KR101796040B1 - Manufacturing methods of high-quality lime for desulfurization from low-grade limestone - Google Patents
Manufacturing methods of high-quality lime for desulfurization from low-grade limestone Download PDFInfo
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- KR101796040B1 KR101796040B1 KR1020150061150A KR20150061150A KR101796040B1 KR 101796040 B1 KR101796040 B1 KR 101796040B1 KR 1020150061150 A KR1020150061150 A KR 1020150061150A KR 20150061150 A KR20150061150 A KR 20150061150A KR 101796040 B1 KR101796040 B1 KR 101796040B1
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- quicklime
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- lime
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
Abstract
The present invention relates to a method for producing high-quality desulfurization lime by removing impurities using physical differences of low-limestone compositions, producing CaO-rich high-quality desulfurizing lime, and increasing the utilization of lower limestone left in waste lime, The present invention relates to a method for upgrading a low-grade limestone for the production of de-activated quicklime including a preparation step, a calcination step, a quick lime grinding step, a primary grinding step, a magnetic separation step, and an air classification step.
Description
The present invention relates to a method for making high-quality quicklime using low-grade or waste limestone generated in a limestone mine through a physical classification method in order to replace high-grade limestone used for making a quicklime product for desulfurization.
The quicklime used to remove the sulfur components generated in the combustion of thermal power generation oil and anthracite coal requires high quality for effective desulfurization. Important characteristics of quicklime used for desulfurization are reactivity and crushability. In order to effectively desulfurize, it must be highly reactive with sulfur. In order to recycle or treat the gypsum produced after the reaction with sulfur, the crushability should be good. The reactivity and grindability are affected by the purity of the quicklime and the average particle size of the particles. The higher the purity and the smaller the average particle size of the particles, the better the reactivity and grindability. Therefore, effective to desulfurization operation are required that a high quality burnt lime, high quality of the limestone reacts with the SiO 2 as a by-product of the problems and calcium oxide, the hardness of the low - grade that the amount is limited to high wear the device gypsum affect gypsum color obtained from limestone mine And it is incompatible with the desulfurization effect.
As a method for solving this problem, Korean Patent No. 121560 proposes a method of obtaining a high-grade calcite concentrate by crushing or crushing calcite ore with a dry refining method of calcite, and then performing a step of sieving and a step of selecting a magnetic force. However, this method does not have an additional impurity removal process after the sieving step and the magnetic separation step, and it is only possible to remove the magnetic impurities due to the classification of the size after crushing and the magnetic force, and thus the quality of the obtained calcite is not uniform, It can not be used for desulfurizing because it can not obtain lime.
Korean Patent No. 1161755 proposes a method of obtaining high-quality quicklime by removing impurities by pulverizing and crushing limestone ore, and calcining, pulverizing, and separating by dry separation. However, this method is a method of calcining limestone ore with a particle size of 200mesh and then calcining the limestone ore with a size of 200mesh. When the limestone is crushed and pulverized, the limestone ore is undifferentiated and put into a large kiln for calcination Limestone stones adhere to the city kiln wall to reduce the firing effect and shorten the lifetime of the kiln. In addition, there is a problem in that impurities are not effectively removed, and it is difficult to remove magnetic impurities, since the calcined limestone is pulverized to remove impurities.
Accordingly, the present invention provides a method for effectively removing impurities through the steps of preparation of limestone ores, firing step, quicklime grinding step, first fractionation step, magnetic force selection step and air classification step.
It is an object of the present invention to provide a method of making high-quality desulfurized quicklime by removing impurities using physical differences of the compositions in the lower limestone to enhance the quality of the lower limestone.
In order to achieve the above object,
The present invention provides a method for upgrading a low limestone for the production of de-activated quicklime, which comprises preparing a limestone gemstone, calcining a calcined lime, crushing a quicklime, a first fractionation step, a magnetic force selection step, and an air classification step .
The present invention eliminates impurities by using physical differences of the compositions in the lower limestone, enables the production of high-quality slag for high-grade desulfurization with a high content of CaO, increases the use of low-grade limestone left to waste, and creates high value- It is effective.
