CN110776268A - Cement clinker and preparation method and application thereof - Google Patents

Cement clinker and preparation method and application thereof Download PDF

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Publication number
CN110776268A
CN110776268A CN201911230839.3A CN201911230839A CN110776268A CN 110776268 A CN110776268 A CN 110776268A CN 201911230839 A CN201911230839 A CN 201911230839A CN 110776268 A CN110776268 A CN 110776268A
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parts
cement clinker
mass content
citric acid
mass
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Inventor
吕鹏飞
董立国
孔祥勇
吕祥泉
胡景昆
杨雷
苏炎
刘占锋
杜延吉
姜维国
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Yatai Group Yitong India Cements Ltd
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Yatai Group Yitong India Cements Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/24Cements from oil shales, residues or waste other than slag
    • C04B7/28Cements from oil shales, residues or waste other than slag from combustion residues, e.g. ashes or slags from waste incineration
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/36Manufacture of hydraulic cements in general
    • C04B7/38Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • C04B7/42Active ingredients added before, or during, the burning process
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/10Production of cement, e.g. improving or optimising the production methods; Cement grinding

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses cement clinker and a preparation method and application thereof, and belongs to the technical field of cement production. The cement clinker comprises the following components in parts by weight: 70-95 parts of limestone, 3-7 parts of coal gangue, 3-7 parts of shale, 2-6 parts of mineral processing powder, 0.5-4 parts of nickel slag, 0.5-4 parts of coal ash and 0.2-1.5 parts of citric acid slag. The invention provides a cement clinker, which uses citric acid residue as mineralizer, and during the production of cement clinker, the citric acid residue can be decomposed into CaO and SO at high temperature 2Gas, which promotes the further generation of liquid phase and lowers the calcination temperature of the clinker, improves the easy-burning property of the raw meal, reduces the coal consumption, and improves the strength of the clinker. In addition, the invention can recycle the citric acid residues and also solves the problem of environmental pollution caused by industrial waste residues.

Description

Cement clinker and preparation method and application thereof
Technical Field
The invention relates to the technical field of cement production, in particular to cement clinker and a preparation method and application thereof.
Background
The cement clinker is a semi-finished product which is prepared by using limestone, clay and iron raw materials as main raw materials, preparing raw materials according to a proper proportion, burning until part or all of the raw materials are molten, and cooling. The conventional cement clinker generally uses natural gypsum, fluorite, industrial chemicals, etc. as a mineralizer.
In addition, the citric acid residues are a chemical deposit generated when the citric acid is produced by lime method in food chemical industry, and if the citric acid residues are not treated, the environment can be seriously polluted.
However, mineralizers such as natural gypsum, fluorite, and industrial chemicals used in conventional cement clinker require consumption of natural resources, and thus, they are expensive and consume a large amount of coal.
Disclosure of Invention
It is an object of embodiments of the present invention to provide a cement clinker that solves the problems set forth in the background art above.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
the cement clinker comprises the following components in parts by weight: 70-95 parts of limestone, 3-7 parts of coal gangue, 3-7 parts of shale, 2-6 parts of mineral processing powder, 0.5-4 parts of nickel slag, 0.5-4 parts of coal ash and 0.2-1.5 parts of citric acid slag.
As a preferable scheme of the embodiment of the invention, the cement clinker comprises the following components in parts by weight: 80-90 parts of limestone, 4-6 parts of coal gangue, 4-6 parts of shale, 3-5 parts of mineral processing powder, 1-3 parts of nickel slag, 1-3 parts of coal ash and 0.5-1 part of citric acid slag.
According to another preferable scheme of the embodiment of the invention, the beneficiation powder contains 45-55% by mass of SiO2, 15-25% by mass of Al2O3, 8-12% by mass of Fe2O3 and 5-10% by mass of CaO.
As another preferable scheme of the embodiment of the invention, the mass content of SiO2 in the nickel slag is 35-45%, the mass content of Al2O3 is 3-6%, the mass content of Fe2O3 is 35-45%, and the mass content of CaO is 3-6%.
According to another preferable scheme of the embodiment of the invention, the mass content of SiO2 in the coal ash is 55-65%, the mass content of Al2O3 is 15-25%, the mass content of Fe2O3 is 5-8%, and the mass content of CaO is 5-8%.
