WO2005121083A1 - Process for the preparation of n-akyl-pyrrolidones - Google Patents
Process for the preparation of n-akyl-pyrrolidones Download PDFInfo
- Publication number
- WO2005121083A1 WO2005121083A1 PCT/GB2005/002170 GB2005002170W WO2005121083A1 WO 2005121083 A1 WO2005121083 A1 WO 2005121083A1 GB 2005002170 W GB2005002170 W GB 2005002170W WO 2005121083 A1 WO2005121083 A1 WO 2005121083A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- distillation
- monoalkylamine
- butyrolactone
- zone
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
Definitions
- the present invention relates to a process for the production of N-alkyl-pyrrolidones. More preferably it relates to the production of N-methyl-pyrrolidone. Most preferably it relates to a process for the production of N-methyl-pyrrolidone by the reaction of ⁇ -butyrolactone with rnonomethylamine in the liquid phase in the absence of a catalyst.
- N-methyl-pyrrolidone and other pyrrolidones are conventionally produced from ⁇ - butyrolactone and the appropriate alkylamine.
- the ⁇ -butyrolactone may be produced by the hydrogenation of maleic esters in the vapour phase.
- the maleic esters are produced from maleic anhydride which in turn is generally produced from the oxidation of butane.
- the process costs are high and since N-methyl-pyrrolidone and other pyrrolidones are commercially important commodity chemicals particularly as solvents or reaction mediums it is desirable to provide a process which provides a cost-effective route to the pyrrolidones.
- N-methyl-pyrrolidone A process for the production of N-methyl-pyrrolidone is described in WO 03/053924.
- the molar ratio of ⁇ -butyrolactone to rnonomethylamine in the reactor is between 1 : 1.08 and 1 : 1.2 at a temperature of from 320°C to 380°C and at a pressure of from 70 to 120 bar. It is suggested that the amount of .water present in the -reaction should not exceed 10 wt%.
- the high temperatures used in the process promote the formation of by-products and compounds which colour the finished N-methyl-pyrrolidone.
- the third stage of the reaction is carried out at a temperature ranging between 250°C and 310°C at the third stage reactor inlet and a residence time ranging between 0.5 and 2.0 hours.
- the rnonomethylamine and ⁇ -butyrolactone combine to form 4-hydroxy-n-methylbutylamide.
- the second step is the reaction of 4-hydroxy-n-methylbutylamide to form N-methylamine.
- the molar ratio of rnonomethylamine to ⁇ -butyrolactone is from about 1.05: 1 to about 1.4: 1.
- IP 2001/002640 A describes a process for the manufacture of N-methyl-pyrrolidone by reacting ⁇ -butyrolactone and rnonomethylamine in the presence of water in which the reactor effluent is fed to a first distillation column where 2 to 15 wt% of the N-methyl- pyrrolidone in the feed is extracted from the column bottom.
- the water, rnonomethylamine and the remaining N-methyl-pyrrolidone are taken from the column top and supplied to a second distillation column where water and rnonomethylamine and water are removed from the top and the N-methyl-pyrrolidone is removed from the bottom of the column.
- the presence of contaminating ⁇ -butyrolactone in the pyrrolidone product may be due not only to unreacted ⁇ -butyrolactone from the feed but also to the formation of ⁇ - butyrolactone in the distillation columns. This is due to the presence of unconverted intermediate 4-hydroxy-n-alkylbutylamide leaving the reactor in the product stream and reverting to ⁇ -butyrolactone and monoalkylamine under the distillation conditions. This reversion reaction is promoted as the monoalkylamine, which is relatively volatile, is driven off during the distillation. This most commonly occurs where the temperature for distillation is relatively high, for example in the column sump. In particular, reversion of the 4-hydroxy-n-alkylbutylamide to the ⁇ -butyrolactone will occur at temperatures greater than about 150°C to 180°C.
- Impurities in the product pyrrolidone may be due to the presence of impurities in the commercially available starting materials.
