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EP2132163A1 - Procédé de fabrication d'éthylénamines à partir d'aan brut - Google Patents

Procédé de fabrication d'éthylénamines à partir d'aan brut

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Publication number
EP2132163A1
EP2132163A1 EP08717206A EP08717206A EP2132163A1 EP 2132163 A1 EP2132163 A1 EP 2132163A1 EP 08717206 A EP08717206 A EP 08717206A EP 08717206 A EP08717206 A EP 08717206A EP 2132163 A1 EP2132163 A1 EP 2132163A1
Authority
EP
European Patent Office
Prior art keywords
aan
hydrogenation
idan
mixture
ammonia
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Withdrawn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
EP08717206A
Other languages
German (de)
English (en)
Inventor
Kirsten Dahmen
Alfred Oftring
Randolf Hugo
Thilo Hahn
Katrin Baumann
Johann-Peter Melder
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
Priority to EP08717206A priority Critical patent/EP2132163A1/fr
Publication of EP2132163A1 publication Critical patent/EP2132163A1/fr
Withdrawn legal-status Critical Current

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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
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/20—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
    • C07C211/21—Monoamines

Definitions

  • the invention relates to a process for preparing an ethylene amine mixture by hydrogenating an aminonitrile mixture over a catalyst, wherein the aminonitrile mixture is prepared from crude AAN. From the resulting Ethylenamingemisch the individual ethyleneamines can be optionally isolated.
  • nitriles can be hydrogenated in the presence of catalysts to the corresponding amines.
  • the known processes provide the desired products, for example primary amines as the main product and secondary and tertiary amines as by-products.
  • the problem here is often that the desired product is obtained with low selectivity and / or low yield, often accompanied by a rapid inactivation of the catalyst used.
  • DE-A 3 003 729 describes a process for hydrogenating aliphatic nitriles, alkylnoxynitriles and alkyleneaminonitriles to primary amines in the presence of a solvent system on a cobalt or ruthenium catalyst.
  • the solvent system used contains, in addition to water and ammonia, an ether or polyether preferably having 4 to 6 carbon atoms, and a carbon to oxygen ratio of 2: 1 to 5: 1, such as dioxane, tetrahydrofuran, methylene glycol dimethyl ether or diethylene glycol dimethyl ether, cyclic ethers such as dioxane and Tetrahydrofuran are particularly preferred.
  • the nitrile component dinitriles are particularly preferred.
  • DE-A 3003 729 does not disclose that compounds which have both a cyano group and an ⁇ -position amino group, such as AAN, can also be used in the process.
  • EP-A 0 382 508 describes a process for the batchwise preparation of non-cyclic, aliphatic polyamines by hydrogenation of non-cyclic, aliphatic polynitriles in the liquid phase over Raney cobalt catalysts, preferably in the presence of anhydrous ammonia.
  • a polynitrile solution is fed to a reaction zone containing the Raney cobalt catalyst in an essentially oxygen-free atmosphere. Throughout the reaction period, the polynitrile solution is fed at a rate no greater than the maximum rate at which the polynitrile reacts with the hydrogen in the reaction zone.
  • a reaction parameter K is named, which is suitable for determining the volumetric feed rate.
  • EP-A 212 986 relates to a further process in which aliphatic polynitriles can be hydrogenated to the corresponding polyamines in the presence of a liquid primary or secondary amine present in the educt stream on a granular Raney cobalt catalyst.
  • EDA the compelling amino acid component
  • IDAN can be hydrogenated to DETA.
  • DE-A 1 154 121 relates to a process for the preparation of ethylenediamine, in which the educts hydrocyanic acid, formaldehyde, ammonia and hydrogen are reacted in the presence of a catalyst in a so-called one-pot process. Both the ammonia and the hydrogen are used in molar excess compared to the present in equimolar amounts of further educts hydrocyanic acid and formaldehyde. In this method, therefore, the AAN formed in situ is not isolated, but further reacted directly with hydrogen.
  • a disadvantage of this method is that the desired products (EDA) is obtained relatively unselective in small quantities.
  • US Pat. No. 3,255,248 describes a process for the hydrogenation of organic nitrogen-carbon compounds, which preferably comprises nitro, N-nitroso, isonitroso, cyano or amino groups substituted with aromatics, to the corresponding liquid phase amines using a cobalt or nickel sintered catalyst.
