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    公开号:ES2553241T9
    申请号:ES13002496.1T
    申请日:2013-05-11
    公开日:2016-02-10
    发明作者:Frank Bullerjahn；Nicolas Spencer；Mohsen Ben Haha；Anca Itul；Dirk Schmitt
    申请人:HeidelbergCement AG；
    IPC主号:
    专利说明:

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    DESCRIPTION
    Procedure for the production of a magnesium silicate cement, belite and calcium aluminate
    The invention relates to a process for the production of a binding agent for building materials, such as a concrete, a mortar or a plaster, and to a binding agent produced in accordance with this procedure, as well as to its use.
    Cement used as a hydraulic binding agent is an important industrial product, which is composed, in essential proportions, of a Portland cement clinker. This clinker is produced by sintering a mixture, which is made of lime, sand, clay and correction materials, at approximately 1,450 ° C. After the reaction at a high temperature, the following phases are presented that contain foreign oxides: one of alite (CaaSiOs, which is also designated as C3S), one of belite (Ca2SiO4, which is also designated as C2S), one of aluminate (Ca3AhO6, which is also designated as C3A) and one of ferrite (Ca2 (AlxFei-x) 2O5, which is also designated as C4AF). In this context, belite is presented mainly in the form of polymorph p. This phase is considered as relatively inert with a small contribution to mechanical resistance at an early age.
    Hydraulic reactivity describes the reaction of a binding agent with water mediating the formation of a solid material. Unlike that of the wing, the hydration of the belita takes place slowly over several months and years.
    It is known that the reactivity of belita with water can be improved by means of a chemical-chemical activation (see patent document of the German Democratic Republic DD 138197 A1), by rapid cooling after the calcination process (see document DD 138197 A1 and German patent application document DE 3414196 A1), as well as by incorporating foreign oxides (see US Patent Document US 5509962 A and DE 3414196 A1). In addition, along with the variant p of the belita, other polymorphs are known that have a better reactivity (the a, a'H, a'L and x) or worse (the y).
    From the reference of H. Ishida, S. Yamazaki, K. Sasaki, Y. Okada, T. Mitsuda, [alpha] -Dicalcium Silicate Hydrate: Preparation, Decomposed Phase, and its Hydration, [= [alpha] hydrate dicalcium silicate: Preparation, decomposed phase and its hydration], J. Am. Ceram. Soc. 76, pages 1707-1712, 1993, a process is known for the production of dicalcium silicate a-hydrate (a-C2SH) at 200 ° C by a hydrothermal treatment for two hours of a calcined lime (CaO) and of a silphic acid to perform the syntheses in the laboratory (with a degree of purity pa (= analytically pure)). In the temperature range of 390-490 ° C the a-C2SH becomes different modifications of the C2S, which, when heating continues to 920-960 ° C, becomes the a'L phase, and when cooling forms the P-C2S The high proportion of y-C2S that is slow to react is disadvantageous in this context.
    Document DE 10 2009 018 632 discloses a process for the production of a binding agent containing belite, in which an intermediate product, which had been produced at 120-250 ° C by means of a hydrothermal treatment of the starting material which has a molar ratio of Ca / (Si + Al) that is between 1.5 and 2.5, is subjected to a reactive grinding at 100 - 200 ° C for a period of time that is between 5 min and 30 min. The fact that reactive grinding is an energetically inefficient stage is disadvantageous in this context. Moreover, only in the case of the addition of fluidizing agents can sufficient compression resistance be achieved after hardening.
    Document DE 10 2005 037 771 discloses a process for the production of a belttic cement, in which dicalcium silicate a-hydrate (a-C2SH) is formed at 100-300 ° C by hydrothermal treatment of the starting material , which contains CaO and SiO2 in the Ca / Si molar ratio of 1.5-2.5. In the range of temperatures between 500 and 1,000 ° C, the a-C2SH is transformed into modifications of the C2S that are hydraulically reactive (beltic cement). In this context, the fact that the calcination process must be carried out at a relatively high temperature (above 500 ° C) is disadvantageous. These high temperatures lead, moreover, to the decrease in the reactivity of the binding agent.
