New generation diethanol isopropanol amine monohexanoate and / or diethanol isopropanol amine dihexanoate based grinding aid with high grinding efficiency, strength enhancer

Abstract

The present invention relates to the grinding aid used in the cement industry, in the clinker grinding phase of cement production and in the preparation of cementitious systems. In particular, the present invention relates to a grinding aid consisting of Diethanol isopropanol amine monohexanoate and / or Diethanol isopropanol amine monohexaonate composition obtained by esterification reaction of Diethanol isopropanol amine with hexanoic acid, and a method of synthesis.

Description

[0001] New Generation Diethanol Isopropanol Amine Monohexanoate And / Or Diethanol Isopropanol Amine Dihexanoate Based Grinding Aid With High Grinding Efficiency, Strength Enhancer

[0002] Field of the Invention

[0003] The present invention relates to the grinding aid used in the cement industry, in the clinker grinding phase of cement production and in the preparation of cementitious systems. In particular, the present invention relates to a grinding aid consisting of Diethanol isopropanol amine monohexanoate and / or Diethanol isopropanol amine dihexaonate composition obtained by esterification reaction of Diethanol isopropanol amine with hexanoic acid, and a method of synthesis.

[0004] State of the Art

[0005] Events such as greenhouse gas emissions, air pollution and climate change are among the main factors that cause global problems. In the process of solving these problems, issues such as developing alternatives to products that cause CO2 emissions during production, renewable energy sources and energy efficiency have gained importance.

[0006] The cement industry causes great damage to the environment in terms of energy, raw material consumption and CO2 emissions. The amount of electricity consumed in the cement industry constitutes 2% of the electricity used worldwide and 5% of the electricity used in industry. However, it accounts for 5-7% of global CO2 emissions. While approximately 1 ,2 tons of raw materials and 130 kWh of energy are consumed to produce one ton of cement, approximately 1 ton of CO2 is produced as a result. According to the Paris climate agreement, greenhouse gas emissions are expected to be reduced by 50% in 2030 and completely to zero in 2050. In this regard, energy efficiency is of great importance in the production processes of products that cause greenhouse gas emissions during production. In cement production, approximately 35% of the energy consumed is spent in the clinker grinding phase. In addition, a significant part of the energy consumed in the grinding stage is wasted by turning into heat, sound and vibration. As a result of the studies carried out to reduce both the energy consumption and cost in question and to reduce the amount of CO2 emitted to the environment, the use of grinding aid (GA) has come to the agenda.

[0007] GAs are adsorbed on the surfaces of grains with the help of high polarity functional groups (-OH, -NH2, -COOR, -SO3 etc.) they contain. Adsorbed GAs neutralize the electrical charges on the surface, preventing the cracks formed in the clinker from closing, preventing the particles from coming together and sticking to the mill surface and / or balls, thus ensuring grinding efficiency.

[0008] It is known that the cement grains produced by the use of GA have different surface energy even though they have the same Blaine fineness value. This situation significantly affects the hydration reactions of cement and cement-additive compatibility. In addition, it has been explained that cements produced by GA consist of smaller and smoother / angular-free grains. This situation may bring with it some negativities.

[0009] In the present art, cement grinding aids are typically selected from the class containing glycols, amines, or amino alcohols, such as alkylene glycols. For example, the European patent numbered EP4132895B1 relates to the compositions of partially protonated alkanolamines and their use in clinker grinding processes. It is stated here that Diethanol isopropanol amine can be used as alkanolamine.

[0010] However, with the developing technology, it has been determined that the performances of the existing GAs are insufficient and there is a significant gap in their development.

[0011] As a result due to the abovementioned disadvantages and the insufficiency of the current solutions regarding the subject matter, a development is required to be made in the relevant technical field. Purpose of the Invention

[0012] The present invention aims to solve the abovementioned disadvantages by being inspired from the current conditions.

[0013] The purpose of the present invention is to provide a new grinding aid with improved grinding performance by changing one or two of the hydroxyl groups in the commercially widely used Diethanol isopropanol amine (DEIPA) as a result of esterification reaction with organic acid, forming an ester of higher polarity.

