CN110436810B - Cement grinding-aiding active powder and preparation method thereof - Google Patents
Cement grinding-aiding active powder and preparation method thereof Download PDFInfo
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- CN110436810B CN110436810B CN201910854270.1A CN201910854270A CN110436810B CN 110436810 B CN110436810 B CN 110436810B CN 201910854270 A CN201910854270 A CN 201910854270A CN 110436810 B CN110436810 B CN 110436810B
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
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- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
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- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
A cement grinding-aiding active powder and a preparation method thereof relate to the field of cement. The cement grinding aid active powder is prepared by reacting raw materials at 600-800 ℃. The main raw materials of the method comprise industrial waste residues such as cloth bag ash, mirabilite slag, phosphorous slag, sulfuric acid slag and the like of a steel plant, and the industrial waste residues are changed into valuable substances through reasonable proportioning, so that the method not only generates actual economic value, but also has profound environmental protection significance. Meanwhile, the cement grinding aid active powder can replace part of clinker in cement in a higher proportion, and the production cost of the cement is obviously reduced. In addition, the cement grinding aid active powder can improve the workability of cement and reduce the processing cost of cement on the premise of basically maintaining the cement.
Description
Technical Field
The invention relates to the field of cement, in particular to cement grinding-aid active powder and a preparation method thereof.
Background
The cement grinding aid active powder is an admixture used for cement clinker, and can play a role in improving the grinding performance of the cement clinker, replacing part of the cement clinker to reduce the production cost and the like. However, in the prior art, although cement admixtures are various, the cement admixtures have limited clinker replacing effect and cannot achieve the effect of obviously reducing the cost. Meanwhile, the addition of these admixtures may adversely affect the workability, strength properties, etc. of cement.
Disclosure of Invention
The invention aims to provide a cement grinding aid active powder which can efficiently replace part of clinker in cement and achieve the aim of reducing cost. Meanwhile, the workability of the cement can be improved on the premise of not influencing the strength of the cement.
The invention also aims to provide a preparation method of the cement grinding aid active powder, which is simple to operate, has low requirements on equipment, and can be used for quickly and conveniently preparing the cement grinding aid active powder.
The embodiment of the invention is realized by the following steps:
a cement grinding-aiding active powder is prepared by reacting raw materials at 600-800 ℃; the raw materials comprise the following components in parts by weight:
10-12 parts of talc ore, 13-15 parts of steel plant bag ash, 8-10 parts of mirabilite slag, 8-12 parts of bauxite ore, 5-8 parts of phosphorous slag, 8-10 parts of sulfuric acid slag and 30-280 parts of phosphogypsum.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides cement grinding aid active powder which is prepared by reacting raw materials at 600-800 ℃. The main raw materials of the cement grinding aid active powder comprise industrial waste residues such as steel mill cloth bag ash, mirabilite slag, phosphorous slag, sulfuric acid slag and the like, and the industrial waste residues are changed into valuable substances through reasonable proportioning, so that the actual economic value is generated, and the cement grinding aid active powder has a far-reaching environment-friendly significance. Meanwhile, the cement grinding aid active powder can replace part of clinker in cement in a higher proportion, and the production cost of the cement is obviously reduced. In addition, the cement grinding aid active powder can improve the workability of cement and reduce the processing cost of cement on the premise of maintaining or improving the strength of the cement.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The concrete description of the cement grinding aid active powder of the embodiment of the invention is provided below.
The embodiment of the invention provides cement grinding aid active powder which is prepared by reacting raw materials at 600-800 ℃; the raw materials comprise the following components in parts by weight:
10-12 parts of talc ore, 13-15 parts of steel plant bag ash, 8-10 parts of mirabilite slag, 8-12 parts of bauxite ore, 5-8 parts of phosphorous slag, 8-10 parts of sulfuric acid slag and 30-280 parts of phosphogypsum.
Cost control has been a concern for large manufacturers in the production of cement. If the clinker of the cement can be replaced by some common industrial waste, the method is undoubtedly a better way for changing waste into valuable and saving cost. Not only generates practical economic value, but also has profound environmental protection significance. However, in the above replacement process, how to ensure a high replacement ratio without causing a significant decrease in cement strength has become an urgent problem to be solved.
Based on the above, the inventor provides the cement grinding-aid active powder which comprises a plurality of industrial wastes such as steel plant cloth bag ash, mirabilite slag, phosphorous slag and sulfuric acid slag, and is obtained by scientific proportioning and reasonable pretreatment. The cement grinding aid active powder has a high substitution ratio on the premise of ensuring the strength of cement, and simultaneously improves the workability, the specific surface area and the like of the cement to a certain extent.
