CN1109002C - Inorganic mineral reinforcer for cement and its prepn. - Google Patents
Inorganic mineral reinforcer for cement and its prepn. Download PDFInfo
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- CN1109002C CN1109002C CN00115681A CN00115681A CN1109002C CN 1109002 C CN1109002 C CN 1109002C CN 00115681 A CN00115681 A CN 00115681A CN 00115681 A CN00115681 A CN 00115681A CN 1109002 C CN1109002 C CN 1109002C
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- Prior art keywords
- cement
- alunite
- sepiolite
- coal gangue
- toughener
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Abstract
The present invention provides an inorganic mineral material reinforcing agent for cement, which comprises 20 to 50% of alunite, 30 to 60% of anhydrous gypsum, 10 to 25% of coal gangue and 0 to 30% of sepiolite according to weight. The reinforcing agent obviously reduces the production cost of the cement, greatly improves the mixing amount of mixed cement materials, and can also sufficiently ensure various performance indexes of the cement at the same time and even improve cement performance. Additionally, the reinforcing agent is also suitable for concrete. The present invention also provides a preparation method of the reinforcing agent.
Description
The present invention relates to a kind of toughener that is used for cement and preparation method thereof.The present invention especially relates to a kind of inorganic mineral reinforcer that is used for cement and preparation method thereof.
As everybody knows, in general the cement produced of manufacture of cement factory has pulverized fuel ash cement, slag cement, complex cement and road cement etc., they obtain by add blended materials such as flyash, slag, flyash and slag respectively in cement clinker, along with the increase strength of cement of adulterant progressively descends, how to improve the consumption of blended material and guarantee that the quality of cement is the target that people study always.
The various cement additive is arranged at present both at home and abroad, for example disclosed a kind of cement composition in the application number of on November 26th, 1987 application is the patent application of JP1987000298167, it is that the mixture that adds sepiolite and cellulose base in cement makes.This cement composition can be used for making the molding body of cement of intensity height and shock resistance excellence.Owing in this cement composition, used organic composition, so expense is higher.
And for example in being the patent application of JP1988000154505, the application number of on June 22nd, 1988 application disclosed a kind of cement composition, it comprises (A) 100 parts by weight of cement, (B) 5-100 weight part inorganic aggregate (it is that the flying dust of 1-100 micron and the ultra-fine grain aggregate of 1-20 weight % such as the micro-silica that particle diameter is the 0.01-1 micron are formed by sphere aggregates such as particle diameter mainly), (C) 3-50 weight part, be preferably 5-300 weight part sepiolite, (D) 0.2-10 weight part fortifying fibre and (E) 0.1-10 weight part are preferably the cellulose mixtures (methylcellulose gum etc.) of 0.5-5 weight part.This cement composition can be used for making the layered product of intensity height, good impact resistance.Same owing to used organic composition, the expense of this cement additire is higher.
Also develop the multiple additive that is used for cement in recent years at home.For example disclosed a kind of cement soundness agent in the application number of December 19 nineteen ninety-five application is 95112816 patent application, it is by alunite, gypsum and zeolite or contain active SiO
2Be that main industrial residue is formed, wherein alunite is 25-50%, and gypsum is 20-30%, zeolite or contain active SiO
2Be that main industrial residue is 25-50%.
The main purpose of above-mentioned all these cement additires all is in order to improve certain performance of cement, but they can not many admixtures blended material, so on the high side.
The present invention is directed to the problems referred to above that exist in the prior art, a kind of inorganic mineral reinforcer that is used for cement is provided.This toughener can reduce the Cement Production cost, increases substantially the addition content of cement mixture, guarantees every performance index of cement simultaneously again fully, even improves the performance of cement.This kind toughener also is applicable to concrete in addition.The present invention also provides the preparation method of this toughener.
The inorganic mineral reinforcer that is used for cement provided by the invention comprises the alunite of 20-50% by weight, the dehydrated gyp-of 30-60%, the coal gangue of 10-25% and the sepiolite of 0-30%.
The alunite that the present invention adopts is a kind of potassium aluminium sulfate solid, and its chemical constitution is KAl
3[SO
4]
2[OH]
6The present invention also can adopt industrial waste alum slag to replace alunite.Perhaps use the mixture of alunite and alum slag.In the present invention, alunite mainly is to be used to shorten cement setting time, improves early strength and keeps later strength.Think after deliberation that after in cement, adding entry alunite combines with the effective constituent of cement and generates a large amount of tetracalcium aluminoferrites, thereby forms rich iron ettringite, has so just improved the folding strength and the ultimate compression strength of cement.
