WO2018072739A1 - Method for comprehensive recycling of by-product slurry during polyphenylene sulfide production - Google Patents

Method for comprehensive recycling of by-product slurry during polyphenylene sulfide production Download PDF

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WO2018072739A1
WO2018072739A1 PCT/CN2017/106950 CN2017106950W WO2018072739A1 WO 2018072739 A1 WO2018072739 A1 WO 2018072739A1 CN 2017106950 W CN2017106950 W CN 2017106950W WO 2018072739 A1 WO2018072739 A1 WO 2018072739A1
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nacl
solution
polyphenylene sulfide
product slurry
licl
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Chinese (zh)
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邓天龙
余晓平
李乾华
吕天生
胡洪铭
郭亚飞
王士强
李珑
陈尚敬
谢晓鸿
张思思
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天津科技大学
重庆聚狮新材料科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
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    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
    • C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0254—Preparatory processes using metal sulfides
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0277—Post-polymerisation treatment
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0277—Post-polymerisation treatment
    • C08G75/0281—Recovery or purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the invention relates to the field of production of polyphenylene sulfide (PPS), in particular to an efficient and comprehensive recycling method for by-product slurry in the industrial production of polyphenylene sulfide.
  • PPS polyphenylene sulfide
  • Polyphenylene sulfide is a thermoplastic special engineering plastic with excellent electrical insulation, flame retardancy and chemical resistance. It is widely used in aerospace, electronics, chemical and many other fields.
  • N-methylpyrrolidone NMP
  • LiCl a large amount of NaCl will be produced as a by-product, which will eventually form salt with LiCl and NMP.
  • Patent CN102276838 recovers NMP by evaporation under reduced pressure, and then recovers lithium by adding phosphoric acid or sodium aluminate to the water extract.
  • the patent CN103965476 is dehydrated under reduced pressure in an inert gas environment, and the NaCl is precipitated and then further decompressed.
  • the NMP is distilled and recovered, and the remaining liquid is cooled and precipitated to recover LiCl; the patent CN102675683 first separates most of the water and NMP in the by-product slurry by vacuum distillation, and then obtains NaCl, LiCl, NMP and water obtained by a spiral evaporator.
  • the viscous material was subjected to forced evaporation to obtain a powdery mixture containing LiCl and NaCl, and then NaCl was separated by methanol extraction and evaporated to dryness to obtain LiCl. It is worth noting that the above method has the disadvantages of low purity of the recovered product and low yield of NMP and LiCl.
  • the remaining 25% to 30% of the NMP will combine with LiCl to form a complex similar to a solid solution, and the mixture is subjected to the mixture.
  • the formed viscous complex is liable to cause problems such as clogging or elimination of the evaporation vessel, it is difficult to industrially produce.
  • the patent CN1345892 recovers lithium by adding carbonate to the by-product slurry, and then adding hydrochloric acid to the filter cake to obtain a halogenated salt catalyst, however, the product yield of the method and The purity is extremely low.
  • the patents CN104277220 and CN102730721 disclose a method for recovering NaCl in a polyphenylene sulfide solvent; and the patent CN104877167 discloses a recycling method of a reagent LiCl in a polyphenylene sulfide production process. It is worth noting that the current recycling method of the PPS by-product slurry is only for one or two components, and the recycling process is cumbersome, and the obtained product purity and yield are low.
  • the object of the present invention is to provide a method for comprehensively recovering NMP, NaCl, LiCl, PPS oligomers in a PPS by-product slurry, and reducing PPS. Production costs and green production of PPS.
  • a method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide characterized in that it comprises the following steps:
  • step 2) adding an acidic solution to the dry waste salt in step 1) for reaction and dissolution leaching, respectively converting Li 2 CO 3 and Na 2 CO 3 into LiCl and NaCl and dissolving into the liquid phase;
  • step 2) the extract is adjusted with a base to adjust the pH and filtered to remove insoluble components, and the liquid phase is further purified by adsorption to remove the dissolved organic components to obtain a solution containing only LiCl and NaCl;
  • step 3 the solution containing only LiCl and NaCl is concentrated by evaporation to precipitate NaCl, and then the solution obtained by separating NaCl is added with Na 2 CO 3 solution to obtain Li 2 CO 3 ;
  • the method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide is characterized in that, in the step 2), the acid used in the dissolution of the lithium-containing waste salt is dissolved, and the acid used is hydrochloric acid.
