CN115353307B - Composite liquid raw material mineralizing agent - Google Patents
Composite liquid raw material mineralizing agent Download PDFInfo
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- CN115353307B CN115353307B CN202211002691.XA CN202211002691A CN115353307B CN 115353307 B CN115353307 B CN 115353307B CN 202211002691 A CN202211002691 A CN 202211002691A CN 115353307 B CN115353307 B CN 115353307B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a composite liquid raw material mineralizer, and belongs to the technical field of cement process additives. The composite raw material mineralizer is prepared from the following components: 10-35 parts of decomposition promoting component, 25-45 parts of mineralizing component, 15-30 parts of organic grinding assisting component and 35-55 parts of water. The additive can eliminate static electricity, relieve the over-grinding phenomenon, effectively improve the grinding efficiency of raw materials, reduce the apparent decomposition energy of calcium carbonate, promote the decomposition reaction of raw materials, improve the formation condition of clinker crystals, promote the sintering of cement clinker and reduce the energy consumption in the preparation process of the cement clinker.
Description
Technical Field
The invention relates to the technical field of cement process additives, in particular to a composite liquid raw material mineralizer.
Background
Cement production generally involves 3 steps of raw material preparation, clinker calcination and cement grinding. Wherein the raw material preparation comprises material crushing, raw material pre-homogenization, raw material proportioning, raw material grinding and homogenization; the clinker calcination comprises coal dust preparation, clinker calcination and cooling; and (5) grinding cement. Wherein clinker calcination is a key factor in determining cement production cost and quality.
In the clinker calcination process, physical and chemical changes such as drying, clay raw material dehydration, carbonate decomposition, solid phase reaction, clinker sintering, clinker cooling and the like mainly occur, wherein the processes of carbonate decomposition, liquid phase formation and the like need to consume a large amount of energy, so that the promotion of carbonate decomposition and the change of liquid phase formation conditions are important.
The addition of small amounts of mineralizing material to the green charge is a common way to accelerate the solid phase reaction and promote sintering. The mineralizer can be introduced to reduce the minimum eutectic temperature, increase the liquid phase quantity, reduce the liquid phase viscosity and reduce the surface tension so as to promote the solid phase reaction and accelerate the formation of clinker minerals. Meanwhile, the content of free calcium oxide in clinker can be effectively reduced, the purposes of improving the combustibility of raw materials and reducing the energy consumption are achieved, and the organic combination of the concepts of energy conservation, consumption reduction, emission reduction and environmental protection in the cement production process is realized.
Disclosure of Invention
The invention aims to solve the technical problems that: the invention aims to provide a composite raw material mineralizer which can promote the decomposition of cement raw materials, is beneficial to reducing the liquid phase temperature and accelerating the firing of cement clinker, and realizes energy conservation, consumption reduction and emission reduction of cement production.
In order to solve the technical problems, the invention provides the following technical scheme:
the composite raw material mineralizer comprises the following raw materials in parts by weight: 10-35 parts of decomposition promoting component, 25-45 parts of mineralizing component, 15-30 parts of organic grinding assisting component and 35-55 parts of water.
Preferably, the decomposition promoting component consists of tetra sodium hydroxyethylidene diphosphonate, ethylenediamine tetra methylene phosphonic acid, and barium chloride.
Preferably, the mass ratio of the tetra sodium hydroxy ethylidene diphosphonate, the ethylenediamine tetramethylene phosphonic acid and the barium chloride is 2:3:2.
preferably, the mineralizing component consists of sodium bisulfate, potassium ferrocyanide, sodium chloride, potassium hexafluorotitanate.
Preferably, the mass ratio of the sodium bisulfate, the potassium ferrocyanide, the sodium chloride and the potassium hexafluorotitanate is 3:8:10:1.
preferably, the organic grinding aid component consists of hydroxypropyl methylcellulose, sodium dodecyl benzene sulfonate and molasses.
