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WO2018109173A1 - Procédé de préparation d'un liant à prise hydraulique et utilisation de la matière première de type ciment à base de celui-ci - Google Patents

Procédé de préparation d'un liant à prise hydraulique et utilisation de la matière première de type ciment à base de celui-ci Download PDF

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Publication number
WO2018109173A1
WO2018109173A1 PCT/EP2017/083050 EP2017083050W WO2018109173A1 WO 2018109173 A1 WO2018109173 A1 WO 2018109173A1 EP 2017083050 W EP2017083050 W EP 2017083050W WO 2018109173 A1 WO2018109173 A1 WO 2018109173A1
Authority
WO
WIPO (PCT)
Prior art keywords
cement
deagglomeration
thermal treatment
asbestos
treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2017/083050
Other languages
German (de)
English (en)
Inventor
Wolfgang Perbix
Winfried MALOMY
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.)
Bn Umwelt Firma GmbH
Ibu Bau and Tec Ug (haftungsbeschrankt) Firma
HOCHSCHULE WISMAR
Original Assignee
Bn Umwelt Firma GmbH
Ibu Bau and Tec Ug (haftungsbeschrankt) Firma
HOCHSCHULE WISMAR
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 Bn Umwelt Firma GmbH, Ibu Bau and Tec Ug (haftungsbeschrankt) Firma, HOCHSCHULE WISMAR filed Critical Bn Umwelt Firma GmbH
Priority to EP17829171.2A priority Critical patent/EP3555016A1/fr
Publication of WO2018109173A1 publication Critical patent/WO2018109173A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/246—Cements from oil shales, residues or waste other than slag from waste building materials, e.g. waste asbestos-cement products, demolition waste
    • 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
    • C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • asbestos fibers which are known to have a pronounced longitudinal characteristic slack when subjected to mechanical stress, break the transition products resulting from the thermal treatment transversely to the fiber axis, so that aftertreatment can produce particles of less than 5 ⁇ m in length. Such particles do not correspond to the fiber definition of the WHO and are considered to be harmless to health.
  • the invention is therefore based on the object to provide an improved method for providing a hydraulically hardening binder, with the recourse to a thermal treatment step and thereby minimized use of resources reliable provision of a cementitious / cementitious binder is possible.
  • the production of asbestos-fiber-free recyclates from asbestos cement waste and their utilization should be made possible by the recovery of hydraulically active phases with simultaneous fiber destruction.
  • a particularly suitable use of the thus obtained cementitious binder should be specified.
  • this object is achieved according to the invention by an asbestos-containing, preferably calcium silicate-bound, particularly preferably cement-bound starting material is subjected to both a thermal treatment and a dry deagglomeration, wherein the starting material in the thermal treatment initially predried in a homogeneous temperature environment, then with rising temperature to a target temperature of at least 600 C and at most 800 C, preferably heated by about 700 C and then maintained over a treatment period of at least 60min and at most 180 min, preferably about 90 minutes, at the target temperature.
  • a target temperature of at least 600 C and at most 800 C
  • the presently provided deagglomeration specifically serves for comminution of the previously thermally treated cement stone structure by dissolving the matrix into individual particles by separating the now only weak bonds between the primary particles newly formed by solid state reactions. It is resorted to that in the present process during the thermal treatment, a softening of the cement paste is made. This is based in particular on the dehydration of calcium silicate (CSH) as a result of the thermal treatment at about 700 C.
  • CSH calcium silicate
  • This metastable phases primarily of the calcium silicate, also referred to as meta-calcium silicate, with microporous structure. The resulting microporosity of the structure is reflected for example in a macroscopically observed high water absorption capacity of the former cement paste.
  • agglomerates in turn have microporous structures characterized only by comparatively weak sinter bridges, so that they can be "deagglomerated" by selected dry comminution techniques with relatively low energy input, comparable to the preparation of colored pigments 83% of thermally treated versus thermally untreated fiber cement boards.
  • the asbestos cement fibers are embrittled so that, after the thermal treatment of the asbestos cement, a softened structure of conversion products of the former cementstone (hydraulic phases newly formed by solid-state reactions) and brittle fibers is produced which is comparatively "light".
  • a softened structure of conversion products of the former cementstone hydroaulic phases newly formed by solid-state reactions
  • brittle fibers is produced which is comparatively "light”.
  • the deagglomeration can thus be controlled by taking into account the required energy requirements so that particles with a certain particle size (according to commercially available cements) are obtained 5 m are present, these are incidentschleusen by means of classifier.
  • the invention instead starts from the surprising finding that the thermal treatment is carried out with suitable Not only leads to the required dehydroxylation of the asbestos ingredients of the asbestos cement feedstock, but also to the dewatering of the hydrate phases of the cement paste and the subsequent solid reactions based new formation of cementitious / cementitious, hydraulically active phases and in conjunction with a suitable crushing technique (deagglomeration) the production fiber-free Recyclates made possible.
