Preparation method and application of environment-friendly cement raw material grinding-aid grinding agent

Abstract

The invention belongs to the technical field of cement production, and discloses a preparation method and application of an environment-friendly cement raw material grinding-aid grinding agent, at room temperature, industrial waste alkali liquor and electrolytic manganese residues are placed in a closed container according to the mass ratio of industrial waste alkali liquor to electrolytic manganese residue dry basis of (1-2): 1, and a slurry solution is prepared after uniform stirring; standing for 0.5-3 hours, and then carrying out solid-liquid separation; the solid phase obtained after solid-liquid separation is the cement raw material grinding-aid grinding agent A, and the liquid phase obtained after solid-liquid separation is heated, an active agent is added, and the mixture is stirred to be uniform to obtain a cement raw material grinding-aid grinding agent B; based on the coprecipitation principle and the principle of treating waste with waste, the raw material grinding aid mineralizer is prepared after the solid waste electrolytic manganese residues and the industrial waste alkali liquor are co-treated, the burnability of the cement raw material is effectively improved while the solid waste is co-treated, the clinker firing heat consumption is reduced, and the production cost is reduced. The method has remarkable environmental protection benefits while saving energy and reducing consumption in cement production.

Description

Technical Field

[0001] The invention belongs to the technical field of cement production, and in particular relates to a preparation method and application of an environmentally friendly cement raw material grinding aid mineralizer. Background Art

[0002] The production process of modern Portland cement can be divided into three main stages, usually referred to as "two grindings and one burning": after the calcium raw materials, silicon-aluminum raw materials and iron raw materials are crushed, mixed in a certain proportion, and ground into raw materials with uniform composition through a raw material vertical mill system or a roller press system, which is called raw material preparation; after the raw materials are dried and dehydrated, preheated and decomposed, solid-phase reacted, clinker sintered and cooled in the pre-decomposition kiln system, the Portland cement clinker with calcium silicate as the main component is obtained, which is called clinker calcination; the Portland cement clinker is added with an appropriate amount of gypsum and specified admixtures and ground together to make cement.

[0003] At present, with the continuous improvement of energy, resources and environmental protection requirements for the development of the cement industry, improving the energy utilization efficiency in the cement production process, saving resources and reducing energy consumption are inevitable requirements for the sustainable development of the cement industry. As far as the cement production process is concerned, 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 materials. The use of advanced technology to improve the burnability of raw materials, 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 materials refers to the difficulty of cement raw materials to form clinker minerals through physical and chemical changes in solid, liquid and gas phase environments. The measures to improve the burnability of raw meal mainly include: controlling the quality of raw materials, rationally proportioning, improving uniformity, adding additives to aid grinding, desulfurization, decomposition, coal saving, etc. to improve the fineness and particle distribution of raw meal (Chinese patent documents CN110981238B, CN112759289B, CN113800796A, CN114620967A, CN115028379B, CN116921049 A, CN117417140A, etc.), or using industrial waste slag 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 slag (Chinese patent documents CN114477844B, CN114804678A, CN116040968A, CN117623671A, CN86108664A, etc.). The above-mentioned auxiliary raw materials are mostly pure chemical reagents, with high utilization costs and low comprehensive benefits.

[0004] Electrolytic manganese slag is a solid waste produced by the wet electrolysis of manganese carbonate ore after sulfuric acid leaching and ammonia neutralization. The pH value is generally 4.00-6.50, and the moisture content is 30-40%. The main mineral components are sulfate (mainly dihydrate gypsum) and SiO 2 (Quartz), 2CaO·SiO 2 ·2H 2 O(C 2 SH 2 ) and Fe 2 O 3 etc., among which SO 3 The proportion of gypsum (if the CaO content is high) is 20-37%, which is more than 45%. That is, electrolytic manganese slag is actually a low-grade industrial by-product chemical gypsum or sulfate waste slag, and also contains a large amount of soluble MnSO 4 NH 4 ) 2 SO 4 MgSO 4 One or more composite dyes. Electrolysis of 1 ton of manganese metal will produce 10-12 tons of electrolytic manganese slag. At present, the annual discharge of electrolytic manganese slag in my country has reached more than 10 million tons, and the cumulative stockpile has reached more than 160 million tons. Due to the large discharge of electrolytic manganese slag, the fine particles of electrolytic manganese slag, and the presence of a large amount of sulfate, ammonia nitrogen and a certain amount of heavy metal harmful elements, if it is allowed to be discharged, it 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 my country's circular economy. At present, the application of electrolytic manganese slag in silicate cement is mainly concentrated in: replacing part of gypsum as a retarder (Chinese patent document CN113603377A), a chromium reducing agent (Chinese patent document CN112110671A) or an admixture (Chinese patent document CN112110671A) in the cement grinding process; using it as a cement raw material or admixture after desulfurization of the reducing agent (Chinese patent documents CN103771734B, CN117486510); using it as a raw material for semi-dry rotary kiln (Chinese patent document CN100369847C); or continuously feeding the electrolytic manganese slag into the kiln tail smoke chamber of the dry rotary kiln production line equipment for coordinated disposal (Chinese patent document CN110986577A). Although electrolytic manganese slag can be used directly as a cement mineralizer (Wang Yong, Research on electrolytic manganese slag as cement mineralizer, Concrete, 2010, (08), 90-93), direct use can easily cause problems such as excessive ammonia and sulfur dioxide content in flue gas.

