CN101439938A - Processing method for manufacturing rapid hardening ferrous aluminate cement from red mud - Google Patents

Processing method for manufacturing rapid hardening ferrous aluminate cement from red mud Download PDF

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Publication number
CN101439938A
CN101439938A CNA2008102333598A CN200810233359A CN101439938A CN 101439938 A CN101439938 A CN 101439938A CN A2008102333598 A CNA2008102333598 A CN A2008102333598A CN 200810233359 A CN200810233359 A CN 200810233359A CN 101439938 A CN101439938 A CN 101439938A
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red mud
cement
aluminate cement
ferrous aluminate
hardening ferrous
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夏杰
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CHONGQING BOSAI MINERALS (GROUP) Co Ltd
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CHONGQING BOSAI MINERALS (GROUP) Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/26—Corrosion of reinforcement resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/29—Frost-thaw resistance
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a method for processing fast hardening ferrous aluminate cement made of red mud. The method comprises: A, processing the red mud, namely drying and grinding the red mud and filtering the red mud by a 100-mesh sieve; B, calculating ingredients in a formula of raw materials by designing compositions of main minerals of clinker aggregate including C2S, C4A3S and C4AF; C, weighing the raw materials by weight percentage: 40 to 55 percent of the red mud, 20 to 30 percent of limestone, 1.5 to 3 percent of ferrous powder, 20 to 30 percent of aluminum ores and 1 to 5 percent of gypsum; D, mixing and calcining, namely mixing and uniformly grinding the ingredients, wherein the calcining temperature is between 1,250 and 1,350 DEG C; and E. preparing different types of fast hardening ferrous aluminate cement. The fast hardening ferrous aluminate cement has the advantages that the fast hardening ferrous aluminate cement has high early strength, good frost resistance, corrosion resistance and high impermeability, is suitable for cold weather construction engineering, salvaging, preparation of shotcrete, production of prefabricated members and so on, makes up for the technical blank of producing the fast hardening ferrous aluminate cement by utilization of the red mud, and creates larger social benefit and economic benefit.

Description

A kind of processing method for manufacturing rapid hardening ferrous aluminate cement from red mud
Technical field the present invention relates to the chemical field of cement material processing, relates in particular to a kind of waste that utilizes in the alumina producing---the working method of manufacturing rapid hardening ferrous aluminate cement from red mud.
The background technology special cement can be divided into six big series product usually, and they are: silicate cement series (except that general cement), aluminate cement series, aluminosulfate cement series, ferro-aluminate cement series, fluoroaluminate cement series, other (comprising no grog, few grog) cement series.At present China yields poorly the special cement production year, only accounts for below 2% of national cement total output, with the industrial scale of developed country 7%～9% suitable gap is arranged.Unreasonable products structure, decoration cement and expansion self-stressed cement proportion are about the same, and oil well cement and hydraulic engineering cement ratio are on the low side, the quick-hardening hih-strength cement critical shortage.Technical equipment, production technique fall behind.
The industry that produces in alumina producing is harmful to the waste residue red mud, and present treatment process all is to be put into red mud dump, has so not only taken land resources, but also has caused environmental pollution.Both at home and abroad the post-treating method of red mud is all paid much attention to, classify this as important difficult problem that aluminium industry is striven needs solution, existing 200610076718.4 disclosed " a kind of method of preparing sulphate aluminium cement by red mud; " it utilizes red mud to prepare sulplo-aluminate equally, because processing condition, technology difficulty but can't prepare fast hardening ferrous aluminate salt cement, develop bigger utilization and economic worth.
Summary of the invention the objective of the invention is in the red mud at alumina producing, because each components in proportions is very near the ratio of ferro-aluminate cement, only need to increase a part of additive and regulate proportioning, just meet the production of ferro-aluminate cement, so not only solved the stacking problem of red mud in the alumina producing, and the ferro-aluminate cement of producing also is to have created new benefit.
