JP2800209B2 - Method for producing polyarylene sulfide - Google Patents
Method for producing polyarylene sulfideInfo
- Publication number
- JP2800209B2 JP2800209B2 JP63315553A JP31555388A JP2800209B2 JP 2800209 B2 JP2800209 B2 JP 2800209B2 JP 63315553 A JP63315553 A JP 63315553A JP 31555388 A JP31555388 A JP 31555388A JP 2800209 B2 JP2800209 B2 JP 2800209B2
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- Japan
- Prior art keywords
- sulfide
- dehydration
- alkali metal
- hydrogen sulfide
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
【発明の詳細な説明】 [産業上の利用分野] 本発明は、ポリアリーレンスルフイド製造工程での副
生硫化水素ガスを、回収すると同時に、製品ポリマの分
子量等の特性値を安定させるポリアリーレンスルフイド
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polymer for recovering hydrogen by-product gas in a polyarylene sulfide manufacturing process and, at the same time, stabilizing characteristic values such as the molecular weight of a product polymer. The present invention relates to a method for producing an arylene sulfide.
[従来の技術] ポリアリーレンスルフイドは、ハロゲン化芳香族(一
般的にはジハロゲン化物であるが、一部1または3以上
のハロゲン化物を添加することもある)とアルカリ金属
スルフイド等を、極性溶媒および少量の水の存在下、20
0〜300℃の高温高圧条件下で、重縮合反応を行なうこと
により製造される。[Prior Art] Polyarylene sulfide comprises a halogenated aromatic (generally a dihalide, but sometimes one or three or more halides may be added) and an alkali metal sulfide. 20 in the presence of polar solvents and small amounts of water
It is produced by performing a polycondensation reaction under high temperature and high pressure conditions of 0 to 300 ° C.
この重縮合反応の前段階として、アルカリ金属スルフ
イドおよび/または水硫化アルカリ金属の、水溶液およ
び/または結晶水を含む固体から水分を除去する脱水工
程が必要である。As a pre-stage of the polycondensation reaction, a dehydration step of removing water from an aqueous solution and / or a solid containing water of crystallization of alkali metal sulfide and / or alkali metal hydrosulfide is required.
この脱水工程は、一般的には、n−メチルピロリドン
等の極性溶媒の存在下で操作され、その溶媒とのコンプ
レツクスを生成する。This dehydration step is generally operated in the presence of a polar solvent such as n-methylpyrrolidone to produce a complex with that solvent.
従来技術のプロセスの一例を第2図に示す。 An example of a prior art process is shown in FIG.
この例は、S源として硫化ソーダ(Na2S)を、ハロゲ
ン化芳香族としてパラジクロルベンゼン(P−DCB)を
使用して、ポリフエニレンサルフアイド(PPS)を製造
する過程の脱水/重合工程を示したものであり、脱水〜
重合工程での極性溶媒としてn−メチルピロリドン(NM
P)を使用したものである。In this example, dehydration / polymerization in the process of producing polyphenylene sulfide (PPS) using sodium sulfide (Na 2 S) as the S source and paradichlorobenzene (P-DCB) as the halogenated aromatic. It shows the process, dehydration ~
N-Methylpyrrolidone (NM) as a polar solvent in the polymerization step
P).
は脱水/重合反応槽、は脱水精溜塔、はコンデ
ンサ、は溜出水受槽である。Denotes a dehydration / polymerization reaction tank, denotes a dehydration rectification tower, denotes a condenser, and denotes a distilled water receiving tank.
