CN104496231A - Method for preparing high-ferric Alite-calcium barium sulphoaluminate cement by using red mud and barium mud - Google Patents
Method for preparing high-ferric Alite-calcium barium sulphoaluminate cement by using red mud and barium mud Download PDFInfo
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- CN104496231A CN104496231A CN201410829622.5A CN201410829622A CN104496231A CN 104496231 A CN104496231 A CN 104496231A CN 201410829622 A CN201410829622 A CN 201410829622A CN 104496231 A CN104496231 A CN 104496231A
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- barium
- alite
- mud
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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
Abstract
The invention discloses a method for preparing high-ferric Alite-calcium barium sulphoaluminate cement by using red mud and barium mud. The mineral phases are as follows in percentage by weight: 5-8% of C(4-x)BxA3S, 15-19% of C2S, 30-45% of C3S, 25-45% of C4AF and 4-8% of C3A; the raw materials are as follows in percentage by weight: 10-20% of clay, 8-30% of red mud, 55-65% of limestones, 3-5% of gypsum, 0.3-0.5% of barium mud, 0-2% of bauxite and 0.4-1% of fluorite. The method comprises the following steps: crushing and homogenizing the raw materials and drying and polishing; preparing a round cake-shaped test sample which is 5cm in radius and 2cm in thickness, and calcining and cooling; and (6) crushing, and doping 8-12% of gypsum or dihydrate gypsum based on the total mass of the material, wherein the grinding fineness is 350m<2>/kg-450m<2>/kg or residue on sieve is 5% by a 200mesh sieve. The high-ferric Alite-calcium barium sulphoaluminate cement disclosed by the invention has the characteristics of low sintering temperature and small volume shrinkage, low cost and durability and the like as high-ferric or high-ferric aluminum industrial wastes and barium-containing industrial waste residues are used as raw materials.
Description
Technical field
The invention belongs to technical field prepared by cement, particularly with red mud and barium mud for raw material preparation is by barium-bearing calcium sulfoaluminate (CBA
), alite (C
3s) with tetracalcium aluminoferrite (C
4aF) the high ferro Alite-barium calcium sulphoaluminate of mineral compound.
Background technology
The development degree of society is promoted day by day, to the infrastructure construction of China and improving constantly of construction quality requirement, for the drawback of traditional portland and shortcoming day by day remarkable, be mainly reflected in and consume a large amount of fat lime stone resource, firing temperature is high, coal resources loss is huge, brings greenhouse gases CO
2with obnoxious flavour SO
x, NO
xquantity discharged increase severely, aggravation carrying capacity of environment, Silicon in Cement acid DFP design too high levels, impel the hydrated cementitious later stage produce shrinkage crack, affect cement mechanics serviceability.
In today that resource growing tension and environmental protection ideas are rooted in the hearts of the people, further reduction production energy consumption, decreasing pollution, be pendulum needs solution badly hot subject at cement industry, many experts and scholars propose the imagination of ecological ideas cement, and the transformation developing direction of cement industry trends towards utilizing industrial waste, pollution waste is made to become second time resource, alleviate the problem of resource anxiety, in grog, allocate the mineral facies of the low heat enthalpy of formation of high-content into, as C
2s and C
4aF etc., reduce the firing temperature of cement, save coal resources and preserve the ecological environment significant.
Red mud is the waste with contaminative produced in aluminum oxide industry production process, often produce 1t aluminum oxide and give off 1 ~ 1.8t red mud simultaneously, according to estimates, the volume of cargo in storage of China's red mud is more than 6,000,000 t, along with the economic steady development of China, the output value of alumina industry increases increasingly, there is the trend only increased in the quantity discharged of red mud, at present, the stacking of red mud brings harm to the mankind and dynamic existence of planting, destroy ecotope, therefore, the comprehensive utilization of research red mud is the hot subject of Chinese scholars research, analyze the chemical composition in red mud, wherein there is abundant irony (Fe
2o
3﹥ 30%), aluminium matter (Al
2o
3﹥ 15%), calcareous (CaO ﹥ 13%) and siliceous (SiO
2﹥ 8%) raw material, can be used as the starting material producing cement, if red mud to be used for the production of green low-energy consumption cement, to solve the problem of complex utilization of red mud, then social and economic development is significant.
