WO2003042155A2 - Procede de preparation de dialkylethylamines a partir de dialkylamines et d'ethylene - Google Patents

Procede de preparation de dialkylethylamines a partir de dialkylamines et d'ethylene Download PDF

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Publication number
WO2003042155A2
WO2003042155A2 PCT/EP2002/012581 EP0212581W WO03042155A2 WO 2003042155 A2 WO2003042155 A2 WO 2003042155A2 EP 0212581 W EP0212581 W EP 0212581W WO 03042155 A2 WO03042155 A2 WO 03042155A2
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WIPO (PCT)
Prior art keywords
ethylene
catalyst
bar
mol
edma
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PCT/EP2002/012581
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German (de)
English (en)
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WO2003042155A3 (fr
Inventor
Frank Funke
Ulrich Steinbrenner
Ralf Böhling
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Basf Aktiengesellschaft
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Priority to AU2002358006A priority Critical patent/AU2002358006A1/en
Publication of WO2003042155A2 publication Critical patent/WO2003042155A2/fr
Publication of WO2003042155A3 publication Critical patent/WO2003042155A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes

Definitions

  • Ethyldimethylamine is an important large-scale product. It is mainly used in the foundry industry, in the so-called cold box process. Small amounts are used in the pharmaceutical industry.
  • Triethylamine can be used in many ways, for example as a starting material for emulsifiers, dispersants, rust preventers or dyeing aids for fibers. TEA is also used in the manufacture of active pharmaceutical ingredients and agrochemicals. It also serves as a catalyst for basic catalyzed reactions.
  • EDMA ethyldimethylamine
  • TAA triethylamine
  • DMA dimethylamine
  • DEA diethylamine
  • EDMA can be prepared according to H. Lehmkuhl, D. Reinehr, Journal of Organometallic Chemistry 1973, 55, 215-220 by reacting tetramethylethylenediamine with ethylene in the presence of alkyl lithium or LiNEt as a catalyst.
  • the addition of DMA to propylene is also described.
  • TEA is produced by adding DEA to ethylene under LiEt catalysis.
  • the use of Li catalysts is described as being particularly advantageous compared to Na catalysts. The formation of by-products and the use of expensive starting material or catalyst are disadvantageous.
  • LiNEt 2 lithium diethylamide
  • the object of the invention is therefore to provide a process by which EDMA and TEA can be produced in good yields and high purity using an inexpensive catalyst.
  • Both TEA and EDMA can be produced in good yield and purity by catalysis of NaNEt or NaNMe 2 .
  • NaNMe 2 is preferred in an amount of 1,0 1.0 mol%, particularly preferably in an amount of 0,8 0.8 mol%, very particularly preferably in an amount of 0,2 0.25 mol% %, - based on DMA - used.
  • the process according to the invention can generally produce EDMA in a yield of Ausbeute 90%, in particular in a yield 95 95%, especially in particular in a yield 99 99%, based on DMA.
  • the yield of TEA is generally ⁇ 40%, especially ⁇ 45%, especially ⁇ 50% - based on DEA.
  • the formation of significant amounts of by-products is not observed. Under certain circumstances, only unreacted dialkylamine can be recovered, which can preferably be reacted again after recycling.
  • the purity of the valuable products EDMA and TEA is generally> 99%.
  • the DMA or DEA used generally has an H 2 O content 0,5 0.5% by weight, preferably 0,3 0.3% by weight, particularly preferably 0,1 0.1% by weight; the MeOH content is generally ⁇ 0.05% by weight, preferably ⁇ 0.03% by weight, particularly preferably ⁇ 0.01% by weight.
  • Styrene, isoprene and butadiene are suitable as “electron scavengers”.
  • Butadiene is preferably used.
  • Suitable inert organic solvents are all inert, saturated hydrocarbons and all saturated (mixed) trialkylamines, the critical point of which is above the melting point of the Na.
  • Preferred solvents are those which are to be produced by the process, that is to say EDMA or TEA.
  • the temperatures in the catalyst preparation are generally 20 to 120 ° C, preferably 30 to 90 ° C, particularly preferably 50 to 70 ° C.
  • the catalyst is preferably produced at pressures from 1 to 200 bar, particularly preferably at pressures from 5 to 50 bar and very particularly preferably at pressures from 10 to 40 bar.
  • N 2 and noble gases are used as protective gas.
  • Their O 2 content is generally 3 to 5% by volume, preferably ⁇ 1% by volume, and their H 2 O content is ⁇ 0.1% by volume.
  • the NaNR catalyst can be prepared both in situ in the reaction space in which the dialkylethylamine is produced, and in a separate vessel and then transferred to the reaction space.
  • the catalyst is preferably produced in a separate vessel and added continuously during the process, so that it is present in the above-mentioned concentration ranges in the reactor space.
  • the NaNR catalyst can be present either homogeneously dissolved in an inert organic solvent or as a suspension if the amount of solvent is reduced in such a way that the solubility product of the catalyst in the solvent in question falls below.
