CN1587157A - High strength silicate clinker and its preparing method - Google Patents

Abstract

The high strength silicate cement clinker contains small amount of P or P and F and tricalcium silicate, which accounts for 66-76 wt% and is rhombohedral lattice tricalcium silicate or the mixture of rhombohedral lattice tricalcium silicate and monoclinic tricalcium silicate. The present invention also provides the preparation process of the high strength silicate cement clinker, and the preparation process includes mainly adding P and F and sintering at 1400-1500 deg.c. The cement clinker has raised tricalcium silicate content, improved tricalcium silicate crystal structure and raised C3S content and thus raised strength.

Description

A kind of high-strength Portland cement clinker and its preparation method

technical field

The invention belongs to the field of general cement in the cement industry, and in particular relates to a high-strength Portland cement clinker and a preparation method thereof.

Background technique

The cement with Portland cement clinker as the main cementitious component is the cement with the largest amount today, including the six general-purpose cements and some special cements such as dam cement, road cement, and white cement, which account for 98% of the total cement consumption. %above. Portland cement clinker mainly contains four major minerals: tricalcium silicate (ie 3CaO·SiO ₂ , usually abbreviated as C ₃ S), dicalcium silicate (ie 2CaO·SiO ₂ , usually abbreviated as C ₂ S), Tricalcium aluminate (ie 3CaO·Al ₂ O ₃ , usually abbreviated as C ₃ A) and tetracalcium aluminoferrite solid solution (ie 4CaO·Al ₂ O ₃ ·Fe ₂ O ₃ , usually abbreviated as C ₄ AF). The total amount of these four minerals in Portland cement clinker accounts for 95% or even higher. Among them, tricalcium silicate crystals are often solid-dissolved with various impurities, also known as "Alite". Tricalcium silicate (C ₃ S) has the highest content in the cement clinker of the silicate system, usually at 50 -60%; Tricalcium silicate is the mineral with the best gelling performance in clinker and the main source of cement strength. During the sintering process of Portland cement clinker, C ₃ S is the mineral with the highest formation temperature, and the full formation of C ₃ S actually represents the sintering of clinker.

The normal firing temperature range of cement clinker in industrial kilns is 1350°C to 1450°C. Advanced cement kilns can be fired at higher temperatures, and the normal firing temperature of clinker is 1400°C to 1500°C. The strength of cement clinker is usually 50MPa-60MPa when the specific surface area is 320m ² /kg-350m ² /kg.

To obtain cement clinker with a tricalcium silicate (C ₃ S) content of about 70%, the existing scheme is as follows: 1. When no firing admixture is mixed, use a firing temperature higher than 1600°C. The fired tricalcium silicate is mostly triclinic or monoclinic crystal, and the strength of the cement made by grinding this clinker will increase, but the firing temperature as high as 1600°C not only wastes a lot of energy, but also It is difficult to meet this high temperature requirement with a kiln. 2. In order to reduce the firing temperature, the low-temperature firing technology of compound mineralizers mixed with fluorine and sulfur mineralizers can reduce the temperature at which a large amount of tricalcium silicate is formed by about 100°C, so that the clinker firing temperature can be reduced. The temperature is lowered by about 100°C, and the heat consumption of firing is reduced by more than 10%. Using the method of adding fluorine-sulfur compound mineralizer, the content of Al ₂ O ₃ in the raw meal is 3-6%, the saturation coefficient of lime is 0.92-0.98, SO ₃ /Al ₂ O ₃ =1.15-1.45, calcined at 1300°C The prepared clinker contains about 70% of tricalcium silicate, 3-10% of anhydrous calcium sulfoaluminate, 3.5-6% of high-temperature calcined gypsum and a small amount of other minerals. The cement made by grinding this clinker has quite high strength, and its 28-day compressive strength reaches about 60MPa of the current national standard (ISO standard). However, the fluorine-sulfur composite mineralizer doped in this method produces sulfur oxide during the clinker firing process, and the volatilized sulfur oxide pollutes the environment and brings serious environmental protection problems.

Invention content

The object of the present invention is to provide a high-strength Portland cement clinker that can be obtained in the normal firing temperature range.

The high-strength Portland cement clinker provided by the present invention contains trace amounts of phosphorus or trace amounts of phosphorus and trace amounts of fluorine, and 66% to 76% by weight of tricalcium silicate, and the tricalcium silicate is a trigonal lattice or a trigonal crystal a mixture of monoclinic and monoclinic lattices.

The above-mentioned high-strength Portland cement clinker specifically includes the following components, by weight percentage:

Tricalcium silicate, that is, C ₃ S 66% to 76%;

Dicalcium silicate, that is, C ₂ S 3~15%;

Tricalcium aluminate, that is, C ₃ A 3-12%;

Tetracalcium aluminoferrite, that is, C ₄ AF 6-14%;

Free calcium oxide, i.e. f-CaO 0-1.2%; and

The balance is other phases; wherein, the trace phosphorus is 0.05%-0.9% calculated as P ₂ O ₅ , and the trace fluorine is 0-1.5% calculated as CaF ₂ .

In the above-mentioned high-strength Portland cement clinker, the weight percentage of the tricalcium silicate is preferably 69%-74%.

Another object of the present invention is to provide an environmentally friendly and energy-saving method for preparing high-strength Portland cement clinker.

The preparation method of the high-strength Portland cement clinker of the present invention is to mix a phosphorus-containing compound or a phosphorus-containing compound and a fluorine-containing compound into the raw meal as a firing admixture, and the firing temperature range is 1400 ° C to 1550 ° C; wherein The dosing amount of the phosphorus-containing compound is 0.1%-0.7% by weight of the raw material in terms of P ₂ O ₅ , and the weight percentage of the fluorine-containing compound in the raw material is 0%-1.2% in terms of ^F- .

In the above method, the doping amount of the phosphorus-containing compound and the fluorine-containing compound is preferably 0.2-0.4% as P ₂ O ₅ , and the fluorine-containing compound is preferably 0-1.0% as ^F- .

In the above method, the phosphorus-containing compound is one or more selected from phosphate rock, phosphorus tailings, phosphorus slag, steel slag, and the fluorine-containing compound is selected from fluorite, fluorite tailings, fluosilicic acid One or more of sodium, fluorine gypsum and fluorine-containing industrial waste.

The preparation method of the above-mentioned high-strength Portland cement clinker is specifically to add 4-12wt% phosphorus slag to 90-96wt% raw meal, wherein the content of _P2O5 in the _phosphorus slag is 1.2%-2%, F ^- 2 to 3%, P ₂ O ₅ and CaF ₂ are brought into through phosphorus slag, and the firing temperature range is 1400°C to 1550°C; the weight percentage of each component in the raw meal is: CaO=66.5% to 67.1%, SiO ₂ = 21.2% to 21.5%, Al ₂ O ₃ = 4.7% to 5.1%, Fe ₂ O ₃ = 2.9% to 3.3%, and the remainder is other components.

The preparation method of the above-mentioned high-strength Portland cement clinker is specifically to add 4-10 wt% phosphate rock to 90-96 wt% raw meal, and the firing temperature range is 1400°C-1550°C; wherein each of the raw meal Component weight percent is:

CaO = 66.4% to 67.3%, SiO ₂ = 21.1% to 21.6%, Al ₂ O ₃ = 4.3% to 5.4%, Fe ₂ O ₃ = 2.6% to 3.6%, and the remainder is other components.

By adopting the above-mentioned technical scheme, the content of tricalcium silicate in the high-strength clinker proposed by the present invention is higher than that of traditional clinker, and the calcined tricalcium silicate is a trigonal lattice or a combination of a trigonal lattice and a monoclinic lattice. In the mixture, the free calcium oxide content of the clinker is lower than 1.2%, the tricalcium silicate content is higher than 65%, and the 28-day compressive strength of the clinker is higher than 65MPa.

The method for preparing high-strength Portland cement clinker in the present invention mainly adds phosphorus and fluorine during the preparation process, so that the clinker can be fired in the normal temperature range (1400-1500 ° C), and by increasing the silicon content in the clinker The strength of cement clinker is improved by increasing the content of tricalcium silicate and improving the crystal structure of tricalcium silicate. By increasing the content of C ₃ S, the strength of cement clinker is also higher than that of traditional cement clinker.

