High-volume industrial waste residue cement mineralization activity exciting agent as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of cement additives, and discloses a high-dosage industrial waste residue cement mineralization activity activator, which comprises a grinding aid and a mineralization enhancer, the grinding aid comprises bio-based alcohol amine, molasses, alpha-olefin sodium sulfonate and water; the mineralization enhancer comprises sodium thiosulfate, sodium thiocyanate, sodium formate and calcium sulfite type desulfurized gypsum. The cement mineralization activity exciting agent is applied to a cement grinding section, a grinding aid and a mineralization enhancer are synchronously doped, and the grinding aid and the mineralization enhancer form a synergistic superimposed effect, so that the technical problem of low 3d strength of cement is solved, and the strength of each age is stably improved by exciting the early hydration activity of the cement and a mixed material.

Description

Technical Field

[0001] The present invention belongs to the technical field of cement additives, and particularly relates to a high-amount industrial waste residue cement mineralization activity activator, a preparation method and an application thereof. Background Art

[0002] With the development of new material modification technology, the application of industrial solid waste in the fields of building materials, road engineering and mine backfilling is gradually expanding. In the process of cement production, the process energy consumption is high and the carbon emission is large. Industrial solid wastes such as fly ash, slag and tailing slag can be used as admixtures for cement after appropriate treatment, which can not only improve the resource utilization efficiency, reduce the production cost, but also reduce carbon emissions. Therefore, using industrial waste residues as cement admixtures to produce cement products is a high-quality comprehensive utilization of industrial solid wastes and an important way for the current cement industry to reduce carbon emissions. Industrial solid wastes such as fly ash, smelting slag and limestone tailings can be hydrated and hardened under the excitation of a mineralizer and the induction of cement hydration, but the strength development rate is relatively slow. As a result, the 28-day strength value of the cement of cement enterprises can meet the requirements specified in GB175-2023 "Common Portland Cement", but the 3-day strength is low, and sometimes the 3-day strength does not meet the standard. Based on this, we propose a high-amount industrial waste residue cement mineralization activity activator, a preparation method and an application thereof. Summary of the Invention

[0003] The first object of the present invention is to provide a high-amount industrial waste residue cement mineralization activity activator to solve the technical problem of low 3-day strength of cement.

[0004] A high-amount industrial waste residue cement mineralization activity activator includes a grinding aid and a mineralization enhancer. Among them, the grinding aid includes bio-based alkanolamine, molasses, α-olefin sulfonate and water; the mineralization enhancer includes sodium thiosulfate, sodium thiocyanate, sodium formate and calcium sulfite type desulfurized gypsum.

[0005] Preferably, the grinding aid is composed of the following components in parts by weight: 24-26 parts of bio-based alkanolamine, 19-21 parts of molasses, 4-6 parts of α-olefin sulfonate and 50 parts of water.

[0006] Preferably, the grinding aid is composed of the following components in parts by weight: 25 parts of bio-based alkanolamine, 20 parts of molasses, 5 parts of α-olefin sulfonate and 50 parts of water.

[0007] Preferably, the mineralization enhancer is composed of the following components in parts by weight: 9-11 parts of sodium thiosulfate, 19-21 parts of sodium thiocyanate, 19-21 parts of sodium formate and 49-51 parts of calcium sulfite type desulfurized gypsum.

[0008] Preferably, the mineralization enhancer is composed of the following components in parts by weight: 10 parts of sodium thiosulfate, 20 parts of sodium thiocyanate, 20 parts of sodium formate, and 50 parts of calcium sulfite type desulfurized gypsum.

[0009] The second object of the present invention is to provide a preparation method of a mineralization activity activator for high-volume industrial waste residue cement, which is used to prepare the above-mentioned mineralization activity activator for high-volume industrial waste residue cement. The specific steps are as follows: (1) Preparation of grinding aid: Stir biobased alkanolamine, molasses, α-olefin sulfonate, and water for 15 - 20 min, mix evenly, and let stand for 2 hours to obtain the grinding aid.

[0010] (2) Preparation of mineralization enhancer: Put sodium thiosulfate, sodium thiocyanate, sodium formate, and calcium sulfite type desulfurized gypsum into a ball mill mixer and grind and mix for 30 - 40 min to obtain the mineralization enhancer.

