A liquid cement mineralizer and method of use thereof

Abstract

The application provides a liquid cement mineralizer and a use method thereof, and belongs to the technical field of cement. The liquid cement mineralizer comprises liquid reagent A and emulsion liquid reagent B. The liquid reagent A is prepared by the following steps: concentrating fluorine-containing acid waste liquid, adding industrial waste sulfuric acid, and filtering. The emulsion liquid reagent B is a quicklime suspension emulsion. The raw material of the application has a wide source, the preparation method is simple, the prepared liquid cement mineralizer is convenient to store and use, the mineralization effect is good, the uniformity of the prepared cement clinker is better, the comprehensive performance is improved, and the application prospect is wide.

Description

Technical Field

[0001] This invention relates to the field of cement technology, specifically to a liquid cement mineralizer and its application method. Background Technology

[0002] Silicate cement is mainly composed of clinker, and the properties of clinker play a crucial role in cement production. The rate of combustion and the sufficiency of chemical reactions during the clinker's reaction directly affect its yield, quality, and energy consumption. The calcination of cement clinker primarily involves the decomposition of carbonates, followed by a solid-phase reaction. As the temperature rises and a liquid phase appears, a final solid-liquid reaction occurs. During clinker production, processes such as the decomposition of CaCO3 and the formation of the liquid phase consume significant amounts of energy, and the reaction rates are relatively slow, thus impacting clinker yield and quality. Adding a small amount of mineralizer to the raw meal before calcination can improve the burnability of the raw meal, increase clinker yield and quality, and reduce energy consumption.

[0003] Mineralizers are classified into single mineralizers and composite mineralizers according to their admixture type. Single mineralizers are those that act as mineralizers on their own (most commonly CaF2), while composite mineralizers are those used simultaneously with two or more mineralizers (such as CaSO4 and CaF2; BaSO4 and CaF2, etc.). Generally speaking, the mineralization effect of a properly proportioned composite mineralizer is better than that of a single mineralizer. The addition of mineralizers has multiple effects on clinker firing: promoting the decomposition of carbonates; accelerating the decomposition of alkali feldspar and mica; enhancing the volatilization of alkali oxides; promoting the breaking of Si-O bonds in crystalline silica (quartz, flint); reducing the viscosity of the liquid phase during clinker formation and increasing the amount of liquid phase; promoting solid-phase reactions; facilitating C3S formation; and lowering the firing temperature, etc.

[0004] However, commonly used cement mineralizers currently have problems such as being environmentally unfriendly and failing to fully utilize industrial waste, making it difficult to meet the requirements of low-carbon and environmental protection. Cement production is a high-energy-consuming and high-carbon-emission industry, and low-carbon, energy-saving, and green production are the core directions for the industry's transformation and upgrading. Existing mineralizers are unable to simultaneously address solid waste utilization and carbon reduction, and cannot meet the technological needs of the cement industry's low-carbon development. In addition, with the development of green building materials, marine cement, new wall materials, and lightweight building materials are placing higher demands on the performance and low-carbon preparation of cementitious clinker, and existing mineralizers are difficult to adapt to the coordinated upgrading of building materials in multiple scenarios. The photovoltaic, semiconductor, and phosphate chemical industries generate a large amount of HF / H2SiF6 waste liquid, which has high disposal costs and significant environmental risks. If these waste liquids can be recycled and utilized through preparation processes, it will not only solve environmental problems but also enable waste utilization and increase the added value of waste materials. Summary of the Invention

[0005] The purpose of this invention is to propose a liquid cement mineralizer and its application method, which is convenient for storage and use, turns industrial waste into treasure, reduces production costs, increases the added value of waste materials, and at the same time has a good mineralization effect, is energy-saving and environmentally friendly, produces cement clinker with better uniformity, and improves overall performance.

[0006] The technical solution of this invention is implemented as follows: This invention provides a liquid cement mineralizer, comprising liquid reagent A and emulsion reagent B. Liquid reagent A is prepared by concentrating a fluoride-containing acidic waste liquid, adding industrial waste sulfuric acid, and filtering. Emulsion reagent B is a quicklime suspension emulsion.

[0007] As a further improvement of the present invention, the mass ratio of the liquid reagent A to the emulsion reagent B is 1:0.1-0.5.

