CN112250332A - High-temperature-resistant cementing material prepared from flint clay serving as raw material - Google Patents
High-temperature-resistant cementing material prepared from flint clay serving as raw material Download PDFInfo
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- CN112250332A CN112250332A CN202010965057.0A CN202010965057A CN112250332A CN 112250332 A CN112250332 A CN 112250332A CN 202010965057 A CN202010965057 A CN 202010965057A CN 112250332 A CN112250332 A CN 112250332A
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions 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 mineral polymers, e.g. geopolymers of the Davidovits type
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00431—Refractory materials
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- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
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- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a high-temperature-resistant cementing material prepared from flint clay serving as a raw material, and belongs to the field of inorganic non-metallic materials. The high-temperature-resistant cementing material prepared by taking flint clay as a raw material is prepared from the following raw materials in parts by mass: 45-80 parts of flint clay, 10-45 parts of certain clay and 6-12 parts of alkali activator. The flint clay and the clay are obtained by calcining flint clay raw ore and clay at 750-900 ℃ for 2 hours, and then grinding the calcined flint clay and clay to obtain powder passing through a 0.08mm square-hole sieve; the alkali activator is water glass solution with modulus of 1.0-1.5 or at least one of NaOH and KOH; the preparation method comprises the steps of taking the calcined flint clay and the clay powder according to a certain mass ratio, adding a proper amount of alkaline activator and water, and fully and uniformly stirring. The prepared cementing material has the characteristics of high strength and high temperature resistance.
Description
Technical Field
The invention relates to a high-temperature-resistant cementing material prepared from flint clay serving as a raw material, and belongs to the field of inorganic non-metallic materials.
Background
Portland cement is one of three basic materials in the building material industry, has wide use and large consumption, and is called as 'grain in the building industry'. Since the invention, production and application of cement, the scale of cement production has been continuously enlarged and the process and equipment have been continuously improved in a half centuryThe variety and the quality of the artificial material are greatly developed and improved, and the artificial material becomes the artificial material with the largest use amount in the world. However, the portland cement used in large quantities at present has some disadvantages and shortcomings as follows: (1) the firing temperature is high (1450 ℃), and the power consumption and the coal consumption are high; (2) the resource consumption is large, the waste gas discharge is large, and the environmental pollution is serious; (3) the high-temperature resistance of the portland cement is poor, and the hydration product of the portland cement contains a large amount of high-alkalinity C-S-H gel and Ca (OH)2Hydration products such as ettringite and the like can generate dehydration reaction on the minerals at high temperature, so that the set cement gradually loses strength.
Therefore, in high-temperature kilns and some building parts needing high temperature resistance, portland cement cannot be used as a cementing material, aluminate cement has weak alkali resistance, high-alumina cement is corroded when contacting with an alkaline solution during use, and a small amount of alkaline compounds are contained in concrete aggregate, so that the high-alumina cement cannot be used in alkali-contacting engineering.
The high temperature resisting cementing material is prepared with flint clay and through mixing with water glass or NaOH or KOH in certain modulus. Under the action of alkali or alkali salt, minerals such as metakaolin and the like are depolymerized into a network-shaped silicon-aluminum-oxygen compound, mainly a spatial three-dimensional network calcium-free polymer formed by silicon oxide and aluminum oxide, and the cement material does not have dehydration phenomenon and structural depolymerization effect in a high-temperature process and does not fear the alkali environment, so that the cement material can keep strength at high temperature.
Disclosure of Invention
The invention provides a high-temperature-resistant cementing material for overcoming the problems that portland cement is not high-temperature-resistant and aluminate cement is not alkali-resistant. The invention provides a high-temperature-resistant cementing material prepared from flint clay serving as a raw material, which is prepared from the following raw materials in parts by mass: 45-80 parts of flint clay, 10-45 parts of clay, 6-12 parts of alkali activator and one or more of the following substances, wherein the content of sulfonated melamine formaldehyde resin water reducing agent is about 1.0-1.3% of the mass of the gelled material powder, the content of naphthalene high-efficiency water reducing agent is about 0.1-0.2% of the mass of the gelled material powder, and the content of sugar calcium retarder is about 0.05-0.1% of the mass of the gelled material powder.
The flint clay is powder obtained by crushing raw flint clay ore into small fragments with the diameter of less than 15mm, calcining the small fragments at the temperature of 750-900 ℃ for 2 hours, preferably at the temperature of 800-850 ℃, grinding the calcined flint clay and sieving the ground flint clay through a 0.08mm square-hole sieve.