  • the reactant is either alone or in the presence of a solvent, such as water, Tetra h yd rofu ran, methanol, ammonia or the reaction product formed, down drizzled down to the catalyst together with the hydrogen.
  • a solvent such as water, Tetra h yd rofu ran, methanol, ammonia or the reaction product formed, down drizzled down to the catalyst together with the hydrogen.
  • unsaturated compounds, such as cyano groups are hydrogenated on the nitrogen atom, the presence of ammonia during the reaction is recommended. This is illustrated in Example 1 of this patent, where aminoacetonitrile is sprinkled on the sintered catalyst in the form of an aqueous solution with liquid
  • EP-A 1 209 146 relates to a further process for the continuous hydrogenation of nitriles to primary amines, wherein the respective nitriles are used in the liquid phase on a suspended, activated Raney catalyst based on an aluminum alloy and the reaction in the absence of ammonia and basic alkali or alkaline earth compounds is performed.
  • AAN and IDAN can also be converted to the corresponding ethyleneamines.
  • the nitrile to be hydrogenated may also be dissolved in an organic solvent, preferably alcohols, amines, amides, in particular N-methylpyrrolidone (NMP) and dimethylformamide (DMF), and ethers or esters are used.
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • US-A 5,079,380 relates to a process for the preparation of AAN, wherein ammonia (NH 3), formaldehyde (HCHO) and hydrogen cyanide (HCN) are reacted at at least 100 0 C.
  • first formaldehyde and hydrocyanic acid can be converted to formaldehyde cyanohydrin (FACH) as an intermediate, which is then reacted with ammonia to form AAN.
  • FACH formaldehyde cyanohydrin
  • the molar ratio of ammonia to FACH or to formaldehyde and hydrogen cyanide is> 4: 1 [mol / mol].
  • the temperatures in the AAN synthesis are 50 to 80 0 C and the pH is about 10.
  • the conversion to IDAN usually takes place at higher temperatures (about 100 to 150 0 C), a lower pH of about 5 to 7 and at a lower ammonia content than in the corresponding synthesis of AAN.
  • Such processes for the preparation of IDAN are described, for example, in EP-A 426 394 or US Pat. No. 4,895,971.
  • IDAN can also be carried out by the reaction of urotropin (hexamethylenetetraamine, HMTA) with hydrocyanic acid and formaldehyde, as described, for example, in US Pat. No. 3,988,360.
  • urotropin hexamethylenetetraamine, HMTA
  • hydrocyanic acid and formaldehyde as described, for example, in US Pat. No. 3,988,360.
  • US-A 2,511,487 relates to a process in which IDAN is prepared starting from AAN.
  • AAN is mixed with FACH in a molar ratio of about 1: 0.3 to 1, 5 [mol / mol] and heated in the presence of a mineral acid stabilizer, such as phosphoric acid at 100 to 150 0 C.
  • a mineral acid stabilizer such as phosphoric acid
  • the reaction preferably takes place at 135 to 150 ° C. and for a maximum of 15 minutes.
  • the process according to US Pat. No. 2,511,487 takes place in a conventional bulb with cooling device.
  • a high conversion is achieved with respective high selectivity, the ratio of DETA to EDA is variable and can be adjusted specifically.
  • step b) hydrogenation of the aminonitrile mixture obtained in step a) in the presence of a catalyst.
  • the process according to the invention has the advantage that the main components of the ethylene amine mixture (EDA and DETA) can be prepared at high conversion and / or selectivity (higher space-time yield).
  • the aminonitrile mixture used is completely or almost completely reacted. This is particularly important in large-scale processes of importance since unreacted educt is usually returned to the production cycle or must be disposed of.
  • Methods in which larger amounts of AAN and / or IDAN are not reacted are of particular disadvantage because of the high instability of the AAN or IDAN.
  • both AAN and IDAN tend to decompose at higher temperatures, so that the decomposition products do not enter the respective circuit.
  • this decomposition can also proceed with explosive violence.
  • the hydrogen cyanide liberated during the decomposition can significantly increase the catalyst consumption. Since in the process according to the invention the aminonitrile mixture can be completely reacted, no efforts have to be made with regard to its return to the production cycle.
  • the process according to the invention is carried out continuously. This is due to the fact that, in principle, the ratio of the starting materials IDAN to AAN in the product with respect to DETA is found again in EDA.
  • EDA the ratio of the starting materials IDAN to AAN in the product with respect to DETA
