CN117157252A - Method for producing ammonia by extracting lithium from salt lake in combined manner through full chain integration - Google Patents
Method for producing ammonia by extracting lithium from salt lake in combined manner through full chain integration Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 95
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 230000010354 integration Effects 0.000 title claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims abstract description 32
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000012267 brine Substances 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- 208000028659 discharge Diseases 0.000 claims abstract description 10
- 230000002687 intercalation Effects 0.000 claims abstract description 10
- 238000009830 intercalation Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 46
- 239000011148 porous material Substances 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 13
- 239000004917 carbon fiber Substances 0.000 claims description 13
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 239000003660 carbonate based solvent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 description 18
- 239000012535 impurity Substances 0.000 description 15
- 238000000746 purification Methods 0.000 description 14
- 150000001768 cations Chemical class 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003110 Mg K Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000009296 electrodeionization Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The disclosure provides a method for producing ammonia by extracting lithium from a full-chain integrated salt lake, which comprises the following steps: (1) Taking a lithium-rich electrode as an anode, taking a first carbon electrode as a cathode, and injecting electrolyte for discharge treatment to obtain a lithium-poor electrode; (2) Taking the lean lithium state electrode as a cathode, taking the second carbon electrode as an anode, and placing the cathode in salt lake brine for one-step constant voltage electrolysis to obtain a lithium intercalation state electrode; (3) Taking the lithium-embedded electrode as an anode, taking the porous carbon electrode as a cathode, separating by using a diaphragm, injecting organic purifying liquid, continuously introducing nitrogen into the organic purifying liquid of the cathode, and carrying out two-step constant-voltage electrolysis; (4) The porous carbon electrode is taken out to be placed in water, the lithium-rich solution is obtained through reaction, and the gas is collected to obtain ammonia.
Description
Technical Field
The disclosure belongs to the technical field of lithium extraction in salt lakes, and relates to a method for producing ammonia by combining lithium extraction in salt lakes through full chain integration.
Background
In recent years, lithium and lithium compounds are widely applied to various fields such as aerospace, electronic machinery, high-energy batteries, nuclear power generation and the like, particularly the field of electric automobiles, and the lithium and lithium compounds are one of very precious green resources and strategic mineral resources in China, so that the exploitation difficulty of the lithium resources is high, the technology is complex, and the full utilization of the lithium resources is limited.
Lithium resources are mainly present in lithium ores and salt lakes, wherein the ratio of the salt lake is far greater than that of the lithium ores, and as the reserve of the lithium ores easy to mine is gradually reduced, the lithium extraction from the salt lake is gradually attracting attention. The cost of extracting lithium from the salt lake is low compared with that of extracting lithium from the ore, and the salt lake is an important source of lithium resource supply. The current mature salt lake lithium extraction method comprises a precipitation method, an adsorption method, a membrane method, an electrodeintercalation method, an extraction method and the like, wherein the precipitation method is the most mature, the history is long, and the process flow is generally as follows: brine, evaporating and concentrating, removing boron, removing calcium and magnesium, and precipitating lithium with sodium carbonate. Although the method has low production cost, the method can only be used for treating brine with low magnesium-lithium ratio and high lithium concentration, has low lithium recovery rate, consumes a large amount of water resources and generates a large amount of wastewater.
The electrodeionization method is characterized in that lithium ions are intercalated into a lattice structure of iron phosphate (lithium-rich electrode) by performing a reduction reaction on the iron phosphate in brine to form lithium iron phosphate (lithium-intercalated electrode), and then the lithium-intercalated electrode is subjected to electrolysisAnd oxidizing in the solution to desorb lithium in the lithium iron phosphate into the electrolyte, thereby completing the extraction of the lithium. However, in the above-mentioned process of adsorbing lithium ions, because of Mg 2+ 、Na + 、K + Plasma size and Li + Near and at a concentration much higher than Li + Therefore, the impurity cations also enter the ferric phosphate during the adsorption process, and are desorbed from the lithium iron phosphate into the electrolyte during the desorption process, so that the electrolyte needs to be treated to obtain a pure lithium salt solution.
At present, no simple and feasible method for directly obtaining pure lithium salt solution for extracting lithium by electric desorption exists.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
The method can obtain ammonia gas while obtaining a low-impurity lithium salt solution, and improves the production value of a salt lake lithium extraction process.
