SYSTEM AND METHOD FOR PREPARING ULTRAFINE SILICA BY LEACHING SILICATE ORE USING HYDROGEN CHLORIDE GAS

Abstract

Provided is a system and a method for preparing ultrafine silica by leaching silicate ore using hydrogen chloride gas, comprising an ore raw material feeding device, an ejector, a stirring tank and a liquid-solid separation device. A circulated material outlet of a stirred tank is connected with a liquid inlet of an ejector through a circulation pipe; a liquid outlet of the ejector is connected with a circulated material inlet of the stirred tank; a material outlet of a raw ore feeding apparatus is connected with the circulation pipe; and the circulated material outlet of the stirred tank is connected with a solid-liquid separation apparatus. Based on the system and method in the present disclosure, an industrially feasible solution for preparing silica by continuously leaching a silicate ore is provided. The dissolution efficiency of ores and the utilization of hydrochloric acid are greatly increased.

Claims

1. A system for preparing ultrafine silica by leaching a silicate ore using hydrogen chloride gas, comprising a raw ore feeding apparatus, an ejector, a stirred tank, and a solid-liquid separation apparatus, wherein a liquid inlet, a liquid outlet, and a gas inlet are arranged on the ejector; a circulated material outlet of the stirred tank is connected with the liquid inlet of the ejector through a circulation pipe; the liquid outlet of the ejector is in connected with a circulated material inlet of the stirred tank; a material outlet of the raw ore feeding apparatus is connected with the circulation pipe; a circulation pump is arranged on the circulation pipe; and the circulated material outlet of the stirred tank is connected with the solid-liquid separation apparatus.

2. The system according to claim 1, wherein the raw ore feeding apparatus comprises a quantitative powder conveying apparatus; and the quantitative powder conveying apparatus is connected with the circulation pipe through a section of feeding pipe.

3. The system according to claim 2, wherein the raw ore feeding apparatus further comprises a premixing tank connected with the quantitative powder conveying apparatus; and a slurry outlet of the premixing tank is connected with the ejector, and a slurry inlet of the premixing tank is connected with the circulation pipe.

4. The system according to claim 1, wherein a steam outlet is arranged on the stirred tank.

5. The system according to claim 4, wherein the steam outlet is connected with the circulation pipe through a cooling water pipe, and a heat exchanger is arranged on the cooling water pipe.

6. The system according to claim 1 wherein the solid-liquid separation apparatus is a sedimentation separator, a hydro-cyclone, a centrifuge or a filter separator.

7. A method for preparing ultrafine silica, wherein the ultrafine silica is prepared by using the system according to claim 1, and the method comprises steps of: pumping powders of the silicate ore into the ejector after the powders are mixed with the circulation liquid conveyed by the circulation pipe by using the raw ore feeding apparatus; sucking the hydrogen chloride gas into the ejector through the gas inlet on the ejector, dissolving the hydrogen chloride gas in the circulation liquid, and obtaining the silica through a reaction between hydrochloric acid and the silicate ore, wherein the reaction is sequentially performed in the ejector, the circulation pipe and the stirred tank; and the circulation liquid is a slurry formed by the silicate ore and water or a reaction liquid obtained after the hydrochloric acid reacts with the silicate ore.

8. The preparation method according to claim 7, wherein the silicate ore could be at least one of feldspar, mica, olivine, garnet, andalusite, epidote, pyroxene, hornblende, wollastonite, talcum, kaolinite, chlorite and serpentine; a particle size of the powders of the silicate ore is not less than 50 mesh; a mass content of SiO.sub.2 in the silicate ore is not less than 40%; a temperature of the reaction in the stirred tank is 70° C. to 120° C.; and a ratio of the volume flow rate of the circulation liquid in the ejector to the hydrogen chloride gas is 2:1 to 3.5:1.

9. The preparation method according to claim 7, wherein continuously adding the powders of the silicate ore to the ejector to implement a continuous preparation of the ultrafine silica.

10. The preparation method according to claim 7, wherein directly adding the powders of the silicate ore to the stirred tank to form a slurry with water; inputting the slurry into the ejector through the circulation pipe; and dissolving the hydrogen chloride gas sucked into the ejector in the slurry, and obtaining the silica through the reaction between the hydrochloric acid and the silicate ore, so that implementing a batch preparation of the ultrafine silica.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0044] FIG. 1 is a schematic diagram of a system for preparing ultrafine silica by leaching a silicate ore using hydrogen chloride gas according to Embodiment 1 of the present disclosure; and

[0045] FIG. 2 is a schematic diagram of a system for preparing ultrafine silica by leaching a silicate ore using hydrogen chloride gas according to Embodiment 2 of the present disclosure.