The high-early-strength type cement of a kind of baric barium-bearing calcium sulfo-aluminate as early-strength type mineral is described during Feng Xiuji applies for a patent (patent No. CN1035486A), wherein the mineral composition weight percent of cement clinker is titanate-containing sulpho-aluminate: 40 ~ 80%, silicate: 10 ~ 50%, aluminate: 0 ~ 20%, ferro-aluminate: 0 ~ 40%, its firing temperature is low, it is 1250 ~ 1350 DEG C, this cement titanate-containing sulpho-aluminate proportion is larger, with cost higher containing barium ore for raw material, cost is high, is applicable to special engineering, and market popularity is restricted.
A kind of preparation method of Alite-barium calcium sulphoaluminate is described in the patent (patent No. CN1513786) of Cheng Xin application, mainly in silicate cement, introduce early-strength type mineral barium-bearing calcium sulfo-aluminate, improve the early strength of silicate cement, improve the volumetric shrinkage slight crack that the hydrated cementitious later stage causes, its cement clinker mineral weight percent is: barium-bearing calcium sulfo-aluminate: 3 ~ 38%, tricalcium silicate: 30 ~ 60%, Dicalcium Phosphate (Feed Grade): 15 ~ 40%, tricalcium aluminate: 3 ~ 20%, ferro-aluminate: 3 ~ 20%.Because the mineral facies content of the tricalcium silicate in cement does not reduce, fundamentally do not improve the present situation of cement industry high pollution, high energy consumption.
Summary of the invention
The object of the invention is to solve above-mentioned deficiency, a kind of cement of taking ore deposit phase system with high ferro alite-barium-bearing calcium sulfo-aluminate as the leading factor be provided,
The present invention takes high-early-strength type barium-bearing calcium sulfoaluminate, Portland clinker and ferro-aluminate cement as the leading factor mineral compound under cryogenic, forms the novel concrete clinker mineral system of taking mineral with high ferro alite-barium-bearing calcium sulfo-aluminate as the leading factor.The feature of this cement integrated silicon acid salt cement, ferro-aluminate cement and barium-bearing calcium sulfoaluminate, have that firing temperature is low, erosion resistance, weather resistance, the feature that with low cost, radioresistance, early strength are high and later strength enhancement rate is stable.Be widely used in repairing rush construction engineering, prefabricated components, GRC goods, low-temperature construction engineering, anti-seawater corrosion engineering.Scholar's research iron content in traditional silicate cement accounted for 8% ~ 12% in the past, mainly in the sintering process of cement, play a part flux, improve the burn-ability of raw material, good gelling whether is had to nourish query mutually to iron, but the ferro-aluminate cement energy-conservation along with excellent property and the appearance of ferric-cement, its firing temperature is generally at about 1300 DEG C, about lower than traditional portland firing temperature 150 DEG C, the cement type that the iron phase mineral of the low heat enthalpy of formation of high-content take mineral as the leading factor is more and more paid attention to gradually, and barium-bearing calcium sulfoaluminate is scholar's research a kind of high-early-strength type mineral out such as Chang Jun in recent years, there is certain microdilatancy characteristic, firing temperature is at about 1350 DEG C, the present invention is by C
4aF and CBA
carry out compound, be incorporated in silicate cement cement system, reduce the content of tricalcium silicate, make mineral facies formation temperature in gelling system about 1300 DEG C formation, save the energy, reduced cost, solve the drawback of the high pollution of traditional portland industry, high energy consumption, aquation later stage cement shrinkage cracking, because barium-bearing calcium sulfo-aluminate is a kind of early-strength type mineral, compensate because of C
4aF content replaces early-strength type mineral C
3the shortcoming that the content of S causes cement early strength low, simultaneously, production high ferro Alite-barium calcium sulphoaluminate, the red bauxite that alumina content is much lower can be adopted, containing high ferro or the industrial residue of high ferro aluminium matter and the industrial residue of baric, its raw material sources are wider, reduce costs further, for process industrial residue provides an effective approach
Concrete steps are:
(1) its cement clinker of high ferro Alite-barium calcium sulphoaluminate is mainly by C
4aF-CBA
-C
3s-C
2s-C
3the ore deposit phase system of A composition, the weight percent of each mineral facies is: C
(4-x)b
xa
3 5% ~ 8%, C
2s15% ~ 19%, C
3s30% ~ 45%, C
4aF25% ~ 45% and C
3a4% ~ 8%, wherein the molecular formula of barium-bearing calcium sulfo-aluminate is: (3-X) CaOXBaO3Al
2o
3caSO
4, X=0.25 ~ 3; Barium-bearing calcium sulfo-aluminate (CBA
) molecular formula be preferably: 2.75CaO0.25BaO3Al
2o
3caSO
4.