Figure 1. Flow chart of a method for upgrading low-grade limestone for the production of burnt lime for desulfurization of the present invention
Figure 2. XRD patterns of waste seams
Figure 3. XRD pattern of calcined lime after firing
Figure 4. XRD patterns of 7,000 overflow and 7,000 underflow after the fresh lime air classifier
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein and the experimental methods described below are well known and commonly used in the art.
The present invention, in one aspect,
Characterized in that the method for removing impurities in the lower limestone comprises a step of preparing a limestone ore, a calcining step, a quick lime crushing step, a first fractionation step, a magnetic separation step, and an air classification step. And a high-definition method.
The method for upgrading the low limestone for the production of the deasphalted quicklime of the present invention will be described in more detail with reference to Fig.
The present invention is characterized in that it comprises a limestone raw stone preparation step, a calcination step, a quick lime crushing step, a first fractionation step, a magnetic force selection step, and an air classification step as a method for upgrading low limestone for the production of deasphalted quicklime.
The limestone gemstone preparation step of the present invention is characterized by using low-grade limestone generated in the process of obtaining high-grade limestone from a limestone mine. Limestone is a rock composed of minerals such as calcite (CaCO 3 ), quartz (SiO 2 ), and magnetite (Fe 2 O 3 ). The higher the ratio of CaCO 3 in the limestone is, the higher the limestone is classified.
Low limestone contains impurities such as SiO 2 and Fe 2 O 3 and is a limestone with less than 85% CaCO 3. When low limestone is calcined, it produces low quality quicklime with a CaO content of less than 48%. Low-quality quicklime having a CaO content of less than 48% can not be used for desulfurization, so it is necessary to remove the impurities and increase the CaO content to improve the quality.
The present invention uses low limestone as a method for improving the quality of low grade limestone by removing impurities in the low grade limestone in order to solve the problem that the high grade limestone deposit is gradually reduced due to high-grade limestone-based mining and the lower limestone is left unattended.
The prepared low limestone is characterized by being crushed to a size of 16-19 mm prior to the calcination process. If the size of the lower limestone is larger than 16mm, there is a problem that the kiln is not put into the large kiln for the calcination process or the calcination does not occur in the lower limestone. On the contrary, when the size of the lower limestone is smaller than 19mm, And the introduced or added fine particles adhere to the inner wall of the large kiln, reducing the efficiency of the firing process and shortening the lifetime of the kiln. In addition, the smaller the size of the limestone ore, the more energy and time it consumes. Therefore, the size of the low limestone ore is preferably 16-19mm.
The calcining step of the present invention is characterized in that CaCO 3 in the lower limestone ores is made into CaO, and the limestone ores are made of quicklime. Within limestone ore CaCO 3 is made of a sintering process during the CO 2 is released CaO.
The calcining step of the present invention is characterized in that the crushed stone-like low limestone ores are calcined at a temperature of 9000 to 1100 ° C for 2 hours to 3 hours. If the firing to lower limestone ore at a temperature below 9000 ℃ firing is under St. effectively occur because there is a problem of burnt lime is not sufficiently made, if the firing at a temperature above 1100 ℃ C 2 S, C 3 in the lower limestone S and the like, thereby making it possible to inhibit the use of quicklime. If the calcination time is less than 2 hours, the limestone ore is not sufficiently calcined and no burnt lime is formed. If the calcination time is longer than 2 hours, the limestone or limestone or limestone or limestone or limestone may be calcined at a high temperature for a long time. Therefore, the calcination temperature of the limestone ores is preferably 1000 ° C. and the calcination time is 2 to 3 hours.
The quicklime pulverization step of the present invention is characterized in that the quicklime made from the lower limestone ores is made into a fine powder using a pulverizer. All kinds of wave crusher used at this time are all possible.
Crushed lime made by firing process is prepared by crushing with fine powder for impurity removal process.
