JPH0475456B2 - - Google Patents
Info
- Publication number
- JPH0475456B2 JPH0475456B2 JP60016436A JP1643685A JPH0475456B2 JP H0475456 B2 JPH0475456 B2 JP H0475456B2 JP 60016436 A JP60016436 A JP 60016436A JP 1643685 A JP1643685 A JP 1643685A JP H0475456 B2 JPH0475456 B2 JP H0475456B2
- Authority
- JP
- Japan
- Prior art keywords
- limestone
- sample
- weight
- quality
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
Description
〔産業上の利用分野〕
本発明は石灰石の品位迅速測定方法に関し、さ
らに詳しくは、加熱重量法によるCO2の減少から
石灰石の品位を短時間に精度よく測定する技術に
関する。
〔従来の技術〕
従来、石灰石の品位の測定は、試薬を用いる滴
定法によつており、その測定法を第８図のブロツ
ク図で示した。このような従来の滴定法そのもの
は、精度が高く信頼性に富むが、その測定値を採
掘や加工のためのデータとして現場で利用するに
は必ずしも適切ではなかつた。
〔発明が解決しようとする課題〕
すなわち、従来の滴定法による石灰石の品位測
定は、
(1) サンプル調整に長時間を要する。またサンプ
ル量が微小なので大きなロツトの代表値とする
には難点がある。
(2) 分析技術に熟練を要する。
(3) 自動化や連続化ができない。
などの問題があり、ばらつきの多い採掘現場や加
工処理工場においける大量処理工程の最適制御等
に利用し難いので、簡易迅速で精度の高い石灰石
品位測定法が望まれていた。
本発明は上記問題を解決する石灰石品位測定技
術を提供することを目的とするものである。
〔課題点を解決するための手段〕
本発明方法は次の技術手段から成る。
(A) 石灰石を５mm以下に破砕してサンプルを調整
する。磨砕を要しないから、簡易に迅速に大量
処理に適し、完全自動化ができる。
(B) サンプルを加熱し、200℃、650℃、1000℃に
それぞれ保持してそれぞれ平衡重量を測定して
W1、W2、W4を測定する。
(C) 次式によつて石灰石品位αを求める。
α（％）＝
｛（W2−W4）／W1｝×（100／44）×100
なお、この式中（100／44）は、CaCO3の分子
量100を、加熱により解離し重量減少を生ずる
CO2の分子量44で除したもので、石灰石中の
CaCO3の含有量、すなわち品位を迅速測定方法
として必要な精度で求める係数である。
第３図は上記本発明方法の工程を示すグラフで
ある。(a)は昇温曲線を示し、(b)は昇温に伴うサン
プルの重量変化を示している。650℃に保持し、
その平衡重量W2と1000℃における平衡重量W4と
の差は炭酸塩鉱物中のCO2の解離分として求めら
れる。
次に、上記本発明方法を好適に実施することの
できる装置は次の構成を有する。
(1) ５mm以下のサンプルを保持する耐熱容器
(2) サンプル保持器を囲繞する加熱装置
(3) 加熱温度を測定制御する温度制御装置
(4) 加熱中のサンプルの重量を連続測定する重量
測定装置。
上記装置の一例は第１図、第２図に示される。
第１図はその縦断面図であり、第２図はその分解
図である。サンプル１を保持する耐熱容器は重量
測定装置７上に載置されており、その周囲を囲繞
して電熱線３，４を配設し、電熱調整用のスライ
ダツクを備えるとともに、温度測定用サーモカツ
プル等の測温センサを付属した温度制御器からな
る温度制御装置を具備している。電熱線３，４は
熱絶縁被覆及び蓋によつて囲まれ、耐火れんが９
を介して架台８によつて支持されている。
本発明方法に用いるサンプルの粒度は、５mm以
下であればよい。従来の滴定法ではデイスクミル
で微粉砕し、その0.8ｇを使用するのに対し、本
発明方法では５mm以下のサンプルを10〜20ｇ使用
することができる。
例えば、粒度が異なる３種類で、粘土鉱物含有
量が同一の大理石の品位を本発明方法によつて測
定した結果を第１表に示したが、５mm以下ではサ
ンプル粒度によつて測定値に有意な差異は認めら
れず、測定可能である。なお、測定に要した時間
は同一であつた。
[Industrial Application Field] The present invention relates to a method for rapidly measuring the quality of limestone, and more particularly, to a technique for measuring the quality of limestone in a short time and with high precision from the reduction of CO 2 by a heating gravimetric method. [Prior Art] Conventionally, the quality of limestone has been measured by a titration method using a reagent, and the measuring method is shown in the block diagram of FIG. Although the conventional titration method itself is highly accurate and reliable, it is not necessarily suitable for using the measured values in the field as data for mining and processing. [Problems to be Solved by the Invention] Namely, measuring the quality of limestone by the conventional titration method requires (1) a long time for sample preparation; Also, since the sample size is so small, it is difficult to use it as a representative value for a large lot. (2) Analytical techniques require skill. (3) Cannot be automated or serialized. Because of these problems, it is difficult to use it for optimal control of mass processing processes at mining sites or processing plants, where there are many variations, so a simple, quick, and highly accurate method for measuring limestone quality has been desired. An object of the present invention is to provide a limestone quality measurement technique that solves the above problems. [Means for solving the problems] The method of the present invention consists of the following technical means. (A) Prepare the sample by crushing the limestone into pieces smaller than 5 mm. Since it does not require grinding, it is suitable for simple and quick mass processing and can be fully automated. (B) The sample was heated and held at 200℃, 650℃, and 1000℃, and the equilibrium weight was measured for each.
