EP0815077A1 - Cyclisation en phase liquide catalysee par dioxyde de titane de nitrile d'acide 6-amino caproique en caprolactame - Google Patents

Cyclisation en phase liquide catalysee par dioxyde de titane de nitrile d'acide 6-amino caproique en caprolactame

Info

Publication number
EP0815077A1
EP0815077A1 EP96919687A EP96919687A EP0815077A1 EP 0815077 A1 EP0815077 A1 EP 0815077A1 EP 96919687 A EP96919687 A EP 96919687A EP 96919687 A EP96919687 A EP 96919687A EP 0815077 A1 EP0815077 A1 EP 0815077A1
Authority
EP
European Patent Office
Prior art keywords
titanium dioxide
caprolactam
liquid phase
water
content
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.)
Withdrawn
Application number
EP96919687A
Other languages
German (de)
English (en)
Inventor
Eberhard Fuchs
Tom Witzel
Klemens Flick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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
Application filed by BASF SE filed Critical BASF SE
Publication of EP0815077A1 publication Critical patent/EP0815077A1/fr
Withdrawn legal-status Critical Current

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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]

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

L'invention concerne la préparation de lactames cycliques par réaction de nitriles d'acide aminocarboxylique avec de l'eau, qui s'effectue en phase gazeuse en présence de catalyseurs hétérogènes à base de dioxyde de titane à teneur en rutile comprise entre 0,1 et 95 % en poids et à teneur en anatase comprise entre 99,9 et 5 % en poids, cela par rapport à la teneur totale en dioxyde de titane.
EP96919687A 1995-05-18 1996-05-07 Cyclisation en phase liquide catalysee par dioxyde de titane de nitrile d'acide 6-amino caproique en caprolactame Withdrawn EP0815077A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19517821 1995-05-18
DE19517821A DE19517821A1 (de) 1995-05-18 1995-05-18 Verfahren zur Herstellung von Caprolactam
PCT/EP1996/001891 WO1996036600A1 (fr) 1995-05-18 1996-05-07 Cyclisation en phase liquide catalysee par dioxyde de titane de nitrile d'acide 6-amino caproique en caprolactame

Publications (1)

Publication Number Publication Date
EP0815077A1 true EP0815077A1 (fr) 1998-01-07

Family

ID=7761968

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96919687A Withdrawn EP0815077A1 (fr) 1995-05-18 1996-05-07 Cyclisation en phase liquide catalysee par dioxyde de titane de nitrile d'acide 6-amino caproique en caprolactame

Country Status (20)

Country Link
EP (1) EP0815077A1 (fr)
JP (1) JPH11505230A (fr)
KR (1) KR19990014859A (fr)
CN (1) CN1075810C (fr)
AU (1) AU700098B2 (fr)
BG (1) BG102027A (fr)
BR (1) BR9608470A (fr)
CA (1) CA2218132A1 (fr)
CZ (1) CZ289460B6 (fr)
DE (1) DE19517821A1 (fr)
EA (1) EA199700402A1 (fr)
HU (1) HU220356B (fr)
MX (1) MX9708676A (fr)
NO (1) NO307964B1 (fr)
NZ (1) NZ308485A (fr)
PL (1) PL323389A1 (fr)
SK (1) SK154897A3 (fr)
TR (1) TR199701385T1 (fr)
TW (1) TW340840B (fr)
WO (1) WO1996036600A1 (fr)

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

Family Cites Families (7)

* 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
US2301964A (en) * 1941-09-12 1942-11-17 Du Pont Method of preparing lactams
JPS4821958B1 (fr) * 1969-01-28 1973-07-02
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
JP2969779B2 (ja) * 1990-05-01 1999-11-02 株式会社明電舎 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
See references of WO9636600A1 *

Also Published As

Publication number Publication date
AU5814796A (en) 1996-11-29
CN1075810C (zh) 2001-12-05
CA2218132A1 (fr) 1996-11-21
NZ308485A (en) 2000-01-28
CZ289460B6 (cs) 2002-01-16
CZ357897A3 (cs) 1998-04-15
BR9608470A (pt) 1998-12-29
HU220356B (hu) 2001-12-28
EA199700402A1 (ru) 1999-06-24
JPH11505230A (ja) 1999-05-18
SK154897A3 (en) 1998-07-08
TR199701385T1 (xx) 1998-04-21
NO307964B1 (no) 2000-06-26
NO975268L (no) 1997-11-17
MX9708676A (es) 1998-02-28
WO1996036600A1 (fr) 1996-11-21
NO975268D0 (no) 1997-11-17
HUP9801131A3 (en) 1999-05-28
DE19517821A1 (de) 1996-11-21
HUP9801131A2 (hu) 1998-08-28
AU700098B2 (en) 1998-12-24
CN1184467A (zh) 1998-06-10
PL323389A1 (en) 1998-03-30
KR19990014859A (ko) 1999-02-25
TW340840B (en) 1998-09-21
BG102027A (en) 1998-08-31

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