CN103304837B - Lithium salt recovery method - Google Patents
Lithium salt recovery method Download PDFInfo
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Abstract
Lithium salt recovery method.Carry out in the following manner: first in inert gas environment, by sulfohydrate and the lithium salts be present in N-Methyl pyrrolidone system, after lithium salts is converted into sulphur lithium hydride by sulphur hydrogenation, solid-liquid separation; Then heated in inert gas environment by the N-Methyl pyrrolidone solution containing sulphur lithium hydride after solid-liquid separation, decomposition and inversion is lithium sulfide precipitation, after solid-liquid separation, collects and obtains lithium sulfide precipitation.The method does not use high-risk hydrogen sulfide, and production process is safe ready more, and removal process is short, reduced investment, and efficiency is high, and the rate of recovery of lithium salts can up to more than 99%.Because steaming solvent NMP without the need to high temperature, it also avoid the pyrolytic decomposition of solvent.For poly arylidene thio-ester is produced, be applicable to different preparation technology/routes, the lithium sulfide of recovery, be recycled without the need to poly arylidene thio-ester preparation directly can be returned.
Description
Technical field
The present invention relates to a kind of recovery method of lithium salts, the recovery particularly to lithium salts in the poly arylidene thio-ester preparation process comprising polyphenylene sulfide.
Background technology
Take polyphenylene sulfide as the poly arylidene thio-ester of representative, it is the novel functional polymer material of a class, there is good high-temperature stability, flame retardant resistance, chemical resistance and good electric performance, processing characteristics and dimensional stability, high temperature resistant and the Industrial processes of resistance to chemical attack film, fiber etc. can be machined for, extrusion molding can also be carried out, injection molding becomes the associated components in the fields such as machinery, automobile, electric, computer, be widely used.
For polyphenylene sulfide, many employings are with the dihalo such as santochlor, Meta Dichlorobenzene aromatic hydroxy compound at present, with the sulphur source compound comprising sodium sulphite etc., in aprotic polar organic solvent (adopting as N-Methyl pyrrolidone etc.), carry out high temperature polycondensation more prepare.Because side product chlorinated sodium is insoluble in reaction system, can deposit together with fluoropolymer resin in polycondensation process, or be wrapped in polymer beads, not only cause the washing of fluoropolymer resin very loaded down with trivial details, and washing and desalting efficiency is not high, the wastewater flow rate of generation is large; And from a large amount of waste water, reclaim sodium-chlor need lot of energy, cause production cost high, environmental stress is large.
In the production process of traditional polyphenylene sulfide, outside sulphur removal source compound, usually also need to use lithium chloride, Lithium Acetate etc. as auxiliary agent.After polyreaction completes, in side product chlorinated sodium, also include lithium chloride or Lithium Acetate, need Separation and Recovery.Adopt as lithium sulfide etc. be raw material containing the sulphur source compound of lithium time, because the lithium chloride of polycondensation process generation can be dissolved in reaction system solvent NMP(N-methyl-2-pyrrolidone) in, the purge process of product can be made to simplify.But because lithium salts consumption is large and price is higher, the cost that lithium salts reclaims becomes affects the key factor whether polyphenylene sulfide production process has commercial viability.
Separation and Recovery to the sodium chloride byproduct containing lithium chloride or Lithium Acetate in tradition polyphenylene sulfide production process, is all through carbonation reaction, reclaims after the lithium chloride in reaction process system is converted into Quilonum Retard, and then apply mechanically after being converted into lithium chloride with hydrochloric acid.A kind of method wherein, after polycondensation terminates, high temperature polymerization slurry is directly entered flasher under the conveying of high-pressure slurry pump, polymer solvent NMP is reclaimed at elevated temperature and reduced pressure, obtain the solid mixture containing fluoropolymer resin, sodium-chlor, lithium chloride and oligopolymer, then use the soluble substance such as sodium-chlor, lithium chloride in a large amount of water dissolution solid matters, obtain water-fast polyphenylene sulfide after filtration and washing, purifying.Saliferous (sodium-chlor, the lithium chloride etc.) aqueous solution after dissolving, through carbonation reaction, lithium chloride is wherein changed into sodium-chlor and water-fast Quilonum Retard with sodium carbonate, reclaim Quilonum Retard after filtration, the aqueous solution of sodium chloride-containing then reclaims sodium-chlor.Another kind method is, polyreaction terminates rear high temperature (80 ~ 150 DEG C) and filters, the lithium chloride and insoluble sodium-chlor that are dissolved in NMP are separated, polymer paste is separated into the filtrate containing lithium chloride, NMP, water etc., and the filter cake two portions containing fluoropolymer resin, sodium-chlor.Filter cake is separated, purification obtains fluoropolymer resin; Filtrate then underpressure distillation is reclaimed after NMP, by the residue water dissolution containing soluble oligomer and a small amount of sodium-chlor and lithium chloride, filtration, after removing water-insoluble, then through above-mentioned carbonation reaction, lithium chloride is changed into Quilonum Retard recovery.These ways of recycling all exist that operational path is long, the rate of recovery is low, and need equally therebetween to use a large amount of water, the problem that wastewater flow rate is large.
