JPH03181423A - Method for separating solvent - Google Patents
Method for separating solventInfo
- Publication number
- JPH03181423A JPH03181423A JP31873789A JP31873789A JPH03181423A JP H03181423 A JPH03181423 A JP H03181423A JP 31873789 A JP31873789 A JP 31873789A JP 31873789 A JP31873789 A JP 31873789A JP H03181423 A JPH03181423 A JP H03181423A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- methanol
- phase
- water
- separation
- 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.)
- Pending
Links
- 239000002904 solvent Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 183
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 57
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008096 xylene Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 22
- 238000005191 phase separation Methods 0.000 abstract description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- -1 xylene Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ポリフェニレンエーテル製造工程で回収した
ベンゼン、トルエン、キシレン、メタノール、水等とを
含む溶媒からベンゼン、トルエン、キシレン等の芳香族
炭化水素及びメタノールを効率よく分離する方法に関し
、さらに詳しく！＋ 晶萱コ＃天仕皐ｌレル専小士ロレ
Ｊ ）ｙ ） −＋１ＮＩＣ東の相との分離速度が優れ
た分離方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention is a process for aromatic carbonization of benzene, toluene, xylene, etc. from a solvent containing benzene, toluene, xylene, methanol, water, etc. recovered in the polyphenylene ether manufacturing process. Learn more about how to efficiently separate hydrogen and methanol! + Akira Kayako #AmeshikolrerusenkojiroreJ)y) -+1Regarding a separation method with excellent separation speed from the NIC East phase.
（従来の技術及び発明が解決しようとする課題）−船釣
に、ポリフェニレンエーテルは、例えば、次式
（式中、Ｒｌ、、、 Ｒ＠は、それぞれ水素原子、ハロ
ゲン原子、アルキル基、シアノ基または置換らしくは非
置換のハイドロカルボッキシ基を表し、そのうち少なく
と６−つは水素原子であり、かつ少なくとも一つは水素
原子以外のものである）で示されるフェノール類を、ベ
ンゼン、トルエン、キシレン等の芳香族炭化水素中で、
あるいは芳香族炭化水素とメタノールとの混合溶媒中で
、銅またはマンガンを含有する錯体触媒の存在下に酸素
または酸素含有気体を接触させて重合する方法が採用さ
れている。(Prior art and problems to be solved by the invention) - For boat fishing, polyphenylene ether has, for example, the following formula (where Rl, ..., R@ are a hydrogen atom, a halogen atom, an alkyl group, a cyano group, respectively) or a substituted or unsubstituted hydrocarboxy group, of which at least 6 are hydrogen atoms and at least one is other than hydrogen atom), benzene, toluene, etc. , in aromatic hydrocarbons such as xylene,
Alternatively, a method has been adopted in which polymerization is carried out by contacting oxygen or an oxygen-containing gas in the presence of a complex catalyst containing copper or manganese in a mixed solvent of aromatic hydrocarbon and methanol.
主か、７のポＩＪフ、ニレンエー子ＩＩ／ Ｌ寸−１ｔ
／！！−巧応液に触媒、副生物等の不純物とともに含ま
れているために、例えばメタノールをこの重合反応液に
加えてポリフェニレンエーテルを析出させたのちに固液
分離し、これをメタノールで洗浄してから、さらに重亜
硫酸ソーダ、ビロリン酸ソーダ等の水溶液で処理して水
分散スラリーとし、次いで固液分離することにより該不
純物を除去して得られる。Lord, 7 Po IJ Fu, Niren Aiko II/L dimension -1t
/! ! - Since the polymerization reaction solution contains impurities such as catalysts and by-products, for example, methanol is added to this polymerization reaction solution to precipitate polyphenylene ether, followed by solid-liquid separation, and this is washed with methanol. It is obtained by further treating with an aqueous solution of sodium bisulfite, sodium birophosphate, etc. to obtain an aqueous dispersion slurry, and then performing solid-liquid separation to remove the impurities.
