CN110759655A - Industrial waste based geopolymer - Google Patents
Industrial waste based geopolymer Download PDFInfo
- Publication number
- CN110759655A CN110759655A CN201910833733.6A CN201910833733A CN110759655A CN 110759655 A CN110759655 A CN 110759655A CN 201910833733 A CN201910833733 A CN 201910833733A CN 110759655 A CN110759655 A CN 110759655A
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- CN
- China
- Prior art keywords
- geopolymer
- industrial waste
- based geopolymer
- steel slag
- mixture
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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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
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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
- C04B7/1535—Mixtures thereof with other inorganic cementitious materials or other activators with alkali metal containing activators, e.g. sodium hydroxide or waterglass
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- 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)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses an industrial waste based geopolymer. The composition of the geopolymer (in mass percent) is as follows: 35-45% of aluminum ash, 10-15% of blast furnace slag, 35-40% of steel slag and 8-15% of metakaolin, wherein an alkaline activator is added according to 30% of the total mass of the raw materials. Grinding the raw materials into powder, uniformly mixing, adding an alkaline activator, stirring, injecting into a mold, demolding, and maintaining at room temperature to obtain the product. The invention has low cost, simple preparation method and easy operation. Meanwhile, the geopolymer provided by the invention adopts common industrial wastes with large yield as main raw materials: the steel slag, the blast furnace slag and the aluminum ash realize the secondary utilization of wastes and have important significance for saving resources and protecting the environment.
Description
The invention belongs to an industrial waste-based geopolymer and a preparation method thereof, and belongs to divisional application of invention application with application date of 2017, 6 and 26 months and application number of 2017104962682, belonging to the technical part of products.
Technical Field
The invention belongs to the field of secondary utilization of solid wastes, and particularly relates to an industrial waste based geopolymer and a preparation method thereof.
Background
Geopolymers (geopolymers) are a new type of alkali-activated gelling material developed in recent 40 years and are made of AlO4And SiO4The inorganic polymer with three-dimensional net structure formed by tetrahedral structure units belongs to non-metallic material. The performance of the cement is similar to that of cement, but the performance of the cement is superior to that of the cement. Compared with common Portland cement, the high-strength Portland cement has the advantages of high strength, acid and alkali resistance, low permeability, low shrinkage, low expansion, low heat conduction, high temperature resistance, good durability and the like. In addition, the traditional portland cement adopts a 'two-grinding and one-burning' process, consumes a large amount of energy sources such as petroleum, coal, natural gas and the like, and simultaneously emits a large amount of greenhouse gases, and the preparation process of the geopolymer has low energy consumption (30 percent of the energy consumption of the traditional cement, 1/20 percent of ceramic, 1/70 percent of steel and 1/150 percent of plastic), CO and CO2The discharge amount is small (1/5 of the traditional portland cement), so that the cement is a pollution-free 'green' environment-friendly material, and has attracted much attention in recent years. The geopolymer is applied to building materials, high-strength materials, solid core solid waste materials, sealing materials, high-temperature resistant materials and the like. In this field, the application of geopolymers in cement is relatively late, only a few basic research papers and reviews are published at present,very few reports have been made on how to prepare high-performance polymer materials.
With the continuous development of the industry, more and more waste is generated. Particularly, in recent decades, the steel industry and the aluminum industry in China are rapidly developed, a large amount of waste residues are generated, and most of the waste residues are not well utilized. The accumulation of a large amount of waste residues not only occupies land resources, but also can cause environmental pollution and potential safety hazard. And the steel slag is not well utilized at present because of easy pulverization. The realization of effective recycling of the waste iron and steel slag is the responsibility and task of iron and steel enterprises. Therefore, how to reasonably and effectively utilize the steel slag resources is one of the important issues facing enterprises in the steel industry, building material industry and the like at home and abroad in recent years.