Preferably, the inventor of the application finds that the influence of the cement grinding aid active powder on the strength of cement is gradually increased along with the increase of the content of phosphogypsum under the condition of keeping other raw materials basically unchanged. Through careful screening, the following two preferred formulations are obtained.
The first type of cement grinding aid active powder comprises the following raw materials in parts by weight:
10-12 parts of talc ore, 13-15 parts of steel plant bag ash, 8-10 parts of mirabilite slag, 8-12 parts of bauxite ore, 5-8 parts of phosphorous slag, 8-10 parts of sulfuric acid slag and 35-45 parts of phosphogypsum.
Preferably, the raw materials comprise, by weight: 10-11 parts of talc ore, 14-15 parts of steel plant bag ash, 8-9 parts of mirabilite slag, 8-10 parts of bauxite ore, 6-8 parts of phosphorous slag, 9-10 parts of sulfuric acid slag and 37-43 parts of phosphogypsum.
The cement grinding aid active powder can replace 4-6% of cement clinker per 1% of the dosage on the premise of ensuring that the strength of the cement is not reduced, and has a high replacement ratio. Meanwhile, the maximum doping amount of the cement can reach about 3%, the total amount of the cement clinker to be replaced reaches 15-18%, the use of the cement clinker can be remarkably saved, and the cement clinker is particularly suitable for being used under the condition of needing long-distance transportation, and the transportation cost and the production cost can be reduced.
The second type of cement grinding aid active powder comprises the following raw materials in parts by weight:
10-12 parts of talc ore, 13-15 parts of steel plant bag ash, 8-10 parts of mirabilite slag, 8-12 parts of bauxite ore, 5-8 parts of phosphorous slag, 8-10 parts of sulfuric acid slag and 240-280 parts of phosphogypsum.
Preferably, the raw materials comprise, by weight: 10-11 parts of talc ore, 14-15 parts of steel plant bag ash, 8-9 parts of mirabilite slag, 8-10 parts of bauxite ore, 6-8 parts of phosphorous slag, 9-10 parts of sulfuric acid slag and 260-280 parts of phosphogypsum.
On the premise of ensuring that the strength of cement is not reduced, the cement grinding aid active powder can replace 2-2.3% of cement clinker at most by 1% of the dosage, and compared with the first type of cement grinding aid active powder, the substitution has no advantage of long-distance transportation, and is more suitable for short-distance use. However, the cement grinding aid active powder has the greatest advantage of high utilization rate of phosphogypsum (the ratio of phosphogypsum in the cement grinding aid active powder is about 80 wt%). It should be noted that, at present, in China, about 2000 million tons of phosphogypsum are discharged every year, the accumulated discharge capacity is nearly hundred million tons, the discharge capacity is the largest one of gypsum waste residues, and the discharged phosphogypsum residues occupy a large amount of land, form slag hills and seriously pollute the environment. Therefore, phosphogypsum is the industrial waste material with the largest yield, the cheapest price and the most recycling requirement in all raw materials. The utilization rate of the phosphogypsum is increased, the consumption of other raw materials in the cement grinding aid active powder can be reduced, the consumption of cement clinker can also be reduced to a certain degree, and more importantly, the phosphogypsum has obvious environmental protection value. The maximum mixing amount of the cement grinding aid active powder is greatly influenced by the quality of phosphogypsum, such as water content, sulfur content and the like, and under the condition of controlling the sulfur content of the cement not to exceed the standard, each factory can balance the mixing amount according to the actual use condition (for example, the mixing amount is equivalent to the original amount of the phosphogypsum added by the factory).
Wherein, the bag ash of the steel plant is the residue collected by a bag dust collector in the steel making process, and mainly contains elements such as carbon, iron, sulfur and the like. In the embodiment of the invention, the iron content of the cloth bag ash of the steel plant is 20-40%.
The phosphorus slag is waste slag generated in the process of producing phosphate fertilizer, and mainly contains calcium oxide, silicon oxide and other components. In the embodiment of the invention, the content of calcium oxide in the phosphorus slag is 45-55%, the content of silicon oxide is 35-45%, and the content of phosphorus is less than 2%.