ところで、このような不純物除去行程で不純物ととちに
除去された、主にベンゼン、トルエン、キシレン、メタ
ノール、水等からなる溶媒は回収し、この溶媒のうちベ
ンゼン、トルエン、キシレン、メタノール等は、各成分
にそれぞれ分離して再利用される。By the way, the impurities and solvents that were removed in this impurity removal process, mainly consisting of benzene, toluene, xylene, methanol, water, etc., are recovered, and among these solvents, benzene, toluene, xylene, methanol, etc. , each component is separated and reused.
これらの分離方法としては１回収した溶媒を静置または
遠心分離して、ベンゼン、トルエン、キシレン等を含有
する芳香族炭化水素の相とメタノール及び水の相とに分
離したのちに、その各相別に精留する方法が知られてい
る。These separation methods include: 1. Standing or centrifuging the recovered solvent to separate it into an aromatic hydrocarbon phase containing benzene, toluene, xylene, etc. and a methanol and water phase; Separate rectification methods are known.
しかしながら、ポリフェニレンエーテルの製造工程で回
収した溶媒には、前記成分のほか、溶媒の乳化を促す低
分子量体等を含むため、相分離に長時間を要したり、ま
た遠心分離すると乳化がさらに進むという欠点があり、
その結果、大規模の分離装置の使用を余儀なくされたり
、また処理能力の低下を強いられるという不都合があっ
た。However, in addition to the above-mentioned components, the solvent recovered in the polyphenylene ether manufacturing process contains low molecular weight substances that promote emulsification of the solvent, so phase separation takes a long time, and emulsification progresses further when centrifuged. There is a drawback that
As a result, there are disadvantages in that it is necessary to use a large-scale separation device and that the processing capacity is forced to be reduced.
また、従来、回収した溶媒の相分離を促進させるために
、特定の第４級アンモニウム塩を添加する方法（特開昭
６１−９５０２４号公報参照）や塩化カルシウム等の無
機塩類または硫酸等の酸類を添加する方法が知られては
いるが、これらの方法は、ランニングコストが高くなっ
たり、相中に固形分が析出し、精留装置に付した際にカ
ラム等を閉塞するという欠点があった。Conventionally, in order to promote phase separation of the recovered solvent, methods of adding specific quaternary ammonium salts (see Japanese Patent Application Laid-Open No. 61-95024), inorganic salts such as calcium chloride, or acids such as sulfuric acid have been proposed. However, these methods have the drawbacks of high running costs and the precipitation of solids in the phase, which can clog the column etc. when it is applied to a rectifier. Ta.
本発明の目的は、芳香族炭化水素の相とメタノール及び
水の相との分離が極めて良好であり、また極めて安価に
溶媒を分離することができる方法を提供することにある
。An object of the present invention is to provide a method that allows very good separation of the aromatic hydrocarbon phase from the methanol and water phases, and also allows the solvent to be separated at an extremely low cost.
（課題を解決するための手段）
本発明者は、ポリフェニレンエーテル製造工程で回収し
た溶媒中の水に対するメタノールの比を特定の範囲にす
ることで、溶媒の芳香族炭化水素の相とメタノール及び
水の相との分離速度が著しく向上することを見出し本発
明に到達した。(Means for Solving the Problems) The present inventor has realized that by adjusting the ratio of methanol to water in the solvent recovered in the polyphenylene ether manufacturing process to a specific range, the aromatic hydrocarbon phase of the solvent and the methanol and water The present invention has been achieved by discovering that the rate of separation from the phase is significantly improved.
すなわち、本発明は、ポリフェニレンエーテル製造工程
で回収したベンゼン、トルエン及び／またはキシレンと
メタノールと水とを含む溶媒から該ベンゼン、トルエン
及び／またはキシレンを相分離する方法において、該溶
媒中の水に対するメタノールの比を５５〜７８重量％に
なるようにして相分離することを特徴とするベンゼン、
トルエン及び／またはキシレン並びにメタノールを分離
する方法である。That is, the present invention provides a method for phase-separating benzene, toluene, and/or xylene recovered from a polyphenylene ether production process from a solvent containing methanol and water. Benzene, characterized in that the phase separation is carried out by adjusting the ratio of methanol to 55 to 78% by weight,
This is a method for separating toluene and/or xylene and methanol.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の分離方法で分離する溶媒は、ポリフェニレンエ
ーテル製造工程で回収した溶媒である。The solvent to be separated by the separation method of the present invention is the solvent recovered in the polyphenylene ether production process.
