CN1837121A - Method for preparing sulphate aluminium cement by red mud - Google Patents
Method for preparing sulphate aluminium cement by red mud Download PDFInfo
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- CN1837121A CN1837121A CNA2006100767184A CN200610076718A CN1837121A CN 1837121 A CN1837121 A CN 1837121A CN A2006100767184 A CNA2006100767184 A CN A2006100767184A CN 200610076718 A CN200610076718 A CN 200610076718A CN 1837121 A CN1837121 A CN 1837121A
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- red mud
- cement
- gypsum
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- aluminosulfate
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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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Abstract
The invention discloses a red mud preparing sulpho-aluminate cement, which is characterized by the following: using 26%-41% red mud to take place of part of aluminium and calcium raw material and whole silica and irony raw material of regular sulpho-aluminate cement production; grinding for certain fineness; desining the C4A3S,C2S,C4AF and main mineral of cement clinker; Preparing sulpho-aluminate cement by alumina, lime carbonate, calcium sulfate and other burdens. The sulpho-aluminate cement has quick induration speed and high early strength.
Description
Technical field
The invention belongs to the technical field of cement material, relating to aluminum oxide industry waste residue red mud is the method that main raw material prepares aluminosulfate cement.
Background technology
Red mud is the high alkalinity mud (pH 10-12.5) of discharging during commercial alumina is produced, and chemical ingredients is mainly: CaO, SiO
2, Fe
2O
3, Al
2O
3Deng, belong to the harmful waste residue of industry, if fail rationally to utilize, can destroy water quality, occupy the arable land, the harm plant-growth causes serious environmental to pollute.China's red mud annual emissions is up to 3,000,000 tons, and utilization ratio only is about 15%.At present, the utilization of red mud mainly concentrates on plastic filler, pavior and aspects such as cement, concrete additive, and major part is not still utilized for air storage.The improvement of red mud has caused domestic and international common concern with comprehensive utilization, is that one of important topic that solves is badly in need of in aluminum current industry.Contain alkali R because of red mud
2O (is Na
2O+K
2O) higher (generally 2.5%～3.0%) can not be directly in a large number as the raw material of firing silicate cement clinker, and major part is to mix as the auxiliary bonding component of the property regulation type of gelling material such as silicate cement or concrete.Compare with silicate cement, alkali is little to the influence of aluminosulfate cement, can utilize high-alkali raw material or industrial residue to produce aluminosulfate cement.
Up to the present, also directly do not utilize red mud to produce the patent report of aluminosulfate cement as batching.A kind of red mud is produced patent (the Chinese patent publication number: 1613809) described method of cement, must handle the alkali content that reduces in the red mud through complicated technology earlier, could do to produce cement producting material, this method cost is higher, is difficult to realize industrialization promotion.
Summary of the invention
The objective of the invention is to utilize red mud directly as raw material, the preparation aluminosulfate cement, be expected to utilize aluminum oxide industry waste residue red mud in a large number in aluminosulfate cement industry, replace resources such as higher bauxitic clay of existing market price and fat lime stone, reduce production costs, have environmental benefit and economic benefit preferably.
The present invention realizes that by such technical scheme it is red mud drying, grinding with special component, same bauxitic clay, and Wingdale, raw materials such as gypsum are by the essential mineral C in the design sulphoaluminate cement clinker
4A
3S, C
2S and C
4The composition of AF is prepared burden, grinding, homogenizing, calcining, makes grog.In order to obtain higher strength property, the grog for preparing mixes the gypsum of different amounts, promptly makes aluminosulfate cement.The product of hydrated cementitious is the mineralogy basis that obtains good strength of cement based on single sulphur type aquation calcium sulphoaluminate (AFm), ettringite (AFt), C-S-H, aluminium glue and iron glue etc.
Concrete steps are as follows:
1. red mud is handled: in 105 ℃ of fully oven dry, decide according to the red mud water content time of drying, and the ball mill grinding is crossed 200 mesh sieves.
