JP4349979B2 - Quality control method for hydraulic composition - Google Patents

Description

  The present invention relates to a quality control method for a hydraulic composition, and in particular, to produce a hydraulic composition such as cement of good quality using sewage sludge, municipal waste, industrial waste, etc. containing phosphorus and fluorine. The present invention relates to a method for quality control of a hydraulic composition.

In recent years, treatment and effective use of general waste such as industrial waste discharged from various industrial activities, sewage sludge and municipal waste discharged from living areas has become an important theme from the viewpoint of environmental conservation. .
Conventionally, sewage sludge has been landfilled after being dewatered and incinerated, and municipal waste has been incinerated in an incinerator at a waste disposal plant. As the shortage becomes more serious, the effective use of these wastes has been demanded, and the movement of using various wastes as cement raw materials is rapidly progressing.

However, many wastes contain fluorine and phosphorus, and the presence of these wastes adversely affects the properties of the resulting cement.
Specifically, when halogen is contained in the cement raw material, production problems such as increased coating of cement production kilns, preheaters, etc. occur, and the cement quality itself obtained depending on the fluorine content etc. is also adversely affected. Be affected.
Moreover, in producing cement, it is known that the phosphorus compound contained in the waste decreases the expression of the compressive strength of the cement as the phosphorus content in the clinker increases.

In view of this, Japanese Unexamined 10-265244 (Patent Document 1), a phosphorus pentoxide _(P 2 _{O 5)} containing waste to be able to use the cement raw _material, containing P 2 _{O 5} The main formula is domestic waste and / or industrial waste, and one or more components selected from calcareous raw materials, aluminosilicate raw materials, and iron raw materials are used as correction raw materials.
Modified HM = CaO concentration / (SiO ₂ concentration− (P ₂ O ₅ concentration / P ₂ O ₅ molecular weight) × SiO ₂ molecular weight × 2 + Al ₂ O ₃ concentration− (P ₂ O ₅ concentration / P ₂ O ₅ molecular weight) × Al ₂ O ₃ molecular weight + Fe ₂ O ₃ concentration)
Modified SM = (SiO ₂ concentration− (P ₂ O ₅ concentration / P ₂ O ₅ molecular weight) × SiO ₂ molecular weight × 2) / Al ₂ O ₃ concentration− (P ₂ O ₅ concentration / P ₂ O ₅ molecular weight) × Al ₂ O ₃ molecular weight + Fe ₂ O ₃ concentration)
Correction IM = (Al ₂ O ₃ concentration− (P ₂ O ₅ concentration / P ₂ O ₅ molecular weight) × Al ₂ O ₃ molecular weight) / Fe ₂ O ₃ concentration index HM, correction SM, and correction IM A method is disclosed in which the raw material is prepared and fired at 1100 to 1600 ° C. to produce a clinker having a P ₂ O ₅ content of 1.0 to 4.5% by weight to obtain a cement composition.

Further, JP-open 2 000-272939 (Patent Document 2), the cement raw material containing a lot of waste phosphorus content, a Mg _additives, are P 2 _{O 5} content of 0.3 to 2.0 A Portland cement clinker obtained by firing a raw material prepared by blending so that the Mg content is 1.0 to 5.0% by weight (firing base) when it is wt% (firing base) is disclosed. .

Further, JP-A open 2 00 0 -1 348 (Patent Document 3), phosphoric acid compound _(P 2 _{O 5)} in sewage sludge and / or burned ash containing a fluorine compound content _{of P} 2 _{O 5} 3 to 15% by weight in terms of F is added, and if necessary, the calcium compound is added so that the CaO addition amount is 100 to 500% by weight with respect to the P ₂ O ₅ content. A method for obtaining a hydraulic material by firing at 1300 ° C. is described.

Furthermore, Japanese Patent Laid-Open No. 2001-130932 (Patent Document 4), which proposes the use of fluorine-containing wastes in cement compositions, discloses a fluorine-containing cement having a free CaO content Y (wt%). And the fluorine content X (% by weight) are as follows:
(1) In the region of 0.08 ≦ X ≦ 0.4 and (2) 0.08 ≦ X ≦ 0.1, 0 ≦ Y ≦ 1.0, (3) 0.1 <X ≦ 0.2 In the region, 0 ≦ Y ≦ 1.4-4X, (4) In the region of 0.2 <X ≦ 0.4, 0 ≦ Y ≦ 0.9−1.5X
A cement that satisfies the requirements is disclosed.