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

[0006] At present, there are few studies on the synergistic utilization of various industrial waste residues to play the role of raw meal grinding aid and mineralizer. How to synergistically utilize various industrial waste residues to prepare cement raw meal grinding aid and mineralizer, and apply it to cement production, while effectively improving the combustibility of cement raw meal and reducing the heat consumption of clinker burning, and having significant environmental benefits while saving energy and reducing consumption in cement production, is a topic that urgently needs to be studied and 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 solution are synergistically treated to prepare the cement raw meal grinding aid mineralizer. While utilizing the synergistic treatment of solid waste, the purpose of effectively improving the burnability of cement raw meal and reducing the heat consumption of clinker burning can be achieved. It 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 method for preparing an environmentally friendly cement raw material grinding aid mineralizer, comprising the following steps: Step 1: at room temperature, placing industrial waste alkali solution and electrolytic manganese slag in a closed container at a mass ratio of 1 to 2:1 between the industrial waste alkali solution and the electrolytic manganese slag on a dry basis, and connecting the closed container to a dilute acid solution or water; Step 2: Stir the mixture in the sealed container to make a slurry solution, and then let it stand for 0.5 to 3 hours to separate the solid and liquid; Step 3: The solid phase after solid-liquid separation is cement raw meal grinding aid mineralizer A, which contains 15-30% water; after the liquid phase after solid-liquid separation is heated to 40-60°C, an activator is added and stirred evenly to obtain cement raw meal grinding aid mineralizer B.

[0009] The electrolytic manganese slag is at least one of wet fresh electrolytic manganese slag, stored 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%.

[0010] The industrial waste alkali liquor is at least one of pulp alkaline sulfite cooking waste liquor and saponification waste alkali liquor from saponification reaction in soap production, has a pH value of 9.0-14.0, and contains at least one of sodium hydroxide, lignin sulfonate, sodium carbonate, sodium sulfate, organic acid salt, potassium hydroxide, and polyol.

[0011] Preferably, the industrial waste alkali liquor is a mixed industrial waste alkali liquor obtained by mixing pulp alkaline sulfite cooking waste liquor and saponification waste alkali liquor from saponification reaction in the production process of cyclic soap in a mass ratio of 2:3.

[0012] The sealed container is connected to a dilute acid solution or water to recover the volatilized ammonia.

[0013] Preferably, the slurry solution in step 2 is allowed to stand for 1 to 2 hours.

[0014] Preferably, the liquid phase heating temperature after solid-liquid separation in step three is 50°C.

[0015] In the step 3, the mass ratio of the liquid phase after solid-liquid separation to the active agent is 0.5 to 2:1.

[0016] The active agent is prepared from the following raw materials in weight percentage: 0-25% of lignin sulfonate, 0-50% of organic acid salt, 30-70% of polyol and 5-20% of sodium dodecyl sulfate.

[0017] The lignin sulfonate includes at least one of sodium lignin sulfonate and calcium lignin sulfonate.

[0018] 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.

[0019] The polyol includes at least one selected from the group consisting of triglycerol, polypropylene glycol, ethylene glycol, propylene glycol, glycerol and polyethylene glycol.

[0020] Preferably, the polyol is obtained by mixing triglycerol, polypropylene glycol and ethylene glycol in a mass ratio of 2:1:1.