[0011] The third object of the present invention is to apply the above-mentioned mineralization activity activator for high-volume industrial waste residue cement to the cement grinding process, synchronously adding 0.45 - 0.55 kg of grinding aid and 0.45 - 0.55 kg of mineralization enhancer per ton of cement, and grinding the cement to the specified fineness.

[0012] Preferably, 0.5 kg of grinding aid and 0.5 kg of mineralization enhancer are added per ton of cement.

[0013] Compared with the disadvantages and deficiencies of the prior art, the present invention has the following beneficial effects: The present invention provides a mineralization activity activator for high-volume industrial waste residue cement, which adopts a two-component system of grinding aid and mineralization enhancer. The mineralization activity activation uses sodium thiosulfate, sodium thiocyanate, sodium formate, and calcium sulfite type desulfurized gypsum, providing sulfur in different forms for the cement hydration environment. Sulfate ions can react with industrial waste residues to form new minerals such as ettringite, filling the voids of cement shrinkage cracks, changing the microstructural defects, and increasing the macroscopic strength. In particular, the sulfite ion structure has high activity characteristics. The sulfite ion structure is trigonal pyramidal, belonging to a weak acid root, and has strong reducibility, which can promote the rearrangement and exchange of ions in the cement hydration system, thus accelerating the destruction of the vitreous structure of industrial waste residues such as fly ash, exposing the silicon-oxygen tetrahedrons, providing more active sites for subsequent hydration reactions, and effectively activating the hydration activity of smelting waste residues such as fly ash. Under the induction of the cement hydration environment, it forms hydration products such as ettringite or C-S-H type cement minerals with calcium hydroxide, significantly improving the early strength. At the same time, the cement grinding aid uses biobased alkanolamine, molasses, and α-olefin sulfonate, which can effectively improve the fineness of cement, especially increasing the content of particles below 45 μm, and has a significant effect on improving the 3d strength. Therefore, the components of the grinding aid and the mineralization enhancer form a synergistic superposition effect, stably improving the strength at each age. Detailed implementation manners

[0014] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0015] A high-dosage industrial waste residue cement mineralization activity activator includes two components: a grinding aid and a mineralization enhancer. Among them, the grinding aid includes bio-based alkanolamine, molasses, α-olefin sulfonate and water; the mineralization enhancer includes sodium thiosulfate, sodium thiocyanate, sodium formate and calcium sulfite type desulfurized gypsum.

[0016] The grinding aid is composed of the following components in parts by weight: 24-26 parts of bio-based alkanolamine, 19-21 parts of molasses, 4-6 parts of α-olefin sulfonate and 50 parts of water.

[0017] Preparation method of the grinding aid: Stir 24-26 parts of bio-based alkanolamine, 19-21 parts of molasses, 4-6 parts of α-olefin sulfonate and 50 parts of water for 15-20 min, mix evenly, and let stand for 2 hours to obtain the grinding aid.

[0018] The mineralization enhancer is composed of the following components in parts by weight: 9-11 parts of sodium thiosulfate, 19-21 parts of sodium thiocyanate, 19-21 parts of sodium formate and 49-51 parts of calcium sulfite type desulfurized gypsum.

[0019] Preparation method of the mineralization enhancer: Put 9-11 parts of sodium thiosulfate, 19-21 parts of sodium thiocyanate, 19-21 parts of sodium formate and 49-51 parts of calcium sulfite type desulfurized gypsum into a ball mill mixer and grind and mix for 30-40 min to obtain it.

[0020] Apply the above high-dosage industrial waste residue cement mineralization activity activator to the cement grinding process, synchronously add the grinding aid and the mineralization enhancer, and grind the cement to the specified fineness.

[0021] Add 0.45-0.55 kg of the grinding aid and 0.45-0.55 kg of the mineralization enhancer to each ton of cement respectively. The cement production mix ratio in each embodiment is: 750 kg of cement clinker, 100 kg of fly ash, 50 kg of slag, 50 kg of limestone, and 50 kg of gypsum.

[0022] Example 1 Preparation of the grinding aid: Stir 24 parts of bio-based alkanolamine, 20 parts of molasses, 6 parts of α-olefin sulfonate and 50 parts of water for 18 min, mix evenly, and let stand for 2 hours to obtain the grinding aid.

