WO2020159167A1 - Procédé de récupération de composés à base d'amide - Google Patents

Procédé de récupération de composés à base d'amide Download PDF

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WO2020159167A1
WO2020159167A1 PCT/KR2020/001208 KR2020001208W WO2020159167A1 WO 2020159167 A1 WO2020159167 A1 WO 2020159167A1 KR 2020001208 W KR2020001208 W KR 2020001208W WO 2020159167 A1 WO2020159167 A1 WO 2020159167A1
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amide
inorganic salt
recovering
waste solution
waste liquid
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PCT/KR2020/001208
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English (en)
Korean (ko)
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조상환
한중진
김한솔
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주식회사 엘지화학
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Publication of WO2020159167A1 publication Critical patent/WO2020159167A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C07C231/24—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/03—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
    • C07D223/08—Oxygen atoms
    • C07D223/10—Oxygen atoms attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings 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
    • C07D233/30—Oxygen or sulfur atoms

Definitions

  • the present invention efficiently recovers amide-based compounds such as N-methyl-2-pyrrolidone from waste liquids containing amide-based compounds such as N-methyl-2-pyrrolidone generated in the polyarylene sulfide production process. It's about how.
  • Polyarylene sulfide typified by polyphenylene sulfide (PPS)
  • PPS polyphenylene sulfide
  • PPS resin it is one of the Super EPs, and because it has good fluidity, it is advantageous to use as a compound by kneading with fillers or reinforcing agents such as glass fibers.
  • NMP N-methyl pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • Amide-based compounds such as N-methyl-2-pyrrolidone used in this way are not only more expensive than conventional organic solvents, but are also known to be the main cause of environmental pollution when discharged in aqueous solutions, and are generally recovered and purified to recycle. Is becoming.
  • amide-based compounds such as N-methyl-2-pyrrolidone have excellent compatibility with water as they have high organic solubility, so they are infinitely mixed with water, and a large amount of inorganic salts are dissolved, such as effluent from the PAS manufacturing process. If it is, it is difficult to distill as it is, various recovery methods have been tried.
  • a process for removing fine powder is added by using a general batch centrifuge, but there is a problem in that it is difficult to remove salts smaller than the mesh size because the inorganic salt is dissolved in water along with a problem in which the fine powder is removed.
  • the present invention to minimize clogging of the distillation column in the distillation process for treating the waste liquid generated in the conventional polyarylene sulfide production process and clogging of the filter in the front of the waste liquid tank and deterioration of efficiency, a specific centrifuge before the distillation process of the waste liquid
  • an amide compound such as N-methyl-2-pyrrolidone
  • a specific centrifuge before the distillation process of the waste liquid By using, an amide compound such as N-methyl-2-pyrrolidone can be efficiently recovered from a waste solution containing an amide compound such as N-methyl-2-pyrrolidone generated in the polyarylene sulfide production process. It is possible to provide a method for recovering an amide-based compound.
  • the present invention is to provide a method for improving the recovery effect of the amide-based compound by lowering the water content of the fine powder such as inorganic salts that may be included in the waste solution.
  • the step of recovering the waste solution containing water, amide-based compounds and inorganic salts generated in the polyarylene sulfide manufacturing process
  • first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
  • the step of recovering the waste solution containing water, amide-based compounds and inorganic salts generated in the polyarylene sulfide manufacturing process Removing the inorganic salt in the waste solution by supplying the waste solution to a decanter centrifuge; And collecting the waste liquid from which the inorganic salt has been removed into a storage tank, and then recovering the amide compound from the waste liquid using a distillation column.
  • the present invention relates to a method for recovering an amide compound such as N-methyl-2-pyrrolidone used as a solvent from waste liquid generated after washing the reaction mixture after polyarylene sulfide polymerization.
  • the waste solution also contains various inorganic salts and impurities generated from a polyarylene sulfide (PAS) manufacturing process.
  • the inorganic salt may include a halide of an alkali metal, and may further include finely divided PPS. More specifically, the inorganic salt contains a halide of an alkali metal having a particle size of 5 to 30um, such as brine containing fine PPS ( ⁇ 100um) and sodium chloride (NaCl) generated in the polymerization process of polyarylene sulfide. .