  • Inert organic solvents are usually those in which the catalyst was prepared.
  • the NaNR 2 catalyst used in the process according to the invention is particularly inexpensive. Since generally only small amounts of catalyst ⁇ 1 mol% - based on the dialkylamine are necessary to achieve high conversions, this makes the entire process according to the invention even more cost-effective.
  • the catalyst activity remains largely constant in a concentration range from 0.1 to 1 mol% and delivers dialkylamine conversions of approximately the same size.
  • the prior art Pure & Applied Chem. 1985, 57 (12), 1917-1926; see in particular Table 1, Run 4
  • meaningful conversions can only be achieved with an amount of catalyst of 5 mol%, the conversion increases with increasing amount of catalyst.
  • the reaction is generally carried out at a temperature of 20 to 200 ° C.
  • the reaction of DMA with ethylene is preferably carried out at a temperature of 30 to 120 ° C., particularly preferably at a temperature of 40 to 90 ° C.
  • the reaction of DEA with ethylene is preferably carried out at a temperature of 30 to 150 ° C., particularly preferably at a temperature of 40 to 120 ° C.
  • the reaction temperature of the process is advantageously controlled by the amount of ethylene added.
  • the ethylene partial pressure is generally 3 to 250 bar, preferably 5 to 100 bar, particularly preferably 20 to 50 bar.
  • the ethylene partial pressure is generally 10 to 250 bar, preferably 20 to 100 bar, particularly preferably 20 to 50 bar.
  • NaH can also be used as a catalyst in the production of EDMA. Here, it is formed in situ as the active species of NaH and Me NH traces NaNMe. 2
  • This NaNMe 2 is prepared analogously to that in CA Brown, Journal of American Chemical Society 1973, 95 (3), 982-983, in JD Halliday et al., Canadian Journal of Chemistry 1978, 56 (11), 1455-1462 and in Houben-Weyl, Methods of Organic Chemistry, Volume XI / 2 nitrogen compounds II and III, Georg Thieme Verlag Stuttgart 1958, 4th edition, pp. 183-187.
  • reaction of DMA with ethylene generally takes place at temperatures from 70 to 160 ° C., preferably at temperatures from 80 to
  • the Ethylene partial pressure is generally 10 to 250 bar, preferably 20 to 100 bar, particularly preferably 30 to 70 bar.
  • the NaH catalyst is generally used in an amount of ⁇ 1 mol%, preferably in an amount of ⁇ 0.8 mol%, particularly preferably in an amount of ⁇ 0.25 mol%.
  • the reaction temperature of the process is advantageously controlled by the amount of ethylene added.
  • the reaction of dialkylamine with ethylene can be carried out batchwise or continuously with partial or full conversion of dialkylamine and / or ethylene. It can be carried out in different reactors. Examples include a bubble column, a stirred tank, a jet loop reactor or a reactor cascade. A combination of the reactor types mentioned is also possible. In the case of discontinuous operation, almost quantitative conversion to EDMA is achieved when using DMA. If one would also like to achieve a quantitative conversion in the case of a continuous procedure of the process, this is possible by using cascaded reactor systems, for example by using a cascaded bubble column. However, you can also connect several reactors in series.
  • a cascaded bubble column means a reactor tower with internals, the individual compartments of the reactor being separated in such a way that backmixing is suppressed.
  • the catalyst can be prepared in the reactor using the methods described. By subsequently adding the reaction starting materials, both catalyst preparation and hydroamination can be carried out in the same reactor.
  • the end of the reaction can be recognized by conventional methods such as on-line gas chromatography (on-line GC), on-line infrared spectroscopy (on-line IR) or on-line determination of the refractive index, as well as by constant pressure or changing heat tone.
  • the reaction mixture can be distilled off directly from the reactor space.
  • the catalyst remains in the reactor space and can be used for further reactions.
  • the separated reaction mixture can continue to separate by distillation. Since the reaction is generally carried out in a batchwise procedure until the DMA is converted almost quantitatively, all that is required is to separate off the excess ethylene in order to obtain EDMA in high purity (see above).
  • the purity can be determined, for example, using gas chromatography analysis. Further purification is advantageously not necessary.
  • the separated ethylene is preferably recycled in whole or in part.
  • the reaction mixture obtained by the continuous procedure can be further purified after being discharged from the reactor space, for example by flash evaporation or distillation.
  • unreacted ethylene and / or DMA are taken off overhead in a distillation column and are preferably returned in whole or in part to the reactor.
  • the desired product EDMA is drawn off via the sump or via a preferably vaporous side draw in the stripping section.