The dehydrated gyp-that the present invention adopts is a kind of high strength gypsum that common gypsum forms after dewatering, and its main component is CaSO
4, it is also referred to as anhydrite.In the present invention, dehydrated gyp-mainly is to be used to improve cement intensity.Equally, also can directly adopt natural anhydrite.
The coal gangue that the present invention adopts is a kind of waste material (low grade coal) of coal, and it mainly contains aluminium sesquioxide and silicon-dioxide, and its ratio is approximately 1: 1, and contains a spot of lime carbonate.Add coal gangue and can be used for regulating activeconstituents in the waste materials such as flyash and slag, i.e. the content of aluminium sesquioxide overcomes because of adding waste material and makes the unsettled shortcoming of cement quality.
The sepiolite that the present invention adopts is a kind of hydrous magnesium silicate fibrous clay mineral of tool chain laminate structure.Its mineral molecular formula is Si
12Mg
8O
30(OH)
6(OH
2)
46H
2O.The weight duple of sepiolite energy absorption moisture own discharges again behind the formation crystal water lentamente, thereby improves the later strength of cement.The present invention also can use wilkinite or white clay to replace sepiolite, has effect same.
In the present invention, in the gross weight of toughener, the consumption of alunite is generally 20-50%, is preferably 25-40%; The consumption of dehydrated gyp-is generally 30-60%, is preferably 35-50%; The consumption of coal gangue is generally 10-25%, is preferably 15-25%; The consumption of sepiolite is generally 0-30%, is preferably 0-15%.At three kinds of cement that the cement mill produces, the best of this toughener is formed and each components contents (by weight) is that the toughener that is used for pulverized fuel ash cement comprises 30% alunite, 50% dehydrated gyp-, 5% sepiolite and 15% coal gangue; The toughener that is used for slag cement comprises 25% alunite, 50% dehydrated gyp-and 25% coal gangue; The toughener that is used for complex cement comprises 37.5% alunite, 37.5% dehydrated gyp-, 12.5% coal gangue and 12.5% sepiolite.
According to the requirement of cement quality, inorganic mineral reinforcer of the present invention accounts for the 3-8% of cement gross weight, is preferably 4-8%.
Inorganic mineral reinforcer of the present invention is not only applicable to cement, and is applicable to concrete, has obtained good effect when being used for concrete equally.
Another aspect of the present invention provides the preparation method of the inorganic mineral reinforcer that is used for cement, and this method comprises respectively calcined alunite, common gypsum and coal gangue 1-4 hour, and the cooling back is mixed in proportion with oven dry refrigerative sepiolite.
The temperature and time of calcining and oven dry depends on reinforced what, used factors such as equipment.In described preparation method, the temperature of calcined alunite is generally 450-600 ℃, is preferably 470-550 ℃, and the best is 500 ℃.The temperature of calcining common gypsum is generally 650-850 ℃, is preferably 680-700 ℃, and the best is 700 ℃.The temperature of calcining coal gangue is generally 500-1000 ℃, is preferably 800-900 ℃.Because coal gangue has the performance of spontaneous combustion, make its spontaneous combustion together and reach the incinerating purpose so usually it is deposited in practice.The temperature that sepiolite is dried is generally 100-300 ℃, is preferably 120-200 ℃, and drying time was generally 1-3 hour, was preferably about 2 hours.Calcination time to alunite, common gypsum and coal gangue generally was respectively 1-4 hour, was preferably 2-3 hour.
The above-mentioned inorganic mineral reinforcer that makes directly is added in the cement clinker, and add waste materials such as flyash, slag then ball milling make ultimate compression strength and the high cement of folding strength.