Preferably, the mass ratio of the hydroxypropyl methylcellulose, the sodium dodecyl benzene sulfonate and the molasses is 3:1:20.
the beneficial effects obtained by the invention are as follows: the composite cement mineralizer has the functions of obviously assisting grinding, mineralizing and decomposing, can effectively reduce the energy consumption during the preparation of cement clinker, realizes energy conservation and emission reduction in the cement industry, and is a raw material mineralizer with excellent performance. The mineralized component in the invention can reduce the eutectic point, reduce the liquid phase generation temperature and the liquid phase viscosity, promote the solid-liquid reaction, accelerate the firing of the cement clinker, and part of elements can enter the structure of silicate phase to form solid solution, thereby improving the thermodynamic stability of clinker minerals and further achieving the effect of improving the quality of the cement clinker; the introduction of the organic acid and the organic acid salt causes the lattice of the carbonate to be distorted, and promotes the decomposition of the calcium carbonate; the organic grinding-assisting components such as hydroxypropyl methyl cellulose, sodium dodecyl benzene sulfonate and the like can eliminate static electricity generated in the physical grinding process, prevent tiny cracks from closing after physical crushing, reduce excessive grinding of materials, and further achieve the effects of improving the machine-hour yield of a raw material grinding machine and reducing the grinding electricity consumption; part of the components are decomposed at high temperature, so that the volatile content is increased, the precipitation rate is accelerated, and the combustion efficiency of the pulverized coal is improved.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate a more complete, accurate and thorough understanding of the present invention's inventive concepts and technical solutions by those skilled in the art.
Example 1:
the composite liquid raw material mineralizer comprises the following raw materials in percentage by weight: 15 parts of decomposition-promoting auxiliary agent, 25 parts of mineralization auxiliary agent, 20 parts of organic grinding-assisting auxiliary agent and 40 parts of water.
The decomposition-promoting auxiliary agent is hydroxy ethylidene disodium, ethylenediamine tetramethylene phosphonic acid and barium chloride according to the mass of 2:3:2, mixing to obtain the product. Tetra sodium hydroxy ethylidene diphosphonate can enter CaCO 3 Promoting CaCO to occur within the crystal lattice of (C) 3 Lattice distortion, lowering lattice energy; ethylenediamine tetramethylene phosphonic acid can reduce CaCO 3 Decomposing the surface activation energy, thereby reducing CaCO 3 Decomposition temperature; at the same time, the introduction of barium chloride can also lead CaCO 3 And lattice defects are generated, the reactivity of the crystal lattice defects is improved, and the decomposition of the crystal lattice defects is promoted.
The mineralization auxiliary agent is sodium bisulfate, potassium ferrocyanide, sodium chloride and potassium hexafluorotitanate according to the mass ratio of 3:8:10:1, and mixing. The sodium bisulfate can reduce the viscosity of the liquid phase, which is favorable for the liquid-solid interface reaction; the potassium ferrocyanide can improve the liquid phase content in the calcination process; sodium chloride also helps to improve the properties of the liquid phase during the high temperature firing process; the elements of potassium hexafluorotitanate can enter the structure of silicate phase to form solid solution, so that the quality of cement clinker is improved; meanwhile, the mineralization components have synergistic effect, so that the minimum eutectic temperature can be further effectively reduced, the liquid phase appearance temperature is reduced, and the firing temperature is enlarged.
The organic grinding aid auxiliary agent is hydroxypropyl methyl cellulose, sodium dodecyl benzene sulfonate and molasses according to the mass ratio of 3:1:20. The hydroxypropyl methyl cellulose can effectively stabilize the material layer, and improves the grinding efficiency of raw materials; anionic surfactant sodium dodecyl benzene sulfonate and molasses can be adsorbed on CaCO 3 The surface eliminates static electricity generated in the physical grinding process, prevents cracks from closing after physical crushing, improves the grinding efficiency of cement, slows down the over grinding phenomenon of raw materials, improves the powder selecting efficiency, remarkably improves the raw material stage and achieves the energy-saving effect.
