CN102765893B - 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
- Publication number
- CN102765893B CN102765893B CN201210243405.9A CN201210243405A CN102765893B CN 102765893 B CN102765893 B CN 102765893B CN 201210243405 A CN201210243405 A CN 201210243405A CN 102765893 B CN102765893 B CN 102765893B
- Authority
- CN
- China
- Prior art keywords
- red mud
- fluorgypsum
- raw material
- cement
- waste residue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
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 cement preparing technical field, relate to the method for preparing quick hardening sulphoaluminate special cement grog taking fluorgypsum and red mud as main raw material.
Background technology
Fluorgypsum is with the byproduct after fluorite and strong sulfuric acid response preparing hydrogen fluoric acid, 1 ton of hydrofluoric acid of every production approximately produces 4 tons of fluorgypsums, China's annual emissions reaches millions of tons, is the third-largest industrial residue that contains gypsum resource in industry by-product gypsum except desulfurated plaster, phosphogypsum.Fluorgypsum main component is anhydrous calciumsulphate (II type calcium sulfate, also claims anhydrite), and purity is higher, between content 80～95%, and SO
3content is higher than natural dihydrate gypsum.But, just going out sulfuric acid or hydrogen fluoride and a small amount of Calcium Fluoride (Fluorspan) of normal residual some amount in the fluorgypsum of the new discharge of Reaktionsofen, pH value, in 2 left and right, belongs to the harmful solid waste that corrodibility is strong.Because fluorgypsum belongs to dehydrated gyp-, hydration reaction slowly, does not possess early strength, and its utilization is subject to serious restriction.Compare other kind industry by-product gypsum, fluorgypsum resource utilization development technique difficulty is larger, and comprehensive utilization quantity is very limited.Processing to fluorgypsum at present, is through lime neutralisation directly discharge after processing simply mostly, but still can causes great environmental pollution.Pass through physics, chemistry and modification again, changed into dihydrate gypsum for building, as compound blended material or the exciting agent of cement, but processing cost is higher.。Therefore, how according to fluorgypsum composition characteristic, the direct application of resource utilization is cheaply current Focal point and difficult point urgently to be resolved hurrily.The file such as China's " building materials industry " 12 " development program ", " large solid waste Comprehensive Utilization Scheme " and " the Ministry of Industry and Information Technology is about the instruction of industry by-product gypsum comprehensive utilization " explicitly calls for, and further add great development and promote industry by-product gypsum the technological approaches that substitutes plaster of paris resource.In various material of construction products, only have sulplo-aluminate special cement to have the call to gypsum resource, and owing to being at high temperature to react synthetic grog, break through the restriction of different crystal water content types to its utilization under the normal temperature of gypsum, can utilize more efficiently the main chemical compositions calcium sulfate in gypsum.In addition, in fluorgypsum, the Calcium Fluoride (Fluorspan) composition of trace can be used as sulphoaluminate cement clinker high temperature well behaved mineralizer when synthetic.
Chinese invention patent application No.201010205647 " a kind of fluorgypsum, phosphogypsum, copper mine tailing is prepared the method for sulphoaluminate cement clinker ", and Chen Jinmei has reported the some or all of method of fluorgypsum as sulphoaluminate cement clinker sulphur raw material of utilizing 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 discharge fluorgypsum that has just gone out Reaktionsofen, and all do not introduce other sulphoaluminate cement clinkers and need aluminium matter, the calcareous trade waste that waits, trade waste utilization is lower generally.
Red mud is to produce the fines strong basicity solid slag producing in 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 producing exceedes 3,000 ten thousand tons, and accumulation volume of cargo in storage reaches 200,000,000 tons.Along with the reduction gradually of increase year after year and the bauxite grade of China's aluminum oxide output, 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, both land occupations, and waste resource, easily causes again environmental pollution and potential safety hazard.Red mud comprehensive utilization still belongs to global problem, in the world red mud is mainly adopted to the disposal options of storing up earthing.China's red mud comprehensive utilization ratio is only 4% at present, mainly for the preparation of building brick, concrete admixture, the fixed material of roadbed etc.In China's " aluminium industry 12 development programs ", clearly propose, accelerate Key Common Technologies research and development, realize red mud science, efficiently utilize, give priority to red mud and produce building material product etc.Building material product is close and consumption is large with red mud in chemical composition, but the high alkalinity of red mud be its in a large number for the biggest obstacle of conventional silicate cement product, must process and could use through dealkalize etc., cause cost up, it is more difficult to promote.Compared with silicate cement, alkali is less on the impact of aluminosulfate cement.
