JPH04275275A - Recovery of isoquinoline and quinaldine - Google Patents
Recovery of isoquinoline and quinaldineInfo
- Publication number
- JPH04275275A JPH04275275A JP6266591A JP6266591A JPH04275275A JP H04275275 A JPH04275275 A JP H04275275A JP 6266591 A JP6266591 A JP 6266591A JP 6266591 A JP6266591 A JP 6266591A JP H04275275 A JPH04275275 A JP H04275275A
- Authority
- JP
- Japan
- Prior art keywords
- quinaldine
- isoquinoline
- coal
- alkylphenols
- distillation
- 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
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000011084 recovery Methods 0.000 title description 2
- 238000004821 distillation Methods 0.000 claims abstract description 22
- 239000003245 coal Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000011269 tar Substances 0.000 claims abstract description 14
- 239000002199 base oil Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims abstract description 11
- 239000011280 coal tar Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract 4
- 238000000034 method Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010533 azeotropic distillation Methods 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical compound C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 14
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- 229940125670 thienopyridine Drugs 0.000 description 8
- 239000002175 thienopyridine Substances 0.000 description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 6
- FBOFHVFMPNNIKN-UHFFFAOYSA-N dimethylquinoline Natural products C1=CC=C2N=C(C)C(C)=CC2=C1 FBOFHVFMPNNIKN-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- DBDCNCCRPKTRSD-UHFFFAOYSA-N thieno[3,2-b]pyridine Chemical compound C1=CC=C2SC=CC2=N1 DBDCNCCRPKTRSD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 4
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 4
- MUDSDYNRBDKLGK-UHFFFAOYSA-N 4-methylquinoline Chemical compound C1=CC=C2C(C)=CC=NC2=C1 MUDSDYNRBDKLGK-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PBYMYAJONQZORL-UHFFFAOYSA-N 1-methylisoquinoline Chemical compound C1=CC=C2C(C)=NC=CC2=C1 PBYMYAJONQZORL-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- 239000002641 tar oil Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- LUYISICIYVKBTA-UHFFFAOYSA-N 6-methylquinoline Chemical compound N1=CC=CC2=CC(C)=CC=C21 LUYISICIYVKBTA-UHFFFAOYSA-N 0.000 description 2
- KDYVCOSVYOSHOL-UHFFFAOYSA-N 7-methylquinoline Chemical compound C1=CC=NC2=CC(C)=CC=C21 KDYVCOSVYOSHOL-UHFFFAOYSA-N 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- SNQSGKQEGKHJCZ-UHFFFAOYSA-N 1,3-dimethylisoquinoline Chemical compound C1=CC=C2C(C)=NC(C)=CC2=C1 SNQSGKQEGKHJCZ-UHFFFAOYSA-N 0.000 description 1
- HJKLEAOXCZIMPI-UHFFFAOYSA-N 2,2-diethoxyethanamine Chemical compound CCOC(CN)OCC HJKLEAOXCZIMPI-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- QGNQEODJYRGEJX-UHFFFAOYSA-N 4h-isoquinoline-1,3-dione Chemical compound C1=CC=C2C(=O)NC(=O)CC2=C1 QGNQEODJYRGEJX-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OUQVKRKGTAUJQA-UHFFFAOYSA-N n-[(1-chloro-4-hydroxyisoquinolin-3-yl)carbonyl]glycine Chemical compound C1=CC=CC2=C(O)C(C(=O)NCC(=O)O)=NC(Cl)=C21 OUQVKRKGTAUJQA-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Landscapes
- Other In-Based Heterocyclic Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は医薬、農薬、顔料等の合
成原料として有用なイソキノリン及びキナルジンの分離
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for separating isoquinoline and quinaldine, which are useful as raw materials for the synthesis of medicines, agricultural chemicals, pigments, and the like.