Measure W 1 , W 2 , and W 4 . (C) Calculate the limestone grade α using the following formula. α (%) = {(W 2 - W 4 )/W 1 } x (100/44) x 100 In this formula, (100/44) means that the molecular weight of CaCO 3 , 100, is dissociated by heating and the weight decreases. produce
It is calculated by dividing the molecular weight of CO 2 by 44, which is the amount of CO 2 in limestone.
This is a coefficient that determines the content of CaCO 3 , that is, the quality, with the necessary accuracy as a rapid measurement method. FIG. 3 is a graph showing the steps of the method of the present invention. (a) shows the temperature increase curve, and (b) shows the weight change of the sample as the temperature increases. Maintained at 650℃,
The difference between the equilibrium weight W 2 and the equilibrium weight W 4 at 1000°C is determined as the dissociated fraction of CO 2 in the carbonate mineral. Next, an apparatus capable of suitably implementing the method of the present invention described above has the following configuration. (1) Heat-resistant container that holds samples of 5 mm or less (2) Heating device that surrounds the sample holder (3) Temperature control device that measures and controls the heating temperature (4) Weight measurement that continuously measures the weight of the sample during heating Device. An example of the above device is shown in FIGS. 1 and 2.
FIG. 1 is a longitudinal sectional view thereof, and FIG. 2 is an exploded view thereof. The heat-resistant container holding the sample 1 is placed on a weight measuring device 7, and surrounding it are heating wires 3 and 4, a slider for electric heating adjustment, and a thermocouple for temperature measurement. It is equipped with a temperature control device consisting of a temperature controller attached to a temperature sensor such as. The heating wires 3, 4 are surrounded by a heat insulating coating and a lid, and are covered with refractory bricks 9.
It is supported by a pedestal 8 via. The particle size of the sample used in the method of the present invention may be 5 mm or less. In contrast to the conventional titration method, which uses 0.8 g of a finely pulverized sample in a disk mill, the method of the present invention allows use of 10 to 20 g of a sample with a size of 5 mm or less. For example, Table 1 shows the results of measuring the quality of three types of marble with different particle sizes and the same clay mineral content using the method of the present invention. No significant differences were observed and are measurable. Note that the time required for the measurements was the same.
