JPH02204419A - Recovery of 2,6-diisopropylnaphthalene - Google Patents
Recovery of 2,6-diisopropylnaphthaleneInfo
- Publication number
- JPH02204419A JPH02204419A JP2512889A JP2512889A JPH02204419A JP H02204419 A JPH02204419 A JP H02204419A JP 2512889 A JP2512889 A JP 2512889A JP 2512889 A JP2512889 A JP 2512889A JP H02204419 A JPH02204419 A JP H02204419A
- Authority
- JP
- Japan
- Prior art keywords
- dipn
- diisopropylnaphthalene
- cyclodextrin
- compound
- filtrate
- 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.)
- Granted
Links
- GWLLTEXUIOFAFE-UHFFFAOYSA-N 2,6-diisopropylnaphthalene Chemical compound C1=C(C(C)C)C=CC2=CC(C(C)C)=CC=C21 GWLLTEXUIOFAFE-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000011084 recovery Methods 0.000 title description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000012141 concentrate Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 11
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 claims description 6
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001116 FEMA 4028 Substances 0.000 abstract description 10
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 abstract description 10
- 235000011175 beta-cyclodextrine Nutrition 0.000 abstract description 10
- 229960004853 betadex Drugs 0.000 abstract description 10
- PMPBFICDXLLSRM-UHFFFAOYSA-N 1-propan-2-ylnaphthalene Chemical compound C1=CC=C2C(C(C)C)=CC=CC2=C1 PMPBFICDXLLSRM-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 abstract description 7
- 238000009835 boiling Methods 0.000 abstract description 6
- 238000005804 alkylation reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000029936 alkylation Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000010555 transalkylation reaction Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 6
- MNIGYIKCFSPQRJ-UHFFFAOYSA-N N,N-bis(2-hydroxypropyl)nitrosamine Chemical compound CC(O)CN(N=O)CC(C)O MNIGYIKCFSPQRJ-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical class CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- -1 polyethylene naphthalate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は２．６−ジイツブロピルナフタレンを含む混合
物から２．６−ジイソプロピルナフタレンを回収する方
法に関する。更に詳しくは、冷却晶析法及び／又は溶剤
晶析法による２、６−ジイソプロピルナフタレンの分離
回収と、濾液中の２．６−ジイソプロピルナフタレンを
β−シクロデキストリンとの包接化合物を形成させるこ
とによって濃縮分離する方法とを組み合わせた高純度の
２．６−ジイソプロピルナフタレンを高収率で製造する
方法である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for recovering 2,6-diisopropylnaphthalene from a mixture containing 2,6-diitubropylnaphthalene. More specifically, 2,6-diisopropylnaphthalene is separated and recovered by cooling crystallization method and/or solvent crystallization method, and 2,6-diisopropylnaphthalene in the filtrate is formed into an inclusion compound with β-cyclodextrin. This is a method for producing high-purity 2,6-diisopropylnaphthalene in high yield by combining a method of concentration and separation using
［従来の技術］
２．６−ジイソプロピルナフタレン（以下２．６−ＤＩ
ＰＮと呼ぶことがある）は最近、高度の弾性特性と共に
優れた引張強度と耐熱性を有するポリエチレンナフタレ
ート繊維や、フィルムの重要な原料である２、６−ナフ
タレンジカルボン酸の原料化合物として注目されている
。[Prior art] 2.6-diisopropylnaphthalene (hereinafter referred to as 2.6-DI
PN (sometimes referred to as PN) has recently attracted attention as a raw material compound for polyethylene naphthalate fibers, which have high elastic properties as well as excellent tensile strength and heat resistance, and 2,6-naphthalene dicarboxylic acid, which is an important raw material for films. ing.