[0008] As a further improvement of the present invention, the liquid reagent A has a fluoride ion concentration of 10-15 g / L, a sulfate ion concentration of 15-40 g / L, and a pH value of 1-3.

[0009] As a further improvement of the present invention, in the liquid reagent A, the fluorinated acidic waste liquid is photovoltaic waste liquid with a fluoride ion concentration of 80-150 mg / L, and the concentration of the industrial waste sulfuric acid is 50-98 wt%.

[0010] As a further improvement of the present invention, the concentration of CaO in the emulsion reagent B is 100-300 g / L.

[0011] As a further improvement of the present invention, solid powder C is added, the amount of which is 1-5 wt% of liquid reagent A. The preparation method of solid powder C is as follows: S1. After uniformly mixing glucose aqueous solution, polyvinyl alcohol, and initiator, cerium oxide and styrene monomer are added. The mixture is heated and stirred under an inert gas atmosphere, centrifuged, washed, and dried to obtain cerium oxide / PS microspheres. S2. Cerium oxide / PS microspheres, water, ethanol, pore-forming agent, and ammonia are mixed evenly, heated and stirred, then alkyl orthosilicate is added, the mixture is stirred and reacted, centrifuged, washed, and dried to obtain cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure. S3. Under an inert atmosphere, cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure were added to a dichloromethane solution containing chlorosulfonic acid, heated under reflux with stirring, centrifuged, washed, and dried to obtain solid powder C.

[0012] During the experiment, the inventors discovered that adding a very small amount of rare earth oxides could significantly improve the mineralization effect of cement. However, directly adding rare earth oxides, such as cerium oxide, to the liquid mineralizer of this invention results in a rapid reaction under acidic conditions or a reaction with fluoride ions to form cerium fluoride precipitate, leading to complete failure. Therefore, the inventors used modern microsphere preparation technology to encapsulate and protect cerium oxide. First, cerium oxide / PS microspheres were prepared by encapsulating cerium oxide in polystyrene. These microspheres can withstand acidic conditions and fluoride ions well. However, because polystyrene is incompatible in aqueous solution and easily precipitates, the addition of cerium oxide is uneven, affecting the performance of cement clinker. Therefore, the inventors considered sulfonating the surface of polystyrene by adding a dichloromethane solution containing chlorosulfonic acid to the surface to introduce sulfonic acid groups, thereby improving hydrophilicity and achieving uniform dispersion in the aqueous phase.

[0013] However, polystyrene is an organic polymer that readily swells and ruptures in dichloromethane solution, leading to encapsulation failure. Therefore, the inventors encapsulated a silica shell on its surface to obtain cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure, forming mesopores. Through these mesopores, the surface of the polystyrene core can be locally sulfonated, making it less prone to swelling and rupture, thus producing solid powder C.

[0014] When the solid powder is added to the liquid mineralizer, the sulfonic acid groups on its surface and the hydrophilic effect of the SiO2 layer ensure uniform dispersion in the aqueous system. Since the solid powder is added after the reaction of the acidic liquid reagent A and the emulsion reagent B, the presence of a small amount of HF in the system may have a certain etching effect on the SiO2 layer. The mesoporous SiO2 layer can withstand low concentrations of HF in the short term, providing a primary barrier. Once the core is exposed, the sulfonated polystyrene shell can still protect the inner cerium oxide from contact with fluoride ions, while the sulfonic acid groups on the surface maintain their hydrophilicity. During calcination, HF easily escapes, reducing the concentration of free fluoride ions in the system. Simultaneously, the polystyrene layer undergoes pyrolysis during calcination, allowing cerium oxide to enter the cementitious material and exert a good mineralization effect.

[0015] As a further improvement of the present invention, in step S1, the mass ratio of glucose aqueous solution, polyvinyl alcohol, initiator, cerium oxide, and styrene monomer is 100:0.5-1.5:0.1-0.5:1-1.5:15-25, the concentration of the glucose aqueous solution is 5-10 wt%, the initiator is ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, or azobisisovalerate, and the heating and stirring reaction temperature is 75-85℃, and the time is 8-12 h; in step S2, the cerium oxide / PS microspheres, water, ethanol, and pore-forming agent... The mass ratio of ammonia and alkyl orthosilicate is 0.1-0.3:50-80:15-25:0.2-0.4:0.5-1.5:0.5-1. The pore-forming agent is hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride, and the alkyl orthosilicate is ethyl orthosilicate or methyl orthosilicate. The heating temperature is 75-85℃ and the time is 14-18h. In step S3, the volume ratio of chlorosulfonic acid to dichloromethane in the dichloromethane solution containing chlorosulfonic acid is 1:1-3, and the heating, reflux, and stirring reaction time is 4-6h.

