CN116478396A - Preparation method of dibenzo-14-crown-4 polyamide for extracting lithium from salt lake - Google Patents
Preparation method of dibenzo-14-crown-4 polyamide for extracting lithium from salt lake Download PDFInfo
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- CN116478396A CN116478396A CN202210041767.3A CN202210041767A CN116478396A CN 116478396 A CN116478396 A CN 116478396A CN 202210041767 A CN202210041767 A CN 202210041767A CN 116478396 A CN116478396 A CN 116478396A
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- crown
- polyamide
- dibenzo
- dicarboxylic acid
- lithium
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 59
- 229920002647 polyamide Polymers 0.000 title claims abstract description 59
- SVJYFWHFQPBIOY-UHFFFAOYSA-N 7,8,16,17-tetrahydro-6h,15h-dibenzo[b,i][1,4,8,11]tetraoxacyclotetradecine Chemical compound O1CCCOC2=CC=CC=C2OCCCOC2=CC=CC=C21 SVJYFWHFQPBIOY-UHFFFAOYSA-N 0.000 title claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- PHQYMDAUTAXXFZ-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C=C1 PHQYMDAUTAXXFZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 claims description 2
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- 239000004642 Polyimide Substances 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- PVDDBYSFGBWICV-UHFFFAOYSA-N 1,4,8,11-tetraoxacyclotetradecane Chemical compound C1COCCOCCCOCCOC1 PVDDBYSFGBWICV-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- -1 crown ether compounds Chemical class 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009292 forward osmosis Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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 provides a preparation method of dibenzo-14-crown-4 polyamide for extracting lithium from a salt lake, and belongs to the technical field of materials. The invention takes diamino dibenzo-14-crown-4 and dicarboxylic acid as monomers, and prepares novel polyamide with a main chain containing dibenzo-14-crown-4 through polycondensation reaction under the condition of a catalyst and a certain reaction temperature, and the novel polyamide is precipitated in a precipitator, and then pure dibenzo-14-crown-4 polyamide is obtained through Soxhlet extraction. The crown ether on the polyamide main chain prepared by the method is uniformly distributed, the crown ether immobilization capacity is improved, and the polyamide main chain has good lithium ion selective adsorption separation performance and higher lithium ion adsorption capacity. In addition, it was also verified that the charge density through the crown ether ring has a significant effect on the adsorption separation performance of lithium ions.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of dibenzo-14-crown-4 polyamide for extracting lithium from a salt lake.
Background
Lithium is the lightest alkali metal, and is an important energy source and strategic resource in the 21 st century because of its many advantages such as high electrochemical activity, high specific heat capacity, and good redox. Lithium and its compounds play an important role in many fields, including nuclear fusion, pharmaceutical, chemical and metallurgical industries, in particular chargeable and dischargeable Li for electronics, electric vehicles and energy storage + Therefore, lithium is recognized as "an energy metal that promotes world progress" in the fields of batteries and the like.
It is counted that during 2010-2017, global lithium consumption increases by about 6% per year, which is expected to reach about 9.5 ten thousand tons by 2025, resulting in a serious shortage of lithium resources. More than 60% of lithium is present in salt lake brines and there are many challenges of low lithium ion concentration and high interfering ion concentration. Therefore, the development of the efficient lithium ion selective separation technology is related to the development of new energy resources and the implementation of economic sustainable development strategy, and has important economic significance and social value.
Currently, among a plurality of interfering ions, mg 2+ And Li (lithium) + Is most difficult because of Mg 2+ And Li (lithium) + Having similar ionic radii in the bare or hydrated state, li + The bare radius (0.068 nm) is only slightly smaller than that of Mg 2+ (0.08nm)，Li + Has a hydration radius of 0.38nm, which is slightly smaller than that of Mg 2+ (0.43 nm). The current common methods for lithium extraction are precipitation, solvent extraction, adsorption and a series of membrane-based separation and extraction methods.
At present, aiming at extracting lithium from salt lake brine in China, the salt lake brine with low concentration is concentrated in a solar evaporation mode, and then, on one hand, lithium ions are directly separated and recovered through a solvent extraction method. The principle of solvent extraction is to add to a solution containing a solute a second liquid that is incompatible therewith and has a greater solubility for the solute. And by utilizing the solubility difference of the solutes in the two phases, part of the solutes are promoted to migrate into the second liquid phase through the interface, so that the purpose of phase inversion and concentration is achieved. However, the method has the problems of equipment corrosion, extractant loss, high extractant price and the like, so that the method is limited in the lithium extraction process.