The clay is powder obtained by crushing the clay into small fragments with the diameter of less than 15mm, calcining the small fragments at the temperature of 750-900 ℃ for 2 hours, preferably at the temperature of 800-850 ℃ for 2 hours, grinding the calcined clay and sieving the ground clay with a 0.08mm square-hole sieve.
The flint clay and the clay powder can be prepared separately or mixed according to a certain proportion and then processed together.
The alkali content of the alkali activator in the invention refers to Na in the added water glass2O + K2The mass fraction of O or Na in NaOH2O in parts by mass or K in KOH2And the mass fraction of O.
The alkali activator is a water glass solution with a modulus of 1.0-1.5, preferably a water glass solution with a modulus of 1.1-1.3, or at least one of NaOH and KOH solutions.
The preparation process of the high-temperature-resistant gelling material disclosed by the invention comprises the following steps of: if one or more of a sulfonated melamine formaldehyde resin water reducing agent, a naphthalene series high-efficiency water reducing agent and a sugar calcium retarder are required to be added, the components are firstly mixed with an alkaline activator solution and water required to be supplemented according to a certain water-cement ratio according to a set proportion and are stirred uniformly, and then flint clay and certain clay powder in the set proportion are added and are stirred uniformly.
The water is industrial water.
The high-temperature-resistant cementing material can be used for high-temperature kilns and some building parts needing high temperature resistance.
Detailed Description
The following describes embodiments of the present invention. The embodiments described are only for the purpose of illustrating and explaining the invention in detail and are not to be construed as limiting the invention.
The invention provides a high-temperature-resistant cementing material prepared from flint clay serving as a raw material, which is prepared from the following raw materials in parts by mass: 50-80 parts of flint clay, 20-40 parts of certain clay, 6-12 parts of alkali activator and one or more of the following substances, wherein the content of sulfonated melamine formaldehyde resin water reducing agent is about 1.0-1.3% of the mass of the gelled material powder, the content of naphthalene high-efficiency water reducing agent is about 0.1-0.2% of the mass of the gelled material powder, and the content of sugar calcium retarder is about 0.05-0.1% of the mass of the gelled material powder.
The flint clay and the clay are powder materials obtained by calcining flint clay raw ore and clay ore at 750-900 ℃ for 2 hours, preferably at 800-850 ℃ for 2 hours, grinding and sieving by a 0.08mm square-hole sieve. The treatment process comprises the following steps: (1) firstly, crushing flint clay raw ore and clay ore into fragments with the size of less than 15 mm; (2) placing crushed crude coke gemstone and clay ore fragments into a kiln for calcination, wherein the calcination system is to heat the raw coke gemstone and clay ore fragments to a design temperature of 750-900 ℃ and preferably a temperature value of 800-850 ℃ from room temperature at 5 ℃ per minute, then preserving the heat for 2 hours, naturally cooling the raw coke gemstone and clay ore fragments to the room temperature along with the kiln after the heat preservation is finished, and other cooling modes are not limited in the invention; (3) and grinding the calcined flint clay and the clay to the fineness of 0.08mm square-hole sieve to obtain powder for later use.
The main mineral components of the flint clay raw ore and certain clay ore are kaolin minerals.
The water glass with the specific modulus can be prepared by adding a proper amount of NaOH or KOH into commercially available liquid water glass. The commercially available liquid water glass and the source of NaOH or KOH are not limited in the present invention and can be obtained by conventional commercially available means.
The NaOH or KOH solution can be prepared by using conventional commercially available NaOH or KOH reagents or industrial products, and the invention is not limited thereto.
The sulfonated melamine formaldehyde resin water reducing agent, the naphthalene high-efficiency water reducing agent and the sugar calcium retarder are obtained by commercial means, and the invention is not limited.
The invention will be further illustrated with reference to some specific examples.
Example 1 was carried out:
preparing raw materials: respectively calcining the flint clay raw ore and the clay ore at 850 ℃, and grinding into flint clay and clay fine powder for later use; commercial water glass solution (modulus =3.1655, Na)2O=7.87wt%, SiO2=24.1 wt%); chemically pure KOH (KOH content 80 wt%).
Adding KOH 33.55g and Na in the water glass solution into 100g of the water glass solution with the preparation modulus of 1.12O+K2O、SiO2And H2The O content is respectively as follows: 22.68wt%, 18.07wt% and 59.25 wt%.
