WO1996036600A1 - Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam - Google Patents

Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam Download PDF

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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
Application number
PCT/EP1996/001891
Other languages
German (de)
English (en)
French (fr)
Inventor
Eberhard Fuchs
Tom Witzel
Klemens Flick
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BR9608470A priority Critical patent/BR9608470A/pt
Priority to SK1548-97A priority patent/SK154897A3/sk
Priority to HU9801131A priority patent/HU220356B/hu
Priority to EP96919687A priority patent/EP0815077A1/de
Priority to EA199700402A priority patent/EA199700402A1/ru
Priority to MX9708676A priority patent/MX9708676A/es
Priority to PL96323389A priority patent/PL323389A1/xx
Priority to JP8534516A priority patent/JPH11505230A/ja
Priority to NZ308485A priority patent/NZ308485A/xx
Priority to AU58147/96A priority patent/AU700098B2/en
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1996036600A1 publication Critical patent/WO1996036600A1/de
Priority to BG102027A priority patent/BG102027A/xx
Priority to NO975268A priority patent/NO307964B1/no

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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)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Polyamides (AREA)
  • Hydrogenated Pyridines (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/EP1996/001891 1995-05-18 1996-05-07 Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam WO1996036600A1 (de)

Priority Applications (12)

Application Number Priority Date Filing Date Title
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
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
EA199700402A EA199700402A1 (ru) 1995-05-18 1996-05-07 Каталитическая циклизация на двуокиси титана в жидкой фазе нитрила 6-аминокапроновой кислоты в капролактам
MX9708676A MX9708676A (es) 1995-05-18 1996-05-07 Preparacion de caprolactama.
BR9608470A BR9608470A (pt) 1995-05-18 1996-05-07 Processo para preparar lactamos cíclos
JP8534516A JPH11505230A (ja) 1995-05-18 1996-05-07 カプロラクタムの製造方法
PL96323389A PL323389A1 (en) 1995-05-18 1996-05-07 Caprolaktam producing method
AU58147/96A AU700098B2 (en) 1995-05-18 1996-05-07 The preperation of caprolactam
SK1548-97A SK154897A3 (en) 1995-05-18 1996-05-07 Method for the preparation of cyclic lactams
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 (cs)
JP (1) JPH11505230A (cs)
KR (1) KR19990014859A (cs)
CN (1) CN1075810C (cs)
AU (1) AU700098B2 (cs)
BG (1) BG102027A (cs)
BR (1) BR9608470A (cs)
CA (1) CA2218132A1 (cs)
CZ (1) CZ289460B6 (cs)
DE (1) DE19517821A1 (cs)
EA (1) EA199700402A1 (cs)
HU (1) HU220356B (cs)
MX (1) MX9708676A (cs)
NO (1) NO307964B1 (cs)
NZ (1) NZ308485A (cs)
PL (1) PL323389A1 (cs)
SK (1) SK154897A3 (cs)
TR (1) TR199701385T1 (cs)
TW (1) TW340840B (cs)
WO (1) WO1996036600A1 (cs)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19738463C2 (de) * 1997-09-03 1999-09-23 Basf Ag Verfahren zur Herstellung von Caprolactam
DE19738464A1 (de) * 1997-09-03 1999-03-04 Basf Ag Verwendung von Formkörpern als Katalysator 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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2029540A (en) * 1935-10-01 1936-02-04 Porteous William Trailer

Patent Citations (6)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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
HUP9801131A2 (hu) 1998-08-28
CZ289460B6 (cs) 2002-01-16
BR9608470A (pt) 1998-12-29
CN1184467A (zh) 1998-06-10
NO975268D0 (no) 1997-11-17
TR199701385T1 (xx) 1998-04-21
DE19517821A1 (de) 1996-11-21
JPH11505230A (ja) 1999-05-18
HUP9801131A3 (en) 1999-05-28
SK154897A3 (en) 1998-07-08
CZ357897A3 (cs) 1998-04-15
CN1075810C (zh) 2001-12-05
NO307964B1 (no) 2000-06-26
NO975268L (no) 1997-11-17
MX9708676A (es) 1998-02-28
PL323389A1 (en) 1998-03-30
HU220356B (hu) 2001-12-28
CA2218132A1 (en) 1996-11-21
NZ308485A (en) 2000-01-28
TW340840B (en) 1998-09-21
AU700098B2 (en) 1998-12-24
KR19990014859A (ko) 1999-02-25
AU5814796A (en) 1996-11-29
EP0815077A1 (de) 1998-01-07
EA199700402A1 (ru) 1999-06-24
BG102027A (en) 1998-08-31

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