WO1996036600A1 - Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam - Google Patents
Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam Download PDFInfo
- Publication number
- WO1996036600A1 WO1996036600A1 PCT/EP1996/001891 EP9601891W WO9636600A1 WO 1996036600 A1 WO1996036600 A1 WO 1996036600A1 EP 9601891 W EP9601891 W EP 9601891W WO 9636600 A1 WO9636600 A1 WO 9636600A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- titanium dioxide
- caprolactam
- liquid phase
- water
- content
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/08—Preparation of lactams from carboxylic acids or derivatives thereof, e.g. hydroxy carboxylic acids, lactones or nitriles
Definitions
- the present invention relates to a new process for the preparation of cyclic lactams by reacting aminocarbonitriles with water in the presence of catalysts.
- US Pat. No. 2,301,964 relates to the uncatalyzed conversion of 6-aminocapronitrile to caprolactam in aqueous solution at 285 ° C. The yields are below 80%.
- FR-A 2 029 540 describes a process for the cyclization of 6-aminocapronitrile to caprolactam by means of homogeneous metal catalysts from the zinc and copper group in aqueous solution, with caprolactam being obtained in yields of up to 83%.
- caprolactam being obtained in yields of up to 83%.
- the complete separation of the catalyst from the valuable product caprolactam poses problems since this forms complexes with the metals used.
- the object of the present invention was therefore to provide a process for the preparation of cyclic lactams by reacting aminocarbonitriles with water which does not have the disadvantages described above.
- the starting materials in the process according to the invention are aminocarbonitriles, preferably those of the general formula I.
- n and m can each have the values 0, 1, 2, 3, 4, 5, 6, 7, 8 and 9 and the sum of n + m is at least 3, preferably at least 4.
- R 1 and R 2 can in principle be substituents of any kind, it should only be ensured that the desired cyclization reaction is not influenced by the substituents.
- R 1 and R 2 are independently Ci-C ⁇ -alkyl or C 5 -C 7 cycloalkyl groups or C 6 -Ci 2 ⁇ aryl groups.
- Particularly preferred starting compounds are aminocarboxylic acid nitriles of the general formula
- m has a value of 3, 4, 5 or 6, in particular 5.
- the starting compound is 6-aminocaproic acid nitrile.
- the reaction is carried out in the liquid phase at temperatures of generally 140 to 320 ° C, preferably 160 to 280 ° C; the pressure is generally in the range from 1 to 250 bar, preferably from 5 to 150 bar, care being taken that the reaction mixture under the conditions used is predominantly, i.e. without the catalyst present in the solid phase, is liquid.
- the residence times are generally in the range from 1 to 120, preferably 1 to 90 and in particular 1 to 60 minutes. In some cases, dwell times of 1 to 10 minutes have proven to be completely sufficient.
- At least 0.01 mol, preferably 0.1 to 20 and in particular 1 to 5 mol, of water are used per mol of aminocarbonitrile.
- the aminocarbonitrile is advantageously in the form of a 1 to 50% by weight, in particular 5 to 50% by weight, particularly preferably 5 to 30% by weight solution in water (in which case the solvent is also the reactant) or used in water / solvent mixtures.
- solvents are alkanols such as methanol, ethanol, n- and i-propanol, n-, i- and t-butanol and polyols such as diethylene glycol and tetraethylene glycol, hydrocarbons such as petroleum ether, benzene, toluene, xylene, lactams such as pyrrolidone or caprolactam or alkyl-substituted lactams such as N-methylpyrrolidone, N-methylcaprolactam or N-ethylcaprolactam and carboxylic acid esters, preferably called carboxylic acids having 1 to 8 carbon atoms.
- Ammonia can also be present in the reaction.
- Mixtures of organic solvents can of course also be used.
- Mixtures of water and alkanols in a water / alkanol weight ratio of 1 to 75 to 25 to 99, preferably 1 to 50 50 to 99 have proven to be particularly advantageous in some cases.
