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
  • 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
  • C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
  • C04B28/008—Mineral polymers other than those of the Davidovits type, e.g. from a reaction mixture containing waterglass
• • 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
  • C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
• • 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
  • C04B2111/00862—Uses not provided for elsewhere in C04B2111/00 for nuclear applications, e.g. ray-absorbing concrete
• • 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 geopolymeric binder based on fly ash, which is intended for the production of pulp, mortar and concrete or for waste fixation, and the 70 to 90 percent by weight of power plant fly ash with a measuring surface of 1 50-600 m 2 / kg and 5 to 15 percent by weight of the alkaline Activator contains, where the activator consists of a mixture of alkaline hydroxide and alkaline silicate, for example water glass, when this activator contains 5 to 15 weight percent Me 2 O and a ratio of Si0 2 / Me 2 0 in the range of 0.6 to 1 , 5, where Me is Na or K.
• the latent hydraulic active ingredients such as granular ones
• Blast furnace slag, power plant fly ash, natural or artificial pozzolana are a component of Portland mixed cements. These substances actively participate in the hydration process of Portland cement if the activating substance is C a (OH) 2 in particular, which is the case of hydration of clinker minerals arises.
• the h ydraulically active substances are also able to form hydrates in the absence of Ca (OH) 2 , which give the substances with measurable mechanical properties.
• Such activators of latent hydraulic substances are some alkaline compounds such as for example Na 2 C0 3, NaOH or Na 2 Si0.
• alkali slag cement The basic information about these binding agents, "alkali slag cement", can be found in the literature, for example in the book by VDGluchovskij: “Soil Silicates", Kijev 1959, further in Proceedings 1st and 2nd International Conference “Alkaline Cements and Concretes", Kijev 1994 , 1999 and many others. In this work, mixtures of latent hydraulic substances (especially slags and others) are described where an alkaline activator in the form of water glass, Na 2 CO 3 and NaOH is used.
• the US Pat. No. 4,410,365 describes a binding material based on ground granular blast furnace slag and alkaline activator, for example NaOH, Na 2 S0 4 .
• an alkaline binding agent with a low water coefficient is described, which is suitable for the preparation of porridge, mortar and concrete.
• the binding material consists of at least 50% of latent hydraulic active substance, such as slag, or synthetic or natural pozzolana, and which has a measuring surface of at least 400 m 2 / kg.
• the binding agent also contains 0.1 to 5% plasticizer and 0.5 to 8% NaOH or Na 2 CO 3 .
• US Pat. No. 5,076,851 describes a gypsum stone-free Portland mixed cement which is 60 to 96.7% of ground Portland cement clinker with a measuring surface of 350 to 550 m 2 / kg and 3 to 40% of ground latent hydraulic material, such as blast furnace slag, fly ash, etc. , contains.
• the binding agent also contains 0.1 to 3% concrete plasticizer and 0.5 to 6% Na 2 C0 3 , NaOH or NaHC0 3 .
• a cement based on power plant fly ash is described in US Pat. No. 5,601,643.
• the binding agent achieves high strengths, especially after treatment at temperatures from 40 to 90 ° C.
• Heavy metal waste is described, which consists of latent hydraulic substances
• alkaline concrete plasticizer based on CaO, Ca (OH) 2 , MgO, Mg (OH) 2) and CaS0 3 or CaS0 4 .
• EP 593130 describes an immobilization process for heavy metal waste using the binding material consisting of fly ash, solution of alkaline activator, the pH of which is greater than 13, possibly containing slag, silicate fly dust or other puzzolans.
• EP 927708 describes a hydraulic binding material consisting of a latent hydraulic substance, such as fly ash, ground slag, an alkaline activator, such as, for example, metal hydroxides of alkaline earths, Portland cement or aluminum cement clinker and
• WO 00/00447 describes an alumina silicate binding material which consists of alumina silicates (blast furnace slag, clay, clinker, fly ash) with an Al 2 0 3 content of more than 5%, fly dust from the cement rotary kiln, an alkaline activator in the form of alkaline hydroxide and CaSO 4 consists. In each case more than 34% slag, more read 5% fly ash, 3 to 10% of alkaline activator and more than 5% CaS0 4 are present in the binding material.
