阅读说明：本技术 一种粗钛渣制备人造金红石工艺 (Process for preparing artificial rutile from coarse titanium slag ) 是由 张裕书 高利坤 穆宇 张少翔 张新良 蒋朋 陈超 刘能云 于 2020-07-09 设计创作，主要内容包括：本发明公开了一种粗钛渣制备人造金红石工艺,包括如下步骤：(1)将粗钛渣依次进行焙烧、水洗处理,实现初步脱钠；(2)将水洗渣经盐酸浸出脱钠制备高钛渣；(3)将盐酸浸出液进行萃取得到粗钪渣；(4)将高钛渣进行煅烧制备人造金红石。在粗钛渣经焙烧水洗、盐酸浸出得到高钛渣,高钛渣煅烧得到人造金红石。即本发明通过焙烧水洗、盐酸浸出两次脱钠处理,可获得含TiO<Sub>2</Sub>93.21％、含Fe1.38％的高钛渣,再通过煅烧高钛渣制得人造金红石,大大提高了粗钛渣的回收利用率。(The invention discloses a process for preparing artificial rutile from coarse titanium slag, which comprises the following steps: (1) sequentially roasting and washing the coarse titanium slag to realize primary sodium removal; (2) leaching the washing slag by hydrochloric acid to remove sodium to prepare high-titanium slag; (3) extracting the hydrochloric acid leaching solution to obtain coarse scandium slag; (4) calcining the high titanium slag to prepare the artificial rutile. Roasting, washing and leaching the coarse titanium slag with hydrochloric acid to obtain high titanium slag, and calcining the high titanium slag to obtain the artificial rutile. Namely, the method can obtain TiO-containing by roasting, washing and hydrochloric acid leaching twice sodium removal treatment 2 93.21 percent and high titanium slag containing 1.38 percent of FeI, and then the artificial rutile is prepared by calcining the high titanium slag, thereby greatly improving the recovery rate of the coarse titanium slag.)

1. The process for preparing the artificial rutile from the coarse titanium slag is characterized by comprising the following steps of:

s1: sequentially roasting and washing the coarse titanium slag to realize primary sodium removal;

s2: leaching the washing slag by hydrochloric acid to remove sodium to prepare high-titanium slag;

s3: extracting the hydrochloric acid leaching solution to obtain coarse scandium slag;

s4: calcining the high titanium slag to prepare the artificial rutile.

2. The process for preparing artificial rutile from the coarse titanium slag as claimed in claim 1, wherein the calcination temperature in step S4 is 800-1100 ℃; the roasting time in the step S4 is 30-90 min.

3. The process for preparing artificial rutile from coarse titanium slag according to claim 1, wherein the step S1 comprises the following substeps:

s11: roasting the coarse titanium slag;

s12: washing the roasted coarse titanium slag with water;

s13: and carrying out solid-liquid separation on the solid-liquid mixture after washing to obtain washing liquid and washing slag.

4. The process for preparing artificial rutile from the coarse titanium slag as claimed in claim 3, wherein the roasting temperature in the step S11 is 300-900 ℃; the roasting time in the step S11 is 30-120 min.

5. The process for preparing artificial rutile from the coarse titanium slag according to claim 3, wherein the water washing liquid-solid ratio in the step S12 is 2:1-8: 1; the water washing time in the step S12 is 30-120 min.

6. The process for preparing artificial rutile from coarse titanium slag according to claim 1, wherein the step S2 comprises the following substeps:

s21: leaching the washing slag with hydrochloric acid to further remove sodium;

s22: and carrying out solid-liquid separation on the leaching mixture to obtain hydrochloric acid leaching solution and high titanium slag.

7. The process for preparing artificial rutile from the coarse titanium slag according to claim 6, wherein the hydrochloric acid leaching concentration in the step S21 is 3-9M/L; the temperature of the hydrochloric acid leaching in the step S21 is 0-180 ℃.

8. The process for preparing synthetic rutile through coarse titanium slag according to claim 6, wherein the hydrochloric acid leaching time in step S21 is 30-120 min; the hydrochloric acid leaching solution solid-to-solid ratio in the step S21 is 2:1-8: 1.

9. The process for preparing artificial rutile from coarse titanium slag according to claim 1, wherein the step S3 comprises the following substeps:

s31: extracting the hydrochloric acid leaching solution to obtain coarse scandium slag and a waste acid solution;

s32: carrying out regeneration process treatment on the waste acid liquid to obtain sodium chloride and hydrochloric acid;

s33: and adding hydrochloric acid into the leaching sodium removal treatment for recycling.

10. The process for preparing artificial rutile from the coarse titanium slag according to claim 9, wherein the step S31 is specifically as follows: and performing three-stage countercurrent extraction on the hydrochloric acid leaching solution to obtain coarse scandium slag and waste acid solution.

