RU2304562C2 - Method of production of high-early-strength portland cement and method of production of concrete on base of this cement - Google Patents

Abstract

FIELD: manufacture of building materials; production of high-early-strength cement and concrete.

SUBSTANCE: high-early-strength Portland cement is produced on basis of calcination of cement raw mix till sintering; cement raw mix contains carbonate, aluminosilicate and ferrous components; it also includes sodium and potassium oxides and sulfuric anhydride; calcination is followed by joint grinding of clinker thus obtained in tubular mill; clinker contains free CaO and free sulfates of alkaline and alkaline-earth metals; water and gypsum component are also introduced; raw mix contains SO₃ at mole ratio of R₂O=Na₂O+0.658K₂O to SO₃= 1.34-1.7 and additionally it contains calcium fluoride at mole ratio of R₂O to fluorine-ion F^- equal to 1.3-2.9; clinker thus obtained contains the following components, mass-%: free Cao, 0.25-1.5; free sulfates of alkaline and alkaline-earth metals, 0.3-1.2; alumina modulus 1.3-1.7; Portland cement contains 0.15-0.3 mass-% of water; grinding is continued till clinker part of Portland cement contains, mass-%: 4CaO.0.5R₂O.0.9 (Al_xFe_y)₂O₃.1.1SO₃.(8-12)H₂O, where R-Na and/or K at x/y from 1.3:1 to 2:1 - 0.15-1.8 and Al(OH)_3-zF_z.SiO(OH)₂ at z+0.5-2.5 - 0.1-0.6. Raw mix contains, mass-%: SO₃, 0.25-1.2 and calcium fluoride in terms of F^-, 0.15-0.4; clinker contains from 0.01 to 0.3 mass-% of free calcium sulfate. Raw mix contains SO₃ in form of sulfates of alkaline and alkaline-earth metals and calcium fluoride in form of fluorite or its ore containing no less than 20 mass-% of fluorite. Portland cement clinker contains, mass-%: tricalcium silicate, 55-75; dicalcium silicate, 3-22; tricalcium aluminate and/or its alkaline derivative, 2-13; fluorine mayenite, 2.5-10; calcium alumoferite 2CaO.(Al₂O₃)_x.(Fe₂O₃)_1-x, where x>0 and >1, 0.5-14; the remainder being free CaO and sulfates of alkaline and alkaline-earth metals. Mineral forming promoter is additionally introduced into raw mix. Criterion of optimal its content is appearance of 3CaO.SiO₂ cellular microstructure in clinker. During calcination, content of fluxes in raw mix is controlled. Use may be made of any gypsum component. During grinding, active mineral additive or standard Portland cement clinker or 0.05-0.4% (of mass of Portland cement) of different intensifying agents may be introduced. During grinding, standard Portland cement clinker is additionally introduced or Portland cement on base of standard clinker is introduced at mass ratio of 5:1 to 1:1. Expanding additive in the amount of 7-15 mass-% is additionally introduced into Portland cement. Water may be introduced into tubular mill by different methods. Method of production of concrete includes mixing of Portland cement with water and fillers, forming this mix and holding it till hardening at temperature of 1-45C and moisture content of 70-100% during 5-24 hours or under conditions of heat and moisture treatment at temperature of 50-85C during 1.5-5.5h.

EFFECT: reduced consumption of fuel; reduced power requirements; increased productivity of furnaces and cement mills; reduced shrinkage; enhanced strength of mixes and concrete.

23 cl, 3 tbl, 2 ex

Description

The invention relates to the field of building materials, and more specifically to the production of cement, mainly with fast hardening in the initial stages, and concrete based on this cement.

A known method of manufacturing quick-hardening Portland cement by firing before sintering the cement raw material mixture and subsequent grinding of the obtained Portland cement clinker together with a gypsum component, for example two-water gypsum, to a specific surface of 350 - 380 m ² / kg, using a clinker containing, in wt.%: Tricalcium silicate (C ₃ S) 60-75, two-calcium silicate (C ₂ S) 5-10, _three- calcium aluminate (C ₃ A) more than 8, four-calcium aluminoferrite (C ₄ AF) more than 8 [Barta R. Chemie a techologie cementu. Praha, Nakl. CAV, 1961, p.235]. A summary of other recommendations on the mineralogical composition of clinker for quick-hardening Portland cement is presented in [Kravchenko IV and others. High-strength and especially quick-hardening cements. - M., Stroyizdat, 1971, p. 35 and below].

However, this method of manufacturing quick-hardening Portland cement is characterized by a relatively slow increase in the strength of the product in the first day of hardening with less than 30% strength achieved at 28 days of age. (In the description in this case and below, the abbreviated notation of chemical compounds used in cement chemistry is used, where oxides are denoted by the first letters of the usual chemical notation, and the numerical coefficients are converted to subscripts. Moreover, A = Al ₂ O ₃ , C = CaO, F = Fe ₂ O ₃ , H = H ₂ O, K = K ₂ O, M = MgO, N = Na ₂ O, S = SiO ₂ , S = SO ₃ , then C ₃ S = 3СаО · SiO ₂ , etc. P.).

To partially get rid of this feature, in the known method for the manufacture of quick-hardening cement by grinding the resulting clinker together with the gypsum component, it is envisaged to achieve a specific surface of more than 400 m ² / kg at a content (wt.%) Of Portland cement clinker C ₃ S 48-75, C ₂ S 0.5-42, C ₃ A 3-18, C ₄ AF 3-23, varying even more widely compared with the previous method [L. Ershov High strength and quick hardening cements. K., Budivelnik. 1975, 187 pp.]. In this method, a higher level of cement strength at one day of age is achieved due to a finer grinding of quick-setting cement. The additional energy consumption for grinding quick-setting cement in comparison with ordinary Portland cement increases, and the specific energy consumption for grinding quick-setting cement reaches 75 kWh / t against 35-40 kWh / t for ordinary Portland cement.

There is also known a method of manufacturing quick-hardening cement by co-grinding Portland cement clinker and gypsum component with the introduction of discrete water into the tube mill, in particular by spraying through a nozzle [Duda V. Cement. Electrical equipment, automation, storage, transportation. Reference manual, t.2, M., Stroyizdat, 1987, p.230]. This reduces the energy consumption for grinding by 10-18%, however, leads to a decrease in the quality and preservation of the properties of Portland cement with fluctuations in the humidity of its components. The intensification of grinding under the action of water occurs due to the Rebinder effect [P. Rebinder Selected Works. Physical and chemical mechanics. - M., Nauka, 1979, 384 pp.], Manifested in the activation of cracking due to a decrease in the surface energy of the crushed solid during sorption of the liquid. However, this effect only partially compensates for the approximately 35% decrease in mill productivity in the production of quick-hardening cement.

The present invention substantially eliminates this drawback.

The closest analogue of the invention in terms of cement production is a method of manufacturing quick-setting cement by firing before sintering a cement raw material mixture containing carbonate, aluminosilicate and ferrous components and including alkali metal oxides of potassium and sodium and sulfuric anhydride having an alumina module of 1.76-1, 9, and subsequent grinding of the obtained Portland cement clinker, including free calcium oxide and free sulfates of alkali and alkaline earth metals, with a gypsum component of cement in rubnoy mill water introduction. The specified raw material mixture includes sulfuric anhydride in an amount of 0.5-1.5 wt.%, The resulting clinker includes free calcium oxide in an amount of 0.5-3 wt.% And free sulfates of alkali and alkaline earth metals in an amount of 0.7-2 wt. %, while water is introduced in an amount of 0.3-0.6 wt.%, and grinding is carried out to obtain in the cement an alkali-containing monosulfohydroaluminoferrite calcium composition 4CaO · 0.5R ₂ O · 0.9 [(Al, Fe) ₂ O _h ] · 1,1SO ₃ · (8-12) H ₂ O, where R = Na, K, in an amount of 0.3-1.0% of the mass of clinker [RF Patent No. 2050725, 1995]. This method allows to accelerate the hardening of the manufactured cement, however, it requires high energy costs for clinker roasting and cement grinding, it is characterized by a reduced productivity of the clinker kiln and cement mill, as well as although it is less compared to the previously known quick-hardening Portland cement, it still has a significant shrinkage of the obtained quick-hardening Portland cement.

The objective of the invention in terms of a method of manufacturing a quick-hardening Portland cement is a significant reduction in these energy costs, a corresponding increase in the productivity of these main technological units, a further increase in the strength of the cement obtained and its other construction and technical properties, in particular a further decrease in shrinkage.

This problem is solved by the fact that in the method of manufacturing quick-hardening Portland cement by firing before sintering a cement raw material mixture containing carbonate, aluminosilicate and ferrous components and including alkali metal oxides - sodium and potassium and sulfuric anhydride, followed by joint grinding in a tube mill of the obtained Portland cement clinker, including free calcium oxide and free sulfates of alkali and alkaline earth metals, with the introduction of water and a gypsum component, the specified cement raw materials this mixture contains sulfuric anhydride SO ₃ in an amount corresponding to the molar ratio of the sum of the content of alkali metal oxides in it in terms of Na ₂ O equivalent - R ₂ O = Na ₂ O + 0,658K ₂ O - to SO ₃ equal to 1.34 -1.7, and additionally calcium fluoride in an amount corresponding to a molar ratio of R ₂ O to fluoride ion F ^- equal to 1.3-2.9, the resulting clinker includes, in wt.%, Free calcium oxide - 0.25 -1.5, free sulfates of alkali and alkaline earth metals in the amount of 0.3-1.2, has an alumina module of 1.3-1.7, water is introduced in an amount of 0.15-0.3% by weight of the specified Portland cement one grinding is carried out to obtain a Portland cement specified in% by weight of clinker its parts: schelochesoderzhaschego calcium monosulfogidroalyumoferrita 4CaO · 0,5R _{2 O · 0,9 (Al x Fe y} ) ₂ O ₃ · ₃ · 1,1SO (8- 12) H ₂ O, where R-Na and / or K at x / y from 1.3: 1 to 2: 1, - 0.15-1.8 and hydroxyl gel Al (OH) _3-z F _z · SiO (OH) ₂ at z = 0.5-2.5, - 0.1-0.6.

In an embodiment of the invention said cement raw mixture contains, in mass%, sulfur trioxide in an amount of 0,25-1,2 and calcium fluoride in terms of F ^-. In an amount of 0.15-0.4, and the resulting therefrom clinker includes free calcium sulfate - 0.01-0.3% of the mass.

In another embodiment of the invention, said cement raw material mixture contains sulfuric anhydride in the form of alkali metal or alkaline earth metal sulfates in the form of the mineral mineral tenardite Na ₂ SO ₄ or arcanite K ₂ SO ₄ , or their mixed crystals and hydrated derivatives, or dical gypsum, or gypsum anhydrite, or anhydrite and calcium fluoride in the form of fluorite or its ore containing fluorite in an amount of not less than 20 wt.%.