2. the design clinker mineral is formed: by weight percentage, preparing sulphate aluminium cement by red mud grog of the present invention consists of:
Calcium sulphoaluminate C
4A
3S:44%～60%
Dicalcium Phosphate (Feed Grade) C2S:30%～48%
Iron calcium aluminate C
4AF:8%～16%
3. prepare burden: contain higher CaO, SiO in the chemical ingredients of red mud
2, Al
2O
3, Fe
2O
3(seeing Table 1 Shandong Aluminum red mud chemical analysis) is similar to the main chemical constitution in the aluminosulfate cement, produces aluminosulfate cement with batchings such as bauxitic clay, Wingdale, gypsum again, can utilize red mud in a large number, also can reduce the cost of aluminosulfate cement.Ingredient groups becomes:
Red mud 26%～41%
Wingdale 27%～44%
4. batch mixing, calcining: with batch mixes, ball milling is even, and calcining temperature is 1250 ℃～1350 ℃.
5. preparation cement: calcination of chamotte below grinding to 200 order, according to the requirement of different sulplo-aluminate kind, adds gypsum once more, makes aluminosulfate cement.The amount of allocating into of gypsum is calculated as follows:
C
G＝0.13×M×A
C/ S
Strong, high strong type aluminosulfate cement M value early: 0～1; Expanded polystyrene veneer aluminosulfate cement M value is: 1～2; From stress pattern sulplo-aluminate M value be: 2～4; Low basicity type sulplo-aluminate M value is: 2.5～3.0
Know-why: a kind of preparing sulphate aluminium cement by red mud of the present invention is a raw material with the red mud of special component, and the chemical analysis composition of red mud sees Table 1, and the red mud XRD analysis is seen Fig. 1.XRD analysis result shows that the crystal form material is mainly calcite, aragonite, β-C in the red mud
2S etc. contain some amorphous silico-aluminate colloids such as C-S-H etc. simultaneously.From chemical constitution and material phase analysis result, red mud is the good raw material of preparation aluminosulfate cement, and the calcite in the red mud and the chemical ingredients of aragonite are lime carbonate, and crystallization is tiny, but crystalline structure difference, their decomposition temperatures are all more than 600 ℃, and degradation production is CaO and CO
2, wherein CaO participates in C in the aluminosulfate cement
2S, C
4A
3S and C
4The formation of AF; β-C in the red mud
2The S composition has good gelling, also is one of main mineral composition in the aluminosulfate cement; The amorphous silico-aluminate colloid of in the red mud some begins to be decomposed into β-C about 700 ℃
2S and calcium aluminate (CA) etc., wherein calcium aluminate participates in C
4A
3The formation of S; Other chemical ingredients such as Fe in the red mud
2O
3Deng, in the sulphoaluminate cement clinker system, form iron phase, mainly with C
4AF is main.With the red mud is main raw material, and with feedstock production aluminosulfate cements such as bauxitic clay, Wingdale, gypsum, the formation course and the main chemical reactions of cement clinker mineral are as follows:
600℃～900℃：
700 ℃, C
2S begins to form:
900 ℃～1100 ℃, C
2The formation of AS and decomposition:
800 ℃～1350 ℃, C
4A
3The formation of S:
1000 ℃～1350 ℃, iron phase forms:
1300 ℃, C
3S begins crystallization:
The method of a kind of preparing sulphate aluminium cement by red mud of the present invention, do not need to change the production technique of traditional aluminosulfate cement, can directly introduce red mud as batching, the aluminosulfate cement of preparation, free CaO content is low in the grog, and burn-ability is good, and essential mineral physically well develops and sees accompanying drawing 1 in the grog, early strength height and later strength are promoted stable, red mud mix the development that does not influence strength of cement.The present invention utilizes preparing sulphate aluminium cement by red mud, also can add red mud, flyash, slag etc. more simultaneously, makes the aluminosulfate cement blended material, has the wide industrial application prospect.
