CN104496231B - A kind of method utilizing red mud and the clay standby high ferro Alite-barium calcium sulphoaluminate of barium - Google Patents
A kind of method utilizing red mud and the clay standby high ferro Alite-barium calcium sulphoaluminate of barium Download PDFInfo
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- CN104496231B CN104496231B CN201410829622.5A CN201410829622A CN104496231B CN 104496231 B CN104496231 B CN 104496231B CN 201410829622 A CN201410829622 A CN 201410829622A CN 104496231 B CN104496231 B CN 104496231B
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- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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Abstract
The invention discloses a kind of method utilizing red mud and the clay standby high ferro Alite-barium calcium sulphoaluminate of barium.(1) percentage by weight of each mineral facies is: C(4-x)BxA3 5%~8%、C2S15%~19%、C3S30%~45%、C4AF25% ~ 45% and C3A4%~8%；(2) percentage by weight of each raw material is: clay 10～20%, red mud 8～30%, limestone 55～65%, Gypsum Fibrosum 3～5%, barium mud 0.3～0.5%, bauxite 0～2%, fluorite 0.4～1%；(4) the broken homogenizing of raw material, drying, grinding；(5) making radius 5cm, thickness is the sample of the round pie of 2cm, calcining, cooling；(6) broken, mix Gypsum Fibrosum or the dihydrate gypsum of gained material gross mass 8-12%, grinding fineness is 350m2/ kg～450m2/ kg or excessively 200 mesh sieves tail over 5%.The features such as it is low that the present invention has firing temperature, and using high ferro or the trade waste of high ferro aluminum matter and the industrial residue of baric is raw material, and volume contraction is little, with low cost and durability.
Description
Technical field
The invention belongs to technical field prepared by cement, prepare by barium-bearing calcium sulfoaluminate (CBA particularly to red mud and barium mud as a raw material), alite (C3S) with tetra calcium aluminoferrite (C4AF) 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, drawback and shortcoming for traditional portland are day by day notable, it is mainly reflected in a large amount of fat lime stone resources of consumption, firing temperature is high, coal resources loss is huge, brings greenhouse gases CO2With harmful gas SOx、NOxDischarge capacity increase severely, aggravate carrying capacity of environment, Silicon in Cement acid DFP design too high levels, promote the hydrated cementitious later stage produce shrinkage crack, affect cement mechanics service behaviour.
In today that resource growing tension and environmental protection ideas are rooted in the hearts of the people, reduce energy consumption further, reduce and pollute, being the hot subject put and need solution at cement industry badly, 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 garbage is made to become second time resource, alleviate the problem that resource is nervous, grog is allocated the mineral facies of the low heat enthalpy of formation of high-load, such as C into2S and C4AF etc., reduce the firing temperature of cement, save coal resources and preserve the ecological environment significant.
Red mud is the garbage with contaminative produced in aluminum oxide industry production process, often produce 1t aluminium 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 discharge capacity of red mud, at present, the stacking of red mud brings harm to the mankind and the dynamic existence planted, destroy ecological environment, 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 (Fe2O330%), aluminum matter (Al2O315%), calcareous (CaO 13%) and siliceous (SiO28%) raw material, as the raw material producing cement, if red mud is used for the production of green low-energy consumption cement, can solve the problem of complex utilization of red mud, then social and economic development is significant.
Feng Xiuji applies for a patent the high-early-strength type cement describing a kind of baric barium-bearing calcium sulfo-aluminate in (patent No. CN1035486A) as early-strength mineral, wherein the mineral composition percentage by weight of clinker is titanate-containing sulpho-aluminate: 40～80%, silicate: 10～50%, aluminate: 0～20%, ferrous aluminate: 0～40%, its firing temperature is low, it it is 1250～1350 DEG C, this cement titanate-containing sulpho-aluminate proportion is bigger, with relatively costly containing barium ore for raw material, cost is high, it is adaptable to special engineering, market popularity is restricted.
