CN104496232A - Method for preparing Alite-barium calcium sulphoaluminate cement from red mud - Google Patents
Method for preparing Alite-barium calcium sulphoaluminate cement from red mud Download PDFInfo
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- CN104496232A CN104496232A CN201410831172.3A CN201410831172A CN104496232A CN 104496232 A CN104496232 A CN 104496232A CN 201410831172 A CN201410831172 A CN 201410831172A CN 104496232 A CN104496232 A CN 104496232A
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- Prior art keywords
- red mud
- alite
- barium
- calcium sulphoaluminate
- gypsum
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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 method for preparing Alite-barium calcium sulphoaluminate cement from red mud. The method comprises the following steps: (1) adopting a mineral phase of Alite-barium calcium sulphoaluminate cement prepared from red mud, wherein the mineral phase consists of the following components in percentage by mass: 5%-8% of C3.75B0.25A3S, 15%-19% of C2S, 40%-60% of C3S, 10%-20% of C4AF and 4%-8% of C3A; (2) according to the mineral phase composition of Alite-barium calcium sulphoaluminate cement, calculating the mixing amount of the following raw materials in percentage by mass: 6%-10% of red mud, 0.3%-0.5% of barium mud, 65%-75% of lime stone, 0.3%-1% of bauxite, 15%-25% of clay, 3%-5% of gypsum and 0.4%-1.5% of fluorite, wherein the fluorite is taken as a mineralizer; (3) crushing, homogenizing, drying, grinding, uniformly mixing, roasting and cooling the raw materials; and (4) adding and grinding gypsum or dihydration gypsum powder which accounts for 5-12% of the total mass until the specific surface area is 350-450m<2>/kg. The method disclosed by the invention is low in sintering temperature, high in early strength, stable in later strength and low in cost, can be used for providing an effective utilization way for comprehensively utilizing the red mud.
Description
Technical field
The invention belongs to the technical field of research of green building material, relate to the waste red mud of aluminum oxide industry generation for Alite-barium calcium sulphoaluminate prepared by raw material.
Background technology
Red mud produces the strong basicity trade waste of discharging in alumina process, (PH 10 ~ 12.5), water ratio is higher, the red mud that China produces aluminum oxide generation is mainly divided into three kinds: Bayer process, integrated process and red mud from sintering process etc., integrated process is roughly the same with sintering process major ingredient, wherein not only has and produces needed for cement
al 2 o 3 ,
fe 2 o 3 ,
caOwith
siO 2 oxide components, and containing a certain amount of 2
caO SiO 2 isoreactivity mineral constituent, does not exist 2 in Bayer process red mud
caO SiO 2 isoreactivity mineral constituent, red mud alkalescence high, cause the surface soil alkalinity stored up, polluted source, the drawbacks such as control expense is large, the waste that red mud damages environment for human survival and causes economic resources serious, red mud is made to fully utilize the difficult problem that becomes international, the quantity discharged of the red mud that comprehensive China is annual is up to 6,000,000 t, along with the development of alumina industry and the reduction of bauxite grade, the quantity discharged of red mud presents the trend of rising, therefore, the comprehensive utilization of red mud is that pendulum is in one of alumina industry key subjects needing solution badly, in red mud, alkali content is too high, can not directly as the raw material producing silicate cement, by barium-bearing calcium sulfo-aluminate (CBA
) mineral facies are incorporated in silicate cement system, improve the alkali-resistivity aggressiveness of silicate cement, forming Alite-barium calcium sulphoaluminate system, mainly there are five kinds of mineral: C in Alite-barium calcium sulphoaluminate grog
(4-X)b
xa
3 , C
3s, C
2s, C
3a and C
4aF, wherein tricalcium silicate (C
3s) content is than great, and its firing temperature is at about 1450 DEG C, and other mineral facies generate temperature all at about 1300 DEG C, makes each mineral facies of cement system well be formed and coexist, Fe in red mud so need to introduce mineralizer
2o
3can be used as good mineralizer, improve the burn-ability of raw material, reduce firing temperature, and red mud medium trace element MgO alkali (Na2O and K2O), TiOi2 all can promote tricalcium silicate (C
3s) well formed with other mineral facies and coexist, grog essential mineral is formed mutually well sees that accompanying drawing illustrates, so utilize red mud as raw material production Alite-barium calcium sulphoaluminate, the comprehensive utilization for red mud provides a kind of Processes For Effective Conversion.
