CN112250330B

CN112250330B - Green environment-friendly cement and preparation method thereof

Info

Publication number: CN112250330B
Application number: CN202010955757.1A
Authority: CN
Inventors: 王成永; 张志丹; 乔国亮
Original assignee: Dengzhou China United Cement Co ltd
Current assignee: Dengzhou China United Cement Co ltd
Priority date: 2020-09-11
Filing date: 2020-09-11
Publication date: 2022-07-12
Anticipated expiration: 2040-09-11
Also published as: CN112250330A

Abstract

The application discloses green environment-friendly cement and a preparation method thereof. The green environment-friendly cement comprises clinker and hydration regulator in a weight ratio of 10 (0.5-0.7), wherein the clinker is prepared from raw materials comprising the following components: 85-87 parts of limestone; 7.5-8.5 parts by weight of shale; 5.0-6.0 parts of non-ferrous metal slag; 3.6-5.4 parts by weight of spinel; 3.6-5.4 parts by weight of dolomite; 0.4-0.6 weight part of pyrite cinder. According to the green environment-friendly cement, the solid wastes of chemical products are added into the raw materials according to a certain proportion, so that the production cost is reduced, the environmental burden is lightened, and the prepared cement has high compressive strength, breaking strength and impermeability. In addition, the application also discloses a preparation method of the green environment-friendly cement, and the preparation method is simple and efficient to operate and high in production efficiency.

Description

Green environment-friendly cement and preparation method thereof

Technical Field

The application relates to the field of cement production, in particular to green environment-friendly cement and a preparation method thereof.

Background

Cement, generally referred to as a powdered hydraulic inorganic cement, is a plastic slurry formed by adding an appropriate amount of water and stirring, and then is hardened in air or water and can firmly bind aggregates such as sand and stone together. For a long time, cement plays an important role in the economic development of the world as one of three main materials for buildings.

With the acceleration of urban construction, the consumption of cement is increasing, and the production of cement requires a large amount of natural materials, especially clay, as raw material, which can cause serious damage to the environment during mining and is not renewable, so that finding and adopting new substitute materials becomes a consensus of technicians in the industry. Meanwhile, a large amount of solid waste is generated in the manufacturing and smelting processes of various chemical products, and the solid waste also causes a great burden on the environment. With the increasing treatment requirements of the country on reduction, resource utilization, harmlessness and the like of industrial solid wastes and the enhancement of environmental awareness in the world and the requirement of developing green industry, many researchers widely perform attempts to use solid wastes for cement preparation, which has become one of new development trends of the cement industry.

However, the existing cement prepared by using industrial solid waste still has the problems of low strength after solidification, easy cracking, poor impermeability and the like, and is generally difficult to use as high-quality cement.

Disclosure of Invention

[ problem ] to

Aiming at the defects in the prior art, one object of the application is to provide green environment-friendly cement, which is prepared by adding solid wastes of chemical products in a certain proportion into raw materials, so that the production cost is reduced, the environmental burden is lightened, and the prepared cement has the advantages of strength and impermeability which are not lost in common portland cement.

The application also aims to provide the preparation method of the green and environment-friendly cement, and the preparation method is simple and efficient to operate and high in production efficiency.

[ solution ]

In order to achieve the above object, according to one embodiment of the present application, there is provided a green and environment-friendly cement comprising clinker and hydration regulator in a weight ratio of 10 (0.5-0.7), wherein the clinker is made from a raw material comprising:

in the green environmental cement, limestone is used as a main component, industrial solid wastes such as nonferrous metal slag and pyrite slag are used, minerals with wide sources such as shale, spinel and dolomite are matched, the cement prepared from raw materials containing the components has small contractibility and difficult cracking in the solidification process, has higher strength and stronger impermeability after solidification, and can inhibit the diffusion of chloride ions and reduce Ca (OH) in the cement₂The content of the sulfate improves the sulfate corrosion resistance. Wherein the non-ferrous slag usually contains 60-70% of iron silicate (fayalite), and the sulfuric acid slag is the residue of a process for preparing sulfuric acid from pyrite and contains 50-65% of Fe₂O₃And a large amount of iron can be introduced into the cement, so that the cement sintering temperature can be adjusted, the ferrite component can be ensured, and the strength of the cement can be improved.