Taking 60 parts by mass of flint clay, 32 parts by mass of clay, 8 parts by mass of water glass solution with the alkali content and the modulus of 1.1, 300 parts by mass of standard sand and the water-cement ratio of 0.5, and calculating to obtain 28.92 parts by mass of water to be added; the test is carried out by adopting the forming, maintaining and strength testing method specified in the national standard GB/T17671-1999 cement mortar strength testing method, and the strength result is shown in Table 1. The 28d high temperature strength test of the test pieces was also performed and is also shown in Table 1.
Example 2 was carried out:
preparing raw materials: calcining the flint clay raw ore and the clay ore in certain places at 800 ℃, and grinding the flint clay raw ore and the clay ore into flint clay fine powder for later use; commercial water glass solution (modulus =3.1655, Na)2O = 7.87wt%， SiO2=24.1 wt%); chemically pure KOH (KOH content: 80 wt%), a commercial sulfonated melamine formaldehyde resin water reducer.
29.09g KOH and Na in the water glass solution are added to every 100g of the water glass solution with the preparation modulus of 1.22O+K2O、SiO2And H2The O content is respectively as follows: 21.23wt%, 18.67wt% and 60 wt%.1wt%。
Taking 50 parts by mass of flint clay, 40 parts by mass of clay, 10 parts by mass of water glass solution with the alkali content and the modulus of 1.1, 1.3 parts by mass of sulfonated melamine formaldehyde resin water reducing agent, 300 parts by mass of standard sand, 0.5 of water-cement ratio and 21.69 parts by mass of water required to be added; the test is carried out by adopting the forming, maintaining and strength testing method specified in the national standard GB/T17671-1999 cement mortar strength testing method, and the strength result is shown in Table 1. The 28d high temperature strength test of the test piece was also performed and is shown in Table 1.
Example 3 of implementation:
preparing raw materials: calcining the flint clay raw ore and the clay ore in certain places at 900 ℃, and grinding the flint clay raw ore and the clay ore into flint clay fine powder for later use; commercial water glass solution (modulus =3.456, Na)2O = 9.00wt%， SiO2=30.97 wt%); chemically pure KOH (the KOH content is 82 wt%), a commercial sulfonated melamine formaldehyde resin water reducing agent and a commercial sugar calcium retarder.
34.40g KOH and Na in the water glass solution are added for each 100g of the water glass solution with the preparation modulus of 1.32O+K2O、SiO2And H2The O content is respectively as follows: 24.31wt%, 23.04wt% and 52.65 wt%.
Taking 70 parts by mass of flint clay, 21 parts by mass of clay, 9 parts by mass of water glass solution with the alkali content and the modulus of 1.3, 1.3 parts by mass of sulfonated melamine formaldehyde resin water reducing agent, 0.05 part by mass of calcium saccharate retarder, 300 parts by mass of standard sand, 0.5 part by mass of water-cement ratio and 30.51 parts by mass of water required to be added; the test is carried out by adopting the forming, maintaining and strength testing method specified in the national standard GB/T17671-1999 cement mortar strength testing method, and the strength result is shown in Table 1. The 28d high temperature strength test of the test piece was also performed and is shown in Table 1.
Example 4 of implementation:
preparing raw materials: calcining the flint clay raw ore and the clay ore in certain places at 750 ℃, and grinding the flint clay raw ore and the clay ore into flint clay fine powder for later use; commercial water glass solution (modulus =3.456, Na)2O = 9.00wt%， SiO2=30.97 wt%); chemically pure KOH (KOH content is 82 wt%), a commercial naphthalene-based superplasticizer and a commercial calcium saccharite retarder.
Preparation ofFor each 100g of the water glass solution with the modulus of 1.5, 27.17g of KOH and Na in the water glass solution are added2O+K2O、SiO2And H2The O content is respectively as follows: 21.78wt%, 24.35wt% and 53.87 wt%.
Taking 45 parts by mass of flint clay, 45 parts by mass of clay, 5 parts by mass of water glass solution with the alkali content of 1.5, 5 parts by mass of KOH, 0.1 part by mass of a commercial naphthalene-based high-efficiency water reducing agent, 0.05 part by mass of a calcium saccharate retarder, 300 parts by mass of standard sand, 0.5 part by mass of a water-cement ratio and 37.63 parts by mass of water to be added; the test is carried out by adopting the forming, maintaining and strength testing method specified in the national standard GB/T17671-1999 cement mortar strength testing method, and the strength result is shown in Table 1. The 28d high temperature strength test of the test piece was also performed and is shown in Table 1.