The sulfuric acid residue is waste residue generated in the process of producing sulfuric acid from pyrite, and mainly contains metal impurities such as ferric oxide and the like. In the embodiment of the invention, the iron content of the pyrite cinder is 40-50%, and the sulfur content is less than 2%.
Phosphogypsum refers to solid waste residue generated when phosphorite is treated by sulfuric acid in phosphoric acid production, and the main component of the phosphogypsum is calcium sulfate. In this example, the content of calcium sulphate in phosphogypsum is > 80%, the phosphorus content is < 2%, and the water content is < 20%.
The five components are common industrial residues, and are recycled, so that the aim of changing waste into valuable can be fulfilled, the waste of resource loss is reduced, the production cost is saved, and the economic benefit is improved. The further limitation of the raw material components is beneficial to standardizing the product quality of the cement grinding aid active powder, so that the cement grinding aid active powder has more stable property and better repeatability when in use.
The embodiment of the invention also provides a preparation method of the cement grinding aid active powder, which comprises the following steps:
s1, reacting the raw materials at 600-800 ℃ for 15-30 min.
S2, after the reaction is finished, grinding the mixed powder obtained in the step S1 into fine powder with the granularity of 20-80 meshes.
The high temperature reaction can reduce the water content of the raw materials and allow for sufficient reaction activation between the components. After the cement clinker is replaced by the cement grinding aid active powder obtained by the method, the strength of the cement is not reduced, the overall fineness of the cement is reduced, the workability and the specific surface area of the cement are increased, and the content of harmful substances is controlled within the range of national standards under a certain replacement ratio.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a cement grinding aid active powder, which comprises the following raw materials in parts by weight:
12 parts of talc ore, 13 parts of bag ash of a steel plant, 10 parts of mirabilite slag, 8 parts of bauxite ore, 8 parts of phosphorous slag, 10 parts of sulfuric acid slag and 35 parts of phosphogypsum.
The raw materials are reacted for 30 min at 600 ℃, and ground into fine powder with the granularity of 20-40 meshes. Thus obtaining the required cement grinding-aiding active powder.
Example 2
The embodiment provides a cement grinding aid active powder, which comprises the following raw materials in parts by weight:
10-parts of talc ore, 15 parts of steel plant cloth bag ash, 8 parts of mirabilite slag, 12 parts of bauxite ore, 5 parts of phosphorous slag, 10 parts of sulfuric acid slag and 45 parts of phosphogypsum.
The raw materials are reacted for 15 min at 800 ℃, and ground into fine powder with the granularity of 40-60 meshes. Thus obtaining the required cement grinding-aiding active powder.
Example 3
The embodiment provides a cement grinding aid active powder, which comprises the following raw materials in parts by weight:
11 parts of talc ore, 14 parts of cloth bag ash of a steel plant, 9 parts of mirabilite slag, 10 parts of bauxite ore, 7 parts of phosphorous slag, 9 parts of sulfuric acid slag and 40 parts of phosphogypsum.
The raw materials are reacted for 20 min at 800 ℃, and ground into fine powder with the granularity of 40-60 meshes. Thus obtaining the required cement grinding-aiding active powder.
Example 4
The embodiment provides a cement grinding aid active powder, which comprises the following raw materials in parts by weight:
10 parts of talc ore, 13 parts of bag ash of a steel plant, 9 parts of mirabilite slag, 10 parts of bauxite ore, 6 parts of phosphorous slag, 10 parts of sulfuric acid slag and 280 parts of phosphogypsum.
The raw materials are reacted for 25 min at 600 ℃, and ground into fine powder with the granularity of 60-80 meshes. Thus obtaining the required cement grinding-aiding active powder.
Example 5
The embodiment provides a cement grinding aid active powder, which comprises the following raw materials in parts by weight:
11 parts of talc ore, 14 parts of cloth bag ash of a steel plant, 10 parts of mirabilite slag, 11 parts of bauxite ore, 7 parts of phosphorous slag, 8 parts of sulfuric acid slag and 260 parts of phosphogypsum.
The raw materials are reacted for 15 min at 700 ℃, and ground into fine powder with the granularity of 40-60 meshes. Thus obtaining the required cement grinding-aiding active powder.
Example 6
The embodiment provides a cement grinding aid active powder, which comprises the following raw materials in parts by weight:
12 parts of talc ore, 14 parts of cloth bag ash of a steel plant, 9 parts of mirabilite slag, 9 parts of bauxite ore, 6 parts of phosphorous slag, 8 parts of sulfuric acid slag and 240 parts of phosphogypsum.
