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
  • 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
  • C07C209/52—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 imines or imino-ethers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
  • C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
  • C07C211/36—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton containing at least two amino groups bound to the carbon skeleton

Definitions

• IPDA Manufacture of IPDA to obtain a high product yield of IPDA.
• IPDA having a high isomer ratio of cis-lPDA to trans-lPDA.
• IPDA with a high cis-trans-ratio (CTR) of 75:25 and more are preferred in applications, which require a short pot-life and a short curing temperature. This is the case in most epoxy and PUR-applications. IPDA with a high CTR is therefore commercially preferred. Some customers specify a CTR of >75:25 for their applications.
• WO2012126956 discloses the hydrogenation of IPNI and/or IPN in a fixed-bed hydrogenation reactor in which the cross-sectional loading, based on the liquid phase passing through the reactor, is in the range of 5 kg/(m 2 s) to 50 kg/(m 2 s).
• the high cross-sectional loading is achieved by utilizing reactors with a slim design, i.e. , reactors in which the ratio of height to diameter of the reactor is in the range of 1 :1 to 500:1.
• the high cross-sectional loading is achieved by recycling a part of the product stream from the hydrogenation reactor.
• the ratio of the recycling stream to the feed stream is in the range of 0.5:1 to 250:1.
• a main difference between operating reactors with a different cross-sectional loading is the degree of back-mixing which may occur in the reactors because of the degree of cross-sectional loading in the reactor.
• the flow characteristic of the feed stream is expected to trend toward the flow characteristic of a continuously stirred tank reactor (CSTR).
• CSTR continuously stirred tank reactor
• the flow characteristic of the feed stream is expected to trend toward the flow characteristic of a plug-flow reactor.
• Back-mixing broadens the residence time distribution of volume elements within a reactor and leads to a more even temperature profile along the axis of the reactor, resulting in a more isothermal profile.
• Plug-flow with little or no back-mixing results in a narrow residence time distribution and a temperature profile with a temperature maximum between the inlet and the outlet of the reactor.
• a fixed bed reactor operated with a high cross-sectional loading and a broader residence time distribution is expected to have a lower degree of conversion of IPNI and partially hydrogenated IPNA, resulting in lower yields of IPDA and higher concentrations of IPNI and IPNA.
• IPDA having a high isomer ratio of cis-lPDA to trans-lPDA.
• WO2012126956 discloses a recycling stream from the second to the first hydrogenation reactor.
• WO2012126956 does not disclose a second hydrogenation reactor or a series of hydrogenation reactors downstream of where the recycle stream from the first reactor or first series of reactors branches off.
• EP3406589 discloses that that the hydrogenation is preferably carried out in a reactor where the educts pass through the reactor in a single pass, i.e. without recycling the effluent from the hydrogenation reactor to the feed.
• the process for the manufacture of IPDA comprises a second hydrogenation reactor or a second series of hydrogenation reactors which are located downstream of where the recycle stream from the first hydrogenation reactor or the first series of hydrogenation reactors to the feed of the first hydrogenation reactor or the first series of hydrogenation reactors branches off.
• the process according to the invention has the following advantages: the first hydrogenation reactor or the first series of hydrogenation reactors can be operated with a higher cross-sectional loading. This higher cross-sectional loading results in a more homogeneous temperature profile in the reactors. Hotspot formation may be significantly reduced. The avoidance of hotspots potentially results in fewer side products, increasing the selectivity and yield of IPDA. In addition, lower temperatures favor a high CTR, which is often desired in IPDA production.
• ammonia can be recycled to the reactor.
• the ammonia load to the downstream IPDA refining section, where hydrogen, ammonia and side products are separated can be reduced by the recycle stream.
• the temperature of the recycle stream may be increased when two or two series of hydrogenation reactors are used. It was found that the hydrogen solubility was increased with increasing temperature. A higher hydrogen solubility in the liquid phase generally results in higher conversion rates and reduced side product formation.
• the second hydrogenation reactor or the second series of hydrogenation reactors can be operated with a lower cross-sectional loading. Thus, the residence time in the reactors can be increased, which generally leads to higher conversions. coupling a first hydrogenation reactor or a first series of hydrogenation reactors with a second or a second series of hydrogenation reactors according to the invention was also surprisingly found to reduce the overall energy duty required for the operation of the thermal equipment. the equipment for cooling and separating the liquid and the gas phase in the downstream process after the last hydrogenation step can be designed with smaller dimensions.
• IPNI and/or IPN is hydrogenated to IPDA.
• the process according to the invention comprises the step a) of a) feeding a stream comprising IPNI and/or IPN to a first hydrogenation reactor or a first series of hydrogenation reactors.