For achieving the above object, the present invention adopts following technical scheme:
A kind of processing method for manufacturing rapid hardening ferrous aluminate cement from red mud may further comprise the steps:
A, processing red mud: 100～110 ℃ of oven dry, make red mud Han Shui Liang ≦ 1%, the ball mill grinding is crossed 100 mesh sieves;
B, composition of raw materials are by design grog essential mineral C 2S, C 4A 3S, C 4The composition of AF calculates batching, and the grog essential mineral is C by weight percentage 2S:25～40%; C 4A 3S:30～45%; C 4AF:10～25%;
C, be main raw material with aluminum oxide industry waste red mud, owing to itself contain a large amount of Fe in red mud and the bauxite 2O 3, SiO 2, Al 2O 3, clay, sandstone only add as additive, press the raw material that takes by weighing of column weight amount per-cent:
Red mud 40～55%; Wingdale 20～30%; Iron powder 1.5～3%; Aluminium ore 20～30%; Gypsum 1～5%;
D, batch mixing, calcining: with the batch mixes among the step C, ball milling is even, and calcination temperature is 1250 ℃～1350 ℃;
E, preparation cement: calcination of chamotte below grinding to 200 order, adds Wingdale and gypsum once more again, with preparation different types of fast hardening ferrous aluminate cement.
Preferably, the CaO content requirement of described Wingdale is greater than 48%; Described MgO content is below 1.5%.
Preferably, in cement pulverizing course, the Wingdale volume is no more than 50%, and gypsum addition is less than 5%; The specific surface area of fast hardening ferrous aluminate salt cement should be controlled at more than the 350m2/kg, is generally the scope of 350～400m2/kg.
The present invention is by experiment repeatedly, the fast hardening ferrous aluminate salt cement that affirmation manufactures by aforesaid method meets building material industry standard JC 435-1991 regulations: with the raw material of proper composition, through the calcining iron phase that is able to, ca aluminosilicate and Calucium Silicate powder is the grog of essential mineral, add an amount of Wingdale and gypsum, the hydraulic cementing materials that the levigate early strength of making is high is fast hard iron aluminate cement.This cement is represented with 3d ultimate compression strength, is divided into 425,525 two labels.
1. the technical requirements of fast hard iron aluminate cement
Specific surface area, time of coagulation, free calcium oxide content should accord with the regulation of following table.
Figure A200810233359D00051
Each age strength requirement index of fast hard iron aluminate cement must not be lower than the numerical value in the following table.
Figure A200810233359D00052
The mineral composition and the strength of cement rule of development of the fast hard iron aluminate cement grog of typical case.
2. the production technique of fast hard iron aluminate cement
2.1 the main chemical compositions of the chemical ingredients of grog and mineral composition grog is CaO, Al 2O 3, Fe 2O 3, SiO 2, SO 3, essential mineral is C 4A 3S (silicoaluminate four calcium), β-C 2S (Dicalcium Phosphate (Feed Grade)), C 4AF (tetracalcium aluminoferrite).Its component content scope sees the following form.
Title Al 2O 3 SiO 2 CaO Fe 2O 3 SO 3 C 4A 3S C 2S C 4AF
Content/% 5～30 6～12 43～46 5～12 1～6 35～55 15～35 15～30
2.2 raw material, fuel
Fast hard iron aluminate cement batching adopts the component batching: Wingdale, red mud from sintering process and Bayer process red mud, iron powder, bauxite, clay, sandstone.Owing to itself contain a large amount of Fe203, SiO2, Al in red mud and the bauxite 2O 3So iron powder, clay, sandstone only add as additive, the amount of adding is decided on the concrete composition in the red mud, and Wingdale mainly is the add-on of regulating CaO, and the CaO content requirement of Wingdale is greater than 48%, and MgO content is below 1.5%; The red mud composition sees the following form.It is 25%～32% that selected bunker coal should be controlled its volatile matter V, ash content A≤25%, calorific value Q 〉=27200kJ/kg.
2.3 calcining
The calciner of fast hard iron aluminate cement grog is a shaft kiln.Firing temperature is generally 1250 ℃～1350 ℃, than low 100 ℃～150 ℃ of silicate cement calcining temperature.Color of clinker is similar to silicate cement, is black, and different with gray sulphoaluminate cement clinker.
