CN102690068A - Manufacture method of cement clinker - Google Patents
Manufacture method of cement clinker Download PDFInfo
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- CN102690068A CN102690068A CN2011103289359A CN201110328935A CN102690068A CN 102690068 A CN102690068 A CN 102690068A CN 2011103289359 A CN2011103289359 A CN 2011103289359A CN 201110328935 A CN201110328935 A CN 201110328935A CN 102690068 A CN102690068 A CN 102690068A
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- China
- Prior art keywords
- cement clinker
- cement
- desulfurization slag
- raw material
- manufacture
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
-
- 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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
-
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
The invention provides a manufacture method of cement clinker with desulfurization slag as raw material, wherein the consumption amount of limestone can be reduced, and cement clinker can be obtained by low-temperature calcination. Limestone, clay, silica and iron can be applied as raw materials. The method is characterized in that the desulfurization slag can be used as part of raw material, the consumption per unit of desulfurization slag is 30 to 400 kg/t. Perferably, in the desulfurization slag, calcium content calculated by CaO is more than 40 weight%, sulphur content is from 0.5 to 10 weitht%, and fluorin content is from 0.03 to 2.0 weight%.
Description
Technical field
The present invention relates to the method for manufacture of desulfurization slag as the cement clinker of part of raw materials use.
Background technology
In general; Cement is in as the cement clinker that burns till thing, to add gypsum to pulverize and make; Cement clinker is with so-called Wingdale, clay, silica, the such raw material of iron material, in cement kiln, burns till and makes with the high temperature about 1450 ℃.As burning till fuel, use the waste of coal, heavy oil, plastic waste etc., but burn till in order to carry out high temperature, a large amount of fuel can be consumed, and along with the burning of fuel, a large amount of CO
2Produce.In addition, because be main raw material, so, also a large amount of CO can take place along with near its thermolysis (decarbonate) 800 ℃ with the Wingdale
2
Existing distinctive CO in such cement manufacturing technology
2Among the genesis mechanism, from the viewpoint of recent global warming issue, reduction carrying capacity of environment etc., the cement industry is also just cut down CO
2The method of generating capacity carried out various researchs.For example, Wingdale is related to the calcium component in the cement clinker, therefore, develops and has reduced the C in the cement clinker
3The low-heat portland cement of S amount, but the result is, with C
3The early strength silicate cement that the content of S is many is compared, and how the usage quantity of Wingdale (consumption rate) does not change.In addition, also studied interpolation CaF in raw material (cement burns till raw material)
2Deng mineralizer, to reduce firing temperature.But these aspects of the stability of the quality of mineralizer, stable supplying, effect are troubling.
On the other hand, the same for the desulfurization slag of the industry byproduct that takes place in the hot metal pretreatment as steelmaking process with other slags such as blast-furnace slags, utilize again with regard to it and also to have carried out various researchs.But, because contain sulphur and fluorine, so in the utilization again in cement field, be not advanced to the degree of blast-furnace slag.
In the utilization again in cement field, for example, in patent documentation 1, recording and narrating has in the cement constituent that has used the mixed cement that is formed by flyash and blast furnace granulated slag etc., is used as alkaline stimulant.In addition, in patent documentation 2, recording and narrating has a kind of chromic material of reduction that is made up of specific desulfurization slag and hydraulicity material.
Though proposed utilization, almost do not obtained research about the manufacturing of the cement clinker that uses the desulfurization slag to the raw material of cement clinker.In patent documentation 3, recording and narrating has a kind of hot metal pretreatment method that is used for being suitable as the raw material that cement raw material uses.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2003-306359 communique
Patent documentation 2: No. 3877583 communique of Japanese Patent
Patent documentation 3: TOHKEMY 2001-262213 communique
As stated,, but how not obtain research, the almost not research of utilization that particularly can handle in a large number as the raw material of cement clinker about utilization again towards the cement field though carried out various researchs for the utilization again of desulfurization slag.According to the desulfurization slag that the invention technology of patent documentation 3 obtains, be as cement raw material with and specially-made special material is therefore, still unclear about using general desulfurization slag to make the technology of cement clinker.
In addition, as above-mentioned, in the manufacturing of cement clinker, from cutting down CO
2The viewpoint of generating capacity is set out, and what need realization is the usage quantity (consumption rate) that reduces Wingdale, advances easy fired.