The preparation method of the present invention can firstly use the existing cement kiln to prepare cement clinker with higher tricalcium silicate content within the normal temperature range, and it is unnecessary to build a high-temperature (above 1600° C.) kiln, thereby saving cost and energy. consumption; the present invention does not use sulfur-containing admixtures, does not produce sulfur oxide pollution in the firing process, and meets environmental protection requirements.

The clinker obtained in the present invention has the characteristics of high self-strength and strong excitation ability to the admixture, can realize high strengthening of cement and a large amount of admixture in cement, and can make up for the disadvantages of concrete with a large amount of mineral admixture. Calcium deficiency problem.

The cement clinker of the present invention can be made into high-strength cement of different strength grades by adding gypsum and mixed materials with different dosages. Within the range of ordinary cement mixture, the cement strength can be greatly improved. Under the same mixture, the national standard GB-175-1999 and GB1344-1999 are used to detect that the cement strength of the present invention is higher than that of ordinary cement clinker. The cement produced is one strength class higher. At the same strength level, the amount of mixed materials is greatly increased compared with the usual clinker. Concrete formulated with this cement has the advantages of particularly high early strength and final strength, and good durability. It is easier to achieve high performance of concrete than traditional cement.

Description of drawings

Fig. 1 is an X-ray diffraction pattern of undoped pure tricalcium silicate (C ₃ S), which belongs to the T ₃ crystal form of the triclinic system.

Fig. 2 is an X-ray diffraction pattern of tricalcium silicate doped with 0.4% P ₂ O ₅ +0.7% CaF ₂ , which belongs to the R crystal form of the trigonal system.

Figure 3 is the X-ray diffraction pattern of the tricalcium silicate solid solution extracted from the cement clinker mixed with P ₂ O ₅ and CaF ₂ , which belongs to the R crystal form of the trigonal system.

Figure 4 is the X-ray diffraction _pattern of tricalcium silicate extracted from the solid solution of tricalcium silicate in the cement clinker mixed with _P2O5 , which belongs to the R crystal form of the trigonal system and the _M1 crystal form of the monoclinic system mixture.

Fig. 5 is the XRD pattern of C ₃ S solid solution when doped with 1% CaF ₂ alone. This tricalcium silicate belongs to the T3 crystal form of the triclinic system.

Fig. 6 is the XRD pattern of C ₃ S solid solution when 1.5% CaF ₂ is single-doped. This tricalcium silicate belongs to the M1 crystal form of the monoclinic system.

Fig. 7 is the XRD pattern of C ₃ S solid solution when doped with 2% CaF ₂ alone, this tricalcium silicate belongs to the crystal form of trigonal crystal system.

Detailed ways

The present invention will solve following technical key:

(1). Improve the burnability of high alite cement clinker. The sinterability of Portland cement clinker becomes worse with the increase of C ₃ S content, and it is difficult to sinter under industrial conditions. In the present invention, first of all, through reasonable adjustment of clinker mineral matching and appropriate doping technology, the burnability of clinker is improved so that it can be produced smoothly in common industrial cement kilns.

In the cement clinker provided by the invention, the content of C ₃ S is 66%-75% (percentage by weight), and the content of free calcium oxide is less than 1.2% (percentage by weight). Mineral composition range: tricalcium silicate (C ₃ S) = 66% to 76%; dicalcium silicate (C ₂ S) = 3 to 15%; tricalcium aluminate (C ₃ A) = 3 to 12%; Tetracalcium aluminoferrite (C ₄ AF) = 6-14%.

The above composition range is converted into the clinker rate value LSF or KH, SM, and IM value ranges used in cement production as follows: LSF = 0.96 ~ 1.00 (or KH = 0.95 ~ 0.99), SM = 1.7 ~ 3.2, IM = 1.2 to 1.9.

(2). Alite lattice activation technology characterized by doping is adopted. Only by increasing the C ₃ S content in the clinker, the strength of the clinker does not necessarily increase, or the increase range is not obvious. The present invention also needs to introduce impurity ion phosphorus or compound phosphorus and fluorine into the conventional chemical composition of cement clinker to control the crystal form and appearance of Alite, make its crystal lattice distorted, increase the amount of defects, activate the crystal lattice, and improve the water content. Chemical activity, so as to obtain high-strength cement clinker. Referring to Fig. 1 to Fig. 4, the crystalline form of alite (C ₃ S) in the cement clinker of the present invention is characterized, from which it can be seen that the pure tricalcium silicate without adding P and F belongs to the triclinic system T ₃ crystal form, tricalcium silicate doped with a small amount of P and F is transformed into monoclinic M1 crystal form and trigonal R crystal form. If F is added alone, tricalcium silicate can also be converted into the R crystal form of the trigonal system, but the required amount of _CaF2 is relatively large (see Figures 5 to 7). The amount of impurities required for compound doping of P and F is less.

In the present invention, phosphorus-containing compounds and fluorine-containing compounds are mainly added as firing admixtures, so that cement clinker with relatively high C ₃ S content can be fired in a normal firing temperature range.

Phosphorus-containing minerals are used as trace doping components. The phosphorus dosage used in the existing research is relatively high, and the conclusion drawn from this is that the addition of phosphorus is beneficial to the formation of dicalcium silicate, but not conducive to the formation of tricalcium silicate, and will even decompose tricalcium silicate. See Table 1. Studies using phosphorus slag batching have also been reported, but limited to the usual tricalcium silicate content range. For example, using electric furnace phosphorous slag as a mineralizer, P ₂ O ₅ content of 0.24-2.26%, the content of tricalcium silicate in clinker is less than 60%, measured according to the original national standard (GB 175-1985), clinker 28 days The compressive strength is lower than 60MPa, equivalent to the current national standard of 50MPa or lower, see Table 2 and Table 3.

Table 1 Effect of phosphorus doping on the formation and decomposition of silicate minerals (1450℃ for 2 hours) Raw material ratio (wt%) C/S P ₂ O ₅ (%) f-CaO(%) Calculation of compound rate or decomposition rate by f-CaO 65.11CaO+ _34.89SiO2 2 0 0.40 About 99% CaO combined with _SiO2 57.85CaO+31SiO ₂ +11.15C ₃ P 2 5.1 0.39 About 99% CaO combined with _SiO2 73.75CaO+ _26.25SiO2 3 0 7.43 About 90% CaO combined with _SiO2 50.53CaO+25.1SiO ₂ +4.375C ₃ P 3 2.0 27.00 About 60% CaO combined with _SiO2 75.44β-C ₂ S+24.56CaO 3 0 8.74 About 64% β-C ₂ S combined with SiO ₂ 75.44β-C ₂ S+24.56CaO+21.8C ₃ P 3 10 21.20 About 14% β-C ₂ S combined with SiO ₂ 93.45C ₃ S+6.55C ₃ P 3 3 2.76 About 11% C ₃ S decomposed 78.15C ₃ S+21.85C ₃ P 3 10 14.30 About 58% C ₃ S decomposition

Table 2 Effect of P ₂ O ₅ content on clinker strength (old national standard GB 175-1985) serial number Clinker rate value (ingredients) P ₂ O ₅ f-CaO Compressive strength (MPa) Kh no P % % 3d 7d 28d P1 0.94 1.80 2.60 0.24 3.80 30.47 51.25 59.88 P2 0.93 1.83 2.57 0.90 3.02 24.40 39.00 57.23 P3 0.91 1.89 2.60 1.54 5.32 19.70 31.46 47.63 P4 0.90 1.89 2.38 2.26 7.27 9.60 17.05 48.51

Table 3 Batching rate and clinker strength of small kiln clinker (old national standard GB 175-1985) Phosphorus slag content% rate value f-CaO(%) C ₃ S (%) Flexural strength (MPa) Compressive strength (MPa) Kh no P 3d 7d 28d 3d 7d 28d 90d 0 0.97 2.71 2.73 5.19 51.33 4.90 5.48 6.86 25.3 32.7 45.8 56.7 10 1.00 3.06 2.83 4.39 60.79 4.31 5.78 7.45 27.5 36.3 50.6 64.7 15 0.98 2.62 2.68 4.20 57.58 5.10 5.78 7.55 27.4 38.6 54.3 70.8 20 0.97 2.29 2.56 3.64 55.38 6.08 7.25 7.94 39.9 51.6 64.4 78.8 30 0.97 4.68 2.88 3.87 62.67 6.57 7.54 8.62 42.2 53.6 67.4 81.3

The present invention is verified by experiments that a small amount of phosphorus-containing compound is mixed into the raw meal as a firing admixture, but the burnability of the raw meal can be improved, the firing process can be improved, and the formation of clinker can be accelerated. When the doping amount is 0.07% to 0.70% by weight based on P ₂ O ₅ in the raw material, firing is relatively easy.