The primary fractionation step of the present invention is a step of sorting crushed lime by crushing in a sieving step using a mesh. This is performed in order to prevent the magnetic material from being efficiently separated at a particle size smaller than a certain size in the magnetic force selection step. The crushed quicklime can be classified into the desired sized quicklime using the meshes of 10 to 325 mouths, respectively. However, in the first stage of the present invention, when the size of the powder is smaller than 10-50 mesh, Since the magnetism of the magnetic material is too weak to react with the magnet in the magnetic separator, it is necessary to sort the quicklime which is filtered at 10-50 mesh for effective magnetic separation. The quicklime of 50mesh or less, in which the magnetic separation effect is remarkably decreased, can be obtained by hydrated lime through the hydration process.
The magnetic force selecting step of the present invention is characterized by removing magnetic impurities using a magnetic separator. Iron oxide contained in quicklime reacts with gypsum, which is a byproduct when using quicklime as a desulfurizing agent, so that gypsum can not be recycled and needs to be removed.
The magnetic separation step of the present invention is characterized in that the magnetic difference between CaO and Fe 2 O 3 is used to remove Fe 2 O 3 contained in the quicklime powder classified in the first dispersion step. Fe 2 O 3 is a magnetic substance containing iron, and CaO is a non-magnetic substance which is not magnetic. When the quicklime powder classified by the use of 10-50 mesh in the first fractionation stage is passed through the magnetic separator, particles containing Fe 2 O 3 as a magnetic material react with the magnet in the magnetic separator, and CaO as non-magnetic material does not react The CaO and the magnetic magnetic material are separated. In the magnetic separation step, not only Fe 2 O 3 but also other magnetic impurities can be removed. At this time, the magnetic separator to be used separates the powder, not the hydrated solution, so a dry type magnetic separator is used.
The air classifying step of the present invention is characterized in that an air classifier is used to remove remaining SiO 2 in the burnt lime powder from which the magnetic material has been removed. SiO 2 and CaO differ in specific gravity. SiO 2 is moved relatively to the calcium oxide powder passes through an air classifier with a weight heavier than the difference CaO removes SiO 2. When the burnt lime powder with Fe 2 O 3 removed is added in the air classifier, the SiO 2 is removed due to the difference in sedimentation speed due to the difference in specific gravity between SiO 2 and CaO. Relatively light CaO is blown up by the wind blowing in the air classifier, and the sedimentation rate is slow, and SiO 2 is heavy, so sedimentation rate is fast. When Fe 2 O 3 is removed, the heavier impurities are dropped into the underflow column, and the light CaO particles are classified into overflow columns according to the air flow. With this principle, not only SiO 2 but also other impurities larger than CaO can be removed.
In the air classification step of the present invention, remaining SiO 2 in the quicklime powder from which the magnetic material is removed is removed, and the purity of CaO in the quicklime is increased, impurities are removed, and high-quality quicklime can be obtained.
The remaining CaO in the impurities filtered through the air classifier can be obtained by hydrated lime.
The present invention includes a three-stage impurity removal process through a first stage of classification, a magnetic separation step, and an air classification stage, and effectively removes impurities using the difference in physical properties of CaO in the quicklime and impurities to obtain high- have.
It is possible to manufacture high-quality desulfurization lime by a series of processes of low-grade limestone through the steps of preparation of limestone ores, firing step, quicklime grinding step, primary fractionation step, magnetic separation step, air classification step of the present invention.
Example
Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the present invention.
In this embodiment, low grade limestone is used in a waste lime loaded in a domestic limestone mine.
The compositional contents in the waste lobes are shown in Table 1.
(Igloss is a substance that is broken down into CO 2 or H 2 O.)
CaCO 3 contained in waste lime (lower limestone) was measured in terms of CaO for comparison with quicklime.
The XRD results of the waste seals are shown in Table 2 and FIG.
The calcite (CaCO 3 ), quartz (SiO 2 ), muscovite (K (OHF 2 ) 2 Al 3 Si 3 O 10 ) and dolomite (MgCa (CO) 3 ) are included in the XRD pattern of Table 2 and Fig. And it is possible to confirm each content through quantitative analysis.