Using lithium sulfide as in the polyphenylene sulfide synthesis technique in sulphur source, by product is lithium chloride, not sodium chloride-containing.After polycondensation terminates, after being separated with polyphenylene sulfide is filtrate containing lithium chloride, NMP, a small amount of water and few oligopolymer.The method of lithium salts is reclaimed in the documents such as US 6503473, US 6566488, US 6646105, US 6939942, mainly to containing adding aqueous sodium hydroxide solution (aqueous sodium hydroxide solution as 48%) in the nmp solution of lithium chloride, lithium chloride is transformed into the lithium hydroxide being insoluble to NMP and sodium-chlor, the NMP suspension containing sodium-chlor and lithium hydroxide is obtained after dehydration, or filter after obtaining the solid of sodium-chlor, lithium hydroxide, use water dissolution again, and reclaim Quilonum Retard with carbonate; Or pass into hydrogen sulfide directly in suspension, lithium hydroxide is transformed into the sulphur lithium hydride that can be dissolved in NMP, thus lithium salts is separated with sodium-chlor.The sulphur lithium hydride obtained reacts with lithium hydroxide further, obtains lithium sulfide recycled, or after sulphur lithium hydride high temperature removal hydrogen sulfide, obtains lithium sulfide recycled.
The Lithium salt recovery method of above-mentioned bibliographical information, not only equally also exists that operational path is long, the lithium salts rate of recovery is low, and wastewater flow rate is large and the problems such as energy consumption height, but also need use high-risk chemical substance hydrogen sulfide (H
2s) gas is high to the requirement of technical process control, dangerous large.
Summary of the invention
For above-mentioned situation, the invention provides one more simple and easy to do, without dangerous, thus have more the Lithium salt recovery method that technical scale uses, and be specially adapted to comprise the recovery to lithium salts in the poly arylidene thio-ester preparation process of polyphenylene sulfide.
The primary process of Lithium salt recovery method of the present invention, can carry out in the following manner:
1': in inert gas environment, by sulfohydrate and the lithium salts be present in N-Methyl pyrrolidone (NMP) system, after lithium salts is converted into sulphur lithium hydride by sulphur hydrogenation, solid-liquid separation.Wherein, the said lithium salts be present in N-Methyl pyrrolidone system, can be included in NMP and dissolve, be partly dissolved or the different states form such as the solution of non-dissolving or suspension.
2': heated in inert gas environment by the N-Methyl pyrrolidone solution containing sulphur lithium hydride after solid-liquid separation, make sulphur lithium hydride decomposition and inversion be the lithium sulfide precipitation being insoluble to NMP, then solid-liquid separation, collects the lithium sulfide precipitation reclaiming and obtain.
Said sulfohydrate in 1' step in aforesaid method, at least one preferably in Sodium sulfhydrate, potassium bisulfide.
Experimental result shows, and in the sulphur hydrogenation of 1' step, said sulfohydrate and lithium can react by the equimolar ratio mode close to theoretical value.Such as, sulfohydrate and lithium can be made to be 0.9 ~ 1.1:1 in mol ratio, more preferably to react under mol ratio is 0.95 ~ 1.05:1 condition.
Heating can be conducive to improving the speed that above-mentioned 1' walks sulphur hydrogenation, but the decomposition temperature (150 DEG C) of the sulphur lithium hydride that Heating temperature generally generates no more than this step, in order to avoid there is decomposition reaction further, generate the lithium sulfide being insoluble to NMP, and mix with other insolubles and affect the rate of recovery.Wherein, the temperature that said 1' step carries out sulphur hydrogenation generally can be 45 ~ 150 DEG C.Temperature is too low, although reaction equally also can be carried out, the reaction times can significant prolongation.Preferred temperature of reaction can be chosen as 65 ~ 130 DEG C.
After 1' step sulphur hydrogenation completes, when the nmp solution containing sulphur lithium hydride after solid-liquid separation carries out the 2' step reaction of thermal degradation conversion, generally can carry out under 135 ~ 180 DEG C of conditions.Preferred decomposition and inversion temperature of reaction can select 150 ~ 180 DEG C.Although sulphur lithium hydride decomposition temperature be 150 DEG C, slightly lower than under the condition of this decomposition temperature, decomposition and inversion process equally also can occur, and just speed of response can be obviously slack-off.When temperature of reaction is too high, then can be attended by the decomposition of solvent NMP.