  • reaction mixture Before the purification, the reaction mixture is optionally subjected to a filtration, for example a nano or membrane filtration, in order to separate off any catalyst carried along with the reaction mixture. All or part of this separated catalyst is preferably returned to the reaction space.
  • a filtration for example a nano or membrane filtration
  • the catalyst is not separated from the reaction mixture, it is obtained in the bottom of the distillation column or in the liquid phase of the flash, and is then preferably also returned to the reactor space.
  • conversions of 50 to 100% can be achieved in the case of the production of EDMA, both in a continuous and in a batchwise procedure. Both in a continuous and in a discontinuous procedure, conversions of 10 to 100%, preferably 25 to 100%, particularly preferably 40 to 100%, are achieved in the production of TEA.
  • the space-time yields in the production of EDMA in a continuous process are generally> 0.05, in particular> 0.1, in particular in particular> 0.2, kg EDMA per liter flow volume and hour [kg / mi] in a discontinuous manner
  • the space-time yields in the continuous process are> 0.02, in particular> 0.05, especially in particular> 0.1 kg TEA per liter flow volume and hour [kg / lh], in a batch process> 0.05, in particular> 0.1, especially> 0.2 kg TEA per liter flow volume and hour [kg / hh].
  • the space-time yield is not proportional to the catalyst concentration in the process according to the invention.
  • the turn-over numbers for NaNMe 2 are generally> 100, especially> 400, especially> 700.
  • the turn-over numbers are generally> 30, especially> 50, especially especially> 80. If particularly pure solvents are used and protic impurities in particular are minimized, even higher turn-over numbers can be achieved.
  • Figures 1 to 3 show systems in which the method according to the invention is preferably carried out.
  • EDMA or TEA are used as solvents for the catalyst.
  • Fig. 1 Plant for the production of dialkylethylamine for continuous operation using a catalyst suspension of NaNR 2 .
  • Fig. 2 Plant for dialkylethylamine production for continuous operation using a catalyst solution of NaNR 2 .
  • R 2 NH is fed continuously via a feed line 1 and ethylene via a feed line 2 to a stirred tank 10 with a heating or cooling jacket, in which the NaNR 2 catalyst is already present as a suspension.
  • the coolant is supplied via line 4 and discharged via line 5.
  • the starting materials are generally allowed to react with one another at 20 to 200 ° C.
  • DMA and ethylene are preferably allowed to react with one another at a temperature of 30 to 120 ° C., particularly preferably at a temperature of 40 to 90 ° C.
  • the production of TEA is preferably carried out at temperatures from 30 to 150 ° C., particularly preferably at temperatures from 40 to 120 ° C.
  • the ethylene partial pressure in the production of EDMA is 3 to 250, preferably 5 to 100 bar, particularly preferably 20 to 50 bar. If TEA is produced, the ethylene partial pressure is generally 10 to 250, preferably 20 to 100 bar, particularly preferably 20 to 50 bar.
  • Part of the reaction mixture is continuously transferred to a flash container 30.
  • the catalyst and any high-molecular impurities that are present are either wholly or partly returned to the reactor space and / or wholly or partly discharged.
  • the gaseous withdrawal of the flash is transferred to a distillation column 40.
  • the more volatile starting materials are withdrawn overhead into a condenser, the gaseous exhaust stream from the condenser 60 being fed back to the reactor via an ejector jet nozzle 50 and the condensate obtained in the condenser 60 in whole or in part as reflux is returned to the distillation column 40 and / or supplied in whole or in part to the reactor 10.
  • the product of value R 2 NEt is the derivative 3 the swamp or Stripping section of the distillation column 40 removed.
  • a heat exchanger 20 is also connected in order to ensure the gas-liquid flow in the column.
  • R 2 NH is fed continuously via a feed line 1 and ethylene via a feed line 2 via a nozzle 80 to a tube bundle heat exchanger 70 with internal cooling, which is used as a reactor and in which one NaNR 2 solution is supplied.
  • the R NH flows inside, while ethylene flows outside.
  • the ethylene partial pressure in the production of EDMA is 3 to 250, preferably 5 to 100 bar, particularly preferably 20 to 50 bar. If TEA is produced, the ethylene partial pressure is generally 10 to 250, preferably 20 to 100 bar, particularly preferably 20 to 50 bar.
  • the starting materials are allowed to react with one another at 20 to 200.degree.
  • DMA and ethylene are preferably allowed to react with one another at a temperature of 30 to 120 ° C., particularly preferably at a temperature of 40 to 90 ° C.
  • the production of TEA is preferably carried out at temperatures from 30 to 150 ° C., particularly preferably at temperatures from 40 to 120 ° C.
  • a part of the reaction mixture is continuously withdrawn from the reactor 70 and transferred directly to a distillation column 40.