Further, the clinker is made from a raw meal comprising:

within the above composition ranges, the cement can exhibit better strength and impermeability after setting.

In the green environmental cement according to the present application, the raw meal further comprises the following components:

10.0-11.8 parts by weight of converter slag;

7.5-9.0 parts of fly ash.

In the application, the converter slag and the fly ash are further added, so that the strength, the crack resistance and the erosion resistance of the cement can be further improved.

Further, the raw meal also comprises the following components:

10.5 parts by weight of converter slag;

8.3 parts of fly ash.

In the green environment-friendly cement, the hydration regulator comprises gypsum (CaSO) with the weight ratio of 1 (0.3-0.5)₄·2H₂O) and anorthite.

In the application, because the non-ferrous metal slag, the sulfuric acid slag and other industrial solid wastes are added as raw material components, after the raw material components are calcined into clinker, the hydration speed of the raw material components is difficult to effectively adjust by simply utilizing gypsum, so that the strength improvement of the cement in the later period of solidification is limited, and therefore, the gypsum and the anorthite are mutually matched to serve as hydration regulators, and the effective improvement of the strength of the cement in the later period of solidification is promoted.

Further, the hydration regulator comprises gypsum and anorthite in a weight ratio of 1: 0.4. Under the condition of the proportion, the hydration regulator can better improve the strength of cement at the later stage of setting.

According to another embodiment of the present application, there is provided a method for preparing the green and environment-friendly cement, comprising the steps of:

(1) mixing and grinding shale, nonferrous metal slag and pyrite cinder, pre-sintering at 190-210 ℃ for 25-30 minutes, and cooling to room temperature to obtain a pre-sintered material;

(2) mixing and grinding limestone, spinel and dolomite, and then uniformly mixing the mixture with the pre-sintering material to obtain a raw material;

(3) calcining the raw material at 1240-1370 ℃ for 30-35 minutes, and cooling to room temperature to obtain clinker; and

(4) and mixing and grinding the clinker and the hydration regulator uniformly.

In the application, the preparation method of the green environment-friendly cement is simple, convenient and efficient to operate and high in production efficiency.

Further, converter slag and fly ash are further added in the step (2) to be mixed and ground.

Further, the preheating temperature in the step (1) may be preferably 200 ℃, and the pre-firing time may be preferably 27 minutes.

Further, the calcination temperature in the step (3) may preferably be 1320 ℃, and the pre-firing time may preferably be 32 minutes.

[ advantageous effects ]

In summary, the present application has the following beneficial effects:

according to the green environment-friendly cement, the solid wastes of chemical products are added into the raw materials according to a certain proportion, the production cost is reduced, the environmental burden is lightened, the green environment-friendly cement is green and environment-friendly, the prepared cement has small contractibility in the solidification process and is not easy to crack, and the cement has higher compressive strength, rupture strength and stronger impermeability after solidification, can inhibit the diffusion of chloride ions and reduce Ca (OH) in the cement₂The content of the sulfate improves the sulfate corrosion resistance.

In addition, the preparation method of the green environment-friendly cement is simple, convenient and efficient to operate and high in production efficiency.

Detailed Description

In order that those skilled in the art can more clearly understand the present application, the present application will be described in further detail with reference to the following examples, but it should be understood that the following examples are only preferred embodiments of the present application, and the scope of the present application as claimed is not limited thereto.

