CN1029469C - Method for mfg. cement with highearly strength and high slag content - Google Patents
Method for mfg. cement with highearly strength and high slag content Download PDFInfo
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- CN1029469C CN1029469C CN92110927A CN92110927A CN1029469C CN 1029469 C CN1029469 C CN 1029469C CN 92110927 A CN92110927 A CN 92110927A CN 92110927 A CN92110927 A CN 92110927A CN 1029469 C CN1029469 C CN 1029469C
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- cement
- slag
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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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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a method for manufacturing cement with high strength and high slag content. The method comprises the following steps: the baked slag, calcium lime, excitant and dispersants are together ground into powder with the BET specific surface area of 400 to 900 m<2>/kg in advance; meanwhile, the mixed powder of clinkers and gypsum is ground into powder with the BET specific surface area of 300 to 600 m<2>/kg; then, the clinkers and the gypsum are uniformly mixed, and the cement with high strength and high slag content can be manufactured. When the method is applied, the disadvantages of low early strength, low grades, etc. in the existing cement with slag can be fundamentally changed. The strength in each period and the slag content are obviously higher than that of the existing cement with slag.
Description
The invention belongs to material of construction cement class.
Slag cement is the maximum cement type of China's output.It has that hydration heat is low, stability is good, good heat resistance, later strength height, can make full use of advantage such as industrial residue.The production method of existing slag cement " cement technology " (Shen Wei, Huang Wenxi, Min Panrong write, press of Wuhan Polytechnical Univ, in July, 1991 first version) the 263rd page done detailed introduction.Its method is: " send into common grinding in the mill by a certain percentage with Portland clinker, gypsum behind the granulation slag drying.According to cement clinker, scoriaceous quality, change grog and the scoriaceous cooperation grinding fineness of cement when, and produce the cement of different labels." still,, have also that early strength is low, setting and harden slow, early strength enhancement rate is low with the slag cement that this method is produced, fine slag contents surpasses 40%(weight), cement mark is shortcoming such as reduction significantly.In order to improve the early strength of slag cement, this data further provides 4 measures: change the mineral composition of grog; Control scoriaceous quality and add-on, improve the grinding fineness of cement; Increase the gypsum add-on.These methods have certain effect to intensity, the especially early strength that improves slag cement.But the amplitude that improves is limited, can not change fundamentally still that the slag cement early strength is low, the not high performance characteristics of label.This mainly is because the prior art slag cement hydration and hardening process of producing is a cement clinker mineral elder generation hydration and hardening, produce certain alkali-activator calcium hydroxide after, slag is just participated in reaction.Because in slag cement, the content of cement clinker mineral reduces relatively, its calcium hydroxide is very fast again to be acted on by the slag component.Therefore, the slag cement premature cure of prior art production is slow, early strength is low.
Improve the grinding fineness of slag cement, very favourable to intensity, the especially early strength that improves slag cement.But because slag is than the difficult mill of grog, when slag with the grog grinding or first grog is roughly ground after, during again with the slag grinding, often grog is ground carefullyyer, and slag is still thicker.And all think in the prior art and increase the fineness of grog in the slag cement, more favourable to cement intensity.In addition, the slag cement that utilizes prior art to produce, because its slag particle is thicker, and slag cement basicity is lower.Therefore behind the slag cement hydration and hardening, most slag particle is aquation fully still, and is present in the cement stone with the form of inertia micro-aggregate, reduces the content of gelatinous mass in the cement stone relatively.So in the slag cement that prior art is produced, along with the increase (content is greater than 40% weight) of slag content, cement mark sharply descends.
So, how to improve the intensity and the scoriaceous volume of slag cement? obviously, efficient ways is fully to improve the aquation rate of slag particle in the slag cement, promptly reduce the residual quantity of slag particle in cement stone, make it more fully aquation become hydrated product, thereby increase the density of cement stone, and increase substantially strength of cement and fine slag contents.
The present invention is described in detail as follows:
Slag (moisture is less than 4% weight), unslaked lime, exciting agent and dispersant after the oven dry are milled to Blain specific surface 400-900m
2/ kg, best 600-800m
2/ kg can obtain super-active slag, is called for short the A component.Simultaneously, with grog and gypsum also combined grinding to Blain specific surface 300-600m
2/ kg, best 400-500m
2/ kg makes the B component.At last A component and B component are mixed with certain proportion, can make cement with highearly strength and high slag content.Use the present invention, can change fundamentally that the slag cement early strength is low, the not high shortcoming of label.Fine slag contents up to 70% situation under, the intensity in each length of time all can be higher than the slag cement that utilizes prior art to produce significantly.
Employed slag is meant the granulated blast-furnace slag that meets the GB203-78 national Specification in the A component.
