CN111320401A - Copper slag portland cement material and preparation method thereof - Google Patents

Copper slag portland cement material and preparation method thereof Download PDF

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Publication number
CN111320401A
CN111320401A CN201811524497.1A CN201811524497A CN111320401A CN 111320401 A CN111320401 A CN 111320401A CN 201811524497 A CN201811524497 A CN 201811524497A CN 111320401 A CN111320401 A CN 111320401A
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copper slag
portland cement
slag
cement material
copper
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CN201811524497.1A
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Inventor
王旭
黄小青
杨义
廖双双
黄丽霖
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Guangxi Green Cement Industry Engineering Institute Co ltd
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Guangxi Green Cement Industry Engineering Institute Co ltd
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Priority to CN201811524497.1A priority Critical patent/CN111320401A/en
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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
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • C04B7/17—Mixtures thereof with other inorganic cementitious materials or other activators with calcium oxide containing activators
    • C04B7/19—Portland cements
    • 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
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production 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)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a copper slag portland cement material and a preparation method thereof, and belongs to the technical field of building materials. The copper slag portland cement material disclosed by the invention comprises the following components in percentage by weight: 5-15% of copper slag, 5-15% of slag, 2-6% of calcium hydroxide and the balance of cement; the preparation method comprises the steps of raw material preparation, copper slag treatment and raw material mixing, and the obtained copper slag portland cement material has excellent strength and corrosion resistance, can be applied to large-volume concrete projects with strong corrosion resistance, such as ocean engineering and the like, has the advantages of simple preparation process, low cost, good development prospect and suitability for popularization and application.