However, the above conventional technology is a proposal for measures for reducing the strength of cement when phosphorus or fluorine is present alone, and no measures for reducing the strength of cement when phosphorus and fluorine are present simultaneously are not proposed or suggested. When the amount of phosphorus and fluorine is increased at the same time, the decrease in strength of the cement is not only a simple sum of the decrease in strength due to phosphorus and the decrease in strength due to fluorine, but phosphorus and fluorine synergistically cause a decrease in strength. Therefore, the above conventional method cannot be applied. Even when materials containing a large amount of phosphorus and fluorine are used at the same time, it is possible to produce hydraulic compositions such as cement with good quality and to expect effective use of waste. Yes.
JP-A-10-265244 JP 2000-272939 A JP 2000-1348 A JP 2001-130932 A

The object of the present invention has been made in view of the above-mentioned problems, and is obtained by using wastes containing phosphorus and fluorine simultaneously as raw materials, or wastes containing phosphorus alone and fluorine. It is possible to easily predict a decrease in strength of a hydraulic composition such as cement obtained by using waste contained alone as a raw material at the same time. Therefore, the phosphorus content and fluorine content in the raw material can be estimated. When controlled in relation to each other, a quality control method for a hydraulic composition capable of suppressing a decrease in strength development is provided.
Further, the object of the present invention is to obtain wastes containing phosphorus and fluorine at the same time as raw materials, or wastes containing phosphorus alone and wastes containing fluorine alone simultaneously as raw materials. Hydraulic composition with good quality that can easily complement the strength by increasing the amount of C ₃ S to an appropriate amount against the predicted strength reduction of the hydraulic composition such as cement obtained by using The quality control method of the hydraulic composition for obtaining the above is provided.

As a result of studies conducted by the present inventors to solve the above-mentioned problems, when the phosphorus content and the fluorine content in the raw material are controlled in association with each other, a decrease in strength can be predicted, and further Found a quality control method capable of complementing the strength that decreases by increasing the amount of C ₃ S by an appropriate amount, and maintaining the quality of the hydraulic composition well, and completed the present invention.

In order to solve the above-mentioned problems, the invention according to claim 1 is directed to a hydraulic composition quality control method using a raw material containing phosphorus and fluorine, and a compressive strength M of a mortar using the hydraulic composition. Is predicted using the following equation (1).
M = M ₀ × (k ₁ · A + k ₂ · B + k ₃ · A · B + 100) / 100 (1)
However, where, _{M 0} is the reference compressive strength of mortar according to the age, A is _P 2 _{O 5} content (mass%), B is fluorine content _{(mass%), k 1, k 2} , k 3 Indicates a coefficient.

The invention according to claim 2 is the hydraulic composition quality control method according to claim 1, wherein the coefficients k ₁ , k ₂ , and k ₃ are given by the following equations (2) to (4): It is characterized by that.
k ₁ = a ₁ × Log (t) + b ₁ ... (2)
k ₂ = a ₂ × Log (t) + b ₂ ... (3)
k ₃ = a ₃ × Log (t) + b ₃ ... (4)
However, in the formula, t is the age (day), and a ₁ , a ₂ , a ₃ , b ₁ , b ₂ , and b ₃ are constants.

Furthermore, the invention according to claim 3 is the hydraulic composition quality control method according to claim 2, wherein the constants a ₁ , a ₂ , a ₃ , b ₁ , b ₂ , b ₃ are phosphorus, fluorine, It calculates from the measurement result of the compressive strength of the mortar which concerns on the hydraulic composition using the raw material containing this, It is characterized by the above-mentioned.

The invention according to claim 4 is the method for controlling quality hydraulic composition according to one of claims 1 to 3, in order to obtain a compressive strength M _T of mortar according to the target, the following equation ( 5) is used to set the required increase amount ΔC of the corrected C ₃ S amount considering free CaO.
M _T −M = p ₁ × ΔC (5)
However, where, M is the formula (1) in compressive strength of the mortar to be calculated, p ₁ indicates a constant that is set in accordance with the age of (day).
The corrected C ₃ S amount is a value obtained by calculating the actual amount of C ₃ S in the clinker after firing in consideration of the unreacted free CaO (free lime) remaining when the clinker is fired. The increased requirement for correction C _{3 S} content, compressive strength M of the mortar was calculated by the formula (1) is, increasing amounts of correction C _{3 S} amount necessary for the compressive strength M _T to target Show.

