CN102765893A - Method for preparing sulphoaluminate special cement clinker from waste residue fluorine gypsum and red mud - Google Patents
Method for preparing sulphoaluminate special cement clinker from waste residue fluorine gypsum and red mud Download PDFInfo
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Abstract
The invention belongs to the technical field of cement preparation, and in particular relates to a method for preparing sulphoaluminate special cement clinker from waste residue fluorine gypsum and red mud. The clinker comprises the following raw materials in percentage by mass: 7 to 15 percent of fluorine gypsum, 32 to 42 percent of red mud, and 24 to 35 percent of limestone and the balance of bauxite. The method comprises the following steps of: uniformly mixing the fluorine gypsum and the red mud, fully performing neutralization reaction and the ageing process for harm reduction, drying, proportioning the limestone and the bauxite, grinding, mixing to obtain a raw material, calcining in a rotary kiln or a vertical kiln, quenching, and grinding to obtain the clinker. A large amount of harmful waste residue fluorine gypsum and red mud which are difficult to treat in fluorine industry and alumina industry are used in sulphoaluminate special cement industry, and can replace natural mineral resources such as the bauxite, the limestone and the gypsum with increasingly reduced reserves, so that obvious environmental and economic benefits are achieved.
Description
Technical field
The invention belongs to the cement production technical field, relating to fluorgypsum and red mud is the method that main raw material prepares quick hardening sulphoaluminate special cement grog.
Background technology
Fluorgypsum is to produce the sub product behind the hydrofluoric acid with fluorite and strong sulfuric acid response; 1 ton of hydrofluoric acid of every production produces 4 tons of fluorgypsums approximately; China's annual emissions reaches millions of ton, be in the industry by-product gypsum except that desulfurated plaster, contain the third-largest industrial residue of gypsum resource the phosphogypsum.The fluorgypsum staple is anhydrous calciumsulphate (II type calcium sulfate is also claimed anhydrite), and purity is higher, between the content 80～95%, and SO
3Content is higher than natural dihydrate gypsum.Yet, just having gone out sulfuric acid or hydrogen fluoride and a spot of Calcium Fluoride (Fluorspan) of normal residual some amount in the fluorgypsum of the new discharging of Reaktionsofen, pH value belongs to the strong harmful solid waste of corrodibility about 2.Because fluorgypsum belongs to dehydrated gyp-, hydration reaction slowly, does not possess early strength, and its utilization receives serious restriction.Compare other kind industry by-product gypsum, fluorgypsum resource utilization development technique difficulty is bigger, and comprehensive utilization quantity is very limited.To the processing of fluorgypsum, be through directly discharging after the lime neutralisation is handled simply mostly, but still can cause great environmental pollution at present.Pass through physics, chemistry and modification again, change it into dihydrate gypsum for building, as the compound blended material or the exciting agent of cement, but processing cost is higher.Therefore, how using according to the direct resource utilization cheaply of fluorgypsum composition characteristic is emphasis and the difficult point that needs to be resolved hurrily at present.China's " building materials industry " 12 " development program ", " large solid waste comprehensive utilization scheme " and files such as " the Ministry of Industry and Information Technology are about the instruction of industry by-product gypsum comprehensive utilization " explicitly call for, and further add great development and promote the technological approaches that industry by-product gypsum substitutes plaster of paris resource.In various material of construction products; Have only the sulplo-aluminate special cement that gypsum resource is had the call; And owing to be at high temperature to react synthetic grog; Broken through under the normal temperature of gypsum different crystal water content types and can utilize the main chemical compositions calcium sulfate in the gypsum more efficiently the restriction of its utilization.In addition, the Calcium Fluoride (Fluorspan) composition of trace can be used as sulphoaluminate cement clinker high temperature well behaved mineralizer when synthetic in the fluorgypsum.
Chinese invention patent application No.201010205647 " a kind of fluorgypsum, phosphogypsum, copper mine tailing prepare the method for sulphoaluminate cement clinker "; And Chen Jinmei has reported the some or all of method of utilizing fluorgypsum as sulphoaluminate cement clinker sulphur raw material at document " fluorgypsum is produced the experimental study of early-strong-fast-hard cement " (master thesis); But whether above-mentioned document is all undeclared is the new discharging fluorgypsum that has just gone out Reaktionsofen; And all do not introduce other sulphoaluminate cement clinkers and need aluminium matter, trade waste such as calcareous, the trade waste utilization is lower generally.
