阅读说明：本技术 一种锆英砂除铁钛工艺 (Process for removing iron and titanium from zircon sand ) 是由 朱志彬 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种锆英砂除铁钛工艺,包括如下步骤：S1、预处理：将含铁钛杂质的锆英砂用球磨机研磨成锆英粉,烘干备用；S2、酸解：将步骤S1所得的锆英粉与足量的硫酸搅拌混合均匀,装入匣钵中；将匣钵放入梭式窑中,开启加温系统,将温度升高到240～270℃,并保温2～4小时,保温结束后降温,冷却至室温；铁钛杂质与硫酸在高温下发生反应生成Ti(SO-4)-2和Fe-2(SO-4)-3；S3、水洗：将步骤S2冷却后的物料进行破碎,破碎后的粉料与足量的水搅拌混合均匀,使得Ti(SO-4)-2和Fe-2(SO-4)-3充分溶解于水中；静止沉淀,倾出清液,沉淀物用可水洗板框压滤机压滤进行固液分离,用足量的水进行水洗,洗至滤液呈中性；S4、烘干：将步骤S3水洗后的物料烘干。经本发明处理后的锆英粉,铁钛杂质含量低,白度高。(The invention discloses a process for removing iron and titanium from zircon sand, which comprises the following steps: s1, preprocessing: grinding zircon sand containing iron and titanium impurities into zircon powder by using a ball mill, and drying for later use; s2, acid hydrolysis: uniformly stirring and mixing the zircon powder obtained in the step S1 with sufficient sulfuric acid, and filling the zircon powder into a sagger; putting the sagger into a shuttle kiln, starting a heating system, raising the temperature to 240-270 ℃, preserving the heat for 2-4 hours, cooling after the heat preservation is finished, and cooling to room temperature; reacting ferrotitanium impurities with sulfuric acid at high temperature to generate Ti (SO) 4 ) 2 And Fe 2 (SO 4 ) 3 (ii) a S3, washing: crushing the material cooled in the step S2, and uniformly stirring and mixing the crushed powder with sufficient water to obtain Ti (SO) 4 ) 2 And Fe 2 (SO 4 ) 3 Fully dissolving in water; standing for precipitation, decanting the clear solution, press-filtering the precipitate with a washable plate-and-frame filter press for solid-liquid separation, washing with sufficient water until the filtrate is neutral; s4, drying: and (5) drying the material washed in the step S3. Zircon treated by the inventionThe content of iron and titanium impurities in the powder is low, and the whiteness is high.)

1. A process for removing iron and titanium from zircon sand is characterized by comprising the following steps:

s1, preprocessing: grinding zircon sand containing iron and titanium impurities into zircon powder with the granularity of 320-330 meshes by using a ball mill, and drying for later use;

s2, acid hydrolysis: the method specifically comprises the following steps:

s2.1, uniformly stirring and mixing the zircon powder obtained in the step S1 with sufficient sulfuric acid, and filling the zircon powder into a sagger;

s2.2, putting the sagger into a shuttle kiln, starting a heating system, raising the temperature to 240-270 ℃, preserving the heat for 2-4 hours, cooling after the heat preservation is finished, and cooling to room temperature; wherein, the iron-titanium impurity and sulfuric acid react at high temperature: TiO 2₂ + 2H₂SO₄ = Ti(SO₄)₂ + 2H₂O，Fe₂O₃ + 3H₂SO₄ = Fe₂(SO₄)₃ + 3H₂O to produce Ti (SO)₄)₂And Fe₂(SO₄)₃；

S3, washing: the method specifically comprises the following steps:

s3.1, crushing the material cooled in the step S2, and uniformly stirring and mixing the crushed powder with sufficient water to obtain Ti (SO)₄)₂And Fe₂(SO₄)₃Fully dissolving in water;

s3.2, standing for precipitation, pouring out clear liquid, performing filter pressing on the precipitate by using a washable plate-and-frame filter press for solid-liquid separation, washing by using sufficient water until filtrate is neutral;

s4, drying: and (5) drying the material washed in the step S3.

