CN102206052A

CN102206052A - Method for cement production utilizing electrolytic manganese slag as cement mineralizer

Info

Publication number: CN102206052A
Application number: CN201010134817XA
Authority: CN
Inventors: 王勇; 叶文号; 甘四洋; 刘恒波; 髙遇事; 万军; 朱孜
Original assignee: GUIZHOU PROV BUILDING MATERIAL SCIENCE INST
Current assignee: GUIZHOU PROV BUILDING MATERIAL SCIENCE INST
Priority date: 2010-03-30
Filing date: 2010-03-30
Publication date: 2011-10-05

Abstract

The invention discloses a method for cement production utilizing electrolytic manganese slag as a cement mineralizer. The method comprises adopting cement raw meal to produce cement and is characterized in that when a cement production process utilizing cement raw meal as raw material is carried out, electrolytic manganese slag as a cement mineralizer is putted into cement raw meal and mix with the cement raw meal and then the mixture of the cement raw meal and the electrolytic manganese slag is utilized as raw material to produce cement. Through utilizing the method provided by the invention, the eutectic point temperature of cement products can be reduced 100 to 110 DEG C and the content of C3S can be increased effectively thus the method has observable effects of energy saving and emission reduction, and improvement of cement quality. The method has a very important meaning of accelerating a circular economy construction and developing an integrated utilization of industrial solid waste manganese slag. Comprised with the prior arts, the present method can reduce calcining temperature in cement production and energy consumption, and also improve a content of C3S in cement, and compression strengths and flexural strengths of cement at different ages.

Description

A kind of method that adopts electrolytic manganese residues to produce cement as cement mineralizing agent

Technical field

The present invention relates to a kind of method that adopts electrolytic manganese residues to produce cement, belong to waste residue utilization and field of energy-saving technology in the manufacture of cement as cement mineralizing agent.

Background technology

Electrolytic manganese residues is the industrial residue that is discharged when handling manganous carbonate breeze, electrolysis production manganese metal with sulphuric acid soln; Its outward appearance is the black fine particle, and water ratio is 30～40%, and post precipitation is the bulk that hardens; Its mineralogical composition is mainly dihydrate gypsum, quartz, aquation Dicalcium Phosphate (Feed Grade) etc.The annual capacity of the electrolytic manganese of China surpasses 1,000,000 tons at present, and the waste residue annual emissions surpasses 6,000,000 tons, because the quantity discharged of electrolytic manganese residues is big, and contain a certain amount of harmful element, can pollute environment, so it is fully utilized, be the trend of the times that promotes China's recycling economy.

The Chemical Composition of electrolytic manganese residues of the prior art is as shown in table 1:

The Chemical Composition of table 1 electrolytic manganese residues

According to the regulation of GB GB/T203-2008 " granulated blast-furnace slag that is used for cement ", it is as follows to calculate manganese slag coefficient of discharge with reference to the slag quality coefficient:

(1) the quality coefficient K=(CaO+MgO+Al of manganese slag ₂O ₃)/(SiO ₂+ MnO+TiO ₂)

＝16.88/35.86

=0.48＜1.2 (defective)

(2) the alkaline coefficient M of manganese slag ₀=(CaO+MgO)/(SiO ₂+ Al ₂O ₃)

＝11.5/36

=0.32＜1 is acid slag

From as seen last, because electrolytic manganese residues active very poor, so the comprehensive utilization of electrolytic manganese residues all is a difficult problem concerning numerous scientific workers.

The major ingredient of electrolytic manganese residues is a calcium sulfate, thereby utilize electrolytic manganese residues to come instead of gypsum to make cement setting retarder in the prior art mostly and use, also favourablely refine manganese with electrolytic manganese residues, (as the Chinese patent literature application number is 200610050961.9 to utilize electrolytic manganese residues to produce reports such as fertilizer or substitute for clay direct production cement, denomination of invention is " utilizing electrolytic manganese residues to produce the method for cement " disclosed technical scheme), but these methods of utilizing electrolytic manganese residues all are the clays that are used for the place of cement raw materials for production, promptly be used for batching as cement producting material, and electrolytic manganese residues can not be used as cement mineralizing agent, be that prior art can not be used electrolytic manganese residues as cement mineralizing agent, can not reduce manufacture of cement calcining temperature and the C that improves in the cement in traditional cement production process ₃S content, so the technology that existing use electrolytic manganese residues is produced cement still is not ideal enough.