• IPN is fully or partially converted to IPNI by imination before feeding IPNI or a mixture of IPNI and unconverted IPN to the first hydrogenation reactor or a first series of hydrogenation reactors.
• the imination of IPN is usually conducted at temperature from 20 to 150°C, preferably 30 to 100°C and more preferably 50 to 90°C and a pressure of 50 to 300 bar, preferably 100 to 250 bar and more preferably 150 to 220 bar.
• hydrogen is added after the imination step. It is however possible, that hydrogen is added prior to the imination step because the imination is usually carried out in the presence of catalysts which do not catalyse the hydrogenation of the imine or nitrile group.
• the temperature during the hydrogenation is usually in the range of 40 to 200°C, preferably 50 to 150°C, more preferably 60 to 140°C and most preferably 60 to 130°C and a pressure of 50 to 300 bar, preferably 100 to 250 bar and more preferably 150 to 220 bar.
• the hydrogenation is preferably carried out in the presence of hydrogenation catalysts, which usually comprise metals or semimetals from groups 1 to 17 of the Periodic Table as well as the rare earth metals.
• Preferred catalyst elements are Ni, Co, Fe, Cu, Ru. Hydrogenation catalysts may also comprise Cr, Cu, Mo. Wo and/or Re.
• Preferred hydrogenation catalysts comprise one or more of Ru and Co,
• the hydrogenation catalysts can of the so-called Raney-type or the metal-oxide type.
• Raney-type catalysts are Raney-Co-catalysts.
• the Raney-type catalysts may be supported or unsupported. Suitable Raney-Catalysts are further described in EP1207149, EP 2649042W02008107226, W02014086039 and WO2016120235,
• the hydrogenation catalysts can also be of the metal-oxide type.
• Metal-oxide catalysts are preferably obtained by precipitation of soluble salts of the catalyst elements in the presence of catalyst supports to obtain the corresponding hydroxides, carbonates and oxides and which are usually transformed to the corresponding oxides during a calcination step.
• the precipitation step may also be conducted without the presence of support materials.
• the hydrogenation catalyst may be produced by impregnation of a catalyst support with soluble salts of the metals.
• the metal-oxides catalysts are usually reduced in the presence of hydrogen prior to their use in the hydrogenation step.
• the reduced catalysts may be passivated by subjecting the reduced catalysts to an oxygen comprising gas in order to form a passivating and protective oxide layer which allows for safe handling and storage.
• the passivated catalysts may be reduced or activated prior to their use in the hydrogenation step. Activation and reduction of the metal oxide catalyst is preferably performed in the same reactor, in which the hydrogenation IPNI is performed.
• the reduction or passivation step may occur prior to the hydrogenation step, but it is also possible to reduce or activate the metal oxide catalysts in-situ during the hydrogenation of IPNI.
• the unreduced or inactivated catalyst is then transformed into its reduced form by the hydrogen present during the hydrogenation reaction.
• Preferred supports are alumina, including but not limited to transitional alumina and non-tradi- tional alumina, titania, zirconia, silica, magnesia, calcium oxide and mixtures thereof.
• the basicity of the feed comprising IPNI and/or IPN is increased prior or during the subsequent hydrogenation step.
• Preferred basic catalysts are those which are disclosed in WO 2008077852.
• Basic compounds can also be added in form of their solutions.
• Suitable basic compounds are ammonium hydroxide and amines.
• Preferred basic compounds are oxides, hydroxides and carbonate, in particular U2O, Na2O, K 2 O, Rb 2 O, Cs 2 O, LiOH, NaOH, KOH, RbOH, CsOH, Li 2 CO3, Na2CO 3 , K 2 CO 3 , Cs 2 CO 3 , Rb 2 CO 3 , MgO, CaO, SrO, BaO, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , MgCO 3 , CaCO 3 , SrCO 3 or
• BaCO 3 In particularly preferred basic compounds are LiOH, NaOH and KOH.
• the basic compounds are preferably added in form of their solutions in water or other suitable solvents, such as alkanols, like Ci-C4-alkanols, in particularly methanol or ethanol, or ethers, such as cyclic ether, in particularly THF or dioxane.
• alkanols like Ci-C4-alkanols
• ethers such as cyclic ether, in particularly THF or dioxane.
• the basic compounds are added in form of their aqueous solutions.
• the concentration of basic compounds in water or other suitable solvents is usually around 0,01 bis 20 percent by weight, preferably 0, 1 bis 10 percent by weight and more preferably 0,2 bis 5 percent by weight.
