Method for controlling free lime content of clinker

Abstract

Provided is a method for controlling a free lime content of a clinker by regulating the free lime content. Here the amount of sulfur trioxide resulting from fuel and the used amount of a fluorine-based mineralizer are regulated using the following Formulas (1) to (3), thereby controlling the free lime content (f.CaO) of the clinker.
f.CaO=0.29e.sup.(0.65A)(A=aSO.sub.3+b)(1)
a=0.0001F+9.2t0.18HM9.2(2)
b=0.0005F32.8t2.9HM+28.4(3) SO.sub.3 is an amount of sulfur trioxide in the clinker; a is a coefficient satisfying Formula (2); b is a coefficient satisfying Formula (3); F is an amount of fluorine in the clinker; when a burning temperature is X C., t=X/1450; and HM is a hydraulic modulus.

Claims

1. A method for controlling a free lime content of a cement clinker, comprising: adding fluorite or fluorine-containing waste that is a fluorine source in the cement clinker and used as a mineralizer to raw materials of the cement clinker, intermixing a waste gypsum board powder with fuel or putting the waste gypsum board powder into a kiln from the kiln outlet part as an SO.sub.3 source in the cement clinker, burning the raw materials of the cement clinker added the fluorite or the fluorine-containing waste in the kiln to produce the cement clinker, calculating the free lime content (f.CaO) of the cement clinker according to Formulas (1) to (3), adjusting an additive amount of fluorite or fluorine-containing waste and an used amount of fuel or an additive amount of waste gypsum according to the calculated free lime content to control the free lime content (f.CaO) so as to fall within a range of 0.5<f.CaO<1.0,
f.CaO=0.29e.sup.(0.65A)(A=aSO.sub.3 +b)(1)
a=0.0001F+9.2t0.18HM9.2(2)
b=0.0005F32.8t+2.9HM+28.4(3) in Formula (1), f.CaO is a free lime content (wt %), SO.sub.3 is an amount (wt %) of sulfur trioxide in the cement clinker, a is a coefficient satisfying Formula (2), b is a coefficient satisfying Formula (3), F is an amount (mg/kg) of fluorine in the cement clinker, t is a coefficient determined based on a temperature of 1450 C. (when a burning temperature is X C., t=X/1450), and HM is a hydraulic modulus.

2. The method for controlling a free lime content of a cement clinker according to claim 1, wherein the amount of fluorine in the cement clinker is equal to or greater than 300 mg/kg.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a graph showing the correspondence between a calculated value of a free lime content and an actual measured value of the free lime content.

(2) FIG. 2 is a graph showing the relationship between the SO.sub.3 amount and the fluorine amount at a burning temperature of 1450 C.

(3) FIG. 3 is a graph showing the relationship between the SO.sub.3 amount and the fluorine amount at a burning temperature of 1350 C.

(4) FIG. 4 is a graph showing the relationship between the SO.sub.3 amount and the fluorine amount at a burning temperature of 1300 C.

DESCRIPTION OF EMBODIMENTS

(5) Hereinafter, the control method of the present invention will be described in detail based on embodiments.

(6) The control method of the present invention is a method for controlling a free lime content of a cement clinker, in which the free lime content (f.CaO) of the clinker is regulated using Formulas (1) to (3).
f.CaO=0.29e.sup.(0.65A)(A=aSO.sub.3+b)(1)
a=0.0001F+9.2t0.18HM9.2(2)
b=0.0005F32.8t2.9HM+28.4(3)

(7) In Formula (1), f.CaO is a free lime content (wt %); SO.sub.3 is the amount (wt %) of sulfur trioxide in the clinker; a is a coefficient satisfying Formula (2); b is a coefficient satisfying Formula (3); F is the amount (mg/kg) of fluorine in the clinker; t is a coefficient determined based on a temperature f 1450 C. (when a burning temperature is X C., t=X/1450); and HM is a hydraulic modulus.

(8) Most of SO.sub.3, which represents an amount of sulfur trioxide in the clinker, results from fuel for burning. Moreover, the SO.sub.3 amount in the clinker is adjusted by intermixing waste gypsum board powder with fuel or by putting the waste gypsum board powder into a kiln from the kiln outlet part. The used amount of fuel or the amount of waste gypsum put into the kiln is adjusted, it is possible to control the SO.sub.3 amount represented using Formula (1).

(9) Moreover, a mineralizer is added to the raw materials of the clinker. Fluorite, fluorine-containing waste (sludge), and the like are used as the mineralizer. Fluorine contained in the clinker mainly results from the mineralizer. Accordingly, for example, by adjusting the additive amount of mineralizer, it is possible to regulate the coefficients a and b of Formulas (2) and (3) including the fluorine amount F and to finally control the SO.sub.3 amount in the clinker represented by Formula (1).

(10) The hydraulic modulus HM is an index represented by HM=CaO/(SiO.sub.2+Al.sub.2O.sub.3+Fe.sub.2O.sub.3). The greater the HM is, the amount of calcium oxide or alite in the clinker increases. As a result, burning reactivity decreases, hence the amount of free lime content increases. Generally, the hydraulic modulus HM of the raw material of the clinker is 1.90 to 2.30.

(11) Furthermore, Formula (1) is satisfied when the fluorine amount F in the clinker is equal to or greater than 300 mg/kg. If the fluorine amount F in the clinker is smaller than this, the correlation between fluorine and SO.sub.3 tends to be weakened, and the free lime content (f.CaO) of the clinker tends to increase greater than the value represented by Formula (1).

EXAMPLES

(12) Examples of the present invention will be described below.

(13) The SO.sub.3 amount in the clinker was measured according to JIS R 5202:2010 Methods for chemical analysis of cement. The fluorine amount in the clinker was measured by X-ray fluorescence analysis (powder briquette method or bead method).