• CZ 289,735 describes an alkaline activated binding agent based on hydraulically active substances, which is intended for the production of pulps, mortar and concretes that harden at temperatures from 15 to 95 ° C. It consists of 35 to 93 percent by weight of power plant fly ash with a measuring surface of 100 to 600 m 3 / kg, 2 to 40 percent by weight of another hydraulically active substance, 5 to 15 percent by weight of alkaline activator, such as a mixture of sodium or calcium water glass and NaOH or KOH is expressed as weight percent Na 2 0, with another hydraulically active substance being ground granular blast furnace slag with the measuring surface 200 to 600 m 2 / kg, and / or ground Portland cement clinker with the measuring surface 200 to 600 m 2 / kg, and / or Natural and / or artificial pozzolana and / or heat-activated natural clay, and the ratio of SiO 2 / Na 2 O in the alkaline activator is 0.4 to 1.0.
• Alkaline fly ash activation produces substances with strengths that exceed the strengths of standard Portland cements.
• Alkaline fly ash activation (with a predominance of Si0 2 content) is a process in which AI atoms (and probably also Ca, Mg) penetrate into the original silicate lattice of the fly ash.
• the alkaline activated binders enable the use of inorganic waste materials.
• the materials based on AA fly ash can be characterized as "chemically bonded ceramics" or geopolymers or as hydrated low-temperature alumina silicate glass.
• the geopolymeric binder based on fly ash which is intended for the production of porridge, mortar and concrete or for waste fixation, and which contains 70 to 90 percent by weight of power plant fly ash with a measuring surface of 150 to 600 m 2 / kg and 5 to 15 percent by weight of alkaline activator, whereby the activator consists of a mixture of alkaline hydroxide and alkaline silicate, for example water glass, when this activator contains 5 to 15 percent by weight Me 2 0 and a ratio of S i0 2 / Me 2 0 in the range of 0.6 to 1.5 where Me is Na or K, according to the invention is that it contains 1 to 15% calcareous compounds, such as CaC0 3 , CaMg (C0 3 ) 2 , CaS0 4 , CaS0 4 .2 H
• the fly ash contains more than 3 percent by weight of CaO, advantageously more than 8 percent by weight of CaO.
• a mixture of low-lime fly ash with CaO content less than 3 percent by weight and high-lime fly ash with Cao content greater than 3 percent by weight can be used.
• the geopolymeric binding agent is used so that the ratio of the mixing water / (fly ash + calcareous compound) is 0.25 to 0.4.
• a suitable filler in the pulps, mortar and concrete or waste fixation is broken limestone or dolomite limestone in the fractions from 0.1 to 32 mm.
• the fillers for the concrete preparation using the geopolymeric binding agent are advantageously Fe oxides, barite or other material for shielding against radioactive radiation and / or inorganic and organic materials containing heavy metals, such as Zn, Ba, Cd, Cu, Zr, Pb, Ni, U, or materials from mineral processing and production, lye by-products.
• the mixture of geopolymer binding agent, mixing water and possibly filler is added to the molds and allowed to harden at temperatures of 20 to 95 ° C.
• the increase in strength of the fly ash-based geopolymer is achieved by the addition of calcareous substances such as CaC0 3 , CaMg (C0 3 ), CaS0 4 , CaS0 4 .2 H 2 0, Ca (OH) 2 , gypsum stone, dolomite limestone, waste gypsum stone from chemical productions, waste gypsum stone from sulfur separation processes, reprocessed cement material from concrete is reached.
• the increase in the CaO content in the fly ash also has a positive effect.
• the increase in strength is possible while lowering the total alkali content and lowering the NaOH content in the alkaline activator, in contrast to known preparation methods for these substances.
• the lowering of the alkaline content and in particular the lowering of additional NaOH addition to the Ms preparation is significant from the point of view of manipulation with this binding material.
• Waste CaS0 4 from chemical and sulfur separating processes and then also reprocessed cement material made of concrete (fine fractions after comminution of the concrete used) can be used as a binding substance component.
• the usual aggregate for the production of mortar and concrete advantageously crushed limestone or dolomite limestone, can be used as an aggregate for this type of binding material.
