CN116177572A - Calcium removal production process of lithium sulfate solution - Google Patents
Calcium removal production process of lithium sulfate solution Download PDFInfo
- Publication number
- CN116177572A CN116177572A CN202211549185.2A CN202211549185A CN116177572A CN 116177572 A CN116177572 A CN 116177572A CN 202211549185 A CN202211549185 A CN 202211549185A CN 116177572 A CN116177572 A CN 116177572A
- Authority
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- China
- Prior art keywords
- resin
- lithium sulfate
- calcium
- storage tank
- ion exchange
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 title claims abstract description 31
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000011575 calcium Substances 0.000 title claims abstract description 28
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 11
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 8
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims 1
- 238000004886 process control Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/02—Column or bed processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/14—Controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a calcium removal production process of a lithium sulfate solution, which adopts an ion exchange resin calcium removal technology to remove calcium from a lithium sulfate purifying solution, wherein the concentration of GaO in the lithium sulfate purifying solution after calcium removal is less than or equal to 5mg/L; wherein, the ion exchange resin decalcification technology is realized by adopting a resin filter with an ion exchange column, the flow rate of the ion exchange column is 15-30 BV/h, and the temperature is 50-70 ℃. According to the invention, through researching the influence of key factors such as temperature, concentration, flow rate and the like on the exchange adsorption capacity of the resin, the behavior of the resin for removing calcium ions is clarified, the optimal technological parameters of process control are obtained, important basis is provided for parameter control in industrial production, and the initial calcium concentration of the lithium sulfate solution is reduced from less than or equal to 30mg/l to less than or equal to 5mg/l.
Description
Technical Field
The invention belongs to the field of lithium sulfate purification, and particularly relates to a calcium removal production process of a lithium sulfate solution.
Background
At present, an alkali precipitation method is adopted for removing calcium from a lithium sulfate solution, as the output of lithium hydroxide of enterprises increases, the flux of intermediate liquid phase materials increases, the liquid sedimentation effect gradually decreases, the calcium index of the lithium sulfate purification liquid is continuously increased and is close to 30mg/l, the control difficulty of subsequent procedures is increased, even no effective removal means is available after calcium impurities enter the system from the purification liquid link in an ionic state, the grade of the final lithium hydroxide product is reduced, the continuous improvement requirement of the market cannot be met, and great economic loss is brought.
Disclosure of Invention
The invention aims to provide a calcium removal production process of a lithium sulfate solution, which aims at deeply removing calcium from the lithium sulfate solution and introduces an ion exchange resin technology to realize a low-cost sustainable calcium removal technology.
In order to achieve the above object, the present invention has the following advantageous effects:
the calcium removing production process of lithium sulfate solution adopts ion exchange resin to remove calcium from the lithium sulfate purifying liquid, and the GaO concentration in the lithium sulfate purifying liquid after calcium removal is less than or equal to 5mg/L; wherein, the ion exchange resin decalcification technology is realized by adopting a resin filter with an ion exchange column, the flow rate of the ion exchange column is 15-30 BV/h, and the temperature is 50-70 ℃.
Further, LSC-500 type resin is arranged in the resin filter.
Further, the resin filter is connected with a regeneration system, the regeneration system comprises a condensate water storage tank and a concentrated sulfuric acid storage tank, the condensate water storage tank and the concentrated sulfuric acid storage tank convey solution to the resin filter at the same speed, and the condensate water storage tank and the concentrated sulfuric acid storage tank are soaked in the resin filter and are kept still for 30-60 min, so that the resin filter is cleaned.
Further, the pH value of the resin cleaning solution is regulated to 6-7 by adding 50% liquid alkali, the resin cleaning solution is conveyed to a leaching and pressing three-time washing water storage tank of the existing metallurgical working section for storage, and the resin cleaning solution enters a lithium hydroxide production system when being subjected to three-time washing through a leaching and pressing filter press.
Further, a calcium ion concentration detector and a pH value detector are arranged at the outlet of the resin filter, and are connected with a control system through the calcium ion concentration detector and the pH value detector, so that linkage control and automatic production are realized.
According to the invention, through researching the influence of key factors such as temperature, concentration, flow rate and the like on the exchange adsorption capacity of the resin, the behavior of the resin for removing calcium ions is clarified, the optimal technological parameters of process control are obtained, important basis is provided for parameter control in industrial production, and the initial calcium concentration of the lithium sulfate solution is reduced from less than or equal to 30mg/l to less than or equal to 5mg/l.