[0016] The present invention further protects a method for using the above-mentioned liquid cement mineralizer, comprising the following steps: before use, stirring and mixing the emulsion reagent B evenly to prevent sedimentation, adding it to the liquid reagent A, stirring and reacting to obtain the liquid cement mineralizer, adding it to the cement raw meal, stirring and mixing evenly, and calcining it according to the conventional cement production process to obtain cement clinker.

[0017] The present invention further protects a method for using the above-mentioned liquid cement mineralizer, comprising the following steps: before use, stirring and mixing the emulsion reagent B evenly to prevent sedimentation, adding it to the liquid reagent A, stirring and reacting, adding solid powder C, stirring and mixing evenly to obtain the liquid cement mineralizer, adding it to the cement raw meal, stirring and mixing evenly, and calcining it according to the conventional cement production process to obtain cement clinker.

[0018] As a further improvement of the present invention, the amount of liquid cement mineralizer added is 8-12 wt% of cement raw meal, and the stirring reaction time is 20-30 min.

[0019] The present invention has the following beneficial effects: This invention uses industrial waste, such as photovoltaic waste liquid and industrial waste sulfuric acid, as raw materials to produce liquid reagent A. This liquid reagent A is then mixed evenly with emulsion reagent B (quicklime emulsion) to produce CaF2 and CaSO4 precipitates. The mixture of these two substances forms a good composite mineralizer with excellent performance. This process transforms industrial waste into valuable resources, reduces production costs, increases the added value of waste materials, and simultaneously provides excellent mineralization effects while being energy-saving and environmentally friendly. Through solid waste resource utilization and reduced calcination energy consumption, carbon emissions throughout the cement production process are significantly reduced, embodying the concept of low-carbon building materials. The resulting clinker is widely applicable to the preparation of cementitious raw materials for marine cement, new wall materials, and lightweight building materials.

[0020] This invention employs two liquid reagents, using a pre-mixing method, to react and generate highly active CaF2 and CaSO4 precipitates. These precipitates are then added to cement raw materials under liquid conditions, improving their dispersibility and avoiding the uneven mixing and localized mineralization issues associated with traditional powdered mineralizers. This results in better homogeneity and improved overall performance of the produced cement clinker. The uniform and efficient mineralization further enhances calcination efficiency, continuously contributing to the low-carbon and high-efficiency development of cement production. The improved clinker homogeneity and overall performance simultaneously ensure the durability of marine cement, the formability of new wall materials, and the mechanical stability of lightweight building materials.

[0021] 3. The raw materials of this invention are widely available, the preparation method is simple, the liquid cement mineralizer obtained is easy to store and use, and the mineralization effect is good. The uniformity of the cement clinker obtained is better, the comprehensive performance is improved, and it has broad application prospects. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 TEM image of solid powder C prepared in Example 1. Detailed Implementation

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] In this embodiment, the photovoltaic waste liquid has a fluoride ion concentration of 80-150 mg / L. The industrial waste sulfuric acid has a concentration of 50-98 wt%. The cement raw material is prepared from 32.5 wt% tricalcium phosphate, 28 wt% calcium carbonate, 19 wt% alumina, 16 wt% barium oxide, and 4.5 wt% silicon dioxide.

[0026] Preparation Example 1: Solid Powder C The preparation method is as follows: S1. Mix 100g of glucose aqueous solution (concentration of 5wt%), 0.5g of polyvinyl alcohol, and 0.1g of azobisisobutyronitrile evenly, then add 1g of cerium oxide and 15g of styrene monomer. Under a nitrogen atmosphere, heat to 75℃, stir and react for 8h, centrifuge, wash, and dry to obtain cerium oxide / PS microspheres. S2. Mix 0.1g cerium oxide / PS microspheres, 50g water, 15g ethanol, 0.2-0.4g cetyltrimethylammonium bromide, and 0.5g ammonia water evenly, heat to 75℃, stir evenly, then add 0.5g methyl orthosilicate, stir and react for 14h, centrifuge, wash, and dry to obtain cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure; S3. Under a nitrogen atmosphere, 0.1 g of cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure were added to 20 mL of a dichloromethane solution containing chlorosulfonic acid (chlorosulfonic acid to dichloromethane volume ratio 1:1). The mixture was heated to reflux and stirred for 4 h. After centrifugation, washing, and drying, solid powder C was obtained. Figure 1 It can be seen that the microsphere has an egg yolk-shell structure. As can be seen from the magnified image in the upper right corner, the shell layer has a uniform mesoporous structure.