[0023] Preparation of mineralization enhancer: 9 parts of sodium thiosulfate, 21 parts of sodium thiocyanate, 21 parts of sodium formate and 49 parts of calcium sulfite type desulfurized gypsum are put into a small ball mill mixer and ground and mixed for 35 minutes to obtain the mineralization enhancer.

[0024] In the cement grinding process, 0.45 kg of grinding aid and 0.55 kg of mineralizer are added synchronously per ton of cement, and the cement is ground to the specified fineness.

[0025] Example 2 Preparation of grinding aid: 26 parts of bio-based alkanolamine, 20 parts of molasses, 4 parts of α-olefin sulfonate and 50 parts of water are stirred for 18 minutes, mixed evenly, and left standing for 2 hours to obtain the grinding aid.

[0026] Preparation of mineralization enhancer: 9 parts of sodium thiosulfate, 19 parts of sodium thiocyanate, 21 parts of sodium formate and 51 parts of calcium sulfite type desulfurized gypsum are put into a small ball mill mixer and ground and mixed for 35 minutes to obtain the mineralization enhancer.

[0027] In the cement grinding process, 0.5 kg of grinding aid and 0.5 kg of mineralizer are added synchronously per ton of cement, and the cement is ground to the specified fineness.

[0028] Example 3 Preparation of grinding aid: 25 parts of bio-based alkanolamine, 19 parts of molasses, 6 parts of α-olefin sulfonate and 50 parts of water are stirred for 18 minutes, mixed evenly, and left standing for 2 hours to obtain the grinding aid.

[0029] Preparation of mineralization enhancer: 11 parts of sodium thiosulfate, 20 parts of sodium thiocyanate, 19 parts of sodium formate and 50 parts of calcium sulfite type desulfurized gypsum are put into a small ball mill mixer and ground and mixed for 35 minutes to obtain the mineralization enhancer.

[0030] In the cement grinding process, 0.55 kg of grinding aid and 0.45 kg of mineralizer are added synchronously per ton of cement, and the cement is ground to the specified fineness.

[0031] Example 4 Preparation of grinding aid: 25 parts of bio-based alkanolamine, 21 parts of molasses, 4 parts of α-olefin sulfonate and 50 parts of water are stirred for 18 minutes, mixed evenly, and left standing for 2 hours to obtain the grinding aid.

[0032] Preparation of mineralization enhancer: 11 parts of sodium thiosulfate, 20 parts of sodium thiocyanate, 20 parts of sodium formate and 49 parts of calcium sulfite type desulfurized gypsum are put into a small ball mill mixer and ground and mixed for 35 minutes to obtain the mineralization enhancer.

[0033] In the cement grinding process, 0.45 kg of grinding aid and 0.55 kg of mineralizer are added synchronously per ton of cement, and the cement is ground to the specified fineness.

[0034] Example 5 Preparation of grinding aid: 24 parts of bio-based alkanolamine, 21 parts of molasses, 5 parts of α-olefin sulfonate and 50 parts of water are stirred for 18 min, mixed evenly, and left standing for 2 hours to obtain the grinding aid.

[0035] Preparation of mineralization enhancer: 10 parts of sodium thiosulfate, 20 parts of sodium thiocyanate, 19 parts of sodium formate and 51 parts of calcium sulfite type desulfurized gypsum are put into a small ball mill mixer and ground and mixed for 35 min to obtain the mineralization enhancer.

[0036] In the cement grinding process, 0.5 kg of grinding aid and 0.5 kg of mineralizer are added to each ton of cement synchronously, and the cement is ground to the specified fineness.

[0037] Example 6 Preparation of grinding aid: 25 parts of bio-based alkanolamine, 19 parts of molasses, 5 parts of α-olefin sulfonate and 50 parts of water are stirred for 18 min, mixed evenly, and left standing for 2 hours to obtain the grinding aid.

[0038] Preparation of mineralization enhancer: 10 parts of sodium thiosulfate, 21 parts of sodium thiocyanate, 19 parts of sodium formate and 50 parts of calcium sulfite type desulfurized gypsum are put into a small ball mill mixer and ground and mixed for 35 min to obtain the mineralization enhancer.

[0039] In the cement grinding process, 0.55 kg of grinding aid and 0.45 kg of mineralizer are added to each ton of cement synchronously, and the cement is ground to the specified fineness.

[0040] The cement prepared by the examples of the present invention is tested according to GB175-2023 "Common Portland Cement", and the test results are shown in Table 1.