  • the amount of hydrochloric acid and water added is 1% to 10% excess of the theoretical amount, and the dissolution leaching time is ⁇ 0.5h.
  • the above-mentioned method for comprehensively recycling by-product slurry in the production process of polyphenylene sulfide is characterized in that the adsorbent used for adsorption purification in step 3) is activated carbon.
  • the method for comprehensively recycling by-product slurry in the production process of polyphenylene sulfide is characterized in that, in the step 4), the solution containing only LiCl and NaCl is concentrated by evaporation, and the solution is concentrated.
  • the lithium ion concentration is ⁇ 5 g/L, and the crystallized NaCl is washed at a liquid-solid ratio of ⁇ 0.5 to remove entrained lithium ions.
  • the method for comprehensively recycling by-product slurry in the production process of polyphenylene sulfide is characterized in that: when the concentrate is subjected to precipitation in step 4) to recover Li 2 CO 3 , the precipitant used is of mass. The concentration of ⁇ 10% Na 2 CO 3 , the precipitation reaction time ⁇ 5 min, and the process is sufficiently stirred, and the precipitated Li 2 CO 3 is washed at a liquid-solid ratio ⁇ 1 to remove entrained chloride ions.
  • the solution after adjusting the pH is returned to the system, and mixed with the solution after adsorption purification, and then concentrated by evaporation.
  • the method of the present invention relates only to conventional operations such as precipitation, dissolution, filtration, adsorption, etc., and thus is easy to industrially produce.
  • the NaCl product obtained by the invention has high purity and can be directly used as a raw material for electrolyzing caustic soda by ion-exchange membrane method, thereby achieving effective docking with the chlor-alkali industry.
  • the Li 2 CO 3 recovered by the invention can be directly used as a commodity or further converted to obtain LiCl, thereby realizing the recycling of the LiCl auxiliary agent in the PPS production process and reducing the production cost of the PPS.
  • the process of the present invention achieves a closed cycle, so that complete recovery of NaCl and LiCl in the PPS by-product slurry can be achieved.
  • FIG. 1 is a flow chart of a process for comprehensive recycling of a polyphenylene sulfide by-product slurry in an embodiment
  • Figure 3 is an XRD pattern of a NaCl product obtained by evaporation crystallization and washing
  • Figure 4 is an XRD pattern of the Li 2 CO 3 product obtained after precipitation and washing.
  • the PPS by-product slurry was recycled in the process scheme shown in FIG.
  • the slurry was distilled under reduced pressure and dried to obtain a dry lithium-containing salt as shown in Fig. 2.
  • the composition of the slurry was XRD (Fig. 3) and quantitative analysis showed that NaCl, Li 2 CO 3 and organic matter were 84.6%, 7% and 6.8%, the other components accounted for 1.6%.
  • the dry waste salt was reacted and leached with a HCl solution at a liquid-solid ratio of 2.9, the leaching time was 2 h, and the control solution end point pH was 3.2.
  • the pH-adjusted solution is recovered by filtration to recover the insoluble PPS oligomer, and the filtered solution is adsorbed and purified with 20-40 mesh activated carbon to remove the dissolved organic component in the solution.
  • the solution after adsorption purification was concentrated by evaporation to obtain NaCl, the evaporation amount of water was 71%, and the single yield of NaCl was 75.95%.
  • the NaCl obtained by crystallization was washed and dried several times at a liquid-solid ratio of 1.0, and finally a NaCl product having a purity of 99.94% was obtained (Fig. 4).
  • the solution after separating Li 2 CO 3 is adjusted to pH 6.5 with a 5% NaOH solution, and the returning process is mixed with the solution after adsorption purification to continue evaporation and concentration to achieve a closed cycle of the mother liquor recycling and the process.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Disclosed is a method for comprehensive recycling of a by-product slurry during polyphenylene sulfide (PPS) production. Na2CO3 is added to the slurry, and then a solvent NMP is recovered by distillation and drying, then an acid solution is used for dissolving and leaching the resulting dry waste salt, the leaching liquor is subjected to pH adjustment and then filtered, with the insoluble components being removed, the liquid phase is subjected to adsorption and purification and evaporation concentration to separate out NaCl, then Na2CO3 is added to the solution with NaCl separated out for precipitation to obtain Li2CO3, the mother liquor with lithium precipitated is subjected to pH adjustment and then mixed with the solution obtained after adsorption and purification, and a closed circulation of the process is achieved. The method can be used in the comprehensive recycling of the by-product slurry during PPS production, the recovered NaCl can be directly used for caustic soda preparation by ionic membrane electrolysis, and Li2CO3 can directly serve as an industrial product or can be further converted into LiCl to serve as a PPS production auxiliary for recycling.