Chinese invention patent ZL200610076718.4 " a kind of method of preparing sulphate aluminium cement by red mud ", disclose red mud and prepared the method for sulplo-aluminate special cement grog, but only utilize red mud, there is no other industrial solid castoff of comprehensive utilization in wider scope.
Aluminosulfate cement is as one of China's four large special cement kinds (white cement, low-heat cement for dam, aluminate cement and aluminosulfate cement), having the good characteristics such as early strong, high-strength, high impervious, high anti-freezing, anti-corrosion, low basicity, microdilatancy and low contraction, is the very important functional materials in field such as special engineered construction and common building underground works and winter construction in airstrip, high rail plate, harbour, road and bridge, harbour, dam, oil well, seabed.Aluminosulfate cement is different from other series cements and is characterised in that in grog preparation process taking gypsum as raw material in grog, to also have a large amount of calcium sulfoaluminate minerals.At 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 China's expanding economy, this series cement is more and more subject to the attention in market, has obtained application widely over 30 years.At present the annual production of China Sulfur aluminate cement is 1,500,000 tons of left and right, 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 special cement.But in sulplo-aluminate special cement production process, need the mineral wealth such as the plaster of paris, bauxitic clay, Wingdale, silica of high-quality, thereby cause its raw materials cost higher, the large-scale application in market is promoted and is restricted.
Summary of the invention
The object of this invention is to provide one and use industrial solid waste residue fluorgypsum and red mud directly as raw material simultaneously, prepare the method for quick hardening sulphoaluminate special cement grog.
For achieving the above object, the present invention adopts following technical scheme:
Utilize waste residue fluorgypsum and red mud to prepare a method for sulplo-aluminate special cement grog, it comprises the following 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. above-mentioned fluorgypsum and red mud are evenly mixed, carry out neutralization reaction ageing mixture operation fully;
C. by the material after neutralization reaction ageing mixture operation 110～150 DEG C of oven dry;
D. material and above-mentioned Wingdale, bauxitic clay after drying are 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 obtains grog through over-quenching, grinding.
Wherein, described red mud and the mass ratio of fluorgypsum are 2:1～6:1,
Described fluorgypsum is the byproduct utilizing after fluorite and vitriol oil preparing hydrogen fluoric acid, and its chemical composition is respectively by mass percentage: CaO32～45%; SO
340～58%; CaF
21.5～6.5%; All the other are inevitable impurity.
Described fluorgypsum is the byproduct utilizing after fluorite and vitriol oil preparing hydrogen fluoric acid, and for just going out the new discharge fluorgypsum of Reaktionsofen, its chemical composition is respectively by mass percentage: CaO32～45%; 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 inevitable impurity.
Described red mud is to adopt Bayer process, sintering process or mixed combining method from bauxite, to extract the waste residue discharging in alumina process, and its chemical composition is respectively by mass percentage: CaO20～40%; Al
2o
38～18%; SiO
210～25%; Fe
2o
310～25%; R
2o2.2～2.7%; PH value is 10.0～13.5; Wherein R is K or Na.
The chemical composition of described bauxitic clay is: Al
2o
3mass percent is greater than 83%, R
2o is less than 0.4%, MgO and is less than 0.4%, Fe
2o
3be less than 2%, wherein R is K or Na.
In described Wingdale, CaO mass percent is greater than 52%.
Described calcining temperature is 1230～1280 DEG C.
In described neutralization reaction ageing mixture operation, the ageing mixture time is 7～15 days.
A sulplo-aluminate special cement grog that utilizes waste residue fluorgypsum and red mud to prepare, the shared mass percent of the each in the preparation raw material of this cement clinker is respectively: fluorgypsum 7～15%, red mud 32～42%, Wingdale 24～35%, all the other are bauxitic clay;
This cement clinker adopts following steps preparation:
1) above-mentioned fluorgypsum and red mud are evenly mixed, carry out neutralization reaction ageing mixture operation fully;
2) by the material after neutralization reaction ageing mixture operation 110～150 DEG C of oven dry;
3) material and above-mentioned Wingdale, bauxitic clay after drying are prepared burden, grinding is mixed and made into raw material;
4) raw material are calcined in rotary kiln or shaft kiln;
5) the material after burning till obtains grog through over-quenching, grinding.