【０００２】0002
【従来の技術】イソキノリンは、ベンズアルデヒドとア
ミノアセタ−ルを縮合させる方法、ホモフタルイミドを
亜鉛末蒸留する方法等、また、キナルジンはアニリン塩
酸塩とパラアルデヒドと反応させる方法等によっても合
成しうるが、工業的にはコ−ルタ−ル又は石炭液化油等
からの留出油を酸抽出して得られるタ−ル塩基から回収
することが有利であり、一般に行われている。しかしな
がら、このようにして回収されたイソキノリンあるいは
キナルジン中には、タ−ル塩基中に存在するチエノピリ
ジンや他のアルキルイソキノリン類やアルキルキノリン
類が不純物として含まれる。これらの不純物はイソキノ
リンあるいはキナルジンと沸点が近接しているため、蒸
留による分離は極めて困難である。BACKGROUND OF THE INVENTION Isoquinoline can be synthesized by condensing benzaldehyde and aminoacetal, by distilling homophthalimide with zinc dust, and quinaldine can be synthesized by reacting aniline hydrochloride with paraaldehyde. Industrially, it is advantageous and commonly practiced to recover distillate oil from coal tar or coal liquefied oil from a tar base obtained by acid extraction. However, the isoquinoline or quinaldine thus recovered contains impurities such as thienopyridine and other alkylisoquinolines and alkylquinolines present in the tar base. Since these impurities have boiling points close to those of isoquinoline or quinaldine, it is extremely difficult to separate them by distillation.
【０００３】このため、コ−ルタ−ル又は石炭液化油か
ら分離して得られたイソキノリン、キナルジン及び他の
タ−ル塩基類を主成分とする石炭系塩基油から回収した
イソキノリンを精製する方法として、イソキノリンと酸
を反応させて結晶性の塩を形成させ、これを再結晶及び
／又は洗浄したのち、アルカリ分解する方法（特開昭６
１−２５４５６４号）やイソキノリンを冷却、晶析する
方法（特開平２−４９７７０号）等が提案されている。
また、キナルジンと酸を反応させて結晶性の塩を形成さ
せ、これを再結晶及び／又は洗浄したのち、アルカリ分
解する方法（特開昭６２−１９８６６５号）やキナルジ
ンと尿素を反応させて付加体を形成させ、これを精製し
たのち、付加体を分解する方法（特開昭５７−３８７７
１号）等も知られている。更に、本発明者らの一人はキ
ナルジンに共沸溶媒として炭素数８のアルキルフェノ−
ル類を加えて共沸蒸留して精製する方法（特開平１−２
６８６７８号）を先に提案した。[0003] Therefore, a method for refining isoquinoline recovered from coal-based base oil containing isoquinoline, quinaldine, and other tar bases as main components obtained by separating it from coal tar or coal liquefied oil is proposed. A method of reacting isoquinoline with an acid to form a crystalline salt, recrystallizing and/or washing the salt, and then decomposing it with an alkali (Japanese Patent Application Laid-open No. 6
1-254564) and a method of cooling and crystallizing isoquinoline (Japanese Unexamined Patent Publication No. 2-49770). In addition, a method of reacting quinaldine with an acid to form a crystalline salt, recrystallizing and/or washing the salt, and then decomposing it with an alkali (Japanese Patent Application Laid-Open No. 198665/1982) and a method of reacting quinaldine with urea to add A method of forming an adduct, purifying it, and then decomposing the adduct (Japanese Patent Application Laid-open No. 57-3877
No. 1) etc. are also known. Furthermore, one of the present inventors added alkylphenol having 8 carbon atoms to quinaldine as an azeotropic solvent.
A method of purification by azeotropic distillation with the addition of substances (Unexamined Japanese Patent Publication No. 1-2
No. 68678) was proposed first.
【０００４】しかしながら、これらの方法は工業的に実
施する上で経済性、廃棄物処理等の点で問題が有るもの
であった。例えば、結晶性の塩を形成させ、これを精製
する方法は酸、アルカリを消費するだけでなく、それを
含む多量の廃液が発生する。イソキノリンを冷却、晶析
する方法では、予め蒸留でイソキノリン純度を高めてお
く必要があるだけでなく、冷却にも多量のエネルギ−を
必要とする。尿素付加体を形成させて精製する方法は、
その操作が煩雑である他、キナルジンと尿素水溶液との
分離性が悪いだけでなく、多量の尿素水溶液の廃液が発
生する。また、キナルジンに共沸溶媒として炭素数８の
アルキルフェノ−ル類を加えて共沸蒸留して精製する方
法も、予めキナルジン純度を高めておく必要がある。[0004] However, these methods have problems in terms of economic efficiency, waste disposal, etc. in industrial implementation. For example, the method of forming and purifying a crystalline salt not only consumes acids and alkalis, but also generates a large amount of waste liquid containing them. In the method of cooling and crystallizing isoquinoline, not only is it necessary to increase the purity of isoquinoline by distillation in advance, but also a large amount of energy is required for cooling. The method for forming and purifying urea adducts is as follows:
The operation is complicated, the separability of quinaldine and urea aqueous solution is poor, and a large amount of waste urea solution is generated. Further, in the method of purifying quinaldine by adding an alkylphenol having 8 carbon atoms as an azeotropic solvent and performing azeotropic distillation, it is necessary to increase the purity of quinaldine in advance.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、高純度で低
硫黄分のイソキノリン及びキナルジンを効率的に製造す
ることを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to efficiently produce isoquinoline and quinaldine with high purity and low sulfur content.
【０００６】[0006]
【課題を解決するための手段】本発明は、 コ−ルタ
−ル又は石炭液化油から分離して得られたイソキノリン
、キナルジン及び他のタ−ル塩基類を主成分とする石炭
系塩基油に、共沸溶媒として炭素数８のアルキルフェノ
−ル類（２，６−キシレノ−ルを除く）を加え、減圧下
で共沸蒸留してイソキノリン及びキナルジンを主成分と
する共沸混合物を留出させ、次いで、得られた共沸混合
物からアルキルフェノ−ル類を分離したのち、イソキノ
リンとキナルジンとを蒸留分離することを特徴とするイ
ソキノリン及び／又はキナルジンの製造方法である。[Means for Solving the Problems] The present invention provides a coal base oil containing isoquinoline, quinaldine and other tar bases as main components obtained by separating coal tar or coal liquefied oil. Add an alkylphenol having 8 carbon atoms (excluding 2,6-xylenol) as an azeotropic solvent, and perform azeotropic distillation under reduced pressure to distill an azeotropic mixture containing isoquinoline and quinaldine as main components. This is a method for producing isoquinoline and/or quinaldine, which is characterized in that the alkylphenols are separated from the azeotropic mixture obtained, and then the isoquinoline and quinaldine are separated by distillation.
【０００７】本発明で原料とする石炭系塩基油は、コ−
ルタ−ル又は石炭液化油から分離して得られたイソキノ
リン、キナルジン及び他のタ−ル塩基を主成分とするも
のであり、これはコ−ルタ−ル又は石炭液化油を蒸留し
て得られるタ−ル油類を、酸水溶液で抽出するなどして
得られる。好ましくは、沸点２３５〜２７０℃の範囲の
留分を主とする留分であり、キノリン、イソキノリン、
キナルジン、８−メチルキノリン、ジメチルキノリン等
のタ−ル塩基類を主成分とし、インド−ル、チエノピリ
ジン等を含有し、イソキノリン濃度が２５〜５０重量％
、キナルジン濃度が１５〜４０重量％の留分である。
このような留分はタ−ル油から酸水溶液で抽出し、これ
をアルカリで分解して得られる留分を蒸留して、キノリ
ンを主体とする留分を分離した残りの留分として得るこ
とができる。これは、キノリン残油とも称される。この
石炭系塩基油に含まれる８−メチルキノリンやチエノピ
リジンはイソキノリン、キナルジンと沸点が近接してお
り、蒸留による分離は困難であり、これを精密蒸留して
得られたイソキノリン中には、例えばキナルジンを０．
５〜３重量％、主としてチエノピリジン類に由来するイ
オウ分３０００〜５０００ｐｐｍを含有し、同様にして
得られたキナルジン中には、例えば８−メチルキノリン
、チエノピリジン類を１０〜１５重量％程度含有する。[0007] The coal-based base oil used as a raw material in the present invention is
It is mainly composed of isoquinoline, quinaldine and other tar bases obtained by separating coal tar or coal liquefied oil, and it is obtained by distilling coal tar or coal liquefied oil. It is obtained by extracting tar oils with an aqueous acid solution. Preferably, it is a distillate mainly having a boiling point in the range of 235 to 270°C, such as quinoline, isoquinoline,
The main component is tar bases such as quinaldine, 8-methylquinoline, dimethylquinoline, etc., and contains indole, thienopyridine, etc., and the isoquinoline concentration is 25 to 50% by weight.
, a fraction with a quinaldine concentration of 15 to 40% by weight. Such a fraction can be extracted from tar oil with an aqueous acid solution, decomposed with an alkali, and then distilled to obtain the remaining fraction after separating the fraction mainly consisting of quinoline. Can be done. This is also called quinoline residual oil. 8-Methylquinoline and thienopyridine contained in this coal-based base oil have boiling points close to those of isoquinoline and quinaldine, making it difficult to separate them by distillation. 0.
Quinaldine obtained in the same manner contains, for example, about 10 to 15% by weight of 8-methylquinoline and thienopyridines.
【０００８】上記石炭系塩基油に加える共沸溶媒は、炭
素数８のアルキルフェノ−ル類（２，６−キシレノ−ル
を除く）であり、具体的には２，３−キシレノ−ル、２
，４−キシレノ−ル、２，５−キシレノ−ル、３，４−
キシレノ−ル、３，５−キシレノ−ル、２−エチルフェ
ノ−ル、３−エチルフェノ−ル及び４−エチルフェノ−
ルがあり、これらの１種又は２種以上の混合物を挙げる
ことができる。なお、２，６−キシレノ−ルは、単独で
加えるときは共沸溶媒としての作用を生じないので使用
できないが、他の炭素数８のアルキルフェノ−ル類に混
合しても格別の不都合は生じないので、例えばキシレノ
−ル類の混合物を共沸溶媒とする場合において、これを
除去する必要はない。また、アルキルフェノ−ル類に通
常混入する不純物あるいは沸点が近似しない他の溶媒が
存在しても差し支えない。これらのアルキルフェノ−ル
類の内、好ましいのは３，４−キシレノ−ル又は３，５
−キシレノ−ルであるが、工業的にはタ−ル油類からア
ルカリ抽出、蒸留等の手段で分離された沸点２１０〜２
３０℃の留分を主とするアルキルフェノ−ル類混合物で
十分である。上記アルキルフェノ−ル類の使用量は、タ
−ル塩基類を主成分とする石炭系塩基油１重量部に対し
アルキルフェノ−ル類０．３〜１重量部、好ましくは０
．４〜０．６重量部である。過剰に加えることは蒸留効
率を低下させるだけであり、過少であることは回収率を
低下させる。The azeotropic solvent added to the above coal base oil is an alkylphenol having 8 carbon atoms (excluding 2,6-xylenol), specifically 2,3-xylenol, 2
, 4-xylenol, 2,5-xylenol, 3,4-
Xylenol, 3,5-xylenol, 2-ethylphenol, 3-ethylphenol and 4-ethylphenol
There are many types of these, and examples include one type or a mixture of two or more types of these. Note that 2,6-xylenol cannot be used when added alone because it does not act as an azeotropic solvent, but there is no particular disadvantage when mixed with other alkylphenols having 8 carbon atoms. Therefore, it is not necessary to remove it, for example, when using a mixture of xylenols as an azeotropic solvent. In addition, there may be no problem in the presence of impurities that are usually mixed in with alkylphenols or other solvents whose boiling points are not close to each other. Among these alkylphenols, 3,4-xylenol or 3,5-xylenol is preferred.
-Xylenol, which has a boiling point of 210 to 2
An alkylphenol mixture containing mainly a 30° C. fraction is sufficient. The amount of the alkylphenols to be used is 0.3 to 1 part by weight, preferably 0.3 to 1 part by weight, per 1 part by weight of coal base oil containing tar bases as the main component.
．． It is 4 to 0.6 parts by weight. Adding too much will only reduce the distillation efficiency, while adding too little will reduce the recovery rate.
【０００９】本発明の共沸蒸留を行うための装置として
は、理論段数８０程度以上のものであればよく、蒸留条
件としては、３００Ｔｏｒｒ以下、好ましくは１００Ｔ
ｏｒｒ以下の減圧がよく、還流比は２０以上、好ましく
は４０以上とすることがよい。この共沸蒸留では、まず
過剰の共沸溶媒が留出し、次にキノリン、８−メチルキ
ノリン、チエノ〔３，２−ｂ〕ピリジン等のチエノピリ
ジン類等が留出し、その後イソキノリン、キナルジン及
びアルキルフェノ−ル類混合物が共沸混合物として留出
する。共沸混合物の概略組成は、例えばイソキノリン３
５〜４５重量％、キナルジン２０〜３０重量％及びアル
キルフェノ−ル類２５〜４５重量％である。The apparatus for carrying out the azeotropic distillation of the present invention may be one having a theoretical plate number of about 80 or more, and the distillation conditions are 300 Torr or less, preferably 100 Torr or less.
A reduced pressure of orr or less is preferable, and the reflux ratio is preferably 20 or more, preferably 40 or more. In this azeotropic distillation, first excess azeotropic solvent is distilled off, then thienopyridines such as quinoline, 8-methylquinoline, and thieno[3,2-b]pyridine are distilled off, and then isoquinoline, quinaldine, and alkylphenol are distilled off. - A mixture of alcohols is distilled out as an azeotrope. The approximate composition of the azeotrope is, for example, isoquinoline 3
5 to 45% by weight, quinaldine 20 to 30% by weight, and alkylphenols 25 to 45% by weight.
【００１０】このようにして得られた共沸混合物は、例
えば５〜２０重量％のアルカリ水溶液で洗浄する方法で
アルキルフェノ−ル類を除去することもできるし、共沸
混合物を７６０〜６００Ｔｏｒｒ程度の常圧近辺で蒸留
することでもアルキルフェノ−ル類の８０〜９５重量％
を除去することができる。アルキルフェノ−ル類除去後
、３００Ｔｏｒｒ以下、好ましくは１００Ｔｏｒｒ以下
の減圧で蒸留するなどの方法によりイソキノリンとキナ
ルジンを蒸留分離すれば、純度９８重量％以上、イオウ
分３００重量ｐｐｍ以下のイソキノリン及び／又は純度
９５重量％以上のキナルジンを得ることができる。[0010] The azeotrope thus obtained can be washed with a 5 to 20% by weight aqueous alkali solution to remove alkylphenols, or the azeotrope can be heated to about 760 to 600 Torr. Distillation at near normal pressure can reduce the amount of alkylphenols by 80 to 95% by weight.
can be removed. After removing the alkylphenols, isoquinoline and quinaldine are separated by distillation using a method such as distillation at a reduced pressure of 300 Torr or less, preferably 100 Torr or less. Quinaldine with a purity of 95% by weight or more can be obtained.
【００１１】[0011]
【作用】イソキノリン、キナルジンを含み、その他のタ
−ル塩基類を主成分とする石炭系塩基油に、共沸溶媒と
してアルキルフェノ−ル類を加えて減圧蒸留すると、キ
ノリン、８−メチルキノリン、チエノピリジン類及びア
ルキルフェノ−ル類の主として４成分系共沸混合物とイ
ソキノリン、キナルジン及びアルキルフェノ−ル類の３
成分系共沸混合物が形成され、前者の方が沸点が低いた
め前者が先に留出し、分離困難な不純物を含まない３成
分系共沸混合物が後から留出して、イソキノリンとキナ
ルジンを効率よく分離できると考えられる。また、沸点
の高い４−メチルキノリン、ジメチルキノリン、インド
−ル等は３成分系共沸混合物より、更に沸点の高い共沸
混合物を形成するものと考えられる。[Action] When alkylphenols are added as an azeotropic solvent to a coal-based base oil containing isoquinoline, quinaldine, and other tar bases as main components and distilled under reduced pressure, quinoline, 8-methylquinoline, A mainly four-component azeotrope of thienopyridines and alkylphenols, and three components of isoquinoline, quinaldine, and alkylphenols.
A component azeotrope is formed, and since the former has a lower boiling point, it is distilled out first, and a ternary azeotrope, which does not contain impurities that are difficult to separate, is distilled out later, producing isoquinoline and quinaldine efficiently. It is thought that it can be separated. Furthermore, 4-methylquinoline, dimethylquinoline, indole, and the like having a high boiling point are considered to form an azeotrope having a higher boiling point than a ternary azeotrope.
【００１２】0012
【実施例】以下、本発明の実施例を示す。実施例におい
て、部は重量部、％は重量％を示す。
実施例１
石炭系塩基油として、コ−ルタ−ルを蒸留して得られた
タ−ル油を酸水溶液で抽出し、アルカリで分解して得ら
れたタ−ル塩基類を主成分とする留分からキノリンを主
体とする留分を留出させた後の残油（組成；キノリン７
．８％、チエノピリジン０．３％、イソキノリン２７．
８％、インド−ル６．８％、キナルジン２１．５％、８
−メチルキノリン３．２％、１−メチルイソキノリン１
．２％、６−及び７−メチルキノリン８．６％、４−メ
チルキノリン５．３％、その他のメチルキノリン及びメ
チルイソキノリン８．３％、ジメチルキノリン及びジメ
チルイソキノリン７．５％及びその他１．３％）を使用
し、この石炭系油１００部に共沸溶媒として、３，５−
キシレノ−ルを主体とするアルキルフェノ−ル類を５０
部加え、理論段数８０段の充填塔型蒸留装置で蒸留した
。蒸留条件は、蒸留圧力５０Ｔｏｒｒ、還流比５０とし
た。このときのイソキノリン、キナルジン及びアルキル
フェノ−ル類の共沸混合物の留出温度は１５６〜１５９
℃であり、留出量は６０部であった。この組成はイソキ
ノリン３７．１％、キナルジン２４．６％及びアルキル
フェノ−ル類３８．３％であり、イオウ分５９０ｐｐｍ
であった。[Examples] Examples of the present invention will be shown below. In the examples, parts are parts by weight, and % is % by weight. Example 1 Coal-based base oil is mainly composed of tar bases obtained by extracting tar oil obtained by distilling coal tar with an acid aqueous solution and decomposing it with an alkali. The residual oil after distilling the fraction mainly composed of quinoline from the fraction (composition: quinoline 7
．． 8%, thienopyridine 0.3%, isoquinoline 27.
8%, indole 6.8%, quinaldine 21.5%, 8
-Methylquinoline 3.2%, 1-methylisoquinoline 1
．． 2%, 6- and 7-methylquinoline 8.6%, 4-methylquinoline 5.3%, other methylquinoline and methylisoquinoline 8.3%, dimethylquinoline and dimethylisoquinoline 7.5% and other 1.3 %), and 3,5-
50% of alkylphenols, mainly xylenol
The mixture was distilled using a packed column type distillation apparatus with 80 theoretical plates. The distillation conditions were a distillation pressure of 50 Torr and a reflux ratio of 50. At this time, the distillation temperature of the azeotropic mixture of isoquinoline, quinaldine and alkylphenols was 156 to 159
℃, and the distilled amount was 60 parts. The composition is 37.1% isoquinoline, 24.6% quinaldine, and 38.3% alkylphenols, with a sulfur content of 590 ppm.
Met.
【００１３】次に、上記共沸混合物１００部を上記と同
じ蒸留装置を使用して蒸留して、イソキノリンとキナル
ジンを分離、回収した。蒸留条件は常圧、還流比５０と
した。最初にアルキルフェノ−ル類（留分１）が２０部
留出し、次いでイソキノリン、キナルジン及びアルキル
フェノ−ル類の混合物１４．６部を中間留分（留分２）
として留出させたのち、蒸留圧力を５０Ｔｏｒｒ、還流
比５０に変更して蒸留を続け、最初にイソキノリン（留
分３）を、次にキナルジン（留分４）をそれぞれ１８．
３部及び６部を留出させた。各留分の留出量、組成を表
１に示す。Next, 100 parts of the above azeotrope was distilled using the same distillation apparatus as above to separate and recover isoquinoline and quinaldine. Distillation conditions were normal pressure and reflux ratio of 50. First, 20 parts of alkylphenols (Fraction 1) were distilled off, and then 14.6 parts of a mixture of isoquinoline, quinaldine and alkylphenols was distilled off as a middle distillate (Fraction 2).
After distilling, the distillation pressure was changed to 50 Torr and the reflux ratio was changed to 50, and the distillation was continued. First, isoquinoline (fraction 3) and then quinaldine (fraction 4) were distilled at 18.
Parts 3 and 6 were distilled off. Table 1 shows the distillation amount and composition of each fraction.
