CN1101629A - Calicining cement technology by adding rare earth poor ore or rare earth waste slag - Google Patents

Calicining cement technology by adding rare earth poor ore or rare earth waste slag Download PDF

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Publication number
CN1101629A
CN1101629A CN94108486A CN94108486A CN1101629A CN 1101629 A CN1101629 A CN 1101629A CN 94108486 A CN94108486 A CN 94108486A CN 94108486 A CN94108486 A CN 94108486A CN 1101629 A CN1101629 A CN 1101629A
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China
Prior art keywords
rare earth
cement
lean ore
waste
raw material
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CN94108486A
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Chinese (zh)
Inventor
吕辉
钟景裕
冯炎犇
文梓芸
樊粤明
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to CN94108486A priority Critical patent/CN1101629A/en
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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
    • C04B7/14—Cements containing slag
    • 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
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • C04B7/42—Active ingredients added before, or during, the burning process
    • C04B7/421—Inorganic materials
    • C04B7/424—Oxides, Hydroxides
    • 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)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention makes use of poor ore or waste slag of rare earth as the additive, with a proportion of 0.5-15% in weight in the green charge. This invention provides an additive of good quality and low cost for the cement industry to raise the strength and also production output of the baked charge, and reduce energy consumption and production cost. It is advantageous for popular application.