[0014] Another purpose of the invention is to increase the grinding performance and cementitious system properties of the DEIPA used as a CCA while reducing the additive cost thanks to the grinding aid containing Diethanol isopropanol amine monohexaonate and / or Diethanol isopropanol amine hexaonate obtained as a result of the esterification reaction of Diethanol isopropanol amine with hexanoic acid.

[0015] In order to fulfill the aforementioned purposes, the invention is a new generation grinding aid with high grinding efficiency, strength enhancer, and comprise Diethanol isopropanol amine monohexaonate and / or Diethanol isopropanol amine dihexaonate obtained by esterification reaction of Diethanol isopropanol amine with hexaonic acid.

[0016] According to one embodiment, the invention may also contain Diethanol isopropanol amine and / or hexanoic acid.

[0017] According to an embodiment of the invention may comprise 27,3 % Diethanol isopropanol amine, 32,3 % hexanoic acid, 36,4 % Diethanol isopropanol amine monohexanoate and 4 % Diethanol isopropanol amine dihexanoate by weight.

[0018] In order to fulfill the purposes described above, the invention is a new generation grinding aid synthesis method with high grinding efficiency, strength enhancer, characterized by comprising the following process steps; i. Evaporation of water by heating diethanol isopropanol amine; ii. Lowering the temperature of the heated Diethanol isopropanol amine to 50-60 degrees Celsius and adding half of the hexanoic acid dropwise; iii. Then, heating again and adding catalyst before the temperature reaches 80 degrees Celsius; iv. Adding the remaining hexaonic acid dropwise; v. Continuing the reaction at approximately 105-115 degrees Celsius and removing the water formed with the ester by applying vacuum repeatedly after the second hour.

[0019] According to an embodiment of the invention, 40-50% Diethanol isopropanol amine, 47-57% Hexanoic acid, 1 -3% catalyst by weight can be used in the synthesis method.

[0020] According to an embodiment of the invention, 46% Diethanol isopropanol amine, 52% hexanoic acid and 2% catalyst by weight can be used.

[0021] According to one embodiment of the invention, sulfuric acid can be used as the catalyst.

[0022] According to one embodiment of the invention, the reaction can be continued at about 1 14 degrees Celsius.

[0023] According to one embodiment of the invention, the reaction can be continued for 3 hours.

[0024] According to an embodiment of the invention, after the second hour of the reaction, vacuum is applied every 15 minutes and the water formed with the ester is removed.

[0025] The structural and characteristic features of the present invention will be understood clearly by the following figures and the detailed description made with reference to these figures and therefore the evaluation shall be made by taking these figures and the detailed description into consideration.

[0026] Figures to Help Understanding the Invention

[0027] Figure 2. a. DEIPA, 1 b. theoretical modeling of the M-DEIPA of the present invention.

[0028] Figure 2. FTIR analysis result graph of M-DEIPA of the present invention.

[0029] Figure 3. GC-MS chromatogram of the M-DEIPA molecules of the present invention and the DEIPA.

[0030] Figure 4.13C NMR spectrum of the M-DEIPA molecule of the present invention. Figure 5.13C NMR spectrum of hexanoic acid suggested by the chemdraw program.

[0031] Figure 6. DEIPA monohexanoate synthesis scheme.

[0032] Figure 7. Graph of relative grinding efficiencies of DEIPA and M-DEIPA.

[0033] Figure 8. Relative flow and consistency retention performance graph.

[0034] Detailed Description of the Invention

[0035] In this detailed description, the inventive modified DEIPA-containing grinding aid and preferred embodiments thereof are described only for a better understanding of the subject matter.

[0036] The invention relates to a new generation Diethanol isopropanol amine monohexaonate and / or Diethanol isopropanol amine dihexaonate based grinding aid with high grinding efficiency, strength enhancer, obtained by esterification reaction of Diethanol isopropanol amine with hexanoic acid and synthesis method.