In an embodiment of the invention, the Portland cement clinker contains, wt.%:

tricalcium silicate 3CaO · SiO ₂ 55-75 dicalcium silicate 2CaO · SiO ₂ 3-22 tricalcium aluminate 3CaO · Al ₂ O ₃ and / or its alkaline derivative R ₂ O · 8СаО · 3Al ₂ O ₃ 2-13 fluoromayenite 11СаО · 7Al ₂ Oz · CaF ₂ 2,5-10 calcium aluminoferrite 2СаО · (Al ₂ O ₃ ) _х · (Fe ₂ O ₃ ) _1-x , where x is greater than 0 and less than 1 0.5-14 free calcium oxide and sulfates alkali and alkaline earth metals rest.

In another embodiment of the invention, a mineral formation promoter is additionally introduced into said cement raw material mixture, including two or more clinker minerals from the group: 3CaO · SiO ₂ , 2CaO · SiO ₂ , 3CaO · Al ₂ O ₃ , 2CaO · (Al ₂ O ₃ ) _x · (Fe ₂ O ₃ ) _1-x , where x is not less than 1/3 and not more than 2/3, 12СаО · 7Al ₂ O ₃ , calcium monoaluminate CaО · Al ₂ О ₃ , dicalcium and monocalcium ferrites - 2СаО · Fe ₂ O ₃ and CaO · Fe ₂ O ₃ and / or alkaline, sulfate and halide derivatives of these minerals and representing mechanical and / or obtained together in the form of clinker or slag, or sediment in the form e of a powder or suspension, a mixture of these minerals, characterized by a basicity value of 1.005-1.07 times higher than the basicity of the eutectic clinker melt, with a mass ratio of promoter to calcium fluoride of 1.8-2.5.

In another embodiment of the invention, a mineral formation promoter is added to said cement raw material mixture, including, wt.%:

3CaO · SiO ₂ 55-80 2CaO SiO ₂ 10-13 3CaO · Al ₂ O ₃ 1-12 2СаО · (Al ₂ O ₃ ) _x · (Fe ₂ O ₃ ) _1-x , where x is greater than 0 and less than 1 10-18 12CaO · 7Al ₂ O ₃ and / or 11CaO · 7Al ₂ O ₃ · CaF ₂ 1-11 CaO · Al ₂ O ₃ 0.5-1.5 2СаО · Fe ₂ O ₃ , CaО · Fe ₂ O ₃ 0.5-1.5 calcium sulfoaluminate 4СаО · (3Al ₂ O ₃ ) · (SO ₃ ) 1-25 calcium sulfate CaSO ₄ 1,5-3,5 calcium oxide CaO 0.1-5 Aluminates and ferrites of alkali metals R (Al, Fe) O ₂ rest,

and which is a mixture of these minerals, mechanical and / or obtained together in the form of clinker or slag, or in the form of a precipitate in the form of a powder, characterized by a basic value of 1.005-1.07 times higher than the basic value of the eutectic clinker melt, with a mass ratio of the promoter to calcium fluoride - 1 4-2.2.

In an embodiment of the invention, a mineral formation promoter is additionally introduced into said cement raw material mixture, including, wt.%:

3CaO · SiO ₂ 55-75 2CaO SiO ₂ 3-22 3CaO · Al ₂ O ₃ and / or its alkaline derivative R ₂ O · 8СаО · 3Al ₂ O ₃ 2-13 12CaO · 7Al ₂ O ₃ and / or 11CaO · 7Al ₂ O ₃ · CaF ₂ 2,5-10 calcium aluminoferrite 2CaO · (Al ₂ O ₃ ) _x · (Fe ₂ O ₃ ) ₁ , where x is greater than 0 and less than 1 0.5-14

free calcium oxide and said sulfates

alkali and alkaline earth metals rest,

and which is a mixture of these minerals, mechanical and / or obtained together in the form of clinker or slag, or in the form of a precipitate in the form of a powder, characterized by a basic value of 1.005-1.07 times higher than the basic value of the eutectic clinker melt, with a mass ratio of the promoter to calcium fluoride - 1 , 0-2.0.

In an embodiment of the invention, the appearance of a 3CaO · SiO ₂ phase _{of a} cellular microstructure in said clinker is used as a criterion for the optimal promoter content.

In another embodiment of the invention, when firing, the content in the specified raw material mixture is regulated according to the sum of minerals: 3СаО · Al ₂ О ₃ and / or R ₂ O · 8СаО · 3Al ₂ O ₃ and 2СаО · (Al ₂ O ₃ ) _х · (Fe ₂ O ₃ ) ₁ , where x is greater than 0 and less than 1, or of 2.65 Al ₂ O ₃ + 1.34 Fe ₂ O ₃ oxides at a level of at least 10 and 6 wt.%, Calculated on plain and white Portland cement clinkers, respectively.

In an embodiment of the invention, natural gypsum from the group of gypsum, gypsum anhydrite, anhydrite, or gypsum-containing waste from the group of phosphogypsum, borogypsum, titanogypsum, a product of neutralization of sulfur dioxide by lime, or a mixture of natural gypsum and gypsum-containing waste from wt. a ratio of 2: 1-1: 2 with a gypsum component content of 1.5-4.5 wt.% in terms of sulfuric anhydride.

In another embodiment of the invention, an active mineral supplement is additionally added during grinding.

In a further embodiment of the invention, during grinding, a grinding intensifier is additionally introduced in an amount of 0.05-0.4% by weight of said Portland cement.

In an embodiment of the invention, a substance from the group is used as a grinding intensifier: amino alcohols and their compositions with hardening accelerators, technical lignosulfonates and their compositions with electrolytes, alkaline earth and / or alkali metal salts of the product of condensation of naphthalene sulfonic acid with formaldehyde, a complex salt of alkaline earth metal and sulfuric and / or nitrogen and / or formic and / or acetic acid with low molecular monosaccharides C ₃ -C _5, the paired mixture of these materials in a weight ratio of from 4: 1 to 1: 4, to count honors 0.05-0.5% by weight of said portland cement.

In another embodiment of the invention, during grinding, an ordinary Portland cement clinker is additionally introduced at a weight ratio of said and conventional Portland cement clinker from 5: 1 to 1: 1.

In an embodiment of the invention, a domol is carried out, in which an ordinary Portland cement clinker or Portland cement based on it is additionally introduced in a weight ratio of said and conventional Portland cement clinker from 5: 1 to 1: 1.

In another embodiment of the invention, Portland cement based on a conventional Portland cement clinker is additionally added with mixing at a weight ratio of said and conventional Portland cement clinker from 5: 1 to 1: 1.

In a further embodiment of the invention, when grinding or mixing with said Portland cement, an expanding additive is additionally introduced, including artificial material containing more than 10 wt.% Al ₂ O ₃ in the form of calcium aluminates from the group: aluminous clinker or aluminous slag, sulfoaluminate clinker or other material, including calcium sulfoaluminates, sulfoferrite clinker or other material, including calcium sulfoferrites, hyperalitic clinker or its grinding product, metallurgical slag, or natural material containing rusting more than 4.5 wt.% water-soluble Al ₂ O ₃ , or a mixture of these materials containing at least 20% of each of them, while the content of expanding additives in the specified Portland cement is 7-16 wt.%.

In an embodiment of the invention, the introduction of water into the tube mill is carried out by spraying in the first or last chamber thereof.

In another embodiment of the invention, the introduction of water into the tube mill is carried out in the form of hygroscopic moisture of clinker and / or active mineral additives.

In a further embodiment of the invention, the introduction of water into the tube mill is carried out in the form of hygroscopic moisture of the clinker and / or active mineral additive.

The invention in part related to the method of manufacturing quick-hardening Portland cement, is:

1) in the formation during firing of the specified raw material mixture of Portland cement clinker, including, in addition to free calcium oxide (indicating the nonequilibrium phase composition of the clinker), also free sulfates of alkaline and alkaline earth metals in an amount of 0.3-1.2 wt.% With alumina module 1 , 3-1.7. Maintaining the presence of alkali metals in the form of precisely sulfates in the indicated amounts corresponds to a reduced amount of other alkaline phases in the clinker, among which there are none useful. Thus, the yield of alkaline derivatives of calcium aluminates, without which it is impossible to do without an alkali content in clinker of more than 0.8%, decreases in the finished clinker, and in particular it becomes less than NC ₈ A ₃ and, above all, KS ₈ A ₃ . These alkaline aluminates, especially the latter, due to extreme hygroscopicity reduce the flowability of cement, make it difficult to average in silos, internal and external transportation, loading and loading operations, finally, accelerate the aging of cement (decrease in activity during long-term storage), and in concrete - accelerate the loss the mobility of the concrete mixture during transportation and storage, reduce the pot life of the latter, increase the resistance of the concrete mixture to the movement of the mixer blades in it, and reduce the handling bridge and worsens sealing and stacking conditions. Among a number of alkaline derivatives of calcium silicates, we note “potassium belites” - highly basic KC ₂₃ S _11-12 and low basic KC ₁₈ S ₁₁ , which are phases from which alite (C ₃ S) is not obtained upon further firing and, therefore, in vain lime is consumed resulting from the decarbonation of the carbonate component of the specified raw material mixture during its calcination. Calsilite K ₂ O · CaO · SiO ₂ , which does not dissolve in the clinker melt up to 1320 ° С, even worse affects alite formation, and at this temperature, releasing the CaO · SiO ₂ group _of reduced basicity into the melt, it directly destroys even the formed alite and certainly prevents the formation of a new alita. It should be noted that alkaline silicates are formed in the calcined material in the temperature range 800-1000 ° С already after the CaSO ₄ mineralizer releases sulfate ions into the calcined material (at 700-780 ° С), therefore, the presence of this mineralizer leads to binding cations of alkali metals and almost completely prevents the delay of alitogenesis by the presence of the mentioned and some other alkaline derivatives of calcium silicates in the calcined material and the finished clinker. The criterion for the successful action of the mineralizer, even in the form of sulfate impurities in the cement raw material mixture, is the presence of free alkali metal sulfates in the clinker, which, with high-quality mixing of the initial cement raw material mixture, ensures the absence of most of these harmful phases in the finished clinker, since the affinity of alkali metal cations to sulfate anions exceeds that with respect to SiO ₄ ^4- and AlO ₄ ^5- anions. However, when p is within 1.3-1.7 in the absence of fluoride, it is impossible to guarantee the absence of KS ₈ A ₃ in the clinker. Only the introduction of a fluoride mineralizer ensures the full presence of predominantly useful phases in the mineralized clinker due to the enhanced sublimation of alkaline impurities. The NC ₈ A ₃ phase, which is retained in the clinker at the indicated level p even in the presence of fluoride and sulfate mineralizers and is usually considered undesirable, is converted into useful using special conditions for clinker grinding, namely, its implementation in the presence of drip moisture, which is essential precisely at an elevated level alumina module;

