid, gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, iduronic acid,
  • sugar acid can be present in the form of the free acid or as a salt.
  • salts of sugar acids can be salts with metals from groups Ia, Ila, Ib, Mb, IVb, Vlllb of the Periodic Table of the Elements.
  • Preferred salts of sugar acids are salts of alkali and alkaline earth metals, iron, cobalt, copper or zinc. Salts with monovalent metals such as lithium, sodium and potassium are particularly preferred.
  • a “sugar alcohol” in connection with the present invention is a polyhydric alcohol which can be obtained from sugars by a redox reaction.
  • Sugar alcohols thus belong to the class of alditols.
  • sugar alcohols include ethylene glycol, glycerine, diglycerine, threitol, erythritol, pentaerythritol, dipentaerythritol, xylitol, ribitol, arabitol, sorbitol, sorbitan, isosorbide, mannitol, dulcitol, fucitol, iditol, inositol, volemitol, lactitol Maltotriitol, Maltotetrait and Polyglycitol.
  • phosphates or phosphonates are used as processing aids.
  • the processing aid accordingly comprises phosphates or phosphonates or consists essentially of these.
  • a "phosphate” in connection with the present invention is a derivative of phosphoric acid.
  • a phosphate can be free phosphoric acid, an oligomer of phosphoric acid and / or a polymer of phosphoric acid such as, for example, diphosphate, triphosphate, tetraphosphate and the like.
  • Phosphates can be in a protonated, partially deprotonated, or fully deprotonated state. They can also be fluorinated. Examples of suitable phosphates are trisodium orthophosphate and tetrasodium pyrophosphate, sodium hexametaphosphate and disodium fluorophosphate.
  • esters of phosphoric acids include, inter alia, mixed esters with the abovementioned carboxylic acids and / or sugar acids, mixed esters with carboxylic acids, in particular with fatty acids, alkyl esters, aryl esters and esters with polyalkylene glycols.
  • Phosphonate also relates to mono-, di-, tri-, tetra-, penta- or hexaphosphonic acids and their oligomers and / or esters.
  • Phosphonates preferably carry organofunctional units. Phosphonates can be protonated, partially deprotonated, or fully deprotonated. Examples of suitable phosphonates are 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 3-aminopropylphosphonic acid, aminotri (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid).
  • PCE in combination with glycerine, glycol and / or alkanolamines. It is also possible to use PCE in combination with a water-absorbing agent. It is also possible to use PCE in combination with a non-ionic surfactant and / or a Gemini surfactant.
  • An advantageous combination can also be at least one alkanolamine, possibly at least one glycol and at least one non-ionic surfactant and / or gemini surfactant.
  • the processing aids can optionally contain further components.
  • solvents or additives as they are common in concrete technology, in particular stabilizers against heat and light, chromium reducers, defoamers, dyes, pigments, preservatives, air entrainers, shrinkage reducers, corrosion inhibitors.
  • one or more processing aids can be selected from the group consisting of polycarboxylate ethers and / or esters (PCE), glycols, organic amines, especially alkanolamines, ammonium salts of organic amines with carboxylic acids, surfactants, especially non-
  • the present invention therefore relates to a method for extracting aggregates and / or pulverulent mineral material from a starting material which comprises hardened mineral binders and aggregates, the method comprising the following steps: a) treatment of the starting material in one Shattering process, in particular under abrasive conditions, wherein the hardened mineral binder is at least partially, in particular essentially completely, carbonated and removed from the surface of the aggregates so that a powdery shattered product is created, b) separating the treated starting material at a predefined grain size limit to the treated To win aggregates with a grain size of at least the predefined limit grain size and / or to win pulverulent mineral material with a grain size below the predefined limit grain size, thereby en indicates that at least one processing aid selected from the group consisting of polycarboxylate ethers and / or esters (PCE), glycols, organic amines, in particular alkanolamines, ammonium salts of organic amines with carboxy
  • PCE poly
  • the sequence and the time at which the at least one processing aid is added is not particularly restricted.
  • the latter can be particularly advantageous if the process aid (s) are added in order to influence the behavior of the aggregates obtained and / or pulverulent mineral materials when used for the production of hydraulic compositions, in particular cement-bound building materials.
  • the one or more processing aids can be used in bulk or as solutions or as dispersions.
  • this mixture can be present and added in the form of a premix, in particular an aqueous solution or dispersion.
  • two or more processing aids it is also possible for two or more processing aids to be added separately from one another. This is particular This is advantageous when the different processing aids cannot be present in the form of a stable mixture, for example because they would react chemically. It is also possible to add different processing aids to different process steps.
  • the carbonation is continued in step a) until a pH of the mixture of 7-10, preferably 7-9, is reached.
  • Another aspect of the present invention relates to the additives and / or pulverulent mineral materials obtainable by the method of the present invention.
  • These additives and / or pulverulent mineral materials are in particular in the form of particles.