[0037] The inventive method for the production of diethanol isopropanol amine monohexaonate and / or diethanol isopropanol amine dihexaonate based grinding aid comprises the following process steps. i. Evaporation of its water by heating diethanol isopropanol amine; ii. Lowering the temperature of the heated Diethanol isopropanol amine to 50-60 degrees Celsius and adding half of the hexanoic acid dropwise; iii. Then, heating again and adding catalyst before the temperature reaches 80 degrees Celsius; iv. Adding the remaining hexaonic acid dropwise; v. Continuing the reaction at 105-1 15 degrees Celsius and removing the water formed with the ester by applying vacuum repeatedly after the second hour.

[0038] In the method of the invention, the presence of process step (i) is necessary to increase the degree of realization of the reaction. Since water is formed as a result of esterification, the presence of water in the environment affects the degree and speed of the reaction. DEIPA boiling point is 145 C. Heating up to 100 C can be done to remove water.

[0039] In the process step (ii) of the method of the invention, if hexanoic acid is suddenly added, a titration reaction may occur. That's why it should be added slowly. Hexanoic acid should not be added when the temperature of DEIPA is above 80 degrees. Chemicals added to the reactor should be added dropwise.

[0040] In the process step (iii) of the method of the invention,, the highest efficiency was achieved when sulfuric acid was used as the catalyst. In order for sulfuric acid to function as a catalyst, the temperature should not exceed 80 degrees at the time of addition.

[0041] In the process step (iv) of the method of the invention, the remainder of the hexanoic acid is added slowly in order for the esterification reaction to occur successfully.

[0042] In the process step (v) of the method of the invention, reaction time and reaction temperature are the parameters that must be taken into consideration for the formation of reaction products. In the method of the present invention, the highest efficiency was achieved by continuing the reaction at about 110 C for 3 hours and vacuuming every 15 minutes after the second hour to remove the water formed with the ester.

[0043] In order to achieve an efficient reaction within the scope of the invention, 40-50% Diethanol isopropanol amine, 47-57% Hexanoic acid, 1-3% Sulfuric acid by weight are used in the total input composition.

[0044] In a preferred embodiment of the invention, 46% Diethanol isopropanol amine, 52% Hexanoic acid, 2% Sulfuric acid by weight are used in the total input composition.

[0045] Diethanol isopropanol amine is widely used as GA. DEIPA comprises 3 OH groups. Since the carboxyl group contained in acetic acid has a higher polarity than the OH group, modified DEIPA is synthesized by replacing the saddle with the OH group in the esterification reaction. Preliminary tests were carried out to ensure suitable conditions for the synthesis to occur, and it was determined that the temperature should be kept around 110 degrees and sulfuric acid should be used as a catalyst. DEIPA monohexaonate, formed as a result of the DEIPA esterification reaction, was carried out according to the synthesis scheme shown below.

[0046] DEIPA monohexaonate

[0047] In alternative applications, esters with higher polarity can be created by modifying the functional groups of GAs comprising hydroxyl groups with this method.

[0048] Experimental Studies

[0049] First of all, 0,7:0, 8 molar DEIPA:Hexanoic acid and 2% of the total mass of sulfuric acid were weighed. First, the water contained in the DEIPA solution was separated. Then, the temperature of the DEIPA was expected to drop to 50-60 degrees. When the temperature reached the desired level, half of the hexanoic acid was added to the DEIPA and the temperature began to be increased while the mixing process continued with the help of a magnetic fish. Sulfuric acid was added dropwise before the temperature reached 80 degrees. After the reaction continued for a while, the remaining hexanoic acid was added dropwise. The temperature was fixed at 110 degrees and the reaction was continued for 3 hours. At the end of 2 hours, the water resulting from the ester formed was removed from the environment by vacuuming. The reaction was terminated when no water was seen coming out of the vacuum after 3 hours.

[0050] Analysis Results

[0051] The structures of DEIPA and M-DEIPA molecules were modeled, and the electron densities of the molecules and the charge values of the electronegative atoms were calculated. By establishing a connection between these calculations and the adsorption power, the grinding aiding powers of the obtained materials were evaluated, and it was aimed to theoretically support the experimental results obtained.