2) in the synthesis during the mentioned grinding regime of the specified cement, two new prehydrates - alkali-containing calcium monosulfohydroaluminoferrite, abbreviated alkali-containing monosulfate (alkali) 4CaO · 0.5R ₂ O · 0.9 (Al _x Fe _y ) ₂ O ₃ · 1.1SO ₃ · (8-12) Н ₂ O, where R-Na and / or К at x / y from 2: 1 to 1.3: 1, and Al (OH) _3-z F _z · SiO (OH) ₂ abbreviated as fluoroaluminosilicon hydrogel (FAKG) at z in the range of 0.5-2.5, formed under the action of film water when grinding cement from one of the initial components - Portland cement clinker. Both reactions for the synthesis of these prehydrates (the term “prehydrates” are proposed in [Hansen WC False set in Portland cement./IV Intemat. Symposium on the Chemistry of Cement. Washington, 1960 / Proceedings, v. 1, ed. Nat. Bur. Stand Monograph, N 43, Washington, 1962, pp.387-403] for the designation of cement hydration products resulting from the interaction of clinker with air moisture during grinding or storage of cement before it begins to mix with water), are mechanochemical, since with simple mixing cement with water SchM and FAKG are not formed. In the latter case, alkali-containing calcium monosulfohydroaluminate, which does not include iron, and fluoroaluminohydrogel, which does not include silicon, appear instead of them. AM and FAKG intensify the grinding of cement, forming in the heads of cracks that open under the impacts of grinding media in the mill due to the separation of a large amount of crystallization water in the AL and the separation of cells in the alite phase of the clinker during the formation of FAKG. After mixing the obtained cement with such prehydrates with water, both of them - SchM and FAKG - have a seed effect on the formation of hydrated phases. This speeds up the formation of structure and contributes to the rapid hardening of cement. The priming role of alkalis and FAKG is evidenced by: a) the rapid growth of the basic reflex of alkalis (8,3-9,5) · 10 ^-10 m, corresponding to the interplanar distance <c> (with the Muller indices of the 001 plane) on the roentgenogram illustrating the growth of alkalis from solution; b) rapid absorption of hydrolytic lime (CH) produced by cement during hydrolysis of alite (C ₃ S) by the formed FAKG; and reduced in this regard, the concentration of lime in the liquid phase of the cement-water suspension, but with a significant allocation of lime cement according to the invention and its equally fast binding. In the test of quick-hardening Portland cement obtained according to the invention, after mixing with water under an optical microscope, long (up to 100 μm) trisulfate fibers (trisulfate form of calcium hydrosulfoaluminate) are visible, which have a greater structure-forming ability and contribute to the cement strength than short barrel-shaped trisulfate fibers formed in the absence of FAK or with a slow increase in the content of this hydrogel without silica and iron oxide, which strengthen the trisulfate structure.

For the first time, a SchM type phase, namely sodium calcium monosulfohydroaluminate of the composition 4CaO · 0.5Na ₂ O · 0.9Al ₂ O ₃ · 1.1SO ₃ · (8-16) H ₂ O, was synthesized by treating trisulfate (ettringite) with sodium hydroxide at the concentration of NaOH in the liquid phase 40-50 g / l [Larionova Z.M. Alkaline-containing form of trisulfate calcium hydrosulfoaluminate. / Physico-chemical studies of hardening and properties of concrete mixtures and concrete / Transactions of NIIZhBa, 1988, b / n, p.32]. Attempts to obtain similar phases with iron did not bring success [Copeland L.E. et al. Chemistry of hydration of Portland cement at ordinary temperature. / Chemistry of cements. Sat Art. under the editorship of H.F. Taylor’s. M., Stroyizdat, 1969, p. 258]), but it was found that the introduction of iron hydroxide gel in monosulfate can increase the interplanar spacing <c> (hkl = 001) on the x-ray of the latter [Turriciani R. Calcium hydroaluminates and related compounds. / Chemistry of cements. Sat Art. under the editorship of H.F. Taylor’s. M., Stroyizdat, 1969, p.203]. Available X-ray diffraction data for related phases are 3CaO · Fe ₂ O ₃ · 3CaSO ₄ · 32Н ₂ O (9.85; 7.47; 2.46 · 10 ^-10 m) ferriettringite, 3СаО · Fe ₂ O ₃ · CaSO ₄ ferrimonosulfate · 12H ₂ O (8.9; 8.02; 3.9 · 10 ^-10 m) and calcium hydroferrite 4СаО · Fe ₂ O ₃ · 13Н ₂ O (8.02; 3.95; 2.94 · 10 ^{- 10} m) in comparison with their aluminate analogues (9.73; 8.86; 2.56 · 10 ^-10 m); (8.9; -; 4.02 · 10 ^-10 m); (8.92; 4.46; 2.45 · 10 ^-10 m), respectively, generally confirm the growth, although not of all interplanar spacings, when iron is introduced [Taylor X. Cement chemistry. Reference edition. Per. from English Doctor of Chemistry A.I. Boykova and prof., Doctor of Engineering T.V. Kuznetsova. M., Mir, 1996, 560 pp.]. A similar effect is produced by alkali metal cations and water. So, for alkaline monosulfate in an iron-free sodium form, with an increase in water content from 8 to 12 molecules, the drift <c> ranges from 8.1 to 9.3 · 10 ^-10 m. For calcium carboaluminates, the drift of the reflex <c> differs lower values, but also increases with increasing content of crystallization water - from 7.1 at 8H ₂ O to, for example, at the phase of composition C ₄ AN ₁₂ · CO ₂ - 7.9 · 10 ^-10 m.

For the first time, a phase of the FAKG type, namely, Al (OH) _3-x F _x , was obtained by reacting with the mineral C ₁₁ A ₇ · CaF ₂ (fluoromayenite) [Uchikawa H. et al. The hydration of jet cement at 20 ° C / Cement and Concrete Research (Philadelphia), 1973, v.3, N 3, p.263-277], but it did not contain silicon. Only when studying the hydrates of the CaO-Al ₂ O ₃ -SiO ₂ -CaF _{2 system, the} Al (OH) _3-x F _x gel obtained in the presence of aqueous silica gel included a small admixture of silica [Massazza F. et al. Solid phase relations in the quaternary system CaO-Al ₂ O ₃ -SiO ₂ -CaF ₂ . / Revue de Materiaux et de Travaux publics (Paris), 1969, N 642, pp. 81-86; Masazza F. VI International Congress on the Chemistry of Cement. M., 1974; Stroyizdat, vol. 1, 1976, presentation in discussion]. This was determined by the amount of lime sorbed without immediate formation of calcium hydroaluminates (HAC), which is impossible in the absence of the specified impurity, the first interacting with lime. The inventors for the first time received FAKG in the form of a prehydrate, which was shown in a similar way - by the interaction of cement made according to the invention, sealed with water with the addition of calcium hydroxide, without the immediate formation of a HAC.

When hardening quick-hardening Portland cement obtained by the method according to the prototype, the hydrate was fixed in a cement stone with characteristic values <c> in the range (8.3-9.5) · 10 ^-10 m on the x-ray. The refractive indices of it are higher than that of purely aluminate alkali carbide, and a light yellow hue indicates an admixture of iron. The presence of fluoride ion in the clinker according to the invention made a difference associated with a decrease in the iron content in alkali metal. By dissolving with ethylene glycol, the A / F ratio in this phase in the cement according to the invention is determined in the range from 2: 1 to 1.3: 1 (versus 3: 1 - 2: 1 in alkali metal mortar according to the prototype). The presence of alkalis in alkali metals, besides potassium and sodium, is confirmed by the decomposition of alkali metals after heating to 75 ° C with a fixed release of alkalis into the solution. The x-ray and morphological characteristics of this prehydrate in the cement obtained according to the invention are similar to iron-containing alkali alloys according to the prototype [RF Patent No. 2050725] despite the reduction in iron content, apparently due to the presence of fluorine atoms in the interstitial sites (interplanar distance <c> in the range (8.3 -9.5) · 10 ^-10 m against (8.1-9.3) · 10 ^-10 m - according to Larionova). The increase in parameter <c> within the indicated intervals is closely related to the amount of water supplied to the mill according to the invention: with more water <c> increases, regardless of the form in which water enters the mill. Due to the presence of fluoride ion, SchM is visible on radiographs almost from the moment of mixing water with cement obtained according to the invention (in cement according to the prototype SchM is visible only 2-3 hours after mixing).

The possibility of synthesizing a phase of such a complex composition mechanochemically can only be explained by the fact that all the starting reagents are contained immediately in one cement component - Portland cement clinker, and only water is added from the outside.

The conditions for the synthesis of this phase in the proposed method are as follows created at the previous stages of the production process - in the preparation of the cement raw mix and its roasting. The choice of an alumina module in the range of 1.3-1.7 (instead of 1.76-1.9 according to the prototype) provides, in the presence of a fluoride ion, along with the uniformity of the appearance of a common clinker melt (alumina module p = 1.3 corresponds to a eutectic at 1170 ° С in the CaO-Al ₂ О ₃ -SiO ₂ -CaF ₂ subsystem), also the single-acceptivity of crystallization of alite from this melt. In such a situation, the glandular “tail” of the clinker melt is excluded, in the presence of alkalis it forms clinker glasses that form films surrounding the crystals of the silicate phases of the clinker and cannot be eliminated by grinding the cement to a specific surface below 380 m ² / kg. These films prevent hydration after cement is mixed with water of the intermediate clinker substance - the amounts of C ₃ A + C ₂ (A, F) + alkali metal sulfates + alkaline earth metal sulfates - even at higher specific surface values (more than 450 m ² / kg) hydration and hardening of cement. At p greater than 1.7, in the presence of fluoride ion, aluminate segregation of the clinker melt occurs, in which low-iron regions can occur in it, the formation of which reduces the average alumina content in calcium aluminoferrites despite the increase in the total alumina content in the cement raw material and clinker. Such calcium aluminoferrites during hydration of cement are less active, which reduces the amount of active minerals in clinker and the initial strength of cement, and, most importantly, increases the yield of pure calcium hydroaluminates in cement, and with it the increase in shrinkage of cement stone during its hardening. Therefore, the optimum p is precisely the interval 1.3-1.7. The presence in the clinker of alkaline and alkaline-earth free sulfates and free calcium oxide creates the conditions for the synthesis of alkali metal from one clinker without the gypsum component during cement grinding, and, therefore, without increasing the degree of cement aggregation observed, for example, during the synthesis of ettringite during cement grinding in as a prehydrate with the participation, in addition to C ₃ A of clinker, also of the gypsum component [B. Yudovich et al. Surface phenomena in high-strength cements and false setting. Proceedings of the Research Institute of Cement, 1977, issue 46, p.40-56]. An increase in the content of free lime in cement above 1.5 wt.% Causes a decrease in the flowability of cement, which causes difficulties when pumping cement to silos from wagons, and from silos to consumable bins of concrete mixing plants in concrete production, and also complicates the set of cement strength, especially in early curing times. A decrease in the amount of free lime in cement of less than 0.25% complicates the manifestation of the intensifying grinding effect of the formation of alkali phosphate and FAKG in the heads of the opening cracks and microcracks due to the lower concentration of the latter due to the reduced porosity of the clinker.

The presence of sulfuric anhydride and fluoride ion in the raw material mixture, their indicated ratios with alkaline oxides and between themselves, as well as their indicated quantities in the clinker, provide for the simultaneous synthesis of alkali phosphate and FAKG in the cement grinding process according to the invention only from crushed clinker and water. The higher content of sulfuric anhydride and fluoride ion in comparison with the above causes difficulties in clinker burning, in particular, formation of melt sag in the clinker refrigerator, clinker granules sticking together at the end of the sintering zone of the clinker kiln and their slower cooling in the clinker refrigerator with the appearance of clinker in the clinker useless for the construction and technical properties of cement) sulfate and fluorine-containing phases - such as C ₂ S · CaSO ₄ or C ₂ S · CaF ₂ ). The lower content of sulfur anhydride and fluoride ion in comparison with the aforementioned weakens the effect of the invention.