かかる溶媒としては、例えば
■フェノール類を重合させる工程で、該フェノール類及
び銅またはマンガンを含有する錯体触媒とン ｔ、ｌご
田し）屯ｈトペ１ノνソ−１−１），エリ乃ｒメ／キ
かはキシレン：またはこれと（これらと）メタノールと
の混合溶媒、
■重合反応終了後に、反応溶液中に生成したポリフェニ
レンエーテルを析出させるために用いたメタノール、
■析出したポリフェニレンエーテルを分別し、それを洗
浄するために用いたメタノール、■洗浄したポリフェニ
レンエーテルを、重亜硫酸ソーダ、ハイドロサルファイ
ド等の含イオウ還元剤及び／またはエチレンジアミンテ
トラ酢酸・ナトリウム塩、ビロリン酸ナトリウム等のキ
レート剤の水溶液中で処理したのちに、処理液中に残存
する有機溶媒をスチームストリッピング法等で留去して
得られたポリフェニレンエーテルの水分散スラリーから
分離した溶媒、
■水分散スラリーから分離したポリフェニレンエーテル
を乾燥する工程で気化した溶媒を回収したもの及び■に
記載の留去した有機溶媒を回収したちのを挙げることが
できる。Such a solvent may be used, for example, in the step of polymerizing phenols, using a complex catalyst containing the phenols and copper or manganese. no rme/ki
xylene: or a mixed solvent of this and methanol; ■ methanol used to precipitate the polyphenylene ether produced in the reaction solution after the polymerization reaction; ■ separate the precipitated polyphenylene ether, and The washed polyphenylene ether is treated in an aqueous solution of a sulfur-containing reducing agent such as sodium bisulfite and hydrosulfide and/or a chelating agent such as ethylenediaminetetraacetic acid sodium salt and sodium birophosphate. After that, the organic solvent remaining in the treatment liquid is distilled off by a steam stripping method or the like, and the solvent is separated from the aqueous slurry of polyphenylene ether obtained. ■ A step of drying the polyphenylene ether separated from the aqueous dispersion slurry. Examples include those in which the vaporized solvent was recovered and the organic solvent distilled off as described in (1) was recovered.
ｔｒお 古せ言−〇）−ごれ乃ｒＦＣれｎ）先１かｔ
出ｊ壬 し ム し°ｒ→■に記載の分別及び洗浄工程
で、触媒、副生物等の不純物とともに回収され（以下、
ここで回収された溶媒を溶媒Ａという）、またの、■及
び■の溶媒の残部は、■に記載の水分散スラリーから分
離した溶媒（以下、溶媒Ｂという）及び■の溶媒（以下
、溶媒Ｃという）としてそれぞれ回収される。tr Old words-〇)-Goreno rFCrenn) 1 or t
During the separation and cleaning process described in section 3.3, it is recovered together with impurities such as catalysts and by-products (hereinafter referred to as
The solvent recovered here is referred to as solvent A), and the remainder of the solvent in ■ and ■ is the solvent separated from the aqueous dispersion slurry described in C).
本発明は、このようにして回収した溶媒中の水に対する
メタノールの比を水とメタノールの合計量に対してメタ
ノールが、５５〜７８重量％、好ましくは５８〜７５重
量％になるようにする。In the present invention, the ratio of methanol to water in the solvent thus recovered is such that methanol is 55 to 78% by weight, preferably 58 to 75% by weight, based on the total amount of water and methanol.