Description

Copper slag portland cement material and preparation method thereof
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a copper slag portland cement material and a preparation method thereof.
Background
The cement material for producing large-volume concrete engineering with strong corrosion resistance, such as ocean engineering, is mainly used for producing a high-performance cement-based material with strong corrosion resistance.
The copper slag is a copper smelting processThe existing domestic method generally adopts a pyrogenic depletion method, a slag beneficiation method and a wet method to refine valuable metals in copper slag, so that the investment and operation cost is relatively high, the additional value of the obtained production product is low, and certain pollution is generated in the process; the unused copper slag occupies land, and can cause the loss of metal resources and environmental pollution, so that a low-cost copper slag utilization approach needs to be explored. The copper slag has a certain content of SiO2FeO, and small amounts of CaO and Al2O3And oxygen-containing compounds such as MgO and the like have good pozzolanic activity, good grindability and mechanical properties, and basic conditions for producing cement-based materials, but no report of producing cement materials by using copper slag is found at present, so that the search for preparing high-performance copper slag portland cement materials with strong corrosion resistance by using copper slag is necessary, and the method has important practical significance for improving the corrosion resistance of the cement-based materials and building ocean engineering.
Disclosure of Invention
The invention aims to provide a copper slag portland cement material and a preparation method thereof.
The technical scheme of the invention is as follows:
the copper slag portland cement material comprises the following components in percentage by weight: 5-15% of copper slag, 5-15% of slag, 2-6% of calcium hydroxide and the balance of cement;
the specific surface area of the copper slag is 368-427m2Per kg, the content of each component in the copper slag is SiO according to weight percentage2≥27.59％、Al2O3≥5.26％、Fe2O3Not less than 59.16%, CaO not less than 3.74%, and MgO not less than 2.2%. The calcium hydroxide is used as an activator in the present invention.
Preferably, the copper slag and the slag are used in equal amount.
As a further optimization of the technical scheme, the copper slag portland cement material consists of the following components in percentage by weight: 10% of copper slag, 10% of slag, 4% of calcium hydroxide and the balance of cement.
Preferably, the contents of the components in the slag are SiO in percentage by weight2≥31.59％、Al2O3≥16.29％、Fe2O3≥1.56％、CaO≥38.84％、MgO≥8.58％。
Preferably, the calcium hydroxide is analytically pure calcium hydroxide.
Preferably, the cement is ordinary portland cement, and the strength of the cement is more than or equal to 42.5 MPa.
A preparation method of the copper slag portland cement material comprises the following steps,
(1) preparation of raw materials: weighing copper slag, calcium hydroxide and cement according to the weight percentage;
(2) and (3) treatment of copper slag: firstly, putting the copper slag into an oven for drying, then grinding by using a ball mill, and finally adding calcium hydroxide to fully stir and uniformly mix;
(3) mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Preferably, the drying temperature is 120-130 ℃, and the drying time is 3-5 h.
The rotating speed of the cylinder of the ball mill used by the invention is 530r/min at most, and the power is 1000W. Preferably, the grinding time is 15-40 min.
The strength parameters of the copper slag portland cement material are as follows: the 118d flexural strength is more than or equal to 8.9MPa, and the 118d compressive strength is more than or equal to 59.0 MPa; the corrosion resistance coefficient of 90d in the magnesium sulfate corrosion resistance test is more than or equal to 1.07.
The copper slag, the calcium hydroxide and the cement are all purchased in the market and do not need to be specially prepared.
The invention principle is as follows: the invention carries out high-temperature smelting, low-temperature cold quenching, drying and grinding on the copper slag, and carries out excitation treatment on the copper slag by an excitant calcium hydroxide to ensure that active ion groups [ SiO ] in the copper slag4]4-And [ AlO ]4]5-The calcium and the calcium are dissolved out rapidly and react with Ca (OH) in the cement2The following reaction was carried out:
SiO2(active) + xCa (OH)2+m1H2O→x1CaO·SiO2·m1H2O(C-S-H)，
Al2O3(active) + xCa (OH)2+m2H2O→x2CaO·Al2O3·m2H2O (C-A-H) forms a C-S-H gel with gelling property and hydrated calcium aluminate (C-A-H), and the two stably exist in an alkaline environment, thereby having positive effects of improving the strength of portland cement and improving the corrosion resistance of the cement.
The invention has the beneficial effects that:
(1) the invention carries out high-temperature smelting, low-temperature cold quenching, drying, grinding and calcium hydroxide excitation treatment on the copper slag to ensure that the active ion group [ SiO ] in the copper slag is activated4]4-And [ AlO ]4]5-When dissolved out rapidly, the dissolved out water is added to cement and then mixed with Ca (OH) in the cement2The following reaction was carried out: SiO 22(active) + xCa (OH)2+m1H2O→x1CaO·SiO2·m1H2O(C-S-H)，Al2O3(active) + xCa (OH)2+m2H2O→x2CaO·Al2O3·m2H2O (C-A-H) forms a C-S-H gel with a gelling property and hydrated calcium aluminate (C-A-H), and the two exist stably in an alkaline environment, so that the copper slag participates in the secondary volcanic ash reaction, the calcium phase content in the cement-based material is reduced, the generation of expansive products such as ettringite is reduced, the compactness of the cement-based material is enhanced, and the corrosion resistance is improved.
(2) According to the invention, the copper slag is used for improving the corrosion resistance of the cement, the specific surface area of the copper slag is matched with the thickness of the slag by treating the copper slag, the volcanic ash activity of the copper slag is ensured to be more easily excited, and the proper amount of slag is used for improving the strength of the cement. The addition of the copper slag and the slag can adjust the plasticity of the production mixed raw materials, is convenient for stirring, forming and processing, and improves the breaking strength, the compressive strength and the corrosion resistance of the product, so that the copper slag portland cement material has excellent strength and corrosion resistance, and can be applied to large-volume concrete projects with strong corrosion resistance, such as ocean engineering and the like.
