CN110981238B - Additive for cement raw material - Google Patents
Additive for cement raw material Download PDFInfo
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- CN110981238B CN110981238B CN201911331697.XA CN201911331697A CN110981238B CN 110981238 B CN110981238 B CN 110981238B CN 201911331697 A CN201911331697 A CN 201911331697A CN 110981238 B CN110981238 B CN 110981238B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/428—Organic materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
- C04B7/424—Oxides, Hydroxides
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses an additive for cement raw materials, belonging to the technical field of additives. The composite material is prepared from the following raw materials in percentage by weight: 0.5-2% of organic grinding aid component, 1-5% of raw material decomposition promoting component, 10-20% of mineralized substance, 3-8% of sulfur fixing component, 0.05-1% of combustion-supporting component and the balance of carrier. When the additive is used for preparing the clinker, the energy consumption in the preparation process of the cement clinker can be effectively reduced, the emission of harmful gas is reduced, the quality of the cement clinker is improved, and the energy conservation and emission reduction of the cement industry are realized.
Description
Technical Field
The invention belongs to the technical field of cement production process additives, and particularly relates to a raw material additive.
Background
Since 2011 in China, the cement yield per year is more than 20 hundred million tons, and by 2018, 1681 cement production lines are accumulated by novel dry-process cement production lines in China, and the designed capacity of clinker is more than 18 hundred million tons. While the cement industry develops, the consumption of resources such as limestone, clay, coal and the like, energy sources and environmental influences are also surprising. With the improvement of the environmental protection consciousness of people, more advanced technology is urgently needed, the consumption of energy and resources in the clinker preparation process is reduced, the emission of harmful gas is reduced, and the sustainable development of the cement industry is realized. The production of raw materials is a basic link in the production process of cement, and the addition of a multifunctional additive which can influence the subsequent working procedure in the grinding process of the raw materials can directly influence the energy consumption and the quality of clinker and the generation and the discharge of pollutants. The additive technology is used for reducing the power consumption and the coal consumption in the clinker preparation process and increasing the clinker strength, so that the clinker consumption can be saved in the cement grinding process, more solid wastes generated by other industries can be absorbed, the clinker quality is improved, more industrial waste residues can be doped to prepare high-strength cement and high-performance concrete, and the additive technology is an effective measure for realizing energy conservation and emission reduction in the cement industry.
Disclosure of Invention
The invention aims to provide an admixture for cement raw materials, which can effectively reduce energy consumption in the preparation process of cement clinker, reduce the emission of harmful gas, improve the quality of the cement clinker and realize energy conservation and emission reduction in the cement industry.
The invention adopts the following technical scheme:
a raw material admixture is prepared from the following raw materials in percentage by weight: 0.5-2% of organic grinding aid component, 1-5% of raw material decomposition promoting component, 10-20% of mineralized substance, 3-8% of sulfur fixing component, 0.05-1% of combustion-supporting component and the balance of carrier.
Preferably, the raw material admixture is prepared from the following raw materials in percentage by weight: 1.5 percent of organic grinding-aid component, 3 percent of raw material decomposition promoting component, 15 percent of mineralized substance, 6 percent of sulfur-fixing component, 0.08 percent of combustion-supporting component and the balance of carrier.
The organic grinding aid component comprises more than two of hydroxyethyl ethylenediamine, nonylphenol polyoxyethylene ether itaconic acid monoester sulfonic acid disodium salt, N-hydroxymethyl acrylamide and polyethyleneimine.
The raw material decomposition promoting component is one of amino trimethylene phosphonic acid and diethylene triamine pentamethylene phosphonic acid.
The mineralized component is bastnaesite powder, the content of rare earth elements in the bastnaesite powder is RE2O3The content is 73-75%.
The sulfur-fixing component is composed of strontium chloride, potassium manganate and catalyst according to the weight ratio (0.1-0.5): (0.1-0.5): 1.
Preferably, the catalyst is one of ferric pyrophosphate and lithium iron phosphate.
The combustion-supporting component comprises modified nano titanium dioxide and a penetrating agent according to the weight ratio (5-14): 1.
The preparation method of the modified nano titanium dioxide comprises the following steps: adding a proper amount of distilled water into an ultrasonic dispersion instrument, then adding 10.0g of phosphotungstic acid, adding 45g of nano titanium dioxide after the phosphotungstic acid is dissolved, ultrasonically dispersing for 20-24h, standing for 2-5h, centrifugally separating, removing an upper layer solution, placing the deposit into an oven for drying, taking out the dried deposit, and placing the deposit into a muffle furnace for calcining for 3-8h at the temperature of 150-430 ℃ to obtain the modified nano titanium dioxide.
The penetrating agent is one of dioctyl sodium sulfosuccinate and alkyl phosphate polyoxyethylene ether.
The carrier is attapulgite.