Red mud is to produce the fines strong basicity solid slag that produces in the alumina process, and 1 ton of aluminum oxide of every production approximately produces 0.8 ~ 1.5 ton of red mud.China is alumina producing big country, and the annual red mud that produces surpasses 3,000 ten thousand tons, and the accumulation volume of cargo in storage reaches 200,000,000 tons.Along with the growth year by year of China's aluminum oxide output and the reduction gradually of bauxite grade, the generation of red mud also will constantly increase, and expect 2015, and red mud accumulative total volume of cargo in storage will reach 3.5 hundred million tons.Red mud is stored up in a large number, and both land occupation was wasted resource, was prone to cause environmental pollution and potential safety hazard again.The red mud comprehensive utilization still belongs to global problem, in the world red mud is mainly adopted the disposal options of storing up earthing.China's red mud comprehensive utilization ratio is merely 4% at present, is mainly used in preparation building brick, concrete admixture, the fixed material of roadbed etc.Clearly propose in China's " aluminium industry 12 development programs ", accelerate the research and development of general character gordian technique, realize red mud science, the efficient utilization, give priority to red mud and produce building material product etc.Building material product is close and consumption is big with red mud on chemical ingredients, but the high alkalinity of red mud is the biggest obstacle that it is used for conventional silicate cement product in a large number, must handle through dealkalize etc. and could use, causes cost up, and popularization is difficulty.Compare with silicate cement, alkali is less to the influence of aluminosulfate cement.
Chinese invention patent ZL200610076718.4 " a kind of method of preparing sulphate aluminium cement by red mud "; The method that red mud prepares sulplo-aluminate special cement grog is disclosed; But only utilized red mud, do not had other industrial solid castoff of comprehensive utilization in wider scope.
Aluminosulfate cement is as one of China's four big special cement kinds (white cement, low-heat cement for dam, aluminate cement and aluminosulfate cement); Having good characteristics such as early strong, high-strength, high impervious, high anti-freezing, anti-corrosion, low basicity, microdilatancy and low contraction, is airstrip, high rail plate, harbour, road and bridge, harbour, dam, oil well, the special engineered construction of submarine and the very important functional materialss in field such as common building underground works and winter construction.Aluminosulfate cement is different from other series cements and is characterised in that it is raw material that grog prepares in the process with the gypsum, also has a large amount of calcium sulfoaluminate minerals in the grog.Present sulplo-aluminate series special cement, it comprise low basicity, soon hard, high-strength, expand and from several different varietiess such as stress.Along with Chinese economic development, this series cement more and more receives the attention in market, has obtained over 30 years widely and has used.The YO of present Chinese aluminosulfate cement is about 1,500,000 tons, and market requirement speedup is swift and violent in recent years, has a high potential, and is considered to one of kind the most promising among the special cement.But need mineral wealth such as the fine plaster of paris, bauxitic clay, Wingdale, silica in the sulplo-aluminate special cement production process, thereby cause its raw materials cost higher, the large-scale application in market is promoted and is restricted.
Summary of the invention
The purpose of this invention is to provide a kind of industrial solid waste residue fluorgypsum and red mud of using simultaneously directly as raw material, prepare the method for quick hardening sulphoaluminate special cement grog.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method of utilizing waste residue fluorgypsum and red mud to prepare sulplo-aluminate special cement grog, it may further comprise the steps:
A. by following ingredient composition, the shared mass percent of each raw material is respectively: fluorgypsum 7 ~ 15%, red mud 32 ~ 42%, Wingdale 24 ~ 35%, all the other are bauxitic clay;
B. with above-mentioned fluorgypsum and red mud uniform mixing, carry out neutralization reaction ageing mixture operation fully;
C. with the material after the neutralization reaction ageing mixture operation 110 ~ 150 ℃ of oven dry;
D. material and above-mentioned Wingdale, the bauxitic clay after will drying prepared burden, grinding is mixed and made into raw material;
E. raw material are calcined in rotary kiln or shaft kiln;
F. the material after burning till promptly gets grog through over-quenching, grinding.
Wherein, the mass ratio of described red mud and fluorgypsum is 2:1 ~ 6:1,
Said fluorgypsum is the sub product that utilizes after the fluorite and the vitriol oil are produced hydrofluoric acid, and its chemical composition is respectively by mass percentage: CaO 32 ~ 45%; SO
340 ~ 58%; CaF
21.5 ~ 6.5%; All the other are unavoidable impurities.
