Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
  • B01F27/60—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
  • B01F27/70—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms
  • B01F27/701—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers
  • B01F27/706—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers with all the shafts in the same receptacle
• • 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
  • C04B7/28—Cements from oil shales, residues or waste other than slag from combustion residues, e.g. ashes or slags from waste incineration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
  • B01F27/60—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
  • B01F27/70—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms
  • B01F27/701—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers
  • B01F27/703—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers with stirrers rotating at different speeds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
  • B01F35/90—Heating or cooling systems
  • B01F35/92—Heating or cooling systems for heating the outside of the receptacle, e.g. heated jackets or burners
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
  • B01F35/90—Heating or cooling systems
  • B01F35/93—Heating or cooling systems arranged inside the receptacle
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28C5/00—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions
  • B28C5/46—Arrangements for applying super- or sub-atmospheric pressure during mixing; Arrangements for cooling or heating during mixing, e.g. by introducing vapour
  • B28C5/466—Heating, e.g. using steam
• • 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
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
  • C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B7/00—Hydraulic cements
  • C04B7/24—Cements from oil shales, residues or waste other than slag
  • C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
• • 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
  • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
• • 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
  • C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P40/00—Technologies relating to the processing of minerals
  • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • 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 invention relates to a method and a device for the production of storage mineral components for the immobilization of pollutants and for the production of components, in particular of building boards and of mixtures.
• gypsum-based building boards using the winding method, which in addition to the gypsum present in the form of CaS0 4 • V 2 H 2 0 also include cement, slags, fly ash, diatomaceous earth, sand, mineral and organic fibers and flocculants (DE- OS 3121256).
• a process for the production of a binder is known for the immobilization of pollutants, the starting materials for the storage components from combustion residues, water-containing substances and CaO being mixed and subjected to a special thermal treatment (DE 197 19 684). The use of this product in building materials is not described in detail.
• the invention is therefore based on the object of using a simple and inexpensive process to produce a product which has an adjustable and high reactivity for pollutant immobilization, and to design a process and an apparatus which allow mixing, conveying and controlled thermal treatment of various substances , in particular of bulk goods, is guaranteed in one facility and creates the possibility of producing light and stable components and / or mixtures which can be used in a variety of ways for interior and exterior construction and consist mainly of residues and natural materials.
• filter ash is brought together with water-containing substances and, if necessary, with CaO.
• Free lime-containing filter ashes such as lignite filter ashes and ashes from fluidized bed combustion or dry desulphurization, but also filter ashes from waste, sewage sludge and hard coal incineration plants can be used as filter ashes. It has been shown that, depending on the free lime contents of the ashes used, a CaO addition of 1 to 50% by weight is sufficient. Particularly favorable results for storage mineral formation can be achieved if 30 to 90, in particular 40 to 70,% by weight of water-containing substance are used in relation to the mixture.
• water-containing substances such as red sludge, aluminum hydroxide, waste water, silicate, ettringite and gypsum sludges has proven to be particularly advantageous. These materials can be used in different degrees of drying.
• the water can be present as crystal water and / or as physically adhering water. This offers the possibility of moisturizing the aforementioned substances, ie. H. to be used without prior preparation.
• this mixture is exposed to a temperature which leads to the release of the crystal water and / or as physically adhering water.
• This temperature depends on the type of water-containing substance and is between 100 and 600 ° C.
• the water reacts with the added and the free CaO present in the filter ash with the brief formation of calcium hydroxide, which reacts further with aluminates and silicates to form the storage mineral phases described above.
• the addition of CaO alone without the process according to the invention in no case leads to an increase in the reactive components since there is no reaction between the calcium oxide and the aluminates or silicates.
• the amount of heat released during hydration supports the formation of the reactive mineral phases and leads to the saving of externally supplied energy in order to maintain the reaction temperature.
• Substances containing water of crystallization are converted into the partially or fully hydrated state by the treatment according to the invention.
• the proportion of active components can also be increased in that substances containing water of crystallization can be reactivated during the dehydration.
• calcium aluminate sulfate hydrates become storage mineral formers in the process according to the invention Anhydrite, bassanite and portlandite converted. These components can be used to store pollutants by forming the ettringite storage mineral.