  • the recycling product thus does not require the high energy expenditure required for comminuting the cement clinker particles by breaking chemical bonds, given its completely different origin.
  • the particles produced as a result of the low-temperature method now being used are agglomerates of smaller particles formed solely by release of water of hydration by solid-state reactions and thus not in the presence of a melting phase.
  • the execution of said deagglomeration is made possible, in particular, by the preceding comparatively "gentle" thermal treatment, in which at first a predrying, preferably at a drying temperature of about 100 ° C., takes place. 120 C, more preferably at about 105 C, is made. Then, a comparatively moderate target temperature is set, which can also precede a comparatively slow, over a certain time interval extending warm-up step. This can be done, for example, by placing the predried material in the treatment oven, which has already been preheated to the target temperature, and thus heating up to the target temperature. Precisely by predrying at a preferred drying temperature of at least 100 ° C., the water bound in the feed can be controlled to escape.
  • the treated material is cooled back to ambient temperature.
  • the intended for this process step cooling period is advantageously selected material-specific and adapted to the starting material and its composition.
  • a comparatively fast and short-term cooling in the manner of a "quenching" or “quenching”, to ambient temperature within a cooling period of at most 10 minutes, particularly preferably of at most 1 minute is provided.
  • the comminution process is carried out during or after the dry deagglomeration until the fibers have a fiber length of at most 5 pm and / or a fiber content of at most 0.1 mass%. It is particularly preferred that the comminution process be carried out until the end product is asbestos-free as defined in the "Technical Rules for Hazardous Substances" (TRGS) using the detection method described in TRGS, the detection limit of which is 0.008% by mass.
  • TRGS Technical Rules for Hazardous Substances
  • the binder obtainable by the method described above is particularly preferably used for applications, in particular in a cement, for earthworks and / or civil engineering.
  • the fiber-free recyclate produced by the process described above hardens hydraulically. It can be used both in pure form and as an additional component of hydraulic binders, for example of cements and / or additives. Its strength development and its 28-day strength are similar to those of standard cements. If rapid solidification is required from an application point of view, it is preferably used without delaying additives or additives. If, on the other hand, a solidification process analogous to the standard cements is required, solidification may be achieved by addition of a sulphate support, e.g. in the form of gypsum or hemihydrate, or by adding a commercially available retarder (concrete admixture).
  • the water claim of the recyclate is in view of its microporosity significantly above the commercial cements. This proves beneficial in a number of applications, for example in its use for soil improvement. Applications requiring lower water requirements are made possible by the addition of concrete liquefiers or plasticizers known from concrete technology.
  • Attritors include a special shredding technique in one Air vortex mill, as it is available, for example, under the name ULTRA ROTOR.
  • the natural fracture sites correspond to the microcracks occurring in the course of dehydration and / or the weak sintered bridges which were formed by the described solid state reactions at a comparatively low temperature level (700 C) and connect the primary particles.
  • the efficiency of the comminution can be increased by the combination with classifiers.
  • the deagglomeration by means of such a fluidized-fluid mill is distinguished from grinding by conventional grinding techniques, in particular by the significantly shorter duration of the required comminuting process, ie the duration of the energy input: compared to, for example, two-stage grinding in a conventional mill, which lasts about 4 hours the residence time of the material in an air vortex mill for the purpose of deagglomeration is preferably only a few seconds or even ⁇ 1 second.
  • Attritors of different types can be advantageously used for energy-efficient deagglomeration, as are used, for example, especially for the treatment of color pigments and / or soft to medium-hard materials.
  • the particular economic advantages of these technologies for the present application lie in the low energy consumption and in the usually short residence times of the feed material in the aggregate, so that comparatively high throughput rates can be achieved in the comminution of the agglomerates.
  • deagglomeration can also be achieved by means of special classical mills suitable for superfine comminution, with a lower energy input being sufficient than in the treatment of thermally unloaded cement stone fragments or clinker obtained from liquid phase sintering.
  • classic mills for the present application, usually requires comparatively long Residence times of the feed material in the mill, so that only very limited throughputs are to be realized, which put the economic viability of the method in question.
  • the deagglomeration can not even be achieved on a case-by-case basis, since the compaction effect of, for example, ball mills sets the excitable particle size too high and the desired desogglomeration is not attainable in a dry state.