    Jiang et al., "Hydrothermal Processing of New Fly Ash Cement", Ceramic Bulletin, 71, 1992, pages 642 to 647 describe the reaction of a fly ash and CaO to form C2S and C12A7 by a hydrothermal treatment (for 4 h at 200 ° C) and a calcination at 500 to 900 ° C. The high temperature that occurs when calcining has a negative impact on the reactivity of the product. In addition, prior treatment for ten hours at 80 ° C is necessary.
    European patent application document EP 12004620.6, which has not been published previously, describes a process for the production of a binding agent, comprising the steps of:
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    a) Make available a starting material that has a Ca / Si molar ratio of 1.5 to 2.5 in the case of whose determination they remain without considering those components that behave in an inert manner within the autoclave when performing a hydrothermal treatment, based on raw materials,
    b) Mix raw materials,
    c) Hydrothermally treat the mixture of starting materials that has been produced in stage b), within an autoclave at a temperature of 100 to 300 ° C and with a period of residence time of 0.1 to 24 h, being from 0.1 to 100 the ratio of water / solid material,
    d) Temper the intermediate product obtained in stage c) at 350 to 495 ° C, with a heating rate of 10-6,000 ° C / min and with a residence time of 0.01-600 min ,
    adding, during mixing and / or in the following stages, 0.1 to 30% by weight of additional elements and / or oxides.
    Pimraksa et al., In "Synthesis of belite cement from lignite fly ash" [Smtet of a belttic cement from a lignite fly ash], Ceram. Int. 35 (2009) 2415-2425 found that a fly ash is suitable as an educt for the production of a belftic cement by hydrothermal treatment and calcination. Hydrothermal treatment takes place at 130 ° C preferably in the presence of NaOH to provide alkaline conditions. The products of the hydrothermal treatment are then calcined at 750 to 950 ° C for 30 minutes, the heating rate being 8 ° C / min until reaching 600 ° C and 4 ° C / min above this temperature. As products, C2S (p and a) and C12A7 are mentioned.
    Most of these proposals are based on high value raw materials. In addition, predominantly a calcination is required at temperatures, which are still very high, and / or an activation of the mixture of raw materials and intermediate products by means of a reactive grinding that has an intense energy consumption.
    Therefore, the mission of proposing a process for the production of binding agents, whereby a high reactivity of the binding agent can be achieved, in order to produce efficient cements thus remains. In this context, an emission of carbon dioxide manifestly smaller than in the case of conventional Portland cements having a high proportion of wings should also be achieved. In addition, a conservation of very valuable natural raw materials is intended, that is to say that they should be able to be replaced, at least partially, in a preferred way, even widely, by means of secondary raw materials.
    Surprisingly, it was finally found that some raw materials that, together with Ca and Si, also contain Mg and Al as well as Fe, by means of a hydrothermal treatment and subsequent tempering at 350 to a maximum of 600 ° C, ideally at at a temperature below 500 ° C, they provide very reactive binding agents.
    Therefore, the problem posed by the mission is solved by a process for the production of a binding agent, which comprises the steps of:
    a) Make available a starting material from raw materials, containing CaO, MgO, SiO2, AhO3 and Fe2O3 or other compounds of these elements, and have a molar ratio of (Ca + Mg) / (Si + Al + Fe) from 1 to 3.5, a molar ratio of Ca: Mg from 0.1 to 100 and a molar ratio of (Al + Fe) / Si from 100 to 0.1, remaining unchecked, when performing the determination of relationships, those components that behave in an inert manner when performing hydrothermal treatment within the autoclave,
    b) Mix raw materials,
    c) Hydrothermally treat the mixture of starting materials, which have been produced in stage b), inside the autoclave at a temperature of 100 to 300 ° C and with a period of residence time of 0.1 to 24 h, being from 0.1 to 100 the ratio of water / solid materials,
    d) Temper the intermediate product, which was obtained in stage c), at 350 to 600 ° C, the heating rate being 10 - 6,000 ° C / min and the residence time period of 0.01 - 600 min.
    Preferably, during mixing in b) and / or in the following stages, 0.1 to 30% by weight of additional elements and / or oxides are added.
    According to the process according to the invention, the molar ratio of the sum of calcium and magnesium to the sum of silicon, aluminum and iron should be 1.0 to 3.5, preferably 1.5 to 2, 5, especially preferably about 2. The ratio of calcium to magnesium is 0.1 to 100, preferably 0.2 to 20, more preferably 0.5 to 5. The ratio of the sum of aluminum and iron to silicon is 0.01 to 100. For a high aluminum content a ratio of the sum of aluminum and iron to silicon of 100 to 10 is preferred and for a medium aluminum content a ratio of 1 is preferred to 20 and for a low aluminum content it is preferred
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    a ratio of 0.01 to 2. When determining these relationships, those compounds that behave in an inert manner in the case of the production procedure are not taken into consideration.