• the invention enables filter ash to be used for immobilization which, up to now, has not been suitable for this application due to a lack of reactivity (e.g. hard coal filter ash, brown coal filter ash with low CaO contents).
• the method according to the invention not only leads to an enrichment of reactive mineral phases for the immobilization of pollutants, but also to an increase in the amount of hydraulically active components. This can be seen from the building material values of the hardening product (see application example).
• a rotary tube with internals for mixing and conveying the material or a stationary or circulating fluidized bed can be used.
• the reactivity of the product can be controlled via the residence time and temperature in the reactor.
• the phase formation increases with increasing temperature and dwell time.
• the method according to the invention thus offers a possibility of adapting the reactivity of the product to the requirements for pollutant immobilization or for building material suitability.
• the residence time can be between 5 and 120 min. vary.
• the starting materials in the form of combustion residues and water-containing substances are fed via an application device to an elongated device which simultaneously functions as a mixer and thermal reactor and that the starting materials are mixed and simultaneously conveyed and thermally treated by means of several paddle shafts, the thermal treatment in Different temperature zones are implemented differently and are carried out in a water vapor atmosphere under different pressure conditions.
• temperatures in the different zones of the reactor and different residence times of the mixture in the device By setting different temperatures in the different zones of the reactor and different residence times of the mixture in the device by changing the conveying speed and varying the zone length, products with different properties can be produced, which are based on the intended immobilization of pollutants and / or are specifically tailored to the building material application.
• the temperatures in the different zones are set between 100 - 400 ° C.
• the starting materials can either be thermally treated with temperatures rising and / or changing in the temperature zones.
• To initiate the necessary "nucleation” it is possible to treat the treated good in one Quantity of 1 - 10% of the total amount due to the beginning of the thermal treatment.
• a water vapor atmosphere of 100-1000 l / m is formed at pressures from 0.1 mbar to 10 bar, preferably between 1 mbar and 5 bar.
• the device is heated either on a gaseous basis or by an electric heater.
• the device for carrying out the method has a feed device and a plurality of lying paddle shafts, which are provided with an electric drive with gear and bearing, and which are guided in a heated, elongated housing which has a further supported bearing and an outlet at its end.
• the elongated housing has a vapor extraction with return and 2 to 8, preferably 4, temperature zones. These are arranged on a length of 10 -90%, preferably 10 -50%, of the length of the housing.
• the material temperature in the zones is measured using thermocouples.
• the heat input takes place by gas burners arranged in a circle on the housing and / or by direct and / or indirect electrical heating, direct heating preferably being implemented in the upper housing region and indirect heating in the lower housing region. Heating by means of steam is also possible.
• the housing is thermally insulated.
• the paddle shafts either have the same or an opposite direction of rotation and their number is adapted to the required throughput.
• the angle of attack of the paddles, based on the shaft axis, is
• a thermally treated mixture of combustion residues, water-containing substances and CaO is used in the manufacture of the binder, which (as reinforcement) is mixed with organic fibers formed from renewable raw materials and / or recycled textiles as well as a natural filler and water, if necessary is then pressed into molds and hardened.
• Lignite, hard coal, fluidized bed filter ash can be considered as combustion residues.
• the water-containing substances can be non- or partially dewatered REA gypsum.
• Hemp and / or flax and / or sisal and / or reed and / or bamboo and / or textiles or the like are used as organic fibers.
• These fibers are intended to give the components to be manufactured significantly higher elasticity values compared to the prior art, which, in conjunction with the special binder and the high strength values to be achieved thereby, make it possible, on the one hand, to produce larger components with thinner wall thicknesses or layer thicknesses as well as load-bearing elements. It is completely irrelevant whether it is used indoors or outdoors because the components are weatherproof, frost-resistant and not very sensitive to water contact.
• the organic fibers are processed before being processed.
• the cockroaches produced during processing are used as fillers for the mixture. This has the advantage that the thermal insulation of the mixture is significantly improved and the mass is reduced via these fillers, which extends the scope of application.
• the mixture described can also be used as plaster, screed, in-situ concrete or the like. The proportion of binder, organic fiber and filler is adjusted depending on the intended use.
• the resulting product is used to immobilize chrome-containing floors.