In order to achieve the purpose of the disclosure, the following technical scheme is adopted in the disclosure:
in a first aspect, an embodiment of the present disclosure provides a method for producing ammonia by combining lithium extraction in a full-chain integrated salt lake, the method comprising the following steps:
(1) Taking a lithium-rich electrode as an anode, taking a first carbon electrode as a cathode, and injecting electrolyte for discharge treatment to obtain a lithium-poor electrode;
(2) Taking the lean lithium state electrode as a cathode, taking the second carbon electrode as an anode, and placing the cathode in salt lake brine for one-step constant voltage electrolysis to obtain a lithium intercalation state electrode;
(3) Placing a lithium-embedded electrode in an anode tank as an anode, placing a porous carbon electrode in a cathode tank as a cathode, separating the cathode tank and the anode tank by using a diaphragm, injecting organic purifying liquid into the anode tank and the cathode tank, continuously introducing nitrogen into the organic purifying liquid in the cathode tank, and carrying out two-step constant-voltage electrolysis;
(4) And taking out the porous carbon electrode, placing the porous carbon electrode in water, reacting to obtain a lithium-rich solution, and collecting generated gas to obtain ammonia.
According to the embodiment of the disclosure, the lean lithium electrode is prepared in advance, then the lean lithium electrode is used as a cathode to extract lithium from a salt lake, so that a lithium intercalation electrode is obtained, lithium in a lattice of the lithium intercalation electrode enters an organic purifying liquid and moves towards the cathode in a subsequent electrolysis process, nitrogen near the cathode is reduced and lithium ions form lithium nitride to be adhered to a porous carbon, other impurity cations cannot react with the nitrogen under the condition to generate stable nitrides, and therefore separation of lithium elements and other impurity cations is realized, other anions cannot be introduced, the porous carbon is placed in water, lithium hydroxide and ammonia can be directly obtained through reaction of the lithium nitride and the water, and the generated ammonia is collected, so that the production value is improved.
Taking lithium iron phosphate as an example of a lithium intercalation electrode, the electrolytic process involves the following equations:
anode: liFePO 4 ＝FePO 4 +Li + +e -
And (3) cathode: 6Li + +6e - +N 2 ＝2Li 3 N
General reaction formula: 6LiFePO 4 +N 2 ＝6FePO 4 +2Li 3 N；
Li 3 The equation for N to water is as follows:
Li 3 N+3H 2 O＝3LiOH+NH 3 ↑。
in one embodiment, the lithium-rich state electrode of step (1) comprises any one of a lithium iron phosphate electrode, a lithium nickel cobalt manganate electrode, or a lithium manganate electrode.
In one embodiment, the electrolyte comprises a potassium chloride solution.
In one embodiment, the concentration of the potassium chloride solution is 0.03 to 0.08mol/L, for example: 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L or 0.08mol/L, etc.
In one embodiment, the voltage of the discharge treatment in step (1) is 1 to 1.5V, for example: 1V, 1.1V, 1.2V, 1.4V, 1.5V, etc.
In one embodiment, the voltage of the one-step constant voltage electrolysis of step (2) is 0.5 to 1V, for example: 0.5V, 0.6V, 0.7V, 0.8V, 1V, or the like.
In one embodiment, the one-step constant voltage electrolysis is performed for a period of 4 to 8 hours, for example: 4h, 5h, 6h, 7h or 8h, etc.
In the embodiment of the disclosure, the lithium-deficient electrode is used as a cathode, and the second carbon electrode is used as an anode to extract lithium from the salt lake, so that the lithium-intercalated electrode is obtained. The obtained lithium-embedded electrode contains higher impurity cations, and the impurity cations adsorbed by the lithium-embedded electrode can be well separated from lithium through a subsequent electrolysis process by using the method disclosed by the embodiment of the disclosure.
In one embodiment, the morphology of the porous carbon electrode of step (3) comprises a mesh.
In one embodiment, the porous carbon electrode has a pore diameter of 2 to 50nm, for example: 2nm, 5nm, 10nm, 20nm or 50nm, etc., preferably 10 to 30nm.
The porous carbon electrode is net-shaped, and the size of a gap is 10-30 nm. The porous carbon electrode with the structure and the gaps can better react with nitrogen, and the purifying efficiency is improved. If the pore diameter is too large, the gas is hardly held in the porous carbon electrode, and the purification efficiency is lowered; if the voids are too small, the gas hardly enters the inside of the porous carbon electrode to react, and also higher purification efficiency cannot be achieved.
In one embodiment, the porous carbon electrode comprises a carbon fiber mat.