    As a starting material, primary and / or secondary materials can be used. In a preferred embodiment, quartz, sand or gravel, an old concrete and fly ash are used as raw materials for the starting material. The desired ratio of (Ca + Mg) / (Si + Al + Fe), Ca: Mg or respectively Al / Si can be presented according to the raw material, and when not present, the materials, before treatment Subsequently, they must be adjusted in terms of chemical composition by adding other participants in the reaction, such as solid materials containing Ca, Mg, Al, Fe or Si in order to adjust the necessary ratio of (Ca + Mg) :( Si + Al + Fe) from 1 to 3.5, the desired ratio of Ca: Mg from 0.1 to 100 or respectively the desired ratio of Al + Fe: If from 100 to 0.1 . In order to increase the proportion of Ca, for example, but not exclusively, a Ca (OH) 2 portlandite or a calcined lime, ashes with a high chemical content of CaO and / or free lime, a clinker of cement as well as a metallurgical sand. For the elevation of the Mg ratio, a calcined dolomite (calcined at> 500 ° C) is suitable. In order to increase the proportion of Al, fly ash rich in aluminum is suitable, but also clays, for example calcined clays, a bauxite, waste materials containing Al and some residues.
    As a general rule, raw materials are optimized in terms of grain size and the distribution of grain sizes. For this, mechanical or thermal treatments are appropriate, and the thermal treatment can also lead to an improvement and an optimization of the mineralogical (chemical) composition. Examples of this are the combustion of carbon (eg from ashes) or the chemical conversion of non-reactive phases into more reactive compounds, such as for example the conversion of SiO2 or C2As into C2S, which at its This time may lead to improved chemical conversion during autoclaving.
    In a preferred embodiment, a starting material is chosen or respectively produced by pretreatment, whose highest grain size is at most 0.1 mm. For this, the finest grain fractions that come from the renewed enrichment of cement-containing binders in construction materials such as concrete and old cements are used in particular. A finer starting material is advantageous both in regard to the reaction rate and also in regard to the expense for grinding the finished cement. In the case of a correspondingly fine starting material, milling can be dispensed with after hydrothermal treatment and tempering. A grinding of the cement obtained is not necessary in most cases or is limited to achieving the usual finenesses of the cements. An intensive "activator" grinding is not necessary and preferably does not take place.
    During the mixing of the raw materials b) or the subsequent stages of the process, an addition of additional elements or oxides is preferably carried out in a proportion of 0.1 to 30% by weight. Sodium, potassium, boron, sulfur, phosphorus or a combination of them are preferred as these additional elements or oxides, which are also briefly designated as foreign oxides. For this, salts and / or hydroxides of alkali metals and / or alkaline earth metals are adapted, for example, but not exclusively, CaSO4-2H2O, CaSO4-1 / 2H2O, CaSO4, CaHPO2'2H2O, CaaP2O8, NaOH , KOH, Na2COa, NaHCOa, K2CO3, MgCO3, MgSO4, Na2Al2O4, Na3PO4, K3PO4, Na2 [B4O5 (OH) 4] 8H2O, CaCl2, Ca (NO3) 2, MgCh, Mg (NO3) 2, AlCh, Al (NO3 ) 3, FeCh, Fe (NO3) 3, Ca (CH3COO) 2, Mg (CH3COO) 2, Al (CH3COO) 3, Ca (HCOO) 2, Mg (HCOO) 2, Al (HCOO) 3, and mixtures of two, three or even more of these compounds. In a preferred embodiment, the mixture of starting materials has a molar ratio of P / Si of about 0.05 and / or one of S / Si of about 0.05 and / or one of Ca / K of about 0 , 05.
    The mixture of raw materials, which optionally has been previously treated as described, can optionally be combined, that is inoculated, with crystallization nuclei containing, for example, calcium silicate hydrates, a Portland clinker, a sand metallurgy, magnesium silicates, a calcium sulfate-aluminate cement (belite), a soluble glass, glass powders, etc. The reaction can be accelerated in this case by means of an inoculation with a proportion of 0.01-30% by weight of crystallization nuclei, in particular of different compounds containing a calcium silicate and a calcium silicate hydrate, in particularly with a-2CaOSiO2'H2O, afwillite, calcium-chondrodite, a and p-Ca2SiO4 and other compounds.