なお、メタノールの比が、５５重量％未滴の場合には、
ベンゼン、トルエン及び／またはキシレンの相と水及び
メタノールの相との分離速度が低下し、例えば相分離に
塔式分離装置を用いる場合には、塔径の大きな分離装置
が必要となるか、または処理能力が極端に低下し、また
遠心分離装置を用いる場合には、溶媒が乳化し、分離効
率が低下する。In addition, when the ratio of methanol is 55% by weight,
The rate of separation between the benzene, toluene and/or xylene phase and the water and methanol phase is reduced, for example, when a column separation device is used for phase separation, a separation device with a large column diameter is required, or Processing capacity is extremely reduced, and when a centrifugal separator is used, the solvent is emulsified and separation efficiency is reduced.
メタノールの比が、７８重量％を超える場合には、ベン
ゼン、トルエン及び／またはキシレンの相と水及びメタ
ノールの相との比重が同一になるかまたは逆転し、相分
離しないかまたは分離速度が著しく低下する。When the ratio of methanol exceeds 78% by weight, the specific gravity of the benzene, toluene and/or xylene phase and the water and methanol phase becomes the same or reverses, and the phase separation does not occur or the separation rate is significantly reduced. descend.
メタノールの比を前記範囲に設定する方法としては、特
に制限はなく、例えば溶媒Ａ、溶媒Ｂ及び溶媒Ｃのうち
のいずれかを組み合わせて混合し、これに水またはメタ
ノールを加えてメタノール濃度を調整してもよいし、ま
た溶媒Ａと溶媒Ｂのみを混合してメタノール濃度を調整
してちよい。There are no particular limitations on the method for setting the ratio of methanol within the above range; for example, any one of solvent A, solvent B, and solvent C may be combined and mixed, and water or methanol is added to this to adjust the methanol concentration. Alternatively, only solvent A and solvent B may be mixed to adjust the methanol concentration.
なお、溶媒Ａと溶媒Ｂのみを用いてメタノール濃度を調
整する場合、調整に用いなかった余分の溶媒Ｂは、後述
する相分離で得られたメタノール及び水の相と合せて精
留することもできる。In addition, when adjusting the methanol concentration using only solvent A and solvent B, the excess solvent B not used for adjustment may be rectified by combining it with the methanol and water phases obtained by phase separation described below. can.
また、溶媒Ｃには、前記不純物をほとんど含まないので
、本発明によらないで、公知の方法で各成分に分離する
こともできる。Moreover, since the solvent C contains almost no impurities, it can be separated into each component by a known method without relying on the present invention.
本発明は、このようにメタノールの比を調整した溶媒を
、公知の分離装置、例えば塔式分離装置、遠心分離装置
等に付してベンゼン、トルエン及び／またはキシレンの
相と水及びメタノールの相とに分離する。In the present invention, the solvent with the methanol ratio adjusted in this manner is subjected to a known separation device, such as a column separation device, a centrifugal separator, etc., to separate a benzene, toluene and/or xylene phase and a water and methanol phase. Separate into two parts.
分離した各相は、例えば精留塔にそれぞれ付して、ベン
ゼン、トルエン及び／またはキシレンの相からは、ベン
ゼン、トルエン及び／またはキシレンの混合溶媒として
分離するかまたは各成分ごとに分離し、水及びメタノー
ルの相からはメタノールを分離して再利用する。The separated phases are each subjected to a rectification column, for example, and the benzene, toluene and/or xylene phase is separated as a mixed solvent of benzene, toluene and/or xylene, or each component is separated, Methanol is separated from the water and methanol phases and recycled.