So far, also directly do not utilize red mud as the patent report of raw material production alite-sulphur barium aluminate cement, describe a kind of method preparing the Alite-barium calcium sulphoaluminate of barium-bearing calcium sulfoaluminate and alite mineral compound in the patent (the disclosed patent No.: CN1513786) of Cheng Xin application, wherein mineral composition is designed to C
(4-X)b
xa
3 : 3 ~ 38%, C
3s:30 ~ 60%, C
2s:15 ~ 40%, C
3a:3 ~ 20%, C
4aF:3 ~ 20%, this cement introduces barium-bearing calcium sulfoaluminate at silicate cement, ratio is 3 ~ 38%, main raw material is barite etc., higher than traditional silicate cement cost, be applicable to special engineering, as: repairing rush construction engineering, prefabricated components, GRC goods, low-temperature construction engineering, anti-seawater corrosion engineering etc., be not suitable for suitability for industrialized production.
Summary of the invention
The object of this invention is to provide a kind of method red mud being prepared Alite-barium calcium sulphoaluminate as raw material, to utilize for the industrial residue red mud of aluminium industry approach of opening up and to reduce the production cost producing Alite-barium calcium sulphoaluminate further, the Cement industryization realizing green ecological less energy-consumption with low cost is produced.
Concrete steps are:
(1) cement clinker is primarily of C
3.75b
0.25a
3 ~ C
2s~C
3s ~ C
4aF ~ C
3the mineral facies system composition of A five yuan, wherein the molecular formula of barium-bearing calcium sulfo-aluminate is: (3-X) CaOXBaO3 Al
2o
3caSO
4(X=0.25 ~ 3), due to the complex chemical composition in red mud, solid solution enters the impurity element of mineral facies than great, and mixing of too much Ba element, reaches the limit of mineral facies solid solution, each mineral facies activity is reduced, affect Alite-barium calcium sulphoaluminate system physical-chemical reaction process, economically consider, increase with Ba element incorporation, the cost producing this kind of cement increases, and preferred barium-bearing calcium sulfoaluminate molecular formula is C
3.75b
0.25a
3 .The present invention's red mud prepares Alite-barium calcium sulphoaluminate mineral facies composition mass percent: C
3.75b
0.25a
3 5% ~ 8%, C
2s 15% ~ 19%, C
3s 40% ~ 60%, C
4aF 10% ~ 20% and C
3a 4% ~ 8%.
(2) form according to the Alite-barium calcium sulphoaluminate mineral facies of step (1), adopt the software for mathematical computing mathematica5.0 that Excel carries, solve Linear Equations, complete red mud, barium mud, Wingdale, bauxitic clay, clay, gypsum, with the computation process of fluorite incorporation, the mass percent of each raw material is: red mud 6% ~ 10%, barium mud 0.3% ~ 0.5%, Wingdale 65% ~ 75%, bauxitic clay 0.3% ~ 1%, clay 15% ~ 25%, gypsum 3% ~ 5% and fluorite 0.4% ~ 1.5%, the mass percent sum of raw material is 100%, wherein fluorite is as mineralizer.
(3) each raw material crushing homogenizing step (2) calculated, dries to water ratio and is less than 1%, and ball mill grinding is crossed 200 mesh sieves and tailed over and be less than 5%, is mixed; Then make the cake of 60mm x10mm, condition sintering 1 ~ 2 hour at calcining temperature is 1270 DEG C ~ 1380 DEG C, the type of cooling adopts cooling mode.