Description

一种聚苯硫醚生产过程中副产物浆料综合回收利用方法Method for comprehensive recycling of byproduct slurry in production process of polyphenylene sulfide 技术领域Technical field
本发明涉及聚苯硫醚(PPS)的生产领域，特别是涉及聚苯硫醚工业化生产中副产物浆料的高效综合回收利用方法。The invention relates to the field of production of polyphenylene sulfide (PPS), in particular to an efficient and comprehensive recycling method for by-product slurry in the industrial production of polyphenylene sulfide.
背景技术Background technique
聚苯硫醚(PPS)是一种热塑性特种工程塑料，具有优良的电绝缘性、阻燃性、耐化学腐蚀性等优异性能，广泛应用于航空航天、电子电器、化工等诸多领域。在采用Na2S和对二氯苯为原料、N-甲基吡咯烷酮(NMP)为溶剂、LiCl为助剂合成PPS过程中，会副产大量的NaCl，其最终会与LiCl和NMP形成含盐、水、NMP等的副产物浆料。由于LiCl和NMP价格昂贵，若不进行副产物浆料的综合回收利用，将导致生产成本的急剧增加和严重的环境污染问题。Polyphenylene sulfide (PPS) is a thermoplastic special engineering plastic with excellent electrical insulation, flame retardancy and chemical resistance. It is widely used in aerospace, electronics, chemical and many other fields. In the process of synthesizing PPS using Na 2 S and p-dichlorobenzene as raw materials, N-methylpyrrolidone (NMP) as solvent and LiCl as auxiliary, a large amount of NaCl will be produced as a by-product, which will eventually form salt with LiCl and NMP. A by-product slurry of water, NMP, or the like. Since LiCl and NMP are expensive, without the comprehensive recycling of by-product slurry, the production cost will increase sharply and serious environmental pollution problems will occur.
目前，针对PPS副产物浆料中NMP和LiCl的回收方法已有相关研究报道。专利CN102276838采用减压蒸干回收NMP，然后再向水浸提液中加入磷酸或铝酸钠沉淀回收锂；专利CN103965476先在惰性气体环境下减压脱水，并沉淀分离NaCl，然后再进一步减压蒸馏回收NMP，剩余液经冷却沉淀回收LiCl；专利CN102675683先通过减压蒸馏分离出副产物浆料中的大部分水和NMP，然后通过螺旋蒸发器对获得的含NaCl、LiCl、NMP、水的粘稠物进行强制蒸干，获得含LiCl和NaCl等的粉状混合物，然后采用甲醇浸提分离NaCl并经蒸发和干燥获得LiCl。值得注意的是，上述方法存在回收的产品纯度低、NMP和LiCl的收率低等缺点。此外，在完成PPS聚合反应后，尽管大部分NMP可以通过常规的方法予以回收，但剩下25％～30％的NMP会与LiCl结合形成类似于固溶体的络合物，在对该部分混合物进行常规蒸发回收NMP过程中，由于形成的粘稠络合物易造成蒸发釜堵塞或排除困难等问题，因此难以工业化生产。At present, there are related research reports on the recovery methods of NMP and LiCl in the PPS by-product slurry. Patent CN102276838 recovers NMP by evaporation under reduced pressure, and then recovers lithium by adding phosphoric acid or sodium aluminate to the water extract. The patent CN103965476 is dehydrated under reduced pressure in an inert gas environment, and the NaCl is precipitated and then further decompressed. The NMP is distilled and recovered, and the remaining liquid is cooled and precipitated to recover LiCl; the patent CN102675683 first separates most of the water and NMP in the by-product slurry by vacuum distillation, and then obtains NaCl, LiCl, NMP and water obtained by a spiral evaporator. The viscous material was subjected to forced evaporation to obtain a powdery mixture containing LiCl and NaCl, and then NaCl was separated by methanol extraction and evaporated to dryness to obtain LiCl. It is worth noting that the above method has the disadvantages of low purity of the recovered product and low yield of NMP and LiCl. In addition, after the completion of the PPS polymerization, although most of the NMP can be recovered by a conventional method, the remaining 25% to 30% of the NMP will combine with LiCl to form a complex similar to a solid solution, and the mixture is subjected to the mixture. In the conventional evaporation and recovery of NMP, since the formed viscous complex is liable to cause problems such as clogging or elimination of the evaporation vessel, it is difficult to industrially produce.