With regard to the input of water during cement grinding, with a more active clinker obtained by the method according to the invention, compared with clinker according to the prototype, with a water content of 0.31-0.35% by weight of the clinker part of cement and higher, as shown by production experience , it is possible to clog the inter-chamber partitions of the cement mill and its outlet grill. At less than 0.15%, the input of water remains the effect of intensification of the grinding only under the action of the water itself, without a noticeable effect from the formation of alkalis and ACH, which reduces the useful effect of the invention.

Thus, we can distinguish the following main elements of the novelty of the invention in comparison with the prototype:

1) the introduction of sulfate mineralizer to a level that guarantees the presence in the finished clinker of free sulfates; this eliminates the difficulties of alitogenesis during firing, associated with the presence in the calcined material of alkaline, primarily sodium, derivatives of calcium silicates and potassium derivatives of calcium aluminate;

2) the introduction of a fluoride mineralizer to guarantee the absence of potassium derivatives of calcium silicates in the material to be fired - the most powerful obstacle to alite formation during clinker firing from all other factors of cement production;

3) the introduction of water during grinding of cement in smaller quantities compared to the prototype, since the amount of harmful phases in the clinker according to the invention is reduced to transfer the sodium derivative of calcium aluminate to the useful phase to obtain alkali prehydrate in the cement, in this case, hardened by the presence of cement in comparison with the prototype it contains impurities of a fluoride ion, which improves the coalescence of this hydrate with the hydrosulfoaluminate component and, through it, with the hydrosilicate component of the main matrix of cement stone, which determines its obtained;

4) obtaining, in the form of a hydrate in cement, also aluminum hydroxide gel — silicon — iron — fluoride more quickly than pure alumohydrogel reacting with the gypsum component of cement and lime with accelerated formation of trisulfate, including silicon, iron oxides and fluoride ion, which facilitates its coalescence with calcium hydrosilicates and provides the formation of a common cement matrix during hardening of quick-hardening Portland cement according to the invention, characterized by increased strength as in the early (1-3 days), and in the later stages of hardening (28 days and later) in comparison with quick-hardening cement according to the prototype.

In embodiments of the invention, clarifying conditions are provided. Thus, Portland cement clinker is preferable with a high content of tricalcium silicate with the sum of the smoothing minerals of tricalcium aluminate and / or fluoromayenite (mayenite) and calcium aluminoferrite 20-26 wt.%. From stereology it is known [Chernyavsky KS. Stereology in metal science. M., Metallurgy, 1977, 280 pp.], That only when the content of the smaller phase of the two (in this case, the intermediate substance represented by the indicated sum of smooth minerals - compared with calcium silicates) is not less than 20% by volume, the probability of meeting the same the phase at any point of contact of the clinker + water + grinding body is different from zero, which is a condition for the increased grindability of the clinker according to the invention. Moreover, due to the presence of the fluoride ion, the clinkers according to the invention of the above composition meet the stereological condition for the synthesis of alkali metals with a ratio of Al ₂ O ₃ / Fe ₂ O ₃ from 2: 1 to 1.3: 1.

We also note that according to the prototype, for the synthesis of alkali metal, cement values require high values of the alumina module (1.76-1.9) and, accordingly, the introduction of, as a rule, long-distance alumina-containing ingredients into the cement raw mix, such as bauxite, overburden is necessary bauxite quarries, kaolin clay, and in the absence of sulfate impurities in the carbonate and aluminosilicate components to provide specified amounts of sulfuric anhydride in the cement raw material mixture, it is necessary to provide additional canine component. The method according to the invention is more technologically advanced, since only the fluoride component fluorite or its ore is required to be introduced into the cement raw material mixture, and the required values in this mixture of the alumina module are supported either by reducing the content of the glandular component, or, as a rule, due to local clays, and the content sulfuric anhydride is usually regulated by a combination of impurities of gypsum and / or anhydrite in the carbonate and aluminosilicate components with a sulfide impurity in the glandular component. The reason for this favorable difference of the method according to the invention is that, as established by its authors, in the presence of fluoride ion less sulfuric anhydride is required compared to the prototype, namely, corresponding to a molar ratio of K ₂ O / SO _{3 of} 1.3-1.7 , significantly exceeding the well-known optimum molar ratio of R ₂ O / SO ₃ close to 1 [Peray K.E. The rotary cement kiln / 2-nd ed. London, Arnold Corp., 1986, p. 118; see also Luginina I.G. and others. Cements from substandard raw materials. Novocherkassk, ed. NSTU, 1994, 233 pp.].

The molar ratio of R ₂ O / F, established according to the present invention in the range of 1.3-2.9, corresponds to the minimum degree of sublimation of fluoride ion during firing of the cement raw material mixture according to the invention. This reduces the need for a fluoride mineralizer and is of great environmental importance.

A feature of the sulfate-fluoride complex mineralizer according to the invention is the ability to significantly accelerate the decomposition processes during firing of a cement raw material mixture of carbonate and aluminosilicate components, respectively, their decarbonization and dehydration, as well as their accompanying and subsequent mineral formation processes in solid phases and primary melts. At the same time, both components of the mineralizer — sulfates and fluorides, by lowering the viscosity of primary melts, act by different mechanisms: sulfates weaken intergrowth bonds in the melt (ionic swarms, including ring formations, represent the basis of the submicrostructure of clinker type melts [Butt Yu.M. et al. Mechanism processes of clinker formation and modification of its structure. / VI International Congress on the chemistry of cement. M., 1974; Transactions. M., Stroyizdat, 1976, v.1, p.132-153; Zhmoidin G.I. and other Slags for of metal refining - Dynamics of CaO-A system properties l ₂ About ₃ -CaF _2. M., Metallurgy, 1986]), and fluorides crush the indicated swarms. This position can be expressed more strictly in terms of cluster chemistry (cluster in English - swarm, cluster): the melt base is calcium aluminates, including rings of AlO ₄ ^5- anions, interconnected and bonded by calcium cations to cubic or rhombohedral networks ( the latter in the presence of alkali metal cations). The indicated nets can be considered as exchange clusters of calcium aluminates with a loosening structure or a change in fluoride of alkali metal sulfates of calcium alkali metal sulfates (the terminology is in accordance with [Gubin S.P. Cluster Chemistry. Fundamentals of classification and structure. M., Science, 1987) ]). In this case, sulfates have a high surface activity, and fluorides - less. Therefore, the former, enhancing the wetting effect of the clinker melt on the furnace lining, can reduce its resistance, and the latter, enhancing the ability of the clinker melt to penetrate into the smallest pores of the calcined material, accelerate the absorption of the melt in the latter and carry sulfates along, reducing the effect of the latter on the furnace lining, but creating the appearance of a small total amount of melt and increasing the abrasive effect of the calcined material on the lining. The experience of the furnace operator in maintaining the required balance of the influence of these components of the complex mineralizer is important here. With a lack of experience and the lack of necessary instrument control, visually the furnace operator may mistake this situation for underheating of the material and add fuel, which can lead to clinker burnout and excessive exhaust gas emissions. There are other necessary conditions for the rational use of the complex mineralizer according to the invention.

To increase the technical effects of the invention and mitigate a number of qualification requirements for production personnel, the mineral formation promoter, a mineral oxide additive, first proposed in the invention according to Eurasian patent No. 002673, 2002 and already tested without mineralizers and when introduced on a number cement plants in Russia with many technical effects, described in detail in this patent. In the present invention, the function of the promoter is to resolve the contradiction inherent in any mineralizer, including the sulfate fluoride according to the invention, namely, the contradiction between sharply reduced (by 50-200 ° C compared to the usual level, i.e., up to 1200-1300 ° C) the clinker sintering temperature in the presence of a particularly effective sulfate-fluoride mineralizer according to the invention and the relatively slow rate of lime assimilation in the calcined material at the indicated temperature. In a normal situation, without a promoter, in the presence of only mineralizers, due to this contradiction, it is necessary to burn clinkers with a low alite content, up to belite compounds, since in alite clinkers burned at such a low temperature, there is often too much free lime that is permissible under the strength conditions ( hydraulic activity), but not allowed under the conditions of sulfate and / or frost resistance, water resistance, etc. An increase in the content of alite in clinker (in particular, from 65 to 75%) practically does not increase the strength and hardening rate of cement. The promoter accelerates the absorption of free lime and alitogenesis precisely at a reduced sintering temperature, due to the presence of a mineralizer. So, the first alite in the presence of a fluoride mineralizer is formed at 950 ° C versus 1270 ° C in its absence [B. Yudovich and others. Ultrahigh-hardening cements for monolithic and precast concrete. Overview. - M., Ed. TsINIS Gosstroy of the USSR, 1978, p.29]. This promoter addition resolves this contradiction and with its help completely solves the problem of obtaining alite clinkers of almost any basicity in the presence of acidic mineralizers. Therefore, in variants of the invention with the additional introduction of the promoter, it is provided to obtain clinker containing alite in a wide range - up to 75 wt.%, With all the ensuing positive consequences: an increase in clinker grindability, cement strength, including in the early stages of hardening, which is especially important for quick-hardening Portland cement, the possibility of increasing in the cement according to the invention the content of active mineral additives without compromising strength, etc.

Thus, the combination of additives of a complex mineralizer and a promoter when introducing the latter into a cement raw material mixture or into a calcined material (using the dry method of cement production uses the first technological method, while the wet method uses the second) harmonizes the clinker formation process, combining low-temperature sintering due to the complex mineralizer and low-temperature mineral formation to the promoter. This substantially enhances the technical effects of the invention. It should be noted that with a decrease in the basicity of the promoter, the required fluoride ion content in the complex sulfate-fluoride mineralizer is reduced. This is reflected in the examples below, as well as in the claims.

The addition of the promoter, providing such specific effects as the appearance of a cellular microstructure of the resulting clinker and the associated significant increase in its grindability, in the process of burning clinker by the wet method, reduces dust formation in the cold end of the furnace due to the astringent action of the promoter. In the rest of the furnace, as shown by the production experiment, the promoted mineralized clinker (below abbreviated as PM clinker according to the invention as compared to M clinker obtained in the presence of the complex sulfate-fluoride mineralizer according to the invention, as well as Pr-clinker obtained according to the prototype without fluoride and K-clinker - a control clinker obtained without a mineralizer and a promoter), both in the dry and in the wet production method, is significantly less prone to clinker dusting. When firing PM-clinker, both normal dust formation in the furnace and irrevocable dust removal are reduced, since the promoter leads to more extended in temperature and time intervals processes of dehydration of aluminosilicate and decarbonization of the carbonate components of the calcined cement raw material, allowing gases to escape from the calcined ₂ and other gases - . and water vapor to a lesser extent disrupt the structure of particles and / or granules of the calcined material than in the absence of a promoter. The refining effect of the promoter, mentioned in Eurasian patent No. 002673, protects the alite in the resulting clinker from the inclusion of fluoride ion impurities in its crystal lattice, which contributes to the special sensitivity of hydration activity of alite with a fluoride impurity in relation to the clinker firing regime, and accordingly protects the calcined clinker the dependence of the hydration activity of alite in the PM-clinker and the specified clinker as a whole on the skill level of the personnel.