Here, the phosphorus-containing compounds include: phosphorus slag, phosphorus rock, phosphorus tailings, steel slag and the like. Fluorine-containing compounds are fluorspar, fluorite tailings, sodium fluorosilicate, fluorogypsum and other fluorine-containing industrial waste residues.

In the present invention, a fluorine-containing compound is added when a small amount of phosphorus-containing compound is added, and the fluorine-containing compound accounts for 0% to 1.2% by weight of the raw meal in terms of ^F- , and the cement raw meal mixed with a small amount of phosphorus-containing compound and fluorine-containing compound , the clinker with high C ₃ S content is fired at a relatively low temperature, the firing temperature ranges from 1400°C to 1550°C, and the strength of the clinker increases, and when it is ground to a specific surface area of 310m ² /kg to 360m ² /kg The 28-day compressive strength of the clinker reaches 65MPa-85MPa, which is 5-20MPa higher than the usual clinker.

Embodiment 1,

Limestone, clay, and quartz sand are used as the main raw materials, and bauxite is used as the correcting raw material. By adding steel slag, fluorite, and phosphorous tailings respectively to introduce trace components, the cement raw meal is prepared. The ratio of each raw meal is shown in Table 1-1. Among them, the dosing amount of P ₂ O ₅ in raw meal is 0.1%~0.34%, and the dosing amount of CaF ₂ is 0.04%~0.39%. is the mass percentage. Among them, steel slag contains a small amount of phosphorus oxide and fluorine, and phosphorus tailings contain a small amount of phosphorus oxide. The rate value and mineral composition of the designed clinker are listed in Table 1-2, where KH is the lime saturation coefficient, SM is the silicic acid rate, IM is the alumina rate, and C ₃ S represents tricalcium silicate (3CaO·SiO ₂ ) , C ₂ S stands for dicalcium silicate (2CaO·SiO ₂ ), C ₃ A stands for tricalcium aluminate (3CaO·Al ₂ O ₃ ), C ₄ AF stands for tetracalcium aluminoferrite (4CaO·Al ₂ O ₃ · Fe ₂ O ₃ ). Raise the temperature of the raw meal and burn it into cement clinker at 1400°C, 1450°C and 1500°C, respectively. The chemical composition of the clinker and the free calcium oxide content at each temperature are shown in Table 1-3, all in the table are mass percentages. From the free calcium oxide data, it can be seen that under the condition of adding trace amounts of fluorine and phosphorus, the cement clinker with high tricalcium silicate content has been fired at 1400°C, 1450°C and 1500°C, which shows that the clinker has a wide range. The firing temperature range is suitable for industrial production. Table 1-4 shows the mineral composition of the clinker fired at 1500°C. Considering the solid solution of impurities in the silicate phase, the content of tricalcium silicate solid solution (also known as Alite) in the clinker is higher than that of The values listed in Table 1-4, while the content of C ₃ A and C ₄ AF is lower than the values listed in the table, and the content of alite in the clinker of numbers A1, A2, A4, A5 and A6 all reaches more than 70%.

Mix 95% of clinker with 5% of natural dihydrate gypsum, grind in a ball mill, and the specific surface area will reach 340m ² /kg-360m ² /kg. The strength is tested by the method specified in the national standard, and the results are listed in the table 1-4. It can be seen from the results in Table 1-4 that the strength of the clinker is very high.

Table 1-1 serial number limestone clay Quartz sand Bauxite plaster fluorite steel slag Phosphorus tailings sum A1 80.4 15.4 0.7 0.3 0 0 3.2 0 100.0 A2 80.1 15.3 0.7 0.3 0 0.4 3.2 0 100.0 A3 79.0 15.1 0.7 0.3 1.4 0.4 3.1 0 100.0 A4 72.0 15.4 0.7 0.3 0 0 3.2 8.4 100.0 A5 72.8 13.5 0.5 0 0 0.4 12.8 0 100.0 A6 64.7 13.6 0.5 0 0 0 12.8 8.4 100.0

Table 1-2 serial number Design clinker rate value Design clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other A1 0.97 2.67 2.00 72.5 6.2 9.5 8.1 3.7 A2 0.97 2.67 1.99 72.4 5.8 9.5 8.0 4.3 A3 0.97 2.68 2.01 71.0 5.9 9.3 7.8 6.0 A4 0.97 2.67 2.00 72.2 6.2 9.5 8.0 4.1 A5 0.98 1.98 0.93 72.0 2.8 4.0 15.8 5.4 A6 0.98 1.99 0.94 71.8 3.2 4.1 15.8 5.1

Table 1-3 serial number Clinker chemical composition/% Clinker free calcium oxide/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ CaF ₂ P ₂ O ₅ other 1400°C 1450°C 1500℃ A1 21.24 5.30 2.65 67.12 2.41 0.00 0.06 0.15 1.07 1.40 1.06 0.98 A2 21.08 5.26 2.64 66.75 2.40 0.00 0.61 0.15 1.11 1.17 1.08 0.88 A3 20.74 5.17 2.58 66.29 2.35 0.99 0.60 0.15 1.13 1.35 1.40 1.22 A4 21.18 5.28 2.64 66.91 2.40 0.00 0.08 0.37 1.04 0.97 1.09 0.37 A5 19.92 4.85 5.19 64.69 3.35 0.00 0.58 0.26 1.13 0.87 0.67 0.81 A6 20.01 4.87 5.20 64.84 3.35 0.00 0.13 0.50 1.00 0.45 0.11 0.17

Table 1-4 serial number Mineral composition at 1500℃/% Compressive strength/MPa Flexural strength/MPa C ₃ S C ₂ S C ₃ A C ₄ AF other 3 days 28 days 3 days 28 days A1 68.4 9.3 9.6 8.1 4.6 5.8 10.1 39.6 70.2 A2 68.7 8.6 9.5 8.0 5.2 6.1 10.5 40.1 70.7 A3 65.9 9.8 9.4 7.8 7.1 5.7 9.5 38.5 68.6 A4 70.6 7.5 9.5 8.0 4.4 6.3 10.7 41.6 71.1 A5 68.6 5.3 4.1 15.8 6.2 6.2 10.2 41.2 70.5 A6 71.0 3.8 4.1 15.8 5.3 5.9 10.8 42.7 73.6

Example 2

Limestone and clay are used as the main raw materials, iron powder is used as the correction raw material, and steel slag, fluorite, gypsum, and phosphorous tailings are mixed respectively, and trace components such as fluorine, phosphorus, and sulfur are introduced from these raw materials to prepare cement raw meal. The content of P ₂ O ₅ in phosphorous tailings is 3.3%. The ratio of each raw meal is shown in Table 2-1, in which the mixing amount of P ₂ O ₅ and CaF ₂ in the raw meal is 0.07%~0.29% and 0.04%~0.41% respectively, the designed clinker ratio and mineral composition See Table 2-2. All in the table are percent by mass. Raw meal is heated up and fired into cement clinker at 1400°C, 1450°C and 1500°C respectively. The chemical composition of clinker and the free calcium oxide content at each temperature are shown in Table 2-3 (all in the table are mass percentages). From the free calcium oxide data, it can be seen that this group of cement clinker with high tricalcium silicate content has basically been fired at 1400°C, 1450°C and 1500°C, indicating that the clinker has a wide firing temperature range. However, the flammability of B2 and B5 raw meal with higher sulfur content mixed with gypsum is slightly worse than that of other groups of raw meal. Table 2-4 shows the mineral composition of the clinker fired at 1500°C. The content of tricalcium silicate solid solution (also known as Alite) in the clinker is higher than the values listed in Table 2-4, while C ₃ A and C ₄ AF content is lower than the values listed in the table. Mix 95% of clinker and 5% of natural dihydrate gypsum, grind them in a ball mill, and the specific surface area will reach 340m ² /kg-360m ² /kg. The strength is tested by the method stipulated in the national standard, and the results are listed in the table 2-4.