Sources of materials

Limestone is purchased from limestone mines in development areas of apricot mountains in Dengzhou city, Henan province;

shale, purchased from shale mine pressed by Tokyo Mazu Tokyo, Nanyang, Henan province;

the non-ferrous metal slag is purchased from non-ferrous metal slag company of Town Phoenix Town, Nanyang city, Henan province;

spinel, available from zhengzhou kory limited, hannah;

dolomite, purchased from a small shop village-wide-five dolomite mine in southern summerheat of Henan province;

the pyrite cinder is purchased from Xixia steel works of Nanyang city, Henan province;

converter slag purchased from Xinyang Steel, Inc., Xinyang City, Henan province;

fly ash, purchased from power plants in the provinces of Henan, China;

gypsum (CaSO)₄·2H₂O) is purchased from the Ming-district Fuxin gypsum building material Ming-district in the city of Daizhou, Hubei province;

anorthite, purchased from south China, south Yang Rong Sansheng Logistics Co., Ltd.

< example >

Example 1

The green and environmentally friendly cement according to the present application was prepared using the following preparation method:

(1) mixing and grinding 8.0kg of shale, 5.4kg of nonferrous metal slag and 0.5kg of pyrite cinder, pre-burning for 27 minutes at 200 ℃, and cooling to room temperature to obtain a pre-burnt material;

(2) mixing and grinding 86.4kg of limestone, 4.1kg of spinel and 4.1kg of dolomite, and then uniformly mixing the mixture with the pre-sintering material to obtain a raw material;

(3) calcining the raw material at 1320 ℃ for 32 minutes, and cooling to room temperature to obtain clinker; and

(4) 100kg of the clinker is taken, 4.3kg of gypsum and 1.7kg of anorthite are mixed and ground uniformly.

Thus, the green and environment-friendly cement according to the application is prepared.

Example 2

(1) mixing and grinding 7.5kg of shale, 5.5kg of nonferrous metal slag and 0.4kg of pyrite cinder, pre-burning for 25 minutes at 200 ℃, and cooling to room temperature to obtain a pre-burned material;

(2) mixing and grinding 85.5kg of limestone, 3.8kg of spinel and 4.2kg of dolomite, and then uniformly mixing the mixture with the pre-sintered material to obtain a raw material;

(3) calcining the raw material at 1280 ℃ for 34 minutes, and cooling to room temperature to obtain clinker; and

Example 3

(1) mixing and grinding 7.6kg of shale, 5.7kg of nonferrous metal slag and 0.5kg of pyrite cinder, pre-burning for 25 minutes at 210 ℃, and cooling to room temperature to obtain a pre-burned material;

(2) mixing and grinding 86.5kg of limestone, 4.7kg of spinel and 3.6kg of dolomite, and then uniformly mixing the mixture with the pre-sintered material to obtain a raw material;

(3) calcining the raw material at 1350 ℃ for 31 minutes, and cooling to room temperature to obtain clinker; and

(4) 100kg of the clinker is taken, 4.0kg of gypsum and 2.0kg of anorthite are mixed and ground uniformly.

Example 4

(1) mixing and grinding 8.0kg of shale, 5.2kg of nonferrous metal slag and 0.6kg of pyrite cinder, pre-burning for 30 minutes at 190 ℃, and cooling to room temperature to obtain a pre-burned material;

(2) mixing and grinding 86.2kg of limestone, 4.2kg of spinel and 4.7kg of dolomite, and then uniformly mixing the mixture with the pre-sintered material to obtain a raw material;

(3) calcining the raw material at 1240 ℃ for 35 minutes, and cooling to room temperature to obtain clinker; and

(4) 100kg of the clinker is taken, 4.6kg of gypsum and 1.4kg of anorthite are mixed and ground uniformly.

