Method for producing dicalcium silicate

Abstract

A process for preparing dicalcium silicate includes providing a starting material comprising calcium carbonate (CaCO.sub.3) and silicon dioxide (SiO.sub.2), wherein a molar ratio of calcium:silicon (C:S) is from 1.5:1 to 2.5:1. At least one of an inorganic alkali metal salt and an alkaline earth metal salt is added as a mineralizing agent to the starting material in an amount of from 0.5 wt.-% to 20 wt.-%, based on a total weight of the starting material. The starting material is reacted with the mineralizing agent in a gas atmosphere having a CO.sub.2 partial pressure of from 0.05 MPa to 0.2 MPa at a temperature of from 900 C. to 1100 C. so as to obtain a dicalcium silicate product. The dicalcium silicate product comprises a content of an unreacted starting material of <5 wt.-% and a total carbon content of <1.5 wt.-%, each based on a weight of the dicalcium silicate product.

Claims

1. A process for preparing dicalcium silicate, the process comprising: providing a starting material comprising calcium carbonate (CaCO.sub.3) and silicon dioxide (SiO.sub.2), wherein a molar ratio of calcium:silicon is from 1.5:1 to 2.5:1; adding at least one of an inorganic alkali metal salt and an alkaline earth metal salt as a mineralizing agent to the starting material in an amount of from 0.5 wt.-% to 20 wt.-%, based on a total weight of the starting material; and reacting the starting material with the mineralizing agent in a gas atmosphere having a CO.sub.2 partial pressure of from 0.05 MPa to 0.2 MPa at a temperature of from 900 C. to 1100 C. so as to obtain a dicalcium silicate product.

2. The process as recited in claim 1, wherein the molar ratio of calcium:silicon of the starting material is from 1.9:1 to 2.1:1.

3. The process as recited in claim 1, wherein the CO.sub.2 partial pressure of the gas atmosphere is from 0.08 MPa to 0.12 MPa.

4. The process as recited in claim 1, wherein the starting material is reacted at a temperatures of from 950 C. to 1050 C.

5. The process as recited in claim 1, wherein the amount of the mineralizing agent added to the starting material is from 1 wt.-% to 10 wt.-%, based on the total weight of the starting material.

6. The process as recited in claim 1, wherein the at least one of an inorganic alkali metal salt and an alkaline earth metal salt as the mineralizing agent is provided as a carbonate, a hydrogencarbonate, a fluoride, a chloride, or a mixture thereof.

7. The process as recited in claim 1, wherein the at least one of an inorganic alkali metal salt and an alkaline earth metal salt as the mineralizing agent is selected from at least one of sodium carbonate (Na.sub.2CO.sub.3), sodium fluoride (NaF), potassium fluoride (KF), calcium fluoride (CaF.sub.2), and magnesium chloride (MgCl.sub.2).

8. The process as recited in claim 1, wherein the mineralizing agent is provided as a mixture of from 0.5 wt.-% to 5 wt.-% Na.sub.2CO.sub.3 and from 0.5 wt.-% to 5 wt.-% CaF.sub.2, in each case based on the weight of the starting material.

9. The process as recited in claim 8, wherein the mixture is from 1 wt.-% to 1.5 wt.-% Na.sub.2CO.sub.3 and from 1 wt.-% to 1.5 wt.-% CaF.sub.2, in each case based on the weight of the starting material.

10. The process as recited in claim 1, further comprising at least partially recovering the mineralizing agent from the dicalcium silicate product.

11. The process as recited in claim 10, wherein the recovering of the mineralizing agent from the dicalcium silicate product is performed by: suspending the dicalcium silicate product comprising an alkali metal compound in water so that the alkali-metal compound decomposes to form an alkali metal hydroxide; adding CO.sub.2 to convert the alkali metal hydroxide into at least one of a carbonate and a hydrogen carbonate; and separating off the at least one of a carbonate and a hydrogen-carbonate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present invention is described in greater detail below on the basis of embodiments and of the drawings in which:

(2) FIG. 1 shows the reaction of the starting materials without a mineralizing agent (Comparative Example);

(3) FIG. 2 shows the reaction of the starting materials with the variation of the CO.sub.2 partial pressure using 5 wt.-% Na.sub.2CO.sub.3 as the mineralizing agent;

(4) FIG. 3 shows the reaction of the starting materials with the variation of the molar ratio of C:S using 5 wt.-% Na.sub.2CO.sub.3 as the mineralizing agent;