２．６−ＤＩＰＮは、ＡｌＣ１，、ＢＦ、等のフリーデ
ルクラフッ触媒、Ｈ，ＳＯ２，ＨＦ等の酸触媒、シリカ
−アルミナ、ゼオライト等の固体酸触媒等の公知のアル
キル化触媒の存在下にナフタレン及び／又はイソプロピ
ルナフタレン類にブロビｌ／ンを反応させるアルギル化
父はナツタ１ノン及び／又はイソプロピルナフタレン類
にイソプロピルナフタレン類及び／又はイソプロピルベ
ンゼン類を反応させるトランスアルキル化反応ｉ、′″
よって得られる。2.6-DIPN is produced in the presence of a known alkylation catalyst such as a Friedel-Craft catalyst such as AlCl, BF, an acid catalyst such as H, SO2, HF, or a solid acid catalyst such as silica-alumina or zeolite. The algylation reaction is to react naphthalene and/or isopropylnaphthalenes with brobyl/one.The algylation reaction is a transalkylation reaction i,''' in which naphthalene and/or isopropylnaphthalenes are reacted with isopropylnaphthalenes and/or isopropylbenzenes.
Therefore, it is obtained.
この反応生成物中には未反応ナフタレン、モノイソプロ
ピルナフタレン、２．６体以外のジイソプロピルナフタ
レン、トリイソプロピルナフタ１ノン等の不純物が含有
され、目的とする２、６ＤＩＰＮの含有率は通常２０〜
３０ｗｔ％である。This reaction product contains impurities such as unreacted naphthalene, monoisopropylnaphthalene, diisopropylnaphthalene other than 2.6-diisopropylnaphthalene, triisopropylnaphthalone, etc., and the target content of 2,6DIPN is usually 20 to 20%.
It is 30wt%.
このような不純物を多く含んだ反応生成物から２．６−
ＤＩＰＮを回収する方法として、蒸留により２．６−Ｄ
ＩＰＮリッグーな留分を回収し、冷却晶析等により融点
の高い２．６−ＤＩＰＮを分離する方法（特公昭５６−
２５３２号公報）が報告されている。しかしながら、こ
の２．６−ＤＩＰＮリッチ留分中には２．６−ＤＩＰＮ
と沸点が近似した２、７−ＤＩＰＮがほぼ１：１の割合
で存在する。このため、留分中の２．６−ＤＩＰＮ濃度
は４０〜５０％程度が限界である。この２゜６・−ＤＩ
ＰＮリッヂ留分を冷却晶析］ニ稈にかけた場合、濾液側
に逃げる２、６−ＤＩＰＮの量が多いため、晶析による
回収率は５０”−６０％と低い。従って濾液中の２．６
−Ｄ Ｉ １） Ｎを更に回収して回収率を向上さぜな
ければ晶析法は経済的に有利な方法ど番」言えない。１
２かし２濾液中の２．６−ＤＩＰＮを更に回収Ｌ２よう
とすれば、−旦２゜６−ＤＩＰＮＪ度を十げてから晶析
工程にかけなければならないが、２．７−ＤＩＰＮを含
有する濾液中の２．６−ＤＩＰＮ濃度を高めるためには
、異性化処理しなＵればならない。From the reaction product containing many such impurities, 2.6-
As a method to recover DIPN, 2.6-D is recovered by distillation.
A method of collecting the IPN-rich fraction and separating 2.6-DIPN, which has a high melting point, by cooling crystallization, etc.
No. 2532) has been reported. However, in this 2.6-DIPN-rich fraction, 2.6-DIPN
2,7-DIPN, which has a boiling point similar to that of 2,7-DIPN, is present in a ratio of approximately 1:1. Therefore, the limit for the concentration of 2.6-DIPN in the fraction is about 40 to 50%. This 2゜6・-DI
When the PN Ridge fraction is subjected to cooling crystallization], the recovery rate by crystallization is as low as 50''-60% because a large amount of 2,6-DIPN escapes to the filtrate side. 6
-DI 1) Unless N is further recovered to improve the recovery rate, the crystallization method cannot be said to be an economically advantageous method. 1
In order to further recover 2.6-DIPN in the filtrate, it is necessary to lower the 2°6-DIPNJ degree and then apply it to the crystallization process. In order to increase the concentration of 2,6-DIPN in the filtrate, it is necessary to perform an isomerization treatment.