- Commercial ⁇ -butyrolactone may be contaminated with tetrahydrofuran.
- Impurities in commercial monoalkylamine may include dialkylamine and trialkylamine.
- the amine used is rnonomethylamine, it may be contaminated with dimethylamine and trimethylamine.
- Tetrahydrofuran, dimethylamine and trimethylamine and other light boiling impurities can concentrate in the distillation column, particularly in a stream which comprises predominately monoalkylamine and water. Their presence will reduce the bubble point of the stream.
- a second alternative solution would be to consider compressing the overhead vapours so that they can be supplied to downstream units or condensed under increased pressure.
- a process for the production of N-alkylpyrrolidone from ⁇ -butyrolactone and monoalkylamine in the liquid phase comprising the steps of: feeding monoalkylamine and ⁇ -butyrolactone, in the absence of water or in the presence of less than about 1 wt% " of water, to a reaction zone to form a reaction mixture; heating the reaction mixture; withdrawing a product stream from the reaction zone and passing the stream to a distillation zone comprising at least one distillation column operated at sub-atmospheric pressure; adding water to the distillation zone; isolating at least one overhead stream from the distillation zone comprising monoalkylamine, water and optionally N-alkyl-pyrrolidone and condensing the overhead stream against cooling water.
- the water added to the distillation zone may be added directly thereto or may be added to the product stream prior before it is fed to the distillation zone. It will be acknowledged that the addition of water to a distillation zone to reduce the cost of separation is contrary to the established teachings.
- a further benefit is that adding water to the distillation zone allows cooling water to be used as the condensing medium which offers substantial cost advantages.
- the monoalkylamine, ⁇ -butyrolactone and any water may be pre-mixed before being added to the reaction zone.
- the reaction will generally be carried out at a molar excess of monoalkylamine. Whilst there is an advantage to operating at lower molar excesses, the advantage diminishes as the molar ratio approaches 1.05:1 and thus the molar excess used in the process of the present invention will generally be at least 1.05: 1, monoalkylamine : ⁇ -butyrolactone. Not wishing to be bound by any theory, it is believed that unreacted ⁇ -butyrolactone can pass through the reactor due to equilibrium restrictions.
- the amount of water present in the reaction mixture is less than 1 wt%. Any water present may be from the ⁇ -butyrolactone feed, from the monoalkylamine feed or from both feeds. Water may also be present in any recycle stream. However, it is preferred that any water present is reduced as much as possible. Thus amounts of less than 0.2 wt% may be utilised. Whilst the reaction can be carried out in the absence of water, the rate of reaction obtained in the absence of water may be unacceptably low.
- the reaction will generally be conducted in the absence of additional catalyst.
- the distillation zone preferably comprises more than one distillation column.
- two or three distillation columns may be used. Where more than one distillation column is used they may each be operated at sub-atmospheric pressure. Any suitable pressure may be used. However, pressures of from about 0.05 bara and about 0.3 bara are particularly suitable. Operating the distillation at the sub-atmospheric pressure enables lower temperatures to be used and thereby minimises the possibility of the reversion reaction of intermediate 4-hydroxy-n-alkylbutylamide to ⁇ -butyrolactone. Thus, the presence of ⁇ -butyrolactone as a contaminant in the product pyrrolidone is minimised.
- the water supplied to the distillation zone may be from any suitable source.
- it may be distilled water.
- the water may be supplied by any suitable method but is preferably supplied directly to the distillation zone.
- the water may be supplied to an overhead condenser or it may be supplied between the distillation column and the overhead condenser or any suitable point may be selected to add water to the distillation zone.
- the water will generally be supplied to the top of the distillation column.
- the amount of water added to the distillation zone will depend on the pressure of the at least one distillation column, the temperature of the available cooling water and the molar excess of monoalkylamine used.
- Any suitable temperature and residence times may be used for the or each distillation columns. Where there is more than one distillation column present.
- the temperatures, pressures and residence time may be the same or different.