Drawings
Fig. 1 is a schematic structural view of the present invention.
Detailed Description
As shown in fig. 1, the present embodiment provides a process for removing calcium from a lithium sulfate solution, which is based on an ion exchange resin calcium removal technology to design a system and a method suitable for removing calcium from a lithium sulfate solution, and specifically comprises the following steps:
(1) Selecting a resin filter as main equipment for removing calcium, wherein an ion exchange column and LSC-500 resin are filled in the resin filter; the feed inlet of resin filter is connected with purifying liquid 2# storage tank, has stored the lithium sulfate solution in the purifying liquid 2# storage tank, and the discharge gate of resin filter is connected with purifying liquid 3# storage tank, and purifying liquid 3# storage tank is used for storing the lithium sulfate purifying liquid up to standard after filtering, and the content of calcium oxide in the lithium sulfate purifying liquid is less than or equal to 5mg/L.
The flow rate of the ion exchange column and the temperature in the resin filter are controlled to realize high-efficiency calcium removal, the flow rate of the ion exchange column is 15-30 BV/h, the flow rate of the lithium sulfate solution flowing into the resin filter can be controlled to realize the control of the flow rate of the ion exchange column, and the temperature is 50-70 ℃; temperature control may be achieved by controlling the temperature within the resin filter or controlling the temperature of the lithium sulfate solution.
(2) The resin filter is connected with a regeneration system, the regeneration system comprises a condensed water storage tank and a concentrated sulfuric acid storage tank, the condensed water storage tank and the concentrated sulfuric acid storage tank are connected through a liquid inlet of the resin filter, and when the resin filter enters a cleaning regeneration state after running at full load, the condensed water storage tank and the concentrated sulfuric acid storage tank are 200m from now 3 The condensed water storage tank is filled with secondary water and mixed with 98% concentrated sulfuric acid to clean the filter resin; in the embodiment, the solution is conveyed to the resin filter at the same speed by controlling the working speed of the pump, and the resin filter is soaked and kept still for 30-60 min, so that the resin filter is cleaned.
(3) After 50% of liquid alkali is added into the resin cleaning solution, the pH value of the resin cleaning solution is regulated to 6-7, the resin cleaning solution is transferred into a leaching and pressing three-time washing water storage tank in the existing metallurgical working section for storage, and enters a lithium hydroxide production system when being washed three times through a leaching and pressing filter press, so that the solution can be recycled, the resource saving is realized, and the water balance and the process conditions of the existing lithium hydroxide production process can not be impacted after the leaching and pulping are carried out through washing water.
(4) And a calcium ion concentration detector and a pH value detector are arranged at the outlet of the resin filter, the calcium ion concentration detector and the pH value detector are connected with a control system to realize linkage control and automatic production, the calcium ion concentration detector is used for detecting the calcium ion concentration of the purifying liquid, and when the calcium ion concentration does not reach the standard, the lithium sulfate solution is stopped to be conveyed and a regeneration system is started to clean the resin filter. The pH value detector detects the pH value of the cleaning solution after cleaning, the pH value is 6-7, the cleaning solution is conveyed to a leaching and pressing three-time washing water storage tank of the existing metallurgical working section for storage, and the cleaning solution enters a lithium hydroxide production system after three-time washing through a leaching and pressing filter press.
In the embodiment, a resin decalcification technology is introduced, the resin decalcification technology is studied, and the purpose of decalcification is achieved through ion exchange. In order to ensure the high-efficiency operation of the resin decalcification system and achieve the purpose of decalcification, the working exchange capacity of the resin and Ca in the solution are researched 2+ The concentration and the flow rate flowing through the ion exchange column affect the decalcification process to obtain the optimal process control technical parameters.
The foregoing is merely a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification and substitution based on the technical scheme and the inventive concept provided by the present invention should be covered in the scope of the present invention.
Claims (5)
1. A calcium removal production process of a lithium sulfate solution is characterized by comprising the following steps of: removing calcium from the lithium sulfate purifying liquid by adopting an ion exchange resin calcium removal technology, wherein the GaO concentration in the lithium sulfate purifying liquid after calcium removal is less than or equal to 5mg/L; wherein, the ion exchange resin decalcification technology is realized by adopting a resin filter with an ion exchange column, the flow rate of the ion exchange column is 15-30 BV/h, and the temperature is 50-70 ℃.