As another preferable scheme of the embodiment of the invention, the mass content of CaO in the citric acid residues is 30-40%, and the mass content of SO3 is 48-58%.
Another object of an embodiment of the present invention is to provide a method for preparing the above cement clinker, which includes the following steps:
weighing limestone, coal gangue, shale, mineral processing powder, nickel slag, coal ash and citric acid slag according to the weight parts for later use;
mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder;
and calcining the raw material powder by taking the coal powder as a fuel to obtain cement clinker, and controlling the sulfur-alkali ratio of the cement clinker to be 0.6-1.
Another object of the embodiments of the present invention is to provide a cement clinker prepared by the above preparation method.
As another preferable scheme of the embodiment of the invention, the saturation ratio of the cement clinker is 0.91-0.92, the silicon rate is 2.6-2.7, the aluminum rate is 1.5-1.6, and the content of free calcium is 1.35-1.46%.
It is a further object of embodiments of the present invention to provide a use of the above cement clinker as a building material.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a cement clinker, which is generated by using industrial waste residue-citric acid residue as a mineralizerIn the process, the citric acid residue can be decomposed into CaO and SO at high temperature 2Gas, which promotes the further generation of liquid phase and lowers the calcination temperature of the clinker, improves the easy-burning property of the raw meal, reduces the coal consumption, and improves the strength of the clinker. In addition, the invention can recycle the citric acid residues, and also solves the problem of environmental pollution caused by industrial residues, so that cement enterprises develop to an environment-friendly way.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This embodiment provides a cement clinker, the method of preparing the cement clinker comprising the steps of:
(1) weighing 70kg of limestone, 7kg of coal gangue, 7kg of shale, 6kg of mineral processing powder, 4kg of nickel slag, 4kg of coal ash and 1.5kg of citric acid slag for later use; wherein, SiO in the mineral processing powder 245% by mass of Al 2O 35% by mass of (C), Fe 2O 3The mass content of (2) is 12%, and the mass content of CaO is 10%; SiO in nickel slag 235% by mass of Al 2O 36% by mass of (C), Fe 2O 3The mass content of (2) is 45%, and the mass content of CaO is 6%; SiO in coal ash 255% by mass of Al 2O 3Is 25% by mass, Fe 2O 3The mass content of (2) is 8%, and the mass content of CaO is 8%; the weight content of CaO in the citric acid residues is 30 percent, and SO 3The mass content of (A) is 58%.
(2) Mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder.
(3) And (2) taking the coal powder as a fuel, placing the raw material powder in a cement kiln for calcination to obtain cement clinker, and controlling the sulfur-alkali ratio of the cement clinker to be 0.6-0.7 so as to facilitate the calcination of the clinker. Wherein the temperature of the cement kiln is controlled as follows: the temperature of the secondary air is controlled to 1050 ℃, the temperature of a kiln tail smoke chamber is 1000 ℃, and the temperature of the outlet of the decomposing furnace is 900 ℃.
Example 2
This embodiment provides a cement clinker, the method of preparing the cement clinker comprising the steps of:
(1) weighing 95kg of limestone, 3kg of coal gangue, 3kg of shale, 2kg of mineral processing powder, 0.5kg of nickel slag, 0.5kg of coal ash and 0.2kg of citric acid slag for later use; wherein, SiO in the mineral processing powder 255% by mass of Al 2O 315% by mass of (C) Fe 2O 3The mass content of (2) is 8%, and the mass content of CaO is 5%; SiO in nickel slag 245% by mass of Al 2O 33% by mass of (B) Fe 2O 3The mass content of (2) is 35%, and the mass content of CaO is 3%; SiO in coal ash 265% by mass of Al 2O 315% by mass of (C) Fe 2O 3The mass content of (2) is 5%, and the mass content of CaO is 5%; the weight content of CaO in the citric acid residues is 40 percent, and SO 3The mass content of (A) is 48%.
(2) Mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder.
(3) And (2) taking coal powder as a fuel, placing the raw material powder in a cement kiln for calcining to obtain cement clinker, and controlling the sulfur-alkali ratio of the cement clinker to be 0.9-1. Wherein the temperature of the cement kiln is controlled as follows: the temperature of the secondary air is controlled to be 1000 ℃, the temperature of a kiln tail smoke chamber is controlled to be 1000 ℃, and the temperature of an outlet of the decomposing furnace is controlled to be 880 ℃.