2.4 grinding
In cement pulverizing course, the Wingdale volume is no more than 50%, and gypsum addition is generally 5%; Specific surface area should be controlled at more than the 350m2/kg, is generally the scope of 350～400m2/kg.
The beneficial effect of a kind of processing method for manufacturing rapid hardening ferrous aluminate cement from red mud of the present invention is, the fast hardening ferrous aluminate salt cement early strengthening and high strengthening of being produced, frost resistance is good, corrosion resisting property is good, has the high permeability resistant energy, be suitable for winter construction engineering, salvaging, preparation sprayed concrete and produce prefabricated components etc., remedied and utilized red mud can produce the blank of fast this technology of hardening ferrous aluminate salt cement, created bigger social benefit and economic worth.
The present invention is further illustrated below the embodiment:
Charge calculation:
1. the specification of quality of raw material
1.1 the red mud composition of our factory:
Material name Al 2O 3 SiO 2 CaO Fe 2O 3 Na 2O
Sintering red mud content 10-20 10-25 40-50 4-8 1-4
Bayer process red mud content 15-30 15-25 20-30 4-10 2-6
1.2 calcareous raw material
All is that the raw material of principal constituent all is calcareous raw material with lime carbonate, as Wingdale, chalk, muddy limestone, inner casing etc., is the main source of calcium oxide in the cement clinker since in red mud existing a large amount of CaO, Wingdale adds and only plays a corrective action, few as far as possible using.
Grade CaO MgO R 2O SO 3 Cl- Flint or quartz
First grade >48 <2.5 <1.0 <1.0 <0.015 <4.0
Seconds 45—48 <3.0 <1.0 <1.0 <0.015 <4.0
1.3 siliceous raw material
The main component SiO of siliceous raw material 2, secondly be Al 2O 3, also have Fe 2O 3, generally produce the 1t grog and need 0.2-0.4t siliceous raw material approximately, in grog, account for 11-17%
Grade Silicate ratio n Aluminium-oxygen modulus p MgO(％) R 2O(％) SO 3(％)
First grade 2.7—3.5 1.5—3.5 <3.0 <4.0 <2.0
Seconds 2.0-2.7 3.5-4.0 Do not limit <3.0 <4.0 <2.0
1.4 other correction material
Have only Wingdale and clayey raw material often can not satisfy the requirement of grog in the production,, often select irony for use, the correction material of siliceous and aluminium matter for remedying the deficiency of composition to chemical ingredients
Figure A200810233359D00081
2. quality of fuel requirement
I am public owing to use bituminous coal, and composition is probably formulated as follows:
Car(％) Var(％) Aar(％) Mar(％) Har(％) 0ar(％) Nar(％) Sar(％)
63.5 14.29 25.5 3.2 0.9 2.9 0.69 0.51
3. the selection of heat consumption of clinker
It is relevant with the calcining whole process that grog burns till hear rate Q (kg/kg grog), except relating to crude fuel character, also relevant with the waste gas heat retrieving arrangement, also relevant with grog heat recovering device (each cooler) etc., technical progress along with dry method nsp kiln firing system tooling, impel hear rate progressively to drop to below 2970KJ/kg advanced person's reached at the 2900KJ/kg from early stage 3765KJ/kg, our factory controls to 3094KJ/kg.