  • specific amino-nitrile mixture compositions in a targeted manner in order to serve the quantity ratios desired in the market.
  • the process according to the invention gives, with high selectivity, an ethylene amine mixture which preferably contains at least 30% EDA, in addition to at least 5% DETA, and optionally further ethylene amines as valuable products.
  • the process according to the invention has the advantage that it is possible to prepare an aminonitrile mixture which contains defined amounts of the two main constituents AAN and IDAN. It is very possible to prepare a mixture containing AAN and from 5 to 70% by weight of IDAN. Thus, with the method according to the invention, an IDAN content in the aminonitrile mixture can be adjusted variably. This is done in a simple way, since only one starting material (AAN) has to be prepared, from which, in part, in the context of the process according to the invention, IDAN is formed.
  • AAN starting material
  • Another essential advantage of the process according to the invention is the fact that, starting from only one starting material (crude AAN), two (main) products (EDA and DETA) can be prepared in variable ratios to one another.
  • IDAN is solid at room temperature and poorly soluble in common inert solvents. Due to the good solubility of the solid aminonitriles in AAN, the handling of solids can be avoided in the process according to the invention. For example, at room temperature only -10% IDAN is soluble in THF, while dissolved in AAN concentrations up to -35% (at 40 0 C -52%) are possible. Another advantage is that the aminonitriles in the raw state under the usual conditions (RT) are only limited shelf life and thus separate production and mixing is impractical.
  • Another disadvantage of the separate preparation of DETA is its strong complexity of the catalyst.
  • the resulting product inhibition results in a relatively slow hydrogenation rate.
  • the product inhibition is significantly lower, so that a significantly higher hydrogenation rate of AAN, probably because of lower complex constants, is possible.
  • the hydrogenation of IDAN is carried out in the presence of at least 30% by weight of AAN as in the process according to the invention, the product inhibition is reduced.
  • the space-time yield of the respective components is greater than in the corresponding hydrogenation of the individual components, or the hydrogenation of the mixture can be carried out at significantly lower pressures, which means significantly lower investment.
  • the crude AAN As a crude AAN, it is generally possible to use any type of AAN in the process according to the invention. Usually, however, the crude AAN is present as an aqueous or aqueous ammoniacal solution.
  • the AAN content in the crude AAN is usually 5 to 98% by weight, preferably 10 to 90% by weight.
  • the solvent is not included in the data in wt .-%.
  • Step a) can be carried out in principle in any device.
  • step a) of the process according to the invention can be carried out in the same apparatus as the previous synthesis of the crude AAN, or step a) is carried out in a separate apparatus.
  • the process according to the invention is preferably carried out in the same reactor as the synthesis of the crude AAN.
  • a single reactor or a single apparatus is preferably used in which the individual steps described (crude AAN preparation, NH 3 removal, partial conversion of AAN to IDAN) are carried out in succession.
  • the desired reaction conditions for each step are set in succession.
  • Suitable reactor types are for example stirred tank, loop reactor, kettle or stirred tank with attached distillation column, each with or without external circulation, the outer circulation is used for temperature control, or the reaction takes place wholly or partly in the outer heat exchanger.
  • the combination of reaction and distillation in a continuous or discontinuous reactive distillation column is possible.
  • ammonia liberated from the apparatus can also be removed when adjusting the desired aminonitrile mixture, for example by distilling NH 3 off.
  • a simultaneous ammonia depletion and aminonitrile mixture synthesis is carried out in a kettle or stirred tank with attached distillation column or in a reactive distillation column.
  • the molar ratio of ammonia to AAN is set to be ⁇ 2.5: 1 [mol / mol].
  • the crude AAN is prepared in a device and subsequently passed through a separate device (V1).
  • the crude AAN is heated at a temperature of 70 to 150 ° C.
  • the temperature is 80 to 130 0 C.
  • the residence time in the device (V1) is preferably at most 30 minutes.
  • a device (V1) are in principle all devices through which the AAN can be passed in the specified temperature range.