    The mixture produced from the raw materials, which has eventually been inoculated as described above, is then subjected to a hydrothermal treatment in an autoclave at a temperature of 100 to 300 ° C, preferably of 150 ° C to 250 ° C. In this case, preferably a ratio of water / solid materials of 0.1 to 100 is preferred, preferably 2 to 20. The residence time periods preferably last 0.1 to 24 hours, more preferably from 1 to 16 hours.
    The mixture of the raw materials can be calcined in an additional stage previously connected. This stage is particularly preferred in the case of the use of industrial by-products or relatively non-reactive or thick materials, respectively, as raw materials. In this case, temperatures of 350 to 1,400 ° C are appropriate, preferably 750 to 1,100 ° C. The duration of the calcination is 0.1-6 hours, preferably about 1 hour. By calcining the
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    Raw materials can be made deliberately usable materials that otherwise can hardly be used or cannot be used at all (eg crystalline ashes, limestone, dolomite and slags, etc.). In this case, the raw fine powder can be optimized, prior to clinker calcination, in terms of its chemical composition, and an improved or greater convertibility in the autoclave is guaranteed. Moreover, there is an advantage that reactive phases can be deliberately produced (eg calcium and / or magnesium aluminates, calcium and / or magnesium silicates, ferrites and calcium oxides and / or magnesium), whose products, after stages c) and d), have especially high contents of X-C2S, a-C2S, C12A7, silicates of Mg, MgO and / or at least one reactive phase, that amorphous against X-rays, and / or a little crystalline phase. An advantage of the use of belite as a raw material for the autoclave process is a phase composition of the final binding agent, which is improved compared to uncalcined raw materials.
    As at least one component of the raw materials for calcining the previously connected clinker or, preferably, directly for the autoclaving stage, a fine powder from an oven or hot can be used. The advantage is that this material is already presented in a deacidified condition in large portions and, as a result, energy can be saved but also additional equipment. Additionally, this makes possible a "self-sufficient manufacturing solution in the factory itself", since the currents or respectively amounts of residual heat can be deliberately used for the autoclaving and tempering process.
    The mixture of starting materials, which has been produced by mixing and eventually calcining the raw materials, is transformed by a hydrothermal treatment, in a manner corresponding to step c), into the intermediate product containing at least one hydrate of calcium silicate or a calcium aluminate hydrate or an aluminum and calcium silicate hydrate or a magnesium silicate hydrate or a calcium magnesium silicate hydrate or a magnesium silicate (aluminum, iron) hydrate or a silicate of magnesium (calcium, aluminum, iron) and possibly other compounds. This is done in an autoclave, at a temperature of 100 to 300 ° C and for a period of residence time of 0.1 to 24 h, the ratio of water / solid materials being 0.1 to 100.
    The intermediate product obtained in step c) contains at least one, and usually several, of said silicate hydrates or respectively calcium and / or magnesium aluminates, typically:
    - from 0.01 to 80% by weight of a-C2SH, different forms of C-S-H, including dellaite, and partially carbonated C-S-H phases as well as amorphous and slightly crystalline phases thereof.
    - from 0.01 to 80% by weight of katoite, Si-katoite, Fe-katoite, also in the form of mono- and hemi-carbonates as well as in the form of amorphous and low crystalline phases,
    - from 0.01 to 80% by weight of magnesium silicates (calcium, aluminum, iron), of some hydrates of these silicates as well as amorphous and low crystalline phases thereof,
    - from 0.01 to 80% by weight of silicates and hydrates of aluminum and / or iron silicates as well as amorphous and low crystalline phases thereof
    - trace and secondary components such as aluminum / iron oxides and hydroxides, C2AS, CH, MgCO3, Mg (OH) 2, quartz and calcite.