[0021] The application of the environmentally friendly cement raw meal grinding aid mineralizer prepared by the above preparation method is specifically as follows: the cement raw meal grinding aid mineralizer A and the cement raw meal grinding aid mineralizer B are respectively measured and added to the cement raw material for grinding; The cement raw material grinding aid mineralizer A can be used as a single component and mixed with other raw materials before grinding, or mixed with limestone, sandstone and other difficult-to-grind materials and then mixed and ground.

[0022] The cement raw material grinding aid mineralizer B is measured as a single component and then added to limestone, sandstone and other hard-to-grind materials for grinding.

[0023] The amount of the cement raw material grinding aid mineralizer A in the cement raw material to be ground (dry basis mass ratio) is 3.0-8.0%.

[0024] The external admixture mass ratio of cement raw meal grinding aid mineralizer A (dry basis) = cement raw meal grinding aid mineralizer A / (cement raw meal to be ground + cement raw meal grinding aid mineralizer A).

[0025] The amount of the cement raw material grinding aid mineralizer B is 0.01-0.2% of the weight of the cement raw material to be ground, preferably 0.08-0.12%.

[0026] The mass ratio of cement raw meal grinding aid mineralizer B added = cement raw meal grinding aid mineralizer B / cement raw meal to be ground.

[0027] The basic principle of the present invention is that after adding alkaline waste liquid to electrolytic manganese slag, soluble Mn 2+ and NH 4 + Enter the solution and fully react with the alkaline components in the waste alkali. Under alkaline conditions, Mn in the electrolytic manganese slag filtrate 2+ Transformed into stable MnO(OH) 2 Precipitated on the solid phase, NH 4 + Converted to NH 3 After release, it is recycled by solvent absorption. The reaction formula is as follows: Mn 2+ +2OH - →Mn(OH) 2 2Mn(OH) 2 +O 2 →2MnO(OH) 2 NH 4 + +OH - →NH 3 +H 2 O The surface active components such as lignin sulfonate, organic acid salt, polyol ether contained in industrial waste alkali liquor are easily adsorbed on the surface of particles, preventing the re-healing of microcracks 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 materials. Organic components such as organic acid salt in industrial waste alkali liquor can also react with calcium carbonate in cement raw materials to produce intermediates, promoting the degradation of CaCO in raw materials. 3 decomposition; calcium sulfate in electrolytic manganese slag and MnO(OH) converted from soluble manganese salts in industrial waste alkali solution2 They can all be used as cement mineralizers to increase the reactivity of silicate minerals and generate a transition phase that is 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; thereby reducing the heat consumption of firing of clinker minerals; at the same time, alkaline components such as sodium hydroxide and sodium carbonate in industrial waste alkali liquid can also reduce the sulfur dioxide content in flue gas and play a role in sulfur fixation.

[0028] The beneficial effects of the present invention are as follows: compared with the prior art, the present invention is based on the co-precipitation principle and the principle of "treating waste with waste", and uses solid waste electrolytic manganese slag and industrial waste alkali liquor for synergistic treatment to prepare raw material grinding aid mineralizer, and fully utilizes the alkaline environment of industrial waste alkali liquor to treat weakly acidic electrolytic manganese slag, while removing the ammonia nitrogen component in the electrolytic manganese slag, converting and precipitating the soluble manganese salt and becoming an effective component of cement mineralizer together with the gypsum phase in the electrolytic manganese slag; and fully utilizes the active ingredients such as lignin sulfonate, organic acid salt, polyol contained in the industrial waste alkali liquor to improve the grindability and burnability of cement raw material, reduce the power consumption of raw material grinding, and reduce the standard coal consumption of clinker burning by 3-6kgce / t while ensuring the quality of clinker; at the same time, silicon, aluminum, calcium, iron, etc. of electrolytic manganese slag can also provide the components required for cement raw material. The present invention achieves the purpose of effectively improving the burnability of cement raw material and reducing the heat consumption of clinker burning while utilizing the synergistic treatment of solid waste, and has significant environmental benefits while saving energy and reducing consumption in cement production. DETAILED DESCRIPTION

[0029] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0030] Unless otherwise specified, the raw materials used in the examples are as follows: Electrolytic manganese slag: A manganese company stored dried electrolytic manganese slag with a moisture content of 18.5% and a pH value of 5.50. Its main chemical components (mass percentage) are: SiO 2 35.12wt.%Fe 2 O 3 5.12wt.%Al 2 O 3 12.01wt.%, CaO9.23wt.%, MgO2.96wt.%, MnO3.43wt.%, SO 3 31.57wt.%TiO 2 0.29wt.%NH 4+ 0.17wt.%.

