Hydraulically Activated Cement Clinker with Additives Containing Alite and Active Belite Phases

Abstract

The invention relates to cement clinker formed by firing clinker prepared with new and improved clinker minerals. This new cement clinker is a boron-modified cement clinker that can contain both alite (tricalcium silicate) and alpha-H-dicalcium silicate phases, is fired at lower temperatures, has lower carbon dioxide emissions, and exhibits hydraulic activation.

Description

1 TARIFF Hydraulic additives containing ALIT and ACTIVE BELIT phases. ACTIVATED CEMENT CLINKER Technical Area The invention results from the cooking of flour prepared with new and improved flour minerals. It is related to cement clinker. This new cement clinker consists of alite (tricalcium silicate) and αH'. Boron-doped, which can also include a dicalcium silicate phase, can be fired at lower temperatures. It is a cement clinker exhibiting hydraulic activation with low carbon dioxide emissions. 5 State of the Art Portland cement is the most widely used hydraulic binder in the world. The composition of the cement includes clinker and gypsum. It is the main component that gives cement its hydraulic properties, while it consists of a mixture of stone and mineral additives. It is clinker. 10 Clinker is an energy-intensive process where the main raw materials are limestone, clay / marl, and, depending on the need, iron ore. Mixing corrective components such as bauxite and silicon wafer in appropriate proportions, drying the mixture... It is produced by grinding the grains, preparing them for cooking, and then cooking them at high temperatures. Before cooking... The energy required for grinding, which is used during the drying and grinding stages of the materials, is also used in the cooking process. Combustion emissions resulting from fuel use and chemical changes in raw materials during cooking 15 The emissions formed after the reactions are emissions released during production. 1 ton of cement Approximately 970 kg of CO2 is released during its production. The hydraulic properties of Portland cement are derived from the clinker in its composition. The hydraulic properties of clinker... Its characteristic feature is that it originates from 4 different compounds formed as a result of cooking reactions. These 4 basic compounds are: Alite (C3S), belite (C2S), tri-calcium aluminate (C3A) and tetra-calcium alumina ferrite (C4AF). 20 Table 1 These basic compounds vary depending on the effect of temperature, the effect of minor elements, and other conditions of the process. (such as fuel used, heat profile, system technology, temperature, pressure, cooling and efficiency) Chemical Name Chemical Formula Cement Nomenclature Tricalcium Silicate - Alite Ca3SiO5 C3S Dicalcium Silicate - Belite Ca2SiO4 C2S Tricalcium Aluminate Al2Ca3O6 C3A Brownmillerite, Fe+3-bearing, syn Ca4Fe2Al2O10 C4AF Lime CaO C Portlandite Ca(OH)2 CH 2 Polymorphic structures are essentially the same but differ in both crystal structure and hydraulic effect. This polymorphic structure can form. This structure affects the quality characteristics of the product. Table 2 Chemical Formula Cement Name CaO C SO2S Al2O3 A Fe2O3 F When clinker compounds are evaluated in terms of their hydraulic properties, 5 C3S (Alit) is a compound with highly active hydraulic properties. (Its polymorphs and... are covered under this patent.) (The features will not be discussed.) C2S (Belit) has 5 polymorphs in its structure. These are α (alpha), αH' (alpha prime high), αL' (alpha The crystal structures are β (prime low), β (beta) and γ (gamma). Of these crystal structures, the γ-C2S gamma polymorph has hydraulic properties. It does not have. 10 The β-C2S beta form is found in Portland cement and is considered a metastable phase, and is only used in this way. It forms during cooling. The α' alpha prime and αH' alpha prime high phases of C2S polymorphs are studied under this patent. This is the structure that will be settled. These phases have high hydraulic properties among other polymorphs of C2S. These are the phases. α' phases are obtained at high temperatures and by using B2O3 in the raw material stage, 15 By incorporating B2O3 into the clinker structure during the chemical reaction stage, both the formation of the α' phase and by ensuring its stabilization and obtaining the active belite phases when the clinker reaches room temperature. It provides this opportunity. Therefore, it improves the clinker's properties. If we examine the early and late strength properties of the 4 basic clinker compounds, C3S and C2S show the highest strength development. The phases are highly effective. 20 Table 3 Feature C3S (al te) C2S (Belt) C3A C4AF Early Strength High Low High Low Late Strength High High Low Low C2S obtained in the structure of clinker after low-temperature production with the addition of B2O3. Although the active form of the compound is obtained, its early strength property is suitable for the cement and concrete industry. It cannot be produced at a level that would be preferable for this purpose. Therefore, obtaining it at low temperatures is 25 While the active C2S phase is formed in the planned clinker, the presence of the C3S phase is also desired. Hydration of C3S, C2S, C3A and C4AF phases found in cement clinker structure, their reaction with water, It is the material that acquires binding properties as a result of this reaction. CSH is formed from the C3S and C2S phases in this reaction. a gel is formed and exhibits binding properties. Among the known applications in the technique are Bogue and Lerch [1] 3 In their studies, they compared the compressive strength of pure cement phases. 