(3) The method takes the copper slag and the slag as raw materials to prepare the copper slag portland cement material with high strength and good corrosion resistance, changes waste into valuable, is favorable for improving the comprehensive utilization rate of resources, protects the environment, and has great economic benefit and social benefit.
(4) The invention has the advantages of simple raw materials, low price, low production cost and simple production process, and is suitable for popularization and application.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the scope of the present invention.
Firstly, raw material selection and pretreatment requirements are as follows:
the specific surface area of the selected copper slag is 368-427m2Per kg, the content of each component in the copper slag is SiO according to the weight percentage2≥27.59％、Al2O3≥5.26％、Fe2O3≥59.16％、CaO≥3.74、MgO≥2.2％。
The contents of all components in the selected slag are SiO in percentage by weight2≥31.59％、Al2O3≥16.29％、Fe2O3≥1.56％、CaO≥38.84％、MgO≥8.58％。
The calcium hydroxide is analytically pure calcium hydroxide.
The selected cement is ordinary portland cement, and the strength of the selected cement is more than or equal to 42.5 MPa.
Preparation method of high-corrosion-resistance low-heat cement material
Comparative example 1
2000g of cement was weighed.
Comparative example 2
400g of slag, 1520g of cement and 80g of calcium hydroxide are weighed.
Example 1
(1) Preparation of raw materials: 200g of copper slag, 200g of slag, 80g of calcium hydroxide and 1520g of cement are weighed.
(2) And (3) treatment of copper slag: firstly, the copper slag is put into an oven at 125 ℃ to be dried for 4h, then is ground for 40min by a ball mill, and finally is added with calcium hydroxide to be fully stirred and uniformly mixed.
(3) Mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Example 2
(1) Preparation of raw materials: weighing 250g of copper slag, 250g of slag, 100g of calcium hydroxide and 1400g of cement.
(2) And (3) treatment of copper slag: firstly, placing the copper slag in a drying oven at 125 ℃ for drying for 4h, then grinding for 35min by using a ball mill, and finally adding calcium hydroxide to fully stir and uniformly mix.
(3) Mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Example 3
(1) Preparation of raw materials: weighing 300g of copper slag, 300g of slag, 120g of calcium hydroxide and 1280g of cement.
(2) And (3) treatment of copper slag: firstly, the copper slag is put into an oven with the temperature of 127 ℃ to be dried for 3.5h, then is ground for 30min by a ball mill, and finally is added with calcium hydroxide to be fully stirred and uniformly mixed.
(3) Mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Example 4
(1) Preparation of raw materials: weighing 150g of copper slag, 150g of slag, 60g of calcium hydroxide and 1640g of cement.
(2) And (3) treatment of copper slag: firstly, the copper slag is placed in a baking oven at 128 ℃ to be baked for 3.5h, then the copper slag is ground for 25min by a ball mill, and finally, calcium hydroxide is added to be fully stirred and uniformly mixed.
(3) Mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Example 5
(1) Preparation of raw materials: 100g of copper slag, 100g of slag, 40g of calcium hydroxide and 1760g of cement are weighed.
(2) And (3) treatment of copper slag: firstly, the copper slag is put into an oven at 123 ℃ to be dried for 4.5h, then is ground for 20min by a ball mill, and finally is added with calcium hydroxide to be fully stirred and uniformly mixed.
(3) Mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Example 6
(1) Preparation of raw materials: 230g of copper slag, 220g of slag, 90g of calcium hydroxide and 1460g of cement are weighed.
(2) And (3) treatment of copper slag: firstly, the copper slag is placed in an oven at 122 ℃ to be dried for 4.5h, then the copper slag is ground for 15min by a ball mill, and finally, calcium hydroxide is added to be fully stirred and uniformly mixed.
(3) Mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Example 7
(1) Preparation of raw materials: weighing 280g of copper slag, 270g of slag, 110g of calcium hydroxide and 1340g of cement.
(2) And (3) treatment of copper slag: firstly, the copper slag is placed in an oven at 121 ℃ to be dried for 5 hours, then the copper slag is ground for 20 minutes by a ball mill, and finally, calcium hydroxide is added to be fully stirred and uniformly mixed.
(3) Mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Example 8
(1) Preparation of raw materials: 160g of copper slag, 170g of slag, 70g of calcium hydroxide and 1600g of cement are weighed.
(2) And (3) treatment of copper slag: firstly, the copper slag is placed in an oven at 120 ℃ to be dried for 5 hours, then the copper slag is ground for 25 minutes by a ball mill, and finally, calcium hydroxide is added to be fully stirred and uniformly mixed.
(3) Mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Example 9
(1) Preparation of raw materials: 120g of copper slag, 135g of slag, 50g of calcium hydroxide and 1695g of cement are weighed.
(2) And (3) treatment of copper slag: firstly, the copper slag is put into an oven at 130 ℃ to be dried for 3h, then is ground for 30min by a ball mill, and finally is added with calcium hydroxide to be fully stirred and uniformly mixed.
(3) Mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
Third, product performance index test
The cement-based materials of comparative examples 1-2 and examples 1-9 were subjected to a strength test and a magnesium sulfate corrosion resistance test (GB/T50082-2009), and the test results are shown in Table 1 below.
TABLE 1 Cement Material Strength test and Corrosion resistance test results
Figure BDA0001904065450000051
As can be seen from Table 1, compared with the cement materials of comparative examples 1 or 2, the flexural strength and compressive strength of the copper slag portland cement materials of examples 1-9 are both improved by more than 5%, and the corrosion resistance coefficient is improved by more than 30%, thus the addition of the copper slag is beneficial to improving the corrosion resistance of the cement materials, the reasonable matching addition of the copper slag and the slag is beneficial to improving the strength and corrosion resistance of the cement materials, so that the comprehensive performance of the copper slag portland cement materials is better, and the copper slag portland cement materials are suitable for being applied to mass concrete engineering with strong corrosion resistance, such as ocean engineering and the like.