Summary of the invention
The problem that invention will solve
The present invention is in order to realize the solution of these problems; It is a kind of with the method for manufacture of desulfurization slag as the cement clinker of the raw material use of cement clinker that its purpose is to provide; Can reduce the usage quantity of Wingdale; Even do not use material, also can carry out the method for manufacture of the cement clinker of stable easy fired as mineralizer.
The method that is used to deal with problems
The method of manufacture of the cement clinker of the application's first invention is a kind of method of manufacture of cement clinker; It is characterized in that; It is " with Wingdale, clay, silica, the iron material method of manufacture as the cement clinker of raw material; except above-mentioned raw materials, also use the desulfurization slag as part of raw materials, the consumption rate of said desulfurization slag is 30～400kg/t ".
The kind of cement clinker; Do not limit the employed cement clinkers of various silicate cements such as preferred ordinary Portland cement, early strength silicate cement, low-heat portland cement, moderate-heat portland cement so long as the employed cement clinker of commercially available cement is then special.
Cement clinker method of manufacture of the present invention has characteristic on raw material, except existing Wingdale, clay, silica, the iron material, also use the desulfurization slag as part of raw materials.Through using the desulfurization slag, can reduce the usage quantity of Wingdale, even and do not use mineralizer, also can easy fired.
In the raw material, the consumption rate of desulfurization slag is 30～400kg/t.When being lower than 30kg/t, the reduction of Wingdale usage quantity does not use the easy fired of mineralizer fully to realize.In addition, if surpass 400kg/t, then be difficult to burn till or waste gas in SO
xIncrease.The manufacturing installation of cement clinker (burning apparatus), method of manufacture (process for calcining) are like existing situation.
The method of manufacture of the cement clinker of the application's second invention, the method for manufacture like the described cement clinker of first invention is characterized in that the " C in the said cement clinker
3The S amount is 70～80% ".
Present inventors had before invented the C in the cement clinker
3The content of S surpasses 70% high reactivity cement grog (Japanese patent application 2010-216942), and preferably the method for manufacture with cement clinker of the present invention is applied in the manufacturing of this high reactivity cement grog.If want to obtain C
3The content of S surpasses 70% high C
3The cement clinker of S then must increase the usage quantity of Wingdale, and carries out high temperature and burn till, but through using the desulfurization slag, then can reduce the usage quantity of Wingdale, also can easy fired, and therefore effect of the present invention is remarkable.C
3The content of S surpasses 80% situation, because be difficult to satisfy the consumption rate of above-mentioned desulfurization slag, so not preferred.
The method of manufacture of the cement clinker of the application's the 3rd invention; Method of manufacture like the described cement clinker of first or second invention; It is characterized in that " said desulfurization slag contains more than the calcium component 40 weight % with the CaO conversion; contain sulphur composition 0.50～10 weight %, contain fluorine composition 0.03～2.0 weight % ".
Because the desulfurization slag contains calcium component in a large number, thus the substitute of Wingdale become, but in order to obtain the reduction effect of Wingdale, the preferred use with the CaO conversion contained the desulfurization slag more than the calcium component 40 weight %.In addition, as one of characteristic of desulfurization slag, though be to contain a large amount of sulphur compositions, the content of preferred sulphur composition is 0.50～10 weight %.When being lower than 0.50 weight %,, then be difficult to obtain effect, if a large amount of the use then is difficult to carry out the raw material blending as mineralizer if do not use the desulfurization slag in a large number.
In addition, if use the sulphur component content to surpass the desulfurization slag of 10 weight %, then have to reduce its combined amount, if so, then the effect as the substitute of Wingdale diminishes.In addition, the desulfurization slag also contains the fluorine composition, and preferred the use contained the desulfurization slag that the fluorine composition is 0.03～2.0 weight %.When being lower than 0.03 weight %, insufficient easily as the effect of mineralizer.When surpassing 2.0 weight %, then possibly cause detrimentally affect to the quality of burnt brick in the cement kiln and cement clinker.
According to the method for manufacture of cement clinker of the present invention, can reduce the amount of the Wingdale that is used for raw material (burning till raw material).In addition, even do not use mineralizer, also can be under than the low temperature of existing firing temperature calcination of cement clinker, therefore can reduce the usage quantity of fuel.Through these reductions, can cut down CO
2Generating capacity.Because not necessarily need use mineralizer, so also can realize the cost cutting of this composition, eliminate the worry of stability aspect these of quality at mineralizer, stable supplying, effect, eliminate the detrimentally affect of using mineralizer to cause separately.In addition, because can handle the desulfurization slag in a large number, can cut down the amount of waste treatment.