［発明が解決しＪ：うとする課題］
発明者らは冷却品＋Ｊｉ法及び／又は溶剤晶析法による
２、６−ＤＩＰＮの回収率をアップさせるため、２．６
−ＤＩＰＮを晶析分離した濾液中の２．６−ＤＩＰＮ濃
度を向上させる方法について鋭意研究した結果、２．６
−ＤＩＰＮがβ−シクロデキスト・リンと包接錯体を生
成し、」二記の包接錯体の生成定数が他の包接錯体（特
に２．７−ＤＩＰＮ）のそれに比べて大きいことに着目
し１、この性質を利用して、２．６−ＤＩＰＮの濃縮分
離剤として、β−シクロデキストリンを用いることによ
り２，６・＝ＤＩＰＮの濃度を向」−゛させることがで
きることを見出し、しかもこの方法が主として２．６−
ＤＩＰき１と２．７−ＤＩＰＮとからなり、２．６−Ｄ
ＩＰＮの濃度が比較的低い原料にも適用できることを見
出し、包接化による濾液中の２．６−ＤＩＰＮの濃縮分
離法と晶析法とを組み合わせることによって、２．６−
ＤＩＰＮの回収率を高め、高純度の２．６−ＤＩＰＮを
製造する方法を完成した。[Problems to be Solved by the Invention] In order to increase the recovery rate of 2,6-DIPN by cooling product + Ji method and/or solvent crystallization method, the inventors
-As a result of intensive research on methods for increasing the 2.6-DIPN concentration in the filtrate obtained by crystallizing and separating DIPN, we found that 2.6-DIPN
-DIPN forms an inclusion complex with β-cyclodextphosphorus, and we focused on the fact that the formation constant of the inclusion complex described in ``2'' is larger than that of other inclusion complexes (especially 2.7-DIPN). 1. Utilizing this property, we discovered that the concentration of 2,6-DIPN can be increased by using β-cyclodextrin as a concentration and separation agent for 2,6-DIPN. The method is mainly 2.6-
Consisting of DIP 1 and 2.7-DIPN, 2.6-D
We discovered that it can be applied to raw materials with a relatively low concentration of IPN, and by combining the concentration separation method of 2.6-DIPN in the filtrate by inclusion and the crystallization method, we succeeded in producing 2.6-DIPN.
We have completed a method for increasing the recovery rate of DIPN and producing highly pure 2.6-DIPN.
［課題を解決するための手段］
すなわち本発明は２．６−ＤＩＰＮを含む混合物を冷却
晶析及び／又は溶剤晶析して２．６−ＤＩＰＮを晶析分
離回収し、一方２．６−ＤＩＰＮを分離した濾液ばβ−
シクロデキストリン溶液と混合し２て２，６−ＤＩＰＮ
−シフロブキス１へリンの包接化合物を形成させ、包接
化合物を回収し、該包接化合物を解離し、得られた２、
６−ＤＩＰＮ濃縮液を晶析工程に循環することを特徴ど
する２、６−ＤＩＰＮの回収方法である。[Means for Solving the Problems] That is, the present invention performs cooling crystallization and/or solvent crystallization of a mixture containing 2.6-DIPN to crystallize and recover 2.6-DIPN, while 2.6-DIPN is crystallized and recovered. The filtrate from which DIPN was separated β-
2,6-DIPN mixed with cyclodextrin solution
- Forming a clathrate of Sifurobukis 1herin, collecting the clathrate, and dissociating the clathrate, resulting in 2,
This is a 2,6-DIPN recovery method characterized by circulating a 6-DIPN concentrate to a crystallization step.