[0046] Symbols in the figures are as follows:

[0047] 1 Dust collector, 2 Material storage tank, 3 Quantitative powder conveying apparatus, 4 Ejector, 5 Circulation pump, 5′ Slurry pump, 6 Stirred tank, 7 solid-liquid separation apparatus, 8 Circulation pipe, 9 Heat exchanger, 10 Cooling water pipe.

DESCRIPTION OF THE EMBODIMENTS

[0048] Unless otherwise specified, experimental methods used in the following embodiments are all conventional methods.

[0049] Unless otherwise specified, materials, reagents, and the like used in the following embodiments can be commercially obtained.

Embodiment 1

[0050] FIG. 1 is a schematic diagram of a preparation system according to a first embodiment of the present disclosure. The system includes a raw ore feeding apparatus, an ejector 4, a stirred tank 6, and a solid-liquid separation apparatus 7. The raw ore feeding apparatus includes a dust collector 1, a material storage tank 2, and a quantitative powder conveying apparatus 3 that are connected in turn. A liquid inlet (not marked in the figure), a liquid outlet (not marked in the figure), and a gas inlet (not marked in the figure) are arranged on the ejector 4. A circulation pipe 8 is connected between the liquid inlet of the ejector 4 and a material discharge port of the stirred tank 6, and the liquid outlet of the ejector 4 is connected with a circulated material inlet of the stirred tank 6. The quantitative powder conveying apparatus 3 adds powders of a raw silicate ore to the circulation pipe 8 through a feeding pipe, and the powders are mixed with materials in the circulation pipe 8. The material discharge port of the stirred tank 6 is connected with the solid-liquid separation apparatus 7. A circulation pump 5 is arranged on the circulation pipe 8, and is used to pump a circulation liquid.

[0051] In the preparation system in the present disclosure, a steam outlet (not marked in the figure) is arranged on the stirred tank 6, and is used to discharge vapor obtained through vaporization and a small amount of unreacted hydrogen chloride gas. The steam outlet is connected with the circulation pipe 8 through a cooling water pipe 10. A heat exchanger 9 is arranged on the cooling water pipe 10, and is used to condense the vapor and the small amount of unreacted hydrogen chloride gas and return the condensed vapor and the condensed unreacted hydrogen chloride gas to the ejector 4. At the same time, some reaction heat can be removed and a reaction temperature remains stable.

[0052] In the preparation system in the present disclosure, the solid-liquid separation apparatus 7 may be a sedimentation separator, a hydro-cyclone, a centrifuge or a filter separator.

[0053] A working process of the preparation system according to the first embodiment of the present disclosure is as follows: Continuous operations are performed. Powders of a raw ore that are conveyed to the material storage tank 2 are continuously added to the circulation pipe 8 by using the quantitative powder conveying apparatus 3 and are mixed with the circulation liquid to form a slurry; the slurry is driven into the ejector 4 at a high speed; negative pressure is formed in the ejector by using the Venturi effect, so that hydrogen chloride gas is sucked for an initial contact reaction; then a reaction liquid enters the stirred tank 6 for a further reaction; some of the slurry reacted in the stirred tank is discharged into the solid-liquid separation apparatus 7 for a solid-liquid separation operation, and some is pumped as a circulation liquid by the circulation pump 5 into the circulation pipe 8.

[0054] In a specific embodiment, the following process conditions are selected: An active ingredient of the powders of the raw ore is CaSiO3, a reaction temperature of the stirred tank is 120° C., a temperature of the hydrogen chloride gas is 250° C., and a ratio of a molar flow rate of the hydrogen chloride gas to a molar flow rate of CaSiO.sub.3 is 2:1. Data that is of a material balance and a heat balance and that is obtained through Aspen simulation is shown in Table 1.

TABLE-US-00001 TABLE 1 Data of a material balance and a heat balance Temper- Flow Compo- Enthalpy ature (kmol/ sition value Material flow (° C.) h) (%, mol) (cal/mol) Ejector CaSiO.sub.3 20 1 3.62 −390601 inlet HCl 250 2 7.23 −20494 H.sub.2O 20 15 54.27 −68402 Circulation H.sub.2O 120 8.64 31.26 −67505 liquid CaCl.sub.2 120 1 3.62 Ejector CaSiO.sub.3 105 1 3.62 −71767 outlet HCl 105 2 7.23 H.sub.2O 105 23.64 85.53 CaCl.sub.2 105 1 3.62 Vapor H.sub.2O 120 7.36 100 −57042 phase outlet of the stirred tank Liquid H.sub.2O 120 8.64 81.2 −67505 phase CaCl.sub.2 120 1 9.4 outlet of SiO.sub.2 120 1 9.4 −216404 the stirred tank Outlet of a H.sub.2O 120 7.78 89.63 −67505 clear liquid CaCl.sub.2 120 0.9 10.37 obtained through solid-liquid separation Outlet of a H.sub.2O 120 0.86 43.88 −67505 solid CaCl.sub.2 120 0.1 5.1 residue SiO.sub.2 120 1 51.02 −216404 obtained through solid-liquid separation