table 2-1 serial number limestone clay iron powder plaster fluorite steel slag Phosphorus tailings sum B1 79.3 16.2 0.4 0 0 4.1 0 100.0 B2 78.5 15.9 0.4 1.3 0 3.9 0 100.0 B3 79.2 16.1 0.4 0 0.4 3.9 0 100.0 B4 73.1 16.2 0.4 0 0 3.9 6.4 100.0 B5 78.2 15.8 0.4 1.4 0.4 3.8 0 100.0

Table 2-2 Design clinker rate value and clinker mineral composition serial number Design clinker rate value Design clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other B1 0.96 2.5 1.6 70.4 7.5 8.2 10.0 3.9 B2 0.97 2.5 1.6 70.8 6.0 8.1 9.7 5.4 B3 0.96 2.5 1.6 70.9 6.6 8.2 9.8 4.5 B4 0.96 2.5 1.6 70.7 7.0 8.3 9.8 4.2 B5 0.97 2.5 1.6 70.8 5.5 8.1 9.6 6.1

Table 2-3 serial number Clinker chemical composition/% Clinker free calcium oxide/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ CaF ₂ P ₂ O ₅ other 1400°C 1450°C 1500℃ B1 21.13 5.21 3.29 66.50 2.51 0.03 0.05 0.12 1.16 1.00 0.69 0.62 B2 20.71 5.11 3.20 66.26 2.46 0.95 0.05 0.11 1.15 1.79 1.40 1.33 B3 20.96 5.17 3.22 66.22 2.48 0.03 0.65 0.11 1.16 1.43 1.04 0.93 B4 21.06 5.19 3.22 66.38 2.48 0.03 0.05 0.43 1.16 1.28 0.74 0.47 B5 20.54 5.06 3.15 65.88 2.44 1.02 0.60 0.11 1.20 1.70 1.44 1.50

Table 2-4 serial number Mineral composition at 1500℃/% Compressive strength/MPa Flexural strength/MPa C ₃ S C ₂ S C ₃ A C ₄ AF other 3 days 28 days 3 days 28 days B1 67.7 9.5 8.2 10.0 4.6 5.6 9.6 37.3 67.4 B2 65.3 10.1 8.1 9.7 6.8 5.6 9.5 36.1 66.2 B3 67.0 9.5 8.3 9.8 5.4 5.8 9.7 37.9 68.3 B4 68.7 8.6 8.3 9.8 4.6 6.0 10.1 39.6 70.1 B5 64.5 10.2 8.1 9.6 7.6 5.5 8.9 35.2 65.5

Example 3

Limestone, clay, iron powder, quartz sand and fly ash are used as raw materials, and phosphate rock is added to introduce trace component P ₂ O ₅ to prepare cement raw meal. The content of P ₂ O ₅ in phosphate rock is 21.3%. See Table 3-1 for the ratio of raw materials, all in the table are mass percentages. The designed clinker ratio and mineral composition are listed in Table 3-2.

Raw meal is heated up and fired into cement clinker at 1400°C, 1450°C and 1500°C respectively. See Table 3-3 for the chemical composition of the clinker and the free calcium oxide content at each temperature, all in the table are mass percentages. From the free calcium oxide data, it can be seen that these cement clinkers with high tricalcium silicate content have been fired at 1400°C, 1450°C and 1500°C under the condition of adding trace phosphorus, which shows that the clinker has good burnability. and wide firing temperature range. Table 3-4 shows the mineral composition of the clinker fired at 1500°C, and the content of alite in the clinker of E4 and E8 is about 70%.

Mix 95% of clinker and 5% of natural dihydrate gypsum, grind them in a ball mill, and the specific surface area will reach 340m ² /kg-360m ² /kg. The strength is tested by the method stipulated in the national standard, and the results are listed in the table 3-4. It can be seen from the results in Table 3-4 that the clinker has reached a higher strength.

Table 3-1 serial number limestone clay iron powder Quartz sand Low Calcium Fly Ash High Calcium Fly Ash Phosphate rock sum E3 81.7 8.6 1.8 3.9 3.0 0 1.0 100.0 E4 80.1 7.0 1.2 3.8 0 6.9 1.0 100.0 E7 80.8 5.8 3.9 4.6 3.9 0 1.0 100.0 E8 79.0 6.4 3.3 3.4 0 6.9 1.0 100.0

Table 3-2 Design clinker rate value Design clinker mineral composition/% serial number K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other E3 0.97 2.50 1.60 72.1 6.3 8.3 9.9 3.3 E4 0.96 2.50 1.62 71.2 6.8 8.4 9.8 3.9 E7 0.97 2.00 1.03 71.2 4.8 5.2 15.3 3.5 E8 0.97 2.00 1.02 70.2 5.2 5.1 15.2 4.2

Table 3-3 serial number Clinker chemical composition/% Free CaO/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ P ₂ O ₅ other 1400°C 1450°C 1500℃ E3 21.19 5.23 3.26 67.14 2.11 0.16 0.32 0.59 1.14 1.29 1.32 E4 21.10 5.21 3.21 66.81 2.22 0.31 0.32 0.82 1.32 1.08 0.46 E7 20.40 5.18 5.02 66.11 2.14 0.33 0.32 0.50 1.20 1.11 0.85 E8 20.29 5.13 5.02 65.68 2.26 0.47 0.32 0.83 1.25 0.57 0.22

Table 3-4 serial number Mineral composition% at 1500℃ Compressive strength (MPa) Flexural strength (MPa) C ₃ S C ₂ S C ₃ A C ₄ AF other 3 days 28 days 3 days 28 days E3 66.6 10.5 8.3 9.9 4.7 5.6 9.5 37.5 67.8 E4 69.2 8.3 8.4 9.8 4.3 6.2 10.5 40.1 70.3 E7 67.6 7.5 5.3 15.3 4.3 5.3 9.8 38.9 68.9 E8 69.2 6.0 5.1 15.3 4.4 5.6 10.7 41.6 71.4

Example 4

Limestone, clay and iron powder are used as main raw materials, mixed with phosphate rock, fluorite and gypsum to introduce trace components P ₂ O ₅ , CaF ₂ , CaSO ₄ to prepare cement raw meal. Among them, the content of P ₂ O ₅ in phosphate rock is 16.6%. See Table 4-1 for each raw meal ratio, and Table 4-2 for the designed clinker ratio and mineral composition. All in the table are percent by mass.

Raise the temperature of the raw meal and burn it at 1450°C±50°C to produce cement clinker. The chemical composition of the clinker is shown in Table 4-3, all in the table are mass percentages. The free calcium oxide content of clinker, the rate of clinker and the clinker mineral composition after deducting free calcium oxide are listed in Table 4-4. From the data of free calcium oxide, it can be seen that under the condition of adding trace amounts of fluorine, phosphorus and sulfur Cement clinker with high tricalcium silicate content has been fired at 1450°C±50°C, indicating that clinker is suitable for industrial production in modern cement kilns. The Alite content of each clinker in Table 4-4 is as high as about 70%.

Mix 95% of clinker with 5% of natural dihydrate gypsum, grind in a ball mill, and the specific surface area reaches 320m ² /kg-350m ² /kg, and test the setting time, stability and Strength, the test results are listed in Table 4-5. From the results in Table 4-5, it can be seen that the setting time of the clinker is normal, in line with the national standard, and the stability is qualified. The strength of the F4 clinker mixed with gypsum in the raw meal is slightly lower, and the 28-day compressive strength of the other two groups of clinker exceeds 70MPa. , and there is still a relatively large increase in the strength in the later stage.