(4) gained material in step (3) is broken, size controlling is at 1mm ~ 3mm, and the gypsum or the dihydrate gypsum powder grinding that add gained material total mass 5 ~ 12% are 350 ~ 450m to 200 mesh sieves tail over 5% to specific surface area excessively
2/ kg, namely makes Alite-barium calcium sulphoaluminate.
(5) carry out sample preparation according to GB/T 17671-1999 " strength of cement mortar detection method ", respectively by cement blanks and moulding and conserving to 1d, 3d and 28d different larval instar, utilize anti-folding and anti-pressing test machine to survey the intensity of cement.
Market analysis: cement of the present invention is that a kind of early strength is higher, the cement type that the cost that later strength enhancement rate is stable is cheaper, compared with common sulplo-aluminate, this cement not only early strength is high, and because of aluminum oxide proportion contained in raw material few, Aluminiferous waste slag (waste red mud) or high-alumina clay can be utilized completely to replace, avoid the shortcoming causing production cost high because of China's bauxitic clay resource scarcity.
The present invention is compared with traditional silicate cement, and its main relative merits are divided into 3 points: (1) is because of barium-bearing calcium sulfo-aluminate (C
3.75b
0.25a
3 ) introducing, add and produce the cost of silicate cement; (2) the Ba element in barium mud and the Fe in red mud
2o
3, can be used as the good mineralizer of cement, improve the burn-ability of raw material, reduce firing temperature, temperature controls, at about 1300 DEG C, to improve the drawback of cement industry high pollution high energy consumption, saves the cost producing cement.(3) utilize waste red mud as the aluminum raw material of the ferriferous raw material and part of producing cement, save the cost producing cement further.Solve because of barium-bearing calcium sulfo-aluminate (C
3.75b
0.25a
3 ) introduce and shortcoming that the production cost that causes raises, should control barium-bearing calcium sulfo-aluminate incorporation, therefore, the preferred molecular formula of design barium-bearing calcium sulfo-aluminate is C
3.75b
0.25a
3 , be 5% ~ 8% at cement Minerals phase composite rate control, the shared in the feed ratio of barium mud is about 0.3% ~ 0.5%, thus makes this cement have market outlook.
Accompanying drawing explanation
Fig. 1 is the XRD analysis figure of embodiment of the present invention red mud.
The XRD analysis figure of Fig. 2 embodiment of the present invention 3 cement clinker.
Embodiment
Embodiment:
To take from Wingdale that the barium mud of the red mud of Pingguo Aluminium Industry Co., Guangxi and the strong chemical industry of Xiangzhou, Guangxi connection and Liuzhou Yu Feng Cement Co., Ltd provide, bauxitic clay, clay, gypsum carry out manufacture of cement experiment. the chemical composition of each raw material is as shown in table 1 below.
Table 1: the chemical composition/% of raw material
。
Embodiment 1:
(1) designing cement clinker mineral composition mass percent is: C
3.75b
0.25a
3 6%, C
2s:15%, C
3s 60%, C
4aF 11%, C
3a 8%.
(2) mass percent of concrete batching add-on is: clay 20.4%, red mud 1.82%, Wingdale 72.5%, gypsum 3.68%, barium mud 0.33%, bauxitic clay 0.31% and fluorite 0.96%, wherein fluorite is as mineralizer.
(3) by each for step (2) raw material crushing homogenizing, dry to water ratio and be less than 1%, ball mill grinding is crossed 200 mesh sieves and is tailed over and be less than 5%, is mixed; Then make the cake of 60mm x10mm, at calcining temperature is 1380 DEG C, condition sinters 1 hour, and the type of cooling adopts cooling mode.
(4) gained material Y90L-4 type crusher in step (3) is carried out fragmentation, size controlling, at 1mm ~ 3mm, adds the gypsum of gained material total mass 6%, then to tail over 5% to specific surface area be 400m to crossing 200 mesh sieves to put into SM2-100 type vibration mill grinding
2/ kg, namely makes Alite-barium calcium sulphoaluminate.