Summary of the invention

The objective of the invention is: provide a kind of and can reduce the manufacture of cement calcining temperature, can improve cement C again ₃The employing electrolytic manganese residues of S content is made the method that cement mineralizing agent is produced cement, to reach energy-conservation and sharp useless purpose.

The present invention is achieved in that a kind of method that adopts electrolytic manganese residues to make cement mineralizing agent production cement of the present invention, comprise and adopt existing cement slurry to produce cement, with cement slurry during as raw material production cement, earlier electrolytic manganese residues is joined in the cement slurry as cement mineralizing agent and mixes, and then the compound that will be mixed with electrolytic manganese residues and cement slurry carries out manufacture of cement traditionally as raw material with cement slurry.

Electrolytic manganese residues is being joined in the cement slurry when mixing with cement slurry as cement mineralizing agent, and the weight part proportioning of its electrolytic manganese residues and cement slurry is: the electrolytic manganese residues that is mixed with 2～10 parts in per 100 parts cement slurry.

When the compound that is mixed with electrolytic manganese residues and cement slurry is carried out manufacture of cement as raw material, produce, but be 1220 ℃～1300 ℃ the calcining temperature of compound by traditional cement production process.

Owing to adopted technique scheme, will the be resulting by experiment an amount of electrolytic manganese quantity of slag of the present invention joins the C that can reduce the calcining temperature of traditional processing technology effectively when carrying out manufacture of cement in the cement slurry and improve product as cement mineralizing agent ₃S content.Be the test comparative result that adopts the present invention and traditional technology below.

When testing, according to cement material balance batching, the Chemical Composition of the existing cement slurry that it adopted is as follows:

Table 2

The KH of corresponding common meal, n, p value are as follows:

According to the common meal Chemical Composition, it is as follows that we calculate each rate value of cement:

(1) lime saturation factor:

KH=(CaO _Always-f-CaO-1.65Al ₂O ₃-0.3Fe ₂O ₃-0.7SO ₃)/2.85SiO ₂

＝(43.93-1.65×2.83-0.35×1.85)2.85×13.02

＝1.041

(2) silicon rate n=SiO ₂/ (Al ₂O ₃+ Fe ₂O ₃)

＝13.02/(2.83+1.85)

＝278

(3) aluminium rate p=Al ₂O ₃/ Fe ₂O ₃

＝2.83/1.85

＝1.53

Prepare burden by above-mentioned cement slurry prescription, in per 100 parts of weight parts of above-mentioned raw material, mix the electrolytic manganese residues oven dry material of 4 parts, 6 parts, 8 parts weight parts in respectively, in silicon molybdenum stove, calcining under 1300 ℃ of temperature then, at 1400 ℃ of temperature lower calcinations, its test-results is as follows with the cement slurry that do not add electrolytic manganese residues:

1, mixes electrolytic manganese residues in and do the XRD tracing analysis of cement mineralizing agent

(1) blank raw material (being traditional cement slurry) at the XRD curve of the cement clinker of 1400 ℃ of temperature lower calcinations shown in Fig. 1 curve table:

Show the cement clinker C of this temperature lower calcination from the XRD tracing analysis of Fig. 1 ₂S reaches 45.49%, C ₃S reaches 13.61%, intermediate phase mineral C ₅₄MA ₂S ₁₆O ₉₀Reach 40.90%.

(2) mix in 4 parts electrolytic manganese residues at the XRD of the cement clinker of 1300 ℃ of temperature lower calcinations curve as shown in Figure 2:

Show from XRD tracing analysis shown in Figure 2, in mix 4 parts electrolytic manganese residues at the cement clinker C of 1300 ℃ of temperature lower calcinations ₂S reaches 39.33%, C ₃S reaches 17.34%, intermediate phase mineral C ₅₄MA ₂S ₁₆O ₉₀Reach 43.3%.C ₃S content is more taller than the content of the cement clinker of 1400 ℃ of temperature lower calcinations, and the electrolytic manganese residues of mixing 4 parts in the explanation has mineralization.

(3) mix in 6 parts electrolytic manganese residues at the XRD of the cement clinker of 1300 ℃ of temperature lower calcinations curve as shown in Figure 3:

Show from XRD tracing analysis shown in Figure 3, in mix 6 parts electrolytic manganese residues at the cement clinker C of 1300 ℃ of temperature lower calcinations ₂S reaches 43.73%, C ₃S reaches 25.94%, intermediate phase mineral C ₅₄MA ₂S ₁₆O ₉₀Reach 30.33%.C ₃S content is more taller than the content of the cement clinker of 1400 ℃ of temperature lower calcinations, the increase with the electrolytic manganese residues volume is described, C ₃S content further increases, and eutectic point reduces significantly, and mineralization is obvious.