Table 4-1 serial number limestone clay iron powder Phosphate rock fluorite plaster sum F3 80.4 16.3 1.6 1.3 0.4 0 100.0 F4 79.2 16.1 1.6 1.3 0.4 1.4 100.0 F9 79.2 16.3 1.6 2.5 0.4 0 100.0

Table 4-2 serial number Design clinker rate value Design clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other F3 0.97 2.53 1.62 71.8 5.8 8.2 9.6 4.5 F4 0.97 2.52 1.61 70.1 6.2 8.0 9.5 6.2 F9 0.97 2.53 1.62 71.5 5.9 8.2 9.6 4.8

Table 4-3 serial number Clinker chemical composition/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ CaF ₂ P ₂ O ₅ other F3 20.94 5.12 3.17 66.38 2.09 0.13 0.61 0.32 1.24 F4 20.61 5.04 3.13 65.87 2.05 1.12 0.61 0.31 1.26 F9 20.88 5.11 3.16 66.16 2.07 0.13 0.61 0.63 1.25

Table 4-4 serial number Free CaO/% Clinker rate value Clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other F3 0.22 0.96 2.53 1.62 70.68 6.62 8.23 9.62 4.85 F4 0.11 0.96 2.52 1.61 69.14 6.67 8.07 9.52 6.60 F9 0.49 0.96 2.53 1.62 70.23 6.86 8.20 9.60 5.11

Table 4-5 serial number Specific surface area/m ² /kg Coagulation time/min stability Flexural strength/Mpa Compressive strength/Mpa initial setting final set 3d 7d 28d 90d 3d 7d 28d 90d F3 328 276 317 qualified 5.9 8.2 10.3 10.4 34.3 50.6 70.9 82.7 F4 341 372 444 qualified 5.9 8.1 9.3 10.4 32.9 53.3 67.3 81.8 F9 337 226 286 qualified 6.2 7.8 9.5 10.2 36.4 51.6 70.6 81.4

Example 5

Limestone, clay and iron powder are used as main raw materials, mixed with phosphate rock and gypsum to introduce trace components P ₂ O ₅ and CaSO ₄ to prepare raw cement meal. Among them, the content of P ₂ O ₅ in phosphate rock is 16.6%. See Table 5-1 for each raw meal ratio, and Table 5-2 for the designed clinker ratio and mineral composition. All in the table are percent by mass.

Raise the temperature of the raw material and burn it at 1450°C±50°C to produce cement clinker. The chemical composition of the clinker is shown in Table 5-3, all in the table are mass percentages. The content of free calcium oxide in clinker, the ratio of clinker and the mineral composition of clinker after deducting free calcium oxide are listed in Table 5-4. From the data of free calcium oxide, it can be seen that under the condition of adding trace phosphorus, high silicon Cement clinker with tricalcium acid content has been fired at 1450°C±50°C, indicating that clinker is suitable for modern cement kiln industrial production. The Alite content of each clinker in Table 5-4 is as high as about 70%.

Mix 95% of clinker and 5% of natural dihydrate gypsum, grind them in a ball mill, and the specific surface area will reach 330m ² /kg-360m ² /kg, and test the setting time, stability and Strength, the test results are listed in Table 5-5. From the results in Table 5-5, it can be seen that the setting time of clinker is slightly longer than that of ordinary portland cement (common setting time is 60-180 minutes), but it is also normal, in line with national standards, and the stability is qualified , high strength, 28-day compressive strength reaches or approaches 70MPa.

Table 5-1 serial number limestone clay iron powder plaster Phosphate rock sum F5 80.9 16.2 1.6 0 1.3 100.0 F6 80.1 16.4 1.6 0 1.9 100.0 F7 79.5 16.4 1.6 0 2.5 100.0 F8 78.3 16.2 1.6 1.4 2.5 100.0

Table 5-2 serial number Design clinker rate value Design clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other F5 0.98 2.52 1.62 74.0 4.2 8.2 9.7 3.9 F6 0.97 2.53 1.62 71.7 6.3 8.3 9.7 4.1 F7 0.97 2.53 1.62 71.6 6.3 8.3 9.6 4.2 F8 0.96 2.52 1.61 69.8 6.7 8.1 9.5 5.9

Table 5-3 serial number Clinker chemical composition/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ P ₂ O ₅ other F5 20.95 5.13 3.18 66.95 2.10 0.13 0.32 1.24 F6 21.07 5.15 3.18 66.65 2.09 0.13 0.47 1.26 F7 21.04 5.15 3.17 66.54 2.09 0.13 0.63 1.25 F8 20.70 5.06 3.14 66.03 2.05 1.12 0.63 1.27

Table 5-4 serial number Free CaO% Clinker rate value Clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other F5 0.73 0.96 2.52 1.62 70.90 6.57 8.23 9.66 4.64 F6 0.47 0.96 2.53 1.62 69.69 7.81 8.29 9.66 4.55 F7 0.40 0.96 2.53 1.62 69.84 7.62 8.27 9.64 4.63 F8 0.27 0.96 2.52 1.61 68.45 7.60 8.11 9.54 6.30

Table 5-5 serial number Specific surface area/m ² /kg Coagulation time/min stability Flexural strength/Mpa Compressive strength/Mpa initial setting final set 3d 7d 28d 3d 7d 28d F5 354 233 283 qualified 5.92 8.08 9.18 35.79 52.10 68.46 F6 348 224 267 qualified 5.90 7.68 9.35 34.31 49.35 70.98 F7 344 219 289 qualified 6.07 7.79 9.31 34.32 49.54 69.73 F8 337 221 279 qualified 5.70 7.63 9.36 34.24 50.52 70.91

Example 6

Limestone, clay, iron powder, steel slag, and quartz sand are used as raw materials to prepare raw cement. The content of P ₂ O ₅ in steel slag is 1.63%. See Table 6-1 for the ratio of raw meal, and see Table 6-2 for the designed clinker ratio and clinker mineral composition. All in the table are percent by mass.

Raise the temperature of the raw material and burn it at 1450°C±50°C to produce cement clinker. The chemical composition of the clinker is shown in Table 6-3, all in the table are mass percentages. The content of free calcium oxide in clinker, the rate of clinker and the mineral composition of clinker after deducting free calcium oxide are listed in Table 6-4. From the data of free calcium oxide, it can be seen that under the condition of adding a small amount of phosphorus with steel slag, Cement clinker with high tricalcium silicate content has been fired at 1450°C±50°C, which shows that clinker is suitable for modern cement kiln industrial production. The Alite content of each clinker in Table 6-4 is as high as about 70%.

Mix 95% of clinker and 5% of natural dihydrate gypsum, grind them in a ball mill, and the specific surface area will reach 330m ² /kg-360m ² /kg, and test the setting time, stability and Strength, the test results are listed in Table 6-5. From the results in Table 6-5, it can be seen that the setting time of the clinker is normal, in line with the national standard, the stability is qualified, and the strength is high.

Table 6-1 serial number limestone clay iron powder Quartz sand steel slag sum F12 73.1 13.7 0.0 0.4 12.8 100.0 F13 74.4 14.0 0.7 0.3 10.6 100.0 F14 76.0 14.3 1.5 0.2 8.0 100.0

Table 6-2 serial number Design clinker rate value Design clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other F12 0.98 1.98 0.94 72.3 2.9 4.1 15.9 4.2 F13 0.98 1.98 0.94 71.9 3.4 4.2 15.9 4.7 F14 0.98 1.98 0.94 72.0 3.4 4.2 15.9 4.5

Table 6-3 serial number Clinker chemical composition/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ CaF ₂ P ₂ O ₅ other F12 20.03 4.90 5.21 65.06 3.37 0.00 0.06 0.32 1.05 F13 20.09 4.92 5.23 65.14 3.17 0.05 0.05 0.27 1.08 F14 20.12 4.94 5.23 65.31 2.93 0.12 0.04 0.20 1.11

Table 6-4 serial number Free CaO% Clinker rate value Clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other F12 0.48 0.97 1.98 0.94 69.74 4.79 4.18 15.85 5.44 F13 0.55 0.97 1.98 0.94 69.63 5.03 4.21 15.91 5.22 F14 0.57 0.97 1.98 0.94 69.75 5.05 4.25 15.90 5.05

Table 6-5 serial number Specific surface area/m ² /kg Coagulation time/min stability Flexural strength/Mpa Compressive strength/Mpa initial setting final set 3d 28d 3d 28d F12 356 217 284 qualified 5.72 10.01 42.14 71.33 F13 345 207 278 qualified 5.36 9.79 40.17 71.71 F14 331 227 272 qualified 5.15 9.54 36.04 68.51

Example 7

为2.47％，通过磷渣带入P₂O₅和CaF₂。生料配比见表7-1，设计的熟料率值和矿物组成见表7-2。Limestone, clay, iron powder, bauxite and phosphorus slag are used as raw materials to prepare cement raw meal. P ₂ O ₅ content in phosphorus slag is 1.7%,

It is 2.47%, and P ₂ O ₅ and CaF ₂ are brought into by phosphorus slag. See Table 7-1 for the ratio of raw meal, and see Table 7-2 for the designed clinker ratio and mineral composition.