(5) carry out sample preparation according to GB/T 17671-1999 " strength of cement mortar detection method ", respectively by cement blanks and moulding and conserving to 1d, 3d and 28d different larval instar, utilize anti-folding and anti-pressing test machine to survey the intensity of cement.
Embodiment 2:
(1) designing cement clinker mineral composition mass percent is: C
3.75b
0.25a
3 6%, C
2s:15%, C
3s 55%, C
4aF 16%, C
3a 8%.
(2) mass percent of concrete batching add-on is: clay 18.5%, red mud 5.64%, Wingdale 70.3%, gypsum 3.64%, barium mud %0.33, bauxitic clay 0.63% and fluorite 0.96%; Wherein fluorite is as mineralizer.
(3) by each for step (2) raw material crushing homogenizing, dry to water ratio and be less than 1%, ball mill grinding is crossed 200 mesh sieves and is tailed over and be less than 5%, is mixed; Then make the cake of 60mm x10mm, at calcining temperature is 1350 DEG C, condition sinters 1 hour, and the type of cooling adopts cooling mode.
(4) gained material Y90L-4 type crusher in step (3) is carried out fragmentation, size controlling, at 1mm ~ 3mm, adds the gypsum of gained material total mass 8%, then to tail over 5% to specific surface area be 400m to crossing 200 mesh sieves to put into SM2-100 type vibration mill grinding
2/ kg, namely makes Alite-barium calcium sulphoaluminate.
(5) carry out sample preparation according to GB/T 17671-1999 " strength of cement mortar detection method ", respectively by cement blanks and moulding and conserving to 1d, 3d and 28d different larval instar, utilize anti-folding and anti-pressing test machine to survey the intensity of cement.
Embodiment 3:
(1) designing cement clinker mineral composition mass percent is: C
3.75b
0.25a
3 6%, C
2s:19%, C
3s 50%, C
4aF 20% and C
3a 8%.
(2) mass percent of concrete batching add-on is: clay 18.2%, red mud 8.4%, Wingdale 68.1%, gypsum 3.6%, barium mud 0.32%, bauxitic clay 0.42% and fluorite 0.96%; Wherein fluorite is as mineralizer.
(3) by each for step (2) raw material crushing homogenizing, dry to water ratio and be less than 1%, ball mill grinding is crossed 200 mesh sieves and is tailed over and be less than 5%, is mixed; Then make the cake of 60mm x10mm, at calcining temperature is 1330 DEG C, condition sinters 1 hour, and the type of cooling adopts cooling mode.
(4) gained material Y90L-4 type crusher in step (3) is carried out fragmentation, size controlling, at 1mm ~ 3mm, adds the dihydrate gypsum powder of gained material total mass 8%, then to tail over 5% to specific surface area be 400m to crossing 200 mesh sieves to put into SM2-100 type vibration mill grinding
2/ kg, namely makes Alite-barium calcium sulphoaluminate.
(5) carry out sample preparation according to GB/T 17671-1999 " strength of cement mortar detection method ", respectively by cement blanks and moulding and conserving to 1d, 3d and 28d different larval instar, utilize anti-folding and anti-pressing test machine to survey the intensity of cement.
Embodiment interpretation of result:
At use for laboratory muffle furnace to above clinker burning, it is 1280 DEG C ~ 1350 DEG C that firing temperature controls, and the physical mechanics property of cement is in table 2.
Table 2: cement mechanical property
XRD analysis is carried out to embodiment 3 grog wherein, has seen Fig. 2.Can see and to prepare in Alite-barium calcium sulphoaluminate clinker mineral system as raw material with red mud, define the gelling system with alite and sulphur barium aluminate compound, further illustrate the advantage utilizing red mud to produce this cement.