Beneficial effect of the present invention is: it has utilized acid waste residue fluorgypsum and high alkalinity waste red mud to combine the sulplo-aluminate special cement grog of preparing high added value for main raw material first, main raw material does not need through independent modification or purifying treatment, the gypsum that can directly replace in a large number reserves day by day to reduce, fluorite, bauxitic clay, Wingdale, the natural mineral resources such as silica, there is recycling rate high, reactive behavior is good, grog easily burns, the features such as firing temperature is low, and setting rate is fast, early strength is high, later strength increases stable, show good high-early-strength feature.The harm reason of falling that it is fluorgypsum as neutralizing agent that the method is used high alkalinity waste red mud first provides new method, for the comprehensive utilization of resources of fluorgypsum and red mud provides new way, also for the raw materials cost that significantly reduces sulplo-aluminate special cement grog provides thinking, environmental pollution, energy efficient, reduction Carbon emission are conducive to economize on resources, reduced, obvious economic benefit and environmental benefit there is.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
The present invention directly utilizes red mud and fluorgypsum to make raw material, does not need each raw material to carry out any independent complicated technology such as purification, modification, can reduce greatly processing cost in early stage, is conducive to the comprehensive utilization in large quantification, short distance footpath.Wherein, red mud is that high alkalinity waste residue can neutralize the acid waste residue fluorgypsum that has just gone out the new discharge of Reaktionsofen, and through the ageing mixture operation of abundant neutralization reaction, the hazardous property of two kinds of waste residues of reduction of maximizing, can avoid the corrosion to equipment simultaneously.And the acid fluorgypsum slag of the new discharge of red mud neutralizing treatment, is expected to replace and at present industrially utilizes lime neutralization to fall harmful method, realizes " treatment of wastes with processes of wastes against one another ", thinking novelty, reduces costs.The realization of this know-why, is must stack through ageing mixture after red mud and fluorgypsum mix, and carries out fully neutralization reaction.
In the present invention, in fluorgypsum, a small amount of Calcium Fluoride (Fluorspan) composition can be used as mineralizer good in grog sintering process, not only can reduce firing temperature, accelerate speed of reaction, and contribute to improve grog productive rate.Fluorite is the mineralizer that Cement industry is good, and its main component is exactly Calcium Fluoride (Fluorspan), but fluorite ore price rises is very fast in recent years.In fluorgypsum, just contain a small amount of Calcium Fluoride (Fluorspan), can be used as the alternative composition of fluorite, do not need additionally to add again, can realize the maximum using of fluorgypsum moiety.Fluorgypsum is difficult to utilize on a large scale in other side, be exactly mainly wherein to contain fluorine element, and the Calcium Fluoride (Fluorspan) that contains in the present invention fluorine element is Hubeiwan.
The present invention can farthest utilize the calcium sulfate in fluorgypsum, replaces the plaster of paris completely.With fluorgypsum compared with the application of the other sides such as retardant, 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 entering completely in clinker mineral of calcium sulfate composition in 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 total alkali Rs higher due to its content
2o(is Na
2o+K
2, and alkali R O)
2o but affects less on aluminosulfate cement, can utilize high-alkali raw material or industrial residue to produce aluminosulfate cement.In addition, in red mud, the higher iron level tetracalcium aluminoferrite in can direct production sulphoaluminate cement clinker, does not need to introduce other ferro-controlling raw materials again, realizes the maximum using of chemical composition in red mud.
It is large 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%.The calcareous raw mineral materialss such as red mud replace lime stone reach 30～42%, and the aluminium matter raw mineral materialss such as substitution of Al alumina reach 10～15%, substitute siliceous raw mineral materials more than 60%, substitute iron mineral raw material and reach more than 90%.