[0055] In a specific example, wollastonite is used as an example of the silicate ore in this example. Wollastonite comes from Shanggao, Jiangxi and has a particle size of 200 mesh (based on the Tyler standard screen). An average ore composition is shown in Table 2.

TABLE-US-00002 TABLE 2 Average ore composition of wollastonite (%) ω (calcium ω (calcium silicate) carbonate) ω (diopside) ω (quartz) ω (garnet) 94.1 1.24 0.86 2.37 0.96

[0056] In a specific example, a volume of the material storage tank is 4 m.sup.3, and a screw feeder is selected as the quantitative powder conveying apparatus. A volume of the stirred tank is 4 m.sup.3, a rotation speed is 30 rpm, a number of added wollastonite powders is 110 kg/h, and an amount of added water is 880 kg/h, and a flow rate of hydrogen chloride gas is controlled to be 45 m.sup.3/h (a molar ratio of the hydrogen chloride gas to the wollastonite powders is 2:1, and the amount of the wollastonite powders is calculated based on SiO.sub.2). A temperature of the stirred tank is set to 80° C., a stay time is 2 h, and a circulation flow rate is 100 kg/h. After sedimentation, a solid residue is further washed, filtered and dried to obtain ultrafine SiO.sub.2. Technical indicators are shown in Table 3.

TABLE-US-00003 TABLE 3 Technical indicators of ultrafine SiO.sub.2 prepared by using powders of a wollastonite ore Silica % 95 Heat loss % 5.8 Loss on ignition % 5.1 DBP absorption value/ml/g 2.98 BET specific surface area/m.sup.2/g 198 pH 6.4 Average particle size/um 10.5 Iron/ppm 180

[0057] In a specific example, serpentine is used as an example of the silicate ore in this example. Serpentine comes from Xinyang, Henan and has a particle size of 200 mesh (based on the Tyler standard screen). An average ore composition is shown in Table 4.

TABLE-US-00004 TABLE 4 Average ore composition of serpentine (%) ω (magnesium oxide) ω (silica) ω (water) 44.3 44.1 12.9

[0058] In a specific example, a volume of the material storage tank is 4 m.sup.3, and a screw feeder is selected as the quantitative powder conveying apparatus. A volume of the stirred tank is 4 m.sup.3, a rotation speed is 30 rpm, a number of added serpentine powders is 91 kg/h, and an amount of added water is 880 kg/h, and a flow rate of the hydrogen chloride gas is controlled to be 45 m.sup.3/h (a molar ratio of the hydrogen chloride gas to the serpentine powders is 2:1, and the amount of the serpentine powders is calculated based on SiO.sub.2). A temperature of the stirred tank is set to 120° C., a stay time is 2 h, and a circulation flow rate is 100 kg/h. After sedimentation, a solid residue is further washed, filtered, dried, and smashed to obtain ultrafine SiO.sub.2. Technical indicators are shown in Table 5.

TABLE-US-00005 TABLE 5 Technical indicators of ultrafine SiO.sub.2 prepared by using powders of a serpentine ore Silica % 95.8 Heat loss % 5.36 Loss on ignition % 6.21 DBP absorption value/ml/g 2.86 BET specific surface area/m.sup.2/g 188 pH 6.35 Average particle size/um 14.1 Iron/nnm 182

Embodiment 2

[0059] FIG. 2 is a schematic diagram of a preparation system according to a second embodiment of the present disclosure. A structure of the preparation system is basically the same as the system shown in FIG. 1. Differences are as follows: A raw ore feeding apparatus further includes a premixing tank 11 connected with a quantitative powder conveying apparatus 3, a slurry outlet of the premixing tank 11 is connected with an ejector 4 and a slurry inlet of the premixing tank 11 is connected with a circulation pipe 8, and some of materials in the circulation pipe 8 are imported into the premixing tank 11 through a circulation pump 5, so that the materials are premixed with added powders of a silicate ore. A slurry obtained after the premixing is input into the ejector 4 through the slurry outlet. A slurry pump 5′ is arranged on a pipe through which the premixing tank 11 is connected with the ejector 4.