• the amount of added basic compound is usually determined in such a way as to yield a molar ratio of basic compound to IPNI and IPN is in the range of 100: 1 000 000 to 10 000: 1 000 000 and more preferably 200: 1 000 000 to 1000:1 000 000.
• the first hydrogenation reactor or the series of first hydrogenation reactions are preferably pressurized reaction vessels.
• each pressurized reaction vessel is a tubular reactor, and more preferably a tubular reactor where the hydrogenation catalyst is arranged in a fixed bed (fixed-bed reactor).
• step a) is conducted in in 1 to 3, more preferably 1 to 2 and even more preferably in one single reactor.
• step a) is conducted in a series of two or more hydrogenation reactors, the feed preferably passes from the feed inlet of the first hydrogenation reactor to the effluent outlet of the last hydrogenation reactor in one pass with preferably no branching-off of any side stream.
• the catalyst load during the hydrogenation is preferably in the range of 0.01 to 10, preferably 0.03 to 5, more preferably 0.05 to 3 kg IPNI and IPNI per kg catalyst per hour.
• step a at least a part of the effluent from the first hydrogenation reactor or the first series of hydrogenation reactors (step a) is fed to a second hydrogenation reactor or a second series of hydrogenation reactors (step b) and at least a part of the effluent from the first hydrogenation or the first series of hydrogenation reactors is recycled to the first hydrogenation reactor or the first series of hydrogenation reactors (step c).
• the mass ratio of the part of the feed from step a) which is fed to step b) and the part of the feed from step a) which is recycled in step c) is preferably in the range of 0.1 :1 to 10:1 , more preferably 0.2:1 to 5:1 and most preferably 0.3:1 to 2:1.
• the part of the effluent from step a) which is fed to step b) and the part which is recycled to step a) is controlled in such a manner that the cross-sectional loading of the first hydrogenation reactor is higher than the cross-sectional loading of the second hydrogen reactor or that at least the cross-sectional loading of at least one hydrogenation reactor in the first series of hydrogenation reactors is higher than the cross-sectional loading of at least one hydrogenation reactor of the second series of hydrogenation reactors.
• the cross-sectional loading of all reactors of the first series of hydrogenation reactors is higher than the cross-sectional loading of all reactors of the second series of hydrogenation reactors.
• the cross sectional loading of the first hydrogenation reactor or each reactor of the first series of hydrogenation reactors is 0.01kg/(m2s) or more, preferably 0.1 kg/(m2s) and more preferably 1 kg/(m2s) or more. In a more preferred embodiment, the cross sectional loading of the first hydrogenation reactor is 4 kg/(m2s) or more, preferably 5 kg/(m2s) and more preferably 7 kg/(m2s).
• the cross sectional loading of the second hydrogenation reactor or each reactor of the second series of hydrogenation reactors is 4 kg/(m2s) or less, preferably 3 kg/(m2s) or less and preferably 2 kg/(m2s) or less.
• the cross sectional loading of the first hydrogenation reactor or each reactor of the first series of hydrogenation reactors is 4 kg/(m2s) or more, preferably 5 kg/(m2s) and more preferably 7 kg/(m2s) or more and the cross sectional loading of the second hydrogenation reactor or each reactor of the second series of hydrogenation reactors is 4 kg/(m2s) or less, preferably 3 kg/(m2s) or less and preferably 2 kg/(m2s) or less.
• the cross-sectional loading of the reactor is calculated by means of formula (1) with the crosssection A of the reactor (unit [m2]) and the mass flow rate m (unit: [kg/s]) of liquid or dissolved reactants, ammonia and optionally solvents and/or further liquid reaction components (e.g., refluxes or liquid recycle streams).
• the gas phase of the reaction e.g., hydrogen, inert gases
• step b) it is preferred to heat that part of the effluent from step a) or the liquid phase from step a-1) which is fed to step b). Heating is preferably carried out by a crossflow heat exchanger in which the heat of the effluent from step b) is used to heat the effluent from step a) or the liquid phase from step a-1). In this way, the heat of reaction generated in step b) is efficiently used to minimize the overall energy consumption of the process.
• the second hydrogenation reactor or the second series of hydrogenation reactors are preferably pressurized reaction vessels.
• each pressurized reaction vessel is a tubular reactor, and more preferably a tubular reactor where the hydrogenation catalyst is arranged in a fixed bed (fixed-bed reactor).
• step a) is conducted in in 1 to 3, more preferably 1 to 2 and even more preferably in one single reactor.