10 and 14 When daily compressive strengths are observed, the factor that has the greatest impact on the short-term compressive strength of C3S is... They determined that it was a phase. For the 10 and 14-day results; C3S > C2S > C3A > C4AF When comparing the compressive strengths after one year, the results are as follows: 5 C3S=C2S>C3A>C4AF The C3S phase, which exhibits rapid hydration, is the most preferred phase in clinker structure due to its high early strength. It is the phase that needs to be obtained in large quantities. The C2S found in clinker has 5 polymorphs. All of these polymorphs are different from each other. They possess hydration properties and contribute differently to compressive strength. 10 are produced industrially. The β phase, β-C2S, is present in the clinker and is formed during cooling. Jelenic and Bezjak [2] made In the studies, the hydration properties of α' and β-C2S polymorphs were investigated and the reaction of the α' phase was examined. They determined that it has a faster speed and exhibits more active hydraulic characteristics. Among the known applications in the field, CaO-B2O3-SiO2 was studied by Fletcher et al. [3] Studies have been conducted on the system, and in these studies, boron has been shown to be incorporated into the structure of dicalcium silicate (C2S) at 15°C. and that the β,α' and α C2S polymorphs are stabilized depending on the amount of boron added. They observed that in this solid solution state, the Ca11(SiO4)4(BO3)2 structure formed during heating. It was suggested that the solid solution mechanism formed 6 (, ', )-Ca2-0.5(SiO4)1-x(BO3)x dicalcium silicate. They continued (x=amount of B2O3, the amount determines the polymorph). In their studies, they found a The other data indicates that if B2O3 is included in the system, the thermal stability of tricalcium silicate (C3S) is disrupted, and 20 It has been stated that C3S is unstable and decomposes into C2S and CaO. In light of this information, C3S... It was determined that stabilization could not be achieved with boron and that there was excess CaO in the designed system, leading to volume expansion. This is the reason why it does not meet the requirements of the TS EN 196-3 standard. In the studies conducted by Tran et al. [4], CaF2 is a solid solution in calcium silicate systems. They investigated its mechanism. They found that C3S, lacking Si-O bonds, contains oxygen within its crystal structure, F-25. It can be replaced by an anion, and since all C2S have Si-O bonds, only C3S has a similar structure. It has determined that it does not participate in the structure of C2S. In this case, C3S was created with a new contribution. It is hypothesized that the C3S phase can be stabilized in the presence of B2O3 in the solid solution. As a result of the research conducted within this scope, it was determined that CaF2 and ZnO are necessary for the C3S phase to be incorporated into the structure. The compounds used involve the C3S phase present in the clinker being incorporated into the crystal lattice by F- and 30 It has been determined that these are compounds that are doped as Zn2+ ions and form at low temperatures. It has been done. 4 Brief Description of the Invention In light of all this information, studies using B2O3 and CaF2 together have shown results at low temperatures. It has been observed that the formation of both the active and active phases is possible. The designed... Due to the presence of both allite and active belite phases in the clinker, it exhibits both early and late strength. It has been observed that optimization can be achieved by making the features suitable as well. 5 The invention relates to fired cement clinker with improved clinker minerals, with the addition of CaF2 and B2O3. The clinker formed as a result of firing in the resulting crucible has superior properties compared to Portland cement. has. The C3S mineral, which was previously shown to be unstable in the presence of B2O3, can now be stabilized thanks to this invention. It has been done. By obtaining the active belite form with C3S and B2O3, which are stabilized as a result of mineralization, 10 The clinker is chemically optimized in terms of hydration for a faster hydration reaction. This shows that thanks to these properties, greater compressive strength can be achieved per unit time. This can be done. The clinker obtained from this flour has lower CaF2 and B2O3 content compared to flour that does not contain CaF2 and B2O3. It has a cooking calorie count. It also has a higher calorie count in the same unit of time compared to farine which does not contain CaF2 and B2O3. It has compressive strength. Its low firing calorific