When the raw material mineralizer prepared in the embodiment is used, the mixing amount is 0.08-1.2% of the weight of raw material per ton of cement raw material.
Example 2:
the composite raw material mineralizer is prepared from the following raw materials in percentage by weight: 10 parts of decomposition-promoting auxiliary agent, 25 parts of mineralization auxiliary agent, 15 parts of organic grinding-assisting auxiliary agent and 35 parts of water.
The decomposition-promoting auxiliary agent is hydroxy ethylidene disodium, ethylenediamine tetramethylene phosphonic acid and barium chloride according to the mass of 2:3:2, mixing to obtain the product.
The mineralization auxiliary agent is sodium bisulfate, potassium ferrocyanide, sodium chloride and potassium hexafluorotitanate according to the mass ratio of 3:8:10:1, and mixing.
The organic grinding aid auxiliary agent is hydroxypropyl methyl cellulose, sodium dodecyl benzene sulfonate and molasses according to the mass ratio of 3:1:20.
Example 3:
the composite liquid raw material mineralizer comprises the following raw materials in percentage by weight: 35 parts of decomposition-promoting auxiliary agent, 45 parts of mineralization auxiliary agent, 30 parts of organic grinding-assisting auxiliary agent and 55 parts of water.
The decomposition-promoting auxiliary agent is hydroxy ethylidene disodium, ethylenediamine tetramethylene phosphonic acid and barium chloride according to the mass of 2:3:2, mixing to obtain the product.
The mineralization auxiliary agent is sodium bisulfate, potassium ferrocyanide, sodium chloride and potassium hexafluorotitanate according to the mass ratio of 3:8:10:1, and mixing.
The organic grinding aid auxiliary agent is hydroxypropyl methyl cellulose, sodium dodecyl benzene sulfonate and molasses according to the mass ratio of 3:1:20.
Comparative example 1: the remainder was the same as in example 1 except that tetrasodium hydroxyethylidene bisphosphonate was not contained.
The decomposition-promoting auxiliary agent is ethylenediamine tetramethylene phosphonic acid and barium chloride according to mass 3:2, mixing to obtain the product.
Comparative example 2: the remainder was the same as in example 1 except that tetra sodium hydroxy ethylidene bisphosphonate was replaced with sodium amino trimethylene phosphonate in equal amount.
Comparative example 3: the remainder was the same as in example 1 except that tetra sodium hydroxyethylidene diphosphonate was replaced with sodium diethylenetriamine penta methylene phosphonate in equal amount.
Raw meal grinding performance test
Taking raw materials of a Chaohu conch cement Limited liability company as experimental samples, drying and crushing the raw materials, uniformly stirring, simulating actual cement raw materials of a factory, grinding with 5000g each time, and setting grinding time to be 12 minutes.
Table 1 raw meal grinding aid performance results
As can be seen from the results in Table 1, the addition of tetra sodium hydroxyethylidene bisphosphonate can effectively reduce the percentage of screen residue of 80 μm, reduce the ratio of the ultra fine powder, and the examples 1 to 3 can effectively reduce the screen residue and alleviate the over grinding phenomenon compared with the comparative examples 1 to 3.
Decomposition Rate test
Taking the kiln-entering raw meal powder of Chaohu conch cement Co-Ltd, drying the raw meal powder at 105 ℃ for 2 hours, uniformly mixing cement raw meal additives with the raw meal powder according to different mixing amounts, filling 1g of mixed raw meal powder into each crucible, uniformly spreading, respectively calcining for 30 minutes at 750 ℃, and measuring the loss on ignition, wherein the result is shown in Table 2:
TABLE 2 decomposition rate test results
The results show that the hydroxy ethylidene disodium has obvious effect of improving loss on ignition, and the improvement effect is obviously higher than that of amino trimethylene sodium phosphonate and diethylene triamine penta methylene sodium phosphonate. The added tetra sodium hydroxy ethylidene diphosphonate can effectively improve the decomposition rate of raw meal powder, and simultaneously, the mineralizer has better grinding assisting effect.