Raise the temperature of the raw meal, and burn it into cement clinker at 1400°C, 1450°C, and 1500°C respectively. The chemical composition of the clinker is shown in Table 7-3. The free calcium oxide of the clinker at each temperature and the clinker after deducting the free calcium oxide See Table 7-4, Table 7-5 and Table 7-6 for ratio values and mineral compositions, all of which are mass percentages. Under the condition of introducing a small amount of phosphorus with phosphorus slag, the cement clinker with high tricalcium silicate content has been fired at 1450°C±50°C, and the tricalcium silicate content of the clinker is higher than 70%, indicating that these clinkers have Very good burnability, suitable for industrial production of modern cement kilns.

Mix 95% by mass of clinker fired at 1450°C and 5% by mass of natural dihydrate gypsum, and grind it in a ball mill until the specific surface area reaches 330m ² /kg-360m ² /kg, and use the method specified in the national standard to test the coagulation Time, stability and strength, the test results are listed in Table 7-7. From the results in Table 7-7, it can be seen that the setting time of the clinker is normal, in line with the national standard, the stability is qualified, and the strength is very high.

Table 7-8 shows the strength of cement mixed with different amounts and types of admixtures. It can be seen from the data in the table that these clinkers are mixed with a large amount of industrial waste as a mixture, and the cement produced still has high strength, which shows that these clinkers have good gelling properties.

Table 7-1 serial number limestone clay iron powder Bauxite Phosphorus slag sum G2 79.7 14.7 1.6 0 4.0 100.0 G3 78.4 13.7 1.7 0.2 6.0 100.0 G4 77.2 12.6 1.8 0.4 8.0 100.0 G5 76.0 11.5 1.8 0.6 10.1 100.0

Table 7-2 Design clinker ratio and mineral composition serial number Design clinker rate value Design clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other G2 0.96 2.70 1.61 72.3 6.9 7.8 9.3 3.80 G3 0.96 2.69 1.60 71.4 7.6 7.8 9.3 3.92 G4 0.96 2.68 1.59 71.7 7.1 7.8 9.4 4.03 G5 0.96 2.70 1.63 72.2 6.6 7.9 9.1 4.14

Table 7-3 serial number Clinker chemical composition/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ CaF ₂ P ₂ O ₅ other G2 21.41 4.89 3.05 66.96 2.14 0.14 0.32 0.11 0.98 G3 21.43 4.90 3.07 66.80 2.15 0.15 0.46 0.16 0.88 G4 21.36 4.90 3.08 66.76 2.16 0.16 0.63 0.22 0.63 G5 21.32 4.89 3.01 66.77 2.18 0.17 0.78 0.27 0.61

Table 7-4 serial number 1400℃Free CaO% Clinker rate value Mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other G2 0.35 0.96 2.70 1.61 70.74 8.02 7.81 9.26 4.17 G3 0.16 0.96 2.69 1.60 70.60 8.16 7.81 9.32 4.11 G4 0.08 0.96 2.68 1.59 71.28 7.45 7.77 9.36 4.14 G5 0.09 0.96 2.70 1.63 71.73 7.00 7.87 9.14 4.26

Table 7-5 serial number 1450℃Free CaO/% 1450 ℃ firing clinker rate value 1450℃ Burned Mineral Composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other G2 0.13 0.96 2.70 1.61 71.63 7.34 7.81 9.26 3.96 G3 0.30 0.95 2.69 1.60 70.04 8.59 7.81 9.32 4.24 G4 0.08 0.96 2.68 1.59 71.28 7.45 7.77 9.36 4.14 G5 0.05 0.96 2.70 1.63 71.90 6.88 7.87 9.14 4.21

Table 7-6 serial number 1500℃Free CaO/% 1500 ℃ firing clinker rate value 1500℃ Burned Mineral Composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF other G2 0.26 0.95 2.70 1.61 71.57 7.78 7.81 9.26 3.58 G3 0.06 0.96 2.69 1.60 71.01 7.86 7.81 9.32 4.00 G4 0.08 0.96 2.68 1.59 71.28 7.45 7.77 9.36 4.14 G5 0.05 0.96 2.70 1.63 71.90 6.88 7.87 9.14 4.21

Table 7-7 serial number Specific surface area/m ² /kg Coagulation time/min stability Flexural strength/Mpa Compressive strength/Mpa initial setting final set 3d 28d 3d 28d G2 342 98 186 qualified 5.92 10.5 41.2 74.5 G3 360 112 188 qualified 6.11 10.3 40.6 75.2 G4 355 105 201 qualified 6.05 10.8 40.5 73.1 G5 336 109 195 qualified 5.88 10.1 40.0 70.6

Table 7-8 clinker Mixed material Specific surface area/m ² /kg Coagulation time/min stability Flexural strength/Mpa Compressive strength/Mpa serial number Dosage/% type Dosage/% initial setting final set 3 days 28 days 3 days 28 days G2 80 slag 15 378 124 188 qualified 5.7 10.3 40.6 75.2 G2 75 fly ash 20 384 135 212 qualified 5.5 9.8 39.3 74.2 G2 60 Lightly burned coal gangue 35 392 115 175 qualified 5.6 9.7 38.6 72.8 G3 75 steel slag 20 368 136 198 qualified 5.8 10.2 40.3 73.6 G3 60 steel slag 35 395 168 226 qualified 5.6 9.9 38.5 71.6 G3 45 steel slag 50 380 182 268 qualified 4.2 8.5 33.6 65.1 G4 40 slag 50 378 175 233 qualified 4.8 9.2 36.5 69.5

G4 30 slag 60 384 251 335 qualified 4.1 8.8 34.1 67.6 G4 25 slag 70 388 285 357 qualified 3.5 8.2 32.2 66.2 G5 65 fly ash 30 390 188 256 qualified 4.6 8.8 33.5 68.2 G5 55 fly ash 40 395 216 276 qualified 4.1 7.9 31.6 64.2 G5 45 fly ash 50 379 258 343 qualified 3.9 7.8 28.7 60.0

Example 8

Limestone, clay, and iron powder are used as main raw materials, and phosphorus slag, phosphorus tailings, fluorite, steel slag, etc. are mixed with P ₂ O ₅ and fluorine as trace components to prepare cement raw meal. P ₂ O ₅ content in phosphorus slag is 1.6%, F ^- is 2.53%. The P ₂ O ₅ content in steel slag is 1.2% and the CaF ₂ content is 0.5%. The content of P ₂ O ₅ in phosphorous tailings is 2.5%. See Table 8-1 for the ratio of raw meal, and see Table 8-2 for the designed clinker ratio and mineral composition.

Raise the temperature of the raw material and burn it at 1450°C±50°C to produce cement clinker. The chemical composition of the clinker is shown in Table 8-3, all in the table are mass percentages. The free calcium oxide content of the clinker, the clinker rate value after deducting the free calcium oxide and the clinker mineral composition are listed in Table 8-4. From the free calcium oxide data, it can be seen that when phosphorus slag, phosphorus tailings, fluorite Under the condition of introducing P ₂ O ₅ and fluorine as trace components such as steel slag, these cement clinkers with high tricalcium silicate content can be completely fired at 1450°C±50°C. The Alite content of each clinker in Table 8-4 is as high as 66%-73%.

Mix 95% of clinker with 5% of natural dihydrate gypsum, and grind it in a ball mill. The specific surface area reaches 310m ² /kg-350m ² /kg. The setting time and stability are tested by the method stipulated in the national standard. The test results are listed in Table 8-5, and the strength measurement results are shown in Table 8-6. From these results, it can be seen that the setting time of the clinker is normal, in line with the national standard, the stability is qualified, and it has high strength.