（実施例）
実施例１
［ポリフェニレンエーテルの合成工程及び溶媒の回収工
程］
撹拌機、温度計、コンデンサー及び空気導入管を備えた
容量１０βのジャケット付きオートクレーブに、キシレ
ン３５７０ｇ、メタノール１２２０ｇ、２．６−シメチ
ルフエノール１２２２ｇ （１０モル）及び水酸化ナト
リウム２４ｇ （０，６モル）を仕込んで均一な溶液と
な（０，３６モル）、ジブチルアミン１５．５ｇ（０，
１２モル）及び塩化マンガン四水和物０．８９ｇ （０
，００４５ｇ）をメタノール１００ｇに溶解した溶液を
加えた。次いでこれを激しく撹拌しながら、温度３５°
Ｃ１圧力は８ｋ ｇ ／ ｃ ｍ ”のもとに、空気を
流量ｌβ７分で１２時間吹き込んで反応させた。(Example) Example 1 [Polyphenylene ether synthesis process and solvent recovery process] 3570 g of xylene, 1220 g of methanol, and 2.6 g of methanol were placed in a jacketed autoclave with a capacity of 10β equipped with a stirrer, thermometer, condenser, and air introduction tube. 1222 g (10 mol) of -dimethylphenol and 24 g (0.6 mol) of sodium hydroxide were charged to form a homogeneous solution (0.36 mol), and 15.5 g (0,3 mol) of dibutylamine were charged.
12 mol) and manganese chloride tetrahydrate 0.89 g (0
, 0045 g) dissolved in 100 g of methanol was added. Then, while stirring vigorously, the temperature was raised to 35°.
The C1 pressure was 8 kg/cm'', and the reaction was carried out by blowing air at a flow rate of lβ for 7 minutes for 12 hours.
次に、この反応液をメタノール２２５０ｇに投入し、ポ
リフェニレンエーテルを析出させたのち、真空濾過機で
ポリフェニレンエーテルを分別した。Next, this reaction solution was poured into 2250 g of methanol to precipitate polyphenylene ether, and then the polyphenylene ether was separated using a vacuum filter.
得られたポリフェニレンエーテルは、さらにメタノール
２４００ｇで洗浄した。The obtained polyphenylene ether was further washed with 2400 g of methanol.
洗浄後のメタノールは回収して、先に分別した７戸液と
合せ、溶媒Ａとした。The methanol after washing was collected and combined with the previously separated Shichinohe liquid to form Solvent A.
洗浄したポリフェニレンエーテルは、撹拌機、温度計、
コンデンサー及び空気導入管を備えた容！ｌＯ℃のジャ
ケット付きオートクレーブに、ビロリン酸ナトリウム１
４ｇ及び重亜硫酸ソーダ入し、７０°Ｃで１時間処理し
たのちに、これにスチームを流量３００ｇ／時間で８時
間吹き込み、有機溶媒を留去して、ポリフェニレンエー
テルの水分散スラリーを得た。Washed polyphenylene ether is heated using a stirrer, thermometer,
Container with condenser and air inlet pipe! Sodium birophosphate in a jacketed autoclave at 10°C.
After treating the mixture at 70°C for 1 hour, steam was blown into the mixture at a flow rate of 300 g/hour for 8 hours, and the organic solvent was distilled off to obtain an aqueous dispersion slurry of polyphenylene ether.
なお、留去した有機溶媒は凝縮させて回収した。Note that the organic solvent that was distilled off was condensed and recovered.
次にポリフェニレンエーテルの水分散スラリーをバスケ
ット型遠心分離機で固液分離した。Next, the water-dispersed slurry of polyphenylene ether was subjected to solid-liquid separation using a basket centrifuge.
分離液は１回収して溶媒Ｂとした。One separated liquid was collected and used as solvent B.
分離したポリフェニレンエーテルは、真空乾燥機にて、
１５０’Ｃで１２時間乾燥した。The separated polyphenylene ether is dried in a vacuum dryer.
It was dried at 150'C for 12 hours.
この乾燥工程で気化したちのは、凝縮させて回収し、先
に凝縮して回収した有機溶媒と合せて溶媒Ｃとした。What was vaporized in this drying process was condensed and recovered, and combined with the organic solvent that had been condensed and recovered earlier to obtain Solvent C.
回収した溶媒Ａ、Ｂ及びＣの成分を第１表に示す。The components of recovered solvents A, B and C are shown in Table 1.