苛性ソーダは1から、硫化ソーダ5水塩は2から、NM
Pは3から、それぞれ厳密にバツチ的に計量されて反応
槽に供給された後、撹拌下で加熱されて水/NMPベーパ6
を発生する。水主成分の脱水精溜塔塔頂ベーパ8はコン
デンサで凝縮され、凝縮液9は還溜液10と溜出液11に分
配され、NMP分の多い脱水精溜塔缶出液7は、脱水反応
に還溜される。排ガス13は、排ガス処理工程に、廃液12
は排水処理工程に送られる。Caustic soda from 1, Sodium sulfide pentahydrate from 2, NM
P is strictly batched from 3 and supplied to the reaction tank, and then heated under stirring to obtain water / NMP vapor 6
Occurs. The top vapor 8 of the dewatering and rectification tower, which is mainly composed of water, is condensed by a condenser, and the condensate 9 is distributed to the retentate 10 and the distillate 11. Returned to the reaction. Exhaust gas 13 is used for waste liquid 12
Is sent to the wastewater treatment process.
脱水工程はバツチ的に操作され、脱水精溜塔内温度等
から、水分が実質的に無くなつたことを確認した後、コ
ンプレツクスは重合反応に使用される。The dehydration step is operated in a batchwise manner, and after confirming from the temperature in the dehydration rectification tower that water has substantially disappeared, the complex is used for the polymerization reaction.
[本発明が解決しようとする問題点] 上記脱水工程に於いては、脱水処理中に一部硫化水素
が飛散しロスする。この飛散現象は次の点で問題とな
る。[Problems to be Solved by the Present Invention] In the above-mentioned dehydration step, hydrogen sulfide is partially scattered during the dehydration treatment and is lost. This scattering phenomenon is problematic in the following points.
1) 有効S分のロス 2) 硫化水素ガスの発生による環境問題 3) 後続する重合工程に於ける有効S分/ハロゲン化
芳香族モル比、アルカリ金属過剰率等の変動要因とな
り、従つて製品ポリマの分子量等各種特性値の変動要因
となること 一般的に、ポリアリーレンスルフイド製造工程での原
料のモル比の精度は、0.2%以下の誤差とする必要のあ
る厳しいものである。1) Loss of effective S content 2) Environmental problems due to generation of hydrogen sulfide gas 3) Variable factors such as effective S content / halogenated aromatic molar ratio, alkali metal excess ratio, etc. in the subsequent polymerization step, and therefore products In general, the accuracy of the molar ratio of the raw materials in the polyarylene sulfide manufacturing process is strict and requires an error of 0.2% or less.
特に、生産速度の変更、原料特にS源原料のロツト切
替、品種切替等により脱水工程の初期組成、加熱速度等
の条件変更があつた後は、硫化水素副生量が変化し、従
つてより一層目標条件との誤差が大きくなることが、安
定操業上の問題であつた。In particular, after conditions such as the initial composition of the dehydration process and the heating rate are changed due to a change in the production rate, a change in the lot of the raw material, in particular, a change in the lot of the S source material, or a change in the type of the raw material, the amount of hydrogen sulfide by-product changes. An even larger error from the target condition was a problem in stable operation.
また、排ガス中の硫化水素は有害な物質であり、アル
カリ水溶液等で吸収した後、活性汚泥処理等で無害化す
る必要がある。In addition, hydrogen sulfide in exhaust gas is a harmful substance, and needs to be detoxified by activated sludge treatment or the like after absorption with an alkaline aqueous solution or the like.
[問題点を解決するための手段およびその作用] 本発明は、アルカリ金属スルフィドおよび/または水
硫化アルカリ金属の、水溶液および/または結晶水を含
む固体を極性溶媒の存在下、水分を除去する脱水工程
と、該脱水工程において得られたコンプレックスとハロ
ゲン化芳香族化合物を重合させる重合工程を有するポリ
アリーレンスルフィドの製造方法において、脱水工程中
に飛散する硫化水素ガスをアルカリ金属水酸化物の水溶
液に吸収させてアルカリ金属スルフィドおよび/または
水硫化アルカリ金属とし、脱水工程および/または重合
工程にリサイクルして再使用することにより、上記の問
題点全てを解決すると同時に、安価なポリアリーレンス
ルフイドの製造方法を提供するものである。[Means for Solving the Problems and Action Thereof] The present invention is directed to dehydration of an aqueous solution of an alkali metal sulfide and / or alkali metal hydrosulfide and / or a solid containing water of crystallization in the presence of a polar solvent to remove water. In the method for producing a polyarylene sulfide having a polymerization step of polymerizing the complex obtained in the dehydration step and the halogenated aromatic compound, hydrogen sulfide gas scattered during the dehydration step is converted into an aqueous solution of an alkali metal hydroxide. By absorbing and converting to alkali metal sulfide and / or alkali metal hydrosulfide and recycling and reusing it in the dehydration step and / or polymerization step, all of the above problems can be solved, and at the same time, inexpensive polyarylene sulfide can be obtained. It is intended to provide a manufacturing method.