[0027] Preparation Example 2: Solid Powder C The preparation method is as follows: S1. Mix 100g of glucose aqueous solution (concentration of 10wt%), 1.5g of polyvinyl alcohol, and 0.5g of azobisisobutyronitrile evenly, then add 1.5g of cerium oxide and 25g of styrene monomer. Under a nitrogen atmosphere, heat to 85℃, stir and react for 12h, centrifuge, wash, and dry to obtain cerium oxide / PS microspheres. S2. Mix 0.3g of cerium oxide / PS microspheres, 80g of water, 25g of ethanol, 0.4g of cetyltrimethylammonium chloride, and 1.5g of ammonia water evenly, heat to 85℃, stir evenly, then add 1g of tetraethyl orthosilicate, stir and react for 18h, centrifuge, wash, and dry to obtain cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure; S3. Under a nitrogen atmosphere, 0.3 g of cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure were added to 20 mL of dichloromethane solution containing chlorosulfonic acid (the volume ratio of chlorosulfonic acid to dichloromethane was 1:3). The mixture was heated to reflux and stirred for 4 h. After centrifugation, washing, and drying, solid powder C was obtained.

[0028] Preparation Example 3 Solid Powder C The preparation method is as follows: S1. Mix 100g of glucose aqueous solution (6wt%), 0.7g of polyvinyl alcohol, and 0.2g of azobisisobutyronitrile evenly, then add 1.2g of cerium oxide and 18g of styrene monomer. Under a nitrogen atmosphere, heat to 78℃, stir and react for 9h, centrifuge, wash, and dry to obtain cerium oxide / PS microspheres. S2. Mix 0.15g cerium oxide / PS microspheres, 60g water, 18g ethanol, 0.25g cetyltrimethylammonium chloride, and 0.7g ammonia water evenly, heat to 78℃, stir evenly, then add 0.6g methyl orthosilicate, stir and react for 15h, centrifuge, wash, and dry to obtain cerium oxide / PS@mesoporous silica microspheres with egg yolk-shell structure; S3. Under a nitrogen atmosphere, 0.15 g of cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure were added to 20 mL of dichloromethane solution containing chlorosulfonic acid (the volume ratio of chlorosulfonic acid to dichloromethane was 1:1), heated to reflux, stirred and reacted for 6 h, centrifuged, washed, and dried to obtain solid powder C.

[0029] Preparation Example 4: Solid Powder C The preparation method is as follows: S1. Mix 100g of glucose aqueous solution (concentration of 8wt%), 1.2g of polyvinyl alcohol, and 0.4g of azobisisobutyronitrile evenly, then add 1.4g of cerium oxide and 22g of styrene monomer. Under a nitrogen atmosphere, heat to 83℃, stir and react for 11h, centrifuge, wash, and dry to obtain cerium oxide / PS microspheres. S2. Mix 0.25g cerium oxide / PS microspheres, 70g water, 22g ethanol, 0.35g cetyltrimethylammonium bromide, and 1.3g ammonia water evenly, heat to 83℃, stir evenly, then add 0.8g tetraethyl orthosilicate, stir and react for 17h, centrifuge, wash, and dry to obtain cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure; S3. Under a nitrogen atmosphere, 0.25 g of cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure were added to 20 mL of dichloromethane solution containing chlorosulfonic acid (the volume ratio of chlorosulfonic acid to dichloromethane was 1:2). The mixture was heated to reflux and stirred for 5 h. After centrifugation, washing, and drying, solid powder C was obtained.

