Preparation method and application of an environment-friendly cement raw meal grinding mineralizer

Abstract

The present invention belongs to the technical field of cement production, and discloses a preparation method and application of an environment-friendly cement raw meal grinding aid and mineralizer. At room temperature, industrial waste alkali liquor and electrolytic manganese slag are placed in a closed container according to the mass ratio of industrial waste alkali liquor to electrolytic manganese slag on a dry basis of 1-2:1, and after being stirred evenly, a slurry solution is made. After standing for 0.5-3 h, solid-liquid separation is carried out; the solid phase after solid-liquid separation is the cement raw meal grinding aid and mineralizer A, and the liquid phase after solid-liquid separation is heated and an active agent is added and stirred evenly to obtain the cement raw meal grinding aid and mineralizer B. Based on the principle of coprecipitation and the principle of "treating waste with waste", the present invention uses solid waste electrolytic manganese slag and industrial waste alkali liquor for co-disposal to prepare a raw meal grinding aid and mineralizer, effectively improving the burnability of cement raw meal while using co-disposed solid waste, reducing the heat consumption of clinker firing, and having significant environmental benefits while saving energy and reducing consumption in cement production.

Description

Technical Field

[0001] The present invention belongs to the technical field of cement production, and particularly relates to a preparation method and application of an environment-friendly grinding aid and mineralizer for cement raw meal. Background Art

[0002] The production process of modern portland cement can be divided into three main stages, usually referred to as "two grinding and one burning": after being crushed, calcareous raw materials, aluminosilicate raw materials and ferrous raw materials are proportioned according to a certain ratio, and then ground by a raw meal vertical mill system or a roller press system to prepare a raw meal with uniform composition, which is called raw meal preparation; the raw meal is calcined in a precalciner kiln system to obtain portland cement clinker mainly composed of calcium silicate after drying and dehydration, preheating and decomposition, solid-phase reaction, clinker sintering and cooling, which is called clinker calcination; the portland cement clinker is ground together with an appropriate amount of gypsum and specified admixtures to make cement.

[0003] Currently, with the continuous improvement of the requirements of energy, resources and environmental protection for the development of the cement industry, improving the energy utilization efficiency in the cement production process, saving resources and reducing energy consumption are the inevitable requirements for the sustainable development of the cement industry. In terms of the cement production process, the clinker calcination process is directly related to the production energy consumption and product performance of cement, and is closely related to the burnability of raw meal. Adopting advanced technologies to improve the burnability of raw meal, reduce the consumption of energy and resources in the clinker preparation process, and reduce the emission of harmful gases is an important way to achieve high-quality and low-carbon development of the cement industry. The burnability of raw meal refers to the degree of difficulty of forming clinker minerals through physical and chemical changes in the solid, liquid and gas phases of cement raw meal. Measures to improve the burnability of raw meal mainly include: controlling the quality of raw materials, reasonably proportioning, improving uniformity, adding additives with functions such as raw meal grinding aid, desulfurization component, decomposition-promoting component, coal-saving, etc. to improve the fineness and particle size distribution of raw meal (Chinese patent documents CN110981238B, CN112759289B, CN113800796A, CN114620967A, CN115028379B, CN116921049A, CN117417140A, etc.), or using industrial waste residues to introduce trace elements or mineralizers (gypsum, fluorite, rare earth elements, etc.) to reduce the firing temperature and heat consumption in the clinker preparation process, and at the same time realize the comprehensive utilization of waste residues (Chinese patent documents CN114477844B, CN114804678A, CN116040968A, CN117623671A, CN86108664A, etc.). Most of the above-mentioned additive raw materials are pure chemical reagents, with high utilization costs and low comprehensive benefits.

[0004] Electrolytic manganese residue is a solid waste generated during the wet electrolysis of metallic manganese, which is produced after the carbon manganese ore is leached with sulfuric acid and neutralized with ammonia. Its pH value is generally 4.00 - 6.50, and the water content is 30 - 40%; the main mineral components are sulfates (mainly gypsum dihydrate), SiO2 (quartz), 2CaO·SiO2·2H2O (C2SH2), Fe2O3, etc. Among them, SO3 reaches 20 - 37%, and when converted to gypsum (when the CaO content is high), it accounts for more than 45%. That is to say, electrolytic manganese residue essentially belongs to low-grade industrial by-product chemical gypsum or sulfate waste residue, and at the same time, it also contains a large amount of soluble MnSO4, (NH4)2SO4, MgSO4 and other one or more composite pollutants. Electrolyzing 1t of metallic manganese will produce 10 - 12t of electrolytic manganese residue. At present, the annual discharge of electrolytic manganese residue in China reaches more than 10 million tons, and the cumulative stockpile reaches more than 160 million tons. Due to the large discharge of electrolytic manganese residue, the particles of electrolytic manganese residue are fine, and it contains a large amount of sulfate radicals, ammonia nitrogen and a certain amount of heavy metal harmful elements. Allowing it to be discharged will seriously pollute surface water, groundwater and soil, and seriously affect the ecological environment. Therefore, comprehensive utilization of it is the general trend to promote the circular economy in China. At present, the application of electrolytic manganese residue in portland cement mainly focuses on: replacing part of the gypsum as a retarder (Chinese patent document CN113603377A), chromium reducing agent (Chinese patent document CN112110671A) or admixture (Chinese patent document CN112110671A) during the cement grinding process; using it as a cement raw material or admixture after desulfurization with a reducing agent (Chinese patent documents CN103771734B, CN117486510); using it as a raw material for a semi-dry rotary kiln (Chinese patent document CN100369847C); or co-disposing by continuously feeding electrolytic manganese residue into the kiln tail flue chamber of the dry process rotary kiln production line equipment (Chinese patent document CN110986577A). Although electrolytic manganese residue can be directly used as a cement mineralizer (Wang Yong, Research on Electrolytic Manganese Residue as Cement Mineralizer, Concrete, 2010, (08), 90 - 93), direct use is likely to cause problems such as excessive ammonia and sulfur dioxide content in the flue gas.