[0031] Pulp sulfite waste liquid: taken from pulp alkaline sulfite cooking waste liquid of a paper company, with a relative density of 1.078g / cm 3, moisture content 50%, pH value 9.5.

[0032] Waste lye from saponification: Waste lye from saponification reaction in the soap production process of a nylon technology company, with a relative density of 1.17 g / cm 3 , water content is 62%, pH value is 13.5.

[0033] Industrial waste alkali liquor (mixed): obtained by mixing the waste liquor from pulp alkaline sulfite cooking and the saponification waste alkali liquor from the saponification reaction in the soap production process in a mass ratio of 2:3.

[0034] Sodium lignin sulfonate, sodium citrate, disodium succinate, sodium valerate, disodium adipate, triglycerol, polypropylene glycol, ethylene glycol, sodium dodecyl sulfate, and sodium humate are all commercially available industrial pure products, and different brands of products do not affect their use.

[0035] The cement raw material grinding aid mineralizer A after solid-liquid separation in the embodiment contains 20% water, and is mixed with other raw materials as a component before being put into the mill.

[0036] The external admixture mass ratio of cement raw meal grinding aid mineralizer A (dry basis) = cement raw meal grinding aid mineralizer A / (cement raw meal to be ground + cement raw meal grinding aid mineralizer A).

[0037] In the embodiment, the cement raw meal grinding aid mineralizer B is measured as a single component and then added to the surface of the measured limestone.

[0038] In the embodiment, the mass ratio of cement raw meal grinding aid mineralizer B added = cement raw meal grinding aid mineralizer B / cement raw meal to be ground.

[0039] The fineness test is carried out in accordance with the standard GB / T1345-2005; the free calcium oxide content 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.

[0040] The organic acid salt in the active agent of Examples 1-6 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. The distribution ratios of the active agents in Examples 1-6 are shown in Table 1.

[0041] Example 1 A method for preparing an environmentally friendly cement raw material grinding aid mineralizer, the specific method is: at room temperature, pulp sulfite waste liquid and electrolytic manganese slag are placed in a closed container according to the mass ratio of pulp sulfite waste liquid 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 gas, the slurry is left to stand for 3 hours, and then vacuum dehydrated by a vacuum belt conveyor to complete solid-liquid separation; the solid phase after solid-liquid separation is the raw material grinding aid mineralizer A, the liquid phase after solid-liquid separation is heated to 40°C, and the activator is added to the liquid phase after solid-liquid separation according to the mass ratio of liquid phase to activator of 0.5:1, and stirred evenly to obtain cement raw material grinding aid mineralizer B. The distribution ratio of each group of the activator is shown in Table 1, and the polyol in the activator is obtained by mixing triglycerol, polyethylene glycol, and propylene glycol in a mass ratio of 2:1:1.

[0042] Industrial experimental effect: An industrial test was carried out on a 6000t / d new dry process cement clinker production line in Hunan. The cement raw material grinding aid mineralizer A of this embodiment was added to the cement raw material at a ratio of 3.0%, and the cement raw material grinding aid mineralizer B of this embodiment was added to the cement raw material at a ratio of 0.10%. Then, the raw material entered the raw material vertical mill system for grinding. The condition for raw material grinding was that the fineness control (200μm square hole sieve residue) was less than 2%; the raw material grinding product was sent to the pre-decomposition kiln system for decomposition and calcination. The calcination conditions ensured that the free calcium oxide in the clinker was qualified.

[0043] Testing: Under the same grinding and calcining conditions, by testing the central control operation parameters of the blank period (5 days), transition period (2 days), and comparison period (5 days), the raw meal mill hourly output, raw meal grinding power consumption, raw meal feed amount into the kiln, raw meal carbonate decomposition rate, decomposition furnace outlet temperature, clinker calcination average standard coal consumption, clinker free calcium oxide qualified rate and clinker compressive strength before and after the use of cement grinding aid mineralizer (blank period, comparison period) were compared to analyze the effect of the raw meal grinding aid mineralizer. The test results are shown in Table 2.