  • the advantages achieved by the invention are in particular that by the inventive combination of upstream thermal treatment and subsequent disagglomeration step and optionally undertaken visual process of asbestos, calciumsilikathydrat-, in particular cement, bound starting material to achieve the fineness of commercial cements or especially those of Comminution required by ultra-fine cements not required for grinding mineral hard rock as well as cement clinker high grinding energy, but with the significantly lower energy input one of the usual deagglomeration process, such as by using an ultra-rotor, can be guaranteed.
  • asbestos-free material can first be produced in the manner of an intermediate product. Due to the additionally provided comminution of the conversion products to a particle size of max. 5 pm, the recycling binder is also fiber-free. The end product is thus free of asbestos fibers, also in the sense of the "Technical Rules for Hazardous Substances” (TRGS) .
  • TRGS Technical Rules for Hazardous Substances
  • the definition of asbestos fibers is that fibers which, according to their "chemical composition", belong to the six asbestos minerals according to section 2.2 .
  • the criterion "asbestos-free" is met, since with the thermal treatment of the starting material at 700 ° C, which is required to activate the new binder anyway, a conversion of Asbestos is initiated, so that the final product because of its chemical mineralogical change is not considered more than asbestos - especially not more than chrysotile - to qualify.
  • FIG. 2 is a flow chart showing the process steps of an alternative process for providing a fiber-free hydraulically setting binder of asbestos-containing, calcium silicate hydrate, especially cement, bonded building materials.
  • FIGS. 1, 2 in each case by way of example by means of its method steps for providing a fiber-free, hydraulically setting binder is in each case provided for the treatment and recycling of cement-bound asbestos waste, the reliable provision of a recourse to a thermal treatment step while minimizing the use of resources Asbestos-free binder should be guaranteed.
  • the delivery of lumpy, possibly roughly pre-shredded or else undivided feed material is provided in method step 1.
  • the material can be supplied in any form in the sense of "as loose material” or “in conventional units” (eg in big bags, which are used in particular for the transport of asbestos cements and thus the delivery form) of the preparation.
  • the feedstock is subjected to a thermal treatment in a treatment step 2.
  • the thermal treatment itself comprises several sub-steps.
  • the material to be treated is initially predried in a suitable environment over a drying period of about 2 hours at a drying temperature of about 105 ° C. in the exemplary embodiment.
  • the heating to the target temperature can take place in the embodiment, by the pre-dried items is introduced into the corresponding preheated treatment furnace.
  • This is configured suitably adjustable so that the proposed thermal conditioning of the material from drying to cooling is possible.
  • a continuous production process is conceivable: the material can be transported, for example by means of a transport device first through a furnace (section) for pre-drying and then into the temperature zone of the furnace or furnace section with the target temperature, before it then to cool from the oven is dissipated.
  • the different temperature ranges could be achieved by connected (single) ovens or by different temperature zones in an oven, e.g. in the rotary kiln, be realized.
  • Last but not least, final process management is a question of cost-effectiveness as a function of material throughput and energy input.
  • the material to be treated is maintained at the target temperature over a treatment period of at least 60 minutes and at most 180 minutes, preferably about 90 minutes, before being cooled again to ambient temperature in a cooling step 8.
  • the further use 20 of the recyclate This has as essential properties: it is asbestos-free with a fiber content of at most 0.1 M%, it is hydraulically hardening and cementitious.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé pour la préparation d'un liant à prise hydraulique exempt de fibres d'asbeste, permettant la préparation d'un matériau de construction contenant de l'asbeste, lié par du silicate de calcium hydraté, en particulier lié par du ciment, faisant appel à une étape de traitement thermique et à une utilisation la plus basse possible des ressources, tout en conservant les valeurs limites pertinentes pour les substances inoffensives du point de vue de la santé. Selon l'invention, une substance de départ contenant de l'asbeste est soumise à un traitement thermique ainsi qu'à une désagglomération sèche, la substance de départ étant chauffée, lors du traitement thermique, d'abord dans un environnement de température homogène, sur une période d'échauffement, à une température croissante jusqu'à une température cible d'au moins 600°C et d'au plus 800°C, de préférence d'environ 700°C, et ensuite maintenue sur une période de traitement d'au moins 60 minutes et d'au plus 180 minutes, de préférence d'environ 90 minutes, à la température cible avant d'être refroidie à température ambiante.
PCT/EP2017/083050 2016-12-16 2017-12-15 Procédé de préparation d'un liant à prise hydraulique et utilisation de la matière première de type ciment à base de celui-ci Ceased WO2018109173A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP17829171.2A EP3555016A1 (fr) 2016-12-16 2017-12-15 Procédé de préparation d'un liant à prise hydraulique et utilisation de la matière première de type ciment à base de celui-ci