Said fluorgypsum is the sub product that utilizes after the fluorite and the vitriol oil are produced hydrofluoric acid, and for just going out the new discharging fluorgypsum of Reaktionsofen, its chemical composition is respectively by mass percentage: CaO 32 ~ 45%; SO
340 ~ 58%; CaF
21.5 ~ 6.5%; H
2SO
4<2%; HF<0.05%; PH value is 1.6 ~ 4.0; All the other are unavoidable impurities.
Said red mud is to adopt Bayer process, sintering process or mixed combining method from bauxite, to extract the waste residue that discharges in the alumina process, and its chemical composition is respectively by mass percentage: CaO 20 ~ 40%; Al
2O
38 ~ 18%; SiO
210 ~ 25%; Fe
2O
310 ~ 25%; R
2O 2.2 ~ 2.7%; PH value is 10.0 ~ 13.5; Wherein R is K or Na.
The chemical composition of said bauxitic clay is: Al
2O
3Mass percent is greater than 83%, R
2O is less than 0.4%, and MgO is less than 0.4%, Fe
2O
3Less than 2%, wherein R is K or Na.
The CaO mass percent is greater than 52% in the said Wingdale.
Said calcining temperature is 1230 ~ 1280 ℃.
In the said neutralization reaction ageing mixture operation, the ageing mixture time is 7 ~ 15 days.
A kind of sulplo-aluminate special cement grog that utilizes the preparation of waste residue fluorgypsum and red mud, this cement clinker shared mass percent of each raw material in the preparation is respectively: fluorgypsum 7 ~ 15%, red mud 32 ~ 42%, Wingdale 24 ~ 35%, all the other are bauxitic clay;
This cement clinker adopts the following steps preparation:
1), carries out neutralization reaction ageing mixture operation fully with above-mentioned fluorgypsum and red mud uniform mixing;
2) with the material after the neutralization reaction ageing mixture operation 110 ~ 150 ℃ of oven dry;
3) material and above-mentioned Wingdale, the bauxitic clay after will drying prepared burden, grinding is mixed and made into raw material;
4) raw material are calcined in rotary kiln or shaft kiln;
5) material after burning till promptly gets grog through over-quenching, grinding.
Beneficial effect of the present invention is: it has utilized acid waste residue fluorgypsum and the high alkalinity waste residue red mud sulplo-aluminate special cement grog for main raw material coproduce high added value first; Main raw material need not pass through independent modification or purifying treatment; Can be directly replace natural mineral resources such as gypsum that reserves reduce day by day, fluorite, bauxitic clay, Wingdale, silica in a large number; Have characteristics such as the recycling rate is high, reactive behavior is good, grog is prone to burn, firing temperature is low; And setting rate is fast, early strength is high, later strength increases and stablizes, and has shown good high-early-strength characteristic.This method uses high alkalinity waste residue red mud to manage the new method that provides as neutralizing agent as the harm of falling of fluorgypsum first; For the comprehensive utilization of resources of fluorgypsum and red mud provides new way; Also thinking is provided for the raw materials cost that reduces sulplo-aluminate special cement grog significantly; Environmental pollution, energy efficient, reduction Carbon emission helped economizing on resources, reduced, tangible economic benefit and environmental benefit had.
Embodiment
Below in conjunction with specific embodiment the present invention is further specified.
The present invention directly utilizes red mud and fluorgypsum to make raw material, need not carry out complicated technologies such as any independent purification, modification processing to each raw material, can reduce the processing cost in early stage greatly, helps the comprehensive utilization in big quantification, short distance footpath.Wherein, red mud has just gone out the acid waste residue fluorgypsum of the new discharging of Reaktionsofen for the high alkalinity waste residue can neutralize, and through the ageing mixture operation of abundant neutralization reaction, the hazardous property of two kinds of waste residues of reduction of maximizing can be avoided corrosion on Equipment simultaneously.And the acid fluorgypsum slag of the new discharging of red mud neutralizing treatment is expected to utilize in the present industry of instead the lime neutralization to fall harmful method, realizes " treatment of wastes with processes of wastes against one another " that thinking is novel, reduces cost.The realization of this know-why is must stack through ageing mixture after red mud and fluorgypsum mix, and carries out neutralization reaction fully.
