CN102745919A - Preparation method of tailing micropowder portland cement - Google Patents

Preparation method of tailing micropowder portland cement Download PDF

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Publication number
CN102745919A
CN102745919A CN2012102104928A CN201210210492A CN102745919A CN 102745919 A CN102745919 A CN 102745919A CN 2012102104928 A CN2012102104928 A CN 2012102104928A CN 201210210492 A CN201210210492 A CN 201210210492A CN 102745919 A CN102745919 A CN 102745919A
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cement
micro mist
mine tailing
grinding
micropowder
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李生钉
彭其雨
林生利
李生许
章国溪
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Fujian Province Xinchuang Huajian Technology Co Ltd
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Fujian Province Xinchuang Huajian Technology Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

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Abstract

A preparation method of tailing micropowder portland cement comprises the following steps of: (1) crude material crushing; (2) raw material preparation; (3) clinker sintering; (4) powder grinding; (5) packaging; wherein the step (4) of powder grinding comprises the following substeps: 1. grinding 95-97% of the clinker and 3-5% of gypsum together with an added cement grinding aid to obtain a clinker micropowder intermediate; 2. adding 0.2-0.5 per thousand kg of polycarboxylic acid-alcohol amine high polymer and 0-5% kg of gypsum into 1 kg of metal tailing slag, mixing, drying and grinding to obtain a tailing micropowder intermediate; 3. mixing and grinding 95-80% of the clinker micropowder intermediate and 5-20% of the tailing micropowder intermediate, or 60-80% of the clinker micropowder intermediate and 20-40% of the tailing micropowder intermediate, or 50-80% of the clinker micropowder intermediate, 15-45% of the tailing micropowder intermediate and 5% of slag powder to obtain various tailing micropowder portland cement. Through individual grinding and then mixing grinding, high fineness and high activity are realized; the potential activity of the tailing is aroused; and the rheological property of the cement is improved.