[0005] Industrial waste alkali liquor comes from at least one of the alkaline sulfite cooking waste liquor of pulp and the saponification waste alkali liquor after saponification reaction during soap production. Components such as lignosulfonate, organic acid salt, sodium hydroxide, sodium carbonate, sodium sulfate, polyol, etc. contained in these waste liquors can play a role in grinding aid and desulfurization during the drying and grinding process of cement raw meal (Chinese patent documents CN109824284A, CN16768507A), but the utilization routes are relatively single.

[0006] At present, there is little research on the synergistic utilization of various industrial waste residues with the functions of raw meal grinding aid and mineralizer. How to prepare a cement raw meal grinding aid mineralizer by synergistically using various industrial waste residues and apply it to cement production, while effectively improving the burnability of cement raw meal and reducing the heat consumption of clinker firing, and having significant environmental benefits while saving energy and reducing consumption in cement production is an urgent research topic to be solved. Summary of the Invention

[0007] In order to solve the above technical problems, the present invention provides a preparation method and application of an environmentally friendly cement raw meal grinding aid mineralizer. Based on the co-precipitation principle and the principle of "treating waste with waste", electrolytic manganese slag and industrial waste alkali liquor are co-disposed to prepare a cement raw meal grinding aid mineralizer, which can effectively improve the burnability of cement raw meal and reduce the heat consumption of clinker firing while utilizing the co-disposed solid waste, and has significant environmental benefits while saving energy and reducing consumption in cement production.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is: a preparation method of an environmentally friendly cement raw meal grinding aid mineralizer, comprising the following steps:

[0009] Step 1: At room temperature, put industrial waste alkali liquor and electrolytic manganese slag into a closed container according to the mass ratio of industrial waste alkali liquor to dry basis of electrolytic manganese slag of 1-2:1, and connect the closed container with dilute acid solution or water;

[0010] Step 2: Stir the mixture in the closed container evenly to make a slurry solution, and perform solid-liquid separation after standing for 0.5-3 h;

[0011] Step 3: The solid phase after solid-liquid separation is the cement raw meal grinding aid mineralizer A, and the cement raw meal grinding aid mineralizer A contains 15-30% moisture; after the liquid phase after solid-liquid separation is heated to 40-60 °C, add an activator and stir evenly to obtain the cement raw meal grinding aid mineralizer B.

[0012] The electrolytic manganese slag is at least one of wet fresh electrolytic manganese slag, stockpiled and dried electrolytic manganese slag, or electrolytic manganese slag mixed with other wastes, with a pH value of 4.00-6.50 and a moisture content of 0-40%.

[0013] The industrial waste alkali liquor is at least one of paper pulp alkaline sulfite cooking waste liquor and saponification waste alkali liquor from the saponification reaction in the soap production process, with a pH value of 9.0-14.0 and containing at least one of sodium hydroxide, lignosulfonate, sodium carbonate, sodium sulfate, organic acid salt, potassium hydroxide, and polyol.

[0014] Preferably, the industrial waste alkali liquor is a mixed industrial waste alkali liquor obtained by mixing paper pulp alkaline sulfite cooking waste liquor and saponification waste alkali liquor from the saponification reaction in the soap production process according to a mass ratio of 2:3.

[0015] The closed container is connected to a dilute acid solution or water to recover the volatilized ammonia gas.

[0016] Preferably, the standing time of the slurry solution in step two is 1 - 2 h.

[0017] Preferably, the heating temperature of the liquid phase after solid-liquid separation in step three is 50 °C.

[0018] In the said step three, the mass ratio of the liquid phase after solid-liquid separation to the active agent is 0.5 - 2:1.

[0019] The active agent is prepared from the following raw materials by weight percentage: lignosulfonate 0 - 25%, organic acid salt 0 - 50%, polyol 30 - 70%, and sodium dodecyl sulfate 5 - 20%.

[0020] The lignosulfonate includes at least one of sodium lignosulfonate and calcium lignosulfonate.