本発明の一例を第1図を用いて説明する。 An example of the present invention will be described with reference to FIG.
機器〜、および、ライン1〜12は、前記第1図と
同じである。は、硫化水素吸収塔であり、厳密に濃度
および、量を測定され14から供給された苛性ソーダによ
つて、硫化水素を含むコンデンサ排ガス中から硫化水素
を吸収し水硫化ソーダとなし、次バツチの脱水工程にリ
サイクル使用する。排ガス16中の硫化水素は少なく、排
ガス処理工程の負荷を激減でき、有効S分の回収もでき
る。また、原料ロツト変更や、脱水条件の変更により、
硫化水素副生率が変化した場合、次バツチからはその誤
差が相殺され特性値が安定する。The equipment and the lines 1 to 12 are the same as those in FIG. Is a hydrogen sulfide absorption tower whose concentration and amount are strictly measured and absorbs hydrogen sulfide from the exhaust gas of the capacitor containing hydrogen sulfide by caustic soda supplied from 14 to form sodium hydrogen sulfide and form the next batch. Used for recycling in the dehydration process. Since the amount of hydrogen sulfide in the exhaust gas 16 is small, the load of the exhaust gas treatment step can be drastically reduced, and the effective S can be recovered. Also, by changing the material lot and the dehydration conditions,
When the hydrogen sulfide by-product rate changes, the error is offset from the next batch, and the characteristic value is stabilized.
硫化水素吸収塔の型式は、アルカリ金属水酸化物の水
溶液に対する硫化水素の吸収速度が速いため、循環ポン
プ付き充填塔型等一般的なもので良く、液張り込み/バ
ブリング型のものでも十分である。The type of the hydrogen sulfide absorption tower is a general type such as a packed tower type with a circulation pump because the absorption rate of hydrogen sulfide to the aqueous solution of the alkali metal hydroxide is high, and a liquid filling / bubbling type is sufficient. .
[実施例] 以下に従来技術のプロセスと本発明の改良点を具体的
に説明するために、前者を比較例1及び2、後者を実施
例1及び2として例示する。EXAMPLES In order to specifically explain the process of the prior art and the improvements of the present invention, the former is illustrated as Comparative Examples 1 and 2, and the latter as Examples 1 and 2.
比較例1 硫化ソーダ5水塩168.14Kg(Na2S 1Kgモル)、48%
苛性ソーダ水溶液1.67Kg(NaOH 0.02Kgモル)とn−メ
チルピロリドン、198.26Kg(2Kgモル)を、第1図に示
すプロセスに於ける撹拌機付き反応槽に供給した後、撹
拌しながら加熱し、発生するベーパは、理論段数5段の
精単塔で還流比1の条件下で処理した。コンデンサ排ガ
スは、10%苛性ソーダ水溶液、22Kg(HaOH 0.055Kgモ
ル)を、液深800mmで張込んだ硫化水素ガス吸収塔に導
入して吸収した。3時間後、精溜塔の塔頂温度が上昇
し、脱水処理が終了したことを確認した後、この吸収液
を分析したところ、初期に仕込んだ苛性ソーダの65モル
%が硫化ソーダとなつており、脱水反応仕込み硫化ソー
ダの1.8モル%が、硫化水素として飛散していることが
分つた。Comparative Example 1 Sodium sulfide pentahydrate 168.14 kg (Na 2 S 1 kg mol), 48%
1.67 kg (2 kg mol) of an aqueous sodium hydroxide solution and 198.26 kg (2 kg mol) of n-methylpyrrolidone and n-methylpyrrolidone were supplied to a reactor equipped with a stirrer in the process shown in FIG. The vapor to be treated was treated under the condition of a reflux ratio of 1 in a single column having 5 theoretical plates. The condenser exhaust gas was absorbed by introducing a 10% aqueous solution of caustic soda, 22 kg (HaOH 0.055 kg mol), into a hydrogen sulfide gas absorption tower filled with a liquid depth of 800 mm. Three hours later, after confirming that the top temperature of the rectifying tower had risen and the dehydration treatment had been completed, the absorption liquid was analyzed. As a result, 65 mol% of the initially charged caustic soda was sodium sulfide. It was found that 1.8 mol% of the sodium sulfide charged in the dehydration reaction was scattered as hydrogen sulfide.