  • the Device (V1) a tubular reactor, a flow tube, a falling film evaporator or a thin film evaporator. These reactor types can be operated individually or connected in cascade. By partially impressed reaction conditions, a reactor cascade can also be realized in a single apparatus, for example in a flow tube with different temperature zones.
  • Step a) of the process according to the invention can be carried out both as (semi) -batch or preferably continuously.
  • the preparation of the aminonitrile mixture takes place directly after the synthesis of the crude AAN.
  • the crude AAN is prepared by reacting ammonia with FACH.
  • the process according to the invention in step a) can be used to prepare aminonitrile mixtures which comprise AAN as main components and 5 to 70% by weight of IDAN.
  • the IDAN content is 5 to 50 wt .-%, more preferably 10 to 40 wt .-%, particularly preferably 10 to 25 wt .-%.
  • the proportion of AAN is usually 30 to 95 wt .-%, preferably 50 to 95 wt .-%, particularly preferably 75 to 90 wt .-%.
  • the above percentages by weight of AAN and IDAN refer to the total amount of aminonitriles present in the mixture.
  • any solvent or other by-products, such as other aminonitriles or other impurities are not included in these quantities.
  • a higher temperature is selected.
  • the higher the selected temperature the higher the IDAN content in the aminonitrile mixture; ii) it is selected as long as possible (but usually not more than 30 minutes), during which the crude AAN is heated.
  • the longer the time during which the crude AAN is exposed to an elevated temperature the higher the IDAN content in the aminonitrile mixture; or iii) the NH 3 content in the device is reduced.
  • a temperature increase favors the NH 3 removal and thus leads according to i) and iii) to a higher IDAN content. As the NH 3 content decreases, so does the
  • the two main components of the aminonitrile mixture are AAN and IDAN.
  • IDAN is a solid at room temperature, while AAN is a liquid, with IDAN largely dissolving in AAN.
  • the aminonitrile mixture obtained in step a) is subjected directly to the hydrogenation as liquid or aqueous solution. Since the aminonitrile mixture can be fed in as liquid of the hydrogenation in the reaction conditions used in step b) of the process according to the invention, it is not absolutely necessary for the hydrogenation of the aminonitrile mixture to be carried out in the presence of another solvent such as an organic solvent.
  • step b) proves to be advantageous since stabilization of the individual components of the aminonitrile mixture, in particular in the presence of the resulting amines, can be achieved, in particular through the use of an organic solvent .
  • solvents makes it possible to achieve a rinsing effect on the catalyst used, as a result of which its service life is increased or its consumption lowered and the catalyst load can be improved.
  • a suitable solvent for step b), which may comprise one or more components, should preferably have the following properties:
  • the solvent should stabilize the components of the aminonitrile mixture, in particular reduce decomposition of AAN or IDAN at the prevailing temperatures;
  • reaction mixture amino acid mixture, water from synthesis and solvent
  • solvent selection should be carried out with regard to a preferably distillative separation of the product after the hydrogenation from the product stream, wherein energetic or expensive apparatus separations (eg engsie- dende mixtures or difficult to separate acetone) are to be avoided.
  • Possible solvents are organic solvents, for example amides, such as N-methylpyrrolidone (NMP) and dimethylformamide (DMF), aromatic and aliphatic hydrocarbons, such as benzene and xylene, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol and tertiary Butanol, amines, such as ethyleneamines, alkylamines, esters, such as methyl acetate or ethyl acetate, and ethers, such as diisopropyl ether, diisobutyl ether, glycol dimethyl ether, diglycol dimethyl ether, dioxane and tetrahydrofuran (THF).
  • ethers preference is given to using ethers, more preferably cyclic ethers and particularly preferably tetrahydrofuran.
  • alcohols in
  • the solution used for the production of ethyleneamines by hydrogenation of the aminonitrile mixture may, in addition to the aminonitrile mixture and optionally the solvent, also contain a proportion of water (from used FACH and reaction water).
  • additional additives may be included in the solution in which the hydrogenation is carried out.
  • hydroxides such as alkali metal hydroxides, alkoxides, amides or amines are suitable as additives.
