Burned cement clinker and method for producing the same

Abstract

This burned cement clinker is a burned cement clinker including at least one selected from the group consisting of fluorine, sulfur, chlorine and bromine, and at least one metallic element(s) selected from the group consisting of elements in groups 3 through 12 of the periodic table. Preferably, the amount of fluorine is within a range from 300 to 750 mg/kg, the amount of sulfur (expressed in terms of SO.sub.3) is within a range from 1.5 to 3.0% by mass, the amount of at least one chlorine equivalent(s) selected from the group consisting of chlorine and bromine is within a range from 150 to 350 mg/kg, and the amount of at least one metallic element selected from the group consisting of elements in groups 3 through 12 of the periodic table is within a range from 0.2 to 0.8% by mass.

Claims

1. A burned cement clinker, comprising: fluorine; sulfur; at least one selected from the group consisting of chlorine and bromine; metallic elements consist of vanadium, cobalt, nickel, copper and zinc; and tricalcium silicate, dicalcium silicate, tricalcium aluminate, and calcium aluminoferrite, wherein, an amount of the metallic elements are within a range from 0.4 to 0.8% by mass, and the amount of the metallic elements corresponds to a sum of the amount of zinc and the amounts of the respective metallic elements expressed in terms of zinc.

2. The burned cement clinker according to claim 1, wherein in the burned cement clinker, the amount of fluorine is within a range from 300 to 750 mg/kg, the amount of sulfur (expressed in terms of SO.sub.3) is within a range from 1.5 to 3.0% by mass, the amount of at least one chlorine equivalent selected from the group consisting of chlorine and bromine is within a range from 150 to 350 mg/kg.

3. The burned cement clinker according to claim 2, wherein the amount of the chlorine equivalent(s) corresponds to a total of the amount of chlorine and the amount of bromine expressed in terms of chlorine.

Description

BEST MODE FOR CARRYING OUT THE INVENTION

(1) The present invention will be specifically described below by way of embodiments.

(2) The present invention is directed to a burned cement clinker, including at least one selected from the group consisting of fluorine, sulfur, chlorine and bromine and at least one metallic element selected from the group consisting of elements in groups 3 through 12 of the periodic table, and a method for producing the same.

(3) [Burned Cement Clinker]

(4) In order to lower the burning temperature of the cement clinker, it has been known for a long time to add the mineralizer containing fluorine, sulfur and chlorine into the cement clinker. In the embodiments according to the present invention, however, at least one selected from the group consisting of fluorine, sulfur, chlorine and bromine and at least one metallic element selected from the group consisting of elements in groups 3 through 12 of the periodic table (hereinafter referred to as metallic elements) are available for the mineralizer component(s). The component containing at least one selected from the group consisting of a fluorine component, a sulfur component, chlorine and bromine and the other component containing the metallic elements may be individually added into the cement raw material to burn, or the mineralizer into which all of the components are incorporated may be added to the cement raw material to burn.

(5) For the cement raw material to which the mineralizer is added, the conventional raw material for the ordinary portland cement may be used. The components in the cement clinker are not intended to be particularly limited as long as it can comply with, for example, Japanese Industrial Standards (JIS).

(6) As the mineralizer component(s), fluorine may be used in the form of calcium fluoride or the like; sulfur may be used the form of anhydrite or the like; chlorine may be used in the form of calcium chloride or the like; and bromine may be used in the form of calcium bromide or the like.

(7) At least one metallic element selected from the group consisting of elements in groups 3 through 12 of the periodic table, which may be used as the mineralizer component(s), may preferably include metallic elements from group IV of the periodic table. Among the metallic elements from group IV, particularly preferred are zinc, vanadium, cobalt, nickel and copper because they are effective at lowering the burning temperature of the cement clinker. More preferably, at least one metallic element selected from the group consisting of zinc, vanadium, cobalt, nickel and copper may be incorporated into the mineralizer as the component(s).

(8) Among the metallic elements, since group V to group XII elements of the periodic table may be unavailable and costly, the metallic elements from group IV may be preferably used. The metallic elements may be especially used in the form of oxides thereof.

(9) Further, fluorine polluted sludge discharged from a semiconductor plant may be used as a fluorine source, and a powder of waste gypsum plaster board may be used as a sulfur source. As a source of the metallic elements, slag occurred during the refining process of copper, zinc and the like; vinyl chloride resin-coated copper wires which are separated from electronic or automotive shredder residues or the like; and vanadium recovered from smoke emission generated in a thermal power plant; and the like are also usable. Further, waste materials including a bromine-based flame retardant and the like may be also available.