[0021] The organic acid salt is obtained by mixing sodium citrate, sodium valerate, disodium succinate, disodium adipate, and sodium humate in a mass ratio of 2:1:1:2:2.

[0022] The polyol includes at least one selected from triglycerol, polypropylene glycol, ethylene glycol, propylene glycol, glycerol, and polyethylene glycol.

[0023] Preferably, the polyol is obtained by mixing triglycerol, polypropylene glycol, and ethylene glycol in a mass ratio of 2:1:1.

[0024] The application of the environment-friendly cement raw meal grinding mineralizer prepared by the above preparation method is as follows: The cement raw meal grinding mineralizer A and the cement raw meal grinding mineralizer B are respectively metered and then separately added to the cement raw materials for grinding.

[0025] The cement raw meal grinding mineralizer A can be used as a single component to be proportioned with other raw materials for grinding, or be mixed and homogenized with difficult-to-grind materials such as limestone and sandstone and then proportioned for grinding.

[0026] The cement raw meal grinding mineralizer B, after being metered as a single component, is incorporated into difficult-to-grind materials such as limestone and sandstone for grinding together.

[0027] The dosage (dry basis mass ratio) of the cement raw meal grinding mineralizer A in the cement raw meal to be ground is: 3.0 - 8.0%.

[0028] The external addition mass ratio (dry basis) of the cement raw meal grinding mineralizer A = cement raw meal grinding mineralizer A / (cement raw meal to be ground + cement raw meal grinding mineralizer A).

[0029] The dosage of the cement raw meal grinding aid and mineralizer B is 0.01 - 0.2% of the weight of the raw meal to be ground, preferably 0.08 - 0.12%.

[0030] The internal doping mass ratio of the cement raw meal grinding aid and mineralizer B = the cement raw meal grinding aid and mineralizer B / the raw meal to be ground.

[0031] The basic principle of the present invention: After adding alkaline waste liquid to electrolytic manganese residue, soluble Mn 2+ and NH4 + enter the solution and react fully with the alkaline components in the waste alkali. Under an alkaline environment, Mn in the filtrate of electrolytic manganese residue 2+ is converted into stable MnO(OH)2 and precipitates in the solid phase, and NH4 + is transformed into NH3 and released and then recycled by solvent absorption. The reaction formulas are as follows:

[0032] Mn 2+ + 2OH - → Mn(OH)2

[0033] 2Mn(OH)2 + O2 → 2MnO(OH)2

[0034] NH4 + + OH - → NH3 + H2O

[0035] The surface active components such as lignosulfonate, organic acid salt, and polyol ether contained in industrial waste alkali liquor are easily adsorbed on the particle surface, preventing the re - healing of micro - cracks and the re - agglomeration of fine particles, thereby reducing the surface energy of materials such as limestone and sandstone and improving the grindability of raw meal. The organic components such as organic acid salts in industrial waste alkali liquor can also react with calcium carbonate in cement raw meal to produce intermediate products, promoting the decomposition of CaCO3 in raw meal; calcium sulfate and soluble manganese salts in electrolytic manganese residue and MnO(OH)2 converted in the environment of industrial waste alkali liquor can all be used as cement mineralizers, improving the reaction activity of silicate minerals, generating transition phases beneficial to the formation of clinker minerals, thereby reducing the firing temperature and liquid phase viscosity, promoting liquid phase crystallization, and improving the quality of clinker; furthermore, reducing the firing heat consumption of clinker minerals; at the same time, the alkaline components such as sodium hydroxide and sodium carbonate in industrial waste alkali liquor can also reduce the sulfur dioxide content in flue gas, playing a role in sulfur fixation.

[0036] The beneficial effects of the present invention are as follows: Compared with the prior art, based on the coprecipitation principle and the principle of "treating waste with waste", the present invention uses solid waste electrolytic manganese slag and industrial waste alkali liquor for co-disposal to prepare a raw meal grinding aid mineralizer. The alkaline environment of the industrial waste alkali liquor is used to treat the weakly acidic electrolytic manganese slag. While removing the ammonia nitrogen component in the electrolytic manganese slag, the soluble manganese salt is converted into a precipitate and together with the gypsum phase in the electrolytic manganese slag becomes an effective component of the cement mineralizer; and the lignosulfonate, organic acid salt, polyol and other active components contained in the industrial waste alkali liquor are fully utilized to improve the grindability and burnability of the cement raw meal, reduce the power consumption of raw meal grinding, and reduce the standard coal consumption for clinker burning by 3-6 kgce / t while ensuring the quality of the clinker. At the same time, silicon, aluminum, calcium, iron, etc. in the electrolytic manganese slag can also provide the components required for the cement raw meal. The present invention can effectively improve the burnability of the cement raw meal and reduce the heat consumption for clinker burning while using co-disposed solid waste, and has significant environmental benefits while saving energy and reducing consumption in cement production. Specific Embodiments

[0037] To better understand the present invention, the content of the present invention will be further clarified below in conjunction with embodiments, but the content of the present invention is not limited to the following embodiments.