The organic grinding-aid components have the function of stabilizing the material layer, and have the function of properly gluing the raw materials, so that gaps among raw material particles are reduced, the material layer is more stable, the grinding of a grinding roller is more sufficient, the grinding efficiency of the raw materials is effectively improved, and the grinding power consumption is saved; the decomposition rate of the raw material can be accelerated by the raw material decomposition promoting component; the mineralized substance can reduce the forming temperature of the liquid phase, increase the quantity of the liquid phase, accelerate the reaction of solid phase, liquid phase and solid-liquid interface, change the viscosity and surface tension of the molten liquid, improve the growth and form of clinker crystals, reduce the sintering temperature and energy consumption of the clinker, and improve the yield and quality of the clinker; the sulfur-fixing component can generate high-temperature stable mineral with sulfur in raw materials and fuels to be solid-dissolved in the clinker, SO that SO in the production process of the clinker is reduced2The emission and the use amount of gypsum in the cement preparation are reduced, and the catalyst can convert SO2Catalytic oxidation to SO3(ii) a The combustion-supporting component is composed of modified nano titanium dioxide and penetrating agent in a specific ratio, and the components are mutually permeated and catalyzed in the combustion processAnd the interaction of oxidation and the like, so that the activation energy of carbon oxidation reaction is reduced, the cracking of macromolecular organic matters is accelerated, the oxygen consumption is reduced, and the macromolecular organic matters are stably and fully combusted, thereby achieving the effect of saving coal. As is well known, nano TiO2Making TiO under the action of ultraviolet ray in sunlight or lamp light2Activating and generating free radicals with high catalytic activity, generating strong photooxidation and reduction capability, and having the characteristics of good stability, high light efficiency, no secondary pollution and the like. However, due to TiO2Is a broadband conductor, has a wider forbidden band of 3.0-3.28 eV, has activity only under ultraviolet light, and has a visible light flame in a cement dry kiln, so that the nano TiO is directly used2As a catalyst, the photocatalytic effect is not significant. Modifying the surface of nano titanium dioxide to generate a large number of active points, and adding TiO2The light absorption range of the photocatalyst is obviously prolonged to a visible light region, so that the photocatalyst has better photocatalytic activity when being applied to a cement dry kiln. The strength of the flame can be enhanced, and the penetration of the flame is stronger. The clinker is calcined in the dry kiln through radiation heat transfer, the stronger the penetrating power of flame, the smaller the temperature difference from the surface layer of the clinker to the cylinder in the kiln, which is beneficial to reducing the energy consumption required by the calcination of the clinker and is easy to generate minerals. And the addition of a proper amount of penetrating agent can improve the activity of the modified titanium dioxide, further reduce the energy consumption required by clinker calcination and promote the generation of stable minerals. The attapulgite has larger specific surface area, a fine pore structure inside, good adsorption performance, can be used as a carrier to uniformly adsorb other components on the surface of the attapulgite, and in addition, the attapulgite has certain viscosity when wet, can stabilize a raw material layer, has dispersibility when dried, can be used as a carrier, and is helpful for opposite milling and production improvement. The material synergistic effect of the multiple functional components can improve the clinker crystal forming condition, optimize the clinker mineral composition and increase the clinker strength.
When the cement raw material admixture is used, the admixture amount is 0.5-1.0% of the raw material weight per ton of cement raw material.
The invention has the beneficial effects that: the invention has the synergistic effect of various components and has obvious grinding aiding, consumption reducing, sulfur fixing and desulfurizing effectsThe effect of nitre is remarkable in economic and social benefits. Especially, after the combustion-supporting components with specific proportion are added, the energy consumption can be greatly reduced, the grinding efficiency of raw materials is improved by more than 15 percent, the standard coal consumption of clinker is reduced by more than 22.1 percent, and SO2The discharge amount is reduced by over 51.8 percent. Meanwhile, the compression strength and the breaking strength of the prepared clinker are also obviously improved, and the clinker is a cement raw material additive with excellent performance.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples
The invention designs 3 specific embodiments according to the weight percentage composition of raw materials, uses the prepared raw material admixture for preparing cement clinker, and tests the performance of the prepared clinker. The compositions of the specific examples are shown in table 1.
Table 1 composition of the raw materials of the different examples
The organic grinding aid component comprises more than two of hydroxyethyl ethylenediamine, nonylphenol polyoxyethylene ether itaconic acid monoester sulfonic acid disodium salt, N-hydroxymethyl acrylamide and polyethyleneimine.
The raw material decomposition promoting component is one of amino trimethylene phosphonic acid and diethylene triamine pentamethylene phosphonic acid.
The mineralized component is bastnaesite powder, the content of rare earth elements in the bastnaesite powder is RE2O3The content is 73-75%.