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016124707.3 2016-12-16
DE102016124707.3A DE102016124707A1 (de) 2016-12-16 2016-12-16 Verfahren zur Bereitstellung eines hydraulisch erhärtenden Bindemittels und Verwendung des darauf basierenden Zement-Grundstoffs

Publications (1)

Publication Number Publication Date
WO2018109173A1 true WO2018109173A1 (fr) 2018-06-21

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PCT/EP2017/083050 Ceased WO2018109173A1 (fr) 2016-12-16 2017-12-15 Procédé de préparation d'un liant à prise hydraulique et utilisation de la matière première de type ciment à base de celui-ci

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EP (1) EP3555016A1 (fr)
DE (1) DE102016124707A1 (fr)
WO (1) WO2018109173A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4332031C1 (de) 1993-09-21 1995-05-11 Nikka Norddeutsche Isolierwerk Verfahren zur Aufbereitung von faserstoffhaltigen Materialien
EP0672469A1 (fr) 1994-03-19 1995-09-20 NIKKA Norddeutsche Isolierwerke GmbH Co. KG. i.K. Procédé pour le traitement de matériaux contenant des fibres dans un broyeur vibrant excentrique
DE19718606A1 (de) 1997-05-02 1998-11-05 Sut Sicherheit Umwelt Technik Verfahren zum Umwandeln asbesthaltiger Materialien
EP1277527A1 (fr) * 2001-07-17 2003-01-22 MVG, Mineralfaser-Verwertungs-Gesellschaft mbH Procédé pour transformer des produits en amiante-ciment en produits en ciment

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE20221250U1 (de) * 1970-04-03 2006-02-09 Mvg Mineralfaser-Verwertungs-Gesellschaft Mbh Vorrichtung zur Umwandlung von Asbestzementprodukten

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4332031C1 (de) 1993-09-21 1995-05-11 Nikka Norddeutsche Isolierwerk Verfahren zur Aufbereitung von faserstoffhaltigen Materialien
EP0672469A1 (fr) 1994-03-19 1995-09-20 NIKKA Norddeutsche Isolierwerke GmbH Co. KG. i.K. Procédé pour le traitement de matériaux contenant des fibres dans un broyeur vibrant excentrique
DE19718606A1 (de) 1997-05-02 1998-11-05 Sut Sicherheit Umwelt Technik Verfahren zum Umwandeln asbesthaltiger Materialien
EP1277527A1 (fr) * 2001-07-17 2003-01-22 MVG, Mineralfaser-Verwertungs-Gesellschaft mbH Procédé pour transformer des produits en amiante-ciment en produits en ciment

Also Published As

Publication number Publication date
EP3555016A1 (fr) 2019-10-23
DE102016124707A1 (de) 2018-06-21

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