[0038] Unless otherwise specified, the raw material information used in the embodiments is as follows:

[0039] Electrolytic manganese slag: The electrolytic manganese slag stockpiled and dried by a manganese industry company, with a moisture content of 18.5% and a pH value of 5.50. Its main chemical components (mass percentage) are: SiO2 35.12 wt.%, Fe2O3 5.12 wt.%, Al2O3 12.01 wt.%, CaO 9.23 wt.%, MgO 2.96 wt.%, MnO 3.43 wt.%, SO3 31.57 wt.%, TiO2 0.29 wt.%, NH 4+ 0.17 wt.%.

[0040] Paper pulp sulfite waste liquor: Taken from the alkaline sulfite cooking waste liquor of a paper industry company, with a relative density of 1.078 g / cm 3 , a moisture content of 50% and a pH value of 9.5.

[0041] Saponified waste alkali liquor: Taken from the saponified waste alkali liquor after the saponification reaction in the soap production process of a nylon technology company, with a relative density of 1.17 g / cm 3 , a water content of 62% and a pH value of 13.5.

[0042] Industrial waste alkali liquor (mixed): The alkaline sulfite cooking waste liquor of paper pulp and the saponified waste alkali liquor after the saponification reaction in the soap production process are mixed evenly according to a mass ratio of 2:3.

[0043] Sodium lignosulfonate, sodium citrate, disodium succinate, sodium valerate, disodium adipate, polyglycerol, polypropylene glycol, ethylene glycol, sodium dodecyl sulfate, and sodium humate are all commercially available industrial pure products. Products of different grades do not affect the use.

[0044] After solid-liquid separation in the example, the cement raw material grinding aid and mineralizer A contains 20% moisture. When formulating the ingredients, it is used as a component and fed into the mill together with other raw materials.

[0045] The external admixture mass ratio (dry basis) of the cement raw material grinding aid and mineralizer A = cement raw material grinding aid and mineralizer A / (raw material to be ground for cement + cement raw material grinding aid and mineralizer A).

[0046] In the example, the cement raw material grinding aid and mineralizer B is separately metered as a component and added to the surface of limestone after batching metering.

[0047] The internal admixture mass ratio of the cement raw material grinding aid and mineralizer B in the example = cement raw material grinding aid and mineralizer B / raw material to be ground for cement.

[0048] The fineness test is carried out in accordance with the standard GB / T1345 - 2005; the content of free calcium oxide in the clinker is determined in accordance with GB / T176 - 2008; the compressive strength of the clinker is carried out in accordance with the standard GB / T17671 - 2021.

[0049] In Examples 1 - 6, the organic acid salts in the surfactant are obtained by mixing sodium citrate, sodium valerate, disodium succinate, disodium adipate, and sodium humate in a mass ratio of 2:1:1:2:2. The component ratios of the surfactant in Examples 1 - 6 are shown in Table 1.

[0050] Example 1

[0051] A preparation method of an environmentally friendly cement raw material grinding aid and mineralizer. The specific method is as follows: At room temperature, pulp sulfite waste liquor and electrolytic manganese slag are placed in a closed container according to a mass ratio of pulp sulfite waste liquor to electrolytic manganese slag (dry basis) of 2:1, mixed and stirred evenly to form a slurry. The closed container is connected to a dilute acid solution through a pipeline to recover the volatilized ammonia. After the slurry is allowed to stand for 3 h, vacuum dehydration is carried out by a vacuum belt filter to complete solid-liquid separation; the solid phase after solid-liquid separation is the raw material grinding aid and mineralizer A. The liquid phase after solid-liquid separation is heated to 40 °C, and according to a mass ratio of liquid phase to surfactant of 0.5:1, the surfactant is added to the liquid phase after solid-liquid separation and stirred evenly to obtain the cement raw material grinding aid and mineralizer B. The component ratios of the surfactant are shown in Table 1. The polyhydric alcohols in the surfactant are obtained by mixing polyglycerol, polyethylene glycol, and propylene glycol in a mass ratio of 2:1:1.

[0052] Industrial experiment effect: An industrial experiment was carried out on a new dry-process cement clinker production line with a capacity of 6000 t / d in Hunan. The cement raw material grinding and mineralizing agent A of this embodiment was incorporated into the cement raw materials at a ratio of 3.0%, and the cement raw material grinding and mineralizing agent B of this embodiment was added to the cement raw materials at a ratio of 0.10%. Then it entered the raw material vertical mill system for grinding. The conditions for raw material grinding were that the fineness control (residue on a 200μm square-hole sieve) was less than 2%; the ground raw material powder was sent to the pre-calciner kiln system for decomposition and calcination, and the calcination conditions ensured that the free calcium oxide in the clinker was qualified.

[0053] Detection: Under the same grinding conditions and calcination conditions, by detecting the central control operation parameters during the blank period (5 days), transition period (2 days), and comparison period (5 days), the hourly output of the raw material mill, the power consumption of raw material grinding, the feeding amount of raw material into the kiln, the carbonate decomposition rate of the raw material into the kiln, the outlet temperature of the decomposition furnace, the average standard coal consumption for clinker calcination, the qualified rate of free calcium oxide in the clinker, and the change in the compressive strength of the clinker before and after using the cement grinding and mineralizing agent (blank period, comparison period) were compared to analyze the effect of the raw material grinding and mineralizing agent. The detection results are shown in Table 2.