In general, a decrease in the sintering temperature of the cement raw material mixture, specific fuel consumption and dust formation in the furnace in the method of manufacturing quick-hardening Portland cement according to the invention allows to obtain a number of additional technical effects - significantly reduce the emission of exhaust gases from the furnaces, and in the latter - the content of nitrogen oxides, increases grindability obtained M- and PM-clinkers and reduce emissions from cement mills of aspiration air and cement dust, and the acceleration of binding fluoride ion into stable clinker minerals reduces the emission of sulfate and fluoride anions from the furnace. In addition, an increase in the activity of M- and PM-clinkers compared with Pr- and K-clinkers allows to increase the content in the cement obtained according to the invention of active mineral additives with equal cement strength and thereby reduce the consumption of clinker per 1 ton of cement and, accordingly specific emission of CO ₂ in the composition of the exhaust gases of a clinker kiln per 1 ton of cement. All this indicates the important environmental significance of the present invention, especially in connection with the Kyoto Protocol and possible quotas for the emission of CO _{2 by} cement plants in countries that have ratified this protocol.

The invention in terms of a method of manufacturing a quick-hardening Portland cement, becomes more clear from the description of an example of its implementation.

Example 1. The method is carried out under industrial conditions by the method of a passive experiment with a selection of a number of suitable compositions prepared by the wet method of raw mixtures and calcined in a gas-fired rotary kiln Portland cement clinker. The resulting clinkers are selected and stored, and they are milled in a three-chamber pipe mill with dimensions 3.2 × 12 m, operating in an open cycle, with chamber lengths l _I = 3,525 m, l _II = 1,758 m, l _III = 5,78 m, with a living cross-section of 0.7, 3 and 1.5% of the cross-sectional area of two inter-chamber partitions and the output grate, respectively, with the following grinding load: I chamber: balls with a diameter of 80 mm - 11 t, 70 mm - 14 t, 60 mm - 11 t , total 36 t; II chamber: balls with a diameter of 60 mm - 2 t, 50 mm - 7 t, 40 mm - 10 t, 30 mm - 8 t, a total of 27 t; III chamber: tsilpebs with dimensions (mm): 12 × 25 - 54 t, 16 × 16 mm - 9 t, 12 × 12 mm - 4 t, a total of 67 t; total load 130 tons

The average grinding fineness of the obtained cement samples was 6-8% of the residue on a sieve with 45 μm cells with a specific surface within 430-470 m ² / kg by the method of breathability.

As a mineralizer used (calculated on dry matter, wt.%):

M1: gypsum stone, including dihydrous calcium sulfate (CaSO ₄ · 2H ₂ O) - 98, argillite impurities - the rest, with the following chemical composition: (loss on ignition) 21.30; SiO ₂ 0.63; Al ₂ O ₃ 0.19; Fe ₂ O ₃ 0.08; CaO 32.60, MgO 0.22; SO ₃ 43.20; R ₂ O 0.46; the amount of 98.68, small impurities - the rest;

M2: enriched fluorspar, including fluorite (CaF ₂ ) 99, quartzite impurities - the rest;

M3: fluorine ore, including fluorspar 32, quartzite and feldspar - the rest, with the following chemical composition: 0.11; SiO ₂ 59.58; Al ₂ O ₃ 0.34; Fe ₂ O ₃ 0.13; CaO 22.97; MgO 0.21; SO ₃ 0.63; F ₂ 15.59; R ₂ O 0.31 and Na ₂ O 0.13; the sum of 99.89, small impurities - the rest.

As a promoter used:

P1: ground clinker composition (wt.%): Three-calcium silicate (3CaO · SiO ₂ ) 55, two-calcium silicate (2CaO · SiO ₂ ) 10, three-calcium aluminate (3CaO · Al ₂ O ₃ ) 4,5, four-calcium aluminoferrite (4CaO · Al ₂ O ₃ · Fe ₂ O ₃ ) 10, mayenite (12CaO · 7Al ₂ O ₃ ) 1, calcium monoaluminate (CaO · Al ₂ O ₃ ) 0.75, calcium ferrites (2CaO · Fe ₂ O ₃ , CaO · Fe ₂ O ₃ ) 0.75, calcium sulfoaluminate (4CaO · 3Al ₂ O ₃ · SO ₃ ) 3.75, calcium sulfate (CaSO ₄ ) 1.5, calcium oxide (CaO _St. ) 5.0, aluminates and ferrites of alkali metals [R (Al, Fe) O ₂ ] - the rest; this clinker is nonequilibrium; upon its firing, calcium monoaluminate, mayenite and the Klein-Troxell phase 9СаО · 2Al ₂ O ₃ · 2SO _{3 are formed first} , upon decomposition of which calcium sulfoaluminate of a more equilibrium composition is formed - the Ragosin phase 4СаО · 3Al ₂ O ₃ · SO ₃ , and the released calcium oxide goes to the formation of tricalcium silicate, coexisting with the Ragozina phase only in this case; in an equilibrium system this is not possible;

P2: clinker of the composition, ground with 3.5% gypsum stone (wt.%): Tricalcium silicate (3CaO · SiO ₂ ) 62, dicalcium silicate (2CaO · SiO ₂ ) 15, tricalcium aluminate (3CaO · Al ₂ O ₃ ) 2, 5, four-calcium aluminoferrite (4CaO · Al ₂ O ₃ · Fe ₂ O ₃ ) 15, MgO 0.67, SO ₃ 0.20, K ₂ O 0.21, Na ₂ O 0.15, other impurities (small components) - the rest;

P3: clinker powder (5% by weight) ground with 5% gypsum stone: three-calcium silicate (3CaO · SiO ₂ ) 63, two-calcium silicate (2CaO · SiO ₂ ) 14, three-calcium aluminate (3CaO · Al ₂ O ₃ ) 2, fluoromayenite ( 11SaO · 7Al ₂ O ₃ · CaF ₂₎ 8 calcium alumina ferrite [2CaO · (Al ₂ O _{3) 2} · (Fe ₂ O _3)] 12 _{communication} CaO 0,5, (R ₂ SO _{4) communication} rest;

P4: ground clinker with 5% gypsum stone (wt.%): Tricalcium silicate (3CaO · SiO ₂ ) 75, dicalcium silicate (2CaO · SiO ₂ ) 5, tricalcium aluminate (3CaO · Al ₂ O ₃ ) 0.5, its alkaline derivative (R ₂ O · 3CaO · 3Al ₂ O ₃ ) 1,5, fluoromayenite (11СаO · 7Al ₂ O ₃ · CaF ₂ ) 2,8, calcium aluminoferrite [2CaO · (Al ₂ O ₃ ) 1,2 · (Fe ₂ O _3)] 12 _{communication} CaO 0,5, (R ₂ SO _{4) communication} rest.

To determine the hydraulic activity of clinkers, they are pre-crushed in a laboratory and / or industrial cement mill with an average of 5 wt.% Gypsum component.

When implementing the method according to the invention in laboratory conditions, grinding is carried out in a bicameral mill lined with cast iron armored plates, with the dimensions of each chamber: length 0.28 m, diameter 0.5 m, rotation speed 48 min ^-1 , drive power 1.1 kW , engine speed 930 min ^-1 , grinding load on one camera (with a clinker 10 kg in each chamber): balls with a diameter of 60 mm 6 kg, diameter 50 mm 8 kg, diameter 40 mm 8 kg, diameter 30 mm 8 kg, tsilpebs with a diameter of 20 mm, a length of 32 mm 25 kg, a total of 55 kg. Before weighing, the clinker is crushed to a fraction of 1-2 mm in a laboratory jaw crusher. According to the data given in table 2, this way results are obtained that are almost similar to the given data of industrial grinding.

Other conditions and results of experiments performed in production and laboratory conditions are presented in tables 1 and 2.

With the introduction of a complex mineralizer and promoter in combination with the specified mineralizer according to the invention, the productivity of the furnaces is increased in comparison with the control mode; while the saving in specific consumption of process fuel is 4-14%, respectively (table 1). Accordingly, the amount of clinker that can be obtained on a given amount of process fuel increases. The temperature of the furnace body, antibatically characterizing the effective thickness of the coating on the surface of the refractory lining in the furnace in the sintering zone, during firing in the presence of a promoter, is fixed at a level of about 40-50 ° C lower than in the control mode; with the introduction of only the mineralizer, significant changes in the indicated temperature are not noted. This characterizes a clear increase in the protective action of the coating and a decrease in the loss of thermal energy into the external environment in the presence of a promoter. There is a decrease in dust return to the furnace under equal operating conditions of filters from 12% of clinker mass during the control firing mode to 3-4% when implementing the method according to the invention with the supply of a promoter in combination with a complex mineralizer, i.e. more than 2.5 times. This characterizes the reduction of the load on the dust collecting devices, increasing the period of their maintenance-free operation during the implementation of the method according to the invention, as well as the important environmental significance of the latter. An approximately twofold decrease in the average granule size and an increase in the uniformity of the particle size distribution of the clinker are also observed with the combination of these mineralizers with the promoter. The appearance of less rigid cellular alite crystals (up to 70% of the total mass of alite) in a clinker fired in the presence of a mineralizer in combination with a promoter can significantly (up to 50%) reduce energy consumption for grinding cement according to the invention without changing the dispersion level (table 2).

Tests of strength indicators obtained according to the invention samples of quick-hardening cement (BTC) is carried out according to GOST 310.4-81. As a result, there is an increase in the strength level of cements based on M- and PM-clinkers at the age of 12 hours from scratch in the control cement and a maximum of 10 MPa in the BTC according to the prototype, up to 14-23 MPa in the BTC according to the invention based on M-clinkers and up to 15 -29 MPa in the BTC according to the invention based on PM-clinkers (table 2).

At the age of 1 day, the characteristic of the relevant data is as follows: 11 MPa in the control cement and 14-18 MPa in the BTC according to the prototype and an increase to 23-35 MPa in the BTC based on M-clinkers and to 27-41 MPa in the BTC based on PM- clinkers according to the invention. These strength indicators in samples of normal hardening indicate the possibility of rejection of heat-moisture treatment (TVO) when using the BTC according to the invention.

The data presented in table 2 regarding the use of TVO for various modes, including steaming and air-conditioning of samples, indicate significant advantages of the BTC according to the invention over the prior art, which can reduce the duration and temperature of heat-moisture treatment, if it is nevertheless necessary for this particular production reinforced concrete products and structures.

Finally, at 28 days of age, the BTC according to the invention is also characterized by an advantage in strength compared with the control cement (53 MPa) and with the BTC according to the prototype (48-53 MPa), namely: on M-clinkers it has a strength of 55-59 MPa and on PM clinkers, the strength is 58-76 MPa, although the observed relative increase in strength at this age is less than in the early stages of hardening.

Even higher strength characteristics of the BTZ according to the invention with the introduction of expandable additives (table 2).