Technical Field

The invention belongs to the technical field of titanium ore recycling, and particularly relates to a process for preparing artificial rutile from coarse titanium slag.

Background

The test sample for preparing artificial rutile from coarse titanium slag is a mixture of coarse titanium slag obtained by back extraction in 6 circulation processes. After analysis, the mixed coarse titanium slag sample contains TiO₂、TFe、Na₂O、Sc₂O₃38.06%, 3.18%, 44.68% and 0.009%, respectively.

The high sodium content in the extraction residue (Na in the dried extraction residue) caused by the high concentration of the alkali liquor used in the titanium back extraction process₂The content of O is about 40 percent), and the high concentration of sodium limits the utilization of the titanium back extraction slag. The sodium removed from the stripping slag is recycled, so that the consumption of a stripping agent NaOH can be greatly reduced, and therefore, experimental research for removing NaOH from the coarse titanium slag and preparing artificial rutile is required.

Disclosure of Invention

The invention provides a process for preparing artificial rutile from coarse titanium slag, which aims to overcome the defects in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a process for preparing artificial rutile from coarse titanium slag comprises the following steps:

s1: sequentially roasting and washing the coarse titanium slag to realize primary sodium removal;

s2: leaching the washing slag by hydrochloric acid to remove sodium to prepare high-titanium slag;

s3: extracting the hydrochloric acid leaching solution to obtain coarse scandium slag;

s4: calcining the high titanium slag to prepare the artificial rutile.

As a further description of the above technical solution: the calcination temperature in the step S4 is 800-1100 ℃; the roasting time in the step S4 is 30-90 min.

As a further description of the above technical solution: the step S1 includes the following sub-steps:

s11: roasting the coarse titanium slag;

s12: washing the roasted coarse titanium slag with water;

s13: and carrying out solid-liquid separation on the solid-liquid mixture after washing to obtain washing liquid and washing slag.

As a further description of the above technical solution: the roasting temperature in the step S11 is 300-900 ℃; the roasting time in the step S11 is 30-120 min.

As a further description of the above technical solution: the water washing liquid solid ratio in the step S12 is 2:1-8: 1; the water washing time in the step S12 is 30-120 min.

As a further description of the above technical solution: the step S2 includes the following sub-steps:

s21: leaching the washing slag with hydrochloric acid to further remove sodium;

s22: and carrying out solid-liquid separation on the leaching mixture to obtain hydrochloric acid leaching solution and high titanium slag.

As a further description of the above technical solution: the hydrochloric acid leaching concentration in the step S21 is 3-9M/L; the temperature of the hydrochloric acid leaching in the step S21 is 0-180 ℃.

As a further description of the above technical solution: the hydrochloric acid leaching time in the step S21 is 30-120 min; the hydrochloric acid leaching solution solid-to-solid ratio in the step S21 is 2:1-8: 1.

As a further description of the above technical solution: the step S3 includes the following sub-steps:

s31: extracting the hydrochloric acid leaching solution to obtain coarse scandium slag and a waste acid solution;

s32: carrying out regeneration process treatment on the waste acid liquid to obtain sodium chloride and hydrochloric acid;

s33: and adding hydrochloric acid into the leaching sodium removal treatment for recycling.

As a further description of the above technical solution: the step S31 specifically includes: and performing three-stage countercurrent extraction on the hydrochloric acid leaching solution to obtain coarse scandium slag and waste acid solution.

The invention has the following beneficial effects:

roasting, washing and leaching the coarse titanium slag with hydrochloric acid to obtain high titanium slag, and calcining the high titanium slag to obtain the artificial rutile. Namely, the method can obtain TiO-containing by roasting, washing and hydrochloric acid leaching twice sodium removal treatment₂93.21 percent and high titanium slag containing 1.38 percent of FeI, and then the artificial rutile is prepared by calcining the high titanium slag, thereby greatly improving the recovery rate of the coarse titanium slag.

Drawings

FIG. 1 is a flow chart of a process for preparing synthetic rutile from coarse titanium slag provided by the invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

As shown in figure 1, the process for preparing the artificial rutile from the coarse titanium slag comprises the following steps:

(1) sequentially roasting and washing the coarse titanium slag to realize primary sodium removal;

(2) leaching the washing slag by hydrochloric acid to remove sodium to prepare high-titanium slag;

(3) extracting the hydrochloric acid leaching solution to obtain coarse scandium slag;

(4) calcining the high titanium slag to prepare the artificial rutile.

In this embodiment, the step (1) includes the following sub-steps:

(11) and roasting the coarse titanium slag.

The roasting temperature in the step (11) is 300-900 ℃; the roasting time in the step (11) is 30-120 min.