[0054]

[0055] As can be seen from Table 2: When 3.0% of the cement raw material grinding and mineralizing agent A and 0.10% of the cement raw material grinding and mineralizing agent B were incorporated while keeping the process quality parameters of the raw material vertical mill unchanged, the grindability of the raw material was greatly improved. Compared with the blank sample, the residue on a 200μm sieve of the ground raw material decreased by 0.23%. The hourly output of the raw material mill increased from 498.05 t to 509.36 t, and the grinding efficiency was significantly improved. When the fineness of the raw material decreased, the hourly output increased by 11.31 t / h (the maximum hourly output of the vertical mill was limited to 510 t / h due to the rated power of the elevator in the storage bin). The power consumption per ton of raw material decreased by 0.95 kW·h; the burnability of the clinker was significantly improved. When the strength of the clinker was basically stable, the daily output of the clinker increased by 72.5 t, the outlet temperature of the decomposition furnace decreased by 5°C, the calcium carbonate decomposition rate of the raw material into the kiln increased by 2.5%, the qualified rate of free calcium oxide increased from 67.5% to 85.9%, an increase of 18.4%, and the standard coal consumption of the clinker decreased by 3.91 kgce / t. It can be seen that this raw material mineralizing and grinding aid can effectively increase the hourly output of the vertical mill, reduce the calcium carbonate decomposition temperature, and improve the qualified rate of free calcium oxide in the clinker, thereby achieving the purpose of improving the burnability of the raw material and reducing coal consumption.

[0056] Example 2

[0057] A preparation method of an environment-friendly grinding aid and mineralizer for cement raw meal. The specific method is different from that of Example 1 in that: in the grinding aid and mineralizer B for cement raw meal, the mass ratio of the liquid phase after solid-liquid separation to the active agent is 1:1. In the components of the active agent (see Table 1), the dosages of sodium lignosulfonate and sodium dodecyl sulfate are adjusted. An industrial test is carried out on a 5000t / d new dry-process cement clinker production line in Shaanxi. The test conditions and detection parameters are different from those of Example 1 in that the dosage of the grinding aid and mineralizer B for cement raw meal is 0.20%, and the condition of raw meal grinding is that the fineness control (residue on a 200μm square-hole sieve) is less than 1.0%. The test results are shown in Table 3.

[0058]

[0059] As can be seen from Table 3: When the process quality parameters of the raw meal vertical mill are kept unchanged, after adding 3.0% of the grinding aid and mineralizer A for cement raw meal and 0.20% of the grinding aid and mineralizer B for cement raw meal, the grindability of the raw meal is greatly improved. Compared with the blank sample, the residue on a 200μm sieve of the discharged raw meal is reduced by 0.1%. The hourly output of the raw meal mill is increased from 458.64t to 486.06t, and the grinding efficiency is significantly improved. When the fineness of the raw meal decreases, the hourly output is increased by 27.42t / h, and the power consumption per ton of raw meal is reduced by 0.21kW·h. The burnability of the clinker is significantly improved. When the strength of the clinker is basically stable, the daily output of the clinker is increased by 110t, the temperature at the outlet of the decomposition furnace is reduced by 13°C, the calcium carbonate decomposition rate of the raw meal entering the kiln is increased by 3.0%, the qualified rate of free calcium oxide is increased from 91% to 100%, an increase of 9%, and the standard coal consumption of the clinker is reduced by 4.09kgce / t. It can be seen that: This grinding aid and mineralizer for raw meal can effectively increase the hourly output of the vertical mill, reduce the calcium carbonate decomposition temperature, and increase the qualified rate of free calcium oxide in the clinker, so as to achieve the purpose of improving the burnability of the raw meal and reducing the coal consumption.

[0060] Example 3

[0061] A preparation method of an environment-friendly grinding aid and mineralizer for cement raw meal. The specific method is as follows: The saponification waste alkali liquor after the saponification reaction in the soap production process and electrolytic manganese slag are placed in a closed container according to the ratio of saponification waste alkali liquor after the saponification reaction in the soap production process: electrolytic manganese slag (dry basis) = 1:1 (mass ratio), and mixed and stirred evenly to form a slurry. The closed container is connected to a dilute acid solution through a pipeline to recover the volatilized ammonia. After the slurry is left standing for 0.5 h, vacuum dehydration is carried out by a vacuum belt filter to complete solid-liquid separation. The solid phase after solid-liquid separation is the grinding aid and mineralizer A for cement raw meal. The liquid phase after solid-liquid separation is heated to 60 °C, and an active agent is added to the liquid phase after solid-liquid separation according to the mass ratio of the liquid phase after solid-liquid separation to the active agent of 2:1, and stirred evenly to obtain the grinding aid and mineralizer B for cement raw meal. The polyols in the active agent are obtained by mixing triglycerol, polypropylene glycol, and glycerol in a mass ratio of 2:1:1. The component ratios of the active agent are shown in Table 1;