Example 3
This embodiment provides a cement clinker, the method of preparing the cement clinker comprising the steps of:
(1) weighing 80kg of limestone, 6kg of coal gangue, 6kg of shale, 5kg of mineral processing powder, 3kg of nickel slag, 3kg of coal ash and lemon1kg of citric acid residues for later use; wherein, SiO in the mineral processing powder 250% by mass of Al 2O 320% by mass of (C), Fe 2O 3The mass content of (2) is 10%, and the mass content of CaO is 8%; SiO in nickel slag 240% by mass of Al 2O 35% by mass of (C), Fe 2O 3The mass content of (A) is 40%, and the mass content of CaO is 5%; SiO in coal ash 2Is 60% by mass, Al 2O 318% by mass of (B) Fe 2O 3The mass content of (2) is 6%, and the mass content of CaO is 7%; the weight content of CaO in the citric acid residues is 35 percent, and SO 3The mass content of (A) is 50%.
(2) Mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder.
(3) And (2) taking coal powder as a fuel, placing the raw material powder in a cement kiln for calcining to obtain cement clinker, and controlling the sulfur-alkali ratio of the cement clinker to be 0.7-0.8. Wherein the temperature of the cement kiln is controlled as follows: the temperature of the secondary air is controlled to be 1100 ℃, the temperature of a kiln tail smoke chamber is controlled to be 1000 ℃, and the temperature of an outlet of the decomposing furnace is controlled to be 920 ℃.
Example 4
This embodiment provides a cement clinker, the method of preparing the cement clinker comprising the steps of:
(1) weighing 90kg of limestone, 4kg of coal gangue, 4kg of shale, 3kg of mineral processing powder, 1kg of nickel slag, 1kg of coal ash and 0.5kg of citric acid slag for later use; wherein, SiO in the mineral processing powder 250% by mass of Al 2O 320% by mass of (C), Fe 2O 3The mass content of (2) is 10%, and the mass content of CaO is 8%; SiO in nickel slag 240% by mass of Al 2O 35% by mass of (C), Fe 2O 3The mass content of (A) is 40%, and the mass content of CaO is 5%; SiO in coal ash 2Is 60% by mass, Al 2O 318% by mass of (B) Fe 2O 3The mass content of (2) is 6%, and the mass content of CaO is 7%; quality of CaO in citric acid residues35% of SO 3The mass content of (A) is 50%.
(2) Mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder.
(3) And (2) taking coal powder as a fuel, placing the raw material powder in a cement kiln for calcining to obtain cement clinker, and controlling the sulfur-alkali ratio of the cement clinker to be 0.7-0.8. Wherein the temperature of the cement kiln is controlled as follows: the temperature of the secondary air is controlled to 1050 ℃, the temperature of a kiln tail smoke chamber is 1000 ℃, and the temperature of the outlet of the decomposing furnace is 900 ℃.
Example 5
This embodiment provides a cement clinker, the method of preparing the cement clinker comprising the steps of:
(1) weighing 84.2kg of limestone, 4.85kg of coal gangue, 5kg of shale, 3.7kg of mineral processing powder, 1.7kg of nickel slag, 1.77kg of coal ash and 0.55kg of citric acid slag for later use; wherein, SiO in the mineral processing powder 249.82% by mass of Al 2O 318.98% by mass of (C) Fe 2O 3The mass content of (2) is 10.61%, and the mass content of CaO is 8.73%; SiO in nickel slag 238.72% by mass of Al 2O 34.37% by mass of (1), Fe 2O 3The mass content of (A) is 40.24%, and the mass content of CaO is 5.03%; SiO in coal ash 259.67% by mass of Al 2O 321.81% by mass of (B) Fe 2O 3The mass content of (2) is 6.74%, and the mass content of CaO is 6.42%; the weight content of CaO in the citric acid residues is 36.6 percent, and SO 3The mass content of (b) is 52.29%. Specifically, the chemical composition analysis of each raw material is shown in table 1 below.
TABLE 1
(2) Mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder.