反応槽に、n−エチルピロリドン128.87Kg(1.3Kgモ
ル)を追加供給した後、更にパラジクロルベンゼン147.
01Kg(1Kgモル)を供給して昇温し、260℃で5時間の反
応をした後、底部抜き出しラインを介して常圧下に吐出
した。After 128.87 kg (1.3 kg mol) of n-ethylpyrrolidone was additionally supplied to the reaction tank, 147.
After supplying 01 kg (1 kg mol) and raising the temperature and reacting at 260 ° C. for 5 hours, the mixture was discharged under normal pressure through a bottom extraction line.
得られた租ポリマのサンプルを、多量の水で洗浄し乾
燥した後に、ER(エクストル−ジヨンレート:温度315.
6℃、荷重345g、オリフイス0.0825吋径・1.25吋長)を
測定したところ30g/10分であつた。A sample of the resulting polymer was washed with a large amount of water and dried, and then the ER (extreme distillate rate: temperature 315.
When measured at 6 ° C., load 345 g, orifice 0.0825 inch diameter / 1.25 inch length), it was 30 g / 10 min.
比較例2 比較例1と同様の設備、手順、仕込み量でテストを行
なうに際し、脱水加熱速度を遅くして、6時間で脱水を
完結した。Comparative Example 2 In conducting a test using the same equipment, procedure, and charged amount as in Comparative Example 1, the dehydration heating rate was reduced, and the dehydration was completed in 6 hours.
この場合、硫化水素吸収液を分析したところ初期に仕
込んだ苛性ソーダの76モル%が硫化ソーダとなつてお
り、脱水槽仕込み硫化ソーダの2.1モル%が硫化水素と
して飛散していることが分つた。In this case, analysis of the hydrogen sulfide absorption liquid showed that 76 mol% of the initially charged caustic soda was sodium sulfide, and that 2.1 mol% of the sodium sulfide charged in the dehydration tank was scattered as hydrogen sulfide.
続いて、比較例1と同様の手順、仕込み量で重合テス
トを行なつた。この場合のポリマのERは、38g/10分であ
つた。Subsequently, a polymerization test was performed using the same procedure and charge as in Comparative Example 1. The ER of the polymer in this case was 38 g / 10 minutes.
実施例1 比較例1に続いて、比較例1で回収された硫化ソーダ
/苛性ソーダ水溶液を使用して、次のテストを実施し
た。Example 1 Following Comparative Example 1, the following test was carried out using the aqueous sodium sulfide / caustic soda solution recovered in Comparative Example 1.
硫化ソーダ5水塩、165.12Kg(0.982Kgモル)、比較
例1での回収硫化ソーダ/苛性ソーダ水溶液の全量(Na
OH 0.019Kgモル、Na2S 0.018Kgモル)と、n−メチル
ピロリドン、198.26Kg(2Kgモル)を、第1図に示すプ
ロセスに於ける撹拌機付き反応槽に供給した。以下の脱
水工程の手順、条件は、比較実施例1と同様とした。Sodium sulfide pentahydrate, 165.12 kg (0.982 kg mol), the total amount of the recovered sodium sulfide / caustic soda aqueous solution in Comparative Example 1 (Na
OH 0.019 Kg mole, Na 2 S 0.018 Kg mole) and 198.26 Kg (2 Kg mole) of n-methylpyrrolidone were supplied to the reactor equipped with a stirrer in the process shown in FIG. The procedure and conditions of the following dehydration step were the same as in Comparative Example 1.