    In the case of the amorphous and low crystalline phases, it is usually a precursor compound for the crystalline phases, such as for example calcium silicates (belite), calcium aluminates (monocalcium aluminates, mayenite), silicates of magnesium (aluminum, iron) (streamers, talcum powder), etc., which do not have any atomic (near) order or have only a small order. This is reflected in the absence of formation of X-ray reflections or in the formation of very strongly disseminated reflections of smaller intensities. A good example of this is a metallurgical sand with a high proportion (> 95%) amorphous. Typical so-called "glass humps" are very pronounced over an interval of 2Thetha, next to which, according to the chemical composition, the main peak (s) of the crystalline phases are presented, for example, akermannite or gehlenite.The degree of crystallization depends on various parameters, such as, for example, the type of the starting material, temperature, pressure and the incorporation of foreign ions.
    In the next step d), the intermediate product is tempered at a temperature of 350 ° C to 600 ° C. In this case, the heating rates are 10-6,000 ° C / min, preferably 20-100 ° C / min and especially preferably about 40 ° C / min, and the period of residence time is 0.01-600 min, preferably 1-120 min and especially preferably 5-60 min. For the decrease in the proportion of Y-C2S, which is slower to react, an additional retention time period has been credited, during heating at 400-440 ° C, from 1 - 120 min, preferably from 10 - 60 min. No reactive grinding takes place. The temperature is preferably 400 to 550 ° C, in particular 400 to 495 ° C. The higher the temperature when calcining, the smaller will preferably be the duration of the calcination. Calcination temperatures below 500 ° C lead to a particularly reactive material, but higher calcination temperatures are however possible and may be convenient.
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    according to the starting material. The temperature and duration of the calcination should be chosen so high that, as far as possible, all starting material is chemically converted. On the other hand, the temperature should be as low as possible, since the reactivity of the product is higher and this limits, in addition, the necessary energy and consequently the costs as well as the damage to the environment.
    After cooling, a product is obtained which comprises at least one C2S calcium silicate, at least one calcium aluminate and at least one amorphous phase against X-rays. As a rule, the product contains the following components:
    • 1 - 95% by weight of reactive calcium aluminates, preferably in the form of a crystalline C12A7, or a few crystalline or amorphous aluminate phases
    • 1 - 80% by weight of magnesium silicates (calcium, aluminum, iron) in the form of crystalline, little crystalline or amorphous phases that may contain foreign ions, such as Fe, Al, Ca
    • 1 - 80% by weight of C2S polymorphs, in the form of crystalline, little crystalline or amorphous phases
    • 1 - 80% by weight of calcium silicate aluminates in the form of crystalline, low crystalline or amorphous phases
    • 1 - 80% by weight of calcium and magnesium silicate aluminates, in the form of crystalline phases that are not very crystalline or amorphous
    • up to 30% by weight of trace and secondary components, in particular C5A3, CA, a calcium oxide, aluminum y-oxide and other aluminum, quartz and / or limestone oxides, CaO, calcium sulfate, MgCO3 , Mg (OH) 2, Fe3O4, iron silicates, such as Fe2SiO4, amorphous phases containing iron and
    • 0 - 30% by weight of hydrates from hydrothermal treatment,
    adding up to 100% of all product proportions, and the sum of calcium silicates, calcium aluminates, calcium aluminum silicates, magnesium silicates and calcium and magnesium silicates at least 30% by weight, so preferably at least 50% by weight and most preferably at least 70% by weight.
    If the fineness of the product is already sufficient (the use of fine raw materials with an appropriate distribution of grain sizes) the product is already the desired hydraulically reactive binding agent or respectively a component thereof. If the fineness is not sufficient or if a binding agent with an especially high fineness is desired, the product can be ground in a known manner, with or without additives, until a desired fineness or distribution of grain sizes is reached. Appropriate finenesses are for example those of 2,000 to 10,000 cm2 / g (according to Blaine).
    The binder may contain, together with the product according to the invention, additionally one or more other components selected from a Portland cement, a fly ash, a metacaolm, a metallurgical sand and a limestone. These components can be added in the desired fineness or they can be ground in common with the product according to the invention.
    The specific surface area according to BET of the binding agent should be 1 to 30 m2 / g. The water content in the binder is generally a maximum of 20% by weight, preferably less than 15% by weight and in particular less than 10% by weight.
    By the process according to the invention, highly hydraulically reactive binding agents can be produced, which are constituted on the basis of C2S, C12A7, magnesium silicates and amorphous phases. These are distinguished by the fact that very reactive C2S polymorphs, a highly reactive magnesium silicate (s), calcium, aluminum, iron, C12A7 and amorphous phases against X-rays are contained as well as little crystalline.