[0052] In this context, the Gaussian 09 program, which has been used extensively by chemists in recent years, was used. The optimizations of the molecules were made in the gas phase environment using the DFT / B3LYP method and the 6-311 ++G(d,p) basis set. Additionally, nbo loads were calculated using the pop=nbo keyword. The optimized structures of the resulting molecules are given in Figure 1 . As can be seen from the figure, the Modified DEIPA molecule subject to the invention has a higher electronegativity value.

[0053] Various analyzes were carried out to prove that the synthesized aid was successfully synthesized. The results and comments of the analyzes are given below.

[0054] Fourier Transform Infrared Spectroscopy (FTIR) Analysis

[0055] The pH value of the synthesized M-DEIPA was measured as 5,36 by pH meter. The FTIR analysis result of the synthesized aid is shown in Figure 2.

[0056] The fact that the carbonyl stretching vibration observed around 1700 cm-1in hexanoic acid and the diffuse OH band observed around 3300 cm'1in the spectrum of the DEIPA molecule were observed simultaneously in the FTIR spectrum of the M-DEIPA molecule supports the formation of the inventive M-DEIPA molecule as a result of the synthesis.

[0057] Gas chromatography mass spectrometry (GC-MS) Analysis

[0058] In order to confirm that the synthesis product was realized, GC-MS spectra of DEIPA and M-DEIPA molecules were taken. A method suitable for similar molecules has been determined in the literature. The resulting GC-MS chromatogram is given in Figure 4. The black chromatogram given in Figure 4 belongs to the DEIPA molecule, and the red chromatogram belongs to the product. When the black chromatogram is scanned in the device library, it is seen that it belongs to DEIPA. However, no equivalent of the chromatogram of the product was found in the library. However, when both chromatograms were compared, a new peak was observed at the 8th and 25th minute. It was determined that in this peak environment, there was a product other than DEIPA with a larger molecular weight than DEIPA.

[0059] These results support that the modified ester molecule is formed in both 1 :1 and 1 :2 ratios (Table 2).

[0060] Table 1 . Percentages of the products formed and the minutes visible in the GC-MS analysis

[0061] Nuclear Magnetic Resonance Spectroscopy (NMR) Analysis

[0062] Finally,13C-NMR analysis was performed on the product to support that the product obtained as a result of the reaction was M-DEIPA. The obtained13C NMR spectrum is shown in Figure 5.

[0063] The spectra obtained by theoretical modeling of the13C NMR spectra of the starting materials hexanoic acid and DEIPA molecules and the product M-DEIPA molecule are given in Figures 5-6. When the spectra of the modeled molecules are examined, it is expected that the carbon peak of hexanoic acid will be observed only at a value of approximately 178 ppm. However, two carbon peaks at 172 and 40ppm were observed in the experimental spectrum in Figure 4. These results support that the M-TIPA molecule was obtained. According to the low peak observed at 172 ppm in the spectrum, it is thought that the molecule with a DEIPA:hexanoic acid ratio of 1 :2 is present in the environment. Grinding Performance of Modified DEIPA

[0064] The grinding performance of the modified DEIPA according to dosage is given in Table 2. The relative grinding efficiencies of DEIPA and Modified DEIPA compared to the control cement without GA are shown in Figure 7.

[0065] Table 2. Grinding Performance of Modified DEIPA

[0066] Number of Grinding Energy Relative revolutions Time (min) Spent (kWh) Energy Blaine required for for target Efficiency fineness target Blaine (%) value Blaine fineness

[0067] (cm2 / g) fineness

[0068] Control 3950 8830 126.1 52.96

[0069] DEIPA-0.025 3805 8300 118.6 49.78 6.00

[0070] DEIPA-0.05 3915 8050 115.0 48.28 8.83

[0071] DEIPA-0.1 3988 8200 117.1 49.18 7.13

[0072] M-DEIPA-0.025 3752 8200 117.1 49.18 7.13

[0073] M-DEIPA-0.05 3860 8000 114.3 47.98 9.40

[0074] M-DEIPA-0.1 3820 7310 104.4 43.84 17.21 As can be seen from the table and figure, the modification process applied to the DEIPA increased the grinding efficiency by approximately 50% compared to DEIPA.