2. The process for removing iron and titanium from zircon sand according to claim 1, which is characterized in that: in step S1, the zircon sand is zircon sand containing ferrotitanium impurities, which is screened from zircon placer ore by jigging, gravity separation, magnetic separation or electric separation.

3. The process for removing iron and titanium from zircon sand according to claim 1, which is characterized in that: in step S1, the zircon powder has a particle size of 325 mesh.

4. The process for removing iron and titanium from zircon sand according to claim 1, which is characterized in that: in step S2.1, the solid-liquid mass ratio of the zircon powder to the sulfuric acid is 1: (0.3-0.5).

5. The process for removing iron and titanium from zircon sand according to claim 1, which is characterized in that: in step S2.1, the solid-liquid mass ratio of the zircon powder to the sulfuric acid is 1: 0.4.

6. the process for removing iron and titanium from zircon sand according to claim 1, which is characterized in that: in step S2.2, the heating system is started, the temperature is raised to 255 ℃, and the temperature is maintained for 3 hours.

7. The process for removing iron and titanium from zircon sand according to claim 1, which is characterized in that: in step S3.1, the solid-to-liquid ratio of the crushed powder to water is 1: (2-4).

8. The process for removing iron and titanium from zircon sand according to claim 1, which is characterized in that: in step S3.1, the solid-to-liquid ratio of the crushed powder to water is 1: 3.

9. the process for removing iron and titanium from zircon sand according to claim 1, which is characterized in that: in step S3.2, the solid-to-liquid ratio of the precipitate to water is 1: 1.

10. the process for removing iron and titanium from zircon sand according to claim 1, which is characterized in that: in step S4, the dried product is packaged.

Technical Field

The invention belongs to the technical field of zircon sand treatment, and particularly relates to a process for removing iron and titanium from zircon sand.

Background

Zirconium is a strategic emerging mineral and is widely applied to the fields of ceramics, glass, nuclear industry, electronics, building materials, medicines, textiles, daily necessities and the like. The zirconium resource beneficiation products are collectively called zircon sand. The zircon sand is not only an important mineral product for extracting zirconium and hafnium metals, but also is directly used in industries such as ceramics, building materials, casting, refractory materials and the like in large quantity. It is an important mineral resource in China, is a basic material related to national safety and civil construction, and is an indispensable part in the Chinese raw material industry. With the rapid development of Chinese economy, the demand for zircon sand mineral resources is gradually increased.

Zircon placer ore is mainly present in pegmatite, granite, gneiss, and is commonly associated with ilmenite and rutile. The raw ore is subjected to jigging, gravity separation, magnetic separation and electric separation to obtain zircon sand concentrate called zircon sand. Some zircon sands have a small amount of impurities such as ferrotitanium and the like to participate in the co-growth in the crystal growth process, the zircon sands are screened out in the mineral separation process (different production areas, the proportion of the impurities is also different, approximately 5-15% of the impurities, and 50-63% of zirconia content), and the impurities such as ferrotitanium and the like have high content, so that the zircon sands have low utilization value, are often used for roadbed landfill and low-end casting, and low-grade refractory materials, or are mixed into high-quality zircon sands by sub-flush to further influence terminal products, and further cause huge resource waste.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a process for removing iron and titanium from zircon sand.

In order to achieve the purpose, the invention adopts the following technical scheme: a process for removing iron and titanium from zircon sand comprises the following steps:

s1, preprocessing: grinding zircon sand containing iron and titanium impurities into zircon powder with the granularity of 320-330 meshes by using a ball mill, and drying for later use;

s2, acid hydrolysis: the method specifically comprises the following steps:

s2.1, uniformly stirring and mixing the zircon powder obtained in the step S1 with sufficient sulfuric acid, and filling the zircon powder into a sagger;

s2.2, putting the sagger into a shuttle kiln, starting a heating system, raising the temperature to 240-270 ℃, preserving the heat for 2-4 hours, cooling after the heat preservation is finished, and cooling to room temperature; wherein, the iron-titanium impurity and sulfuric acid react at high temperature: TiO 2₂+ 2H₂SO₄＝Ti(SO₄)₂+2H₂O，Fe₂O₃+3H₂SO₄＝Fe₂(SO₄)₃+3H₂O to produce Ti (SO)₄)₂And Fe₂(SO₄)₃；