Among the present invention in the fluorgypsum a spot of Calcium Fluoride (Fluorspan) composition can be used as mineralizer good in the grog sintering process, not only can reduce firing temperature, accelerate speed of reaction, and help to improve the grog productive rate.Fluorite is the good mineralizer of Cement industry, and its staple is exactly a Calcium Fluoride (Fluorspan), but fluorite ore deposit price rises is very fast in recent years.Just contain a spot of Calcium Fluoride (Fluorspan) in the fluorgypsum, can be used as the alternative composition of fluorite, do not need extra interpolation again, can realize the maximum using of fluorgypsum moity.Fluorgypsum is difficult to utilize on a large scale in others, mainly be exactly wherein to contain fluorine element, and the Calcium Fluoride (Fluorspan) that contains fluorine element in the present invention is useful component.
The present invention can farthest utilize the calcium sulfate in the fluorgypsum, replaces the plaster of paris fully.Compare in the application of others such as retardant with fluorgypsum; Technology of the present invention is at high temperature to react to carry out; Do not rely on the kind (whether being semi-hydrated gypsum or dihydrate gypsum) of gypsum crystalline phase, can realize in the clinker mineral of entering fully of calcium sulfate composition in the fluorgypsum.
The recycling rate of red mud of the present invention is high.Red mud can not a large amount of uses in traditional portland be because the higher total alkali R of its content
2O (is Na
2O+K
2And alkali R O),
2O but influences less to aluminosulfate cement, can utilize high-alkali raw material or industrial residue to produce aluminosulfate cement.In addition, but the celite in the higher iron level direct production sulphoaluminate cement clinker in the red mud does not need to introduce other ferro-controlling raw materials again, realizes the maximum using of chemical composition in the red mud.
It is big that the present invention substitutes amount to natural mineral resource, can significantly reduce the consumption of natural mineral resource.Fluorgypsum substitutes plaster of paris raw mineral materials and reaches 100%, substitutes natural fluorite raw mineral materials and reaches 100%.Calcareous raw mineral materialss such as red mud replace lime stone reach 30 ~ 42%, and aluminium matter raw mineral materialss such as substitution of Al alumina reach 10 ~ 15%, substitute siliceous raw mineral materials more than 60%, substitute the iron mineral raw material and reach more than 90%.
Method chemical reactivity of the present invention is good, and the grog burn-ability is good.Fluorgypsum and red mud are high reactivity, the fine particle constituents that temperature is handled the back discharging in the process; Mineral composition percent crystallinity degree wherein is low, crystal grain is tiny, specific surface area is big, surface imperfection is many, activation energy is low; Reactive behavior is good in clinker burning, and speed of reaction is high, and the burn-ability of grog is good.
The present invention is energy efficient, reduction Carbon emission significantly.Cement industry is the high pollution industry of high energy consumption and high carbon dioxide discharging.Particle is thin, hardness is low, accumulation is loose because itself forms for main raw material red mud among the present invention and fluorgypsum, and grindability is good, can practice thrift the energy consumption of raw grinding.In addition; Red mud and fluorgypsum chemical reactivity are good, the good mineralization of Calcium Fluoride (Fluorspan) composition in the fluorgypsum; Can under minimum 1230 ℃ lesser temps, be prone to obtain the good grog of reaction, the firing temperature of grog reduces significantly, compares that the sulphoaluminate cement clinker firing temperature can reduce by 70 ℃ on the market; Compare Portland clinker and can reduce by 220 ℃, have obvious power savings advantages.And, contain the consumption that the quicklime composition can reduce the Wingdale mineral by a relatively large margin among the present invention in the red mud, reduce decomposition of limestone and produce the Carbon emission in the quicklime process.