[0075] The presence of both DEIPA, mono ester and diester, and hexanoic acid in the product obtained as a result of the synthesis can be seen from the analysis results. It has been observed that the chemicals present in the resulting product show an unpredictable synergistic effect, causing an increase in performance.

[0076] It has been determined that the obtained aid give positive results not only in grinding performance but also in flow and mechanical performances. The flow performance of the resulting product is shown in Table 3. Table 3. PCE requirement and time-dependent flow values of mortar mixtures for target flow (20±2 cm)

[0077] Flow values at a constant PCE dosage (cm)

[0078] PCE Requirement for 40 60

[0079] 0 min 20 min

[0080] Target Flow (%) min min

[0081] Control 0.12 24.0 19.5 20 16.8

[0082] DEIPA-0.025 0.12 22 16.3 15.8 14.2

[0083] DEIPA-0.05 0.13 24.5 17.4 16.3 13.9

[0084] DEIPA-0.1 0.13 21.8 16.9 15.6 13.8

[0085] M-DE I PA-0.025 0.1 21.4 18.6 16.9 15.4

[0086] M-DE I PA-0.05 0.05 22.8 18.2 16.8 14.5

[0087] M-DE I PA-0.1 0.09 21.2 18.8 17.2 15.2

[0088] As seen in figure and table, the fact that the modified aid causes less PCE requirement for the target flow value and positively affects the thickening performance is thought to be due to the synergistic effect of the additive ingredients.

[0089] In Table 4, the 28-day compressive strength of the additives and their relative values compared to the control mixture are given.

[0090] Table 4. 28-day compressive strength values of mixtures

[0091] Compressive Relative

[0092] Strength Compressive Streng

[0093] (MPa) (%)

[0094] Control 43.15 100

[0095] DEIPA-0.025 51.05 105.7

[0096] DEIPA-0.05 44.45 92.0

[0097] DEIPA-0.1 51.25 106.1

[0098] M-DEIPA-0.025 53.55 110.9

[0099] M-DEIPA-0.05 54.85 113.6

[0100] M-DEIPA-0.1 47.5 98.3

Claims

CLAIMS1. A new generation grinding aid with high grinding efficiency, strength enhancer, characterized by comprising; Diethanol isopropanol amine monohexaonate and / or Diethanol isopropanol amine dihexaonate obtained by esterification reaction of Diethanol isopropanol amine with hexaonic acid.

2. The grinding aid according to claim 1 , characterized by comprising Diethanol isopropanol amine and / or hexanoic acid.

3. The grinding aid according to claim 2, characterized by comprising; 27,3% Diethanol isopropanol amine, 32,3% hexanoic acid, 36,4% Diethanol isopropanol amine monohexanoate and 4% Diethanol isopropanol amine dihexanoate by weight.

4. A new generation grinding aid synthesis method with high grinding efficiency, strength enhancer, characterized by comprising the following process steps; i. Evaporation of its water by heating diethanol isopropanol amine; ii. Lowering the temperature of the heated Diethanol isopropanol amine to 50-60 degrees Celsius and adding half of the hexanoic acid dropwise; iii. Then, heating again and adding catalyst before the temperature reaches 80 degrees Celsius; iv. Adding the remaining hexaonic acid dropwise; v. Continuing the reaction at approximately 105-115 degrees Celsius and removing the water formed with the ester by applying vacuum repeatedly after the second hour.

5. The method according to claim 4, characterized in that; 40-50% Diethanol isopropanol amine, 47-57% Hexanoic acid, 1-3% catalyst by weight are used.

6. The method according to claim 4, characterized in that; 46% Diethanol isopropanol amine, 52% Hexanoic acid, 2% catalyst by weight are used.

7. The method according to claim 4, characterized in that; sulfuric acid is used as catalyst.

8. The method according to claim 4, characterized in that; the reaction is continued at about 110 ‘C.

9. The method according to claim 4, characterized in that; the reaction is continued for 3 hours.

10. The method according to claim 4, characterized in that; the water formed together with the ester is drawn off by vacuuming every 15 minutes after the second hour of the reaction.

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