(5) FIG. 4 shows the reaction of the starting materials with the variation of the content of Na.sub.2CO.sub.3 as the mineralizing agent;

(6) FIG. 5 shows the reaction of the starting materials with the variation of the temperature using 5 wt.-% Na.sub.2CO.sub.3 as the mineralizing agent;

(7) FIG. 6 shows the total carbon content with the variation of the temperature using 5 wt.-% Na.sub.2CO.sub.3 as the mineralizing agent;

(8) FIG. 7 shows the reaction of the starting materials with the variation of the temperature using 2 wt.-% KF as the mineralizing agent;

(9) FIG. 8 shows the reaction of the starting materials with the variation of the content of KF as the mineralizing agent;

(10) FIG. 9 shows the reaction of the starting materials with the variation of the temperature using 2 wt.-% NaF as the mineralizing agent;

(11) FIG. 10 shows the reaction of the starting materials with the variation of the content of Ca.sub.2F as the mineralizing agent;

(12) FIG. 11 shows the reaction of the starting materials with the variation of the CO.sub.2 partial pressure using a mixture of 1 wt.-% Na.sub.2CO.sub.3 and 1 wt.-% CaF.sub.2 as the mineralizing agent; and

(13) FIG. 12 shows the reaction of the starting materials using pure Na.sub.2CO.sub.3 or Na.sub.2CO.sub.3 recovered from process products as the mineralizing agent.

DETAILED DESCRIPTION

(14) In an embodiment of the present invention, the energy-efficient production of dicalcium silicate from starting materials containing calcium carbonate CaCO.sub.3 and silicon dioxide SiO.sub.2 can, for example, occur at a molar ratio of C:S of 2:1 according to the equation (1):
2CaCO.sub.3+SiO.sub.2.fwdarw.Ca.sub.2SiO.sub.4+2CO.sub.2(1).

(15) The reaction enthalpy in this reaction is H=115 kJ/mol of Ca and thus about 35% lower than the pure thermal decomposition of calcium carbonate CaCO.sub.3 without addition of SiO.sub.2 according to the equation (2):
CaCO.sub.3.fwdarw.CaO+CO.sub.2(2)

(16) which has a reaction enthalpy of H=178 kJ/mol of Ca.

(17) To convert starting materials containing CaCO.sub.3 and SiO.sub.2 in a molar ratio of C:S of from 1.5:1 to 2.5:1, for example, from 1.9:1 to 2.1:1, for example, 2:1, very completely into dicalcium silicate, it is necessary to add a mineralizing agent in the form of an inorganic alkali metal salt or an alkaline earth metal salt, for example, a carbonate, a hydrogencarbonate, a fluoride, a chloride, or a mixture thereof, for example, sodium carbonate Na.sub.2CO.sub.3, sodium fluoride NaF, potassium fluoride KF, calcium fluoride CaF.sub.2, magnesium chloride MgCl.sub.2, or a mixture thereof,

(18) in an amount of from 0.5 wt.-% to 20 wt.-% inclusive, for example, from 2 wt.-% to 10 wt.-% inclusive, in each case based on the sum of the starting materials.

(19) In an embodiment of the present invention, in particular for the selective preparation of .sub.L-, -C.sub.2S and amorphous dicalcium silicate, the starting materials can, for example, be initially charged in a molar ratio of C:S of from 1.9 to 2.1. As the mineralizing agent, from 0.5 to 10 wt.-% inclusive of Na.sub.2CO.sub.3, or a mixture of from 0.5 to 5 wt.-% inclusive of Na.sub.2CO.sub.3 and from 0.5 to 5 wt.-% inclusive of CaF.sub.2, in each case based on the sum of the starting materials, can be added.

(20) In an embodiment of the present invention which gives the highest yield of .sub.L- and/or -C.sub.2S combined with low costs, a mixture of from 0.5 to 1.5 wt.-% inclusive of Na.sub.2CO.sub.3 and from 0.5 to 1.5 wt.-% inclusive of CaF.sub.2 can, for example, be used as the mineralizing agent.

(21) In an embodiment of the present invention which gives the highest observed yield of .sub.L-C.sub.2S, a mixture of from 4 to 6 wt.-% inclusive of Na.sub.2CO.sub.3 without addition of CaF.sub.2 can, for example, be used as the mineralizing agent.

