# Patent

## Title
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 SO3) 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.

## Background
TECHNICAL FIELD
The present invention is related to a burned cement clinker which may be burned at lower temperature than in the past; and a method for producing the same. More particularly, the present invention is related to a burned cement clinker which permits a reduced burning temperature with the addition of fluorine, chlorine and sulfur, as well as a certain metal component, and a method for producing the same.
Priority is claimed on Japanese Patent Application No. 2010-056745 filed on Mar. 12, 2010, the content of which is incorporated herein by reference.
BACKGROUND ART
During the process for producing cement, there is a need for an enormous amount of heat energy to burn a cement clinker at high temperature. Forming a principal mineral alite contained in the cement clinker requires a high temperature burning process which uses enormous amounts of energy. Addition of mineralizers such as fluorides has been known in the past in order to lower the temperature of formation of alite and accelerate its reaction.
For instance, Patent Document 1 (Japanese Unexamined Patent Application, First Publication No. 2009-161412) discloses a cement composition, produced by adding a chlorine-containing compound and gypsum into a ground cement clinker which is made from chlorine-containing wastes and further contains each given amount of fluorine, sulfur and chlorine.
Patent Document 2 (Japanese Unexamined Patent Application, First Publication No. 2009-179512) discloses a cement composition, wherein the cement composition includes a cement clinker ground product containing each given amount of fluorine, sulfur and chlorine, and gypsum, an expansive material and the like
Patent Document 3 (Japanese Unexamined Patent Application, First Publication No. 2009-190904) discloses a soil stabilizer containing gypsum and a cement clinker ground product containing each given amount of fluorine, sulfur and chlorine.
It has been traditionally considered the advantage for the conventionally-known cement composition or the soil stabilizer to use the cement clinker which may be burned at low temperature. However, the burned cement clinker disclosed in Examples in Patent Document 1 includes about 1,500 to about 2,200 mg/kg of fluorine to lower the burning temperature to between 1,270 and 1,300° C. The burned cement clinkers disclosed in the Examples in Patent Documents 2 and 3 contain about 1,000 mg/kg of fluorine to burn them at the burning temperature of 1,370° C. Thus, any of the conventional burned cement clinkers which might be burned at low temperature would contain a large amount of fluorine.
However, fluorine contained in the cement clinker could be factors of deterioration in the quality, including markedly retard setting of the cement, and therefore, it deems undesirable to increase the amount of fluorine.
CITATION LIST
Patent Document
Patent Document 1:


    Japanese Unexamined Patent Application, First Publication No. 2009-161412

Patent Document 2:

    Japanese Unexamined Patent Application, First Publication No. 2009-179512

Patent Document 3:

    Japanese Unexamined Patent Application, First Publication No. 2009-190904


DISCLOSURE OF INVENTION
Technical Problem
The mineralizer containing fluorine, chlorine and sulfur has been used conventionally in order to lower the burning temperature. The burned cement clinker of the present invention is directed to permit a markedly reduced burning temperature of the cement clinker without further increasing the amounts of fluorine and chlorine to accomplish the economical production of the cement clinker by adding as the mineralizer component(s) fluorine, chlorine and sulfur, as well as one or more of metallic element(s) selected from the group consisting of elements in groups 3 through 12 of the periodic table. Moreover, cement made by using the burned cement clinker of the present invention may operate similarly to the traditional ordinary portland cement. Also, the cement made by using the burned cement clinker of the present invention may also comply with current Japanese Industrial Standards (JIS R 5210), official information, technical specification required by academic societies and the like.
Solution to Problem
The present invention is directed to a burned cement clinker which has solved the problems abovementioned through the following constitutions and a method for producing the same.
[1] 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.

[2] The burned cement clinker according to [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 SO3) 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, and the amount of at least one of metallic element(s) 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.

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

[4] The burned cement clinker according to [2] or [3], wherein the metallic element(s) are at least one of metallic element(s) selected from the group consisting of vanadium, cobalt, nickel, copper and zinc, and the amount of the metallic element(s) corresponds to the sum of the amount of zinc and the amounts of the respective metallic elements expressed in terms of zinc.

[5] A method for producing a burned cement clinker comprises: a step of adding, to a cement clinker raw material, a mineralizer which includes a component containing at least one selected from the group consisting of a fluorine component, a sulfur component, chlorine and bromine, and a component containing at least one metallic element selected from the group consisting of elements in groups 3 through 12 of the periodic table, and then burning them; or a step of adding the respective components to each cement clinker raw material, and then burning them.