TABLE 1 results of strength test (MPa) of examples
Claims (10)
1. A high temperature resistant cementing material prepared by taking flint clay as a raw material is characterized in that: the feed is prepared from the following raw materials in parts by mass: 45-80 parts of flint clay, 10-45 parts of certain clay and 6-12 parts of alkali activator.
2. The flint clay according to claim 1, which is a powder obtained by crushing raw flint clay into small fragments with the size of 15mm or less, calcining at 750-900 ℃ for 2 hours, preferably at 800-850 ℃ for 2 hours, grinding the calcined flint clay, and sieving with a 0.08mm square-hole sieve.
3. The clay according to claim 1, which is a powder obtained by crushing clay into small pieces of 15mm or less, calcining at 750-900 ℃ for 2 hours, preferably at 800-850 ℃ for 2 hours, grinding the calcined clay, and sieving with a 0.08mm square-hole sieve.
4. The flint clay and the clay of claims 1, 2 and 3 can be prepared by processing separately or by mixing in a certain proportion and then processing together.
5. The alkali content of the alkali activator according to claim 1, which is Na in added water glass2O + K2The mass fraction of O or Na in NaOH2O in parts by mass or K in KOH2And the mass fraction of O.
6. The alkali activator according to claim 1 is at least one of a water glass solution having a modulus of 1.0 to 1.5, preferably a water glass solution having a modulus of 1.1 to 1.3, or a NaOH or KOH solution.
7. The modulus as claimed in claim 5, which is SiO in alkali silicate in water glass solution2：R2And R represents Na element or K element.
8. The high-temperature-resistant gelling material of claims 1-6, wherein the water is provided by the water in the alkaline activator and the additional water during stirring and molding.
9. The high-temperature-resistant cementing material according to claim 1 to 7, which further comprises one or more of a sulfonated melamine formaldehyde resin water reducing agent, a naphthalene-based high-efficiency water reducing agent and a sugar calcium retarder.
10. The high temperature resistant cementitious material of claim 8, if added, the sulfonated melamine formaldehyde resin water reducer is present in an amount of about 1.0-1.3% by mass of the cementitious material powder, the naphthalene based superplasticizer is present in an amount of about 0.1-0.2% by mass of the cementitious material powder, and the calcium saccharite retarder is present in an amount of about 0.05-0.1% by mass of the cementitious material powder.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491658A (en) * | 2011-12-08 | 2012-06-13 | 湖南科技大学 | Method for preparing geopolymeric material from bentonite |
| CN102515579A (en) * | 2011-12-08 | 2012-06-27 | 湖南科技大学 | Method for preparing geological polymeric material by using low-grade kaolin |
| CN102875041A (en) * | 2012-10-25 | 2013-01-16 | 湖南科技大学 | Method for preparing room-temperature curing one-component alkali-activated cement with calcination at low temperature |
| CN104098282A (en) * | 2013-04-03 | 2014-10-15 | 神华集团有限责任公司 | Geopolymer composition, geopolymer material and preparation method of geopolymer material |
| TN2013000451A1 (en) * | 2013-10-30 | 2015-03-30 | Ct Nat De Rech En Sciences Des Materiaux Cnrsm | Process for obtaining geopolymer cement from a Tunisian clay |
-
2020
- 2020-09-15 CN CN202010965057.0A patent/CN112250332A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491658A (en) * | 2011-12-08 | 2012-06-13 | 湖南科技大学 | Method for preparing geopolymeric material from bentonite |
| CN102515579A (en) * | 2011-12-08 | 2012-06-27 | 湖南科技大学 | Method for preparing geological polymeric material by using low-grade kaolin |
| CN102875041A (en) * | 2012-10-25 | 2013-01-16 | 湖南科技大学 | Method for preparing room-temperature curing one-component alkali-activated cement with calcination at low temperature |
| CN104098282A (en) * | 2013-04-03 | 2014-10-15 | 神华集团有限责任公司 | Geopolymer composition, geopolymer material and preparation method of geopolymer material |
| TN2013000451A1 (en) * | 2013-10-30 | 2015-03-30 | Ct Nat De Rech En Sciences Des Materiaux Cnrsm | Process for obtaining geopolymer cement from a Tunisian clay |
Non-Patent Citations (1)
| Title |
|---|
| 孙凤金 等: "地聚物胶凝材料制备工艺的研究", 《山东建材》 * |
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