The preparation method describing a kind of Alite-barium calcium sulphoaluminate in the patent (patent No. CN1513786) of Cheng Xin application, main introducing early-strength mineral barium-bearing calcium sulfo-aluminate in portland cement, improve the early strength of portland cement, improve the volume contraction slight crack that the hydrated cementitious later stage causes, its cement clinker mineral percentage by weight is: barium-bearing calcium sulfo-aluminate: 3～38%, tricalcium silicate: 30～60%, dicalcium silicate: 15～40%, tricalcium aluminate: 3～20%, ferrous aluminate: 3～20%.Owing to 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 invention aims to solve above-mentioned deficiency, it is provided that a kind of cement taking ore deposit phase system with high ferro alite-barium-bearing calcium sulfo-aluminate as the leading factor,
High-early-strength type barium-bearing calcium sulfoaluminate, Portland clinker and ferrous aluminate cement are taken as the leading factor mineral compound under cryogenic by the present invention, form the novel concrete clinker mineral system 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, ferrous aluminate cement and barium-bearing calcium sulfoaluminate, have that firing temperature is low, corrosion resistance, durability, the feature that with low cost, radiation resistance, early strength high and later strength enhancement rate is stable.It is widely used in repairing rush construction engineering, prefabricated components, GRC goods, low-temperature construction engineering, anti-seawater corrosion engineering.Scholar's research ferrum content in traditional portland 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, to whether ferrum has good gelling to nourish query mutually, but the appearance of the ferrous aluminate cement energy-conservation along with function admirable and ferric-cement, its firing temperature is typically in about 1300 DEG C, about lower 150 DEG C than traditional portland firing temperature, the ferrum phase mineral of the low heat enthalpy of formation of high-load are taken the cement type of mineral as the leading factor and are 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 C4AF and CBACarry out compound, it is incorporated in portland cement cement system, reduce the content of tricalcium silicate, make the mineral facies formation temperature in gelling system about 1300 DEG C formation, save the energy, reduced cost, solve the drawback of traditional portland industry high pollution, high energy consumption, aquation later stage cement shrinkage cracking, owing to barium-bearing calcium sulfo-aluminate is a kind of early-strength mineral, compensate because of C4AF content replaces early-strength mineral C3The content of S causes the shortcoming that cement early strength is low, simultaneously, produce high ferro Alite-barium calcium sulphoaluminate, the red bauxite that alumina content is much lower can be adopted, industrial residue containing high ferro or high ferro aluminum matter and the industrial residue of baric, its raw material sources are wider, reduce cost further, provide an effective approach for processing industrial residue
Concretely comprise the following steps:
(1) its clinker of high ferro Alite-barium calcium sulphoaluminate is mainly by C4AF-CBA-C3S-C2S-C3The ore deposit phase system of A composition, the percentage by weight of each mineral facies is: C(4-x)BxA3 5%~8%、C2S15%~19%、C3S30%~45%、C4AF25% ~ 45% and C3A4% ~ 8%, wherein the molecular formula of barium-bearing calcium sulfo-aluminate is: (3-X) CaO XBaO 3Al2O3·CaSO4, X=0.25～3；Barium-bearing calcium sulfo-aluminate (CBA) molecular formula be preferably: 2.75CaO 0.25BaO 3Al2O3·CaSO4。
(2) calculating its raw material of high ferro Alite-barium calcium sulphoaluminate composition according to step (1) is by weight percentage: CaO:40～64%, SiO2: 10～25%, Al2O3: 5～15%, Fe2O3: 6～18%, SO3: 0.5～1.5%, BaO:0.3～0.6% and CaF2: 0.4～1%.
(3) form according to the Alite-barium calcium sulphoaluminate mineral facies of step (1), adopt the Excel software for mathematical computing mathematica5.0 carried, solve Linear Equations, complete the calculating process of red mud, barium mud, limestone, bauxite, clay, Gypsum Fibrosum and fluorite incorporation, the percentage by weight of each raw material: clay 10～20%, red mud 8～30%, limestone 55～65%, Gypsum Fibrosum 3～5%, barium mud 0.3～0.5%, bauxite 0～2%, fluorite 0.4～1%.
(4) the broken homogenizing of each raw material step (3) calculated, is respectively dried to moisture content less than 1%；Ball mill grinding is crossed 200 mesh sieves and is tailed over less than 5% so that it is composition is uniform, grinding mixes to raw material.
(5) raw material that step (4) mixes being made radius 5cm, thickness is the sample of the round pie of 2cm, is 1270 in calcining heat~1350Lower condition sinters 1 ~ 2 hour, and the type of cooling adopts cooling mode.