(2) calculating its raw material of high ferro Alite-barium calcium sulphoaluminate composition according to step (1) is by weight percentage: CaO:40 ~ 64%, SiO
2: 10 ~ 25%, Al
2o
3: 5 ~ 15%, Fe
2o
3: 6 ~ 18%, SO
3: 0.5 ~ 1.5%, BaO: 0.3 ~ 0.6% and CaF
2: 0.4 ~ 1%.
(3) 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 the computation process of red mud, barium mud, Wingdale, bauxitic clay, clay, gypsum and fluorite incorporation, the weight percent of each raw material: clay 10 ~ 20%, red mud 8 ~ 30%, Wingdale 55 ~ 65%, gypsum 3 ~ 5%, barium mud 0.3 ~ 0.5%, bauxitic clay 0 ~ 2%, fluorite 0.4 ~ 1%.
(4) each raw material crushing homogenizing step (3) calculated, dries respectively to water ratio and is less than 1%; Ball mill grinding is crossed 200 mesh sieves and is tailed over and be less than 5%, makes its uniform composition, and grinding is to raw material mixing.
(5) raw material that step (4) mixes are made radius 5cm, thickness is the sample of the round pie of 2 cm, is 1270 in calcining temperature
~ 1350
lower condition sintering 1 ~ 2 hour, the type of cooling adopts cooling mode.
(6) step (5) gained material is broken, size controlling, at 1mm ~ 3mm, mixes gypsum or the dihydrate gypsum of gained material total mass 8-12%, then to put into vibration mill grinding fineness be 350m
2/ kg ~ 450m
2/ kg or excessively 200 mesh sieves tail over 5%, are prepared into Alite-barium calcium sulphoaluminate.
(7) cement blanks and moulding and conserving is to different larval instar such as 1d, 3d, 28d, utilizes anti-folding and anti-pressing to measure the intensity of cement.
The features such as it is low that the present invention has firing temperature, and use high ferro or the trade waste of high ferro aluminium matter and the industrial residue of baric to be raw material, volumetric shrinkage is little, with low cost and weather resistance.
Accompanying drawing explanation
The XRD analysis figure of Fig. 1 red mud.
Fig. 2 is the different C of the embodiment of the present invention
4the cement clinker XRD analysis figure of the content of AF.
Embodiment
To take from the barium mud of the red mud of Pingguo Aluminium Industry Co., Guangxi and the strong chemical industry of Xiangzhou, Guangxi connection, Wingdale, 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 phase composite weight percent is: C
3.75b
0.25a
3 6%, C
2s:19%, C
3s 42%, C
4aF 25% and C
3a 8%.
(2) the software for mathematical computing mathematica5.0 adopting Excel to carry, the weight percent calculating raw material is: clay 15.66%, red mud 12.53%, Wingdale 66.15%, gypsum 3.6%, barium mud 0.33%, bauxitic clay 1.15% and fluorite 0.58%.
