WO2010121990A2 - Verfahren zur herstellung von mda über die stufe des aminals - Google Patents
Verfahren zur herstellung von mda über die stufe des aminals Download PDFInfo
- Publication number
- WO2010121990A2 WO2010121990A2 PCT/EP2010/055126 EP2010055126W WO2010121990A2 WO 2010121990 A2 WO2010121990 A2 WO 2010121990A2 EP 2010055126 W EP2010055126 W EP 2010055126W WO 2010121990 A2 WO2010121990 A2 WO 2010121990A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formaldehyde
- content
- highly concentrated
- aminal
- solution
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
Definitions
- the invention relates to a process for the preparation of methylenediphenyldiamine (MDA), wherein formaldehyde and aniline are first converted to aminal. After at least partial removal of water, an acid catalyst is added to the aminal to give MDA.
- MDA methylenediphenyldiamine
- Formaldehyde is used in highly concentrated form with a CH 2 O content> 50 wt .-%, wherein the formaldehyde is prepared by oxidative dehydrogenation from methanol.
- WO 2004/078691 relates to a process for the thermal stabilization of highly concentrated formaldehyde solutions having a formaldehyde content ⁇ 70% by weight against solid precipitation.
- the highly concentrated formaldehyde solution is heated immediately after its preparation with a special heating rate to temperatures of 80 to 200 0 C and then stored in this temperature range.
- step a) formaldehyde is used as highly concentrated formaldehyde having a CH 2 O content> 50 wt .-% and the formaldehyde is prepared by oxidative dehydrogenation from methanol.
- formaldehyde is used as highly concentrated formaldehyde having a CH 2 O content of> 50% by weight, preferably> 70% by weight, in particular> 80% by weight.
- Methods for the preparation of highly concentrated formaldehyde with a CH 2 O content> 50 wt .-% are known in the art.
- formaldehyde is used which has been prepared by oxidative dehydrogenation from methanol.
- formaldehyde is used which has been prepared by fatty oxidative dehydrogenation.
- fat means that the molar ratio of methanol to acid substance in the feed to the synthesis of formaldehyde is equal to or exceeds 2: 1.
- the highly concentrated formaldehyde can be used as an aqueous solution or in gaseous form.
- the aqueous formaldehyde solution is heated to an evaporation temperature T for the following applies:
- the evaporation of the aqueous formaldehyde solutions of this embodiment takes place in a stirred tank, a helical tube, a film evaporator or another apparatus with a heat exchanger characteristic.
- the pressure during the evaporation is 0.1 to 50 bar.
- a wavy film flow is set in the helical tube evaporator by the appropriate choice of the geometry thereof as well as the operating conditions, in particular the total amount flow and the gas content in the two-phase mixture, which is passed through the helical tube evaporator.
- the condensed fraction of the vapor stream and / or the bottom stream from the helical tube evaporator can be completely or partially recycled into the preheater.
- step a) a highly concentrated formaldehyde solution having a CH 2 O content> 50 wt .-% is used, which is stabilized against solid precipitation by immediately after its preparation at a heating rate of at least 5 ° C. / min is heated to a temperature of at least 80 to a maximum of 200 0 C and stored at a temperature in this range.
- the heating rate is at least 10 ° C / min and / or it is heated to a temperature of at least 100 to a maximum of 150 0 C.
- the high concentration formaldehyde solution is obtained from a low concentration formaldehyde solution in a film evaporator.
- T ' min (c) A + B x (c / 100) + C x (c / 100) 2 + D x (c / 100) 3 and
- the pressure during the evaporation is 0.1 to 50 bar.
- the molar CH 2 O to H 2 O ratio is> 1.4.
- step b) of the process according to the invention the removal of water takes place from the aminal obtained in step a).
- a water content of 0 to 5 wt .-% is adjusted based on the aminal.
- the water falls on the one hand as the second main product in the aminal synthesis according to step a), on the other hand it is present at least in traces in the educt used in step a) (highly concentrated formaldehyde with a CH 2 O content> 50 wt .-%) ,
- acidic catalysts strong organic or strong inorganic acids can be used. Suitable acids are, for example, hydrochloric acid (HCl), sulfuric acid, phosphoric acid and methanesulfonic acid. Preference is given to using aqueous hydrochloric acid in the process according to the invention.
- the aqueous hydrochloric acid is usually present in concentrations of 25 to 36 wt .-% before.
- gaseous HCl is preferably used.
- the addition of the acidic catalyst is carried out in catalytic amounts. This means that based on the aminal a significantly lower amount of catalyst is used.