Unslaked lime is meant the Chemicals that Lime Factory produces, and its main component is CaO.The weight percent content of unslaked lime in the A component is 2-10%, and the best is 4-6%.Add unslaked lime and can absorb the moisture of also not drying in the slag, help to improve mill output, improve the slag milling fineness, the back generation of CaO suction simultaneously Ca(OH)
2, enough Ca(OH are provided also for scoriaceous early hydration and prehydration)
2The source.Unslaked lime content very little, role is little; Content is too high, then in cement stone too much Ca(OH will be arranged)
2Crystal exists, and is unfavorable to cement intensity.
Exciting agent can be with commercially available Chemicals NaOH or Na
2CO
3Or Na
2SO
4In the A component, the weight percent content of exciting agent is 0.5-5.0%, and the best is 1.0-3.0%.Exciting agent can destroy the vitreous structure in the slag effectively, makes its short texture, promotes the Ca in the vitreum effectively
2+, AlO
5-, Al
3+, SiO
4-Ion and Ca(OH)
2Combination.Its content acts on little very little; Content is too much, will increase cement cost.
Dispersion agent can be with commercially available Chemicals urea or trolamine or calcium lignin sulphonate.In the A component, the weight percent content of dispersion agent is 0.01-0.10%, and the best is 0.03-0.07%.Dispersion agent can pass through its absorption on the slag particle surface, prevents cohesion and conglomeration between slag particle.Slag particle is fully disperseed, simultaneously exciting agent is scattered in the slag particle surface fully equably.Destroy scoriaceous vitreous structure, make slag in grinding machine, just obtain activating more fully and carry out a small amount of aquation and produce a small amount of hydrated product crystal seed.After slag cement added water, these are activatory and have the active slag of a small amount of hydrated product crystal seed in advance, under the effect of moisture, promptly with Ca(OH)
2, CaSO
4Deng effect, aquation becomes hydrated product.Quicken scoriaceous hydration rate effectively, reduce the slag residual quantity, make slag obtain sufficient aquation.Thereby improve the density of cement stone, increase substantially the intensity of slag cement.Dispersant acts on little very little; Content is too many, not only increases cement cost, also will reduce strength of cement.
Grog in the B component is meant the Portland clinker that each cement mill produces.Gypsum is meant the plaster of paris that meets the GB5483-85 national Specification.
The weight percent of gypsum in the B component is with SO
3Count 3-11%, best 6-8%.Content is too low, and then strength of cement is lower, and cement setting is very fast; Content is too high, will make the hydrated cementitious later stage continue to form ettringite, reduces strength of cement, even causes that stability is defective.
With A component and B component uniform mixing in certain proportion, can produce cement with highearly strength and high slag content of the present invention.Wherein the weight percent of A component is 40-80%, and the best is 50-70%.The A component concentration is very few, and the strength of cement of being produced is not high, and the cost height; Content is too much, and strength of cement is not high yet.
Example 1
Raw materials used chemical ingredients sees Table 1, the raw material that utilizes table 1 with different proportioning combined grindings after, make the A component sample of a series of different proportionings and different fineness, the results are shown in Table 2.Simultaneously with grog and gypsum with different proportioning combined grindings to different fineness, make a series of B component samples, the results are shown in Table 3.A component and B component are uniformly mixed into cement with highearly strength and high slag content of the present invention in certain proportion, and carry out ruggedness test by GB GB177-85 " Test method for strength of hydraulic cement mortar ", gained the results are shown in Table 4.Carry out time of coagulation and stability check by GB GB1346-77 " cement normal consistency water consumption, time of coagulation, the stability method of inspection " simultaneously, by experimental result as can be known, the presetting period of all cement is all between 1.5 hours to 2.5 hours in the table 4, all between 3 hours to 5 hours, stability is all qualified for final setting time.All meet national standard.
In order to compare, by prior art grog, slag, gypsum to different fineness, are made control sample with the certain proportion combined grinding, proportioning and fineness are shown in Table 5.Carry out ruggedness test by identical method, gained the results are shown in Table 6.As seen utilize each age strength of the prepared cement of the present invention all to be higher than significantly and utilize the prepared cement of prior art.In utilizing the prepared cement of prior art, when fine slag contents greater than 40%(weight) time, intensity significantly descends.Improve cement fineness, though can improve strength of cement, the amplitude that improves is limited.When further raising fineness, its effect is just little.And utilize slag content in the prepared cement of the present invention up to 70%(weight) situation under, also have very high intensity.