Disclosure of Invention
One of the purposes of the invention is to research and develop an industrial waste-based geopolymer and a preparation method thereof, wherein the geopolymer is prepared by adding a small amount of metakaolin into aluminum ash, blast furnace slag and steel slag and performing polymerization reaction under the action of an alkaline activator, so that the purpose of recycling waste is achieved.
The invention is realized by the following technical scheme:
a preparation method of an industrial waste-based geopolymer comprises the following steps:
(1) respectively grinding aluminum ash, blast furnace slag, steel slag and metakaolin into powder of 10-20 mu m, and then uniformly mixing to obtain a mixture; in the mixture, the mass percent of the steel slag is 35-45%, and the mass percent of the aluminum ash is 35-45%;
(2) mixing Na2SiO3Uniformly stirring the solution and NaOH solution according to the mass ratio of 1:10 to obtain an alkaline activator;
(3) and mixing the alkaline activator with the mixture, stirring for 20-30 min, injecting into a mold, drying at 60 ℃ for 24h, demolding, and curing at room temperature to obtain the industrial waste-based geopolymer.
The invention also discloses a preparation method of the industrial waste based geopolymer precursor system, which comprises the following steps:
(1) respectively grinding aluminum ash, blast furnace slag, steel slag and metakaolin into powder of 10-20 mu m, and then uniformly mixing to obtain a mixture; in the mixture, the mass percent of the steel slag is 35-45%, and the mass percent of the aluminum ash is 35-45%;
(2) mixing Na2SiO3Uniformly stirring the solution and NaOH solution according to the mass ratio of 1:10 to obtain an alkaline activator;
(3) and (3) mixing the alkaline activator with the mixture, and stirring for 20-30 min to obtain the industrial waste based geopolymer precursor system.
In the technical scheme, the concentration of the NaOH solution is 8 mol/L.
In the technical scheme, the mixture comprises the following components in percentage by mass: 35-45% of aluminum ash, 10-15% of blast furnace slag, 35-45% of steel slag and 8-12% of metakaolin.
In the technical scheme, the dosage of the alkaline activator is 30 percent of the mass of the mixture.
Blast furnace slag and steel slag are main solid wastes generated by steel enterprises, blast furnace slag is main solid waste generated in a blast furnace ironmaking process, and steel slag is formed in a converter or electric furnace smelting process. Steel slag cannot be applied to industrial use due to its easy pulverization, resulting in a large amount of steel slag being disposed of in landfills. The invention is limited by combining other components, and a large amount of steel slag is added, so that the obtained geopolymer has excellent performance, and the problem that the existing steel slag cannot be applied or can be only used in a small amount is solved.
The aluminum ash is a product of cooling and processing molten slag generated in the production process of electrolytic aluminum or cast aluminum; it contains a number of impurities which the prior art considers to affect the gelling process of the geopolymer and is therefore not suitable for the preparation of geopolymers, and there is no report on the relationship of aluminium ash to geopolymers. According to the invention, the geopolymer with excellent performance is prepared by limiting the proportion of each component, particularly the matching of the steel slag and the aluminum ash and combining a maintenance process, so that the problems in the prior art are thoroughly solved.
The traditional raw material for the preparation of geopolymers is mainly calcined kaolinite, i.e. metakaolin. Calcining kaolinite at the high temperature of 600-700 ℃ for 6 hours, mixing the kaolinite and an alkali activator into slurry, pouring the slurry into a mold, standing and maintaining the slurry at the temperature of room temperature to 70 ℃, wherein the cost is relatively high and the resource is exhausted; according to the invention, only a small amount of metakaolin is adopted, and the proportion limitation of other waste raw materials is combined, so that the geopolymer which has good strength and meets the application standard can be obtained.