Example 5

(1) mixing and grinding 8.3kg of shale, 5.0kg of nonferrous metal slag and 0.6kg of pyrite cinder, pre-burning for 30 minutes at 190 ℃, and cooling to room temperature to obtain a pre-burned material;

(2) mixing and grinding 85.2kg of limestone, 5.4kg of spinel and 4.5kg of dolomite, and then uniformly mixing the mixture with the pre-sintering material to obtain a raw material;

(3) calcining the raw material at 1370 ℃ for 30 minutes, and cooling to room temperature to obtain clinker; and

Example 6

(2) mixing and grinding 86.1kg of limestone, 4.1kg of spinel, 4.1kg of dolomite, 10.5kg of converter slag and 8.3kg of fly ash, and then uniformly mixing with the pre-sintered material to obtain a raw material;

(4) 100kg of clinker is taken, 3.3kg of gypsum and 1.7kg of anorthite are mixed and ground uniformly.

Example 7

(1) mixing and grinding 7.9kg of shale, 5.6kg of nonferrous metal slag and 0.4kg of pyrite cinder, pre-burning for 30 minutes at 190 ℃, and cooling to room temperature to obtain a pre-burned material;

(2) mixing and grinding 87.0kg of limestone, 4.5kg of spinel, 3.8kg of dolomite, 10.0kg of converter slag and 7.9kg of fly ash, and then uniformly mixing with the pre-sintered material to obtain a raw material;

(4) 100kg of the clinker is taken, 4.7kg of gypsum and 2.3kg of anorthite are mixed and ground uniformly.

Example 8

(1) mixing and grinding 8.5kg of shale, 6.0kg of nonferrous metal slag and 0.5kg of pyrite cinder, pre-burning at 1210 ℃ for 25 minutes, and cooling to room temperature to obtain a pre-burned material;

(2) mixing and grinding 85kg of limestone, 3.6kg of spinel, 5.4kg of dolomite, 10.8kg of converter slag and 7.5kg of fly ash, and then uniformly mixing with the pre-sintered material to obtain a raw material;

(4) 100kg of the clinker is taken, 3.6kg of gypsum and 1.4kg of anorthite are mixed and ground uniformly.

Example 9

(1) mixing and grinding 8.1kg of shale, 5.8kg of nonferrous metal slag and 0.4kg of pyrite cinder, pre-burning at 200 ℃ for 26 minutes, and cooling to room temperature to obtain a pre-burned material;

(2) mixing and grinding 86.7kg of limestone, 5.2kg of spinel, 4.0kg of dolomite, 11.8kg of converter slag and 9.0kg of fly ash, and then uniformly mixing with the pre-sintered material to obtain a raw material;

(3) calcining the raw material at 1290 ℃ for 33 minutes, and cooling to room temperature to obtain clinker; and

(4) 100kg of the clinker is taken, 5.4kg of gypsum and 1.6kg of anorthite are mixed and ground uniformly.

Example 10

(1) mixing and grinding 7.7kg of shale, 5.9kg of nonferrous metal slag and 0.6kg of pyrite cinder, pre-burning for 27 minutes at 200 ℃, and cooling to room temperature to obtain a pre-burnt material;

(2) mixing and grinding 85.7kg of limestone, 5.0kg of spinel, 5.0kg of dolomite, 11.2kg of converter slag and 8.7kg of fly ash, and then uniformly mixing with the pre-sintered material to obtain a raw material;

Comparative example 1

The following preparation method was used to prepare the cement:

(1) mixing and grinding 7.0kg of shale, 6.5kg of nonferrous metal slag and 0.2kg of pyrite cinder, pre-burning for 27 minutes at 200 ℃, and cooling to room temperature to obtain a pre-burnt material;

(2) mixing and grinding 90.0kg of limestone, 3.2kg of spinel and 5.6kg of dolomite, and then uniformly mixing the mixture with the pre-sintering material to obtain a raw material;

(4) 100kg of the clinker is taken, 5.0kg of gypsum and 1.0kg of anorthite are mixed and ground uniformly.

Comparative example 2

The following preparation method was used to prepare the cement:

(1) mixing and grinding 9.0kg of shale, 4.5kg of nonferrous metal slag and 0.8kg of pyrite cinder, pre-burning for 27 minutes at 200 ℃, and cooling to room temperature to obtain a pre-burnt material;

(2) mixing and grinding 82.0kg of limestone, 5.6kg of spinel and 3.2kg of dolomite, and then uniformly mixing with the pre-sintering material to obtain a raw material;

Comparative example 3

Cement was prepared in the same manner as in example 1 of the present application, except that clay was used instead of shale.