脱水処理が終了後の硫化水素吸収液を分析したとこ
ろ、初期に仕込んだ苛性ソーダの67モル%が硫化ソーダ
となつており、脱水反応仕込み硫化ソーダの1.84モル%
が、硫化水素として飛散していることが分つた。An analysis of the hydrogen sulfide absorbing solution after the completion of the dehydration treatment revealed that 67 mol% of the initially charged caustic soda was sodium sulfide, and 1.84 mol% of the sodium sulfide charged in the dehydration reaction.
However, it was found that it was scattered as hydrogen sulfide.
反応槽に、n−メチルピロリドン128.87Kg(1.3Kgモ
ル)を追加供給した後、更に、パラジクロルベンゼン14
7.01Kg(1Kgモル)を供給した後昇温し、以下の重合工
程の手順、条件は比較例1と同様とした。After 128.87 kg (1.3 kg mol) of n-methylpyrrolidone was additionally supplied to the reaction tank, p-dichlorobenzene 14
After supplying 7.01 kg (1 kg mol), the temperature was raised, and the procedure and conditions of the following polymerization step were the same as in Comparative Example 1.
得られたポリマのERを測定したところ、29g/10分であ
つた。When the ER of the obtained polymer was measured, it was 29 g / 10 minutes.
実施例2 硫化ソーダ回収液を、実施例1での回収液の全量を使
用し、その他の脱水/重合条件は実施例1と同様として
繰り返しテストを実施した。Example 2 A test was repeatedly performed using the same amount of the sodium sulfide recovery liquid as in Example 1 except that the same amount of the recovery liquid as in Example 1 was used.
硫化ソーダ回収液での苛性ソーダ転化率は、66%、ポ
リマのERは、29g/10分であつた。The sodium hydroxide conversion in the sodium sulfide recovery liquid was 66%, and the ER of the polymer was 29 g / 10 minutes.
実施例3 比較例2に続き、硫化ソーダ回収液を、比較例2での
回収液の全量を使用、脱水速度は比較実施例2と同様と
し、その他の脱水/重合条件は実施例2と同様としてテ
ストを実施した。硫化ソーダ回収液での苛性ソーダ転化
率は、77%、ポリマのERは、30g/10分であつた。Example 3 Following Comparative Example 2, a sodium sulfide recovery liquid was used in the same amount as in Comparative Example 2, and the dehydration rate was the same as in Comparative Example 2, and the other dehydration / polymerization conditions were the same as in Example 2. The test was carried out. The caustic soda conversion in the sodium sulfide recovery liquid was 77%, and the ER of the polymer was 30 g / 10 minutes.
第1図は、本発明による改良プロセスの一例として第2
図に示した従来技術のプロセスに、本発明の硫化水素回
収リサイクル工程を付加したフローチヤートを示したも
のである。 第2図は、従来技術によるプロセスの一例として、硫化
ソーダ(Na2S)とパラジクロルベンゼン(DCB)とをn
−メチルピロリドン(NMP)溶媒下で反応させポリフエ
ニレンサルフアイド(PPS)を製造するフローチヤート
を示したものである。FIG. 1 shows a second example of an improved process according to the invention.
1 shows a flow chart in which the hydrogen sulfide recovery / recycling step of the present invention is added to the conventional process shown in the figure. FIG. 2 shows an example of a prior art process in which sodium sulfide (Na 2 S) and paradichlorobenzene (DCB)
1 shows a flow chart for producing polyphenylene sulfide (PPS) by reacting in a methylpyrrolidone (NMP) solvent.