As above, from various viewpoints, can both make cement clinker with the form that helps to reduce carrying capacity of environment.
Embodiment
Below, illustrate in greater detail the present invention based on an embodiment example.Also have, the present invention does not receive the qualification of the embodiment of following explanation.
At first, describe for the desulfurization slag that uses among the present invention.
[desulfurization slag]
From the molten iron that blast furnace is emitted, high density contains and can cause dysgenic sulphur composition to the quality of steel, therefore uses sweetening agent to carry out desulfurization and handles.Sweetening agent has various, but from the angle of cheapness, uses with the CaO fimily desulfurizing agent (CaO-CaF of lime as principal constituent mostly
2).Handling the slag that obtains through this desulfurization is exactly desulfurization slag (CaO is the desulfurization slag), and except containing in a large number the calcium component, it also contains sulphur composition, silica composition, alumina composition and iron, also contains the fluorine composition of trace.
Secondly, the method for manufacture for cement clinker of the present invention describes.
[manufacturing of cement clinker]
(1) blending of raw material
The invention is characterized in the raw material of cement clinker, except existing Wingdale, clay, silica, the iron material, also use above-mentioned desulfurization slag.Each raw material is allocated design based on the kind (mineral composition, chemical constitution) of the cement clinker of making, and the raw material blending process in making through existing cement clinker (metering of each raw material, the mixing pulverizing in former abrasive lapping machine, the mixing in mixing silo etc.) is concocted.Because the desulfurization slag contains calcium component in a large number, so utilize again as the Wingdale substitute.In addition, because also contain iron, silica composition, alumina composition, so also can on the direction that reduces clay, silica, each amount of iron material, adjust.
According to aforementioned reason, the desulfurization slag is that the scope of 30～400kg/t is added in consumption rate, and with other raw materials mix.In addition, according to aforementioned reason, preferably convert with CaO and contain more than the calcium component 40 weight %, containing the sulphur composition is 0.50～10 weight %, and containing the fluorine composition is 0.03～2.0 weight %.
In the present invention, be easy fired though burn till,, do not need to add existing material (CaF as mineralizer (mineralizer/ flux) for this reason
2, NaF, MgF
2, Na
2SiF
6, MgSiF
6, BaF
2, CaSO
4, CaSO
42H
2O etc.).This be because, the effect that contained sulphur composition and fluorine composition have played mineralizer in the desulfurization slag.
As aforementioned, the method for manufacture of cement clinker of the present invention is fit to make the C in the cement clinker
3The content of S surpasses 70% high reactivity cement grog (with reference to Japanese patent application 2010-216942).Make C
3S＞70% and C
3Many, the C of S
2The high reactivity cement grog that S is few is easy to burn till.
(2) grog burns till
Through the raw material (blending raw material) of cement clinker of blending, be sent to burning apparatus and carry out grog and burn till.Burning apparatus gets final product with existing cement clinker burning apparatus (cement kiln, preheater etc.), and process for calcining is also like existing method.Firing temperature is preferably 1240～1410 ℃, can carry out more in the past than the easy fired that hanged down 100～200 ℃.Thus, because can reduce the usage quantity of fuel such as coal, so can suppress CO
2Generating capacity.The cement clinker that burns till through grog cooled off as in the past, coarse reduction.
(3) cement clinker
The kind of the cement clinker that can be made method of manufacture of the present invention does not limit especially, is the C in the cement clinker
3The S amount is 30～50% low-heat portland cement, moderate-heat portland cement, various cement clinkers such as 50～70% ordinary Portland cement, early strength silicate cement.As aforementioned, wherein, the C in cement clinker
3The content of S surpasses in 70% the high reactivity cement grog (with reference to Japanese patent application 2010-216942), the particularly manufacturing of 70～80% high reactivity cement grog, preferably uses method of manufacture of the present invention.High reactivity cement grog is the cement clinker that is used for the manufacturing of high warm nature cement, is C based on the mineral composition of the calculated value of Bogue formula
3S＞70%, C
2S＜5%.
(4) trial-production of cement clinker
In order to confirm effect of the present invention, utilize electric furnace to carry out grog and burn till, manufacture experimently various cement clinkers.
1) uses raw material
Wingdale, clay, silica, iron material have used existing cement to make employed industrial raw material.The desulfurization slag uses three kinds of calcium components, sulphur composition, the different desulfurization slag of fluorine composition.Show chemical ingredients and ratio (wt%) thereof in the table 1.