Description

Calicining cement technology by adding rare earth poor ore or rare earth waste slag
The present invention relates to cement manufacturing method, be specifically related to the technology that a kind of interpolation contains the material cement baking of trace rare-earth element.
In recent years, the development of China's Cement industry is very fast.But will reach energy-saving and cost-reducing on the basis of existing technology, improve that cement produces, the purpose of quality, fundamental way is to improve burnability of raw material, quickens clinker mineral and forms reaction.Up to now, being used for the additive major part that cement burns till the aspect is all types of mineralizers.What use at most after people's research and the eighties is fluorine, sulphur type composite mineralizer, facts have proved that fluorine, sulphur type composite mineralizer are as long as use suitably, can improve burnability of raw material, the acceleration clinker mineral forms, increase grog simultaneously and burn till amount of liquid phase, the reduction grog burns till liquid phase and temperature and liquid phase viscosity occur, improves cement product, quality, the purpose that cuts down the consumption of energy thereby reach.But fluorine, sulphur type composite mineralizer be if improper use causes the cement performance abnormality easily, as cement suddenly coagulate, disadvantage such as slow setting, early strength are low; And because above-mentioned mineralizer can form HF, SO in calcination process 2, SO 3Deng corrosive gases, big to equipment corrosion.In addition, the basic raw material of fluorine, sulphur type composite mineralizer mainly is fluorite and gypsum, and the price of these two kinds of materials is all than higher, especially gypsum, because the cement mill amount ratio is bigger, supply falls short of demand to cause amount of gypsum, so that its price even also higher than cement price is unfavorable for reducing production costs.
In addition, some industrial residue also is used as mineralizer and is used for manufacture of cement, for example: Pb-Zn tailings, copper mine tailing, barite lean ore and sulfurous iron ore etc.Though the relative gypsum of these mineralizer prices is cheap, also can reach the effect of gypsum mineralizer, above-mentioned mineralizer source is still extensive inadequately, is unfavorable for applying.Therefore seek more inexpensive, wide material sources and additive of fine quality remains a Cement industry difficult problem anxious to be solved.
The objective of the invention is to overcome the shortcoming of background technology, a kind of employing super quality and competitive price, resourceful additive are provided, and fire the production method of high quality cement clinker with the common grinding of raw material, the additive that adopts this law to select for use, not only to overcome the unfavorable factor of fluorite, gypsum compound mineralizer, and to increase substantially cement clinker strength, and improve cement clinker output, cut down the consumption of energy.
The objective of the invention is to realize by following measure.
A kind of in cement slurry the technology of blast blending cement baking, it is characterized in that adopting rare earth lean ore or rare earth waste to make additive uses, it is that 0.5～15% amount is mixed in the cement slurry with weight percent, make black meal or common meal with the common grinding of raw material then, reenter the kiln calcining, produce high quality cement clinker.
The rare earth lean ore that is added in the above-mentioned cement baking technology refers to various low-grade rare-earth mineral and other, and all contain clay, shale, coal, siliceous correction material and the ferro-controlling raw material of rare earth element; Rare earth waste then refer to all contain the mine tailing of rare earth element, shale slag or refine rare earth metal after remaining metallurgical slag.Can adopt following dual mode that rare earth lean ore or rare earth waste are mixed in the cement slurry:
(1) when cement raw mix proportioning, mixes separately with burden balance;
(2) before the batching of cement slurry, in advance rare earth lean ore or rare earth waste and other cement raw material are allocated in proportion, and allocated into burden balance again after being mixed.
During this cement raw mix proportioning, mix proper amount of rare-earth lean ore or rare earth waste, and make black meal or common meal, go into the kiln calcining with the common grinding of other raw material.Because the rare earth element in rare earth lean ore or the rare earth waste has stronger roasting effect and the mineralization of helping, in the grog sintering process, not only can reduce and burn till liquid phase and temperature occurs, reduce and burn till liquid phase viscosity, increase and burn till amount of liquid phase, thereby help the formation and development of grog mesosilicic acid DFP mineral, improve grog mesosilicic acid three calcium contentss, and can improve the cement clinker mineral activity, especially Dicalcium Phosphate (Feed Grade) hydration activity, thus the cement slurry burn-ability improved, quicken clinker mineral and form reaction, improve cement clinker product, quality, cut down the consumption of energy.
Rare earth lean ore or residue doping quantity are determined by following two aspect factors:
1, rare earth lean ore or rare earth waste volume are relevant with rare earth element kind and content in rare earth lean ore or the rare earth waste.
Ree content in rare earth lean ore or the rare earth waste is generally 0.01～0.3%, and content is high more, volume is few more; Volume is also relevant with the rare earth element kind in rare earth lean ore or the waste residue, and containing light rare earths is that main lean ore volume should lack, and promptly volume can be controlled in 0.5～5% scope in raw material; Containing heavy rare earth element is that main lean ore volume should be many, and volume can be controlled in 3～15% scopes.
2, the volume of rare earth lean ore or rare earth waste is relevant with rare earth lean ore or the main chemical constitution of rare earth waste.
General rare earth lean ore or the main chemical constitution of rare earth waste are SiO 2, Al 2O 3, Fe 2O 3, CaO, MgO promptly to clay form similar since clay this as one of cement raw material, so under the condition that does not influence raw meal proportioning rate value, can mix,, mix appropriate amount if when big, will be principle then to satisfy batching rate value to the influence of batching rate value more.
The present invention has compared following advantage with background technology:
1, adopt the present invention can improve cement clinker quality, promptly increase substantially cement clinker strength, free calcium oxide content obviously reduces in the grog simultaneously, and in addition, grog can not change because of mixing of rare earth lean ore or rare earth waste time of coagulation.
Use the quality of the cement clinker that cement clinker that the present invention produces and use technology not produce to compare, its 1 day ultimate compression strength can improve 6～34%, ultimate compression strength can improve 8～34% in 3 days, ultimate compression strength can improve 10～30% in 7 days, ultimate compression strength can improve 10～50% in 28 days, simultaneously, the grog stability is obviously improved, and this technology is much better than the effect of other additive to the effect of improving the grog performance.
2, the rare earth lean ore is in China, and particularly Guangdong Province's reserves are very abundant, and a large amount of rare earth lean ores does not refine to be worth and extensively discarded in barren hill because its rare earth metal content is low; In addition, because the rare earth metal content of rare-earth mineral itself is very low, general all in some thousandths of, each rare earth refinery has to discharge a large amount of rare earth wastes in refining the rare earth metal process, the waste residue of discharge has occupied a large amount of farmlands and soil, cause environmental pollution, the present invention is turned waste into wealth it, helps reducing cost, and helps applying.
3, major ingredient is similar to general clay composition in the rare earth lean ore of the present invention's employing, not only can not bring harmful component into, and the cement clinker performance is had no adverse effect.And can be used as clay product and use.
4, the additive that adopts of the present invention can be because of not producing corrosive gases in calcination process, and etching apparatus so help prolonging service life of equipment, also helps applying.
5, because rare earth lean ore quality is loose, friability spy is good, do not need to add special-purpose disintegrating apparatus, rare earth lean ore or rare earth waste addition manner can adopt independent batching, also can before raw material, mix in advance, allocate into burden balance again after arranging in pairs or groups evenly in proportion with other cement raw material, need not to increase dosing device.
In sum, the present invention has solved not only that present cement produces, quality is low, the difficult problem that energy consumption is high, and avoided the shortcoming of fluorite, gypsum compound mineralizer, saved investment simultaneously.This technology is grasped easily, is easy to apply.
Fig. 1 makes the performance measurement result of the made cement of additive for the rare earth lean ore of the different volumes of embodiment 1 usefulness.
Fig. 2 makes the performance measurement result of the made cement of additive for the rare earth lean ore of the different volumes of embodiment 2 usefulness.
Be described in further detail in conjunction with following embodiment:
Embodiment 1:
Adopt the positive cement two factory's materials of Pingyuan County, Guangdong Province stone, and make complete black meal A with its actual production batching rate value O, at A OThe basis on add the rare earth lean ore of different volumes shown in Figure 1, each raw material ratio is adjusted slightly simultaneously, to guarantee to add each the sample (A behind the rare earth lean ore 1, A 2, A 3, A 4, A 5) composition and A OBasically identical.Again with the raw material A for preparing 1, A 2, A 3, A 4, A 5Levigate respectively, in blender, add water and mix oven dry after three hours, be pressed into pat, and place silicon molybdenum electric furnace to burn to 1400 ℃, insulation was come out of the stove after half an hour, and the blowing chilling is made grog, adds 5% industrial dihydrate gypsum grinding then to 3000 ± 10 meters of specific surface areas 2/ kilogram is promptly made high grade cement.When measuring its clean slurry ultimate compression strength, mix and stir, adopt 2 * 2 * 2(centimetre by standard water gray scale water consumption) the lab scale mold forming, curing temperature is 20 ± 2 ℃, its measurement result is as shown in Figure 1.
Embodiment 2:
Adopt Nanhai County cement mill, Guangdong Province material, and make full common meal B with its actual production batching rate value O, at B OThe basis on add the rare earth lean ore of taking from Xinxing County of different volumes shown in Figure 2, each raw material ratio is adjusted slightly simultaneously, to guarantee to add each the sample (B behind the rare earth lean ore 1, B 2, B 3, B 4, B 5) composition and B OBasically identical.Again with the raw material B for preparing 1, B 2, B 3, B 4, B 5Levigate respectively, in blender, add water and mix oven dry after three hours, be pressed into pat, and place silicon molybdenum electric furnace to burn to 1400 ℃, insulation was come out of the stove after half an hour, and the blowing chilling is made grog, adds 5% industrial dihydrate gypsum grinding then to 3000 ± 10 meters of specific surface areas 2/ kilogram is promptly made high grade cement.When measuring its clean slurry ultimate compression strength, mix and stir, adopt 2 * 2 * 2(centimetre by standard water gray scale water consumption) the lab scale mold forming, curing temperature is 20 ± 2 ℃, its measurement result is as shown in Figure 2.