A kind of method of utilizing fluorgypsum and red mud to prepare sulplo-aluminate special cement grog of the present invention the steps include:
1. choose each component raw material, wherein, the shared mass percent of each raw material is respectively: fluorgypsum 7 ~ 15%, red mud 32 ~ 42%, Wingdale 24 ~ 35%, all the other are bauxitic clay.
In this step; Directly utilize red mud and fluorgypsum to make raw material, the mass ratio of described red mud and fluorgypsum is 2:1 ~ 6:1, need not carry out any independent complicated technologies such as purifying treatment to each raw material; Greatly reduce the processing cost in early stage, help the comprehensive utilization in big quantification, short distance footpath.
Said fluorgypsum is the sub product that utilizes after the fluorite and the vitriol oil are produced hydrofluoric acid, and its chemical composition is respectively by mass percentage: CaO 32 ~ 45%, SO
340 ~ 58%, CaF
21.5 ~ 6.5%, all the other are unavoidable impurities; Preferably, described fluorgypsum is the sub product that utilizes after the fluorite and the vitriol oil are produced hydrofluoric acid, and for just going out the new discharging fluorgypsum of Reaktionsofen, its chemical composition is respectively by mass percentage: CaSO
480 ~ 95%, CaF
21.5 ~ 6.5%, H
2SO
4<2%, HF<0.06%, pH value is 1.6 ~ 4.0, and all the other are unavoidable impurities.
Described red mud is meant that mainly Bayer process, sintering process and mixed combining method technology extracts the red mud of alumina process discharging from bauxite, and its chemical composition is respectively by mass percentage: CaO20 ~ 40%; Al
2O
38 ~ 18%; SiO
210 ~ 25%; Fe
2O
310 ~ 25%; PH value is 10.0 ~ 13.5; R
2O 2.2 ~ 2.7%; Wherein R is K or Na.
2. with above-mentioned fluorgypsum and red mud uniform mixing, carry out neutralization reaction ageing mixture operation fully, the ageing mixture time is 7 ~ 15 days.
3. the material after the neutralization reaction ageing mixture operation is being dried more than 110 ℃.
4. the material after will drying is prepared burden with raw materials such as the Wingdale of choosing, bauxitic clays, grinding is mixed and made into raw material.
Described bauxitic clay, wherein Al
2O
3Mass percent is greater than 83%, R
2O is less than 0.4%, and MgO is less than 0.4%, Fe
2O
3Less than 2%, all the other are SiO
2The composition surplus; Wherein R is K or Na.
Described Wingdale, wherein the CaO mass percent is greater than 52%.
5. raw material are burnt till in rotary kiln or shaft kiln, said firing range is 1230 ~ 1280 ℃.
6. the material that burns till is promptly got grog through over-quenching, grinding.
Adopt certain company sintering process for alumina production process to discharge the fluorgypsum etc. that old red mud, certain company's Acid of Hydrofluoric Acid Production of stacking just gone out the new discharging of Reaktionsofen and be raw material; Through batching, uniform mixing; Ageing mixture 10 days; With batchings such as Wingdale, bauxitic clays, the process grinding is blended in the rotary kiln and burns till, and promptly gets quick hardening sulphoaluminate special cement grog behind chilling, the grinding after 150 ℃ of oven dry.
Embodiment 1:
The concrete batching add-on (mass percent) of extraordinary sulplo-aluminate special cement raw material: fluorgypsum 8%, red mud 36%, Wingdale 33%, bauxitic clay 23%, 1230 ~ 1280 ℃ of calcining temperatures.
Embodiment 2:
The concrete batching add-on (weight percent) of concrete extraordinary sulplo-aluminate special cement raw material: fluorgypsum 10%, red mud 38%, Wingdale 27%, bauxitic clay 25%, 1230 ~ 1280 ℃ of calcining temperatures.
Embodiment 3:
The concrete batching add-on (weight percent) of concrete extraordinary sulplo-aluminate special cement raw material: fluorgypsum 11%, red mud 39%, Wingdale 24%, bauxitic clay 26%, 1230 ~ 1280 ℃ of calcining temperatures.