When manufacturing the hydraulic composition using the raw material containing phosphorus and fluorine according to the invention according to claim 1, the amount of P ₂ O ₅ contained in the mortar is obtained by using the above formula (1). Since the compressive strength can be easily predicted based on the amount of fluorine, it is possible to appropriately adjust in advance the amount of raw material containing phosphorus and fluorine in obtaining the required compressive strength.
As a result, it can be obtained by using waste containing phosphorus and fluorine at the same time as raw materials, or by using waste containing phosphorus alone and waste containing fluorine alone as raw materials at the same time. It is possible to provide a quality control method of a hydraulic composition for obtaining a hydraulic composition having good quality, which can suppress a decrease in strength development of a hydraulic composition such as cement. .

According to the invention of claim 2, in addition to the above-described effect, the coefficients k ₁ , k ₂ , k ₃ used in the equation (1) are expressed in terms of the age (days) as in the equations (2) to (4). Therefore, it is possible to predict the compressive strength of the mortar at the focused age, and to more appropriately adjust the usage amount of the raw material containing phosphorus and fluorine.
Moreover, as in the invention according to claim 3, in addition to the above effects, the constants a ₁ , a ₂ , a ₃ , b ₁ , b ₂ , b ₃ used in the equations (2) to (4) are Since it can be easily calculated from the measurement result of the compressive strength of the mortar according to the hydraulic composition using the raw material containing phosphorus and fluorine, the compressive strength of the mortar using the formula (1) This prediction can be carried out very simply.

In addition to the above effects, the invention according to claim 4 predicts in advance a decrease in strength of a hydraulic composition using a raw material containing phosphorus and fluorine, and increases C ₃ S to compensate for the decrease. By using the above equation (5), the amount can be easily predicted.
Therefore, it can be obtained by using wastes containing phosphorus and fluorine simultaneously as raw materials, or can be obtained by using wastes containing phosphorus alone and wastes containing fluorine alone as raw materials at the same time. Since the desired strength can be imparted to the hydraulic composition such as cement, the quality can be maintained at a high quality, and the active use of waste can be promoted.
Furthermore, it is possible to produce a hydraulic composition that effectively uses waste at a low cost.

The quality control method of the present invention will be described using the following preferred examples, but is not limited thereto.
In the present invention, the phosphorus and fluorine contained affect the hydration reactivity and content of C ₃ S and reduce the compressive strength of the mortar. Moreover, the mortar compressive strength of these two components is reduced. The mechanism for lowering has been found to have an interaction, and the present invention has been achieved.

In the quality control method for a hydraulic composition according to the present invention, the influence of the contents of phosphorus and fluorine on the compressive strength of mortar is predicted using a model formula.
The model formula is formed in consideration of the effect of phosphorus content, the effect of fluorine content, the effect of interaction with phosphorus and fluorine, and the effect of age.

The compressive strength M of the mortar considering the influence of phosphorus and fluorine is expressed using the following equation (1).
M = M ₀ × (k ₁ · A + k ₂ · B + k ₃ · A · B + 100) / 100 (1)
However, _{M 0} is the reference compressive strength of mortar according to the age, A is _P 2 _{O 5} content (mass%), B is fluorine content _{(mass%), k 1, k 2} , k 3 is the coefficient Show.
In the formula (1), the first term (k ₁ · A) in parentheses means the influence of phosphorus content, and the second term (k ₂ · B) shows the effect of fluorine content. Furthermore, the third term (k ₃ · A · B) means the influence of the interaction between phosphorus and fluorine, and the fourth term (100) does not contain phosphorus and fluorine (or waste containing phosphorus and fluorine). If not available), is a term which is provided to represent the reference compressive strength of the model formula ducks Rutaru.

Furthermore, in order to consider the influence of age, the coefficients k ₁ , k ₂ , k ₃ of the above equation (1) are given by the following equations (2) to (4).
k ₁ = a ₁ × Log (t) + b ₁ ... (2)
k ₂ = a ₂ × Log (t) + b ₂ ... (3)
k ₃ = a ₃ × Log (t) + b ₃ ... (4)
However, t is the age _{(days), a 1, a 2,} a 3, b 1, b 2, b 3 indicates a constant.