Method chemical reactivity of the present invention is good, and grog burn-ability is good.Fluorgypsum and red mud are high reactivity, the fine particle constituents discharging after heat-treated under medium temperature, mineral composition degree of crystallinity degree is wherein low, crystal grain is tiny, specific surface area is large, surface imperfection is many, activation energy is low, in clinker burning, reactive behavior is good, 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 discharge.Particle is thin, hardness is low, it is loose to pile up because itself forms for main raw material red mud in the present invention and fluorgypsum, and grindability is good, can save 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 fluorgypsum, can under the lesser temps of minimum 1230 DEG C, easily obtain the good grog of reaction, the firing temperature of grog reduces significantly, compare sulphoaluminate cement clinker firing temperature on market and can reduce by 70 DEG C, compare Portland clinker and can reduce by 220 DEG C, there is obvious power savings advantages.And, in the present invention, in red mud, contain calcium oxide composition and can reduce by a relatively large margin the consumption of Wingdale mineral, reduce decomposition of limestone and produce the Carbon emission in calcium oxide 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, described red mud and the mass ratio of fluorgypsum are 2:1～6:1, do not need each raw material to carry out the complicated technologies such as any independent purifying treatment, greatly reduce processing cost in early stage, be conducive to the comprehensive utilization in large quantification, short distance footpath.
Described fluorgypsum is the byproduct utilizing after fluorite and vitriol oil preparing hydrogen fluoric acid, and its chemical composition is respectively by mass percentage: CaO32～45%, SO
340～58%, CaF
21.5～6.5%, all the other are inevitable impurity; Preferably, described fluorgypsum is the byproduct utilizing after fluorite and vitriol oil preparing hydrogen fluoric acid, and for just going out the new discharge 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, all the other are inevitable impurity.
Described red mud, mainly refers to that Bayer process, sintering process and mixed combining method technique extracts the red mud of alumina process discharge 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
2o2.2～2.7%; Wherein R is K or Na.
2. above-mentioned fluorgypsum and red mud are evenly mixed, carry out neutralization reaction ageing mixture operation fully, the ageing mixture time is 7～15 days.
3. the material after neutralization reaction ageing mixture operation is dried more than 110 DEG C.
4. the material after drying is prepared burden with the raw material such as Wingdale, bauxitic clay chosen, 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%, MgO and is less than 0.4%, Fe
2o
3be less than 2%, all the other are SiO
2composition surplus; Wherein R is K or Na.
Described Wingdale, wherein CaO mass percent is greater than 52%.
5. raw material are burnt till in rotary kiln or shaft kiln, described firing range is 1230～1280 DEG C.
6. the material burning till is obtained to grog through over-quenching, grinding.
Adopting 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 discharge of Reaktionsofen is raw material, through batching, evenly mixing, ageing mixture 10 days, after 150 DEG C of oven dry with the batching such as Wingdale, bauxitic clay, be blended in rotary kiln and burn till through grinding, after chilling, grinding, obtain quick hardening sulphoaluminate special cement grog.
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 DEG C 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 DEG C 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 DEG C of calcining temperatures.
Embodiment result: the grog that utilizes fluorgypsum, red mud to prepare quick hardening sulphoaluminate special cement to the present invention carries out X ray X-ray powder diffraction analysis (XRD), the essential mineral of finding grog is calcium sulphoaluminate, Dicalcium Phosphate (Feed Grade), tetracalcium aluminoferrite, diffraction peak is sharp-pointed, degree of crystallinity is good, free calcium oxide does not detect, shows that the burn-ability of grog is good.Use scanning electron microscope (SEM) to observe to grog, find the main mine phase calcium sulphoaluminate crystal grain shape or tabular that assumes diamond in shape, crystalline form is grown complete, and average grain size 1 μ m left and right, shows that the essential mineral in grog physically well develops.
Gained grog is allocated the blended materials such as gypsum into and is made quick hardening sulphoaluminate special cement by " aluminosulfate cement: GB20472-2006 " national standard, research grog hydrating capacity.Result shows, hydrated product is with ettringite, the aluminium glue AH of low sulfur type hydrated calcium aluminate sulfate, column and the needle-like of tightly packed sheet
3, C-S-H isocolloid is main, mutually interts, cementing, reinforces and fine and close water mudrock structure, shown the mechanical characteristic of excellent high-early-strength, meets the performance requriements of " aluminosulfate cement: GB20472-2006 " middle quick hardening sulphoaluminate cement.In the embodiment of the present invention, utilize time of coagulation of the quick hardening sulphoaluminate special cement that fluorgypsum, preparing sulphate aluminium cement by red mud grog be equipped with and mechanical property in table 1:
Table 1 fluorgypsum and red mud are prepared sulplo-aluminate special cement time of coagulation and mechanical strength performance
Method of the present invention is harmful solid waste consumption large (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 easily realizes.The method products obtained therefrom is sulplo-aluminate special cement grog, the special cement that belong to prepared aluminosulfate cement early-strong-fast-hard type, low temperature resistant, acid and alkali-resistance corrode, be widely used in rush repair engineering as airstrip, highway etc., and winter construction engineering, underground works, seabed engineering etc., there is higher economic worth.The method does not need to change traditional cement production process, can in various cement kilns, produce, and changes the line of production and easily realizes.