为解决NMP与LiCl形成络合物的问题，专利CN1345892通过向副产物浆料中加入碳酸盐方式沉淀回收锂，然后向滤饼中加入盐酸获得卤化盐催化剂，然而该法的产品收率和纯度均极低。除上述方法外，专利CN104277220和CN102730721公开了一种回收聚苯硫醚溶剂中NaCl的方法；专利CN104877167公开了一种聚苯硫醚生产工艺中助剂LiCl的循环利用方法。值得注意的是，目前对PPS副产物浆料的回收利用方法仅针对一种或两种组分进行回收，且回收工艺过程繁琐、所获得的产品纯度和收率均较低。In order to solve the problem of the formation of complexes between NMP and LiCl, the patent CN1345892 recovers lithium by adding carbonate to the by-product slurry, and then adding hydrochloric acid to the filter cake to obtain a halogenated salt catalyst, however, the product yield of the method and The purity is extremely low. In addition to the above methods, the patents CN104277220 and CN102730721 disclose a method for recovering NaCl in a polyphenylene sulfide solvent; and the patent CN104877167 discloses a recycling method of a reagent LiCl in a polyphenylene sulfide production process. It is worth noting that the current recycling method of the PPS by-product slurry is only for one or two components, and the recycling process is cumbersome, and the obtained product purity and yield are low.
有鉴于此，为实现PPS的绿色生产，并降低生产成本，我们开发一种高效的PPS副产物 浆料的溶剂回收、有机杂质的除去与净化、综合回收利用氯化钠和碳酸锂的方法，这对于促进PPS行业绿色可持续发展具有重要意义。In view of this, in order to achieve green production of PPS and reduce production costs, we have developed an efficient PPS by-product. The solvent recovery of the slurry, the removal and purification of organic impurities, and the comprehensive recovery of sodium chloride and lithium carbonate are important for promoting the green sustainable development of the PPS industry.
发明内容Summary of the invention
针对现有PPS生产副产物浆料回收利用技术方法中存在的不足，本发明的目的是提供一种综合回收PPS副产物浆料中NMP、NaCl、LiCl、PPS齐聚物的方法，降低PPS的生产成本，并实现PPS的绿色生产。In view of the deficiencies in the existing PPS production by-product slurry recycling technology, the object of the present invention is to provide a method for comprehensively recovering NMP, NaCl, LiCl, PPS oligomers in a PPS by-product slurry, and reducing PPS. Production costs and green production of PPS.