Calcining performance of cement clinker
Taking the kiln-entering raw meal powder of Chaohu conch cement Co., ltd., drying the raw meal powder at 105 ℃ for 3 hours, transferring the raw meal powder into 950 ℃ for calcination for 30 minutes, then transferring the raw meal powder into a high-temperature furnace for calcination for 30 minutes at 1350 ℃ and 1450 ℃, and rapidly cooling the raw meal powder to measure the free calcium oxide.
Surprisingly, the results in table 3 show that tetra sodium hydroxyethylidene diphosphonate also has a weaker mineralization effect and can reduce the content of free calcium oxide to a limited extent, while the components such as sodium aminotrimethylene phosphonate, sodium diethylenetriamine penta methylene phosphonate and the like have no tendency to reduce the content of free calcium oxide, even have no situation of descending and ascending. The hydroxy ethylidene disodium is obviously better than amino trimethylene sodium phosphonate, diethylene triamine pentamethylene sodium phosphonate and the like in mineralization effect.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by the above embodiments, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (1)
1. The composite raw material mineralizer is characterized by comprising the following raw materials in parts by weight: 10-35 parts of decomposition promoting components, 25-45 parts of mineralizing components, 15-30 parts of organic grinding assisting components and 35-55 parts of water;
the decomposition promoting component consists of tetra sodium hydroxy ethylidene diphosphonate, ethylenediamine tetramethylene phosphonic acid and barium chloride; the mass ratio of the hydroxy ethylidene diphosphonic acid to the ethylenediamine tetramethylene phosphonic acid to the barium chloride is 2:3:2;
the mineralized component consists of sodium bisulfate, potassium ferrocyanide, sodium chloride and potassium hexafluorotitanate; the mass ratio of the sodium bisulfate to the potassium ferrocyanide to the sodium chloride to the potassium hexafluorotitanate is 3:8:10:1, a step of;
the organic grinding-assisting component consists of hydroxypropyl methyl cellulose, sodium dodecyl benzene sulfonate and molasses; the mass ratio of the hydroxypropyl methylcellulose to the sodium dodecyl benzene sulfonate to the molasses is 3:1:20.
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Family Cites Families (5)
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US4089695A (en) * | 1976-08-17 | 1978-05-16 | Martin Marietta Corporation | Hydraulic cement mixes and process for improving hydraulic cement mixes |
PL2842922T3 (en) * | 2013-09-03 | 2018-05-30 | Heidelbergcement Ag | Fluxes/Mineralizers for calcium sulfoaluminate cements |
CN112745052A (en) * | 2020-12-24 | 2021-05-04 | 铜川声威建材有限责任公司榆林分公司 | Improved grinding aid |
CN112759289B (en) * | 2020-12-31 | 2023-03-10 | 安徽海螺新材料科技有限公司 | Cement raw material additive with grinding-aid and decomposition-promoting effects |
CN113788635B (en) * | 2021-10-09 | 2022-08-16 | 贵州德隆水泥有限公司 | Production method of general cement without polluting chromium element |
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Effective date of registration: 20230901 Address after: 241000 No. 1-301, Area G, Construction Headquarters, Jiangbei New Area, Wuhu City, 150 meters south of Tongjiang Avenue, Jiangbei New Area, Wanjiang New Industry Cluster (except the trusteeship area), Wuhu City Patentee after: Anhui Conch Material Technology Co.,Ltd. Address before: 241000 No. 39, Wenhua Road, Zhangjiashan street, Jinghu District, Wuhu City, Anhui Province Patentee before: Anhui Conch Preparation Engineering Technology Co.,Ltd. |
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