阅读说明：本技术 一种钛基铝酸盐水泥及其制备方法 (Titanium-based aluminate cement and preparation method thereof ) 是由 张康康 马淑龙 苏玉柱 赵春燕 陈茂峰 曹望 李燕京 高长贺 于 2021-09-18 设计创作，主要内容包括：本发明提供一种钛基铝酸盐水泥及其制备方法。该钛基铝酸盐水泥的原料包括钛铁渣和石灰石,所述钛铁渣和所述石灰石的重量比为53～63：37～47。本发明提供的钛基铝酸盐水泥能实现钛铁渣的大规模高值化利用,并缓解铝矾土资源紧张的难题,减少生产过程中的碳排放,助力推动碳达峰。本发明所制备的铝酸盐水泥还具有较普通铝酸盐水泥更优的力学性能和更高的耐温性能。(The invention provides titanium-based aluminate cement and a preparation method thereof. The titanium-based aluminate cement comprises raw materials of titanium-iron slag and limestone, wherein the weight ratio of the titanium-iron slag to the limestone is 53-63: 37 to 47. The titanium-based aluminate cement provided by the invention can realize large-scale high-value utilization of the titanium-iron slag, relieve the problem of bauxite resource shortage, reduce carbon emission in the production process and boost the carbon to reach the peak. The aluminate cement prepared by the invention also has better mechanical property and higher temperature resistance than the ordinary aluminate cement.)

1. The titanium-based aluminate cement is characterized in that raw materials of the titanium-based aluminate cement comprise titanium iron slag and limestone, and the weight ratio of the titanium iron slag to the limestone is 53-63: 37 to 47.

2. The titanium-based aluminate cement of claim 1, wherein the specifications of the titanium slag include: al (Al)₂O₃>60％，TiO₂<16％，CaO＜20％，MgO<2％，SiO₂<1％，Fe₂O₃<1％，K₂O and Na₂Sum of O<0.5% loss on ignition<1％。

3. The titanium-based aluminate cement according to claim 1 or 2, wherein the limestone raw material specification requirements include: al (Al)₂O₃<5％，TiO₂<1％，CaO>50％，MgO<2.5％，SiO₂<5％，Fe₂O₃<2％，K₂O and Na₂Sum of O<0.6 percent and the ignition loss is 40 to 45 percent.

4. The titanium-based aluminate cement according to claim 1, wherein the titanium-based aluminate cement comprises the following raw materials in parts by weight:

53-63 parts of ferrotitanium slag

37-47 parts of limestone

Preferably, the mineral phase composition of the titanium-based aluminate cement comprises: the calcium aluminate, the calcium dialuminate, the calcium titanate, the aluminum cubic column stone, the dicalcium ferrite, the magnesia-alumina spinel and the dodecacalcium heptaluminate are preferably selected from the following components in parts by mass: 35 to 60 percent of calcium aluminate, 10 to 35 percent of calcium dialuminate, 10 to 15 percent of calcium titanate, and 10 to 25 percent of the sum of the aluminum square column, the dicalcium ferrite, the magnesia-alumina spinel and the dodecacalcium heptaaluminate.

5. A process for preparing a titanium-based aluminate cement according to any one of claims 1 to 4, comprising the steps of: the raw materials of the titanium-based aluminate cement are proportioned and ground according to the proportion to obtain cement raw materials, the cement raw materials are burnt to obtain clinker, and the clinker is subjected to quenching and secondary grinding.

6. The method for preparing titanium-based aluminate cement according to claim 5, wherein in the compounding process, Am is 0.75-0.95; preferably, Am is 0.80-0.90; more preferably, Am is 0.85 to 0.88.

7. The method for preparing titanium-based aluminate cement according to any one of claims 5-6, wherein in the grinding process, the ferro-titanium slag and the limestone are respectively ground and then mixed or mixed and ground together; preferably, the ferrotitanium slag and the limestone are ground to fineness of less than or equal to 200 meshes.