- step c) a much smaller amount of water is introduced into the reaction system compared to step a), provided that the acidic catalyst is used as an aqueous solution.
- the acidic catalyst By adding the acidic catalyst, the rearrangements of the aminals described above can be via the aminobenzylaniline intermediates to MDA.
- HCl is predominantly bound to aniline and MDA, the specific amount of HCl used is calculated from the stated degrees of protonation.
- the process according to the invention produces 4,4'-MDA as the main product and also 2,4'-MDA and 2,2'-MDA as by-products and optionally further higher homologs.
- MDA in the weight ratio of the isomers 2,4'-MDA to 4,4'-MDA of between 0.05 and 0.15 can be obtained.
- the addition of the acidic catalyst to the aminal with a water content of 0 to 5 wt .-% in step c) is preferably carried out by mixing, in particular at temperatures of 20 to 60 0 C.
- the mixing of aminal with a water content of 0 to 5 wt. -% with the acidic catalyst is preferably carried out with a specific power input of> 10 kW / m 3 mixing space, more preferably of> 20 kW / m 3 mixing space.
- the aminal at temperatures of 20 to 100 0 C and / or at water contents of 0 to 20 wt .-% rearranged to MDA (implemented).
- the amount of acidic catalyst is chosen so that a degree of protonation of ⁇ 15%, preferably from 5 to 14%, particularly preferably from 6 to 13% is set.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012505185A JP2012524046A (ja) | 2009-04-20 | 2010-04-19 | アミナールの段階を介したmdaの製造方法 |
CN201080017676.1A CN102405208B (zh) | 2009-04-20 | 2010-04-19 | 通过缩醛胺阶段制备亚甲基二苯基二胺(mda)的方法 |
US13/265,271 US8710267B2 (en) | 2009-04-20 | 2010-04-19 | Process for preparing MDA via the stage of the aminal |
EP10715797A EP2421816A2 (de) | 2009-04-20 | 2010-04-19 | Verfahren zur herstellung von methylendiphenyldiamin (mda) über die stufe des aminals |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09158207.2 | 2009-04-20 | ||
EP09158207 | 2009-04-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2010121990A2 true WO2010121990A2 (de) | 2010-10-28 |
WO2010121990A3 WO2010121990A3 (de) | 2010-12-23 |
Family
ID=42732425
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2010/055126 WO2010121990A2 (de) | 2009-04-20 | 2010-04-19 | Verfahren zur herstellung von mda über die stufe des aminals |
Country Status (6)
Country | Link |
---|---|
US (1) | US8710267B2 (de) |
EP (1) | EP2421816A2 (de) |
JP (1) | JP2012524046A (de) |
KR (1) | KR20110138288A (de) |
CN (1) | CN102405208B (de) |
WO (1) | WO2010121990A2 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105358524B (zh) * | 2013-04-24 | 2018-02-16 | 科思创德国股份公司 | 制备二苯基甲烷系列的二胺和多胺的方法 |
CN115181027B (zh) * | 2022-07-25 | 2023-09-22 | 万华化学集团股份有限公司 | 一种生产dam过程中控制废盐水中难处理苯胺类杂质的方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1063221B1 (de) | 1999-06-07 | 2003-11-05 | Basf Aktiengesellschaft | Verfahren zur Umsetzung einer ein Gemisch enthaltenden Lösung |
WO2004078678A2 (de) | 2003-03-04 | 2004-09-16 | Basf Aktiengesellschaft | Verfahren zur erzeugung hochkonzentrierter formaldehydlösungen |
WO2004078690A1 (de) | 2003-03-04 | 2004-09-16 | Basf Aktiengesellschaft | Verfahren zur bereitstellung hochkonzentrierten gasförmigen formaldehyds |
WO2004078691A1 (de) | 2003-03-04 | 2004-09-16 | Basf Aktiengesellschaft | Verfahren zur thermischen stabilisierung hochkonzentrierter formaldehydlösungen |
WO2005077877A1 (de) | 2004-02-11 | 2005-08-25 | Basf Aktiengesellschaft | Verfahren zur herstellung einer hochkonzentrierten formaldehydlösung |
EP1616890A1 (de) | 2004-07-05 | 2006-01-18 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyaminen der Diphenylmethanreihe bei niedriger Protonierung |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0629204B2 (ja) * | 1984-09-28 | 1994-04-20 | 三井東圧化学株式会社 | 高濃度ホルマリンの製造方法 |