(3) each raw material crushing homogenizing step (2) calculated, dries respectively to water ratio and is less than 1%; Ball mill grinding is crossed 200 mesh sieves and is tailed over and be less than 5%, makes its uniform composition, and grinding is to raw material mixing.
(4) raw material that step (3) mixes are made radius 5cm, thickness is the sample of the round pie of 2 cm, is 1300 in calcining temperature
lower condition sinters 1 hour, and the type of cooling adopts cooling mode.
(5) step (5) gained material Y90L-4 type crusher is carried out fragmentation, size controlling, at 1mm ~ 3mm, mixes the gypsum of gained material total mass 8%, then to put into vibration mill grinding fineness be 400m
2/ kg, is prepared into Alite-barium calcium sulphoaluminate.
(6) cement blanks and moulding and conserving is to different larval instar such as 1d, 3d, 28d, utilizes anti-folding and anti-pressing to measure the intensity of cement.
Embodiment 2:
(1) designing cement clinker mineral phase composite weight percent is: C
3.75b
0.25a
3 6%, C
2s:19%, C
3s 37%, C
4aF 30% and C
3a 8%.
(2) the software for mathematical computing mathematica5.0 adopting Excel to carry, the weight percent calculating raw material is: clay 13.79%, red mud 16.4%, Wingdale 63.86%, gypsum 3.57%, barium mud 0.33%, bauxitic clay 1.47% and fluorite 0.58%.
(3) each raw material crushing homogenizing step (2) calculated, dries respectively to water ratio and is less than 1%; Ball mill grinding is crossed 200 mesh sieves and is tailed over and be less than 5%, makes its uniform composition, and grinding is to raw material mixing.
(4) raw material that step (3) mixes are made radius 5cm, thickness is the sample of the round pie of 2 cm, is 1290 in calcining temperature
lower condition sinters 1 hour, and the type of cooling adopts cooling mode.
(5) step (5) gained material Y90L-4 type crusher is carried out fragmentation, size controlling, at 1mm ~ 3mm, mixes the gypsum of gained material total mass 10%, then to put into vibration mill grinding fineness be 400m
2/ kg, is prepared into Alite-barium calcium sulphoaluminate.
(6) cement blanks and moulding and conserving is to different larval instar such as 1d, 3d, 28d, utilizes anti-folding and anti-pressing to measure the intensity of cement.
Embodiment 3:
(1) designing cement clinker mineral phase composite weight percent is: C
3.75b
0.25a
3 6%, C
2s:19%, C
3s 32%, C
4aF 35% and C
3a 8%.
(2) the software for mathematical computing mathematica5.0 adopting Excel to carry, the weight percent calculating raw material is: clay 11.95%, red mud 20.34%, Wingdale 61.64%, gypsum 3.55%, barium mud 0.33%, bauxitic clay 1.8% and fluorite 0.39%.
(3) each raw material crushing homogenizing step (2) calculated, dries respectively to water ratio and is less than 1%; Ball mill grinding is crossed 200 mesh sieves and is tailed over and be less than 5%, makes its uniform composition, and grinding is to raw material mixing.
(4) raw material that step (3) mixes are made radius 5cm, thickness is the sample of the round pie of 2 cm, is 1290 in calcining temperature
lower condition sinters 1 hour, and the type of cooling adopts cooling mode.
(5) step (5) gained material Y90L-4 type crusher is carried out fragmentation, size controlling, at 1mm ~ 3mm, mixes the gypsum of gained material total mass 12%, then to put into vibration mill grinding fineness be 400m
2/ kg, is prepared into Alite-barium calcium sulphoaluminate.
(6) cement blanks and moulding and conserving is to different larval instar such as 1d, 3d, 28d, utilizes anti-folding and anti-pressing to measure the intensity of cement.