本发明提供的技术方案和工艺过程如下：The technical solutions and processes provided by the present invention are as follows:
一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于它包括如下步骤：A method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide, characterized in that it comprises the following steps:
1)在聚苯硫醚副产物浆料中加入Na2CO3破坏N-甲基吡咯烷酮与锂形成的络合物，使锂转化为Li2CO3，浆料再经蒸馏和干燥分离回收NMP和水，并获得含NaCl、Li2CO3、Na2CO3、PPS齐聚物的干废盐；1) Adding Na 2 CO 3 to the polyphenylene sulfide by-product slurry to destroy the complex of N-methylpyrrolidone and lithium, converting lithium into Li 2 CO 3 , and separating and recovering the NMP by distillation and drying And water, and obtain a dry waste salt containing NaCl, Li 2 CO 3 , Na 2 CO 3 , PPS oligomer;
2)向步骤1)中的干废盐中加入酸性溶液进行反应和溶解浸提，使Li2CO3和Na2CO3分别转化为LiCl和NaCl并溶解进入液相；2) adding an acidic solution to the dry waste salt in step 1) for reaction and dissolution leaching, respectively converting Li 2 CO 3 and Na 2 CO 3 into LiCl and NaCl and dissolving into the liquid phase;
3)步骤2)中浸提液用碱调节pH并过滤去除不溶组分，液相再经吸附净化去除溶解态有机组分，获得只含LiCl和NaCl的溶液；3) In step 2), the extract is adjusted with a base to adjust the pH and filtered to remove insoluble components, and the liquid phase is further purified by adsorption to remove the dissolved organic components to obtain a solution containing only LiCl and NaCl;
4)步骤3)中只含LiCl和NaCl的溶液经蒸发浓缩析出NaCl，再向分离NaCl后的浓缩液中加入Na2CO3溶液沉淀获得Li2CO3；4) In step 3), the solution containing only LiCl and NaCl is concentrated by evaporation to precipitate NaCl, and then the solution obtained by separating NaCl is added with Na 2 CO 3 solution to obtain Li 2 CO 3 ;
5)步骤4)中沉淀并分离Li2CO3后的母液经调pH后与吸附净化后的溶液混后，实现工艺的闭合循环。5) The mother liquor after the precipitation and separation of Li 2 CO 3 in step 4) is adjusted to pH and then mixed with the solution after adsorption purification to achieve a closed cycle of the process.
而且，所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤2)中对含锂废盐进行酸性水溶液溶解浸提时，所用酸为盐酸，加入的盐酸和水的量均比理论量过量1％～10％，溶解浸提时间≥0.5h。Moreover, the method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide is characterized in that, in the step 2), the acid used in the dissolution of the lithium-containing waste salt is dissolved, and the acid used is hydrochloric acid. The amount of hydrochloric acid and water added is 1% to 10% excess of the theoretical amount, and the dissolution leaching time is ≥0.5h.
而且，所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤3)中对浸提液进行pH调节时，所用的碱为质量浓度≥5％的NaOH，调节终点为pH＝5.0～9.0。Moreover, the method for comprehensively recycling by-product slurry in the production process of polyphenylene sulfide is characterized in that: when the pH of the extract is adjusted in step 3), the alkali used is a mass concentration ≥ 5%. The NaOH was adjusted to pH = 5.0 to 9.0.
而且，所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤3)中吸附净化所用的吸附剂为活性炭。Moreover, the above-mentioned method for comprehensively recycling by-product slurry in the production process of polyphenylene sulfide is characterized in that the adsorbent used for adsorption purification in step 3) is activated carbon.
而且，所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤4)中对只含LiCl和NaCl的溶液进行蒸发浓缩时，浓缩后的溶液中锂离子浓度≥5g/L，结晶析出的NaCl在液固比≥0.5的水量下进行洗涤，以去除夹带的锂离子。Moreover, the method for comprehensively recycling by-product slurry in the production process of polyphenylene sulfide is characterized in that, in the step 4), the solution containing only LiCl and NaCl is concentrated by evaporation, and the solution is concentrated. The lithium ion concentration is ≥5 g/L, and the crystallized NaCl is washed at a liquid-solid ratio of ≥0.5 to remove entrained lithium ions.
而且，所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在 步骤4)中对浓缩液进行沉淀回收Li2CO3时，所用的沉淀剂为质量浓度≥10％的Na2CO3，沉淀反应时间≥5min，且该过程充分搅拌，沉淀获得的Li2CO3在液固比≥1的水量下进行洗涤，以去除夹带的氯离子。Moreover, the method for comprehensively recycling by-product slurry in the production process of polyphenylene sulfide is characterized in that: when the concentrate is subjected to precipitation in step 4) to recover Li 2 CO 3 , the precipitant used is of mass. The concentration of ≥10% Na 2 CO 3 , the precipitation reaction time ≥ 5 min, and the process is sufficiently stirred, and the precipitated Li 2 CO 3 is washed at a liquid-solid ratio ≥ 1 to remove entrained chloride ions.
而且，所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤5)中对沉淀并分离Li2CO3后的溶液调节pH时，所用的酸为质量浓度≥5％的HCl，调节终点为pH＝5.0～9.0，调节pH后的溶液返回***，并与吸附净化后的溶液混合后继续蒸发浓缩。Moreover, the method for comprehensively recycling by-product slurry in the production process of polyphenylene sulfide is characterized in that the acid used in the step of adjusting the pH of the solution after separating and separating Li 2 CO 3 in step 5) For HCl with mass concentration ≥ 5%, the end point of the adjustment is pH=5.0-9.0. The solution after adjusting the pH is returned to the system, and mixed with the solution after adsorption purification, and then concentrated by evaporation.