  • a filter is installed at the front end of the waste liquid storage tank or a general centrifuge is used, but the filter of the front end tube of the storage tank for collecting the waste liquid may be blocked, and a solid material may be accumulated under the storage tank to block the discharge port.
  • a general centrifugal separator since solids are accumulated for each batch, there is a problem in that it must be continuously removed, which is inefficient.
  • the solid material of the inorganic salt contained in the waste liquid is removed before distilling the waste liquid by using a decanter centrifuge, and the amide compound contained in the waste liquid is increased by preventing the clogging of the distillation column and increasing distillation efficiency. It can increase the separation efficiency.
  • the inorganic salt can be removed and separated from the waste solution more efficiently than in the prior art, thereby improving processability.
  • a small amount of impurities can be removed.
  • the waste liquid supplied to the decanter-type centrifugal separator may be waste liquid generated in the process of synthesizing and washing polyarylene sulfide.
  • the present invention proceeds to a solvent recovery process after separation of the waste liquid, which is separately discharged after polymerization, so that the separation process of inorganic salts such as fine PPS and NaCl can be performed more efficiently than before.
  • the method for recovering the amide-based compound may be performed according to the process shown in FIG. 1.
  • the present invention does not perform a distillation process to recover the amide-based compound by collecting the waste solution generated in the manufacturing process of polyarylene sulfide directly into the storage tank, decanter type before collecting into the storage tank Using a centrifuge (Decanter type centrifuge), it is characterized in that to remove the solid material, such as inorganic salts from the waste liquid.
  • the solid material may include finely divided polyarylene sulfide.
  • a step of removing the inorganic salt in the waste liquid by supplying a waste liquid containing water, an amide-based compound and an inorganic salt generated in a polyarylene sulfide manufacturing process to a decanter type centrifuge .
  • the waste solution containing water and the amide compound is transferred to a storage tank for collection.
  • a step of recovering the amide-based compound from the waste liquid is performed using a distillation column. Through this, 99% or more of the amide compound can be recovered from the waste solution, and the recovered amide compound can be recycled to the polymerization process.
  • the reaction mixture after polymerization in the polyarylene sulfide production process is subjected to a process of separating the main reactant, polyarylene sulfide, by washing and filtering in a conventional manner, and waste liquid is generated in this process.
  • the washing and filtration process is a step of washing with one or more of amide-based compounds and water to remove impurities such as an oligomer generated after polymerization in a reaction product or an alkali metal halide such as sodium chloride (NaCl). to be.
  • the filter size used (for example, 300 um) has very low removal efficiency.
  • the filter size (for example, 75 um) has very low efficiency or clogging, and solids are only accumulated under the centrifuge. As a result, the continuous process is impossible as a one-time operation.
  • the present invention is characterized in that the separation and removal of inorganic salts from the waste liquid by using a decanter-type centrifugal separator that performs a specific horizontal rotation.
  • the step of removing the inorganic salt in the waste solution about 25% by weight or more or about 25 to 40% by weight of the inorganic salt may be removed based on the total weight of the waste solution.
  • the inorganic salt separated in the step of removing the inorganic salt in the waste solution may have a water content of 45% or less or 30 to 45% calculated by the following Equation 1.
  • Moisture content (%) [(Weight before drying of separated inorganic salt-weight after drying of separated inorganic salt)/ Weight before drying of separated inorganic salt] ⁇ 100
  • the present invention is a polyarylene sulfide after the polymerization reaction mixture of the polyarylene sulfide in a general method after the polymerization process of the polyarylene sulfide in the polymerization reactor (1) And it is possible to obtain a waste solution containing an inorganic salt. Then, the waste liquid (2) is supplied to the decanter-type centrifuge (3) through the separation process, inorganic salts such as NaCl can be removed through the stream (4).
  • the waste liquid from which the inorganic salt has been removed may be supplied to the storage tank 6 through the stream 5, and the waste liquid discharged from the storage tank may be supplied to the distillation column 8 through the stream 7.
  • This process can be performed continuously, unlike the batch process of a typical centrifuge. Therefore, by using the above method, it is not necessary to periodically remove inorganic salts including finely divided solid materials such as NaCl, and the efficiency of a filter or mesh used as a filtering means for the conventional inorganic salts when a certain operation is performed Falling shortcomings can be overcome.