By substituting the above equation (1) from equation (2) (4), the compressive strength of the mortar in consideration of influence of phosphorus and fluorine M, the reference compressive strength M ₀ of the mortar according to the timber of age And constants a ₁ , a ₂ , a ₃ , b ₁ , b ₂ , and b ₃ are specified, A of P ₂ O ₅ (mass%), B of fluorine (mass%) , And age (day) as a function of t.

Cement clinker having the basic composition shown in Table 1 was pulverized to prepare a mortar.
Raw materials are all used reagents, the phosphorus source tricalcium phosphate; (reagent manufactured by Wako Pure Chemical Industries, Ltd.), the fluorine source calcium fluoride; using (reagent manufactured by Wako Pure Chemical Industries, Ltd.) Table 1 shows values converted into P ₂ O ₅ and F, respectively.

Specifically, the compressive strength M of the mortar in consideration of the influence of phosphorus and fluorine was obtained as follows.
Based on the clinker chemical composition shown in Table 1 above, the phosphorus content and fluorine content in the clinker were changed as shown in Table 2, and 30 types of clinker were produced in an electric furnace.
Specifically, the phosphorus content contained in the cement clinker is 0.05, 0.2, 0.4, 0.8, 1.2, 1.6 mass%, and the fluorine content is 0.05. , 0.1, 0.2, 0.4, and 0.6% by mass, and a total of 30 types of clinker were produced in an electric furnace. Trial of 30 types of cement using each clinker and reagent dihydrate gypsum (manufactured by Wako Pure Chemical Industries, Ltd.), and the mortar compressive strength of each predetermined age (3 days, 7 days, 28 days, 91 days). It was measured.
In addition, when increasing / decreasing the content of phosphorus and fluorine, the content of tricalcium phosphate and calcium fluoride in Table 1 is increased / decreased, and the total amount of C ₂ S is decreased by decreasing the content of C ₂ S. The composition was adjusted.

  Each raw material used in manufacturing each clinker is mixed and pulverized for 30 minutes using a test ball mill, and 10 parts by mass of water is added to 100 parts by mass of the mixed and pulverized raw material, and the kneaded product is kneaded. After forming into a rectangular shape of 150 × 100 × 20 mm and drying, it was fired at 1475 ° C. for 1 hour using a siliconite electric furnace, and then rapidly cooled to the atmosphere to obtain 30 types of clinker (Table 2).

Using the clinker and the reagent dihydrate gypsum (made by Wako Pure Chemical Industries, Ltd.) having 30 kinds of compositions shown in Table 2, the dihydrate gypsum in the cement is represented by 2 SO ₃ as shown in Table 1. Each cement was trially prepared by mixing in an amount of 0.000% by mass, mixing and pulverizing to a fineness of 3400 cm ² / g.

Using each of the obtained cements, according to JIS R 5201 “Cement physical testing method, (5) Strength test (a) Compressive strength”, the mortar compressive strength is set to a predetermined age (3 days, 7 days, 28 days, 91 days).
The measurement results are shown in Table 2 and FIG.

  Referring to Table 2 and FIG. 1, from 3 to 28 days of age, the mortar compressive strength tends to decrease remarkably as phosphorus and fluorine increase. In the case of 0.1% or less, it was recognized that the mortar compressive strength increased as phosphorus increased.

Next, regarding the value of the mortar compressive strength obtained in Table 2, the P ₂ O ₅ content, the fluorine content, and the age in Table 2 are expressed by the above formula (1) (from the above formula (2) ( 4) is substituted, and the mortar reference compressive strength M ₀ and the constants a ₁ , a ₂ , a ₃ , b ₁ , b ₂ , b ₃ are calculated.
In the calculation, in order to obtain the optimum value, the standard compressive strength and each constant of the mortar were determined by the least square method. Table 3 shows the calculated standard compressive strength of the mortar. The calculated constants are as follows.

a ₁ = 12.11, b ₁ = -15.04
a ₂ = −3.00, b ₂ = −6.40
a ₃ = 24.77, b ₃ = −79.30

Table 4 shows the strength of the predicted mortar predicted according to the phosphorus and fluorine contents based on the model formula obtained by substituting the calculated constant into the formula (1).
When Table 4 is compared with the actual measurement results (Table 2), the deviation from the predicted value of the measured value is about several percent or less, and this model formula is effective in predicting the compressive strength of the mortar. it is understood that available.