As above-mentioned, recovery method of the present invention, is carry out under the protection of inert gas environment, usually can selects the rare gas elementes such as the most frequently used nitrogen or argon gas.Rare gas element in reaction system, can adopt common mode, is directly sent in the space of reaction system by rare gas element, displaces air.According to aforesaid method of the present invention, walk in the decomposition and inversion reaction of sulphur lithium hydride at 2', in degradation production, have hydrogen sulfide (H
2s) gas produces.Therefore, as the preferred mode of one, at least walk said inert gas environment in decomposition and inversion reaction process at 2', bubbling mode can be adopted, rare gas element is made to send into reactive system by reactant, to reach the H contributing to producing in decomposition and inversion process simultaneously
2deviating from of S gas, improves conversion reaction speed, shortens the time of pyrolytic conversion reaction.To the H produced in decomposition and inversion process
2s gas, then in a conventional manner with the alkaline solution absorption that sodium hydroxide/aqueous solutions of potassium etc. is commonly used, can form corresponding sulfohydrate, before namely returning after process further, the sulphur hydriding process of 1' step recycles.
For improving the rate of recovery of lithium salts further, above-mentioned 1' step is after sulphur hydrogenation and solid-liquid separation, washings and 1' with after anhydrous NMP washing, can be walked to the solution after solid-liquid separation and merge by separated solids (filter cake), jointly for being carried out at the decomposition and inversion reaction of 2' step.
The NMP suspension of the Containing Sulfur lithium obtained is reclaimed through aforesaid method of the present invention, except obtaining lithium sulfide solid and nmp solvent through solid-liquid separation, return the preparation for poly arylidene thio-esters such as polyphenylene sulfides respectively, even can directly with the NMP form of suspension of lithium sulfide for the preparation of corresponding polyarylene sulfide resin.
The Lithium salt recovery method that the present invention is above-mentioned, utilize the different solubility characteristics of different substances in coordinative solvent to carry out changing and realize being separated, what avoid current bibliographical information need by the mode of the complete evaporate to dryness of solvent (as NMP) mixture containing compositions such as lithium chlorides, but can directly adopt the corresponding solution/suspension containing lithium salts to transform.In addition, also without the need to through the said unnecessary and complicated carbonation reaction process of above-mentioned document, the lithium salts such as lithium chloride are first converted into insoluble Quilonum Retard, or first being converted into after lithium hydroxide through hydroxide reaction is reclaimed again.In removal process; the inventive method is not only complete in using high-risk chemical hydrogen sulfide; and whole process can be run in the system of fully-closed (inert gas environment); whole process is safe and reliable; technological process is short; reduced investment, efficiency is high, and the rate of recovery of lithium salts can up to more than 99%.Owing to steaming solvent NMP without the need to high temperature, it also avoid the pyrolytic decomposition of solvent.Particularly for the production of poly arylidene thio-ester, recovery method of the present invention not only goes for adopting the multiple production process of lithium salts catalysis (as traditional sodium sulphite-dihalo aromatic hydrocarbons synthesis polyphenylene sulfide technique at present, the polyphenylene sulfide synthesis technique etc. of lithium sulfide-dihalo aromatic hydrocarbons) in recovery to lithium salts, and with the lithium salts that the form of lithium sulfide reclaims, without the need to further conversion, just can directly return the building-up processes such as polyphenylene sulfide and be recycled.
Embodiment is by the following examples described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following example.Without departing from the idea case in the present invention described above, the various replacement made according to ordinary skill knowledge and customary means or change, all should comprise within the scope of the invention.
Embodiment
embodiment 1
Always salt-containing liquid 419.7g(wherein moisture 5g, NMP359g, NaCl 49.7g, the LiCl 6g after polyphenylene sulfide is produced) in, under stirring and nitrogen protection, add 7.2g Sodium sulfhydrate, 45 ~ 55 DEG C of reactions 6 hours.After sulphur hydrogenation completes, adularescent insolubles produces, airtight filtration, and the anhydrous NMP washing of filter cake 40g, drying, can obtain solid sodium chloride 57g.