[0044]

[0045] It can be seen from Table 2 that: when the raw material vertical mill process quality parameters remain unchanged, when 3.0% cement raw material grinding aid mineralizer A and 0.10% cement raw material grinding aid mineralizer B are added, the raw material grindability is greatly improved. Compared with the blank sample, the 200μm sieve residue of the raw material out of the mill is reduced by 0.23%, and the raw material mill output per hour is increased from 498.05t to 509.36t. The grinding efficiency is significantly improved. When the raw material fineness decreases, the output per hour is increased by 11.31t / h (storage The rated power of the hoist is limited, and the maximum output of the vertical mill is 510t / h). The power consumption per ton of raw material is reduced by 0.95kW·h; the burnability of clinker is significantly improved. Under the condition that the strength of clinker is basically stable, the daily output of clinker is increased by 72.5t, the outlet temperature of the decomposition furnace is reduced by 5℃, the decomposition rate of calcium carbonate of raw material entering the kiln is increased by 2.5%, the qualified rate of free calcium oxide is increased from 67.5% to 85.9%, an increase of 18.4%, and the standard coal consumption of clinker is reduced by 3.91kgce / t. It can be seen that the raw material mineralization grinding aid can effectively increase the output of the vertical mill, reduce the decomposition temperature of calcium carbonate, and increase the qualified rate of free calcium oxide in clinker, thereby achieving the purpose of improving the burnability of raw material and reducing coal consumption.

[0046] Example 2

[0047] A method for preparing an environmentally friendly cement raw material grinding aid mineralizer, the specific method is different from Example 1 in that: in the cement raw material grinding aid mineralizer B, the mass ratio of the liquid phase after solid-liquid separation to the active agent is 1:1, and the dosage of sodium lignin sulfonate and sodium dodecyl sulfate is adjusted in the components of the active agent (see Table 1). An industrial test was carried out on a 5000t / d new dry process cement clinker production line in Shaanxi. The test conditions and test parameters are different from those in Example 1 in that the dosage of the raw material grinding aid mineralizer B is 0.20%, and the condition for raw material grinding is fineness control (200μm square hole sieve residue) is less than 1.0%. The test results are shown in Table 3.

[0048]

[0049] It can be seen from Table 3 that: when the process quality parameters of the raw meal vertical mill are kept unchanged, after adding 3.0% raw meal grinding aid mineralizer A and 0.20% raw meal grinding aid mineralizer B, the grindability of the raw meal is greatly improved. Compared with the blank sample, the 200μm sieve residue of the raw meal discharged from the mill is reduced by 0.1%, the output of the raw meal mill per unit hour is increased from 458.64t to 486.06t, and the grinding efficiency is significantly improved. When the raw meal fineness decreases, the unit output increases by 27.42t / h, and the power consumption per ton of raw meal decreases by 0.21kW·h; the burnability of the clinker is significantly improved. When the clinker strength is basically stable, the daily output of clinker increases by 110t, the outlet temperature of the calciner decreases by 13℃, the decomposition rate of calcium carbonate of the raw meal entering the kiln increases by 3.0%, the qualified rate of free calcium oxide increases from 91% to 100%, an increase of 9%, and the standard coal consumption of clinker decreases by 4.09kgce / t. It can be seen that the raw meal mineralization grinding aid can effectively increase the hourly output of the vertical mill, reduce the decomposition temperature of calcium carbonate, and increase the qualified rate of free calcium oxide in the clinker, thereby achieving the purpose of improving the burnability of the raw meal and reducing coal consumption.

[0050] Example 3

[0051] A method for preparing an environmentally friendly cement raw material grinding aid mineralizer, the specific method is: saponification waste alkali liquor from saponification reaction in soap production process and electrolytic manganese slag are placed in a closed container according to the saponification waste alkali liquor from saponification reaction in 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 gas, and the slurry is left to stand for 0.5 hours and then vacuum dehydrated by a vacuum belt conveyor to complete solid-liquid separation; the solid phase after solid-liquid separation is cement raw material grinding aid mineralizer A, the liquid phase after solid-liquid separation is heated to 60°C, and the activator is added to the liquid phase after solid-liquid separation at a mass ratio of 2:1 to the activator, and the activator is stirred evenly to obtain cement raw material grinding aid mineralizer B. The polyol in the activator is obtained by mixing triglycerol, polypropylene glycol, and glycerol in a mass ratio of 2:1:1, and the distribution ratio of each group of the activator is shown in Table 1; Industrial experimental results: An industrial test was conducted on a 5000t / d new dry process cement clinker production line in Shaanxi. The cement raw material grinding aid mineralizer A of this embodiment was added to the cement raw material at a ratio of 8.0%, and the cement raw material grinding aid mineralizer B of this embodiment was added to the cement raw material at a ratio of 0.01%. The raw materials were then fed into a raw material roller press system for grinding. The raw material grinding condition was that the fineness (200μm) was controlled to be less than 5%. The raw material grinding product was fed into a pre-decomposition kiln system for decomposition and calcination. The calcination conditions ensured that the free calcium oxide in the clinker was qualified.