value reduces energy requirements and clinker binder 15 It helps reduce CO2 emissions because it lowers the emissions factor. This is achieved with flour. The resulting clinker has lower CO2 emissions. Explanation of the Figures Figure 1: Steps in industrial production Figure 2: X-ray Diffraction and Rietveld Analysis of OPC Clinker 20 Figure 3: X-ray Diffraction and Rietveld Analysis of Boron-Doped Clinker Figure 4: X-ray Diffraction and Rietveld Analysis of Fluorine-Doped Clinker Figure 5: X-ray Diffraction and Rietveld Analysis of Boron and Fluorine-Doped Clinker Detailed Description of the Invention The subject of the invention is cement clinker, crushing of raw materials, mixing of raw materials, and processing of raw materials. It is produced by grinding and firing the raw material to obtain clinker (Figure 1). Invention The subject is clinker, alkali waste, aragonite, calcite, cement flue dust, cement stone, chalk, limestone, marble, marl, clay, mud, shale, iron ore, bauxite, fluorite, colemanite, ulexite, borax (five-hydroxide, ten-hydroxide) It can be used as a raw material. The subject of the invention is cement clinker, containing approximately 64-66.5% CaO by weight in the clinker product, approximately 30 20.5-21.5% SiO2, approximately 5.3-5.8% Al2O3, approximately 3.4-3.8% Fe2O3, approximately 1.4-1.8% MgO, approximately 0.5-1.5% SO3, approximately 0.5-1.5% K2O, approximately 0.1-0.5% Na2O, approximately 0.2-1% CaF2, It contains approximately 0.2-1% B2O3. The invention describes a proposed and preferred oxide for the industrial production of cement clinker. percentages, Lime Saturation Factor (LSF), Aluminum Modulus (ALM), clinker subject to the invention The CaF2 / B2O3 ratio and Sodium Equivalent (Na2O Equivalent) are shown in Table 4. 𝐾𝐷𝐹 = (100 ∗ 𝐶𝑎𝑂) 2.8 ∗ 𝑆𝑖𝑂 + 1.18 ∗ 𝐴𝑙 𝑂 + 0.65 𝐹𝑒 𝑂 𝐴𝐿𝑀 = 𝐴𝑙 𝑂 𝐹𝑒 𝑂 𝑁𝑎 𝑂 = 𝑁𝑎 𝑂 + 0.658 ∗ 𝐾 𝑂 Table 4: Clinker oxide percentage (suggested, recommended) Ox ts Recommended Recommended Recommended CaO 64.0-66.5 64.5-66.0 SO2 20.5-21.5 20.6-21.1 Al2O3 5.3-5.8 5.3-5.8 Fe2O3 3.4-3.8 3.4-3.8 MgO 1.4-1.8 1.4-1.8 SO3 0.5-1.5 0.8-1.2 Na2Odenk 0.4-1.5 0.6-1.4 CaF2 0.20-1.0 0.30-0.80 B2O3 0.20-1.0 0.30-0.80 CaF2 / B2O3 0.8-1.7 0.9-1.5 ALM 1.30-1.7 1.4-1.6 KDF 95.0-98.5 96-98.5 Cement clinker contains approximately 52-65% C3S, 2-10% β-C2S, 5-25% α'-C2S, and 2- by weight. 8% C3A, 7-15% C4AF, 0.1-3% lime, 0.1-3% periclase and approximately 0.1-5% minor minerals are obtained. is being done. X-ray diffraction and Rietveld analysis were used to determine the phases and percentages in Portland cement. The results of the analysis are shown in Table 5. Portland cement contains 7.63% β-C2S. It contains the β-C2S phase and 70.56% Alite (C3S) phase. The β-C2S phase forms during cooling. and is present in Portland cement without admixture. The α'-C2S phase was not found in clinker. 15 Table 5: Phase analysis of OPC clinker Phase Name R Percentage Al te M3 43.75 C3S <m1>26.82 C2S_beta 7.76 C2S_AlphaPr me_DelaTorre 0.73 C2S alpha 0.13 C2S gamma 0.06 C3A_cub c 4.69 C3A_orthorhomb c 0.73 Brownm ller te, Fe+3-bear ng, syn 12.12 6 Per class 0.48 L me 0.93 Portland 0.09 Aphth tal te 0.65 Arcan te 0.11 Langbe n te 0.58 Thenard te 0.37 C3A_monocl nc 0 Quartz 0 Rietveld analysis of clinker, which was fired with only boron added to the flour, after X-ray diffraction. The analysis of the alite (C3S) phase in clinker obtained by boron doping is shown in Table 6. It was determined that the formed belite phase did not consist of the α'-C2S phase. Table 6: Phase analysis of boron-doped clinker 5 Phase Name R Percentage Al te M3 0.41 C3S <m1>0 C2S_beta 0 C2S_AlphaPr me_DelaTorre 72.95 C2S alpha 0.96 C2S gamma 0.12 C3A_cub c 3.04 C3A_orthorhomb c 1.39 Brownm ller te, Fe+3-bear ng, syn 11.32 Per klaz 1.12 L me 3.3 Portland 3.31 Aphth tal te 0.57 Arcan te 0.19 Langbe n te 1.04 Thenard te 0.19 C3A_monocl nc 0 Quartz 0.09 Rietveld analysis of clinker, which was fired with only fluorine added to the flour, after X-ray diffraction. The analysis is shown in Table 7. Fluorine-added clinker contains β- similar to Portland cement. It has been observed that the C2S phase can be stabilized, but fluorine can alter the eutectic point. It is possible to achieve liquid phase formation at earlier temperatures, and as a result, the specific heat dissipation is reduced to 10. It reduces. Table 7: Fluorine-doped clinker phase analysis Phase Name R Percentage Al te M3 51.65 7 C3S <m1>17.67 C2S_beta 9.40 C2S_AlphaPr me_DelaTorre 0.32 C2S alpha 0 C2S gamma 0 C3A_cub c 3.25 C3A_orthorhomb c 0.16 Brownm ller te, Fe+3-bear ng, syn 13.22 Per klaz 1.02 L me 0.63 Portland 0.14 Aphth tal te 1.40 Arcan te 0.06 Langbe n te 0.58 Thenard te 0.49 C3A_monocl nc 0 Quartz 0 Rietveld analysis of clinker, which is fired after adding boron and fluorine to the flour, was performed using X-ray diffraction. The analysis is shown in Table 8. Stabilization of the α'-C2S phase in boron and fluorine-doped clinker. It has been observed that this is possible and in this case, the C3S phase is also stabilized. Table 8: Phase analysis of boron and fluorine-doped clinker 5 Phase Name R Percentage Al te M3 45.2 C3S <m1>15.34 C2S_beta 5.36 C2S_AlphaPr me_DelaTorre 