[0062] Industrial experiment effect: An industrial experiment was carried out on a new dry-process cement clinker production line with a daily output of 5000 t / d in Shaanxi. The grinding aid and mineralizer A for cement raw meal in this example was incorporated into the cement raw materials at a ratio of 8.0%, and the grinding aid and mineralizer B for cement raw meal in this example was added to the cement raw materials at a ratio of 0.01%. Then, it entered the raw material roller press for grinding. The conditions for raw meal grinding were that the fineness control (200 μm) was less than 5%; the raw meal grinding product was sent to the precalciner system for decomposition and calcination, and the calcination conditions ensured that the free calcium oxide in the clinker was qualified.

[0063] The detection method is the same as that in Example 1, and the detection results are shown in Table 4.

[0064]

[0065] It can be seen from Table 4 that: When 8.0% of the grinding aid and mineralizer A for cement raw meal and 0.01% of the grinding aid and mineralizer B for cement raw meal are incorporated while keeping the technological quality parameters of the raw meal roller press unchanged, the grindability of the raw meal is greatly improved. Compared with the blank sample, the residue on a 200-μm sieve of the raw meal out of the mill is reduced by 0.1%, the hourly output of the raw meal mill is increased from 567 t to 593 t, the grinding efficiency is significantly improved. When the fineness of the raw meal decreases, the hourly output increases by 26 t / h, and the power consumption per ton of raw meal decreases by 0.19 kW·h; the burnability of the clinker is significantly improved. When the strength of the clinker is basically stable, the daily output of the clinker increases by 21 t, the temperature at the outlet of the decomposition furnace decreases by 5 °C, the decomposition rate of calcium carbonate in the raw meal entering the kiln increases by 2.1%, the qualified rate of free calcium oxide increases from 96.7% to 98.3%, an increase of 1.6%, and the standard coal consumption of the clinker decreases by 4.44 kgce / t. It can be seen that: This raw meal mineralization and grinding aid can effectively improve the hourly output of the roller press, reduce the calcium carbonate decomposition temperature, and improve the qualified rate of free calcium oxide in the clinker, so as to achieve the purpose of improving the burnability of the raw meal and reducing the coal consumption.

[0066] Example 4

[0067] A preparation method of an environment-friendly cement raw meal grinding mineralizer, the specific method is different from that of Example 3 in that: in the cement raw meal grinding mineralizer B, the mass ratio of the liquid phase after solid-liquid separation to the active agent is 1:1, and the components of the active agent (see Table 1) are also different. An industrial test was carried out on a new dry-process cement clinker production line with a daily output of 5000t / d in Hunan. The test conditions and detection parameters are different from those of Example 3 in that the dosage of the cement raw meal grinding mineralizer B is 0.02%, the raw meal mill uses a vertical mill system, and the conditions for raw meal grinding are that the fineness control (residue on a 200μm square hole sieve) is less than 5.0%. The test results are shown in Table 5.

[0068]

[0069] It can be seen from Table 5 that: when the process quality parameters of the raw meal roller press are kept unchanged, after adding 8.0% of the raw meal grinding mineralizer A and 0.02% of the raw meal grinding mineralizer B, the grindability of the raw meal is greatly improved. Compared with the blank sample, the residue on a 200μm sieve of the discharged raw meal is reduced by 0.1%, the hourly output of the raw meal mill is increased from 464.59t to 478.84t, the grinding efficiency is significantly improved. When the fineness of the raw meal decreases, the hourly output increases by 14.25t / h, and the power consumption per ton of raw meal decreases by 0.88kW·h; the burnability of the clinker is significantly improved. When the strength of the clinker is basically stable, the daily output of the clinker increases by 38t, the temperature at the outlet of the decomposition furnace decreases by 5℃, the calcium carbonate decomposition rate of the raw meal entering the kiln increases by 1.9%, the qualified rate of free calcium oxide increases from 94.05% to 97.06%, an increase of 3.01%, and the standard coal consumption of the clinker decreases by 4.58kgce / t. It can be seen that: this raw meal mineralization grinding aid can effectively improve the hourly output of the raw meal vertical mill, reduce the calcium carbonate decomposition temperature, and improve the qualified rate of free calcium oxide in the clinker, so as to achieve the purpose of improving the burnability of the raw meal and reducing the coal consumption.

[0070] Example 5

[0071] A preparation method of an environment-friendly grinding aid and mineralizer for cement raw meal. The specific method is as follows: Mix industrial waste alkali solution (mixed): electrolytic manganese slag (dry basis) = 1.5:1 (mass ratio) in a closed container, stir evenly to form a slurry. The closed container is connected to a dilute acid solution through a pipeline to recover the volatilized ammonia. After the slurry stands for 1.5 h, vacuum dehydration is carried out by a vacuum belt filter to complete solid-liquid separation. The solid phase after solid-liquid separation is the grinding aid and mineralizer A for cement raw meal. Heat the liquid phase after solid-liquid separation to 50 °C, and add an active agent to the liquid phase after solid-liquid separation according to the mass ratio of the liquid phase after solid-liquid separation to the active agent of 1.5:1, and stir evenly to obtain the grinding aid and mineralizer B for cement raw meal. The polyhydric alcohol in the active agent is obtained by mixing triglycerol, polypropylene glycol, and ethylene glycol according to the mass ratio of 2:1:1. The component ratios of the active agent are shown in Table 1.