Many researches show that the mineral composition and the self-property of raw materials have great influence on the mechanical properties of the geopolymer and the synthesis process of the geopolymer, and particularly, after different aluminosilicate minerals are mixed with kaolinite, the polymerization reaction has great difference, so that the product properties are different. The research on preparing geopolymer by using solid waste has the most use of fly ash at home and abroad. Chemical components of the industrial solid waste are different, and mineral compositions of the industrial solid waste are also greatly different, for example, the chemical components, the mineral compositions, Si/Al, CaO content, alkali excitant types and the like in raw materials have great influence on the performance of the prepared geopolymer, so that the performance of the prepared geopolymer is also greatly different, for example, the performance of the prepared geopolymer is also obviously different by adopting kaolin of different producing areas; the geopolymer prepared from the fly ash is considered to have the best compression strength and breaking strength in the prior art. According to the invention, the waste is taken as the main material, only about one layer of metakaolin is added, the influence of impurity components in each waste is solved, the prepared geopolymer has excellent performance and meets the application requirement through parameter limitation and reasonable compatibility; overcomes the technical prejudice that applicable geopolymers can not be obtained mainly from wastes and only the fly ash can be used for preparing waste substrate geopolymers in the prior art.
The polymers of the crystalline phase and the glassy phase in the raw material largely affect the activity of the raw material, but the change of polymerization of the solid aluminosilicate when it exerts its gelling properties is also complicated. The geopolymer prepared in which range the polymerization degree of the glass body is in has the best performance, the activity indexes of the aluminosilicate industrial waste residue and the like are evaluated, further research is needed, and no relevant theoretical guidance exists in the prior art.
The raw materials used by the geopolymer are mainly industrial wastes with high yield at present, and a new way is provided for the secondary utilization of the wastes.
Alkali-activated cement reaction products have been the focus of research and have been difficult for various scholars to unify. Firstly, the crystallization degree of a reaction product is low, and the existing testing means is difficult to accurately describe and measure; secondly, different students have different research means and experimental conditions; in addition, the reaction products vary with the activator system. The existing geopolymer generally has the phenomenon of early coagulation, the early strength is high, but the later strength is not greatly increased, because the early coagulation of the geopolymer prevents the raw materials from further hydration; the geopolymer of the invention exists in the reactants as structural water after solidification in the forming and reaction processes, and the final product mainly comprises ionic bonds and covalent bonds and auxiliary Van der Waals bonds, thereby having excellent performance.
Detailed Description
The present invention is further described with reference to the following examples, but it should be noted that the examples are only for illustrating the technical solutions of the present invention, and not for limiting the same.
Grinding aluminum ash, blast furnace slag, steel slag and metakaolin into powder of 10-20 mu m, and then uniformly mixing according to the proportion shown in Table 1 to obtain a raw material mixture. With Na2SiO3And evenly stirring the solution and NaOH solution (8 mol/L) according to the mass ratio of 1:10 to obtain the alkaline activator. Adding alkaline excitation (30% of the total mass of the raw material mixture) into the raw material mixture, and stirring for 20-30 min to obtain uniformly mixed slurry. Then the slurry is injected into a mould (40 mm multiplied by 160 mm) and dried for 24 hours in a drying oven (temperature 60 ℃); then demoulding is carried out, and the compressive strength is about 50 MPa. Curing for 28 days at room temperature (more than 20 ℃) after demolding, and then testing the compressive strength; weighing the initial mass of the geopolymer sample, respectively soaking the geopolymer sample into 4mol/L NaOH solution (adopting hydrochloric acid with the concentration of 1mol/L, soaking for 10 minutes), recording the initial time, taking out the geopolymer sample after 30 minutes, drying the geopolymer sample in a 50 ℃ oven for 1 hour, weighing again, and calculating the mass retention rate; the results are shown in table 1 below,obviously, the product performance of the invention is far superior to the industry standard and the related national standard.
The geopolymer prepared by the method has the advantages of excellent mechanical strength, strong acid and alkali resistance, no special treatment in the preparation process, no white frost on the surface and low shrinkage rate, and in addition, the product has stable performance, and the compression strength error of ten batches of products is less than 0.1 percent, thereby overcoming the defects that the components and properties of industrial byproducts or waste residues are usually large due to the large utilization of the industrial byproducts or waste residues in the prior art, and the quality and the performance of the product are difficult to stabilize in the actual production.
