CN111732119B - Process for preparing aluminum ammonium sulfate by crystallization of two-stage leaching raffinate - Google Patents
Process for preparing aluminum ammonium sulfate by crystallization of two-stage leaching raffinate Download PDFInfo
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- CN111732119B CN111732119B CN202010654973.2A CN202010654973A CN111732119B CN 111732119 B CN111732119 B CN 111732119B CN 202010654973 A CN202010654973 A CN 202010654973A CN 111732119 B CN111732119 B CN 111732119B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
- C01F7/76—Double salts, i.e. compounds containing, besides aluminium and sulfate ions, only other cations, e.g. alums
- C01F7/762—Ammonium or alkali metal aluminium sulfates
- C01F7/765—Ammonium aluminium sulfates
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Abstract
The invention discloses a process for preparing aluminum ammonium sulfate by crystallizing two-stage leaching raffinate, which comprises the following steps: (1) Adding ammonium sulfate into the raffinate to perform ammonium-aluminum reaction, and crystallizing to obtain an aluminum-ammonium sulfate crude product; (2) Adding a dissolving solution into the coarse product of the aluminum ammonium sulfate for dissolving and filtering, and performing vacuum crystallization to obtain a purer coarse product of the aluminum ammonium sulfate; (3) Adding deionized water into the purer aluminum ammonium sulfate crude product for dissolving, and freezing and crystallizing to obtain a pure aluminum ammonium sulfate product. Firstly, obtaining an aluminum ammonium sulfate crude product through an ammonium-aluminum reaction; then, vacuum crystallization and filtration are carried out to obtain a crude product of aluminum ammonium sulfate with the purity of more than 80 percent; finally, the aluminum ammonium sulfate product with the concentration of about 99 percent is obtained by freezing, crystallizing and filtering. Therefore, the invention effectively recycles the aluminum in the second-stage leaching raffinate, and further purifies the recycled aluminum ammonium sulfate crude product to meet the requirement of industrial use.
Description
Technical Field
The invention belongs to the technical field of titanium ore recycling, and particularly relates to a process for preparing aluminum ammonium sulfate by crystallizing second-stage leaching raffinate.
Background
After the second-stage leaching solution is used for extracting titanium, the content of titanium and iron in the solution is low, and the preparation of aluminum ammonium sulfate with higher purity is facilitated. The prior art has added (NH) to the second leach raffinate 4 ) 2 SO 4 The ammonium aluminum reaction is carried out, and after the reaction, the feed liquid is added into a crystallizer to carry out aluminum ammonium sulfate crystallization, however, the aluminum ammonium sulfate crystal prepared in the mode is a crude product of the aluminum ammonium sulfate, and contains a lot of impurities, so that the research on a crystallization and purification process of the aluminum ammonium sulfate is needed.
Disclosure of Invention
The invention provides a process for preparing aluminum ammonium sulfate by crystallizing two-stage leaching raffinate, which aims to overcome the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the process for preparing the ammonium aluminum sulfate by crystallizing the second-stage leaching raffinate comprises the following steps:
s1: adding ammonium sulfate into the raffinate to perform ammonium-aluminum reaction, and crystallizing to obtain an aluminum ammonium sulfate crude product;
s2: adding a dissolving solution into the coarse product of the aluminum ammonium sulfate for dissolving and filtering, and performing vacuum crystallization to obtain a purer coarse product of the aluminum ammonium sulfate;
s3: adding deionized water into the purer aluminum ammonium sulfate crude product for dissolving, and freezing and crystallizing to obtain a pure aluminum ammonium sulfate product.
As a further description of the above technical solution: the step S1 includes the following substeps:
s11: heating raffinate, and adding ammonium sulfate according to a certain ammonium-aluminum molar ratio to react aluminum sulfate in the raffinate with the ammonium sulfate to generate aluminum ammonium sulfate;
s12: after the reaction, the feed liquid is added into a crystallizer to crystallize aluminum ammonium sulfate to obtain a crude product of the aluminum ammonium sulfate.
As a further description of the above technical solution: the heating temperature in the step S11 is 60-120 ℃; the reaction time in the step S11 is 10-60min; the molar ratio of ammonium to aluminum in the step S11 is 1:1-1:5.
As a further description of the above technical solution: the dissolving solution in the step S2 is pure water.
As a further description of the above technical solution: the step S2 includes the following substeps:
s21: adding pure water into the crude product of the aluminum ammonium sulfate for dissolving;
s22: filtering the pure water solution to remove undissolved impurities;
s23: vacuum crystallizing the filtered solution to obtain a purer coarse product of the ammonium aluminum sulfate;
s24: the purer aluminum ammonium sulfate crude product is washed by washing water.
As a further description of the above technical solution: the step S2 further comprises the following substeps:
s25: and returning the washed filtrate to the step S21 for dissolving the crude product of the aluminum ammonium sulfate.
As a further description of the above technical solution: the vacuum degree in the step S23 is 2000-2600Pa.
As a further description of the above technical solution: the crystallization time in the step S23 is 30-90min.