The carbon fiber felt disclosed by the embodiment of the disclosure has a penetrating porous structure, has extremely high specific surface area and conductivity, and can ensure high-speed reaction.
In one embodiment, the membrane of step (3) comprises a PTFE membrane.
In one embodiment, the solvent of the organic cleaning solution in step (3) comprises any one or a combination of at least two of carbonate solvents, lipid solvents or ether solvents.
In one embodiment, the solute of the organic purge comprises hexafluorophosphateLithium acid, liLSI or LiClO 4 Any one or a combination of at least two of these.
In one embodiment, the molar concentration of solute in the organic purge of step (3) is between 0.5 and 1.5mol/L, for example: 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, etc.
In one embodiment, the two-step constant voltage electrolysis of step (3) has a voltage of 1.5 to 2.5V, for example: 1.5V, 1.8V, 2V, 2.2V, 2.5V, etc., preferably 1.8 to 2.2V.
In one embodiment, the two-step constant voltage electrolysis is performed for a period of 4 to 10 hours, for example: 4h, 5h, 6h, 8h or 10h, etc.
As an alternative to the embodiments of the present disclosure, the method includes the steps of:
(1) Taking a lithium-rich electrode as an anode, taking a first carbon electrode as a cathode, injecting 0.03-0.08 mol/L electrolyte, and performing discharge treatment under 1-1.5V to obtain a lithium-poor electrode;
(2) Placing the lean lithium state electrode as a cathode and the second carbon electrode as an anode in salt lake brine, and carrying out constant voltage electrolysis for 4-8 hours at the next step of 0.5-1V to obtain a lithium intercalation state electrode;
(3) Placing a lithium-embedded electrode in an anode tank as an anode, placing a porous carbon electrode with the pore diameter of 2-50 nm in a cathode tank as a cathode, separating the cathode tank and the anode tank by using a PTFE diaphragm, injecting organic purifying liquid with the molar concentration of 0.5-1.5 mol/L into the anode tank and the cathode tank, continuously introducing nitrogen into the organic purifying liquid in the cathode tank, and carrying out two-step constant-voltage electrolysis for 4-10 h under the voltage of 1.5-2.5V;
(4) And taking out the porous carbon electrode, placing the porous carbon electrode in water, reacting to obtain a lithium-rich solution, and collecting generated gas to obtain ammonia.
The present disclosure has the following beneficial effects:
(1) The method can obtain ammonia gas while obtaining the lithium salt solution with low impurities, and improves the production value of the salt lake lithium extraction process.
(2) The lithium extraction method of the salt lake can still ensure higher lithium recovery rate, and the obtained lithium-rich solution has extremely low impurity cation content, can be directly used for preparing battery-grade lithium hydroxide, can recover ammonia gas and improves the production value.
Other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description.
Drawings
The accompanying drawings are included to provide a further understanding of the technology herein, and are incorporated in and constitute a part of this specification, illustrate technology herein and together with the description serve to explain, without limitation, the technology herein.
FIG. 1 is a schematic diagram of an apparatus for a full-chain integrated salt lake lithium extraction combined ammonia production method according to an embodiment of the disclosure, wherein the apparatus comprises a 1-lean lithium electrode, a 2-second carbon electrode, 3-salt lake brine, a 4-embedded lithium electrode, a 5-carbon fiber felt porous carbon electrode, a 6-purifying device, a 7-anode tank, an 8-cathode tank and a 9-diaphragm.
Detailed Description
The technical scheme of the present disclosure is further described below by means of specific embodiments. It should be apparent to those skilled in the art that the examples are merely provided to aid in the understanding of the present disclosure and should not be construed as a specific limitation on the present disclosure.
Brine compositions used in examples and comparative examples of the present disclosure are shown in table 1 below:
TABLE 1
| Substance (B) | Li | Na | Mg | K |
| Concentration (g/L) | 0.26 | 23.20 | 50.12 | 4.47 |
The lithium iron phosphate electrodes used in the examples and comparative examples of the present disclosure were each prepared by the following method:
mixing a lithium iron phosphate material with a binder PVDF and conductive graphite according to a mass ratio of 8:1:1, adding the mixture into NMP, mixing to form positive electrode slurry, and coating the positive electrode slurry on a titanium mesh with a coating density of 100mg/cm 2 The coating area is 10 x 10cm 2 And (3) drying at 120 ℃ for 10 hours, and cooling to obtain the lithium iron phosphate electrode.