1) In order to determine the appropriate firing temperature, firing temperature condition tests were performed, with the fixed test conditions: feeding 50g of the raw materials, roasting for 60min, washing with calcine at a washing liquid-solid ratio of 5:1 at normal temperature for 60min, leaching the washing slag with hydrochloric acid at an acid concentration of 4M/L at a leaching temperature of 90 ℃ for 60min, and leaching at a leaching liquid-solid ratio of 4.

And (3) test results: the roasting temperature is low, although the leaching rate of sodium is high, the loss of titanium is large, the leaching rate of titanium is reduced along with the temperature rise to 700 ℃, when the temperature reaches 900 ℃, the leaching index is not greatly influenced, and therefore, the suitable roasting temperature is 700 ℃.

2) Test for calcination time

The fixed test conditions were: feeding 50g of the raw materials, wherein the roasting temperature is 700 ℃, the solid-to-solid ratio of the roasted sand washing liquid is 5, the washing temperature is normal temperature, and the washing time is 60 min; the roasting time test result shows that the proper roasting time is 60min, and Na is added₂The rate of O elimination was 72.66%.

(12) And washing the roasted coarse titanium slag with water.

The solid-to-liquid ratio of the washing liquid in the step (12) is 2:1-8: 1; the washing time in the step (12) is 30-120 min.

3) Washing liquid-solid ratio test

The fixed test conditions were: 50g of the raw materials are fed, the roasting temperature is 700 ℃, the roasting time is 60min, the water washing temperature is normal temperature, and the water washing time is 60 min. The results of the water washing liquid-solid ratio test show that the appropriate liquid-solid ratio is 6:1, and the Na2O removal rate is 75.31%.

4) Water washing temperature test

The fixed test conditions were: feeding 50g of the raw materials, roasting at 700 ℃, roasting time of 60min, roasted sand water washing liquid-solid ratio of 6:1, and water washing time of 60 min. The washing temperature test result shows that the rising of the washing temperature has little influence on the index of sodium removal, so the washing under the normal temperature condition can be considered.

5) Water wash time test

The fixed test conditions were: feeding 50g of the raw materials, roasting at 700 ℃, roasting for 60min, and washing the roasted sand with water at the normal temperature, wherein the solid-to-liquid ratio of the roasted sand to water is 6: 1. The water washing time test result shows that the proper water washing time is 60 min.

In conclusion, the TiO-containing coarse titanium slag can be obtained by roasting the coarse titanium slag at the roasting temperature of 700 ℃, the roasting time of 60min, the calcine water washing liquid-solid ratio of 6, the water washing temperature of normal temperature and the water washing time of 60min₂、TFe、Na₂The O content is 70.17%, 5.87% and 20.35% of washing slag, and the sodium removal rate is 75.31%.

The index results of the sodium elution of the crude titanium slag water obtained under the proper roasting-water washing conditions are shown in the table 1-1. As can be seen from tables 4-11, the coarse titanium slag was roasted and washed to obtain a titanium-containing slag containing TiO₂70.17％、Sc₂O₃Washing titanium slag with water of 0.019 percent, wherein the washing liquid contains TiO₂、TFe、Al₂O₃、Na₂O is respectively 0.047g/L, 0.10g/L and 0.046g/L, Na₂And O38.62 g/L is sodium hydroxide solution with low impurity content, and can be returned to the titanium back-extraction for recycling, so that the consumption of NaOH for titanium back-extraction is reduced.

TABLE 1-1 crude titanium slag Water washing test results

(13) And carrying out solid-liquid separation on the solid-liquid mixture after washing to obtain washing liquid and washing slag. Wherein, the water washing liquid can be used in the titanium back extraction to realize the recycling.

In this embodiment, the step (2) includes the following sub-steps:

(21) and (3) leaching the washing slag by hydrochloric acid to further remove sodium.

The hydrochloric acid leaching concentration in the step (21) is 3-9M/L; the temperature of hydrochloric acid leaching in the step (21) is 0-180 degrees; the hydrochloric acid leaching time in the step (21) is 30-120 min; the hydrochloric acid leaching solution solid-to-solid ratio in the step (21) is 2:1-8: 1.

6) Hydrochloric acid leaching concentration test

The conditions of the fixed test are as follows: 30g of feed, 90 ℃ of hydrochloric acid leaching temperature, 60min of leaching time and 6 of leaching solution-solid ratio. The leaching hydrochloric acid concentration test result shows that the suitable acidity is 7M/L.

7) Hydrochloric acid leaching temperature test

The fixed test conditions were: 30g of feed, 7M/L of acidity, 60min of leaching time and 6 of leaching solution-solid ratio. The temperature test result of the leached hydrochloric acid shows that the proper leaching temperature is 90 ℃.