• the eluate concentration of the material to be treated is 600 mg / 1 Cr 6 +.
• 50 kg of the soil are mixed intensively with 20 kg of the ash treated according to the invention with the addition of 18 kg of water for 2 minutes.
• 20 kg of the untreated ash are added to the same amount of contaminated material.
• Proctor cylinders are made from the mix, which are stored in a moist place until tested after 28 days.
• the immobilization rate improves from 77% to 97% in the present example.
• the compressive strength increases by 148% when using the material treated according to the invention.
• the storage minerals Chromatettringit and Monochromat are detected by X-ray in the hardened material.
• the starting materials are fed to the feed device 1 and pass through this into the housing 6 with paddle shafts 5, which are driven by a drive 2 with a gear 3 and are supported by the bearings 4 and 7.
• the rotatable paddle shafts 5 convey and mix the starting materials evenly and in a controlled manner towards the outlet 8.
• the reactor for a system of 10 t / h should, for. B. about 6 m in length and about 1 m in diameter.
• the housing 6 is thermally insulated and divided into the temperature zones 1-4, which are equipped with an electric heater. In the upper area of the housing 6 there is a direct electric heater and in the lower area an indirect heater.
• the temperature to be set in the different zones is between 100 - 400 ° C. Heating is carried out separately for each zone using a computer-controlled program.
• Temperature zone I can have, for example, a temperature of 150-200 ° C, temperature zone II 200-300 ° C, temperature zone III 300-350 ° C and temperature zone IV 350-300 ° C.
• the speed of the paddle shafts 5 can be varied so that the residence time of the mixture can be regulated. In the example, it can be 20 rpm. be.
• the targeted thermal treatment in the 4 temperature zones with a special dwell time in the housing can produce 6 substances that are almost optimally adapted to the intended use. These can have either high or low early high strength, compressive strength, bending tensile strength or special thermal insulation properties as well as very good immobilization properties.
• a binder which is composed of a calcined mixture of 40 M% ettringite sludge and 60 M% hard coal ash, is used to produce a building structure, in particular a building board.
• This binder is in the dry state with 1 -10 M%, preferably 3 M%, organic fibers, such as. B. hemp with a fiber length of 1-3 cm, mixed intensively.
• Mixing is preferably carried out in a compulsory mixer with the addition of mixing water and is carried out after approx. 2 min. completed.
• the water requirement of the mixture is between 20-40% by mass, preferably 30% by mass.
• the mixture is poured into molds and sets hydraulically. The dimensions of the mold are approx. 2 x 1 m, whereby the building boards have a thickness of 10 - 20 mm.
• the plates examined after 28 days of storage had the following values:
• the panels are weatherproof and have sufficient resistance to frost / thawing, so that they are suitable for both interior and exterior construction.
• Example 2 -insulating building material
• the binder used to manufacture the heat-insulating building material is composed of 40 M% ettringite sludge and 60 M% hard coal ash and has been calcined. Residues from the processing of plant fibers (cockroaches) are added to this binder in a proportion of 10 -80% by mass, preferably 50% by mass, and in a compulsory mixer with a mixing time of max. 2 min. intensely mixed. The amount of mixing water added is between 15 -25% by mass, preferably 20% by mass. The resulting mixture is placed in formwork on site or processed into thermal insulation bricks / panels. The mixtures examined achieved one

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Ceramic Engineering (AREA)
• Structural Engineering (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Combustion & Propulsion (AREA)
• Mechanical Engineering (AREA)
• Inorganic Chemistry (AREA)
• Processing Of Solid Wastes (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)

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• 1998
  • 1998-05-07 EP EP98925550A patent/EP0980344A1/de not_active Withdrawn
  • 1998-05-07 WO PCT/EP1998/002680 patent/WO1998051634A1/de not_active Application Discontinuation
  • 1998-05-07 SI SI9820045A patent/SI20068A/sl unknown
  • 1998-05-07 HU HU0002115A patent/HUP0002115A3/hu unknown
  • 1998-05-07 SK SK1536-99A patent/SK153699A3/sk unknown
  • 1998-05-07 DE DE19880619T patent/DE19880619D2/de not_active Expired - Fee Related

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