Table 1 unit: weight percent (%)
Raw material loss on ignition SiO
2Al
2O
3Fe
2O
3CaO MgO SO
3
Grog 0.8 20.04 5.24 3.83 66.31 2.29 0.50
Gypsum 20.17 7.34 1.97 0.61 30.24 0.56 38.58
Slag-35.78 11.95 2.39 44.85 3.50 0.45
Lime 4.64 11.12 6.74 1.66 73.52 1.18 0.50
Table 2 unit: weight percent (%)
Exciting agent dispersion agent specific surface
Numbering slag lime three these quality of second are long-pending
NaOH Na
2CO
3Na
2SO
4Urea
Hydramine calcium sulphonate m
2/ kg
A1 94.99 2 3.0 - - - - 0.01 643
A2 93.97 4 2.0 - - - - 0.03 650
A3 89.93 6 4.0 - - - - 0.07 660
A4 88.90 10 1.0 - - - - 0.10 670
A5 94.42 5 0.5 - - 0.08 - - 640
A6 92.40 5 2.5 - - 0.10 - - 695
A7 89.99 5 5.0 - - 0.01 - - 686
A8 94.47 5 - 0.5 - 0.03 - - 693
A9 92.49 5 - 2.5 - - 0.01 - 715
A10 89.92 5 - 5.0 - - 0.08 - 710
A11 94.40 5 - - 0.5 - 0.10 - 687
A12 92.45 5 - - 2.5 - 0.05 - 779
A13 89.97 5 - - 5.0 - 0.03 - 820
A14 91.95 5 - - 3.0 - - 0.05 668
A15 90.95 5 - - 4.0 0.05 - - 570
A16 90.95 5 - 4.0 - 0.05 - - 398
A17 91.95 5 - 3.0 - 0.05 - - 903
Table 3 unit: weight percent (%)
The B set of dispense is than specific surface area in the B component
Numbering grog gypsum SO
3Content (%) m
2/ kg
B1 93.5 6.5 2.98 297
B2 85.0 15.0 6.21 354
B3 80.0 20.0 8.12 320
B4 72.0 28.0 11.16 410
B5 85.0 15.0 6.21 470
B6 85.0 15.0 6.21 602
Table 4
Numbering cement proportion (%) folding strength MPa ultimate compression strength MPa
(weight percent) 3 days 7 days 28 days 3 days 7 days 28 days
C1 60%A1+40%B2 8.0 10.8 11.8 40.1 51.3 65.4
C2 60%A2+40%B2 8.2 11.0 12.1 41.5 52.2 66.1
C3 60%A3+40%B2 8.3 11.2 12.3 42.1 52.7 66.8
C4 60%A4+40%B2 7.9 10.6 11.4 39.8 50.4 65.0
C5 60%A5+40%B2 7.8 10.3 11.4 39.5 49.8 63.9
C6 60%A6+40%B2 8.1 11.1 12.2 41.7 52.5 66.3
C7 60%A7+40%B2 8.0 11.0 11.7 40.2 51.1 65.1
C8 60%A8+40%B2 7.8 10.2 11.3 39.6 49.9 63.7
C9 60%A9+40%B2 8.0 11.0 12.1 41.5 52.1 66.1
C10 60%A10+40%B2 8.2 11.3 12.2 40.8 51.9 65.8
C11 60%A11+40%B2 7.7 10.1 11.1 39.5 49.7 63.4
C12 60%A12+40%B2 8.1 11.2 12.2 41.6 52.3 66.4
C13 60%A13+40%B2 8.4 11.5 12.4 42.2 52.9 66.9
C14 60%A14+40%B2 8.2 11.1 12.3 41.4 52.4 66.2
C15 60%A15+40%B2 8.0 10.8 11.8 41.0 51.9 65.8
C16 60%A16+40%B2 7.5 9.3 10.7 38.5 48.7 60.5
C17 60%A17+40%B2 8.7 11.8 12.9 43.5 53.8 68.4
C18 60%A1+40%B1 7.7 10.4 11.3 39.2 50.2 64.5
C19 60%A1+40%B3 8.3 11.2 12.2 41.7 52.4 66.5
C20 60%A1+40%B4 7.8 10.6 11.5 39.8 50.5 64.8
C21 60%A1+40%B5 8.4 11.4 12.0 42.1 52.8 65.1
C22 60%A1+40%B6 8.6 11.6 12.2 42.5 53.1 65.3
C23 40%A9+60%B1 6.5 8.2 9.7 35.1 45.6 60.4
C24 50%A12+50%B5 7.1 9.6 10.8 36.2 54.7 67.8
C25 70%A15+30%B6 8.7 11.9 12.6 40.3 50.7 61.8
C26 80%A6+20%B4 8.0 11.3 12.4 35.2 42.3 55.2
C27 40%A3+60%B3 6.7 8.3 9.8 35.2 45.7 60.5
C28 50%A7+50%B1 6.9 9.4 10.6 36.0 54.3 67.5
C29 70%A11+30%B3 8.2 11.4 12.4 40.0 50.1 61.4
C30 80%A14+20%B5 8.1 11.4 12.6 35.3 42.5 55.7
C31 40%A17+60%B6 7.2 8.5 10.0 36.0 46.1 60.8
C32 55%A4+45%B4 7.6 10.4 11.3 39.6 50.3 64.6
C33 75%A8+25%B5 7.4 8.9 10.7 36.9 47.3 62.2
Table 5 is by the cement contrast sample of prior art preparation
Numbering cement proportion (weight percent) specific surface area
Grog gypsum slag (m
2/ kg)
D0 95 5 0 405
D1 55 5 40 402
D2 45 5 50 408
D3 35 5 60 406
D4 25 5 70 410
D5 15 5 80 405
D6 35 5 60 307
D7 35 5 60 512
D8 35 5 60 630
D9 35 5 60 750
The performance of table 6 contrast sample cement
Numbering folding strength MPa ultimate compression strength MPa
3 days 7 days 28 days 3 days 7 days 28 days
D0 5.8 6.8 8.5 32.7 40.2 55.1
D1 4.8 6.0 8.0 21.1 32.3 48.2
D2 4.5 6.1 7.7 19.2 31.3 43.2
D3 4.2 5.7 7.5 17.1 27.5 40.3