Compare with the additive in the prior art, the inorganic mineral reinforcer that the present invention makes has beyond thought excellent effect.At first owing to used toughener of the present invention can increase substantially the addition content of cement mixture, for example the addition content of flyash can be up to 30-65%, and scoriaceous addition content can be up to 20-70%, and flyash and scoriaceous total addition content can be up to 55-60%.Calculate with the scale of producing 100000 tons of cement mill per year, use toughener of the present invention can strengthen the addition content of blended material, actual output can be up to 150,000 tons about.Average production cost is per ton to be reduced about 20 yuan, and factory's net profit can reach more than 2,000,000 yuan.It two can regulate cement setting time arbitrarily from 10 minutes to 12 hours, has so just enlarged the range of application of prepared cement.It three is the early strengths that improve cement, and for example the ultimate compression strength after 3 days can be up to more than the 26MPa, and Portland cement can only reach 18-21MPa.It four is that the anti-folding that makes cement, freeze proof and anti-permeability performance all increase.It five is the hydration heat that reduce cement, and for example 3 days hydration heat is 50-60J/g, has facilitated the construction of cement like this.Its six toughener of the present invention also can be used for concrete, and two kinds of purposes of a kind of like this additive have improved service efficiency.Toughener of the present invention in addition belongs to inorganic mineral material, nontoxic pollution-free, and stable performance is stored under the dry environment and undergoes no deterioration.
The present invention will be described further in conjunction with following certain embodiments, and what should understand is that the present invention is not limited to these embodiment.In the following embodiments, unless otherwise indicated, umber all by weight.In the following embodiments, adopt determinator measurement time of coagulation time of coagulation; Ultimate compression strength employing resistance to compression load is that 30 tons compression testing machine is measured; It is the bending test machine measurement of 11.7MPa that folding strength adopts the load of anti-folding; Hydration heat adopts the hydrating heat measuring instrument to measure.Alunite in the following embodiments, common gypsum, coal gangue and sepiolite can be purchased or directly obtain from the mining area.
Embodiment 1
Respectively in the shaft kiln of 500 centimetres of 3 100 cm x 100 cm x with the temperature calcined alunite of 450 ℃, 650 ℃ and 500 ℃, common gypsum and coal gangue 4 hours.Getting 2 parts of alunites, 4 parts of dehydrated gyp-s and 2 parts of coal gangues after the cooling mixes in agitator and makes toughener.This toughener and 30 parts of slags and 62 parts of cement clinkers are carried out ball milling in ball mill, make slag cement.Measure three days and 28 days ultimate compression strength and folding strength of this cement, and the hydration heat of cement setting time and three days, the results are shown in Table 1.
Embodiment 2
Respectively in the shaft kiln of 500 centimetres of 3 100 cm x 100 cm x with the temperature calcined alunite of 550 ℃, 700 ℃ and 850 ℃, common gypsum and coal gangue 2.5 hours.Be set to 300 ℃ drying in oven sepiolite in addition in a temperature, the time is 1 hour.Getting 2.4 parts of alunites, 4 parts of dehydrated gyp-s, 1.2 parts of coal gangues and 0.4 part of sepiolite after the cooling mixes in agitator and makes toughener.This toughener and 40 parts of flyash and 52 parts of cement clinkers are carried out ball milling in ball mill, make pulverized fuel ash cement.Press the performance of embodiment 1 described this cement of measurement.The results are shown in Table 1.
Embodiment 3
Respectively in the shaft kiln of 500 centimetres of 3 100 cm x 100 cm x with the temperature calcined alunite of 600 ℃, 850 ℃ and 1000 ℃, common gypsum and coal gangue 1 hour.Be set to 100 ℃ drying in oven sepiolite in addition in a temperature, the time is 3 hours.Getting 3 parts of alunites, 3 parts of dehydrated gyp-s, 1 part of coal gangue and 1 part of sepiolite after the cooling mixes in agitator and makes toughener.This toughener and 30 parts of flyash, 30 parts of slags and 32 parts of cement clinkers are carried out ball milling in ball mill, make complex cement.Press the performance of embodiment 1 described this cement of measurement.The results are shown in Table 1.
Embodiment 4
Respectively in the shaft kiln of 500 centimetres of 3 100 cm x 100 cm x with 550 ℃, 7003 and 900 ℃ temperature calcined alunite, common gypsum and coal gangue 3 hours.Be set to 110 ℃ drying in oven sepiolite in addition in a temperature, the time is 2 hours.Getting 0.6 part of alunite, 0.9 part of dehydrated gyp-, 0.6 part of coal gangue and 0.9 part of sepiolite after the cooling mixes in agitator and makes toughener.This toughener and 70 parts of slags and 27 parts of cement clinkers are carried out ball milling in ball mill, make slag cement.Press the performance of embodiment 1 described this cement of measurement.The results are shown in Table 1.