Description

A kind of preparation method of mine tailing micro mist silicate cement
Technical field:
The present invention relates to method for production of cement, each method of system of particularly a kind of mine tailing micro mist silicate cement.
Background technology:
Cement is as topmost building structural materials, and demand grows with each passing day.But the cement mill is well-known source of pollution, and non-renewable resource such as a large amount of Wingdale of manufacture of cement consumption, clay, coal is discharged number simultaneously in hundred million tons CO 2, SO 2And NO xIn waste gas and dust, problems such as the resource consumption of its production process, energy consumption and environmental pollution are very outstanding, and developing ecology cement and green cement are the directions that realizes the Cement industry Sustainable development.
Relating to silicate cement product and preparation method thereof in the existing public technology has: like patent of invention CN1213654A " with the composite Portland cement of industrial residue production "; Be to utilize industrial residue to produce composite Portland cement; Its raw material are pressed the high saturation ratio batching; The admixture weight percent adds operation through homogenizing, fragmentation, grinding etc. again and processes product greater than 30% the blended material of forming with phosphorus slag, phosphogypsum, flyash, Wingdale in the grog after calcining; Patent of invention CN1616372A " industrial tailings silicate cement " then discloses a kind of industrial tailings cement technology, and it is to carry out combined grinding to 80 μ m according to the cement clinker of certainweight proportioning, gypsum and the magnesia mine tailing of treated calcium to tail over≤3% process etc.
Tradition manufacture of cement basic technology is generally:
1, the fragmentation of cement raw material: in the cement production process, most of raw material will carry out fragmentation, like Wingdale.
2, cement slurry preparation: with the necessary raw material of manufacture of cement: be mixed into mill by certain mass than Wingdale (75-90%), clay (10-20%), various correction material (about 5%), process the raw material powder of certain fineness, accomplish raw material and prepare.The general independent grinding of coal becomes the coal dust of certain fineness, acts as a fuel.
3, burning till of cement clinker: raw material get into a series of solid state reaction take place in the kiln, accomplish burning till of grog:
4, cement grinding: (the existing general active mixed material that adopts has: slag, slag powders, flyash, calcareous addition of volcano with cement clinker+gypsum+blended material; Nonactive blended material has, and contains above active mixed material (it is as nonactive blended material that activity index is lower than standard), Wingdale, sandstone) go into mill, be milled to 80 microns square hole sieves and tail over and be not more than 10% or represent with specific surface area, be not less than 300m 2/ kg is cement flour.
5, cement packing: the cement packed and in bulk two kinds of shipping modes of having dispatched from the factory.
This type technological merit is to digest some trade wastes, produces the cement that meets certain needs.Its defective is: grog (mine tailing) is with other mineral mix grinding together; Owing to the finished particle coupling un-reasonable phenomenon that the difference of grindability degree causes is outstanding; Do not reach and excite and transfer various material potential chemistry and physical action function, used mine tailing is confined to the magnesia mine tailing of calcium basically.
Summary of the invention:
The objective of the invention is to overcome above-mentioned defective, a kind of preparation method of mine tailing micro mist silicate cement is provided.
Scheme of the present invention is: comprise the fragmentation of step (1) cement raw material; (2) cement slurry preparation; (3) burning till of cement clinker: (4) cement grinding; (5) cement packing; It is characterized in that: step (4) cement grinding each be step by step: 1. by weight percentage; Cement clinker 95-97%, gypsum 3-5%, wherein the gypsum addition content is no more than 3.5% weight ratio with sulfur trioxide content in the fine powder of cement clinker and exceeds; Mix outward account for cement clinker and gypsum total amount and the 0.02-0.05% cement grinding aid; Go into the ball mill grinding, finish fineness is controlled at 80 microns and tails over≤and 2%, promptly get grog micro mist intermediate product;