The data obtained also indicate that the quick-hardening cement according to the invention is also characterized by lower values of shrinkage deformation of the cement stone (data for linear deformations) in comparison with the corresponding indicators of the control (from clinker without mineralizer) and the known (made according to the prototype method) quick-hardening Portland cement. The use of expanding additives of various types makes it possible to increase the concentration of alkali and FAKH prehydrates according to the invention from 1.3 to 3 times, which, in addition to hardening, reduces the content of expanding additives required to achieve practical shrinkage of BTZ according to the invention from 12-20% according to published data ( see, in particular, in the works of [Kravchenko I.V. Expanding cements. M., Stroyizdat, 1962, 164 pp .; Mehta PK et al. Expansive cements. Moscow, Preprint to VI Internat. Congress on the Chemistry of Cements. 1974, 45 pp. A. Zvezdov. Physico-mechanical properties of slag concrete n and tensile cement. Author's abstract of Candidate of dissertation for the degree of candidate of technical sciences M., NIIZhB, 1981, 20 pp.) up to 7-16% (table 2).

In terms of the manufacture of quick-hardening Portland cement, the method is easily feasible under industrial conditions, since the introduction of water into the mill proceeds without difficulty, and if there are conditions for averaging and adjusting the cement raw material mixture, it can be maintained within the required chemical composition, and clinker - according to the average content of free calcium oxide and sulfates of alkali and alkaline earth metals - does not meet significant difficulties.

Free calcium sulphate, like free magnesium sulphate, in industrial conditions occurs in clinkers according to the invention in large quantities (more than 0.15 wt.%) In only one case - when a part of the calcite-containing component of the cement raw material mixture is supplied together with the sulfate impurity from the hot end a rotary kiln directly to the sintering zone (in line 1 this corresponds to line 5), but, unlike the others, this clinker was obtained in a laboratory simulating production conditions from a finished production clinker suitable composition which, after cooling, pulverized and doshihtovyvayut lime and magnesia, tableted, is calcined in a furnace, heated kerosene; the temperature is selected by trial firing - according to the degree of sublimation of alkali metal sulfates and X-ray data on the presence of free sulfates of Ca and Mg. Milling of cement with moistening of the mixture of grinding from the atomizer was carried out in a laboratory mill.

A promoter of a rational chemical-mineralogical composition accelerates the growth of microphase nuclei and then crystallization of clinker minerals by accelerating the formation of nuclei in the melt, increasing the stability of the nuclei at the time of separation from the melt, their activity in solidification with collective crystallization and increasing the selectivity of the latter, facilitating integration into the prepared cell lattice only the required fragments for a given set of minerals.

As a criterion for the optimal content of the complex mineralizer and its amount with the promoter in the calcined material, ultimately, cement strength values at the age of 1 day and 28 days are used. To select the current optimum supply of the promoter to the calcined material, the criterial characteristic of the promoted clinker is used - the presence of an alite cellular microstructure determined by petrographic analysis, often using an aqueous (1-10%) ascorbic acid solution as an etchant. With the current production control, the concentrations of the complex mineralizer or its combination with the promoter are noted, starting from which the increase in the supply of the complex mineralizer and the promoter is ineffective for changing the clinker structure, and this level of supply of the complex mineralizer or its combination with the promoter is considered optimal.

The active mineral additive introduced into the cement, as follows from the above data, slightly reduces the strength of the cement according to the invention in comparison with that which does not contain the additive in the early stages of hardening, but at the same time remains higher than the strength of the cement according to the prototype, and even more so, of the control cement, not containing the specified additives. Moreover, the latter also slightly increases the shrinkage deformation of the cement-based cement stone according to the invention, but these deformations and with the specified additive remain lower than that of the cement stone according to the prototype and the control cement that do not contain the specified additive. At the same time, it is recommended to use active mineral additives in the composition of the BTZ according to the invention that do not contribute to the growth of shrinkage, namely: from natural additives of volcanic origin, and from artificial ones, mainly slags and ashes, which do not contain harmful impurities, such as sulfides. The results obtained are similar to those observed when using blast furnace granulated slag.

Grinding intensifiers of the indicated types do not prevent the growth of the early cement strength according to the invention when they are introduced within the indicated limits, although some of them (amino alcohols) are introduced in amounts of 0.05-0.07% of the mass of the clinker part of cement, and such as lignosulfonates exhibit the maximum intensifying effect at an order of magnitude greater content in cement, the latter slightly increasing the shrinkage deformation of cement stone, which is taken into account by limiting their introduction into cement at a level of 0.4% of the mass of cement.

In order to save the fluoride part of the mineralizer and the promoter, quick-hardening Portland cement according to an embodiment of the invention is also made from a mixture of clinker obtained according to the invention and conventional clinker, ground together, or a mixture of the obtained cement based on M- or PM-clinker with cement based on K- or Pr -clinker, or any other Portland cement called ordinary (this term is used in the literature to denote Portland cement that complies with current standards [Butt Yu.M. et al. Chemical technology yazhuschih materials. Textbook for high schools. M., Graduate School, 1980, s.382]). In this case, the upper limit of the content of conventional Portland cement clinker and Portland cement in the BTZ according to the invention is considered to be 20% of the mass of the cement mixture, since the technical effects of the invention, from energy consumption for grinding to strength indicators and shrinkage, are reduced slightly. But only in this case, a significant economic effect is achieved, in which it makes sense to bear the costs of in-plant and other transport and other work on the implementation of this mixing. The physico-chemical basis for the possibility of introducing significant amounts of ordinary cement into the specified mixture is Malinin, discovered for the first time [Yu. S. Malinin Study of the composition and properties of the main clinker mineral alite and its role in Portland cement. Abstract. diss. for a job. student step. Dr. tech. sciences. M., Mosk. chemical technologist Institute of them. DI Mendeleev, 1969. - 28 p.] Effect of inheritance of the composition and submicrostructure of the first hydrates formed in cement stone by the hydrates of the same name, which subsequently formed. That is why conventional Portland cement, which generates its hydrates after hydrates of quick-hardening Portland cement according to the invention, to a large extent joins its hydrates to the existing ones, without noticeably violating the composition and the emerging submicrostructure of the neoplasms, which are favorable for the growth of strength and reduction of cement stone shrinkage. The effect of Malinin with high quality ordinary Portland cement allows you to enter it to wt. 1: 1 ratios with M- and PM-clinkers and cements based on the latter, although the effect of the invention with an increase in the content of ordinary Portland cement in the mixture naturally decreases gradually.

With a further increase in the content of conventional clinker and Portland cement in a mixture of cements, the technical effects of the invention disappear.

Fully technical effects of the invention can be obtained by implementing a set of conditions for the manufacture of quick-hardening cement based on the invention and its rational use in concrete.

The state of the art in the manufacture of concrete based on quick-hardening cements is characterized by the work [I. Kravchenko High strength and particularly quick hardening Portland cement. M., Stroyizdat, 1971, ch. V], the basic provisions of which remain valid at the present time. The advantages of the known method for the manufacture of concrete on quick-hardening cements are accelerated hardening, shortening the time to reach standard strength (stripping, shipping, grade = design), a good reaction to the action of hardening accelerators, the possibility of reducing cement consumption in concrete when the specified standard strength is achieved compared to used in parallel with conventional Portland cement without active mineral additives and especially with active mineral additives. The main drawback is the growth of shrinkage deformation of concrete on quick-hardening cements and the associated increased loss of prestressing in prestressed steel reinforcement of reinforced concrete products and structures made of this concrete.

A known method of manufacturing concrete based on quick-hardening Portland cement by mixing the latter with water and aggregates, laying and molding the mixture and keeping the concrete obtained before hardening, characterized in that they use quick-hardening cement containing not more than 5% C ₃ A and not less than 55% C ₃ S, in order to reduce the shrinkage caused mainly by the minerals C ₃ A and C ₂ S contained in this cement [Sheikin A.E. Structure, strength and crack resistance of cement stone. M., Stroyizdat, 1974, 199 pp.]. Otherwise, during the operation of products and structures made of this concrete, cracks appear in them. In addition, when grinding fast-hardening cement, it is necessary to reduce the content of both coarse and fine fractions of particles in it - less than 5 and more than 60 microns, respectively, since their presence adversely affects the deformation properties of concrete and its durability. The fact of the adverse effect of large particles of cement (more than 60 microns) on the strength and durability of concrete during its long hardening is now universally recognized [Mchedlov-Petrosyan OP et al. Late stages of cement hydration. // Cement, 1982, No. 9, p.15-17]. However, no guidance is given on how to implement the recommended increase in uniformity in the particle size distribution of cement. And with heterogeneous granulometric composition of cement and heat-moisture treatment (TBO) of concrete, the formation of secondary ettringite (trisulfate hydrosulfoaluminate calcium 3СаО · Al ₂ О ₃ · 3CaSO ₄ · 32H ₂ O) is possible after its completion, because during the process of heat-moisture treatment, especially in the presence of clinker oxides or sulfates of alkali metals (sodium, potassium), the already formed ettringite (primary) decomposes into the initial components - sulfate, hydroaluminates and calcium hydroferrites (the latter - in the presence of ettrin ite iron impurities), calcium hydroxide and water with concomitant inevitable recrystallization hydrosilicate carcass cement paste in concrete composition and the loss of part of the bound water and the decrease in strength.

There is also a known method of manufacturing concrete based on quick hardening Portland cement [Mchedlov-Petrosyan O.P. Chemistry of Inorganic Building Materials, ed. 2nd. M., Stroyizdat, 1988, 303 pp.], In which the mechanism of recrystallization of the bulk of calcium hydrosilicates caused by alkaline clinker impurities entering the liquid phase of concrete during TBO is discussed in detail. In this case, the transition of primary ettringite to 3СаО · Al ₂ О ₃ · CaSO ₄ · 12Н ₂ O monosulfate with the release of 2CaSO ₄ and approximately 20Н ₂ O is considered as a “trigger” for a whole cascade of recrystallization processes affecting all hydrated components of the cement stone included in concrete composition. To prevent this, a low C ₃ A content in cement is recommended, which reduces the growth rate of concrete strength in the early stages of hardening (one day). This disadvantage is eliminated by the present invention in part regarding a method of manufacturing concrete based on quick-setting cement.

Closest to the invention in terms of the manufacture of concrete based on quick hardening Portland cement is a method of manufacturing concrete products based on the specified cement, obtained by firing before sintering a cement raw material mixture containing sulfuric anhydride and having an alumina module of 1.76-1.9, and subsequent grinding obtained Portland cement clinker containing free calcium oxide and free sulfates of alkali and alkaline earth metals, with a gypsum component in a tube mill with the introduction of water, including mixing said cement with water and aggregates, laying and molding the resulting mixture, and holding it until the concrete has hardened [RF Patent No. 2050725, 1994] at an ambient temperature of 10-85 ° C and a relative humidity of 50-100% for 2-6 hours. Experiments performed show that in this method the cement after grinding contains alkali prehydrate in an amount of 0.3-1% of clinker mass. In this case, for the first time, despite the presence of alkali metal oxides in the clinker, the liberation of the bulk of cement hydration products - calcium hydrosilicates - from alkali metal oxides due to their binding to the specified alkali-containing calcium monosulfohydroaluminoferrite (AL) is achieved.