[0072] Industrial experiment effect: An industrial experiment was carried out on a 5000 t / d new dry-process cement clinker production line in Hebei. The grinding aid and mineralizer A for cement raw meal in this example was incorporated into the cement raw materials at a ratio of 5.0%, and the grinding aid and mineralizer B for cement raw meal in this example was added to the cement raw materials at a ratio of 0.08%. Then it entered the raw material vertical mill system for grinding. The conditions for raw meal grinding were that the fineness control (residue on a 200-μm square-hole sieve) was less than 2.0%. The raw meal grinding product was sent to the pre-decomposition kiln system for decomposition and calcination, and the calcination conditions ensured that the free calcium oxide in the clinker was qualified.

[0073] The detection method is the same as that in Example 1, and the detection results are shown in Table 6.

[0074]

[0075] It can be seen from Table 6 that: When the process quality parameters of the raw meal vertical mill remain unchanged, after incorporating 5.0% of the grinding aid and mineralizer A for cement raw meal and 0.08% of the grinding aid and mineralizer B for cement raw meal, the grindability of the raw meal is greatly improved. Compared with the blank sample, the residue on a 200-μm sieve of the raw meal out of the mill is reduced by 0.2%. The hourly output of the raw meal mill increases from 532.75 t to 573.70 t, and the grinding efficiency is significantly improved. When the fineness of the raw meal decreases, the hourly output increases by 40.95 t / h, and the power consumption per ton of raw meal decreases by 1.01 kW·h. The burnability of the clinker is significantly improved. When the strength of the clinker is basically stable, the daily output of the clinker increases by 12 t, the temperature at the outlet of the decomposition furnace decreases by 15 °C, the decomposition rate of calcium carbonate in the raw meal entering the kiln increases by 1.5%, the qualified rate of free calcium oxide increases from 89.58% to 94.79%, an increase of 5.21%, and the standard coal consumption of the clinker decreases by 5.06 kgce / t. It can be seen that: This grinding aid and mineralizer for raw meal can effectively improve the hourly output of the raw meal vertical mill, reduce the calcium carbonate decomposition temperature, and improve the qualified rate of free calcium oxide in the clinker, so as to achieve the purpose of improving the burnability of the raw meal and reducing the coal consumption.

[0076] Example 6

[0077] A preparation method of an environment-friendly grinding aid and mineralizer for cement raw meal, the difference from Example 5 in the specific method lies in that: the components of the active agent (see Table 1) are different. An industrial test was carried out on a new dry-process cement clinker production line with a daily output of 5000 t / d in Shaanxi. The difference in test conditions and detection parameters from Example 5 is that the dosage of grinding aid and mineralizer B for raw meal is 0.12%, the raw meal mill adopts a roller press system, and the condition for raw meal grinding is that the fineness control (residue on a 200-μm square-hole sieve) is less than 4.0%. The test results are shown in Table 7.

[0078]

[0079] It can be seen from Table 7 that: when 5.0% of grinding aid and mineralizer A for raw meal and 0.12% of grinding aid and mineralizer B for raw meal are incorporated while keeping the technological quality parameters of the raw meal roller press unchanged, the grindability of the raw meal is greatly improved. Compared with the blank sample, the residue on a 200-μm sieve of the raw meal leaving the mill is reduced by 0.5%, the hourly output of the raw meal mill is increased from 523.96 t to 565.74 t, the grinding efficiency is significantly improved. When the fineness of the raw meal decreases, the hourly output increases by 41.78 t / h, and the power consumption per ton of raw meal decreases by 0.76 kW·h; the burnability of the clinker is significantly improved. When the strength of the clinker is basically stable, the daily output of the clinker increases by 192 t, the temperature at the outlet of the decomposition furnace decreases by 15 °C, the decomposition rate of calcium carbonate in the raw meal entering the kiln increases by 1.5%, the qualified rate of free calcium oxide increases from 88.89% to 95.84%, an increase of 6.95%, and the standard coal consumption of the clinker decreases by 6.43 kgce / t. It can be seen that: this grinding aid and mineralizer for raw meal can effectively increase the hourly output of the raw meal vertical mill, reduce the calcium carbonate decomposition temperature, and increase the qualified rate of free calcium oxide in the clinker, so as to achieve the purpose of improving the burnability of the raw meal and reducing the coal consumption.

