CN112500108A - High-flow gypsum-based all-solid-waste cementing material and preparation method thereof - Google Patents

High-flow gypsum-based all-solid-waste cementing material and preparation method thereof Download PDF

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Publication number
CN112500108A
CN112500108A CN202011413139.0A CN202011413139A CN112500108A CN 112500108 A CN112500108 A CN 112500108A CN 202011413139 A CN202011413139 A CN 202011413139A CN 112500108 A CN112500108 A CN 112500108A
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solid
slag powder
gypsum
phosphogypsum
waste
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谭洪波
杜超
马保国
李相国
蹇守卫
黄健
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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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
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C04B28/142Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
    • C04B28/143Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
    • 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
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/243Phosphorus-containing polymers
    • 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
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • C04B40/0046Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
    • 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
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40Surface-active agents, dispersants
    • C04B2103/408Dispersants
    • 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
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention provides a high-flow gypsum-based all-solid-waste cementing material and a preparation method thereof, and the high-flow gypsum-based all-solid-waste cementing material comprises the following components in percentage by mass: nano-micron modified phosphogypsum slurry: 40-45%, slag powder: 40-45% of steel slag powder: 3.5-7.5%, dispersion stabilizer: 0.1-0.5%, and the balance of water. The high-flow gypsum-based all-solid-waste cementing material has the characteristics of good rheological property, high strength and the like, the net slurry fluidity of the high-flow gypsum-based all-solid-waste cementing material reaches more than 300mm, and the 28d mortar compressive strength of the high-flow gypsum-based all-solid-waste cementing material reaches more than 42.5MPa, wherein, the steel slag powder can completely replace cement clinker, thereby not only saving the using amount of the cementing material, but also greatly reducing the total cost.