Embodiment result: the grog that utilizes fluorgypsum, red mud to prepare the quick hardening sulphoaluminate special cement to the present invention carries out X ray powder crystal diffraction analysis (XRD); The essential mineral of finding grog is calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), celite; Diffraction peak is sharp-pointed, percent crystallinity is good; Free calcium oxide does not detect, and shows that the burn-ability of grog is good.Grog utilization scanning electron microscope (SEM) is observed, found the main mine phase calcium sulphoaluminate crystal grain shape or tabular that assumes diamond in shape, crystalline form is grown complete, about average grain size 1 μ m, shows that the essential mineral in the grog physically well develops.
The gained grog is allocated blended material such as gypsum into by " aluminosulfate cement: GB20472-2006 " national standard and is processed the quick hardening sulphoaluminate special cement, research grog hydrating capacity.The result shows that hydrated product is with tightly packed flaky low sulfur type aquation calcium sulphoaluminate, column and acicular ettringite, aluminium glue AH
3, the C-S-H isocolloid is main, interts each other, glued, reinforces and fine and close water mudrock structure, shown the mechanical characteristic of excellent high-early-strength, satisfies the performance requriements of " aluminosulfate cement: GB20472-2006 " middle quick hardening sulphoaluminate cement.Utilize the time of coagulation and the mechanical property of the quick hardening sulphoaluminate special cement of fluorgypsum, the outfit of preparing sulphate aluminium cement by red mud grog to see table 1 in the embodiment of the invention:
Table 1 fluorgypsum and red mud prepare sulplo-aluminate special cement time of coagulation and mechanical strength performance
Method of the present invention is harmful solid waste consumption big (red mud and fluorgypsum utilize total amount to reach 40 ~ 57%) not only, and flow process is simple, and energy efficient, and product economy is worth high, changes the line of production and realizes easily.This method products obtained therefrom is a sulplo-aluminate special cement grog; Prepared aluminosulfate cement belongs to early-strong-fast-hard type, low temperature resistant, acid and alkali-resistance erosive special cement; Be widely used in rush repair engineering such as aircraft runway, highway etc.; And winter construction engineering, underground works, seabed engineering etc., have higher economic value.This method need not change traditional cement production process, can in various cement kilns, produce, and changes the line of production and realizes easily.
Claims (10)
1. method of utilizing waste residue fluorgypsum and red mud to prepare sulplo-aluminate special cement grog, it is characterized in that: it may further comprise the steps:
A. by following ingredient composition, the shared mass percent of each raw material is respectively: fluorgypsum 7 ~ 15%, red mud 32 ~ 42%, Wingdale 24 ~ 35%, all the other are bauxitic clay;
B. with above-mentioned fluorgypsum and red mud uniform mixing, carry out neutralization reaction ageing mixture operation fully;
C. with the material after the neutralization reaction ageing mixture operation 110 ~ 150 ℃ of oven dry;
D. material and above-mentioned Wingdale, the bauxitic clay after will drying prepared burden, grinding is mixed and made into raw material;
E. raw material are calcined in rotary kiln or shaft kiln;
F. the material after burning till promptly gets grog through over-quenching, grinding.
2. method according to claim 1 is characterized in that: the mass ratio of described red mud and fluorgypsum is 2:1 ~ 6:1.
3. method according to claim 1 is characterized in that: said fluorgypsum is the sub product that utilizes after the fluorite and the vitriol oil are produced hydrofluoric acid, and its chemical composition is respectively by mass percentage: CaO32 ~ 45%; SO
340 ~ 58%; CaF
21.5 ~ 6.5%; All the other are unavoidable impurities.
4. method according to claim 3 is characterized in that: said fluorgypsum is the sub product that utilizes after the fluorite and the vitriol oil are produced hydrofluoric acid, and for just going out the new discharging fluorgypsum of Reaktionsofen, its chemical composition is respectively by mass percentage: CaO 32 ~ 45%; SO
340 ~ 58%; CaF
21.5 ~ 6.5%; H
2SO
4<2%; HF<0.05%; PH value is 1.6 ~ 4.0; All the other are unavoidable impurities.
5. method according to claim 1 is characterized in that: said red mud is to adopt Bayer process, sintering process or mixed combining method from bauxite, to extract the waste residue that discharges in the alumina process, and its chemical composition is respectively by mass percentage: CaO 20 ~ 40%; Al
2O
38 ~ 18%; SiO
210 ~ 25%; Fe
2O
310 ~ 25%; R
2O 2.2 ~ 2.7%; PH value is 10.0 ~ 13.5; Wherein R is K or Na.