[0052] The detection method is the same as in Example 1, and the detection results are shown in Table 4.

[0053]

[0054] It can be seen from Table 4 that: when the process quality parameters of the raw meal roller press remain unchanged, after adding 8.0% raw meal grinding aid mineralizer A and 0.01% raw meal grinding aid mineralizer B, the grindability of the raw meal is greatly improved. Compared with the blank sample, the 200μm sieve residue of the milled raw meal is reduced by 0.1%, the output of the raw meal mill per unit hour is increased from 567t to 593t, and the grinding efficiency is significantly improved. When the raw meal fineness decreases, the unit output increases by 26t / h, and the power consumption per ton of raw meal decreases by 0.19kW·h; the burnability of the clinker is significantly improved. When the clinker strength is basically stable, the daily output of clinker increases by 21t, the outlet temperature of the decomposition furnace decreases by 5℃, the decomposition rate of calcium carbonate of 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 clinker decreases by 4.44kgce / t. It can be seen that the raw meal mineralization grinding aid can effectively increase the hourly output of the roller press, reduce the decomposition temperature of calcium carbonate, and increase the qualified rate of free calcium oxide in the clinker, thereby achieving the purpose of improving the burnability of the raw meal and reducing coal consumption.

[0055] Example 4

[0056] A method for preparing an environmentally friendly cement raw material grinding aid mineralizer, the specific method is different from Example 3 in that: in the cement raw material grinding aid 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 5000t / d new dry process cement clinker production line in Hunan. The test conditions and test parameters are different from those in Example 3 in that the dosage of cement raw material grinding aid mineralizer B is 0.02%, the raw material mill adopts a vertical mill system, and the raw material grinding condition is fineness control (200μm square hole sieve residue) is less than 5.0%. The test results are shown in Table 5.

[0057]

[0058] It can be seen from Table 5 that: when the process quality parameters of the raw meal roller press remain unchanged, after adding 8.0% raw meal grinding aid mineralizer A and 0.02% raw meal grinding aid mineralizer B, the grindability of the raw meal is greatly improved. Compared with the blank sample, the 200μm sieve residue of the milled raw meal is reduced by 0.1%, the raw meal mill output per unit hour is increased from 464.59t to 478.84t, and the grinding efficiency is significantly improved. When the raw meal fineness decreases, the unit 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 clinker strength is basically stable, the daily clinker output increases by 38t, the outlet temperature of the calciner decreases by 5℃, the decomposition rate of calcium carbonate 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 clinker decreases by 4.58kgce / t. It can be seen that the raw meal mineralization grinding aid can effectively increase the hourly output of the raw meal vertical mill, reduce the decomposition temperature of calcium carbonate, and increase the qualified rate of free calcium oxide in the clinker, thereby achieving the purpose of improving the burnability of the raw meal and reducing coal consumption.

[0059] Example 5

[0060] A method for preparing an environmentally friendly cement raw material grinding aid mineralizer, the specific method is: industrial waste alkali solution (mixed): electrolytic manganese slag (dry basis) = 1.5:1 (mass ratio) is placed in a closed container 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 gas, the slurry is left to stand for 1.5 hours, and then vacuum dehydration is performed by a vacuum belt conveyor to complete solid-liquid separation; the solid phase after solid-liquid separation is the raw material grinding aid mineralizer A, the liquid phase after solid-liquid separation is heated to 50°C, and the activator is added to the liquid phase after solid-liquid separation at a mass ratio of 1.5:1 to the activator, and the activator is stirred evenly to obtain the cement raw material grinding aid mineralizer B. The polyol in the activator is obtained by mixing triglycerol, polypropylene glycol, and ethylene glycol at a mass ratio of 2:1:1, and the distribution ratio of each group of the activator is shown in Table 1.