[table 1]
Use the kind and the chemical ingredients of raw material
| igJoss | SiO2 | Al2O3 | Fe2O3 | CaO | MgO | Na2O | K2O | TiO2 | P2O5 | MnO | T-S | F | |
| Wingdale | 42.8 | 1.7 | 0.4 | 0.3 | 53.4 | 1.0 | 0.01 | 0.05 | 0.03 | 0.03 | 0.01 | 0.01 | 0.0 |
| Clay | 1.7 | 55.6 | 27.7 | 5.2 | 4.2 | 1.4 | 0.20 | 0.83 | 1.82 | 0.39 | 0.01 | 0.90 | 0.0 |
| Silica | 0.3 | 93.6 | 0.4 | 1.1 | 1.5 | 0.7 | 1.23 | 0.18 | 0.04 | 0.01 | 0.04 | 0.80 | 0.0 |
| Iron material | 33.0 | 4.6 | 2.5 | 49.1 | 3.5 | 0.6 | 0.37 | 0.30 | 0.18 | 0.17 | 0.25 | 0.00 | 0.0 |
| Desulfurization slag A | 21.0 | 5.6 | 3.7 | 3.5 | 55.5 | 0.9 | 0.13 | 0.02 | 0.13 | 0.04 | 0.22 | 9.30 | 0.20 |
| Desulfurization slag B | 15.6 | 10.9 | 4.1 | 6.8 | 53.1 | 4.1 | 0.05 | 0.03 | 0.31 | 0.03 | 0.32 | 1.60 | 0.03 |
| Desulfurization slag C | 14.0 | 14.8 | 10.1 | 10.6 | 41.3 | 4.9 | 0.12 | 0.07 | 0.43 | 0.19 | 1.75 | 0.50 | 1.88 |
2) raw material blending
Each allotment (consumption rate) of manufacturing experimently each raw material of cement clinker is presented in the table 2.Trial-production 1, trial-production 5, trial-production 9, trial-production 13, trial-production 17 are the relatively article that do not contain the desulfurization slag, are enforcement article of the present invention beyond it.Blending is at 100 ℃ each raw material of exsiccant to be mixed with mortar to carry out.Wingdale, clay, silica, iron material use in advance and have carried out the material of pulverizing with rasper.Also has the C in the table 2
3The S amount, expression is based on the ratio (%) in the trial-production cement clinker of Bogue formula calculating.
The amount of desulfurization slag that can know interpolation is many more, and the usage quantity of Wingdale and clay is significantly reduced.
3) grog burns till
Blending raw material class is granulated into the size about particle diameter 30mm, this particle is put into electric furnace,, under the maximum temperature of 1200～1450 ℃ scopes, keep burning till in 5 hours with the heat-up rate intensification of 10 ℃/min.Resulting trial-production grog is placed on the indoor chilling that carries out after electric furnace takes out, thereafter, pulverize with the 250rpm ball mill, makes it all the screen cloth through 75 μ m.The free lime amount of respectively manufacturing experimently cement clinker after measure pulverizing is tried to achieve the free lime amount and is 1% temperature, with it as optimum burning temperature-forming.Optimum burning temperature-forming is presented in the table 2, and the ratio of the main chemical compositions of resulting trial-production cement clinker is presented in the table 3, and the ratio of forming based on this essential mineral is presented in the table 4.
[table 2]
Each manufactures experimently the raw material consumption rate and the optimum burning temperature-forming of cement clinker
Can know that like above-mentioned table 2 along with amount (consumption rate) increase of desulfurization slag, optimum burning temperature-forming reduces.
[table 3]
The ratio that main chemical compositions in the cement clinker is formed
[table 4]
The ratio that essential mineral in the cement clinker is formed
[performance of cement clinker]
In order to confirm above-mentioned performance of respectively manufacturing experimently cement clinker, in the cement clinker of trial-production 1～12, add with SO
3Be scaled the dihydrate gypsum of 2.2 weight % and mix pulverizing, process Blaine value (specific surface area value) 3300cm respectively
2Trial-production cement about/g.In trial-production 13～20, mix and pulverize with SO
3Be scaled the dihydrate gypsum of 2.2 weight %, process Blaine value 4500cm
2Trial-production cement about/g.The trial-production cement of processing carries out the compressive strength test of JIS mortar according to JIS R 5201.The test-results in the 3 days length of time, 7 days, 28 days is presented in the table 5.