本发明的优点和积极效果是：The advantages and positive effects of the present invention are:
1、本发明方法仅涉及常规的沉淀、溶解、过滤、吸附等操作，因此易于工业化生产。1. The method of the present invention relates only to conventional operations such as precipitation, dissolution, filtration, adsorption, etc., and thus is easy to industrially produce.
2、本发明所获得的NaCl产品纯度高，可以直接作为离子膜法电解制烧碱的原料，从而实现与氯碱工业的有效对接。2. The NaCl product obtained by the invention has high purity and can be directly used as a raw material for electrolyzing caustic soda by ion-exchange membrane method, thereby achieving effective docking with the chlor-alkali industry.
3、本发明回收的Li2CO3可以直接作为商品或经进一步转化获得LiCl，从而实现PPS生产过程中LiCl助剂的循环使用，降低PPS的生产成本。3. The Li 2 CO 3 recovered by the invention can be directly used as a commodity or further converted to obtain LiCl, thereby realizing the recycling of the LiCl auxiliary agent in the PPS production process and reducing the production cost of the PPS.
4、本发明工艺实现闭合循环，因此可以实现PPS副产物浆料中NaCl和LiCl的全部回收。4. The process of the present invention achieves a closed cycle, so that complete recovery of NaCl and LiCl in the PPS by-product slurry can be achieved.
附图说明DRAWINGS
图1是实施例子中聚苯硫醚副产物浆料综合回收利用工艺流程图；1 is a flow chart of a process for comprehensive recycling of a polyphenylene sulfide by-product slurry in an embodiment;
图2是副产物浆料经干燥后的含NaCl、Li2CO3等的干废盐XRD图；2 is an XRD pattern of dry waste salt containing NaCl, Li 2 CO 3 , etc. after drying of the by-product slurry;
图3是经蒸发结晶和洗涤后获得的NaCl产品XRD图；Figure 3 is an XRD pattern of a NaCl product obtained by evaporation crystallization and washing;
图4是经沉淀和洗涤后获得的Li2CO3产品XRD图。Figure 4 is an XRD pattern of the Li 2 CO 3 product obtained after precipitation and washing.
具体实施方式detailed description
下面结合附图和具体实施例对本发明做进一步说明。The invention will be further described below in conjunction with the drawings and specific embodiments.
以图1所示工艺方案对PPS副产物浆料进行回收利用。浆料经减压蒸馏和干燥后获得图2所示的含锂干废盐，其组成经XRD(图3)和定量分析表明，NaCl、Li2CO3、有机物分别为84.6％、7％和6.8％，其他组分占1.6％。The PPS by-product slurry was recycled in the process scheme shown in FIG. The slurry was distilled under reduced pressure and dried to obtain a dry lithium-containing salt as shown in Fig. 2. The composition of the slurry was XRD (Fig. 3) and quantitative analysis showed that NaCl, Li 2 CO 3 and organic matter were 84.6%, 7% and 6.8%, the other components accounted for 1.6%.
在液固比为2.9条件下用HCl溶液对干废盐进行反应和浸提，浸提时间为2h，控制溶液终点pH＝3.2。然后用5％的NaOH溶液对浸提液pH进行调节，控制终点pH＝6.8。调节pH后的溶液经过滤回收不溶PPS齐聚物，并用20～40目的活性炭对过滤后的溶液进行吸附净化，以除去溶液中溶解态有机组分。The dry waste salt was reacted and leached with a HCl solution at a liquid-solid ratio of 2.9, the leaching time was 2 h, and the control solution end point pH was 3.2. The pH of the extract was then adjusted with a 5% NaOH solution to control the endpoint pH = 6.8. The pH-adjusted solution is recovered by filtration to recover the insoluble PPS oligomer, and the filtered solution is adsorbed and purified with 20-40 mesh activated carbon to remove the dissolved organic component in the solution.