  • the distillation column 8 may also overcome the clogging phenomenon due to inorganic salts such as finely divided NaCl or the limit of distillation efficiency.
  • the decanter-type centrifuge used in the present invention to remove the inorganic salt in the liquid, by using a centrifugal force, by creating a solid and liquid layer on the wall surface of the decanter-type centrifuge, it is possible to separate and remove the solid Device.
  • the decanter-type centrifugal separator may have a structure in which a cylindrical cylinder and a conical cylinder are combined to provide a horizontally installed bowl and a screw conveyor in which shafts and screws are coupled.
  • a pipe for supplying the waste liquid to be separated is provided inside the shaft, and can be connected to a device that performs a washing process.
  • the decanter-type centrifugal separator may be separately provided with an outlet for removing inorganic salts from the waste liquid and an outlet from which the inorganic salts have been removed.
  • the bowl and the screw conveyor rotate at different speeds, and the solid having a high specific gravity and a liquid having a small specific gravity can be separated by the action of the centrifugal force due to the speed difference. Therefore, when the decanter-type centrifugal separator is used, a solid substance (solid content) containing inorganic salt in the waste liquid may be sedimented and discharged through a separate outlet after being settled to the lower portion inside the bowl.
  • the liquid having a small specific gravity separated from the decanter-type centrifuge can be discharged through a separate line and transferred to a storage tank.
  • an amide compound and a small amount of polyarylene sulfide may be included, and then the amide compound can be separated and recovered through a distillation process.
  • the operating conditions of the decanter type centrifuge can be used by operating for 30 seconds to 5 minutes or 30 seconds to 2 minutes at 1500G to 3100G.
  • the speed is 1500 G or less, the separation speed becomes slower and the operation time becomes longer, and if it is 3100 G or more, even if the water content reaches a threshold value and increases the gravitational acceleration, the water content does not decrease.
  • G in the speed of the centrifuge may mean G-force, and may be used that is adjusted within the range according to the radius of the rotor of the decanter type centrifuge.
  • the step of removing the inorganic salt in the waste solution is preferably performed at room temperature and atmospheric pressure of 20 °C to 25 °C.
  • the present invention does not operate a decanter type centrifuge under high temperature and high pressure conditions by supplying a waste liquid to a general extraction column or a batch centrifugal separator, so that processability can be improved.
  • a decanter type centrifugal separator after the above-described waste liquid is introduced into a decanter type centrifugal separator, and performed under normal temperature and normal pressure, process equipment under high temperature and high pressure conditions is unnecessary.
  • the amide-based compound in the waste liquid is separated and recovered from the bottom of the distillation column in a series of distillation processes, and the recovered amide-based compound (10) is re-polymerized through the circulation pump (11) (1) And can be reused.
  • water 9 may be separated and discharged to the top of the distillation column.
  • the specific type of distillation column that can be used in the recovery process of the amide-based compound is not particularly limited.
  • a general compressor, reboiler, and condenser may be included in the distillation process.
  • the distillation column may include a column including an extraction region and a distillation region.
  • the manufacturing process of the polyarylene sulfide may be performed according to a method well known in the art, and after the polymerization of the polyarylene sulfide is completed, a washing process may be performed to collect waste liquid.
  • the fine liquid of the polyarylene sulfide is removed from the reaction mixture of the polyarylene sulfide production process through a pre-treatment process using a filtration means.
  • the filtration means may be performed according to methods well known in the art, and the method is not limited.
  • the present invention effectively separates amide compounds such as N-methyl-2-pyrrolidone from waste liquids containing various inorganic salts and impurities generated from a process for manufacturing polyarylene sulfide (PAS).
  • PAS polyarylene sulfide
  • the composition of the waste liquid introduced into the distillation column through the decanter-type centrifuge and the storage tank may include a composition in which inorganic salts and impurities, which are halides of alkali metals, are removed.
  • the impurity may include fine powders such as polyarylene sulfide.
  • the waste solution may further include at least one selected from the group consisting of a small amount of alkali metal hydrosulfide, alkali metal sulfide, dihalogenated aromatic compound, and polyarylene sulfide together with water and an amide compound.