The raw materials are reacted for 15 min at 600 ℃, and ground into fine powder with the granularity of 60-80 meshes. Thus obtaining the required cement grinding-aiding active powder.
Test example 1
The cement grinding aid active powder provided by the embodiment 3 is added into a certain brand of commercially available cement in a blending amount of 1wt%, and the dosage of cement clinker is correspondingly reduced by 1wt%, 2wt%, 4wt%, 6wt% and 8wt%, so that samples 1-7 are prepared, and the cement without the cement grinding aid active powder is used as a blank sample. The strength and specific surface variation were measured under the same conditions, and the results are reported in table 1.
TABLE 1 Cement grinding aid active powder incorporation test
As can be seen from Table 1, after the cement grinding aid active powder provided by the embodiment 3 of the invention is doped into cement, when the reduction amount of clinker is not more than 6wt% (samples 1-4), the strength of the cement grinding aid active powder is 22-24 Mpa in 3 days, the strength of the cement grinding aid active powder is 32-35 Mpa in 28 days, and the strength of the cement grinding aid active powder is not lower than 20Mpa and 32Mpa measured by a blank sample in 3 days or 28 days. And on the strength of 3 days, the improvement of the sample 1-4 is more obvious, which shows that the early strength of the cement is favorably improved after the cement grinding aid active powder is added. However, at clinker reductions of more than 6wt% and up to 8wt% (sample 5), the 28-day strength of the cement is significantly reduced. Therefore, the cement grinding aid activity provided by the embodiment 3 of the invention can replace up to 6wt% of cement clinker per 1wt% of the addition amount on the premise of not influencing the cement strength.
Test example 2
The cement grinding aid active powder provided by the embodiment 4 is added into a certain brand of commercially available cement in a blending amount of 1wt%, and the dosage of cement clinker is correspondingly reduced by 1wt%, 1.5wt%, 2wt%, 2.3wt% and 2.5wt%, so that samples 6-10 are prepared, and the cement without the cement grinding aid active powder is used as a blank sample. The strength change was measured under the same conditions, and the recorded results are shown in table 2.
TABLE 2 Cement grinding aid active powder incorporation test
As can be seen from Table 2, after the cement grinding aid active powder provided by the embodiment 4 of the invention is doped into cement, when the reduction amount of clinker is not more than 2.3wt% (samples 6 to 9), the strength of the cement grinding aid active powder is 21 to 23MPa in 3 days, the strength of the cement grinding aid active powder is 32 to 34MPa in 28 days, and the strength of the cement grinding aid active powder is not lower than 20MPa and 32MPa measured by a blank sample in 3 days or 28 days. However, when the clinker reduction exceeded 2.3wt% and reached 2.5wt% (sample 10), the 3-day strength and 28-day strength of the cement were significantly reduced. Therefore, the cement grinding aid activity provided by the embodiment 4 of the invention can replace up to 6wt% of cement clinker per 1wt% of the addition amount on the premise of not influencing the cement strength.
Test example 3
The cement grinding aid active powder provided in examples 1-6 is added into a certain brand of commercially available cement in a blending amount of 1wt%, and the dosage of cement clinker is correspondingly reduced, wherein the reduction amount of examples 1-3 is 6wt%, the reduction amount of examples 4-6 is 2wt%, and the cement without the cement grinding aid active powder is taken as a blank example. The strength change was measured under the same conditions, and the recorded results are shown in table 3.
TABLE 3 Cement grinding aid active powder incorporation test
As can be seen from Table 2, the cement grinding aid active powder provided by the examples 1-3 of the present invention has substantially no change in strength when the amount of the cement clinker is 1wt% instead of 6wt% compared with the unblended blank case; when the cement grinding aid active powder with the content of the phosphogypsum increased, provided by the embodiments 4-6 of the invention, is used for replacing 2wt% of cement clinker by 1wt%, compared with the unblended blank case, the strength is basically unchanged; the cement grinding aid active powder provided by the embodiment of the invention can effectively reduce the dosage of cement clinker. At the same timeAfter the cement grinding aid active powder provided by the embodiments 1-6 of the invention is added, the specific surface area of the cement is 350 m2The dosage is increased to 370-380 m2In addition, according to the test of a small grinding comparison experiment, the overall fineness of the cement is reduced by 1% -1.2% after the cement grinding aid active powder of the examples 1-3 is doped into the cement, and the overall fineness of the cement is reduced by 0.6% -1% after the cement grinding aid active powder of the examples 4-6 is doped into the cement. Therefore, the cement grinding aid active powder provided by the embodiment of the invention has certain effects on improving the specific surface of cement and reducing the fineness of the cement.