2. according to weight percent meter, promptly the metal tailings slag of 1kg adds the poly carboxylic acid one hydramine type high molecular polymer of 0.2-0.5 ‰ kg, gypsum addition content 0 one 5%kg, and uniform mixing is after the oven dry grinding becomes specific surface area is 800-400m 2The fine powder of/kg; Wherein the gypsum addition content is no more than 3.5% weight ratio with sulfur trioxide content in the finished product active mixed material and exceeds; Metal tailings is that calcium is magnesia, any type in the high-silicon type, alumina-silica type, the siliceous type of iron, alkali alumina-silica type, calcium alumina-silica type, multiple composition shaped metal mine tailing, metal tailings loss on ignition≤10%, sulfur trioxide content≤3%.Promptly get mine tailing micro mist intermediate product;
3. by percentage to the quality, method for preparing gained grog micro mist intermediate product 95-80%, mine tailing micro mist intermediate product 5-20%, combined grinding to specific surface area is that 800-400m/kg promptly gets mine tailing micro mist ordinary Portland cement;
Or by percentage to the quality, method for preparing gained grog micro mist intermediate product 60-80%, mine tailing micro mist intermediate product 20-40%, the combined grinding specific surface area is 800-400m 2/ kg promptly gets mine tailing micro mist Portland pozzolana cement;
Or by percentage to the quality, method for preparing gained grog micro mist intermediate product 50-80%, mine tailing micro mist intermediate product 15-45%, slag powders 5%, combined grinding specific surface area are 800-400m 2/ kg promptly gets mine tailing micro mist composite Portland cement.
The invention has the advantages that: independent mix grinding again behind the grinding, under the gelling of high fineness and high reactivity chamotte powder, excitation, can transfer the lateral reactivity of mine tailing better; On the other hand, ultra-fine mine tailing micro mist has vitreous state gelling material speciality, has good shape effect and micro aggregate effect.The flucculation structure of grog micro powder granule is opened, significantly improved the rheological of mine tailing micro mist silicate cement.
Embodiment:
As stated
1, mine tailing loss on ignition≤10%, sulphur trioxide≤3%; The mine tailing radioactive indicator meets GB6566-2010 standard-required (the radioactive material nucleic is limited the quantity of); Leaching toxicity each item index of mine tailing (removing pH) meets the leach liquor harm constituent concentration limit value among the GB5085.3-2007 " the Hazardous wastes judging standard leaches toxicity and differentiates "; PH meets the standard limited value among the GB5085.1-2007 " discriminating of Hazardous wastes judging standard corrodibility ".
2. slag (slag) powder is by GB/T18046-2008 " GBFS that is used for cement and concrete " standard-required.
The mine tailing micro mist silicate cement mine tailing micro mist mechanism of action of the present invention:
One, the lateral reactivity component that fully excites mine tailing and contained through physical excitation and chemi-excitation.
Two. through grinding with mine tailing micro mist specific surface area control>=400m 2/ kg reaches physical excitation.
Theoretical according to mechanical activation, grinding can significantly improve the lateral reactivity of metal tailings.
Mine tailing becomes in the fine powder process through grinding, and the part external energy is converted into mine tailing particulate surface energy, makes its surface present metastable state, has increased surperficial reactive behavior.Along with the mine tailing grain diameter reduces, specific surface area increases, as mine tailing micro mist specific surface area>=400m 2During/kg; The intensive grinding process makes the generation lattice distortion in various degree of mine tailing particle, brilliant material size decreases, and the surface forms unformed or amorphous substance; Its " shape effect " and " micro aggregate effect " are not fully exerted, thereby have increased the quantity of mine tailing reactive group.
2, through adding poly carboxylic acid-hydramine type high molecular polymer, rely on the effect of its surfactivity ability and functional group, change the physicochemical property on the mine tailing micro powder granule interface, realize the mine tailing superfine pulverizing as the special-purpose exciting agent of mine tailing.The mutual coordinative role of anionic functional group in functional group and the macromolecular structure, the SiO in the mine tailing 2Crystal with contain Al 2O 3Mineral obtain better solubility, the potential reactive components that mine tailing contained obtains exciting more greatly, the Ca (HO) that these components can be separated out with hydrated cementitious 2Or CaSO 4Reaction generates the stable compound with gelating property.