  • the waste solution is o-dichlorobenzene (o-DCB), m-dichlorobenzene (m-DCB), p-dichlorobenzene (p-DCB), sodium hydrogen sulfide (NaSH), sulfide together with water and amide compounds It may also include one or more selected from the group consisting of sodium (Na 2 S), and polyphenylene sulfide (PPS).
  • the composition of the waste solution after washing in the polyarylene sulfide production process includes, as described above, an amide-based compound such as NMP from about 20% to about 70% by weight, or from about 30% to about 60% by weight
  • the composition of brine containing sodium chloride (NaCl) may include about 30% to about 80% by weight, or about 40% to about 70% by weight.
  • the waste solution may further include p-DCB, NaSH, Na 2 S and other impurities including dispersed PPS microparticles within about 10% by weight, or within about 5% by weight, based on the total weight of the solution medium. have.
  • impurities include 2-pyrrolidinone, 1-methyl-2,5-pyrrolidione (1-methyl-2,5-pyrrolidione) and 3-chloro-N-methylaniline (3-Chloro- N-Methylaniline) and the like, and may be one or more of them.
  • the composition of the waste liquid collected in the storage tank contains an amide-based compound such as NMP from about 15% to about 65% by weight, or from about 20% to about 60% by weight, of sodium chloride (NaCl)-free water.
  • the composition may be up to about 25% by weight or from about 20% to about 30% by weight.
  • the waste solution may further include p-DCB, NaSH, Na 2 S, and other impurities including dispersed PPS microparticles within about 5% by weight, or within about 3% by weight, based on the total weight of the solution medium. have.
  • amide compounds include amide compounds such as N,N-dimethylformamide or N,N-dimethylacetamide; Pyrrolidone compounds such as N-methyl-2-pyrrolidone (NMP) or N-cyclohexyl-2-pyrrolidone; Caprolactam compounds such as N-methyl- ⁇ -caprolactam; Imidazolidinone compounds such as 1,3-dialkyl-2-imidazolidinone; Urea compounds such as tetramethyl urea; Or a phosphoric acid amide compound, such as hexamethylphosphate triamide, etc. are mentioned, It can be one or more of these.
  • Pyrrolidone compounds such as N-methyl-2-pyrrolidone (NMP) or N-cyclohexyl-2-pyrrolidone
  • Caprolactam compounds such as N-methyl- ⁇ -caprolactam
  • Imidazolidinone compounds such as 1,3-dialkyl-2-imidazolidinone
  • Urea compounds such
  • the specific production method of the polyarylene sulfide and the specific separation and recovery method of the amide compound may refer to Examples described later.
  • the method for producing polyarylene sulfide or the method for separating and recovering an amide-based compound is not limited to the contents described herein, and the method for preparing and separating and recovering is generally employed in the technical field to which the present invention pertains.
  • the step(s) of the above-described manufacturing method and separation and recovery method may be changed by the step(s), which is usually changeable.
  • the present invention by removing the inorganic salt from the waste liquid generated in the polymerization process of polyarylene sulfide using a decanter centrifuge, clogging phenomenon caused by fine inorganic salts that may occur during the distillation process or It is possible to recover the high-purity amide-based compound by improving the performance of separation efficiency of the amide-based compound such as N-methyl-2-pyrrolidone from the waste liquid generated in the polyarylene sulfide production process by preventing a decrease in distillation efficiency.
  • FIG. 1 is a schematic view showing a process for recovering an amide-based compound from the waste solution generated in the polymerization process of polyarylene sulfide according to an embodiment of the present invention.
  • Figure 2 is a schematic diagram showing a conventional process for recovering an amide-based compound from the waste solution generated in the polymerization process of polyarylene sulfide according to Comparative Example 1.
  • Figure 3 is a schematic diagram showing a conventional process for recovering an amide-based compound from the waste solution generated in the polymerization process of polyarylene sulfide according to Comparative Example 2.
  • Sodium sulfide was prepared by mixing 1 equivalent of 70% sodium hydrogen sulfide (NaSH) and 1.05 equivalent of sodium hydroxide (NaOH) (ie 1:1.05 ratio) to make a PPS polymer. At this time, 0.4 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP), and 4.72 equivalents of deionized water (DI water) were added to the reactor. Here, equivalent weight means molar equivalent weight (eq/mol). At this time, the solid reagent was first added and then added in the order of NMP and deionized water. Then, the reactor was stirred at about 150 rpm, and dehydrated by heating to 190° C.