Description of drawings
The XRD analysis figure of Fig. 1 red mud
Fig. 2 is cement clinker XRD analysis figure of the present invention.
Fig. 3 is the SEM figure of cement clinker essential mineral of the present invention.
Fig. 4 is the hydrated cementitious of the present invention XRD analysis figure in each length of time.
Fig. 5 a, Fig. 5 b are hydrated cementitious 3d of the present invention, 28d SEM in length of time collection of illustrative plates.
Embodiment
Adopt and discharge the old red mud of stacking in Shandong Aluminium Industrial Corp's alumina by sintering smelting process, red mud is pale brown colour table caking shape, and through 105 ℃ of abundant oven dry 48 hours, grinding was crossed 200 mesh sieves.Press the component design batching, grinding in ball mill is crossed 200 mesh sieves, 1275 ℃～1300 ℃ calcinings down, calcines 40 minutes, and air-cooled to room temperature, grinding to 200 order promptly gets grog once more, and the amount of allocating into of gypsum is C by formula
G=0.13 * M * A
C/ S calculates, the gypsum coefficient M=0 in the present embodiment.
Embodiment 1: the design cement clinker mineral is formed C
4A
3S 60%, C
2S 24%, C
4AF 16%; Concrete batching add-on (weight percentage): red mud 40.34%, Wingdale 26.42%, bauxitic clay 22.98%, gypsum 10%.
Embodiment 2: the design cement clinker mineral is formed C
4A
3S 56%, C
2S 30%, C
4AF 14%; Concrete batching add-on (weight percentage): red mud 37.39%, Wingdale 30.49%, bauxitic clay 22.71%, gypsum 9.41%.
Embodiment 3: the design cement clinker mineral is formed C
4A
3S 52%, C
2S 36%, C
4AF 12%; Concrete batching add-on (weight percentage): red mud 34.02%, Wingdale 34.73%, bauxitic clay 22.43%, gypsum 8.82%.
Embodiment result:
To the present invention utilize preparing sulphate aluminium cement by red mud and each in length of time hydrated characteristic, carry out XRD, sem analysis shows, who knows essential mineral C
4A
3S etc. physically well develop, and hydrated product interts mutually, tamps based on the AFt and the C-S-H isocolloid of petal-shaped or flaky AFm, short cylinder, and the paste structure densification is that cement obtains high-intensity main source.Utilize the mechanical property of preparing sulphate aluminium cement by red mud to see Table 2 in the embodiment of the invention, and compare with mace board 425 label quick hardening sulphoaluminate cements that match Yang Tezhongshuinichang in Beijing produces:
Table 1 red mud chemical analysis (WB%)
| Raw material | CaO SiO 2 Fe 2O 3/FeO Al 2O 3 MgO Na 2O K 2O P 2O 5 TiO 2 MnO Loss Total |
| Red mud | 35.14 18.14 13.33 7.42 1.32 2.23 0.46 0.23 3.35 0.05 17.87 99.57 |
Table 2 preparing sulphate aluminium cement by red mud mechanical property
| Numbering/the length of time d | Ultimate compression strength/folding strength unit: MPa | |||
| | 3d | | 28d | |
| Embodiment | ||||
| 1 | 32.5/6.5 | 38.0/7.7 | 45.2/9.6 | 64.0/12.2 |
| | 41.0/8.0 | 49.5/8.9 | 60.0/9.5 | 65.0/12.4 |
| | 38.4/8.3 | 48.5/7.4 | 49.0/9.8 | 63.5/10.6 |
| Mace board 425 label quick hardening sulphoaluminate cements | 35.0/7.0 | 43.5/9.6 | 50.5/10.5 | 53.0/11.2 |
Claims (6)
1, a kind of aluminosulfate cement that utilizes the red mud preparation, it is characterized in that: red mud dosage in raw material is 26%～41%, and other raw material dosage is (weight percent):
Bauxitic clay 20%～25%
Wingdale 27%～44%
Gypsum 7%～10%.