• step b) is conducted in a series of two or more hydrogenation reactors, the feed preferably passes from the feed inlet of the first hydrogenation reactor of the second series of hydrogenation reactors to the effluent outlet of the last hydrogenation reactor in the second series of hydrogenation reactors in one pass, with preferably no branching-off of any side stream.
• the catalyst load during the hydrogenation in step b) is preferably in the range of 0.01 to 10, preferably 0.03 to 5, more preferably 0.05 to 3 kg IPNI and IPNI per kg catalyst per hour.
• the reaction conditions are substantially similar to the reaction conditions and catalysts used in step a), as specified above.
• the temperature in the second hydrogenation reactor or the second series of hydrogenation reactors is 5 to 40°C, preferably 10 to 30°C above the temperature of the first hydrogenation reactor or the first series of hydrogenation reactors.
• the pressure of the second hydrogenation reactor or the second series of hydrogenation reactors is slightly lower than the pressure in the first hydrogenation reactor or the first series of hydrogenation reactors.
• a part of the effluent obtained from step b) is recycled to the first hydrogenation reactor or the first series of hydrogenation reactors or the second hydrogenation reactor or the second series of hydrogenation reactors.
• This embodiment has the advantage of providing further flexibility for finetuning the cross-sectional loading of each hydrogenation reactor or series of hydrogenation reactors to further optimize the yield and the selectivity for I PDA.
• that part of the effluent from step b) which is recycled back to the step a) is cooled, preferably to a temperature in the range of 30 to 100°C, more preferably 40 to 85°C and most preferably 50 to 70°C. Cooling the recycle stream has the advantage that the formation of hotspots in the first hydrogenation reactor or the first series of hydrogenation reactors in step a) may be avoided.
• the CTR may be positively influenced.
• the process according to the present invention comprises an additional step b-1) after step b) in which the effluent from the second hydrogenation reactor or the second series of hydrogenation reactors is fed to a phase separator wherein the effluent is separated into a gas phase and a liquid phase.
• the effluent from step b) is cooled prior to feeding it into additional step b-1), as set out in the preceding paragraph.
• the gas phase obtained in step b-1) is preferably recycled to step a) or step b) so that ammonia and/or hydrogen present in the gas phase can be directly used for the hydrogenation reaction in step a) or b). If the gas phase is directly recycled to steps a) and/or b), the subsequent refining section for the removal of hydrogen and/or ammonia from the effluent from step b) can be dimensioned smaller because the equipment will need to handle lower amounts of hydrogen and/or ammonia.
• the effluent from step b) or step b-1), usually comprises cis-lPDA, trans-lPDA, IPNA, hydrogen, ammonia, components having a boiling point higher than cis-lPDA and optionally components having a boiling point lower than trans-lPDA.
• step b) or step b-1 When the effluent comprises hydrogen and ammonia, that part of the effluent from step b) or step b-1), which is not recycled, is usually worked-up by first separating hydrogen and ammonia.
• the separation of hydrogen is preferably carried out by subjecting the effluent to a high-pressure separator which usually results in the separation of a gaseous phase, comprising hydrogen and some ammonia, and a liquid phase comprising ammonia, cis-lPDA, trans-lPDA, IPNA, components having a boiling point higher than IPNA and optionally, components having a boiling point lower than trans-lPDA.
• a high-pressure separator which usually results in the separation of a gaseous phase, comprising hydrogen and some ammonia, and a liquid phase comprising ammonia, cis-lPDA, trans-lPDA, IPNA, components having a boiling point higher than IPNA and optionally, components having a boiling point lower than trans-lPDA.
• the high-pressure separator is usually operated at pressure slightly lower than the pressure at which the hydrogenation reactor is operated, preferably of 2 to 350 bar, preferably 10 to 240 bar and more preferably 30 to 210 bar.
• the gaseous phase is preferably compressed to the reaction pressure and recycled to the hydrogenation reactor.
• the liquid phase from the high-pressure separator is usually subjected to one or more separation step, in which ammonia is separated from the rest of the components.
• separation steps may comprise one or more flash operations, stripping operations or distillation operations to obtain an ammonia fraction and the crude IPDA fraction.
• ammonia is separated in one or more distillation columns.
• the distillation column is usually operated at pressures in the range of 5 to 50, preferably 10 to 40 and more preferably 15 to 30 bar.
• a second ammonia removal step is conducted after the first ammonia removal step.
• Such a second step is preferably conducted in another distillation column usually operated at 1.5 to 20, preferably 2 to 15 and more preferably 3.5 to 10 bar.
• composition of the effluent from step b) after removal of ammonia and/or hydrogen is usually denoted as “crude IPDA”.
• Figure 1 shows the simplest embodiment of the invention.