13.87 C2S alpha 0.73 C2S gamma 0 C3A_cub c 3.72 C3A_orthorhomb c 0.4 Brownm ller te, Fe+3- bear ng, syn 12.26 Per class 0.81 L me 0.31 Portland 0.02 Aphth tal te 0.71 Arcan te 0.22 Langbe n te 0.44 Thenard te 0.62 C3A_monocl nc 0 Quartz 0 8 Tests were conducted according to TS-EN 196-1 to compare the compressive strengths of the obtained clinkers. This was performed and the results are shown in Table 9. The specific surface area is the specific surface value. To determine this, the tests were carried out according to TS EN 196-6. The tests were in the range of 3100-3200 cm2 / gr. This process has been repeated. Table 9 shows the result of one of the examples. All clinkers conform to TS EN 196-1. In compressive strength tests, the maximum SO3 content is 3.5% in accordance with the TS EN 197-1 standard. It was ground with a sulfate source in such a way as to be. OPC (Ordinary Portland Cement) is a fluorine-modified, boron and fluorine-modified clinker. In order to make a comparison, the grinding process will be carried out in such a way that they have the same specific surface area values. It has been done. Even though boron-added clinker has a higher specific surface area value, the first day pressure While it could not demonstrate the required strength, it showed a compressive strength of 26.6 MPa in 28 days. Due to its high CaO content... Therefore, the volume expansion was found to be 40 mm. It exhibits low strength and high volume. Its expansion exhibited unsatisfactory properties according to TS EN 196-3 standards. This was only the case with fluorine-added clinker. However, some improvement was observed compared to OPC clinker. This was obtained in clinker with boron and fluorine additives. Improved low strength properties and approximately 20% increase in 28-day strength compared to OPC clinker. It varies between 48-54 MPa. In the example in Table 9, this value is 53.0 MPa. This increase is 15 Thanks to this invention, it is possible for C3S and α'-C2S phases to be present simultaneously in the clinker. This is due to the fact that two phases with a high degree of hydration have a faster hydraulic binding property. By demonstrating this, it has enabled the achievement of higher strength in 28 days. However, TS EN Since experiments were carried out according to 196-1, no chemical or mineral additives were included in the clinkers. No improvements in product performance using chemical or mineral additives have been made. 20 This is achievable, therefore it is possible to reach higher values ​​in all strength classes. The same applies to the specific surface area. As the specific surface area increases, the surface area also increases. achieving higher strength in all strength classes at high specific surface values It is possible. In boron-added clinker, the volume expansion is 40 mm according to the standard TS EN 196-3. While previously having invalid values, this problem has been resolved in clinker with boron and fluorine additives, and it conforms to the TS EN 196-3 standard. It has been made suitable. In addition, the specific heat consumption of boron and fluorine-added clinker is similar to that of Portland. Compared to cement clinker, it provides 2-6% energy savings. It also produces lower heat. By reducing its consumption, it lowers the heat required for cooking and provides greater compressive strength in 28 days. By demonstrating its ability to reduce the clinker binding factor, it can lower CO2 emissions during production. It provides a reduction. In the boron and fluorine-modified clinker composition that is the subject of the invention, 30 in the example given in Table 9. Although the start time is shown as 230 minutes and the end time as 360 minutes, tests have shown that these values ​​are not accurate. The average duration was observed to be 175 minutes and 320 minutes, respectively. 35 9 Table 9: Comparison of clinkers according to TS EN 196-1 and TS EN 196-3 OPC Boron-Doped Fluorine-Doped Boron and Fluorine Additive Specific surface area (cm2 / g) 3112 3458 3130.00 3118 B1 (MPa) 17.5 - 16.2 12.4 B2 (MPa) 27.4 6.8 26.6 24.1 B7 (MPa) 37.2 15.0 39.9 42.9 B28 (MPa) 43.9 26.6 47.8 53.0 % water 24.2 23.8 24.4 24.2 P. Head (min) 145 220 205 230 P.End (min.) 215 340 330 360 Volume (mm) Width (mm) 1 40 1 1 B1: Compressive strength on day 1, B2: Compressive strength on day 2, B7: Compressive strength on day 7, B28: Compressive strength on day 28, P.Başı: Priz Start, End: Power Outage, Volume Expansion, mm: Volume expansion, millimeters References 5 [1] Rogue, RH and Lerch, William. (1934) 'Hydration of Portland cement compounds', Industrial and Engineering Chemistry, 26(8), pp. 837–847. doi:10.1021 / ie50296a007. [2] I. Jelenic, A. Bezjak, On the hydration kinetics of α′- and β- modifications of dicalcium silicate, 1981 [3] Fletcher, JG and Glasser, FP (1993) 'Phase relations in the system CaO-B2O3-SiO2', Journal of 10 Materials Science, 28(10), pp. 2677–2686. doi:10.1007 / bf00356203. [4] Thuan T. Tran, Duncan Herfort, Hans J. Jakobsen, And Jørgen Skibsted Site preferences of fluoride guest ions in the calcium silicate phases of Portland cement from 29Si{19F} CP-REDOR NMR spectroscopy, 2009