(22) The process of the present invention is carried out: in a gas atmosphere having a CO.sub.2 partial pressure p.sub.CO2 of from 0.05 to 0.2 MPa, for example, from 0.08 to 0.12 MPa, and at temperatures of from 900 to 1100 C., for example, from 950 to 1050 C., for example, for a time of from 10 minutes to 5 hours, for example, in a range from 30 minutes to 1 hour.

(23) Pure CO.sub.2 is liberated in the calcination reaction of calcium carbonate (see equation 1). In the case of external reactor heating or integrated oxy-fuel combustion of carbon-containing fuels, the CO.sub.2 partial pressure p.sub.CO2 corresponds approximately to the total pressure p.sub.tot. In the case of integrated oxy-fuel combustion of fuels containing C and H, the CO.sub.2 partial pressure p.sub.CO2 corresponds approximately to the total pressure p.sub.tot of the dry gas. The CO.sub.2 both from the raw material and also from the fuel can then, optionally after drying, be utilized directly together or alternatively be disposed of by underground storage (analogous to carbon dioxide capture and storage, CCS).

(24) In an embodiment of the present invention, the process can, for example, be carried out so that at least part of the mineralization agents containing alkalis, in particular Na.sub.2CO.sub.3, can be recovered from the process product and used again.

(25) For this purpose, the dicalcium silicate-containing product obtained in the present process can, for example, be suspended in water, for example, at a temperature up to 250 C., so that alkali metal-containing compounds present therein are decomposed and dissolved predominantly as alkali metal hydroxides in order to then react with introduced carbon dioxide CO.sub.2 to form carbonates and/or hydrogencarbonates, e.g., Na.sub.2CO.sub.3 and/or NaHCO.sub.3. After the carbonates and/or hydrogencarbonates have been separated off, they are recirculated as mineralizing agent to the process.

(26) The product prepared by the process of the present invention then displays a particularly high quality as long as it has a content of unreacted starting material of less than 5 wt.-% and a total carbon content below 1.5 wt.-%, in each case based on the sum of the process products. The total carbon content is defined as the proportion by weight of carbon in the total process product, including the material present in amorphous form in the product. The content of -C.sub.2S should be below 5 wt.-%.

(27) The process of the present invention includes the following advantages.

(28) The process of the present invention allows for the energy-efficient preparation of dicalcium silicate, in particular having a molar ratio of Ca:Si very close to 2:1, from starting materials customary in the building industry which contain calcium carbonate CaCO.sub.3 and silicon dioxide SiO.sub.2. The yield of .sub.L- and -C.sub.2S in the process product can be adjusted by selection of the process parameters CO.sub.2 partial pressure and temperature and also the mineralizing agent.

(29) The dicalcium silicate obtained by this process is particularly suitable as a starting material for the process described in DE 10 2009 018 632 B4.

(30) The present invention is illustrated below with the aid of illustrative Examples and the Figures.

(31) In all experiments, the natural raw materials: limestone as the source of calcium carbonate CaCO.sub.3; and quartz flour as the primary source of silicon dioxide SiO.sub.2;

(32) were used as starting materials. Said natural raw materials additionally have further constituents, e.g., Mg.

(33) The following composition was determined by means of X-ray fluorescence analysis for the quartz flour used:

(34) TABLE-US-00001 Oxide Wt.-% Al.sub.2O.sub.3 0.052 CaO 0.017 K.sub.2O 0.112 Na.sub.2O 0.008 SiO.sub.2 97.74

(35) The following composition was determined by means of X-ray fluorescence analysis for the limestone used:

(36) TABLE-US-00002 Oxide Wt.-% CO.sub.2 42.8 Na.sub.2O 0.02 MgO 0.48 Al.sub.2O.sub.3 0.70 SiO.sub.2 1.84 P.sub.2O.sub.5 0.37 SO.sub.2 0.07 K.sub.2O 0.18 CaO 53.1 TiO.sub.2 0.04 Fe.sub.2O.sub.3 0.34 SrO 0.03

COMPARATIVE EXAMPLE

Without a Mineralizing Agent

(37) For comparison, the starting materials were reacted at a molar ratio of C:S=2 at a CO.sub.2 partial pressure (p.sub.CO2) of 0.1 MPa for 2 hours at temperatures of 850-1100 C. without the addition of a mineralizing agent.