The sulfur-fixing component comprises strontium chloride, potassium manganate and a catalyst according to the weight ratio (0.1-0.5): (0.1-0.5): 1.
The combustion-supporting components are modified nano titanium dioxide and a penetrating agent according to the weight ratio (5-14): 1.
The preparation method of the modified nano titanium dioxide comprises the following steps: adding a proper amount of distilled water into an ultrasonic dispersion instrument, then adding 10.0g of phosphotungstic acid, adding 45g of nano titanium dioxide after the phosphotungstic acid is dissolved, ultrasonically dispersing for 20-24h, standing for 2-5h, centrifugally separating, removing an upper layer solution, placing the deposit into an oven for drying, taking out the dried deposit, and placing the deposit into a muffle furnace for calcining for 3-8h at the temperature of 150-430 ℃ to obtain the modified nano titanium dioxide.
The penetrating agent is one of dioctyl sodium sulfosuccinate and alkyl phosphate polyoxyethylene ether.
The carrier is attapulgite.
Comparative example 1
An admixture for cement raw materials, which has the same raw material composition as that of example 2, the only difference being: wherein the combustion-supporting component is nano titanium dioxide.
Comparative example 2
An admixture for cement raw materials, which has the same raw material composition as that of example 2, the only difference being: wherein the combustion-supporting component is modified nano titanium dioxide.
Comparative example 3
An admixture for cement raw materials, which has the same raw material composition as that of example 2, the only difference being: wherein the combustion-supporting component is dioctyl sodium sulfosuccinate or alkyl phosphate polyoxyethylene ether.
Comparative example 4
An admixture for cement raw materials, which has the same raw material composition as that of example 2, the only difference being: the combustion-supporting component comprises modified nano titanium dioxide and a penetrating agent according to the weight ratio of 2: 1.
Comparative example 5
An admixture for cement raw materials, which has the same raw material composition as that of example 2, the only difference being: the combustion-supporting component comprises modified nano titanium dioxide and a penetrating agent according to the weight ratio of 4: 1.
Comparative example 6
An admixture for cement raw materials, which has the same raw material composition as that of example 2, the only difference being: the combustion-supporting component comprises modified nano titanium dioxide and a penetrating agent according to the weight ratio of 16: 1.
Comparative example 7
An admixture for cement raw materials, which has the same raw material composition as that of example 2, the only difference being: the combustion-supporting component comprises modified nano titanium dioxide and a penetrating agent according to the weight ratio of 18: 1.
Application test example
The raw material admixtures prepared in the above examples 1 to 3 and comparative examples 1 to 7 were added to cement raw materials in an amount of 0.8% of the weight of the raw materials per ton of the cement raw materials, the raw materials were ground using a vertical mill, and then introduced into a cement dry kiln at 5000t/d to be calcined to obtain corresponding clinker, and then the amount of the raw materials not added with the admixture of the present invention was used as a blank comparative example. The raw mix ratios and limestone composition used are shown in table 2 below, and the table hour yield of raw meal and the performance results of the produced clinker are shown in table 3.
TABLE 2 raw material weight percentage ratios and limestone components used
Table 3 results of performance testing
Wherein SO2The emissions were determined as described in GB/T37249-2018. As can be seen from the above-mentioned Table 3, when the raw material admixture of the present invention is used for preparing clinker, the raw material powder yield is improved by more than 15%, the standard coal consumption is reduced by more than 22.1%, the loss on ignition is remarkably reduced, and SO is remarkably reduced, compared with the data without using the admixture of the present invention2The discharge amount is reduced by over 51.8 percent. The 3d flexural strength of the prepared clinker is more than or equal to 6.1MPa, and the 3d compressive strength is more than or equal to 31.5 MPa; the 28d flexural strength is more than or equal to 11.2MPa, the 28d compressive strength is more than or equal to 53.6MPa, and the mechanical property is also obviously improved. It can be seen from the data of comparative examples 1 to 3 that the properties of the clinker and the energy consumption and yield in the preparation process can be significantly influenced when the composition ratio of the combustion-supporting components of the invention is changed. From the results of comparative examples 4 to 7, it can be seen that when the ratio of the modified nano titanium dioxide to the penetrant in the combustion-supporting component is less than 5: 1 or more than 14:1, no matter the yield, the standard coal energy consumption and the SO2The discharge amount and the ignition loss areThe mechanical properties of the flexural strength and the compressive strength are reduced, which shows that the raw materials of the invention have obvious synergistic effect, and the technical effect of the invention can be achieved only by proportioning in a specific proportion range, thus having good economic and environmental protection effects.