- the process according to the invention is carried out in the presence of titanium dioxide catalysts which have a rutile content in the range from 0.1 to 95, preferably from 1 to 90% by weight and an anatase content in the range from 99.9 to 5, preferably from 99 to 10 wt .-%, each based on the total content of titanium dioxide.
- the reaction is carried out in a fixed bed, the catalysts being used in the form of strands or tablets, the tablets and strands preferably having a diameter between 1 and 10 mm.
- titanium dioxide powder which already has the desired content of anatase and rutile or which is obtained by pyrolysis either starting from a pure anatase modification or a mixed form is used
- Anatase and rutile phases or a mixture of pure anatase and rutile modifications are obtained by using the appropriate temperature and residence time (both are known to the person skilled in the art, for example from Catalysis Today 14, (1992) 225-242). pyrolyzed until the desired anatase to rutile ratio is reached.
- Corresponding powders are available on the market, for example the titanium dioxide powders P25® (20 to 30% by weight of rutile and 80 to 70% by weight of anatase) from Degussa as well as S150® and S140® (each 100% by weight). % Anatas) by Finti-Kemira.
- the titanium dioxide can be used as such or as a supported catalyst, whereby it can usually be applied to a mechanically and chemically stable support, usually with a high surface area.
- the titanium dioxide can have been produced by precipitation from aqueous solutions, e.g. after the sulfate process or by other methods such as the pyrogenic production of fine titanium dioxide powders, which are commercially available.
- the rutile / anatase-containing titanium dioxide can be mixed with other oxides such as aluminum oxide, zirconium oxide or cerium oxide.
- oxides or their precursor compounds which can be converted into the oxides by calcining, can be prepared from solution, for example, by co-precipitation. In general, a very good distribution of the two oxides used is obtained.
- the oxide or Precursor mixtures can also be precipitated by precipitation of one oxide or precursor in the presence of the second oxide or precursor, which is present as a suspension of finely divided particles.
- Another method consists in mechanical mixing of the oxide or precursor powder, this mixture being able to be used as a starting material for the production of strands or tablets.
- a ceramic support can be coated with titanium dioxide in a thin layer by hydrolysis of titanium isopropylate or other Ti alkoxides.
- Another suitable compound is TiCl.
- Suitable carriers are powders, extrudates or tablets of titanium dioxide itself or other stable oxides such as silicon dioxide. The carriers used can be designed to be macroporous in order to improve the mass transport. It is important that care is taken in the pyrolysis of the titanium dioxide that both rutile and anatase phases occur in the above-mentioned areas.
- the process according to the invention gives cyclic lactams, in particular caprolactam, in high yield with good selectivities and good constancy of the catalyst activity.
- a solution of 6-aminocapronitrile (ACN) in water and ethanol was introduced into the in a heated tubular reactor of 25 ml (diameter 6 mm; length 800 mm) filled with titanium dioxide in the form of tablets or strands at 100 bar weight ratios given in the table.
- the product stream leaving the reactor was analyzed by gas chromatography. The results are also shown in the table. table