なお、得られたポリフェニレンエーテルは、１）４０ｇ
で着色もほとんどなく、極限粘度０．５１の良質なポリ
フェニレンエーテルであつた。In addition, the obtained polyphenylene ether is 1) 40g
It was a high quality polyphenylene ether with almost no coloring and an intrinsic viscosity of 0.51.
第１表
第１表中のその他は、溶媒を分取し、１５０’ｃで５時
間乾燥して得られた蒸発残渣の重量から換算した。Other values in Table 1 were calculated from the weight of the evaporation residue obtained by separating the solvent and drying it at 150'C for 5 hours.
〔相分離工程１
溶媒Ａの全量（８０６５ｇ）と溶媒Ｃの全量（２５７０
ｇ）と２１７２ｇの溶媒Ｂとを混合して、水に対するメ
タノール比を６５重量％に調整した６
次に、塔頂にオーバーフロー管、塔下端に排出管及び塔
中央部近傍にフィード管を備えた塔形分離装置（内径：
５ｃｍ、高さ：３０ｃｍ）を用いてメタノール濃度を調
整した溶媒を相分離した。[Phase separation step 1 Total amount of solvent A (8065 g) and total amount of solvent C (2570 g)
g) and 2172 g of solvent B were mixed to adjust the methanol to water ratio to 65% by weight.6 Next, an overflow pipe was provided at the top of the column, a discharge pipe was provided at the bottom end of the column, and a feed pipe was provided near the center of the column. Tower type separator (inner diameter:
5 cm, height: 30 cm) to phase-separate the solvent in which the methanol concentration was adjusted.
なお、相分離は、溶媒を塔形分離装置のオーバーフロー
管まで満たして、予めキシレン相と水及びメタノールの
相の２相を形成させてから、溶媒を連続的にフィード管
から導入した。溶媒の導入流量は、８Ｉ２／時間、導入
時間は、１．５時間であった。In the phase separation, the column separator was filled up to the overflow pipe with the solvent to form two phases, a xylene phase and a water and methanol phase, and then the solvent was continuously introduced from the feed pipe. The introduction flow rate of the solvent was 8 I2/hour, and the introduction time was 1.5 hours.
その結果、塔内で２相の界面は移動することもなく、オ
ーバーフロー管からキシレン相を５排出管から水及びメ
タノール相をそれぞれ連続的に分離することができた。As a result, the interface between the two phases did not move within the column, and it was possible to continuously separate the xylene phase from the overflow pipe and the water and methanol phases from the five discharge pipes.
比較例１
塔弐分離装置に導入する溶媒のメタノール比を、溶媒Ａ
の全Ｊｌ （８０６５ｇ）と溶媒Ｃの全量（２５７０ｇ
）と溶媒Ｂの全量（６３８０ｇ）とを混合して、４４．
６重量％に調整したほかは、実施例１と同様に相分離し
た。Comparative Example 1 The methanol ratio of the solvent introduced into the column separation device was changed to
total Jl (8065g) and total amount of solvent C (2570g
) and the total amount of solvent B (6380 g), and 44.
Phase separation was carried out in the same manner as in Example 1, except that the amount was adjusted to 6% by weight.
相の界面は塔内を上昇し、水及びメタノールの相がオー
バーフロー管から流出して運転の中止を余儀なくされた
。The phase interface rose in the column and the water and methanol phases exited the overflow tube, forcing the operation to be shut down.
実施例２〜４及び比較例２〜４
４００ｇの溶媒Ａに溶媒Ｂの量を第２表に示すように変
化させて混合し、メタノール比の異なる溶媒を６種類調
製した。Examples 2 to 4 and Comparative Examples 2 to 4 400 g of solvent A was mixed with varying amounts of solvent B as shown in Table 2 to prepare six types of solvents with different methanol ratios.
それぞれの溶媒中の水に対するメタノール比を第２表に
示す。The methanol to water ratio in each solvent is shown in Table 2.