Quick-hardening Portland cement, obtained according to the prototype, containing alkali metal oxide as a seed for crystallization of hydrated neoplasms, after preparation of the concrete mix, it begins to form alkaline cementite in larger quantities in comparison with the control cement, which forms either ettringite or monosulfate, or their mixture without the participation of alkali metal oxides, as in the control cement in the first hours after mixing, the content of the latter in the liquid phase is small. Therefore, in the liquid phase of a stone based on control cement, spontaneous crystallization of alkali metal liquids from the liquid phase is not possible without seeding. When, after 6-12 hours, the required threshold for the concentration of R ₂ O in the liquid phase (1400 mg in terms of Na ₂ O per 0.1 L) is reached, then in concretes based on control cement, the concentration of Al ₂ O ₃ falls below that required for alkali metal level (600 mg / 0.1 L), in particular to almost zero at the control Portland cement, due to the binding of soluble alumina to hydroaluminates and calcium hydrosulfoaluminates. This is directly evidenced by the simplest experiment with alizarin-S staining the concrete preparation on control Portland cement according to the prototype at the age of 1 day due to the presence of water-soluble Al (OH) ₃ and leaving colorless preparations on the control Portland cement. In this case, the alkaline oxides in concrete at the BTC according to the prototype, the hydroaluminate and hydrosulfoaluminate phases bind to a greater extent, namely, in the amount of 10-15% of their total content in hardening cement versus 7-8% in concrete based on control cement. The alkaline oxides remaining in the liquid phase are bound to the calcium hydrosilicates of cement stone into complex compounds — complex phases leading to phase transitions and concrete strength drops [Volzhensky A.V. Mineral binders (Technology and properties). Ed. 4th, rev. and add. M., Stroyizdat, 1986, 479 pp.]. In concrete products manufactured according to the prototype, alkaline oxides are bonded to a greater extent in alkali metals, and calcium hydrosilicates are relatively freer from them. It is this that leads to a faster increase in the strength of the specified concrete both in the early and in the late stages of hardening, especially in natural conditions (10-25 ° C), when the surface of the concrete is moistened to protect it from drying out, which ensures an ongoing increase in the concentration of alkali metal in concrete . TBO does not change this position either in the form of steaming (since the alkali metal material that fails at temperatures above 70 ° С does not completely disappear and due to the preserved seeds it reappears when the products are cooled after the steaming is completed, partially freeing the liquid phase from alkali metal oxides), nor in the form " cold fog "(10-15 ° С at 100% humidity), as this mode is favorable for crystallization of alkali metals.

The iron and silicon-containing alkali-reinforced concrete in the concrete obtained according to the invention is thermodynamically more stable than pure aluminate ettringite, monosulphate and alkaline monosulphate, which can be easily verified by thermodynamic calculation, as well as in practice: after all steaming, all known concretes form on the surface of concrete C ₃ AH ₆ - cubic calcium hydroaluminate crystallizing with increasing volume and destructively affects the strength and durability of concrete, and as a result of acceleration of dehydration through pores formed ve uschy to raise concrete shrinkage strain. The specified calcium hydroaluminate in lateral lighting is clearly visible on the surface of concrete in the form of bright "stars". For concrete based on cement obtained according to the prototype, the amount of C ₃ AN _{6 is} significantly reduced, which leads to a more rapid and long-term increase in the strength of concrete according to the prototype compared to the known one. The BTC-based concrete according to the invention, obtained under conditions conducive to the stability of alkali metal, before the mass formation of hydrosulfoaluminate phases begins, is completely free of cubic calcium hydroaluminate and is therefore characterized by increased strength both in early and late hardening periods.

FACT promotes the introduction of silica and iron oxide impurities into both the alkali metal oxide and through it into the hydrosulfoaluminate complex - trisulfate, and directly into the latter, since it is able to chemisorb the sulfate ion faster than other hydrated phases. This is evidenced by the acceleration and increase in the degree of binding of the sulfate ion from the gypsum component of cement to the hydrated phases of the cement stone. This is important because free SO ₃ has a harmful effect on cement stone in view of the formation of "secondary ettringite" [Sheikin A.E. and others. The structure, strength and crack resistance of concrete. M., Stroyizdat, 1981, 192 pp.], Expanding in the already existing matrix of cement stone, destroying it.

When hardening in natural conditions of concrete products obtained by the proposed method, the completeness of binding of SO ₃ in alkali metal alloys up to zero free gypsum content is achieved in 2-3 hours versus 4-6 hours in concrete at the BTC according to the prototype or 18-24 hours in concrete on control cement, which allows unhindered increase in the strength of concrete on cement according to the invention in the early stages of hardening and to avoid the release of strength during subsequent hardening. This can be seen, in particular, from the reduced intensity of the free gypsum reflex at an interplanar distance of 4.29 · 10 ^-10 m and the increased intensity of the alkaline gypsum reflex at an interplanar distance of (8.3-9.5) · 10 ^-10 m on X-ray diffraction patterns of cement stone, isolated from concrete obtained according to the invention by crushing the latter and screening out aggregates, which corresponds to a degree of gypsum binding of about 85%. When it is achieved, further binding is almost always ensured while maintaining the humidity above 50% (this is a condition for the presence of films of liquid water in the hydroaluminoferrite-containing phases of the cement stone) for another 1-6 hours. This follows from the experiments.

Note that FAKG causes staining of alizarin with a fixed amount of this phase in a brighter color compared to any known Portland cement, including free aluminum hydroxide. If necessary, this method can be used for the quantitative determination of FAKG, since AM does not interfere with this. It is also possible to use the method for determining water-soluble alumina standardized for active mineral additives to determine the FAKG. In this case, the main role of the FACT, including fluoride ion, is the seed effect on the entire soluble hydroalumina released during the decomposition of calcium hydroaluminates, which did not manage to contact gypsum in the liquid phase. It is precisely this that makes it possible to completely eliminate the formation of the cubic hydroaluminate mentioned above, to incorporate all this alumina into the main matrix of cement stone thanks to impurities of silica and fluoride, and thereby increase its strength both in early and late hardening periods.

A method of manufacturing concrete based on quick-hardening Portland cement involves mixing said Portland cement with water and aggregates, molding the resulting mixture and holding it until it hardens at an ambient temperature of 1-45 ° C and a relative humidity of 70-100% for 5-24 hours or under conditions of heat and moisture treatment at an ambient temperature of 50-85 ° C for 1.5-5.5 hours

The invention in terms of a method of manufacturing concrete becomes clearer from the following example of its implementation.

Example 2. On the basis of quick-hardening Portland cement obtained according to the invention, concrete is made including, in addition to cement, also:

- fine aggregate - sand quartz fraction 1-5 mm, containing in wt.%: quartz 97, feldspars 2, dark-colored minerals - epidote and other impurities 1 with a voidness of 38% by volume;

- coarse aggregate - crushed stone granite fractions of 5-20 mm, containing in wt.%: granite 95, quartzite 3, mica and other impurities 2, with a voidness of 42% by volume;

- drinking tap water.

All materials meet the requirements of relevant standards and specifications.

To prepare the samples, we used a horizontal laboratory mixer, forced action, with a capacity of 100 l, a vibration plate with an oscillation frequency of 50 Hz and mechanical fastening of molds for 10 × 10 × 10 cm cube samples made of ferrous metal with standard processing quality to the table surface. Tests of the samples were carried out after their storage in air-wet conditions (100% relative humidity at a temperature of 17 ÷ 23 ° C). During the first days of storage, to prevent evaporation of moisture from the surface of the samples, the mold was covered with a cloth of coarse canvas moistened with water.

We used a concrete mixture of increased mobility (compared to the prototype) with an Abrams cone draft of 14 cm, since it is known that such mixtures prevail in monolithic construction (the ratio in Western Europe of monolithic and precast concrete in the total volume of construction for 2004 according to available statistics is 60:40, while in Russia - 35:65, but the share of monolithic construction is growing rapidly). In such mixtures, the need for quick-hardening cements is higher, since their use directly reduces the time and cost of construction of buildings and structures, especially when refusing heat and moisture treatment of concrete.

The study of the process of hydration of cement in concrete was carried out according to the following method. Before or after the strength tests of the samples, pieces were taken that did not contain the external faces of the sample, the coarse aggregate grains were beaten with a geological hammer, the remaining mass was crushed on a laboratory jaw crusher, and screening was taken through a sieve with 1 mm mesh. These operations were carried out for no more than 1 hour after the tests. The obtained grains were quartered, placed in a desiccator above water to avoid drying, triturated in a mechanical mortar and subjected to: 1) differential thermal analysis on a Paulikov-Erdei instrument at a heating rate of 8 deg / min, atmosphere — air, standard — corundum, Pt / PtRh thermocouple ; 2) X-ray diffraction analysis on a DRON-2 diffractometer, CuK _α radiation, Al filter, goniometer movement speed - 0.5 deg / min. The initial powder was completely sieved before analysis through a No. 006 sieve (60 μm). No methods for preserving the samples to stop the hydration process were used; all analyzes were completed no later than 5 hours after testing the sample for strength. Alizarin staining was carried out by applying a 2% alcohol solution to the surface of the stone and observing the surface of polished sections of the latter under a microscope, allowing viewing in reflected light. The quantitative assessment of the content of FAKG in the form of prehydrates in cement and the hydrated phase in cement stone was carried out by staining by comparison with reference samples, including an inert material with the addition of 0.2-3% synthetic FAKG, made from the starting hydroxides with stirring and holding with the addition of fluorides ion with sodium fluoride for 3 days at 30 ± 3 ° C. A quantitative assessment of the content and composition of alkalis was carried out using a quantitative x-ray analysis according to the intensity of the above-mentioned analytical reflection on powder x-ray diffraction patterns.

The test results of the physical and mechanical properties of concrete, corresponding to products made according to the invention, are presented in table 3. The samples were kept in a laboratory room with a temperature and humidity measurement by a hygrometer, as well as in a steaming and air-conditioning chambers.

From the above data it follows that the concrete according to the invention both during heat-moisture treatment and especially when hardening in natural conditions (5-20 ° C) is ahead in terms of strength of known concrete of the same composition on control Portland cement and quick-hardening cement according to the prototype.

A significant advantage of the concrete obtained according to the invention is the intensive increase in strength by 28 days due to the release of calcium hydrosilicates from alkaline oxides, despite their presence in the raw mix and clinker in significant quantities, as well as the prevention of strength drops due to the absence of secondary recrystallization processes and improving the fusion of hydrated neoplasms into a single matrix of cement stone. In practice, a further increase in strength was observed by 3, 6, and 12 months of hardening.

The data presented indicate that the obtained quick-hardening Portland cement according to the invention and concrete based on this quick-hardening Portland cement really radically differ from those known for both increased strength characteristics during hardening under natural conditions and accelerated binding of calcium sulfate to high-water hydrates, primarily to a new mineral, alkaline calcium monosulfogidroalyumoferrit with high iron content, which has a high level ratio R ₂ O / Al ₂ O _3, b izkim to 0.5, which is much greater than the possibility of linking the alkali oxides in the tri or bisulfate form calcium gidrosulfoalyuminatov in which the ratio R ₂ O / Al ₂ O ₃ is less than 0.1 on a molar basis. That is what allows in the method according to the invention, firstly, to release calcium hydrosilicates from alkaline oxides, which improves crystallization and increases the strength of the crystalline intergrowth of calcium hydrosilicates - the basis of the strength of cement stone and concrete; secondly, to increase the rate of its growth in the early stages of hardening - 12-24 hours after mixing the cement with water and obtain concrete products based on the cement according to the invention that do not require heat treatment.