(6) being crushed by step (5) gained material, size controlling, at 1mm ~ 3mm, mixes Gypsum Fibrosum or the dihydrate gypsum of gained material gross mass 8-12%, and placing into grinding fineness in vibromill is 350m2/ kg～450m2/ kg or excessively 200 mesh sieves tail over 5%, prepare 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 using high ferro or the trade waste of high ferro aluminum matter and the industrial residue of baric is raw material, and volume contraction is little, with low cost and durability.
Accompanying drawing explanation
The XRD analysis figure of Fig. 1 red mud.
Fig. 2 is embodiment of the present invention difference C4The clinker XRD analysis figure of the content of AF.
Detailed description of the invention
Take from the red mud of Pingguo Aluminium Industry Co., Guangxi and the strong barium mud of chemical industry of Xiangzhou, Guangxi connection, limestone, bauxite, clay, Gypsum Fibrosum carry out manufacture of cement experiment. and 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) design cement clinker mineral phase composition percentage by weight is: C3.75B0.25A3 6%、C2S:19%、C3S42%、C4AF25% and C3A8%。
(2) adopting the Excel software for mathematical computing mathematica5.0 carried, the percentage by weight calculating raw material is: clay 15.66%, red mud 12.53%, limestone 66.15%, Gypsum Fibrosum 3.6%, barium mud 0.33%, bauxite 1.15% and fluorite 0.58%.
(3) the broken homogenizing of each raw material step (2) calculated, is respectively dried to moisture content less than 1%；Ball mill grinding is crossed 200 mesh sieves and is tailed over less than 5% so that it is composition is uniform, grinding mixes to raw material.
(4) raw material that step (3) mixes being made radius 5cm, thickness is the sample of the round pie of 2cm, is 1300 in calcining heatLower condition sinters 1 hour, and the type of cooling adopts cooling mode.
(5) being crushed by step (5) gained material Y90L-4 type disintegrating machine, size controlling, at 1mm ~ 3mm, mixes the Gypsum Fibrosum of gained material gross mass 8%, and placing into grinding fineness in vibromill is 400m2/ kg, prepares 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) design cement clinker mineral phase composition percentage by weight is: C3.75B0.25A3 6%、C2S:19%、C3S37%、C4AF30% and C3A8%。
(2) adopting the Excel software for mathematical computing mathematica5.0 carried, the percentage by weight calculating raw material is: clay 13.79%, red mud 16.4%, limestone 63.86%, Gypsum Fibrosum 3.57%, barium mud 0.33%, bauxite 1.47% and fluorite 0.58%.
(3) the broken homogenizing of each raw material step (2) calculated, is respectively dried to moisture content less than 1%；Ball mill grinding is crossed 200 mesh sieves and is tailed over less than 5% so that it is composition is uniform, grinding mixes to raw material.
(4) raw material that step (3) mixes being made radius 5cm, thickness is the sample of the round pie of 2cm, is 1290 in calcining heatLower condition sinters 1 hour, and the type of cooling adopts cooling mode.
(5) being crushed by step (5) gained material Y90L-4 type disintegrating machine, size controlling, at 1mm ~ 3mm, mixes the Gypsum Fibrosum of gained material gross mass 10%, and placing into grinding fineness in vibromill is 400m2/ kg, prepares 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) design cement clinker mineral phase composition percentage by weight is: C3.75B0.25A3 6%、C2S:19%、C3S32%、C4AF35% and C3A8%。
(2) adopting the Excel software for mathematical computing mathematica5.0 carried, the percentage by weight calculating raw material is: clay 11.95%, red mud 20.34%, limestone 61.64%, Gypsum Fibrosum 3.55%, barium mud 0.33%, bauxite 1.8% and fluorite 0.39%.
(3) the broken homogenizing of each raw material step (2) calculated, is respectively dried to moisture content less than 1%；Ball mill grinding is crossed 200 mesh sieves and is tailed over less than 5% so that it is composition is uniform, grinding mixes to raw material.
(4) raw material that step (3) mixes being made radius 5cm, thickness is the sample of the round pie of 2cm, is 1290 in calcining heatLower condition sinters 1 hour, and the type of cooling adopts cooling mode.