本発明においてＧ」先ず２．６−ＤＩＰＮを含む混合物
をＯ〜−２０℃に冷却し、２．６−ＤＩＰＮを析出させ
る６２．６−ＤＩＰＮを含む混合物としては、アルギル
化反応またはトランスアルキル化反応生成物を蒸留して
、未反応のナフタレン、モノイソプロピルナフタレンを
主とする低沸点留分およびトリおよびテトライソプロピ
ルナフタｌノンを主とする高沸点留分を除去したジイソ
プロピルナフタレン留分、またはこれを更に精密蒸留し
て２．６−ＤＩＰＮの濃度をアップさせた留分を用いる
。析出した結晶は濾過、分離して高純度の２．６−ＤＩ
ＰＮが得られる。In the present invention, the mixture containing 62.6-DIPN is first cooled to O to -20°C to precipitate 2.6-DIPN. A diisopropylnaphthalene fraction obtained by distilling the reaction product to remove unreacted naphthalene, a low-boiling fraction mainly containing monoisopropylnaphthalene, and a high-boiling fraction mainly containing tri- and tetraisopropylnaphthalone, or this diisopropylnaphthalene fraction. A fraction obtained by further precision distillation to increase the concentration of 2.6-DIPN is used. The precipitated crystals are filtered and separated to obtain high purity 2.6-DI.
PN is obtained.
結晶を分離した残りの濾液にはなお相当量の２．６−Ｄ
ＩＰＮが含まれているが、その濃度を高めるためにβ−
シクロデキストリンによる包接化処理を行なう。包接化
処理は先ずβ−シクロデキストリンを水に溶解あるいは
懸濁させ、これに上記晶析後の濾液を加え、激しく撹拌
する。β−シクロデキストリンの濃度は０．５〜１．５
％が適当である。β−シクロデキストリン水溶液と２．
６−ＤＩＰＮ含有混合物との混合割合は、β−シクロデ
キストリンのモル数が２．６−ＤＩＰＮのそれの０．５
〜１０倍になるようにする。撹拌はできるだけ激しく行
うことが好ましく、数十分から数時間行う。なお、温度
は常温でも良いが反応速度の点からは、加温、例えば３
０〜４５℃程度にするのがよい。混合液はシクロデキス
トリン包接化合物の生成により白濁する。撹拌終了後、
反応生成物をろ過し、水にて洗浄後、アセトンで洗浄乾
燥することによって、白色固体の包接化合物を得る。こ
の白色固体中には、２．６−ＤＩＰＮ以外の有機化合物
の包接化合物も含まれているが、これらをいったん６０
〜７０℃以上の熱水中で解離させ、β−シクロデキスト
リンと分離することにより２．６−ＤＩＰＮが濃縮され
た液が得られる。この濃縮液を再び冷却、晶析工程に循
環することによって、高純度２．６−ＤＩＰＮを高収率
で得ることができる。The remaining filtrate after separating the crystals still contains a considerable amount of 2.6-D.
Contains IPN, but to increase its concentration β-
Inclusion treatment with cyclodextrin is performed. In the inclusion treatment, β-cyclodextrin is first dissolved or suspended in water, the filtrate after the crystallization is added thereto, and the mixture is vigorously stirred. The concentration of β-cyclodextrin is 0.5-1.5
% is appropriate. β-cyclodextrin aqueous solution; 2.
The mixing ratio with the mixture containing 6-DIPN is such that the number of moles of β-cyclodextrin is 2.5 of that of 6-DIPN.
Make it ~10 times as large. Stirring is preferably performed as vigorously as possible, and is performed for several tens of minutes to several hours. Note that the temperature may be room temperature, but from the viewpoint of reaction rate, heating, for example 3
The temperature is preferably about 0 to 45°C. The mixture becomes cloudy due to the formation of cyclodextrin inclusion compounds. After stirring,
The reaction product is filtered, washed with water, washed with acetone, and dried to obtain a white solid clathrate compound. This white solid also contains clathrate compounds of organic compounds other than 2,6-DIPN, but once these are
A liquid in which 2.6-DIPN is concentrated is obtained by dissociating it in hot water at ~70°C or higher and separating it from β-cyclodextrin. By cooling this concentrated solution again and circulating it to the crystallization step, high purity 2.6-DIPN can be obtained in high yield.