4. Pei Liao calculating
The composition title loss SiO 2 Al 2O 3 Fe 2O 3 CaO MgO K 2O Na 2O Total amount
Wingdale 41.31 5.17 0.83 0.33 50.74 0.8 0 0 99.18
Red mud 24 16.2 10.1 5.35 42.87 0.73 0 0.75 100
Aluminium ore 35 7.3 52.15 4.12 0 0.46 0 0 99.03
Powdered iron ore 14.16 19.14 8.92 51.51 3.38 2.5 0 0 99.61
Ash content of coal 0 56.8 21.53 11.84 3.38 1.88 0 0 95.43
4.1 at according to the characteristics of red mud composition and the content requirement of grog itself, setting rate value KH=0.082+0.01, n=0.52+0.1, p=3.7+0.1
4.2 calculate by the grog rate value of setting
If chemical ingredients ∑=98% of grog
Calculating all data of raw-meal ingredient with try and error method below finishes in EXCEL
Fe 2 O 3 = &Sigma; ( 2.8 KH + 1 ) ( p + 1 ) n + 2.65 P + 1.35 = 6.92 %
Al 2O 3＝p×Fe 2O 3＝25.61％
SiO 2＝n(Al 2O 3+Fe 2O 3)＝16.91％
CaO＝∑-Fe 2O 3-Al 2O 3-SiO 2＝48.56％
Be Microsoft Excel below, set the q=3094KJ/kg grog
Figure A200810233359D0009091926QIETU
Can calculate by top form:
Composition Wingdale Red mud Iron powder Aluminium ore
Ratio 26.51335 47.5325 2.131973 23.82217
△KH＝|0.8252-0.82|＝0.005<0.01
△n＝|0.522-0.52|＝0.002<0.01
△p＝|3.6901-3.7|＝0.0099<0.01
Calculate as can be seen with more surely closing of setting.
5. the coiled of grog
After preparing raw material, firing temperature is generally 1250 ℃～1350 ℃, than low 100 ℃～150 ℃ of silicate cement calcining temperature.Grog mainly forms by solid state reaction, need not specially to hang kliner coating during calcining.
The mineral composition of grog can be used assays such as petrographic analysis, X ray and infrared spectra behind sintering, and the grog composition calculates with chemical ingredients in industrial and mining enterprises at present, gets f-CaO=0.8 by f-CaO＜1, and it is as follows to obtain the grog composition
Composition C 2S C 4A3S C 4AF
Ratio 34.6 38.2 19.8
6. the grinding of cement
In cement pulverizing course, the Wingdale volume is no more than 50%, and gypsum addition is generally 5%; Specific surface area should be controlled at more than the 350m2/kg, is generally the scope of 350～400m2/kg.

Claims (3)

1, a kind of processing method for manufacturing rapid hardening ferrous aluminate cement from red mud is characterized in that may further comprise the steps:
A, processing red mud: 100～110 ℃ of oven dry, make red mud Han Shui Liang ≦ 1%, the ball mill grinding is crossed 100 mesh sieves;
B, composition of raw materials are by design grog essential mineral C 2S, C 4A 3S, C 4The composition of AF calculates batching, and the grog essential mineral is C by weight percentage 2S:25～40%; C 4A 3S:30～45%; C 4AF:10～25%;
C, be main raw material with aluminum oxide industry waste red mud, owing to itself contain a large amount of Fe in red mud and the bauxite 2O 3, SiO 2, Al 2O 3, clay, sandstone only add as additive, press the raw material that takes by weighing of column weight amount per-cent:
Red mud 40～55%; Wingdale 20～30%; Iron powder 1.5～3%; Aluminium ore 20～30%; Gypsum 1～5%;
D, batch mixing, calcining: with the batch mixes among the step C, ball milling is even, and calcination temperature is 1250 ℃～1350 ℃;
E, preparation cement: calcination of chamotte below grinding to 200 order, adds Wingdale and gypsum once more again, with preparation different types of fast hardening ferrous aluminate cement.
2, a kind of processing method for manufacturing rapid hardening ferrous aluminate cement from red mud as claimed in claim 1 is characterized in that: the CaO content requirement of described Wingdale is greater than 48%; Described MgO content is below 1.5%.
3, a kind of processing method for manufacturing rapid hardening ferrous aluminate cement from red mud as claimed in claim 1 is characterized in that: in cement pulverizing course, the Wingdale volume is no more than 50%, and gypsum addition is less than 5%; The specific surface area of fast hardening ferrous aluminate salt cement should be controlled at more than the 350m2/kg, is generally the scope of 350～400m2/kg.