[0080] Generally speaking, the grinding aid and mineralizer for raw meal prepared from two kinds of industrial waste alkali liquors of electrolytic manganese slag both have the function of increasing the output of the raw meal grinding system and reducing the heat consumption for clinker burning. Due to the differences in the actual raw fuels and production processes of cement enterprises, there are significant differences in the application effects of the grinding aid and mineralizer for cement raw meal. When ensuring the quality of the clinker, the standard coal consumption for clinker burning is reduced by more than 3.91 kgce / t.

[0081] The above embodiments are only examples for explaining the present invention, specific implementation manners and implementation effects, and they are not limitations of the present invention. Based on the present disclosure, some modifications or improvements without creative contributions can be made, which are obvious to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present disclosure all fall within the scope protected by the present disclosure.

Claims

1. A preparation method of an environmentally friendly cement raw meal grinding mineralizer, characterized in that It includes the following steps: Step 1: At room temperature, place industrial waste alkali liquor and electrolytic manganese residue in a closed container according to the mass ratio of industrial waste alkali liquor to dry basis of electrolytic manganese residue being 1-2:

1. The closed container is connected to a dilute acid solution or water. Step 2: After stirring the mixture in the closed container evenly to form a slurry solution, let it stand for 0.5-3 h and then carry out solid-liquid separation. The solid phase after solid-liquid separation is the grinding aid and mineralizer A for cement raw meal, and the grinding aid and mineralizer A for cement raw meal contains 15-30% moisture; after the liquid phase after solid-liquid separation is heated to 40-60 °C, add an active agent and stir evenly to obtain the grinding aid and mineralizer B for cement raw meal. The industrial waste alkali liquor is obtained by mixing spent sulfite liquor from pulp soda sulfite cooking and spent alkali liquor from saponification reaction in soap production according to the mass ratio of 2:

3. The active agent is prepared from the following raw materials by weight percentage: 0-25% of lignosulfonate, 0-50% of organic acid salt, 30-70% of polyol, and 5-20% of sodium dodecyl sulfate. During application, the grinding aid and mineralizer A for cement raw meal and the grinding aid and mineralizer B for cement raw meal are separately metered and then added to the cement raw materials separately for grinding.

2. The preparation method of an environment-friendly cement raw meal grinding mineralizer according to claim 1, characterized in that: The electrolytic manganese residue is at least one of wet fresh electrolytic manganese residue, stockpiled and dried electrolytic manganese residue, and electrolytic manganese residue mixed with other wastes, with a pH value of 4.00-6.50 and a moisture content of 0-40%.

3. The preparation method of an environment-friendly cement raw meal grinding mineralizer according to claim 1, characterized in that: The pH value of the industrial waste alkali liquor is 9.0-14.0, and it contains at least one of sodium hydroxide, lignosulfonate, sodium carbonate, sodium sulfate, organic acid salt, potassium hydroxide, and polyol.

4. The preparation method of an environment-friendly cement raw meal grinding mineralizer according to claim 1, characterized in that: In step 2, the slurry solution stands for 1-2 h and then solid-liquid separation is carried out; in step 3, the liquid phase after solid-liquid separation is heated to 50 °C; the mass ratio of the liquid phase after solid-liquid separation to the added active agent is (0.5-2):

1.

5. The preparation method of an environment-friendly cement raw meal grinding mineralizer according to claim 1, characterized in that: The lignosulfonate in the active agent includes at least one of sodium lignosulfonate and calcium lignosulfonate; the organic acid salt is obtained by mixing sodium citrate, sodium valerate, disodium succinate, disodium adipate, and sodium humate according to the mass ratio of 2:1:1:2:

2.

6. The preparation method of an environmentally friendly cement raw meal grinding mineralizer according to claim 1, characterized in that: The polyol includes at least one of triglycerol, polypropylene glycol, ethylene glycol, propylene glycol, glycerol, and polyethylene glycol.

7. The preparation method of an environment-friendly cement raw meal grinding and mineralizing agent according to claim 6, characterized in that: The polyol is obtained by mixing triglycerol, polypropylene glycol, and ethylene glycol according to the mass ratio of 2:1:

1.

8. Use of a cement raw material grinding and mineralizing agent prepared by the preparation method of the environment-friendly cement raw material grinding and mineralizing agent according to any one of claims 1-7, characterized in that: The dry basis mass ratio of the grinding aid and mineralizer A for cement raw meal in the cement raw meal to be ground is: 3.0-8.0%; the dosage of the grinding aid and mineralizer B for cement raw meal is 0.01-0.2% of the weight of the cement raw meal to be ground.

9. Application of the grinding aid and mineralizer for cement raw meal prepared by the preparation method of the environment-friendly grinding aid and mineralizer for cement raw meal according to claim 8, characterized in that: The dosage of the grinding aid and mineralizer B for cement raw meal is 0.08-0.12% of the weight of the cement raw meal to be ground; the grinding aid and mineralizer A for cement raw meal is used alone as a component and mixed with other raw materials for grinding, or mixed and homogenized with difficult-to-grind materials such as limestone and sandstone and then mixed for grinding; the grinding aid and mineralizer B for cement raw meal is metered alone as a component and then incorporated into difficult-to-grind materials such as limestone and sandstone for grinding together.

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