8. The process for preparing titanium-based aluminate cement according to any one of claims 5 to 7, wherein the firing temperature-raising system comprises: the temperature is raised for 40-60 min from room temperature to 300 ℃; the temperature is increased for 80-120 min at 300-1000 ℃; the temperature is increased for 30-50 min at 1000-1200 ℃; the temperature is 1200-1340 ℃, and the heating time is 60-80 min; maintaining the temperature at 1340 ℃ for 25-35 min.

9. The process for the preparation of titanium-based aluminate cement according to any one of claims 5 to 8, wherein the clinker is quenched by air cooling.

10. The process for preparing titanium-based aluminate cement according to any one of claims 5 to 9, wherein the fineness of the clinker ground twice is 325 mesh < 20%.

Technical Field

The invention relates to the technical field of aluminate cement materials, in particular to titanium-based aluminate cement and a preparation method thereof.

Background

The ferrotitanium is an important raw material for producing electronic products, aerospace products, military products and the like, and with the development of ferrotitanium industry, the quantity of ferrotitanium slag is increased, so that a large amount of occupied land is accumulated, and the environmental pollution is serious, so that research and research on large-scale high-valued utilization of ferrotitanium slag are urgently needed.

The production of ordinary aluminate cement is that natural bauxite and limestone are selected to prepare raw material, and then calcined into clinker by rotary kiln at high temperature, and then milled to prepare aluminate cement, and because of the production of aluminium products, the demand of bauxite in the market is very large, the more main application direction of bauxite resources relative to limited bauxite resources is the production of aluminium oxide and metal aluminium, the high-quality bauxite resources which can be applied to the aluminate cement direction are very limited, in addition, the ferrotitanium slag contains about 10% of calcium oxide, and the calcium source which is not calcium carbonate can not discharge carbon dioxide in the calcination process, so that the carbon emission in the production process can be reduced, and the boosting can push the carbon to reach the peak.

Disclosure of Invention

The invention provides titanium-based aluminate cement and a preparation method thereof, which are used for realizing large-scale high-value utilization of titanium-iron slag and relieving the problem of bauxite resource shortage. The aluminate cement also has better mechanical property and higher temperature resistance than the ordinary aluminate cement.

The invention firstly provides titanium-based aluminate cement, which comprises titanium iron slag and limestone in a weight ratio of 53-63: 37 to 47.

The invention discovers that the content of aluminum oxide in the ferrotitanium slag is higher (can reach more than 70 percent), the content of silicon oxide and iron oxide is very low, bauxite is replaced by bauxite to be used as an aluminum source of aluminate cement, the aluminate cement is prepared by the ferrotitanium slag and limestone, the problems of stacking and pollution of the ferrotitanium slag are solved, the problem of high-quality bauxite resource shortage is relieved, positive social benefits and remarkable economic benefits are achieved, in addition, the ferrotitanium slag contains about 10 percent of calcium oxide, and the calcium source which is not calcium carbonate can not discharge carbon dioxide in the sintering process, so the carbon emission in the production process can be reduced, and the boosting force can push the carbon to reach the peak; and the aluminate cement prepared by the ferrotitanium slag and the limestone also has better mechanical property and higher temperature resistance than the common aluminate cement.

According to the titanium-based aluminate cement provided by the invention, the index requirements of the titanium-iron slag comprise: al (Al)₂O₃>60％，TiO₂<16％，CaO＜20％，MgO<2％，SiO₂<1％，Fe₂O₃<1％，K₂O and Na₂Sum of O<0.5% loss on ignition<1％。

According to the titanium-based aluminate cement provided by the invention, the index requirements of the limestone raw material comprise: al (Al)₂O₃<5％，TiO₂<1％，CaO>50％，MgO<2.5％，SiO₂<5％，Fe₂O₃<2％，K₂O and Na₂Sum of O<0.6 percent and the ignition loss is 40 to 45 percent.