CNA2008102333598A 2008-12-16 2008-12-16 Processing method for manufacturing rapid hardening ferrous aluminate cement from red mud Pending CN101439938A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102491657A (en) * 2011-11-22 2012-06-13 中国铝业股份有限公司 Method for producing polymerization cementitious material with red mud and bauxite tailings
CN103833245A (en) * 2014-02-23 2014-06-04 桂林理工大学 Method for preparing high-iron cement by utilizing red mud
CN103922618A (en) * 2014-03-26 2014-07-16 天津振兴水泥有限公司 Micro-expansion moderate heat portland cement and preparation method thereof
CN104496232A (en) * 2014-12-29 2015-04-08 桂林理工大学 Method for preparing Alite-barium calcium sulphoaluminate cement from red mud
CN104788031A (en) * 2015-03-23 2015-07-22 苏州市德莱尔建材科技有限公司 Aluminate cement and preparation method thereof
CN108328950A (en) * 2018-03-16 2018-07-27 山东大学 A kind of red mud cooperates with the method that other solid wastes prepare ferrous aluminate cement
CN109020273A (en) * 2018-08-20 2018-12-18 深圳大学 A kind of preparation method of nanometer of ferrous aluminate cement
CN111848060A (en) * 2020-05-25 2020-10-30 山东高速集团有限公司 Solid waste-based marine existing structure repair material and preparation method and application thereof
CN112479609A (en) * 2020-12-22 2021-03-12 汝州市东江建筑工业科技有限公司 All-solid-waste aluminum ferrite cement clinker for prefabricated parts and preparation method thereof
WO2021190045A1 (en) * 2020-03-27 2021-09-30 河南理工大学 High-iron and low-calcium silicate cement and preparation method therefor
CN114014567A (en) * 2021-11-22 2022-02-08 济南大学 Method for directly preparing cement clinker from high-alkali red mud
CN115124314A (en) * 2022-06-28 2022-09-30 嘉华特种水泥股份有限公司 Sprayed concrete and preparation method thereof
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102491657A (en) * 2011-11-22 2012-06-13 中国铝业股份有限公司 Method for producing polymerization cementitious material with red mud and bauxite tailings
CN102491657B (en) * 2011-11-22 2013-07-17 中国铝业股份有限公司 Method for producing polymerization cementitious material with red mud and bauxite tailings
CN103833245A (en) * 2014-02-23 2014-06-04 桂林理工大学 Method for preparing high-iron cement by utilizing red mud
CN103833245B (en) * 2014-02-23 2016-01-13 桂林理工大学 A kind of method utilizing red mud to prepare ferric-cement
CN103922618A (en) * 2014-03-26 2014-07-16 天津振兴水泥有限公司 Micro-expansion moderate heat portland cement and preparation method thereof
CN104496232A (en) * 2014-12-29 2015-04-08 桂林理工大学 Method for preparing Alite-barium calcium sulphoaluminate cement from red mud
CN104788031A (en) * 2015-03-23 2015-07-22 苏州市德莱尔建材科技有限公司 Aluminate cement and preparation method thereof
CN108328950A (en) * 2018-03-16 2018-07-27 山东大学 A kind of red mud cooperates with the method that other solid wastes prepare ferrous aluminate cement
CN109020273A (en) * 2018-08-20 2018-12-18 深圳大学 A kind of preparation method of nanometer of ferrous aluminate cement
CN109020273B (en) * 2018-08-20 2021-01-12 深圳大学 Preparation method of nano-ferrous aluminate cement
WO2021190045A1 (en) * 2020-03-27 2021-09-30 河南理工大学 High-iron and low-calcium silicate cement and preparation method therefor
CN111848060A (en) * 2020-05-25 2020-10-30 山东高速集团有限公司 Solid waste-based marine existing structure repair material and preparation method and application thereof
CN112479609A (en) * 2020-12-22 2021-03-12 汝州市东江建筑工业科技有限公司 All-solid-waste aluminum ferrite cement clinker for prefabricated parts 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
CN115124314A (en) * 2022-06-28 2022-09-30 嘉华特种水泥股份有限公司 Sprayed concrete and preparation method thereof
CN115838250A (en) * 2022-12-01 2023-03-24 济南大学 Red mud-based admixture and clinker as well as preparation method and application thereof
CN115838250B (en) * 2022-12-01 2023-10-27 济南大学 Red mud-based admixture, clinker, and preparation method and application thereof

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