2, the aluminosulfate cement that utilizes the red mud preparation according to claim 1 is characterized in that: composition of raw materials is by design grog essential mineral C
4A
3S, C
2S and C
4The composition of AF etc. calculates batching, method of design and proportioning raw materials following (weight percent):
C
4A
3S： 44％～60％
C
2S： 24％～48％
C
4AF： 8％～16％。
3, the aluminosulfate cement that utilizes red mud preparation according to claim 1 is characterized in that: can in above-mentioned cement clinker, add admixtures such as a certain amount of gypsum or Wingdale and grind and form,
The amount of allocating into of gypsum is calculated by following formula:
C
G＝0.13×M×A
c/ S
C
G---the massfraction (ratio of gypsum and grog) that gypsum mixes, establishing grog is 1;
A
C---who knows middle C
4A
3The massfraction of S;
S---SO in the gypsum
3Massfraction;
M---gypsum coefficient, different aluminosulfate cement kind gypsum dosage differences, the M span is between 0～4.
4, a kind of method of utilizing preparing sulphate aluminium cement by red mud, it is characterized in that: be to be main raw material with aluminum oxide industry waste residue red mud, part replaces the aluminium matter and the calcareous raw material of conventional aluminosulfate cement production usefulness, all replace siliceous and ferriferous raw material, grinding is to certain fineness, composition by design sulfur aluminate cement clinker mineral, batchings such as red mud and bauxitic clay, Wingdale, gypsum are evenly calcined the back through ball milling, fire sulphoaluminate cement clinker, allocate gypsum again into and prepare different types of aluminosulfate cement.
5, the method for utilizing the aluminosulfate cement of red mud preparation according to claim 4, it is characterized in that: the cement burning temperature is: 1250 ℃～1350 ℃.
6, the method for utilizing the aluminosulfate cement of red mud preparation according to claim 4, it is characterized in that: red mud is through thorough drying (105 ℃), below grinding to 200 order.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100767184A CN100360451C (en) | 2006-04-20 | 2006-04-20 | Method for preparing sulphate aluminium cement by red mud |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100767184A CN100360451C (en) | 2006-04-20 | 2006-04-20 | Method for preparing sulphate aluminium cement by red mud |
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| Publication Number | Publication Date |
|---|---|
| CN1837121A true CN1837121A (en) | 2006-09-27 |
| CN100360451C CN100360451C (en) | 2008-01-09 |
Family
ID=37014655
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|---|---|---|---|
| CNB2006100767184A Expired - Fee Related CN100360451C (en) | 2006-04-20 | 2006-04-20 | Method for preparing sulphate aluminium cement by red mud |
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Cited By (26)
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|---|---|---|---|---|
| CN101891406A (en) * | 2010-07-12 | 2010-11-24 | 山东大学 | Method for preparing cement with red mud and desulfurized gypsum |
| CN102092971A (en) * | 2011-01-11 | 2011-06-15 | 天津城市建设学院 | Method for preparing road silicate cement from red mud |
| CN102424535A (en) * | 2011-09-14 | 2012-04-25 | 南昌大学 | Method for preparing low-alkality sulphate aluminium cement by using lepidolite sulfuric acid method |
| CN102531423A (en) * | 2012-02-08 | 2012-07-04 | 赵广明 | Method for producing cement clinker by utilizing red mud |
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| CN115572085A (en) * | 2022-11-03 | 2023-01-06 | 常熟理工学院 | Preparation method of sulphate aluminium magnesium salt cement and product thereof |
| CN115572085B (en) * | 2022-11-03 | 2023-05-23 | 常熟理工学院 | Preparation method of magnesium aluminum sulfate cement and product thereof |
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