Filter gained filtrate 409g, under stirring and nitrogen (passing into through reactant in bubbling mode) protection, be warming up to 135 ~ 150 DEG C, decomposition and inversion reacts 6 hours.The H produced in reaction process
2the S gas NaOH solution of 30% absorbs.The 406.5g NMP obtained and lithium sulfide solution, the synthesis for polyphenylene sulfide capable of circulation.
embodiment 2
Always salt-containing liquid 451g(wherein moisture 4g, NMP401g, the LiCl 46g after polyphenylene sulfide is produced) in, under stirring and nitrogen protection, add 66g Sodium sulfhydrate, 135 ~ 150 DEG C of reactions 2 hours.After sulphur hydrogenation completes, the white insolubles of airtight filtration, the anhydrous NMP washing of filter cake 60g, drying, can obtain solid sodium chloride 62.5g.
Under stirring and nitrogen (passing in bubbling mode) protection, being warming up to 160 ~ 180 DEG C by filtering the filtrate 512g obtained, reacting 2 hours.The H produced in reaction process
2the S gas NaOH solution of 50% absorbs.The 490g NMP obtained and lithium sulfide solution, the synthesis for polyphenylene sulfide capable of circulation.
embodiment 3
Always salt-containing liquid 517g(wherein moisture 5g, NMP450g, NaCl 52g, the LiCl 10g after polyphenylene sulfide is produced) in, under stirring and nitrogen protection, add 17g potassium bisulfide, 90 ~ 100 DEG C of reactions 3 hours.After reaction, adularescent insolubles produces, airtight filtration, by anhydrous for filter cake 50g NMP washing, drying, can obtain solid sodium chloride 65g.
Gained filtrate 516g will be filtered under stirring and nitrogen (or argon gas, pass in bubbling mode) are protected, be warming up to 160 ~ 170 DEG C, react 4 hours.Produce in reaction process H
2the S gas KOH solution of 40% absorbs.The 509g NMP obtained and lithium sulfide solution, the synthesis for polyphenylene sulfide capable of circulation.
Claims (11)
1. Lithium salt recovery method, is characterized in that carrying out in the following manner:
1': in inert gas environment, by sulfohydrate and the lithium salts be present in N-Methyl pyrrolidone system, after lithium salts is converted into sulphur lithium hydride by sulphur hydrogenation, solid-liquid separation;
2': heated in inert gas environment by the N-Methyl pyrrolidone solution containing sulphur lithium hydride after solid-liquid separation, decomposition and inversion is lithium sulfide precipitation, after solid-liquid separation, collects and obtains lithium sulfide precipitation.
2. the method for claim 1, is characterized in that the mol ratio of said sulfohydrate and lithium salts in 1' step is 0.9 ~ 1.1:1.
3. method as claimed in claim 2, is characterized in that the mol ratio of said sulfohydrate and lithium salts in 1' step is 0.95 ~ 1.05:1.
4. the method for claim 1, is characterized in that in 1' step, said sulfohydrate is the sulfohydrate of at least one in sodium and potassium.
5. the method for claim 1, is characterized in that said 1' walks sulphur hydrogenation and carries out under 45 ~ 150 DEG C of heating conditions.
6. method as claimed in claim 5, is characterized in that the temperature of said 1' step sulphur hydrogenation is 65 ~ 130 DEG C.
7. the method for claim 1, is characterized in that the decomposition and inversion reaction that said 2' walks is carried out under 135 ~ 180 DEG C of conditions.
8. method as claimed in claim 7, is characterized in that the decomposition and inversion temperature of reaction that said 2' walks is 150 ~ 180 DEG C.
9. the method for claim 1, it is characterized in that said 1' walks through sulphur hydrogenation and after solid-liquid separation, after separated solids dry N-methylpyrrolidone washing precipitation, the solution obtained after washings and solid-liquid separation merges, for being carried out at the reaction of 2' step.
10. the method as described in one of claim 1 to 9, it is characterized in that at least 2' walks said inert gas environment in decomposition and inversion reaction is to send into reaction environment by reactant in bubbling mode by rare gas element.
11. methods as described in one of claim 1 to 9, it is characterized in that at least 2' walks said inert gas environment in decomposition and inversion reaction is nitrogen or ar gas environment.
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| CN106495190B (en) * | 2016-09-12 | 2018-03-09 | 天津科技大学 | A kind of calcining of abraum salt containing lithium recovery method |
| CN107892314A (en) * | 2017-11-16 | 2018-04-10 | 新疆中泰新鑫化工科技股份有限公司 | The method that lithium chloride is reclaimed from the residual slurries of kettle of the lithium chloride containing catalyst |
| CN113929061A (en) * | 2021-10-12 | 2022-01-14 | 深圳高能时代科技有限公司 | Method for recovering lithium nitride waste |
| CN114725490B (en) * | 2022-03-25 | 2023-11-07 | 广东马车动力科技有限公司 | Integrated sulfide solid electrolyte and preparation method and application thereof |
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