As a further description of the above technical solution: the step S3 includes the following substeps:
s31: adding deionized water into the purer coarse product of the aluminum ammonium sulfate for dissolving;
s32: freezing and crystallizing the deionized water solution to obtain a crystallization solution;
s33: filtering the crystallization solution to obtain a pure ammonium aluminum sulfate product and a filtrate;
s34: the filtrate is returned to step S24 and used as washing water.
As a further description of the above technical solution: the freezing and crystallizing temperature in the step S32 is-30-15 ℃; the freezing and crystallizing time in the step S32 is 30-90min.
The invention has the following beneficial effects:
firstly, obtaining an aluminum ammonium sulfate crude product through an ammonium-aluminum reaction; then, vacuum crystallization and filtration are carried out to obtain a crude product of aluminum ammonium sulfate with the purity of more than 80 percent; finally, the aluminum ammonium sulfate product with the concentration of about 99 percent is obtained by freezing, crystallizing and filtering. Therefore, the invention effectively recycles the aluminum in the second-stage leaching raffinate, and further purifies the recycled aluminum ammonium sulfate crude product so as to meet the requirements of industrial use.
Drawings
FIG. 1 is a flow chart of a process for preparing ammonium aluminum sulfate by two-stage leaching raffinate crystallization.
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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
As shown in figure 1, the process for preparing the ammonium aluminum sulfate by the crystallization of the two-stage leaching raffinate comprises the following steps:
(1) Adding ammonium sulfate into the raffinate to perform ammonium-aluminum reaction, and crystallizing to obtain an aluminum-ammonium sulfate crude product;
(2) Adding a dissolving solution into the coarse product of the aluminum ammonium sulfate for dissolving and filtering, and performing vacuum crystallization to obtain a purer coarse product of the aluminum ammonium sulfate;
(3) Adding deionized water into the purer aluminum ammonium sulfate crude product for dissolving, and freezing and crystallizing to obtain a pure aluminum ammonium sulfate product.
Firstly, obtaining an aluminum ammonium sulfate crude product through an ammonium-aluminum reaction; then, vacuum crystallization and filtration are carried out to obtain a crude product of aluminum ammonium sulfate with the purity of more than 80 percent; finally, the aluminum ammonium sulfate product with the concentration of about 99 percent is obtained by freezing, crystallizing and filtering. Therefore, the invention effectively recycles the aluminum in the second-stage leaching raffinate, and further purifies the recycled aluminum ammonium sulfate crude product to meet the requirement of industrial use.
In this embodiment, the step (1) includes the following sub-steps:
(11) Heating raffinate, and adding ammonium sulfate according to a certain ammonium-aluminum molar ratio to react aluminum sulfate in the raffinate with the ammonium sulfate to generate aluminum ammonium sulfate;
(12) After the reaction, the feed liquid is added into a crystallizer for aluminum ammonium sulfate crystallization, and then the crude product of the aluminum ammonium sulfate and the crystallization tail liquid are obtained by filtration.
In the present embodiment, the heating temperature in step (11) is 60-120 ℃, preferably, the heating temperature in step (11) is 80 ℃; the reaction time in the step (11) is 10-60min, and preferably, the reaction time in the step (11) is 30min; the molar ratio of ammonium to aluminum in the step (11) is 1:1-1:5, and preferably, the molar ratio of ammonium to aluminum in the step (11) is 1:3.
In this embodiment, the dissolving solution in the step (2) is pure water.
In this embodiment, the step (2) includes the following sub-steps:
(21) Adding pure water into the crude product of the aluminum ammonium sulfate for dissolving;
(22) Filtering the pure water solution to remove undissolved impurities;
(23) Carrying out vacuum crystallization and filtration on the filtered solution to obtain a purer coarse product of the ammonium aluminum sulfate;
(24) The purer aluminum ammonium sulfate crude product is washed by washing water.
(25) And (5) returning the washed filtrate to the step (21) for dissolving the crude product of the aluminum ammonium sulfate.
In the embodiment, the vacuum degree in the step (23) is 2000-2600Pa, and preferably, the vacuum degree in the step (23) is 2400Pa; the crystallization time in the step (23) is 30-90min, and preferably, the crystallization time in the step (23) is 60min.
In this embodiment, the step (3) includes the following sub-steps:
(31) Adding deionized water into the purer aluminum ammonium sulfate crude product for dissolving;
(32) Freezing and crystallizing the deionized water solution to obtain a crystallization solution;
(33) Filtering the crystallization solution to obtain a pure aluminum ammonium sulfate product and a filtrate;
(34) The filtrate is returned to step (24) for use as wash water.