Claims (1)
1. utilize red mud to prepare a method for Alite-barium calcium sulphoaluminate, it is characterized in that concrete steps are:
(1) red mud prepare Alite-barium calcium sulphoaluminate mineral facies composition mass percent be: C
3.75b
0.25a
3 5% ~ 8%, C
2s 15% ~ 19%, C
3s 40% ~ 60%, C
4aF 10% ~ 20% and C
3a 4% ~ 8%;
(2) form according to the Alite-barium calcium sulphoaluminate mineral facies of step (1), adopt the software for mathematical computing mathematica5.0 that Excel carries, solve Linear Equations, complete red mud, barium mud, Wingdale, bauxitic clay, clay, gypsum, with the computation process of fluorite incorporation, the mass percent of each raw material is: red mud 6% ~ 10%, barium mud 0.3% ~ 0.5%, Wingdale 65% ~ 75%, bauxitic clay 0.3% ~ 1%, clay 15% ~ 25%, gypsum 3% ~ 5% and fluorite 0.4% ~ 1.5%, the mass percent sum of raw material is 100%, wherein fluorite is as mineralizer,
(3) by each for step (2) raw material crushing homogenizing, dry to water ratio and be less than 1%, ball mill grinding is crossed 200 mesh sieves and is tailed over and be less than 5%, is mixed; Then make the cake of 60mm x10mm, condition sintering 1 ~ 2 hour at calcining temperature is 1270 DEG C ~ 1380 DEG C, the type of cooling adopts cooling mode;
(4) gained material in step (3) is broken, size controlling is at 1mm ~ 3mm, and the gypsum or the dihydrate gypsum powder grinding that add total mass 5 ~ 12% are 350 ~ 450m to 200 mesh sieves tail over 5% to specific surface area excessively
2/ kg, namely makes Alite-barium calcium sulphoaluminate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117838A (en) * | 2017-05-27 | 2017-09-01 | 济南大学 | A kind of sulphoaluminate cement clinker containing tricalcium silicate and preparation method thereof |
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| CN1513786A (en) * | 2003-08-14 | 2004-07-21 | 济南大学 | Alite-barium calcium sulfur aluminate cement |
| CN1837121A (en) * | 2006-04-20 | 2006-09-27 | 中国地质大学（北京） | Method for preparing sulphate aluminium cement by red mud |
| CN101439938A (en) * | 2008-12-16 | 2009-05-27 | 重庆市博赛矿业（集团）有限公司 | Processing method for manufacturing rapid hardening ferrous aluminate cement from red mud |
| CN102765890A (en) * | 2012-08-03 | 2012-11-07 | 尹小林 | Method using titanium gypsum and acetylene sludge to prepare high-calcium sulphoaluminate or high-sulfur clinkers |
| CN103833245A (en) * | 2014-02-23 | 2014-06-04 | 桂林理工大学 | Method for preparing high-iron cement by utilizing red mud |
-
2014
- 2014-12-29 CN CN201410831172.3A patent/CN104496232A/en active Pending
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| CN1513786A (en) * | 2003-08-14 | 2004-07-21 | 济南大学 | Alite-barium calcium sulfur aluminate cement |
| CN1837121A (en) * | 2006-04-20 | 2006-09-27 | 中国地质大学（北京） | Method for preparing sulphate aluminium cement by red mud |
| CN101439938A (en) * | 2008-12-16 | 2009-05-27 | 重庆市博赛矿业（集团）有限公司 | Processing method for manufacturing rapid hardening ferrous aluminate cement from red mud |
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|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117838A (en) * | 2017-05-27 | 2017-09-01 | 济南大学 | A kind of sulphoaluminate cement clinker containing tricalcium silicate and preparation method thereof |
| CN107117838B (en) * | 2017-05-27 | 2020-04-03 | 济南大学 | Sulphate aluminium cement clinker containing tricalcium silicate and preparation method thereof |
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Application publication date: 20150408 |
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