Example 1
The embodiment provides a method for producing ammonia by extracting lithium from a full-chain integrated salt lake, wherein a device diagram used by the method is shown in fig. 1, and the method comprises the following steps:
(1) Taking a lithium iron phosphate electrode as an anode, taking a first carbon electrode as a cathode, injecting 0.05mol/L potassium chloride solution, and performing discharge treatment under 1.2V to obtain a lithium-poor electrode 1;
(2) Taking the lean lithium state electrode 1 as a cathode, taking the second carbon electrode 2 as an anode, placing the cathode in salt lake brine 3, and carrying out constant voltage electrolysis for 6 hours at the next step of 0.8V to obtain a lithium intercalation state electrode 4;
(3) Placing the lithium-intercalated electrode 4 in an anode tank 7 of a purification device 6 to serve as an anode, placing a carbon fiber felt porous carbon electrode 5 (with a pore size of 20 nm) in a cathode tank 8 of the purification device 6 to serve as a cathode, separating the anode tank 7 and the cathode tank 8 by a PTFE diaphragm 9, injecting DMC solution (organic purifying liquid) of 1mol/L lithium hexafluorophosphate into each of the anode tank 7 and the cathode tank 8, continuously introducing nitrogen into the organic purifying liquid of the cathode tank 8, and carrying out 2V secondary constant voltage electrolysis for 6 hours;
(4) And taking out the carbon fiber felt porous carbon electrode 5, placing the carbon fiber felt porous carbon electrode in water, reacting to obtain a lithium-rich solution, and collecting generated gas to obtain ammonia.
Example 2
The embodiment provides a method for producing ammonia by extracting lithium from a full-chain integrated salt lake, wherein a device diagram used by the method is shown in fig. 1, and the method comprises the following steps:
(1) Taking a lithium iron phosphate electrode as an anode, taking a first carbon electrode as a cathode, injecting 0.08mol/L potassium chloride solution, and performing discharge treatment at 1V to obtain a lithium-deficient electrode 1;
(2) Taking the lean lithium state electrode 1 as a cathode, taking the second carbon electrode 2 as an anode, placing the cathode in salt lake brine 3, and carrying out constant voltage electrolysis for 8 hours at the next 0.5V step to obtain a lithium intercalation state electrode 4;
(3) Placing the lithium-intercalated electrode 4 in an anode tank 7 of a purification device 6 to serve as an anode, placing a carbon fiber felt porous carbon electrode 5 (with a pore size of 25 nm) in a cathode tank 8 of the purification device 6 to serve as a cathode, separating the anode tank 7 and the cathode tank 8 by a PTFE diaphragm 9, injecting DMC solution (organic purifying liquid) of 1mol/L lithium hexafluorophosphate into each of the anode tank 7 and the cathode tank 8, continuously introducing nitrogen into the organic purifying liquid of the cathode tank 8, and carrying out two-step constant-voltage electrolysis for 6h under 1.5V;
(4) And taking out the carbon fiber felt porous carbon electrode 5, placing the carbon fiber felt porous carbon electrode in water, reacting to obtain a lithium-rich solution, and collecting generated gas to obtain ammonia.
Example 3
The embodiment provides a method for producing ammonia by extracting lithium from a full-chain integrated salt lake, wherein a device diagram used by the method is shown in fig. 1, and the method comprises the following steps:
(1) Taking a lithium iron phosphate electrode as an anode, taking a first carbon electrode as a cathode, injecting 0.05mol/L potassium chloride solution, and performing discharge treatment under 1.2V to obtain a lithium-poor electrode 1;
(2) Taking the lean lithium state electrode 1 as a cathode, taking the second carbon electrode 2 as an anode, placing the cathode in salt lake brine 3, and carrying out constant voltage electrolysis for 6 hours at the next step of 0.8V to obtain a lithium intercalation state electrode 4;
(3) Placing the lithium-intercalated electrode 4 in an anode tank 7 of a purification device 6 to serve as an anode, placing a carbon fiber felt porous carbon electrode 5 (with a pore size of 20 nm) in a cathode tank 8 of the purification device 6 to serve as a cathode, separating the anode tank 7 and the cathode tank 8 by a PTFE diaphragm 9, injecting DMC solution (organic purifying liquid) of 1mol/L lithium hexafluorophosphate into each of the anode tank 7 and the cathode tank 8, continuously introducing nitrogen into the organic purifying liquid of the cathode tank 8, and carrying out two-step constant-voltage electrolysis for 6h under 2.5V;
(4) And taking out the carbon fiber felt porous carbon electrode 5, placing the carbon fiber felt porous carbon electrode in water, reacting to obtain a lithium-rich solution, and collecting generated gas to obtain ammonia.