- Example catalyst form sulfate content rutile anatase BET A U S [%] [%] [m / g]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Polyamides (AREA)
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX9708676A MX9708676A (es) | 1995-05-18 | 1996-05-07 | Preparacion de caprolactama. |
AU58147/96A AU700098B2 (en) | 1995-05-18 | 1996-05-07 | The preperation of caprolactam |
JP8534516A JPH11505230A (ja) | 1995-05-18 | 1996-05-07 | カプロラクタムの製造方法 |
BR9608470A BR9608470A (pt) | 1995-05-18 | 1996-05-07 | Processo para preparar lactamos cíclos |
NZ308485A NZ308485A (en) | 1995-05-18 | 1996-05-07 | Titanium dioxide-catalysed cyclisation in the liquid phase of 6-amino caproic acid nitrile to caprolactam |
EA199700402A EA199700402A1 (ru) | 1995-05-18 | 1996-05-07 | Каталитическая циклизация на двуокиси титана в жидкой фазе нитрила 6-аминокапроновой кислоты в капролактам |
PL96323389A PL323389A1 (en) | 1995-05-18 | 1996-05-07 | Caprolaktam producing method |
SK1548-97A SK154897A3 (en) | 1995-05-18 | 1996-05-07 | Method for the preparation of cyclic lactams |
HU9801131A HU220356B (hu) | 1995-05-18 | 1996-05-07 | 6-Amino-kapronitril titán-dioxiddal katalizált ciklizálása kaprolaktámmá folyékony fázisban |
EP96919687A EP0815077A1 (de) | 1995-05-18 | 1996-05-07 | Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam |
BG102027A BG102027A (en) | 1995-05-18 | 1997-11-06 | Method of liquid phase cyclization catalyzed with titanium dioxide of nitrile of 6-aminocapronic acid to caprolactam |
NO975268A NO307964B1 (no) | 1995-05-18 | 1997-11-17 | Titandioksydkatalysert cyklisering i flytende fase av 6- aminokapronsyrenitril til kaprolaktam |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19517821A DE19517821A1 (de) | 1995-05-18 | 1995-05-18 | Verfahren zur Herstellung von Caprolactam |
DE19517821.1 | 1995-05-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996036600A1 true WO1996036600A1 (de) | 1996-11-21 |
Family
ID=7761968
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/001891 WO1996036600A1 (de) | 1995-05-18 | 1996-05-07 | Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam |
Country Status (20)
Country | Link |
---|---|
EP (1) | EP0815077A1 (de) |
JP (1) | JPH11505230A (de) |
KR (1) | KR19990014859A (de) |
CN (1) | CN1075810C (de) |
AU (1) | AU700098B2 (de) |
BG (1) | BG102027A (de) |
BR (1) | BR9608470A (de) |
CA (1) | CA2218132A1 (de) |
CZ (1) | CZ289460B6 (de) |
DE (1) | DE19517821A1 (de) |
EA (1) | EA199700402A1 (de) |
HU (1) | HU220356B (de) |
MX (1) | MX9708676A (de) |
NO (1) | NO307964B1 (de) |
NZ (1) | NZ308485A (de) |
PL (1) | PL323389A1 (de) |
SK (1) | SK154897A3 (de) |
TR (1) | TR199701385T1 (de) |
TW (1) | TW340840B (de) |
WO (1) | WO1996036600A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19738464A1 (de) * | 1997-09-03 | 1999-03-04 | Basf Ag | Verwendung von Formkörpern als Katalysator zur Herstellung von Caprolactam |
DE19738463C2 (de) * | 1997-09-03 | 1999-09-23 | Basf Ag | Verfahren zur Herstellung von Caprolactam |
CN101890370B (zh) * | 2010-08-05 | 2012-05-30 | 上海交通大学 | 基于纳米二氧化钛和聚膦腈的复合光催化剂及其制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2301964A (en) * | 1941-09-12 | 1942-11-17 | Du Pont | Method of preparing lactams |
FR2029540A1 (en) * | 1969-01-28 | 1970-10-23 | Asahi Chemical Ind | Epsilon caprolactam by one step synthesis |
US4625023A (en) * | 1985-09-03 | 1986-11-25 | Allied Corporation | Selective conversion of aliphatic and aromatic aminonitriles and/or dinitriles into lactams |
US4628085A (en) * | 1985-09-03 | 1986-12-09 | Allied Corporation | Use of silica catalyst for selective production of lactams |