[0030] Preparation Example 5: Solid Powder C The preparation method is as follows: S1. Mix 100g of glucose aqueous solution (7wt%), 1g of polyvinyl alcohol, and 0.3g of azobisisobutyronitrile evenly, then add 1.3g of cerium oxide and 20g of styrene monomer. Under a nitrogen atmosphere, heat to 80℃, stir and react for 10h, centrifuge, wash, and dry to obtain cerium oxide / PS microspheres. S2. Mix 0.2g of cerium oxide / PS microspheres, 65g of water, 20g of ethanol, 0.3g of cetyltrimethylammonium bromide, and 1g of ammonia water evenly, heat to 80℃, stir evenly, then add 0.7g of tetraethyl orthosilicate, stir and react for 16h, centrifuge, wash, and dry to obtain cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure; S3. Under a nitrogen atmosphere, 0.2 g of cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure were added to 20 mL of dichloromethane solution containing chlorosulfonic acid (the volume ratio of chlorosulfonic acid to dichloromethane was 1:2). The mixture was heated to reflux and stirred for 5 h. After centrifugation, washing, and drying, solid powder C was obtained.

[0031] Comparative Preparation Example 1 Compared to Preparation Example 5, the difference lies in that step S2 is omitted. Cerium oxide / PS microspheres are directly added to a dichloromethane solution containing chlorosulfonic acid (the volume ratio of chlorosulfonic acid to dichloromethane is 1:2). The surface of the microspheres swells rapidly, and the volume expands, possibly exhibiting a gel-like state. The microspheres gradually lose their shape, the edges become blurred, and ultimately the microspheres cannot maintain their shape.

[0032] Comparative Preparation Example 2 The difference from preparation example 5 is that step S3 is omitted.

[0033] The preparation method is as follows: S1. Mix 100g of glucose aqueous solution (7wt%), 1g of polyvinyl alcohol, and 0.3g of azobisisobutyronitrile evenly, then add 1.3g of cerium oxide and 20g of styrene monomer. Under a nitrogen atmosphere, heat to 80℃, stir and react for 10h, centrifuge, wash, and dry to obtain cerium oxide / PS microspheres. S2. Mix 0.2g of cerium oxide / PS microspheres, 65g of water, 20g of ethanol, 0.3g of cetyltrimethylammonium bromide, and 1g of ammonia water evenly, heat to 80℃, stir evenly, then add 0.7g of tetraethyl orthosilicate, stir and react for 16h, centrifuge, wash, and dry to obtain cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure, which is solid powder C.

[0034] Comparative preparation example 3 The difference from preparation example 5 is that steps S2 and S3 are omitted.

[0035] The preparation method is as follows: 100g of glucose aqueous solution (7wt%), 1g of polyvinyl alcohol, and 0.3g of azobisisobutyronitrile were mixed evenly, and then 1.3g of cerium oxide and 20g of styrene monomer were added. The mixture was heated to 80℃ under a nitrogen atmosphere and stirred for 10h. After centrifugation, washing, and drying, cerium oxide / PS microspheres were obtained, which is solid powder C. Example 1

[0036] This embodiment provides a liquid cement mineralizer, comprising liquid reagent A and emulsion reagent B, with a mass ratio of 1:0.1.

[0037] The liquid reagent A is prepared by concentrating photovoltaic waste liquid, adding industrial waste sulfuric acid, filtering, and then obtaining liquid reagent A with a fluoride ion concentration of 10 g / L, a sulfate ion concentration of 15 g / L, and a pH value of 3.

[0038] The emulsion reagent B is a quicklime suspension emulsion with a CaO concentration of 300 g / L.

[0039] Instructions for use: Before use, stir and mix emulsion reagent B evenly to prevent sedimentation, add it to liquid reagent A, stir and react for 30 minutes to obtain liquid cement mineralizer, add it to cement raw meal at a dosage of 12 wt% of cement raw meal, stir and mix evenly, and calcine according to conventional cement production process to obtain cement clinker. Example 2

[0040] This embodiment provides a liquid cement mineralizer, comprising liquid reagent A and emulsion reagent B, with a mass ratio of 1:0.5.

[0041] The liquid reagent A is prepared by concentrating photovoltaic waste liquid, adding industrial waste sulfuric acid, filtering, and then obtaining liquid reagent A with a fluoride ion concentration of 15 g / L, a sulfate ion concentration of 40 g / L, and a pH value of 1.

[0042] The emulsion reagent B is a quicklime suspension emulsion with a CaO concentration of 100 g / L.