With reference to Table 4, for example, the predicted mortar strength (α) corresponding to the content values of P ₂ O ₅ (mass%) and F (mass%) will be specifically described below.
When the contained P ₂ O ₅ is 0.4 mass% and F is 0.2 mass% and the age is 28 days, the above constants a ₁ , a ₂ , a ₃ , b ₁ , b ₂ , b ₃ and Substituting material age t = 28 into the above formulas (2) to (4), k ₁ is 2.48, k ₂ is -10.74, and k ₃ is -43.46. A numerical value is obtained. (1) by substituting the coefficient values of _{k 1,} k 2, _{k 3} in formula, and substituting the reference compressive strength values 61.5N / mm ² of mortar of 28 days as shown in Table 3, P The predicted mortar strength of a mortar containing 0.4% by mass of ₂ O ₅ and 0.2% by mass of F is 58.7 N / mm ² .

Similarly, when P ₂ O ₅ contained is 0.8 mass% and F is 0.4 mass% and the age is 7 days, k ₁ is −4.81, k ₂ is −8.935, k ₃ can be obtained coefficient value of -58.37, the equation (1) to the motor reference compressive strength of Rutaru of _{k 1,} k 2, by substituting the coefficient values of _{k 3,} 7 days shown in Table 3 of substituting a value 44N / mm _^2, the prediction mortar strength of mortar containing P 2 _{O 5} 0.4 wt% to 0.8 wt%, and F is a 32.5N / mm ^2.

  Thus, the value of each coefficient k1, k2, k3 in the prediction formula of the mortar of the said Formula (1) regarding each obtained mortar, and the mortar obtained from the said Formula (1) using the said coefficient The predicted strength values are shown in Table 4.

Comparing the predicted strength values of each mortar shown in Table 4 with the actually measured mortar strength values shown in Table 2, P ₂ O ₅ was 0.4 mass% and F was 0.2 mass%. The predicted strength value of the mortar containing 28 days of age is 58.7 N / mm ² from Table 4, the actually measured mortar strength value is 60.0 N / mm ² from Table 2, and P The value of the predicted strength of mortar containing ₂ mass% of O ₅ and 0.4 mass% of F at 7 days of age is 32.5 N / mm ² from Table 4, and is the actual measured mortar strength. value 32.8N / mm ² next to Table 2, the values of the prediction strength, measured values and are approximately the value of the equivalent mortar strength is obtained, the pre Hakashiki the mortar strength, phosphorus and fluorine It can be seen that it is extremely effective in predicting the strength of mortar containing.

Further, the predicted mortar strength obtained from the prediction formula (1) of the mortar strength is compared with the compressive strength of the mortar desired at a predetermined age. For example, considering the case of setting to the same value as the reference compressive strength of mortar of each timber age for use in strength prediction equation compressive strength of the mortar which is desired at a given wood age, the P ₂ O ₅ 0 The predicted strength value (α) of mortar containing 4% by weight and 0.2% by weight of F at 28 days of age is 58.7 N / mm ² , and the desired mortar compressive strength shown in Table 4 Compared with (β) 61.5 N / mm ² , it can be seen that the strength of 2.8 N / mm ² decreases.
When the P ₂ O ₅ content is 0.8% by mass and F is 0.4% by mass, the expected mortar strength at the age of 7 days is 32.5 N / mm ² and the desired mortar strength is obtained. is is 44N / mm ^2, it can be seen that the strength of 11.5N / mm ² is reduced.

If the strength obtained at a given age is less than the desired mortar strength by about 3 N / mm ² or more, it is problematic to actually use it as a cement. For example, P ₂ O ₅ is reduced to 0 In the case of a mortar containing 0.8% by mass and 0.2% by mass of F (having a desired mortar strength at a given age of 7 days), it is 6.6 N compared to the desired mortar strength at a given age. / since the intensity of the mm ² is reduced, in order to suppress the reduction in mortar strength to 3N / mm ² or less, to prepare a mortar containing F 0.2 mass%, the cement used compositions The amount of P ₂ O ₅ -containing raw material used in the process of preparing the raw material so that P ₂ O ₅ is reduced to 0.4% by mass or less or corresponding to quality control such as increasing the fineness is required.