(10) Preferably, in the burned cement clinker, the amount of fluorine is within a range from 300 to 750 mg/kg, the amount of sulfur (expressed in terms of SO.sub.3) is within a range from 1.5 to 3.0% by mass, the amount of at least one chlorine equivalent(s) selected from the group consisting of chlorine and bromine is within a range from 150 to 350 mg/kg and the amount of at least one metallic element selected from the group consisting of elements in groups 3 through 12 of the periodic table is within a range from 0.2 to 0.8% by mass.

(11) Less than 300 mg/kg of the amount of fluorine may not result in the sufficiently reduced burning temperature, or more than 750 mg/kg of the amount of fluorine may lead to deterioration in the quality of the resulting cement. Accordingly, the amount of fluorine is more preferably 400 mg/kg or more and 750 mg/kg or less, even more preferably 500 mg/kg or more and 700 mg/kg or less. Less than 1.5% by mass of the amount of sulfur (expressed in terms of SO.sub.3) may not result in the sufficiently reduced burning temperature, or more than 3.0% by mass of the amount of sulfur may lead to strength decreasing of the resulting cement, and therefore, it would be undesirable. Accordingly, the amount of sulfur (expressed in terms of SO.sub.3) is more preferably 2.0% by mass or more and 3.0% by mass or less, and even more preferably 2.2% by mass or more and 2.8% by mass or less.

(12) The amount of the chlorine equivalent(s) corresponds to the total of the amount of chlorine and the amount of bromine expressed in terms of chlorine. Specifically, it corresponds to the sum of the amount of chlorine [Cl] and the content of bromine expressed in terms of chlorine ([atomic ratio of Cl/Br, 0.444][weight of Br]), that is ([Cl]+0.444[Br]). Less than 150 mg/kg of the amount of the chlorine equivalent(s) may not result in the sufficiently reduced burning temperature, or more than 350 mg/kg of the amount of the chlorine equivalent(s) may fail to meet the standards of the cement. Accordingly, the amount of the chlorine equivalent(s) is more preferably 175 mg/kg or more and 330 mg/kg or less, and even more preferably 200 mg/kg or more and 300 mg/kg or less.

(13) The amount of metallic elements corresponds to the sum of the amount of zinc [Zn] and the amount of the respective metallic elements expressed in terms of zinc. Specifically, it corresponds to the sum as follows:

(14) The amount of V expressed in terms of zinc=[atomic ratio of Zn/V][amount of V]=1.284[V];

(15) The amount of Co expressed in terms of zinc=[atomic ratio of Zn/Co][amount of Co]=1.110[Co];

(16) The amount of Ni expressed in terms of zinc=[atomic ratio of Zn/Ni][content of Ni]=1.114[Ni]; and

(17) The amount of Cu expressed in terms of zinc=[atomic ratio of Zn/Cu][content of Cu]=1.029[Cu],
and thus, the amount of metallic elements is calculated from the following formula:[Zn]+1.284[V]+1.110[Co]+1.114[Ni]+1.029[Cu].

(18) Less than 0.2% by mass of the content of metallic elements may not result in the sufficiently reduced burning temperature, or more than 0.8% by mass of the amount of metallic elements may lead to strength decreasing of the resulting cement, and therefore, it would be undesirable. Accordingly, the amount of metallic elements is more preferably 0.3% by mass or more and 0.7% by mass or less, and even more preferably 0.4% by mass or more and 0.6% by mass or less.

(19) [Method for Production]

(20) Fluoride such as calcium fluoride, a sulfuric compound such as type II anhydrite, a chloride such as calcium chloride and the like are added into the cement raw materials along with oxides of the metallic elements so that in the resulting burned cement clinker, the amount of fluorine is within a range from 300 to 750 mg/kg, the amount of sulfur (as SO.sub.3) is within a range from 1.5 to 3.0% by mass, the amount of chlorine equivalent(s) is within a range from 150 to 350 mg/kg and the amount of metallic elements is within a range from 0.2 to 0.8% by mass, followed by burning. Alternately, the mineralizer into which all of the above components are incorporated may be first prepared to add to the cement raw material, followed by burning. Also, the mineralizer into which all of the above components are incorporated may be provided by blowing it from Kiln burner's end to the cement raw material.

(21) The cement raw materials may include a mixture containing limestone, clay, silica and iron material, as well as wastes containing constituents utilizable for the cement raw materials, and the like.