[0043] Instructions for use: Before use, stir and mix emulsion reagent B evenly to prevent sedimentation, add it to liquid reagent A, stir and react for 30 minutes to obtain liquid cement mineralizer, add it to cement raw meal at a dosage of 8 wt% of cement raw meal, stir and mix evenly, and calcine according to conventional cement production process to obtain cement clinker. Example 3

[0044] This embodiment provides a liquid cement mineralizer, comprising liquid reagent A and emulsion reagent B, with a mass ratio of 1:0.3.

[0045] The liquid reagent A is prepared by concentrating photovoltaic waste liquid, adding industrial waste sulfuric acid, filtering, and then obtaining liquid reagent A with a fluoride ion concentration of 12 g / L, a sulfate ion concentration of 25 g / L, and a pH value of 2.

[0046] The emulsion reagent B is a quicklime suspension emulsion with a CaO concentration of 200 g / L.

[0047] Instructions for use: Before use, stir and mix emulsion reagent B evenly to prevent sedimentation, add it to liquid reagent A, stir and react for 30 minutes to obtain liquid cement mineralizer, add it to cement raw meal at a dosage of 10 wt% of cement raw meal, stir and mix evenly, and calcine according to conventional cement production process to obtain cement clinker. Example 4

[0048] This embodiment provides a liquid cement mineralizer, comprising liquid reagent A, emulsion reagent B, and solid powder C prepared in Preparation Example 1, with a mass ratio of 1:0.3:0.01.

[0049] The liquid reagent A is prepared by concentrating photovoltaic waste liquid, adding industrial waste sulfuric acid, filtering, and then obtaining liquid reagent A with a fluoride ion concentration of 12 g / L, a sulfate ion concentration of 25 g / L, and a pH value of 2.

[0050] The emulsion reagent B is a quicklime suspension emulsion with a CaO concentration of 200 g / L.

[0051] Instructions for use: Before use, stir and mix the emulsion reagent B evenly to prevent sedimentation, add it to the liquid reagent A, stir and react for 30 minutes, add the solid powder C, stir and mix evenly to obtain the liquid cement mineralizer, add it to the cement raw meal at a dosage of 10 wt% of the cement raw meal, stir and mix evenly, and calcine according to the conventional cement production process to obtain cement clinker. Example 5

[0052] Compared with Example 4, the difference is that the liquid cement mineralizer includes liquid reagent A, emulsion reagent B and solid powder C obtained in Preparation Example 2, with a mass ratio of 1:0.3:0.05. Example 6

[0053] Compared with Example 4, the difference is that the liquid cement mineralizer includes liquid reagent A, emulsion reagent B and solid powder C obtained in Preparation Example 3, with a mass ratio of 1:0.3:0.02. Example 7

[0054] The difference from Example 4 is that the liquid cement mineralizer includes liquid reagent A, emulsion reagent B and solid powder C obtained in Preparation Example 4, with a mass ratio of 1:0.3:0.03. Example 8

[0055] Compared with Example 4, the difference is that the liquid cement mineralizer includes liquid reagent A, emulsion reagent B and solid powder C obtained in Preparation Example 5, with a mass ratio of 1:0.3:0.04.

[0056] Comparative Example 1 The difference compared to Example 8 is that the solid powder C was prepared from Comparative Preparation Example 2. When added to the cement raw meal, localized agglomeration occurred.

[0057] Comparative Example 2 The difference compared to Example 8 is that the solid powder C was prepared from Comparative Preparation Example 3. Upon addition to the cement raw meal, most of the solid powder C agglomerated.

[0058] Comparative Example 3 The difference from Example 8 is that solid powder C is replaced by an equal mass of cerium oxide.

[0059] The calcination temperature test results of the cement clinker prepared in Examples 1-8 and Comparative Examples 1-2, as well as the cement clinker without mineralizer, are shown in Table 1.

[0060] Table 1

[0061] As shown in the table above, compared with the control group cement without mineralizer, the liquid cement mineralizer prepared by this invention can significantly reduce the calcination temperature. In Examples 4-8, solid powder C was added, and due to the addition of rare earth cerium oxide, the calcination temperature was further reduced. In Comparative Examples 1 and 2, localized and mostly agglomerated solid powder C occurred, and its effect on reducing the calcination temperature was not as significant as in Example 8. In Comparative Example 3, cerium oxide rapidly degraded, and the effect was not obvious.