The titanium-based aluminate cement comprises the following raw materials in parts by weight:

53-63 parts of ferrotitanium slag

37-47 parts of limestone

In the invention, the mineral phase composition of the titanium-based aluminate cement comprises: the calcium aluminate, the calcium dialuminate, the calcium titanate, the aluminum cubic column stone, the dicalcium ferrite, the magnesia-alumina spinel and the dodecacalcium heptaluminate are preferably selected from the following components in parts by mass: 35 to 60 percent of calcium aluminate, 10 to 35 percent of calcium dialuminate, 10 to 15 percent of calcium titanate, and 10 to 25 percent of the sum of the aluminum square column, the dicalcium ferrite, the magnesia-alumina spinel and the dodecacalcium heptaaluminate.

In the invention, titanium-based calcium aluminate cement with calcium monoaluminate, calcium dialuminate and calcium titanate as main mineral phases is prepared from a titanium-containing composite phase material and limestone. Limestone is a building material and industrial raw material containing calcium carbonate as a main component. The ferrotitanium slag is industrial solid waste slag generated in the smelting process of ferrotitanium, the generation amount of the slag is quite large, the proportion of the ferrotitanium alloy to the ferrotitanium slag is about 1:1 generally in the process of producing the ferrotitanium by an external smelting method, and the ferrotitanium slag is a high-melting-point composite phase material containing various mineral phases such as calcium titanoaluminate, calcium hexaaluminate, calcium dialuminate, calcium titanate and the like.

The invention also provides a preparation method of the titanium-based aluminate cement, which comprises the following steps: the raw materials of the titanium-based aluminate cement are proportioned and ground according to the proportion to obtain cement raw materials, the cement raw materials are burnt to obtain clinker, and the clinker is subjected to quenching and secondary grinding.

According to the preparation method of the titanium-based aluminate cement, Am (aluminate alkalinity coefficient) is 0.75-0.95 in the batching process; preferably, Am (aluminate alkalinity coefficient) is 0.80-0.90; more preferably, Am (aluminate alkalinity index) is 0.85 to 0.88.

According to the preparation method of the titanium-based aluminate cement, the ferrotitanium slag and the limestone are respectively ground and then mixed or mixed and milled in the grinding process; preferably, the ferrotitanium slag and the limestone are ground to fineness of less than or equal to 200 meshes.

According to the preparation method of the titanium-based aluminate cement provided by the invention, the temperature rise system of the sintering comprises the following steps: the temperature is raised for 40-60 min from room temperature to 300 ℃; the temperature is increased for 80-120 min at 300-1000 ℃; the temperature is increased for 30-50 min at 1000-1200 ℃; the temperature is 1200-1340 ℃, and the heating time is 60-80 min; maintaining the temperature at 1340 ℃ for 25-35 min.

According to the preparation method of the titanium-based aluminate cement, the clinker is quenched in an air cooling mode.

According to the preparation method of the titanium-based aluminate cement provided by the invention, the fineness of the clinker ground for the second time is 325 meshes, and the residue is less than 20%.

According to a preferred embodiment provided by the present invention, the preparation of the titanium-based aluminate cement comprises the following steps:

1) selecting applicable raw materials, including ferrotitanium slag and limestone; the main chemical index requirements of the ferrotitanium slag comprise: al (Al)₂O₃>60％，TiO2<16％，CaO＜20％，MgO<2％，SiO₂<1％，Fe₂O₃<1％，K₂O and Na₂Sum of O<0.5% loss on ignition<1 percent; the main chemical index requirements of the limestone raw material comprise: al (Al)₂O₃<5％，TiO₂<1％，CaO>50％，MgO<2.5％，SiO₂<5％，Fe₂O₃<2％，K₂O and Na₂Sum of O<0.6 percent and the ignition loss is 40 to 45 percent.

2) Calculating the ratio of the ferrotitanium slag to the limestone in the raw materials according to the chemical composition of the ferrotitanium slag and the limestone, and grinding the ferrotitanium slag and the limestone according to the ratio and then mixing, or mixing and grinding together until the fineness reaches below 200 meshes to prepare the cement raw material;

3) firing the cement raw material according to a heating system to prepare clinker;

the temperature rising system of the firing is as follows: heating for 40-60 min from room temperature to 300 ℃; heating for 80-120 min from 300 ℃ to 1000 ℃; raising the temperature from 1000 ℃ to 1200 ℃ for 30-50 min; heating from 1200 ℃ to 1340 ℃ for 60-80 min; maintaining the temperature at 1340 ℃ for 25-35 min;

4) after firing, air cooling and quenching are carried out on clinker;

5) and performing secondary grinding on the quenched clinker in a grinding machine until the fineness of the clinker reaches 325 meshes and the residual is less than 20 percent, and preparing the titanium-based aluminate cement.