Embodiment interpretation of result:
At use for laboratory muffle furnace to above clinker burning, firing temperature is 1290 DEG C ~ 1300 DEG C, and the physical mechanics property of cement is in table 2.
Table 2: cement mechanical property
Carried out XRD analysis to three groups of grogs, see Fig. 2, result shows: adopt in red mud and barium mud production high ferro Alite-barium calcium sulphoaluminate clinker mineral system, define with C
4aF, C
3s and CBA
take the novel concrete of ore deposit phase system as the leading factor, the compound further illustrating these two kinds of mineral with coexist, and the industrial residue of red bauxite and high ferro that alumina content is low or high ferro aluminium matter and the Barium Residue can be adopted to be this cement of raw material production, reduce costs further.
Claims (1)
1. utilize a method for red mud and the clay standby high ferro Alite-barium calcium sulphoaluminate of barium, it is characterized in that concrete steps are:
(1) weight percent of each mineral facies of high ferro Alite-barium calcium sulphoaluminate is: C
(4-x)b
xa
3 5% ~ 8%, C
2s15% ~ 19%, C
3s30% ~ 45%, C
4aF25% ~ 45% and C
3a4% ~ 8%, wherein the molecular formula of barium-bearing calcium sulfo-aluminate is: (3-X) CaOXBaO3Al
2o
3caSO
4, X=0.25 ~ 3;
(2) calculating its raw material of high ferro Alite-barium calcium sulphoaluminate composition weight percent according to step (1) is: CaO:40 ~ 64%, SiO
2: 10 ~ 25%, Al
2o
3: 5 ~ 15%, Fe
2o
3: 6 ~ 18%, SO
3: 0.5 ~ 1.5%, BaO: 0.3 ~ 0.6% and CaF
2: 0.4 ~ 1%;
(3) 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 the computation process of red mud, barium mud, Wingdale, bauxitic clay, clay, gypsum and fluorite incorporation, the weight percent of each raw material is: clay 10 ~ 20%, red mud 8 ~ 30%, Wingdale 55 ~ 65%, gypsum 3 ~ 5%, barium mud 0.3 ~ 0.5%, bauxitic clay 0 ~ 2%, fluorite 0.4 ~ 1%;
(4) each raw material crushing homogenizing step (3) calculated, dries respectively to water ratio and is less than 1%; Ball mill grinding is crossed 200 mesh sieves and is tailed over and be less than 5%, makes its uniform composition, and grinding is to raw material mixing;
(5) raw material that step (4) mixes are made radius 5cm, thickness is the sample of the round pie of 2 cm, is 1270 in calcining temperature
~ 1350
lower condition sintering 1 ~ 2 hour, the type of cooling adopts cooling mode;
(6) step (5) gained material is broken, size controlling, at 1mm ~ 3mm, mixes gypsum or the dihydrate gypsum of gained material total mass 8-12%, then to put into vibration mill grinding fineness be 350m
2/ kg ~ 450m
2/ kg or excessively 200 mesh sieves tail over 5%, are prepared into Alite-barium calcium sulphoaluminate.
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|---|---|---|---|
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Cited By (3)
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| CN113683328A (en) * | 2021-09-08 | 2021-11-23 | 河南科技大学 | Radiation-proof heavy aggregate prepared from wastes and preparation method thereof |
| CN115838250A (en) * | 2022-12-01 | 2023-03-24 | 济南大学 | Red mud-based admixture and clinker as well as preparation method and application thereof |
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| CN105314899A (en) * | 2015-11-25 | 2016-02-10 | 济南大学 | Low-heat cement capable of efficiently utilizing industrial waste gypsum |
| CN113683328A (en) * | 2021-09-08 | 2021-11-23 | 河南科技大学 | Radiation-proof heavy aggregate prepared from wastes and preparation method thereof |
| CN115838250A (en) * | 2022-12-01 | 2023-03-24 | 济南大学 | Red mud-based admixture and clinker as well as preparation method and application thereof |
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| CN104496231B (en) | 2016-07-06 |
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