Claims (3)

1, a kind of in cement slurry the technology of blast blending cement baking, it is characterized in that, adopting rare earth lean ore or rare earth waste to make additive uses, it is that 0.5～15% amount is mixed in the cement slurry with weight percent, make black meal or common meal with the common grinding of raw material then, reenter the kiln calcining, produce high quality cement clinker.
2, interpolation rare earth lean ore according to claim 1 or rare earth waste cement baking technology is characterized in that, the rare earth lean ore refers to various low-grade rare-earth mineral and other, and all contain clay, shale, siliceous correction material and the ferro-controlling raw material of rare earth element; Rare earth waste then refer to all contain the mine tailing of rare earth element, shale slag or refine rare earth metal after remaining metallurgical slag.
3, according to claim 1,2 described interpolation rare earth lean ores or rare earth waste cement baking technology, it is characterized in that, can adopt following dual mode will release native lean ore or rare earth waste mixes in the cement slurry:
(1) when the batching of cement slurry, mixes separately with burden balance;
(2) before cement raw mix proportioning, in advance rare earth lean ore or rare earth waste and other cement raw material are allocated in proportion, and allocated into burden balance again after being mixed.
CN94108486A 1994-07-27 1994-07-27 Calicining cement technology by adding rare earth poor ore or rare earth waste slag Pending CN1101629A (en)

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CN94108486A CN1101629A (en) 1994-07-27 1994-07-27 Calicining cement technology by adding rare earth poor ore or rare earth waste slag

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CN94108486A CN1101629A (en) 1994-07-27 1994-07-27 Calicining cement technology by adding rare earth poor ore or rare earth waste slag

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1047960C (en) * 1995-12-15 2000-01-05 化学工业部北京化工研究院 Catalyst for ammoniation reaction
CN111548031A (en) * 2020-05-18 2020-08-18 江苏启坤循环经济产业技术开发有限公司 Novel mineral powder prepared from industrial waste residue neutralization slag and preparation method thereof
CN111548030A (en) * 2020-05-14 2020-08-18 江苏启坤循环经济产业技术开发有限公司 Treatment method of neutralized slag in building material
CN113185154A (en) * 2021-01-11 2021-07-30 中国地质科学院矿产综合利用研究所 Method for preparing cement clinker by using rare earth tailings

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1047960C (en) * 1995-12-15 2000-01-05 化学工业部北京化工研究院 Catalyst for ammoniation reaction
CN111548030A (en) * 2020-05-14 2020-08-18 江苏启坤循环经济产业技术开发有限公司 Treatment method of neutralized slag in building material
CN111548031A (en) * 2020-05-18 2020-08-18 江苏启坤循环经济产业技术开发有限公司 Novel mineral powder prepared from industrial waste residue neutralization slag and preparation method thereof
CN113185154A (en) * 2021-01-11 2021-07-30 中国地质科学院矿产综合利用研究所 Method for preparing cement clinker by using rare earth tailings

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