JPH0415766A (ja) * | 1990-05-01 | 1992-01-21 | Meidensha Corp | 濃淡画像処理装置 |
DE4339648A1 (de) * | 1993-11-20 | 1995-05-24 | Basf Ag | Verfahren zur Herstellung von Caprolactam |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2029540A (en) * | 1935-10-01 | 1936-02-04 | Porteous William | Trailer |
-
1995
- 1995-05-18 DE DE19517821A patent/DE19517821A1/de not_active Withdrawn
-
1996
- 1996-05-02 TW TW085105277A patent/TW340840B/zh active
- 1996-05-07 NZ NZ308485A patent/NZ308485A/xx unknown
- 1996-05-07 JP JP8534516A patent/JPH11505230A/ja active Pending
- 1996-05-07 AU AU58147/96A patent/AU700098B2/en not_active Ceased
- 1996-05-07 BR BR9608470A patent/BR9608470A/pt unknown
- 1996-05-07 MX MX9708676A patent/MX9708676A/es unknown
- 1996-05-07 EP EP96919687A patent/EP0815077A1/de not_active Withdrawn
- 1996-05-07 CZ CZ19973578A patent/CZ289460B6/cs not_active IP Right Cessation
- 1996-05-07 PL PL96323389A patent/PL323389A1/xx unknown
- 1996-05-07 CA CA002218132A patent/CA2218132A1/en not_active Abandoned
- 1996-05-07 EA EA199700402A patent/EA199700402A1/ru unknown
- 1996-05-07 SK SK1548-97A patent/SK154897A3/sk unknown
- 1996-05-07 HU HU9801131A patent/HU220356B/hu not_active IP Right Cessation
- 1996-05-07 TR TR97/01385T patent/TR199701385T1/xx unknown
- 1996-05-07 KR KR1019970708204A patent/KR19990014859A/ko not_active Application Discontinuation
- 1996-05-07 WO PCT/EP1996/001891 patent/WO1996036600A1/de not_active Application Discontinuation
- 1996-05-07 CN CN96194001A patent/CN1075810C/zh not_active Expired - Fee Related
-
1997
- 1997-11-06 BG BG102027A patent/BG102027A/xx unknown
- 1997-11-17 NO NO975268A patent/NO307964B1/no not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2301964A (en) * | 1941-09-12 | 1942-11-17 | Du Pont | Method of preparing lactams |
FR2029540A1 (en) * | 1969-01-28 | 1970-10-23 | Asahi Chemical Ind | Epsilon caprolactam by one step synthesis |
US4625023A (en) * | 1985-09-03 | 1986-11-25 | Allied Corporation | Selective conversion of aliphatic and aromatic aminonitriles and/or dinitriles into lactams |
US4628085A (en) * | 1985-09-03 | 1986-12-09 | Allied Corporation | Use of silica catalyst for selective production of lactams |
JPH0415766A (ja) * | 1990-05-01 | 1992-01-21 | Meidensha Corp | 濃淡画像処理装置 |
DE4339648A1 (de) * | 1993-11-20 | 1995-05-24 | Basf Ag | Verfahren zur Herstellung von Caprolactam |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 71, no. 19, 10 November 1969, Columbus, Ohio, US; abstract no. 90878, FUKADA, TOSHIO ET AL: ".omega.-Aminoalkanenitriles" XP002009482 * |
Also Published As
Publication number | Publication date |
---|---|
CN1075810C (zh) | 2001-12-05 |
HUP9801131A3 (en) | 1999-05-28 |
NO975268D0 (no) | 1997-11-17 |
KR19990014859A (ko) | 1999-02-25 |
NZ308485A (en) | 2000-01-28 |
BG102027A (en) | 1998-08-31 |
BR9608470A (pt) | 1998-12-29 |
EP0815077A1 (de) | 1998-01-07 |
EA199700402A1 (ru) | 1999-06-24 |
AU5814796A (en) | 1996-11-29 |
CA2218132A1 (en) | 1996-11-21 |
HU220356B (hu) | 2001-12-28 |
CZ289460B6 (cs) | 2002-01-16 |
CN1184467A (zh) | 1998-06-10 |
HUP9801131A2 (hu) | 1998-08-28 |
AU700098B2 (en) | 1998-12-24 |
DE19517821A1 (de) | 1996-11-21 |
MX9708676A (es) | 1998-02-28 |
JPH11505230A (ja) | 1999-05-18 |
TW340840B (en) | 1998-09-21 |
PL323389A1 (en) | 1998-03-30 |
TR199701385T1 (xx) | 1998-04-21 |
NO307964B1 (no) | 2000-06-26 |
NO975268L (no) | 1997-11-17 |
CZ357897A3 (cs) | 1998-04-15 |
SK154897A3 (en) | 1998-07-08 |
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