• a feed comprising IPNI and/or IPN is fed into a first hydrogenation reactor R1 in which at least a part of the IPNI and/or IPN is converted to IPDA.
• a part of the effuent from reactor R1 (step a) is recycled to the feed of reactor R1 .
• the other part of the effluent from reactor R1 (step a) is fed into a second hydrogenation reactor R2.
• a second hydrogenation reactor R2 By splitting the effluent from step a) into a recycle stream and a feed stream to the second hydrogenation reactor R2, it is possible of operating both reactors with a different cross- sectional loading.
• By operating reactor R1 with a higher cross-sectional loading allows for the avoidance of hot spots leading to the formation of undesired side products.
• Operating reactor R2 with a lower cross-sectional loading allows to increase the conversion of IPNI and/or IPN.
• the dimensions of reactor R2 may be reduced due to the lower feed rate.
• the recycle stream is cooled, which allows for further reduction of hotspots in reactor R1.
• the part of the effluent from reactor R1 which is fed to reactor R2 may be heated prior to entering reactor R2 in order to increase the conversion rate in reactor R2.
• some heat from the effluent of reactor R2 is used to heat the feed to reactor R2 in a cross-flow heat exchanger. It is also possible to recycle a part of the effluent from Step b) to the the feed of reactor R1 and/or to the reactor R2.
• Figure 2 shows an embodiment of the invention comprising a first series of two hydrogenation reactor R1-1 and R1-2 (step a) and a second series of two hydrogenenation reactors R2-1 and R2-2 (step b).
• a part of the effluent from the first series of hydrogenation reactors (R1-1 and R1-2) is recycled to the feed of reactor R1-1.
• a part of the effluent from reactor R1-2 may also be recycled directly to reactor R1-2.
• the other part of the effluent from the first series of hydrogenation reactors (R1-1 and R1-2) is fed into the first reactor R2-1 of the second series of hydrogenation reactors.
• the recycle stream from reactor R1-1 may be cooled prior to feeding it into reactors R1-1 or R1-2.
• the effluent from reactor R1-2 which is fed to reactor 2-1 may be heated, preferably with a cross-flow heat exchanger utilizing the heat of the effluent stream from reactor R2-2.
• a part of the effluent from reactor R2-2 may also be recycled to reactors R1-1 or R1-2 or R-21 or R2-1 to allow for improved flexibility for finetuning the individual cross-sectional loadings to the individual reactors.
• FIG 3 shows the embodiment shown and described in Figure 1 with an additional separator for carrying out step a-1) and another separator for carrying out step b-1).
• step a-1 the effluent from reactor R1 is separated into a gas and a liquid phase. A part of the liquid phase is recycled to the feed of reactor R1 . The other part of the liquid phae is fed into reactor R2. The separated gas feed is reintroduced into the feed stream for reactor R2.
• step b-1 the effluent from reactor R2 is separated into a gas phase and a liquid phase.
• the gas phase is recycled to the feed of reactor R1 with the help of a compressor.
• the cooler at the outlet of reactor R2 is optional and allows to cool the effluent from reactor R2 prior to step b-1).
• the process according to the invention has the following advantages: the first hydrogenation reactor or the first series of hydrogenation reactors can be operated with a higher cross-sectional loading. This higher cross-sectional loading results in a more homogeneous temperature profile in the reactors. Hotspot formation may be significantly reduced. The avoidance of hotspots potentially results in fewer side products, increasing the selectivity and yield of IPDA. In addition, lower temperatures favor a high CTR, which is often desired in IPDA production.
• ammonia can be recycled to the reactor.
• the ammonia load to the downstream IPDA refining section, where hydrogen, ammonia and side products are separated can be reduced by the recycle stream.
• the temperature of the recycle stream may be increased when two or two series of hydrogenation reactors are used. It was found that the hydrogen solubility was increased with increasing temperature. A higher hydrogen solubility in the liquid phase generally results in higher conversion rates and reduced side product formation.
• the second hydrogenation reactor or the second series of hydrogenation reactors can be operated with a lower cross-sectional loading. Thus, the residence time in the reactors can be increased, which generally leads to higher conversions. coupling a first hydrogenation reactor or a first series of hydrogenation reactors with a second or a second series of hydrogenation reactors according to the invention was also surprisingly found to reduce the overall energy duty required for the operation of the thermal equipment. the equipment for cooling and separating the liquid and the gas phase in the downstream process after the last hydrogenation step can be designed with smaller dimensions.

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• 2023
  • 2023-11-23 WO PCT/EP2023/082817 patent/WO2024115263A1/en not_active Ceased
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