  • acidic additives such as silicates, may additionally be included in the solution. These substances can be added as a pure substance or dissolved in a solvent. The process according to the invention is preferably carried out without the addition of additives.
  • step b) no ammonia is added to the solution in which the hydrogenation according to step b) is carried out. If still Ammonia is contained in the aminonitrile mixture obtained from step a) or is released as a by-product in the hydrogenation, this is not disturbing. Optionally existing ammonia can be removed by methods known to those skilled in the art, for example by distillation.
  • catalysts for the hydrogenation of the nitrile function to the amine catalysts can be used, which as active species one or more elements of the 8th subgroup of the periodic table (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt), preferred Fe, Co, Ni, Ru or Rh, more preferably Co or Ni.
  • the catalysts may additionally contain one or more promoters.
  • Raney catalysts are used in the process according to the invention, preferably Raney cobalt or Raney nickel catalysts and particularly preferably with at least one of the elements Cr, Ni or Fe doped Raney cobalt, or with one of the elements Mo, Cr or Fe doped Raney nickel catalysts.
  • the catalysts can be used as unsupported catalysts or supported.
  • the preferred carriers are metal oxides such as Al 2 O 3 , SiC> 2 , ZrC> 2 , TiC> 2 , mixtures of metal oxides or carbon (activated carbons, carbon blacks, graphite).
  • the oxidic catalysts are activated before use outside the reactor or in the reactor by reduction of the metal oxides in a hydrogen-containing gas stream at elevated temperature. If the catalysts are reduced outside the reactor, then passivation by an oxygen-containing gas stream or embedding in an inert material can be done to avoid uncontrolled oxidation in air and to allow safe handling. Organic solvents such as alcohols but also water or an amine, preferably the reaction product, can be used as the inert material.
  • An exception in the activation are the skeletal catalysts, which by leaching with aqueous base, such. As described in EP-A 1 209 146, can be activated.
  • the catalysts are used as powder, grit or shaped body (preferably extrudates or tablets).
  • Particularly preferred fixed bed catalysts are the full cobalt contacts disclosed in EP-A1 742 045, doped with Mn, P, and alkali metal (Li, Na, K, Rb, Cs).
  • the catalytically active mass of these catalysts consists of hydrogen before reduction 55 to 98 wt .-%, in particular 75 to 95 wt .-%, cobalt, 0.2 to 15 wt .-% phosphorus, 0.2 to 15 wt .-% manganese and 0.05 to 5 wt .-% Alkali metal, especially sodium, each calculated as oxide.
  • catalysts disclosed in EP-A 963 975 whose catalytically active composition before treatment with hydrogen contains 22 to 40% by weight ZrO 2 , 1 to 30% by weight oxygen-containing compounds of copper, calculated as CuO, 15 to 50% by weight of oxygen-containing compounds of nickel, calculated as NiO, the molar Ni: Cu ratio being greater than 1, 15 to 50% by weight of oxygenated compounds of cobalt, calculated as CoO, 0 to 10% by weight.
  • % oxygen-containing compounds of aluminum and / or manganese calculated as Al 2 O 3 or MnO 2 , and containing no oxygen-containing compounds of molybdenum, for example the catalyst A disclosed in this document with the composition 33% by weight Zr, calculated as ZrO 2 , 28 wt% Ni, calculated as NiO, 1 1 wt% Cu, calculated as CuO and 28 wt% Co, calculated as CoO.
  • catalysts disclosed in EP-A 696 572 whose catalytically active composition before reduction with hydrogen contains 20 to 85% by weight of ZrO 2 , 1 to 30% by weight of oxygen-containing compounds of copper, calculated as CuO, 30 to 70 wt .-% oxygen-containing compounds of nickel, calculated as NiO, 0.1 to 5 wt .-% oxygen-containing compounds of molybdenum, calculated as Mo ⁇ 3, and 0 to 10 wt .-% oxygen-containing compounds of aluminum and / or manganese, calculated as AI 2 O 3 or MnO 2 contains.
  • the specifically disclosed in this document catalyst having the composition 31, 5 wt .-% ZrO 2 , 50 wt .-% NiO, 17 wt .-% CuO and 1, 5 wt .-% MoO 3 .
  • catalysts described in WO-A-99/44984 comprising (a) iron or a compound based on iron or mixtures thereof, (b) from 0.001 to 0.3 wt .-% based on (a) Promoters based on 2, 3, 4 or 5 elements selected from the group AI, Si, Zr, Ti, V, (c) from 0 to 0.3 wt .-% based on (a) a compound based on an alkali and / or alkaline earth metal, and (d) from 0.001 to 1 wt .-% based on (a) manganese.
  • Raney catalysts are preferably used.
  • the active catalyst is produced as a 'metal sponge' from a binary alloy (nickel, iron, cobalt, with aluminum or silicon) by dissolving a partner with acid or alkali. Residues of the original alloying partner often act synergistically.