Embodiment 5
Respectively in the shaft kiln of 500 centimetres of 3 100 cm x 100 cm x with the temperature calcined alunite of 600 ℃, 700 ℃ and 950 ℃, common gypsum and coal gangue 2.3 hours.Getting 3 parts of alunites, 2.4 parts of dehydrated gyp-s and 0.6 part of coal gangue after the cooling mixes in agitator and makes toughener.This toughener and 65 parts of flyash and 29 parts of cement clinkers are carried out ball milling in ball mill, make pulverized fuel ash cement.Press the performance of embodiment 1 described this cement of measurement.The results are shown in Table 1.
Embodiment 6
Respectively in the shaft kiln of 500 centimetres of 3 100 cm x 100 cm x with the temperature calcined alunite of 550 ℃, 770 ℃ and 650 ℃, common gypsum and coal gangue 3 hours.Be set to 120 ℃ drying in oven sepiolite in addition in a temperature, the time is 2.5 hours.Getting 2 parts of alunites, 3 parts of dehydrated gyp-s, 1 part of coal gangue and 1 part of sepiolite after the cooling mixes in agitator and makes toughener.This toughener and 20 parts of slags and 73 parts of cement clinkers are carried out ball milling in ball mill, make slag cement.Press the performance of embodiment 1 described this cement of measurement.The results are shown in Table 1.
Embodiment 7
Respectively in the shaft kiln of 500 centimetres of 3 100 cm x 100 cm x with the temperature calcined alunite of 550 ℃, 700 ℃ and 800 ℃, common gypsum and coal gangue 3.5 hours.Be set to 200 ℃ drying in oven sepiolite in addition in a temperature, the time is 2.5 hours.Getting 1.4 parts of alunites, 2.8 parts of dehydrated gyp-s, 0.7 part of coal gangue and 2.1 parts of sepiolites after the cooling mixes in agitator and makes toughener.This toughener and 40 parts of flyash and 53 parts of cement clinkers are carried out ball milling in ball mill, make pulverized fuel ash cement.Press the performance of embodiment 1 described this cement of measurement.The results are shown in Table 1.
Embodiment 8
Respectively in the shaft kiln of 500 centimetres of 3 100 cm x 100 cm x with the temperature calcined alunite of 500 ℃, 700 ℃ and 800 ℃, common gypsum and coal gangue 3 hours.Getting 2.4 parts of alunites, 4.8 parts of dehydrated gyp-s and 0.8 part of coal gangue after the cooling mixes in agitator and makes toughener.This toughener and 30 parts of slags and 62 parts of cement clinkers are carried out ball milling in ball mill, make slag cement.Measure three days and 28 days ultimate compression strength and folding strength of this cement, and the hydration heat of cement setting time and three days, the results are shown in Table 1.
Embodiment 9
Toughener and 97 parts of concrete that embodiment 4 is made stir in stirrer.Make concrete.The ultimate compression strength that this concrete reached in the time of 28 days surpasses with 15% of proportioning concrete (not adding toughener).
Comparative Examples 1
With 4 parts of dehydrated gyp-s, 64 parts of cement clinkers and 32 parts of flyash ball milling in ball mill, make pulverized fuel ash cement.Press the performance of embodiment 1 described this cement of measurement.The results are shown in Table 1.