Claims (8)
1. utilize waste residue fluorgypsum and red mud to prepare a method for sulplo-aluminate special cement grog, it is characterized in that: it comprises the following 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; Described fluorgypsum is the byproduct utilizing after fluorite and vitriol oil preparing hydrogen fluoric acid, and for just going out the new discharge fluorgypsum of Reaktionsofen, its chemical composition is respectively by mass percentage: CaO32～45%; SO
340～58%; CaF
21.5～6.5%; All the other are inevitable impurity; Described red mud is to adopt Bayer process, sintering process or mixed combining method from bauxite, to extract the waste residue discharging in alumina process, and its chemical composition is respectively by mass percentage: CaO20～40%; Al
2o
38～18%; SiO
210～25%; Fe
2o
310～25%; R
2o2.2～2.7%, each component concentration sum is 100%; PH value is 10.0～13.5; Wherein R is K or Na;
B. above-mentioned fluorgypsum and red mud are evenly mixed, carry out neutralization reaction ageing mixture operation fully;
C. by the material after neutralization reaction ageing mixture operation 110～150 DEG C of oven dry;
D. material and above-mentioned Wingdale, bauxitic clay after drying are 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 obtains grog through over-quenching, grinding.
2. method according to claim 1, is characterized in that: described red mud and the mass ratio of fluorgypsum are 3.8:1～6:1.
3. method according to claim 1, is characterized in that: the chemical composition of described fluorgypsum is respectively by mass percentage: CaO32～45%; 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 inevitable impurity.
4. method according to claim 1, is characterized in that: the chemical composition of described bauxitic clay is: Al
2o
3mass percent is greater than 83%, R
2o is less than 0.4%, MgO and is less than 0.4%, Fe
2o
3be less than 2%, wherein R is K or Na.
5. method according to claim 1, is characterized in that: in described Wingdale, CaO mass percent is greater than 52%.
6. method according to claim 1, is characterized in that: described calcining temperature is 1230～1280 DEG C.
7. method according to claim 1, is characterized in that: in described neutralization reaction ageing mixture operation, the ageing mixture time is 7～15 days.
8. a sulplo-aluminate special cement grog that utilizes waste residue fluorgypsum and red mud to prepare, is characterized in that:
The shared mass percent of the each in the preparation raw material of this cement clinker is respectively: fluorgypsum 7～15%, red mud 32～42%, Wingdale 24～35%, all the other are bauxitic clay; Described fluorgypsum is the byproduct utilizing after fluorite and vitriol oil preparing hydrogen fluoric acid, and for just going out the new discharge fluorgypsum of Reaktionsofen, its chemical composition is respectively by mass percentage: CaO32～45%; SO
340～58%; CaF
21.5～6.5%; All the other are inevitable impurity; Described red mud is to adopt Bayer process, sintering process or mixed combining method from bauxite, to extract the waste residue discharging in alumina process, and its chemical composition is respectively by mass percentage: CaO20～40%; Al
2o
38～18%; SiO
210～25%; Fe
2o
310～25%; R
2o2.2～2.7%, each component concentration sum is 100%; PH value is 10.0～13.5; Wherein R is K or Na;
This cement clinker adopts following steps preparation:
1) above-mentioned fluorgypsum and red mud are evenly mixed, carry out neutralization reaction ageing mixture operation fully;
2) by the material after neutralization reaction ageing mixture operation 110～150 DEG C of oven dry;
3) material and above-mentioned Wingdale, bauxitic clay after drying are prepared burden, grinding is mixed and made into raw material;
4) raw material are calcined in rotary kiln or shaft kiln;
5) the material after burning till obtains grog through over-quenching, grinding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210243405.9A CN102765893B (en) | 2012-07-13 | 2012-07-13 | Method for preparing sulphoaluminate special cement clinker from waste residue fluorine gypsum and red mud |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210243405.9A CN102765893B (en) | 2012-07-13 | 2012-07-13 | Method for preparing sulphoaluminate special cement clinker from waste residue fluorine gypsum and red mud |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102765893A CN102765893A (en) | 2012-11-07 |
| CN102765893B true CN102765893B (en) | 2014-07-23 |