[0061] Industrial experiment effect: An industrial experiment was carried out on a 5000t / d new dry process cement clinker production line in Hebei Province. The cement raw material grinding aid mineralizer A of this embodiment was added to the cement raw material at a ratio of 5.0%, and the cement raw material grinding aid mineralizer B of this embodiment was added to the cement raw material at a ratio of 0.08%. The raw materials were then ground in a raw material vertical mill system. The raw material grinding condition was that the fineness control (200μm square hole sieve residue) was less than 2.0%. The raw material grinding product was sent to a pre-decomposition kiln system for decomposition and calcination. The calcination conditions ensured that the free calcium oxide in the clinker was qualified.

[0062] The detection method is the same as in Example 1, and the detection results are shown in Table 6.

[0063]

[0064] It can be seen from Table 6 that: when the raw meal vertical mill process quality parameters remain unchanged, after adding 5.0% cement raw meal grinding aid mineralizer A and 0.08% cement raw meal grinding aid mineralizer B, the raw meal grindability is greatly improved. Compared with the blank sample, the 200μm sieve residue of the raw meal out of the mill is reduced by 0.2%, the raw meal mill output per unit hour is increased from 532.75t to 573.70t, and the grinding efficiency is significantly improved. When the raw meal fineness decreases, the unit output increases by 40.95t / h, and the power consumption per ton of raw meal decreases by 1.01kW·h; the burnability of the clinker is significantly improved. When the clinker strength is basically stable, the daily clinker output increases by 12t, the outlet temperature of the calciner decreases by 15℃, the decomposition rate of calcium carbonate of 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 clinker decreases by 5.06kgce / t. It can be seen that the raw meal mineralization grinding aid can effectively increase the hourly output of the raw meal vertical mill, reduce the decomposition temperature of calcium carbonate, and increase the qualified rate of free calcium oxide in the clinker, thereby achieving the purpose of improving the burnability of the raw meal and reducing coal consumption.

[0065] Example 6

[0066] A method for preparing an environmentally friendly cement raw material grinding aid mineralizer, the specific method is different from Example 5 in that: the components of the active agent (see Table 1) are different. An industrial test was carried out on a 5000t / d new dry process cement clinker production line in Shaanxi. The test conditions and test parameters are different from those in Example 5 in that the dosage of the raw material grinding aid mineralizer B is 0.12%, the raw material mill adopts a roller press system, and the raw material grinding condition is that the fineness control (200μm square hole sieve residue) is less than 4.0%. The test results are shown in Table 7.

[0067]

[0068] It can be seen from Table 7 that: when the process quality parameters of the raw meal roller press remain unchanged, when 5.0% raw meal grinding aid mineralizer A and 0.12% raw meal grinding aid mineralizer B are added, the grindability of the raw meal is greatly improved. Compared with the blank sample, the 200μm sieve residue of the milled raw meal is reduced by 0.5%, the raw meal mill output per unit hour is increased from 523.96t to 565.74t, and the grinding efficiency is significantly improved. When the raw meal fineness decreases, the unit output increases by 41.78t / h, and the power consumption per ton of raw meal decreases by 0.76kW·h; the burnability of the clinker is significantly improved. When the clinker strength is basically stable, the daily clinker output increases by 192t, the outlet temperature of the calciner decreases by 15℃, the decomposition rate of calcium carbonate of 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 clinker decreases by 6.43kgce / t. It can be seen that the raw meal mineralization grinding aid can effectively increase the hourly output of the raw meal vertical mill, reduce the decomposition temperature of calcium carbonate, and increase the qualified rate of free calcium oxide in the clinker, thereby achieving the purpose of improving the burnability of the raw meal and reducing coal consumption.

[0069] In general, the raw meal grinding aid mineralizers prepared from the two industrial waste alkali solutions of electrolytic manganese slag can increase the output of the raw meal grinding system and reduce the heat consumption of clinker burning. Due to the differences in the actual raw materials and production processes of cement enterprises, there are great differences in the effects of using cement raw meal grinding aid mineralizers. While ensuring the quality of clinker, the standard coal consumption of clinker burning is reduced by more than 3.91kgce / t.