    Otherwise, the binding agent may also contain y-Ca2SiO4. The formation of this polymorph is avoided in the case of the production of a Portland cement by rapid cooling of the clinker, since this polymorph, according to current opinion, makes no contribution to the development of mechanical strength. Surprisingly, it was found that this phase, produced by the process according to the invention at a temperature <500 ° C, shows a good reactivity differentiating itself from the production procedures used so far.
    Unlike the documents of DE 10 2009 018 632, DE 10 2007 035 257, DE 10 2007 035 258 and DE 10 2007 035 259 no reactive grinding is carried out, since this stage has an intense energy consumption and the products produced from In this way, they have a smaller reactivity than that of the products that have been produced with the procedure described here, based on raw materials that are composed in a different way.
    Unlike the current proposals with a use of raw materials containing aluminum, the tempering temperature is limited to below 600 ° C, preferably below 550 ° C and in particular below 500 ° C , so that very reactive polymorphs of some phases containing Mg, C2S and others are obtained, and an amorphous phase is obtained against X-rays. In this way a very high reactivity and hydration and development are established. of relatively fast mechanical resistance based on the calcium and magnesium silicate hydrates that have been formed.
    The invention must be explained with the help of the following Examples, but not limited to the embodiments that have been especially described. Provided that it is not indicated or that something else is not imperatively established from the series of circumstances, the percentage data refer to the weight, 10 in case of doubt the total weight of the mixture.
    The invention also relates to all combinations of preferred embodiments, as long as these are not redprocally excluded. The data "approximately" or "approx." in conjunction with a numerical data they mean that higher or lower values are included at least 10% or higher or lower values by 5% and in any case higher or lower values around 1%
    15 Example 1
    From the raw materials listed in Table 1, mixtures of starting materials were produced, one of them with 37.8% portlandite, 29% brucite and 32.6% of a fine silica powder , as well as, for comparison, a second mixture with 63.7% CaO and 36.3% of a fine silica powder.
    Table 1
     Raw material  Portlandite CaO Brucita Fine silica powder
     Lost by calcination 1,050 ° C  24.33 31.04 2.73%
     SiO2        94.05%
     Al2O3        0.61%
     TiO2        0
     MnO        0
     Fe2O3        0.40%
     CaO  75.67% 100% 0.31%
     MgO      68.96% 0.59%
     K2O        1.12%
     Na2O        0.21%
     SO3        0
     P2O5        0.04%
    The two mixtures of starting materials were mixed in each case with water in a ratio of water / solid materials of 10 and treated in an autoclave for 16 hours at 185 ° C. Intermediates were tempered at 500 ° C for 1 hour. The products obtained were reacted in a caliometer with a water / solid materials ratio of 0.5 for the hydraulic reactivity check. The accumulated heat fluxes and heat fluxes that are obtained are shown in Figures 1 and 2. It is recognized that the product with the magnesium content according to the invention has more reactive components.
    Example 2
    From the raw materials listed in Table 2, a mixture of starting materials with 27.65% of portlandite and 72.24% of a metallurgical sand was produced and this was reacted in a manner corresponding to Example 1 for give a binding agent. The product was reacted in a caliometer with a ratio of water / solid materials of 0.5, for checking the hydraulic reactivity. In addition, as a comparison, the same materials were reacted in a caliometer without hydrothermal treatment or tempering with a water / solid material ratio of 0.5. The heat fluxes or respectively the cumulative heat fluxes that were measured are represented in Figures 3 or respectively 4.
    Table 2
     Raw material  Portlandite Metallurgical Arena
     Lost by calcination 1,050 ° C  24.33 1.37%
     SiO2    35.84%
     Al2O3    11.06%
     TiO2    0.99%
     MnO    0.34%
     Fe2O3    0.44%
     CaO  75.67% 38.99%
     MgO    8.19%
     K2O    0.49%
     Na2O    0.15%
     SO3    3.18%
     P2O5    0.00%
     Amorphous Phases    92.6%
    From the Examples it becomes clear that the process according to the invention leads to products that have high reactivity, which can be used, as such or in admixture with other substances, as a binding agent. Compared with the production of a Portland cement, the use of energy is reduced in part by 5. In addition, secondary products and waste materials can be used to a much greater extent.