Two, mine tailing micro mist cement is in process of setting, and the active ingredient that mine tailing provides has been participated in cement hydration process, and Portland clinker mineral aquation generated hydrated calcium silicate CaSiO2.nH before this 2O (C-S-H), drated calcium aluminate CaAl 2O 4.nH 2O (C-A-H) and calcium hydroxide Ca (OH) 2Deng.Second step was active ingredient and the effect of above-mentioned aquation resultant in the mine tailing micro mist.Along with the prolongation of hydration time, mine tailing lateral reactivity component and the reaction of grog resultant are more abundant.The mine tailing active ingredient has been participated in the secondary reaction in the hydrated cementitious, generates the lower hydrated calcium silicate of solubleness, drated calcium aluminate etc.Its particle is that matrix can form crystal adhesion structure, helps improving water mudrock structure and endurance quality.Strength of cement obtains bigger performance, and the cement later strength is higher.Its reaction formula is following;
Ca(OH) 2+SiO 2+nH 2O→C-S-H (1)
C-S-H+SiO 2+nH 2O→C-S-H (2)
3CaO.Al 2O 3，6H 2O+xSiO 2→3CaO.Al 2O 3.xSiO 2(6-2x)H 2O+2xH 2O (3)
Embodiment one
Mine tailing micro mist silicate cement provided by the invention, preparation mine tailing micro mist normal silicate 52.5 cement:
By percentage to the quality, grog micro mist 95%, mine tailing micro mist 5%, combined grinding promptly gets.
Proof test is cartogram 1 as a result
Embodiment two
Mine tailing micro mist silicate cement provided by the invention, preparation mine tailing micro mist normal silicate 42.5 cement; By percentage to the quality, grog micro mist 85%, mine tailing micro mist 15%, combined grinding promptly gets.
Proof test is cartogram 2 as a result
Figure DEST_PATH_GSB00000898662100062
Embodiment three
Mine tailing micro mist silicate cement provided by the invention, preparation mine tailing micro mist volcano grey matter silicate 32.5R cement:
By percentage to the quality, grog micro mist 70%, mine tailing micro mist 30%, combined grinding promptly gets.
Proof test is cartogram 3 as a result
Figure DEST_PATH_GSB00000898662100071
Embodiment four
Mine tailing micro mist silicate cement provided by the invention, preparation mine tailing micro mist composition silicate 12.5R cement:
By percentage to the quality, grog micro mist 75%, mine tailing micro mist volume 20%, slag micropowder 5%, combined grinding promptly gets.
Proof test is cartogram 4 as a result
Figure DEST_PATH_GSB00000898662100081
Embodiment five
Mine tailing micro mist silicate cement provided by the invention, preparation mine tailing micro mist composition silicate 32.5 cement: by percentage to the quality, and grog micro mist 55%, mine tailing micro mist volume 40%, slag micropowder 5%, combined grinding promptly gets.
Proof test is cartogram 5 as a result
Figure DEST_PATH_GSB00000898662100082
Conclusion:
Implement to produce in the checking; By percentage to the quality, the mine tailing accounting is when the 5-20% scope, and each the kind strength of cement variation of said mine tailing micro mist silicate shows as: by percentage to the quality; Mine tailing is in the 5-10% scope, and mine tailing micro mist silicate cement is slightly higher than grog micro mist 28d intensity; Mine tailing is in the 10-25% scope, and along with increasing progressively of mine tailing mass percent, mine tailing micro mist silicate cement presents the situation of steadily successively decreasing than grog micro mist 28d intensity; Mine tailing is in the 25-50% scope, and along with increasing progressively of mine tailing mass percent, mine tailing micro mist silicate cement appears than grog micro mist 28d intensity and adds quick depletion situation.Proof test result shows, by percentage to the quality, in the mine tailing micro mist accounting 5-45% scope, can produce the cement that satisfies GB175-2007 " general purpose portland cement " P.C32.5 to P.O52.5 equal strength grade.Cement performance indexs such as the stability of mine tailing micro mist silicate cement, time of coagulation all meet the requirement of GB175-2007 " general purpose portland cement ".
The positively effect that the present invention's innovation is produced is:
1, product mine tailing micro mist silicate cement of the present invention has enriched the silicate cement kind.
2, adopt " little abrading-ball effect ", through mix grinding again behind the independent grinding, mine tailing and grog micro mist " shape effect " and " micro aggregate effect " are not fully exerted.Under the gelling of high fineness and high reactivity chamotte powder, excitation, can transfer the lateral reactivity of mine tailing better; On the other hand; The mine tailing micro mist is as the vitreous state gelling material; Have good shape effect, the flucculation structure of grog micro powder granule is opened, significantly improved the rheological of mine tailing micro mist silicate cement; And the glass microballon top layer that the mine tailing micro mist is included meeting cross connection in hydration process, growth has play a part important to strength of cement.Therefore; The physical and mechanical property of mine tailing micro mist silicate cement is superior to ordinary Portland cement; The consumptive use of water normal consistence of clean slurry is lower than ordinary Portland cement, and hydration heat is than the low 30-50% of other silicate cements, and advantage such as have a water resisting property, porosity is low, pore structure is good.