In this embodiment, the freezing crystallization temperature in the step (32) is-30-15 ℃; the freezing and crystallizing time in the step (32) is 30-90min, and preferably, the freezing and crystallizing time in the step (32) is 60min.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
As shown in figure 1, after the titanium is extracted from the second-stage leaching solution, the content of titanium and iron in the solution is low, and the preparation of aluminum ammonium sulfate with higher purity is facilitated. Heating the leaching solution to 80 ℃, and adding (NH) according to the molar ratio of ammonium to aluminum of 1:3 4 ) 2 SO 4 And (3) carrying out an ammonium-aluminum reaction, maintaining the reaction temperature at 80 ℃, reacting for 30min, adding the feed liquid into a crystallizer after the reaction for carrying out aluminum ammonium sulfate crystallization, and then filtering to obtain an aluminum ammonium sulfate crystallization crude product. The purification of the crude product of the ammonium aluminum sulfate crystallization is carried out by two times, wherein the first time adopts vacuum crystallization (namely primary recrystallization), the vacuum degree of a system is controlled to be 2400Pa, the crystallization time is 60min, more than 80 percent of the crude product of the ammonium aluminum sulfate is obtained by filtering, the second time adopts freezing crystallization (namely secondary recrystallization), the crystallization temperature is controlled to be less than or equal to 15 ℃, the crystallization time is 60min, and about 99 percent of the ammonium aluminum sulfate product is obtained by filtering.
Dissolving the first vacuum crystallization product by using deionized water, performing second freezing crystallization (namely, secondary recrystallization), and performing crystallization and purification twice to obtain the final aluminum ammonium sulfate product. The filtrate of the second freezing crystallization is returned as the washing water of the first vacuum crystallization product, the washed liquid is used for dissolving the crude product of the aluminum ammonium sulfate, the insoluble impurities are filtered for the first vacuum crystallization (namely, the first recrystallization) after the crude product of the aluminum ammonium sulfate is dissolved, and the filtrate of the first vacuum crystallization is returned as the diluting filtration make-up water of the leached ore pulp to form a closed circuit.
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.
Claims (9)
1. The process for preparing the ammonium aluminum sulfate by crystallizing the second-stage leaching raffinate is characterized by comprising the following steps of:
s1: adding ammonium sulfate into the raffinate to perform ammonium-aluminum reaction, and crystallizing to obtain an aluminum-ammonium sulfate crude product;
s2: adding a dissolving solution into the coarse product of the aluminum ammonium sulfate for dissolving and filtering, and performing vacuum crystallization to obtain a purer coarse product of the aluminum ammonium sulfate;
s3: adding deionized water into the crude product of the purer aluminum ammonium sulfate for dissolving, and freezing and crystallizing to obtain a pure aluminum ammonium sulfate product;
the step S1 includes the following substeps:
s11: heating raffinate, and adding ammonium sulfate according to a certain ammonium-aluminum molar ratio to react aluminum sulfate in the raffinate with the ammonium sulfate to generate aluminum ammonium sulfate;
s12: after the reaction, adding the feed liquid into a crystallizer to crystallize aluminum ammonium sulfate to obtain a crude product of the aluminum ammonium sulfate;
the second-stage leaching raffinate is a solution with low titanium and iron contents after the second-stage leachate is used for extracting titanium; the molar ratio of ammonium to aluminum in the step S11 is 1:1-1:5.
2. The process for preparing aluminum ammonium sulfate by two-stage leach raffinate crystallization according to claim 1, wherein the heating temperature in the step S11 is 60-120 ℃; the reaction time in the step S11 is 10-60min.
3. The process for preparing ammonium aluminum sulfate by crystallization of two-stage leach raffinate according to claim 1, wherein the dissolving solution in the step S2 is pure water.
4. The process for preparing aluminum ammonium sulfate by two-stage leach raffinate crystallization according to claim 3, wherein the step S2 comprises the following substeps:
s21: adding pure water into the crude product of the aluminum ammonium sulfate for dissolving;
s22: filtering the pure water solution to remove undissolved impurities;
s23: vacuum crystallizing the filtered solution to obtain a crude product of purer ammonium aluminum sulfate;
s24: the purer aluminum ammonium sulfate crude product is washed by washing water.
5. The process for preparing ammonium aluminum sulfate by crystallization of two-stage leach raffinate according to claim 4, wherein the step S2 further comprises the following substeps:
s25: and returning the washed filtrate to the step S21 for dissolving the crude product of the aluminum ammonium sulfate.
6. The process for preparing ammonium aluminum sulfate by two-stage leaching raffinate crystallization in claim 4, wherein the vacuum degree in the step S23 is 2000-2600Pa.
7. The process for preparing ammonium aluminum sulfate by crystallization of two-stage leach raffinate according to claim 4, wherein the crystallization time in the step S23 is 30-90min.
8. The process for preparing aluminum ammonium sulfate by two-stage leach raffinate crystallization according to claim 1, wherein the step S3 comprises the following substeps:
s31: adding deionized water into the purer coarse product of the aluminum ammonium sulfate for dissolving;
s32: freezing and crystallizing the deionized water dissolved solution to obtain a crystallization solution;
s33: filtering the crystallization solution to obtain a pure ammonium aluminum sulfate product and a filtrate;
s34: the filtrate is returned to step S24 and used as washing water.
9. The process for preparing ammonium aluminum sulfate by crystallization of two-stage leach raffinate according to claim 8, wherein the freezing and crystallizing temperature in the step S32 is-30-15 ℃; the freezing and crystallizing time in the step S32 is 30-90min.
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