Table 8-1 serial number limestone clay iron powder Phosphorus slag fluorite Phosphorus tailings steel slag sum H3 77.5 12.8 0.3 6.0 0 0 3.4 100.0 H5 78.8 13.7 1.5 6.0 0 0 0 100.0 H6 74.6 13.7 1.5 6.0 0 4.2 0 100.0 H7 78.8 13.7 1.5 6.0 0.5 0 0 100.0 H9 71.1 13.8 0.7 0 0 8.4 0 100.0 H10 74.1 16.8 0.7 5.0 0 8.4 0 100.0

Table 8-2 Design clinker rate value Design clinker mineral composition/% serial number K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF sum H3 0.968 2.03 1.65 68.9 5.5 10.0 11.4 95.71 H5 0.974 2.81 1.64 74.9 4.8 7.6 8.8 96.12 H6 0.974 2.81 1.64 74.8 4.8 7.6 8.7 95.96 H7 0.974 2.81 1.64 74.9 4.8 7.6 8.8 96.12 H9 0.967 2.80 2.18 73.0 6.1 9.8 7.3 96.24 H10 0.967 2.80 2.18 73.0 6.1 9.8 7.3 96.24

Table 8-3 serial number Clinker chemical composition/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ CaF ₂ P ₂ O ₅ H3 20.05 6.15 3.73 65.82 2.68 0.04 0.31 0.24 H5 21.39 4.72 2.88 67.23 2.15 0.14 0.14 0.15 H6 21.36 4.71 2.88 67.12 2.15 0.14 0.30 0.23 H7 21.39 4.72 2.88 67.23 2.15 0.14 0.14 0.15 H9 21.35 5.23 2.40 67.30 2.08 0.06 0.32 0.24 H10 21.35 5.23 2.40 67.30 2.08 0.06 0.32 0.24

Table 8-4 1450℃Free CaO/% 1450 ℃ firing clinker rate value Mineral Composition of Clinker Burned at 1450℃/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF CaSO ₄ total H3 0.62 0.96 2.03 1.65 66.27 7.47 9.98 11.35 0.06 95.13 H5 1.00 0.96 2.81 1.64 70.72 7.98 7.64 8.76 0.23 95.33 H6 1.46 0.95 2.81 1.64 68.70 9.41 7.63 8.75 0.23 94.72 H7 0.48 0.97 2.81 1.64 72.83 6.38 7.64 8.76 0.23 95.85 H9 0.85 0.95 2.80 2.18 69.43 8.84 9.80 7.29 0.10 95.47 H10 0.27 0.96 2.80 2.18 71.79 7.06 9.80 7.29 0.10 96.05

Table 8-5 serial number Fineness Coagulation time/min stability 0.080μm sieve residue/% Specific surface area/m ² /kg initial setting final set H3 3.92 315.5 166 241 qualified H5 1.20 345.7 182 248 qualified H6 2.03 303.1 159 255 qualified H7 1.81 326.8 292 354 qualified H9 2.03 329.0 155 228 qualified H10 1.56 341.2 158 222 qualified

Table 8-6 serial number Flexural strength/Mpa Compressive strength/Mpa 3d 7d 28d 90d 3d 7d 28d 90d H3 6.39 8.26 9.41 10.53 36.72 50.90 72.88 75.71 H5 6.88 8.49 10.22 10.17 41.41 57.66 78.11 77.57 H6 7.06 9.10 10.10 9.81 42.70 57.87 74.48 81.53 H7 7.03 9.16 10.82 11.10 42.60 61.19 84.76 85.54 H9 6.03 8.59 10.09 10.38 31.84 46.89 66.85 75.74 H10 7.20 9.20 11.09 10.84 41.01 56.46 72.99 79.09

Example 9

Limestone, clay, iron powder, quartz sand and fly ash are used as raw materials, phosphate rock and phosphate slag are added to introduce trace component P ₂ O ₅ , fluorite is added to introduce CaF ₂ , and the cement raw meal is prepared. See Table 9-1 for the ratio of raw materials.

Raise the temperature of the raw meal and burn it at 1450°C to produce cement clinker. The chemical composition of the clinker is shown in Table 9-2. The free calcium oxide, rate and mineral composition of the clinker are shown in Table 9-3. The content is about 70%.

Mix 95% of clinker and 5% of natural dihydrate gypsum, and grind them in a ball mill. The specific surface area is shown in Table 9-4. The strength is tested by the method specified in the national standard, and the results are listed in Table 9-5. It can be seen from the results in Table 9-5 that the clinker has reached a very high strength.

Table 9-1 serial number limestone clay iron powder Phosphate rock fly ash Phosphorus slag fluorite I8 73.6 11.3 1.8 0 1.3 9.2 0.4 I9 80.2 16.3 1.6 1.5 0 0 0.4

Table 9-2 serial number Clinker chemical composition/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ CaF ₂ P ₂ O ₅ I8 20.95 5.10 3.13 66.18 2.12 0.16 0.82 0.46 I9 20.91 5.12 3.16 66.40 2.08 0.13 0.61 0.35

Table 9-3 serial number 1450℃Free CaO/% Clinker rate value Clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF CaSO ₄ total I8 0.19 0.96 2.54 1.63 70.10 7.17 8.24 9.51 0.28 95.30 I9 0.30 0.96 2.53 1.62 70.80 6.53 8.22 9.61 0.22 95.38

Table 9-4 serial number Coagulation time/min Fineness stability initial setting final set 0.080 Sieve residue/% Specific area/m ² /kg I8 251 354 4.4 312.2 qualified I9 213 280 6.3 327.9 qualified

Table 9-5 serial number Flexural strength/Mpa Compressive strength/Mpa 3d 7d 28d 90d 3d 7d 28d 90d I8 7.28 8.81 10.19 10.88 42.5 57.9 75.6 81.4 I9 6.80 8.74 10.34 10.49 41.1 56.5 76.6 83.3

Example 10

Limestone, clay, iron powder produced by Huaxin, limestone and clay produced by Shimen are used as main raw materials, quartz sand and fly ash are used as correction materials, and phosphorus rock, phosphorus tailings and phosphorus slag are added to introduce trace components P ₂ O ₅ , mixed with fluorite to introduce CaF ₂ , and made into cement raw meal. See Table 10-1 and Table 10-2 for the ratio of raw materials.

Burn the raw meal at 1450°C to make cement clinker. The chemical composition of the clinker is shown in Table 10-3. The free calcium oxide of the clinker is less than 1%. The ratio and mineral composition of the clinker are shown in Table 10-4. The content of alite in the middle is about 70%.

Mix 95% of clinker and 5% of natural dihydrate gypsum, and grind them in a ball mill. The specific surface area is shown in Table 10-5. The strength is tested by the method specified in the national standard, and the results are listed in Table 10-5. It can be seen from the results in Table 10-5 that the clinker has reached a very high strength. Among them, the K1S1 sample is made of K1 clinker 65% + gypsum 5% + slag 30%. It can be seen that the strength of cement is still high after adding 30% slag.

Comparing the K7 cement clinker with the high-quality cement clinker normally produced by the original cement plant, the results are listed in Table 10-6. Table 10-6 Zhonghua New Cement refers to the high-quality Portland cement clinker of existing cement plants, and K7 is the cement clinker fired in the present invention. Mix in 40% calcined coal gangue and 5% natural dihydrate gypsum respectively to make cement, measure the cement strength, the results are listed in Table 10-6, it can be seen that the cement made by the burnt clinker of the present invention The strength is higher, about 10MPa higher than that of the existing high-quality cement. Even if 40% coal gangue is mixed in, the 28-day compressive strength can still reach 66MPa.

Table 10-1 serial number Huaxin Limestone Huaxin clay Huaxin Iron Powder Phosphate rock Phosphorus slag fly ash Quartz sand Phosphorus tailings fluorite K1 78.8 13.7 1.5 0 6.0 0 0 0 0.4 K4 82.0 14.2 1.4 0.7 0 0 1.7 0 0.4 K7 77.3 14.1 1.6 0 0 1.0 0 6.0 0.4

Table 10-2 serial number Raw material ratio/% Stone Gate Limestone Shimen stone cinder Huaxin Iron Powder Shimen Phosphate Rock Phosphorus slag fly ash fluorite K2 82.8 11.7 1.4 0.7 0 3.4 0.4 K3 80.0 8.7 1.6 0 6.1 3.6 0.4

Table 10-3 serial number Clinker chemical composition/% SiO ₂ Al ₂ O _{3 Fe2O3 _} CaO MgO SO ₃ CaF ₂ P ₂ O ₅ total K1 21.39 4.72 2.88 67.23 2.15 0.14 0.14 0.12 98.78 K2 20.87 4.62 2.83 65.56 2.20 0.34 0.27 0.21 96.90 K3 21.10 4.68 2.86 66.08 2.20 0.31 0.14 0.12 97.50 K4 21.26 4.70 2.88 66.76 2.07 0.11 0.27 0.21 98.26 K7 20.51 5.40 3.29 65.67 3.51 0.13 0.11 0.09 98.70