8) Hydrochloric acid leaching time test

The fixed test conditions were: 30g of feed, 7M/L of acidity, 90 ℃ of hydrochloric acid leaching temperature and 6 solid ratio of leachate. The leaching time test result shows that the suitable leaching time is 60 min.

9) Solid ratio test of hydrochloric acid leaching solution

The fixed test conditions were: 30g of feed, 7M/L of acidity, 90 ℃ of hydrochloric acid leaching temperature and 60min of leaching time, and the leaching solution solid-to-solid ratio test result shows that the suitable leaching solution solid-to-solid ratio is 6: 1. Under these conditions, the sodium removal rate was 99.58%. The combined sodium removal rate of the crude titanium slag in the roasting-washing section is 75.31%, the reduced hydrochloric acid leaching removal rate is 24.59%, and the total sodium removal rate of the washing and the acid leaching reaches more than 99%.

The results of the tests on the calcined water washed slag under suitable hydrochloric acid leaching conditions to obtain high titanium slag are given in tables 1-2.

TABLE 1-2 test results of hydrochloric acid leaching to prepare high titanium slag

Components	TiO2	TFe	Al2O3	Na2O	Sc2O3
						High titanium slag (%)	92.17	1.03	0.12	0.12	32
Acid leachate (g/L)	1.03	6.82	0.55	16.34	32.96

As can be seen from tables 1-2, the TiO content obtained by calcining and washing the crude titanium slag₂68.27％、Sc₂O₃Washing titanium slag with 0.019% water, leaching with hydrochloric acid to obtain the product containing TiO₂92.17% high titanium slag, the hydrochloric acid leaching solution contains Sc₂O₃32.96mg/L, and scandium recovery can be carried out again, namely the comprehensive recovery of scandium brought into the coarse titanium slag during the titanium extraction is completed. The waste acid after scandium extraction can obtain partial hydrochloric acid for recycling according to the traditional waste hydrochloric acid regeneration process, and the waste residue can be independently treated to recover industrial sodium chloride without influencing the environment.

(22) And carrying out solid-liquid separation on the leaching mixture to obtain hydrochloric acid leaching solution and high titanium slag.

In this embodiment, the step (3) includes the following sub-steps:

(31) extracting the hydrochloric acid leaching solution to obtain coarse scandium slag and a waste acid solution;

(32) carrying out regeneration process treatment on the waste acid liquid to obtain sodium chloride and hydrochloric acid;

(33) and adding hydrochloric acid into the leaching sodium removal treatment for recycling.

The step (31) is specifically as follows: and performing three-stage countercurrent extraction on the hydrochloric acid leaching solution to obtain coarse scandium slag and waste acid solution.

10) Scandium extraction test of hydrochloric acid leach solution

The test conditions were: the extractant adopts KG-1 (20%) +1^#Solvent (5%) +2^#Solvent (75%), extracting under the condition that O/A is 1:10, shaking for 5 min; the stripping agent used for the loaded organic phase is KG-2(3M), and the stripping O/A is 6: 1. The extraction and back-extraction test results show that the extraction rate of scandium extracted by three-stage countercurrent extraction is up to more than 99.99%, the extraction rates of titanium and iron are particularly low, namely 15.53% and 1.32%, respectively, and the extraction conditions of the extractant (KG-1) can also effectively extract scandium in the hydrochloric acid leachate after the washing of the crude titanium slag.

In the embodiment, step (4) calcines the high titanium slag to prepare synthetic rutile.

The calcination temperature in the step (4) is 800-1100 ℃; the roasting time in the step (4) is 30-90 min.

11) Test for calcination time

The calcination temperature is 1000 ℃, and the calcination time test result shows that the calcination loss does not change greatly after the calcination time exceeds 60min, so that the calcination test time can be determined to be 60min, and TiO₂The grade is improved from 92.17% to 97.24%.

12) Calcination temperature test

The calcination temperature test is mainly used for observing the crystal form change at different temperatures. The calcination time is selected to be 60min, and different calcination temperature test results show that the temperature is opposite to the loss on ignition and TiO₂Grade is not greatly affected, but TiO₂The crystal form has larger transformation along with the temperature change. Therefore, the calcination temperature is preferably 1100 ℃.

Roasting, washing and leaching the coarse titanium slag with hydrochloric acid to obtain high titanium slag, and calcining the high titanium slag to obtain the artificial rutile. Namely, the method can obtain TiO-containing by roasting, washing and hydrochloric acid leaching twice sodium removal treatment₂93.21 percent and high titanium slag containing 1.38 percent of FeI, and then the artificial rutile is prepared by calcining the high titanium slag, thereby greatly improving the recovery rate of the coarse titanium slag.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.