The supplied limestone was crushed to 16-19 mm, and the limestone was crushed by calcination at 1000 ° C (
The XRD results of the burnt lime formed after firing are shown in Fig.
It was confirmed that CaCO 3 was changed to CaO by the XRD pattern of burnt lime in FIG. 3, and it was confirmed that all of the CaCO 3 was formed without CaCO 3 .
The calcined quicklime was prepared as a fine powder using Jaw crusher and Cone crusher. After that, sieves were sieved using mesh of 10-20-50-70-100-150-200-325 mouth.
Table 3 shows the results of the quicklime supply and discharge obtained by grinding and burning the calcined quicklime.
10 The amount of the quicklime powder remaining after passing through the mseh of the mouth is 44.67g, the amount of the quicklime remaining after passing through the 10 mouth mesh and the remaining quicklime powder is 10-20 mesh, and the amount of the quicklime remaining is 158.6g. The amount of quicklime powder passed through the mesh is 44.65g.
From Table 3, it is possible to grasp the size distribution of particles after grinding.
Using the mesh, the primary lime was separated into a magnetic powder and a non-magnetic powder through a dry magnetic separator (Model L-4-10, Eriz Manufacturing Co., USA).
Table 4 shows the results of magnetic powder and non-magnetic component of each mesh.
From Table 4, it can be seen that the magnetic force selection efficiency of the quicklime powder remaining between 10-50mesh is good, and the magnetic force selection efficiency of the quicklime powder smaller than 10mesh or larger than 50mesh is lowered.
From Table 3 and Table 4, it can be seen that when the quick lime powder is selected from 10-50 mseh, the yield is good and the magnetic separation efficiency is high.
The step of removing impurities was carried out using an air classifier (HOSOKAWA ALPINE, D-86199, Augsburg, Germany). The air classification step was carried out by removing the impurities with a wind intensity of 7,000 rpm.
The compositional differences of 7,000 overflow and 7,000 underflow classified through the air classifier are shown in Table 5 and FIG.
(Based on limestone)
(0.55)
(0.55)
(53.03)
(Based on limestone)
(5.22)
(47.10)
As shown in Table 5 and Fig. 4, the SiO 2 content of the 7,000 overflows with impurities removed was significantly reduced (less than 5 wt.%) And the CaO content was improved to 50 to 54 wt.% .
Through the above examples, the low-cost calcium lime obtained by calcining the low-grade limestone is firstly mixed with the SiO 2 and the Fe 2 O 3 by means of the limestone raw stone preparation step, calcination step, quicklime grinding step, primary fractionation step, O 3 is removed, and the content of CaO is increased, and the purity is increased. Therefore, it can be seen that low grade limestone can be improved in quality with high quality quicklime through the present invention.
Although the present invention has been described in detail with respect to a method for improving the quality of low limestone for the production of deasphalted lime, various modifications are possible within the scope of the present invention. Therefore, the spirit and scope of the appended claims should not be limited to the detailed description and preferred forms contained herein.
-
Claims (7)
The primary distribution stage separates the burnt lime between the mouths of 10 to 50 mesh,
Wherein the air classification step selects impurities having a specific gravity larger than that of CaO in the material having undergone the primary dispersion step.
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| KR102187201B1 (en) * | 2018-11-15 | 2020-12-07 | 한국지질자원연구원 | Manufacture of complex for biodegradable bone joining using precursors produced by high purity of natural limestone |
| CN110981228B (en) * | 2019-12-30 | 2021-11-30 | 贵州安凯达实业股份有限公司 | High-calcium active lime |
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| KR101161755B1 (en) * | 2012-02-24 | 2012-07-03 | 한국지질자원연구원 | Method enhancing the grade of limestone |
| KR101380806B1 (en) | 2012-12-12 | 2014-04-04 | 주식회사 포스코 | Method for processing sludge |
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| KR101161755B1 (en) * | 2012-02-24 | 2012-07-03 | 한국지질자원연구원 | Method enhancing the grade of limestone |
| KR101380806B1 (en) | 2012-12-12 | 2014-04-04 | 주식회사 포스코 | Method for processing sludge |
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