Description

High-flow gypsum-based all-solid-waste cementing material and preparation method thereof
Technical Field
The invention relates to the technical field of cementing materials, in particular to a high-flow gypsum-based all-solid-waste cementing material and a preparation method thereof.
Background
The phosphogypsum is an industrial byproduct of wet-process phosphoric acid production of phosphorus chemical enterprises, and the main component of the phosphogypsum is CaSO4·2H2O is one of the solid wastes with the largest discharge amount in the chemical industry, the resource utilization rate of the phosphogypsum in China is about 20 percent at present, a large amount of accumulated phosphogypsum causes serious ecological environment problems, and the comprehensive utilization of the phosphogypsum resources is accelerated. The steel slag is solid waste in the ferrous metallurgy industry, and the quantity of the steel slag is continuously increased along with the continuous development of the current ferrous industry, so that the steel slag not only occupies a large amount of land and causes serious pollution to the environment, but also brings potential harm to the production and life of people.
As a cement production country, the total amount of cement produced in China every year accounts for about 60% of the total world production, a large amount of energy and natural resources are consumed in the cement production process, and a large amount of harmful gas and dust are discharged. According to statistics, about 1.5t of limestone is consumed for producing 1t of cement clinker, a large amount of natural resources such as petroleum and coal and electric energy are consumed, and about 1t of CO is discharged in the process2And a large amount of nitrogen and sulfur oxides, which are the most powerful causes of greenhouse effect and acid rain phenomenon, greatly increase environmental load and pose great threat to the natural environment and human health.
Disclosure of Invention
In view of the above, the present invention aims to provide a new concept of fully utilizing solid waste, that is, a high flow state gypsum-based all-solid waste cementing material is manufactured by using phosphogypsum as a main cementing material and using steel slag powder and slag powder as admixture. The cementing material completely uses solid wastes, does not consume cement clinker, not only promotes the reasonable utilization of the solid wastes, but also greatly saves energy and resources, and compared with cement-based cementing materials, the high-flow-state gypsum-based completely-solid waste cementing material basically does not reduce the later strength, and slightly improves the rheological property and the volume stability.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a high flow state gypsum based full solid waste cementing material comprises the following components by mass percent: nano-micron modified phosphogypsum slurry: 40-45%, slag powder: 40-45% of steel slag powder: 3.5-7.5%, dispersion stabilizer: 0.1-0.5%, and the balance of water.
Optionally, the nano-micro modified phosphogypsum slurry is a nano-micro modified phosphogypsum slurry prepared by the following method:
mixing the phosphogypsum, the steel slag powder, the slag powder and the dispersion stabilizer according to the mass ratio of the dry-basis phosphogypsum to the steel slag powder to the dispersion stabilizer of 45 to (2-5) to (0.7 to 0.5) and the water-solid ratio of 0.5, and then carrying out wet grinding treatment until the median particle size of slurry particles is 5-10 mu m, thus obtaining the nano-micron modified phosphogypsum slurry.
Optionally, the wet-milling treated mill body is a zirconia mill body, the zirconia mill body has a grading of 7 mm: 5 mm: 3 mm: 1mm ═ 1: 2: 4: 3, and the zirconia mill body has a mass of 2 times the total mass of the dry-based phosphogypsum, the steel slag powder, the slag powder and the dispersion stabilizer.
Optionally, the grinding rotation speed of the wet grinding process is 400rpm, and the grinding time is 60 min.
Optionally, the phosphogypsum is a byproduct gypsum of the phosphating chemical industry; the water content of the phosphogypsum is 16-18 percent, and the content of the dihydrate gypsum is 90-95 percent.
Optionally, the slag powder is grade S95 slag powder; the specific surface area of the steel slag powder is 400-500 m2Per kg, the median particle diameter is 15-25 μm.
Optionally, the dispersion stabilizer is a phosphate polymer; the molecular weight of the phosphate polymer is 10000-30000, and the molecular structural formula of the phosphate polymer is as follows:
Figure BDA0002816468530000031
wherein m, n and p are 3.5: 1 to (0.1-0.2).
The second purpose of the invention is to provide a method for preparing the high-flow gypsum-based all-solid-waste cementing material, which comprises the following steps:
and (2) uniformly mixing the nano-micron modified phosphogypsum slurry, the steel slag powder and the slag powder, adding the water and the dispersion stabilizer, uniformly stirring, and then curing and forming to obtain the high-flow gypsum-based all-solid-waste cementing material.
Compared with the prior art, the high-flow gypsum-based all-solid-waste cementing material has the following advantages:
1. the high-flow gypsum-based all-solid-waste cementing material has the characteristics of good rheological property, high strength, good volume stability and the like, the net slurry fluidity reaches more than 300mm, and the 28d mortar compressive strength reaches more than 42.5MPa, wherein, the steel slag powder can completely replace cement clinker, thereby not only saving the using amount of the cementing material, but also greatly reducing the total cost.
2. The preparation process is simple and easy to operate, the parameters are easy to control, and the method is easy to popularize and apply.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The raw material of the invention is phosphogypsum which is a byproduct of phosphating chemical industry, the water content of the phosphogypsum is 16-18 percent, and the content of dihydrate gypsum is 90-95 percent; the slag powder is commercially available S95 grade mineral powder; the steel slag is taken from Wuhan steel Limited company, is in black granular shape, is dried in a drying oven at 110 ℃ after being crushed, and is ground in a small mill with the test of phi 500mm multiplied by 500mm to obtain the steel slag with the specific surface area of 400-500 m2Steel slag/kg with median particle size of 15-25 μmPulverizing; the dispersion stabilizer is a phosphate ester polymer, the molecular weight of the phosphate ester polymer is 10000-30000, and the molecular structure of the phosphate ester polymer is as follows:
Figure BDA0002816468530000041
wherein m, n and p are 3.5: 1 to (0.1-0.2).
The present invention will be described in detail with reference to examples.
The raw material compositions of the high flow gypsum-based all-solid-waste cement of examples 1 to 6 of the present invention are shown in table 1.
TABLE 1
Figure BDA0002816468530000051