吸附净化后的溶液经蒸发浓缩获得NaCl，水分蒸发量为71％，NaCl的单次收率为75.95％。结晶获得的NaCl在液固比为1.0的水量下进行多次洗涤并烘干，最终获得纯度达99.94％的NaCl产品(图4)。 The solution after adsorption purification was concentrated by evaporation to obtain NaCl, the evaporation amount of water was 71%, and the single yield of NaCl was 75.95%. The NaCl obtained by crystallization was washed and dried several times at a liquid-solid ratio of 1.0, and finally a NaCl product having a purity of 99.94% was obtained (Fig. 4).
再将分离NaCl后的溶液加入到饱和Na2CO3溶液中(Na2CO3过量2％)，该过程充分搅拌，加料和搅拌时间为20min，沉淀获得的Li2CO3的单次收率为82.16％，平均粒径为64.3μm。Li2CO3经分离并在液固比为1.5的水量下进行多次洗涤并烘干，最终获得纯度达99.81％的Li2CO3产品(图6)。The solution after separation of NaCl was added to a saturated Na 2 CO 3 solution (2% excess of Na 2 CO 3 ), the process was thoroughly stirred, the addition and stirring time was 20 min, and the single yield of the precipitated Li 2 CO 3 was obtained. It was 82.16% and the average particle diameter was 64.3 μm. Li 2 CO 3 was separated and washed and dried several times at a liquid-solid ratio of 1.5 to finally obtain a Li 2 CO 3 product having a purity of 99.81% (Fig. 6).
分离Li2CO3后的溶液用5％NaOH溶液调节pH＝6.5后，返回工艺与吸附净化后的溶液混合，以继续蒸发浓缩，实现母液循环利用和工艺的闭合循环。The solution after separating Li 2 CO 3 is adjusted to pH 6.5 with a 5% NaOH solution, and the returning process is mixed with the solution after adsorption purification to continue evaporation and concentration to achieve a closed cycle of the mother liquor recycling and the process.
以上显示和描述了本发明的实施例，或者附图的技术方案，均体现了本发明的优点和高效地从PPS副产物浆料中回收NMP、NaCl、LiCl的效果。应当理解的是，优选实施例对本发明的技术方案进行的详细说明是示意性而非限制性的，本领域技术人员在阅读本发明说明书的基础上，可以根据上述说明加以改进或变换，如将实施例中对过滤前浸提液pH的调节改为对过滤后浸提液的调节，所有这些改进和变换都应属于本发明所附权利要求的保护范围。 The embodiments of the present invention have been shown and described above, or the technical solutions of the drawings, all embody the advantages of the present invention and the effect of efficiently recovering NMP, NaCl, LiCl from the PPS by-product slurry. The detailed description of the preferred embodiments of the present invention is intended to be illustrative and not restrictive, and those skilled in the art can In the examples, the adjustment of the pH of the leachate prior to filtration is changed to the adjustment of the leachate after filtration, all of which are within the scope of the appended claims.

Claims (7)

  1. 一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于它包括如下步骤：A method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide, characterized in that it comprises the following steps:
    1)在聚苯硫醚副产物浆料中加入Na2CO3破坏N-甲基吡咯烷酮与锂形成的络合物，使锂转化为Li2CO3，浆料再经蒸馏和干燥分离回收NMP和水，并获得含NaCl、Li2CO3、Na2CO3、PPS齐聚物的干废盐；1) Adding Na 2 CO 3 to the polyphenylene sulfide by-product slurry to destroy the complex of N-methylpyrrolidone and lithium, converting lithium into Li 2 CO 3 , and separating and recovering the NMP by distillation and drying And water, and obtain a dry waste salt containing NaCl, Li 2 CO 3 , Na 2 CO 3 , PPS oligomer;
    2)向步骤1)中的干废盐中加入酸性溶液进行反应和溶解浸提，使Li2CO3和Na2CO3分别转化为LiCl和NaCl并溶解进入液相；2) adding an acidic solution to the dry waste salt in step 1) for reaction and dissolution leaching, respectively converting Li 2 CO 3 and Na 2 CO 3 into LiCl and NaCl and dissolving into the liquid phase;
    3)步骤2)中浸提液用碱调节pH并过滤去除不溶组分，液相再经吸附净化去除溶解态有机组分，获得只含LiCl和NaCl的溶液；3) In step 2), the extract is adjusted with a base to adjust the pH and filtered to remove insoluble components, and the liquid phase is further purified by adsorption to remove the dissolved organic components to obtain a solution containing only LiCl and NaCl;
    4)步骤3)中只含LiCl和NaCl的溶液经蒸发浓缩析出NaCl，再向分离NaCl后的浓缩液中加入Na2CO3溶液沉淀获得Li2CO3；4) In step 3), the solution containing only LiCl and NaCl is concentrated by evaporation to precipitate NaCl, and then the solution obtained by separating NaCl is added with Na 2 CO 3 solution to obtain Li 2 CO 3 ;
    5)步骤4)中沉淀并分离Li2CO3后的母液经调pH后与吸附净化后的溶液混后，实现工艺的闭合循环。5) The mother liquor after the precipitation and separation of Li 2 CO 3 in step 4) is adjusted to pH and then mixed with the solution after adsorption purification to achieve a closed cycle of the process.