[table 5]
The compressive strength test-results
Can know by last table, the desulfurization slag is used for the raw material (blending raw material) of cement clinker, even burn till (easy fired), with the C of various degree to carry out grog more in the past than the temperature of hanging down 100～200 ℃
3The existing article of S amount (trial-production 1, trial-production 5, trial-production 9, trial-production 13, trial-production 17) are compared, and still embody not a halfpenny the worse intensity.
The method of manufacture of cement clinker of the present invention, its far reaching a bit are, have realized a large amount of processing of the desulfurization slag of difficult treatment in the past, and can stablize and obtain C
3The S amount is 70～80% high reactivity cement grog.
Claims (3)
1. the method for manufacture of a cement clinker; It is characterized in that; It is with Wingdale, clay, silica, the iron material method of manufacture as the cement clinker of raw material; Except above-mentioned raw materials, also use the desulfurization slag as part of raw materials, the consumption rate of said desulfurization slag is 30～400kg/t.
2. the method for manufacture of cement clinker according to claim 1 is characterized in that, the C in the said cement clinker
3The S amount is 70～80%.
3. the method for manufacture of cement clinker according to claim 1 and 2 is characterized in that, said desulfurization slag contains more than the calcium component 40 weight % with the CaO conversion, contains sulphur composition 0.50～10 weight %, contains fluorine composition 0.03～2.0 weight %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-062040 | 2011-03-22 | ||
| JP2011062040A JP5730087B2 (en) | 2011-03-22 | 2011-03-22 | Cement clinker manufacturing method |
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|---|---|
| CN102690068A true CN102690068A (en) | 2012-09-26 |
| CN102690068B CN102690068B (en) | 2016-10-26 |
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| Country | Link |
|---|---|
| JP (1) | JP5730087B2 (en) |
| KR (1) | KR101845278B1 (en) |
| CN (1) | CN102690068B (en) |
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| CN106045348A (en) * | 2016-05-27 | 2016-10-26 | 成都金池塘科技有限公司 | Disposal method of desulfurization enriching agent |
| CN106746780A (en) * | 2015-11-20 | 2017-05-31 | 甘肃曼特睿尔公路材料研发有限责任公司 | A kind of environment protecting cement of use slag and preparation method thereof |
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| JP6323484B2 (en) * | 2016-03-22 | 2018-05-16 | 住友大阪セメント株式会社 | Cement clinker composition and blast furnace cement composition |
| JP6500277B2 (en) * | 2016-03-22 | 2019-04-17 | 住友大阪セメント株式会社 | Cement clinker composition and portland cement composition |
| KR101859214B1 (en) * | 2016-09-05 | 2018-06-28 | 경기대학교 산학협력단 | Blast Furance Slag Composition With Integration Gasification Combined Cycle Slag |
| CN107973534B (en) * | 2017-11-23 | 2021-02-09 | 华润水泥技术研发有限公司 | Application of high-silicon low-crystallization siliceous raw material in production of cement clinker |
| CN108328949B (en) * | 2018-01-22 | 2021-03-26 | 江西亚东水泥有限公司 | Cement clinker production method |
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| JP2019031440A (en) * | 2018-11-02 | 2019-02-28 | 住友大阪セメント株式会社 | Cement clinker composition and portland cement composition |
| CN111792856A (en) * | 2020-07-17 | 2020-10-20 | 广西大学 | Method for preparing cement clinker by utilizing Guangxi lead-zinc tailing slag and application thereof |
| CN112279529A (en) * | 2020-11-10 | 2021-01-29 | 攀枝花钢城集团有限公司 | Method for improving silicon and aluminum content in sintered cement by using converter steel slag |
| KR102576649B1 (en) * | 2021-05-26 | 2023-09-08 | 한일시멘트 주식회사 | Low carbon and low energy cement clinker, manufacturing method of the same and manufacturing method of cement using the same |
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| CN106746780A (en) * | 2015-11-20 | 2017-05-31 | 甘肃曼特睿尔公路材料研发有限责任公司 | A kind of environment protecting cement of use slag and preparation method thereof |
| CN106045348A (en) * | 2016-05-27 | 2016-10-26 | 成都金池塘科技有限公司 | Disposal method of desulfurization enriching agent |
| CN106045348B (en) * | 2016-05-27 | 2018-02-02 | 成都金池塘科技有限公司 | A kind of method of disposal of desulfurization richness agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102690068B (en) | 2016-10-26 |
| KR20120107833A (en) | 2012-10-04 |
| JP2012197197A (en) | 2012-10-18 |
| KR101845278B1 (en) | 2018-04-04 |
| JP5730087B2 (en) | 2015-06-03 |
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