Claims

REQUESTS 1. It is a cement clinker with the following characteristics: 64-66.5% CaO, 20.5-21.5% SiO2, 5.3-5.8% by weight. Al2O3, 3.4-3.8% Fe2O3, 1.4-1.8% MgO, 0.5-1.5% SO3, 0.5-1.5% K2O, 0.1-0.5% Na2O, It contains 0.2-1% CaF2, 0.2-1% B2O3 and 52-65% C3S, 2-10% β-C2S, 5-25% α'-C2S, 5 with mineral phases of 2-8% C3A, 7-15% C4AF, 0.1-3% Lime and 0.1-3% Periclase. It is the fact that.

2. A method of clinker production, characterized by the process of producing clinker according to Claim 1. The ratio of CaF2 / B2O3 used should be between 0.8 and 1.

7.

3. A clinker production method according to Claim 2, characterized by the use of certain methods during production. The CaF2 / B2O3 ratio should preferably be between 0.9 and 1.

5. 10 4. According to claim 1, it is clinker with a specific surface area of ​​3100-3200 cm2 / gr on the 28th day. It has a pressure value of 48-54 MPa.

5. According to claim 1, it is clinker with a specific surface area of ​​3100-3200 cm2 / gr and a setting point. The average length of the start is 175 minutes.

6. According to claim 1, it is clinker with a specific surface area of ​​3100-3200 cm2 / gr and a setting time of 15. The average length of the final product is 320 minutes.

7. It is a cement, and its characteristic is that it is produced using clinker according to Claim 1.

8. It is Portland cement and its characteristic is that it contains cement clinker according to Claim 1. 25 35 40