2, mix the glue sand test result of electrolytic manganese residues cement mineralizing agent in, as shown in table 3

The physical and mechanical property of manganese slag mineralizer calcine cement: table 3

Annotate: under the oblique line data for mix each age strength of mineralizer with blank 1400 ℃ each in length of time respective intensities ratio, i.e. intensity raising percentage ratio.

Above-mentioned X-ray diffraction and glue sand test result show, mix the cement slurry of 4～6 parts of electrolytic manganese residues, although its calcining temperature is lower 100 ℃ than barren, and the C of cement ₃S content is than conventional temperature incinerating cement C ₃S content is taller, and its anti-folding, each age strength of resistance to compression be all than the height of blank raw material, and during 4 parts of manganese slag mineralizer incorporations, firing temperature reduces by 100 ℃, and 28 days folding strengths improve 15%, ultimate compression strength improves 5%; During 6 parts of manganese slag mineralizer incorporations, firing temperature reduces by 100 ℃, and 28 days folding strengths improve 29%, ultimate compression strength improves 16%.It is the most obvious that the mineralizer of electrolytic manganese residues acts on this scope.

Can find out that by above-mentioned experimental data the present invention can reduce cement and burn till 100～110 ℃ of eutectic point temperature, and can effectively increase C ₃The content of S, the good results are evident for its effects of energy saving and emission reduction and raising cement quality.This is significant to the comprehensive utilization of accelerating Recycling Economy Construction and expansion industrial solid castoff manganese slag.The present invention compared with prior art, the advantage that the present invention not only has can be reduced the manufacture of cement calcining temperature, reduce energy expenditure can improve cement C but also have ₃Advantages such as S content and the anti-folding of raising cement, each age strength of resistance to compression.

Description of drawings

Fig. 1 is that blank raw material are at the XRD of the cement clinker of 1400 ℃ of temperature lower calcinations graphic representation;

Fig. 2 mixes 4 parts of electrolytic manganese residues at the XRD of the cement clinker of 1300 ℃ of temperature lower calcinations graphic representation in being;

Fig. 3 mixes 6 parts electrolytic manganese residues in being at the XRD of the cement clinker of 1300 ℃ of temperature lower calcinations graphic representation.

Embodiment

The present invention is described in further detail below in conjunction with embodiment.

Embodiments of the invention: a kind of method that adopts electrolytic manganese residues to produce cement as cement mineralizing agent of the present invention comprises that the existing cement slurry of employing and traditional cement production process carry out manufacture of cement, with cement slurry during as raw material production cement, industrial residue-the electrolytic manganese residues that is discharged when earlier the available technology adopting sulphuric acid soln being handled manganous carbonate breeze or electrolysis production manganese metal joins in the cement slurry as cement mineralizing agent and mixes with cement slurry, and its electrolytic manganese residues during mixing (siccative behind the deduction moisture content) with the weight part proportioning of cement slurry (siccative behind the deduction moisture content) is: mix 2～10 parts electrolytic manganese residues in per 100 parts cement slurry; And then the compound that will be mixed with electrolytic manganese residues and cement slurry is as raw material and adopt traditional cement production process to carry out manufacture of cement, and when producing, the temperature that will be controlled at 1220 ℃～1300 ℃ to the calcining temperature of compound gets final product.

Claims

1. method that adopts electrolytic manganese residues to produce cement as cement mineralizing agent, comprise and adopt cement slurry to produce cement, it is characterized in that: with cement slurry during as raw material production cement, earlier electrolytic manganese residues is joined in the cement slurry as cement mineralizing agent and mixes, and then the compound that will be mixed with electrolytic manganese residues and cement slurry is produced by traditional cement production process as raw material with cement slurry.

2. employing electrolytic manganese residues according to claim 1 is produced the method for cement as cement mineralizing agent, it is characterized in that: electrolytic manganese residues is being joined in the cement slurry when mixing with cement slurry as cement mineralizing agent, and the weight part proportioning of its electrolytic manganese residues and cement slurry is: the electrolytic manganese residues that is mixed with 2～10 parts in per 100 parts cement slurry.

3. employing electrolytic manganese residues according to claim 1 and 2 is produced the method for cement as cement mineralizing agent, it is characterized in that: when the compound that will be mixed with electrolytic manganese residues and cement slurry carries out manufacture of cement as raw material, produce by traditional cement production process, but be 1220 ℃～1300 ℃ the calcining temperature of compound.