Comparative example 4

Cement was produced in the same manner as in example 1 of the present application, except that non-ferrous slag and pyrite cinder were not added.

< test examples >

The cement produced in examples 1 to 10 and comparative examples 1 to 4 was used for performance testing. Specifically, the initial setting time and the final setting time of the cement are tested according to a test method in JC/T453-2004 'self-stress cement physical inspection method'; testing the compressive strength and the flexural strength of the cement according to the method in GB/T17671-1999 Cement mortar Strength test; and evaluating the impermeability grade of the cement according to GB 50164-2008 concrete quality control Standard, and the test results are shown in Table 1.

[ Table 1]

As can be seen from the above table 1, the green environmental protection cements prepared according to examples 1 to 10 of the present application have a long initial setting time and final setting time due to the addition of the hydration modifier, which contribute to the sufficient growth and extension of hydrated crystals in the cement, ultimately resulting in excellent compressive strength, flexural strength and impermeability of the cement. And under the condition that converter slag and fly ash are further added, the compressive strength and the flexural strength of the cement are further improved.

In contrast, comparative examples 1 and 2, which employ a formulation outside the range of the present application, resulted in cements having reduced compressive strength, flexural strength and impermeability, which indicates that compositions (particularly industrial solid wastes) not in any formulation can achieve the properties of the cements of the present application; comparative example 3, in which clay commonly used in the art was used instead of shale, although most of the properties were improved as compared with comparative examples 1 and 2, there was a clear gap as compared with the examples of the application; and comparative example 4, which excludes the use of industrial solid wastes, shows a significant decrease in the properties thereof, indicating that these industrial solid wastes contribute to the improvement of the strength and impermeability of cement as well.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims

1. The green environment-friendly cement is characterized by comprising 10 (0.5-0.7) by weight of clinker and 1 (0.3-0.5) by weight of hydration regulator, wherein the clinker is prepared from the following raw materials:

85-87 parts of limestone;

7.5 to 8.5 weight portions of shale;

5.0 to 6.0 weight portions of non-ferrous metal slag;

spinel 3.6-5.4 weight portions;

3.6 to 5.4 weight portions of dolomite;

0.4-0.6 weight part of pyrite cinder;

10.0-11.8 parts by weight of converter slag;

7.5 to 9.0 parts of fly ash.

2. The green environmental protection cement according to claim 1, wherein said clinker is prepared from raw materials of the following components:

86.1 parts by weight of limestone;

8.0 parts of shale;

5.4 parts of non-ferrous metal slag;

4.1 parts by weight of spinel;

4.1 parts by weight of dolomite;

0.5 part by weight of pyrite cinder;

10.5 parts by weight of converter slag;

8.3 parts of fly ash.

3. A method for preparing green environmental cement according to any one of claims 1 to 2, characterized by comprising the following steps:

(1) mixing and grinding shale, nonferrous metal slag and pyrite cinder, pre-sintering at the temperature of 190-210 ℃ for 25-30 minutes, and cooling to room temperature to obtain a pre-sintered material;

(2) mixing and grinding limestone, spinel, dolomite, converter slag and fly ash, and then uniformly mixing with the pre-sintered material to obtain a raw material;

(3) calcining the raw material at 1240-1370 ℃ for 30-35 minutes, and cooling to room temperature to obtain clinker;

(4) and mixing and grinding the clinker and the hydration regulator uniformly.

4. The manufacturing method according to claim 3, wherein the preheating temperature in the step (1) is 200 ℃ and the pre-firing time is 27 minutes.

5. The method according to claim 3, wherein the calcination temperature in the step (3) is 1320 ℃, and the calcination time is 32 minutes.