  • the catalyst and any high-boiling impurities collect at the bottom of the column and are wholly or partially returned from there to the reactor space and / or wholly or partially discharged.
  • the more volatile starting materials are drawn off at the top of the distillation column 40 into a condenser 60, the gaseous draw stream of the condenser 60 being fed to the feed of the reactor via an ejector jet nozzle 50, and the condensate of the condenser 60 being wholly or partly returned to the distillation column 40 as reflux and / or all or part of the reactor 70 is fed via the nozzle 80.
  • the product of value R 2 NEt is removed via a side draw 7 in the stripping section of the distillation column.
  • a heat exchanger 20 is also connected in order to ensure the gas-liquid flow in the column.
  • the method according to the invention is also preferred in a cascaded bubble column 90 with an integrated gas circulation reactor, which can be equipped with internal and / or external cooling, as used in a system according to FIG. 3.
  • a cascaded column of this type in the case of Me 2 NH, a yield of ⁇ 95%, in particular ⁇ 99%, in particular ⁇ 99.5%, based on Me 2 NH, can be achieved even in the case of continuous driving.
  • the dialkylamine R 2 NH is preferably introduced into the bubble column from above via a feed line 1 via a nozzle 80.
  • the ethylene is introduced into the column from below via a feed line 2 at a partial pressure of 3 to 250 bar, preferably 5 to 100 bar, particularly preferably 20 to 50 bar.
  • the ethylene partial pressure is from 10 to 250 bar, preferably from 20 to 100 bar, particularly preferably from 20 to 50 bar.
  • the reaction temperature in the column is 20 to 200 ° C.
  • the reaction temperature is preferably 30 to 120 ° C, particularly preferably 40 to 90 ° C.
  • the production of TEA is preferably carried out at temperatures from 30 to 150 ° C., particularly preferably at temperatures from 40 to 120 ° C.
  • the reaction mixture is continuously removed from the lowest compartment of the column and transferred to a flash container 30.
  • the more volatile constituents are evaporated and, after condensation in an intermediate condenser 60, transferred to a buffer container 100. If they still contain catalyst, the less volatile constituents - after admixing to the volatile constituents drawn off from the bubble column and after preheating via a heat exchanger 20 - are wholly or partly mixed with the dialkylamine flowing into the bubble column and thus returned to the reactor space. If the less volatile components no longer contain a catalyst, they are removed. Dissolved ethylene can still escape from the buffer tank 100 via line 8.
  • the gaseous discharge from the condenser 60 is admixed by means of ejector nozzles 50 to the dialkylamine flowing into the bubble column and thus returned to the reactor space.
  • the dialkylethylamine product of value condensed in the buffer container 100 is removed via a discharge line 3.
  • examples 1 to 7 DMA or DEA are reacted with ethylene in the presence of NaNMe 2 or NaNEt 2 as a catalyst, the amount of catalyst being varied. The results are tabulated, with RZA space-time yield means and is given in kg product per liter flow volume and hour.
  • examples 8 to 10 the reaction in the presence of NaNR 2 as a catalyst and in the presence of NaH as a catalyst, NaNR 2 only being formed in situ, is compared with one another.
  • Example 1 was repeated with 10 mmol sodium dimethylamide in 5 g dodecane.
  • Example 3 Production of EDMA at a catalyst concentration of 0.12 mol%
  • Example 1 was repeated with 5 mmol sodium dimethylamide in 2.5 g dodecane.
  • Example 4 was repeated with 30 mmol sodium dimethylamide in 10 g dodecane.
  • the reaction rate is still 73% of the original reaction rate.
  • the turnover number can be increased drastically with a slight reduction in the reaction rate.
  • Embodiment 4 was repeated at 90 ° C.
  • Example 6 was repeated with 30 mmol sodium diethylamide in 10 g dodecane.
  • Embodiment 10 is a diagrammatic representation of Embodiment 10:
  • a comparison of the exemplary embodiments 8, 9 and 10 shows that - even if NaNMe 2 is only formed in situ - similarly good sales are achieved.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation de dialkyléthylamines R2NEt à partir de dialkylamines R2NH et d'éthylène en la présence de dialkylamide de sodium NaNR2 en tant que catalyseur, avec R = méthyle ou éthyle, la concentration en NaNR2 étant </= 1,0 % molaire, de préférence </= 0,8 % molaire, de préférence </= 0,25 % molaire les pourcentages se rapportant à R2NH - lorsque R = éthyle.
PCT/EP2002/012581 2001-11-12 2002-11-11 Procede de preparation de dialkylethylamines a partir de dialkylamines et d'ethylene WO2003042155A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002358006A AU2002358006A1 (en) 2001-11-12 2002-11-11 Method for producing dialkyl ethyl amines from dialkyl amines and ethylene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2001155525 DE10155525A1 (de) 2001-11-12 2001-11-12 Verfahren zur Herstellung von Dialkylethylaminen aus Dialkylaminen und Ethylen
DE10155525.3 2001-11-12