[0041] Table 1: Test results of cement technical indicators It can be seen from the test data in Table 1 that when the admixture content of the cement reaches 20%, after adding the grinding aid and the mineralization enhancer, the 3d and 28d strengths of the cement both meet the specified values and the requirements of the surplus coefficient in GB175-2023 "Common Portland Cement".

[0042] The method for activating the activity of industrial waste residues added to the cement of this patent includes physical activation and chemical activation. The main measure of physical activation is the high-fineness grinding of the grinding aid, which not only increases the surface area of the hydration reaction but also destroys the original crystal structure of the waste residue, and the activity index is relatively high. The chemical activation of this patent is to use sodium thiosulfate, sodium thiocyanate and sodium formate to change the hydration environment of the waste residue, accelerate the breaking and dissolution of the silicon-oxygen-aluminum-oxygen bonds in the vitreous body or mineral components of the waste residue, thereby activating its activity. And under the induction of the cement hydration environment, it forms hydration products such as ettringite or C-S-H type cement minerals together with calcium hydroxide, significantly improving the early strength.

[0043] Thus, the industrial technical problem of low 3-day strength of cement under the condition of high content of industrial waste residue is solved. It can be seen from the data in Table 1 that the strength values at different ages all meet the national standard requirements, and the strength development is relatively stable. There is no situation where the 28-day strength decreases or does not increase after using the activator.

[0044] The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A high-dosage industrial waste slag cement mineralization activity activator, characterized in that: The invention comprises a grinding aid and a mineralization enhancer. The grinding aid comprises bio-based alcohol amine, molasses, sodium α-olefin sulfonate and water; and the mineralization enhancer comprises sodium thiosulfate, sodium thiocyanate, sodium formate and calcium sulfite type desulfurized gypsum.

2. The high-dosage industrial waste slag cement mineralization activity activator as claimed in claim 1, characterized in that: The grinding aid is composed of the following components in parts by weight: 24-26 parts of bio-based alcohol amine, 19-21 parts of molasses, 4-6 parts of sodium α-olefin sulfonate and 50 parts of water.

3. The high-dosage industrial waste slag cement mineralization activity activator as claimed in claim 1, characterized in that: The mineralization enhancer is composed of the following components in parts by weight: 9-11 parts of sodium sulfite, 19-21 parts of sodium thiocyanate, 19-21 parts of sodium formate and 49-51 parts of calcium sulfite type desulfurized gypsum.

4. The high-dosage industrial waste slag cement mineralization activity activator as claimed in claim 2, characterized in that: The grinding aid is composed of the following components in parts by weight: 25 parts of bio-based alcohol amine, 20 parts of molasses, 5 parts of sodium α-olefin sulfonate and 50 parts of water.

5. The high-dosage industrial waste slag cement mineralization activity activator as claimed in claim 3, characterized in that: The mineralization enhancer is composed of the following components in parts by weight: 10 parts of sodium sulfite, 20 parts of sodium thiocyanate, 20 parts of sodium formate and 50 parts of calcium sulfite type desulfurized gypsum.

6. A high-dosage industrial waste slag cement mineralization activity activator, used for preparing the high-dosage industrial waste slag cement mineralization activity activator as claimed in any one of claims 1 to 5, characterized in that: The steps include: (1) Preparation of grinding aid: stirring bio-based alcohol amine, molasses, sodium α-olefin sulfonate and water for 15-20 minutes, mixing evenly, and standing for 2 hours to prepare a grinding aid; (2) Preparation of mineralization enhancer: Sodium thiosulfate, sodium thiocyanate, sodium formate and calcium sulfite type desulfurized gypsum are placed in a ball mill mixer and ground and mixed for 30-40 minutes to obtain a mineralization enhancer.

7. An application of a high-dosage industrial waste slag cement mineralization activity activator, wherein the high-dosage industrial waste slag cement mineralization activity activator as claimed in any one of claims 1 to 5 is applied to a cement grinding process, characterized in that: 0.45~0.55kg of grinding aid and 0.45~0.55kg of mineralization enhancer are added simultaneously for every ton of cement.

8. The use of the high-dosage industrial waste slag cement mineralization activity activator as claimed in claim 7, characterized in that: Add 0.5kg of grinding aid and mineralizer to every ton of cement.

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