Claims (1)

1. the preparation method of a mine tailing micro mist silicate cement comprises the fragmentation of step (1) cement raw material; (2) cement slurry preparation; (3) cement clinker burns till; (4) cement grinding; (5) cement packing is characterized in that: step (4) cement grinding each be step by step: 1. by weight percentage, and cement clinker 95-97%; Gypsum 3-5%; Wherein the gypsum addition content is no more than 3.5% weight ratio with sulfur trioxide content in the fine powder of cement clinker and exceeds, mix outward account for cement clinker and gypsum total amount and the 0.02-0.05% cement grinding aid, go into the ball mill grinding; Finish fineness is controlled at 80 microns and tails over≤and 2%, promptly get grog micro mist intermediate product;
2. according to weight percent meter, promptly the metal tailings slag of 1kg adds poly carboxylic acid-hydramine type high molecular polymer of 0.2-0.5 ‰ kg, gypsum addition content 0-5%kg, and uniform mixing is after the oven dry grinding becomes specific surface area is 800-400m 2The fine powder of/kg; Wherein the gypsum addition content is no more than 3.5% weight ratio with sulfur trioxide content in the finished product active mixed material and exceeds; Metal tailings is that calcium is magnesia, any type in the high-silicon type, alumina-silica type, the siliceous type of iron, alkali alumina-silica type, calcium alumina-silica type, multiple composition shaped metal mine tailing, metal tailings loss on ignition≤10%, sulfur trioxide content≤3%.Promptly get mine tailing micro mist intermediate product;
3. by percentage to the quality, method for preparing gained grog micro mist intermediate product 95-80%, mine tailing micro mist intermediate product 5-20%, combined grinding to specific surface area is 800-400m 2/ kg promptly gets mine tailing micro mist ordinary Portland cement;
Or by percentage to the quality, method for preparing gained grog micro mist intermediate product 60-80%, mine tailing micro mist intermediate product 20-40%, the combined grinding specific surface area is 800-400m 2/ kg promptly gets mine tailing micro mist Portland pozzolana cement;
Or by percentage to the quality, method for preparing gained grog micro mist intermediate product 50-80%, mine tailing micro mist intermediate product 15-45%, slag powders 5%, combined grinding specific surface area are 800-400m 2/ kg promptly gets mine tailing micro mist composite Portland cement.
CN2012102104928A 2012-06-18 2012-06-18 Preparation method of tailing micropowder portland cement Pending CN102745919A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104261714A (en) * 2014-09-12 2015-01-07 中节能六合天融环保科技有限公司 Method for preparing tailing ultrafine powder by compounding many kinds of metal tailings
CN104402279A (en) * 2014-10-24 2015-03-11 中节能六合天融环保科技有限公司 Preparation technology of tailing ultrafine powder used in cement mixture and concrete admixture
CN110746132A (en) * 2019-10-29 2020-02-04 汉阴县天元工业废渣科技开发有限公司 Method for producing superfine cement by ball mill serial milling
CN115893898A (en) * 2022-11-25 2023-04-04 厦门兑泰新材料科技有限公司 Composite admixture of metal tailings and granulated blast furnace slag and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1213654A (en) * 1998-10-01 1999-04-14 四川省绵竹市齐福水泥厂 Prodn. of composite portland cement by utilizing industrial waste residue
CN1594173A (en) * 2004-07-05 2005-03-16 南京师范大学 Alkali resistant aggregate reaction cement added with composite industrial residue and its firing method
CN1616372A (en) * 2003-11-11 2005-05-18 夏根华 Portland cement of industrial tailing
CN101844882A (en) * 2010-05-14 2010-09-29 武汉理工大学 Composite portland cement and preparation method thereof
CN101955330A (en) * 2010-09-15 2011-01-26 福建省新创化建科技有限公司 Polycarboxylic acid-alcohol amine type high-molecular grinding aid and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1213654A (en) * 1998-10-01 1999-04-14 四川省绵竹市齐福水泥厂 Prodn. of composite portland cement by utilizing industrial waste residue
CN1616372A (en) * 2003-11-11 2005-05-18 夏根华 Portland cement of industrial tailing
CN1594173A (en) * 2004-07-05 2005-03-16 南京师范大学 Alkali resistant aggregate reaction cement added with composite industrial residue and its firing method
CN101844882A (en) * 2010-05-14 2010-09-29 武汉理工大学 Composite portland cement and preparation method thereof
CN101955330A (en) * 2010-09-15 2011-01-26 福建省新创化建科技有限公司 Polycarboxylic acid-alcohol amine type high-molecular grinding aid and preparation method thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104261714A (en) * 2014-09-12 2015-01-07 中节能六合天融环保科技有限公司 Method for preparing tailing ultrafine powder by compounding many kinds of metal tailings
CN104402279A (en) * 2014-10-24 2015-03-11 中节能六合天融环保科技有限公司 Preparation technology of tailing ultrafine powder used in cement mixture and concrete admixture
CN110746132A (en) * 2019-10-29 2020-02-04 汉阴县天元工业废渣科技开发有限公司 Method for producing superfine cement by ball mill serial milling
CN115893898A (en) * 2022-11-25 2023-04-04 厦门兑泰新材料科技有限公司 Composite admixture of metal tailings and granulated blast furnace slag and preparation method thereof

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Application publication date: 20121024