D4 3.8 5.2 7.1 15.2 25.3 36.1
D5 3.0 4.8 6.5 12.1 22.1 30.3
D6 3.6 4.9 6.8 14.5 24.1 38.1
D7 4.8 6.2 8.2 18.0 29.2 42.5
D8 5.6 6.7 8.3 21.5 33.3 45.6
D9 5.8 6.8 8.3 22.8 33.9 45.4
Claims (7)
1, cement with highearly strength and high slag content manufacture method is characterized in that: the slag after will drying, unslaked lime, exciting agent and dispersant grinding are to Bo Shi specific area 400-900m
2/ kg makes the A component; Simultaneously, also with grog and gypsum combined grinding to Bo Shi specific area 300-600m
2/ kg makes the B component; At last 40-80% (weight) A component and 20-60% (weight) B component uniform mixing are made slag cement.
2, manufacture method according to claim 1 is characterized in that: the unslaked lime weight percent content of A component is 2-10%.
3, according to claim 1 and 2 described manufacture method, it is characterized in that: the exciting agent in the A component is NaOH or Na
2CO
3Or Na
2SO
4
4, manufacture method according to claim 3 is characterized in that: the weight percentage of exciting agent in the A component is 0.5-5.0%.
5, manufacture method according to claim 1 is characterized in that: the dispersion agent in the A component is with urea or trolamine or calcium lignin sulphonate.
6, manufacture method according to claim 5 is characterized in that: the weight percentage of dispersion agent in the A component is 0.01-0.10%.
7, manufacture method according to claim 1 is characterized in that: the gypsum weight percentage in the B component is with SO
3Count 3-11%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92110927A CN1029469C (en) | 1992-09-29 | 1992-09-29 | Method for mfg. cement with highearly strength and high slag content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92110927A CN1029469C (en) | 1992-09-29 | 1992-09-29 | Method for mfg. cement with highearly strength and high slag content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1071902A CN1071902A (en) | 1993-05-12 |
| CN1029469C true CN1029469C (en) | 1995-08-09 |
Family
ID=4945042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92110927A Expired - Fee Related CN1029469C (en) | 1992-09-29 | 1992-09-29 | Method for mfg. cement with highearly strength and high slag content |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1029469C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110460C (en) * | 1999-06-25 | 2003-06-04 | 孟云芳 | Composite cement |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072618C (en) * | 1995-10-10 | 2001-10-10 | 阎振甲 | Synthetic material with industrial sludge as base material and its prodn process |
| CN102167526B (en) * | 2011-01-21 | 2012-10-24 | 河海大学 | Low-shrink alkali slag cement composition and preparation method thereof |
| AT511689B1 (en) * | 2011-07-08 | 2016-05-15 | Holcim Technology Ltd | HYDRAULIC BINDER |
| CN102827593B (en) * | 2012-09-14 | 2015-10-21 | 中国石油大学(华东) | A kind of deepwater well cementing mortar architecture activated based on slag |
| EP2746237B1 (en) * | 2012-12-19 | 2020-02-12 | HeidelbergCement AG | Activator for cement |
| CN112960920A (en) * | 2021-04-27 | 2021-06-15 | 天津金石建材科技有限公司 | Green ecological environment-friendly cement and preparation method thereof |
-
1992
- 1992-09-29 CN CN92110927A patent/CN1029469C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110460C (en) * | 1999-06-25 | 2003-06-04 | 孟云芳 | Composite cement |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1071902A (en) | 1993-05-12 |
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