2. The process for the decalcification production of a lithium sulfate solution according to claim 1, wherein: the LSC-500 resin is arranged in the resin filter.
3. The process for the decalcification production of a lithium sulfate solution according to claim 1, wherein: the resin filter is connected with a regeneration system, the regeneration system comprises a condensed water storage tank and a concentrated sulfuric acid storage tank, the condensed water storage tank and the concentrated sulfuric acid storage tank convey solution to the resin filter at the same speed, and the condensed water storage tank and the concentrated sulfuric acid storage tank are soaked in the resin filter and are static for 30-60 min, so that the resin filter is cleaned.
4. A process for the decalcification production of a lithium sulfate solution according to claim 3, wherein: the pH value of the resin cleaning solution is regulated to 6-7 by adding 50% liquid alkali, the resin cleaning solution is conveyed to a leaching and pressing three-time washing water storage tank of the existing metallurgical working section for storage, and the resin cleaning solution enters a lithium hydroxide production system when being subjected to three-time washing through a leaching and pressing filter press.
5. The process for the decalcification production of a lithium sulfate solution according to claim 1, wherein: and a calcium ion concentration detector and a pH value detector are arranged at the outlet of the resin filter, and are connected with a control system through the calcium ion concentration detector and the pH value detector, so that linkage control and automatic production are realized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211549185.2A CN116177572A (en) | 2022-12-05 | 2022-12-05 | Calcium removal production process of lithium sulfate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211549185.2A CN116177572A (en) | 2022-12-05 | 2022-12-05 | Calcium removal production process of lithium sulfate solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116177572A true CN116177572A (en) | 2023-05-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211549185.2A Pending CN116177572A (en) | 2022-12-05 | 2022-12-05 | Calcium removal production process of lithium sulfate solution |
Country Status (1)
| Country | Link |
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| CN (1) | CN116177572A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293532A (en) * | 2014-07-28 | 2016-02-03 | 李明雄 | Calcium removal process for lithium chloride solution during production |
| CN106881159A (en) * | 2017-03-23 | 2017-06-23 | 南京大学 | A kind of ion exchange resin fixed bed counter-current regeneration device and its application method |
| CN107540003A (en) * | 2017-10-13 | 2018-01-05 | 山东鲁北企业集团总公司 | Lithium sulfate thickening-purification technology liquid and preparation method thereof in one kind production battery-level lithium carbonate technique |
| CN211688289U (en) * | 2020-02-26 | 2020-10-16 | 天齐锂业（江苏）有限公司 | Device for removing impurity ions in lithium sulfate solution |
| CN113072081A (en) * | 2021-03-25 | 2021-07-06 | 四川恩特普环保科技有限公司 | Impurity removal process for lithium sulfate purification completion liquid |
| CN114272961A (en) * | 2021-12-20 | 2022-04-05 | 江西永兴特钢新能源科技有限公司 | Ion exchange resin regeneration method for removing impurities from lithium sulfate solution |
-
2022
- 2022-12-05 CN CN202211549185.2A patent/CN116177572A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293532A (en) * | 2014-07-28 | 2016-02-03 | 李明雄 | Calcium removal process for lithium chloride solution during production |
| CN106881159A (en) * | 2017-03-23 | 2017-06-23 | 南京大学 | A kind of ion exchange resin fixed bed counter-current regeneration device and its application method |
| CN107540003A (en) * | 2017-10-13 | 2018-01-05 | 山东鲁北企业集团总公司 | Lithium sulfate thickening-purification technology liquid and preparation method thereof in one kind production battery-level lithium carbonate technique |
| CN211688289U (en) * | 2020-02-26 | 2020-10-16 | 天齐锂业（江苏）有限公司 | Device for removing impurity ions in lithium sulfate solution |
| CN113072081A (en) * | 2021-03-25 | 2021-07-06 | 四川恩特普环保科技有限公司 | Impurity removal process for lithium sulfate purification completion liquid |
| CN114272961A (en) * | 2021-12-20 | 2022-04-05 | 江西永兴特钢新能源科技有限公司 | Ion exchange resin regeneration method for removing impurities from lithium sulfate solution |
Non-Patent Citations (1)
| Title |
|---|
| 罗代暄等: "《化学试剂与精细化学品合成基础 有机分册》", 31 May 1991, 高等教育出版社, pages: 180 * |
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