On the other hand, firstly, the separation of lithium ions and interfering ions is carried out by utilizing an adsorption method, a nanofiltration method and the like, then, the concentration is carried out on the lithium-rich solution by utilizing reverse osmosis, forward osmosis and the like, and finally, the recovery of lithium ions is carried out by adopting a precipitation method. Among the lithium extraction steps, separation is the most important step, and the adsorption method is paid attention to because of the advantages of green environment protection, portability and the like, wherein the traditional adsorption method generally adopts manganese-titanium ion sieve oxide, but the defects of small adsorption capacity, high dissolution loss rate, short service life, difficult recovery and the like limit the wide application of the adsorption method. In recent years, attention has been paid to artificially synthesized crown ether compounds because of their unique charge effect and size control effect. Crown ethers commonly applied to lithium ion adsorption comprise 15-crown-5, 14-crown-4 and 12-crown-4, the diameters of the cavities of the crown ethers are close to those of lithium ions, and the crown ethers have certain binding capacity to lithium ions, so that the crown ethers are ideal materials for researching selective adsorption separation of magnesium and lithium.
At present, a common research mode is to combine crown ether with a membrane to prepare a membrane adsorbent with selective adsorption, generally scientists use a polymer membrane as a carrier to introduce crown ether onto the surface of the membrane in a grafting mode, and although the method has good progress in the aspect of selective adsorption of lithium ions, the method has the defects of few adsorption sites and uneven distribution of crown ether, so that wider application of the method is limited. The application CN202010073422.7 describes dibenzocrown polyimide, a preparation method and application, and the crown ether is connected into a polymer main chain, so that the uniformity of crown ether adsorption site distribution is effectively improved, and 5.6mgg is also shown in an adsorption experiment of lithium ions -1 The adsorption capacity of the lithium ion of the catalyst is higher than that of the lithium ion, but the crown ether immobilization capacity of the obtained product is not high and can only reach 1.3mmol g -1 . Therefore, it would be worth further investigation how the crown ether immobilization of the product could be further improved.
Disclosure of Invention
Aiming at the defects of the prior research, the invention provides a preparation method of dibenzo-14-crown-4 polyamide for extracting lithium from salt lake, and crown ether on a polyamide main chain prepared by the method is uniformly distributed, so that the crown ether immobilization capacity is greatly improved, and the preparation method has good lithium ion selective adsorption separation performance and lithium ion adsorption capacity. In addition, it was also verified that the charge density of the crown ether ring has a significant effect on the adsorption separation performance of lithium ions.
In order to solve the technical problems, the invention provides a preparation method of dibenzo-14-crown-4 polyamide polymer for extracting lithium from a salt lake, which comprises the following steps:
the novel polyamide is prepared by taking diamino dibenzo-14-crown-4 and dicarboxylic acid as monomers through polycondensation reaction at a certain reaction temperature under the presence of a catalyst, and the pure dibenzo-14-crown-4 polyamide is obtained through precipitation and Soxhlet extraction of the novel polyamide in a precipitator.
Preferably, the method specifically comprises the following steps:
adding diaminodibenzo-14-crown-4 and dicarboxylic acid into a solvent for dissolution, adding a catalyst, heating to 120-150 ℃ for reaction for 2-6 hours, precipitating the obtained novel polyamide in a precipitant when the reaction is hot after the reaction is finished, and filtering to obtain the novel polyamide;
and (3) carrying out Soxhlet extraction on the novel polyamide, extracting for 3-4 hours at 60-70 ℃, removing solvent and small molecular impurities which are not completely reacted, and carrying out vacuum drying until the quality is unchanged, thus obtaining the pure dibenzo-14-crown-4 polyamide.
Preferably, the dibenzo-14-crown-4 polyamide has the following structural formula:
wherein m and n are each the degree of polymerizationAny integer value selected from 1-10000, which are the same or different; r is R 1 And R is 2 May be the same or different and is selected fromAny of the C2-20 linear alkanes, and any mixtures thereof.
Preferably, the dicarboxylic acid is selected from aromatic dicarboxylic acid or aliphatic dicarboxylic acid, wherein the aromatic dicarboxylic acid is selected from at least one of dicarboxylic acid selected from isophthalic acid and 2, 2-bis- (4-carboxyphenyl) -hexafluoropropane, and the aliphatic dicarboxylic acid is at least one of C2-20-containing linear dicarboxylic acid.