β−シクロデキストリン−２，６−ＤＩＰＮ包接化合物
から２．６−ＤＩＰＮを得るには種々の方法がある。例
えば、包接化合物を熱水に溶解させ、包接錯体を解離さ
せた後、解離した２、６−ＤＩＰＮをジエチルエーテル
等の適当な有機溶媒を用いて抽出する方法や包接化合物
を水に懸濁させ、ジエチルエーテル等の適当な有機溶媒
を加えて振とうし、２．６−ＤＩＰＮを有機層に抽出す
る方法等がある。There are various methods for obtaining 2,6-DIPN from the β-cyclodextrin-2,6-DIPN clathrate. For example, methods include dissolving the clathrate in hot water to dissociate the clathrate complex, and then extracting the dissociated 2,6-DIPN using an appropriate organic solvent such as diethyl ether, or dissolving the clathrate in water. There is a method of suspending the suspension, adding a suitable organic solvent such as diethyl ether, shaking, and extracting 2,6-DIPN into the organic layer.
この有機層から有機溶媒を除去すると、２．６−ＤＩＰ
Ｎ？！４縮混合物を得ることができる。When the organic solvent is removed from this organic layer, 2.6-DIP
N? ! A 4-condensed mixture can be obtained.
なお、以上の全ての過程において、シクロデキストリン
分子自体は分解することがないので、回収再利用が可能
である。In all of the above processes, the cyclodextrin molecules themselves are not decomposed, so they can be recovered and reused.
かくして、本発明においては冷却晶析及び／又は溶剤晶
析によって高純度の２．６−ＤＩＰＮが結晶として得ら
れるのみならず、濾液中の２．６−ＤＩＰＮも循環回収
されるので２．６−ＤＩＰＮの回収率はきわめて高い。Thus, in the present invention, not only high-purity 2.6-DIPN is obtained as crystals by cooling crystallization and/or solvent crystallization, but also 2.6-DIPN in the filtrate is recycled and recovered. - The recovery rate of DIPN is extremely high.
［実施例］ 以下実施例によって本発明をさらに具体的に説明する。[Example] The present invention will be explained in more detail below with reference to Examples.
ナフタレンとプロピレンとのアルキル化反応生成物を蒸
留し、ナフタレン、モノイソプロピルナフタレンを主と
する低沸点留分（〜３００℃）、ジイソプロピルナフタ
レン留分（３００〜３１０℃）およびトリおよびテトラ
イソプロピルナフタレンを主とする高沸点留分（３１０
℃〜）に分留した。２．６−ＤＩＰＮを約４１％含有す
るジイソプロピルナフタレン留分を一１０℃に冷却晶析
し、結晶を濾過分離して白色板状結晶が得られた（２．
６−ＤＩＰＮの純度８０．３％）。 次にβ−シクロデ
キストリンの１％水溶液５０ｍ１２に上記冷却晶析の濾
液０．２５ｇを加え、４０℃にて２時間激しく撹拌した
。反応生成物をメンブランフィルタ−で濾過し、水で洗
浄した後、アセトンで洗浄・乾燥した。この包接化合物
を水に懸濁させ、ジエチルエーテルを加え、油水分離を
行った。The alkylation reaction product of naphthalene and propylene is distilled to produce a low boiling point fraction (~300℃) mainly consisting of naphthalene and monoisopropylnaphthalene, a diisopropylnaphthalene fraction (300~310℃), and tri- and tetraisopropylnaphthalene. Main high boiling point distillate (310
℃～). A diisopropylnaphthalene fraction containing about 41% of 2.6-DIPN was crystallized by cooling to -10°C, and the crystals were separated by filtration to obtain white plate-like crystals (2.
6-DIPN purity 80.3%). Next, 0.25 g of the filtrate from the cooling crystallization was added to 50 ml of a 1% aqueous solution of β-cyclodextrin, and the mixture was vigorously stirred at 40° C. for 2 hours. The reaction product was filtered with a membrane filter, washed with water, and then washed with acetone and dried. This clathrate compound was suspended in water, diethyl ether was added, and oil and water were separated.
本実施例における主な成分の組成を表１に示す。これは
、ガスクロマトグラフ法で分析したもので、表中の数字
は各成分の面積百分率値である。Table 1 shows the composition of the main components in this example. This was analyzed by gas chromatography, and the numbers in the table are area percentage values of each component.