  2. 根据权利要求1所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤2)中对含锂废盐进行酸性水溶液溶解浸提时，所用酸为盐酸，加入的盐酸和水的量均比理论量过量1％～10％，溶解浸提时间≥0.5h。The method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide according to claim 1, wherein in the step 2), when the lithium-containing waste salt is dissolved and leached by the acidic aqueous solution, the acid used is The amount of hydrochloric acid, hydrochloric acid and water added is 1% to 10% excess of the theoretical amount, and the dissolution leaching time is ≥0.5h.
  3. 根据权利要求1所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤3)中对浸提液进行pH调节时，所用的碱为质量浓度≥5％的NaOH，调节终点为pH＝5.0～9.0。The method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide according to claim 1, wherein when the pH of the extract is adjusted in step 3), the alkali used is a mass concentration ≥ 5% NaOH, the end point of the adjustment is pH = 5.0 ~ 9.0.
  4. 根据权利要求1所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤3)中吸附净化所用的吸附剂为活性炭。The method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide according to claim 1, characterized in that the adsorbent used for adsorption purification in step 3) is activated carbon.
  5. 根据权利要求1所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤4)中对只含LiCl和NaCl的溶液进行蒸发浓缩时，浓缩后的溶液中锂离子浓度≥5g/L，结晶析出的NaCl在液固比≥0.5的水量下进行洗涤，以去除夹带的锂离子。The method for comprehensively recycling by-product slurry in the production process of polyphenylene sulfide according to claim 1, wherein in the step 4), the solution containing only LiCl and NaCl is concentrated by evaporation, and then concentrated. The lithium ion concentration in the solution is ≥5 g/L, and the crystal precipitated NaCl is washed at a liquid-solid ratio of ≥0.5 to remove entrained lithium ions.
  6. 根据权利要求1所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤4)中对浓缩液进行沉淀回收Li2CO3时，所用的沉淀剂为质量浓度≥10％的Na2CO3，沉淀反应时间≥5min，且该过程充分搅拌，沉淀获得的Li2CO3在液固比≥1的水量下进行洗涤，以去除夹带的氯离子。The method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide according to claim 1, characterized in that: in the step 4), the precipitant used in the precipitation of the concentrated liquid to recover Li 2 CO 3 For Na 2 CO 3 with mass concentration ≥10%, the precipitation reaction time is ≥5min, and the process is fully stirred, and the precipitated Li 2 CO 3 is washed at a liquid-solid ratio ≥1 to remove entrained chloride ions.
  7. 根据权利要求1所述的一种聚苯硫醚生产过程中副产物浆料综合回收利用方法，其特征在于：在步骤5)中对沉淀并分离Li2CO3后的溶液调节pH时，所用的酸为质量浓度≥5％的HCl，调节终点为pH＝5.0～9.0，调节pH后的溶液返回***，并与吸附净化后的溶液混合 后继续蒸发浓缩。 The method for comprehensively recycling and utilizing by-product slurry in the production process of polyphenylene sulfide according to claim 1, wherein in the step 5), the pH of the solution after sedimentation and separation of Li 2 CO 3 is adjusted. The acid is HCl with a mass concentration of ≥5%, and the end point of the adjustment is pH=5.0-9.0. The solution after adjusting the pH is returned to the system, and after mixing with the solution after adsorption purification, evaporation and concentration are continued.
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