In summary, the embodiment of the invention provides a cement grinding aid active powder, which is prepared by reacting raw materials at 600-800 ℃. The main raw materials of the cement grinding aid active powder comprise industrial waste residues such as steel mill cloth bag ash, mirabilite slag, phosphorous slag, sulfuric acid slag and the like, and the industrial waste residues are changed into valuable substances through reasonable proportioning, so that the actual economic value is generated, and the cement grinding aid active powder has a far-reaching environment-friendly significance. Meanwhile, the cement grinding aid active powder can replace part of clinker in cement in a higher proportion, and the production cost of the cement is obviously reduced. In addition, the cement grinding aid active powder can improve the workability of cement and reduce the processing cost of cement on the premise of basically maintaining the cement.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The cement grinding aid active powder is characterized by being prepared by reacting raw materials at 600-800 ℃; the raw materials comprise the following components in parts by weight:
10-12 parts of talc ore, 13-15 parts of steel plant bag ash, 8-10 parts of mirabilite slag, 8-12 parts of bauxite ore, 5-8 parts of phosphorous slag, 8-10 parts of sulfuric acid slag and 30-280 parts of phosphogypsum.
2. The cement grinding aid active powder as recited in claim 1, characterized in that the raw materials comprise, in parts by weight:
10-12 parts of talc ore, 13-15 parts of steel mill cloth bag ash, 8-10 parts of mirabilite slag, 8-12 parts of bauxite ore, 5-8 parts of phosphorous slag, 8-10 parts of sulfuric acid slag and 35-45 parts of phosphogypsum.
3. The cement grinding aid active powder as recited in claim 1, characterized in that the raw materials comprise, in parts by weight:
10-12 parts of talc ore, 13-15 parts of bag ash of a steel plant, 8-10 parts of mirabilite slag, 8-12 parts of bauxite ore, 5-8 parts of phosphorous slag, 8-10 parts of sulfuric acid slag and 240-280 parts of phosphogypsum.
4. The cement grinding aid active powder as claimed in any one of claims 1 to 3, wherein the iron content of the cloth bag ash of the steel plant is 20% to 40%.
5. The cement grinding aid active powder as recited in claim 4, wherein the phosphorus slag is waste slag generated in a process of producing phosphate fertilizer, the content of calcium oxide in the phosphorus slag is 45% -55%, the content of silicon oxide is 35% -45%, and the content of phosphorus is less than 2%.
6. The cement grinding aid active powder as recited in claim 5, wherein the pyrite cinder is waste cinder generated in the production of sulfuric acid, the iron content of the pyrite cinder is 40% -50%, and the sulfur content is less than 2%.
7. The cement grinding aid active powder as claimed in claim 6, wherein the content of calcium sulfate in phosphogypsum is more than 80%, the phosphorus content is less than 2%, and the water content is less than 20%.
8. A method for preparing a cement grinding aid active powder as defined in any one of claims 1 to 7, comprising:
reacting the raw materials at 600-800 ℃ for 15-30 min; after the reaction is finished, grinding the mixture into fine powder with the granularity of 20-80 meshes.
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| GB1143516A (en) * | 1966-06-10 | 1969-02-26 | Grace W R & Co | Improvements relating to additives for minerals |
| CN1111143C (en) * | 2000-11-15 | 2003-06-11 | 王先进 | Composite grinding aiding and reinforcing stabilizer for cement |
| CN1216826C (en) * | 2002-03-04 | 2005-08-31 | 四川省资中县助利建材厂 | Cement additive |
| CN100368333C (en) * | 2005-07-25 | 2008-02-13 | 王明贵 | Compound cement grinding aid and its production method |
| RU2371402C2 (en) * | 2007-12-29 | 2009-10-27 | Закрытое акционерное общество "ИМЭТСТРОЙ" (ЗАО "ИМЭТСТРОЙ") | Method of producing cement with mineral additive |
| CN104529223B (en) * | 2015-01-22 | 2017-02-01 | 东阿东昌天汇科技有限公司 | Cement grinding aid taking industrial residue as raw material and preparation method of cement grinding aid |
| CN110105019A (en) * | 2019-05-24 | 2019-08-09 | 安徽工业大学 | The method for preparing high-strength foam concrete using waste paper-making pulp, slurry |
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