From the description and examples of the invention, it follows that it is characterized by a number of novelty elements that are not derived from the prior art, and significantly exceeds the latter in properties of cement and concrete, products based on it.

The above also indicates the preparedness of the invention for industrial implementation.

Claims (23)

1. A method of manufacturing a quick-hardening Portland cement by firing before sintering a cement raw material mixture containing carbonate, aluminosilicate and ferrous components and including alkali metal oxides - sodium and potassium and sulfuric anhydride, followed by joint grinding in a tube mill of the obtained Portland cement clinker, including free calcium oxide and free sulfates of alkali and alkaline earth metals, with the introduction of water and gypsum component, characterized in that the specified cement raw material mixture contains sulfuric anhydride SO ₃ is present in an amount corresponding to the molar ratio of the sum of the content of alkali metal oxides in it in terms of the Na ₂ O equivalent - R ₂ O = Na ₂ O + 0,658K ₂ O - to SO ₃ equal to 1.34-1 , 7, and additionally calcium fluoride in an amount corresponding to a molar ratio of R ₂ O to fluoride ion F ^- equal to 1.3-2.9, the resulting clinker includes, wt.%, Free calcium oxide 0.25-1, 5, free sulfates of alkali and alkaline earth metals in the amount of 0.3-1.2, has an alumina module of 1.3-1.7, water is introduced in an amount of 0.15-0.3% of the weight of the specified Portland cement, grinding is carried out to obtain in the specified Portland cement, in% by weight of its clinker part: alkaline monosulfohydroaluminoferrite calcium 4СаО · 0.5R ₂ O · 0.9 (Al _x Fe _y ) ₂ O ₃ -1.1SO ₃ · (8-12) Н ₂ O, where R is Na and / or K at x / y from 1.3: 1 to 2: 1, - 0.15-1.8 and hydroxyl gel Al (OH) _3-z F _z · SiO (OH) ₂ with z = 0.5-2.5, - 0.1-0.6. 2. The method according to claim 1, characterized in that the specified cement raw mix contains, wt.%, Sulfuric anhydride in an amount of 0.25-1.2 and calcium fluoride in terms of F ^- in the amount of 0.15-0.4 and the clinker obtained from it includes free calcium sulfate - 0.01-0.3% of the mass. 3. The method according to claim 1, characterized in that the cement raw material mixture contains sulfuric anhydride in the form of sulfates of alkali or alkaline-earth metals in the form of a mineral of tenardite Na ₂ SO ₄ or arcanite K ₂ SO ₄ , or their mixed crystals and hydrated derivatives or gypsum, or gypsum anhydrite, or anhydrite, and calcium fluoride in the form of fluorite or its ore containing fluorite in an amount of not less than 20 wt.%. 4. The method according to any one of claims 1 to 3, characterized in that the Portland cement clinker contains, wt.%: tricalcium silicate 3CaO · SiO ₂ 55-75 dicalcium silicate 2CaO · SiO ₂ 3-22 tricalcium aluminate 3CaO · Al ₂ O ₃ and / or its alkaline derivative R ₂ O · 8СаО · 3Al ₂ O ₃ 2-13 fluoromayenite 11СаО · 7Al ₂ O ₃ · CaF ₂ 2,5-10 calcium aluminoferrite 2CaO · (Al ₂ O ₃ ) _x · (Fe ₂ O ₃ ) ₁ , where x is greater than 0 and less than 1 0.5-14 free calcium oxide and sulfates alkali and alkaline earth metals rest 5. The method according to claim 1, characterized in that the mineral formation promoter is additionally introduced into said cement raw material mixture, including two or more clinker minerals from the group: 3CaO · SiO ₂ , 2CaO · SiO ₂ , 3CaO · Al ₂ O ₃ , 2CaO · (Al ₂ O ₃ ) _x · (Fe ₂ O ₃ ) _1-x , where x is not less than 1/3 and not more than 2/3, 12СаО · 7Al ₂ O ₃ , calcium monoaluminate CaО · Al ₂ О ₃ , dicalcium and monocalcium ferrites - 2CaO · Fe ₂ O ₃ and CaO · Fe ₂ O ₃ and / or alkaline, sulfate and halide derivatives of these minerals, and which is mechanical and / or obtained together in the form of clinker or slag, or sludge in the form of a powder or suspension, a mixture of these minerals, characterized by a basicity value of 1.005-1.07 times higher than the basicity of the eutectic clinker melt, with a mass ratio of promoter to calcium fluoride of 1.8-2.5. 6. The method according to claim 1, characterized in that the mineral formation promoter is additionally introduced into said cement raw mix, including, wt.%: 3CaO · SiO ₂ 55-80 2CaO SiO ₂ 10-13 3СаО · Al ₂ О ₃ 1-12 2CaO · (Al ₂ O ₃ ) _x · (Fe ₂ O ₃ ) _1-x , where x is greater than 0 and less than 1 10-18 12 CaO · 7Al ₂ O ₃ and / or 11 Cao · 7Al ₂ O ₃ · CaF ₂ 1-11 CaO · Al ₂ O ₃ 0.5-1.5 2СаО · Fe ₂ O ₃ , CaО · Fe ₂ O ₃ 0.5-1.5 calcium sulfoaluminate 4СаО · (3Al ₂ O ₃ ) · (SO ₃ ) 1-25 calcium sulfate CaSO ₄ 1,5-3,5 calcium oxide CaO 0.1-5 Aluminates and ferrites of alkali metals R (Al, Fe) O ₂ rest, and which is a mixture of these minerals, mechanical and / or obtained together in the form of clinker or slag, or in the form of a precipitate in the form of a powder, characterized by a basic value of 1.005-1.07 times higher than the basic value of the eutectic clinker melt, with a mass ratio of the promoter to calcium fluoride - 1 4-2.2. 7. The method according to claim 1, characterized in that the mineral formation promoter is additionally introduced into said cement raw mix, including, wt.%: 3CaO · SiO ₂ 55-75 2CaO SiO ₂ 3-22 3CaO · Al ₂ O ₃ and / or its alkaline derivative R ₂ O · 8СаО · 3Al ₂ O ₃ 2-13 12CaO · 7Al ₂ O ₃ and / or 11CaO · 7Al ₂ O ₃ · CaF ₂ 2,5-10 calcium aluminoferrite 2CaO · (Al ₂ O ₃ ) _x · (Fe ₂ O ₃ ) ₁ , where x is greater than 0 and less than 1 0.5-14 free calcium oxide and sulfates alkali and alkaline earth metals rest, and which is a mixture of these minerals, mechanical and / or obtained together in the form of clinker or slag, or in the form of a precipitate in the form of a powder, characterized by a basic value of 1.005-1.07 times higher than the basic value of the eutectic clinker melt, with a mass ratio of the promoter to calcium fluoride - 1 , 0-2.0. 8. A method according to any one of claims 5-7, characterized in that as a criterion for the optimal content promoter used emergence phase 3SaO · SiO ₂ cellular microstructure in said clinker. 9. The method according to claim 1, characterized in that during firing, the content in the specified raw material mixture is regulated according to the sum of the minerals 3CaO · Al ₂ O ₃ and / or R ₂ O · 8CaO · 3Al ₂ O ₃ and 2CaO · (Al ₂ O _{3) x} · (Fe ₂ O _{3) 1-x,} where x is greater than 0 and less than 1, or 2,65Al ₂ O ₃ + 1,34Fe ₂ O _3, oxides of at least 10 and 6 wt.%, based respectively on plain and white Portland cement clinkers. 10. The method according to claim 1, characterized in that the natural gypsum from the group: gypsum stone, gypsum anhydrite, anhydrite, or gypsum-containing waste from the group: phosphogypsum, borogypsum, titanogypsum, a product of neutralization of sulfur dioxide by lime, is used as a gypsum component when grinding or a mixture of natural gypsum and gypsum-containing production waste in wt. a ratio of 2: 1-1: 2 with a gypsum component content of 1.5-4.5 wt.% in terms of sulfuric anhydride. 11. The method according to claim 1, characterized in that when grinding an additional active mineral supplement is added. 12. The method according to claim 1, characterized in that during grinding, an additional grinding intensifier is added in an amount of 0.05-0.4% by weight of said Portland cement. 13. The method according to p. 12, characterized in that as a grinding intensifier, a substance is used from the group: amino alcohols and their compositions with hardening accelerators, technical lignosulfonates and their compositions with electrolytes, an alkaline earth and / or alkali metal salt of a product of condensation of naphthalene sulfonic acid with formaldehyde, complex salt of an alkaline earth metal and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight C ₃ -C ₅ monosaccharides, paired mixtures of these materials, in a weight ratio of 4 : 1 to 1: 4, in an amount of 0.05-0.5% by weight of said Portland cement. 14. The method according to claim 1, characterized in that when grinding, an ordinary Portland cement clinker is additionally introduced at a weight ratio of said and conventional Portland cement clinker from 5: 1 to 1: 1. 15. The method according to p. 14, characterized in that carry out the domol, in which additionally enter the usual Portland cement clinker with a mass ratio of the specified and ordinary Portland cement clinkers from 5: 1 to 1: 1. 16. The method according to claim 1, characterized in that a domol is carried out, in which an ordinary Portland cement clinker or Portland cement based on it is additionally introduced at a mass ratio of said and conventional Portland cement clinker from 5: 1 to 1: 1. 17. The method according to claim 1, characterized in that Portland cement is additionally introduced when mixing based on a conventional Portland cement clinker at a weight ratio of said and conventional Portland cement clinker from 5: 1 to 1: 1. 18. The method according to claim 17, characterized in that a domol is carried out in which Portland cement is additionally introduced based on a conventional Portland cement clinker at a weight ratio of said and conventional Portland cement clinker from 5: 1 to 1: 1. 19. The method according to claim 1, characterized in that when grinding or mixing with the specified Portland cement, an expanding additive is additionally introduced, including artificial material containing more than 10 wt.% Al ₂ O ₃ in the form of calcium aluminates, from the group: alumina clinker or alumina slag, sulfoaluminate clinker or other material including calcium sulfoaluminates, sulfoferrite clinker or other material including calcium sulfoferrites, hyperalitic clinker or its grinding product, metallurgical slag, or natural material, with containing more than 4.5 wt.% water-soluble Al ₂ O ₃ , or a mixture of these materials containing at least 20% of each of them, while the content of expanding additives in the specified Portland cement is 7-16 wt.%. 20. The method according to claim 1, characterized in that the introduction of water into the tube mill is carried out by spraying in its first or last chamber. 21. The method according to claim 1 or 11, characterized in that the introduction of water into the tube mill is carried out in the form of hygroscopic moisture of the clinker and / or active mineral additives. 22. The method according to claim 1 or 12, characterized in that the introduction of water into the tube mill is carried out with an aqueous solution of the intensifier grinding. 23. A method of manufacturing concrete based on quick-hardening Portland cement made according to any one of claims 1 to 22, comprising mixing said Portland cement with water and aggregates, molding the resulting mixture and holding it until it hardens at an ambient temperature of 1-45 ° C and a relative humidity of 70- 100% for 5-24 hours or under conditions of heat and moisture treatment at an ambient temperature of 50-85 ° C for 1.5-5.5 hours