S3, washing: the method specifically comprises the following steps:

s3.1, crushing the material cooled in the step S2, and uniformly stirring and mixing the crushed powder with sufficient water to obtain Ti (SO)₄)₂And Fe₂(SO₄)₃Fully dissolving in water;

s3.2, standing for precipitation, pouring out clear liquid, performing filter pressing on the precipitate by using a washable plate-and-frame filter press for solid-liquid separation, washing by using sufficient water until filtrate is neutral;

s4, drying: and (5) drying the material washed in the step S3.

Preferably, in step S1, the zircon sand is zircon sand containing ferrotitanium impurities, which is screened from zircon raw ore by jigging, gravity separation, magnetic separation or electric separation.

Preferably, in step S1, the zircon powder has a particle size of 325 meshes.

Preferably, in step S2.1, the solid-liquid mass ratio of the zircon powder to the sulfuric acid is 1: (0.3-0.5).

Preferably, in step S2.1, the solid-liquid mass ratio of the zircon powder to the sulfuric acid is 1: 0.4.

preferably, in step S2.2, the warming system is turned on, the temperature is raised to 255 ℃, and the incubation is continued for 3 hours.

Preferably, in step S3.1, the solid-to-liquid ratio of the crushed powder to water is 1: (2-4).

Preferably, in step S3.1, the solid-to-liquid ratio of the crushed powder to water is 1: 3.

preferably, in step S3.2, the solid-to-liquid ratio of the precipitate to water is 1: 1.

preferably, in step S4, the food is dried and then packaged.

Compared with the prior art, the invention has the following beneficial effects: the invention has simple process, easy operation and lower cost, the used materials are easy to obtain and cheap, and the sulfuric acid with proper solid-liquid mass ratio and the proper sulfuric acidThe technical means of heating temperature, proper heat preservation time and the like are organically combined, so that the zircon powder obtained by the treatment of the invention has impurities (Fe)₂O₃、TiO₂) Low content, high whiteness and the like, and good impurity removal effect; the invention has obvious effect of treating the sand with the iron and titanium content of less than 1.5 percent and wide applicability.

Drawings

FIG. 1 is a process flow diagram of an embodiment of the present invention.

FIG. 2 shows the amount of acid and TiO₂The relationship of the contents.

FIG. 3 shows the incubation time with TiO₂The relationship of the contents.

Detailed Description

In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.

The first embodiment is as follows: as shown in fig. 1, a process for removing iron and titanium from zircon sand comprises the following steps:

s1, preprocessing: grinding zircon sand containing iron and titanium impurities into zircon powder with the granularity of 320-330 meshes by using a ball mill, and drying for later use;

s2, acid hydrolysis: the method specifically comprises the following steps:

s2.1, uniformly stirring and mixing the zircon powder obtained in the step S1 with sufficient sulfuric acid, and filling the zircon powder into a sagger;

s2.2, putting the sagger into a shuttle kiln, starting a heating system, raising the temperature to 240-270 ℃, preserving the heat for 2-4 hours, cooling after the heat preservation is finished, and cooling to room temperature; wherein, the iron-titanium impurity and sulfuric acid react at high temperature: TiO 2₂+ 2H₂SO₄＝Ti(SO₄)₂+2H₂O，Fe₂O₃+3H₂SO₄＝Fe₂(SO₄)₃+3H₂O to produce Ti (SO)₄)₂And Fe₂(SO₄)₃；

S3, washing: the method specifically comprises the following steps:

s3.1, crushing the material cooled in the step S2, and stirring the crushed powder with sufficient waterMixing to obtain Ti (SO)₄)₂And Fe₂(SO₄)₃Fully dissolving in water;

s3.2, standing and precipitating, pouring out clear liquid, performing filter pressing on the precipitate by using a washable plate-and-frame filter press to perform solid-liquid separation, washing by using sufficient water until the filtrate is neutral (namely the pH is 7 or the pH is approximately equal to 7);

s4, drying: and (5) drying the material washed in the step S3.