(22) Addition of the mineralizer components into the cement raw materials may result in the reduced burning temperature, and thereby, make it possible to burn the cement clinker at the temperature of 1,300 C. or lower. In particular, the temperature required for burning of the cement clinker to make the burned cement clinker may be 1,200 C. or higher and 1,300 C. or lower.

EXAMPLES

(23) Examples of the present embodiment and Comparative Examples will be illustrated below.

(24) [Preparation of Raw Materials, Test Method]

(25) To provide an industrial raw material for the ordinary portland cement and a cement clinker having given modulus values, reagents calcium carbonate, silicon oxide, aluminum oxide and ferric oxide were used. In addition, calcium fluoride, type II anhydrite, calcium chloride and oxides of the metallic elements were used as the mineralizer components to be contained in the cement clinker.

(26) The materials were blended so that the cement clinker composition is as shown in Table 1 and the modulus values and the mineral composition of the cement clinker are as reported in Table 2 to burn the blend in an electric furnace at 1,300 C. for 90 minutes. Progress of burning was monitored by measuring the amount of free-lime (free calcium oxide/f-CaO) in the cement clinker. The amount of free-lime was determined by a standard test method The Cement Association of Japan Standard (JCAS) I-01: 1997 Method for Determination of Free Calcium Oxide.

(27) The burned cement clinker to which gypsum was added so as to be 2% by mass of the amount of SO.sub.3 was ground in a test mill to reduce it to a powder mostly having 3,300 cm.sup.2/g of specific surface, as measured by Blaine's air permeability method, resulting in a cement. Using the cement, setting time and strength at the material age of 28 days were determined according to JIS R 5201.

(28) TABLE-US-00001 TABLE 1 [Chemical Composition of Cement Clinker] SiO.sub.2 Al.sub.2O.sub.3 Fe.sub.2O.sub.3 CaO MgO SO.sub.3 Na.sub.2O K.sub.2O TiO P.sub.2O.sub.5 MnO Total 22.07 5.73 2.97 66.25 1.22 0.43 0.29 0.31 0.18 0.23 0.03 99.71 Note: Represented in % by mass

(29) TABLE-US-00002 TABLE 2 [Modulus values of Cement Clinker and Mineral Composition as measured by Bouge calculation] HM SM IM AI LSD C.sub.3S C.sub.2S C.sub.3A C.sub.4AF 2.15 2.54 1.93 3.85 0.921 57.9 19.6 10.2 9 Note: HM: hydraulic modulus, SM: silica modulus, IM: iron modulus, AI: activity index, LSD: lime saturation degree, C.sub.3S: tricalcium silicate, C.sub.2S: dicalcium silicate, C.sub.3A: tricalcium aluminate, C.sub.4AF: calcium aluminoferrite (each mineral composition is represented in % by mass)

Test Example 1

(30) A cement clinker was prepared using as a mineralizer fluorine in an amount of the cement clinker shown in Table 3 and modifying chemical abundance of all the rest components as shown in Tables 1 and 2, and burned to make a cement. Preparation of the cement was conducted according to the method described above for adding gypsum into the cement clinker and then grinding them. Table 3 shows the amount of free-lime in each cement clinker and setting time of each cement. Table 3 shows that addition of fluorine leads to a decrease in the amount of free-lime, and as a result, a mineralizing action to lower the burning temperature may be observed. Table 3 also shows that whereas the setting time takes too long at 950 mg/kg of the amount of fluorine, the amount of free-lime is approximately 3% by mass at 260 mg/kg of the content of fluorine, and then, it results in inadequate burning. Therefore, the appropriate amount of fluorine is considered to be within a range from 300 to 750 mg/kg.

(31) TABLE-US-00003 TABLE 3 Amount of F (fluorine) f-CaO No. (mg/kg) (% by mass) Setting time Remarks A1 150 3.95 2:21 Inadequate burning A2 260 2.96 2:15 Inadequate burning A3 400 1.84 2:24 A4 750 1.36 2:40 A5 950 0.95 3:06 Too long setting time