次に、各溶媒をそれぞれｉｆｆの撹拌機付きガラス製シ
リンダーに投入して８００ ｒ ｐｍ、で１５分間撹拌
した後静置し、有機溶媒相と水・アルコール相の界面の
移動速度を測定し、相分離速度とした。Next, each solvent was put into a glass cylinder equipped with an IF stirrer, stirred at 800 rpm for 15 minutes, and left to stand, and the movement speed at the interface between the organic solvent phase and the water/alcohol phase was measured. It was taken as the phase separation rate.
結果を第２表に示す。The results are shown in Table 2.
第２表
実施例２ ４００ １９０ ５７ ２３００
実施例３ ４００ １３５ ６５ ３２００
実施例４４００ ８４ ７５ ２５００比
較例２４００ ４６９ ３５ ３０比較例
３ ４００ ２３３ ５２ １０００比較例
４４００ ６３ ８０ ＊第２表中、
＊は、界面が明確に現れず、相分離速度が測定不能であ
ったことを示す。Table 2 Example 2 400 190 57 2300
Example 3 400 135 65 3200
Example 4400 84 75 2500 Comparative example 2400 469 35 30 Comparative example 3 400 233 52 1000 Comparative example 4400 63 80 *In Table 2,
* indicates that the interface did not clearly appear and the phase separation rate could not be measured.
実施例５
４００ｇの溶媒Ａに２３３ｇの溶媒Ｂを混合し、さらに
メタノールを１９３ｇ追加してメタノール比を６５％に
調整し、実施例２と同様にして相分離速度を測定した。Example 5 400 g of solvent A was mixed with 233 g of solvent B, and 193 g of methanol was further added to adjust the methanol ratio to 65%, and the phase separation rate was measured in the same manner as in Example 2.
相分離速度は、３２００ｍｍ／ｈｒ、であった。The phase separation rate was 3200 mm/hr.
実施例６
実施例３と同様に調製した溶媒（メタノール比；６５重
量％）をホモジナイザーを用いて、１００００回転で１
０分間混合したのちに、小型卓上遠心分離器［日立製作
所■製］を用いて、１５００Ｇで１分間遠心分離した。Example 6 A solvent prepared in the same manner as in Example 3 (methanol ratio: 65% by weight) was heated at 10,000 rpm using a homogenizer.
After mixing for 0 minutes, centrifugation was performed at 1500G for 1 minute using a small desktop centrifuge [manufactured by Hitachi, Ltd.].
その結果、キシレン相と水及びメタノールの相との界面
は明確に現れており、分離は良好であった。As a result, the interface between the xylene phase and the water and methanol phases was clearly visible, and the separation was good.
比較例５
比較例３と同様に調製した溶媒（メタノール比：５２重
量％）にしたほかは、実施例５と同様に遠心分離した。Comparative Example 5 Centrifugation was performed in the same manner as in Example 5, except that a solvent prepared in the same manner as in Comparative Example 3 (methanol ratio: 52% by weight) was used.
その結果、溶媒は乳化状態を呈しており、キシレン相は
ほとんど現れず、分離は行われなかった。As a result, the solvent was in an emulsified state, almost no xylene phase appeared, and no separation was performed.
（発明の効果） 本発明によると次のような効果を奏することができる。(Effect of the invention) According to the present invention, the following effects can be achieved.
（１）ポリフェニレンエーテル製造工程で回収したベン
ゼン、トルエン及び／またはキシレンとメタノールと水
とを含む溶媒からベンゼン、トルエン及び／またはキシ
レンの相と水及びメタノールの相とを効率よく、かつ安
価に相分離することができる。(1) A phase of benzene, toluene and/or xylene and a phase of water and methanol are efficiently and inexpensively mixed from a solvent containing benzene, toluene and/or xylene, methanol and water recovered in the polyphenylene ether manufacturing process. Can be separated.
（２）相分離の効率がよいので、各相を分離するときに
大規模な装置を用いる必要がない。(2) Since phase separation is efficient, there is no need to use large-scale equipment to separate each phase.
（３）分離した相に固形分を析出しないので、装置の例
えばカラム等を閉塞するおそれがない。(3) Since no solid content is precipitated in the separated phase, there is no risk of clogging the equipment, such as a column.