(38) As shown in FIG. 1, in this comparative example, a yield of .sub.L-C.sub.2S of 2.95 wt.-% could be detected only at 1100 C., while the yield of -C.sub.2S rose from 6.40 wt.-% to 15.59 wt.-% with rising temperature over the entire temperature range. Considerable amounts of unreacted quartz, CaO and CaCO.sub.3 were present in the process product. The total carbon content was above 1.5 wt.-%.

Example 1

Variation of the CO2 Partial Pressure using 5 wt.-% Na2CO3 as the Mineralizing Agent

(39) In a first example, the starting materials were reacted at C:S=2 at a CO.sub.2 partial pressure of 0.0065-0.25 MPa for 2 hours at a temperature of 1000 C. with addition of 5 wt.-% of the mineralizing agent Na.sub.2CO.sub.3, based on the sum of the starting materials.

(40) As shown in FIG. 2, a yield of -C.sub.2S of 35.40 wt.-% was obtained even at a low p.sub.CO2=0.0065 MPa and, with increasing pressure, this decreased to 29.03 wt.-% at P.sub.CO2=0.1 MPa and to 8.90 wt.-% at p.sub.CO2=0.25 MPa.

(41) As also shown in FIG. 2, no yield of .sub.L-C.sub.2S could be detected at a low p.sub.CO2 of only 0.0065 MPa. Only at p.sub.CO2=0.05 MPa were 18.52 wt.-% of .sub.L-C.sub.2S observed; the value increased to 36.31 wt.-% at p.sub.CO2=0.1 MPa and even to 48.62 wt.-% at p.sub.CO2=0.25 MPa.

(42) As is finally shown in FIG. 2, the highest total yield of .sub.L- and -C.sub.2S of 65.34 wt.-% was obtained with the addition of 5 wt.-% of the mineralizing agent Na.sub.2CO.sub.3 at 1000 C. and p.sub.CO2=0.1 MPa.

Example 2

Variation of the Molar Ratio of C:S Using 5 wt.-% of Na2CO3 as the Mineralizing Agent

(43) In a second example, the starting materials were reacted at the molar ratios C:S=1, C:S=2 and C:S=3, in each case at p.sub.CO2=0.1 MPa for 2 hours at a temperature of 1000 C. with addition of 5 wt.-% of the mineralizing agent Na.sub.2CO.sub.3, based on the sum of the starting materials.

(44) As shown in FIG. 3, the highest yield both of .sub.L-C.sub.2S and of -C.sub.2S and thus also the highest total yield were obtained at C:S=2.

Example 3

Variation of the Content of Na2CO3 as the Mineralizing Agent

(45) In a third example, the starting materials were reacted at C:S=2 and p.sub.CO2=0.1 MPa for 2 hours at a temperature of 1000 C. with the addition of the mineralizing agent Na.sub.2CO.sub.3, with the proportion of Na.sub.2CO.sub.3, based on the sum of the starting materials, being varied from 1 wt.-% to 10 wt.-%.

(46) As shown in FIG. 4, the highest yield both of .sub.L-C.sub.2S and of -C.sub.2S and thus also the highest total yield of 65.34 wt.-% were obtained at a proportion of 5 wt.-% of the mineralizing agent Na.sub.2CO.sub.3.

Example 4

Variation of the Temperature using 5 wt.-% of Na2CO3 as the Mineralizing Agent

(47) In a fourth example, the starting materials were reacted at C:S=2 and p.sub.CO2=0.1 MPa for 2 hours, in each case at temperatures of 850-1100 C., with the addition of 5 wt.-% of the mineralizing agent Na.sub.2CO.sub.3, based on the sum of the starting materials.

(48) As shown in FIG. 5, high total yields as the sum of the yields of .sub.L- and -C.sub.2S of 54.25-65.34 wt.-% were obtained in the range from 950 C. to 1050 C., with a total yield of 65.34 wt.-% at 1000 C. being determined as optimum. At this temperature, the chemical and thermal stress on the reactor material and the energy consumption is also reduced compared to higher temperatures.

(49) As FIG. 5 likewise shows, although the total yield of .sub.L- and -C.sub.2S increases again at 1100 C., this is associated with a higher chemical and thermal stress on the reactor material and a higher energy consumption.

(50) As can be seen from FIG. 6, the total carbon content is in the desired target range of below 1.5 wt.-% in the temperature range of 900-1100 C., based on the sum of the reaction products, while at 850 C., it is 2 wt.-%, which is still above the preferred target range.