[0060] A working process of the preparation system according to the second embodiment of the present disclosure is as follows: Continuous operations are performed. Powders of a raw ore that are conveyed to a material storage tank 2 are continuously added to the premixing tank 11 by using the quantitative powder conveying apparatus 3 and are uniformly mixed with a specific amount of water through stirring to form a slurry; the slurry is driven into the ejector 4 through the slurry pump 5′ at a high speed; negative pressure is formed in the ejector by using the Venturi effect, so that hydrogen chloride gas is sucked for an initial contact reaction; then a reaction liquid enters a stirred tank 6 for a further reaction; some of the slurry reacted in the stirred tank is discharged into the solid-liquid separation apparatus 7 for a solid-liquid separation operation, and some is pumped as a circulation liquid by the circulation pump 5 into the circulation pipe 11 through the circulation pipe 8.

[0061] In a specific example, wollastonite is used as an example of the silicate ore in this example. Wollastonite comes from Shanggao, Jiangxi and has a particle size of 200 mesh (based on the Tyler standard screen). An average ore composition is shown in Table 2.

[0062] In a specific example, a volume of the material storage tank is 4 m.sup.3, and a screw feeder is selected as the quantitative powder conveying apparatus. A volume of the premixing tank is 3 m.sup.3, a volume of the stirred tank is 4 m.sup.3, a rotation speed is 30 rpm, a number of added wollastonite powders is 110 kg/h, and an amount of added water is 880 kg/h, and a flow rate of the hydrogen chloride gas is controlled to be 45 m.sup.3/h (a molar ratio of the hydrogen chloride gas to the wollastonite powders is 2:1, and the amount of the wollastonite powders is calculated based on SiO.sub.2). A temperature of the stirred tank is set to 80° C., a stay time is 2 h, and a circulation flow rate is 100 kg/h. After sedimentation, a solid residue is further washed, filtered and dried to obtain ultrafine SiO.sub.2. Technical indicators are shown in Table 6.

TABLE-US-00006 TABLE 6 Technical indicators of ultrafine SiO.sub.2 prepared by using powders of a wollastonite ore Silica % 96.3 Heat loss % 5.76 Loss on ignition % 5.24 DBP absorption value/ml/g 2.85 BET specific surface area/m.sup.2/g 214 pH 6.31 Average particle size/um 12.9 Iron/ppm 182

[0063] In a specific example, wollastonite is still used as an example of the silicate ore in this example. Wollastonite comes from Shanggao, Jiangxi and has a particle size of 200 mesh (based on the Tyler standard screen). An average ore composition is shown in Table 2.

[0064] In a specific example, intermittent operations are performed. 110 kg of wollastonite powders are added to the stirred tank, 880 kg of water are added, and a flow rate of hydrogen chloride gas is controlled to be 45 m.sup.3/h (a molar ratio of the hydrogen chloride gas to the wollastonite powders is 2:1, and an amount of the wollastonite powders is calculated based on SiO.sub.2). A temperature of the stirred tank is set to 80° C., a reaction time is 1 h, and a circulation flow rate is 100 kg/h. After sedimentation, a solid residue is further washed, filtered and dried to obtain ultrafine SiO.sub.2. Technical indicators are shown in Table 7.

TABLE-US-00007 TABLE 7 Technical indicators of ultrafine SiO.sub.2 prepared through intermittent operations Silica % 95.5 Heat loss % 5.72 Loss on ignition % 5.19 DBP absorption value/ml/g 2.95 BET specific surface area/m.sup.2/g 189 pH 6.4 Average particle size/um 14.1 Iron/ppm 180

[0065] It should be noted that, according to common knowledge of a person of ordinary skill in the art, corresponding measurements such as a temperature measurement and a liquid level measurement, a control system, and a corresponding valve are further set on a decomposition reactor and a regeneration reactor, and are not indicated in the accompanying drawings one by one. This does not mean that the conventional designs are not included in the process of the present disclosure. It is also a conventional design common to a person of ordinary skill in the art that a feed rate of raw materials in the present disclosure is adjusted based on a conversion rate and a material balance, and the conventional designs are also not indicated in the present disclosure one by one. This does not mean that the conventional design is not included in the process of the present disclosure.

[0066] In accordance with the embodiments of the present disclosure, as described above, the embodiments are not described in detail, and are not intended to limit the present disclosure to be only the described specific embodiments. Obviously, many modifications and variations are possible in light of the forgoing description. The embodiments have been selected and described in detail to better explain the principle and actual application of the present disclosure, so that a person skilled in the art can take full advantage of the present disclosure and a use modified based on the present disclosure.