石灰石を加熱すること次の減量反応を生ずる。
() 200℃前後：
付着水や粘土鉱物の結晶水の一部が揮発す
る。
このときの反応後重量をW1とする。
() 650℃まで：
粘土鉱物中の結合水がすべて解離する。
このときの反応後重量をW2とする。
() 800℃前後：
MgCO3→MgO＋CO2↑
このときの反応後重量をW3とする。
() 1000℃前後：
CaCO3→CaO＋CO2↑
このときの反応後重量をW4とする。
上記反応の中のCO2の解離分からCaCO3の重量
を換算し、品位を求める。
石灰石品位α（％）
＝｛（W2−W4）／W1｝×（100／44）×100
この場合、粘土鉱物中の結晶水の解離と石灰石
中のCO2の解離とを明確に区別しなければならな
い。通常、石灰石採掘の際、石灰石中に混入し、
かつ加熱減量を生ずるものは粘土鉱物である。そ
の例としてモンモリロナイトの単体の加熱曲線を
求めたところ、第６図のようになつた。第６図か
ら明らかなように、650℃で30分保持すれば結晶
水の解離は平衡に達する。これにより粘土鉱物中
の結合水の解離は、650℃に設定すればよことが
確認された。また石灰石サンプル中には粘土の量
は少ないので、650℃の保持時間は30分より短縮
することができる。
品位既知で粒度の異なる大理石とモンモリロナ
イトとを混合し、予め計算によつて求めた混合物
の品位と本発明方法による測定結果とを比較しこ
れを第２表に示した。
第２表から明らかなように、本発明方法による
測定精度は±１％以内に充分収まつており本発明
方法の精度のよさが確認された。
モンモリロナイト以外の他の粘土鉱物やドロマ
イト、黄鉄鉱等が混在する場合についてもこれら
鉱物の熱特性が把握できれば温度設定の調節によ
つて各鉱物の含有量すなわち化学組成の推定が可
能である。
Heating limestone produces the following weight loss reaction. () Around 200℃: Some of the attached water and crystallized water of clay minerals evaporate. The weight after the reaction at this time is defined as W 1 . () Up to 650℃: All bound water in clay minerals dissociates. The weight after reaction at this time is defined as W 2 . () Around 800℃: MgCO 3 →MgO＋CO 2 ↑ The weight after reaction at this time is W 3 . () Around 1000℃: CaCO 3 →CaO+CO 2 ↑ The weight after reaction at this time is W 4 . The weight of CaCO 3 from the dissociation of CO 2 in the above reaction is converted to determine the quality. Limestone grade α (%) = {(W 2 − W 4 )/W 1 }×(100/44)×100 In this case, the dissociation of crystal water in clay minerals and the dissociation of CO 2 in limestone are clearly defined. must be distinguished. Usually mixed into limestone during limestone mining,
Also, clay minerals cause loss of weight on heating. As an example, when the heating curve of montmorillonite was determined, it was as shown in Figure 6. As is clear from FIG. 6, the dissociation of crystal water reaches equilibrium when held at 650°C for 30 minutes. This confirmed that dissociation of bound water in clay minerals can be achieved by setting the temperature to 650℃. Also, since the amount of clay in the limestone sample is small, the holding time at 650°C can be shorter than 30 minutes. Marble and montmorillonite of known quality and different particle sizes were mixed, and the quality of the mixture determined by calculation in advance was compared with the results measured by the method of the present invention, and the results are shown in Table 2. As is clear from Table 2, the measurement accuracy by the method of the present invention was well within ±1%, confirming the high accuracy of the method of the present invention. Even when clay minerals other than montmorillonite, dolomite, pyrite, etc. are mixed, if the thermal properties of these minerals can be understood, it is possible to estimate the content of each mineral, that is, the chemical composition, by adjusting the temperature setting.
第１図に示す装置を用いて、本発明方法によつ
て石灰石の品位の測定を行つた。
るつぼにほぼ一杯になるまでサンプルを入れ、
（約15ｇ）石英ガラス製の台にのせ、るつぼを囲
繞して加熱炉を置き、温度制御器を使用して平
均、
５(A)×25(V)＝125(W)
の電力を用い、第３図ａに示す温度上昇曲線に従
つて加熱した。サンプル１，２，３について、温
度と重量との関係は第７図ａ，ｂ，ｃのようにな
つた。それぞれ各温度における重量を読み、1000
℃まで加熱し、重量変化がなくなるまで続行し
た。その結果を次の第３表に示した。
サンプル１，３は従来の滴定法による全ライム
測定値（T.L値）が既知のもの、サンプル２はサ
ンプル１の粉砕前の25mm以下のサンプルを鉄乳鉢
ですりつぶしたものである。
測定値から計算した石灰石の品位は滴定法によ
る分析値とよい一致が見られる。
The quality of limestone was measured by the method of the present invention using the apparatus shown in FIG. Pour the sample into the crucible until it is almost full.
(approximately 15 g) was placed on a quartz glass stand, a heating furnace was placed surrounding the crucible, and an average power of 5 (A) x 25 (V) = 125 (W) was used using a temperature controller. Heating was carried out according to the temperature rise curve shown in Figure 3a. For Samples 1, 2, and 3, the relationships between temperature and weight were as shown in Figure 7 a, b, and c. Read the weight at each temperature, 1000
Heating was continued until there was no change in weight. The results are shown in Table 3 below. Samples 1 and 3 have known total lime measurement values (TL values) by conventional titration methods, and sample 2 is a sample of sample 1 with a size of 25 mm or less, which was ground in an iron mortar before being crushed. The quality of limestone calculated from the measured values is in good agreement with the titration analysis value.