- the cooling water used may be made of any suitable temperature. Temperatures of from about 5°C to about 35°C may be used. The condensing of the overhead stream will generally take place in a heat exchanger.
- the flow rate of the cooling water may be adjusted to provide process-side condensing temperature goals.
- This goal may be set at any suitable level above the maximum temperature of the cooling medium.
- the goal could be selected to be from about 1 to about 30°C above the maximum temperature of the cooling water. This will have the benefit of minimising the amount of water that has to be added to the distillation as the temperature of the available cooling water changes. For example, in temperate climates in winter when the cooling water is much colder than in the summer, the amount of water added to the at least one distillation column can be reduced.
- the monoalkylamine utilised will preferably comprise less than 0.5 wt% and more preferably less than 0.1 wt% total dimethylamine and trimethylamine alkylamine content.
- the process of the present invention will generally provide almost complete conversion of monoalkylamine and ⁇ -butyrolactone such that the concentration of ⁇ -butyrolactone leaving the reactor is generally less than 500 ppm and may be less than 100 ppm. It will also generally provide conversion of the intermediate amide at the exit from the reactor of above 98%.
- the reactor may be a piston-type reactor that has flow through separate compartments to prevent remixing of products.
- the monoalkylamine is preferably rnonomethylamine such that the product obtained is N- methyl-pyrrolidone .
- ⁇ -butyrolactone is fed in line 1 and then mixed with monoalkylamine, such as rnonomethylamine, which is fed in line 2. It will also be mixed with recycled monoalkylamine fed in line 3 from downstream. The mixture is fed in line 4 to a reaction zone 5 and heated to the required reaction temperature. The temperature is maintained at the required level by heat exchange.
- monoalkylamine such as rnonomethylamine
- a stream 6 of reactor effluent which substantially comprises N-alkylpyrrolidone, water, monoalkylamine, and a small quantity of 4-hydroxy- n-alkylbutylamide and heavy by-products, is fed to the distillation zone which comprises a first distillation column 8, a second distillation column 9 and a third distillation zone 10 through which at least some of the reactor effluent passes sequentially It will be understood that some of the reactor effluent may be withdrawn prior to the distillation zone, some may be removed after the first distillation column, and/or some may be removed after the second distillation column.
- the first distillation column 8 is operated at sub-atmospheric pressure.
- a stream of N-alkyl-pyrrolidone, 4-hydroxy-n-alkylbutylamide and heavy byproducts is removed from the bottom of column 8 in line 12.
- a stream 13 comprising N- alkyl-pyrrolidone, water and rnonomethylamine is removed from the top of the first distillation column 8 and fed to the second distillation column 9 which is operated at sub- atmospheric pressure. Water is added to this column 9 in line 14.
- a stream of N-alkylpyrrolidone is removed from the bottom of column 9 in line 15.
- a stream 16 comprising water and monoalkylamine is removed from the top of the second distillation column 9 and fed to the third distillation column 10 where the monoalkylamine is separated overhead and recycled in line 3. The water is removed in line 17.
- the quantity of water added to the first distillation column 8 in line 11 is controlled so that stream 6 can be condensed at the pressure of distillation column 8 using available cooling water.
- the quantity of water added in line 14 to the second distillation column 9 is controlled so that stream 13 can be condensed at the pressure of the second distillation column 9 using available cooling water.
- Example 1 relates to a process for the production N-methyl-pyrrolidone in accordance with the present invention in the absence of water in the reactor and the addition of water to the second distillation column and Comparative Example 1 corresponds to the process described in JP2001/002640 A.
- Table 1 sets out the water needed in a mixture of monomethylamine and water to achieve a bubble point of 40°C or greater.
- the cooling water temperature can be taken hypothetically as 40°C.
- the minimum temperature approach for the condenser on the second distillation column (9) is 10°C
- the process side bubble point must be 50°C to condense the overheads from the second distillation column. It is necessary to add about 2.3 moles of water per mole of ⁇ -butyrolactone fed to the reactor to the second distillation column to elevate the bubble point of the monomethylamine and water mixture to 50°C.