Preferably, the molar ratio of diaminodibenzo-14-crown-4 to dicarboxylic acid added is 1:1.
Preferably, the aliphatic dicarboxylic acid is added in an amount of 0% to 100% and the corresponding dibenzo-14-crown-4 polyamide has a crown ether content in the main chain of 1.46 to 2.60mmol g -1 。
Preferably, the solvent is at least one selected from anhydrous N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; the catalyst is at least one system selected from triphenylphosphine oxide/pyridine, dicyclohexylcarbodiimide/N, N-lutidine and triphenylphosphine/diethyl azodicarboxylate, wherein the molar ratio of any two of the systems is 0.01:1-100:1.
Preferably, the precipitating agent is at least one selected from methanol, ethanol and isopropanol; the solvent used in the Soxhlet extraction is at least one selected from methanol, ethanol and isopropanol.
Preferably, the dibenzo-14-crown-4 polyamide obtained has an ion adsorption of 0.83mg g -1 -40mg g -1 Lithium ion pair Na + 、K + 、Mg + The separation factor selectivity of (2) reaches 5-60.
Preferably, the concentration is 10mg L -1 In LiCl solution, the obtained dibenzo-14-crown-4 polyamide had an adsorption amount of lithium ions of 0.53mg g -1 -1.8mg g -1 。
In addition, the crown ether ring charge density is tested by the computer simulation based on the density functional theory, and the result shows that compared with the polyimide crown ether ring charge density (-0.111 to-0.311 a. U) with similar structure, the oxygen atom charge density (-0.157 to-0.399 a. U) in the polyamide crown ether ring is higher, which also leads to the polyamide having larger binding energy (-507.9 vs-467.3kJ mol) for lithium ions than polyimide -1 ) So that the polyamide has larger lithium ion adsorption capacity.
Compared with the prior art, the invention has the advantage that the crown ether immobilization amount on the polymer and the charge density on the crown ether ring can be obviously improved. Dibenzo-14-crown-4 is used as a functional monomer and is fixed on a polyamide molecular main chain through a polycondensation reaction, so that the polyamide molecular main chain has excellent lithium ion selective adsorption separation performance and higher lithium ion adsorption capacity, and further proves that the crown ether ring charge density and the polyamide main chain crown ether immobilization capacity are improved, and the lithium ion adsorption capacity can be effectively improved.
In addition, the polymer has the basic properties of polyamide high molecular materials, including excellent high temperature resistance and solvent resistance, is easy to process and form, can be processed into powder, particles, films, polymer microporous films and the like, and has easy industrial implementation of the preparation process and wide application prospect.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of PA0, PA50 and PA100 synthesized in example 1, example 2 and example 3 of the present invention;
FIG. 2 is the lithium ion adsorption performance of PA0, PA50 and PA100 synthesized in example 1, example 2 and example 3 of the present invention;
FIG. 3 is a graph showing the selective adsorption properties of dibenzo-14-crown-4 polyamide (PA 100) prepared in example 1 of the present invention for lithium, magnesium, sodium, potassium ions;
FIG. 4 is a graph of charge density and adsorption energy with lithium ions calculated from the simulation of dibenzo-14-crown-4 polyamide (PA 100) (FIG. 4 b) prepared in example 1 of the present invention with the dibenzo-14-crown-4 polyimide (FIG. 4 a) of comparative example 1.
Detailed Description
The following examples will provide those skilled in the art with a more complete understanding of the present invention and are not intended to limit the invention in any way.
Example 1
Preparation method of dibenzo-14-crown-4 polyamide (PA 0,0% aliphatic dicarboxylic acid): 0.33g of diaminodibenzo-14-crown-4 and 0.3992 g of 2, 2-bis- (4-carboxyphenyl) -hexafluoropropane were dissolved in 2.17mL of anhydrous N-methylpyrrolidone (NMP), and reacted at 120℃for 6 hours under the protection of argon. After the reaction is finished, precipitating the product in methanol, filtering to obtain a precipitate, carrying out Soxhlet extraction, and vacuum drying for 12 hours to obtain the dibenzo-14-crown-4 polyamide material (PA 0), wherein the molecular structural formula of the dibenzo-14-crown-4 polyamide material is shown as follows.