  • NaSH 70% sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • DI water deionized water
  • reaction mixture was heated to 230°C to react for 2 hours, heated to 255°C to react for 2 hours, and then 3 equivalents of distilled water was added and stirred for 5 minutes to obtain a reaction mixture containing PPS polymer.
  • the waste solution after washing contained NMP-containing aqueous medium, brine (NaCl aqueous solution), wherein the composition of NMP was 5 to 40% by weight and the composition of brine containing NaCl was 1 to 15% by weight, water 20 to 95% by weight was included.
  • the waste solution contains about 10 weights of other impurities including microparticles such as p-DCB, NaSH, Na 2 S, differential PPS, and 2-pyrrolidinone, relative to the total weight of the solvent of NMP and brine. %.
  • Sodium sulfide was prepared by mixing 1 equivalent of 70% sodium hydrogen sulfide (NaSH) and 1.05 equivalent of sodium hydroxide (NaOH) (ie 1:1.05 ratio) to make a PPS polymer. At this time, 0.4 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP), and 4.72 equivalents of deionized water (DI water) were added to the reactor. Here, equivalent weight means molar equivalent weight (eq/mol). At this time, the solid reagent was first added and then added in the order of NMP and deionized water. Then, the reactor was stirred at about 150 rpm, and dehydrated by heating to 190° C.
  • NaSH 70% sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • DI water deionized water
  • reaction mixture was heated to 230°C to react for 2 hours, heated to 255°C to react for 2 hours, and then 3 equivalents of distilled water was added and stirred for 10 minutes to obtain a reaction mixture containing PPS polymer.
  • p-DCB para-dichlorobenzene
  • NMP N-methyl-2-pyrrolidone
  • the waste solution after washing contained NMP-containing aqueous medium, brine (NaCl aqueous solution), wherein the composition of NMP was 5 to 40% by weight and the composition of brine containing NaCl was 1 to 15% by weight, water 20 to 95% by weight was included.
  • the waste solution contains about 10 weights of other impurities including microparticles such as p-DCB, NaSH, Na 2 S, differential PPS, and 2-pyrrolidinone, relative to the total weight of the solvent of NMP and brine. %.
  • the waste solution obtained from the washing process after the PPS polymerization of Preparation Example 1 is supplied to a decanter-type centrifuge (3) before collecting it into a storage tank for distillation, as shown in FIG. 1, and the waste solution containing solids such as NaCl and PPS is used as a waste solution. Removed from. This process was performed as a continuous process.
  • the liquid obtained from the decanter-type centrifuge contained 20% by weight of NMP and 80% by weight of water, and the mixed solution of this composition was collected into a storage tank (6), and then introduced into a distillation column through a stream (7), N
  • the separation and purification recovery process of -methyl-2-pyrrolidone (NMP) was performed. That is, at a flow rate of 700 kg/hr, stream 7 was introduced into the mixed liquid supply port located at the first stage of the distillation column having 15 theoretical stages to perform the NMP separation process. In the distillation process, the temperature at the top of the column was 134°C and the temperature at the bottom of the column was performed at 183°C.
  • the NMP recovered from the waste liquid was 99.9% by weight or more of pure (99.9%) NMP with respect to all components.
  • Example 2 When removing solids including fine powders such as NaCl and PPS, except that the operating time of the decanter centrifuge was changed from 120sec to 30sec, in the same manner as in Example 1, the waste solution obtained from the washing process after PPS polymerization was treated. , N-methyl-2-pyrrolidone was separated and recovered using the process of FIG. 1. The characteristics of each stream in Example 2 are also the same as in Example 1.
  • the NMP recovered from the waste liquid was 99.9% by weight or more of pure (99.9%) NMP with respect to all components.
  • the waste solution obtained from the washing process after the PPS polymerization of Preparation Example 1 is supplied to a decanter-type centrifugal separator (3) before being collected into a storage tank for distillation as shown in FIG. 1, and the solid solution containing fine powders such as NaCl and PPS is used as a waste solution. Removed from. This process was performed as a continuous process.