    权利要求:
    Claims (15)
    [1]
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    1. Procedure for the production of a binding agent, comprising the steps of
    a) make available a starting material from one or more raw materials, containing CaO, MgO, SiO2, Al2O3 and Fe2O3 or other compounds of these elements. and the starting material having a molar ratio of (Ca + Mg) / (Si + Al + Fe) of 1.0 to 3.5, a molar ratio of Ca / Mg of 0.1 to 100 and a molar ratio of Al / Si of 100 to 0.1, in the case of whose determination they remain without taking into consideration those components that behave in an inert manner when performing a hydrothermal treatment in an autoclave,
    b) mix the raw materials to give a mixture of starting materials,
    c) hydrothermally treating the mixture of starting materials that has been produced in step b) within an autoclave at a temperature of 100 to 300 ° C and with a period of residence time of 0.1 to 24 h, being of 0.1 to 100 the ratio of water / solid materials, and
    d) temper the intermediate product that has been obtained in step c) at 350 to 600 ° C, the heating rate being 10-6,000 ° C / min and the residence time period of 0.01-600 min.
    [2]
    2. Method according to claim 1, characterized in that during mixing in b) and / or in the following stages, 0.1 to 30% by weight of additional elements and / or oxides is added.
    [3]
    3. Method according to claim 1 or 2, characterized in that the raw materials are chosen from CaO, Ca (OH) 2, some (hydrates) of carbonates (hydroxides) of Ca asf as of Mg, MgO, Mg (OH ) 2, slag / metallurgical sands, ashes, some Portland cement clinkers, a Portland cement, some elaborate cement bricks, CSAB, CAC, some glass powders, a soluble glass and some fine natural stone powders (e.g. Basalt, granite, etc.) in an appropriate mixture.
    [4]
    4. Method according to at least one of claims 1 to 3, characterized in that an additional calcination process is carried out between the mixing of the starting materials in b) and the hydrothermal treatment in c) from 350 to 1,400 °, preferably from 750 to 1,100 ° C.
    [5]
    5. Method according to at least one of claims 1 to 4, characterized in that a retention time period is set for dehydration in step d) during heating at a temperature of 350-600 ° C from 1 -120 min.
    [6]
    Method according to at least one of claims 2 to 5, characterized in that sodium, potassium, boron, sulfur, chlorine, nitrogen or phosphorus or combinations thereof are used as additional elements.
    [7]
    Method according to at least one of claims 2 to 6, characterized in that alkali metal and / or alkaline earth metal salts and / or hydroxides are used as a source for the additional elements and / or oxides .
    [8]
    8. Method according to claim 7, characterized in that the metal salts and / or hydroxides
    Alkaline and / or alkaline earth metals are selected from the set consisting of CaSO4'2H2O, CaSO4-1 / 2H2O, CaSO4, CaHPO2'2H2O, Ca3P2Os, NaOH, KOH, Na2CO3, NaHCO3, K2CO3, MgCO3, MgSO4 Na2AhO4 , Na3PO4, K3PO4, Na2 [B4O5 (OH) 4] -8H2O, CaCl2, Ca (NO3) 2, MgCh, Mg (NO3) 2, AlCla, Al (NO3) 3, FeCh, Fe (NO3) 3
    Ca (CH3COO) 2, Mg (CH3COO) 2, Al (CH3COO) 3, Ca (HCOO) 2, Mg (HCOO) 2, Al (HCOO) 3, or mixtures thereof.
    [9]
    Method according to one of claims 1 to 8, characterized in that before the hydrothermal treatment in c) the mixture of 0.01 to 30% by weight of inoculation cores containing silicate hydrates of calcium, a Portland clinker, a metallurgical sand, magnesium silicates, a calcium aluminate sulfate cement (belite), a soluble glass and / or a glass powder.
    [10]
    10. A binding agent, which is obtainable by a process according to at least one of claims 1 to 9.
    [11]
    11. A binding agent according to claim 10, characterized in that the binding agent comprises at least one aluminum silicate, a calcium aluminate, a calcium and aluminum silicate, a magnesium silicate (calcium, aluminum, iron) or a calcium and magnesium silicate and at least one amorphous phase against X-rays, at least 30% by weight being the sum of calcium silicates, calcium aluminates, aluminum and calcium silicates, magnesium silicates (calcium, aluminum, iron) and calcium and magnesium silicates.