Example 2
Process for the preparation of dibenzo-14-crown-4 polyamide (PA 50, 50% isophthalic acid): 0.33g of diaminodibenzo-14-crown-4, 0.083g of isophthalic acid and 0.196g of 2, 2-bis- (4-carboxyphenyl) -hexafluoropropane were dissolved in 1.83mL of anhydrous N-methylpyrrolidone (NMP), and reacted for 6 hours at 120℃under the protection of argon at a controlled reaction temperature. After the reaction is finished, precipitating the product in methanol, filtering to obtain a precipitate, carrying out Soxhlet extraction, and vacuum drying for 12 hours to obtain the dibenzo-14-crown-4 polyamide material (PA 50), wherein the molecular structural formula of the dibenzo-14-crown-4 polyamide material is shown as follows.
Example 3
Process for the preparation of dibenzo-14-crown-4 polyamide (PA 100, 100% isophthalic acid): 0.33g of diaminodibenzo-14-crown-4 and 0.166g of isophthalic acid are taken and dissolved in 1.49mL of anhydrous N-methylpyrrolidone (NMP), and the reaction temperature is controlled to be 120 ℃ for 6 hours under the protection of argon. After the reaction is finished, precipitating the product in methanol, filtering to obtain a precipitate, carrying out Soxhlet extraction, and vacuum drying for 12 hours to obtain the dibenzo-14-crown-4 polyamide material (PA 100), wherein the molecular structural formula of the dibenzo-14-crown-4 polyamide material is shown as follows.
As shown in FIG. 1, from examples 1-3 1 As can be seen from the H NMR chart, PA0 is a polyamide prepared by adding only 2, 2-bis (4-carboxyphenyl) hexafluoropropane monomer, and it can be found that a vibration signal peak of hydrogen proton on the benzene ring of 2, 2-bis (4-carboxyphenyl) hexafluoropropane occurs at chemical shift delta=8.03 to 7.50 ppm; PA100 is a polyamide prepared by adding only isophthalic acid monomer, and a signal peak of three hydrogen protons on the benzene ring of isophthalic acid appears at chemical shift δ=8.50 to 7.65 ppm. PA50 1 The H NMR graph shows simultaneous hydrogen proton characteristic resonance signal peaks on the benzene rings of 2, 2-bis (4-carboxyphenyl) hexafluoropropane and isophthalic acid at chemical shifts δ=8.50 to 7.51ppm, and hydrogen proton signal peaks on dibenzo-14-crown-4 at chemical shifts δ=7.50 to 6.93ppm and δ=4.17 to 2.16ppm, respectively, demonstrating the successful preparation of three different crown ether solids polyamide.
As shown in FIG. 2, the concentration was 10mg L -1 In LiCl solution (A), the adsorption amount of PA100 to lithium ions is 0.95mg g -1 Far above PA50 (0.69 mg g) -1 ) And PA0 (0.53 mg g) -1 ) The proportional relation between the crown ether immobilization amount and the adsorption amount is proved.
As shown in FIG. 3, the concentration was 100mg L -1 Li of (2) + 、Na + ，K + And Mg (magnesium) 2+ In the ion mixed solution, PA100 is used for Li + The adsorption capacity of (a) was 18.5. 18.5mgg -1 Far higher than other ion adsorption amount, li + For Na + 、K + 、Mg + The selectivity of the separation factors of (2) is 14, 26 and 8.5 respectively, so that the selective adsorption separation of lithium ions is realized. The test method for the selective adsorption separation performance of lithium ions comprises the following steps:
adopts LiCl and MgCl as ionic salt solution solutes 2 The mixture of NaCl and KCl, the solvent is ultrapure water,the concentration of each ionic salt was set at 100mg L -1 The adsorption experiment temperature is 25 ℃, and the adsorption time is 5 hours.
Comparative example 1
The preparation method of the dibenzo-14-crown-4 polyimide comprises the following steps: 0.33g of diaminodibenzo-14-crown-4 and 0.45g of 4, 4-hexafluoroisopropyl phthalic anhydride are taken and dissolved in 5.2mL of m-methylphenol, 0.05g of isoquinoline is added as a catalyst, and the reaction is carried out for 5 hours at 180 ℃ under the protection of argon. And precipitating the product in ethanol after the reaction is finished, filtering to obtain a precipitate, carrying out Soxhlet extraction, and drying in vacuum for 12 hours to obtain the dibenzo-14-crown-4 polyimide material, wherein the molecular structural formula of the dibenzo-14-crown-4 polyimide material is shown as follows.