Table 1
| Sequence number | Toughener (part) | Cement clinker (part) | Slag (part) | Flyash (part) | Ultimate compression strength (MPa) | Folding strength (MPa) | Three days hydration heat (J/g) | Time of coagulation | |||||
| Alunite | Dehydrated gyp- | Coal gangue | Sepiolite | Three days | 28 days | Three days | 28 days | ||||||
| Embodiment 1 | 2 | 4 | 2 | 62 | 30 | 29 | 59 | 5.8 | 9.3 | 50 | 4 hours | ||
| Embodiment 2 | 2.4 | 4 | 1.2 | 0.4 | 52 | 40 | 30 | 60 | 5.9 | 9.4 | 50 | 5 hours | |
| Embodiment 3 | 3 | 3 | 1 | 1 | 32 | 30 | 30 | 29 | 58 | 5.6 | 9.2 | 55 | 4 hours |
| Embodiment 4 | 0.6 | 0.9 | 0.6 | 0.9 | 27 | 70 | 26 | 46 | 4.0 | 8.0 | 60 | 8 hours | |
| Embodiment 5 | 3 | 2.4 | 0.6 | 29 | 65 | 26 | 51 | 5.1 | 8.8 | 60 | 12 hours | ||
| Embodiment 6 | 2 | 3 | 1 | 1 | 73 | 20 | 28 | 59 | 5.6 | 9.1 | 58 | 3.5 hour | |
| Embodiment 7 | 1.4 | 2.8 | 0.7 | 2.1 | 53 | 40 | 28 | 58 | 5.3 | 9.0 | 60 | 10 minutes | |
| Embodiment 8 | 2.4 | 4.8 | 0.8 | 62 | 30 | 29 | 60 | 5.4 | 9.2 | 56 | 4 hours | ||
| Comparative Examples 1 | 4 | 64 | 32 | 16.75 | 42.9 | 3.1 | 7.1 | -- | 6 hours | ||||
Can clearly be seen that from top embodiment and listed data, no matter the cement that is added with toughener of the present invention (is pulverized fuel ash cement, slag cement, still ultimate compression strength complex cement) and folding strength are all obviously than the height of the Portland cement that does not add toughener of the present invention, and hydration heat descends, the less calories that is produced when in cement, adding entry like this, thus the pucker ﹠ bloat of cement all very little, help cement stabilizing.The cement setting time that is added with toughener of the present invention in addition can be adjusted to 12 hours from 10 minutes, and it just can be applicable to the widespread use from the emergency work to the mass concrete engineering like this.
Claims (6)
1. inorganic mineral reinforcer that is used for cement, by weight, it comprises the alunite of 20-50%, the dehydrated gyp-of 30-60%, the coal gangue of 10-25% and the sepiolite of 0-30%, wherein alunite is a calcined alunite and getting under 450-600 ℃ calcining temperature, dehydrated gyp-is a calcining common gypsum and getting under 650-850 ℃ calcining temperature, coal gangue is a calcining coal gangue and getting under 500-1000 ℃ calcining temperature, and sepiolite is an oven dry sepiolite and getting under 100-300 ℃ bake out temperature.
2. toughener as claimed in claim 1, it comprises 25% alunite, 50% dehydrated gyp-and 25% coal gangue.
3. toughener as claimed in claim 1, it comprises 30% alunite, 50% dehydrated gyp-, 5% sepiolite and 15% coal gangue.
4. toughener as claimed in claim 1, it comprises 37.5% alunite, 37.5% dehydrated gyp-, 12.5% coal gangue and 12.5% sepiolite.
5. one kind prepares the method that is used for the inorganic mineral reinforcer of cement as claimed in claim 1, it comprises calcined alunite respectively, common gypsum and coal gangue 1-4 hour, the cooling back is mixed in proportion with oven dry refrigerative sepiolite, wherein the calcining temperature of alunite is 450-600 ℃, the calcining temperature of common gypsum is 650-850 ℃, the calcining temperature of coal gangue is 500-1000 ℃, the bake out temperature of sepiolite is 100-300 ℃, by weight, the blending ratio of each raw material is the alunite of 20-50%, the dehydrated gyp-of 30-60%, the coal gangue of 10-25% and the sepiolite of 0-30%.
6. method as claimed in claim 5, wherein the drying time of sepiolite is 1-3 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00115681A CN1109002C (en) | 2000-05-15 | 2000-05-15 | Inorganic mineral reinforcer for cement and its prepn. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00115681A CN1109002C (en) | 2000-05-15 | 2000-05-15 | Inorganic mineral reinforcer for cement and its prepn. |
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|---|---|
| CN1323755A CN1323755A (en) | 2001-11-28 |
| CN1109002C true CN1109002C (en) | 2003-05-21 |
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| CN00115681A Expired - Fee Related CN1109002C (en) | 2000-05-15 | 2000-05-15 | Inorganic mineral reinforcer for cement and its prepn. |
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| CN101935192B (en) * | 2010-09-10 | 2013-04-24 | 廖传海 | Anti-cracking and anti-permeability lightweight aggregate insulating concrete |
| CN107804984A (en) * | 2017-11-06 | 2018-03-16 | 甘肃恒亚水泥有限公司 | A kind of high strength cement and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094018A (en) * | 1994-05-05 | 1994-10-26 | 安宇 | Be used to improve the inorganic strengthening agent of hydraulic cement |
-
2000
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094018A (en) * | 1994-05-05 | 1994-10-26 | 安宇 | Be used to improve the inorganic strengthening agent of hydraulic cement |
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| CN1323755A (en) | 2001-11-28 |
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