  • These aggregates and / or powdery mineral materials differ from fresh or clean aggregates in particular in that they can carry a minimal amount of hardened residual binder on the surface and contain the processing aids used in free, bound, converted or adsorbed form.
  • fresh or clean aggregates are aggregates which, in particular, have never come into contact with mineral binders, in particular with cement-like material.
  • the aggregates and / or pulverulent mineral materials comprise hardened mineral binder in an amount of 0.0001-25% by weight, preferably 0.01-10% by weight, in particular 0.01-1% by weight, based on on the total weight of the aggregates.
  • a porosity measured according to the EN 1097-6 standard, of the additives and / or pulverulent mineral materials is ⁇ 10% by volume, in particular ⁇ 5% by volume, in particular ⁇ 2% by volume.
  • the porosity is typically> 0.1% by volume, in particular> 1% by volume.
  • the porosity is preferably 1.52% by volume.
  • the aggregates preferably have a particle size of at least 125 ⁇ m or at least 250 ⁇ m.
  • the powdery mineral material has a particle size below 250 ⁇ m, preferably below 125 ⁇ m.
  • a delicacy of the powdery mineral Material is in particular in the range of 0.5-1000 m2 / g, preferably 0.5-500 m2 / g, in particular 0.5-100 m2 / g.
  • the fineness refers to the surface area calculated from nitrogen sorption (BET).
  • the pulverulent mineral material comprises or consists of carbonated hydrates of the cement-bound hardened binder, optionally with residual hydrates and / or oxides, e.g. quartz.
  • aluminate products and / or sulfates can also be present.
  • the powdery mineral material has the same oxide composition as the hardened binder and like fractions of aggregates with a grain size below the limit grain size, e.g. below 250 ⁇ m or below 125 ⁇ m.
  • Such powdery mineral materials with grain sizes in the nanometer to micrometer range and / or a high specific surface are particularly advantageous when they are used as filler and / or supplementary cement-like material and / or raw material for cement production and / or ash improvement technology.
  • the fineness of the powdery building material can in particular increase the speed of the early hydration of hydraulic compositions, in particular cement-bound building materials.
  • such materials do not need to be milled for use in binder compositions.
  • the powdered mineral materials obtained can be mixed with cement easily and without additional effort.
  • the aggregates obtainable by the process of the invention and / or the pulverulent mineral materials can advantageously be used for the production of binder compositions, in particular hydraulically setting compositions such as cement-bound building materials and especially mortar and / or concrete compositions.
  • the pulverulent mineral material obtainable by the process of the present invention can preferably be used as a filler and / or supplementary cement-like material, in particular for the production of hydraulically setting compounds, in particular mortar and / or concrete compounds.
  • the present invention therefore relates to the use of aggregates and / or pulverulent mineral material obtained in a process as described above for the production of hydraulic compositions, preferably cement-bound building materials, in particular mortar or concrete
  • Another aspect of the present invention relates to a method for producing hydraulically setting compositions, in particular mortar or concrete compositions, comprising the steps (i) extraction of aggregates and / or pulverulent mineral material according to the method defined above using processing aids and (ii ) Mixing the aggregates obtained and / or pulverulent mineral materials with mineral binders, in particular hydraulic binders, and optionally further additives and / or water.
  • workable hydraulically setting compositions can be produced, e.g. mortar or concrete compositions.
  • the ratio of water to binder in the compositions can be selected in the range from 0.2-0.8, in particular 0.3-0.6, preferably 0.3-0.5.
  • the present invention therefore relates to a mortar or concrete containing at least one aggregate and / or pulverulent mineral material obtained in a method as described above.
  • pulverulent mineral material according to the present invention was produced in a dry process.
  • completely hydrated cement of type CEM I was ground in a pin mill under a CC> 2 atmosphere (5 vol% CO2) to a particle size of 0-250 ⁇ m.
  • This powder is called powder-1.
  • pulverulent mineral material according to the present invention was produced in a wet process. This method was identical to the method described in WO2014154741 (p. 18, lines 2-29). This powder is called powder-2.
  • Composite binders were produced by mixing powder-1 or powder-2 with cement of the type CEM I 42.5 R in a tumble mixer until a visually homogeneous powder was obtained. The composite binders were called binders C - E and were composed as follows:
  • the slump was determined based on EN 1015-3 with a cone of 39 cm 3 volume at various times after the end of the mixing process. Slump of ⁇ 60 mm was not measured and was given as « ⁇ 60» in each case.
  • the start of solidification was determined using an isothermal heat calorimetry method based on ASTM C1702-17. For this purpose, the exothermicity of hydration was recorded with a CAL 8000 device from Calumetrix. The start of solidification corresponds to that point on the curve of the heat development over time at which a first local minimum was measured.
  • Compressive strengths and flexural strengths were measured according to standard EN 196-1.