TABLE 1 lithium ion adsorption energy of the polymers obtained in example 1 and comparative example 1
FIG. 4 is a graph showing the charge density calculated by simulation of dibenzo-14-crown-4 polyamide (PA 100) (FIG. 4 b) prepared in example 1 of the present invention and the dibenzo-14-crown-4 polyimide (FIG. 4 a) of comparative example 1, as can be seen from the graph, the oxygen atoms (ranging from-0.157 to-0.329 a. U) in the hole ring of the crown ether of the polyamide have a higher charge density than the oxygen atoms (ranging from-0.111 to-0.311 a. U) in the polyimide. And as can be seen from the data in Table 1, polyamide and Li + (-507.9kJ mol -1 ) The adsorption energy of the combination is far higher than that of polyimide and Li + Is (-467.3 kJ mol) -1 )。
The foregoing is merely illustrative of preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (10)
1. A method for preparing dibenzo-14-crown-4 polyamide for extracting lithium from salt lake, which is characterized by comprising the following steps:
the novel polyamide is prepared by taking diamino dibenzo-14-crown-4 and dicarboxylic acid as monomers through polycondensation reaction at a certain reaction temperature under the presence of a catalyst, and the pure dibenzo-14-crown-4 polyamide is obtained through precipitation and Soxhlet extraction of the novel polyamide in a precipitator.
2. The preparation method according to claim 1, characterized by comprising the following steps:
adding diaminodibenzo-14-crown-4 and dicarboxylic acid into a solvent for dissolution, adding a catalyst, heating to 120-150 ℃ for reaction for 2-6 hours, precipitating the obtained novel polyamide in a precipitant when the reaction is hot after the reaction is finished, and filtering to obtain the novel polyamide;
and (3) carrying out Soxhlet extraction on the novel polyamide, extracting for 3-4 hours at 60-70 ℃, removing solvent and small molecular impurities which are not completely reacted, and carrying out vacuum drying until the quality is unchanged, thus obtaining the pure dibenzo-14-crown-4 polyamide.
3. The process according to claim 1 or 2, wherein the dibenzo-14-crown-4 polyamide has the following structural formula:
wherein m and n are respectively polymerization degree and are selected from any integer value between 1 and 10000, and are the same or different; r is R 1 And R is 2 Identical or different, selected fromC2-20 linear alkane.
4. The production method according to claim 1 or 2, wherein the dicarboxylic acid is selected from an aromatic dicarboxylic acid selected from at least one of isophthalic acid and 2, 2-bis- (4-carboxyphenyl) -hexafluoropropane or an aliphatic dicarboxylic acid which is at least one of C2-20-containing linear dicarboxylic acids.
5. The process according to claim 1 or 2, wherein the molar ratio of diaminodibenzo-14-crown-4 to dicarboxylic acid added is 1:1.
6. The process according to claim 5, wherein the aliphatic dicarboxylic acid is added in an amount of 0% to 100% and the corresponding dibenzo-14-crown-4 polyamide has a crown ether content in the main chain of 1.46 to 2.60mmol g -1 。
7. The production method according to claim 1 or 2, wherein the solvent is at least one selected from the group consisting of anhydrous N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; the catalyst is at least one system selected from triphenylphosphine oxide/pyridine, dicyclohexylcarbodiimide/N, N-lutidine and triphenylphosphine/diethyl azodicarboxylate, wherein the molar ratio of any two of the systems is 0.01:1-100:1.
8. The preparation method according to claim 1 or 2, wherein the precipitating agent is at least one selected from methanol, ethanol, isopropanol; the solvent used in the Soxhlet extraction is at least one selected from methanol, ethanol and isopropanol.
9. The process according to claim 1 or 2, wherein the dibenzo-14-crown-4 polyamide obtained has an ion adsorption of 0.83mg g -1 -40mg g -1 Lithium ion pair Na + 、K + 、Mg + The separation factor selectivity of (2) reaches 5-60.
10. The method according to claim 1 or 2, wherein the concentration is 10mg L -1 In LiCl solution, the obtained dibenzo-14-crown-4 polyamide had an adsorption amount of lithium ions of 0.53mg g -1 -1.8mg g -1 。
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