Claims (1)
ゼン、トルエン及び／またはキシレンとメタノールと水
とを含む溶媒から該ベンゼン、トルエン及び／またはキ
シレンを相分離する方法において、該溶媒中の水に対す
るメタノールの比を５５〜７８重量％になるようにして
相分離することを特徴とするベンゼン、トルエン及び／
またはキシレン並びにメタノールを分離する方法。(1) A method for phase-separating benzene, toluene and/or xylene from a solvent containing methanol and water collected in a polyphenylene ether production process, in which the ratio of methanol to water in the solvent is Benzene, toluene and/or
Or a method to separate xylene and methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31873789A JPH03181423A (en) | 1989-12-11 | 1989-12-11 | Method for separating solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31873789A JPH03181423A (en) | 1989-12-11 | 1989-12-11 | Method for separating solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03181423A true JPH03181423A (en) | 1991-08-07 |
Family
ID=18102387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31873789A Pending JPH03181423A (en) | 1989-12-11 | 1989-12-11 | Method for separating solvent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03181423A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001083587A1 (en) * | 2000-04-28 | 2001-11-08 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyphenylene ether |
| JP2001335631A (en) * | 2000-05-26 | 2001-12-04 | Mitsubishi Gas Chem Co Inc | Production method of polyphenylene ether |
| JP2001348426A (en) * | 2000-06-09 | 2001-12-18 | Mitsubishi Gas Chem Co Inc | Method for producing polyphenylene ether |
| JP2002003594A (en) * | 2000-06-26 | 2002-01-09 | Mitsubishi Gas Chem Co Inc | Method of producing polyphenylene ether |
| EP1167421A3 (en) * | 2000-06-19 | 2002-04-10 | Mitsubishi Gas Chemical Company, Inc. | Production process of polyphenylene ether |
| SG110017A1 (en) * | 2002-02-01 | 2005-04-28 | Mitsubishi Gas Chemical Co | Production process of polyphenylene ethers |
| JP2016520038A (en) * | 2013-04-24 | 2016-07-11 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Diphenylmethane series diamine and polyamine production method |
-
1989
- 1989-12-11 JP JP31873789A patent/JPH03181423A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001083587A1 (en) * | 2000-04-28 | 2001-11-08 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyphenylene ether |
| EP1207175A4 (en) * | 2000-04-28 | 2003-05-28 | Mitsubishi Gas Chemical Co | Process for producing polyphenylene ether |
| US6759507B1 (en) | 2000-04-28 | 2004-07-06 | Mitsubishi Gas Chemical Co., Inc. | Process for producing polyphenylene ether |
| JP2001335631A (en) * | 2000-05-26 | 2001-12-04 | Mitsubishi Gas Chem Co Inc | Production method of polyphenylene ether |
| JP2001348426A (en) * | 2000-06-09 | 2001-12-18 | Mitsubishi Gas Chem Co Inc | Method for producing polyphenylene ether |
| JP4591638B2 (en) * | 2000-06-09 | 2010-12-01 | 三菱瓦斯化学株式会社 | Process for producing polyphenylene ether |
| EP1167421A3 (en) * | 2000-06-19 | 2002-04-10 | Mitsubishi Gas Chemical Company, Inc. | Production process of polyphenylene ether |
| US6586567B2 (en) | 2000-06-19 | 2003-07-01 | Mitsubishi Gas Chemical Company Inc. | Production process of polyphenylene ether |
| SG100736A1 (en) * | 2000-06-19 | 2003-12-26 | Mitsubishi Gas Chemical Co | Production process of polyphenylene ether |
| JP2002003594A (en) * | 2000-06-26 | 2002-01-09 | Mitsubishi Gas Chem Co Inc | Method of producing polyphenylene ether |
| SG110017A1 (en) * | 2002-02-01 | 2005-04-28 | Mitsubishi Gas Chemical Co | Production process of polyphenylene ethers |
| JP2016520038A (en) * | 2013-04-24 | 2016-07-11 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Diphenylmethane series diamine and polyamine production method |
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