表１
２．６−ＤＩＰＮ濃度が向上した包接化合物は７０℃の
熱水で解離し、ついで油水分離し、油Ｍを一１０℃に冷
却して晶析操作を行ない、結晶を濾過、分離して純度８
３．２％の２．６−ＤＩＰＮが得られた。Table 1 The clathrate compound with improved 2.6-DIPN concentration is dissociated with hot water at 70°C, then oil and water are separated, oil M is cooled to -10°C and crystallized, and the crystals are filtered and separated. Purity 8
3.2% of 2.6-DIPN was obtained.
［発明の効果］
本発明においては、２．６−ＤＩＰＮ−シクロデキスト
リン包接化合物形成による２、６−ＤＩＰＮの濃縮法と
、冷却晶析法による２、６−ＤＩＰＮの分離回収とを組
み合わせたことにより、従来回収が困難であった冷却晶
析工程における濾液中の２．６−ＤＩＰＮを有効に利用
することができ、２．６−ＤＩＰＮを含む混合物からの
２．６−Ｄ Ｉ ＰＮ回収率が著しく向」ニジた。[Effect of the invention] In the present invention, a method for concentrating 2,6-DIPN by forming a 2,6-DIPN-cyclodextrin clathrate compound and separating and recovering 2,6-DIPN by a cooling crystallization method are combined. This makes it possible to effectively utilize 2.6-DIPN in the filtrate in the cooling crystallization step, which has traditionally been difficult to recover, and to recover 2.6-DIPN from a mixture containing 2.6-DIPN. The rate has significantly increased.
Claims (1)
を冷却晶析及び／又は溶剤晶析して２，６−ジイソプロ
ピルナフタレンを晶析分離回収し、２，６−ジイソプロ
ピルナフタレンを分離した濾液とβ−シクロデキストリ
ン溶液を接触させ、２，６−ジイソプロピルナフタレン
−シクロデキストリンの包接化合物を形成させ、包接化
合物を回収し、該包接化合物を解離し、得られた２，６
−ジイソプロピルナフタレン濃縮液を晶析工程へ循環す
ることを特徴とする２，６−ジイソプロピルナフタレン
の回収方法。(1) A mixture containing 2,6-diisopropylnaphthalene is subjected to cooling crystallization and/or solvent crystallization to crystallize, separate and recover 2,6-diisopropylnaphthalene, and the filtrate from which 2,6-diisopropylnaphthalene is separated and β- A cyclodextrin solution is brought into contact to form an inclusion compound of 2,6-diisopropylnaphthalene-cyclodextrin, the inclusion compound is collected, and the inclusion compound is dissociated to obtain the 2,6-diisopropylnaphthalene-cyclodextrin inclusion compound.
- A method for recovering 2,6-diisopropylnaphthalene, which comprises circulating a diisopropylnaphthalene concentrate to a crystallization step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1025128A JP2590412B2 (en) | 1989-02-03 | 1989-02-03 | Method for recovering 2,6-diisopropylnaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1025128A JP2590412B2 (en) | 1989-02-03 | 1989-02-03 | Method for recovering 2,6-diisopropylnaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02204419A true JPH02204419A (en) | 1990-08-14 |
| JP2590412B2 JP2590412B2 (en) | 1997-03-12 |
Family
ID=12157314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1025128A Expired - Lifetime JP2590412B2 (en) | 1989-02-03 | 1989-02-03 | Method for recovering 2,6-diisopropylnaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2590412B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117185889A (en) * | 2023-08-25 | 2023-12-08 | 涉县津东经贸有限责任公司 | Industrial production process for preparing diisopropylnaphthalene |
-
1989
- 1989-02-03 JP JP1025128A patent/JP2590412B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117185889A (en) * | 2023-08-25 | 2023-12-08 | 涉县津东经贸有限责任公司 | Industrial production process for preparing diisopropylnaphthalene |
| CN117185889B (en) * | 2023-08-25 | 2024-02-06 | 涉县津东经贸有限责任公司 | Industrial production process for preparing diisopropylnaphthalene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2590412B2 (en) | 1997-03-12 |
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