• the geopolymeric binding agent can also be used for the preparation of materials for shielding against radioactive radiation, for example for the preparation of heavy concrete or of substances that contain shielding materials such as Fe oxides, barite, etc. in the highest possible amount.
• the geopolymeric binding agent can be used to fix both inorganic and organic wastes, waste materials that contain heavy metals such.
• the geopolymeric binding material represents a new type of inorganic binding material which enables the processing of inorganic waste - the fly ash - as the basic raw material.
• the Fly ash has so far been used as a component of Portland cement or as a component of concrete mixtures. A significant part of waste fly ash is stored or mixed with waste gypsum stone and z. B. deposited in the exploited premises.
• the mixing of fly ash with waste gypsum stone e.g. from sulfur separation processes
• the waste gypsum stone from sulfur separation processes with limestone method
• contains Ca which comes from a non-renewable raw material, which is limestone.
• the geopolymeric binding material represents a possibility of using the mixture of fly ash and waste gypsum stone at a much higher level than depositing this mixture on the landfill.
• the geopolymeric binding agent does not require an energetically demanding production process in comparison to other inorganic binding agents, especially to Portland cement.
• the production of Portland cement involves an energetically demanding process of raw material preparation (conveying, crushing, grinding and mixing some raw material components) and subsequent burning out to temperatures of 1450 ° C. A part of the cement production is also the energetically demanding grinding of the clinker.
• These methods which require energy and raw materials, do not apply to the production of the geopolymer binding material according to the invention, because in principle it is not necessary to grind or sort the basic raw material - the power plant waste fly ash (although it is possible to optimize the properties of the binding material) and no energetically demanding heating process such as burnout is required.
• short-term heating to temperatures of 60 to 90 is sufficient to optimize the properties of the binding material ° C, or in some cases this warming is not even necessary at all.
• the geopolymeric binding material is a new type of inorganic binding material, which in principle does not produce any C0 2 emissions because, in contrast to the production of Portland cement or plaster, it is not necessary to use limestone (as a component of the raw material mixture). to burn.
• This binding agent represents a potential perspective for reducing the emissions of "greenhouse gases", the main producers of which, in addition to the metallurgical and power plant industries, are the cement factories and lime distilleries.
• Another ecological aspect of the geopolymer binding material, according to the invention, is the possibility of fixing waste materials and substances that contain heavy metals.
• the power plant fly ash with the composition in weight percent was used as follows for the preparation of porridges, mortar and concretes made of geopolymer binding material:
• the alkaline activator was made of water glass with the composition
• Example 3
• Mortar was prepared from the fly ash according to Example 1, where sand with the fraction 0-2 mm was used as filler.
• a calcareous substance was added to the fly ash, which was represented by ground limestone with a particle size of up to 80 mm, ground dolomite limestone with a particle size of up to 150 ⁇ m and waste gypsum stone with a particle size of up to 30 ⁇ m.
• the mixtures without the addition of the calcareous substance correspond to the known methods, e.g. B. according to US 5,601, 643 and CZ 289,735.
• Mortar was prepared from the fly ash according to Example 1, where sand with the
• Fraction 0-2 mm was used as filler.
• a reprocessed cement material was added to the fly ash, which represented the fraction 0-0.5 mm from crushed cement concrete or from crushed aerated concrete.
• Example 8 A mixture of the fly ash according to Example 1 and fly ash A was used to prepare the mortar, the composition of which is given in the table below: SiO z Al 2 0 3 Fe 2 0 3 CaO MgO so 3 K 2 0 Na 2 0 Ti0 2 P2O5 Burned substances
• fly ash was used with the following
• the invention can be used in construction.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Geology (AREA)
• Geochemistry & Mineralogy (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Environmental & Geological Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Combustion & Propulsion (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Processing Of Solid Wastes (AREA)

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Cited By (26)

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Citations (10)

• 2002
  • 2002-03-20 CZ CZ20021011A patent/CZ292875B6/cs not_active IP Right Cessation
• 2003
  • 2003-03-18 SK SK33-2004A patent/SK332004A3/sk unknown
  • 2003-03-18 AU AU2003213989A patent/AU2003213989A1/en not_active Abandoned
  • 2003-03-18 WO PCT/CZ2003/000020 patent/WO2003078349A1/de not_active Application Discontinuation

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