Claims (1)
硫化アルカリ金属の、水溶液および/または結晶水を含
む固体を極性溶媒の存在下、水分を除去する脱水工程
と、該脱水工程において得られたコンプレックスとハロ
ゲン化芳香族化合物を重合させる重合工程を有するポリ
アリーレンスルフィドの製造方法において、脱水工程中
に飛散する硫化水素ガスをアルカリ金属水酸化物の水溶
液に吸収させてアルカリ金属スルフィドおよび/または
水硫化アルカリ金属とし、脱水工程および/または重合
工程にリサイクルして再使用することを特徴とするポリ
アリーレンスルフィドの製造方法。1. A dehydration step for removing a water content of an aqueous solution and / or water of crystallization of an alkali metal sulfide and / or an alkali metal hydrosulfide in the presence of a polar solvent, and a complex obtained in the dehydration step. In a method for producing a polyarylene sulfide having a polymerization step for polymerizing a halogenated aromatic compound, hydrogen sulfide gas scattered during a dehydration step is absorbed by an aqueous solution of an alkali metal hydroxide to form an alkali metal sulfide and / or an alkali hydrosulfide. A method for producing a polyarylene sulfide, which is used as a metal and is recycled and reused in a dehydration step and / or a polymerization step.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63315553A JP2800209B2 (en) | 1988-12-14 | 1988-12-14 | Method for producing polyarylene sulfide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63315553A JP2800209B2 (en) | 1988-12-14 | 1988-12-14 | Method for producing polyarylene sulfide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02160833A JPH02160833A (en) | 1990-06-20 |
JP2800209B2 true JP2800209B2 (en) | 1998-09-21 |
Family
ID=18066731
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JP63315553A Expired - Lifetime JP2800209B2 (en) | 1988-12-14 | 1988-12-14 | Method for producing polyarylene sulfide |
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Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5840830A (en) * | 1996-02-21 | 1998-11-24 | Kureha Kagaku Kogyo K.K. | Process for producing poly(arylene sulfide) |
ATE469186T1 (en) * | 2001-09-27 | 2010-06-15 | Kureha Corp | METHOD FOR PRODUCING POLYARYLENE SULFIDE |
AU2003292586A1 (en) | 2002-12-27 | 2004-07-29 | Kureha Chemical Industry Company, Limited | Process for producing and method of cleaning polyarylene sulfide, and method of purifying organic solvent used for cleaning |
DE60325896D1 (en) | 2002-12-27 | 2009-03-05 | Kureha Corp | METHOD FOR PRODUCING POLYARYLENEULFIDE |
JP2010083780A (en) * | 2008-09-30 | 2010-04-15 | Toray Ind Inc | Method for separatively recovering high-boiling component having boiling point of 200°c or higher, and manufacturing method of polyarylene sulfide |
JP6402971B2 (en) * | 2014-05-15 | 2018-10-10 | Dic株式会社 | Sulfiding agent and method for producing polyarylene sulfide resin |
JP6438180B1 (en) * | 2017-01-18 | 2018-12-12 | 株式会社クレハ | Method for producing polyarylene sulfide and apparatus for producing polyarylene sulfide |
CN114008111B (en) * | 2019-07-09 | 2022-07-26 | 株式会社吴羽 | Method for producing polyarylene sulfide, method for dehydration treatment, and apparatus for producing polyarylene sulfide |
JP7331661B2 (en) * | 2019-11-27 | 2023-08-23 | Dic株式会社 | Method for producing sulfidating agent and polyarylene sulfide resin |
CN111167146A (en) * | 2019-12-26 | 2020-05-19 | 重庆市中润化学有限公司 | NMP waste liquid is retrieved with dehydration tower |
JP7413820B2 (en) * | 2020-02-17 | 2024-01-16 | Dic株式会社 | Sulfidating agent and method for producing polyarylene sulfide resin |
CN114621441B (en) * | 2022-04-27 | 2024-01-30 | 浙江新和成特种材料有限公司 | Recyclable hydrogen sulfide waste gas Process for preparing recycled polyphenylene sulfide |
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1988
- 1988-12-14 JP JP63315553A patent/JP2800209B2/en not_active Expired - Lifetime
Also Published As
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JPH02160833A (en) | 1990-06-20 |
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