The research of geopolymer materials still belongs to the beginning stage in China, and the further research on the formation mechanism, the preparation process and the application development of geopolymer materials not only has higher academic value, but also has far-reaching beneficial influence on the economic construction of China. The invention may be embodied in other forms without departing from the spirit or essential characteristics thereof, and it is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (6)
1. An industrial waste-based geopolymer, characterized in that the preparation method of the industrial waste-based geopolymer comprises the following steps:
(1) respectively grinding aluminum ash, blast furnace slag, steel slag and metakaolin into powder, and then uniformly mixing to obtain a mixture; in the mixture, the mass percent of the steel slag is 35-45%, and the mass percent of the aluminum ash is 35-45%;
(2) mixing Na2SiO3Uniformly stirring with NaOH solution to obtain an alkaline activator;
(3) and mixing the alkaline activator with the mixture, stirring for 20-30 min, injecting into a mold, drying at 60 ℃ for 24h, demolding, and curing at room temperature to obtain the industrial waste-based geopolymer.
2. The industrial waste-based geopolymer according to claim 1, wherein the concentration of the NaOH solution is 8 mol/L.
3. The industrial waste-based geopolymer as claimed in claim 1, wherein the mixture comprises, in mass percent: 35-45% of aluminum ash, 10-15% of blast furnace slag, 35-45% of steel slag and 8-12% of metakaolin.
4. The industrial waste-based geopolymer according to claim 1, wherein the amount of the alkali-activator is 30% by mass of the mixture.
5. The industrial waste-based geopolymer as claimed in claim 1, wherein the aluminum ash, the blast furnace slag, the steel slag and the metakaolin are ground into powders of 10 to 20 μm, respectively.
6. The industrial waste-based geopolymer as claimed in claim 1, wherein Na is added2SiO3And uniformly stirring the mixture and NaOH solution according to the mass ratio of 1: 10.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910833733.6A CN110759655B (en) | 2017-06-26 | 2017-06-26 | Industrial waste based geopolymer |
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| CN201910833733.6A CN110759655B (en) | 2017-06-26 | 2017-06-26 | Industrial waste based geopolymer |
| CN201710496268.2A CN107188442B (en) | 2017-06-26 | 2017-06-26 | A kind of trade waste base geological polymer and preparation method thereof |
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| CN110759655A true CN110759655A (en) | 2020-02-07 |
| CN110759655B CN110759655B (en) | 2021-11-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107663035B (en) * | 2017-10-18 | 2020-05-22 | 浙江大学 | Preparation method of aluminum ash based geopolymer cementing material |
| CN108840711A (en) * | 2018-07-23 | 2018-11-20 | 昆明理工大学 | A kind of lightweight building block and preparation method |
| CN109336434A (en) * | 2018-12-21 | 2019-02-15 | 福州大学 | A kind of preparation method of underground heat clay base geological polymer |
| CN109903875A (en) * | 2019-02-28 | 2019-06-18 | 西南科技大学 | A kind of method that phosphate polymer solidifies boracic nuclear waste |
| CN110066146A (en) * | 2019-04-23 | 2019-07-30 | 南昌大学 | The recycling of tungsten slag and reuse method |
| CN112341017B (en) * | 2020-10-30 | 2022-04-15 | 北京科技大学 | Method for preparing high-strength geopolymer cementing material from aluminum ash |
| CN112441782A (en) * | 2020-11-24 | 2021-03-05 | 内蒙古财经大学 | Preparation method of transparent geopolymer |
| CN113233855B (en) * | 2021-05-24 | 2022-07-01 | 深圳市聚和星环境有限公司 | Method for processing fireproof plate by using industrial solid waste |
| CN114394774B (en) * | 2021-12-28 | 2023-04-07 | 武汉大学(肇庆)资源与环境技术研究院 | Geopolymer and preparation precursor, preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN107188442B (en) | 2019-10-29 |
| CN107188442A (en) | 2017-09-22 |
| CN110759655B (en) | 2021-11-05 |
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