  • the soluble alloying component is wholly or partly extracted with alkali, for which example aqueous sodium hydroxide solution can be used.
  • alkali for which example aqueous sodium hydroxide solution can be used.
  • the catalyst can then z. B. be washed with water or organic solvents.
  • Activation of the catalysts by leaching the soluble component may be either in the reactor itself or prior to charging to the reactor.
  • the preactivated catalysts are sensitive to air and pyrophoric and are therefore usually under a medium such.
  • a medium such as water, an organic solvent or a substance that is present in the reaction according to the invention (solvent, starting material, product) stored and handled or embedded in an organic compound which is solid at room temperature.
  • the present invention uses a cobalt skeletal catalyst composed of a Co / Al alloy by leaching with aqueous alkali metal hydroxide solution, e.g. Sodium hydroxide solution, and subsequent washing with water was obtained and preferably contains as promoters at least one of the elements Fe, Ni, Cr.
  • aqueous alkali metal hydroxide solution e.g. Sodium hydroxide solution
  • such catalysts typically contain 1 to 30% by weight Al, especially 2 to 12% by weight Al, very particularly 3 to 6% by weight Al, 0 to 10% by weight Cr, especially 0.1 - 7 wt .-% Cr, more preferably 0.5 to 5 wt .-% Cr, in particular 1, 5 - 3.5 wt .-% Cr, 0 - 10 wt .-% Fe, especially 0.1 -.
  • a cobalt skeleton catalyst "Raney 2724" from W. R. Grace & Co. can be used as catalyst in the process according to the invention.
  • a nickel skeleton catalyst A 4000 Johnson Matthey can be used advantageously.
  • This catalyst has the following composition
  • the catalysts may optionally be regenerated with decreasing activity and / or selectivity by methods known to those skilled in the art, for example as disclosed in WO 99/33561 and the publications cited therein.
  • the regeneration of the catalyst can be carried out in the actual reactor (in situ) or on the removed catalyst (ex situ). In the case of fixed-bed processes, regeneration is preferably carried out in situ, in the case of suspension processes it is preferred to remove part of the catalyst continuously or batchwise, regenerate it ex situ and recycle it.
  • the temperatures at which step is carried out) of the process according to the invention b are in a range of 40 to 150 0 C, preferably from 70 to 140 0 C.
  • the pressure prevailing in the hydrogenation is generally from 5 to 300 bar, preferably from 30 to 250 bar, more preferably from 40 to 160 bar.
  • step a) If appropriate, one or more of the purification steps i) - iii) listed below can be carried out between step a) and step b).
  • ammonia can be completely or partially separated from the mixture and, if appropriate, if necessary after work-up, be recycled to the AAN synthesis. This can be done in one or more stages in an evaporator or an evaporator cascade, wherein different pressures or temperatures can be set from stage to stage.
  • the removal of ammonia can also take place in a distillation column, which is advantageous since HCN present in the aminonitrile mixture can be removed in this way.
  • the aminonitrile mixture obtained in step a) can either be used directly or after ammonia removal or after ammonia and water separation by adsorption of impurities on an adsorbent, e.g. Activated carbon or ion exchanger, be cleaned. This can e.g. carried out in an adsorption column filled with the adsorbent.
  • an adsorbent e.g. Activated carbon or ion exchanger
  • the aminonitrile mixture (in step b) is fed at a rate of hydrogenation which is not greater than the rate at which the aminonitrile mixture reacts with hydrogen in the hydrogenation.
  • the feed rate is preferably adjusted so that virtually full conversion is achieved. This is influenced by temperature, pressure, type of mixture, amount and type of catalyst, the reaction medium, mixing quality of the reactor contents, residence time, etc.
  • the optimal driving conditions can differ significantly in the hydrogenation of individual amino nitriles.
  • the driving conditions to be set are only slightly different depending on the composition and thus easier to optimize.
  • the flexibility of the machines and apparatus used is only slightly required, as it is standard by commercially available devices (eg flow rate of pumps, operating temperature of heat exchangers, pressure rating of the apparatus etc.).
  • the solvent can first be completely mixed with the aminonitrile mixture.
  • the resulting solution which may optionally also contain water and other additives, is then fed into the reaction vessel containing the catalyst.