    [12]
    12. A binder according to claim 12, the binder being characterized in that it comprises the following components:
    10
    fifteen
    twenty
    1-95% by weight of reactive calcium aluminates, preferably in the form of a crystalline C12A7,
    0 of a few crystalline or amorphous aluminate phases
    1-80% by weight of magnesium silicates (calcium, aluminum, iron) in the form of crystalline, little crystalline or amorphous phases that may contain foreign ions such as those of Ca, Fe, Al,
    1 - 80% by weight of C2S polymorphs in the form of crystalline, little crystalline or amorphous phases
    1-80% by weight of calcium silicate aluminates in the form of crystalline, poorly crystalline phases or
    amorphous
    1-80% by weight of calcium magnesium aluminate silicates, in the form of crystalline, low crystalline or amorphous phases and up to 30% by weight of trace and secondary components, in particular C5A3, CA, a calcium oxide, the y-aluminum oxide and other oxides of aluminum, quartz and / or limestone, CaO, a calcium silicate, MgCO3, Mg (OH) 2, FeO, Fe2O3, Fe3O4, iron silicates such as Fe2SiO4, phases amorphous that contain iron and
    0-30% by weight of some hydrates from the hydrothermal treatment.
    [13]
    13. A binding agent according to one of claims 10 to 12, characterized in that the specific surface area according to BET of the binding agent is in the range of 1 to 30 m2 / g.
    [14]
    14. A binding agent according to one of claims 10 to 13, characterized in that the chemically combined water content is at most 20% by weight, preferably less than 15% by weight, especially preferably of less than 10% by weight.
    [15]
    15. Use of the binding agent according to one of claims 10 to 14, for the production of construction materials, in particular of a concrete, a mortar or a plaster.
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    同族专利:
    公开号 | 公开日
    AU2014267719B2|2017-09-07|
    ES2553241T3|2015-12-07|
    HK1213238A1|2016-06-30|
    DK2801558T3|2015-11-30|
    AU2014267718B2|2017-08-24|
    CN105143139A|2015-12-09|
    BR112015026454A2|2017-07-25|
    EP2801557B1|2015-09-16|
    CN105143138B|2017-12-29|
    CA2911192A1|2014-11-20|
    UA113253C2|2016-12-26|
    HK1213237A1|2016-06-30|
    EP2801558B1|2015-11-04|
    ES2559469T3|2016-02-12|
    CA2907893C|2018-02-20|
    EP2801559B1|2016-02-03|
    EA201592158A1|2016-03-31|
    US10065888B2|2018-09-04|
    PL2801559T3|2016-06-30|
    DK2801557T3|2015-12-14|
    US20160075598A1|2016-03-17|
    EP2801557B9|2016-01-20|
    PT2801557E|2015-11-26|
    CA2911192C|2018-02-20|
    US20160107933A1|2016-04-21|
    US9604879B2|2017-03-28|
    AU2014267718A1|2015-11-26|
    EP2801559A1|2014-11-12|
    EP2801558A1|2014-11-12|
    CA2907893A1|2014-11-20|
    CN105143138A|2015-12-09|
    ES2564432T3|2016-03-22|
    AU2014267717B2|2017-03-09|
    US20160102021A1|2016-04-14|
    PL2801557T3|2016-01-29|
    WO2014183845A1|2014-11-20|
    US9718731B2|2017-08-01|
    AU2014267717A1|2015-11-26|
    EP2801557A1|2014-11-12|
    EA201592152A1|2016-03-31|
    UA112149C2|2016-07-25|
    EA201592154A1|2016-03-31|
    AU2014267719A1|2015-11-26|
    WO2014183844A1|2014-11-20|
    PL2801558T3|2016-04-29|
    AU2014267717C1|2017-08-10|
    MA38557B1|2018-09-28|
    ES2559469T5|2018-10-23|
    EP2801558B2|2018-07-04|
    CA2908543C|2017-09-26|
    PL2801558T5|2018-11-30|
    BR112015026029A2|2017-07-25|
    WO2014183846A1|2014-11-20|
    MA38557A1|2016-10-31|
    EA029898B1|2018-05-31|
    DK2801559T3|2016-04-11|
    EA028010B1|2017-09-29|
    CA2908543A1|2014-11-20|
    CN105143139B|2017-03-22|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    EP13002496.1A|EP2801557B9|2013-05-11|2013-05-11|Method for producing a magnesium silicate belite calcium aluminate cement|
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