Claims (10)

1. The copper slag portland cement material is characterized by comprising the following components in percentage by weight: 5-15% of copper slag, 5-15% of slag, 2-6% of calcium hydroxide and the balance of cement;
the specific surface area of the copper slag is 368-427m2Per kg, the content of each component in the copper slag is SiO according to weight percentage2≥27.59％、Al2O3≥5.26％、Fe2O3≥59.16％、CaO≥3.74、MgO≥2.2％。
2. The copper slag portland cement material according to claim 1, wherein the amount of the copper slag is equal to that of the slag.
3. The copper slag portland cement material according to claim 2, wherein the copper slag portland cement material consists of the following components in percentage by weight: 10% of copper slag, 10% of slag, 4% of calcium hydroxide and the balance of cement.
4. The copper slag portland cement material according to any one of claims 1 to 3, wherein the slag contains components in an amount of SiO in percentage by weight2≥31.59％、Al2O3≥16.29％、Fe2O3≥1.56％、CaO≥38.84％、MgO≥8.58％。
5. A copper slag portland cement material according to any one of claims 1 to 3, wherein the calcium hydroxide is analytically pure calcium hydroxide.
6. The copper slag portland cement material according to any one of claims 1 to 3, wherein the cement is ordinary portland cement having a strength of 42.5MPa or more.
7. A method for producing a copper slag portland cement material according to any one of claims 1 to 6, comprising the steps of,
(1) preparation of raw materials: weighing copper slag, calcium hydroxide and cement according to the weight percentage;
(2) and (3) treatment of copper slag: firstly, putting the copper slag into an oven for drying, then grinding by using a ball mill, and finally adding calcium hydroxide to fully stir and uniformly mix;
(3) mixing raw materials: and fully stirring and uniformly mixing the slag, the cement and the treated copper slag to obtain the copper slag portland cement material.
8. The method for preparing the copper slag portland cement material according to claim 7, wherein the drying temperature is 120-130 ℃ and the drying time is 3-5 h.
9. The method for preparing a copper slag portland cement material according to claim 7, wherein the grinding time is 15-40 min.
10. A copper slag portland cement material obtained by the preparation method according to any one of claims 7 to 9, wherein the strength parameter of the copper slag portland cement material is: the 118d flexural strength is more than or equal to 8.9MPa, and the 118d compressive strength is more than or equal to 59.0 MPa; the corrosion resistance coefficient of 90d in the magnesium sulfate corrosion resistance test is more than or equal to 1.07.
CN201811524497.1A 2018-12-13 2018-12-13 Copper slag portland cement material and preparation method thereof Pending CN111320401A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN105541255A (en) * 2016-01-11 2016-05-04 福州大学 Copper slag-base low silicon iron tailing filling material and preparation technology thereof
CN108164164A (en) * 2017-12-26 2018-06-15 中国建筑材料科学研究总院有限公司 Complex cement and preparation method thereof
CN108483953A (en) * 2018-03-09 2018-09-04 江西科技学院 A kind of low hydration heat copper ashes base composite gelled material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101085044B1 (en) * 2010-11-03 2011-11-18 주식회사 씨엠디기술단 Inorgarnic binder for manufacturing secondary concrete product
CN104529197A (en) * 2015-01-22 2015-04-22 北京矿冶研究总院 Preparation method of novel composite cementing material
CN105541255A (en) * 2016-01-11 2016-05-04 福州大学 Copper slag-base low silicon iron tailing filling material and preparation technology thereof
CN108164164A (en) * 2017-12-26 2018-06-15 中国建筑材料科学研究总院有限公司 Complex cement and preparation method thereof
CN108483953A (en) * 2018-03-09 2018-09-04 江西科技学院 A kind of low hydration heat copper ashes base composite gelled material and preparation method thereof

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Application publication date: 20200623