6. method according to claim 1 is characterized in that: the chemical composition of said bauxitic clay is: Al
2O
3Mass percent is greater than 83%, R
2O is less than 0.4%, and MgO is less than 0.4%, Fe
2O
3Less than 2%, wherein R is K or Na.
7. method according to claim 1 is characterized in that: the CaO mass percent is greater than 52% in the said Wingdale.
8. method according to claim 1 is characterized in that: said calcining temperature is 1230 ~ 1280 ℃.
9. method according to claim 1 is characterized in that: in the said neutralization reaction ageing mixture operation, the ageing mixture time is 7 ~ 15 days.
10. sulplo-aluminate special cement grog that utilizes the preparation of waste residue fluorgypsum and red mud is characterized in that:
This cement clinker shared mass percent of each raw material in the preparation is respectively: fluorgypsum 7 ~ 15%, red mud 32 ~ 42%, Wingdale 24 ~ 35%, all the other are bauxitic clay;
This cement clinker adopts the following steps preparation:
1), carries out neutralization reaction ageing mixture operation fully with above-mentioned fluorgypsum and red mud uniform mixing;
2) with the material after the neutralization reaction ageing mixture operation 110 ~ 150 ℃ of oven dry;
3) material and above-mentioned Wingdale, the bauxitic clay after will drying prepared burden, grinding is mixed and made into raw material;
4) raw material are calcined in rotary kiln or shaft kiln;
5) material after burning till promptly gets grog through over-quenching, grinding.
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| CN104446050A (en) * | 2014-12-19 | 2015-03-25 | 青岛理工大学 | Sulphoaluminate cement taking petroleum coke desulfurization residues and red mud as raw materials |
| CN106698989A (en) * | 2016-12-29 | 2017-05-24 | 安徽华塑股份有限公司 | High temperature resistant cement |
| CN106698986A (en) * | 2016-12-27 | 2017-05-24 | 嘉华特种水泥股份有限公司 | Production method of sulfoaluminate cement clinker |
| CN108862206A (en) * | 2018-07-03 | 2018-11-23 | 贵州省贵福生态肥业有限公司 | The technique that a kind of ardealite and red mud prepare aluminium coproduction humic acid complex fertilizer |
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| CN103496862A (en) * | 2013-09-30 | 2014-01-08 | 河南铝镁耐材股份有限公司 | Calcium aluminate cement production method |
| CN103496862B (en) * | 2013-09-30 | 2015-05-06 | 河南铝镁耐材股份有限公司 | Calcium aluminate cement production method |
| CN104446050A (en) * | 2014-12-19 | 2015-03-25 | 青岛理工大学 | Sulphoaluminate cement taking petroleum coke desulfurization residues and red mud as raw materials |
| CN106698986A (en) * | 2016-12-27 | 2017-05-24 | 嘉华特种水泥股份有限公司 | Production method of sulfoaluminate cement clinker |
| CN106698986B (en) * | 2016-12-27 | 2018-10-23 | 嘉华特种水泥股份有限公司 | A kind of preparation method of sulphoaluminate cement clinker |
| CN106698989A (en) * | 2016-12-29 | 2017-05-24 | 安徽华塑股份有限公司 | High temperature resistant cement |
| CN108862206A (en) * | 2018-07-03 | 2018-11-23 | 贵州省贵福生态肥业有限公司 | The technique that a kind of ardealite and red mud prepare aluminium coproduction humic acid complex fertilizer |
| CN111252774A (en) * | 2020-01-19 | 2020-06-09 | 刘文治 | Method for producing silica sol by using desulfurized gypsum and fly ash through treating waste with waste |
| CN111646714A (en) * | 2020-05-08 | 2020-09-11 | 张延年 | Portland cement clinker and preparation method thereof |
| CN114014567A (en) * | 2021-11-22 | 2022-02-08 | 济南大学 | Method for directly preparing cement clinker from high-alkali red mud |
| CN114014567B (en) * | 2021-11-22 | 2023-01-24 | 济南大学 | Method for directly preparing cement clinker from high-alkali red mud |
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