(3) And calcining the raw material powder by taking the coal powder as a fuel to obtain cement clinker, and controlling the sulfur-alkali ratio of the cement clinker to be 0.6-0.7. Wherein the temperature of the cement kiln is controlled as follows: the temperature of the secondary air is controlled to 1050 ℃, the temperature of a kiln tail smoke chamber is 1000 ℃, and the temperature of the outlet of the decomposing furnace is 900 ℃.
Example 6
This embodiment provides a cement clinker, the method of preparing the cement clinker comprising the steps of:
(1) weighing 84kg of limestone, 4.75kg of coal gangue, 5kg of shale, 3.7kg of mineral processing powder, 1.7kg of nickel slag, 1.77kg of coal ash and 0.85kg of citric acid slag for later use; wherein, SiO in the mineral processing powder 249.82% by mass of Al 2O 318.98% by mass of (C) Fe 2O 3The mass content of (2) is 10.61%, and the mass content of CaO is 8.73%; SiO in nickel slag 238.72% by mass of Al 2O 34.37% by mass of (1), Fe 2O 3The mass content of (A) is 40.24%, and the mass content of CaO is 5.03%; SiO in coal ash 259.67% by mass of Al 2O 321.81% by mass of (B) Fe 2O 3The mass content of (2) is 6.74%, and the mass content of CaO is 6.42%; the weight content of CaO in the citric acid residues is 36.6 percent, and SO 3The mass content of (b) is 52.29%. Specifically, the chemical composition analysis of each raw material used in this example was the same as in example 5, as shown in table 1 above.
(2) Mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder.
(3) And (2) taking coal powder as a fuel, placing the raw material powder in a cement kiln for calcining to obtain cement clinker, and controlling the sulfur-alkali ratio of the cement clinker to be 0.7-0.8. Wherein the temperature of the cement kiln is controlled as follows: the temperature of the secondary air is controlled to 1050 ℃, the temperature of a kiln tail smoke chamber is 1000 ℃, and the temperature of the outlet of the decomposing furnace is 900 ℃.
Example 7
This embodiment provides a cement clinker, the method of preparing the cement clinker comprising the steps of:
(1) weighing 83.9kg of limestone, 4.65kg of coal gangue, 5kg of shale, 3.7kg of mineral processing powder, 1.7kg of nickel slag, 1.77kg of coal ash and 1.05kg of citric acid slag for later use; wherein, SiO in the mineral processing powder 249.82% by mass of Al 2O 318.98% by mass of (C) Fe 2O 3The mass content of (2) is 10.61%, and the mass content of CaO is 8.73%; SiO in nickel slag 238.72% by mass of Al 2O 34.37% by mass of (1), Fe 2O 3The mass content of (A) is 40.24%, and the mass content of CaO is 5.03%; SiO in coal ash 259.67% by mass of Al 2O 321.81% by mass of (B) Fe 2O 3The mass content of (2) is 6.74%, and the mass content of CaO is 6.42%; the weight content of CaO in the citric acid residues is 36.6 percent, and SO 3The mass content of (b) is 52.29%. Specifically, the chemical composition analysis of each raw material used in this example was the same as in example 5, as shown in table 1 above.
(2) Mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder.
(3) And (2) taking coal powder as a fuel, placing the raw material powder in a cement kiln for calcining to obtain cement clinker, and controlling the sulfur-alkali ratio of the cement clinker to be 0.8-0.9. Wherein the temperature of the cement kiln is controlled as follows: the temperature of the secondary air is controlled to 1050 ℃, the temperature of a kiln tail smoke chamber is 1000 ℃, and the temperature of the outlet of the decomposing furnace is 900 ℃.
Comparative example 1
The comparative example provides a cement clinker, the method of preparation of which comprises the steps of:
(1) weighing 84.5kg of limestone, 5kg of coal gangue, 5kg of shale, 3.8kg of mineral processing powder, 1.7kg of nickel slag and 1.77kg of coal ash for later use; the chemical component analysis of the raw materials such as limestone, coal gangue, shale, beneficiation powder, nickel slag, coal ash and the like used in the comparative example is the same as that of example 5, as shown in table 1 above.
(2) Mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder.
(3) And (3) taking coal powder as a fuel, and placing the raw material powder in a cement kiln for calcination to obtain cement clinker. Wherein the temperature of the cement kiln is controlled as follows: the temperature of the secondary air is controlled to 1050 ℃, the temperature of a kiln tail smoke chamber is 1000 ℃, and the temperature of the outlet of the decomposing furnace is 900 ℃.