Table 10-4 serial number Clinker rate value Clinker mineral composition/% K H SM IM C ₃ S C ₂ S C ₃ A C ₄ AF sum K1 0.974 2.81 1.64 74.9 4.8 7.6 8.8 96.12 K2 0.970 2.80 1.64 72.3 5.3 7.5 8.6 93.63 K3 0.967 2.80 1.64 72.3 6.0 7.6 8.7 94.49 K4 0.973 2.81 1.63 74.2 4.9 7.6 8.7 95.50 K7 0.967 2.36 1.64 70.1 5.9 8.7 10.0 94.75

Table 10-5 serial number Specific surface area/m ² /kg Flexural strength/Mpa Compressive strength/Mpa 3d 7d 28d 3d 7d 28d K1 458 7.51 8.33 9.91 44.1 60.9 77.3 K1S1 407 6.02 7.84 10.41 29.2 46.6 71.2 K2 479 8.19 8.20 10.13 46.1 62.7 81.4 K3 491 8.07 8.70 10.27 48.2 61.0 80.2 K4 488 8.42 8.73 9.98 51.7 65.6 81.2 K7 514 8.21 8.10 9.58 52.1 66.0 79.2

Table 10-6 Clinker Mixed material Specific surface area/m ² /kg Flexural strength/Mpa Compressive strength/Mpa serial number Amount/% type Dosage/% 3d 7d 28d 3d 7d 28d K7 95 none 0 362 6.77 8.93 10.65 38.6 56.3 78.2 K7 55 coal gangue 40 362 4.91 7.26 9.66 22.4 40.6 66.7 Huaxin Cement 95 none 0 386 5.27 6.90 9.22 33.2 45.8 64.5 Huaxin Cement 55 coal gangue 40 407 4.82 6.55 8.10 23.1 32.5 55.6

Example 11

Limestone, clay, steel slag, iron powder, phosphorous slag, fluorite and sandstone are used as ingredients, and two clinkers are fired at 1400°C to 1550°C. Their rate values and mineral compositions are the same, as listed in Table 11-1. The difference is that the clinker control sample has no P and F in the raw meal, and the other sample has a small amount of P and F in the raw meal, and contains 0.3% P ₂ O ₅ and 0.7% CaF ₂ in the clinker. Grind 95% clinker and 5% dihydrate gypsum together until the specific surface area is 350±10m ² /kg, and the strength measurement results are listed in Table 11-2. It can be seen that the tricalcium silicate in the clinker containing trace amounts of P and F is a mixture of the R crystal form and the M1 crystal form mainly in the trigonal crystal form (see Figure 4), and its 28-day compressive strength is more than 5MPa higher than that of the comparative sample .

Table 11-1 Clinker rate value Mineral composition/w% LSF SM IM C ₃ S C ₂ S C ₃ A C ₄ AF 0.99 2.56 1.63 71.6 6.2 8.6 9.4

Table 11-2 sample C ₃ S crystal form Coagulation time/min Flexural strength/MPa Compressive strength/MPa initial setting final set 3d 7d 28d 3d 7d 28d Comparative sample M ₁ +T ₃ 151 301 5.48 7.03 9.47 31.3 45.4 64.8 Doped F+P sample R+M ₁ 226 286 6.15 7.81 9.48 36.42 51.58 70.6

Example 12

Using limestone, clay, steel slag, iron powder, phosphorous slag, fluorite and bauxite as ingredients, burn three clinkers at 1400°C to 1550°C. Their rate values and mineral compositions are the same, as listed in Table 12-1. The difference is that the control clinker sample is not mixed with P and F in the raw meal, one clinker sample is mixed with a small amount of P in the raw meal, and the other clinker sample is mixed with a small amount of P and F in the raw meal. The amounts of these adulterants contained in the clinker are listed in Table 12-2. These three clinkers do not belong to cement clinkers with high tricalcium silicate. This example compares the influence of doping on clinker strength. Grind 95% clinker and 5% dihydrate gypsum together until the specific surface area is 350±10m ² /kg, and the strength measurement results are listed in Table 12-2. It can be seen that the tricalcium silicate in the clinker containing a small amount of ^P (0.4% P ₂ O ₅ ) is a mixture of the trigonal R crystal form and the monoclinic M1 crystal form (see Figure 4), and its 28-day compressive strength is compared to The sample height is about 5MPa. Tricalcium silicate in the clinker containing trace amounts of P and F (0.4% P ₂ O ₅ +0.6% CaF ₂ ) is dominated by trigonal R crystals (see Figure 3), and its 28-day compressive strength ratio is compared The sample height is about 10MPa.

Table 12-1 Clinker rate value Clinker mineral composition/w% LSF SM IM C ₃ S C ₂ S C ₃ A C ₄ AF 0.93 2.18 1.66 53.73 20.42 9.91 11.16

Table 12-2 sample C ₃ S crystal form Coagulation time/min Flexural strength/MPa Compressive strength/MPa initial setting final set 3d 7d 28d 3d 7d 28d Control clinker M1+T3 208 305 4.1 5.4 8.6 23.2 25.4 53.7 Contains 0.4% _{P2O5 clinker} R+M 271 391 5.9 6.9 8.7 29.2 41.0 58.6 Contains 0.4% P ₂ O ₅ +0.6% CaF ₂ clinker R 232 326 6.2 7.2 9.0 33.0 42.1 63.6

Claims (8)

1, a kind of high strength silicate clinker is characterized in that, wherein contains trace amounts of phosphorus or trace amounts of phosphorus and Trace Fluoride, and the tricalcium silicate of weight percent 66%～76%, and tricalcium silicate is the mixture of trigonal lattice or trigonal lattice and monoclinic lattice.

2, high strength silicate clinker according to claim 1 is characterized in that, it comprises following component, by weight the percentage ratio meter:

Tricalcium silicate, i.e. C ₃S 66%～76%;

Dicalcium Phosphate (Feed Grade), i.e. C ₂S 3～15%;

Tricalcium aluminate, i.e. C ₃A 3～12%;

Tetracalcium aluminoferrite, i.e. C ₄AF 6～14%;

Free calcium oxide, promptly f-CaO 0～1.2%; And

Surplus is other phase; Wherein, described trace amounts of phosphorus is with P ₂O ₅Count 0.05%～0.9%, described Trace Fluoride is with CaF ₂Count 0～1.5%.

3, high strength silicate clinker according to claim 1 is characterized in that, described tricalcium silicate weight percent is 69%～74%.

4, the preparation method of high strength silicate clinker is characterized in that, mixes P contained compound or P contained compound and fluorochemicals as burning till admixture in raw material, and firing range is 1400 ℃～1550 ℃; Wherein, the P contained compound incorporation is with P ₂O ₅The weight percent that meter accounts for raw material is 0.1%～0.7%, and fluorochemicals is with F ^-The weight percent that meter accounts for raw material is 0%～1.2%.

According to the preparation method of the described high strength silicate clinker of claim 4, it is characterized in that 5, P contained compound and fluorochemicals incorporation are with P ₂O ₅Count 0.2～0.4%, fluorochemicals is with F ^-Count 0～1.0%.

6, according to the preparation method of claim 4 or 5 described high strength silicate clinkers, it is characterized in that, described P contained compound is to be selected from Rock Phosphate (72Min BPL), phosphorus mine tailing, phosphorus slag, the slag one or more, described fluorochemicals is for being selected from fluorite, fluorite mine tailing, one or more in Sodium Silicofluoride, fluorgypsum and the fluorine-containing industrial residue.

7, according to the preparation method of claim 4 or 5 described high strength silicate clinkers, it is characterized in that, in the raw material of 90～96wt%, add the phosphorus slag of 4～12wt%, wherein P in the phosphorus slag ₂O ₅Content 1.2%～2%, F ^-Be 2～3%, bring P into by phosphorus slag ₂O ₅And CaF ₂, firing range is 1400 ℃～1550 ℃; Wherein each weight percentages of components is in the raw material: CaO=66.5%～67.1%, SiO ₂=21.2%～21.5%, Al ₂O ₃=4.7%～5.1%, Fe ₂O ₃=2.9%～3.3%, remain and be other compositions.

8, according to the preparation method of claim 4 or 5 described high strength silicate clinkers, it is characterized in that, add the Rock Phosphate (72Min BPL) of 4～10wt% in the raw material of 90～96wt%, firing range is 1400 ℃～1550 ℃; Wherein each weight percentages of components is in the raw material:

CaO=66.4%～67.3%, SiO ₂=21.1%～21.6%, Al ₂O ₃=4.3%～5.4%, Fe ₂O ₃=2.6%～3.6%, remain and be other compositions.

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