[0062] Performance Test 1: The setting time of each group of cement clinker prepared by Examples 1-8 and Comparative Examples 1-2, as well as cement clinker without mineralizer, was determined according to the standard described in GB 1346 "Test Methods for Standard Consistency Water Requirement, Setting Time and Soundness of Cement". The compressive strength of the cement paste specimen was determined using a CMT5504 electronic universal testing machine. The test results are shown in Table 2.

[0063] Table 2

[0064] As shown in the table above, compared with the control group cement without added mineralizer, the liquid cement mineralizer prepared in this invention can significantly prolong the setting time, increase the compressive strength, and significantly improve the cement performance. In Comparative Examples 1 and 2, localized and mostly agglomerated solid powder C occurred, and its improvement effect was not as good as in Example 8. In Comparative Example 3, cerium oxide rapidly degraded, and the effect was not obvious.

[0065] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A liquid cement mineralizer, characterized in that, The reagent comprises liquid reagent A and emulsion reagent B. Liquid reagent A is prepared by concentrating a fluoride-containing acidic waste liquid, adding industrial waste sulfuric acid, and filtering. Emulsion reagent B is a quicklime suspension emulsion. The mass ratio of liquid reagent A to emulsion reagent B is 1:0.1-0.

5. Solid powder C was also added, at an amount of 1-5 wt% of liquid reagent A. The preparation method of solid powder C is as follows: S1. After uniformly mixing glucose aqueous solution, polyvinyl alcohol, and initiator, cerium oxide and styrene monomer are added. The mixture is heated and stirred under an inert gas atmosphere, centrifuged, washed, and dried to obtain cerium oxide / PS microspheres. S2. Cerium oxide / PS microspheres, water, ethanol, pore-forming agent, and ammonia are mixed evenly, heated and stirred, then alkyl orthosilicate is added, the mixture is stirred and reacted, centrifuged, washed, and dried to obtain cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure. S3. Under an inert gas atmosphere, cerium oxide / PS@mesoporous silica microspheres with an egg yolk-shell structure were added to a dichloromethane solution containing chlorosulfonic acid, heated and stirred under reflux, centrifuged, washed, and dried to obtain solid powder C.

2. The liquid cement mineralizer according to claim 1, characterized in that, The liquid reagent A has a fluoride ion concentration of 10-15 g / L, a sulfate ion concentration of 15-40 g / L, and a pH value of 1-3.

3. The liquid cement mineralizer according to claim 1, characterized in that, In the liquid reagent A, the fluorinated acidic waste liquid is photovoltaic waste liquid with a fluoride ion concentration of 80-150 mg / L, and the industrial waste sulfuric acid has a concentration of 50-98 wt%.

4. The liquid cement mineralizer according to claim 1, characterized in that, In the emulsion reagent B, the concentration of CaO is 100-300 g / L.

5. The liquid cement mineralizer according to claim 1, characterized in that, In step S1, the mass ratio of glucose aqueous solution, polyvinyl alcohol, initiator, cerium oxide, and styrene monomer is 100:0.5-1.5:0.1-0.5:1-1.5:15-25. The concentration of the glucose aqueous solution is 5-10 wt%. The initiator is ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, or azobisisovalerate. The heating and stirring reaction temperature is 75-85℃, and the time is 8-12 h. In step S2, the cerium oxide / PS microspheres, water, ethanol, pore-forming agent, ammonia, and orthosilicone... The mass ratio of the alkyl ester is 0.1-0.3:50-80:15-25:0.2-0.4:0.5-1.5:0.5-1. The porogen is hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride. The alkyl orthosilicate is ethyl orthosilicate or methyl orthosilicate. The heating temperature is 75-85℃ and the time is 14-18h. In step S3, the volume ratio of chlorosulfonic acid to dichloromethane in the dichloromethane solution containing chlorosulfonic acid is 1:1-3. The heating, reflux, and stirring reaction time is 4-6h.

6. A method of using the liquid cement mineralizer as described in any one of claims 1-5, characterized in that, Includes the following steps: Before use, stir and mix the emulsion reagent B evenly to prevent sedimentation, add it to the liquid reagent A, stir and react, add the solid powder C, stir and mix evenly to obtain the liquid cement mineralizer, add it to the cement raw meal, stir and mix evenly, and calcine according to the conventional cement production process to obtain cement clinker.

7. The method of use according to claim 6, characterized in that, The amount of liquid cement mineralizer added is 8-12 wt% of the cement raw meal, and the stirring reaction time is 20-30 min.

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