Example 5

Variation of the Temperature Using 2 wt.-% of KF as the Mineralizing Agent

(51) In a fifth example, the starting materials were reacted at C:S=2 and p.sub.CO2=0.1 MPa for 2 hours, in each case at temperatures of 850-1100 C., with the addition of 2 wt.-% of the mineralizing agent KF, based on the sum of the starting materials.

(52) As shown in FIG. 7, high yields of -C.sub.2S of up to 76.83 wt.-% were obtained in the range from 900 C. to 1100 C., while the yield of .sub.L-C.sub.2S was below 5 wt.-%.

Example 6

Variation of the Content of KF as the Mineralizing Agent

(53) In a sixth example, the starting materials were reacted at C:S=2 and p.sub.CO2=0.1 MPa for 2 hours at a temperature of 900 C. with the addition of the mineralizing agent KF, with the proportion of KF, based on the sum of the starting materials, being varied from 0.5 wt.-% to 5 wt.-%.

(54) As shown in FIG. 8, the highest yield of -C.sub.2S of 76.83 wt.-% was obtained at a proportion of 2 wt.-% of the mineralizing agent KF.

Example 7

Variation of the Temperature Using 2 wt.-% of NaF as the Mineralizing Agent

(55) In a seventh example, the starting materials were reacted at C:S=2 and p.sub.CO2=0.1 MPa for 2 hours, in each case at temperatures of 850-1100 C., with the addition of 2 wt.-% of the mineralizing agent NaF, based on the sum of the starting materials.

(56) As shown in FIG. 9, high yields of -C.sub.2S of up to 69.03 wt.-% were obtained in the range from 900 C. to 1100 C., while the yield of .sub.L-C.sub.2S was far lower.

Example 8

Variation of the Content of CaF2 as the Mineralizing Agent

(57) In an eighth example, the starting materials were reacted at C:S=2 and p.sub.CO2=0.1 MPa for 2 hours at a temperature of 1000 C. with addition of the mineralizing agent CaF.sub.2, with the proportion of CaF.sub.2, based on the sum of the starting materials, being varied from 1 wt.-% to 5 wt.-%.

(58) As shown in FIG. 10, high yields of -C.sub.2S were obtained at the proportions of the mineralizing agent CaF.sub.2 employed, while the yields of .sub.L-C.sub.2S were extremely small.

Example 9

Variation of the CO2 Partial Pressure Using a Mixture of 1 wt.-% of Na2CO3 and 1 wt.-% of CaF2 as the Mineralizing Agent

(59) In a ninth example, the starting materials were reacted at C:S=2 and CO.sub.2 partial pressures of 0.003 MPa or of 0.1 MPa for 2 hours at a temperature of 1000 C. with addition of a mixture of 1 wt.-% of Na.sub.2CO.sub.3 and 1 wt.-% of CaF.sub.2 as the mineralizing agent, based on the sum of the starting materials.

(60) As shown in FIG. 11, a yield of -C.sub.2S of 13.06 wt.-% was obtained even at a low p.sub.CO2=0.003 MPa, and this increased significantly to 58.01 wt.-% at p.sub.CO2=0.1 MPa. Compared to the studies at p.sub.CO2=0.1 MPa, in which only 1 wt.-% of Na.sub.2CO.sub.3 or only 1 wt.-% of CaF.sub.2 were used as the mineralizing agent, the use of the mixture of 1 wt.-% of Na.sub.2CO.sub.3 and 1 wt.-% of CaF.sub.2 as the mineralizing agent led to the highest observed yield of -C.sub.2S.

Example 10

Use of 5 wt.-% of Na2CO3 as the Mineralizing Agent in Pure Form or in the Form of Material Recovered from the Process Products

(61) In a tenth example, the starting materials were reacted at C:S=2 and p.sub.CO2=0.1 MPa for 2 hours at a temperature of 1000 C. with addition of 5 wt.-% of the mineralizing agent Na.sub.2CO.sub.3, based on the sum of the starting materials.

(62) As shown in FIG. 12, the following differences were obtained depending on whether pure Na.sub.2CO.sub.3 or Na.sub.2CO.sub.3 recovered from the process products was used. In the latter case, a small proportion of sodium hydrogencarbonate is present and this preferentially leads to formation of -C.sub.2S, while the sum of .sub.L-C.sub.2S and -C.sub.2S remains about the same.

(63) The present invention is not limited to embodiments described herein; reference should be had to the appended claims.