The invention has the beneficial effects that: the titanium-based aluminate cement provided by the invention can realize large-scale high-value utilization of the ferrotitanium slag, relieves the problem of shortage of bauxite resources, and has important significance for saving the bauxite resources, reducing carbon emission in the production process, boosting the carbon to reach the peak and realizing high-value utilization of metallurgical solid waste ferrotitanium slag. The aluminate cement prepared by the invention also has better mechanical property and higher temperature resistance than common aluminate cement, has better temperature resistance than common aluminate cement, and can be better used as a bonding agent for refractory castable.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.

The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.

In the present invention, Am means an aluminate basicity coefficient and represents Al₂O₃The degree of saturation with CaO, the formula is as follows:

example 1

The embodiment provides a titanium-based aluminate cement, which comprises the following raw materials in part by weight:

1. raw material preparation, the chemical composition of the selected ferrotitanium slag and limestone are shown in table 1.

Table 1 chemical composition of the feed stock in example 1

The ferrotitanium slag and the limestone are respectively ground into 200 meshes.

2. Preparing raw materials, calculating the ingredient composition according to Am which is 0.80, and determining that the ground raw materials are prepared according to the following parts by weight:

60.3 parts of ferrotitanium slag

39.7 portions of limestone

The sum of the mass percentages of the materials is 100 percent.

3. Mixing the ferrotitanium slag and the limestone raw material according to the mass percentage to obtain a mixture;

4. firing the mixture according to a firing system to obtain clinker;

the specific temperature-raising system is shown in Table 2:

table 2 example 1 temperature rising System

Temperature rising zone	Time of temperature rise/minute
		Room temperature to 300 DEG C	50
300℃～1000℃	100
		1000℃～1200℃	40
1200℃～1340℃	75
		1340℃～1340℃	30

5. Air cooling and quenching the sintered clinker;

6. and (3) performing secondary grinding on the quenched clinker until the fineness is 325 meshes and the screen residue is less than 20%.

The performance indexes of the above examples are shown in Table 3. In the present disclosure, the setting time is measured in GB/T201-2015 appendix A standard, the flexural strength and compressive strength are measured in GB/T17671-1999 standard, the chemical composition is measured in GB/T205-2008 standard, the mineral phase composition is quantitatively analyzed by XRD full spectrum fitting, and the refractoriness is measured in GB/T7322-2007 standard.

Table 3 example 1 performance index

Example 2

The embodiment provides a titanium-based aluminate cement, which comprises the following raw materials in part by weight:

1. the raw material preparation, the chemical composition of the selected ferrotitanium slag and limestone are shown in the following table.

Table 4 chemical composition of raw materials in example 2

Grinding the ferrotitanium slag and the limestone to 200 meshes.

2. Preparing raw materials, calculating the ingredient composition according to Am which is 0.85, and determining that the ground raw materials are prepared according to the following parts by weight:

59.0 parts of ferrotitanium slag

41.0 parts of limestone

The sum of the mass percentages of the materials is 100 percent.

3. Mixing the ferrotitanium slag and the limestone raw material according to the mass percentage to obtain a mixture;

4. firing the mixture according to a firing system to obtain clinker;

the specific temperature-raising system is shown in Table 5:

TABLE 5 example 2 temperature ramp System

Temperature rising zone	Time of temperature rise/minute
		Room temperature to 300 DEG C	50
300℃～1000℃	100
		1000℃～1200℃	40
1200℃～1340℃	75
		1340℃～1340℃	30

5. Air cooling and quenching the sintered clinker;

6. and (3) performing secondary grinding on the quenched clinker until the fineness is 325 meshes and the screen residue is less than 20%.