Further, in the case of a mortar containing 0.8% by mass of P ₂ O ₅ and 0.6% by mass of F (having a desired mortar strength at a predetermined material age of 28 days), it is predicted from Table 4. mortar strength decreased to 45.9N / mm ^2, significantly strength decreases with 15.6N / mm ² as compared to the mortar strength 61.5N / mm ² as desired.
Since cement whose strength is greatly reduced in this way is a problem in actual use, there is a need for quality control measures such as the need to reduce the amount of raw materials containing P ₂ O ₅ and F containing raw materials. I understand that it is necessary.

Next, a method for complementing the decrease in compressive strength of mortar due to phosphorus and fluorine content will be described.
Mortar strength of cement is that known is a single high correlation between C _{3 S} (alite) content in the cement, Therefore, the compressive strength M _T of mortar to a target before firing The relationship with the amount of C ₃ S (% by mass) (C _MT ) can be expressed using the following equation (5).
M _T = p ₁ × (C _MT −4.07D _MT ) + p ₂ ... (5-1)
However, 4.07D _MT is the amount of C ₃ S calculated from the amount of free CaO (mass%) (D _MT ) that did not react even when the clinker was fired, and p ₁ and p ₂ are the age (days) ) Indicates the constant set for each. In particular, in the present invention, a value obtained by subtracting 4.07 × free CaO amount from C ₃ S amount calculated from CaO including free CaO (free lime), for example, (C _MT −4.07D _MT ) is calcined. This is the actual amount of C ₃ S in the subsequent clinker, and this value is referred to as a corrected C ₃ S amount.

Similarly, for the compressive strength M of the predicted mortar of the formula (1), when C ₃ S amount (% by mass) is C _M and free CaO amount (% by mass) is D _M ,
M = p ₁ × (C _M −4.07D _M ) + p ₂ ... (5-2)
In the represented, from the above formulas (5-1) and (5-2), can be calculated correction _{C 3} S content should be increased in order to obtain a compressive strength _{M T} of the desired mortar (% by mass). The increase amount ΔC of the correction C ₃ S amount is expressed using the following equation (5).
M _T −M = p ₁ × ΔC (5)
However, ΔC = (C _MT −4.07D _MT ) − (C _M −4.07D _M ) is meant.

The left-hand side of equation (5) represents the difference between the compressive strength M _T of the desired mortars and compressive strength M of the mortar which contains phosphorus and fluorine is calculated from equation (1), the compression strength is insufficient The value of the height is shown.
ΔC on the right side of the equation (5) indicates a corrected C ₃ S amount (% by mass) that should be increased to compensate for the decreasing compressive strength of the mortar.

The constants p ₁ and p ₂ included in the formula (5-1) or (5-2) are numerical values set by experiments, and specifically, the C ₃ S content (mass%) in the cement clinker. Various types of clinker were produced in an electric furnace while changing (C), and the obtained mortar compressive strength and the amount of free CaO (mass%) (D) were measured for each predetermined age (day). For example, the constants p ₁ and p ₂ were obtained by the method of least squares by substituting these values into the C _MT and D _MT on the left side and the right side of the formula (5-1).

Actually, in order to calculate the constants p ₁ and p ₂ , the C ₃ S content in the cement clinker was changed, and four types of clinker were produced in an electric furnace, and the mortar compressive strength obtained at a predetermined age. Was measured.
The C ₃ S content of the reference mortar of the cement clinker having the basic composition shown in Table 1 was increased and decreased, and the corrected C ₃ S content was adjusted accordingly. The method for producing the cement was the same as that for adjusting the phosphorus and fluorine contents described above, and the compressive strength of the mortar was also based on JIS R 5201.
The measurement results are shown in Table 5.

By using the measurement results in Table 5 and substituting each numerical value into the formula (5-1) or (5-2), the constants p ₁ and p ₂ were calculated for each age by the least square method. The calculation results are shown in Table 6.