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WO2003042155A2 true WO2003042155A2 (fr) 2003-05-22
WO2003042155A3 WO2003042155A3 (fr) 2003-10-09

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2501556A (en) * 1949-12-16 1950-03-21 Du Pont Alkali metals and their hydrides as catalysts in amine condensation
US2750417A (en) * 1953-04-14 1956-06-12 Ethyl Corp Amine alkylation
US2984687A (en) * 1956-04-27 1961-05-16 Standard Oil Co Catalytic process for n-alkylation of amines
WO2002000597A2 (fr) * 2000-06-28 2002-01-03 Basf Aktiengesellschaft Procede de production d'alkylamines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2501556A (en) * 1949-12-16 1950-03-21 Du Pont Alkali metals and their hydrides as catalysts in amine condensation
US2750417A (en) * 1953-04-14 1956-06-12 Ethyl Corp Amine alkylation
US2984687A (en) * 1956-04-27 1961-05-16 Standard Oil Co Catalytic process for n-alkylation of amines
WO2002000597A2 (fr) * 2000-06-28 2002-01-03 Basf Aktiengesellschaft Procede de production d'alkylamines

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PEZ, GUIDO P. ET AL.: PURE & APPL. CHEM., Bd. 57, Nr. 12, 1985, Seiten 1917-1926, XP001091218 in der Anmeldung erw{hnt *
STEINBORN, DIRK ET AL.: Z. CHEM. , Bd. 29, Nr. 9, 1989, Seiten 333-334, XP001091225 *

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AU2002358006A1 (en) 2003-05-26
WO2003042155A3 (fr) 2003-10-09
DE10155525A1 (de) 2003-05-22

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