- the N-methyl-pyrrolidone produced in accordance with the present invention can be produced in a cost-effective manner. In addition, it will have good colour due to the absence of impurities.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2005800189718A CN1964943B (en) | 2004-06-09 | 2005-06-01 | Process for the preparation of n-akyl-pyrrolidones |
US11/570,179 US7834196B2 (en) | 2004-06-09 | 2005-06-01 | Process for the preparation of N-alkyl-pyrrolidones |
EP05747165A EP1633708B1 (en) | 2004-06-09 | 2005-06-01 | Process for the preparation of n-alkyl-pyrrolidones |
DE602005000377T DE602005000377T2 (en) | 2004-06-09 | 2005-06-01 | PROCESS FOR THE PREPARATION OF N-ALKYL-PYRROLIDONES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0412875.7 | 2004-06-09 | ||
GBGB0412875.7A GB0412875D0 (en) | 2004-06-09 | 2004-06-09 | Process |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005121083A1 true WO2005121083A1 (en) | 2005-12-22 |
Family
ID=32732194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2005/002170 WO2005121083A1 (en) | 2004-06-09 | 2005-06-01 | Process for the preparation of n-akyl-pyrrolidones |
Country Status (8)
Country | Link |
---|---|
US (1) | US7834196B2 (en) |
EP (1) | EP1633708B1 (en) |
KR (1) | KR101122687B1 (en) |
CN (1) | CN1964943B (en) |
DE (1) | DE602005000377T2 (en) |
GB (1) | GB0412875D0 (en) |
TW (1) | TWI343913B (en) |
WO (1) | WO2005121083A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007131929A1 (en) * | 2006-05-16 | 2007-11-22 | Basf Se | Process for continuously preparing n- ethyl-2-pyrrolidone (nep) |
US20100286411A1 (en) * | 2006-04-06 | 2010-11-11 | Basf Se | Process for the preparation of an n-alkyl lactam with improved colour quality |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101125853B1 (en) * | 2009-07-29 | 2012-03-28 | 에스케이종합화학 주식회사 | Process for preparing of n-methyl pyrrolidone |
US8717016B2 (en) | 2010-02-24 | 2014-05-06 | Infineon Technologies Ag | Current sensors and methods |
JP5776231B2 (en) * | 2011-03-09 | 2015-09-09 | 三菱化学エンジニアリング株式会社 | NMP distillation equipment |
US9617142B1 (en) | 2015-09-30 | 2017-04-11 | Mems Drive, Inc. | MEMS grid for manipulating structural parameters of MEMS devices |
US9630836B2 (en) | 2015-09-30 | 2017-04-25 | Mems Drive, Inc. | Simplified MEMS device fabrication process |
CN111978184A (en) * | 2020-09-14 | 2020-11-24 | 安徽英特力工业工程技术有限公司 | Retrieve device of methylamine in follow NMP crude |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH06228088A (en) * | 1993-01-28 | 1994-08-16 | Mitsubishi Kasei Corp | Production of pyrrolidones |
JP2001354647A (en) * | 2000-06-14 | 2001-12-25 | Mitsubishi Chemicals Corp | N-methyl-2-pyrrolidone composition and method for producing the same |
WO2003053924A1 (en) * | 2001-11-20 | 2003-07-03 | Basf Aktiengesellschaft | Method for the continuous production of n-methyl-2-pyrrolidone (nmp) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US2964535A (en) * | 1957-07-22 | 1960-12-13 | Monsanto Chemicals | Purification of nu-methyl pyrrolidone |
CN1043758C (en) * | 1993-12-27 | 1999-06-23 | 化学工业部北京化工研究院 | Improved production method of N-methyl pyrrolidone and alpha-pyrrolidone |