本発明は次の効果を奏する。
(a) 測定時間が従来約８時間を要していたが、１
時間程度に短縮される。
(b) 薬品を使用しないので、熟練者でなくても測
定できる。
(c) 含有水分、粘土鉱物の結晶水等の測定を同時
に行うことができる。
(d) 測定の自動化が可能であり、その測定値を工
程制御等に直接利用することが可能である。
The present invention has the following effects. (a) Measurement time used to take about 8 hours, but now 1
reduced to about an hour. (b) Since no chemicals are used, measurements can be performed even by non-experts. (c) Water content, water of crystallization of clay minerals, etc. can be measured simultaneously. (d) Measurement can be automated, and the measured values can be used directly for process control, etc.
第１図は本発明方法の実施に用いられる装置の
縦断面図、第２図はその分解図、第３図は本発明
方法の工程を示すグラフ、第４図は水平管状炉の
(a)縦断面図、(b)側面図、第５図は自動測定装置の
実施例のブロツク図、第６図はモンモリロナイト
の加熱曲線、第７図は実施例の温度と重量との関
係を示すグラフ、第８図は従来の滴定法による全
ライム（T.L値）の測定法の工程を示すブロツク
図である。
１……サンプル、２……耐熱容器、３，４……
電熱線、５……温度制御器、１０……プログラム
温度制御器、１１……サイリスタ、１２……電気
炉、１３……水平管状炉。
Figure 1 is a longitudinal sectional view of the apparatus used to carry out the method of the present invention, Figure 2 is an exploded view thereof, Figure 3 is a graph showing the steps of the method of the present invention, and Figure 4 is a horizontal tube furnace.
(a) Longitudinal sectional view, (b) Side view, Fig. 5 is a block diagram of an embodiment of the automatic measuring device, Fig. 6 is a heating curve of montmorillonite, and Fig. 7 shows the relationship between temperature and weight of the embodiment. The graph shown in FIG. 8 is a block diagram showing the steps of a conventional titration method for measuring total lime (TL value). 1...Sample, 2...Heat-resistant container, 3, 4...
Heating wire, 5... Temperature controller, 10... Program temperature controller, 11... Thyristor, 12... Electric furnace, 13... Horizontal tubular furnace.
Claims (1)
してサンプルを調製し、該サンプルをステツプ状
に昇温し、200℃、650℃、1000℃にそれぞれ保持
して、それぞれ平衡重量を測定してW1、W2、
W4とし、該測定値から下式により石灰石の品位
を算出することを特徴とする石灰石の品位迅速測
定方法。 石灰石の品位（％） ＝｛（W2−W4）／W1｝×（100／44）×100[Claims] 1. Prepare a sample by crushing limestone containing clay minerals into pieces of 5 mm or less, raise the temperature of the sample in steps, hold it at 200°C, 650°C, and 1000°C, respectively. Measure the equilibrium weight and find W 1 , W 2 ,
A method for quickly measuring the quality of limestone, characterized in that W is 4 , and the quality of limestone is calculated from the measured value using the following formula. Limestone quality (%) = {(W 2 − W 4 )/W 1 }×(100/44)×100
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1643685A JPS61176834A (en) | 1985-02-01 | 1985-02-01 | Method and instrument for quick measurement of grade of limestone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1643685A JPS61176834A (en) | 1985-02-01 | 1985-02-01 | Method and instrument for quick measurement of grade of limestone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61176834A JPS61176834A (en) | 1986-08-08 |
| JPH0475456B2 true JPH0475456B2 (en) | 1992-11-30 |
Family
ID=11916180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1643685A Granted JPS61176834A (en) | 1985-02-01 | 1985-02-01 | Method and instrument for quick measurement of grade of limestone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61176834A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100758428B1 (en) * | 2001-11-21 | 2007-09-14 | 주식회사 포스코 | Automatic measuring device for quicklime hydration in vertical kiln |
| KR101042491B1 (en) | 2008-09-29 | 2011-06-16 | 현대제철 주식회사 | Method of measuring the moisture content of quicklime and the purity of complex calcium compounds |
| CN102128943B (en) * | 2010-11-30 | 2013-01-30 | 湖南三德科技发展有限公司 | Sample sending and taking manipulator for industrial analyzer |
| CN102128944B (en) * | 2010-12-23 | 2013-01-30 | 湖南三德科技发展有限公司 | The positioning device of the automatic sample feeding mechanism on the sulfur determination instrument |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56125647A (en) * | 1980-03-07 | 1981-10-02 | Toshiba Corp | Thermogravimetric analyzing method and its apparatus |
| JPS58109842A (en) * | 1981-12-24 | 1983-06-30 | Shimadzu Corp | Apparatus for measuring evaporation weight and evaporation heat value simultaneously |
-
1985
- 1985-02-01 JP JP1643685A patent/JPS61176834A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61176834A (en) | 1986-08-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |