CN1222143A - ε－己内酰胺的纯化方法 - Google Patents
ε－己内酰胺的纯化方法 Download PDFInfo
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- CN1222143A CN1222143A CN97195500A CN97195500A CN1222143A CN 1222143 A CN1222143 A CN 1222143A CN 97195500 A CN97195500 A CN 97195500A CN 97195500 A CN97195500 A CN 97195500A CN 1222143 A CN1222143 A CN 1222143A
- Authority
- CN
- China
- Prior art keywords
- neixianan
- purifying
- caprolactam
- hydride
- epsilon
- Prior art date
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 150000004678 hydrides Chemical class 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004411 aluminium Substances 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910010082 LiAlH Inorganic materials 0.000 claims 1
- -1 hydride hydrogen Chemical class 0.000 claims 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000746 purification Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical class NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YTIHIRCOUAPRCS-UHFFFAOYSA-N Dl-norleucinamide Chemical compound CCCCC(N)C(N)=O YTIHIRCOUAPRCS-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RNJCXDJXPXWMDK-UHFFFAOYSA-N [AlH3].COCCO[Na] Chemical compound [AlH3].COCCO[Na] RNJCXDJXPXWMDK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AWSFEOSAIZJXLG-UHFFFAOYSA-N azepan-2-one;hydrate Chemical compound O.O=C1CCCCCN1 AWSFEOSAIZJXLG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/16—Separation or purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
- Detergent Compositions (AREA)
Abstract
粗制的己内酰胺经过与铝或硼的氢化物配合物反应得到纯化。
Description
本发明涉及ε-己内酰胺的纯化方法。
ε-己内酰胺是生产聚酰胺(尼龙6)的重要原料，它在工业上有各种各样的生产方法，最普遍选用的是环己酮肟的贝克曼(Beckmann)重排(K.Weissermel,H.J.Arpe,Indutrielle Organische Chemie,4thedition,PP.272)，另外选用的一种方法是，由甲苯经过苯甲酸制得的环己烷酸与亚硝酰基磺酸进行重排形成ε-己内酰胺。其它方法是基于ω-氨基己酸衍生物，在适当的催化剂的存在下，一般为酸性催化剂，进行环化形成ε-己内酰胺，例如，6-氨基己酸酯(EP-A376123)或6-氨基己腈(EP569741)。
所有ε-己内酰胺生产方法都有副产物的形成，其种类和数量依赖于方法的原理、原料的质量和方法的过程参数。而另一方面，ε-己内酰胺必须达到高的纯度要求，特别是在纤维制造方面。由于这一原因，每种生产方法都要求有它自己的完善的纯化工艺。例如，Process EconomicProgram No.41B,Caprolactam and Nylon6,March1988,PP.69列举了各种不同的纯化方法。
这些纯化方法通常是萃取、蒸馏和/或结晶工艺的组合，高度沾污的己内酰胺馏分，如己内酰胺纯化残留物，经常进行催化氢化处理，一般在去除催化剂之后，是馏出物的分离净化或者回到纯化循环。用瑞尼镍(Raney Nickel)对粗制的ε-己内酰胺进行悬浮催化氢化的情形(EP-A-13824l,JP-A-60-21145)，其催化剂的去除存在问题；ε-己内酰胺在催化剂固定床上进行氢化的情形，催化剂的中毒或活性降低问题很可能一直悬而未决。
本发明的目的是提供一种低消耗的可通用的ε-己内酰胺纯化方法。我们发现，使用铝或硼的氢化物配合物意想不到地达到了这一目的。
据此本发明提供的纯化ε-己内酰胺的方法包括使粗制的ε-己内酰胺与铝或硼的氢化物配合物反应。
适宜于本发明方法的铝或硼的氢化物配合物优选硼氢化钠、硼氢化锂、硼氢化钾、硼氢化钙、氰基硼氢化钠、甲氧基乙氧基氢化铝钠、三叔丁氧基氢化铝锂。
所用氢化物形式的氢的量当然取决于ε-己内酰胺中杂质的浓度，根据所要还原的杂质，保持存在过量的氢化物形式的氢。根据化学计算所需要的氢化物形式的氢，优选过量1.5-5倍。
据发现，在本发明的纯化ε-己内酰胺方法中，使用硼氢化物时，要获得足够的反应速度，须加入基于粗制ε-己内酰胺10-50％重量份的水。
在优选的实施方案中，反应进行时，依据粗制ε-己内酰胺的量，加入0.5-5mol％，特别优选1-4mol％的NaBH4和10-50％重量份的水。硼氢化钠可以使用固体形式或市场买得到的水溶液形式。
反应需要在10-150℃温度范围内进行，特别优选20-100℃。反应时间范围是0.5-200h，优选1-100h。
反应结束后，水和已被还原的杂质经轻度减压蒸馏除去，甚至也可以在反应中间，利用轻度减压将水和杂质连续蒸馏掉。其后，反应混合物进行常规的减压蒸馏(0.5-8mmHg)，得到纯ε-己内酰胺馏分，其UV数(见下文)小于10。
本发明的方法适用于纯化任何常规生产方法生产的ε-己内酰胺，本方法特别适合于纯化从ω-氨基己酸衍生物制备的ε-己内酰胺，例如，从ω-氨基己酸、ω氨基己酰胺、ω-氨基己酸酯和ω-氨基己腈。
实施例由ω-氨基己腈衍生物环化制备的ε-己内酰胺的纯化
ε-己内酰胺的纯度按照UV数确定。使用径厚度d=5cm的液槽，对50％重量浓度的己内酰胺水溶液在280-400nm波长范围内，每隔10nm测定一次吸收强度，所有吸收强度的总和定义为UV数，纯化的ε-己内酰胺的UV数不应超过10。实施例1按照DE-A4339648制备ε-己内酰胺
100重量份的ω-氨基己腈溶于1000重量份的乙醇和30重量份的水中，在220℃、保留时间为12min的条件下，通过二氧化钛(脱钛矿)固定床，将溶剂蒸馏掉，由此达到的粗制己内酰胺用于随后的纯化工序。粗制ε-己内酰胺的纯化
将70重量份的粗制己内酰胺和30重量份的水置于装有蒸馏接头的搅拌釜中，与1％重量份(按粗制己内酰胺计)的硼氢化钠混合，100h后，将反应混合物进行分馏处理，ε-己内酰胺在119℃(2mbar)馏出，其UV数是3.1。实施例2
通过贝克曼重排(参见Process Economic Program(SRI Report)No.41B,Caprolactam and Nylon6,March1988)制备的粗制己内酰胺，在0.4％重量份的NaBH4存在下，按照实施例1的方法进行反应，24h后，将反应混合物进行分馏处理，ε-己内酰胺在125℃(3mbar)馏出，其UV数是3.5。
Claims (4)
1．纯化ε-己内酰胺的方法，包括将ε-己内酰胺与铝或硼的氢化物配合物反应。
2．按照权利要求1的方法，其中氢化物配合物选自NaBH4、LiBH4、KBH4、Ca(BH4)2、NaAlH2(OCH3)(OC2H5)、LiAlH(Ot-Bu)3和Na BH3CN。
3．按照在先权利要求之一的方法，其中所用氢化物氢的量，基于所要纯化的ε-己内酰胺的量，为2-20mol％。
4．按照权利要求2-5任意一项权利要求的方法，其中，基于所要纯化的ε-己内酰胺的量，在0.5-5mol％的NaBH4和10-50％重量份的水存在下，使ε-己内酰胺进行反应。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19623662A DE19623662A1 (de) | 1996-06-13 | 1996-06-13 | Verfahren zur Reinigung von epsilon-Caprolactam |
| DE19623662.2 | 1996-06-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1222143A true CN1222143A (zh) | 1999-07-07 |
| CN1081630C CN1081630C (zh) | 2002-03-27 |
Family
ID=7796883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97195500A Expired - Fee Related CN1081630C (zh) | 1996-06-13 | 1997-06-13 | ε－己内酰胺的纯化方法 |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US5952493A (zh) |
| EP (1) | EP0906277B1 (zh) |
| JP (1) | JP2000511919A (zh) |
| KR (1) | KR100447767B1 (zh) |
| CN (1) | CN1081630C (zh) |
| AU (1) | AU3338597A (zh) |
| BR (1) | BR9709708A (zh) |
| CA (1) | CA2257917A1 (zh) |
| CZ (1) | CZ290955B6 (zh) |
| DE (2) | DE19623662A1 (zh) |
| ES (1) | ES2164352T3 (zh) |
| ID (1) | ID17328A (zh) |
| MY (1) | MY120214A (zh) |
| RU (1) | RU2201920C2 (zh) |
| TR (1) | TR199802581T2 (zh) |
| TW (1) | TW406072B (zh) |
| WO (1) | WO1997047596A1 (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7022844B2 (en) | 2002-09-21 | 2006-04-04 | Honeywell International Inc. | Amide-based compounds, production, recovery, purification and uses thereof |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2752336A (en) * | 1956-06-26 | For the pu | ||
| US2786052A (en) * | 1957-03-19 | Process of purifying caprolactam | ||
| DE75083C (de) * | CH. HAGENMÜLLER in Erfurt, Karthäuserstr. 31 | Dampf-Wachsschmelzapparat mit Prefsvorrichtung | ||
| FR1087136A (fr) * | 1952-11-15 | 1955-02-21 | Stamicarbon | Procédé pour purifier des lactames |
| CH326165A (de) * | 1954-07-30 | 1957-12-15 | Inventa Ag | Verfahren zur Reinigung von Lactamen |
| NL279434A (zh) * | 1961-06-07 | |||
| DE1253716B (de) * | 1961-09-28 | 1967-11-09 | Basf Ag | Verfahren zur Reinigung von Lactamen |
| FR1334780A (fr) * | 1962-09-28 | 1963-08-09 | Basf Ag | Procédé pour l'épuration de lactames |
| JPS6020377B2 (ja) * | 1975-05-27 | 1985-05-21 | 宇部興産株式会社 | ε−カプロラクタムの製造方法 |
| DE2845075A1 (de) * | 1978-10-17 | 1980-05-08 | Basf Ag | Verfahren zur reinigung von rohcaprolactam |
| JPS6021145A (ja) * | 1983-07-14 | 1985-02-02 | Nissan Motor Co Ltd | 鋳物砂用粘結剤 |
| NL8303028A (nl) * | 1983-08-31 | 1985-03-18 | Stamicarbon | Winning van caprolactam uit caprolactam-bevattend destillatie-residu. |
| DE3843791A1 (de) * | 1988-12-24 | 1990-07-05 | Basf Ag | Verfahren zur herstellung von caprolactam |
| BE1007298A3 (nl) * | 1993-07-19 | 1995-05-09 | Dsm Nv | Werkwijze voor het zuiveren van een water-epsilon-caprolactam mengsel. |
| TW268941B (zh) * | 1993-08-20 | 1996-01-21 | Sumitomo Chemical Co | |
| DE4339648A1 (de) * | 1993-11-20 | 1995-05-24 | Basf Ag | Verfahren zur Herstellung von Caprolactam |
| FR2714379B1 (fr) * | 1993-12-23 | 1996-02-02 | Rhone Poulenc Chimie | Procédé de préparation de lactame. |
-
1996
- 1996-06-13 DE DE19623662A patent/DE19623662A1/de not_active Withdrawn
-
1997
- 1997-06-09 ID IDP971961A patent/ID17328A/id unknown
- 1997-06-13 CA CA002257917A patent/CA2257917A1/en not_active Abandoned
- 1997-06-13 KR KR10-1998-0710214A patent/KR100447767B1/ko not_active IP Right Cessation
- 1997-06-13 AU AU33385/97A patent/AU3338597A/en not_active Abandoned
- 1997-06-13 TW TW086108203A patent/TW406072B/zh not_active IP Right Cessation
- 1997-06-13 ES ES97929183T patent/ES2164352T3/es not_active Expired - Lifetime
- 1997-06-13 RU RU99100727/04A patent/RU2201920C2/ru not_active IP Right Cessation
- 1997-06-13 EP EP97929183A patent/EP0906277B1/de not_active Expired - Lifetime
- 1997-06-13 US US09/202,094 patent/US5952493A/en not_active Expired - Fee Related
- 1997-06-13 JP JP10501222A patent/JP2000511919A/ja not_active Withdrawn
- 1997-06-13 BR BR9709708A patent/BR9709708A/pt active Search and Examination
- 1997-06-13 CZ CZ19984075A patent/CZ290955B6/cs not_active IP Right Cessation
- 1997-06-13 DE DE59704606T patent/DE59704606D1/de not_active Expired - Fee Related
- 1997-06-13 CN CN97195500A patent/CN1081630C/zh not_active Expired - Fee Related
- 1997-06-13 MY MYPI97002639A patent/MY120214A/en unknown
- 1997-06-13 WO PCT/EP1997/003098 patent/WO1997047596A1/de active IP Right Grant
- 1997-06-13 TR TR1998/02581T patent/TR199802581T2/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE19623662A1 (de) | 1997-12-18 |
| US5952493A (en) | 1999-09-14 |
| CA2257917A1 (en) | 1997-12-18 |
| CZ407598A3 (cs) | 1999-04-14 |
| CZ290955B6 (cs) | 2002-11-13 |
| TR199802581T2 (xx) | 1999-03-22 |
| AU3338597A (en) | 1998-01-07 |
| EP0906277A1 (de) | 1999-04-07 |
| JP2000511919A (ja) | 2000-09-12 |
| EP0906277B1 (de) | 2001-09-12 |
| KR100447767B1 (ko) | 2005-01-15 |
| CN1081630C (zh) | 2002-03-27 |
| KR20000016618A (ko) | 2000-03-25 |
| MY120214A (en) | 2005-09-30 |
| TW406072B (en) | 2000-09-21 |
| DE59704606D1 (de) | 2001-10-18 |
| ES2164352T3 (es) | 2002-02-16 |
| RU2201920C2 (ru) | 2003-04-10 |
| BR9709708A (pt) | 1999-08-10 |
| WO1997047596A1 (de) | 1997-12-18 |
| ID17328A (id) | 1997-12-18 |
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