Test Example 2

(32) A cement clinker was prepared by using as a mineralizer fluorine and sulfur to adjust the content of fluorine and the amount of SO.sub.3 in the cement clinker to 750 mg/kg and the SO.sub.3 value shown in Table 4, respectively, and modifying chemical abundance of all the rest components as shown in Tables 1 and 2, and burned as a whole to make a cement. Preparation of the cement was conducted according to the method described above for adding gypsum into the cement clinker and then grinding them. The amount of free-lime in each cement clinker, as well as setting time and the strength of each cement are shown in Table 4. As shown in Table 4, the addition of SO.sub.3 leads to a decrease in the amount of free-lime, and as a result, a mineralizing action to lower the burning temperature may be observed. Table 4 also shows that whereas 4% by mass of the content of SO.sub.3 leads to the strength decreasing of the cement (at its material age of 28 days), 0.5% by mass of the amount of SO.sub.3, resulting in more than 1% by mass of the amount of free-lime. Therefore, the preferable amount of SO.sub.3 is considered to be within a range from 1.5% by mass to 3% by mass in order to provide the cement with sufficient strength and to lower the burning temperature of the cement clinker.

(33) TABLE-US-00004 TABLE 4 Amount of SO.sub.3 f-CaO (% by Setting Strength No. (% by mass) mass) Time (N/mm.sup.2) Remarks B1 0.5 0.36 2:40 6.25 B2 2 0.95 2:35 61 B3 3 0.84 2:24 60.8 B4 4 0.87 2:30 58.2 Strength decreasing

Test Example 3

(34) A cement clinker was prepared by using as a mineralizer fluorine, sulfur and chlorine to adjust the content of fluorine, the content of SO.sub.3 and the amount of the chlorine equivalent in the cement clinker to 750 mg/kg, 2% by mass and the value shown in Table 5, respectively, and modifying chemical abundance of all the rest components as shown in Tables 1 and 2, and burned as a whole to make a cement. Preparation of the cement was conducted according to the method described above for adding gypsum into the cement clinker and then grinding them. The amount of free-lime in each cement clinker, as well as setting time and the strength of each cement are shown in Table 5. As shown in Table 5, the addition of chlorine leads to a decrease in the amount of free-lime, and thereby a mineralizing action may be observed, and that whereas at 80 mg/kg of the amount of chlorine equivalent, the setting time of the cement is 2 hours 35 minutes and is slightly longer, the cement fails to meet the standards of the cement at 520 mg/kg of the amount of the chlorine equivalent. Therefore, the preferable amount of the chlorine equivalent is considered to be within a range from 150 mg/kg to 350 mg/kg.

(35) TABLE-US-00005 TABLE 5 Chlorine equivalents f-CaO Setting Strength No. (mg/kg) (% by mass) Time (N/mm.sup.2) Remarks C1 80 0.95 2:35 61 C2 175 0.74 2:28 62.5 C3 330 0.71 2:25 62.3 C4 520 0.72 2:15 60.8 Nonconformity Note: The cement C4 fails to meet the standards of the cement.

Example 1

(36) A cement clinker was prepared by using as a mineralizer fluorine, sulfur, chlorine and a metallic elements to adjust the amount of fluorine, the content of SO.sub.3 and the amount of the chlorine equivalent in the cement clinker to 750 mg/kg, 2% by mass and 330 mg/kg, respectively, adjusting the amount of the metallic elements to the value shown in Table 6 and modifying chemical abundance of all the rest components as shown in Tables 1 and 2, and burned as a whole to make a cement. Preparation of the cement was conducted according to the method described above for adding gypsum into the cement clinker and then grinding them. The amount of free-lime in each cement clinker, as well as setting time and the strength of each cement are shown in Table 6. The amount of metallic elements corresponds to the sum of the amount of zinc, and the amounts of vanadium, cobalt, nickel and copper expressed in terms of zinc (Zn+1.284 V+1.110 Co+1.114 Ni+1.029 Cu). As shown in Table 6, the addition of metallic elements leads to a considerable decrease in the amount of free-lime and also provides substantial burning even when burned at 1,300 C., and thereby, a mineralizing action may be observed. On the other hand, whereas 0.1% by mass of the amount of metallic elements leads to slightly too much of the amount of free-lime, 1.0% by mass of the amount of metallic elements leads to the strength decreasing of the cement. Therefore, the appropriate amount of metallic elements is considered to be within a range from 0.2 to 0.8% by mass.

(37) TABLE-US-00006 TABLE 6 Amout of metallic elements f-CaO Setting Strength No. (% by mass) (% by mass) Time (N/mm.sup.2) Evaluation D1 0.1 0.71 2:25 62.3 B D2 0.2 0.55 2:26 61 A D3 0.8 0.5 2:28 61.3 A D4 1 0.47 2:43 56 strength decreasing Note: Evaluation A indicates that the cement meets the criteria, and B indicates that the cement has slightly too much of the amount of free-lime.