  • a portion of the solvent may be initially introduced together with the catalyst in the reaction vessel, after which the solution is added.
  • a portion of the solvent may also be added to the reaction vessel separately from the solution containing the aminonitrile mixture, the solvent and optionally water. Since an AAN / IDAN mixture is used, a completely separate metered addition of the solvent is conceivable.
  • the AAN / IDAN mixture is added as aqueous or ammonia aqueous solution and the addition of the organic solvent is carried out separately.
  • step b) for the preparation of ethylene amines by hydrogenation of aminonitrile mixtures can be carried out continuously, semicontinuously or batchwise in customary reaction vessels suitable for catalysis in a fixed bed, fluidized bed, suspension process.
  • Reaction vessels are suitable for carrying out the hydrogenation, in which it is possible to contact the aminonitrile mixture and the catalyst with the gaseous hydrogen under pressure.
  • the hydrogenation in suspension mode can be carried out in a stirred reactor, jet loop reactor, jet nozzle reactor, bubble column reactor, or in a cascade of such identical or different reactors.
  • a stirred reactor jet loop reactor, jet nozzle reactor, bubble column reactor, or in a cascade of such identical or different reactors.
  • a fixed bed catalyst tubular reactors but also tube bundle reactors are conceivable.
  • the aminonitrile mixture is applied in a bottom-up or trickle-bed procedure.
  • the hydrogenation of the nitrile groups takes place with the release of heat, which usually has to be removed.
  • the heat can be removed by built-in heat exchanger surfaces, cooling jacket or external heat exchanger in a circulating circuit around the reactor.
  • the hydrogenation reactor or a hydrogenation reactor cascade can be run in straight passage.
  • a circulation cycle way possible, in which a portion of the reactor discharge is returned to the reactor inlet, preferably without prior workup of the circulation stream. In this way, an optimal dilution of the reaction solution can be achieved.
  • the circulation stream can be cooled by means of an external heat exchanger in a simple and cost-effective manner and thus the heat of reaction can be removed.
  • the reactor can also be operated adiabatically, wherein the temperature rise of the reaction solution can be limited by the cooled circulation stream. Since the reactor does not have to be cooled even then, a simple and cost-effective design is possible.
  • An alternative is a cooled tube bundle reactor (only in the case of the fixed bed). A combination of the two modes is conceivable. Here, preferably a fixed bed is followed by a suspension reactor.
  • the process according to the invention gives an ethylene amine mixture which comprises as main component EDA and DETA and as secondary components further ethylene amines (eg piperazine).
  • the ratio of the educts AAN and IDAN is found in principle after the hydrogenation in the corresponding products EDA and DETA again.
  • further DETA can be formed from AAN.
  • the DETA portion of the resulting amine mixture containing EDA as a major component may increase by 1-10% by weight.
  • the product obtained may optionally be further purified, for example by separating the solvent, water and / or the catalyst, if used, by methods known to those skilled in the art.
  • the two main products EDA and DETA
  • the two main products can be isolated from the ethylene amine mixture jointly or individually by methods known to those skilled in the art. If the two main products are isolated together, for example by distillation, they can then be isolated in the two individual products. Ultimately, pure EDA and pure DETA are thus obtained.
  • Other impurities, by-products or further ethylene amines can likewise be separated from the ethylene amine mixture by methods known to the person skilled in the art.
  • step b) of the process according to the invention is carried out using tetrahydrofuran or methanol as the solvent.
  • the temperature in the hydrogenation is preferably 80 to 140 0 C, the pressure preferably 40 to 160 bar.
  • the hydrogenation is carried out without the addition of ammonia.
  • the catalyst loading is preferably 0.3 to 20 mol of nitrile (corresponds to ⁇ 0.2 g to 12 g of AAN / g of cat), preferred Example 1 to 10 moles of nitrile ( ⁇ 0.5g-6g) per gram of catalyst per hour.
  • the excess ammonia can be partially or completely removed by flash evaporation.
  • the product mixture contains the following approximate composition:
  • VWZ residence time in the flow tube selectivity (AAN + IDAN): in all cases> 98%
  • Example 3 continuous hydrogenation / 30% by weight of water