Family
ID=47093506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210243405.9A Active CN102765893B (en) | 2012-07-13 | 2012-07-13 | Method for preparing sulphoaluminate special cement clinker from waste residue fluorine gypsum and red mud |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102765893B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114014567B (en) * | 2021-11-22 | 2023-01-24 | 济南大学 | Method for directly preparing cement clinker from high-alkali red mud |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432544A (en) * | 2003-02-20 | 2003-07-30 | 张振秋 | Sulphoaluminate cement clinker producing process with industrial waste |
| 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 |
| CN101857389A (en) * | 2010-06-22 | 2010-10-13 | 武汉理工大学 | Method for preparing sulphoaluminate cement clinker with fluorgypsum, phosphogypsum and copper tailings |
-
2012
- 2012-07-13 CN CN201210243405.9A patent/CN102765893B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432544A (en) * | 2003-02-20 | 2003-07-30 | 张振秋 | Sulphoaluminate cement clinker producing process with industrial waste |
| 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 |
| CN101857389A (en) * | 2010-06-22 | 2010-10-13 | 武汉理工大学 | Method for preparing sulphoaluminate cement clinker with fluorgypsum, phosphogypsum and copper tailings |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102765893A (en) | 2012-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102765893B (en) | Method for preparing sulphoaluminate special cement clinker from waste residue fluorine gypsum and red mud | |
| Lawrence | The production of low-energy cements | |
| CN100360451C (en) | Method for preparing sulphate aluminium cement by red mud | |
| CN103304170B (en) | Method for producing sulphate aluminum cement | |
| CN101367629B (en) | Manufacture of sulphur aluminate cements with electrolytic manganesium residue and method of manufacturing the same | |
| US8177903B2 (en) | Hydraulic binder with a base of sulfoaluminate clinker and portland clinker | |
| CA2817870C (en) | High performance sulfo-aluminous clinker | |
| CN100513341C (en) | Method for producing cement and vitriol from high silicon ardealite | |
| CN101891406B (en) | Method for preparing cement with red mud and desulfurized gypsum | |
| CN101913786B (en) | Method for preparing special cement by circulating fluidized bed combustion ash | |
| CN104788032A (en) | Belite cement and preparation method thereof | |
| CN109133684A (en) | A kind of high iron belite aluminate cement clinker and preparation method thereof | |
| MX2012014995A (en) | Method for producing a clinker for hydraulic cement with low co2 emission and high resistance. | |
| CN111393047A (en) | High-iron belite cement and preparation method thereof | |
| CN101885589A (en) | Compound sulfate cement | |
| KR20180014373A (en) | Calcium Sulfoaluminate-Based Clinker Composition Used Disposal Resources, Cement Composition Containing the Clinker Composition, and Method for Manufacturing the Cement Composition | |
| CN105502973A (en) | Calcium-poor and silicon-rich ecological cement and application thereof | |
| CN113354311A (en) | Resource-saving low-carbon cement clinker and preparation method thereof | |
| Seifu et al. | Effect of oyster shell powder addition on hydration of Portland cement-calcium sulfoaluminate cement-blast furnace slag or-metakaolin ternary cement | |
| KR100313709B1 (en) | Process for producing cement clinker using ironworks slag | |
| CN108585575B (en) | Cement retarder and preparation method and application thereof | |
| CN1092747A (en) | High-efficiency concrete expansion admixture and manufacture method thereof | |
| CN1733641A (en) | Silicate cement and its production method | |
| CN104129939B (en) | A kind of sulphate aluminium cement of modified ardealite preparation and preparation method thereof | |
| CN1696073A (en) | Method for producing sulfuric acid associated with high Belite cement through anhydrite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170111 Address after: 100081 Beijing city Haidian District Daliushu Village No. 19 South Institute of Technology Building 801-810 Patentee after: BEIJING IRON & STEEL RESEARCH XINZHI ENGINEERING TECHNOLOGY CENTER CO.,LTD. Address before: 100081 Haidian District Institute of South Road, Beijing, No. 76 Patentee before: China Iron & Steel Research Institute Group Patentee before: Xinye High Technology Group Co., Ltd. |