Example 4
This example differs from example 1 only in that the pore diameter of the porous carbon electrode is 2nm, and other conditions and parameters are exactly the same as those of example 1.
Example 5
This example differs from example 1 only in that the pore diameter of the porous carbon electrode is 50nm, and other conditions and parameters are exactly the same as those of example 1.
Example 6
This example differs from example 1 only in that the lithium iron phosphate electrode was replaced with a lithium manganate electrode, and other conditions and parameters were exactly the same as example 1.
The preparation method of the lithium manganate electrode comprises the following steps:
LiMn is added to 2 O 4 Mixing the material, a binder PVDF and conductive graphite according to the mass ratio of 8:1:1, adding the mixture into NMP, mixing to form positive electrode slurry, and coating the positive electrode slurry on a titanium mesh with the coating density of 100mg/cm 2 The coating area is 10 x 10cm 2 And (3) drying at 120 ℃ for 10 hours, and cooling to obtain the lithium manganate electrode.
Example 7
This example differs from example 1 only in that the organic purge solution was changed to a TEGDME solution of LISFI at 1mol/L, and the other conditions and parameters were exactly the same as in example 1.
Comparative example 1
This comparative example was different from example 1 only in that the organic cleaning solution was changed to an aqueous solution of 1mol/L NaCl, and the other conditions and parameters were exactly the same as in example 1.
Performance test:
ICP testing was performed on the lithium-rich solutions obtained in examples 1 to 7 and comparative example 1, and the test results are shown in table 1:
TABLE 1
From table 1, it can be seen that, according to examples 1 to 7, a higher lithium recovery rate can still be ensured by the salt lake lithium extraction method disclosed by the present disclosure, and the obtained lithium-rich solution has extremely low impurity cation content, and can be directly used for preparing battery-grade lithium hydroxide, and meanwhile, ammonia gas can be recovered, so that the production value is improved. The lithium-rich solution obtained in the comparative example has higher impurity content, needs to be subjected to a subsequent series of purification treatment, and the recovery rate is further reduced, and meanwhile, the lithium extraction cost is also improved.
As can be seen from comparison of examples 1 and examples 2-3, in the method disclosed in this disclosure, the voltage in step (3) affects the lithium extraction effect, the voltage is controlled to be 1.8-2.2V, the lithium extraction effect is better, if the voltage is too low, the deintercalated lithium ions cannot be sufficiently converted into lithium nitride, if the voltage is too high, the electrolyte may generate byproducts to cover the surface of the porous carbon electrode, which affects the formation of lithium nitride, and after multiple recycling, the recovery rate of lithium is further reduced.
As can be seen from comparison of examples 1 and 4-5, in the method disclosed in this disclosure, the pore size of the porous carbon electrode used in step (3) affects the lithium extraction effect, the pore diameter of the porous carbon electrode is controlled to be 10-30 nm, the lithium extraction effect is better, if the pore size is too small, gas is difficult to enter the inside of the porous carbon electrode to react, and higher purification efficiency cannot be achieved, if the pore size is too large, gas is difficult to keep in the porous carbon electrode, the contact area and time between the gas and the porous carbon electrode are shorter, the purification efficiency is reduced, and meanwhile, the recovery rate of lithium is also reduced.
As can be seen from the comparison of example 1 and example 6, the use of different types of electrodes also has an effect on the lithium extraction effect, the lithium manganate electrode has a higher selectivity for Li, and the lithium manganate electrode is used to obtain a lithium-rich solution having a lower impurity content.
As can be obtained by comparing example 1 with example 7, the organic cleaning solutions used in the present disclosure are wide in variety, and different kinds of organic cleaning solutions can achieve good effects.
As can be seen from a comparison of example 1 and comparative example 1, the present disclosure uses an organic purification liquid, lithium in the lattice of the lithium-intercalated electrode enters the organic purification liquid and moves toward the cathode, nitrogen near the cathode is reduced to form lithium nitride with lithium ions to attach to the porous carbon, and other impurity cations cannot react with nitrogen under such conditions to produce stable nitrides, thereby realizing separation of lithium element from other impurity cations, and at the same time, other anions cannot be introduced, and using a conventional electrolyte, lithium element cannot be separated from other impurity cations, resulting in more impurities in the lithium-rich solution, and further purification is required.