(14) The free lime content (f.CaO) of the clinker was measured according to JCAS I-01:1997 Quantification of free calcium oxide.

(15) The burning temperature coefficient t is a coefficient determined based on a temperature of 1450 C. When the burning temperature is 1350 C., t=1350/1450=0.93, and when the burning temperature is 1450 C., t=1450/1450=1.00.

Example 1

(16) The SO.sub.3 amount, fluorine amount, and free lime content (f.CaO) of the produced dement clinker were measured. The results are shown in Table 1 together with the hydraulic modulus HM and the burning temperature coefficient t. Moreover, the free lime content (estimated f.CaO), which is calculated by plugging the hydraulic modulus of the raw material, the burning temperature coefficient, the measured SO.sub.3 amount, and the fluorine amount into Formula (1), is also shown in Table 1. In addition, the relationship between the free lime content (estimated f.CaO) based on Formula (1) and the actual measured free lime content (f.CaO) is shown in FIG. 1.

(17) As shown in Table 1, a difference between the free lime content (f.CaO) based on Formula (1) and the actual measured free lime content (f.CaO) is small and within a narrow range as shown in FIG. 1. This shows that Formula (1) showing the free lime content (f.CaO) of the clinker is highly reliable, and accordingly, it is possible to reliably control the free lime content (f.CaO) of the clinker based on Formula (1).

Example 2

(18) FIG. 2 and FIG. 3 show the relationship between the SO.sub.3 amount and the fluorine amount that make the free lime content (f.CaO) at each burning temperature fall within a range of 0.5<f.CaO<1.0 based on Formula (1) when each of the raw materials of the clinker having the hydraulic modulus HM of 1.9, 2.1, and 2.3 is burned at 1300 C., 1350 C., and 1450 C. respectively. In the drawings, the shaded area is in a range of 0.5<f.CaO<1.0. By adjusting the SO.sub.3 amount and the fluorine amount, it is possible to control the free lime content to fall within a range of 0.5<f.CaO<1.0.

(19) TABLE-US-00001 TABLE 1 SO.sub.3 F t HM f.CaO Estimated f.CaO Example 1 1.83 1160 1.00 1.89 0.18 0.30 Example 2 0.43 1015 1.00 1.89 0.21 0.38 Example 3 0.84 2455 1.00 2.31 0.26 0.50 Example 4 2.64 2610 1.00 2.31 0.26 0.42 Example 5 0.41 305 1.00 1.88 0.33 0.46 Example 6 1.83 1150 0.93 1.90 0.36 0.64 Example 7 2.11 340 1.00 1.89 0.38 0.35 Example 8 2.00 5000 0.93 2.10 0.39 0.36 Example 9 1.62 2535 1.00 2.31 0.39 0.46 Example 10 3.05 2370 0.93 2.30 0.41 0.51 Example 11 2.09 340 0.93 1.91 0.43 0.66 Example 12 1.72 1450 1.00 2.30 0.46 0.58 Example 13 2.62 1605 1.00 2.30 0.46 0.49 Example 14 0.84 1625 1.00 2.30 0.49 0.63 Example 15 2.01 2670 0.93 2.30 0.49 0.81 Example 16 2.00 2440 0.93 2.10 0.50 0.61 Example 17 0.50 5000 0.93 2.10 0.50 0.58 Example 18 2.00 5000 0.90 2.10 0.55 0.50 Example 19 2.00 1340 0.93 2.10 0.56 0.77 Example 20 1.73 645 1.00 2.31 0.56 0.70 Example 21 0.43 1020 0.93 1.90 0.56 1.41 Example 22 2.00 2700 0.90 2.10 0.63 0.80 Example 23 0.88 595 1.00 2.31 0.66 0.84 Example 24 3.15 2740 0.90 2.31 0.71 0.50 Example 25 2.72 695 1.00 2.30 0.74 0.56 Example 26 1.12 2780 0.93 2.31 0.82 1.23 Example 27 3.05 1580 0.93 2.31 0.84 0.57 Example 28 0.50 5000 0.90 2.10 0.86 1.10 Example 29 1.10 1595 0.93 2.31 0.87 1.71 Example 30 2.07 1565 0.93 2.31 0.87 1.00 Example 31 2.00 1390 0.90 2.10 1.14 1.06 Example 32 2.12 2700 0.90 2.30 1.20 1.03 Example 33 0.50 620 0.93 2.10 1.25 2.21 Example 34 2.00 655 0.93 2.31 1.63 1.25 Example 35 1.10 675 0.93 2.30 1.86 2.17 Example 36 0.50 2310 0.90 2.10 1.95 2.49 Example 37 1.15 2650 0.90 2.31 2.41 2.09 Example 38 1.15 1635 0.90 2.31 3.39 2.71 Example 39 0.50 1195 0.90 2.10 3.52 3.50 Example 40 1.16 670 0.90 2.30 4.44 3.45 Example 41 0.50 640 0.90 2.10 4.89 4.15 Note: SO.sub.3 is an SO.sub.3 amount (wt %) in the clinker; F is a fluorine amount (mg/kg) in the clinker; t is a coefficient determined based on a burning temperature (1.00 = 1450/1450, 0.93 = 1350/1450); f.CaO is an actual measured value (wt %); and Estimated f.CaO is a value calculated (wt %) based on Formula (1).

INDUSTRIAL APPLICABILITY

(20) The present invention can be applied to a method for controlling the free lime content (f.CaO) of the clinker by adjusting the used amount of fuel or the additive amount of waste gypsum as an SO.sub.3 source in the clinker, and adjusting the additive amount of fluorite or fluorine-containing waste that is a fluorine source in the clinker and used as a mineralizer using the Formula (1).