In this embodiment, in step S1, the zircon sand is preferably, but not limited to, zircon sand containing iron and titanium impurities that is screened from zircon raw ore by jigging, gravity separation, magnetic separation or electric separation.

In this embodiment, in step S2.1, the solid-liquid mass ratio of the zircon powder to the sulfuric acid is preferably, but not limited to, 1: (0.3-0.5). Wherein the sulfuric acid is concentrated sulfuric acid, namely pure H with the mass fraction of more than or equal to 70 percent₂SO₄An aqueous solution of (a).

In this embodiment, in step S3.1, the solid-to-liquid ratio of the pulverized powder to water is preferably, but not limited to, 1: (2-4).

In this embodiment, in step S3.2, the solid-to-liquid ratio of the precipitate to water is preferably, but not limited to, 1: 1.

in this embodiment, in step S4, it is preferable, but not limited to, to perform packing after drying.

Example two: as shown in fig. 1, a process for removing iron and titanium from zircon sand differs from the first embodiment in that: (1) in step S1, the zircon powder has a particle size of 325 meshes; (2) in step S2.1, the solid-liquid mass ratio of the zircon powder to the sulfuric acid is 1: 0.4; (3) step S2.2, starting a heating system, raising the temperature to 255 ℃, and preserving the heat for 3 hours; (4) in step S3.1, the solid-to-liquid ratio of the crushed powder to water is 1: 3.

the principle of the invention is as follows: because the impurities such as ferrotitanium and the like and the zircon sand are symbiotic, the impurities are crushed to a certain fineness, the impurities such as ferrotitanium and the like and the zircon sand are fully stripped, and the impurities can be fully contacted and reacted with acid. TiO in zircon sand₂、Fe₂O₃Equal impurities are insoluble in water or dilute sulfurAcid, but soluble in hot concentrated sulfuric acid, reacts to form Ti (SO)₄)₂、Fe₂(SO₄)₃ZrSiO in zircon sand capable of dissolving in water₄Does not react with sulfuric acid. So that the resultant is washed with ZrSiO repeatedly₄And separating to improve the quality of the zircon sand.

The following experimental tests were carried out on placer ores with different sulfuric acid dosages, different heat preservation times and different origin of origin, according to the following: GB/T4984 and GB/T5950 and 2008, please see tables 1-5 for experimental results.

Table 1: analysis of influence of acid amount

From the experimental results shown in table 1 and fig. 2, it can be found that: when the acid amount reaches 1: 0.2 or more, Fe₂O₃、TiO₂The content can reach the standard value of the concentrate in JC/T2333-2015. Therefore, in order to obtain stable quality, in this example, the amount of sulfuric acid used was controlled to be 1: (0.3-0.5).

Table 2: influence test analysis of incubation time

From the experimental results shown in table 2 and fig. 3, it can be found that: TiO when the holding time is less than 2 hours₂The content of the concentrate is a little higher than the standard value of the concentrate in JC/T2333-2015. Therefore, considering the quality and energy consumption, the first embodiment controls the heat preservation time to be 2-4 hours.

Table 3: placer test analysis of different production site sources

From the experimental results shown in table 3, it can be found that: the iron content of the Vietnam sand, Australian sand and African sand 2 treated by the process can reach the standard value of the iron content of the first-grade concentrate in JC/T2333-2015; the titanium content of the Vietnam sand, the African sand 1 and the African sand 2 can reach the standard value of the titanium content of the primary concentrate in JC/T2333-2015; and the whiteness is obviously improved. The process has obvious effect of treating the sand with the iron and titanium contents of less than 1.5 percent, and has wide applicability.

It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.