  • Example 1 illustrates the effectiveness of various processing aids in a method according to the invention.
  • the types and specified in Tables 3 and 4 Quantities of processing aids were added in each case during the production of the powder-1 before the start of the disintegration process.
  • the powdery mineral material obtained, with or without processing aids was tested as part of a composite binder in mortar mixes.
  • 450 g each of the binder specified in Tables 2 and 3 were mixed with 1350 g sand (CEN standard sand 0-2 mm) and 225 g water.
  • Examples 1-4 to 1-10 and 1-12 to 1-14 are inventive, while Examples 1-1, 1-2, 1-3 and 1-11 are comparative non-inventive examples.
  • processing aids according to the invention generally improve the slump and the strengths. This applies to a comparison of the mortar samples containing binders containing pulverulent mineral material and processing aids according to the present invention with mortar samples containing the same binder but no processing aids (cf.Examples 1-4 to 1-10 with Example 1-3 and Examples 1-12 to 1- 14 with example 1-11). Using a combination of PCE and alkanolamine results in another Improvement compared to the use of PCE alone (see Table 4).
  • process aids according to the invention results in a cement containing 18% by weight of a powdered mineral material from a process according to the invention having essentially the same or improved strengths as a standardized CEM III / A-LL (see example 1-2 with the inventive examples).
  • Example 2 illustrates the effectiveness of process auxiliaries according to the invention for preventing the starting material from caking tendency, in particular demolition rubble or building rubble for a method according to the present invention.
  • a low caking tendency of the starting material is important in a method according to the invention, since otherwise the carbonation and fragmentation cannot proceed efficiently.
  • the tendency to caking was tested in a procedure based on standard EN 1097-6.
  • the stability of a compacted concrete sand cone is evaluated.
  • crushed concrete sand (0-4 mm, water requirement according to EN 1097-6 of 10.5% by weight) was first dried at 110 ° C and then wetted with water in the amount specified in Table 5. The stability of such a sample was then tested in accordance with EN 1097-6 by assessing the tendency of a cone of concrete sand to disintegrate.
  • samples of the same crushed concrete sand wetted with water were mixed with the processing aids indicated in Table 5 in the amount indicated there. The stability of these samples was also tested in accordance with EN 1097-6.
  • a free-flowing mixture can be obtained by adding a suitable amount of processing aid. That is to say, the tendency of a starting material to clog can be reduced, which is a great advantage with regard to the feasibility of a method according to the invention.
  • Example 3 illustrates the effectiveness of processing aids in a wet process.
  • the types and amounts of processing aids given in Table 6 were each added during the production of Powder-2 before the start of the disintegration process.
  • the obtained powdery mineral Material with or without processing aids was tested as part of a composite binder in cement suspensions.
  • the respective binder was mixed with water in a weight ratio of binder to water of 0.4.
  • Examples 3-3 to 3-5 are inventive while Examples 3-1 and 3-2 are comparative non-inventive examples.
  • the start of solidification was determined using a heat flow curve, which was measured in an isothermal process based on the ASTM C1702-17 standard. An i-CAL 8000 device from Calmetrix was used. The start of solidification is the time at which a first local minimum of the heat flow was reached over time. Table 6: Examples 3-1 to 3-5

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Abstract

L'invention se rapporte à l'utilisation d'auxiliaires de traitement, choisis dans le groupe constitué par les éthers et/ou les esters de polycarboxylate (PCE), les glycols, les amines organiques, en particulier les alcanolamines, les sels d'ammonium issus d'amines organiques avec des acides carboxyliques, les tensioactifs, en particulier les tensioactifs non ioniques, les tensioactifs jumelés, le stéarate de calcium, l'acide phosphonique alcoxylé ou les esters d'acide phosphorique, le 1,3-propanediol, les acides carboxyliques, les amino-alcools sulfonés, l'acide borique, les sels de l'acide borique, le borax, les sels de l'acide phosphorique, le gluconate, le sulfate de fer, le sulfate d'étain, les sels d'antimoine, les sels alcalins, les sels alcalino-terreux, les lignosulfonates, la glycérine, la mélamine, les sulfonates de mélamine, un moyen d'absorption d'eau sous la forme d'un polymère superabsorbant ou sous la forme d'un phyllosilicate, les agents anti-mottant, les sucres, les acides sacchariques, les alcools de sucre, les phosphates, des phosphonates et les mélanges de ces derniers, dans un procédé d'obtention d'agrégats et/ou d'un matériau minéral de type poudre à partir d'un matériau de départ, contenant un liant minéral durci et des agrégats.
EP21705970.8A 2020-02-25 2021-02-19 Auxiliaires de traitement et leur utilisation dans un procédé d'obtention d'agrégats et/ou d'un matériau minéral de type poudre Pending EP4110742A1 (fr)

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CA3168999A1 (fr) 2021-09-02

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