[6] The method for producing a burned cement clinker according to [5], wherein, a mineralizer is added to a cement clinker raw material, and burning them, and the mineralizer includes a component containing any one or more elected from the group consisting of a fluorine component, a sulfur component, chlorine and bromine, and a component containing metallic element(s) 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 (expressed in terms of SO3) 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(s) 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.

Advantageous Effects of Invention
According to the present invention, the burned cement clinker includes at least any one selected from the group consisting of fluorine, sulfur, chlorine and bromine and any one or more metallic element(s) selected from the group consisting of elements in groups 3 through 12 of the periodic table to permit the burning temperature of the cement clinker to be lowered without increasing the amount of fluorine. In particular, the cement clinker may be burned at a temperature of 1,300° C. or lower even if the amount of fluorine therein is from 300 to 750 mg/kg.
For instance, as shown in Example 1, the burned cement clinker obtained by burning the cement clinker at 1,300° C. so that in the burned cement clinker, the content of fluorine is within a range from 300 to 750 mg/kg, the content of sulfur (expressed in terms of SO3) is within a range from 1.5 to 3.0% by mass, the content of any one or more chlorine equivalent(s) selected from the group consisting of chlorine and bromine is within a range from 150 to 350 mg/kg and the content of any one or more metallic element(s) 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 may have 1.0% by mass or less the amount of free-lime, which indicates that the cement clinker has been substantially burned. Moreover, cement made using the burned cement clinker may have 60 N/mm2 or more of strength at its material age of 28 days and also operate in a matter similar to the conventional ordinary portland cement.


BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be specifically described below by way of embodiments.
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.
[Burned Cement Clinker]
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.
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).
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.
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).
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.
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.
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 SO3) 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.
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 SO3) 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 SO3) 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.
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.
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:
The amount of V expressed in terms of zinc=[atomic ratio of Zn/V]×[amount of V]=1.284×[V];
The amount of Co expressed in terms of zinc=[atomic ratio of Zn/Co]×[amount of Co]=1.110×[Co];
The amount of Ni expressed in terms of zinc=[atomic ratio of Zn/Ni]×[content of Ni]=1.114×[Ni]; and
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].

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.
[Method for Production]
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 SO3) 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.
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.
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
Examples of the present embodiment and Comparative Examples will be illustrated below.
[Preparation of Raw Materials, Test Method]
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.
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”.
The burned cement clinker to which gypsum was added so as to be 2% by mass of the amount of SO3 was ground in a test mill to reduce it to a powder mostly having 3,300 cm2/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.







TABLE 1







[Chemical Composition of Cement Clinker]


















SiO2
Al2O3
Fe2O3
CaO
MgO
SO3
Na2O
K2O
TiO
P2O5
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













TABLE 2







[Modulus values of Cement Clinker and Mineral


Composition as measured by Bouge calculation]















HM
SM
IM
AI
LSD
C3S
C2S
C3A
C4AF





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, C3S: tricalcium silicate, C2S: dicalcium silicate, C3A: tricalcium aluminate, C4AF: calcium aluminoferrite (each mineral composition is represented in % by mass)






Test Example 1
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.











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
A cement clinker was prepared by using as a mineralizer fluorine and sulfur to adjust the content of fluorine and the amount of SO3 in the cement clinker to 750 mg/kg and the SO3 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 SO3 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 SO3 leads to the strength decreasing of the cement (at its material age of 28 days), 0.5% by mass of the amount of SO3, resulting in more than 1% by mass of the amount of free-lime. Therefore, the preferable amount of SO3 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.












TABLE 4






Amount of SO3
f-CaO (% by
Setting
Strength



No.
(% by mass)
mass)
Time
(N/mm2)
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
A cement clinker was prepared by using as a mineralizer fluorine, sulfur and chlorine to adjust the content of fluorine, the content of SO3 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.












TABLE 5






Chlorine







equivalents
f-CaO
Setting
Strength


No.
(mg/kg)
(% by mass)
Time
(N/mm2)
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
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 SO3 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.












TABLE 6






Amout of metallic







elements
f-CaO
Setting
Strength



No.
(% by mass)
(% by mass)
Time
(N/mm2)
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.

## 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 SO3) 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.