The raw material composition of the nano-micron modified phosphogypsum slurry in the high-flow-state gypsum-based all-solid waste cementing materials of the embodiments 1 to 6 of the invention is shown in table 2, and the kind and performance of the dispersion stabilizer are shown in table 3.
The nano-micron modified phosphogypsum slurry in the high flow state gypsum-based all-solid waste cementing material of the embodiment 1-the embodiment 6 is prepared according to the following method, and the specific preparation process is as follows:
1) weighing the raw materials according to the table 2, wherein the water consumption is weighed according to the water-solid ratio of 0.5, namely the water/(dry-based phosphogypsum + steel slag powder + dispersion stabilizer) is 0.5 by mass ratio, wherein the water content of the phosphogypsum in the water-in-water is 18.0% as in example 1, if the water content is calculated according to 45g of dry-based phosphogypsum, 5g of steel slag powder, 0.7g of slag powder and 0.1g of dispersion stabilizer, the actually weighed amount of the phosphogypsum is 54.88g, the water consumption is 25.40g according to the water-solid ratio of 0.5, and the additional water required is 15.52g by considering the water contained in the actually weighed phosphogypsum;
2) adding the phosphogypsum, the steel slag powder, the dispersion stabilizer (the dispersant of each example is shown in table 3) and water weighed in the step 1) into a ball milling tank, putting a zirconia grinding body with the gradation of 7 mm: 5 mm: 3 mm: 1mm ═ 1: 2: 4: 3 as a grinding medium, wherein the mass of the zirconia grinding body is 2 times of the total mass of the dry-based phosphogypsum, the steel slag powder, the slag powder and the dispersion stabilizer, grinding at the speed of 400rpm for 60 minutes, and filtering out the grinding body to obtain the nano-micron modified phosphogypsum slurry with the median particle size shown in table 2.
TABLE 2
Figure BDA0002816468530000061
TABLE 3
Examples m:n:p Molecular weight
Example 1 3.5:1:0.1 10000
Example 2 3.5:1:0.15 19420
Example 3 3.5:1:0.2 30000
Example 4 3.5:1:0.2 30000
Example 5 3.5:1:0.15 19420
Example 6 3.5:1:0.1 10000
After the nano-micron modified phosphogypsum slurry used in each embodiment of the invention is prepared, the high-flow-state gypsum-based all-solid-waste cementing material of the embodiments 1 to 6 of the invention is prepared according to the following method, and the specific preparation process is as follows:
1) weighing the raw materials according to the table 1;
2) uniformly mixing the nano-micron modified phosphogypsum slurry, the steel slag powder and the slag powder weighed in the step 1), adding water and a dispersion stabilizer (the type of the dispersing agent in each embodiment is shown in table 3), uniformly stirring, and curing and forming to obtain the high-flow gypsum-based all-solid-waste cementing material.
The performance of the high flow gypsum-based all-solid-waste cementitious materials of examples 1 to 6 of the present invention was tested, and the test results are shown in table 1. Wherein the 28d mortar compressive strength is tested with reference to the specification GB/T17671-1999.
As can be seen from Table 1, the high-flow gypsum-based all-solid-waste cementing material prepared by completely replacing cement clinker with steel slag has a net slurry fluidity of more than 300mm and a 28d mortar compressive strength of more than 42.5 MPa.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. The high-flow gypsum-based all-solid-waste cementing material is characterized by comprising the following components in percentage by mass: nano-micron modified phosphogypsum slurry: 40-45%, slag powder: 40-45% of steel slag powder: 3.5-7.5%, dispersion stabilizer: 0.1-0.5%, and the balance of water.
2. The high flow gypsum-based all-solid-waste cementitious material of claim 1, wherein the nano-micron modified phosphogypsum slurry is a nano-micron modified phosphogypsum slurry prepared by the following method:
mixing the phosphogypsum, the steel slag powder, the slag powder and the dispersion stabilizer according to the mass ratio of the dry-basis phosphogypsum to the steel slag powder to the dispersion stabilizer of 45 to (2-5) to (0.7 to 0.5) and the water-solid ratio of 0.5, and then carrying out wet grinding treatment until the median particle size of slurry particles is 5-10 mu m, thus obtaining the nano-micron modified phosphogypsum slurry.
3. The high flow gypsum-based all-solid waste cementitious material according to claim 2, characterised in that the wet-milled grinding bodies are zirconia grinding bodies, the grading of which is 7 mm: 5 mm: 3 mm: 1mm ═ 1: 2: 4: 3, and the mass of which is 2 times the total mass of the dry-based phosphogypsum, the steel slag powder, the slag powder and the dispersion stabiliser.
4. The high flow gypsum-based all-solid waste cementitious material of claim 2, wherein the wet grinding process has a grinding speed of 400rpm and a grinding time of 60 min.
5. The high flow gypsum-based all-solid-waste cementitious material of claim 2, characterised in that the phosphogypsum is a phosphatization chemical by-product gypsum; the water content of the phosphogypsum is 16-18 percent, and the content of the dihydrate gypsum is 90-95 percent.
6. The high flow gypsum-based all-solid-waste cementitious material of claim 2, wherein the slag powder is grade S95 slag powder; the specific surface area of the steel slag powder is 400-500 m2Per kg, the median particle diameter is 15-25 μm.
7. The high flow gypsum-based all-solid-waste cementitious material of claim 2, wherein the dispersion stabilizer is a phosphate polymer; the molecular weight of the phosphate polymer is 10000-30000, and the molecular structural formula of the phosphate polymer is as follows:
Figure FDA0002816468520000021
wherein m, n and p are 3.5: 1 to (0.1-0.2).
8. A method of preparing a high flow gypsum-based all solid waste cementitious material as claimed in any one of claims 1 to 7, characterised by the steps of:
and (2) uniformly mixing the nano-micron modified phosphogypsum slurry, the steel slag powder and the slag powder, adding the water and the dispersion stabilizer, uniformly stirring, and then curing and forming to obtain the high-flow gypsum-based all-solid-waste cementing material.
CN202011413139.0A 2020-12-04 2020-12-04 High-flow gypsum-based all-solid-waste cementing material and preparation method thereof Pending CN112500108A (en)

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CN102745924A (en) * 2012-07-13 2012-10-24 武汉理工大学 Phosphogypsum-modifying method capable of shortening coagulating time of phosphogypsum-based cement concrete
CN103253921A (en) * 2013-04-15 2013-08-21 武汉理工大学 Cement concrete preventing corrosion of chlorine salt and preparation method thereof
CN108147760A (en) * 2017-12-18 2018-06-12 固岩科技发展有限公司 A kind of method for producing Ardealite block
CN108191365A (en) * 2017-12-18 2018-06-22 固岩科技发展有限公司 A kind of method using ardealite material cementing fill metal mine
CN111978061A (en) * 2020-08-31 2020-11-24 湖北工业大学 Preparation method of high-water-resistance anhydrous phosphogypsum cementing material

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