  • Moisture content (%) [(Weight before drying of separated inorganic salt-weight after drying of separated inorganic salt)/ Weight before drying of separated inorganic salt] ⁇ 100
  • the inorganic salt may contain a trace amount of finely divided PSS.
  • the total amount of NaCl and finely divided PPS separated in 50 ml of the waste liquid was 1 ml or less, and solids observable in the waste liquid were still present.
  • the waste solution obtained from the washing process after the PPS polymerization of Preparation Example 1 was removed by using a general centrifugal separator that proceeds in a batch operation before collecting it into a storage tank for distillation as shown in FIG. 3 to remove solids including fine powders such as NaCl and PPS. .
  • the reaction mixture obtained after the PPS polymerization was filtered and washed with NMP, and then 50 ml of the resulting waste liquid was collected in a conical tube, and treated at 4000 rpm (about 1500 G) at room temperature and pressure for 3 minutes with a centrifuge.
  • the total amount of NaCl and fine PPS separated in 50 ml of waste liquid was 11.3 ml, and the waste liquid was 38.7 ml.
  • solid matters accumulated in the centrifuge must be removed each time, continuous operation was impossible and processability was deteriorated.
  • the waste solution obtained from the washing process after the PPS polymerization of Preparation Example 2 was attempted to remove solids including fine powders such as NaCl and PPS using a general filter before collecting the waste solution obtained in the storage tank for distillation as shown in FIG. 2.
  • reaction mixture obtained after the PPS polymerization was filtered and washed with NMP, and then 50 ml of the resulting waste liquid was collected in a conical tube, and treated at a room temperature and a normal pressure in a batch centrifuge at 7000 rpm for 10 minutes.

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  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

La présente invention concerne un procédé destiné à la récupération de composés à base d'amide, selon lequel, des sels inorganiques sont éliminés à partir de déchets liquides à l'aide d'une centrifugeuse de type décanteur à température ambiante et à pression normale, avant une étape de distillation qui permet de séparer et de récupérer des composés à base d'amide à partir de déchets liquides comprenant des composés à base d'amide tels que N-méthyl-2-pyrrolidone générés dans un procédé de polymérisation de sulfure de polyarylène et de sels inorganiques, et faisant apparaitre un bouchage par fine poudre de PPS, qui peut être généré dans l'étape de distillation, et qui permet d'empêcher des sels inorganiques ou de perdre l'efficacité de distillation, et par conséquent, des composés à base d'amide tels que N-méthyl-2-pyrrolidone dans les déchets liquides sont récupérés de manière efficace.
PCT/KR2020/001208 2019-01-28 2020-01-23 Procédé de récupération de composés à base d'amide WO2020159167A1 (fr)

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KR10-2019-0010742 2019-01-28
KR1020190010742A KR102688627B1 (ko) 2019-01-28 2019-01-28 아미드계 화합물의 회수 방법

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JP2003275773A (ja) * 2002-03-22 2003-09-30 Dainippon Ink & Chem Inc ポリフェニレンスルフィドの排水処理方法
KR20050087860A (ko) * 2002-12-27 2005-08-31 구레하 가가쿠 고교 가부시키가이샤 폴리아릴렌술피드의 제조 방법 및 세정 방법, 및 세정에사용한 유기 용매의 정제 방법
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JPH0593068A (ja) * 1991-09-05 1993-04-16 Idemitsu Petrochem Co Ltd ポリアリーレンスルフイドオリゴマーの分離方法
JP2003275773A (ja) * 2002-03-22 2003-09-30 Dainippon Ink & Chem Inc ポリフェニレンスルフィドの排水処理方法
KR20050087860A (ko) * 2002-12-27 2005-08-31 구레하 가가쿠 고교 가부시키가이샤 폴리아릴렌술피드의 제조 방법 및 세정 방법, 및 세정에사용한 유기 용매의 정제 방법
JP2011111548A (ja) * 2009-11-27 2011-06-09 Toray Ind Inc アルカリ金属ハロゲン化物の連続回収方法
KR20130026454A (ko) * 2010-05-19 2013-03-13 가부시끼가이샤 구레하 폴리아릴렌술피드의 제조 방법 및 폴리아릴렌술피드

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