In order to compensate for the decrease in the compressive strength of the mortar due to the phosphorus and fluorine contents by increasing the amount of C ₃ S, the above formulas (1) and (5) are solved as an equation for the amount of increase ΔC in the corrected C ₃ S amount. Thus, it is possible to calculate the increase amount ΔC. Further, the predicted compressive strength M of the mortar which contains phosphorus and fluorine was calculated by the equation (1), in conjunction with compressive strength M _T of the desired mortar becomes a target, by substituting the equation (5) Thus, the increase amount ΔC of the correction C ₃ S amount can be easily calculated. Based on the increase amount of the corrected C ₃ S amount calculated in this way, for example, a necessary amount of limestone can be added to the raw material to increase the C ₃ S amount.
Table 7 shows the amount of increase in correction C ₃ S necessary to obtain the desired mortar compressive strength shown in Table 4 when the phosphorus and fluorine contents are changed. .
FIG. 2 shows the desired mortar shown in Table 4 when the P ₂ O ₅ content is adjusted to 0.05 to 1.0% and the F content is adjusted to 0.05 to 0.3%. it is a diagram showing the increased amount of the correction C _{3 S} amount required to obtain the compression strength.

Referring to Table 7 and FIG. 2, the increase in the amount of correction C ₃ S necessary to obtain the desired compressive strength of the mortar increases remarkably as both phosphorus and fluorine increase up to the age of 7 days. To do. In the age of 28 days, when the fluorine content is 0.05% by mass or less, the desired compressive strength of the mortar is obtained over the entire range of 0.05 to 1% by mass of P ₂ O _5. Therefore, it is possible to reduce the amount of correction C ₃ S necessary for the purpose within a range of 5% by mass or less. On the other hand, it is understood that when the fluorine content is 0.05% by mass or more, the amount of correction C ₃ S required to obtain the desired compressive strength of mortar increases remarkably as both phosphorus and fluorine increase. Is done.

The quality control method of the present invention is obtained by using waste containing phosphorus and fluorine at the same time as raw materials, or waste containing phosphorus alone and waste containing fluorine alone at the same time. Since it is possible to predict a decrease in strength of a hydraulic composition such as cement obtained as a raw material, when the phosphorus content and the fluorine content in the raw material are controlled in relation to each other, the strength The decrease in expression can be suppressed, and furthermore, the reduced strength can be easily complemented by increasing the amount of C ₃ S appropriately, and a hydraulic composition having good quality can be obtained. Therefore, effective use of waste will be promoted.

It is a graph which shows the mortar compressive strength for every age at the time of changing content of phosphorus and a fluorine. It is a graph showing the increase of C _{3 S} to compensate for the reduction in mortar compressive strength with phosphorus and fluorine.

Claims (4)

In the quality control method of the hydraulic composition using the raw material containing phosphorus and fluorine,
A quality control method for a hydraulic composition, wherein the compressive strength M of a mortar using the hydraulic composition is predicted using the following formula (1).
M = M ₀ × (k ₁ · A + k ₂ · B + k ₃ · A · B + 100) / 100 (1)
However, where, _{M 0} is the reference compressive strength of mortar according to the age, A is _P 2 _{O 5} content (mass%), B is fluorine content _{(mass%), k 1, k 2} , k 3 Indicates a coefficient. The quality control method of the hydraulic composition according to claim 1, wherein the coefficients k ₁ , k ₂ , and k ₃ are given by the following equations (2) to (4): Quality control method.
k ₁ = a ₁ × Log (t) + b ₁ ... (2)
k ₂ = a ₂ × Log (t) + b ₂ ... (3)
k ₃ = a ₃ × Log (t) + b ₃ ... (4)
However, in the formula, t is the age (day), and a ₁ , a ₂ , a ₃ , b ₁ , b ₂ , and b ₃ are constants. The hydraulic composition according to claim 2, wherein the constants a ₁ , a ₂ , a ₃ , b ₁ , b ₂ , and b ₃ are raw materials containing phosphorus and fluorine. A quality control method for a hydraulic composition, which is calculated from the measurement result of the compressive strength of the mortar according to the invention. In the quality control method of the hydraulic composition of according to one of claims 1 to 3, further, in order to obtain a compressive strength M _T of mortar the target, using the following equation (5), free CaO A quality control method for a hydraulic composition, characterized in that an increase required amount ΔC of a correction C ₃ S amount considering the amount is set.
M _T −M = p ₁ × ΔC (5)
However, where, M is the formula (1) in compressive strength of the mortar to be calculated, p ₁ indicates a constant that is set in accordance with the age of (day).

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