Claims (3)
1. The raw material admixture is characterized by being prepared from the following raw materials in percentage by weight: 0.5-2% of organic grinding-aid component, 1-5% of raw material decomposition promoting component, 10-20% of mineralized substance, 3-8% of sulfur-fixing component, 0.05-1% of combustion-supporting component and the balance of carrier;
the organic grinding-aid components comprise more than two of hydroxyethyl ethylenediamine, nonylphenol polyoxyethylene ether itaconic acid monoester sulfonic acid disodium salt, N-hydroxymethyl acrylamide and polyethyleneimine;
the raw material decomposition promoting component is one of amino trimethylene phosphonic acid and diethylenetriamine pentamethylene phosphonic acid;
the sulfur-fixing component is composed of strontium chloride, potassium manganate and catalyst according to the weight ratio (0.1-0.5): (0.1-0.5): 1, preparing a composition; the catalyst is one of ferric pyrophosphate and lithium iron phosphate;
the combustion-supporting component comprises modified nano titanium dioxide and a penetrating agent according to the weight ratio (5-14): 1, preparing a composition;
the preparation method of the modified nano titanium dioxide comprises the following steps: adding a proper amount of distilled water into an ultrasonic dispersion instrument, then adding 10g of phosphotungstic acid, adding 45g of nano titanium dioxide after the phosphotungstic acid is dissolved, ultrasonically dispersing for 20-24h, standing for 2-5h, centrifugally separating, removing an upper layer solution, putting the deposit into an oven for drying, taking out the dried deposit, and putting the dried deposit into a muffle furnace for calcining for 3-8h at the temperature of 430 ℃ to obtain the modified nano titanium dioxide;
the penetrating agent is one of dioctyl sodium sulfosuccinate and alkyl phosphate polyoxyethylene ether;
the carrier is attapulgite.
2. A raw admixture according to claim 1, characterized in that it is made from the following raw materials in weight percent: 1.5 percent of organic grinding-aid component, 3 percent of raw material decomposition promoting component, 15 percent of mineralized substance, 6 percent of sulfur-fixing component, 0.08 percent of combustion-supporting component and the balance of carrier.
3. A raw material admixture according to claim 1 or 2, wherein the mineralized substance is bastnaesite powder, the content of rare earth elements in bastnaesite powder being RE2O3The content is 73-75%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112028509B (en) * | 2020-09-21 | 2022-08-02 | 临沂德艺科技发展有限公司 | Additive for dry-process cement pit clinker production |
| CN112062487B (en) * | 2020-09-21 | 2022-03-15 | 临沂德艺科技发展有限公司 | Additive for cement clinker production |
| CN112661428A (en) * | 2020-12-24 | 2021-04-16 | 江西富创新材料有限公司 | Raw cement additive and application thereof |
| CN112759289B (en) * | 2020-12-31 | 2023-03-10 | 安徽海螺新材料科技有限公司 | Cement raw material additive with grinding-aid and decomposition-promoting effects |
| CN113416010A (en) * | 2021-07-31 | 2021-09-21 | 山西天润恒德新材料有限公司 | Raw material grinding aid for cement clinker firing process |
| CN113480231A (en) * | 2021-08-24 | 2021-10-08 | 山东众森科技股份有限公司 | Energy-saving cement raw material grinding aid and preparation method thereof |
| CN116921049A (en) * | 2023-05-19 | 2023-10-24 | 山东诚港新材料科技有限公司 | Cement raw material grinding-aid catalyst |
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| CN1244513C (en) * | 2004-07-09 | 2006-03-08 | 朱效荣 | High efficiency catalyst for cement |
| DE102005057896A1 (en) * | 2005-12-02 | 2007-06-14 | Basf Ag | Use of comb polymers as grinding aids for cementitious preparations |
| CN101089153A (en) * | 2006-06-14 | 2007-12-19 | 宫志利 | Industrial hot puffed briquette |
| CN101210209B (en) * | 2006-12-27 | 2011-07-27 | 哈尔滨绿万家环保科技有限公司 | Application of coal modifier in shaft kiln incineration and producing technique thereof |
| CN102295970B (en) * | 2011-07-29 | 2013-09-18 | 山东宏艺科技股份有限公司 | Coal combustion improver |
| CN104150795A (en) * | 2014-08-19 | 2014-11-19 | 王秀贵 | Coal saving and fast burning agent and preparation method thereof |
| CN107164013A (en) * | 2017-06-01 | 2017-09-15 | 严生 | A kind of powder nanometer catalytically fixed sulphur agent and preparation method thereof of new type nonaqueous cement raw material |
| CN110316985A (en) * | 2018-06-20 | 2019-10-11 | 杭州斯曼特建材科技有限公司 | A kind of cement slurry grinding aid |
| CN109336458B (en) * | 2018-12-17 | 2021-08-17 | 鸡西市恒昌新材料科技有限公司 | Cement grinding aid |
| CN110218021A (en) * | 2019-05-29 | 2019-09-10 | 南京永能新材料有限公司 | A kind of high-molecular cement grinding aid and preparation method thereof |
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