[0070] The above embodiments are merely examples of the explanation, specific implementation and implementation effect of the present invention, and are not limitations of the present invention. Based on the present disclosure, some modifications or improvements without creative contributions may be made thereto, which will be apparent to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present disclosure all belong to the scope of protection claimed in the present disclosure.

Claims

1. A method for preparing an environmentally friendly cement raw material grinding aid mineralizer, characterized in that: The following steps are involved: Step 1: at room temperature, placing industrial waste alkali solution and electrolytic manganese slag in a closed container at a mass ratio of 1 to 2:1 between the industrial waste alkali solution and the electrolytic manganese slag on a dry basis, and connecting the closed container to a dilute acid solution or water; Step 2: Stir the mixture in the sealed container to make a slurry solution, and then let it stand for 0.5 to 3 hours to separate the solid and liquid; Step 3: The solid phase after solid-liquid separation is cement raw meal grinding aid mineralizer A, which contains 15-30% water; after the liquid phase after solid-liquid separation is heated to 40-60°C, an activator is added and stirred evenly to obtain cement raw meal grinding aid mineralizer B.

2. The method for preparing an environmentally friendly cement raw material grinding aid mineralizer according to claim 1, characterized in that: The electrolytic manganese slag is at least one of wet fresh electrolytic manganese slag, stored 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%.

3. The method for preparing an environmentally friendly cement raw material grinding aid mineralizer according to claim 1, characterized in that: The industrial waste alkali liquor is at least one of the waste liquor from pulp alkaline sulfite cooking and the saponification waste alkali liquor from the saponification reaction in the soap production process, has a pH value of 9.0-14.0, and contains at least one of sodium hydroxide, lignin sulfonate, sodium carbonate, sodium sulfate, organic acid salt, potassium hydroxide, and polyol.

4. The method for preparing an environmentally friendly cement raw material grinding aid mineralizer according to claim 3, characterized in that: The industrial waste alkali liquor is obtained by mixing the waste liquor of pulp alkaline sulfite cooking and the saponification waste alkali liquor from the saponification reaction in the soap production process in a mass ratio of 2:

3.

5. The method for preparing an environmentally friendly cement raw material grinding aid mineralizer according to claim 1, characterized in that: In step 2, the slurry solution is allowed to stand for 1 to 2 hours before solid-liquid separation. 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 to 2:

1.

6. The method for preparing an environmentally friendly cement raw material grinding aid mineralizer according to claim 1, characterized in that: The active agent is prepared by including the following raw materials in weight percentage: 0-25% of lignin sulfonate, 0-50% of organic acid salt, 30-70% of polyol and 5-20% of sodium dodecyl sulfate; wherein the lignin sulfonate includes at least one of sodium lignin sulfonate and calcium lignin sulfonate; 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.

7. The method for preparing an environmentally friendly cement raw material grinding aid mineralizer according to claim 6, characterized in that: The polyol includes at least one selected from the group consisting of triglycerol, polypropylene glycol, ethylene glycol, propylene glycol, glycerol and polyethylene glycol.

8. The method for preparing an environmentally friendly cement raw material grinding aid mineralizer according to claim 7, characterized in that: The polyol is obtained by mixing triglycerol, polypropylene glycol and ethylene glycol in a mass ratio of 2:1:

1.

9. An application of a cement raw meal grinding aid mineralizer prepared by the preparation method of the environmentally friendly cement raw meal grinding aid mineralizer according to any one of claims 1 to 8, characterized in that: Cement raw meal grinding aid mineralizer A and cement raw meal grinding aid mineralizer B are measured separately and added to cement raw materials for grinding; the dry basis weight ratio of cement raw meal grinding aid mineralizer A in the cement raw meal to be ground is: 3.0-8.0%; the weight of cement raw meal grinding aid mineralizer B is 0.01-0.2% of the weight of the cement raw meal to be ground.

10. Use of the cement raw meal grinding aid mineralizer prepared by the preparation method of the environment-friendly cement raw meal grinding aid mineralizer according to claim 9, characterized in that: The dosage of cement raw meal grinding aid mineralizer B is 0.08-0.12% of the weight of cement raw meal to be ground; cement raw meal grinding aid mineralizer A is used as a single component and mixed with other raw materials before grinding, or mixed with limestone, sandstone and other difficult-to-grind materials and then mixed and ground; cement raw meal grinding aid mineralizer B is used as a single component and measured, and then mixed with limestone, sandstone and other difficult-to-grind materials for grinding.

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