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

Abstract

L'invention concerne un procédé de fabrication d'un mélange éthylénamine comportant les étapes suivantes : a) de l'aminoacétonitrile (AAN) brut essentiellement libre de formaldéhyde-cyanhydrine (FACH) est chauffé à une température de 50 à 150 ° de manière à former un mélange aminonitrile contenant de l'aminoacétonitrile (AAN) et 5 à 70 % en poids d'iminodiacétonitrile (IDAN); et b) le mélange aminonitrile obtenu en a) est hydrogéné en présence d'un catalyseur. Il est possible d'isoler de l'éthylène-diamine (EDA) et/ou de la diéthylène-triamine (DETA) et éventuellement d'autres éthylénamines à partir des mélanges éthylénamine obtenus.
EP08717206A 2007-03-01 2008-02-28 Procédé de fabrication d'éthylénamines à partir d'aan brut Withdrawn EP2132163A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08717206A EP2132163A1 (fr) 2007-03-01 2008-02-28 Procédé de fabrication d'éthylénamines à partir d'aan brut

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07103288 2007-03-01
EP08717206A EP2132163A1 (fr) 2007-03-01 2008-02-28 Procédé de fabrication d'éthylénamines à partir d'aan brut
PCT/EP2008/052405 WO2008104578A1 (fr) 2007-03-01 2008-02-28 Procédé de fabrication d'éthylénamines à partir d'aan brut

Publications (1)

Publication Number Publication Date
EP2132163A1 true EP2132163A1 (fr) 2009-12-16

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EP08717206A Withdrawn EP2132163A1 (fr) 2007-03-01 2008-02-28 Procédé de fabrication d'éthylénamines à partir d'aan brut

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US (1) US7960590B2 (fr)
EP (1) EP2132163A1 (fr)
JP (1) JP2010520167A (fr)
KR (1) KR20090122437A (fr)
CN (1) CN101622222A (fr)
WO (1) WO2008104578A1 (fr)

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JP5415286B2 (ja) * 2007-03-01 2014-02-12 ビーエーエスエフ ソシエタス・ヨーロピア エチレンアミン混合物の製造方法
KR20090122436A (ko) * 2007-03-01 2009-11-30 바스프 에스이 에틸렌디아민의 제조 방법
KR20090122434A (ko) * 2007-03-01 2009-11-30 바스프 에스이 에틸렌아민의 제조 방법
KR20090121293A (ko) * 2007-03-01 2009-11-25 바스프 에스이 아미노 니트릴의 제조 방법
CN102256932B (zh) 2008-12-19 2014-09-10 巴斯夫欧洲公司 制备纯三乙醇胺(teoa)的方法
CN102485711B (zh) * 2010-12-03 2013-12-11 万华化学集团股份有限公司 一种n1-(2-氨乙基)-1,2-乙二胺的制备方法
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US9096497B2 (en) 2011-08-31 2015-08-04 Basf Se Process for preparing EDDN and EDMN
US8952156B2 (en) 2011-08-31 2015-02-10 Basf Se Process for working up reaction outputs from the hydrogenation of EDDN or EDMN
WO2013030172A1 (fr) 2011-08-31 2013-03-07 Basf Se Procédé de régénération de catalyseurs de raney
US9012638B2 (en) 2011-08-31 2015-04-21 Basf Se Process for preparing EDDN and/or EDMN by conversion of FACH and EDA
EP2684862B1 (fr) * 2012-04-01 2018-11-14 Wanhua Chemical Group Co., Ltd. Procédé de préparation de n-(2-aminoéthyl)éthane-1,2-diamine
CN102924286B (zh) * 2012-10-31 2014-06-11 万华化学集团股份有限公司 一种n1-(2-氨乙基)-1,2-乙二胺的制备方法
WO2014131620A1 (fr) 2013-02-28 2014-09-04 Basf Se Procédé de production d'éthylène diamine en utilisant de l'acide prussique dépourvu de so2
CN103601644B (zh) * 2013-11-21 2015-07-29 万华化学集团股份有限公司 一种n1-(2-氨乙基)-1,2-乙二胺的制备方法
CN103752345B (zh) * 2014-01-28 2015-08-12 江西中浩高新材料股份有限公司 用于制备乙撑胺的催化剂
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CN113365975B (zh) * 2019-03-20 2024-10-25 三菱瓦斯化学株式会社 苯二甲胺的制造方法
CN117658825A (zh) * 2023-11-16 2024-03-08 陕西泰丰永兴新材料科技有限公司 一种处理氨基乙腈加氢反应输出物的方法

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KR20090122437A (ko) 2009-11-30
WO2008104578A1 (fr) 2008-09-04
CN101622222A (zh) 2010-01-06
JP2010520167A (ja) 2010-06-10
US20100121109A1 (en) 2010-05-13
US7960590B2 (en) 2011-06-14

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