Wherein, the calculation formula of the sulfur-alkali ratio mentioned in the above examples is as follows: S/R = N 1/(0.85N 2+1.29N 3) In the formula N 1、N 2、N 3SO in raw material and coal powder respectively 3、K 2O、Na 2The number of moles of O.
The cement clinker obtained in the above examples 5 to 7 and comparative example 1 was subjected to physicochemical property analysis, and the saturation ratio, silicon ratio, aluminum ratio, free calcium content, sulfur-alkali ratio, three-day strength, and coal consumption in the production process of the cement clinker were respectively detected, and the detection results are shown in table 2 below.
TABLE 2
Figure 847988DEST_PATH_IMAGE002
From the above table 2, it can be seen that, in the embodiment of the present invention, by adding the citric acid residues as the mineralizer, the coal consumption of cement clinker production can be reduced by about 1.9%, and the three-day strength of the cement clinker can be improved by about 10%.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. The cement clinker is characterized by comprising the following components in parts by weight: 70-95 parts of limestone, 3-7 parts of coal gangue, 3-7 parts of shale, 2-6 parts of mineral processing powder, 0.5-4 parts of nickel slag, 0.5-4 parts of coal ash and 0.2-1.5 parts of citric acid slag.
2. The cement clinker of claim 1, wherein the cement clinker comprises the following components in parts by weight: 80-90 parts of limestone, 4-6 parts of coal gangue, 4-6 parts of shale, 3-5 parts of mineral processing powder, 1-3 parts of nickel slag, 1-3 parts of coal ash and 0.5-1 part of citric acid slag.
3. A cement clinker according to claim 1 or 2, characterised in that the beneficiated powder contains SiO 245-55% of Al 2O 315-25% of Fe 2O 3The mass content of the CaO is 8-12%, and the mass content of the CaO is 5-10%.
4. A cement clinker as claimed in claim 1 or 2, wherein SiO is present in said nickel slag 235-45% of Al 2O 3The mass content of the alloy is 3-6 percent, and Fe 2O 3The mass content of the composite is 35-45%, and the mass content of CaO is 3-6%.
5. A cement clinker as claimed in claim 1 or 2, wherein SiO is present in said coal ash 255-65% of Al 2O 315-25% of Fe 2O 3The mass content of the composite is 5-8%, and the mass content of CaO is 5-8%.
6. The cement clinker according to claim 1 or 2, wherein the mass content of CaO in the citric acid residues is 30-40%, and SO is 3The mass content of the composite is 48-58%.
7. A method for the preparation of cement clinker according to any of claims 1 to 6, characterized in that it comprises the following steps:
weighing limestone, coal gangue, shale, mineral processing powder, nickel slag, coal ash and citric acid slag according to the weight parts for later use;
mixing the limestone, the coal gangue, the shale, the mineral processing powder, the nickel slag, the coal ash and the citric acid slag together, and grinding to obtain raw material powder;
and calcining the raw material powder by taking the coal powder as a fuel to obtain cement clinker, and controlling the sulfur-alkali ratio of the cement clinker to be 0.6-1.
8. A cement clinker produced by the production method according to claim 7.
9. The cement clinker according to claim 8, wherein the cement clinker has a saturation ratio of 0.91 to 0.92, a silicon ratio of 2.6 to 2.7, an aluminum ratio of 1.5 to 1.6, and a free calcium content of 1.35 to 1.46%.
10. Use of a cement clinker as defined in any one of claims 1 to 6 and 8 to 9 as a building material.
CN201911230839.3A 2019-12-05 2019-12-05 Cement clinker and preparation method and application thereof Pending CN110776268A (en)

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CN111646722A (en) * 2020-05-15 2020-09-11 湖南武源建材有限责任公司 Concrete reinforcing agent and preparation process thereof
CN115557720A (en) * 2022-10-28 2023-01-03 安徽海螺制剂工程技术有限公司 Cement clinker mineralization reinforcing agent

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CN115557720A (en) * 2022-10-28 2023-01-03 安徽海螺制剂工程技术有限公司 Cement clinker mineralization reinforcing agent

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