BE1012013A6 (en) | 1998-04-09 | 2000-04-06 | Pantochim Sa | METHOD FOR PRODUCING N-methyl. |
JP2000256312A (en) | 1999-03-10 | 2000-09-19 | Tonen Chem Corp | Production of pyrrolidones |
JP2001002640A (en) | 1999-06-18 | 2001-01-09 | Tonen Chem Corp | Production of high-purity pyrrolidone compound |
JP2001354646A (en) | 2000-06-14 | 2001-12-25 | Mitsubishi Chemicals Corp | Pyrrolidone composition and method for producing the same |
-
2004
- 2004-06-09 GB GBGB0412875.7A patent/GB0412875D0/en not_active Ceased
-
2005
- 2005-06-01 DE DE602005000377T patent/DE602005000377T2/en active Active
- 2005-06-01 EP EP05747165A patent/EP1633708B1/en not_active Ceased
- 2005-06-01 WO PCT/GB2005/002170 patent/WO2005121083A1/en active Application Filing
- 2005-06-01 CN CN2005800189718A patent/CN1964943B/en not_active Expired - Fee Related
- 2005-06-01 US US11/570,179 patent/US7834196B2/en not_active Expired - Fee Related
- 2005-06-08 TW TW094118924A patent/TWI343913B/en not_active IP Right Cessation
-
2006
- 2006-12-07 KR KR20067025817A patent/KR101122687B1/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06228088A (en) * | 1993-01-28 | 1994-08-16 | Mitsubishi Kasei Corp | Production of pyrrolidones |
JP2001354647A (en) * | 2000-06-14 | 2001-12-25 | Mitsubishi Chemicals Corp | N-methyl-2-pyrrolidone composition and method for producing the same |
WO2003053924A1 (en) * | 2001-11-20 | 2003-07-03 | Basf Aktiengesellschaft | Method for the continuous production of n-methyl-2-pyrrolidone (nmp) |
Non-Patent Citations (4)
Title |
---|
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; TANAKA, MINORU ET AL: "Manufacture of pyrrolidone compound with little discoloration", XP002313360, retrieved from STN Database accession no. 1995:340667 * |
DATABASE CASREACT [online] ISE, YOKO ET AL: "N-methyl-2-pyrrolidone composition and method for its preparation", XP002313359, Database accession no. 136:53678 * |
PATENT ABSTRACTS OF JAPAN vol. 018, no. 601 (C - 1274) 16 November 1994 (1994-11-16) * |
PATENT ABSTRACTS OF JAPAN vol. 2002, no. 04 4 August 2002 (2002-08-04) * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100286411A1 (en) * | 2006-04-06 | 2010-11-11 | Basf Se | Process for the preparation of an n-alkyl lactam with improved colour quality |
WO2007131929A1 (en) * | 2006-05-16 | 2007-11-22 | Basf Se | Process for continuously preparing n- ethyl-2-pyrrolidone (nep) |
US7994350B2 (en) | 2006-05-16 | 2011-08-09 | Basf Se | Process for continuously preparing N-ethyl-2-pyrrolidone (NEP) |
KR101388760B1 (en) | 2006-05-16 | 2014-04-25 | 바스프 에스이 | Process for continuously preparing n-ethyl-2-pyrrolidone (nep) |
Also Published As
Publication number | Publication date |
---|---|
US20070270596A1 (en) | 2007-11-22 |
GB0412875D0 (en) | 2004-07-14 |
US7834196B2 (en) | 2010-11-16 |
KR101122687B1 (en) | 2012-03-09 |
CN1964943A (en) | 2007-05-16 |
DE602005000377D1 (en) | 2007-02-08 |
EP1633708B1 (en) | 2006-12-27 |
DE602005000377T2 (en) | 2007-04-26 |
KR20070020500A (en) | 2007-02-21 |
TWI343913B (en) | 2011-06-21 |
EP1633708A1 (en) | 2006-03-15 |
TW200616947A (en) | 2006-06-01 |
CN1964943B (en) | 2010-12-15 |
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