【００１４】[0014]
【表１】[Table 1]
【００１５】[0015]
【発明の効果】本発明の方法によれば、タ−ル塩基類を
主成分とするタ−ル系塩基油に不純物として存在し、通
常の蒸留によっては分離困難な８−メチルキノリン、チ
エノピリジン類等の不純物を除去して、高純度で低イオ
ウ分のイソキノリン及び／又はキナルジンを効率よく製
造することができる。[Effects of the Invention] According to the method of the present invention, 8-methylquinoline and thienopyridine, which exist as impurities in tar base oil containing tar bases as a main component and are difficult to separate by ordinary distillation, can be removed. By removing impurities such as, isoquinoline and/or quinaldine with high purity and low sulfur content can be efficiently produced.
Claims (2)
して得られたイソキノリン、キナルジン及び他のタ−ル
塩基類を主成分とする石炭系塩基油に、共沸溶媒として
炭素数８のアルキルフェノ−ル類（２，６−キシレノ−
ルを除く）を加え、減圧下で共沸蒸留してイソキノリン
及びキナルジンを主成分とする共沸混合物を留出させ、
次いで、得られた共沸混合物からアルキルフェノ−ル類
を分離したのち、イソキノリンとキナルジンとを蒸留分
離することを特徴とするイソキノリンの回収方法。Claim 1: Coal base oil containing isoquinoline, quinaldine, and other tar bases obtained by separation from coal tar or coal liquefied oil as an azeotropic solvent with a carbon number of 8 of alkylphenols (2,6-xylene-
), and azeotropically distilled under reduced pressure to distill an azeotropic mixture containing isoquinoline and quinaldine as main components,
1. A method for recovering isoquinoline, which comprises separating alkylphenols from the resulting azeotrope and then separating isoquinoline and quinaldine by distillation.
して得られたイソキノリン、キナルジン及び他のタ−ル
塩基類を主成分とする石炭系塩基油に、共沸溶媒として
炭素数８のアルキルフェノ−ル類（２，６−キシレノ−
ルを除く）を加え、減圧下で共沸蒸留してイソキノリン
及びキナルジンを主成分とする共沸混合物を留出させ、
次いで、得られた共沸混合物からアルキルフェノ−ル類
を分離したのち、イソキノリンとキナルジンとを蒸留分
離することを特徴とするキナルジンの回収方法。Claim 2: Coal-based base oil containing isoquinoline, quinaldine, and other tar bases obtained by separation from coal tar or coal liquefied oil as an azeotropic solvent with a carbon number of 8 of alkylphenols (2,6-xylene-
), and azeotropically distilled under reduced pressure to distill an azeotropic mixture containing isoquinoline and quinaldine as main components,
A method for recovering quinaldine, characterized in that the alkylphenols are then separated from the obtained azeotropic mixture, and then isoquinoline and quinaldine are separated by distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06266591A JP3159457B2 (en) | 1991-03-04 | 1991-03-04 | Method for recovering isoquinoline and quinaldine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06266591A JP3159457B2 (en) | 1991-03-04 | 1991-03-04 | Method for recovering isoquinoline and quinaldine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04275275A true JPH04275275A (en) | 1992-09-30 |
| JP3159457B2 JP3159457B2 (en) | 2001-04-23 |
Family
ID=13206819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06266591A Expired - Fee Related JP3159457B2 (en) | 1991-03-04 | 1991-03-04 | Method for recovering isoquinoline and quinaldine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3159457B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734400A (en) * | 2018-07-18 | 2020-01-31 | 河北中化鑫宝化工科技有限公司 | Process for producing isoquinoline and process for separating isoquinoline |
| CN111471008A (en) * | 2019-01-23 | 2020-07-31 | 安阳师范学院 | Preparation method of quinoline, isoquinoline and various methylquinolines |
| CN113461613A (en) * | 2021-07-19 | 2021-10-01 | 上海万容医药化工有限公司 | Method for purifying isoquinoline |
-
1991
- 1991-03-04 JP JP06266591A patent/JP3159457B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734400A (en) * | 2018-07-18 | 2020-01-31 | 河北中化鑫宝化工科技有限公司 | Process for producing isoquinoline and process for separating isoquinoline |
| CN111471008A (en) * | 2019-01-23 | 2020-07-31 | 安阳师范学院 | Preparation method of quinoline, isoquinoline and various methylquinolines |
| CN113461613A (en) * | 2021-07-19 | 2021-10-01 | 上海万容医药化工有限公司 | Method for purifying isoquinoline |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3159457B2 (en) | 2001-04-23 |
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