(5) being crushed by step (5) gained material Y90L-4 type disintegrating machine, size controlling, at 1mm ~ 3mm, mixes the Gypsum Fibrosum of gained material gross mass 12%, and placing into grinding fineness in vibromill is 400m2/ kg, prepares 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
Three groups of grogs having been carried out XRD analysis, has seen Fig. 2, result shows: adopts red mud and barium mud to produce in high ferro Alite-barium calcium sulphoaluminate clinker mineral system, defines with C4AF、C3S and CBATake the novel concrete of ore deposit phase system as the leading factor, further illustrate the compound of both mineral and coexist, and can to adopt industrial residue and the Barium Residue of red bauxite and high ferro that alumina content is low or high ferro aluminum matter be this cement of raw material production, reduce cost further.
Claims (1)
1. the method utilizing red mud and the clay standby high ferro Alite-barium calcium sulphoaluminate of barium, it is characterised in that concretely comprise the following steps:
(1) percentage by weight of each mineral facies of high ferro Alite-barium calcium sulphoaluminate is: C(4-x)BxA3 5%~8%、C2S15%~19%、C3S30%~45%、C4AF25% ~ 45% and C3A4% ~ 8%, wherein the molecular formula of barium-bearing calcium sulfo-aluminate is: (4-X) CaO XBaO 3Al2O3·CaSO4, X=0.25～3；
(2) calculating its raw material of high ferro Alite-barium calcium sulphoaluminate composition percentage by weight according to step (1) is: CaO:40～64%, SiO2: 10～25%, Al2O3: 5～15%, Fe2O3: 6～18%, SO3: 0.5～1.5%, BaO:0.3～0.6% and CaF2: 0.4～1%；
(3) form according to the Alite-barium calcium sulphoaluminate mineral facies of step (1), adopt the Excel software for mathematical computing mathematica5.0 carried, solve Linear Equations, completing the calculating process of red mud, barium mud, limestone, bauxite, clay, Gypsum Fibrosum and fluorite incorporation, the percentage by weight of each raw material is: clay 10～20%, red mud 8～30%, limestone 55～65%, Gypsum Fibrosum 3～5%, barium mud 0.3～0.5%, bauxite 0～2%, fluorite 0.4～1%；
(4) the broken homogenizing of each raw material step (3) calculated, is respectively dried to moisture content less than 1%；Ball mill grinding is crossed 200 mesh sieves and is tailed over less than 5% so that it is composition is uniform, grinding mixes to raw material；
(5) raw material that step (4) mixes being made radius 5cm, thickness is the sample of the round pie of 2cm, is that at 1270 DEG C ~ 1350 DEG C, condition sinters 1 ~ 2 hour in calcining heat, and the type of cooling adopts cooling mode；
(6) being crushed by step (5) gained material, size controlling, at 1mm ~ 3mm, mixes the dihydrate gypsum of gained material gross mass 8-12%, and placing into grinding fineness in vibromill is 350m2/ kg～450m2/ kg or excessively 200 mesh sieves tail over 5%, prepare into Alite-barium calcium sulphoaluminate.
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| CN105314899B (en) * | 2015-11-25 | 2017-09-29 | 济南大学 | It is a kind of efficiently to utilize the low-heat cement of industrial waste gypsum |
| CN113683328B (en) * | 2021-09-08 | 2022-06-03 | 河南科技大学 | Radiation-proof heavy aggregate prepared from wastes and preparation method thereof |
| CN115838250B (en) * | 2022-12-01 | 2023-10-27 | 济南大学 | Red mud-based admixture, clinker, and preparation method and application thereof |
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| CN1513786A (en) * | 2003-08-14 | 2004-07-21 | 济南大学 | Alite-barium calcium sulfur aluminate cement |
| CN1810696A (en) * | 2006-01-18 | 2006-08-02 | 内蒙古西水创业股份有限公司 | Freeze-thaw resisting cement and its production process |
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| JP2004269304A (en) * | 2003-03-07 | 2004-09-30 | Taiheiyo Cement Corp | Red mud treatment method and cement clinker production method |
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| CN1810696A (en) * | 2006-01-18 | 2006-08-02 | 内蒙古西水创业股份有限公司 | Freeze-thaw resisting cement and its production process |
| CN101886954A (en) * | 2010-07-09 | 2010-11-17 | 济南大学 | Cement-based temperature sensing element for positive and negative temperature automatic measurement |
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