Claims (16)
1. A method for producing ammonia by extracting lithium from salt lake in a combined manner through full-chain integration, which comprises the following steps:
(1) Taking a lithium-rich electrode as an anode, taking a first carbon electrode as a cathode, and injecting electrolyte for discharge treatment to obtain a lithium-poor electrode;
(2) Taking the lithium-poor electrode as a cathode, taking a second carbon electrode as an anode, and placing the cathode in salt lake brine for one-step constant-voltage electrolysis to obtain a lithium-intercalated electrode;
(3) Placing the lithium-intercalated electrode in an anode tank as an anode, placing a porous carbon electrode in a cathode tank as a cathode, separating the cathode tank and the anode tank by using a diaphragm, injecting organic purifying liquid into the anode tank and the cathode tank, continuously introducing nitrogen into the organic purifying liquid in the cathode tank, and carrying out two-step constant-voltage electrolysis;
(4) And taking out the porous carbon electrode, placing the porous carbon electrode in water, reacting to obtain a lithium-rich solution, and collecting generated gas to obtain ammonia.
2. The method of claim 1, wherein the lithium-rich state electrode of step (1) comprises any one of a lithium iron phosphate electrode, a lithium nickel cobalt manganate electrode, or a lithium manganate electrode.
3. The method of claim 1 or 2, wherein the electrolyte comprises a potassium chloride solution.
4. A method according to claim 3, wherein the concentration of the potassium chloride solution is 0.03 to 0.08mol/L.
5. The method according to any one of claims 1 to 4, wherein the voltage of the discharge treatment in the step (1) is 1 to 1.5V.
6. The method of any one of claims 1-5, wherein the voltage of the one-step constant voltage electrolysis of step (2) is 0.5-1V;
optionally, the time of the one-step constant voltage electrolysis is 4-8 hours.
7. The method of any one of claims 1-6, wherein the morphology of the porous carbon electrode of step (3) comprises a mesh.
8. The method of any one of claims 1-7, wherein the porous carbon electrode has a pore diameter of 2-50 nm.
9. The method of claim 8, wherein the porous carbon electrode has a pore diameter of 10 to 30nm.
10. The method of any one of claims 1-9, wherein the porous carbon electrode comprises a carbon fiber mat.
11. The method of any one of claims 1-10, wherein the membrane of step (3) comprises a PTFE membrane.
12. The method of any one of claims 1-11, wherein the solvent of the organic purge in step (3) comprises any one or a combination of at least two of a carbonate-based solvent, a lipid-based solvent, or an ether-based solvent;
optionally, the solute of the organic cleaning solution comprises lithium hexafluorophosphate, liFSI or LiClO 4 Any one or a combination of at least two of these.
13. The method of any one of claims 1-12, wherein the molar concentration of solute in the organic purge of step (3) is between 0.5 and 1.5mol/L.
14. The method of any one of claims 1-13, wherein the voltage of the two-step constant voltage electrolysis of step (3) is 1.5-2.5V;
optionally, the time of the two-step constant voltage electrolysis is 4-10 h.
15. The method of claim 14, wherein the voltage of the two-step constant voltage electrolysis of step (3) is 1.8-2.2V.
16. The method according to any one of claims 1-15, wherein the method comprises the steps of:
(1) Taking a lithium-rich electrode as an anode, taking a first carbon electrode as a cathode, injecting 0.03-0.08 mol/L electrolyte, and performing discharge treatment under 1-1.5V to obtain a lithium-poor electrode;
(2) Placing the lean lithium state electrode as a cathode and the second carbon electrode as an anode in salt lake brine, and carrying out constant voltage electrolysis for 4-8 hours at the next step of 0.5-1V to obtain a lithium intercalation state electrode;
(3) Placing a lithium-embedded electrode in an anode tank as an anode, placing a porous carbon electrode with the pore diameter of 2-50 nm in a cathode tank as a cathode, separating the cathode tank and the anode tank by using a PTFE diaphragm, injecting organic purifying liquid with the molar concentration of 0.5-1.5 mol/L into the anode tank and the cathode tank, continuously introducing nitrogen into the organic purifying liquid in the cathode tank, and carrying out two-step constant-voltage electrolysis for 4-10 h under the voltage of 1.5-2.5V;
(4) And taking out the porous carbon electrode, placing the porous carbon electrode in water, reacting to obtain a lithium-rich solution, and collecting generated gas to obtain ammonia.
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