DE3714606A1 (de) * | 1987-05-01 | 1988-11-10 | Bayer Ag | Verfahren zur herstellung von mehrkernigen aromatischen polyaminen |
DE4112131A1 (de) * | 1991-04-13 | 1992-10-15 | Bayer Ag | Verfahren zur herstellung von mehrkernigen aromatischen polyaminen |
ES2103193B1 (es) * | 1995-05-16 | 1998-04-01 | Patentes Novedades Sa | Procedimiento para la preparacion en continuo de soluciones acuosas de formaldehido. |
IT1318591B1 (it) * | 2000-06-22 | 2003-08-27 | Eni Spa | Procedimento per la rigenerazione di catalizzatori zeolitici. |
JP2004300085A (ja) * | 2003-03-31 | 2004-10-28 | Mitsui Takeda Chemicals Inc | 4,4’−メチレンジアニリンの製造方法 |
DE10347438A1 (de) * | 2003-10-13 | 2005-05-04 | Bayer Materialscience Ag | Verfahren zur Herstellung von Di- und Polyaminen der Diphenylmethanreihe |
US7012585B2 (en) | 2004-02-06 | 2006-03-14 | Eastman Kodak Company | OLED apparatus having improved fault tolerance |
DE102004052370A1 (de) * | 2004-10-28 | 2006-05-04 | Bayer Materialscience Ag | Verfahren zur Herstellung von Di- und Polyaminen der Diphenylmethanreihe |
DE102005006692A1 (de) * | 2005-02-15 | 2006-08-24 | Bayer Materialscience Ag | Verfahren zur Herstellung von Di-und Polyaminen der Diphenylmethanreihe |
JP4973832B2 (ja) * | 2005-11-29 | 2012-07-11 | 日本ポリウレタン工業株式会社 | ポリメチレンポリフェニルポリアミンの連続式生産方法 |
WO2009027416A1 (de) | 2007-08-30 | 2009-03-05 | Basf Se | Verfahren zur aufarbeitung von abwässern aus der nitrierung |
EP2200976B1 (de) | 2007-09-19 | 2011-11-23 | Basf Se | Verfahren zur herstellung von isocyanaten |
MY159275A (en) | 2007-10-09 | 2016-12-30 | Basf Se | Method for separating trioxane from a trioxane/ formaldehyde/ water mixture by means of pressure change rectification |
EP2234996B1 (de) | 2007-12-19 | 2013-08-28 | Basf Se | Verfahren zur Herstellung von Roh-Trioxan |
-
2010
- 2010-04-19 CN CN201080017676.1A patent/CN102405208B/zh not_active Expired - Fee Related
- 2010-04-19 EP EP10715797A patent/EP2421816A2/de not_active Withdrawn
- 2010-04-19 KR KR1020117027565A patent/KR20110138288A/ko not_active Application Discontinuation
- 2010-04-19 WO PCT/EP2010/055126 patent/WO2010121990A2/de active Application Filing
- 2010-04-19 JP JP2012505185A patent/JP2012524046A/ja active Pending
- 2010-04-19 US US13/265,271 patent/US8710267B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1063221B1 (de) | 1999-06-07 | 2003-11-05 | Basf Aktiengesellschaft | Verfahren zur Umsetzung einer ein Gemisch enthaltenden Lösung |
WO2004078678A2 (de) | 2003-03-04 | 2004-09-16 | Basf Aktiengesellschaft | Verfahren zur erzeugung hochkonzentrierter formaldehydlösungen |
WO2004078690A1 (de) | 2003-03-04 | 2004-09-16 | Basf Aktiengesellschaft | Verfahren zur bereitstellung hochkonzentrierten gasförmigen formaldehyds |
WO2004078691A1 (de) | 2003-03-04 | 2004-09-16 | Basf Aktiengesellschaft | Verfahren zur thermischen stabilisierung hochkonzentrierter formaldehydlösungen |
WO2005077877A1 (de) | 2004-02-11 | 2005-08-25 | Basf Aktiengesellschaft | Verfahren zur herstellung einer hochkonzentrierten formaldehydlösung |
EP1616890A1 (de) | 2004-07-05 | 2006-01-18 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyaminen der Diphenylmethanreihe bei niedriger Protonierung |
Also Published As
Publication number | Publication date |
---|---|
EP2421816A2 (de) | 2012-02-29 |
CN102405208A (zh) | 2012-04-04 |
US8710267B2 (en) | 2014-04-29 |
WO2010121990A3 (de) | 2010-12-23 |
KR20110138288A (ko) | 2011-12-26 |
JP2012524046A (ja) | 2012-10-11 |
US20120035396A1 (en) | 2012-02-09 |
CN102405208B (zh) | 2015-02-25 |
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