The performance indexes of the above examples are shown in Table 6. In the present invention, the setting time is measured according to GB/T201-2015 appendix A standard, the flexural strength and compressive strength are measured according to GB/T17671-1999 standard, the chemical composition is measured according to GB/T205-2008 standard, the mineral phase composition is quantitatively analyzed by XRD full spectrum fitting, and the refractoriness is measured according to GB/T7322-2007 standard.

Table 6 example 2 performance index

Comparative example 1

The comparative example provides a titanium-based aluminate cement without using ferrotitanium slag, which comprises the following raw materials in percentage by weight:

1. raw material preparation, bauxite and limestone were selected with chemical compositions as shown in the following table.

TABLE 7 chemical composition of the feed in comparative example 1

Grinding bauxite and limestone to 200 meshes.

2. Preparing raw materials, calculating the ingredient composition according to Am which is 0.85, and determining that the ground raw materials are prepared according to the following parts by weight:

bauxite 54.0 parts

46.0 parts of limestone

The sum of the mass percentages of the materials is 100 percent.

3. Mixing bauxite and limestone according to the mass percentage to obtain a mixture;

4. firing the mixture according to a firing system to obtain clinker;

the specific temperature-raising system is shown in Table 8:

TABLE 8 comparative example 1 temperature elevation System

5. Air cooling and quenching the sintered clinker;

6. and (3) performing secondary grinding on the quenched clinker until the fineness is 325 meshes and the screen residue is less than 20%.

The performance index of comparative example 1 is shown in Table 9. The setting time is measured according to GB/T201-2015 appendix A standard, the flexural strength and compressive strength are measured according to GB/T17671-1999 standard, the chemical composition is measured according to GB/T205-2008 standard, the mineral phase composition is quantitatively analyzed by XRD full spectrum fitting, and the refractoriness is measured according to GB/T7322-2007 standard.

TABLE 9 comparative example 1 Performance index

Comparative example 2

The comparative example provides a titanium-based aluminate cement with Am being 0.70, which comprises the following raw materials in percentage by weight:

1. the raw material preparation, the chemical composition of the selected ferrotitanium slag and limestone are shown in the following table.

TABLE 10 chemical composition of the feedstock of comparative example 2

Grinding the ferrotitanium slag and the limestone to 200 meshes.

2. Preparing raw materials, calculating the ingredient composition according to Am which is 0.70, and determining that the ground raw materials are prepared according to the following parts by weight:

63.2 parts of ferrotitanium slag

36.8 portions of limestone

The sum of the mass percentages of the materials is 100 percent.

3. Mixing the ferrotitanium slag and the limestone raw material according to the mass percentage to obtain a mixture;

4. firing the mixture according to a firing system to obtain clinker;

the specific temperature-raising system is shown in Table 11:

TABLE 11 comparative example 2 temperature elevation System

Temperature rising zone	Time of temperature rise/minute
		Room temperature to 300 DEG C	50
300℃～1000℃	100
		1000℃～1200℃	40
1200℃～1340℃	75
		1340℃～1340℃	30

5. Air cooling and quenching the sintered clinker;

6. and (3) performing secondary grinding on the quenched clinker until the fineness is 325 meshes and the screen residue is less than 20%.

The performance index of comparative example 2 is shown in Table 12. In the present invention, the setting time is measured according to GB/T201-2015 appendix A standard, the flexural strength and compressive strength are measured according to GB/T17671-1999 standard, the chemical composition is measured according to GB/T205-2008 standard, the mineral phase composition is quantitatively analyzed by XRD full spectrum fitting, and the refractoriness is measured according to GB/T7322-2007 standard.

TABLE 12 Performance index for comparative example 2

The strength of the titanium-based aluminate cement prepared by using the metallurgical solid waste ferrotitanium slag is higher than that of common aluminate cement, the temperature resistance is also better than that of the common aluminate cement, and the titanium-based aluminate cement can be used as a bonding agent for refractory castable. The method has important significance for saving bauxite resources, reducing carbon emission in the production process, boosting the carbon to reach the peak and realizing high-value utilization of the metallurgical solid waste ferrotitanium slag.

Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.